JP2017179244A - Foamed body and method for producing foamed body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a foamed body excellent in a balance between fire retardancy and weight saving.SOLUTION: Provided is a foamed body in which a filler is dispersed into a matrix resin having a three-dimensional structure, where, provided that the maximum calorific value velocity of the foamed body measured in accordance with a heat release test according to FAR25.853 (Appendix F, Part IV) is defined as v1 and the maximum calorific value velocity of a non-foamed resin molded body including a matrix resin and a filler is defined as V2, the maximum calorific value velocity ratio (X1/V2) is 0.9 or lower.SELECTED DRAWING: Figure 1

Description

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

  Various non-combustible films have been developed as flame retardant members. As this type of technology, for example, there is a technology described in Patent Document 1. According to this document, a noncombustible film in which a silica compound is added to a polyimide resin is described (claims 1, 6, and 14 of Patent Document 1).

International Publication 2012/169591 Pamphlet

  However, as a result of studies by the present inventors, it has been found that the non-combustible film described in the above document has room for improvement in terms of the balance between flame retardancy and weight reduction.

  The present inventor has focused on the relationship between flame retardancy and weight reduction in the foam structure, and as a result of further studies, the foam with a filler dispersed in a matrix resin having a three-dimensional structure has a maximum heat generation rate ratio. It has been found that it becomes an index indicating the balance between flame retardancy and weight reduction. As a result of further diligent research based on such knowledge, it was found that the balance between flame retardancy and weight reduction was improved by setting the maximum heat generation rate ratio to a predetermined value or less, and the present invention was completed.

According to the present invention,
A foam in which a filler is dispersed in a matrix resin having a three-dimensional structure,
The maximum heat generation amount of the non-foamed resin molded body containing the matrix resin and the filler, where V1 is the maximum heat generation rate of the foam, measured by a heat release test according to FAR 25.853 (Appendix F, Part IV). When the speed is V2,
A foam having a maximum heat generation rate ratio (V1 / V2) of 0.9 or less is provided.

Also according to the invention,
A method for producing a foam for producing the foam,
Preparing a slurry in which a thermosetting resin, a filler, and a thermally expandable microcapsule are mixed, and obtaining the foamed paper by making the slurry; and
The foamed paper product is disposed by disposing the foamed paper product in a part of the inside of the mold, expanding the thermally expandable microcapsule, and expanding the foamed paper product to the entire interior of the mold. And a step of obtaining a foam made of the molded article.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the foam and the foam excellent in the balance of a flame retardance and weight reduction are provided.

It is a perspective schematic diagram which shows an example of the foamable papermaking concerning this embodiment. It is a cross-sectional schematic diagram which shows an example of the manufacturing method of the foamable papermaking concerning this embodiment. It is a cross-sectional schematic diagram which shows an example of the manufacturing method of the foam which concerns on this embodiment.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same reference numerals are given to the same components, and the description will be omitted as appropriate.

The outline of the foam of this embodiment will be described.
The foam of this embodiment is a foam in which a filler is dispersed in a matrix resin having a three-dimensional structure.
In the foam of this embodiment, the maximum heat generation rate of the foam measured by a heat release test in accordance with FAR 25.853 (Appendix F, Part IV) is V1, and the foam-free resin includes a matrix resin and a filler. When the maximum heat generation rate of the molded body is V2, the maximum heat generation rate ratio (V1 / V2) can be 0.9 or less.

  Here, aircraft interior materials mounted on US-based aircraft meet the very strict combustion standards specified by FAR 25.853 (United States Federal Aircraft Materials Test) specified by FAA (United States Federal Aviation Administration). There is a need. In addition, aircraft members mounted in aircraft are also required to satisfy this combustion standard.

As a result of studying the flame retardancy according to such advanced flame retardancy standards, the present inventor has come to focus on the relationship between flame retardancy and weight reduction in the foam structure. As a result of further studies, it has been found that the maximum heat generation rate ratio is an index indicating a balance between flame retardancy and weight reduction in a foam in which a filler is dispersed in a matrix resin having a three-dimensional structure.
That is, it has been found that the balance between flame retardancy and weight reduction of a foam can be evaluated by indicating the flame retardancy of the foam relative to the non-foamed molded article.
As a result of further diligent research based on such knowledge, it was found that the balance between flame retardancy and weight reduction was improved in the foam structure by setting the maximum heat generation rate ratio to a predetermined value or less, and the present invention was completed. It came to do.

  According to this embodiment, the foam excellent in the balance of a flame retardance and weight reduction is realizable.

  Hereinafter, the foam of this embodiment will be described in detail.

  The foam of this embodiment has a structure in which a filler is dispersed in a matrix resin having a three-dimensional structure. In the present embodiment, the matrix resin having a three-dimensional structure may be composed of, for example, a cured resin having a three-dimensional network structure. Examples of the cured resin include a cured product of a thermosetting resin. Moreover, as said filler, a fiber filler can be used, for example.

In the foam of this embodiment, the maximum heat generation rate of the foam is V1, and the maximum heat generation rate of the matrix resin made of a material obtained by removing the foaming agent from the foam is V2.
The maximum heat generation rates V1 and V2 are measured by a heat release test based on FAR25.853 (Appendix F, Part IV).

  In the present embodiment, the non-foamed resin molded body (non-foamed body) can include a matrix resin and a filler. That is, the non-foamed body may be configured using a matrix resin made of a material obtained by removing the foaming agent from the foamed body. As a non-foamed material which becomes a reference in the heat release test, for example, a resin molded body (cured body) containing the matrix resin and filler of the same type as the foamed material can be used. The non-foamed body may be composed of the same type of member (same kind of matrix resin, filler, additive, etc.) used for the foam, excluding the foaming agent, and has the same shape and volume. Also good. Such a non-foamed body may have a configuration in which voids of the foamed body are embedded with a matrix resin. In this embodiment, as an example of a non-foamed body, it is composed of the same type of material as the foam to be compared, and the weight ratio of the other materials excluding the matrix resin is the same, and the volume voids of the foamed body You may use what increased the volume of the matrix resin by the rate.

  In the present embodiment, the upper limit value of the maximum heat generation rate ratio (V1 / V2) is, for example, 0.9 or less, preferably 0.8 or less, and more preferably 0.7 or less. Thereby, a flame retardance can be improved, implement | achieving weight reduction. The lower limit value of the maximum heat generation rate ratio (V1 / V2) is not particularly limited, but may be, for example, 0.1 or more, 0.15 or more, or 0.2 or more. Thereby, the balance of a flame retardance and weight reduction can be improved.

Further, the upper limit value of the maximum heat generation rate V1 of the foam of the present embodiment is not particularly limited, but is, for example, 100 kW / m ² or less, preferably 90 kW / m ² or less, and more preferably 80 kW / m ^2. It is as follows. Thereby, a flame retardance can be improved, implement | achieving weight reduction. Further, the lower limit value of the maximum heat generation rate V1 of the foam is not particularly limited, but may be, for example, 10 kW / m ² or more, 15 kW / m ² or more, or 20 kW / m ² or more. Thereby, the balance of a flame retardance and weight reduction can be improved.

In the present embodiment, the heat generation after 2 minutes of the foam is H1, and the heat generation after 2 minutes of the non-foamed resin molded body containing the matrix resin and the filler is H2.
At this time, the upper limit of the calorific value ratio (H1 / H2) after 2 minutes is, for example, 0.9 or less, preferably 0.8 or less, and more preferably 0.7 or less. Thereby, a flame retardance can be improved, implement | achieving weight reduction. Moreover, the lower limit of the calorific value ratio (H1 / H2) after 2 minutes is not particularly limited, but may be, for example, 0.3 or more, 0.4 or more, or 0.5 or more. Thereby, the balance of a flame retardance and weight reduction can be improved.

In addition, the upper limit value of the calorific value H1 after 2 minutes of the foam of the present embodiment is not particularly limited, but is, for example, 90 kW · min / m ² or less, preferably 80 kW · min / m ² or less, More preferably, it is 70 kW · min / m ² or less. Thereby, a flame retardance can be improved, implement | achieving weight reduction. Further, the lower limit value of the calorific value H1 after 2 minutes of the foam is not particularly limited, but may be, for example, 10 kW · min / m ² or more, 20 kW · min / m ² or more, or 30 kW · min / m. ^Two or more may be sufficient. Thereby, the balance of a flame retardance and weight reduction can be improved.

  Moreover, it is preferable that the foam of this embodiment has the said maximum heat generation rate and the emitted-heat amount after the said 2 minutes from a viewpoint used for an aircraft component. With such a foam, an aircraft component having an excellent balance between flame retardancy and weight reduction can be realized.

  The lower limit value of the volume porosity of the foam of the present embodiment is, for example, preferably 5% or more, more preferably 10% or more, and further preferably 15% or more. Thereby, a flame retardance and weight reduction can be improved. On the other hand, the upper limit value of the volume porosity of the foam may be, for example, 90% or less, 80% or less, or 70% or less. Thereby, the balance between flame retardancy and strength can be improved.

  In the present embodiment, the method for measuring the volume porosity of the foam is not particularly limited, but can be calculated by, for example, image analysis. Specifically, the following measuring method can be used. That is, first, the vicinity of the center of the foam is cut out. The image of the cross-section of the cut foam was binarized, and the area ratio between the matrix phase composed of a matrix resin such as a thermosetting resin and the cellular phase composed of bubbles was expressed as volume porosity (foam material volume after foam molding). Fraction (volume%)).

The foam structure of the foam of this embodiment may have a closed cell structure or an open cell structure. In the foam of the present embodiment, the whole may have a closed cell structure from the viewpoint of balance between strength and flame retardancy, and from the viewpoint of balance between weight reduction, flame retardancy and strength, closed cell structure. In addition, some of them may have an open cell structure.
In this embodiment, the closed cell structure means a structure having a plurality of spaces (bubbles) isolated from the outside by a cured body of a thermosetting resin. In such a closed cell structure, since gas is suppressed from passing between adjacent spaces, a structure having excellent airtightness can be realized.

  When the foam of this embodiment has a closed cell structure, the lower limit of the size of the bubble in the closed cell structure is not particularly limited, but may be, for example, 5 μm or more, or 10 μm or more. On the other hand, the upper limit value of the bubble size is not particularly limited, but may be, for example, 500 μm or less, or 400 μm or less.

Further, the lower limit value of the density of the foam of the present embodiment may be, for example, 0.1 g / cm ³ or more, 0.2 g / cm ³ or more, or 0.3 g / cm ³ or more. Thereby, the balance between strength and weight reduction can be achieved. On the other hand, the upper limit of the density of the foam is, for example, 1.6 g / cm ³ or less, preferably 1.55 g / cm ³ or less, 1.5 g / cm ³ or less is more preferable. Thereby, the balance of weight reduction and a flame retardance can further be improved.

The lower limit value of the specific strength indicating the tensile strength per density at room temperature of the foam of the present embodiment may be, for example, 50 MPa / (g / cm ³ ) or more, or 60 MPa / (g / cm ³ ) or more. 70 MPa / (g / cm ³ ) or more. Thereby, intensity | strength and weight reduction can be improved. On the other hand, the upper limit of the specific strength is not particularly limited, for ^{example, 200MPa / (g / cm 3} ) may be ^{less, 180MPa / (g / cm 3} ) may be less, 150MPa / (g / cm ³ ) The following may be used. Thereby, a balance between flame retardancy and strength can be achieved. The tensile strength can be measured, for example, at room temperature (25 ° C.) with a tensile tester (Tensilon Universal Material Tester, manufactured by A & D).

Further, the lower limit value of the specific bending strength indicating the bending strength per density of the foam of the present embodiment is not particularly limited, but may be, for example, 50 MPa / (g / cm ³ ) or more, and 70 Pa / (g / cm ^3). ) Or more. The upper limit value of the specific bending strength indicating the bending strength per density of the foam is not particularly limited. For example, it may be 300 MPa / (g / cm ³ ) or less, or may be 280 Pa / (g / cm ³ ) or less. Good. Thereby, the foam excellent in the balance of a flame retardance, a shapeability, and weight reduction is realizable. The bending strength can be measured according to JIS K6911 at room temperature (25 ° C.).

Further, the foam specific modulus showing a flexural modulus per density at room temperature of the present embodiment is not particularly limited, for example, it can be a 2GPa / (g / cm ³⁾ or more, 3GPa / (g / cm ³ ) Or more. Moreover, the specific elastic modulus showing the bending elastic modulus per density at room temperature of the foam is not particularly limited, but may be, for example, 30 GPa / (g / cm ³ ) or less, or 25 GPa / (g / cm ³ ) or less. Good. Thereby, the foam excellent in the balance of a flame retardance, a shapeability, and weight reduction is realizable. The bending elastic modulus can be measured according to JIS K6911 at room temperature (25 ° C.).

  The lower limit value of the glass transition temperature (Tg) of the foam of the present embodiment may be, for example, 100 ° C. or higher, preferably 120 ° C. or higher, and more preferably 150 ° C. or higher. Thereby, heat resistance can be improved and it can be used for the place where heat history, such as a heat-generating member, arises, for example. On the other hand, the upper limit value of the glass transition temperature (Tg) of the foam is not particularly limited, but may be, for example, 350 ° C. or less. The glass transition temperature (Tg) can be measured by, for example, a differential scanning calorimeter (DSC-2920, manufactured by TA Instruments).

  Moreover, the foam of this embodiment may be comprised entirely or partially by the molded object of a foamable papermaking body. In the present embodiment, from the viewpoint of production stability, it is preferable that the entire foam is composed of a foamed paper product (foamed product).

Hereinafter, the foamable papermaking product and the foamed molded product of this embodiment will be described.
<Foaming paper 10>
FIG. 1 is a schematic perspective view showing an example of the foamable papermaking product 10 of the present embodiment.
The foamable papermaking body 10 of the present embodiment is a papermaking body in which the thermally expandable microcapsules C are dispersed.

  Here, in the present specification, the term “papermaking” is generally used as a technical term indicating the state of an object obtained by using a method of spreading a fiber material. Regarding the state of this thing, it describes in the patent gazette 1 (patent 4675276) and the patent gazette 2 (patent 5426399), for example. According to the document, the papermaking product is described as a wet solid content remaining on a filter after a liquid component is dehydrated from a raw material slurry in which raw materials such as fibers and resins are dispersed in a dispersion medium. ing. The said wet state here means the uncured state before performing heat processing, ie, the uncured state before post-cure.

  In the present embodiment, the foamable paper-making body 10 may be a sheet shape or a three-dimensional shape processed into a shape imitating a desired molded product shape (that is, a shape of an element). And the molded object (foaming molded object 50) can be obtained by performing foam molding, such as heat processing, with respect to this foamable papermaking body 10. FIG. The foamed molded body 50 is a cured product of the foamable papermaking body 10.

The foamable papermaking body 10 according to the present embodiment is obtained by a papermaking method.
As shown in FIG. 1, the foamable papermaking body 10 obtained by the papermaking method has structural features 1 to 3 in the following points.
(Feature 1) The fiber filler B and the thermally expandable microcapsule C are randomly oriented in a plan view of the surface of the foamable papermaking body 10.
(Characteristic 2) In the cross-sectional view in the thickness direction of the foamable papermaking product 10, the orientation state of the fiber filler B is highly controlled, and the fiber filler B is oriented in a specific direction. In other words, the fiber filler B is in a laminated state in the thickness direction of the foamable papermaking product 10.
(Feature 3) The fiber fillers B are bound by the binder resin A.
As described above, in the foamable papermaking product 10 shown in FIG. 1, the binder resin A, the fiber filler B, and the thermally expandable microcapsule C are entangled randomly in the surface direction, and such a surface structure overlaps in the thickness direction. It has such a papermaking structure.

In addition, the foamable papermaking body 10 can be used as a material for obtaining a foamed molded body 50 by molding into a desired shape by foaming treatment.
The resin in the foamable papermaking product 10 is not completely cured, for example, in a B stage state. Therefore, the foamable papermaking product 10 can be deformed into another shape. And the foaming paper-making body 10 can obtain the foaming molding 50 by foaming and complete-hardening resin by heating at the curing temperature of binder resin A which is a thermosetting resin.

Subsequently, the component which comprises the foamable papermaking body 10 is demonstrated.
(Binder resin A)
The binder resin A is not particularly limited as long as it functions as a binder that connects the fiber fillers B, but for example, a thermosetting resin can be used.
As said thermosetting resin, a phenol resin, an epoxy resin, unsaturated polyester resin, a melamine resin, a polyurethane resin etc. are mentioned, for example. These resins can be appropriately selected and used as necessary, and one kind may be used alone, or two or more kinds may be used in combination.
From the viewpoint of mechanical properties and heat resistance, it is preferable to use at least one of a phenol resin and an epoxy resin. Moreover, it is preferable to use a phenol resin from a viewpoint of coexistence in the dimension in weight reduction and a high dimension of strength.

  The thermosetting resin may have a granular or powdery shape. Thereby, the intensity | strength of the foaming molding 50 obtained by foaming and hardening the foamable papermaking body 10 can be improved more effectively. Although the reason for this is not clear, when the foamable papermaking product 10 is heated and pressurized to foam, the thermosetting resin has a granular or powdery shape, so that the impregnation property of the thermosetting resin at the time of melting is improved. It is estimated that the interface between the fiber filler B and the thermosetting resin is well formed.

As the thermosetting resin, for example, one having an average particle size of 500 μm or less and a solid state at room temperature can be used. Thereby, in the manufacturing process of the foamable papermaking body 10, it can make it easy to form the aggregation state of a thermosetting resin. Moreover, in the manufacturing process of the foamable papermaking body 10, from the viewpoint of obtaining a varnish-like material composition, the average particle size of the thermosetting resin is more preferably 1 nm or more and 300 μm or less.
The thermosetting resin having such an average particle diameter can be obtained by performing a pulverization process using, for example, an atomizer pulverizer.
The average particle size of the thermosetting resin is determined, for example, by using a laser diffraction particle size distribution measuring device such as SALD-7000 manufactured by Shimadzu Corporation as the average particle size based on a 50% particle size. Can do.

  The thermosetting resin contained in the foamable papermaking product 10 is preferably in a semi-cured state. The semi-cured thermosetting resin is completely cured in the process of producing the foamable paper product 10 and then foaming it into a desired shape by heating and pressurizing. Thereby, the foaming molding 50 excellent in the balance of high intensity | strength and weight reduction is obtained.

(Fiber filler B)
The fiber filler B is obtained by cutting a fiber yarn or a long fiber bundle into a predetermined length.
The average fiber length of the fiber filler B is preferably 0.1 mm or more from the viewpoint of obtaining a special structure by papermaking, more preferably 2 mm or more, and 2.5 mm or more from the viewpoint of obtaining mechanical strength. It is more preferable that it is 4 mm or more. On the other hand, from the viewpoint of obtaining good dispersibility, it is preferably 20 mm or less, more preferably 15 mm or less, and further preferably 12 mm or less.

  Examples of the fiber filler B include glass fiber, carbon fiber, metal fiber, ceramic fiber, wholly aromatic polyamide (aramid), wholly aromatic polyester, wholly aromatic polyester amide, wholly aromatic polyether, wholly aromatic polycarbonate, Totally aromatic polyazomethine, polyphenylene sulfide (PPS), poly (para-phenylenebenzobisthiazole) (PBZT), polybenzimidazole (PBI), polyetheretherketone (PEEK), polyamideimide (PAI), polyimide, polytetra Examples include fluoroethylene (PTFE) and poly (para-phenylene-2,6-benzobisoxazole) (PBO). These fiber fillers B can be appropriately selected and used as necessary, and one kind may be used alone, or two or more kinds may be used in combination.

  Further, from the viewpoint of achieving a balance between weight reduction and strength, inorganic fibers may be used, and glass fibers may be preferably used. Moreover, when using glass fiber, you may use what gave the aminosilane process. The aminosilane treatment is performed by impregnating glass fibers with an amino group-containing silane coupling agent solution, or by applying an amino group-containing silane coupling agent solution to glass fibers.

  Examples of amino group-containing silane coupling agents include N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, and γ-aminopropyl. Methyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β An amino group-containing alkoxysilane such as (aminoethyl) -γ-aminopropylmethyldiethoxysilane, and hydrolysates thereof. These amino group-containing silane coupling agents may be used alone or in combination of two or more.

  From the viewpoint of increasing strength, the content of the fiber filler B may be, for example, 10% by weight or more, or 20% by weight or more with respect to the binder resin A (thermosetting resin). From the viewpoint of balancing strength and weight reduction, for example, the binder resin A (thermosetting resin) may be 80% by weight or less, 75% by weight or less, or 70% by weight or less. It may be 50% by weight or less.

(Thermal expansion microcapsule C)
The thermally expandable microcapsule C is a particle obtained by microencapsulating a volatile liquid foaming agent with a thermoplastic shell polymer having a gas barrier property. The thermally expandable microcapsule C functions as a foaming agent by the following mechanism. That is, while the outer shell of the capsule is softened by heating, the liquid foaming agent contained in the capsule is vaporized and the pressure is increased. As a result, the particles expand and hollow spherical particles (foamed particles of the thermally expandable microcapsule C) are formed.

Examples of the liquid blowing agent include low-boiling hydrocarbons such as isopentane, isobutane, and isopropane.
Examples of the thermoplastic shell polymer include polyacrylonitrile, vinylidene chloride-acrylonitrile copolymer, vinylidene chloride-methyl methacrylate copolymer, vinylidene chloride-ethyl methacrylate, acrylonitrile-methyl methacrylate copolymer, acrylonitrile-ethyl methacrylate, and the like. Can be mentioned. These may be used alone or in combination of two or more.

  Examples of the thermally expandable microcapsule C include commercially available products such as EXPANSEL (manufactured by Nippon Philite), Microsphere F50, Microsphere F60 (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.), Advancel EM (manufactured by Sekisui Chemical Co., Ltd.). Product can be used.

  The content of the heat-expandable microcapsule C may be 0.05% by weight or more with respect to the binder resin A (thermosetting resin) from the viewpoint of reducing the density of the foamed molded body 50, and 0.1% by weight. % Or more. Further, from the viewpoint of expressing an appropriate strength of the foamed molded product 50, it may be 10% by weight or less or 5% by weight or less with respect to the binder resin A (thermosetting resin).

  In addition, the foamable papermaking body 10 in this embodiment can contain components, such as a pulp, a flocculant, and various additives other than the said component.

(pulp)
The foamable papermaking body 10 of the present embodiment may include pulp. Pulp is a fiber material having a fibril structure and is different from the fiber filler B. Pulp can be obtained, for example, by mechanically or chemically fibrillating the fiber material.
Since the pulp can be made together with the binder resin A, the fiber filler B, and the heat-expandable microcapsule C at the time of manufacturing the foamable papermaking product 10, these can be more effectively aggregated, and thus more stable foaming. It becomes possible to realize manufacture of the papermaking body 10.

  Examples of the pulp include cellulose fibers such as linter pulp and wood pulp, natural fibers such as kenaf, jute and bamboo, para-type wholly aromatic polyamide fibers (aramid fibers) and copolymers thereof, aromatic polyester fibers, poly Examples include fibrillated organic fibers such as benzazole fibers, meta-type aramid fibers and copolymers thereof, acrylic fibers, acrylonitrile fibers, polyimide fibers, and polyamide fibers. Pulp may be used individually by 1 type and may use 2 or more types together.

  The content of the pulp may be 0.5% by weight or more, 1% by weight or more, or 2% by weight or more with respect to the binder resin A (thermosetting resin). Thereby, aggregation of the thermosetting resin at the time of papermaking can be generated more effectively, and further stable production of the foamable papermaking body 10 can be realized. On the other hand, the pulp content may be 10% by weight or less, 8% by weight or less, or 5% by weight or less with respect to the binder resin A (thermosetting resin). Thereby, it becomes possible to improve the mechanical characteristic and thermal characteristic of the foaming molding 50 more effectively.

(Flocculant)
The foamable papermaking body 10 of the present embodiment may include a flocculant. The aggregating agent has a function of aggregating the binder resin A, the fiber filler B, and the thermally expandable microcapsule C in the form of a flock when the foamable papermaking product 10 is manufactured. For this reason, manufacture of the more stable foamable papermaking body 10 is realizable.

  Examples of the flocculant include cationic polymer flocculants, anionic polymer flocculants, nonionic polymer flocculants, and amphoteric polymer flocculants. More specifically, for example, cationic polyacrylamide, anionic polyacrylamide, Hoffman polyacrylamide, mannic polyacrylamide, amphoteric copolymerized polyacrylamide, cationized starch, amphoteric starch, polyethylene oxide and the like can be mentioned. These flocculants may be used individually by 1 type, and may use 2 or more types together. In the flocculant, the polymer structure and molecular weight, the amount of functional groups such as hydroxyl groups and ionic groups, and the like can be adjusted according to the required characteristics.

  The content of the flocculant is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, and 0.1% by weight with respect to the binder resin A (thermosetting resin). It is still more preferable that it is above. Thereby, in manufacture of the foamable papermaking body 10, the improvement of a yield can be aimed at. On the other hand, the content of the flocculant is preferably 1.5% by weight or less, more preferably 1% by weight or less, and more preferably 0.5% by weight with respect to the binder resin A (thermosetting resin). More preferably, it is as follows. Thereby, in manufacture of the foamable papermaking body 10 using a papermaking method, it becomes possible to perform a dehydration process etc. more easily and stably.

  The foamable papermaking body 10 in the present embodiment can further use various additives for the purpose of adjusting production conditions and expressing required physical properties. For example, thermoplastic resins, inorganic powders for improving properties, metal powders, stabilizers such as antioxidants and UV absorbers, flame retardants, mold release agents, plasticizers, resin curing catalysts and accelerators, pigments , Dry paper strength improver, wet strength strength improver, yield improver, drainage improver, size fixer, rosin sizing agent for acidic papermaking, rosin sizing agent for neutral papermaking, alkyl Examples thereof include sizing agents such as ketene dimer sizing agents, alkenyl succinic anhydride sizing agents and specially modified rosin sizing agents, and coagulants such as sulfuric acid bands, aluminum chloride and polyaluminum chloride.

  The foamable papermaking body 10 of this embodiment may have aramid microfibers as an additive. Thereby, the handleability of the papermaking body which dried the foaming papermaking body 10 can be made favorable.

<Method for Producing Foamable Paper 10>
FIG. 2 is a schematic cross-sectional view showing the manufacturing process of the foamable papermaking product 10.
The method for producing the foamable paper product 10 of the present embodiment is to mix the binder resin A, the fiber filler B, and the thermally expandable microcapsule C, and then paper the mixture by a papermaking method to produce the foamable paper product 10. A process of obtaining. Here, the papermaking method uses a papermaking technique which is one of papermaking techniques as shown in FIG.

  Hereinafter, with reference to FIG. 2, the manufacturing method of the foamable papermaking body 10 by a wet papermaking method is explained in full detail.

  First, as shown to Fig.2 (a), binder resin A, the fiber filler B, and the heat | fever expansible microcapsule C are added to a solvent, and it stirs, mixes, and disperses. At this time, you may add other components except a flocculant among the components mentioned above in a solvent. Thereby, the varnish-like material composition (slurry) for forming the foamable papermaking body 10 can be obtained.

  A method of dispersing each component in a solvent is not particularly limited, and examples thereof include a method of stirring using a disperser.

The solvent is not particularly limited, but it is difficult to volatilize in the process of dispersing the constituent materials of the material composition, and it is easy to remove the solvent in order to suppress remaining in the foamed papermaking product. From the standpoint of suppressing the increase in energy due to, the one having a boiling point of 50 ° C. or higher and 200 ° C. or lower is preferable.
Examples of the solvent include alcohols such as water, ethanol, 1-propanol, 1-butanol and ethylene glycol, ketones such as acetone, methyl ethyl ketone, 2-heptanone and cyclohexanone, ethyl acetate, butyl acetate, methyl acetoacetate, Examples thereof include esters such as methyl acetoacetate and ethers such as tetrahydrofuran, isopropyl ether, dioxane and furfural. These solvents may be used alone or in combination of two or more. Among these, it is more preferable to use water because the supply amount is abundant, the cost is low, the environmental load is low, the safety is high, and the handling is easy.

  Subsequently, a flocculant may be further added to the obtained slurry. Thereby, it becomes easier to obtain the aggregate F formed by aggregating the binder resin A, the fiber filler B, and the thermally expandable microcapsule C in the solvent in a floc form (FIG. 2B).

  Then, the foamable papermaking body 10 can be obtained by papermaking the slurry which mixed the binder resin A, the fiber filler B, the thermally expansible microcapsule C, etc. with a filter.

Specifically, as shown in FIG. 2B, the above-described slurry is introduced into a container provided with a mesh 30 (filter) having a sheet-like bottom surface. Then, the solvent in the slurry is passed through the mesh 30 and discharged out of the container, and the aggregate F in the slurry is left on the mesh 30 (filter). Thereby, the aggregate F and the solvent can be separated from each other.
Here, by appropriately selecting the shape of the mesh 30, it is possible to adjust the shape of the foamable paper product to be obtained.
Thereafter, the agglomerate F obtained on the filter (mesh 30) may be subjected to a drying treatment, for example, in a drying furnace to further remove the solvent remaining in the agglomerate F.
As described above, the foamable papermaking product 10 shown in FIG. 2C is manufactured.

By using a papermaking method as shown in FIG. 2 (b), the foamable papermaking body 10 is formed along the surface of the filter. Such a foamable papermaking body 10 has a structure in which fiber fillers B entangled randomly in the plane direction are laminated in the thickness direction. By having a structure in which the fiber fillers B are entangled, it is possible to obtain a foamable papermaking product 10 that is lightweight but has excellent strength.
Further, by using the papermaking method, the dispersion of the thermally expandable microcapsules C in the foamable papermaking product 10 can be increased.

<Foamed molded product 50>
The foamed molded product 50 of the present embodiment is a molded product of the foamable papermaking product 10 and has a cell structure in which bubbles D formed by foaming the thermally expandable microcapsules C are dispersed in the molded product.

<Method for Manufacturing Foam Molded Body 50>
The manufacturing method of the foaming molding 50 of this embodiment prepares the slurry which mixed the thermosetting resin (binder resin A), the filler (fiber filler B), and the thermally expansible microcapsule C, and forms this slurry. A step of obtaining the foamable papermaking product 10 by,
The foamable papermaking body 10 is disposed in a part of the inside of the molds 40 and 41, the thermally expandable microcapsule C is expanded, and the foamable papermaking body 10 is expanded to the whole inside of the molds 40 and 41. The process of obtaining the foam (foaming molding 50) which consists of a molding of the foamable papermaking body 10 by this can be included.

FIG. 3 is a schematic cross-sectional view showing an example of a method for producing a foam according to the present embodiment.
Hereinafter, with reference to FIG. 3, the manufacturing method of the foaming molding 50 is explained in full detail.

  First, as shown to Fig.3 (a), the foamable papermaking body 10 is arrange | positioned inside the metal mold | die 40,41 (metal mold cavity). At this time, the volume of the mold cavity including the mold 40 and the mold 41 is assumed to be larger than the volume of the foamable papermaking product 10. Thereby, the foamable papermaking body 10 which is a raw material can be arrange | positioned in the state which the inside of metal mold | die 40,41 is not completely filled, ie, what is called a short shot.

Next, foam molding is performed on the foamable papermaking product 10. For example, as shown in FIG. 3B, the heat-expandable microcapsule C is expanded by the heat treatment, and the foamable papermaking product 10 is expanded. The expanded foamed paper product 10 is filled in the entire mold cavity. At this time, the foamable papermaking product 10 is formed by the internal pressure (stress from the molds 40 and 41) due to the foaming of the thermally expandable microcapsule C, and the foamed molded product 50 is obtained. Thereby, it can shape | mold to the foaming molding 50 which has a predetermined shape.
In the above-described foam molding step, the curing reaction of the binder resin A proceeds, and a matrix resin having a three-dimensional structure (cured resin body having a three-dimensional network structure) is formed in the foam molded body 50. Further, the thermally expandable microcapsule C expands by the above heat treatment, and bubbles D (hollow spherical particles) are formed.
Thus, the foaming molding 50 of this embodiment can be manufactured by the short shot method. By using the short shot method, the foamable papermaking product 10 can be formed using the foaming pressure generated by the expansion of the bubbles of the thermally expandable microcapsule C.

  Although the said heat processing is not specifically limited, For example, it is good also as about 160-250 degreeC and about 10 to 30 minutes. In the manufacturing method of the foam molded body 50 of the present embodiment, the molding pressure is not applied from the outside, but the internal pressure in the molds 40 and 41 is, for example, about 1.5 to 5 MPa.

Here, an injection molding method etc. are mentioned as a method of applying a molding pressure from the outside. In this method, the thermally expandable microcapsule cannot be foamed due to the filling pressure or holding pressure, and the bubbles are destroyed.
On the other hand, in the manufacturing method of the foamed molded product 50 of this embodiment, since no molding pressure is applied from the outside, unexpanded of the thermally expandable microcapsule C and destruction of the bubbles D can be sufficiently suppressed. .

  In the present embodiment, the maximum heat generation rate ratio and the heat generation are appropriately selected by appropriately selecting the types and contents of the components in the foamable papermaking product 10 and the production methods of the foamable papermaking product 10 and the foamed molded product 50. It is possible to control the quantity ratio. Among these, for example, glass fiber is used as the fiber filler B, the dispersibility of the fiber filler B and the thermally expandable microcapsule C is improved by a papermaking method, and the expansion ratio and the bubble size are appropriately set by a short shot method. The control method and the like are listed as elements for setting the maximum heat generation rate ratio and the heat generation amount ratio in a desired numerical range. Further, as a method of increasing the expansion ratio by the short shot method, for example, the thermal expansion microcapsule C is increased, and the content of the matrix resin (binder resin A) and the content of the fiber filler B are decreased by the expansion ratio. Is mentioned.

  The foam of this embodiment can be used, for example, for components of transport aircraft such as aircraft and Shinkansen.

  As mentioned above, although embodiment of this invention was described with reference to drawings, these are the illustrations of this invention, Various structures other than the above are also employable.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail with reference to an Example, this invention is not limited to description of these Examples at all.

The materials used in the examples and comparative examples are as follows.
(Thermosetting resin)
Thermosetting resin 1: phenol resin (phenol resin, “PR51723”, manufactured by Sumitomo Bakelite Co., Ltd.)
(Filler)
Fiber filler 1: Glass fiber (chopped strand “CS3J 891”, manufactured by Nittobo Co., Ltd.)
Fiber filler 2: PAN-based carbon fiber (Tenax (registered trademark) HT C110, manufactured by Toho Tenax Co., Ltd., average fiber length 3 mm)
(Foaming agent)
Foaming agent 1: Thermally expandable microcapsule ("Advancel (registered trademark) EM-304", manufactured by Sekisui Chemical Co., Ltd.)
(Other additives)
Aramid microfiber 1: Aramid microfiber ("Tiara", manufactured by Daicel FineChem Co., Ltd.)

(Manufacture of foamable paper products)
<Examples 1-3>
(Manufacture of foamable paper products)
In Examples 1 to 3, foamable paper products were produced in the following manner at the blending ratios shown in Table 1 (raw material volume fraction [Vol%] after foaming).
First, a thermosetting resin pulverized to an average particle size of 100 μm (50% particle size based on mass) with an atomizer pulverizer, a filler, a foaming agent, and an additive are added to water, and 30 times with a disperser. Stir for minutes to give a mixture. Here, it added to 10000 weight part of water with respect to a total of 100 weight part of the constituent material which consists of a thermosetting resin, a filler, a foaming agent, and an additive.
Next, a flocculant (synthetic smectite: smecton (manufactured by Kunimine Kogyo Co., Ltd.)) dissolved in water in advance was added in an amount of 0.2% by weight based on the total of the constituent materials described above, and the constituent materials were aggregated in a floc form. .
Subsequently, the obtained agglomerates were separated from water with a 30 mesh metal net. Thereafter, the agglomerates remaining on the metal net were subjected to dehydration pressing, and further placed in a drier at 70 ° C. for 3 hours for drying to obtain a foamable paper product. The yield was 97%.
(Manufacture of foam)
In Examples 1 to 3, the foamable paper products obtained were placed in a 4 mm-thick mold and subjected to heat treatment at 180 ° C. for 10 minutes to produce foams made of foam-molded products. At this time, the internal pressure in the mold was 2 MPa. In Examples 1 to 3, foam molding was performed by the short shot method. The following evaluation was performed about the obtained foam. The results are shown in Table 1. In addition, the raw material volume fraction after foam molding of the foaming agent in Table 1 indicates the volume porosity of the foam.

<Comparative Examples 1-3>
(Manufacture of papermaking)
In Comparative Examples 1 to 3, paper products were produced in the following manner at the blending ratios shown in Table 1 (raw material volume fraction after compression molding [Vol%]).
First, a thermosetting resin pulverized to an average particle size of 100 μm (50% particle size based on mass) with an atomizer pulverizer, a filler, and an additive are added to water, and stirred for 30 minutes with a disperser. A mixture was obtained. Here, it added to 10000 weight part of water with respect to a total of 100 weight part of the constituent material which consists of a thermosetting resin, a filler, and an additive.
Next, a flocculant (synthetic smectite: smecton (manufactured by Kunimine Kogyo Co., Ltd.)) dissolved in water in advance was added in an amount of 0.2% by weight based on the total of the constituent materials described above, and the constituent materials were aggregated in a floc form. .
Subsequently, the obtained agglomerates were separated from water with a 30 mesh metal net. Thereafter, the agglomerates remaining on the metal net were subjected to dehydration pressing, and further placed in a drier at 70 ° C. for 3 hours for drying to obtain a papermaking product. The yield was 97%.
(Manufacture of non-foamed products)
In Comparative Examples 1 to 3, the obtained paper product was placed in a 4 mm-thick mold, subjected to heat treatment at 180 ° C. for 10 minutes, and a non-foamed product made of the paper product was produced by compression molding. did. At this time, the molding pressure was 10 MPa. The following evaluation was performed about the obtained non-foamed body. The results are shown in Table 1.

  In the said Table 1, the resin weight ratio of the foam of Examples 1-3 with respect to the non-foam of Comparative Examples 1-3 was 0.67, 0.72, and 0.69, respectively. Moreover, the sample weight ratio of Examples 1-3 with respect to the non-foamed material of Comparative Examples 1-3 was 0.80, 0.88, and 0.84, respectively. Here, the resin weight ratio means the weight ratio of the content of the thermosetting resin contained in the foam to the content of the thermosetting resin contained in the non-foamed body. The sample weight ratio (of all the components including the thermosetting resin and filler) means the weight ratio of the weight of the foam to the weight of the non-foam.

(Evaluation)
Density: measured by a method based on JIS K-7112 A method.
-Tensile strength: Measured by a method based on JIS K-7162.
Specific strength: Calculated by dividing the tensile strength by the density.
Density, tensile strength, and specific strength were measured at room temperature of 25 ° C.
The maximum heat generation rate, the heat generation amount for 2 minutes, and the heat generation amount for 5 minutes were measured by a heat release test according to FAR 25.853 (Appendix F, Part IV) using a test piece (150 mm × 150 mm × 1 mmt).

  It turned out that the foam of Examples 1-3 is excellent in the balance of a flame retardance and weight reduction. Moreover, as a result of performing cross-sectional observation of the foams of Examples 1 to 3, it was found that the foams had a closed cell structure. On the other hand, the non-foamed body (non-foamed resin molded body) of Comparative Examples 1 to 3 was found to have reduced flame retardancy.

  As described above, the present invention has been described more specifically based on the embodiments. However, these are exemplifications of the present invention, and various configurations other than the above can be adopted.

DESCRIPTION OF SYMBOLS 10 Expandable paper-making body 30 Mesh 40 Mold 41 Mold 50 Foam molded body A Binder resin B Fiber filler C Thermally expansible microcapsule D Bubble F Aggregate

Claims (13)

A foam in which a filler is dispersed in a matrix resin having a three-dimensional structure,
The maximum heat generation amount of the non-foamed resin molded body containing the matrix resin and the filler, where V1 is the maximum heat generation rate of the foam, measured by a heat release test according to FAR 25.853 (Appendix F, Part IV). When the speed is V2,
A foam having a maximum heat generation rate ratio (V1 / V2) of 0.9 or less. The foam according to claim 1,
When the heat generation amount after 2 minutes of the foam is H1, and the heat generation amount after 2 minutes of the non-foamed resin molding containing the matrix resin and the filler is H2, the heat generation ratio after 2 minutes ( A foam having a ratio H1 / H2) of 0.9 or less. The foam according to claim 1 or 2,
A foam in which the matrix resin includes a cured body of a thermosetting resin. The foam according to any one of claims 1 to 3,
Specific strength showing a tensile strength per density at room ^{temperature, 50MPa / (g / cm 3} ) or more 200MPa / (g / cm ³⁾ or less, foam. The foam according to any one of claims 1 to 4,
A foam having a density of 0.1 g / cm ³ or more and 1.6 g / cm ³ or less. The foam according to any one of claims 1 to 5,
A foam having a volume porosity of 5% or more and 90% or less. The foam according to any one of claims 1 to 6,
A foam having a closed cell structure. The foam according to any one of claims 1 to 7,
A foam in which the filler comprises a fiber filler. The foam according to any one of claims 1 to 8,
The filler is glass fiber, carbon fiber, metal fiber, ceramic fiber, wholly aromatic polyamide (aramid), wholly aromatic polyester, wholly aromatic polyester amide, wholly aromatic polyether, wholly aromatic polycarbonate, wholly aromatic poly Azomethine, polyphenylene sulfide (PPS), poly (para-phenylenebenzobisthiazole) (PBZT), polybenzimidazole (PBI), polyetheretherketone (PEEK), polyamideimide (PAI), polyimide, polytetrafluoroethylene (PTFE) ), A foam comprising at least one selected from the group consisting of poly (para-phenylene-2,6-benzobisoxazole) (PBO). The foam according to any one of claims 1 to 9,
A foam made of a molded body of foam paper. The foam according to any one of claims 1 to 10,
Foam used for aircraft components. The foam according to claim 3,
A foam in which the thermosetting resin contains an epoxy resin or a phenol resin. A method for producing a foam for producing the foam according to any one of claims 1 to 12,
Preparing a slurry in which a thermosetting resin, a filler, and a thermally expandable microcapsule are mixed, and obtaining the foamed paper by making the slurry; and
The foamed paper product is disposed by disposing the foamed paper product in a part of the inside of the mold, expanding the thermally expandable microcapsule, and expanding the foamed paper product to the entire interior of the mold. And a step of obtaining a foam comprising the molded article.

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