JP2012166386A - Multilayered structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a multilayered structure reducing weight and simultaneously maintaining excellent flame resistance, being excellent in moldability, and being excellent in heat resistance.SOLUTION: The multilayered structure includes: a foaming layer comprised of a foaming bead molding where the flame resistance measured based on a UL-94 vertical method (20 mm vertical burning test) of a UL standard is V-0 or V-1; and a high gap layer of at least one layer.

Description

  The present invention relates to a multilayer structure.

  Conventionally, plastics and metals have been adopted as materials for internal parts and containers of automobiles and electronic devices. Since plastics are lighter than metals and the like, they are used for electronic devices, sundries, automobile parts, and the like. On the other hand, from the viewpoint of energy saving or the like, there is a demand for a material that is lighter and has more excellent physical properties such as strength and impact resistance. One candidate for such a material is a resin foam molding.

  As resin foam moldings, flame retardant resin foam beads to which a flame retardant is added and molded articles thereof are known (Patent Documents 1 and 2). A multilayer foam sheet in which resin foams are laminated is known (Patent Document 3).

JP 2000-95892 A No. 2003-004552 JP 2007-320264 A

  By using the resin foam molding, the weight reduction is satisfactory as compared with conventional plastics and metals. However, since the resin foam molded body contains a large amount of air, it is easy to burn and cannot be applied to electronic devices and automotive parts that require flame retardancy.

  In order to improve the flame retardancy of a resin foam molded article, for example, as disclosed in Patent Documents 1 and 2, a resin foam molded article to which a flame retardant is added is known. However, by adding a flame retardant, an excellent flame retardancy improving effect can be obtained with an unfoamed resin molded product, but the flame retardant improving effect is significantly lower with a resin foam molded product than with an unfoamed resin molded product. This is because when compared with a molded product of the same size, the resin foam molded product has a smaller amount of resin per unit volume than an unfoamed resin molded product, so it is difficult to form a carbonized layer, and the combustion time becomes longer. Because it ends up. In addition, since the resin foam molded body has a small amount of resin, it tends to be softened by the heat of combustion, and as a result, the resin dripping easily occurs during combustion.

  On the other hand, when the amount of the flame retardant added to the resin foam molded body is increased, the mechanical properties such as strength and impact resistance are reduced, although the flame retardancy improving effect is improved. In addition, when the flame retardant has a property of plasticizing a resin, there are problems such as a decrease in heat resistance of the resin foam molded body and a decrease in expansion viscosity due to a decrease in elongation viscosity. For this reason, it has been extremely difficult to facilitate not only molding processability to resin foam moldings but also easy processing into complicated and fine shapes, and simultaneously satisfy weight reduction and flame retardancy improvement.

  On the other hand, like the multilayer foam sheet disclosed in Patent Document 3, a resin foam molded body (multilayer structure) in which resin foams are laminated is excellent in physical properties such as heat insulation. However, a multilayer structure having excellent physical properties such as heat insulation and sufficient flame retardancy, including the multilayer foam sheet disclosed in Patent Document 3, has not been known so far.

  Therefore, an object of the present invention is to provide a multilayer structure that maintains excellent flame retardancy as well as weight reduction, is excellent in molding processability, and is excellent in heat insulation.

The present invention provides the following [1] to [10].
[1] A foamed layer formed of a foamed bead molded body having a flame retardancy of V-0 or V-1 measured according to UL standard UL-94 vertical method (20 mm vertical combustion test), and at least one layer A multilayer structure comprising a high void layer.
[2] The multilayer structure according to [1], wherein the concentration of the aliphatic hydrocarbon gas in the foam layer is 1000 ppm by volume or less.
[3] The multilayer structure according to [1] or [2], wherein the foamed bead molded body is made of a base resin including a polyphenylene ether resin or a polycarbonate resin and a flame retardant.
[4] The multilayer structure according to [1] or [2], wherein the foamed bead molded body is made of a base resin containing a polyphenylene ether resin and a flame retardant.
[5] The multilayer structure according to [3] or [4], wherein the base resin further contains a polystyrene-based resin.
[6] The multilayer structure according to any one of [3] to [5], wherein the base resin further contains a rubber component.
[7] The base resin contains 40 to 94% by mass of a polyphenylene ether resin, 5 to 20% by mass of a flame retardant, and 0.3 to 10% by mass of a rubber component, and the balance is made of a polystyrene resin. [3] The multilayer structure according to any one of [6].
[8] The multilayer structure according to any one of [3] to [7], wherein the flame retardant is a non-halogen flame retardant.
[9] The multilayer structure according to any one of [1] to [8], wherein the high void layer is a layer made of a foamed resin or a layer made of an inorganic material.
[10] The high void layer is a layer made of a foamed resin obtained by foaming a polyolefin resin or a polystyrene resin, or a layer made of an inorganic material selected from the group consisting of an inorganic material having a fine porous structure, rock wool and glass wool. The multilayer structure according to any one of [1] to [8].
[11] A heat insulating material comprising the multilayer structure according to any one of [1] to [10].

  According to the present invention, it is possible to provide a multilayer structure having excellent flame retardancy as well as weight reduction, excellent molding processability, and excellent heat resistance and heat insulation.

  The multilayer structure of the present invention has excellent heat resistance, heat insulation, and flame retardancy, so products and members of complicated shapes that cannot be easily achieved with metals or unfoamed resins, such as significantly Chassis components, deck boards, door trims, ceiling members, and other automotive parts for electronic devices that enable simplified assembly, structural materials for office automation equipment, insulation materials for hot water tanks, etc., even in high-temperature environments with high dimensional accuracy Can be provided.

  The present invention will be specifically described below. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

[Multilayer structure]
The multilayer structure of the present invention has a foam layer and at least one high void layer. For example, a two-layer structure in which a high void layer is laminated on a foam layer and a three-layer structure in which a high void layer is laminated on the front and back surfaces of the foam layer can be used. The high void layer may be a laminate of two or more layers. When there are a plurality of high void layers, they may be layers formed from the same material, or may be layers formed from different materials.

  Since the foamed layer in the multilayer structure of the present invention is made of a foamed bead molded product, it can be processed into a fine and complicated shape. Further, the high void layer can be molded according to the shape of the foam layer. Therefore, the shape of the multilayer structure can be arbitrarily formed according to the shape of a product, member, or the like in which the multilayer structure is used.

  The thermal conductivity of the multilayer structure of the present invention is not particularly limited, but is preferably 0.020 to 0.060 W / m · K, more preferably 0.025 to 0.050 W / m · K, and more preferably 0.030 to 0. 0.045 W / m · K is even more preferred. When the thermal conductivity is 0.020 to 0.060 W / m · K, the heat insulating property of the multilayer structure is further improved, and it can be suitably used for various applications such as a hot water tank heat insulating material.

[Foam layer]
The foamed layer is made of a foamed bead molded body having a flame retardancy of V-0 or V-1 measured according to UL standard UL-94 vertical method (20 mm vertical combustion test). By providing such a foamed layer, the multilayer structure of the present invention is excellent in flame retardancy and heat resistance regardless of the type and characteristics of the resin layer. That is, the multilayer structure of the present invention can maintain excellent flame retardancy as well as weight reduction, has excellent heat resistance, and can be easily processed into a fine and complicated shape.

  The shape and size of the foamed layer (foamed bead molded product) can be arbitrarily set according to the shape of a product or member in which the multilayer structure is used. The shape and size of the foamed layer can be controlled by, for example, the shape and size of the molding die used when producing the foamed bead molded body.

  The thickness of the foam layer is preferably from 3.0 to 50 mm, more preferably from 5.0 to 30 mm. In addition, the thickness of a foamed layer means the intermediate value of the maximum thickness and the minimum thickness including the case where a foamed layer has a complicated shape.

[Foamed beads molded body]
The foamed bead molded body according to the present invention has a flame retardancy measured according to UL standard UL-94 vertical method (20 mm vertical combustion test) of V-0 or V-1. The foamed bead molded body means a molded body obtained by molding foamed beads.

  In general, the higher the expansion ratio is, the more air is contained and the more difficult it is to achieve flame retardancy. However, the foamed bead molded product according to the present invention is a UL standard UL-94 vertical method even when the expansion ratio is high. The flame retardancy measured according to (20 mm vertical combustion test) satisfies V-1 or more. The UL standard UL-94 vertical method (20 mm vertical combustion test) is a test that gives an index of the flame retardancy of a resin. Specifically, a test piece of a specific size is mounted vertically on the clamp, and a 10-second indirect flame with a 20 mm flame is performed. The flammable combustion duration, the presence or absence of combustion up to the position of the clamping clamp, and the burning fallen object V-0, V-1, V-2, or non-conformity is determined by the presence or absence of cotton ignition. Usually, the UL-94 vertical method (20 mm vertical combustion test) is used for flame retardancy evaluation in unfoamed resin. Since unfoamed resin is easier to impart flame retardancy than resin foam, it is a severe test for resin foam.

  The foamed bead molded body according to the present invention has a flame retardance measured in accordance with the UL standard UL-94 vertical method (20 mm vertical combustion test) satisfying V-1 or higher, so that It can be used as an alternative material in parts that require high flame resistance, such as those that have mainly been used for resins and metals, and at the same time, it is possible to obtain light weight and excellent moldability to molded products. It is done.

  The closed cell ratio of the expanded bead molded product according to the present invention is preferably as high as possible, preferably 50% or more, and more preferably 60% or more. When the closed cell ratio is 50% or more, there is little adverse effect on the compressive strength, residual strain, etc. of the expanded bead molded body, and the expanded bead molded body has excellent physical properties.

  The expansion ratio of the foamed bead molded body according to the present invention is not particularly limited, but is preferably 1.5 to 40 cc / g, and more preferably 2 to 25 cc / g. When the expansion ratio is in the range of 1.5 to 40 cc / g, it is easy to maintain excellent flame retardancy while taking advantage of the weight reduction.

  Although the heating dimensional change rate of the foamed bead molded body according to the present invention is not particularly limited, it is preferably 10% or less, more preferably 5% or less, and further preferably 3% or less at 100 ° C. When the heating dimensional change rate is 10% or less, the heat resistance is excellent, so it can be applied to a member used in a high temperature environment, and can be stored for a long time in a high temperature environment in summer. Is possible.

  The deflection temperature under load (HDT) of the foamed bead molded product according to the present invention is not particularly limited, but is preferably 60 ° C. or higher, more preferably 70 ° C. or higher. When the deflection temperature under load is 60 ° C. or higher, the heat resistance is excellent and the same effect as described above can be obtained.

  The concentration of the aliphatic hydrocarbon gas contained in the foamed bead molded product according to the present invention is preferably 1000 ppm by volume or less. In the present specification, the concentration of the aliphatic hydrocarbon gas is a value (volume) obtained by dividing the volume of the aliphatic hydrocarbon gas contained in the expanded bead molded body by the volume of the expanded bead molded body. ppm), and 1 volume ppm (hereinafter also simply referred to as “ppm”) corresponds to 0.0001 volume%. The same applies to the concentration of the aliphatic hydrocarbon gas remaining in the expanded beads.

  Examples of the aliphatic hydrocarbon gas include propane, n-butane, i-butane, n-pentane, i-pentane, neopentane and the like. When the concentration of the aliphatic hydrocarbon gas is 1000 ppm or less, the seed fire does not smolder for a long time during combustion (referred to as glowing). In the combustion test such as UL-94, the glowing time is specified in addition to the combustion time, and if the residual gas amount is small, it becomes possible to clear the combustion test, in particular, the standard of V-0.

[Foamed beads]
The foam beads used for the foam bead molded body are obtained by foaming a base resin. The expanded beads preferably have an average particle diameter of 0.5 to 10 mm, and more preferably 0.7 to 5 mm. When the average particle diameter of the expanded beads is 0.5 to 10 mm, the molded expanded beads having a complicated and fine shape can be formed more easily.

  The density of the expanded beads is preferably 0.033 to 0.80 g / cc, more preferably 0.04 to 0.67 g / cc, and 0.05 to 0.5 g / cc. Further preferred. When the density of the expanded beads is 0.033 to 0.80 g / cc, it becomes even easier to satisfy desired flame retardancy while satisfying weight reduction.

  The expansion ratio of the expanded beads is not particularly limited, but is preferably 1.5 to 30 cc / g, and more preferably 2 to 20 cc / g. When the expansion ratio is in the range of 1.5 to 30 cc / g, the flame retardancy tends to be easily maintained while taking advantage of weight reduction. When adjusting to a desired expansion ratio in multiple stages, the primary expansion ratio is preferably 1.4 to 10 cc / g. Within this range, the cell size tends to be uniform, and the secondary foaming ability tends to be imparted.

  The higher the closed cell ratio of the expanded beads, the better, preferably 50% or more, more preferably 60% or more. When the closed cell ratio is 50% or more, the foamed beads tend to be more excellent in moldability into a foamed bead molded body.

[Base resin]
The base resin includes at least a resin component. In addition to these, for example, a flame retardant, a rubber component and the like may be included.

  Examples of the resin component include thermoplastic resins and thermosetting resins. Examples of the thermoplastic resin include polyolefin resins such as polyethylene, polypropylene, EVA (ethylene-vinyl acetate copolymer), polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, ABS (acrylonitrile-butadiene-styrene) resin, and AS (acrylonitrile). -Styrene) resin, polystyrene resin, methacrylic resin, polyamide resin, polycarbonate resin, polyphenylene ether resin, polyimide resin, polyacetal resin, polyester resin, acrylic resin, cellulose resin, styrene resin, poly Thermoplastic elastomers such as vinyl chloride, polyurethane, polyester, polyamide, 1,2-polybutadiene, fluororubber, polyamide, polyacetal, polyester, fluorine Thermoplastic engineering plastics, rubber powder and the like. These may be used alone or in combination. Moreover, you may use the resin modified and bridge | crosslinked in the range which does not impair the objective of this invention. Examples of the thermosetting resin contained in the base resin include amino resins such as phenol resins, urea resins, and melamine resins, unsaturated polyester resins, and epoxy resins.

  Among these, a thermoplastic resin containing a polyphenylene ether resin or a polycarbonate resin is preferable in terms of improving flame retardancy.

  In the present specification, the polycarbonate resin is preferably a carbonate resin derived from bisphenols and phosgene (or diphenyl carbonate), and has a high glass transition point and heat resistance. Examples of such polycarbonate resins include 2,2′-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2′-bis (4-hydroxyphenyl) butane (bisphenol B), 1,1. '-Bis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) methane (bisphenol F), 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane 1,1-bis (4-hydroxyphenyl) -1-phenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,2-bis (4-hydroxyphenyl) ethane, etc. Polycarbonates are preferred. These polycarbonates generally have a glass transition point (Tg) of 140-155 ° C.

  The polycarbonate resin preferably has a weight average molecular weight of 18,000 to 60,000.

  In this specification, the weight average molecular weight is a calibration curve (standard polystyrene) obtained by measuring by gel permeation chromatography (GPC) and measuring the molecular weight of the peak of the chromatogram from measurement of commercially available standard polystyrene. The weight average molecular weight was determined using the following formula.

  Polycarbonate resins can be mixed with one or more other types of resins, such as polyethylene resins, polypropylene resins, acrylonitrile-butadiene-styrene copolymers (ABS resins), polystyrene resins, polyethylene terephthalate, Examples include polybutylene terephthalate, acrylonitrile-styrene copolymer (AS resin), syndiotactic polystyrene, polyphenylene oxide, polyacetal, polymethyl methacrylate, polyphenylene sulfide, polyethersulfone, polyarylate, polyamide, polyimide, or polyethylene naphthalate. It is done.

  When mixed with other resins, the content of the polycarbonate resin is preferably 50% by mass or more, and more preferably 70% by mass or more from the viewpoint of flame retardancy.

In this specification, the polyphenylene ether resin refers to a polymer represented by the following general formula (1). Here, in general formula (1), R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen, halogen, alkyl group, alkoxy group, phenyl group, or halogen and benzene in general formula (1). A haloalkyl group or haloalkoxy group having at least two carbon atoms between the ring and not containing a 3α-carbon is shown. N is an integer representing the degree of polymerization.

  As the polyphenylene ether resin, those having a weight average molecular weight of 20,000 to 60,000 are preferable.

Examples of polyphenylene ether resins include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, and poly (2-methyl-6-ethyl). -1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-ethyl-6) -Propyl-1,4-phenylene) ether, poly (2,6-dibutyl-1,4-phenylene) ether, poly (2,6-dilauryl-1,4-phenylene) ether, poly (2,6-diphenyl) -1,4-diphenylene) ether, poly (2,6-dimethoxy-1,4-phenylene) ether, poly (2,6-diethoxy-1,4-phenylene) ether , Poly (2-methoxy-6-ethoxy-1,4-phenylene) ether, poly (2-ethyl-6-stearyloxy-1,4-phenylene) ether, poly (2,6-dichloro-1,4-phenylene) Phenylene) ether, poly (2-methyl-6-phenyl-1,4-phenylene) ether, poly (2,6-dibenzyl-1,4-phenylene) ether, poly (2-ethoxy-1,4-phenylene) Examples include ether, poly (2-chloro-1,4-phenylene) ether, poly (2,6-dibromo-1,4-phenylene) ether, but are not limited thereto. Among these, R ¹ and R ² are preferably an alkyl group having 1 to 4 carbon atoms, and R ³ and R ⁴ are preferably hydrogen or an alkyl group having 1 to 4 carbon atoms. These may be used alone or in combination of two or more.

  Polyphenylene ether resins can be mixed with one or more other types of resins. Examples include polystyrene resins, polyolefin resins represented by polypropylene, engineering plastic resins represented by polyamide, and polyphenylene sulfide. Examples thereof include super engineering plastic resins. Among these, it is preferable to mix with a polystyrene-type resin from the point of workability improvement.

  In this specification, the polystyrene-based resin refers to a copolymer having styrene and a styrene derivative as a main component in addition to a homopolymer of styrene and a styrene derivative. Examples of the styrene derivative include o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, α-methylstyrene, β-methylstyrene, diphenylethylene, chlorostyrene, bromostyrene, and the like. It is not limited.

  Examples of the homopolymer polystyrene resin include polystyrene, poly α-methylstyrene, polychlorostyrene, and the like. Examples of the polystyrene resin of the copolymer include styrene-butadiene copolymer and styrene-acrylonitrile copolymer. Styrene-maleic acid copolymer, styrene-maleic anhydride copolymer, styrene-maleimide copolymer, styrene-N-phenylmaleimide copolymer, styrene-N-alkylmaleimide copolymer, styrene-N-alkyl Substituted phenylmaleimide copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-methyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-n-alkyl acrylate copolymer, styrene -N-alkyl meta In addition to a relate copolymer and an ethyl vinyl benzene-divinyl benzene copolymer, terpolymers such as ABS and butadiene-acrylonitrile-α-methyl benzene copolymer may also be mentioned, but are not limited thereto. .

  Also included are graft copolymers such as styrene graft polyethylene, styrene graft ethylene-vinyl acetate copolymer, (styrene-acrylic acid) graft polyethylene, styrene graft polyamide and the like. These may be used alone or in combination of two or more.

  As the polystyrene resin, those having a weight average molecular weight of 180,000 to 500,000 are preferable.

  The base resin preferably contains a flame retardant from the viewpoint of improving flame retardancy. Examples of flame retardants include organic flame retardants and inorganic flame retardants. Examples of organic flame retardants include halogen compounds represented by bromine compounds and non-halogen compounds represented by phosphorus compound silicone compounds. is there. Examples of the inorganic flame retardant include metal hydroxides represented by aluminum hydroxide and magnesium hydroxide, antimony trioxide, and antimony compounds represented by antimony pentoxide.

  Among the above flame retardants, from the viewpoint of the environment, non-halogen flame retardants are preferable, and phosphorus flame retardants and silicone flame retardants are more preferable, but the invention is not limited thereto.

  As the phosphorus-based flame retardant, one containing phosphorus or a phosphorus compound can be used. Examples of phosphorus include red phosphorus. Examples of phosphorus compounds include phosphate esters and phosphazene compound groups having a bond between a phosphorus atom and a nitrogen atom in the main chain. Examples of phosphate esters include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate , Crecresyl phenyl phosphate, dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, hydroxyphenyl diphenyl phosphate, resorcinol bisdiphenyl phosphate, etc., and compounds obtained by modifying these with various substituents and various condensation types These phosphate ester compounds are also included. Among these, from the viewpoints of heat resistance, flame retardancy, and foamability, triphenyl phosphate and a phosphate compound represented by the general formula (2) are preferable.

ここで、一般式（２）中、Ｑ^１〜Ｑ^８は、それぞれ独立に、水素、ハロゲン、アルキル基、アルコキシ基、フェニル基を示す。一般式（２）におけるＱ^１〜Ｑ^４で好ましいのは水素又はメチル基である。一般式（２）におけるＱ^５、Ｑ^６で好ましいのは水素であり、Ｑ^７、Ｑ^８で好ましいのはメチル基である。一般式（２）におけるｍは１以上の整数である。該リン酸エステル化合物はｍ量体の混合物であっても構わない。一般式（２）におけるｎ１〜ｎ４は、それぞれ独立に１〜５の整数であり、ｎ５及びｎ６は、それぞれ独立に１〜４の整数である。

Here, in the general formula ^(2), Q 1 ~Q ⁸ each independently represent hydrogen, halogen, alkyl group, alkoxy group, phenyl group. Preferable Q ^{1 to} Q ⁴ in the general formula (2) are hydrogen or a methyl group. In the general formula (2), Q ⁵ and Q ⁶ are preferably hydrogen, and Q ⁷ and Q ⁸ are preferably a methyl group. M in the general formula (2) is an integer of 1 or more. The phosphate ester compound may be a mixture of m-mers. In the general formula (2), n1 to n4 are each independently an integer of 1 to 5, and n5 and n6 are each independently an integer of 1 to 4.

  In addition, (mono or poly) organosiloxanes can be used as the silicone flame retardant. Examples of (mono or poly) organosiloxanes include monoorganosiloxanes such as dimethylsiloxane and phenylmethylsiloxane, and polydimethylsiloxane, polyphenylmethylsiloxane, and copolymers thereof obtained by polymerizing these. And organopolysiloxanes. In the case of organopolysiloxane, the bonding group of the main chain or branched side chain is hydrogen or an alkyl group or a phenyl group, preferably a phenyl group, a methyl group, an ethyl group, or a propyl group, but is not limited thereto. . As the terminal linking group, any of a hydroxyl group, an alkoxy group, an alkyl group, and a phenyl group is used. There is no restriction | limiting in particular also in the shape of silicones, Arbitrary things, such as oil shape, gum shape, varnish shape, powder shape, pellet shape, can be utilized.

  Further, conventionally known various flame retardants and flame retardant aids, for example, cyclic nitrogen compounds, specific examples thereof include melamine, ammelide, ammelin, benzoguanamine, succinoguanamine, melamine cyanurate, melam, melem, methone, melon Compounds having a triazine skeleton such as sulfates thereof, alkali metal hydroxides or alkaline earth metal hydroxides such as magnesium hydroxide and aluminum hydroxide containing crystal water, zinc borate compounds, zinc stannate compounds Etc. may also be used. Moreover, you may include not only 1 type but multiple combinations.

  It is more preferable that the base resin contains a rubber component from the viewpoint of improving foamability.

Examples of the rubber component include, but are not limited to, butadiene, isoprene, 1,3-pentadiene, and the like. These are preferably dispersed in the form of particles in a continuous phase made of polystyrene resin. As a method for adding these rubber components, the rubber component itself may be added, or a resin such as a styrene elastomer or a styrene-butadiene copolymer may be used as a rubber component supply source. In the latter case, the ratio (R) of the rubber component can be calculated by the following formula.
R = C × Rs / 100
C: Rubber concentration (mass%) in the rubber component supply source
Rs: Rubber supply source content in the base resin (mass%)

  In addition to the above, the base resin includes other thermoplastic resins, antioxidants, thermal stabilizers, lubricants, pigments, dyes, weather resistance improvers, impact modifiers, glass beads, inorganic fillers. Further, a nucleating agent such as talc and the like may be added as long as the object of the present invention is not impaired. In particular, it is preferable to add polytetrafluoroethylene (PTFE) to the base resin. PTFE is suitable for preventing dripping during a combustion test, and is effective in improving flame retardancy.

  The content of the resin component in the base resin is preferably 40 to 100% by mass and more preferably 45 to 95% by mass with respect to the total amount of the base resin.

  When the base resin includes a polyphenylene ether resin as a resin component, the content of the polyphenylene ether resin is preferably 40 to 94% by mass with respect to the total amount of the base resin, and is 45 to 90% by mass. More preferably, it is more preferably 50 to 85% by mass.

  When the base resin includes a polycarbonate resin as a resin component, the content of the polycarbonate resin is preferably 70 to 97% by mass, and 80 to 95% by mass with respect to the total amount of the base resin. Is more preferable, and it is still more preferable that it is 82-90 mass%.

  As for content of the flame retardant in base-material resin, 5-20 mass% is preferable with respect to base-material resin whole quantity. When the content of the flame retardant is 5% by mass or more, desired flame retardancy tends to be easily exhibited. When it is 20% by mass or less, the plasticizing effect of the base resin by the flame retardant becomes appropriate, and the heat resistance tends to be improved. Furthermore, the expansion viscosity of the resin at the time of foaming can be improved, the foaming ratio can be further increased, the closed cell ratio of the foamed beads is further improved, and the molding processability to the foamed bead molded body is further improved. Become. Thus, it is very important to adjust the balance between flame retardancy and foamability.

  When the base resin contains a rubber component, the content of the rubber component is preferably 0.3 to 10% by mass, more preferably 0.5 to 8% by mass, and 1 to 5% by mass with respect to the total amount of the base resin. % Is more preferable. When it is 0.3% by mass or more, desired flame retardancy tends to be easily exhibited. Furthermore, if it is 0.5% by mass or more, the resin is excellent in flexibility and elongation, the foamed cell membrane is difficult to break at the time of foaming, the foaming ratio is increased, and foamed beads having excellent moldability after foaming are easily obtained. Tend to be. When flame retardancy is regarded as important, it is preferable to add more polyphenylene ether-based resin and flame retardant, but both of these tend to have an adverse effect on foaming properties as the addition amount increases. In such a composition, a rubber component is suitable for imparting foamability. This is particularly important in bead foaming in which the temperature is gradually raised from room temperature and the resin is foamed in a non-molten state, and is greatly different from extrusion foaming in which a molten resin is foamed. From the viewpoint of the degree of freedom of the shape of the molded product, a foamed bead that can be filled into a desired mold and molded is more advantageous than an extruded foam that is extruded into a plate shape. It is very useful to achieve both foaming.

  On the other hand, if the content of the rubber component is 10% by mass or less, the desired flame retardancy tends to be easily exhibited. Furthermore, it is in the tendency for sufficient heat resistance to be acquired as it is 8 mass% or less. The shape of the rubber particles is not particularly limited, and a so-called salami structure in which a plurality of polystyrene resin fine particles are encapsulated inside a particle having a rubber component as an outer shell may be formed, and the rubber component is an outer shell. A so-called core-shell structure in which a single styrene resin fine particle is encapsulated inside the particle may be used. The rubber particle size of the rubber component is not particularly limited, but is preferably 0.5 to 5.0 μm for the salami structure and 0.1 to 1.0 μm for the core-shell structure. If it is within this range, it tends to easily exhibit more excellent foamability.

  The base resin preferably contains, for example, a polyphenylene ether resin, a polystyrene resin, a flame retardant, and a rubber component. In this case, the content of each component is 40 to 94% by mass of a polyphenylene ether resin, 5 to 20% by mass of a flame retardant, and 0.3 to 10% by mass of a rubber component, and the balance is preferably made of a polystyrene resin. .

  When the content of the polyphenylene ether-based resin is 40% by mass or more, the heat resistance is further improved, and the flame retardancy, particularly the resin dripping prevention performance during combustion tends to be remarkably improved. In order to prevent dripping of the resin during combustion, it is important to (1) shorten the combustion time and (2) increase the heat resistance of the resin (make it difficult to soften), but just increasing the amount of flame retardant added (2) has an adverse effect, and in order to prevent resin dripping in a thinner sample, the content of the polyphenylene ether-based resin is preferably 40% by mass or more.

  On the other hand, if the content of the polyphenylene ether resin exceeds 94% by mass, the temperature required for processing such as foaming and molding tends to increase rapidly, which not only increases utility costs but also requires special equipment. It is inferior to actual productivity.

  The content of the polyphenylene ether resin in the base resin is more preferably 45 to 90% by mass, and still more preferably 50 to 85% by mass. By setting the content to 45 to 90% by mass, the foaming temperature and the molding temperature tend to be lower while maintaining flame retardancy and heat resistance, and the processing tends to be easier.

  In addition, content of a polystyrene-type resin is suitably adjusted so that the said other component may become desired content.

  The base resin can also contain, for example, a polycarbonate-based resin and a flame retardant. In this case, the content of each component can be, for example, 80 to 95% by weight of a polycarbonate resin and 5 to 20% by weight of a flame retardant.

  The shape of the base resin is not particularly limited, and examples thereof include beads, pellets, spheres, and irregular pulverized products. The magnitude | size becomes like this. Preferably it is 0.2-5.0 mm, More preferably, it is 0.2-3.0 mm. When the size is within this range, the foamed beads after foaming have an appropriate size and are easy to handle, and the filling during molding tends to be denser.

[Method for producing foam bead molded body]
Next, the manufacturing method of the foam bead molded object which concerns on this invention is demonstrated.

  The foamed bead molded body according to the present invention includes a foaming agent contained in (impregnated in) a base resin (impregnation step), and foamed beads are formed by foaming (foaming step). It can be obtained by filling and foaming (molding process).

  In the impregnation step, the method of adding a foaming agent to the base resin is not particularly limited, and a generally performed method can be applied. As a method of containing a foaming agent, a method using an aqueous medium using a suspension system such as water (suspension impregnation), or a method using a thermally decomposable foaming agent such as sodium deuterium hydrogen (foaming agent decomposition method) , A method of bringing the gas into an atmosphere of a critical pressure or higher and bringing it into a liquid phase (contacting with the base resin), a method of bringing the gas into contact with the base resin in a gas phase under a high pressure atmosphere below the critical pressure (gas phase) Impregnation) and the like. Of these, the method of vapor phase impregnation in a high-pressure atmosphere below the critical pressure is particularly preferable. The method of impregnating in the gas phase has better solubility of the gas in the resin than the suspension impregnation carried out under a high temperature condition, and makes it easy to increase the content of the foaming agent. Therefore, it is easy to achieve a high expansion ratio, and the bubble size in the base resin is likely to be uniform. Similarly, the blowing agent decomposition method is not only carried out under high temperature conditions, but not all of the added pyrolytic foaming agent becomes gas, so that the amount of gas generation tends to be relatively small. Therefore, the vapor phase impregnation has an advantage that the foaming agent content can be easily increased. Moreover, compared with liquid phase impregnation, facilities such as a pressure device and a cooling device are likely to be more compact, and the facility cost can be easily suppressed.

  The gas phase impregnation conditions are not particularly limited, but the atmospheric pressure is preferably 0.5 to 6.0 MPa. Moreover, 5-30 degreeC is preferable and, as for atmospheric temperature, 7-15 degreeC is more preferable. When the atmospheric pressure and the atmospheric temperature are in the above ranges, gas dissolution in the base resin is more likely to proceed more efficiently. In particular, if the ambient temperature is low, the amount of impregnation increases, but the impregnation rate is slow, and if the ambient temperature is high, the amount of impregnation decreases, but the impregnation rate tends to increase. In order to proceed, it is preferable to set the above atmospheric temperature.

  A foaming agent is not specifically limited, The gas generally used can be used. Examples thereof include air, carbon dioxide gas, nitrogen gas, oxygen gas, ammonia gas, hydrogen gas, argon gas, helium gas, neon gas and other inorganic gases, trichlorofluoromethane (R11), dichlorodifluoromethane (R12), chlorodifluoromethane. (R22), tetrachlorodifluoroethane (R112) dichlorofluoroethane (R141b) chlorodifluoroethane (R142b), difluoroethane (R152a), fluorocarbons such as HFC-245fa, HFC-236ea, HFC-245ca, HFC-225ca, propane, n -Saturated hydrocarbons such as butane, i-butane, n-pentane, i-pentane, neopentane, dimethyl ether, diethyl ether, methyl ethyl ether, isopropyl ether, n-butyl ether Ethers such as tellurium, diisopropyl ether, furan, furfural, 2-methylfuran, tetrahydrofuran, tetrahydropyran, dimethyl ketone, methyl ethyl ketone, diethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, methyl i-butyl ketone, methyl n- Ketones such as amyl ketone, methyl n-hexyl ketone, ethyl n-propyl ketone, ethyl n-butyl ketone, alcohols such as methanol, ethanol, propyl alcohol, i-propyl alcohol, butyl alcohol, i-butyl alcohol, and t-butyl alcohol Formic acid methyl ester, formic acid ethyl ester, formic acid propyl ester, formic acid butyl ester, formic acid amyl ester, propionic acid methyl ester, propionic acid ethyl ester Carboxylic acid esters, methyl chloride, chlorinated hydrocarbons such as ethyl chloride, and the like.

  From the viewpoint of flame retardancy, the foaming agent preferably has no flammability or flame support, and inorganic gas is more preferable from the viewpoint of gas safety. In addition, the inorganic gas is less soluble in the resin than the organic gas such as hydrocarbon, and the gas is likely to escape from the resin after the foaming process or the molding process, so that there is an advantage that the dimensional stability of the molded product over time is further improved. Further, the plasticization of the resin by the residual gas hardly occurs, and there is an advantage that excellent heat resistance is easily expressed from an earlier stage after molding. Among the inorganic gases, carbon dioxide gas is preferable from the viewpoint of solubility in the resin and ease of handling, and the impregnation amount is preferably 3 to 13% by mass with respect to the resin. More preferably, it is 3.5-10 mass%.

  When the impregnation amount of the carbon dioxide gas is 3% by mass or less, it becomes difficult to achieve a higher expansion ratio, the bubble size tends to vary, and the variation in the expansion ratio among the expanded beads tends to increase. When the amount is 13% by mass or more, the bubble size becomes small and the cell tends to be over-foamed, so that the closed cell ratio tends to be difficult to be maintained.

  The foaming method in the foaming step is not particularly limited. For example, the foaming method is a method in which the gas dissolved in the base resin is expanded under a high pressure condition at a stretch in a low pressure atmosphere, or heated by pressurized steam, etc. Examples include a method of expanding a gas dissolved in the material resin. Among these, the method of heating and foaming is particularly preferable. This is because the bubble size inside the foam beads is likely to be uniform as compared with a method in which a high pressure condition is opened to a low pressure atmosphere all at once. In addition, there is an advantage that it is easy to control the expansion ratio, particularly the low expansion ratio product.

  Pressurized steam can be foamed more uniformly and efficiently, for example, by introducing it from a number of steam holes from the bottom of the foaming furnace and stirring the resin with stirring blades. The rotation speed of the stirring blade is preferably 20 to 120 rpm, more preferably 50 to 90 rpm. If the rotational speed is 20 rpm or less, the pressurized water vapor does not hit uniformly, and foam control tends to be difficult or problems such as blocking occur. If it is 120 rpm or more, the foamed beads are damaged by the stirring blades. The closed cell ratio tends to decrease or the desired expansion ratio cannot be obtained.

  When foaming the foamed beads to a desired foaming ratio, in the foaming process, the foamed beads may be foamed to a desired foaming ratio in one stage, or may be foamed in multiple stages such as secondary foaming and tertiary foaming. In the case of foaming in multiple stages, it is preferable to pressurize the pre-beads (referring to beads not subjected to foaming in the final stage) with an inorganic gas before foaming in each stage. The gas used for the pressure treatment is not particularly limited, but inorganic gas is preferable from the viewpoint of flame retardancy and gas safety. Examples of inorganic gas include air, carbon dioxide gas, nitrogen gas, oxygen gas, ammonia gas, hydrogen gas, argon gas, helium gas, neon gas, etc. From the viewpoint of ease of handling and economy, carbon dioxide gas and air are Although it is preferable, it is not limited thereto. The method of the pressure treatment is not particularly limited, and examples thereof include a method in which preliminary beads are filled in a pressure tank, an inorganic gas is supplied into the tank, and pressure is applied.

  In order to set the concentration of the aliphatic hydrocarbon gas contained in the expanded beads to 1000 ppm or less, for example, an inorganic gas is used as a blowing agent, or the expanded beads are arbitrarily heated at a high temperature (for example, between 40 ° C. and 80 ° C. It can be carried out by passing through a “ripening process” in which the gas remaining for a long time is released under conditions that can be set).

  In the molding step, the foamed beads can be molded by a general molding method.

  Examples of the molding method include, but are not limited to, a method in which foamed beads are filled into a mold and foamed by heating, and at the same time, the beads are fused together and then solidified by cooling and molded. . The filling method of the expanded beads is not particularly limited. For example, the cracking method in which the mold is filled in a slightly opened state during filling, or the compression method in which the beads are compressed by compressing the mold while the mold is closed. A compression cracking method in which cracking is performed after filling with the compressed beads may be used.

  It is preferable to perform a pressurizing step in which a pressurizing process is performed in an inorganic gas atmosphere before filling the expanded beads. This is because by applying the pressure treatment, it is possible to apply a constant gas pressure to the bubbles in the foam beads, and it becomes easier to perform foam molding more uniformly. The pressure source for performing the pressure treatment is not particularly limited, but it is preferable to use an inorganic gas from the viewpoints of flame retardancy, heat resistance and dimensional stability described above. Examples of inorganic gas include air, carbon dioxide gas, nitrogen gas, oxygen gas, ammonia gas, hydrogen gas, argon gas, helium gas, neon gas, etc. From the viewpoint of ease of handling and economy, carbon dioxide gas and air are Although it is preferable, it is not limited thereto. The method of the pressure treatment is not particularly limited, and examples thereof include a method in which foaming beads are filled in a pressure tank and an inorganic gas is supplied into the tank to pressurize the tank.

  By using foam beads in the molding process, it is possible to produce a molded body having a fine shape or a complicated shape by a known in-mold molding method, and it is also characterized by widening the range of usable applications.

  For example, using a pair of conventional molds for molding foam beads in the mold, filling the mold beads with the foam beads under pressurized atmospheric pressure or reduced pressure, and closing the mold, the mold cavity volume is 0 to 0. Compressed so as to decrease by 70%, then heated by supplying a heating medium such as steam into the mold, and heat-fused foam beads (for example, Japanese Patent Publication No. 46-38359), Expanding the foam beads with pressurized gas in advance to increase the pressure inside the foam beads, increasing the secondary foamability of the foam beads, and maintaining the secondary foamability while maintaining the secondary foam performance. Is filled in a mold cavity, and the mold is closed, and then a heating medium such as steam is supplied into the mold and heated to heat-fuse the foamed beads (for example, Japanese Patent Publication No. 51-22951). And the like.

  In addition, after filling the cavities pressurized above the atmospheric pressure with the compressed gas with the expanded beads pressurized above the pressure, a heating medium such as steam is supplied into the cavities and heated, and the expanded beads It is also possible to mold by a compression filling molding method (Japanese Patent Publication No. 4-46217). In addition, after filling foam beads with high secondary foaming power obtained under special conditions into a pair of mold cavities under atmospheric pressure or reduced pressure, a heating medium such as steam is then supplied. It can also be molded by a normal pressure filling molding method (Japanese Patent Publication No. 6-49795) or a method combining the above methods (Japanese Patent Publication No. 6-22919) or the like in which heating and fusing of the expanded beads are performed. .

(High void layer)
In the present specification, the high void layer means a layer having a high ratio (porosity) of gas contained in the layer (excluding a layer formed of the above-mentioned foamed bead molded body). A high porosity means, for example, 30% or more. Since the multilayer structure of the present invention includes such a high void layer, it has excellent heat insulating properties. The high void layer is preferably formed, for example, from a foamed resin obtained by foaming a resin, a porous structure, a fine porous structure, a fiber structure, or an inorganic material having a fine fiber structure.

  The resin constituting the foamed resin may be a thermoplastic resin, a thermosetting resin, or the like, but is preferably a thermoplastic resin because the rigidity of the multilayer structure can be further improved. Specific examples of the thermoplastic resin include polyolefin resins such as polyethylene resins and polypropylene resins, polystyrene resins, heat-resistant polystyrene resins, modified polyphenylene ether resins, polyethylene terephthalate (PET) resins, and polyamides. Examples of the (nylon) resin, polycarbonate resin, and thermosetting resin include, but are not limited to, melamine resin and phenol resin. Moreover, these can be used individually or in combination of 2 or more types. Of these, polyolefin resins and polystyrene resins are preferred from the viewpoint of processability and performance.

  The foamed resin includes other thermoplastic resins, the above-mentioned flame retardants, antioxidants, thermal stabilizers, lubricants, pigments, dyes, weather resistance improvers, impact modifiers, glass beads, inorganic fillers, A nucleating agent such as talc or the like may be added within a range not impairing the object of the invention. In particular, from the viewpoint of further improving the flame retardancy of the multilayer structure, it is preferable to include the above-mentioned flame retardant in the foamed resin.

  The expansion ratio of the foamed resin is not particularly limited, but is preferably 1.5 to 40 cc / g, and more preferably 2 to 25 cc / g. When the expansion ratio is in the range of 1.5 to 40 cc / g, it is easy to maintain excellent flame retardancy while taking advantage of the weight reduction.

  Although the heating dimensional change rate of the foamed resin is not particularly limited, it is preferably 10% or less, more preferably 5% or less, and further preferably 3% or less at 100 ° C. When the heating dimensional change rate is 10% or less, the heat resistance is excellent, so it can be applied to a member used in a high temperature environment, and can be stored for a long time in a high temperature environment in summer. Is possible.

  The deflection temperature under load (HDT) of the foamed resin is not particularly limited, but is preferably 60 ° C. or higher, and more preferably 70 ° C. or higher. When the deflection temperature under load is 60 ° C. or higher, the heat resistance is excellent and the same effect as described above can be obtained.

  Specifically, the inorganic material used for the high void layer is an inorganic material having a microporous structure (for example, Microtherm (trade name, manufactured by Nippon Microtherm Co., Ltd.), which is a material in which a microporous structure is formed by silica particles. ), Rock wool, glass wool and the like, but are not limited thereto. The microporous structure is a porous structure formed from a cell structure smaller than the mean free path of air molecules.

  The thickness of the high void layer is preferably 3 to 100 mm, more preferably 5 to 50 mm. When the thickness of the high void layer is in this range, the heat insulating property of the multilayer structure is more excellent. Moreover, the ratio of the thickness of the foam layer to the thickness of the high void layer is preferably 33.3 to 0.06, more preferably 20 to 0.1, and more preferably 10 to 0.6. Is more preferable. When the ratio of the thickness of the foamed layer to the thickness of the high void layer is within this range, the flame retardancy and heat resistance of the multilayer structure are further significantly improved.

[Method for producing multilayer structure]
The multilayer structure of the present invention can be produced by, for example, producing the above-mentioned foamed bead molded body, foamed resin or inorganic material used for the high void layer, and then bonding them.

  Adhesion between the foamed bead molded body (foamed layer) and the high void layer is performed using heat fusion or an adhesive, but is not limited thereto. Moreover, you may laminate | stack without using anything.

  The heat fusion is preferably performed when the resin used for the foamed resin and the resin used for the foamed bead molded body are resins having good adhesion to each other. Specifically, after the foamed resin and the foamed bead molded body are melted to such an extent that they can be fused, they can be brought into contact with each other and bonded. In addition, even when resins with poor adhesion are used, it is possible to bond the foamed resin (high void layer) and the foamed bead molded body (foamed layer) more firmly due to the anchor effect of corona treatment, etc. It is. Further, the surface of the foam molded product can be roughened by physical cutting or the like so that it can be more firmly bonded.

  The adhesive used for bonding the high void layer and the foamed layer is not particularly limited as long as it can bond resins or resins and inorganic materials, for example, acrylic, epoxy, vinyl acetate, etc. Can be used.

  The multilayer structure of the present invention is particularly useful as a heat insulating material for tanks and houses because it is lightweight and has excellent heat resistance, heat insulation, and flame retardancy. In addition, it is used in various tanks and other high-temperature environments, and can also be used for materials that require flame resistance and heat insulation. This is very useful because it can be used for fine and complicated members that require high accuracy, and at the same time, it can satisfy weight reduction.

  Next, the present invention will be described more specifically based on examples and comparative examples. However, the present invention is not limited to the following examples.

The evaluation methods used in the examples and comparative examples are described below.
(1) Density After measuring the weight W (g) of the foam (foamed beads or foamed bead molded body), the volume V (cc) was measured by the submerging method, and the weight divided by the volume W / V ( g / cc) was defined as density.

(2) Foaming ratio After measuring the weight W (g) of the foam (foam beads or foam bead molded body), the volume V (cc) is measured by the submerging method, and the volume is divided by the weight V / W. (Cc / g) was taken as the expansion ratio.

Ｖｘ：発泡ビーズ又は発泡ビーズ成形体の真の容積（ｃｍ^３）
Ｖａ：発泡ビーズ又は発泡ビーズ成形体の容積（発泡倍率×重量）（ｃｍ^３）
Ｗ ：発泡ビーズ又は発泡ビーズ成形体の重量（ｇ）
ρ ：発泡ビーズ又は発泡ビーズ成形体の基材樹脂の密度（ｇ／ｃｍ^３） (3) Closed cell ratio The true volume (Vx) of a foamed bead or foamed bead molded body having a known foaming ratio (cc / g) was measured using an air comparison type hydrometer manufactured by Beckman Co., Ltd. The closed cell ratio: S (%) was calculated from the equation.

Vx: True volume of foamed beads or foamed bead molded body (cm ³ )
Va: Volume of foam beads or foam bead molded body (foaming magnification × weight) (cm ³ )
W: Weight of expanded beads or molded beads (g)
ρ: Density (g / cm ³ ) of base resin of foam beads or foam bead molded body

(4) Concentration of Aliphatic Hydrocarbon Gas A foam (foamed beads or foamed bead molded body) sample was charged in an appropriate amount into a headspace bottle and heated at a temperature above the foam sample softening point for about 1 hour. Thereafter, the gas in the headspace bottle was quantified by gas chromatography (manufactured by Shimadzu Corporation, GC14B). Helium (He) was used as a carrier gas and controlled in a constant flow mode (about 30 ml / mim). In addition, the column (PorapakQ, 80/100 mesh, 3.2 mmφ × 2.1 m) was heated and held at 50 to 150 ° C. and detected by a thermal conductivity detector (TCD). Calculate the volume of the aliphatic hydrocarbon gas from the detected area area and the calibration curve created with the standard gas sample, and divide by the volume of the foam sample to calculate the concentration (ppm) of the aliphatic hydrocarbon gas. did. In Tables 1 and 2, “aliphatic hydrocarbon gas concentration” is simply expressed as “gas concentration”.

(5) Flame retardance A test based on the UL-94 vertical method (20 mm vertical combustion test) of the US UL standard was conducted to evaluate the flame retardancy. The measurement method is shown below.
The obtained foam (foamed beads or foamed bead molded body) was molded into a test piece having a length of 125 mm, a width of 13 mm, and a thickness of 3 mm, and the test piece was determined using five test pieces. The test piece was vertically attached to the clamp, 10-second indirect flame with 20 mm flame was performed twice, and V-0, V-1, V-2, and non-conformity were determined by the combustion behavior. Those not corresponding to the following were considered non-conforming (x).
V-0: The flaming combustion duration is within 10 seconds for both the first time and the second time, and the total of the second flammable combustion time and the flameless combustion time is within 30 seconds. The total burning time is within 50 seconds, there is no specimen that burns to the position of the clamping clamp, and there is no cotton ignition by burning fallen objects.
V-1: The flammable combustion duration is within 30 seconds for both the first and second time, and the total of the second flammable combustion duration and the flameless combustion time is within 60 seconds. The total burning time is within 250 seconds, there is no specimen that burns to the position of the clamping clamp, and there is no cotton ignition by burning fallen objects.
V-2: The flammable combustion duration is within 30 seconds for both the first and second time, and the total of the second flammable combustion duration and the flameless combustion time is within 60 seconds. The total burning time is within 250 seconds, there is no test piece that burns to the position of the clamping clamp, and there is cotton ignition due to burning fallen objects.

(6) Heating dimensional change rate About the foamed bead molded object immediately after shaping | molding, the test based on the dimensional stability evaluation and B method of JISK6767 was done, and the heating dimensional change rate was evaluated. The evaluation temperature was 100 ° C.

(7) Molding processability The foaming bead molding processability was evaluated by molding a flat plate (300 mm x 300 mm x 17 mm) from the foamed beads using a molding machine K-68 manufactured by Kurz. The obtained foamed bead molded body has no gaps on the surface, the foamed beads are firmly fused to each other, and the plate-like is ○, the surface has a gap or is not plate-like × It was.

(8) Deflection temperature under load (HDT)
The foamed bead molded body was evaluated by a test based on JIS K7191 Flatwise B method. Specifically, a test piece having a sample size of 12.7 mm × 127 mm × 6.4 mm was prepared from the foamed bead molded body, and the temperature rising rate was 2 ° C./min from 30 ° C. while applying a distance between fulcrums of 64 mm and a load of 0.45 MPa. The temperature when the deflection reached 0.34 mm was evaluated as HDT.

(9) Average particle diameter The average particle diameter of the expanded beads was determined as follows. The major axis and minor axis of each foamed bead were obtained from an optical micrograph of the foamed bead, and the average value of the major axis and the minor axis was taken as the particle diameter (mm) of each foamed bead. The particle diameter was determined for 5 to 10 randomly selected expanded beads, and the average value was defined as the average particle diameter (mm).

(10) Thermal conductivity (λ)
In accordance with JIS A1412, the thermal conductivity (λ) (W / m · K) of the multilayer structure was determined. Specifically, a 30 cm square multi-layer structure that was allowed to stand for 24 hours in a room controlled at a temperature of 23 ° C. and a relative humidity of 50% was used as a sample, and a thermal conductivity measuring device (trade name: HC-074A- 304, manufactured by Eihiro Seiki Co., Ltd.), the sample was placed between a 30 ° C. high temperature plate and a 10 ° C. low temperature plate, and the thermal conductivity was measured.

(11) Flame retardancy of multilayer structure A test based on the UL-94 vertical method (20 mm vertical combustion test) was performed on the prepared multilayer structure sample, and the time required for the 125 mm length sample to burn out was measured. . The time until burning out was 30 seconds or more, or a fire extinguished on the way was marked with ◯, and the thing less than 30 seconds was marked with x.

[Example 1]
60% by mass of polyphenylene ether resin (PPE) (trade name: Zylon TYPE S201A, manufactured by Asahi Kasei Chemicals Corporation), 18% by mass of non-halogen flame retardant (bisphenol A-bis (diphenyl phosphate) (BBP)), 10% by mass of impact-resistant polystyrene resin (HIPS) having a rubber concentration of 6% by mass (content of rubber component in the base resin is 0.6% by mass) and general-purpose polystyrene resin (PS) (trade names: GP685, PS Japan) 12 mass% was added, and it extruded after heat-melt-kneading with the extruder, and produced the base-material resin pellet. According to the method described in Example 1 of JP-A-4-372630, the base resin pellets are accommodated in a pressure-resistant container, the gas in the container is replaced with dry air, and then carbon dioxide (gas) is injected as a blowing agent. The base resin pellet was impregnated with 7% by mass of carbon dioxide over a period of 3 hours under the conditions of pressure 3.2 MPa and temperature 11 ° C., and the base resin pellet was rotated at 77 rpm in a foaming furnace. While foaming with pressurized steam. Table 1 shows the expansion ratio and closed cell ratio of the obtained expanded beads. The concentration of the aliphatic hydrocarbon gas in the expanded beads was measured immediately after the expansion, and was below the detection limit (50 ppm).

  The foamed beads were pressurized to 0.5 MPa over 1 hour, then held at 0.5 MPa for 8 hours, and subjected to pressure treatment. This is filled in an in-mold mold having water vapor holes, heated with pressurized steam to expand and fuse the foam beads together, cooled, and taken out from the mold to obtain a foam bead molded body. It was. The concentration of the aliphatic hydrocarbon gas in the obtained foamed bead molded product was measured and found to be below the detection limit (50 ppm). This foamed bead molded body had flame retardancy of V-0 and good heat resistance (Table 1).

  A polystyrene foam was laminated on the foamed bead molded body (thickness 20 mm) by heat fusion to obtain a multilayer structure. The obtained multilayer structure exhibited good thermal conductivity and flame retardancy (Table 1).

[Example 2]
Manufacture and evaluation were performed in the same manner as in Example 1 except that the thickness of the polystyrene foam was changed from 20 mm to 10 mm. The foamed bead molded body of Example 2 exhibited excellent flame retardancy and heat resistance as in Example 1 (Table 1). In addition, the multilayer structure of Example 2 exhibited good thermal conductivity and flame retardancy as in Example 1 (Table 1).

[Example 3]
Manufacture and evaluation were performed in the same manner as in Example 1 except that the thickness of the polystyrene foam was changed from 20 mm to 10 mm and the thickness of the foamed bead molded body was changed from 20 mm to 10 mm. The foamed bead molded body of Example 3 exhibited excellent flame retardancy and heat resistance as in Example 1 (Table 1). Moreover, the multilayer structure of Example 3 showed good thermal conductivity and flame retardance as in Example 1 (Table 1).

[Example 4]
Manufacture and evaluation were performed in the same manner as in Example 1 except that a polyethylene foam (trade name: Sunnylite, manufactured by Asahi Kasei Construction Materials Co., Ltd., thickness 20 mm) was used instead of the polystyrene foam (thickness 20 mm). . The foamed bead molded body of Example 4 exhibited excellent flame retardancy and heat resistance as in Example 1 (Table 1). In addition, the multilayer structure of Example 4 showed good thermal conductivity and flame retardancy as in Example 1 (Table 1).

[Example 5]
Example in which an inorganic heat insulating material (trade name: Microtherm, manufactured by Nihon Microtherm Co., Ltd., thickness 20 mm) was used instead of the polystyrene foam (thickness 20 mm), and it was simply laminated without performing heat fusion. Production and evaluation were performed in the same manner as in Example 1. The foamed bead molded body of Example 5 exhibited excellent flame retardancy and heat resistance as in Example 1 (Table 1). In addition, the multilayer structure of Example 5 showed good thermal conductivity and flame retardancy as in Example 1 (Table 1).

[Examples 6 to 9]
Using triphenyl phosphate (TPP) as a flame retardant instead of BBP, using HIPS with a rubber concentration of 19% by mass instead of HIPS with a rubber concentration of 6% by mass, composition of each component, and expansion ratio The production and evaluation were carried out in the same manner as in Example 1 except that was changed as shown in Table 1. In Example 9, BBP and TPP were used in combination. The foamed bead molded bodies of Examples 6 to 9 exhibited excellent flame retardancy and heat resistance as in Example 1 (Table 1). In addition, the multilayer structures of Examples 6 to 9 showed good thermal conductivity and flame retardancy as in Example 1 (Table 1).

[Example 10]
Manufacture and evaluation were performed in the same manner as in Example 6 except that n-butane was used as a blowing agent instead of carbon dioxide. However, the concentration of the aliphatic hydrocarbon gas in the foam beads was measured after the foam beads were aged at 80 ° C. for 6 months after foaming. As a result, it was 800 ppm.
When the performance evaluation of the foamed bead molded body of Example 10 was performed, the combustion time was longer than that of the foamed bead molded body of other Examples, but the V-1 standard was satisfied and the flame retardancy was excellent. It was a thing. In addition, the foamed bead molded body of Example 10 showed excellent heat resistance similarly to the foamed bead molded body of other Examples (Table 1). Furthermore, the multilayer structure of Example 10 showed good thermal conductivity and flame retardancy as well as the multilayer structures of other examples (Table 1).

[Example 11]
Table 1 shows that polycarbonate resin (PC) (trade name: FPR3000 (manufactured by Mitsubishi Engineering Plastics)) was used instead of PPE, HIPS and PS were not used, the composition of each component, and the expansion ratio. The production and evaluation were conducted in the same manner as in Example 1 except that the changes were made as shown in Fig. 1. Even if a polycarbonate-based resin was used as the base resin, the flame retardancy, foamability and heat resistance of the foamed bead molded product were used. In addition, the thermal conductivity and flame retardancy of the multilayer structure were good without any deterioration (Table 1).

[Example 12]
Manufacture and evaluation were conducted in the same manner as in Example 11 except that polycarbonate resin (PC / ABS) (trade name: MB3800 (manufactured by Mitsubishi Engineering Plastics)) was used instead of PC. The foamed bead molded body showed excellent flame retardancy and heat resistance as in Example 11. (Table 1) The multilayer structure of Example 12 had good heat conduction as in Example 11. Rate and flame retardancy (Table 1).

[Comparative Examples 1-5]
Example 1 except that HIPS with a rubber concentration of 19% by mass was used instead of HIPS with a rubber concentration of 6% by mass, the composition of each component, and the expansion ratio were changed as shown in Table 2. Were manufactured and evaluated.
Since the foamed bead molded body of Comparative Example 1 has a low polyphenylene ether-based resin ratio, the flame retardancy is less than V-2 even at a low foaming ratio, and the thermal dimensional stability (heating dimensional change rate) is also extremely inferior. It became.
In Comparative Example 2, since the ratio of the polyphenylene ether-based resin was too high, foreign matters were frequently generated due to thermal deterioration during extrusion during the production of the base resin pellets, and a foamed bead molded body worthy of evaluation could not be obtained.
The foamed bead molded body of Comparative Example 3 exhibited almost no flame retardancy because the amount of the flame retardant was too small.
In Comparative Example 4, since there were too many flame retardants, the closed cell ratio of the expanded beads was greatly reduced, and the expanded bead molded product was not obtained.
In Comparative Example 5, since no rubber component is used, cell membrane breakage occurs due to resin flexibility and insufficient elongation, and molding processability is deteriorated, and a good foamed bead molded body cannot be obtained. It was.

[Comparative Examples 6-7]
Manufacture and evaluation were performed in the same manner as in Example 10 except that the aging conditions of the expanded beads until the evaluation of the concentration of the aliphatic hydrocarbon gas was changed.
In Comparative Example 6, after the foamed beads were aged at 40 ° C. for half a year, the concentration of the aliphatic hydrocarbon gas was measured. As a result, it was 1320 ppm. When the flame retardant evaluation of the foamed bead molded body of Comparative Example 6 was carried out, no resin dripping occurred during combustion, but the combustion time was long, and any of V-0, V-1, and V-2 was applicable. It was not suitable.
In Comparative Example 7, after the foamed beads were aged at 40 ° C. for 3 months, the concentration of the aliphatic hydrocarbon gas was measured. As a result, it was 15380 ppm. When the flame retardant evaluation of the foamed bead molded body of Comparative Example 7 was carried out, the sample burned up with flames. In addition, the thermal dimensional stability was inferior.

[Comparative Example 8]
Instead of foam beads, a film molded body was used in which the base resin prepared with the components and composition shown in Table 2 was formed into a film shape (sample size: 300 μm × 150 mm × 150 mm) with a heating press without foaming. Except for the above, production and evaluation were carried out in the same manner as in Example 1.
When a film molded body is used for foaming instead of foam beads, although foaming occurs, it is difficult to fill a complex-shaped mold, and it is impossible to mold into a fine and complex shape. Moreover, the thickness of the foamed film molded body after foaming was less than 3 mm, and the flame retardancy was evaluated.

  The multilayer structure of the present invention maintains high flame retardancy, heat resistance, and heat insulation as well as weight reduction, and is particularly suitable as a structural material for automobile members and OA equipment.

Claims (11)

  A foamed layer comprising a foamed bead molded product having a flame retardancy of V-0 or V-1 measured according to UL standard UL-94 vertical method (20 mm vertical combustion test), and at least one high void layer A multilayer structure comprising:   The multilayer structure according to claim 1, wherein the concentration of the aliphatic hydrocarbon gas in the foam layer is 1000 ppm by volume or less.   The multilayer structure according to claim 1 or 2, wherein the foamed bead molded body is made of a base resin including a polyphenylene ether resin or a polycarbonate resin and a flame retardant.   The multilayer structure according to claim 1 or 2, wherein the foamed bead molded body is made of a base resin containing a polyphenylene ether resin and a flame retardant.   The multilayer structure according to claim 3 or 4, wherein the base resin further contains a polystyrene-based resin.   The multilayer structure according to any one of claims 3 to 5, wherein the base resin further contains a rubber component.   The said base resin contains 40-94 mass% of polyphenylene ether-type resin, 5-20 mass% of flame retardants, and 0.3-10 mass% of rubber components, and the remainder consists of polystyrene-type resin. The multilayer structure according to any one of 6.   The multilayer structure according to any one of claims 3 to 7, wherein the flame retardant is a non-halogen flame retardant.   The multilayer structure according to any one of claims 1 to 8, wherein the high void layer is a layer made of a foamed resin or a layer made of an inorganic material. The high void layer is a layer made of a foamed resin obtained by foaming a polyolefin resin or a polystyrene resin, or a layer made of an inorganic material selected from the group consisting of an inorganic material having a microporous structure, rock wool, and glass wool. Item 9. The multilayer structure according to any one of Items 1 to 8.   The heat insulating material which consists of a multilayer structure as described in any one of Claims 1-10.