JPH10114005A - Foamed laminate and production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a foamed laminate to shorten a manufacturing time to freely control a shape recovery time and production method thereof. SOLUTION: After a breathing path is punched on a desired part of a closed cell resin foam as a raw material, this closed cell resin foam is compressed to be obtained a shape recovering foam 4, and a curable material 6 is coated on a breathing path forming surface of this shape recovering foam to be cured to form a sealed layer having a desired gas permeability closing at least an entrance of the breathing path.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a foam laminate and a method for producing the same.

[0002]

2. Description of the Related Art The inventors of the present invention have disclosed a shape-recovered foam having a delayed shape-recovery property, which comprises a closed-cell resin foam, in which a ventilation path extending from a surface to a desired closed cell is formed. The manufacturing method has already been proposed (see Japanese Patent Application No. 8-7244).

[0003] The shape recovery foam can control the shape recovery time by providing an air passage, and can be used in a wider variety of applications than a conventional shape recovery foam without an air passage. In some cases, there is an advantage that the compression time can be reduced when a closed cell resin foam (hereinafter, referred to as “raw material foam”) as a raw material is compressed to obtain a shape recovery foam.

That is, by increasing the area occupied by the ventilation passages and the number of ventilation passages, the compression time can be shortened and the shape recovery time can be shortened.

However, in the case of this shape-recovery foam, in order to obtain a shape-recovery foam requiring a slow shape recovery time, the size of the passage or the area occupied by the air passage is reduced. It is necessary to do. Therefore, there is a problem that the compression time must be lengthened and the production time is still too long. In addition, there is a problem that it is difficult to finely control the shape recovery time.

[0006]

SUMMARY OF THE INVENTION In view of such circumstances, an object of the present invention is to provide a foam laminate in which the production time can be reduced and the shape recovery time can be freely controlled, and a method for producing the same. And

[0007]

In order to achieve the above object, the foam laminate according to the present invention is made of a closed-cell resin foam, and is provided with an air passage extending from the surface to desired closed cells. Thus, a configuration is adopted in which a seal layer having a desired gas permeability is laminated on the shape recovery foam having delayed shape recovery properties so as to close at least the entrance of the ventilation path.

On the other hand, in the method for producing a foam laminate according to the present invention, a step of forming an air passage in a desired portion of a closed-cell resin foam as a raw material, and a step of compressing the closed-cell resin foam to recover its shape The method includes a step of obtaining a foam, and a step of applying a curable substance to a ventilation path forming surface of the shape-recovery foam and then curing the curable substance to form a seal layer.

In the present invention, the shape-recovery foam refers to a closed-cell resin foam as a raw material, which is compressed by applying a compressive strain (preferably strain within the elastic region of the resin) for a predetermined time or more, and decompresses. Then, it has a property of gradually recovering to the original thickness while being balanced with the inner and outer pressures of the bubbles by the elastic recovery force of the resin. That is, when compressive strain is applied to the closed-cell foam as a raw material, the internal pressure of the closed cells constituting the foam increases, and immediately after the external force is removed, the foam returns to the original shape immediately. If the strain is held for more than time, the gas inside the bubble gradually escapes from the bubble film due to the gas permeability of the resin, the internal pressure and the external pressure balance, and even if the external force is removed, instantaneous shape recovery does not occur, When the compression is released, the thickness gradually recovers while being balanced with the inner and outer pressures of the bubbles by the elastic recovery force of the resin.

When the closed-cell resin foam is compressed, the temperature at the time of compression is determined by the softening point of the resin constituting the closed-cell resin foam (glass transition point for amorphous resin, melting point for crystalline resin). Is the softening point). That is, when compression is performed at a temperature equal to or higher than the softening point, there is a possibility that the shape-recovery foam of the shape-recovery foam after removal of the weight may lose its shape-recovery ability.
Further, the compression method is not particularly limited, for example, a method in which a closed cell foam is passed between two endless belts arranged facing each other at a desired interval and compressed between the endless belts,
There is a method of compressing between two press plates and maintaining the compressed state for a predetermined time.

The closed cell ratio of the shape-recovery foam is determined by the required recovery amount of the shape-recovery foam itself, and can be used if it is about 5% or more. A particularly preferred range is 60% to 60%. 100%. The resin constituting the shape-recovery foam is not particularly limited, but a resin having a compression set (according to JIS K 6767) of 20% or less, particularly 10% or less is preferable because of excellent shape recovery.

Examples of such a resin include the following thermoplastic resins or thermosetting resins.

[Thermoplastic resin] Olefinic resins such as polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-vinyl acetate copolymer, polymethyl acrylate,
Acrylic resins such as polymethyl methacrylate and ethylene-ethyl acrylate copolymer; styrene resins such as butadiene-styrene, acrylonitrile-styrene, styrene, styrene-butadiene-styrene, styrene-isoprene-styrene and styrene-acrylic acid; Vinyl chloride resins such as acrylonitrile-polyvinyl chloride and polyvinyl chloride-ethylene; polyvinyl fluoride resins such as polyvinyl fluoride and polyvinylidene fluoride; amide resins such as 6-nylon, 6.6-nylon and 12-nylon , Saturated ester resins such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate,
Polyphenylene oxide, polyacetal, polyphenylene sulfide, silicone resin, thermoplastic urethane resin, polyetheretherketone, polyetherimide, various elastomers, and crosslinked products thereof.

[Thermosetting resin] Epoxy resin, phenolic resin, melamine resin, urethane resin, imide resin, urea resin, silicone resin, and cured product of unsaturated polyester resin.

Among the above resins, those having particularly excellent shape recovery properties include olefin resins, styrene resins, amide resins, acrylic copolymers, soft polyurethanes, soft vinyl chloride resins, polyacetals, silicone resins, and various elastomers. Are particularly mentioned. Known foaming methods, including those described in the Plastic Foam Handbook, may be used, and any method may be used.

The liquefied gas used as a foaming agent in the present invention is not particularly limited. Examples thereof include aliphatic hydrocarbons such as butane, pentane and hexane; aromatic hydrocarbons such as benzene, toluene and xylene; acetone; Ketone hydrocarbons such as methyl ethyl ketone, alcohol hydrocarbons such as methanol, ethanol and propanol;
1-dichloro-1-fluoroethane, 2.2-dichloro-1-1.1-trifluoroethane, 1.1.1.2-
Examples include halogenated hydrocarbons such as tetrafluoroethane and monochlorodifluoromethane, and water. Further, among these foaming agents, a foaming agent which liquefies at normal temperature is preferable.

When the resin constituting the shape-recovery foam is polyethylene (foaming temperature 100 to 110 ° C.), methanol (boiling point 64.51 ° C.), ethanol (boiling point 78.32 ° C.), acetone ( Boiling point 56.5 ° C),
Pentane (boiling point 36.07 ° C.), hexane (boiling point 68.
74 ° C.), benzene (boiling point 80.1 ° C.), ethyl ether (boiling point 34.48 ° C.), and water (boiling point 100 ° C.) are preferably used.

Further, the shape-recovery foam has a filler,
A reinforcing fiber, a colorant, an ultraviolet absorber, an antioxidant, a flame retardant, and the like may be mixed as necessary.

Examples of the filler include calcium carbonate, talc, clay, magnesium oxide, zinc oxide, carbon black, silicon dioxide, titanium oxide, glass powder, glass beads and the like. As a reinforcing fiber,
For example, glass fiber, single-layer fiber and the like can be mentioned. Examples of the coloring agent include pigments such as titanium oxide.

The antioxidant is not particularly limited as long as it is generally used, and examples thereof include tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane and thiodiamine. Dilauryl propionate, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, and the like.

Examples of the flame retardant include brominated flame retardants such as hexabromophenyl ether and decabromodiphenyl ether; phosphoric acid-containing flame retardants such as ammonium polyphosphate, trimethyl phosphate and triethyl phosphate; melamine derivatives; and inorganic flame retardants. One type or a mixture of two or more types may be mentioned.

The shape of the shape-recovered foam is not particularly limited, and examples thereof include a sheet, a rod, and a tube, wherein the shape before shape recovery and the shape after shape recovery are not similar. Is preferred.

The shape of the ventilation path is not limited to a straight line, but is not particularly limited to a spiral shape or an arc shape. The cross-sectional shape of the air passage is not particularly limited, and examples thereof include a circle, a triangle, a square, a star, a line, and a wavy line.

If the diameter (cross-sectional area) of the ventilation path is too large, the bubble structure may be destroyed and the original shape may not be recovered, so that the diameter is about 7 mm ² (when the cross section is circular, the diameter is about 3 mm).
The following is preferable, and the maximum (width) is more preferably equal to or smaller than the average cell diameter of the closed cells, and the interval between the centers of the ventilation paths is not particularly limited. When the cross section of the air passage is larger than the bubble diameter, the distance between the outer edges of adjacent air passages is preferably equal to or larger than the bubble diameter. Most preferably, the pores are smaller in diameter than the average cell diameter of the cells and are perforated in the shape-recovery foam at a rate of 10 cells / cm ² or more.

The depth of the ventilation path is determined by the recovery time, and is not particularly limited. It is preferable that the depth of the ventilation path reaches three or more closed cells from the surface. Further, the ventilation path may be provided perpendicular to the surface of the foam,
It may be provided at a predetermined angle with respect to the surface. Moreover, you may make it provide spirally toward the inside of a shape recovery foam.

The method of perforating the ventilation path is not particularly limited, but in the case of providing a hole-shaped ventilation path, a needle (Kenyama),
A method using a drill, an electron beam, a laser beam, or the like can be used. When a groove-shaped ventilation path is provided, a cutter (knife) is used.
And the like. It should be noted that the step of forming the ventilation path and the step of contracting the closed-cell resin foam as a raw material may be performed in any order, or may be performed in parallel at the same time. .

However, when a gas having high gas permeability is used as the foaming agent, when the compressed state is maintained, or when the ventilation path is not allowed to penetrate to the back side (especially in the case of a thin material), the ventilation path is formed. It is preferable to perform the step of performing the first step. In other words, when a gas having high gas permeability is used as the foaming agent, or when the compressed state is maintained, the gas must be removed from the bubbles during shrinkage. Can reduce the time required for shrinkage.

In the case where the ventilation path is not penetrated to the back side, if the closed cell resin foam as a raw material is first contracted to form a shape recovery foam and then the ventilation path is formed, the thickness of the shape recovery foam is reduced. Due to the thinness, a needle or the like may penetrate. The curable substance is not particularly limited as long as it can be cured to form a seal layer having a desired gas permeability. For example, a photo-curable or electron beam-curable resin such as an acrylic resin and this resin A composition comprising as a main component, a resin which is cured by moisture such as a silicone resin or a moisture-curable polyurethane resin, and a composition comprising this resin as a main component, a resin which is cured by oxygen in the air such as a polysulfide resin, and Examples of the composition include a composition containing the resin as a main component, and a composition that is cured by cooling such as a hot melt adhesive in a molten state.

When a composition that cures by cooling is used, the melting point of the composition is equal to or higher than the operating temperature of the foamed laminate, that is, the composition is cured at the operating temperature. It is preferable that the melting point be equal to or lower than the melting point of the shape-recovery foam so that the shape recovery property is not impaired by applying too much heat to the body.

Further, a fire-resistant layer, a waterproof layer, a soft material layer, an adhesive layer, and the like may be laminated on the foam laminate of the present invention, if necessary. The refractory layer is not particularly limited. For example, at least one selected from the group consisting of a thermoplastic resin or a rubber composition having tackiness, a phosphorus compound, and neutralized heat-expandable graphite. What was formed with the refractory resin composition containing the refractory material is preferable. Further, an inorganic filler may be added in addition to these refractory materials.

[0031] The thermoplastic resin constituting the refractory resin composition is not particularly limited, but may be a polyolefin resin such as a polyethylene resin or a polypropylene resin.
Poly (1-) butene resin, polypentene resin, polystyrene resin, acrylonitrile-butadiene-styrene resin, polycarbonate resin, polyphenylene ether resin, acrylic resin, polyamide resin,
Examples thereof include polyvinyl chloride resins and the like. Among them, polyolefin resins are preferable, and polyethylene resins are more preferable.

As the polyethylene resin, for example,
Ethylene homopolymer, ethylene-based copolymer, a mixture thereof, ethylene-vinyl acetate copolymer,
Examples include an ethylene-acrylate copolymer. Examples of the copolymer containing ethylene as a main component include ethylene-α olefins containing 1-ethylene as a main component (1-hexene, 4-methyl-1pentene, 1-octene, 1-octene).
Butene, 1-pentene) copolymer.

Examples of the rubber composition include natural rubber, isoprene rubber (IR), and butadiene rubber (B
R), 1.2-polybutadiene rubber (1.2-BR),
Styrene-butadiene rubber (SBR), chloroprene rubber (CR), nitrile rubber (NBR), butyl rubber (I
IR), ethylene-propylene rubber (EPM, EPD)
M), chlorosulfonated polyethylene (CSM), acrylic rubber (ACM, ANM), epichlorohydrin rubber (CO, ECO), polyvulcanized rubber (T), silicone rubber (Q), fluoro rubber (FKM, FZ), urethane rubber (U) and the like, and vulcanization may be performed after the addition of the refractory material. However, since a non-vulcanized rubber can have an adhesive property, a refractory layer is used as an adhesive layer. It is also possible and preferable.

The phosphorus compound is not particularly restricted but includes, for example, various phosphoric esters such as red phosphorus, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate; Metal phosphates such as sodium phosphate, potassium phosphate and magnesium phosphate; ammonium polyphosphates such as ammonium polyphosphate and melamine-modified ammonium polyphosphate;
Methylphosphonic acid, dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, 2-methylpropylphosphonic acid, 2.3-dimethyl-butylphosphonic acid, octylphosphonic acid, phenylphosphonic acid, dioctylphenyl Compounds represented by the following general formula (1) such as phosphonate, dimethylphosphinic acid, methylethylphosphinic acid, methylpropylphosphinic acid, diethylphosphinic acid, diphenylphosphinic acid, and bis (4-methoxyphenyl) phosphinic acid are exemplified. .

[0035]

Embedded image

In the formula, R ₁ and R ₃ are hydrogen, carbon number 1 to 1
6 linear or branched alkyl groups, or 6 carbon atoms
Represents up to 16 aryl groups. R ₂ is a hydroxyl group, a linear or branched alkyl group having 1 to 16 carbon atoms, a linear or branched alkoxyl group having 1 to 16 carbon atoms,
Represents an aryl group having 6 to 16 carbon atoms or an aryloxy group having 6 to 16 carbon atoms.

The above phosphorus compounds may be used alone or in combination of two or more. The neutralized heat-expandable graphite is, for example, a powder of natural scale graphite, quiche graphite or the like, an inorganic acid such as concentrated sulfuric acid, nitric acid or selenic acid, and concentrated nitric acid, perchloric acid, perchlorate or permanganate. Since the graphite intercalation compound was formed by treating with a strong oxidizing agent such as salt, dichromate, hydrogen peroxide, etc., the crystalline compound maintaining the carbon layer structure was further converted to ammonia, aliphatic lower amine. , Alkali metal compounds, alkaline earth metal compounds and the like.

The aliphatic lower amine is not particularly restricted but includes, for example, monomethylamine, dimethylamine, trimethylamine, ethylamine, propylamine, butylamine and the like. Examples of the alkali metal compound and the alkaline earth metal compound include hydroxides, oxides, carbonates, sulfates, and organic acid salts such as potassium, sodium, calcium, barium, and magnesium.

The particle size of the neutralized heat-expandable graphite is 2
Those having 0 to 200 mesh are preferable. That is, if the particle size is smaller than 200 mesh, the degree of swelling of the graphite is small, and the refractory heat insulating effect cannot be obtained. If the particle size is larger than 20 mesh, there is an effect in that the degree of swelling is large, but it is kneaded with the resin. In such a case, the dispersibility may be poor and physical properties may be reduced.

The inorganic filler is not particularly limited. For example, silica, diatomaceous earth, alumina, zinc oxide,
Titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, calcium hydroxide, magnesium hydroxide, aluminum hydroxide,
Basic magnesium oxide, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawn knight, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, calcium silicate, talc, clay, mica, montmorillonite, bentonite, activated clay, Sepiolite, imogolite, sericite, glass fiber, glass beads, silica-based balloon, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balloon, charcoal powder, various metal powders, potassium titanate, Magnesium sulfate "MOS", lead zirconate titanate, aluminum borate, molybdenum sulfide,
Examples include silicon carbide, stainless steel fiber, zinc borate, various magnetic powders, slag fiber, fly ash, dehydrated sludge, etc. Among them, calcium hydroxide, magnesium hydroxide, and aluminum hydroxide which dehydrate when heated and have an endothermic effect It is preferable to use a hydrous inorganic substance such as

The mixing ratio between the thermoplastic resin or the rubber composition having tackiness and the refractory material is not particularly limited.
The total amount of the phosphorus compound and the neutralized thermally expandable graphite is 20 to 200 parts by weight, the inorganic filler is 50 to 500 parts by weight, and the phosphorus compound and the neutralized thermal expansion are 0 parts by weight. It is preferable that the ratio of the exfoliated graphite be 9: 1 to 1: 9.

Further, a blowing agent may be added to the thermoplastic resin composition constituting the refractory layer, if necessary. Examples of the foaming agent include, but are not particularly limited to, melamine, urea, dicyandiamide, ammonium phosphate, pentaerythritol, and the like.

The method of forming the refractory layer is not particularly limited. For example, in the case of a sheet, an extrusion molding method, a calender molding method or a casting method may be used. Tubing is performed afterwards, and in the case of a mold, an injection molding method, a press molding method and the like are exemplified. The method of laminating the refractory layer is a method in which the molded article obtained by the above molding method is joined via an adhesive, or the molded article is heated and joined by fusing with the resin of the shape recovery foam or the sealing layer. Is mentioned.

As the adhesive to be used for bonding, an adhesive suitable for both the resin of the shape-recovery foam and the resin of the molded article can be appropriately selected. The layered portion of the refractory layer may be on the entire surface of the foamed laminate, only on the seal layer side, or only on the side where the seal layer is not provided.

For example, when the foamed laminate is in the form of a sheet, the surface may or may not contribute to the shape recovery of the shape-recovery foam. The surface contributing to shape recovery refers to the side peripheral surface of the shape recovery foam in the case of a shape recovery foam that recovers shape only in the thickness direction.

The moisture-proof layer is provided when it is necessary to further enhance the moisture-proof property and the water resistance, and is formed of a material having high moisture-permeation resistance. The material having a high moisture-permeation resistance for forming the moisture-proof layer is not particularly limited, and examples thereof include metal materials such as aluminum, stainless steel, lead, iron, copper, zinc, and tin, and resin materials such as polyethylene and polypropylene. Of these, aluminum is preferred in view of economy.

The laminated surface of the moisture-proof layer is not particularly limited, and may be either a surface contributing to shape recovery of the shape-recovery foam or a surface not contributing to shape recovery. The method of laminating the moisture-proof layer on the foam laminate is not particularly limited, but a method of bonding with an adhesive is generally used. The bonding time may be before or after the shape recovery foam is manufactured from the closed cell resin foam.

The adhesive used for bonding is not particularly limited, but, for example, a chloroprene-based or acrylic-based adhesive is preferably used. The thickness of the moisture-proof layer is appropriately determined depending on the moisture-permeation resistance of the material constituting the moisture-proof layer, required airtightness, performance such as heat insulation, but the following depends on the surface on which the moisture-proof layer is provided and the material of the moisture-proof layer. It is preferable to make the thickness as shown in FIG.

[When a moisture-proof layer is provided on a surface that does not recover its shape and the moisture-proof layer is formed of a metal material]
It is preferably about 1 to 300 µm, more preferably about 1 to 100 µm. That is, if the thickness is too small, pinholes may be generated in the moisture-proof layer, and sufficient moisture-proof performance may not be obtained. If the thickness is too large, the weight may be heavy, the followability is poor, and the cost may increase.

[When a moisture-proof layer is provided on the surface whose shape is to be recovered and the moisture-proof layer is formed of a metal material] The thickness of the moisture-proof layer is 0.01
It is preferably about 100 μm, more preferably about 1 μm to 50 μm. In other words, if the thickness is too small, pinholes may be generated in the moisture-proof layer and sufficient moisture-proof performance may not be obtained.If the thickness is too large, the moisture-proof layer is laminated on the closed-cell resin foam, and then the closed-cell foam is formed. When an attempt is made to produce a shape-recovery foam by compressing the body, the moisture-proof layer tends to peel off during compression in the thickness direction, and there is a possibility that the moisture-proof layer cannot be compressed in the desired direction, for example, by being deformed obliquely.

[When a moisture-proof layer is provided on a surface that does not recover its shape, and the moisture-proof layer is formed of a resin material]
It is preferably about 000 μm, more preferably about 10 to 300 μm. That is, if the thickness is too small, pinholes may be generated in the moisture-proof layer, and sufficient moisture-proof performance may not be obtained. If the thickness is too large, handling becomes poor because of heavy weight. Also, the cost increases.

[When a moisture-proof layer is provided on the surface whose shape is to be recovered and the moisture-proof layer is formed of a resin material] The thickness of the moisture-proof layer is 1 to 50.
It is preferably about 0 μm, and more preferably about 10 to 100 μm. In other words, if the thickness is too small, pinholes may be generated in the moisture-proof layer and sufficient moisture-proof performance may not be obtained.If the thickness is too large, the moisture-proof layer is laminated on the closed-cell resin foam, and then the closed-cell foam is formed. When an attempt is made to produce a shape-recovery foam by compressing the body, the moisture-proof layer tends to peel off during compression in the thickness direction, and there is a possibility that the moisture-proof layer cannot be compressed in the desired direction, for example, by being deformed obliquely.

When the moisture-proof layer is made of a material having poor corrosion resistance, it is preferable to cover the surface of the moisture-proof layer with a corrosion-resistant material. Examples of the corrosion resistant material include synthetic resins such as polyethylene and polypropylene.

The adhesive layer is used when the foam laminate is fixed to the mounting portion, and can be appropriately selected according to the use of the foam laminate. Examples of the adhesive layer include acrylic, ethylene-vinyl acetate, urethane, and rubber. System, styrene-butadiene system,
Pressure-sensitive adhesives such as styrene-isoprene-based adhesives, and hot-melt adhesives, and if the storage is good,
A reaction type adhesive may be used.

The soft material layer is preferably provided when the mounting surface of the foam laminate is uneven, and the material for forming the soft material layer is not particularly limited. Elastomers, polyester-based elastomers, polyamide-based elastomers, natural rubber, butyl rubber, isoprene rubber and the like can be mentioned.

An appropriate range of the thickness of the soft material layer is determined by the sealing property and the gas permeability, and the thickness of the soft material layer is, for example, one of the difference of the surface unevenness so as to follow the surface unevenness of the sealing portion.
It is preferable to design the thickness so as to be from / 2 to 5 times, and the shape is recovered by gas permeation. Therefore, the optimum thickness is set depending on the time required for the shape recovery. In addition, since the gas permeability differs depending on the type of the soft material,
For the actual optimum thickness, it is preferable to test and prepare a foamed laminate, but it is preferable that the thickness be approximately 30 μm to 3 mm.
Is preferable. That is, when the thickness is less than 30 μm, the followability to the uneven surface is poor and the sealing property is poor. When the thickness exceeds 3 mm, the gas permeability is poor and a considerable time may be required for recovery.

The method of laminating the soft material layer is not particularly limited, and is a method which is carried out immediately after the production of the closed cell resin foam as a raw material, and a method which is performed after the closed cell resin foam is shrunk to obtain a shape recovery foam. And a method of performing the same. The former method is used when laminating a closed cell resin foam and a polymer material sheet to be a soft material layer by heat fusion, and the latter method is often used when laminating by bonding via an adhesive. Although it is used, it is preferable to laminate by heat fusion.

The thermal fusion is obtained, for example, by superimposing a foam and a polymer material sheet to be a polymer material thin film and applying pressure while heating at least one of the interfaces by high-frequency heating or the like. be able to. In addition, as for the heat fusion temperature, when the fusion is performed in a state where the foam is contracted, it is preferable that only the surface of the foam is equal to or higher than the softening point. It may be higher than the melting point.

However, it is preferable that the soft material layer is provided along the surface of the shape-recovered foam which does not recover its shape.

[0060]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below.
This will be described in detail with reference to the drawings. FIG. 1 shows an embodiment of a method for producing a foam laminate according to the present invention.

In this manufacturing method, first, a plate 2 on which a large number of needles 21 are planted is pressed against the raw material foam 1 from above the raw material foam 1 which advances toward the winding device 9, and As shown in FIG. 2A, a ventilation path 3 is formed on the surface of the raw material foam 1 at a desired pitch to reach internal closed cells. Next, the raw material foam 1 ′ in which the ventilation passage 3 was formed was pressed by the belt press device 11 and contracted to a desired thickness to obtain a shape-recovered foam 4 as shown in FIG. Thereafter, a photo-curable resin 6 as a curable substance, which is applied in a layer form to the release paper 5 by a roll coater method, is transferred and applied to the upper surface of the shape-recovery foam 4 in a layer state, and the photo-curable resin 6 is used to form a ventilation path. 3 opening.

Then, the shape-recovery foam 4 ′ coated with the photo-curable resin 6 is passed through a light irradiation device 7 to cure the photo-curable resin 6, as shown in FIG. Foam laminate 8 in which seal layer 6 ′ is laminated on shape recovery foam 4
Is to be obtained. Since the opening of the ventilation path 3 of the obtained foamed laminate 8 is closed by the sealing layer 6 ′, the external atmosphere can enter the ventilation path 3 only gradually through the sealing layer 6 ′. Therefore, even if many air passages 3 are provided, the thickness of the seal layer 6 ′ and the seal layer 6 ′
The shape recovery time can be freely set by selecting the material of the curable substance constituting the above.

In addition, since a large number of ventilation paths 3 may be provided at the manufacturing stage, the time required for contraction can be reduced.

[0064]

Embodiments of the present invention will be described below in more detail.

Example 1 100 parts by weight of low-density polyethylene (trade name: G201, manufactured by Sumitomo Chemical Co., Ltd.) and azodicarbonamide as a blowing agent (decomposition peak temperature: 200 ° C.)
20 parts by weight and 2 parts by weight of zinc stearate are φ65 mm
Was set in a single-screw extruder (set at 135 ° C.) and kneaded, and the kneaded product was extruded onto a sheet with a thickness of 2.4 mm. And 750 on both sides of this extruded sheet
Irradiation of an electron beam of kv × 5 Mrad is performed to crosslink, and the crosslinked product is heated and foamed at 240 ° C. to have a thickness of 8 mm, an expansion ratio of 41 times,
A raw material foam having an average cell diameter of 720 μm and a closed cell ratio of 80% was obtained.

This raw material foam was 100 mm long × 100 mm wide.
After cutting to a size of 500 mm, holes serving as air passages penetrating the front and back surfaces of the cut pieces were formed at a hole opening interval of 2.5 mm (hole opening density: 16 holes / cm ² ) using a needle having a diameter of 500 μm. .
Next, this perforated raw material foam is compressed between press plates provided with 1 mm spacers to obtain a shape-recovered foam in a contracted state having a thickness of 1 mm, a length of 100 mm, a width of 100 mm and a shrinkage of 12.5%. Was. The time required for compression was 45 minutes.

A photo-curable resin composition having the following composition was applied as a curable material at 30 μm to the front and back surfaces of the thus obtained shape-recovery foam, and irradiated with a metal halide lamp of 80 W for 30 seconds from a distance of 20 cm. The photocurable resin composition was cured to obtain a foamed laminate.

[Photocurable Resin Composition] 100 parts by weight of methyl methacrylate 30 parts by weight of dipentaerythritol hexamethacrylate 30 parts by weight of pentaerythritol trimethacrylate

Example 2 A foamed laminate was obtained in the same manner as in Example 1 except that the thickness of the photocurable resin composition was changed to 50 μm. (Example 3) The coating thickness of the photocurable resin composition was 100 μm.
A foamed laminate was obtained in the same manner as in Example 1, except that

(Example 4) Modified silicone (Sekisui Chemical Co., Ltd., trade name: Sekisui modified silicone) as a curable substance was used instead of the photo-curable resin composition to obtain a 100 μm thick front and back surface of the shape-recovery foam. In a state in which release paper is laminated on the curable substance layer, the resin is sandwiched between press plates and left for 3 days while suppressing the shape recovery of the foam, and the denatured silicone is cured to form a seal layer. Other than
A foam laminate was obtained in the same manner as in Example 1.

(Example 5) The modified silicone was applied with a thickness of 2
A foam laminate was obtained in the same manner as in Example 4 except that the thickness was set to 00 μm. (Example 6) A foamed laminate was obtained in the same manner as in Example 4 except that the modified silicone was applied in a thickness of 500 µm.

Example 7 A modified polysulfide (manufactured by Sekisui Chemical Co., Ltd., trade name: Sekisui modified thiosealer) was used as a curable substance instead of the modified silicone.
A foam laminate was obtained in the same manner as in Example 4. (Example 8) Modified polysulfide was applied to a thickness of 200 μm.
Except having changed to m, it carried out similarly to Example 7, and obtained the foaming laminated body.

Example 9 A foam laminate was obtained in the same manner as in Example 7 except that the thickness of the modified polysulfide silicone was changed to 500 μm. (Example 10) As a curable substance, α-cyanoacrylate (manufactured by Toa Gosei Chemical Industry Co., Ltd., trade name: Aron Alpha G)
EL-10) was replaced with 30 μl instead of the photocurable resin composition.
m was applied to the front and back surfaces of the shape-recovery foam, left for 15 minutes, and the curable substance was cured to form a seal layer, thereby obtaining a foam laminate in the same manner as in Example 1. .

Example 11 A foam laminate was obtained in the same manner as in Example 10 except that the coating thickness of α-cyanoacrylate was changed to 50 μm. Example 12 The coating thickness of α-cyanoacrylate was 10
A foamed laminate was obtained in the same manner as in Example 10 except that the thickness was changed to 0 μm.

(Example 13) A hot-melt adhesive in a molten state (Esdine 8620S, manufactured by Sekisui Chemical Co., Ltd.) having a thickness of 100 μm was applied to the surface of a release paper as a curable substance to form a hot-melt adhesive layer. Is formed on release paper, the hot-melt adhesive layer is pressed against the front and back surfaces of the shape-recovery foam obtained in Example 1, the hot-melt adhesive is transferred, and the hot-melt adhesive is cooled and cured. Thus, a sealing layer was formed to obtain a foamed laminate. The time required for cooling and curing was 30 seconds.

Example 14 A foam laminate was obtained in the same manner as in Example 13, except that the thickness of the hot melt adhesive applied was 200 μm. (Example 15) The coating thickness of the hot melt adhesive was 500 μm.
Except having set it as m, it carried out similarly to Example 13, and obtained the foaming laminated body.

Comparative Example 1 A shape-recovery foam similar to that of Example 1 was obtained. (Comparative Example 2) Using a needle having a diameter of 500 µm, a hole serving as an air passage penetrating the front and back surfaces of the cut piece was formed in the raw material foam cut into a size of 100 mm in length × 100 mm in width, and a hole interval of 5 mm.
Example 1 except that the holes were drilled at a hole density of 4 holes / cm ^2.
In the same manner as in the above, a shape recovery foam was obtained. The time required for compression was 2 hours.

Comparative Example 3 Using a needle having a diameter of 500 μm, a hole serving as a ventilation passage penetrating the front and back surfaces of the cut piece was formed in the raw material foam cut into a size of 100 mm long × 100 mm wide by 10 mm. A shape-recovery foam was obtained in the same manner as in Example 1 except that the hole was drilled at a hole-piercing density of 1 hole / cm ² . The time required for compression was 12 hours.

The shape recovery times of the foamed laminates obtained in Examples 1 to 15 and the shape-recovered foams of Comparative Examples 1 to 3 were measured, and the results were compared with those of Examples and Comparative Examples. The results are shown in Table 1 together with the compression time during production.

[0080]

[Table 1]

Table 1 clearly shows that the foam laminate of the present invention can reduce the time required for producing the shape-recovery foam and can control the shape-recovery time to a predetermined time.

[0082]

The foam laminate and the method for producing the same according to the present invention are configured as described above, so that the production time can be shortened and the shape recovery time can be set freely. Accordingly, manufacturing workability is improved, and the range of use as a sealing material and the like is expanded.

In particular, if the ventilation path is provided as described in claim 2, the manufacturing time of the shape-recovery foam can be shortened without impairing the shape-recovery property of the shape-recovery foam.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing an embodiment of a method for producing a foam laminate according to the present invention, and schematically explaining a production apparatus thereof.

FIG. 2 is an explanatory diagram schematically illustrating a cross-sectional shape of a shape-recovery foam in each manufacturing process of the manufacturing method in FIG. 1; FIG. 2A illustrates a raw material foam provided with an air passage; FIG. 2B shows a cross section of the shape recovery foam, and FIG. 2C shows a cross section of the foam laminate.

[Explanation of symbols]

 Reference Signs List 1 raw material foam (closed-cell resin foam) 1 'raw material foam (after perforation) 4 shape-recovery foam 4' shape-recovery foam (transferred photocurable resin) 6 photocurable Resin (curable substance) 6 'Seal layer 8 Foamed laminate

Claims (3)

[Claims] 1. A gas-permeable foam made of a closed-cell resin foam, having a ventilation path extending from the surface to a desired closed cell, and having a delayed shape-recovering property, has a desired gas permeability. A foam laminate in which a sealing layer is laminated so as to close at least an entrance of the ventilation path. 2. The foam laminate according to claim 1, wherein the air passage has a diameter smaller than the average cell diameter of the closed cells and is formed in the shape recovery foam at a rate of 10 cells / cm ² or more. 3. A step of forming an air passage in a desired portion of a closed-cell resin foam as a raw material, a step of compressing the closed-cell resin foam to obtain a shape-recovery foam, The method for producing a foamed laminate according to claim 1 or 2, further comprising: applying a curable substance to the air passage forming surface, and then curing the curable substance to form a seal layer.