JP2019038145A - Resin foam composite plate and structure containing the same - Google Patents

Abstract

To provide a resin foam composite plate which can more surely improve a bond strength to an external member, is strongly bonded to the external member with a small joint material, and can maintain a peel strength even in high temperature environment.SOLUTION: A resin foam composite plate has a resin foamed body and a fiber, and is provided with a coexistent region where the resin foamed body coexists with the fiber, where resin lumps are formed on the coexistence region, when one direction in the plane on the main surface of the resin foamed body composite plate is represented by X, a direction that is perpendicular to the main surface and is separated from the main surface is represented by Y, a magnitude in the X direction of the resin lumps is represented by x (mm) and a magnitude in the Y direction thereof is represented by y (mm), the resin lumps satisfying x≥0.1 and y≥0.2 are observed in X-Y cross section.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a resin foam composite plate provided with a coexistence region in which fibers and a resin foam coexist, and a structure including the composite plate.

  There is known a resin foam composite plate in which face materials are directly laminated on the surface of a resin foam. FIG. 9 shows a schematic cross-sectional view of a conventionally known resin foam composite plate 900. The resin foam composite board 900 is usually obtained by supplying a foamed resin to the surface of the face material 90 made of a fibrous material and curing the foamed resin to obtain a resin foam 80. Here, before the resin foam 80 is cured, the foamed resin partially penetrates into the face material 90. Therefore, a coexistence region 82 where the resin foam 80 coexists with fibers is formed in the vicinity of the interface between the resin foam 80 and the face material 90 formed in this way.

  The resin foam composite plate is used for various purposes in addition to using it alone, and joining it to an external member such as a resin sheet, a resin plate, a metal plate, and a wooden plate.

  However, in such a resin foam composite plate, conventionally, the bonding strength between the resin foam and the face material has been insufficient. Therefore, in the product in which the resin foam composite plate and the external member are joined via the face material, the face material is removed from the resin foam when used or after being installed in a place where it is required. As a result of peeling, there was anxiety that the integrity of the resin foam composite plate and the external member was lost.

  On the other hand, in patent document 1, the nonwoven fabric which has a fiber fixed part in the surface is laminated | stacked on the single side | surface of a resin foam, and the area ratio which the total of the area of this fiber fixed part occupies in the surface of this nonwoven fabric is 2% The present invention provides a resin foam composite plate in which the adhesive strength between the resin foam and the face material is improved by using a nonwoven fabric of 17% or less.

Japanese Patent Laid-Open No. 2017-13376

  Here, in the structure in which the resin foam composite plate and the external member described in Patent Document 1 are joined, the joint strength between the resin foam composite plate and the external member is determined between the joining surfaces of the layers or the layers between the layers. However, depending on the case, the internal strength of the face material or the interlayer strength in the face material may correspond to this.

Therefore, the inventors first used a fluid adhesive as the bonding material and increased the coating amount, and as a result, the bonding strength between the resin foam composite plate and the external member could be sufficiently increased. However, on the other hand, when this was placed in a high-temperature environment, a cavity was generated between the external member and the resin foam composite plate, and the adhesive strength decreased over time. This is considered to be due to the fact that the solvent component contained in the adhesive was vaporized and the force for peeling the resin foam composite plate and the external member worked. For this reason, it has been newly found that a method for increasing the amount of adhesive cannot be adopted for a product used in a high temperature environment.
Furthermore, it has also been found that discoloration occurs over time, particularly when a sheet-like material is used for the external member.

  In view of such circumstances, the present invention is a resin foam composite plate having a coexistence region in which the resin foam coexists with fibers, represented by a resin foam composite plate in which a face material is directly laminated on the surface of the resin foam. In addition, the bonding strength with the external member can be improved more reliably, and the amount of the bonding material necessary for expressing a certain amount of bonding strength can be suppressed, which is excellent in the environment and high. An object of the present invention is to provide an excellent resin foam composite plate in which the peel strength does not decrease even in a high temperature environment and the discoloration of the external member derived from the bonding material hardly occurs while maintaining the bonding strength. Furthermore, an object of the present invention is to provide a structure including the composite plate and an external member.

  The inventors of the present invention have a resin lump formed on the coexisting region of the resin foam composite plate, wherein one direction in the plane of the main surface of the resin foam composite plate is X, orthogonal to the main surface, and the main surface. Resin that satisfies x ≧ 0.1 and y ≧ 0.2, where Y is the direction away from the surface, and x (mm) is the size of the resin mass in the X direction and y (mm) is the size in the Y direction. The present inventors have found that a resin foam composite plate in which lumps are observed in an XY cross section is effective for achieving the above object, and has completed the present invention.

That is, the present invention provides the following [1] to [5].
[1] a resin foam;
And having fibers,
A resin foam composite board provided with a coexistence region where the resin foam coexists with the fibers,
A resin mass is formed on the coexistence region,
The size of the resin mass in the X direction is x (mm), where X is one in-plane direction on the main surface of the resin foam composite plate, Y is the direction perpendicular to the main surface and away from the main surface. ), A resin foam composite plate in which the resin mass satisfying x ≧ 0.1 and y ≧ 0.2 is observed in the XY cross section when the size in the Y direction is y (mm).
[2] The resin foam composite plate according to [1], wherein one or more resin lumps are present per 25 cm ^{2 on the} main surface of the resin foam composite plate.
[3] The resin foam composite plate according to [1] or [2], wherein a material of the resin block and a material of the fiber are the same.
[4] The resin foam composite plate according to any one of [1] to [3], wherein a fiber body mainly composed of the fibers is mixed with the resin mass on the coexistence region.
[5] It further includes an external member and a bonding material provided on one side of the external member,
A structure including the resin foam composite plate according to any one of [1] to [4], wherein the external member and the resin lump are bonded via the bonding material.

  Since the resin foam composite plate of the present invention has the above-described configuration, it is possible to further firmly and firmly join the external member. In addition, in the bonding of the resin foam composite plate and the external member, it is possible to suppress the amount of bonding material used to express a certain amount of bonding strength, while maintaining a high bonding strength while being excellent in the environment, Even under a high temperature environment, the peel strength does not decrease, and discoloration of the external member derived from the bonding material hardly occurs, which is excellent.

It is a typical perspective view of the resin foam composite board according to one mode in an embodiment of the present invention. It is a schematic cross section in the XY plane of FIG. It is the schematic cross section which expanded the A section of FIG. It is a typical perspective view of the resin foam composite board according to another aspect in embodiment of this invention. It is a schematic cross section in the XY plane of FIG. It is the schematic cross section which expanded the B section of FIG. It is typical sectional drawing of the structure containing the resin foam composite board by one Embodiment of this invention. It is a schematic cross section of the structure containing the resin foam composite board by another embodiment of this invention. It is a schematic cross section of the resin foam composite board by a prior art.

  DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention (hereinafter, may be referred to as “this embodiment”) will be described in detail with reference to the drawings. In the drawings, for convenience of explanation, the actual ratios are exaggerated from the actual ratios, unlike the actual thickness ratios of the respective components. Prior to the description of the present embodiment, the correspondence between FIGS. FIG. 1 is a schematic perspective view of a resin foam composite plate 100 according to an embodiment of the present invention, and FIG. 2 is a schematic cross-sectional view (XY cross section) along the XY plane in FIG. FIG. 3 is an enlarged schematic cross-sectional view of a portion A in FIG. 4 is a schematic perspective view of a resin foam composite plate 200 according to another embodiment of the present invention, and FIG. 5 is a schematic cross-sectional view along the XY plane in FIG. 2 (XY cross section). Indicates. FIG. 6 is an enlarged schematic cross-sectional view of a portion B in FIG. In principle, the same components are denoted by the same reference numerals, and redundant description is omitted.

  First, a resin foam composite plate 100 according to an aspect of the present embodiment will be described with reference to FIGS. The resin foam composite plate 100 includes a resin foam 10 and fibers 20, and a coexistence region 12 where the resin foam 10 coexists with the fibers 20 is provided. Then, the resin mass 30 is formed on the coexistence region 12. Here, assuming that one in-plane direction on the main surface 100M of the resin foam composite plate 100 is X, and the direction perpendicular to the main surface 100M and away from the main surface 100M is Y, the size of the resin mass 30 in the X direction is large. When the thickness is x (mm) and the size in the Y direction is y (mm), the resin mass satisfying x ≧ 0.1 and y ≧ 0.2 is observed in the XY cross section.

  In addition, the main surface in the resin foam composite board of this invention shall point out the surface by which the resin lump is formed in a resin foam composite board.

  As described above, the resin foam composite plate 100 is provided with the coexistence region 12 where the resin foam 10 coexists with the fibers 20. The fiber 20 is a fiber constituting a face material used when the resin foam 10 is molded, and the coexistence region is obtained when the foamed resin penetrates into the face material before the foamed resin is cured and becomes the resin foam 10. 12 is formed. Therefore, in this embodiment, the coexistence region 12 where the resin foam 10 and the fiber 20 coexist constitutes the outermost layer of the resin foam 10 constituting the resin foam composite plate.

  Various materials can be used for the face material used when the resin foam composite plate of the present embodiment is molded. The face material may be, for example, either a woven fabric or a non-woven fabric, and if it is a non-woven fabric, it can use non-woven fabrics manufactured by various manufacturing methods such as dry method, spunbond method, needle punch method, water jet method, Both short fiber and long fiber can be used.

  It is preferable that the fibers constituting these face materials are made of a material that is melt-treated by a method such as exposure to high temperature or treatment with chemicals to cause fusion or fixation within the face material. That is, a fiber made of a material that does not dissolve in a thermoplastic resin that melts when exposed to high temperatures or a solvent contained in a bonding material such as an adhesive, such as ethyl acetate or methyl ethyl ketone, but dissolves in other organic solvents. It is.

Examples of the fiber material having such properties include polyesters such as polyethylene, polypropylene, and polyethylene terephthalate, polyamides such as nylon 6, nylon 6,6, polyacrylonitrile, polyacetal, and cellulose.
In particular, when it is desired to further increase the peel strength of the external member, the elongation is 45 to 250% in both length and width, the tensile strength is 100 N / 5 cm or more in length, 50 N / 5 cm or more in width, and the tensile strength in both length and width is It is preferable to use a face material of 600 N / 5 cm or less. Also preferred basis weight of the surface material ^{is 20g / m 2 ~300g / m 2} .
When the face material is a non-woven fabric, the density of the nodal points between the fiber bundle formed by thermocompression bonding or a needle is preferably 5 to 300 / cm ² , more preferably 7 to 130 pieces / cm ² . The size of one nodal point is preferably 0.05 mm2 to ³ mm2. If the density and size of the knots are within this range, the y / x value described later can be easily maintained at 5 or less.

  In the resin foam composite plate 100, the resin lump 30 formed on the coexistence region 12 is formed as a result of the fusing and fixing occurring in the face material by performing the above-described melting treatment. A direction in the plane of the main surface 100M of the resin foam composite plate 100 is X, a direction orthogonal to the main surface 100M and away from the main surface 100M is Y, and the size in the X direction is x (mm). Assuming that the size in the Y direction is y (mm), the resin mass 30 satisfying x ≧ 0.1 and y ≧ 0.2 is observed in the XY cross section.

  The direction X can be any direction in the plane of the resin foam composite plate 100, particularly in the direction along the surface of the coexistence region 12. Moreover, as shown in FIG. 1, since the resin lump 30 can be formed by the above-mentioned melting process, it will be scattered in the surface of the main surface 100M. It should be understood that the description of the resin mass 30 in FIG. 1 is a schematic illustration and does not represent the actual number of resin masses 30. Therefore, if an arbitrary XY cross section (that is, a cross section in the thickness direction) perpendicular to the main surface 100M is obtained, the resin mass 30 in the XY cross section of the resin foam composite plate 100 that has undergone the above-described melting treatment. Will be observed. 1 and 2, the surface of each component is illustrated as if it were a flat surface. However, as shown in FIG. 3, the surface of each component actually has some fluctuation. Moreover, since the resin lump 30 can be formed by the above-described melting treatment, it usually has an irregular (non-geometric) shape, as schematically shown in FIG. The fact that the resin lump 30 is scattered, the surface is fluctuated, and the resin lump 30 has an irregular (non-geometric) shape is the same in FIGS.

  The above-mentioned resin lump 30 refers to what exists as a solid material in which at least fibers are substantially integrated. As for the magnitude | size of the resin lump 30, said x is 0.1 mm or more, Preferably it is 1.5 mm or less, More preferably, it is 1 mm or less.

  The y is 0.2 mm or more, preferably 1.5 mm or less, more preferably 1 mm or less. Furthermore, it is preferable that x and y satisfy y / x ≧ 0.3. In addition, the magnitude of y tends to increase as the amount of the above-described melting process performed per unit time in a unit area increases. y / x is preferably 1 or more, preferably 5 or less, more preferably 3 or less, from the viewpoint of maintaining a bonding force with an external member via a bonding material described later.

  In addition, in the resin foam composite board 100, it is preferable that the resin mass 30 is integrated with the fibers 20 coexisting with the resin foam 10 from the viewpoint of maintaining the bonding strength.

  Note that dust, dust, and the like that can be directly bonded to the main surface of the resin foam composite plate of the present embodiment due to the adhesive component on the main surface of the resin foam composite plate do not correspond to the resin mass in the present invention. These can be discriminated based on whether or not the location is easily changed by an extremely weak external force.

  The x and y can be measured by the method described later in (Evaluation Method) “(1) Measurement of x and y in resin mass”.

  In the present embodiment, the resin foam composite plate includes a coexistence region where the resin foam and fibers coexist as described above. In the present embodiment, on the main surface of the resin foam composite plate, the fiber body 25 mainly composed of fibers may be mixed with the resin mass or the fiber body may not exist. Good. In addition, a fiber body is the part which maintained the fibrous form when it melted in order to form the resin lump from the face material mentioned above. In the resin foam composite board 200 according to another aspect according to the present embodiment shown in FIGS. 4 to 6, the fiber body 25 mainly composed of fibers is mixed with the resin mass 30 on the coexistence region 12.

  Whether or not the fiber body 25 exists on the coexistence region 12 of the resin foam composite plate, that is, whether or not the fibers constituting the face material remain as the fiber body 25 on the main surface of the resin foam composite plate even after melting. This depends on the amount of the melting treatment performed per unit time in the unit area of the main surface of the resin foam composite plate. When the amount of the melting treatment increases, the fiber body 25 does not exist.

  It should be noted that the surface of the coexistence region 12 where the resin mass 30 does not exist (particularly see FIGS. 2 and 5) is not the case where the melted face material is deposited as a thin layer (not shown). There are cases.

Moreover, it is preferable that at least one resin lump 30 is present per 25 cm ^{2 on} the main surface of the resin foam composite plates 100 and 200. More preferably, it is 3 or more, more preferably 10 or more, and most preferably 20 or more.

  The number of resin lumps can be measured by the method described in “(2) Number of resin lumps” in (Evaluation Method) described later.

  In the structure of the present invention in which the resin foam composite plate and the external member are joined (hereinafter sometimes referred to as “structure”), the resin foam composite plate and the external member are interposed via the joining material. And joined. The structure of the present invention can generally be formed by bonding an external member to the main surface of the resin foam composite plate.

  As shown in FIG. 7, the structure 300 including the resin foam composite plate 100 further includes an external member 40 and a bonding material 60 provided on one surface of the external member 40, and the external member 40 and the resin mass 30. Are bonded via the bonding material 60.

  As shown in FIG. 8, the structure 400 including the resin foam composite plate 200 further includes an external member 40 and a bonding material 60 provided on one surface of the external member 40. The lump 30 is bonded via the bonding material 60.

  In FIG. 7, the melted face material is deposited as a thin layer (not shown) at the interface between the coexistence region 12 where the resin lump 30 does not exist and the bonding material 60, and the case where it is not. There is.

  Here, the bonding material 60 is a material for bonding the external member 40 and the resin foam composite plates 100, 200, and examples thereof include a double-sided pressure-sensitive adhesive sheet and an adhesive.

  As the adhesive used as the bonding material 60, an adhesive that can adhere these to the outer member 40 and the main surfaces 100M and 200M of the resin foam composite plates 100 and 200 is used.

Examples of the external member 40 include one of a board-like material, a sheet-like material, and a film-like material, and combinations thereof. Board-like materials include ordinary plywood, structural plywood, particle board, OSB, and other wood-based boards, and wood wool cement board, wood chip cement board, gypsum board, flexible board, medium density fiber board, calcium silicate board , Magnesium silicate plates, volcanic glassy multilayer plates, metal panels, etc. A structure joined to a metal panel is known as a sandwich panel. In addition, as a sheet-like material, a vinyl chloride sheet, a vulcanized rubber-based sheet, a non-vulcanized rubber-based sheet, a thermoplastic olefin-based sheet, an ethylene vinyl acetate sheet, a modified asphalt-based sheet, and a film-like material as a polyethylene film , Plastic moisture-proof film, asphalt waterproof paper, aluminum foil (with or without holes). In particular, a structure bonded to a resin sheet is used for a waterproof heat insulating panel or the like.
In addition, as a liquid adhesive used when using a vinyl chloride material for the resin sheet or the resin plate as the external member 40, an SBR adhesive, a nitrile rubber adhesive, an epoxy adhesive, or the like can be used. .

  Although not shown, in the structure in which the resin foam composite plate of the present embodiment and the external member are joined, a fiber body 25 mainly composed of fibers derived from a face material on the main surface of the resin foam composite plate. Is present, the bonding material 60 may coexist in the interior.

  Here, the bonding agent 60 coexists with the fiber body 25, for example, in order to bond the resin foam composite plate of the present embodiment to an external member, a liquid adhesive is previously applied to the resin foam composite plate as the bonding material 60. As a result of the application, there may be mentioned a case where the adhesive has soaked into the fibers constituting the fiber body 25.

  Although various foamed resins can be used as the resin foam 10 in the resin foam composite plates 100 and 200 of the present embodiment, thermosetting properties such as heat-resistant polyurethane, polyisocyanurate, phenol resin, and epoxy resin are available. Resins, solvent-resistant crosslinked polyethylene, crosslinked polypropylene, crosslinked polyvinyl chloride and the like are preferable.

Note that these resin foam 10 in the case of utilizing a heat insulating purposes, it is preferable density of 15 kg / ^{m 3} or more 60 kg / ^{m 3} or less. More preferably, it is 20 kg / m ³ or more and 50 kg / m ³ or less. The closed cell ratio is preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more.

  The density refers to a value measured by the method described in “(3) Density of resin foam” in (Evaluation Method) described later. Moreover, the said closed cell rate says the value measured by the method as described in "(4) Closed cell rate of resin foam" of the below-mentioned (evaluation method).

  It is conceivable to use hydrocarbons as the foaming agent used when forming the resin foam 10. The hydrocarbon is preferably a cyclic or chain alkane, alkene or alkyne having 3 to 7 carbon atoms, specifically, normal butane, isobutane, cyclobutane, normal pentane, isopentane, cyclopentane, neopentane, normal hexane, Examples include isohexane, 2,2-dimethylbutane, 2,3-dimethylbutane, and cyclohexane. Among these, pentanes such as normal pentane, isopentane, cyclopentane, and neopentane, and butanes such as normal butane, isobutane, and cyclobutane are preferably used. These hydrocarbons may be used alone or in combination of two or more.

  When a mixture of hydrocarbon and other components is used as the blowing agent, the hydrocarbon content in the blowing agent is preferably 5% by mass or more, more preferably 10% by mass or more, and 20% by mass. % Or more is more preferable.

It is also conceivable to use hydrofluoroolefin-based foaming agents such as chlorinated hydrofluoroolefins and non-chlorinated hydrofluoroolefins as constituents as foaming agents. Specific examples of the chlorinated hydrofluoroolefin include trans-1-chloro-3,3,3-trifluoropropene (product name: Solstice (registered trademark) LBA). Specifically, 1,3,3,3-tetrafluoro-1-propene (product name: Solstice (registered trademark) 1234ze), 2,3,3,3-tetrafluoro-1-propene, 1,1,4,4,4-hexafluoro-2-butene and the like. Chlorinated hydrofluoroolefin and / or non-chlorinated hydrofluoroolefin may be used alone or in combination of two or more. When the hydrofluoroolefin-based foaming agent is used, the bonding strength between the resin foam and the face material before the resin lump 30 is formed can be further increased.
When using a mixture of a hydrofluoroolefin foaming agent such as chlorinated hydrofluoroolefin and non-chlorinated hydrofluoroolefin as a foaming agent and another foaming agent, the content ratio of the hydrofluoroolefin foaming agent in the foaming agent is: Preferably it is 20 mass% or more, More preferably, it is 50 mass% or more, More preferably, it is 70 mass% or more.
As the blowing agent, chlorinated hydrocarbons such as chlorinated aliphatic hydrocarbons can also be used. As said chlorinated aliphatic hydrocarbon, a C2-C5 linear or branched thing etc. are mentioned, for example. The number of bonded chlorine atoms is preferably 1 to 4, and examples thereof include dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride and the like. Of these, propyl chloride and isopropyl chloride, which are chloropropanes, are more preferable. The chlorinated hydrocarbons may be used alone or in combination of two or more.
When a mixture of chlorinated hydrocarbon and other components is used as the blowing agent, the content of the chlorinated hydrocarbon in the blowing agent is preferably 5% by mass or more, more preferably 10% by mass or more. Preferably, it is 20 mass% or more.

  Any of the above-described foaming agents can be used in combination. For example, combinations of hydrocarbons with chlorinated hydrofluoroolefins and / or non-chlorinated hydrofluoroolefins, combinations of chlorinated hydrofluoroolefins and / or non-chlorinated hydrofluoroolefins with chlorinated hydrocarbons, hydrocarbons and chlorine A combination of a chlorinated hydrocarbon and a combination with a chlorinated hydrofluoroolefin and / or a non-chlorinated hydrofluoroolefin. The amount of the foaming agent used is preferably about 2 to 15% by mass with respect to the resin contained in the foamable resin composition used when forming the resin foam layer.

  When the resin is foamed, a foam nucleating agent may be included. Examples of the foam nucleating agent include low-boiling substances having a boiling point lower by 50 ° C. or more than the foaming agent such as nitrogen, helium, argon, and air.

  The foam nucleating agent is, for example, aluminum hydroxide powder, aluminum oxide powder, calcium carbonate powder, talc, clay (kaolin), quartzite powder, quartz sand, mica, calcium silicate powder, wollastonite, glass powder. Solid foam nucleating agents such as glass beads, fly ash, silica fume, gypsum powder, borax, slag powder, inorganic powder such as alumina cement and Portland cement, and organic powder such as resin foam powder may be used. The said foam nucleating agent may be used independently and may be used in combination of 2 or more types.

  The amount of the foam nucleating agent added to the foaming agent is preferably 0.1% by mass or more and 1.0% by mass or less, more preferably 0.2% by mass or more and 0.6% by mass or less with respect to the total amount of the foaming agent (100% by mass). The mass% or less is more preferable. If the amount of the foam nucleating agent is 0.1% by mass or more, uniform foaming is likely to occur, and if the amount of the foaming nucleating agent is 1.0% by mass or less, the foaming rate of the resin is easily controlled. Therefore, when the resin foam 10 is formed, the foamed resin can be easily infiltrated into the face material, and the bonding strength between the face material and the resin foam can be easily secured.

Further, in addition to the foam nucleating agent, a curing agent, a surfactant, a plasticizer, a flame retardant, an extender, and the like can be included.
Examples of the curing agent include components capable of forming a crosslinked body with a resin skeleton, such as urea.
As the surfactant, for example, an ethylene oxide-propylene oxide block copolymer is preferably used. Further, castor oil alkylene oxide adducts, silicone surfactants, polyoxyethylene sorbitan fatty acid esters, and the like are also included. These may be used individually by 1 type and may be used in combination of 2 or more type. Among these, inclusion of either a castor oil alkylene oxide adduct or a silicone-based surfactant is preferable in that the foam has a smaller cell diameter and an increased strength. It is also preferable in terms of enhancing the flammability.
The alkylene oxide in the castor oil alkylene oxide adduct is preferably ethylene oxide or propylene oxide. These may be used alone or as a mixture of two or more.
The number of moles of alkylene oxide added in the castor oil alkylene oxide adduct is more than 20 moles and less than 60 moles, more preferably 21 to 40 moles per mole of castor oil. Such a castor oil alkylene oxide adduct has a hydrophobic group mainly composed of a long-chain hydrocarbon group of castor oil and a hydrophilic group mainly composed of a polyoxyalkylene group formed by alkylene oxide arranged in a balanced manner in the molecule. And good surface activity is exhibited. Thereby, the bubble diameter of a resin foam becomes small. In addition, flexibility is imparted to the bubble wall, and the generation of cracks is prevented.
Examples of the silicone surfactant include a copolymer of dimethylpolysiloxane and polyether, and an organopolysiloxane compound such as octamethylcyclotetrasiloxane. Among them, a copolymer of dimethylpolysiloxane and polyether is preferably used in that more uniform and finer bubbles can be obtained.
The structure of the copolymer of dimethylpolysiloxane and polyether is, for example, an ABA type in which polyether chains are bonded to both ends of the siloxane chain, and a plurality of siloxane chains and a plurality of polyether chains are alternately bonded (AB ) _N- type, branched type in which a polyether chain is bonded to each end of a branched siloxane chain, and a pendant type in which a polyether chain is bonded in addition to the end of the siloxane chain.
Examples of the copolymer of dimethylpolysiloxane and polyether include dimethylpolysiloxane-polyoxyalkylene copolymer.
As for carbon number of the oxyalkylene group in polyoxyalkylene, 2 or 3 is preferable. 1 type or 2 types or more may be sufficient as the oxyalkylene group which comprises polyoxyalkylene.
Specific examples of the dimethylpolysiloxane-polyoxyalkylene copolymer include dimethylpolysiloxane-polyoxyethylene copolymer, dimethylpolysiloxane-polyoxypropylene copolymer, dimethylpolysiloxane-polyoxyethylene-polyoxypropylene copolymer. A polymer etc. are mentioned.
The copolymer of dimethylpolysiloxane and polyether is preferably a polyether having an alkyl group at the end or a hydroxyl group, more preferably a hydroxyl group.
The content of the surfactant in the resin foam is preferably 1 to 10 parts by mass and more preferably 2 to 5 parts by mass per 100 parts by mass of the resin. If the content of the surfactant is not less than the above lower limit value, the bubble diameter tends to be uniform and fine. If it is below the said upper limit, a closed-cell ratio tends to become high and is preferable.
The mass ratio of the foaming agent to the surfactant in the resin foam is preferably 1: 1 to 6: 1 from the viewpoint of forming a good foamed state.
As the plasticizer, glycol compounds such as alkylene glycol ethers can be used. Specific examples include alkylene glycol alkyl ether, ethylene glycol methyl ether, propylene glycol methyl ether, and the like.
Flame retardants include red phosphorus, sodium phosphate, sodium dihydrogen phosphate, ammonium polyphosphate, phosphate esters such as chlorine-containing phosphate esters, ammonium phosphates, melamine phosphates, aluminum phosphates, boron Examples include acid, sodium borate, zinc borate, ammonium carbonate, wollastonite (needle filler), expanded graphite, silicones, and the like.
As the extender, an inorganic filler is preferable in terms of enhancing fire resistance. Examples of the inorganic filler include metal hydroxides and oxides of metals such as aluminum hydroxide, magnesium hydroxide, calcium oxide, magnesium oxide, aluminum oxide, zinc oxide, titanium oxide, and antimony oxide, and metal powders such as zinc; Metal carbonates such as calcium, magnesium carbonate, barium carbonate, zinc carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; alkaline earth metal hydrogen carbonates such as calcium hydrogen carbonate and magnesium hydrogen carbonate; sulfuric acid Examples include calcium, barium sulfate, calcium silicate, mica, talc, bentonite, zeolite, silica gel, and the like. However, when a strong acid is used for forming the foam, it is necessary to add the metal powder and carbonate within a range that does not affect the adjustment of the pot life. These inorganic fillers may be used alone or in combination of two or more.
These extenders also function as a protective agent for capturing hydrogen fluoride. When a fluorinated olefin is used as a foaming agent, it is known that hydrogen fluoride is generated by decomposition, or that hydrogen fluoride used as a raw material for the production remains as an impurity in the resin foam (see Table 2014). -511930). This hydrogen fluoride reacts with the siloxane bond constituting the hydrophobic part of the silicone-based surfactant to reduce the surface active action. Therefore, the filler may be added to the foam resin as a protective agent.

(Evaluation method)
The measurement methods of the physical property values described above are listed below.

(1) x in resin mass, measured resin foam composite plate of y, or which in a structure obtained by bonding the outer member, any 25 cm ² square to the surface of the resin foam composite plate (5 cm × 5 cm) Is cut in the thickness direction with a cutting tool such as a cutter, and an evaluation sample is cut out.

  The cut surface of the cut out evaluation sample is observed with a digital microscope RH-2000 manufactured by Hilox Corporation. The resin mass is in contact with the resin foam of the resin foam composite plate, and the contact length with the resin foam is x. As described above, as schematically shown in FIGS. 3 and 6, the surfaces of the coexistence region 12 and the fiber body 25 have some fluctuations, but are derived from the melting treatment of the face material. Therefore, the height difference between these surfaces is at most about several tens of μm. Therefore, it is assumed that the contact surface between the resin mass 30 and the coexistence region 12 or the fiber body 25 is a substantially flat surface, and the resin foam composite plate from the reference plane connecting both ends of the position where x is measured. Let y be the maximum distance in the thickness direction (vertical direction). Note that the values of x and y can be measured using a length measurement function of the digital microscope.

(2) Number of resin blocks The evaluation sample cut out in (1) is further cut in the thickness direction at intervals of 1 cm to form five rods. All the cut surfaces of these five samples are observed with a digital microscope as in (1), and the number of resin masses satisfying x ≧ 0.1 and y ≧ 0.2 is counted, and the resin mass per 25 cm ^2. The number of

(3) Density of resin foam A 20 cm square rectangular parallelepiped is cut out from the resin foam to obtain a sample, and the mass and volume of the sample are measured and determined. Measured according to JIS K 7222: 2005.

(4) Closed Cell Ratio of Resin Foam When the thickness of the resin foam is 25 mm or more using a cutting tool such as a band saw at the center position in the thickness direction of the resin foam, a 25 mm square cube is cut out as a sample. In addition, when the thickness of the resin foam is less than 25 mm, the thickness after removal of the face material (when the fiber material derived from the face material remains or when there is a face material on the back side) is 25 mm both vertically and horizontally. Cut a rectangular parallelepiped as a sample. And sample volume V (cm < ³ >) is measured by the standard usage method of an air comparison type hydrometer (1000 type | mold, Tokyo Science company make). The closed cell ratio in the resin foam is the volume of the bubble wall (W / ρ) calculated from the sample volume V from the sample volume W (g) and the density ρ of the resin composition constituting the resin foam as shown in the following formula. ) Is subtracted by the apparent volume Va (cm ³ ) calculated from the outer dimensions of the sample, and measured according to ASTM D 2856 (Method C).
Closed cell ratio (%) = ((V−W / ρ) / Va) × 100

(5) Adhesive strength of external member From the molded structure, a rod-shaped structure having an area of 30 mm width and 150 mm length is cut out and used as an evaluation sample. When the external member is a flexible material, a 30 mm long notch is formed along the surface of the evaluation sample at the end in the length direction of the evaluation sample and at a location close to the external member in the foam layer. , Create a knob allowance including an external member, pinch this knob allowance after fixing the evaluation sample, perform 90 ° peeling of the external member over a length of 85 mm by Shimadzu Autograph AG-X, The average value of strength is defined as the 90 ° peel strength of the sample. The pulling speed of the external member is 200 mm / min.

  In the case where the external member is a non-flexible material such as a thick resin molded body, metal plate, wood, etc., the same incision as described above is made in the evaluation sample with a width of 30 cm and a length of 150 cm, and the external member penetrates A hole is provided, and a non-stretchable string, rope, metal parts, etc. are attached using the through-hole to create a knob allowance. After fixing the evaluation sample, the knob allowance is picked, and Shimadzu Autograph AG-X 90 ° peel strength test. The pulling speed of the external member is 200 mm / min.

  In addition, the coexistence area | region 12 by this embodiment can be confirmed by observation with a scanning electron microscope (Scanning Electron Microscope; SEM).

  Hereinafter, the present invention will be described in more detail based on examples in which a phenol resin foam is used as a resin foam and a vinyl chloride sheet is used as an external member as a representative example.

Example 1
While producing a phenol resin foam in the following manner, a resin lump according to the present invention was formed to produce a resin foam composite plate. Furthermore, using a vinyl chloride sheet as an external member, a structure including a resin foam composite plate was produced and evaluated.

<Synthesis of phenolic resin>
The reactor was charged with 3500 kg of a 52% by weight aqueous formaldehyde solution and 2510 kg of 99% by weight phenol, stirred with a propeller rotating stirrer, and the temperature inside the reactor was adjusted to 40 ° C. with a temperature controller. Next, the temperature was raised while adding a 50 mass% aqueous sodium hydroxide solution to advance the reaction. When the Ostwald viscosity reached 60 centistokes (measured value at 25 ° C.), the reaction solution was cooled, and 570 kg of urea (corresponding to 15 mol% of the charged amount of formaldehyde) was added. Thereafter, the reaction solution was cooled to 30 ° C., and the pH was neutralized to 6.4 with a 50 mass% aqueous solution of paratoluenesulfonic acid monohydrate. When the viscosity and water content of the reaction solution (thermosetting resin composition) obtained after dehydration at 60 ° C. were measured, the viscosity at 40 ° C. was 5,800 mPa · s, and the water content was 5% by mass. It was.

<Preparation of phenol resin composition>
A block copolymer of ethylene oxide-propylene oxide (manufactured by BASF, product name “Pluronic (registered trademark) F-127) as a surfactant with respect to 96.5 parts by mass of the dehydrated reaction liquid mainly composed of a phenol resin. ]) Was mixed at a ratio of 3.5 parts by mass. 9. Mixture of 30% by mass of cyclopentane and 70% by mass of trans-1-chloro-3,3,3-trifluoropropene as a blowing agent with respect to 100 parts by mass of the obtained surfactant-containing phenol resin composition. Mixing 0 parts by weight, nitrogen as a foam nucleating agent 0.3% by weight with respect to the blowing agent, and 11 parts by weight of a mixture of 80% by weight of xylene sulfonic acid and 20% by weight of diethylene glycol as a curing catalyst. The phenol resin composition was obtained by supplying to the head.

  Here, the mixer to be used has a surfactant-containing phenol resin composition and a foaming agent inlet on the upper side surface, and a curing catalyst inlet on the side surface near the center of the stirring unit where the rotor stirs. After the stirring unit, a pin mixer connected to a distribution unit having a nozzle for discharging foam was used. It has a plurality of nozzles and is designed so that the mixed phenol resin composition is uniformly distributed. A temperature sensor is set on the central side and the bottom of the mixer so that the temperature inside the system can be measured. Furthermore, a temperature control jacket is provided to enable adjustment of the mixer temperature. The temperature measured by this temperature sensor was 36.4 ° C.

<Manufacture of phenolic resin foam>
Based on JIS L 1913: 2010, the basis weight is 70 g / m ² , the thickness is 0.46 mm, the tensile strength is 200 N / 5 cm width in the longitudinal direction, the transverse direction is 70 N / 5 cm width, the elongation is 50% in the longitudinal direction, A span made of polypropylene fibers having circular crimped portions with a diameter of 0.5 mm at intervals of 1.5 mm and a circular cross-section with a diameter of 20 μm, measured as 70% in the transverse direction and tear strength of 7.0 N in the longitudinal direction Bond nonwoven fabric was used as a face material. While moving the nonwoven fabric, the phenol resin composition was supplied onto the nonwoven fabric through a multiport distribution pipe.

The same kind of non-woven fabric is further coated on the phenol resin composition supplied on the non-woven fabric, sent to an 85 ° C. slat type double conveyor and cured with a residence time of 15 minutes, and then cured in an oven at 110 ° C. for 2 hours. Thus, a resin foam composite plate having a thickness of 30 mm was obtained. The slat type double conveyor used at this time is provided with a passage for moisture so that moisture generated during curing can be discharged to the outside. The density of the resin foam of the molded phenol resin foam composite plate was 27 kg / m ^{3 when} the density of the phenol resin composition was 1.3 kg / cm ³ and the closed cell ratio was 90%.

  The fibers constituting the face material (hereinafter referred to as face material fibers in the examples) using the Ishizaki Electric Mfg. Shear-pledget PJ-214A on the surface material surface of the nonwoven fabric of the resin foam composite board thus produced. Hot air was blown until the surfaces of the two melted and began to fuse together. Thereafter, when the cross section in the thickness direction of the resin foam composite plate was cut out and observed by the method of (2), 0.1 ≦ x ≦ 1, together with the fibrous body of the nonwoven fabric face material on the surface of the resin foam composite plate, Three resin lumps satisfying 0.2 ≦ y ≦ 1 and y / x ≧ 0.3 were confirmed.

Subsequently, a structure was prepared using a vinyl chloride sheet as an external member and a nitrile rubber liquid adhesive as a bonding material. Specifically, a nitrile rubber-based liquid adhesive having a viscosity of 4500 mPa · s containing 55% by mass of methyl ethyl ketone was applied to the molten nonwoven fabric face material with 300 g per m ² using a comb iron. Similarly, 150 g of liquid adhesive per 1 m ² was applied to one side of a 2 mm vinyl chloride sheet. After 15 minutes, the adhesive-coated surface of the vinyl chloride sheet and the adhesive-coated surface of the resin foam were bonded together to obtain a structure. After placing this in an environment of 23 ° C. and 50% humidity for 2 days, the 90 ° peel strength of the vinyl chloride sheet was measured by the method of (5) above, which was 25 N / 25 mm. In order to simulate a high temperature environment, this sample was further left standing in an oven at 90 ° C. for 2 weeks and heated, but the appearance of the vinyl chloride sheet was not changed, and the 90 ° peel strength was not changed. Subsequently, the sample was allowed to stand in a 90 ° C. oven, and the appearance of the vinyl chloride sheet after 2 months (including the first 2 weeks, the same applies hereinafter) was observed, but no discoloration was observed.

(Example 2)
Based on JIS L 1913: 2010 as the upper and lower face materials, the basis weight is 100 g / m ² , the thickness is 1.0 mm, the tensile strength is 245 N / 5 cm width in the vertical direction, 80 N / 5 cm width in the horizontal direction, the elongation is vertical It has a circular crimped part with a diameter of 1 mm at intervals of 2 mm and a cross-section of 40 μm in width and 5 μm in thickness. A resin foam composite board was molded in the same manner as in Example 1 except that a spunbond nonwoven fabric made of crimped polypropylene fibers was used. When this resin foam composite plate was subjected to the melting treatment of the surface fiber in the same manner as in Example 1, and the cross section in the thickness direction of the resin foam composite plate was cut out and observed by the method (2), Ten resin masses satisfying 0.1 ≦ x ≦ 1, 0.2 ≦ y ≦ 1, and y / x ≧ 0.3 were confirmed on the surface of the resin foam composite plate together with the fibrous body of the nonwoven fabric face material. Thereafter, a structure using a vinyl chloride sheet as an external member was prepared in the same manner as in Example 1, and the 90 ° peel strength of the vinyl chloride sheet was measured. As a result, it was 28 N / 25 mm. Further, this sample was allowed to stand in an oven at 90 ° C. for 2 weeks, but the appearance of the vinyl chloride sheet was not changed, and the 90 ° peel strength was not changed. Subsequently, the sample was left in an oven at 90 ° C., and the appearance of the vinyl chloride sheet after 2 months was observed, but no discoloration was observed.

(Example 3)
After molding the resin foam composite board using the same nonwoven fabric as in Example 2 as the upper and lower nonwoven fabrics, on the surface of the nonwoven fabric face material of the resin foam composite board, using Ishizaki Electric Manufacturing Share Pragjet PJ-214A, Even after the surfaces of the face material fibers were melted and started to fuse with each other, high-temperature hot air was blown continuously for a while. Thereafter, when the cross section in the thickness direction of the resin foam composite plate was cut out and observed by the method (2), a fibrous body of the nonwoven fabric face material was not confirmed on the surface of the resin foam composite plate. 47 resin masses satisfying ≦ x ≦ 1, 0.2 ≦ y ≦ 1, and y / x ≧ 0.3 were confirmed. Thereafter, a structure using a vinyl chloride sheet as an external member was prepared in the same manner as in Example 1, and the 90 ° peel strength of the vinyl chloride sheet was measured. As a result, it was 30 N / 25 mm. Further, this sample was allowed to stand in an oven at 90 ° C. for 2 weeks, but the appearance of the vinyl chloride sheet was not changed, and the 90 ° peel strength was not changed. Subsequently, the sample was left in an oven at 90 ° C., and the appearance of the vinyl chloride sheet after 2 months was observed, but no discoloration was observed.

Example 4
Resin foam in the same manner as in Example 2 except that 10.6 parts by mass of a mixture of 30% by mass of isochloropropane and 70% by mass of trans-1-chloro-3,3,3-trifluoropropene was used as the foaming agent. A composite plate was formed. When this resin foam composite plate was subjected to the melting treatment of the surface fiber in the same manner as in Example 1, and the cross section in the thickness direction of the resin foam composite plate was cut out and observed by the method (2), Ten resin masses satisfying 0.1 ≦ x ≦ 1, 0.2 ≦ y ≦ 1, and y / x ≧ 0.3 were confirmed on the surface of the resin foam composite plate together with the fibrous body of the nonwoven fabric face material. Thereafter, a structure using a vinyl chloride sheet as an external member was prepared in the same manner as in Example 2, and the 90 ° peel strength of the vinyl chloride sheet was measured and found to be 28 N / 25 mm. Further, this sample was allowed to stand in an oven at 90 ° C. for 2 weeks, but the appearance of the vinyl chloride sheet was not changed, and the 90 ° peel strength was not changed. Subsequently, the sample was left in an oven at 90 ° C., and the appearance of the vinyl chloride sheet after 2 months was observed, but no discoloration was observed.

(Comparative Example 1)
A resin foam composite plate was produced in the same manner as in Example 1 except that the surface treatment was not performed on the surface material. Although the cross section in the thickness direction of the resin foam composite plate was cut out and observed by the method (2), no resin lump was confirmed. Thereafter, a structure using a vinyl chloride sheet as an external member was produced in the same manner as in Example 1, and the 90 ° peel strength of the vinyl chloride sheet was measured. As a result, it was 16 N / 25 mm.

(Comparative Example 2)
A resin foam composite plate was produced in the same manner as in Example 2 except that the surface treatment of the face material was not performed. Although the cross section in the thickness direction of the resin foam composite plate was cut out and observed by the method (2), no resin lump was confirmed. Thereafter, a structure using a vinyl chloride sheet as an external member was prepared in the same manner as in Example 1, and the 90 ° peel strength of the vinyl chloride sheet was measured. As a result, it was 20 N / 25 mm.

(Comparative Example 3)
A resin foam composite plate was produced in the same manner as in Example 2 except that the surface treatment of the face material was not performed. Although the cross section in the thickness direction of the resin foam composite plate was cut out and observed by the method (2), no resin lump was confirmed. Thereafter, a nitrile rubber-based liquid adhesive having a viscosity of 4500 mPa · s containing 55% by mass of methyl ethyl ketone was applied onto the molten nonwoven fabric surface material using a comb iron, and 900 g per 1 m ² , and 2 mm thick vinyl chloride. Similarly, 400 g of liquid adhesive per 1 m ² was applied to one side of the sheet. After 15 minutes, the adhesive-coated surface of the vinyl chloride sheet and the adhesive-coated surface of the resin foam were bonded together to obtain a structure. After placing this in an environment of 23 ° C. and 50% humidity for 2 days, the 90 ° peel strength of the vinyl chloride sheet was measured by the method of (5) above, which was 27 N / 25 mm. Further, when this sample was allowed to stand in an oven at 90 ° C. for 2 weeks, a plurality of blisters occurred on the surface of the vinyl chloride sheet. When one of the swollen portions was cut out and confirmed, it was confirmed that a cavity was formed between the vinyl chloride sheet and the resin foam composite plate. Moreover, it was 10 N / 25mm when 90 degree peeling strength of the swelling part which was not cut out was measured. Moreover, when the sample was allowed to stand in an oven at 90 ° C. with respect to the same type of sample and the appearance of the vinyl chloride sheet after two months was observed, discoloration was confirmed on the surface.

  The above production conditions and evaluation results are summarized in Table 1 below.

From the above results, it was confirmed that in Examples 1 to 4 in which resin lumps satisfying the conditions of the present invention were formed, the peel strength of the structure was superior to Comparative Examples 1 and 2. Therefore, it has confirmed that the resin foam composite board by Examples 1-3 strengthened joining to an external member much more reliably.

  Moreover, although the peeling strength of the structure by the comparative example 3 is comparable as Examples 1-4, it has confirmed that a large amount of joining materials were required and swelling and discoloration would occur in a high temperature environment. . Therefore, the resin foam composite plates according to Examples 1 to 4 that satisfy the conditions of the present invention can be firmly bonded to the external member with a small amount of bonding material, and can maintain the peel strength even in a high temperature environment. This is also advantageous in that no discoloration occurs.

  The resin foam composite plate of the present embodiment can increase the bonding strength with respect to a structure in which the bonding strength with an external member is not sufficient because the in-layer peel strength of the conventional surface material is low. It is easy to handle, and it is easy to maintain the peel strength even in a high temperature environment. The structure of the present embodiment can be used as a product that can be used, for example, in a place that requires heat insulation.

DESCRIPTION OF SYMBOLS 10 Resin foam 12 Coexistence area 20 Fiber 25 Fiber 30 Resin lump 40 External member 60 Joining material 100 Resin foam composite board 200 Resin foam composite board 300 Structure 400 Structure

Claims (5)

Resin foam,
And having fibers,
A resin foam composite board provided with a coexistence region where the resin foam coexists with the fibers,
A resin mass is formed on the coexistence region,
The size of the resin mass in the X direction is x (mm), where X is one in-plane direction on the main surface of the resin foam composite plate, Y is the direction perpendicular to the main surface and away from the main surface. ) When the size in the Y direction is y (mm), the resin mass is observed in the XY cross section where the resin mass satisfies x ≧ 0.1 and y ≧ 0.2. . 2. The resin foam composite plate according to claim 1, wherein at least one resin mass is present per 25 cm ^{2 on the} main surface of the resin foam composite plate.   The resin foam composite board according to claim 1 or 2, wherein a material of the resin lump and a material of the fiber are the same.   The resin foam composite board according to any one of claims 1 to 3, wherein a fibrous body mainly composed of the fibers is mixed with the resin mass on the coexistence region. An external member, and a bonding material provided on one side of the external member;
The structure containing the resin foam composite board as described in any one of Claims 1 thru | or 4 with which the said external member and the said resin lump are joined via the said joining material.