JP2005231118A - Phenol resin foam laminated sheet and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a phenol resin foam laminated sheet wherein a metal foil layer being the outermost layer of a surface material is hard to peel. <P>SOLUTION: In the phenol resin foam laminated sheet, the surface material contains a nonwoven fabric layer, a first adhesive layer, a second adhesive layer different from the first adhesive layer and a metal foil layer in this order and is provided at least on one side of a phenol resin foam so that the nonwoven fabric layer of the surface material comes into contact with the surface of the phenol resin foam. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a phenolic resin foam laminate used mainly for civil engineering and construction, and a method for producing the same.

As a phenol resin foam laminate of this type, Patent Document 1 discloses a phenol resin foam laminate obtained by laminating an aluminum foil with an adhesive via a nonwoven fabric on one or both sides of a phenol resin foam. It is disclosed.
Since the surface of this conventional phenol resin foam laminate is an aluminum foil layer, it is excellent in heat resistance, flame retardancy, heat ray reflectivity and design (high quality).
JP 2003-239417 A

  As a method for producing a phenolic resin foam laminate, (a) a method in which a face material is integrated with a phenol resin foam prepared in advance by an adhesive, and (b) an acidic curing agent, a foaming agent, etc. are added to the phenol resin composition. There is a method of integrating the phenol resin foam and the face material while supplying the face material to the obtained phenol resin foam composition and curing the phenol resin foam composition. When the phenol resin foam laminate is manufactured by the method (b) above, when the phenol resin foam composition is cured and the phenol resin foam is integrated with the face material, the hot water vapor generated by the curing reaction is generated. It stays in the lower part of the aluminum foil layer of the face material, and the aluminum foil layer of the face material peels off, so that a desired phenolic resin foam laminate cannot be obtained. There was a point.

  Therefore, the present invention eliminates the drawbacks of the prior art described above, and there is no peeling between the phenol resin foam and the face material, and a novel phenol resin foam excellent in heat resistance, flame retardancy, heat ray reflectivity and design properties. An object of the present invention is to provide a body laminate and a method for industrially producing the phenol resin foam laminate.

  In order to achieve the above object, the present inventors have conducted research, and as a face material, between the nonwoven fabric layer and the metal foil layer (for example, an aluminum foil layer), the first adhesive layer and the second adhesive agent are used. Using a face material having a layer, supplying the face material so as to come into contact with the phenol resin foam composition from which the nonwoven fabric layer of the face material is discharged, and curing the phenol resin foam composition, the phenol resin foam When the surface material and the face material are integrated, the hot water vapor generated by the curing reaction of the phenol resin foam composition does not stay in the lower part of the metal foil layer of the face material. It has been found that a phenolic resin foam laminate having excellent heat resistance, flame retardancy, heat ray reflectivity, and design can be obtained.

The present invention has been completed based on this finding,
(1) A face material comprising at least one surface of a phenolic resin foam, the nonwoven fabric layer, the first adhesive layer, the second adhesive layer different from the first adhesive layer, and the metal foil layer in this order. A phenolic resin foam laminate, wherein the nonwoven fabric layer of the face material is provided so as to contact the surface of the phenolic resin foam,
(2) The phenol resin foam laminate according to (1) above, wherein the nonwoven fabric layer includes at least one selected from inorganic fiber paper, inorganic fiber nonwoven fabric, and organic fiber nonwoven fabric,
(3) The phenol resin foam laminate according to (1) or (2) above, wherein the metal foil layer is made of an aluminum foil.
(4) The first adhesive layer contains at least one selected from polyolefin resin, vinyl acetate resin, acrylic resin, epoxy resin, urethane resin, silicone resin and synthetic or natural rubber, and the second adhesive layer is When the first adhesive layer contains an olefin resin, the olefin resin contained in the first adhesive layer and the olefin resin contained in the second adhesive layer are different types. The phenolic resin foam laminate according to any one of (1) to (3) above,
(5) Any one of said (1)-(4) whose thickness of said 1st adhesive bond layer is 5-100 micrometers, and whose thickness of said 2nd adhesive bond layer is 5-100 micrometers. Any one of said (1)-(5) which has a resin-coated layer on the phenol resin foam laminated board as described in (6) and a metal foil layer.
The phenolic resin foam laminate according to the item,
(7) The face material including at least the nonwoven fabric layer, the first adhesive layer, the second adhesive layer, and the metal foil layer in this order is opposed to the phenol resin foam composition from which the nonwoven fabric layer of the face material is discharged. It supplies so that it may contact, a phenol resin foam composition is hardened, and a phenol resin foam and a face material are integrated, The said (1)-(5) any one of the above-mentioned characterized by the above-mentioned. A method for producing a phenolic resin foam laminate,
Is to provide.

The reason why the phenol resin foam laminate of the present invention is firmly bonded to the phenolic resin foam and the face material without causing the problem of peeling of the metal foil of the face material, which has been a problem in the past. According to the estimation of the present inventors, it is as follows.
The phenolic resin foam laminate of the present invention comprises a first adhesive layer and a second adhesive layer different from the first adhesive layer between the nonwoven fabric layer and the metal foil layer in the face material. There are two adhesive layers, and the second adhesive layer in contact with the metal foil layer in the face material has the effect of escaping the thermal water vapor derived from the curing reaction of the phenol resin foam composition from the end to the outside. Therefore, water vapor does not stay in the lower part of the metal foil layer of the face material. Moreover, the 1st adhesive bond layer which contact | connects the nonwoven fabric layer in a face material acts as an original adhesive agent, and can couple | bond a phenol resin foam and a face material firmly.
For this reason, the phenol resin foam laminate of the present invention has the technical effect that the metal foil layer of the face material does not peel and the phenol resin foam and the face material are firmly bonded.
Since the thermal water vapor generated when the phenolic resin foam composition is cured can be effectively dissipated to the outside, the phenolic resin foam and the face material are integrated by supplying and curing the phenol resin foam composition to the face material. In this case, the present invention can be particularly preferably used.

First, the phenol resin foam laminate of the present invention will be described.
The phenol resin foam laminate of the present invention uses a phenol resin foam as a base material.
As a phenol resin foam as a base material, as described in JP-A-6-93128, a phenol resin foam composition obtained by adding, for example, an acidic curing agent, a foam stabilizer, a foaming agent, or the like to a phenol resin is cured. Can be obtained.

  Phenol resins used include phenol, cresol, xylenol, paraalkylphenol, paraphenylphenol, resorcin, etc. A resol type phenol resin obtained by reacting in the presence of an alkaline catalyst such as calcium hydroxide, hexamethylenetetramine, trimethylamine or triethylamine is preferred, but is not limited thereto.

Examples of the acidic curing agent used include inorganic acids such as sulfuric acid and phosphoric acid, and organic acids such as benzenesulfonic acid, paratoluenesulfonic acid, naphtholsulfonic acid, and phenolsulfonic acid, but are not limited thereto. .
Examples of the foam stabilizer used include, but are not limited to, silicone-based nonionic surfactants and modified castor oil.

  Examples of the blowing agent used include low boiling point aliphatic hydrocarbons such as pentane, hexane, and heptane, ethers such as isopropyl ether, chlorinated aliphatic hydrocarbons such as methylene chloride, trichloromonofluoromethane, and trichlorotrifluoroethane. Examples include, but are not limited to, fluorine compounds or a mixture of these compounds.

The above phenol resin foam composition contains metal oxides such as aluminum oxide and zinc oxide, metal powders such as zinc, magnesium and aluminum, and powdery basic substances such as calcium carbonate, magnesium carbonate, barium carbonate and zinc carbonate. You may let them.
The phenol resin foam can have any shape, but in the case of a rectangular parallelepiped, the thickness between its two main surfaces is preferably 0.5 to 20 cm, particularly 2 to 10 cm.

  The phenolic resin foam laminate of the present invention is formed by providing a face material on at least one surface of the phenol resin foam, and the face material comprises a nonwoven fabric layer, a first adhesive layer, and a second adhesive material. It includes at least an adhesive layer and a metal foil layer.

  As the nonwoven fabric constituting the nonwoven fabric layer, any nonwoven fabric may be used as long as it is fibrous, has voids, and is hydrophobic, but at least selected from inorganic fiber paper, inorganic fiber nonwoven fabric, and organic fiber nonwoven fabric. Those containing one kind are preferably used. Examples of inorganic fiber paper and inorganic fiber nonwoven fabric include those composed of glass fiber, carbon fiber, silicon carbide fiber, etc., and organic fiber nonwoven fabric includes polyester fiber, vinylon fiber, polyolefin fiber, polyamide fiber, etc. Kraft paper.

  As described above, the non-woven fabric layer is made of a non-woven fabric having a fibrous shape, voids, and hydrophobicity. Therefore, in the production of the phenol resin foam laminate, the thermal water vapor generated during the foam curing of the phenol resin composition is absorbed. However, a part of it escapes to the outside from the end of the nonwoven fabric layer, but the remaining hot water vapor is transferred to the first adhesive layer and the second adhesive layer thereon.

The nonwoven fabric layer has a thickness of preferably 0.1 to 1 mm, particularly preferably 0.2 to 0.6 mm, and a basis weight of 10 to 200 g / m ² , particularly preferably 30 to 150 g / m ² .
The metal foil layer that constitutes the face material together with the non-woven fabric layer is for imparting heat resistance, flame retardancy, heat ray reflectivity, and design to the phenolic resin foam laminate. Although not limited to aluminum foil and stainless steel foil, aluminum foil is particularly preferable. The type of aluminum foil is not particularly limited, but an aluminum foil specified in JIS H 4160 is suitable. The thickness of the metal foil layer is usually 7 to 100 μm, preferably 10 to 50 μm.

  In the phenolic resin foam laminate of the present invention, the most characteristic configuration is that the adhesive layer present between the nonwoven fabric layer and the metal foil layer of the face material is the first adhesive layer and the second adhesive agent. This is a two-layer structure composed of layers.

  The first adhesive layer is provided in contact with the non-woven fabric layer in the face material, and in order to exert the function as an original adhesive that firmly bonds the phenol resin foam and the face material, The adhesive of the first adhesive layer is at least one selected from resins known as adhesives, such as polyolefin resins, vinyl acetate resins, acrylic resins, epoxy resins, urethane resins, silicone resins, and synthetic or natural rubber. Things can be used. Examples of the polyolefin resin include a polyethylene resin such as a low density polyethylene resin (LDPE).

  The second adhesive layer is provided in contact with the metal foil layer in the face material. The adhesive of the second adhesive layer is generated by a curing reaction of the phenol resin foam composition, and the nonwoven fabric layer. In order to escape the thermal water vapor that has risen through the first adhesive layer from the end portion to the outside, a resin having a relatively low affinity with water vapor or water is preferably used. Modified polyolefin resins such as polyolefin resins such as polyethylene resins, ethylene-vinyl acetate resins, ethylene-vinyl acetate resin partial or complete hydrolysates, ethylene-acrylic acid ester-anhydride group-containing monomer terpolymers, etc. Can be mentioned.

  In addition, when the adhesive agent of a 1st adhesive bond layer is polyolefin resin and the adhesive agent of a 2nd adhesive bond layer is modified polyolefin resin, both shall use another kind of polyolefin resin. For example, when the adhesive of the first adhesive layer is a polyethylene resin, a modified polyolefin resin is used as the adhesive of the second adhesive layer.

  The thickness of the first adhesive layer is preferably 5 to 100 μm, particularly preferably 15 to 45 μm, in order to achieve the purpose of strong bonding between the phenol resin foam and the face material. Further, the thickness of the second adhesive layer is preferably 5 to 100 μm, particularly preferably 15 to 45 μm, in order to achieve the purpose of escape of water vapor from the end portion to the outside.

Next, the method of the present invention for producing a phenolic resin foam laminate will be described.
According to the method of the present invention, first, a face material including at least a nonwoven fabric layer, a first adhesive layer, a second adhesive layer, and a metal foil layer in this order is prepared.
The face material having the above-described structure is extruded into two layers so as not to mix the adhesive to be the first adhesive layer and the adhesive to be the second adhesive layer through the die, thereby forming the first adhesive layer. Obtained by integrating a non-woven fabric to be a non-woven fabric layer on the adhesive side, and inserting between a pair of rolls while supplying a metal foil to be a metal foil layer to the adhesive side to be the second adhesive layer It is done.

  According to the method of the present invention, the face material obtained in this way is supplied so that the nonwoven fabric layer of the face material is in face-to-face contact with the discharged phenol resin foam composition, and the phenol resin foam composition is cured. Then, by integrating the phenolic resin foam and the face material, a phenol resin foam laminate is obtained, but the used face material has high adhesion between the nonwoven fabric layer and the metal foil layer. Due to having the first adhesive layer and the second adhesive layer having water vapor escaping property, the phenol resin foam and the face material are firmly bonded, and due to the residence of hot water vapor generated when the phenol resin foam composition is cured Since the problem of peeling of the metal foil layer in the face material does not occur, a phenol resin foam laminate having desired heat resistance, flame retardancy, heat ray reflectivity, and design can be obtained.

Below, the manufacture example of the phenol resin foam laminated board by which the face material was provided in the two surfaces of the phenol resin foam is demonstrated concretely based on FIG.
In FIG. 1, the phenol resin foam laminate manufacturing apparatus 10 includes a pair of upper and lower conveyors 11 and 12 that are opposed to each other with an interval of about the thickness of the phenol resin foam. In addition to these, the lower conveyors 11 and 12 are endless steel belt conveyors in which an endless steel belt 13 is wound around a plurality of rollers 14, and are driven with the conveyance speed synchronized.

  The manufacturing apparatus 10 includes support portions 15 and 16 that are wound around the face materials 3 and 3 in a roll shape and are rotatably supported, corresponding to the upper and lower conveyors 11 and 12, respectively. , 12 are driven so that the face materials 3 and 3 wound around the support portions 15 and 16 are respectively fed out and conveyed along the conveying surfaces of the upper and lower conveyors 11 and 12 and mixed by the mixer 17. The phenol resin foam composition 18 is supplied onto the face material 3 on the lower conveyor 12 through a guide tube 19 so as to be supplied between the pair of face materials 3 and 3. Moreover, the manufacturing apparatus 10 includes a heating device 20 for thermosetting the phenol resin foam composition 18 that is supplied between the pair of face members 3 and 3 and conveyed downstream.

  Further, the manufacturing apparatus 10 has the edges 3a, 3a along the conveying direction of the pair of face materials 3, 3 conveyed by the pair of upper and lower conveyors 11, 12 on both sides (the front side and the other side in the drawing; the front side in the figure). (Only shown in the figure) is provided with closing means 21 for connecting and closing in the middle of conveyance. The closing means 21 may be a sewing device such as a sewing machine for sewing the edges 3a and 3a of the pair of face materials 3 and 3, or an adhesive device for bonding with an adhesive member. A landing gear may be used. A guide member 22 for guiding the edge portions 3 a and 3 a of the pair of face members 3 and 3 from the upstream side toward the closing means 21 is attached to the closing means 21.

  According to such a manufacturing apparatus 10, when driving of the upper and lower conveyors 11, 12 is started, the support parts 15, 16 rotate, the face materials 3, 3 are fed out and conveyed, and the mixer 17 The phenol resin foam composition 18 is supplied between the pair of face materials 3 and 3 to be conveyed via the lower face material 3. At this time, the edge portions 3a and 3a along the conveying direction of the pair of face materials 3 and 3 are guided by the guide member 22 and sent to the closing means 21, and are sewn, bonded or fused by the closing means 21. Thus, a closed space is formed between the pair of face members 3 and 3, and the phenol resin foam composition 18 is foamed in the closed space and is thermally cured by the heating device 20 to form the phenol resin foam 2. Face materials 3 and 3 are laminated and conveyed on both sides of the phenol resin foam 2, and finally, the edge portions 3 a and 3 a that are joined and closed are removed, thereby obtaining the phenol resin foam laminate 1. It is done.

  According to such a method for producing the phenol resin foam laminate 1, the face materials 3 and 3 are continuously run side by side, and the phenol resin foam composition 18 is placed between the running face materials 3 and 3. By supplying and foam-curing, since the face materials 3, 3 are continuously laminated integrally on both surfaces of the foam-cured phenol resin foam 2, the phenol resin foam laminate 1 is It can be obtained easily and the manufacturing cost can be reduced.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to these Examples.
Example 1
As the nonwoven fabric, Cumulus VH-4260 (Nippon Vilene Co., Ltd. glass fiber nonwoven fabric basis weight 60 g / m ² ) was used as the first adhesive layer, and Jeremix LD JZ788K (Nippon Polyolefin Co., Ltd. polyethylene-based adhesive). As the second adhesive layer, Lexpearl ET 182G (produced by Nippon Polyolefin Co., Ltd., ethylene-acrylic acid ester-anhydride group-containing monomer terpolymer adhesive), and as the metal foil, aluminum foil (JIS H 4160) Are laminated together and integrated by a hot melt method (300 ° C.), and the nonwoven fabric layer, the first adhesive layer, the second adhesive layer and the metal foil layer are arranged in this order. The face material possessed by was obtained.
On the other hand, a resol-type phenol resin is used as the phenol resin, and 84 parts by weight of phenol, 558 parts by weight of 37% formalin, and 11.1 parts by weight of sodium hydroxide are charged into the flask at 90 ° C. Then, the reaction solution was neutralized for 60 minutes, neutralized by adding oxalic acid so that the pH of the reaction solution was 7.0 to 7.3, and dehydrated at 80 ° C. under reduced pressure. The obtained resol type phenol resin was 3.0% by weight of free phenol and 1.9% by weight of free formalin.
20 parts by weight of phenolsulfonic acid as an acidic curing agent and 7 parts by weight of methylene chloride as a foaming agent were added to the resol type phenolic resin obtained above and stirred to obtain a resol type phenolic resin foamed composition.
The obtained resol type phenolic resin foam composition was supplied to the production apparatus shown in FIG. 1 together with the face material obtained above to produce a phenolic resin foam laminate, but the obtained phenolic resin foam laminate was obtained. Had no peeling of the metal foil layer in the face material, and had excellent heat resistance, flame retardancy, heat ray reflectivity, and design.

  For comparison, a phenolic resin foam laminate was used in the same manner as in Example 1 except that a face material comprising a non-woven fabric layer, a first adhesive layer, and a metal foil layer was used without the second adhesive layer. However, peeling of the metal foil in the face material was observed.

Example 2
As a material for the nonwoven fabric layer constituting the face material, a glass fiber nonwoven fabric (Nippon Vilene Co., Ltd. Cumulus VH-4260 basis weight 60 g / m ² ) or a polyester fiber nonwoven fabric (Unitika Ltd. Marix FLV basis weight 70 g / m) ² , fineness 3.1 denier, thickness 0.21 mm) as the material of the first adhesive layer, Jeremix LD JZ 788K (Nippon Polyolefin Co., Ltd. polyethylene adhesive), second Lexpearl ET 182G (ethylene polyolefin acrylate-acid anhydride group-containing monomer terpolymer) manufactured by Nippon Polyolefin Co., Ltd. as the material for the adhesive layer, and aluminum foil (JIS H 4160) as the material for the metal foil layer. Using a multi-layer laminating apparatus equipped with a multi-layer laminating die. A face material composed of a first adhesive layer, a second adhesive layer, and a metal foil layer was obtained.
On the other hand, a resol-type phenol resin foam composition was obtained as the phenol resin foam composition by performing the method described in Example 1 again.
The obtained face material and resol-type phenolic resin foam composition were supplied to the production apparatus shown in FIG. 1 to produce a phenolic resin foam laminate, but as shown in Table 1, the nonwoven fabric layer was a glass fiber nonwoven fabric. In the case of the polyester fiber nonwoven fabric, peeling of the metal foil layer of the face material was not recognized.
On the other hand, in the case where the adhesive layer of the face material is only the first adhesive layer and lacks the second adhesive layer, and the case where only the second adhesive layer lacks the first adhesive layer, Table 1 As shown in Fig. 4, peeling of the metal foil layer of the face material was observed regardless of whether the nonwoven fabric layer was a glass fiber nonwoven fabric or a polyester fiber.

  ADVANTAGE OF THE INVENTION According to this invention, the phenol resin foam laminated board which is excellent in heat resistance, a flame retardance, heat ray reflectivity, and designability, and does not peel | exfoliate the outermost metal foil layer is obtained. Can be widely used in civil engineering and architecture fields.

It is the schematic of the manufacturing apparatus of a phenol resin foam laminated board.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Phenolic resin foam laminated board, 3 ... Face material, 3a ... Edge of face material, 10 ... Manufacturing apparatus, 11 ... Upper conveyor, 12 ... Lower conveyor, 13 ... Endless steel belt, 14 ... Multiple rollers, DESCRIPTION OF SYMBOLS 15,16 ... Surface material support part, 17 ... Mixer, 18 ... Phenolic resin foam composition, 19 ... Guide pipe, 20 ... Heating device, 21 ... Closure means, 22 ... Guide member.

Claims (7)

  On at least one surface of the phenol resin foam, a face material comprising at least a nonwoven fabric layer, a first adhesive layer, a second adhesive layer different from the first adhesive layer, and a metal foil layer in this order, A phenolic resin foam laminate, wherein the nonwoven fabric layer of the face material is provided in contact with the surface of the phenolic resin foam.   The phenol resin foam laminate according to claim 1, wherein the nonwoven fabric layer includes at least one selected from inorganic fiber paper, inorganic fiber nonwoven fabric, and organic fiber nonwoven fabric.   The phenolic resin foam laminate according to claim 1 or 2, wherein the metal foil layer is made of an aluminum foil.   The first adhesive layer includes at least one selected from polyolefin resin, acrylic resin, epoxy resin, urethane resin, silicone resin and synthetic or natural rubber, the second adhesive layer includes polyolefin resin, When one adhesive layer contains an olefin resin, the olefin resin contained in the first adhesive layer and the olefin resin contained in the second adhesive layer are different types. 2. The phenolic resin foam laminate according to claim 1.   The phenol resin foam according to any one of claims 1 to 4, wherein the first adhesive layer has a thickness of 5 to 100 µm, and the second adhesive layer has a thickness of 5 to 100 µm. Body laminate board. The phenol resin foam laminate according to any one of claims 1 to 5, which has a resin coat layer on the metal foil layer.   A face material including at least the nonwoven fabric layer, the first adhesive layer, the second adhesive layer, and the metal foil layer in this order is brought into face-to-face contact with the phenol resin foam composition from which the nonwoven fabric layer of the face material is discharged. The phenol resin foam laminated board according to claim 1, wherein the phenol resin foam composition and the face material are integrated by curing the phenol resin foam composition. Manufacturing method.

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