JP2009234261A - Foamed laminate excellent in heat insulation efficiency - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a foamed laminate for a heat insulation material having a remarkable effect of improving heat insulation efficiency. <P>SOLUTION: A foamed laminate having a remarkable effect of improving heat insulation efficiency can be obtained by making a foamed laminate having at least one structure in which a foamed layer is laminated in the thickness direction through a non-foamed layer containing a heat radiation suppressing material. A heat ray reflecting material such as carbon graphite, and an aluminum compound, or a heat ray absorbing material such as carbon black, and an antimony compound is preferable as a heat radiation suppressing material. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a 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, the thermal insulation performance of the foam board has been dramatically improved. On the extension line of the prior art, there is a view that a further improvement of the thermal insulation performance cannot be easily expected.

  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, the technology disclosed in Patent Document 7 is limited to polypropylene resin foams with low heat insulation performance, and this technology is polystyrene resin foam board, polyurethane resin foam board, polyphenol resin foam with high heat insulation performance. When applied to boards, it was considered difficult to improve thermal insulation performance. In fact, there is no disclosure of the technology to which Patent Document 7 is applied to polystyrene resin foam boards, polyurethane resin foam boards, polyphenol resin foams, and the like.

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 foaming laminated body for heat insulating materials which has the remarkable improvement effect of heat insulation performance, without using chlorofluorocarbons 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.
・ Heat insulation performance is improved by sandwiching a material with a known heat ray radiation suppression effect (heat ray radiation suppression material) between the foam layers in addition to the known aluminum foil that has the effect of improving the heat insulation performance by being sandwiched between the foam layers. thing.
・ By adding additives such as aluminum paste, carbon graphite, and carbon black that can be kneaded into the resin to the non-foamed layer constituent resin, a heat ray radiation suppressing material can be easily obtained, and the aluminum foil has been laminated so far. A foamed laminate having a structure comprising a foamed layer / non-foamed layer (containing a heat ray radiation suppressing material) / foamed layer by an industrially advantageous coextrusion method or the like, without going through complicated steps required at the time. The body is obtained.
・ Polystyrene resin foam, phenolic resin foam, polyurethane, which had been considered to have better heat insulation performance than polypropylene resin foam and had difficulty in improving heat insulation performance compared to polypropylene resin foam Insulation-based resin foam also improves heat insulation performance by sandwiching a heat ray radiation suppressing material between foam layers.
-Insulation performance is improved more than foamed laminates that have multiple structures consisting of foamed layer / non-foamed layer (containing heat ray radiation suppression material) / foamed layer in the thickness direction of the foamed laminate. To be done.

That is, the present invention
[1] A foam laminate having at least one structure in which a foam layer is laminated via a non-foam layer in the thickness direction, wherein the non-foam layer contains a heat ray radiation suppressing material. body,
[2] The foamed laminate according to [1], wherein the foamed laminate has a plurality of structures in which a foamed layer is laminated via a non-foamed layer in the thickness direction,
[3] The foam laminate according to [1] or [2], wherein the heat ray radiation suppressing material is a heat ray reflecting material and / or a heat ray absorbing material,
[4] The foam laminate according to [4], wherein the heat ray reflective material includes at least one selected from the group consisting of an aluminum compound, a magnesium compound, a silver compound, and a titanium compound,
[5] The foam laminate according to [3] or [4], wherein the heat ray reflective material is an aluminum foil.
[6] The foam laminate according to [3] or [4], wherein the heat ray reflective material includes an aluminum paste,
[7] The foam laminate according to [3] or [4], wherein the heat ray reflective material contains carbon graphite,
[8] The foam laminate according to [2] or [3], wherein the heat ray reflective material contains titanium oxide,
[9] The foam laminate according to [3], wherein the heat ray absorbing material includes at least one selected from the group consisting of carbon black, metal sulfate, and antimony compounds.
[10] The foamed laminate according to [3] or [9], wherein the heat ray absorbing material contains carbon black,
[11] The foam laminate according to [3] or [9], wherein the heat ray absorbing material contains antimony oxide.
[12] The foam laminate according to [3] or [9], wherein the heat ray absorbing material contains barium sulfate,
[13] The resin constituting the foam layer is at least one selected from the group consisting of a polystyrene-based resin, a polyphenylene ether-based resin, or a modified polyphenylene ether-based resin, a phenol-based resin, and a polyurethane-based resin. [1] to [12], the foamed laminate according to any one of the above,
[14] The foamed laminate according to [13], wherein the resin constituting the foamed layer is a polystyrene-based resin, and [15] a thermal conductivity at 20 ° C. of 0.034 W / m · K or less. The foamed laminate according to any one of [1] to [14], wherein
About.

The effects of the present invention are as follows.
-Heat insulation performance is improved by taking a foam laminate structure in which the foam layer is laminated in the thickness direction via a non-foam layer containing a heat ray radiation suppressing material.
-Heat insulation performance is further improved by repeating a structure composed of a non-foamed layer / foamed layer containing a foamed layer / heat ray radiation suppressing material a plurality of times.

  Since the above effect can be combined with the prior art for improving the heat insulating property of the foam board, it can be expected to provide a foam board having an excellent heat insulation performance that has not been obtained conventionally.

Sectional drawing of the foaming lamination sheet which shows one example of this invention Sectional drawing of the foaming lamination sheet which shows one example of this invention Sectional drawing of the foaming lamination sheet which shows one example of this invention Sectional drawing of the foaming lamination sheet which shows one example of this invention Sectional drawing of the foaming lamination sheet which shows one example of this invention Sectional drawing of the foaming lamination sheet which shows one example of this invention Sectional drawing of the foaming lamination sheet which shows one example of this invention Sectional drawing of the foaming lamination sheet which shows one example of this invention Sectional drawing of the foaming lamination sheet which shows one example of this invention

  The foamed laminate of the present invention needs to have at least one structure in which a foamed layer is laminated via a non-foamed layer in the thickness direction, and includes a heat ray radiation suppressing material in the non-foamed layer.

The foam layer constituting the 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 cell structures. The shape is not particularly limited, and examples thereof include a film shape, a sheet shape, and a board shape. Among these, a sheet shape and a board shape are easy to express heat insulation performance and can give lightweight to the foamed laminate. Is preferred.

The non-foamed layer constituting the foamed laminate of the present invention refers to a layer having a density exceeding 500 kg / m ³ and includes a heat ray radiation suppressing material as a constituent material. The shape of the non-foamed layer is preferably a film shape or a sheet shape because it can impart lightness to the foamed laminate. The configuration of the non-foamed layer is not particularly limited and may be a single layer or multiple layers. For example, the non-foamed layer may be formed of a single heat ray radiation suppressing material, a heat ray radiation suppressing material, a heat ray radiation suppressing material, and a heat ray radiation. Examples include a composite of materials that do not have an inhibitory effect.

The heat ray radiation suppressing material contained in the non-foamed layer constituting the foamed 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). It refers to a material having characteristics, and a material whose black body emissivity is smaller than that of the resin constituting the foam layer.
Examples of the heat ray radiation suppressing material include a heat ray reflecting material and a heat ray absorbing material described below.

  The said heat ray reflective material contains the substance (henceforth a "heat ray reflector") which has the characteristic to reflect and scatter the light of near infrared or infrared region (for example, wavelength range of about 800-3000 nm). It refers to a material, and the structure thereof is not particularly limited. For example, the heat ray reflector is composed of a single substance, the heat ray reflector is composed of a plurality of heat ray reflectors, and the heat ray reflector is combined with a substance having no heat ray reflection characteristics. (For example, a resin formed by adding a heat ray reflective agent, etc.).

  The heat ray reflective agent 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), and specifically, scaly graphite, Carbon graphite such as earth graphite and artificial graphite, aluminum compounds such as aluminum and aluminum oxide, zinc compounds such as zinc aluminate; magnesium compounds such as hydrotalcite; silver compounds such as silver: titanium, titanium oxide And titanium compounds such as 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, carbon graphite, aluminum compound, magnesium compound due to its great thermal conductivity reduction effect, cost advantage, good handling properties including environmental compatibility and safety, etc. A material containing a silver compound or a titanium compound is preferable. Among these, aluminum foil obtained by rolling; carbon graphite obtained by kneading, aluminum paste, and a material containing titanium oxide in the resin are more preferable because of excellent balance between thermal conductivity reduction effect and cost. .

  The shape of the heat ray reflective material is not particularly limited, and examples thereof include a flat sheet shape, a flat film shape, a corrugated sheet shape, and a corrugated film shape. Among these, processability, cost, and heat conduction are included. A flat film shape is preferable from the viewpoint of an effect of reducing the rate.

  When the shape of the heat ray reflective material is a flat film, the thickness is a balance between the effect of reducing the thermal conductivity of the foam laminate and the density of the foam laminate (that is, the effect of reducing the heat conductivity by the heat ray reflector is large, And a foamed laminate having a low density is obtained), preferably 10 to 1000 μm, more preferably 10 to 500 μm, particularly preferably 10 to 200 μm, and most preferably 15 to 100 μm.

  The heat ray reflective agent is a roll of the heat ray reflective agent itself; sputtering on a base film, physical vapor deposition such as vacuum vapor deposition, film formation of the heat ray reflective agent by chemical vapor deposition, etc .; It is processed and produced into a heat ray reflective material by forming a resin film obtained by, for example; forming a resin latex or resin solution obtained by adding a heat ray reflective agent; In addition, the preparation method of the heat ray reflective material using the resin latex / resin solution is preferable because a film in which the heat ray reflective agent is uniformly dispersed can be easily obtained.

  When the heat ray reflective material is made of a resin film, a resin sheet or the like to which a heat ray reflective agent is added, the amount of the heat ray reflective agent is appropriately set depending on the type of the heat ray reflective agent and the thickness of the heat ray reflective material. As for the foamed laminate, it is possible to prepare a heat ray reflective material having a desired thickness and set an addition amount so that there is almost no change in absorbance at 800 to 3000 nm in the spectrum measured by an infrared spectrophotometer (IR). This is preferable because the balance between the thermal conductivity reduction effect and the cost is excellent.

  When the heat ray reflective material is a resin film / resin sheet or the like to which a heat ray reflective agent is added, the resin to which the heat ray reflective agent is added includes a foam layer in order to ensure good adhesion to the foam layer. It is preferable to select a resin that is compatible with the constituent resin. In addition, even if the resin does not have compatibility with the resin constituting the foam layer, the resin layer is laminated through a resin layer having adhesiveness and adhesiveness that exhibits an anchor effect with the foam layer. Is also possible.

  The resin having adhesiveness / adhesiveness is not particularly limited, and polyolefin resin, vinyl chloride resin, vinylidene chloride resin, vinyl alcohol resin, ethylene-vinyl alcohol copolymer resin, acrylic resin, styrene -Butadiene copolymer resin, natural rubber resin, chloroprene resin, and tackifier resins such as rosins, rosin derivatives, petroleum resins, terpene resins, phenol resins, rosin phenol resins, and ketone resins. The resin composition etc. which mix | blend are mentioned. Those obtained by processing these into a film shape / sheet shape by an extrusion method or the like, and those obtained by drying these latexes into a film shape / sheet shape are preferable because the foamed laminate of the present invention can be easily produced.

  In addition, by adding a heat-reflecting agent to the adhesive / adhesive resin layer, the adhesion of the non-foamed layer containing the heat-reflecting agent to the foamed layer can be improved. By combining with a film that does not contain an agent, the rigidity of the non-foamed layer can be improved, and handling properties can be improved.

  The heat ray absorbing material is a material containing a substance having a property of absorbing light in the near infrared or infrared region (for example, a wavelength region of about 800 to 3000 nm) (hereinafter referred to as “heat ray absorbent”). The configuration is not particularly limited. For example, the heat ray absorbent is composed of a single substance, the heat ray absorbent is composed of a plurality of heat ray absorbents, and the heat ray absorbent is combined with a substance having no heat ray absorption characteristics ( For example, a resin obtained by adding a heat ray absorbent, etc.) can be used.

  The heat ray absorber 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 region of about 800 to 3000 nm), and specifically, carbon black, carbon powder. ; Metal sulfates such as barium sulfate, strontium sulfate, calcium sulfate, mercalite, halothrite, alumite, iron alumite; antimony compounds such as ATO and antimony oxide; tin oxide, indium oxide, zinc oxide, ITO, anhydrous Metal oxides such as zinc antimonate; ammonium, urea, imonium, aminium, cyanine, polymethine, anthraquinone, dithiol, copper ion, phenylenediamine, phthalocyanine, benzotriazole, benzophenone , Oxalic anilide, cyanoacrylate, ben Organic dyes and pigments triazole and the like; and the like.

  As a heat-absorbing material, carbon black, metal sulfate or antimony compound due to its large thermal conductivity reduction effect, cost advantage, good handling properties including environmental compatibility and safety, etc. Among these, materials containing carbon black, antimony oxide or barium sulfate obtained by kneading are more preferable because they have an excellent effect of reducing thermal conductivity and cost.

  The shape of the heat-absorbing material is not particularly limited, and examples thereof include a flat sheet shape, a flat film shape, a corrugated sheet shape, and a corrugated film shape. Among these, processability, cost, and heat conduction are included. A flat film shape is preferable from the viewpoint of an effect of reducing the rate.

  When the shape of the heat ray absorbing material is a flat film, the thickness is a balance between the effect of reducing the thermal conductivity of the foam laminate and the density of the foam laminate (that is, the effect of reducing the heat conductivity by the heat ray absorbing material is large, and From 10 to 1000 μm is preferable, from 10 to 500 μm is more preferable, from 10 to 200 μm is more preferable, and from 15 to 100 μm is particularly preferable.

  The heat ray absorbent is formed by rolling the heat ray absorbent itself; sputtering of the heat ray absorbent onto a substrate film, physical vapor deposition such as vacuum vapor deposition, film formation by chemical vapor deposition, etc .; It is processed and produced into a heat ray reflective material by film formation of a resin obtained by melt kneading or the like; formation of a resin latex or resin solution obtained by adding a heat ray absorbent; In addition, the preparation method of the heat ray absorbing material using the resin latex / resin solution is preferable because a film in which the heat ray absorbent is uniformly dispersed can be easily obtained.

  When the heat-absorbing material comprises a resin film / resin sheet to which a heat-absorbing agent is added, the addition amount is appropriately set according to the type of heat-absorbing agent and the thickness of the heat-ray-absorbing material. It is possible to prepare a heat-absorbing material having a predetermined thickness and set the addition amount so that there is almost no change in absorbance at 800 to 3000 nm in the spectrum measured by an infrared spectrophotometer (IR). A good balance between the reduction effect and cost is preferable.

  When the heat-absorbing material comprises a resin film / resin sheet to which a heat-absorbing agent is added, the resin to which the heat-absorbing agent is added constitutes the foaming layer in order to ensure good adhesion to the foaming layer. It is preferable to select a resin that is compatible with the resin. In addition, even if the resin does not have compatibility with the resin constituting the foam layer, the resin can be laminated via an adhesive / adhesive resin that exhibits an anchor effect with the foam layer. It is.

  The resin having adhesiveness / adhesiveness is not particularly limited, and polyolefin resin, vinyl chloride resin, vinylidene chloride resin, vinyl alcohol resin, ethylene-vinyl alcohol copolymer resin, acrylic resin, styrene -Butadiene copolymer resin, natural rubber resin, chloroprene resin, and tackifier resins such as rosins, rosin derivatives, petroleum resins, terpene resins, phenol resins, rosin phenol resins, and ketone resins. The resin composition etc. which mix | blend are mentioned. Those obtained by processing these into a film shape / sheet shape by an extrusion method or the like, and those obtained by drying these emulsion latexes into a film shape / sheet shape are preferable because the foamed laminate of the present invention can be easily produced.

  Moreover, by adding a heat ray absorbent to the adhesive / adhesive resin layer, the adhesion of the non-foamed layer containing the heat ray absorbent to the foamed layer can be improved, and further, a commercially available heat ray absorbent By combining with a film that does not contain an agent, the rigidity of the non-foamed layer can be improved, and handling properties can be improved.

  As the constituent resin of the foam layer constituting the foam laminate of the present invention, both a thermosetting resin and a thermoplastic resin are preferably used.

  The thermosetting resin is not particularly limited, and examples thereof include epoxy resins, polyurethane resins, phenol resins, melamine resins, urea resins, unsaturated polyester resins, and the like. A mixture of more than one species can be used. Among these, phenol resins and polyurethane resins are preferable because of excellent heat insulation performance and easy filling and foaming steps.

  There are no particular limitations on the formulation and manufacturing method of the foamed layer made of a phenolic resin, and examples thereof include those described in JP 2000-801761 A, JP 2001-114922 A, JP 2002-309030 A, and the like. It is possible to manufacture using a blending and manufacturing method.

  There is no particular limitation on the blending and manufacturing method of the foamed layer made of polyurethane resin, and for example, it is manufactured using the blending and manufacturing method described in JP-A-8-231667, JP-A-2007-332203, etc. 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. Among these, polystyrene resins, polyphenylene ether resins, and modified polyphenylene ether resins are preferable, and styrene resins are more preferable because of excellent heat insulation performance and easy moldability.

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

  It does not specifically limit as a foaming agent used when obtaining the foaming layer which comprises the foaming laminated body of this invention, For example, propane, n-butane, i-butane, n-pentane, i-pentane, neopentane, etc. Saturated hydrocarbons having 3 to 5 carbon atoms; ethers such as dimethyl ether, diethyl ether, methyl ethyl ether, isopropyl ether, n-butyl ether, diisopropyl ether, furan, furfural, 2-methyl furan, tetrahydrofuran, tetrahydropyran; acetone, methyl ethyl ketone , Ketones such as diethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, methyl i-butyl ketone, methyl n-amyl ketone, methyl n-hexyl ketone, ethyl n-propyl ketone, ethyl n-butyl ketone; Alcohols such as ethanol, propyl alcohol, i-propyl alcohol, butyl alcohol, i-butyl alcohol, t-butyl alcohol; methyl formate, ethyl formate, propyl formate, butyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate , Esters such as butyl acetate, amyl acetate, methyl propionate and ethyl propionate; halogenated alkyls such as methyl chloride and ethyl chloride; inorganic foaming agents such as water and carbon dioxide; and azo compounds and tetrazoles A chemical foaming agent etc. are mentioned. 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 flammability, flame retardancy or heat insulation of the foam, and more preferably n-butane, i-butane, propane, dimethyl ether, water, Carbon dioxide.

  When producing a foamed layer comprising a thermoplastic resin constituting the foamed laminate of the present invention, the amount of foaming agent added or injected into the thermoplastic resin is appropriately selected according to the setting value of the foaming ratio, etc. However, usually, the total amount of the foaming agent is preferably 1 to 20 parts by weight, more preferably 3 to 8 parts by weight with respect to 100 parts by weight of the thermoplastic resin. When the total addition amount of the foaming agent is 1 to 20 parts by weight, there is no void in the foam, and a foam layer with an appropriate foaming ratio that can control flame retardancy is obtained. The characteristics are expressed.

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

  When water is used as a foaming agent, processability and generation of bubbles having a bubble diameter of 0.25 mm or less (hereinafter also referred to as small bubbles) and bubbles having a bubble diameter of 0.3 to 1 mm (hereinafter also referred to as large bubbles). From the viewpoint of easiness, the content of water with respect to 100% by weight of the total amount of the foaming agent is preferably 1 to 80% by weight, more preferably 2 to 70% by weight, and particularly preferably 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; AEROSIL manufactured by Nippon Aerosil Co., Ltd. By adding one or two or more of anhydrous silica having a silanol group (in the present specification, these substances are collectively referred to as “water-absorbing substance”), the small bubbles, The effect | action which a bubble generate | occur | produces can further be improved and the moldability of the foam obtained, productivity, and heat insulation performance further improve.

  These water-absorbing substances are used because they absorb water that is not compatible with the thermoplastic resin to form a gel and can be uniformly dispersed in the thermoplastic resin in the gel state. Is done.

  The amount of the water-absorbing substance used in producing the foamed layer constituting the foamed laminate of the present invention is appropriately adjusted depending on the amount of water added, etc., but generally 100 parts by weight of the thermoplastic resin 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. 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. A foamed laminate having good heat insulation performance is obtained.

  The layered silicate used in producing the foamed layer constituting the foamed laminate of the present invention comprises a tetrahedral sheet mainly composed of silicon oxide and an octahedral sheet principally composed of metal hydroxide. The tetrahedron sheet and the octahedron sheet form a unit layer, a unit layer single structure, or a plurality of unit layers laminated between layers through cations, etc., and primary particles It exists as an aggregate (secondary particle). 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. One or more selected from Z and one or more selected from the group consisting of Si and Al, where H ₂ O represents a water molecule bonded to an interlayer ion, and n represents 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, 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, and the following general formula (III)
_{(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. Among these, smectite group clay and swellable mica are preferable from the viewpoint of dispersibility in the obtained foam, and more preferably sodium between layers such as montmorillonite, bentonite, hectorite, synthetic smectite, and swellable fluorine mica. Swellable mica having ions is preferred.

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

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

  The average cell diameter in the foam layer made of the thermoplastic resin constituting the 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 0.4 mm. preferable.

  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 insulation performance of the resulting 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.

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

  In the production of the foam layer constituting the foam laminate of the present invention, flame retardant, flame retardant aid, silica, talc, calcium silicate, wollastonite, kaolin, clay, mica, zinc oxide, oxidation as necessary Inorganic compounds such as titanium and calcium carbonate, processing aids such as sodium stearate, magnesium stearate, barium stearate, liquid paraffin, olefin wax, stearyl amide compound, phenolic antioxidant, phosphorus stabilizer, nitrogen It is preferable to add additives such as light stabilizers such as system stabilizers, sulfur stabilizers, benzotriazoles and hindered amines, antistatic agents, and colorants such as 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 foam laminate of the present invention is preferably produced by extrusion foam molding.
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) A thermoplastic resin is mixed with one or more additives selected from the additives as necessary, and then a heat-melted composition is prepared, and then the composition and the remaining addition are added. If necessary, mix the thermoplastic resin again, supply to the extruder and melt by heating.
The thermoplastic resin, if necessary, the additive is supplied to heating and melting means such as an extruder, and then the foaming agent is added to the thermoplastic resin under high-pressure conditions at any stage, and there is no fluid gel, It can be produced by cooling to a temperature suitable for extrusion foaming and extrusion foaming the fluid gel through a die to a low pressure region to form a foamed layer, but is not limited thereto.

  There are no particular limitations on the heating temperature, melt kneading time, and melt kneading means when heating and kneading the thermoplastic resin and additives 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 foam laminate of the present invention depends on the thickness of the foam laminate and the number of non-foam layers in the foam laminate (number of units comprising foam layer / non-foam layer / foam layer). It is selected appropriately.

  The structure of the non-foamed layer constituting the foamed 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 multiple layers can be adopted. The thickness is appropriately selected according to the thickness of the foam laminate and the number of non-foam layers in the foam laminate (number of units comprising foam layer / non-foam layer / foam layer). Is preferable, 2-500 μm is more preferable, 3-300 μm is particularly preferable, and 5-100 μm is most preferable. When the thickness of the non-foamed layer is in the range of 1 to 1000 μm, a foamed laminate having light weight and heat insulation is obtained.

  The method for producing the foamed laminate of the present invention, particularly the method for laminating the foamed layer and the non-foamed layer, is not particularly limited. For example, the outermost surface (the surface to be adhered to the foamed layer) has adhesiveness / adhesiveness. A method in which a non-foamed layer (or that has been given tackiness / adhesiveness) is formed into a film or a sheet in advance, and this is sandwiched between the pre-formed foamed layers, followed by pressure bonding; A method of melt-kneading and using a non-foamed layer and a foamed layer, and sandwiching the non-foamed layer between the foamed layers. Thereafter, a method of thermocompression bonding; a method in which the constituent resins of the non-foamed layer and the foamed layer are melt-kneaded using different extruders, the melted resins are joined together in multiple layers and laminated, and then foam molding is performed. .

  Among these, the non-foamed layer having adhesiveness / adhesiveness is preliminarily formed into a film shape or a sheet shape because it is excellent in productivity, and the quality of the obtained foamed laminate is stable. A method of sandwiching and pressing with a foam layer and a method of melt-kneading the constituent resins of the non-foam layer and the foam layer using different extruders, joining the melted resins in multiple layers, and laminating them are preferable.

  The method of sandwiching the non-foamed layer having an adhesive between the foamed layers and performing pressure bonding is not particularly limited, and is a method of pressing at room temperature or heat using a press; a method of pressure bonding between a plurality of rolls; And how to do it.

  A method of melt-kneading the constituent resins of the non-foamed layer and the foamed layer using different extruders, and joining the molten resins in a multilayer shape and laminating them is not particularly limited. For example, JP-A-4-278323 After making a laminated flow composed of a plurality of layers as described in the publication, etc., a method of repeating division and lamination, making a plurality of divided flows as described in JP 2005-523831 A, JP 2004-249520 A, etc. After that, there is a method of sequentially laminating.

  As the structure of the foam laminate of the present invention, it is necessary to have at least one structure composed of foam layer / non-foam layer / foam layer in the thickness direction of the foam laminate, and foam layer / non-foam layer / foam layer / Non-foamed layer / Foamed layer, preferably a plurality of structures comprising foamed layer / non-foamed layer / foamed layer, more preferably 3 or more, still more preferably 5 or more, 7 layers It is particularly preferable to have 10 or more layers, and most preferable to have 10 layers or more. By providing a plurality of non-foamed layers containing a heat ray radiation suppressing material in the thickness direction of the foam laminate, an excellent heat conductivity reduction effect that cannot be obtained with a single non-foamed layer (heat ray radiation suppressing material) appears. it can.

  The thickness of the 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 of the foamed laminate of the present invention at an average temperature of 20 ° C. 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.

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

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

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

  Evaluation methods for Examples and Comparative Examples are as follows.

(1) Foam dimensions (unit: mm)
Thickness: For three foams sampled at different times, the thickness in the center in the width direction (horizontal direction orthogonal to the extrusion direction) was measured, and the average value was calculated.
Width: For three foams sampled at different times, the center width in the thickness direction was measured, and an average value was calculated.

(2) Density of foam (unit: kg / m ³ )
The obtained resin foam was cut into a rectangular parallelepiped shape so as to have a test piece volume of 50 cm ³ or more in the full width and full thickness in the width direction (horizontal direction orthogonal to the extruding direction) to obtain a test piece. With respect to this test piece, the foam density was measured according to the method described in JIS K7222-1999 “Foamed Plastics and Rubber—Measurement of Apparent Density”.

(3) Thermal conductivity (unit: W / mK)
The thermal conductivity of the extruded resin foam after 30 days from the production was measured at 20 ° C. according to JIS A9511 (1995).

(Production Example 1)
For 100 parts by weight of polystyrene (manufactured by PS Japan Co., Ltd., trade name: G9401, MFR = 2.5 g / 10 min), talc (manufactured by Hayashi Kasei Co., Ltd., trade name: TALCAN PAWDER PK-Z) 0.2 weight Part, 4 parts by weight of hexabromocyclododecane (trade name: SAYTEX HP-900, manufactured by Albemarle Corporation) as a halogen-based flame retardant, 0.5 barium stearate (trade name: barium stearate, manufactured by Sakai Chemical Industry Co., Ltd.) 0.5 Part by weight, stabilizer (manufactured by Ciba Specialty Chemicals, Inc., trade name: IRGANOX B911 [hindered phenol-based antioxidant IRGANOX1076: octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate and phosphorus stabilizer IRGAFOS168: Tri (1: 1 mixture of 2,4-di-t-butylphenyl) phosphite]) 0.3 parts by weight, liquid paraffin (manufactured by Nippon Oil Corporation, trade name: Polybutene LV-50) 0.2 The mixture consisting of parts by weight was dry blended to obtain a styrene resin composition.
The styrenic resin composition was supplied at 50 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, and a polystyrene resin is used as a foaming agent in the vicinity of the tip of the first extruder (side connected to the second extruder). 4% by weight of i-butane (manufactured by Mitsui Chemicals) and 2.0% by weight of dimethyl ether (Mitsui Chemicals) were pressed into the melted styrene-based resin composition with respect to 100% by weight of the composition. Under the present circumstances, the resin pressure in the front-end | tip of a 1st extruder was 8-19 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 there is a rectangular cross-section gap of 1.2 mm in the thickness direction and 50 mm in the width direction provided at the tip of the second extruder. From the die lip, the styrene resin composition was extruded into the atmosphere to obtain a rectangular parallelepiped foam having a thickness of 25 mm and a width of 200 mm. The temperature of the die lip was set to 85 ° C.
The obtained foam was cut off from both sides to 20 mm in the width direction to a width of 160 mm, and evaluated after 30 days of curing.
The density of the extruded foam after curing for 30 days was 33 kg / m ³ and the thermal conductivity was 0.032 W / mK.

(Production Example 2)
0.1 weight of talc (manufactured by Hayashi Kasei Co., Ltd., trade name: TALCAN PAWDER PK-Z) with respect to 100 parts by weight of polystyrene (manufactured by PS Japan Corporation, trade name: 680, MFR = 7.0 g / 10 min) Parts, calcium stearate (manufactured by Sakai Chemical Industry Co., Ltd., trade name: calcium stearate), 0.3 parts by weight, bentonite (manufactured by Toyoshun Mining Co., Ltd., trade name: bentonite L), 1.0 part by weight, Aerosil (Nippon Aerosil Co., Ltd.) A styrene-based resin composition obtained by dry blending a mixture of 0.1 part by weight made by company, trade name: AEROSIL, and 0.2 part by weight liquid paraffin (manufactured by Nippon Oil Corporation, trade name: Polybutene LV-50) It was.
The styrenic resin composition was supplied at 45 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). Of 100% by weight of the resin composition, 4.0% by weight of i-butane (Mitsui Chemicals Co., Ltd.), 2.0% by weight of dimethyl ether (Taiyo Liquefied Gas Co., Ltd.) and 0.6% by weight of water were melted. The styrenic resin composition was 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 122 ° C., and there is a rectangular cross-section gap of 1.2 mm in the thickness direction and 50 mm in the width direction provided at the tip of the second extruder. From the die lip, the styrene resin composition was extruded into the atmosphere to obtain a rectangular parallelepiped foam having a thickness of 28 mm and a width of 220 mm. The temperature of the die lip was set to 85 ° C.
The obtained foam was cut into portions of 20 mm in the width direction from both ends to a width of 180 mm, and the portions from both ends in the thickness direction to 2 mm were deleted to a thickness of 24 mm, and divided into 6 in the thickness direction (for each layer) Evaluation was performed after 30 days of curing.
The foam density of the extruded foam slice product after 30-day curing was 32 kg / m ³ , and the thermal conductivity of 12 sliced products was 0.0333 W / mK.

Example 1
Acrylic emulsion (manufactured by Nissin Chemical Industry Co., Ltd., trade name: Vinibrand 7000R) as an adhesive layer was applied to both sides of an aluminum foil (Toyo Aluminum) having a thickness of 12 μm for 24 μm, and then at 100 ° C. for 1 hour in a thermostatic bath. It was made to dry and the non-foamed layer 1 was obtained. The obtained non-foamed layer 1 had a structure of pressure-sensitive adhesive layer (14 μm) / aluminum foil (12 μm) / pressure-sensitive adhesive layer (14 μm).
The non-foamed layer 1 is sandwiched between two foamed layers (12.5 mm) obtained by dividing the foam obtained in Production Example 1 in the thickness direction as shown in FIG. 1, and two iron plates (6 mm thick) Was inserted and pressed (pressure: about 0.1 to 0.2 MPa) to obtain a sample. Tables 1 and 3 show the thermal conductivity measurement results of the obtained samples.

(Example 2)
Heat-reflective film having a thickness of 55 μm (manufactured by NI Teijin Ltd., trade name: LEFTEL ZC05G [PET film (30 μm) on one side with an adhesive layer (25 μm) and the other side coated with a hard coat layer) A film having a four-layer structure in which a film is laminated]) is coated with an acrylic emulsion (manufactured by Nissin Chemical Industry Co., Ltd., trade name: Viniblanc 7000R) as a pressure-sensitive adhesive layer in a thermostatic chamber. The non-foamed layer 2 was obtained by drying at 100 ° C. for 1 hour. The thickness of the acrylic pressure-sensitive adhesive layer of the obtained non-foamed layer 2 was 14 μm.
The non-foamed layer 2 is sandwiched between two foamed layers (12.5 mm) obtained by dividing the foam obtained in Production Example 1 in the thickness direction as shown in FIG. 1 and two iron plates (6 mm thick). The sample was inserted between and pressed (pressure of about 0.1 to 0.2 MPa) to obtain a sample. Table 1 shows the thermal conductivity measurement results of the obtained samples.

(Example 3)
Heat-absorbing film having a thickness of 62 μm (manufactured by Sumitomo Osaka Cement Co., Ltd., trade name: Ray Barrier Leftel TFI3836A [PET film (30 μm) with a pressure-sensitive adhesive layer (30 μm) on one side and a hard coat layer containing antimony oxide on the other side) A film having a three-layer structure in which (2 μm) is laminated]) is coated with an acrylic emulsion (made by Nissin Chemical Industry Co., Ltd., trade name: Viniblanc 7000R) as a pressure-sensitive adhesive layer, and then a thermostatic bath. The non-foamed layer 3 was obtained by drying at 100 ° C. for 1 hour. The thickness of the acrylic pressure-sensitive adhesive layer of the obtained non-foamed layer 3 was 14 μm.
The non-foamed layer 3 is sandwiched between two foamed layers (12.5 mm) obtained by dividing the foam obtained in Production Example 1 in the thickness direction as shown in FIG. 1, and two iron plates (6 mm thick) The sample was inserted between and pressed (pressure: about 0.1 to 0.2 MPa) to obtain a sample. Table 1 shows the thermal conductivity measurement results of the obtained samples.

(Comparative Example 1)
Acrylic emulsion (manufactured by Nissin Chemical Industry Co., Ltd., trade name: VINYBRAN) as an adhesive layer on both sides of a 20 μm thick polystyrene film (product name: OPS film [GPPS biaxially stretched film] manufactured by Asahi Kasei Life & Living) 7000R) was applied to each 24 μm and then dried at 100 ° C. for 1 hour in a thermostatic bath to obtain a non-foamed layer 4. The obtained non-foamed layer 4 had a structure of pressure-sensitive adhesive layer (14 μm) / OPS film (20 μm) / pressure-sensitive adhesive layer (14 μm).
The non-foamed layer 4 is sandwiched between two foamed layers (12.5 mm) obtained by dividing the foam obtained in Production Example 1 in the thickness direction as shown in FIG. 1, and two iron plates (6 mm thick) And a sample was obtained by pressure bonding (pressure: about 0.1 to 0.2 MPa) using a press machine. Table 1 shows the thermal conductivity measurement results of the obtained samples.

(Comparative Example 2)
The foam obtained in Production Example 1 was divided into two in the thickness direction. Two obtained foamed layers (12.5 mm) were stacked, and the thermal conductivity was measured. Tables 1 and 3 show the thermal conductivity measurement results.

Example 4
Acrylic emulsion (manufactured by Nissin Chemical Industry Co., Ltd., trade name: Viniblanc 7000R, solid content 60) on both sides of a polystyrene film (made by Asahi Kasei Life & Living, trade name: OPS film [GPPS biaxially stretched film]) having a thickness of 20 μm %) After adding 8.3 parts by weight of aluminum paste (trade name: 561SW (particle size: 16 μm, solid content: 72%)) manufactured by Showa Aluminum Powder Co., Ltd. in 100 parts by weight and applying 44 μm of each uniformly dispersed product. And it was made to dry at 100 degreeC in a thermostat for 1 hour, and the non-foaming layer 5 was obtained. The obtained non-foamed layer 5 had a structure of aluminum paste 10% added pressure-sensitive adhesive layer (28 μm) / OPS film (20 μm) / aluminum paste 10% added pressure-sensitive adhesive layer (28 μm).
As shown in FIG. 2, the non-foamed layer 5 is sandwiched between the sixth and seventh sheets from the upper side of the sample in which 12 foam slices (thickness 2.0 mm) obtained in Production Example 2 are stacked. A sample was obtained by inserting between the steel plates (thickness 6 mm) and pressure bonding (pressure: about 0.1 to 0.2 MPa).
Tables 2 and 3 show the thermal conductivity measurement results of the obtained samples.

(Example 5)
Acrylic emulsion (manufactured by Nissin Chemical Industry Co., Ltd., trade name: Viniblanc 7000R, solid content 60) on both sides of a polystyrene film (made by Asahi Kasei Life & Living, trade name: OPS film [GPPS biaxially stretched film]) having a thickness of 20 μm %) After adding 7.4 parts by weight of aluminum paste (product name: 770SW (particle size: 40 μm, solid content: 81%)) manufactured by Showa Aluminum Powder Co., Ltd. in 100 parts by weight and applying 44 μm of each uniformly dispersed product. And it was made to dry at 100 degreeC in a thermostat for 1 hour, and the non-foaming layer 6 was obtained. The obtained non-foamed layer 6 had a structure of 10% aluminum paste added adhesive layer (30 μm) / OPS film (20 μm) / 10% aluminum paste added adhesive layer (30 μm).
As shown in FIG. 2, the non-foamed layer 6 is sandwiched between the sixth and seventh sheets from the upper side of the sample in which 12 foam slices (thickness 2.0 mm) obtained in Production Example 2 are stacked. It inserted between the steel plates (6 mm thickness) and pressure-bonded (pressure: about 0.1-0.2 MPa), and the sample was obtained. Table 2 shows the thermal conductivity measurement results of the obtained sample.

(Example 6)
Acrylic emulsion (manufactured by Nissin Chemical Industry Co., Ltd., trade name: Viniblanc 7000R, solid content 60) on both sides of a polystyrene film (made by Asahi Kasei Life & Living, trade name: OPS film [GPPS biaxially stretched film]) having a thickness of 20 μm %) Carbon graphite (trade name: X-10 (flaky graphite average particle size: 10 μm, solid content: 98.6%) manufactured by Ito Graphite Industries Co., Ltd.) in 100 parts by weight was added and dispersed uniformly. Each of these was coated at 44 μm and then dried in a thermostatic bath at 100 ° C. for 1 hour to obtain a non-foamed layer 7. The obtained non-foamed layer 7 was a carbon graphite 10% added pressure-sensitive adhesive layer (29 μm) / OPS film (20 μm). ) / Carbon graphite 10% added pressure-sensitive adhesive layer (29 μm).
As shown in FIG. 2, the non-foamed layer 7 is sandwiched between the sixth and seventh sheets from the upper side of the sample in which 12 foam slices (thickness 2.0 mm) obtained in Production Example 2 are stacked. It inserted between the steel plates (6 mm thickness), and it pressure-bonded (pressure: about 0.1-0.2 MPa), and obtained the sample. Tables 2 and 4 show the thermal conductivity measurement results of the obtained samples.

(Example 7)
Acrylic emulsion (manufactured by Nissin Chemical Industry Co., Ltd., trade name: Viniblanc 7000R, solid content 60) on both sides of a polystyrene film (made by Asahi Kasei Life & Living, trade name: OPS film [GPPS biaxially stretched film]) having a thickness of 20 μm %) Carbon Graphite (product name: AGB-5 (manufactured graphite average particle size 5.6 μm, solid content 98.6%)) 6.1 parts by weight was added to 100 parts by weight and uniformly dispersed. 44 μm of each was applied and dried in a thermostatic bath at 100 ° C. for 1 hour to obtain a non-foamed layer 8. The obtained non-foamed layer 8 was a pressure-sensitive adhesive layer (30 μm) / OPS containing 10% carbon graphite. The structure was as follows: film (20 μm) / carbon graphite 10% added pressure-sensitive adhesive layer (30 μm).
As shown in FIG. 2, the foamed layer 8 is sandwiched between the sixth and seventh sheets from the upper side of the sample in which 12 foam slices (thickness 2.0 mm) obtained in Production Example 2 are stacked. A sample was obtained by inserting between the steel plates (thickness 6 mm) and pressure bonding (pressure: about 0.1 to 0.2 MPa).
Table 2 shows the thermal conductivity measurement results of the obtained sample.

(Example 8)
Acrylic emulsion (manufactured by Nissin Chemical Industry Co., Ltd., trade name: Viniblanc 7000R, solid content 60) on both sides of a polystyrene film (made by Asahi Kasei Life & Living, trade name: OPS film [GPPS biaxially stretched film]) having a thickness of 20 μm %) After adding 60 parts by weight of titanium oxide (made by Ishihara Sangyo Co., Ltd., trade name: Taipei CR-50 (particle diameter: 0.25 μm) and uniformly dispersing 44 μm each in 100 parts by weight, It was dried at 100 ° C. for 1 hour in a thermostatic bath to obtain a non-foamed layer 9. The obtained non-foamed layer 9 was a titanium oxide 10% added adhesive layer (29 μm) / OPS film (20 μm) / titanium oxide 10% added. The structure was a pressure-sensitive adhesive layer (29 μm).
As shown in FIG. 2, the non-foamed layer 9 is sandwiched between the sixth and seventh sheets from the upper side of the sample in which 12 foam slices (thickness 2.0 mm) obtained in Production Example 2 are stacked. It inserted between the steel plates (6 mm thickness) and pressure-bonded (pressure: about 0.1-0.2 MPa), and the sample was obtained.
Table 2 shows the thermal conductivity measurement results of the obtained sample.

Example 9
Acrylic emulsion (manufactured by Nissin Chemical Industry Co., Ltd., trade name: Viniblanc 7000R, solid content 60) on both sides of a polystyrene film (made by Asahi Kasei Life & Living, trade name: OPS film [GPPS biaxially stretched film]) having a thickness of 20 μm %) After adding 6.0 parts by weight of barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., trade name: Variace B-35 (particle diameter: 0.3 μm) to 100 parts by weight, 44 μm of each uniformly dispersed product was applied. And dried in a thermostatic bath at 100 ° C. for 1 hour to obtain a non-foamed layer 10. The obtained non-foamed layer 10 was a 10% barium sulfate-added pressure-sensitive adhesive layer (29 μm) / OPS film (20 μm) / barium sulfate 10 % Added pressure-sensitive adhesive layer (29 μm).
As shown in FIG. 2, the non-foamed layer 10 is sandwiched between the sixth and seventh sheets from the upper side of the sample in which 12 foam slices (thickness 2.0 mm) obtained in Production Example 2 are stacked. It inserted between the steel plates (6 mm thickness) and pressure-bonded (pressure: about 0.1-0.2 MPa), and the sample was obtained.
Table 2 shows the thermal conductivity measurement results of the obtained sample.

(Comparative Example 3)
A sample obtained by stacking 12 foam slices (thickness 2.0 mm) obtained in Production Example 2 was inserted between two iron plates (6 mm thickness) and pressure-bonded (pressure: about 0.1 to 0.2 MPa). Sample.
Tables 2 and 4 show the thermal conductivity measurement results of the obtained samples.

(Example 10)
Two non-foamed layers 1 were produced in the same manner as in Example 1. Two non-foamed layers 1 are sandwiched between foamed layers (8.3 mm) obtained by dividing the foam obtained in Production Example 1 into three in the thickness direction, as shown in FIG. 3, and two iron plates (6 mm And a sample was obtained by pressure bonding (pressure: about 0.1 to 0.2 MPa) using a press machine.
Table 3 shows the thermal conductivity measurement results of the obtained samples.

Example 11
Three non-foamed layers 1 were produced in the same manner as in Example 1. As shown in FIG. 4, three non-foamed layers 1 are sandwiched between foamed layers (6.3 mm) obtained by dividing the foam obtained in Production Example 1 into four in the thickness direction, and two iron plates (6 mm And a sample was obtained by pressure bonding (pressure of about 0.1 to 0.2 MPa) using a press machine.
Table 3 shows the thermal conductivity measurement results of the obtained samples.

Example 12
Four non-foamed layers 1 were produced in the same manner as in Example 1. As shown in FIG. 5, four non-foamed layers 1 are sandwiched between foamed layers (5.0 mm) obtained by dividing the foam obtained in Production Example 1 into five in the thickness direction, and two iron plates (6 mm And a sample was obtained by pressure bonding (pressure: about 0.1 to 0.2 MPa) using a press machine.
Table 3 shows the thermal conductivity measurement results of the obtained samples.

(Comparative Example 4)
The foam obtained in Production Example 1 was divided into three in the thickness direction. Three obtained foamed layers (8.3 mm) were stacked, and the thermal conductivity was measured. Table 3 shows the thermal conductivity measurement results.

(Comparative Example 5)
The foam obtained in Production Example 1 was divided into four in the thickness direction. Four obtained foamed layers (6.3 mm) were stacked, and the thermal conductivity was measured. Table 3 shows the thermal conductivity measurement results.

(Comparative Example 6)
The foam obtained in Production Example 1 was divided into five in the thickness direction. Five foam layers (5.0 mm) obtained were stacked and the thermal conductivity was measured. Table 3 shows the thermal conductivity measurement results.

(Example 13)
Two non-foamed layers 5 were produced in the same manner as in Example 4. As shown in FIG. 6, the non-foamed layer 5 is formed between the fourth and fifth sheets and the eighth sheet from the upper side of the sample in which 12 foam slices (thickness 2.0 mm) obtained in Production Example 2 are stacked. A sample was obtained by inserting between two iron plates (thickness 6 mm) and pressing (pressure: about 0.1-0.2 MPa).
Table 4 shows the thermal conductivity measurement results of the obtained sample.

(Example 14)
Three non-foamed layers 5 were produced in the same manner as in Example 4. As shown in FIG. 7, the non-foamed layer 5 is a sixth sheet between the third and fourth sheets from the upper side of a sample in which 12 foam slices (thickness 2.0 mm) obtained in Production Example 2 are stacked. Between the first and seventh sheets and between the ninth and tenth sheets, inserted between two iron plates (6 mm thick), and pressure-bonded (pressure: about 0.1 to 0.2 MPa). Obtained.
Table 4 shows the thermal conductivity measurement results of the obtained sample.

(Example 15)
Five non-foamed layers 5 were produced in the same manner as in Example 4. As shown in FIG. 8, the non-foamed layer 5 is a fourth sheet between the second and third sheets from the upper side of a sample in which 12 foam slices (thickness 2.0 mm) obtained in Production Example 2 are stacked. And 5th sheet, 6th sheet and 7th sheet, and 8th sheet and 9th sheet. Inserted between 2 steel plates (6mm thickness) and crimped (pressure: about 0) 0.1-0.2 MPa) to obtain a sample.
Table 4 shows the thermal conductivity measurement results of the obtained sample.

(Example 16)
In the same manner as in Example 4, 11 non-foamed layers 5 were produced. As shown in FIG. 9, the non-foamed layer 5 is sandwiched between each foamed layer of 12 samples of the foam slice (thickness 2.0 mm) obtained in Production Example 2, and two iron plates (6 mm thick). ) And pressure bonding (pressure: about 0.1 to 0.2 MPa) to obtain a sample.
Table 4 shows the thermal conductivity measurement results of the obtained sample.

(Example 17)
Two non-foamed layers 7 were produced by the same method as in Example 6. As shown in FIG. 6, the non-foamed layer 7 is formed between the fourth and fifth sheets and the eighth sheet from the upper side of the sample in which 12 foam slices (thickness 2.0 mm) obtained in Production Example 2 are stacked. A sample was obtained by inserting between two iron plates (thickness 6 mm) and pressing (pressure: about 0.1-0.2 MPa).
Table 4 shows the thermal conductivity measurement results of the obtained sample.

(Example 18)
Three non-foamed layers 7 were produced in the same manner as in Example 6. As shown in FIG. 7, the non-foamed layer 7 is a sixth sheet between the third and fourth sheets from the upper side of the sample in which 12 foam slices (thickness 2.0 mm) obtained in Production Example 2 are stacked. Between the first and seventh sheets and between the ninth and tenth sheets, inserted between two iron plates (6 mm thick), and pressure-bonded (pressure: about 0.1 to 0.2 MPa). Obtained.
Table 4 shows the thermal conductivity measurement results of the obtained sample.

Example 19
Five non-foamed layers 7 were produced in the same manner as in Example 6. As shown in FIG. 8, the non-foamed layer 7 is a fourth sheet between the second and third sheets from the upper side of a sample in which 12 foam slices (thickness 2.0 mm) obtained in Production Example 2 are stacked. And 5th sheet, 6th sheet and 7th sheet, and 8th sheet and 9th sheet. Inserted between 2 steel plates (6mm thickness) and crimped (pressure: about 0) 0.1-0.2 MPa) to obtain a sample.
Table 4 shows the thermal conductivity measurement results of the obtained sample.

(Example 20)
In the same manner as in Example 6, 11 non-foamed layers 7 were produced. As shown in FIG. 9, the non-foamed layer 7 is sandwiched between each foamed layer of 12 samples of the foam slice (thickness 2.0 mm) obtained in Production Example 2, and two iron plates (6 mm thick). ) And pressure bonding (pressure: about 0.1 to 0.2 MPa) to obtain a sample.
Table 4 shows the thermal conductivity measurement results of the obtained sample.

  From the results of Tables 1 and 2, it can be seen that by sandwiching a non-foamed layer containing a heat radiation suppression material between two foamed layers, the thermal conductivity is reduced and the heat insulation performance is improved. Further, from the results of Tables 3 and 4, it can be seen that as the repeating unit of the non-foamed layer / foamed layer containing the foamed layer / heat ray radiation suppressing material increases, the thermal conductivity decreases and the heat insulation performance is further improved. .

1 Foam layer 2 Non-foam layer

Claims (15)

  A foamed laminate having at least one structure in which a foamed layer is laminated via a non-foamed layer in the thickness direction, wherein the non-foamed layer includes a heat ray radiation suppressing material. .   2. The foamed laminate according to claim 1, comprising a plurality of structures in which a foamed layer is laminated via a non-foamed layer in the thickness direction.   The foamed laminate according to claim 1 or 2, wherein the heat ray radiation suppressing material is a heat ray reflecting material and / or a heat ray absorbing material.   The foam laminate according to claim 3, wherein the heat ray reflective material contains at least one selected from the group consisting of carbon graphite, an aluminum compound, a magnesium compound, a silver compound, and a titanium compound.   The foamed laminate according to claim 3 or 4, wherein the heat ray reflective material is an aluminum foil.   The foamed laminate according to claim 3 or 4, wherein the heat ray reflective material contains an aluminum paste.   The foamed laminate according to claim 3 or 4, wherein the heat ray reflective material contains carbon graphite.   The foamed laminate according to claim 3 or 4, wherein the heat ray reflective material contains titanium oxide.   The foamed laminate according to claim 3, wherein the heat ray absorbing material contains at least one selected from the group consisting of carbon black, metal sulfate, and antimony compounds.   The foamed laminate according to claim 3 or 9, wherein the heat ray absorbing material contains carbon black.   The foam laminate according to claim 3 or 9, wherein the heat-absorbing material contains antimony oxide.   The foamed laminate according to claim 3 or 9, wherein the heat ray absorbing material contains barium sulfate.   The resin constituting the foam layer is at least one selected from the group consisting of polystyrene resins, polyphenylene ether resins, modified polyphenylene ether resins, phenol resins, and polyurethane resins. The foaming laminated body of any one of -12.   The foamed laminate according to claim 13, wherein the resin constituting the foamed layer is a polystyrene-based resin.   The foamed laminate according to any one of claims 1 to 14, wherein the thermal conductivity at 20 ° C is 0.034 W / m · K or less.

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