JP5470924B2 - Extruded foam laminate with excellent heat insulation performance - Google Patents

Description

  The present invention relates to an extruded foam laminate suitably used as a heat insulating material for buildings, automobiles, civil engineering and the like.

  In the field of building materials, automotive interior materials, etc., phenolic resin foam boards, polyurethane resin foam boards, and polystyrene resin foam boards are widely used as heat insulating materials.

  In recent years, as the demand for comfort and energy saving in living spaces has increased, the heat insulation performance of conventionally used heat insulating materials has been demanded. Various studies have been made such as study, study of foaming agent type, study of additives, study of cell structure, etc. (see, for example, Patent Documents 1 to 6).

  As a result of these studies, there is a view that the heat insulation performance of the foam board has been dramatically improved, and on the extension line of the prior art, a region where further improvement of the heat insulation performance cannot easily be expected is reached.

  On the other hand, chlorofluorocarbons, which are one type of foaming agent that gives good insulation performance to foamed boards, are considered to be the causative substances that destroy the ozone layer. It ’s been a long time since the abolition was screamed.

  Under such circumstances, in order to further improve the heat insulation performance of the foam board, an approach different from the viewpoint of the studies that have been conventionally performed is necessary.

  As a new attempt for improving the heat insulation performance of the foam board, there is a technique disclosed in Patent Document 7. This is an invention in which an aluminum foil is sandwiched between two polypropylene resin foams, and the thermal insulation performance is remarkably improved by sandwiching the aluminum foil. However, since the technology disclosed in Patent Document 7 is a technology in which an aluminum foil is sandwiched by post-processing after the foam is manufactured, the cell internal pressure of the foam is under reduced pressure immediately after the foam is manufactured, so that the outside air is touched. Therefore, inflow of air having a higher thermal conductivity than the foaming agent into the cell occurs, and the heat insulation performance is lowered. For this reason, the further improvement of heat insulation performance is anticipated by suppression of the air inflow in a foam cell.

  Furthermore, since the technology disclosed in Patent Document 7 is limited to only the aluminum foil that is a material incompatible with the resin constituting the foam layer and the material that is incompatible with the foam layer, the foam layer and the aluminum foil. When laminating the layers, it is essential to have an adhesive. As a result, the technique disclosed in Patent Document 7 needs to be improved in order to reach an industrialization level such as complicated processes and disadvantageous costs.

JP 2008-13659 A JP 2007-154006 A JP 2001-114922 A JP 2002-309030 A JP-A-8-231667 JP 2007-332203 A JP 2001-179866 A

  This invention solves the said subject, and it aims at providing the extrusion foaming laminated body for heat insulating materials which has the improvement effect of a remarkable heat insulation performance, without using CFCs as a foaming agent.

As a result of intensive studies to solve the above-mentioned problems, the present inventor found the following matters and completed the present invention.
(1) By using a coextrusion method as a manufacturing method of a foaming laminated body, a non-foaming layer suppresses the penetration | invasion of the air into the foaming layer cell which generate | occur | produces immediately after manufacture.
(2) By adding additives such as aluminum paste and carbon graphite that can be kneaded into the resin to the constituent resin of the non-foamed layer, it becomes possible to easily impart a heat ray radiation suppressing effect to the non-foamed layer. The foamed layer / non-foamed layer (containing heat ray radiation suppressing material) / foamed by an industrially advantageous coextrusion method without going through the complicated steps required when laminating conventional aluminum foils A foam laminate having a structure composed of layers is obtained.
(3) In the thickness direction of the foamed laminate, the foamed laminate having a plurality of non-foamed layers including a heat ray radiation suppressing material coated on both sides with a foamed layer has more heat insulation performance than the foamed laminate having only one layer. To be improved.

That is, the present invention
[1] An extruded foam laminate obtained by joining a molten resin containing a foaming agent and a molten resin not containing a foaming agent in a thickness direction under high pressure, and then releasing it under atmospheric pressure. foam laminate, the thickness direction foamed layer are laminated through a non-foamed layer, Ri Na foaming layer are laminated on both surfaces of the non-foamed layers of all, an outermost foaming layer, a non-foamed layer there which has a structure that exist 1-5 layers, characterized in that it comprises at least one of the heat ray radiation suppressor to non foamed layer, extruded foam laminate,
[2] The extruded foam laminate according to [1], wherein the heat ray radiation suppressing material is a heat ray reflecting material and / or a heat ray absorbing material,
[3] The extruded foam laminate according to [2], wherein the heat ray reflective material is at least one selected from the group consisting of an aluminum compound, a magnesium compound, a silver compound, and a titanium compound. ,
[4] The extruded foam laminate according to [2] or [3], wherein the heat ray reflective material is an aluminum paste,
[5] The extruded foam laminate according to [2] or [3], wherein the heat ray reflective material is titanium oxide.
[6] The extruded foam laminate according to [2], wherein the heat ray absorbing material is at least one selected from the group consisting of carbon graphite, carbon black, metal sulfate, and an antimony compound.
[7] The extruded foam laminate according to [2] or [6], wherein the heat ray absorbing material is carbon graphite,
[8] The extruded foam laminate according to [2] or [6], wherein the heat ray absorbing material is carbon black,
[9] The extruded foam laminate according to [2] or [6], wherein the heat ray absorbing material is antimony oxide,
[10] The extruded foam laminate according to [2] or [6], wherein the heat ray absorbing material is barium sulfate ,
[ 11 ] The extrusion according to any one of [1] to [ 10 ], wherein the resin constituting the foamed layer is a polystyrene resin, a polyphenylene resin, or a modified polyphenylene resin. Foam laminate,
[ 12 ] The extruded foam laminate according to [ 11 ], wherein the resin constituting the foamed layer is a polystyrene-based resin, and [ 13 ] a thermal conductivity at 20 ° C. of 0.034 W / mK or less. It is related with the extrusion foaming laminated body of any one of [1]-[ 12 ] characterized by being.

The effects of the foamed laminated structure of the present invention are as follows.
-The heat insulation performance of a foaming laminated body can be improved by taking the foaming laminated body structure by which the foaming layer was laminated | stacked through the non-foaming layer containing a heat ray radiation suppression material in the thickness direction.
-The heat insulation performance of a foaming laminated body can be improved more by increasing the number of the non-foaming layers containing the heat ray radiation suppression material in a foaming laminated body.
-By using the co-extrusion method as a manufacturing method of the foam laminate, the non-foaming layer can suppress the intrusion of air into the foaming layer cell that occurs immediately after the manufacturing, and particularly the both sides of the foaming layer in the thickness direction. By taking the structure covered with the foam layer, the intrusion of air from the outside air into the foam layer cell is suppressed, and the heat insulation performance of the resulting foam laminate can be further improved.
Since the effect of the above-mentioned foamed laminated structure can be combined with other conventional techniques aimed at improving the heat insulating property of the foamed board, it can be expected to provide a foamed board having an unprecedented heat insulating performance.

FIG. 1 is a schematic diagram showing the measurement position of the thickness of the extruded foam laminate according to the present invention. FIG. 2 is a schematic diagram showing the measurement position of the width of the extruded foam laminate according to the present invention. FIG. 3 is a schematic diagram showing the density measurement position of the extruded foam laminate according to the present invention. FIG. 4 is a schematic diagram showing the cut-out position of the test piece for measuring the partial pressure of air in the bubbles of the extruded foam laminate according to the present invention. FIG. 5 is a schematic diagram of a cross-section in the width direction of the extruded foam laminate according to the present invention. FIG. 6 is a schematic view of a cross section in the width direction of the extruded foam laminate according to the present invention.

  The extruded foam laminate of the present invention is obtained by a coextrusion method in which a molten resin containing a foaming agent and a molten resin not containing a foaming agent are merged in the thickness direction under high pressure and then released under atmospheric pressure. It is preferable that the foamed layer has a structure in which the foamed layer is laminated via the non-foamed layer in the thickness direction, and the non-foamed layer includes a heat ray radiation suppressing material.

The foam layer constituting the extruded foam laminate of the present invention refers to a layer having a density of 500 kg / m ³ or less and having a plurality of honeycomb-like cell structures (hereinafter sometimes referred to as “bubbles”). Say. The shape is not particularly limited, and examples include a film shape, a sheet shape, and a board shape. Among these, a sheet shape, a board, and the like, since heat insulation performance is easily exhibited and light weight can be imparted to the extruded foam laminate. Shape is preferred.

The non-foamed layer constituting the extruded foam laminate of the present invention refers to a layer having a density of more than 500 kg / m ³ , and the shape thereof can be imparted to the extruded foam laminate by a lightweight, film shape, sheet shape. Preferably, the resin composition contains at least one kind of heat ray radiation suppressing material in the resin.

  The heat ray radiation suppressing material contained in the non-foamed layer constituting the extruded foam laminate of the present invention reflects, scatters and absorbs light in the near infrared or infrared region (for example, a wavelength region of about 800 to 3000 nm). This means a substance having a black body emissivity smaller than that of the resin constituting the foamed layer and the non-foamed layer.

  Examples of the heat ray radiation suppressing material include a heat ray reflecting material and a heat ray absorbing material described below.

  The heat ray reflective material is not particularly limited as long as it is a substance that reflects and scatters light in the near infrared or infrared region (for example, a wavelength region of about 800 to 3000 nm). Specifically, aluminum, aluminum oxide Aluminum compounds such as zinc aluminate; magnesium compounds such as hydrotalcite; silver compounds such as silver: titanium compounds such as titanium, titanium oxide, strontium titanate; stainless steel, nickel, tin Silver, copper, bronze, shirasu balloon, ceramic balloon, microballoon, pearl mica and the like. These may be used alone or in combination of two or more.

  As a heat ray reflective material, aluminum compound, magnesium compound, from the point that heat conductivity reduction effect is great, cost advantage, environmental compatibility, good handling including safety, etc. Silver-based compounds or titanium-based compounds are preferable, and among these, aluminum paste and titanium oxide are more preferable because of the excellent balance between the thermal conductivity reduction effect and cost.

  The amount of heat ray reflective material added to the non-foamed layer constituent resin is appropriately set according to the type of heat ray reflective material and the thickness of the non-foamed layer, but as an indicator, a predetermined amount of heat ray reflective material is added to the non-foamed constituent resin. After melt-kneading, a film having the same thickness as the non-foamed layer was prepared, and the absorbance obtained at 800 to 3000 nm in the spectrum obtained by infrared spectrophotometer (IR) measurement of the film hardly changed even when the addition amount was increased. It is preferable to set the minimum amount that reaches a region where there is not present as the addition amount because the balance between the reduction effect of the thermal conductivity of the extruded foam laminate and the cost is excellent.

  The said heat ray absorber means the substance which has the characteristic which absorbs the light of near infrared or infrared region (for example, wavelength range of about 800-3000 nm).

  The heat ray absorbing material is not particularly limited as long as it is a substance that absorbs light in the near infrared or infrared region (for example, a wavelength range of about 800 to 3000 nm). Specifically, carbon black, carbon powder ; Metal sulfates such as barium sulfate, strontium sulfate, calcium sulfate, mercalite, halothrite, alumite, iron alumite; antimony compounds such as antimony trioxide, antimony oxide, and anhydrous zinc antimonate; tin oxide, indium oxide Metal oxides such as zinc oxide, indonium tin oxide, etc .; ammonium, urea, imonium, aminium, cyanine, polymethine, anthraquinone, dithiol, copper ion, phenylenediamine, phthalocyanine, benzo Triazole, benzophenone, oxalic anilide, shear Acrylate, organic dyes and pigments benzotriazole and the like; and the like.

  As heat-absorbing materials, carbon graphite, carbon black, metal sulfate, etc. from the viewpoints of great thermal conductivity reduction effect, cost advantage, good environmental friendliness, and good handling including safety. Salts or antimony compounds are preferred, and among these, carbon graphite, carbon black, antimony oxide or barium sulfate is more preferred because of its excellent thermal conductivity reduction effect and cost balance.

  The amount of heat-absorbing material added to the non-foamed constituent resin is set as appropriate depending on the type of heat-absorbing material and the thickness of the non-foamed layer. After melt-kneading, a film having the same thickness as the non-foamed layer was prepared, and the absorbance obtained at 800 to 3000 nm in the spectrum obtained by infrared spectrophotometer (IR) measurement of the film hardly changed even when the addition amount was increased. It is preferable to set the minimum amount that reaches a region where there is not present as the addition amount because the balance between the reduction effect of the thermal conductivity of the extruded foam laminate and the cost is excellent.

  As the constituent resin of the foam layer constituting the extruded foam laminate of the present invention, a thermoplastic resin is preferably used because extrusion foam molding is possible.

The thermoplastic resin is not particularly limited, and is, for example, a styrene resin such as polystyrene; a polyolefin resin such as polypropylene, polyethylene, or an ethylene propylene random copolymer; a polyamide resin such as nylon 6, nylon 66, or nylon 12. Polyester resins such as polyethylene terephthalate and polybutylene terephthalate; polycarbonate resins; polyphenylene ether resins, modified polyphenylene ether resins; polyoxymethylene resins, polyarylate resins, polyphenylene sulfide resins, polyacrylonitrile, polyvinyl alcohol, ethylene -Vinyl acetic acid copolymer, polyacrylic acid, polymethyl methacrylate, thermoplastic phenol resin, etc. are mentioned, and these are used alone or in combination of two or more. It is possible to use Te.
Of these, polystyrene resins, polyphenylene ether resins, and modified polyphenylene ether resins, which are mixed resins of polystyrene resins and polyphenylene ether resins, are preferred because of their excellent heat insulation performance and easy moldability. Styrene resins Is more preferable.

  The styrenic resin is not particularly limited, and for example, a styrene homopolymer obtained only from a styrene monomer, a random, block or graft obtained from a monomer copolymerizable with a styrene monomer and styrene or a derivative thereof. Examples thereof include copolymers, post-brominated polystyrene, modified polystyrene such as rubber-reinforced polystyrene, and ABS resin. These can be used alone or in admixture of two or more.

  Examples of monomers copolymerizable with styrene include methylstyrene, dimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, bromostyrene, dibromostyrene, tribromostyrene, chlorostyrene, dichlorostyrene, and trichlorostyrene. Polyfunctional vinyl compounds such as divinylbenzene, (meth) acrylic compounds such as acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, methacrylonitrile, α-chloroacrylonitrile, acrylonitrile , Diene compounds such as budadiene or derivatives thereof, unsaturated carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, N-methylmaleimide, N-butylmaleimide N-alkyl-substituted maleimide compounds such as N-cyclohexylmaleimide, N-phenylmaleimide, N-4-diphenylmaleimide, N-2-chlorophenylmaleimide, N-4-bromophenylmaleimide, N-1-naphthylmaleimide; It is done. These can be used alone or in admixture of two or more.

  In particular, when a styrene resin is used as the foam layer constituting the extruded foam laminate of the present invention, styrene homopolymer, styrene-acrylonitrile copolymer, (meth) acrylic acid copolymer are used from the viewpoint of workability of the foam. It is more preferable to use polymerized polystyrene, maleic anhydride-modified polystyrene, styrene-unsaturated dicarboxylic anhydride-N-alkyl-substituted maleimide copolymer, and impact-resistant polystyrene, and most preferably styrene homopolymer.

  The foam layer of the extruded foam laminate of the present invention is obtained by press-fitting a foaming agent into a molten foam layer-constituting resin under high pressure and releasing it to the atmosphere. , Propane, n-butane, i-butane, n-pentane, i-pentane, neopentane and other saturated hydrocarbons having 3 to 5 carbon atoms; dimethyl ether, diethyl ether, methyl ethyl ether, isopropyl ether, n-butyl ether, diisopropyl ether , Furan, furfural, 2-methylfuran, tetrahydrofuran, tetrahydropyran, and other ethers; acetone, methyl ethyl ketone, diethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, methyl i-butyl ketone, methyl n-amyl ketone, methyl n- Hexyl ketone, ethi ketones such as n-propyl ketone and ethyl n-butyl ketone; alcohols such as methanol, ethanol, propyl alcohol, i-propyl alcohol, butyl alcohol, i-butyl alcohol and t-butyl alcohol; methyl formate, ethyl formate, formic acid Esters such as propyl, butyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, methyl propionate and ethyl propionate; alkyl halides such as methyl chloride and ethyl chloride; water, dioxide Examples thereof include inorganic foaming agents such as carbon, and chemical foaming agents such as azo compounds and tetrazole. These foaming agents can be used alone or in admixture of two or more.

  Among the foaming agents, n-butane, i-butane, propane, dimethyl ether, diethyl ether, methyl ethyl ether, methyl chloride, ethyl chloride, and the like are preferable from the viewpoint of foamability and foam moldability. Water and carbon dioxide are preferable from the viewpoints of combustibility, flame retardancy of foam and heat insulation. From the viewpoint of excellent environmental compatibility, n-butane, i-butane, propane, dimethyl ether, water and carbon dioxide are more preferable.

  The amount of the foaming agent that is press-fitted into the molten foam layer-constituting resin (thermoplastic resin) is appropriately selected according to the setting value of the foaming ratio, etc., but usually the total amount of the foaming agent is the thermoplastic resin. It is preferable to set it as 1-20 weight part with respect to 100 weight part, and it is more preferable to set it as 3-8 weight part. When the total press-fitting amount of the foaming agent is 1 to 20 parts by weight, there is no void in the foam, and a foamed layer having an appropriate foaming ratio that can control the flame retardancy is obtained. Properties such as heat insulation are manifested.

The pressure when the foaming agent is press-fitted is not particularly limited as long as it is higher than the internal pressure of an extruder or the like.
The average cell diameter in the foam layer made of the thermoplastic resin constituting the extruded foam laminate of 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 mm. 4 mm.

  In addition, when water is used as a foaming agent, a comparatively small bubble with a bubble diameter of approximately 0.25 mm or less (small bubble) and a bubble diameter of approximately 0.3 mm to 1 mm in the foam. A foam layer with a characteristic bubble structure in which large bubbles (large bubbles) are mixed in a sea-island shape is obtained. In order to contribute to the improvement of the heat insulating performance of the obtained extruded foam laminate, it is preferable to use water as a foaming agent.

Furthermore, in the foam layer having a specific cell structure in which small bubbles with a bubble diameter of 0.25 mm or less and large bubbles with 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 98%, more preferably 10 to 90%, particularly preferably 20 to 80%, and most preferably 25 to 70. %. When the area ratio of the small bubbles is in the range of 5 to 98%, a foamed layer having excellent heat insulation performance and excellent moldability capable of adjusting the foam thickness can be obtained.
When water is used as the foaming agent, the content of water with respect to the total amount of the foaming agent is preferably 1 to 80% by weight, more preferably 2 to 70% by weight, from the viewpoint of ease of forming small bubbles and large bubbles and processability. Particularly preferred is 3 to 60% by weight.

  When water is used as the foaming agent, water-absorbing or water-swelling layered silicates such as smectite and swellable fluoromica or organically treated products thereof, water-absorbing polymers, silanols such as AEROSIL manufactured by Nippon Aerosil Co., Ltd. By adding one or more of anhydrous silica having a group and the like (herein, these substances are collectively referred to as “water-absorbing substance”), the small bubbles and the large bubbles are added to the foam. Can be further improved, and the moldability, productivity and heat insulation performance of the resulting foam can be further improved.

  Here, it is considered that the water-absorbing substance used can absorb water that is not compatible with the thermoplastic resin to form a gel, and can be uniformly dispersed in the thermoplastic resin in a gel state. Used from.

  The amount of the water-absorbing substance used when producing the foamed layer constituting the extruded foam laminate of the present invention is appropriately adjusted depending on the amount of water added, etc. The amount is preferably 0.2 to 10 parts by weight, more preferably 0.3 to 8 parts by weight, and particularly preferably 0.5 to 7 parts by weight with respect to parts. When the added amount of the water-absorbing substance is 0.2 to 10 parts by weight, water is well dispersed in the extruder, and a foamed layer having a good cell structure free from bubble unevenness and voids is obtained, and there is no variation. An extruded foam laminate having good heat insulation performance can be obtained.

  The layered silicate used in producing the foamed layer constituting the extruded foam laminate of the present invention is a tetrahedral sheet mainly composed of silicon oxide and an octahedral sheet mainly composed of metal hydroxide. Primary particles having a structure in which the tetrahedron sheet and the octahedron sheet form a unit layer, and the unit layer has a single structure or a plurality of unit layers are laminated between each other via cations, and the like. Exist as aggregates (secondary particles). Specific examples of the layered silicate include, for example, smectite clay and swellable mica.

The smectite clay is represented by the following general formula (I)
X _0.2-0.6 Y _2-3 Z ₄ O ₁₀ (OH) ₂ .nH ₂ O... General formula (I)
(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, and the like, or a substitution product, a derivative thereof, or a mixture thereof. .

The swellable mica is represented by the following general formula (II)
X _0.5-1.0 Y _2-3 (Z ₄ O ₁₀ ) (F, OH) ₂ ... General formula (II)
(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) Z is one or more selected from the group consisting of Si, Ge, Al, Fe, and B), and is natural or synthesized.

  These are water, a polar organic compound that is compatible with water in 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 swellable mica have a structure similar to vermiculites, and such vermiculites and the like can also be used. The vermiculite-equivalent products include three octahedron type and two 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 (III)
(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. Of these, smectite clay and swellable mica are preferred from the viewpoint of dispersibility in the resulting foam, and have sodium ions between layers such as montmorillonite, bentonite, hectorite, synthetic smectite, and swellable fluorine mica. Swellable mica is more 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, but is preferably 0.2 to 10 parts by weight with respect to 100 parts by weight of the thermoplastic resin. Part by weight is more preferred, 0.5 to 7 parts by weight is particularly preferred, and 1 to 5 parts by weight is most preferred.

  If the smectite content is less than 0.2 parts by weight, the amount of water adsorbed by the smectite is insufficient with respect to the amount of water injected, and pores due to poor dispersion of water tend to occur in the extruder, resulting in a defective molded body. .

  On the other hand, when the content of smectite exceeds 10 parts by weight, the amount of inorganic powder present in the thermoplastic resin becomes excessive, so that uniform dispersion in the thermoplastic resin becomes difficult, and bubble unevenness occurs. 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 preferably 0.02 to 20, more preferably 0.1 to 10, particularly preferably 0.15 to 5, and most preferably in the range of 0.25 to 2, in terms of weight ratio. preferable.

The density of the foamed layer made of the thermoplastic resin constituting the extruded foam laminate of the present invention is 500 kg / m ³ or less as described above, but it is 20 to 50 kg / g in order to give lighter weight and excellent heat insulation. m ³ is preferable, and 25 to 35 kg / m ³ is more preferable. When the density is in the range of 20 to 50 kg / m ³ , an extruded foam laminate having light weight and heat insulation can be obtained.

  In the production of the foamed layer constituting the extruded foam laminate of the present invention, if necessary, flame retardant, flame retardant aid, silica, talc, calcium silicate, wollastonite, kaolin, clay, mica, zinc oxide , Inorganic compounds such as titanium oxide and calcium carbonate, processing aids such as sodium stearate, magnesium stearate, barium stearate, liquid paraffin, olefin wax, stearyl amide compound, phenolic antioxidant, phosphorus stabilizer It is preferable to add additives such as nitrogen-based stabilizers, sulfur-based stabilizers, light-resistant stabilizers such as benzotriazoles and hindered amines, colorants such as antistatic agents and pigments.

  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 foam layer made of the thermoplastic resin constituting the extruded foam laminate of the present invention is produced by extrusion foam molding by a co-extrusion method.

As a molding method of extrusion foam molding, for example,
(I) The thermoplastic resin is mixed with the additive as necessary, and then melted by heating.
(Ii) One or more selected from the above-mentioned additives are mixed with the thermoplastic resin, if necessary, and then melted by heating, and the remaining additive is added to the thermoplastic resin as it is, or liquefied or melted as necessary. Then heat and mix,
(Iii) One or more additives selected from the above-mentioned additives are mixed with a thermoplastic resin in advance, and then a heated and melted composition is prepared. Then, the composition and the remaining additive are prepared. , If necessary, mix the thermoplastic resin again, supply to the extruder and melt by heating,
Such as thermoplastic resin, if necessary, supply the additive to the heat-melting extruder, then add the foaming agent to the thermoplastic resin under high pressure conditions at any stage, no flow gel, extrusion foaming Cooling to a suitable temperature, supplying the fluidized gel to a multi-layer laminating apparatus such as a feed block, joining with a molten resin not containing a foaming agent, and then extruding and foaming to a low pressure region through a die to form a foamed layer. Can be manufactured.

  There are no particular limitations on the heating temperature, melt kneading time, and melt kneading means when heating and kneading the thermoplastic resin and an additive such as a foaming agent. Although the heating temperature should just be more than the temperature which the thermoplastic resin to be used melt | dissolves, the temperature which suppresses the molecular degradation of resin by the influence of a flame retardant etc. as much as possible, for example, about 150-280 degreeC is preferable. The melt-kneading time varies depending on the extrusion amount per unit time, the melt-kneading means, and the like, and thus cannot be determined unconditionally. However, the time required for uniformly dispersing and mixing the thermoplastic 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 normal extrusion foaming. However, in order to suppress the molecular deterioration of the resin as much as possible, it is preferable to use a low shear type screw shape 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 layer constituting the extruded foam laminate of the present invention is equal to the thickness of the extruded foam laminate and the number of foam layers in the extruded foam laminate (number of units comprising foam layer / non-foam layer / foam layer). It is selected as appropriate.

  The resin constituting the non-foamed layer in the present invention (hereinafter sometimes referred to as “non-foamed layer constituting resin”) is compatible with the foamed layer constituting resin in order to ensure good adhesion to the foamed layer. It is preferable to select a thermoplastic resin. Even if the resin does not have compatibility with the foam layer-constituting resin, it is possible to select a resin having adhesiveness and adhesiveness that exhibits an anchor effect with the foam layer.

  Examples of the thermoplastic resin having compatibility with the resin constituting the foam layer include styrene resins such as polystyrene; polyolefin resins such as polypropylene, polyethylene, and ethylene propylene random copolymer; nylon 6, nylon 66, and nylon Polyamide resins such as 12, polyester resins such as polyethylene terephthalate and polybutylene terephthalate; polycarbonate resins; polyphenylene ether resins, modified polyphenylene ether resins; polyoxymethylene resins, polyarylate resins, polyphenylene sulfide resins, poly Examples include acrylonitrile, polyvinyl alcohol, ethylene-vinyl acetic acid copolymer, polyacrylic acid, polymethyl methacrylate, and thermoplastic phenolic resins. Others can be used by mixing two or more kinds. Among these, polystyrene resins, polyolefin resins, polyphenylene ether resins, and modified polyphenylene ether resins are preferred because they are excellent in compatibility with the resin constituting the foam layer and are easy to mold. A resin is more preferable.

  The styrenic resin is not particularly limited, and for example, a styrene homopolymer obtained only from a styrene monomer, a random, block or graft obtained from a monomer copolymerizable with a styrene monomer and styrene or a derivative thereof. Examples thereof include copolymers, post-brominated polystyrene, modified polystyrene such as rubber-reinforced polystyrene, and ABS resin. These can be used alone or in admixture of two or more.

  Examples of monomers copolymerizable with styrene include methylstyrene, dimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, bromostyrene, dibromostyrene, tribromostyrene, chlorostyrene, dichlorostyrene, and trichlorostyrene. Polyfunctional vinyl compounds such as divinylbenzene, (meth) acrylic compounds such as acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, methacrylonitrile, α-chloroacrylonitrile, acrylonitrile , Diene compounds such as budadiene or derivatives thereof, unsaturated carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, N-methylmaleimide, N-butylmaleimide N-alkyl-substituted maleimide compounds such as N-cyclohexylmaleimide, N-phenylmaleimide, N-4-diphenylmaleimide, N-2-chlorophenylmaleimide, N-4-bromophenylmaleimide, N-1-naphthylmaleimide; It is done. These can be used alone or in admixture of two or more.

  In particular, when a styrene resin is used as the non-foamed layer constituting the extruded foam laminate of the present invention, styrene homopolymer, styrene acrylonitrile copolymer, (meth) acrylic acid are used from the viewpoint of compatibility with the foamed layer. It is more preferable to use a copolymerized polystyrene, a maleic anhydride-modified polystyrene, a styrene-unsaturated dicarboxylic anhydride-N-alkyl-substituted maleimide copolymer, and an impact-resistant polystyrene, and most preferably a styrene homopolymer.

  Examples of adhesive and adhesive resins include polyolefin resins, vinyl chloride resins, vinylidene chloride resins, vinyl alcohol resins, ethylene-vinyl alcohol copolymer resins, acrylic resins, and styrene-butadiene copolymers. Resins, natural rubber resins, chloroprene resins, and resins obtained by blending the above resins with rosins, rosin derivatives, petroleum resins, terpene resins, phenol resins, rosin phenol resins, ketone resins, etc. Examples thereof include compositions.

  The structure of the non-foamed layer constituting the extruded foam laminate of the present invention is not particularly limited as long as the non-foamed layer contains a radiation suppressing material, and any structure of a single layer or a multi-layer can be adopted. The thickness of the non-foamed layer is appropriately selected according to the thickness of the extruded foam laminate and the number of foam layers in the extruded foam laminate (number of units composed of foam layer / non-foam layer / foam layer). 10 to 500 μm is preferable, 20 to 300 μm is more preferable, 30 to 200 μm is particularly preferable, and 40 to 100 μm is most preferable. When the thickness of the non-foamed layer is in the range of 10 to 500 μm, an extruded foam laminate having light weight and heat insulation can be obtained.

  In the production of the non-foamed layer constituting the extruded foam laminate of the present invention, it is essential to add the heat ray radiation suppressing material, but if necessary, plasticizer, flame retardant, flame retardant aid, silica , Talc, calcium silicate, wollastonite, kaolin, clay, mica, zinc oxide, titanium oxide, calcium carbonate and other inorganic compounds, sodium stearate, magnesium stearate, barium stearate, liquid paraffin, olefin wax, stearyl Processing aids such as amide compounds, phenolic antioxidants, phosphorus stabilizers, nitrogen stabilizers, sulfur stabilizers, light-resistant stabilizers such as benzotriazoles and hindered amines, antistatic agents, pigments, etc. It is preferable to add an additive such as a colorant.

  Among these additives, the plasticizer is used in the production of the extruded foam laminate of the present invention so as not to disturb the flow at the resin joining interface, and the melt viscosity of the non-foamed layer constituting resin is contained in the foaming agent. Since it works effectively when adjusting to the melt viscosity of the resin, it is preferably added.

The plasticizer added to the non-foamed layer constituting resin is not particularly limited, and any compound generally used as a plasticizer can be used. For example, dimethyl phthalate (DMP), diethyl phthalate (DEP) ), Dibutyl phthalate (DBP), di-2-ethylhexyl phthalate (DOP), dinormaloctyl phthalate (DNOP), diisononyl phthalate (DINP), dinonyl phthalate (DNP), diisodecyl phthalate (DIDP), butyl benzyl phthalate (BBP), phthalic acid esters such as phthalic acid混基ester _(C 6 _{~C 11);} dioctyl adipate (DOA), diisononyl adipate (DINA), dialkyl adipate (C6,8,10 ) (610A), dialkyl adipate _{(C 7, C 9) (} 79A) Azerai Dioctyl acid (DOZ) dibutyl sebacate (DBS), dioctyl sebacate (DOS), tricresyl phosphate (TCP), tributyl acetylcitrate (ATBC), epoxidized soybean oil (ESBO), trioctyl trimellitic acid (TOTM), Non-phthalic acid esters such as chlorinated paraffin, and the like.

  The amount of plasticizer added to the non-foamed layer constituting resin is appropriately selected depending on the target melt viscosity, but is preferably 1 to 20 parts by weight, and 2 to 15 parts by weight with respect to 100 parts by weight of the non-foamed layer constituting resin. More preferably, 3 to 12 parts by weight is particularly preferable, and 4 to 10 parts by weight is preferable. When the addition amount of the plasticizer is in the range of 1 to 20 parts by weight with respect to 100 parts by weight of the non-foamed layer constituting resin, a non-foamed layer with no discharge fluctuation during extrusion and no surface bleed-out after extrusion is obtained. .

The non-foamed layer made of the thermoplastic resin constituting the extruded foam laminate of the present invention is produced by extrusion foaming by a coextrusion method.
As a molding method of extrusion foam molding by the coextrusion method of the non-foamed layer, for example,
(I) After mixing the thermoplastic resin with a heat ray radiation suppressing material and, if necessary, the additive, heat melting.
(Ii) After mixing one or more materials selected from the heat ray radiation suppressing material and, if necessary, the additive into the thermoplastic resin, the mixture is heated and melted, and the remaining additive is liquefied as it is or as necessary. Or melt and add and mix by heating.
(Iii) A heat-radiation-suppressing material and, if necessary, one or more additives selected from the above additives are mixed with a thermoplastic resin in advance, and then a heat-melted composition is prepared. The remaining additive, if necessary, mixing the thermoplastic resin again, supplying to the extruder and melting by heating,
Etc., thermoplastic resin, heat radiation suppression material, if necessary, the additive is supplied to an extruder, heated melt kneaded, supplied to a multilayer laminating apparatus such as a feed block, and merged with the foaming agent-containing resin Thereafter, it can be produced by extrusion foaming through a die to a low pressure region to form a foam layer.

  There are no particular limitations on the heating temperature, melt kneading time, and melt kneading means when the thermoplastic resin, heat radiation suppression material, and other additives are heated and melt kneaded. The heating temperature may be equal to or higher than the temperature at which the thermoplastic resin to be used melts, but the temperature difference is within ± 10 ° C even if it is equal to or different from the set temperature of the multilayer laminating apparatus to which the molten resin is supplied. Is preferred. When the temperature difference is ± 10 ° C. or less, it is possible to obtain a good extruded multilayer laminate in which there is no bubble breakage at the interface portion between the foamed layer and the non-foamed layer and there is no adhesion failure. 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, but is required for uniformly dispersing and mixing the thermoplastic resin, the heat ray radiation suppressing material, and the additive. Time 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 resin extrusion. However, in order to suppress the molecular deterioration of the resin as much as possible, it is preferable to use a low shear type screw shape for the screw shape.

  The extruded foam laminate of the present invention is obtained by a method in which the constituent resins of the non-foamed layer and the foamed layer are melt-kneaded using different extruders, and the melted resins are joined together in a multilayer shape and laminated, and then foam-molded. Manufactured.

  As a method of performing melt-kneading for each of the constituent resins of the non-foamed layer and the foamed layer using different extruders, and joining and laminating each melted resin in a multilayer shape with a multilayer laminating apparatus, it is not particularly limited, for example, A method of repeating splitting and laminating after making a laminated flow composed of a plurality of layers described in a feed block method, a multi-manifold method, Japanese Patent Application Laid-Open No. 4-278323, etc. generally used for coextruded films, -523831 gazette, Unexamined-Japanese-Patent No. 2004-249520, etc. WHEREIN: After making the some division | segmentation flow, the method of laminating | stacking sequentially is mentioned.

  The temperature of the multilayer laminating apparatus when producing the extruded foam laminate is preferably equal to or less than ± 10 ° C. even if it is equal to or different from the resin temperature of the foaming agent-containing molten resin supplied to the multilayer laminating apparatus. When the temperature difference is ± 10 ° C. or less, molding with a die is possible at an appropriate foaming temperature, and an extruded multilayer laminate having a foam layer with a high magnification and a low closed cell ratio can be obtained.

  The pressure in the multilayer laminating apparatus when producing the extruded foam laminate is set to a pressure at which the foaming agent-containing molten resin supplied to the multilayer laminating apparatus does not foam in the multilayer laminating equipment. However, the pressure that does not cause foaming in the multi-layer laminating apparatus cannot be generally set because it depends on the type of foaming agent, the amount of foaming agent, and the temperature of the foaming agent-containing molten resin.

  The extruded foam laminate of the present invention has a structure in which a foam layer is laminated via a non-foamed layer in the thickness direction of the extruded foam laminate, such as foam layer / non-foamed layer / foamed layer. preferable. This is because, in a structure in which the foam layer is laminated on both surfaces of the non-foam layer, the effect of reducing the thermal conductivity by the heat ray radiation inhibitor contained in the non-foam layer is effective. In addition, in the structure in which the foam layer is laminated only on one side of the non-foam layer, such as non-foam layer / foam layer / non-foam layer, the effect of reducing the thermal conductivity by the heat ray radiation inhibitor contained in the non-foam layer is fully manifested. There is a tendency not to.

  More preferably, there are a plurality of non-foamed layers such as foamed layer / non-foamed layer / foamed layer / non-foamed layer / foamed layer. This is achieved by providing a plurality of non-foamed layers containing a heat ray radiation suppressing material in the thickness direction of the extruded foam laminate, resulting in excellent thermal conductivity reduction that cannot be obtained with a single non-foamed layer (radiation suppressing material). This is due to the effect.

  The thickness of the extruded foam laminate 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 impart a preferable heat insulating property, bending strength and compressive strength, the thickness of a normal plate-like material is less than a thin material such as a sheet. Some are preferred, usually 10 to 150 mm, preferably 20 to 100 mm.

  The equivalent thermal conductivity at 20 ° C. of the extruded foam laminate of the present invention is preferably 0.034 W / m · K (0.0292 kcal / m · hr · ° C.) or less, and 0.032 W / m · K (0. 0275 kcal / m · hr · ° C. or less, more preferably 0.030 W / m · K (0.0258 kcal / m · hr · ° C.) or less.

  A foam laminate having an equivalent thermal conductivity of 0.034 W / m · K or less is suitably used as a building material application, and contributes to the provision of a comfortable living space.

  The extruded foam laminate of the present invention has various uses, for example, building materials such as flooring materials, wall materials, and roofing materials, heat insulation materials for cold cars, vehicle bumpers, from the viewpoint of its excellent light weight and heat insulation properties. It can be suitably used for automobile members such as automobile ceiling materials and civil engineering members such as antifreezing agents for ground.

  Next, the present invention will be described in detail based on examples, but the present invention is not limited to such examples. Unless otherwise specified, “%” represents wt%.

  Evaluation methods for Examples and Comparative Examples are as follows.

(1) Extruded foam laminate dimensions (unit: mm)
Thickness: For three foamed laminates sampled at different times, as shown in FIG. 1, the thickness at the center (the middle point in the width direction) in the width direction (horizontal direction orthogonal to the extrusion direction) was measured, The average value was calculated.
Width: For three foamed laminates sampled at different times, as shown in FIG. 2, the width at the center in the thickness direction (midpoint in the thickness direction) was measured, and the average value was calculated.

(2) Density of extruded foam laminate (unit: Kg / m ³ )
Density of resin foam laminate:
For three extruded foam laminates sampled at different times, as shown in FIG. 3, after deleting the upper and lower 2 mm portions in the thickness direction, the width direction is the length of the obtained laminate, The length in the extrusion direction was selected so that the volume of the test piece was 50 cm ³ or more, and the test piece was cut into a rectangular parallelepiped shape.
About the obtained test piece, according to the method as described in JIS K7222-1999 "foaming plastics and rubber-measurement of apparent density", the foam density was measured and the average value was computed.

(3) Thermal conductivity (unit: W / m · K)
JIS A9511 (1995) was used to measure the thermal conductivity of three extruded foam laminates that were sampled at different times and passed 5 days after production, using a thermal conductivity measuring device (HC-074-300, manufactured by Eihiro Seiki Co., Ltd.). The average value was calculated by measuring at 20 ° C.

(4) Partial pressure of air in extruded foam laminate The three extruded foam laminates sampled at different times and 5 days after production were deleted from the cut surface as shown in FIG. Then, the width direction is 25 mm from the center in the width direction, the length direction is 25 mm, and the thickness direction is cut out with the thickness of the laminate, and the amount of air in the extruded foam laminate is measured with a gas chromatograph (GC-14A manufactured by Shimadzu Corporation). ) Was analyzed and measured, and the average value was calculated to determine the partial pressure of the air in the extruded foam laminate.

Example 1
[Method for producing molten resin containing foaming agent]
Talc (manufactured by Hayashi Kasei Co., Ltd., trade name: TALCAN PAWDER PK-Z) 1.0 weight with respect to 100 parts by weight of polystyrene (manufactured by PS Japan Co., Ltd., trade name: G9401, MFR = 2.2 g / 10 min) Part, calcium stearate (manufactured by Sakai Chemical Industry Co., Ltd., trade name: calcium stearate) 0.3 part by weight, liquid paraffin (manufactured by Nippon Oil Corporation, trade name: polybutene LV-50) 0.2 part by weight Were dry blended to obtain a styrene resin composition. The styrenic resin composition was supplied at a rate of 32 kg / hour to a two-stage extruder in which a first extruder having a diameter of 65 mm and a second extruder having a diameter of 90 mm were connected in series.
The styrenic resin composition supplied to the first extruder is heated to 200 ° C. and kneaded. As a foaming agent near the tip of the first extruder (side connected to the second extruder), a styrenic resin composition is used. Styrenic resin composition obtained by melting 4.0% by weight of i-butane (manufactured by Mitsui Chemicals) and 2.0% by weight of dimethyl ether (manufactured by Taiyo Liquefaction Gas Co., Ltd.) with respect to 100% by weight of the resin composition Press fit into. Under the present circumstances, the resin pressure in the front-end | tip of a 1st extruder is 8-15 MPa, and the press injection pressure of the foaming agent was set to + 0.5-3 MPa with respect to this.
In the second extruder connected to the first extruder, after the resin temperature is cooled to 130 ° C., it is divided into two, and two types of molten resin containing a foaming agent are provided at the tip of the second extruder It supplied to the feed block for 3 layer multilayer lamination (made by Pla Giken Co., Ltd.).
[Method for producing molten resin containing no foaming agent]
4. Aluminum paste (manufactured by Showa Aluminum Powder Co., Ltd., trade name: SAP CS420) as a heat ray radiation suppressing material with respect to 100 parts by weight of polystyrene (PS Japan Co., Ltd., trade name: 679, MFR = 18 g / 10 min). 0 parts by weight and 4.0 parts by weight of dimethyl phthalate (trade name: DMP, manufactured by Daihachi Chemical Industry Co., Ltd.) as a plasticizer were added to prepare a master batch in advance.
The obtained resin was supplied to an extruder having a diameter of 50 mm at 4 kg / hour. The supplied resin was heated to 140 ° C., melted and kneaded, and supplied to the feed block for the two-kind / three-layer multi-layer lamination without diversion.
[Method for Producing Extruded Foam Laminate by Merging Melt Resin Containing Foaming Agent and Molten Resin Not Containing Foaming Agent in Thickness Direction]
In the feed block for the two-type, three-layer multi-layer lamination, the temperature of which is adjusted to 135 ° C., the molten resin (one layer) containing no foaming agent is divided into two in the thickness direction under a pressure of 3.0 MPa. The melted resin containing the foaming agent thus formed was sandwiched between the melted resin, and each was joined at a thickness of 11 mm / 3 mm / 11 mm.
After that, it has a rectangular cross-section of 2.8 mm in thickness direction and 50 mm in width direction, and a merged multilayer flow is extruded into the atmosphere from a die lip temperature-controlled at 80 ° C., and a rectangular parallelepiped shape with a thickness of 25 mm and a width of 220 mm. Thus, an extruded foam laminate having a three-layer structure of foamed layer / non-foamed layer / foamed layer (see FIG. 5; each thickness is 12.4 mm / 0.2 mm / 12.4 mm) was obtained.
The density of the obtained extruded foam laminate was 39 Kg / m ³ , the thermal conductivity measured 5 days after production was 0.0313 W / m · K, and the partial pressure of air in the laminate bubbles was 0.89 atm. there were.

(Comparative Example 1)
In the production of a molten resin not containing a foaming agent, from the foamed layer / non-foamed layer / foamed layer in the shape of a rectangular parallelepiped having a thickness of 25 mm and a width of 240 mm by the same operation as in Example 1 except that no aluminum paste is added to polystyrene. A three-layer structure (see FIG. 5; each thickness is 12.4 mm / 0.2 mm / 12.4 mm) was obtained.
The density of the obtained extruded foam laminate was 40 kg / m ³ , the thermal conductivity measured after 5 days from manufacture was 0.0316 W / m · K, and the partial pressure of air in the laminate bubbles was 0.97 atm. Met.

  A comparison between Example 1 and Comparative Example 1 confirmed that the thermal conductivity reduction effect of 0.0003 W / m · K was obtained by containing 5 parts by weight of aluminum paste in the non-foamed layer.

(Comparative Example 2)
Except that the molten resin (B) not containing the foaming agent was not supplied into the feed block for the two-type, three-layer multi-layer lamination, the same operation as in Example 1 was performed, and only the foam layer was in the shape of a rectangular parallelepiped having a thickness of 25 mm and a width of 250 mm. An extruded foam board was obtained.
The density of the obtained extruded foam board is 41 kg / m ³ , the thermal conductivity measured after 5 days of manufacture is 0.0321 W / m · K, and the partial pressure of air in the foam bubbles is 0.97 atm. there were.

(Example 2)
[Method for producing molten resin containing foaming agent]
For 100 parts by weight of polystyrene (manufactured by PS Japan Co., Ltd., trade name: 680, MFR = 7.0 g / 10 min), talc (manufactured by Hayashi Kasei Co., Ltd., trade name: TALCAN PAWDER PK-Z) 0.2 weight Part, calcium stearate (manufactured by Sakai Chemical Industry Co., Ltd., trade name: calcium stearate) and liquid paraffin (manufactured by Nippon Oil Corporation, trade name: Polybutene LV-50) 0.2 part by weight Were dry blended to obtain a styrene resin composition.
The styrenic resin composition was supplied at 37 kg / hour to a two-stage extruder in which a first extruder having a diameter of 65 mm and a second extruder having a diameter of 90 mm were connected in series. The styrene resin composition supplied to the first extruder is melt-kneaded by heating to 200 ° C., and polystyrene is used as a foaming agent in the vicinity of the tip of the first extruder (side connected to the second extruder). In a styrene resin composition in which 4.0% by weight of i-butane (Mitsui Chemicals Co., Ltd.) and 4.0% by weight of dimethyl ether (Taiyo Liquefied Gas Co., Ltd.) are melted with respect to 100% by weight of the resin resin composition. Press-fitted. Under the present circumstances, the resin pressure in the front-end | tip of a 1st extruder was 8-15 MPa, and the press injection pressure of the foaming agent was set to + 0.5-3 MPa with respect to this. In the second extruder connected to the first extruder, the resin temperature is cooled to 120 ° C. and then divided into two, and a molten resin containing a foaming agent is provided at the tip of the second extruder 3 types 3 Supplied to a feed block for multi-layer lamination (Pura Giken Co., Ltd.).
[Method for producing molten resin containing no foaming agent]
Aluminum paste (Showa Aluminum Powder Co., Ltd., trade name: SAP CS420) 5.0 as a heat ray radiation suppressing material with respect to 100 parts by weight of polystyrene (manufactured by PS Japan Corporation, trade name: 679, MFR = 18 g / 10 min). A master batch was prepared in advance by adding 4.0 parts by weight of dimethyl phthalate (trade name: DMP, manufactured by Daihachi Chemical Industry Co., Ltd.) as a plasticizer.
The obtained resin was supplied to an extruder having a diameter of 50 mm at 2 kg / hour. The supplied resin was heated to 130 ° C., melted and kneaded, and supplied into the above-mentioned feed block for the two-type / three-layer multi-layer lamination without splitting.
[Method for Producing Extruded Foam Laminate by Merging Melt Resin Containing Foaming Agent and Molten Resin Not Containing Foaming Agent in Thickness Direction]
In the feed block for the two-type, three-layer multi-layer lamination, the temperature of which is adjusted to 130 ° C., the molten resin (one layer) containing no blowing agent is divided into two in the thickness direction under a pressure of 3.6 MPa. Each of them was joined with a molten resin containing the foaming agent thus formed so as to have a thickness of 12 mm / 1 mm / 12 mm.
The combined multi-layer flow was supplied to a die (manufactured by Pla Giken Co., Ltd.) having the same function as the function of dividing and laminating the multi-layer flow described in JP-A-4-278323. Afterwards, the multi-layer flow that has a rectangular cross-section of thickness direction 0.8mm and width direction 50mm and temperature controlled at 80 ° C is extruded into the atmosphere, and a rectangular parallelepiped shape with a thickness of 25mm and a width of 225mm. 5 layer structure consisting of foamed layer / non-foamed layer / foamed layer / non-foamed layer / foamed layer (see FIG. 6, thicknesses of 6.0 mm / 0.05 mm / 12.9 mm / 0.05 mm / 6. 0 mm) was obtained.
The density of the obtained extruded foam laminate is 37 kg / m ³ , the thermal conductivity measured after 5 days of manufacture is 0.0302 W / m · K, and the partial pressure of air in the laminate bubbles is 0.31 atm. there were.
(Example 3)
Example 2 except that 5 parts by weight of titanium oxide (trade name: Tipeke R-780-2, manufactured by Ishihara Sangyo Co., Ltd.) was added in place of 5 parts by weight of the aluminum paste in the production of the molten resin containing no foaming agent. In the same manner as above, a rectangular solid with a thickness of 25 mm and a width of 230 mm and comprising a foamed layer / non-foamed layer / foamed layer / non-foamed layer / foamed layer (see FIG. 6, each thickness is 6.0 mm / (0.05 mm / 12.9 mm / 0.05 mm / 6.0 mm).
The density of the obtained extruded foam laminate was 38 kg / m ³ , the thermal conductivity measured after 5 days from manufacture was 0.0307 W / m · K, and the partial pressure of air in the laminate bubbles was 0.29 atm. Met.

Example 4
In the production of a molten resin not containing a foaming agent, except that 5 parts by weight of carbon graphite (product name: X-10, scale-like, particle size 10 μm) was added instead of 5 parts by weight of aluminum paste, By the same operation as in Example 2, a rectangular parallelepiped shape having a thickness of 25 mm and a width of 240 mm and comprising a foamed layer / non-foamed layer / foamed layer / non-foamed layer / foamed layer (see FIG. 6, each thickness is 6 0.0mm / 0.05mm / 12.9mm / 0.05mm / 6.0mm) extruded foam laminate was obtained.
The density of the obtained extruded foam laminate is 36 Kg / m ³ , the thermal conductivity measured after 5 days from manufacture is 0.0300 W / m · K, and the partial pressure of air in the laminate bubbles is 0.28 atm. Met.
(Comparative Example 3)
In the production of a molten resin not containing a foaming agent, a foamed layer / non-foamed layer / foamed layer / non-foamed cuboid having a thickness of 25 mm and a width of 220 mm was performed in the same manner as in Example 2 except that no aluminum paste was added. An extruded foam laminate having a five-layer structure composed of layers / foamed layers (see FIG. 6; the respective thicknesses are 6.0 mm / 0.05 mm / 12.9 mm / 0.05 mm / 6.0 mm) was obtained.
The density of the obtained extruded foam laminate was 37 kg / m ³ , the thermal conductivity measured after 5 days from manufacture was 0.0308 W / m · K, and the partial pressure of air in the laminate bubbles was 0.29 atm. Met.

  Further, in comparison with Example 2 and Comparative Example 2, in the five-layer extruded foam laminate having two foam layer / non-foam layer / foam layer structures, by containing 5 parts by weight of aluminum paste, A thermal conductivity reduction effect of 0.0006 W / m · K was confirmed. This is larger than the reduction effect in the extruded foam laminate of the three-layer structure (FIG. 5) having one foam layer / non-foam layer (containing 5 parts by weight of aluminum paste) / foam layer structure of Example 1. Met.

  Further, by comparing Examples 3 and 4 with Comparative Example 2, by containing 5 parts by weight of titanium oxide in the non-foamed layer, 0.0001 W / m · K and by containing 5 parts by weight of carbon graphite. A thermal conductivity reduction effect of 0.0008 W / m · K was confirmed.

(Comparative Example 4)
Except that the molten resin (B) not containing the foaming agent was not supplied into the feed block for the two-type three-layer multi-layer lamination, the same operation as in Example 2 was carried out to form a rectangular parallelepiped having a thickness of 31 mm and a width of 240 mm. An extruded foam board was obtained. The density of the obtained extruded foam board is 34 Kg / m ³ , the thermal conductivity measured after 5 days of production is 0.0315 W / m · K, and the partial pressure of air in the foam bubbles is 0.53 atm. there were.

  Examples 2, 3 and 4 having a multilayer structure composed of five layers (FIG. 6) of foamed layer / non-foamed layer / foamed layer / non-foamed layer / foamed layer are comparative examples 3 having a single-layer structure composed of only the foamed layer. It can be seen that the partial pressure of air in the bubbles is smaller than

The extruded foam laminate of the present invention has various uses, for example, building materials such as flooring materials, wall materials, and roofing materials, heat insulation materials for cold cars, vehicle bumpers, from the viewpoint of its excellent light weight and heat insulation properties. It can be suitably used for automobile members such as automobile ceiling materials and civil engineering members such as antifreezing agents for ground.

1. 1. Thickness measurement position of extruded foam laminate 2. Width measurement position of extruded foam laminate 3. Density measurement site of extruded foam laminate 4. Foam layer Non-foamed layer

Claims (13)

An extruded foam laminate obtained by joining a molten resin containing a foaming agent and a molten resin not containing a foaming agent in the thickness direction under high pressure, and then releasing it under atmospheric pressure,
Pressing the starting foam laminate, the thickness direction foamed layer are laminated through a non-foamed layer, Ri Na foaming layer are laminated on both surfaces of the non-foamed layers of all, an outermost layer foamed layer, the non with foamed layer has a structure that exist 1-5 layers, characterized in that at least one of the heat ray radiation suppressor to non foamed layers, extruded foam laminate.   The extruded foam laminate according to claim 1, wherein the heat ray radiation suppressing material is a heat ray reflecting material and / or a heat ray absorbing material.   The extruded foam laminate according to claim 2, wherein the heat ray reflective material is at least one selected from the group consisting of an aluminum compound, a magnesium compound, a silver compound, and a titanium compound.   The extruded foam laminate according to claim 2 or 3, wherein the heat ray reflective material is an aluminum paste.   The extruded foam laminate according to claim 2 or 3, wherein the heat ray reflective material is titanium oxide.   The extruded foam laminate according to claim 2, wherein the heat ray absorbing material is at least one selected from the group consisting of carbon graphite, carbon black, metal sulfate, and antimony compounds.   The extruded foam laminate according to claim 2 or 6, wherein the heat ray absorbing material is carbon graphite.   The extruded foam laminate according to claim 2 or 6, wherein the heat ray absorbing material is carbon black.   The extruded foam laminate according to claim 2 or 6, wherein the heat ray absorbing material is antimony oxide. The extruded foam laminate according to claim 2 or 6, wherein the heat ray absorbing material is barium sulfate . The extruded foam laminate according to any one of claims 1 to 10 , wherein the resin constituting the foam layer is a polystyrene resin, a polyphenylene resin, or a modified polyphenylene resin. The extruded foam laminate according to claim 11 , wherein the resin constituting the foam layer is a polystyrene-based resin. The extruded foam laminate according to any one of claims 1 to 12 , wherein the thermal conductivity at 20 ° C is 0.034 W / mK or less.

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