JP3781845B2 - Polymer material composite - Google Patents

Description

[0001]
[Industrial application fields]
The present invention relates to a polymer material composite in which a gap between fibers of a flexible sheet-like material composed of fibers is filled with a polymer blend material. More specifically, the spring characteristics can be easily controlled and the stability is improved. The present invention also relates to a polymer material composite that is excellent in workability and can be suitably used for building materials, vehicle interior materials, and the like.
[0002]
[Prior art]
Conventionally, examples of the sheet-like material used as a cushioning material for building materials, vehicle interior materials, and electrical products include sheets of foamed resin materials such as urethane foam, thick nonwoven fabrics, and three-dimensional fabrics. In order to improve the cushioning properties, it is necessary to soften the elastic body as a material, and a porous resin material or a gel-like substance having a large void is usually used.
[0003]
However, urethane foam with large voids is largely deformed with respect to the load, and sufficient cushioning properties cannot be obtained, and the gel-like substance has shape retaining properties but is not in the direction that originally requires cushioning properties. Since it is also flexible in the direction (for example, in the horizontal direction), there are disadvantages such as initial deformation at the time of load, sag during use, creep and the like. On the other hand, thick three-dimensional non-woven fabrics and woven fabrics have a problem in shape recovery when loaded under initial deformation and no load because the cushioning properties depend on the flexibility of the fiber material. . Furthermore, these sheet-like materials are limited in the selection of materials to be used, the manufacturing method such as the blending method and the knitting method, and it has been difficult to obtain the desired spring characteristics.
[0004]
[Problems to be solved by the invention]
As is apparent from the above description, the object of the present invention is to easily control the spring characteristics that can be suitably used for building materials, vehicle interior materials, electric cushions, etc., and workability during handling. It is an object of the present invention to obtain a polymer material composite excellent in stability without causing adverse effects such as settling and creep during use.
[0005]
[Means for Solving the Problems]
The inventors have disclosed a polymer blend material having a very low elastic modulus and excellent properties as described in JP-A-5-239256, and a flexible sheet material such as a thick three-dimensional nonwoven fabric or woven fabric. It was found that the notation problem can be solved by filling the voids in the above to form a composite, and the present invention has been completed.
[0006]
That is, the cushion material made of the polymer material composite of the present invention is made up of a flexible sheet material made of fibers and having voids inside, and a polymer material composite made of a polymer blend material. a cushion material, (1) polymer blends material comprises a low molecular weight material and a high molecular organic material, and is the weight ratio of low molecular weight material and a polymer organic material is 1.0 or more, ( 2) all formed inside the air gap of said flexible sheet-like material polymer blend material is filled, (3) said polymer blend on one surface of the flexible sheet-like material A surface layer made of only the material is formed.
[0007]
Here, as the flexible sheet-like material, at least two layers of knitted or woven fiber layers are connected to each other through a cushion yarn structure, and a part of the three-dimensional fiber sheet or fibers is bonded. A non-woven fabric having a three-dimensional structure formed in this manner is preferably exemplified.
[0008]
Furthermore, it is preferable that the high molecular organic material is a thermoplastic elastomer selected from a hydrogenated product of a butadiene polymer or a hydrogenated product of a butadiene-styrene copolymer.
[0009]
Thus, by filling the polymer blend material into the voids formed in the thick flexible sheet-like material, the thickness of the polymer blend material filled inside is reduced in the thickness direction. The shape retention of the flexible sheet-like material is expressed in the horizontal direction of the sheet while taking advantage of various properties including the elastic modulus, so that adverse effects such as settling and creep during use can be significantly reduced.
[0010]
In the present invention, a sheet made of only the polymer blend material is laminated on one surface of the flexible sheet-like material, and a composite in which the characteristics of the polymer blend material are emphasized can be easily obtained. A cushion material made of a polymer material composite having desired spring characteristics can be manufactured.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
[0012]
FIG. 1 shows a structure in which a polymer blend material is filled and cured in voids formed between fibers in a flexible sheet-like material in a polymer material composite of the present invention (hereinafter referred to as a composite as appropriate) . It is a schematic sectional drawing which shows the made part .
[0013]
The composite 10 has a polymer blend material 22 in a gap 20 formed between fibers in a flexible sheet-like material 18 in which two knitted fiber layers 12 and 14 are bonded to each other via a cushion yarn 16. Filled and cured. The polymer blend material 22 is filled in all the gaps 20 formed between the fibers, and the polymer blend material 22 is filled also in the thickness direction of the composite 10. In other words, this state can be said to be a state in which the sheet made of the polymer blend material 22 is impregnated with the flexible sheet material 18 as a reinforcing material.
[0014]
In this specific example, the flexible sheet-like material 18 is connected via the cushion yarn 16 that joins the two knitted fiber layers 12 and 14 to each other. Any flexible sheet-like material composed of fibers can be used as long as it has voids that can be filled with the polymer blend material. As this aspect, for example, at least two knitted or woven fiber layers are connected to each other via a cushion yarn structure, such as a sheet-like material described as a spacing textile material in JP-A-8-49142. Examples thereof include a sheet material such as a three-dimensional fiber sheet, a similar three-dimensional fiber sheet in which the fiber layer is a nonwoven fabric, and a three-dimensional fabric woven with an orthogonal structure or a plain weave structure.
[0015]
In the polymer material composite of the present invention, the polymer blend material described in JP-A-5-239256 is preferably exemplified as the polymer blend material filled in the gaps of the sheet-like material.
[0016]
Below, the said polymer blend material used suitably is demonstrated in detail. This polymer blend material includes a low molecular material and a high molecular organic material, the weight ratio of the low molecular material and the high molecular organic material is 1.0 or more, and the high molecular organic material is a three-dimensional continuous network. It has a skeleton structure. The low molecular weight material used for the polymer blend material is a material having a viscosity at 100 ° C. of 5 × 10 ⁵ centipoise or less, and preferably 1 × 10 ⁵ centipoise or less from the viewpoint of the effect. If it adds from a viewpoint of molecular weight, the number average molecular weight of a low molecular material is 20,000 or less, Preferably it is 10,000 or less from the point of an effect, More preferably, it is 5,000 or less. In general, a liquid or liquid material is suitably used at room temperature. Moreover, both hydrophilic and hydrophobic low molecular weight materials can be used.
[0017]
Any low molecular weight material can be used as long as it satisfies the above-mentioned conditions. Although not particularly limited, the following materials can be exemplified.
[0018]
(1) Softener: Softeners for various rubbers or resins such as mineral oils, vegetable oils, and synthetic oils. Examples of mineral oils include aromatic, naphthenic and paraffinic process oils. Examples of vegetable oils include castor oil, cottonseed oil, linseed oil, rapeseed oil, soybean oil, palm oil, palm oil, peanut oil, wax, pine oil, olive oil and the like. Examples of synthetic oils include aromatics.
[0019]
(2) Plasticizer: Phthalic acid ester, phthalic acid mixed ester, aliphatic dibasic acid ester, glycol ester, fatty acid ester, phosphoric acid ester, stearic acid ester, and other ester plasticizers, epoxy plasticizer, etc. Plasticizers for plastics or plasticizers for NBR such as phthalates, adipates, sebacates, phosphates, polyethers, and polyesters.
[0020]
(3) Tackifier: Tackifiers such as coumarone resin, coumarone-indene resin, phenol terpene resin, petroleum hydrocarbon, rosin derivative and the like.
[0021]
(4) Oligomer: Crown ether, fluorine-containing oligomer, polyisobutylene, xylene resin, chlorinated rubber, polyethylene wax, petroleum resin, rosin ester rubber, polyalkylene glycol diacrylate, liquid rubber (polybutadiene, styrene-butadiene rubber, butadiene- Acrylonitrile rubber, polychloroprene, etc.), silicone oligomers, various oligomers such as poly-α-olefins.
[0022]
(5) Lubricants: Hydrocarbon lubricants such as paraffin and wax, fatty acid lubricants such as higher fatty acids and oxy fatty acids, fatty acid amide lubricants such as fatty acid amides and alkylene bis fatty acid amides, fatty acid lower alcohol esters, fatty acid polyhydric alcohol esters Various lubricants such as ester lubricants such as fatty acid polyglycol esters, alcohol lubricants such as aliphatic alcohols, polyhydric alcohols, polyglycols and polyglycerols, metal soaps, and mixed lubricants.
[0023]
In addition, latex, emulsion, liquid crystal, bituminous composition, clay, inorganic silicon oil, phosphazene, and the like are also suitable as low molecular weight materials. Furthermore, animal oil such as cow oil, pig oil, horse oil, bird oil or fish oil: hydrocarbon, halogenated hydrocarbon, alcohol, phenol, ether, acetal, ketone, fatty acid, ester, Suitable organic solvents such as nitrogen compounds and sulfur compounds: petroleums, water, and aqueous solutions. These components may be used alone or in combination of two or more.
[0024]
Low molecular weight materials are selected and optimized by considering the required characteristics of laminated structures, vibration control applications, and compatibility with other organic polymer materials that are used in polymer compositions. Used in large quantities.
[0025]
The high molecular organic material used in the present invention is a material having a function of effectively holding a low molecular material and is an important component for achieving the object of the present invention. Specifically, in order to enable a uniform composition containing a large amount of low molecular weight material, a polymer blend material holding a large amount of low molecular weight material using a large amount of low molecular weight material and a smaller amount of high molecular weight organic material. This is used by filling the gaps between the fibers. Here, “holding” the low molecular weight material means that the low molecular weight material is uniformly dispersed in the three-dimensional continuous network skeleton structure formed by the polymer organic material, and does not bleed or bleed is suppressed. Means. Of course, depending on the purpose of the polymer blend material, the degree of bleeding can be easily controlled.
[0026]
The polymer organic material of the present invention can be used as long as it is a material that forms a polymer blend material having a function as described above and holds a large amount of low molecular weight materials, but is usually a thermoplastic polymer. Various materials having a material or this polymer material as a constituent element are used.
[0027]
As the polymer organic material, a thermoplastic polymer organic material having a number average molecular weight of 20,000 or more, particularly 30,000 or more, particularly 40,000 or more is preferable. For example, styrene-based (butadiene styrene-based, isoprene styrene-based, etc. ), Vinyl chloride-based, olefin-based (butadiene-based, isoprene-based, ethylene-propylene-based, etc.), ester-based, amide-based, urethane-based thermoplastic elastomers, and their hydrogenated products, other modified products, styrene , ABS, olefin (ethylene, propylene, ethylene propylene, ethylene styrene, propylene styrene, etc.), acrylate (methyl acrylate, etc.), methacrylate (methyl methacrylate, etc.) ), Carbonate, acetal, nylon Halogenated polyether (such as chlorinated polyether), halogenated olefin (such as vinyl chloride, tetrafluoroethylene, fluorinated-ethylene chloride, fluorinated ethylenepropylene), cellulose (acetylcellulose, ethylcellulose) Type), vinylidene type, vinyl butyral type, alkylene oxide type (propylene oxide type etc.), and rubber modified products of these resins. Of these, thermoplastic elastomers are preferably used from the viewpoint of effects.
[0028]
Among these, those in which hard blocks such as crystal structures and aggregate structures are easily formed and soft blocks such as amorphous structures are preferably combined together.
[0029]
The low molecular material and the high molecular weight organic material in the present invention are partially described in JP-A-5-239256 and JP-A-5-194663. As the polymer organic material, those described as a medium material having a three-dimensional continuous network skeleton structure disclosed in this publication are preferably used as representative materials in the present invention. Examples include a hydrogenated product, a hydrogenated product of a butadiene-styrene copolymer, and an ethylene-propylene copolymer. Among them, a hydrogenated product of a butadiene polymer and a hydrogenated product of a butadiene-styrene copolymer are more preferable. .
[0030]
The polymer blend material used in the composite of the present invention has a three-dimensional continuous network skeleton structure formed of a polymer organic material, and the average diameter of the skeleton is 50 μm or less, preferably 30 μm or less. The average diameter of (mesh) is 500 μm or less, preferably 300 μm or less, and the volume fraction of the polymer organic material is expressed as [volume of polymer organic material / (volume of polymer organic material + volume of low molecular material)] × When defined as 100 (%), the volume fraction of the polymer organic material is preferably 30% or less, particularly preferably 25% or less.
[0031]
The polymer organic material in the present invention is not particularly limited, but can be used in a normal bulk form, granular form, gel form, foam form, non-woven form, etc., but is in a gel form, in particular, a thermoplastic polymer. A gel-like material having a three-dimensional continuous uniform network skeleton structure is effective. Further, it can be used in a form in which a capsule containing a low molecular material is incorporated.
[0032]
Further, in obtaining a polymer blend material containing a large amount of a low molecular material and a high molecular organic material, the weight ratio of the low molecular material and the high molecular organic material is 1.0 or more, and is 2.0 or more in view of the effect. Is preferable, and 3.0 or more is more preferable. If the weight ratio is less than 1.0, it is difficult to obtain a polymer blend material having a very low elastic modulus, and the object of the present invention may not be achieved.
[0033]
As a method for producing a polymer blend material including a low molecular material and a high molecular organic material, an optimal method including a known method may be used depending on the kind, characteristics, mixing ratio, etc. of the low molecular material and the high molecular organic material to be used. There is no particular restriction. The method described in the above-mentioned JP-A-5-239256 is also one method.
[0034]
A particularly preferred method is to uniformly contain a large amount of low molecular weight material by kneading a thermoplastic high molecular material, which is a high molecular weight organic material, and a low molecular weight material using a high-shearing special mixer capable of performing high-speed stirring. In addition, there is a method of obtaining a low molecular material-holding polymer organic material composite in which the low molecular material is less bleed. As such a high shear type special mixer, in particular, a high shearing force and a high shearing speed can be given between the fixed wall and the rotating rotor, and the stirring speed is 300 rpm or more, preferably 500 rpm or more, Those having a stirring speed of 1000 rpm or more are preferable. Incidentally, when a high-molecular organic material and a low-molecular material are mixed at a low speed using a general roll, a rotor-type mixer, a cylinder-type mixer, etc., the object of the present invention can be achieved even if the same material is used. It is not possible to obtain a uniform three-dimensional continuous network skeleton structure of a polymer organic material having physical properties compatible with
[0035]
These polymer blend materials can be used in combination with rubber chemicals such as various vulcanization accelerators, anti-aging agents, and ultraviolet absorbers as required.
[0036]
If necessary, the polymer blend material of the present invention may further contain the following filler. For example, clay, diatomaceous earth, carbon black, silica, talc, barium sulfate, calcium carbonate, magnesium carbonate, metal oxide, mica, graphite, aluminum hydroxide and other scaly inorganic fillers, various metal powders, wood chips, Glass powder, ceramic powder, granular or powdered solid filler such as granular or powdered polymer, other various natural or artificial short fibers, long fibers (for example, straw, hair, glass fiber, metal fiber, various other polymer fibers) Etc.) can be blended.
[0037]
Moreover, weight reduction can be achieved by mix | blending an organic hollow filler which consists of hollow fillers, for example, inorganic hollow fillers, such as a glass balloon and a silica balloon, a polyvinylidene fluoride, a polyvinylidene fluoride copolymer, etc. Furthermore, in order to improve various physical properties such as weight reduction, various foaming agents can be mixed, and gas can be mixed mechanically during mixing.
[0038]
The polymer blend material used in the composite of the present invention has an advantage that the elastic modulus can be controlled to an extremely low range because it can hold a low molecular material such as a large amount of liquid.
[0039]
The polymer material composite of the present invention can be produced by a known method using the respective constituent materials. For example, a method in which a flexible sheet material is placed in a mold, and a polymer blend material in a molten state is injected and cured can be used.
[0040]
The polymer material composite of the present invention can be used in a wide range of industrial fields. In particular, since the spring characteristics can be easily controlled and a desired cushioning property can be obtained, the building material and the vehicle interior material can be obtained. It is suitably used for vehicle seats and cushioning materials for electrical products.
[0041]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the examples as long as the gist of the present invention is not exceeded.
[0042]
Various measurements were performed by the following methods.
The number average molecular weight was measured by gel permeation chromatography [GPC: Tosoh GMH-XL (two in series)], and the differential refractive index (RI) was used as a standard and in terms of polystyrene using monodisperse polystyrene.
[0043]
Tan δ was measured using a shear type dynamic viscoelasticity tester (manufactured by Toyo Seiki Co., Ltd.) at a temperature of 25 ° C., a strain of 10%, and a frequency of 5 Hz.
[0044]
The shear modulus was measured at 25 ° C. using a shear type dynamic viscoelasticity tester (manufactured by Toyo Seiki Co., Ltd.) at a temperature of 25 ° C.
[0045]
The viscosity and solubility parameters of the liquid were measured by conventional methods.
[0046]
( Reference Example 1)
As a flexible sheet-like material, a 30 cm square polyethylene spacing textile material having a thickness of 5 mm was prepared.
[0047]
88% by volume of polyisobutylene (Nisseki Polybutene, Nippon Petrochemical Co., Ltd., molecular weight 280) is used as the low molecular weight material, and a 2-block copolymer of polybutadiene and butadiene-styrene random copolymer is hydrogenated as the high molecular weight organic material. A high-shear type is obtained by using 12% by volume of a diblock copolymer of polyethylene and ethylene-styrene random copolymer (block polyethylene content 35% by weight, styrene content 12% by weight, number average molecular weight 110,000). The polymer blend material was obtained by mixing (120 ° C., 3,500 rpm) for 25 minutes with a mixer (TK auto homomixer: manufactured by Tokushu Kika Kogyo Co., Ltd.). When this composition was observed with an electron microscope, it was confirmed that it had a three-dimensional continuous network skeleton structure (cell diameter: 2 to 15 μm) and retained a low molecular weight material therein.
[0048]
The flexible sheet-like material is placed in a mold, and the resulting polymer blend material is poured into the mold to a height of 5 mm, filling the voids between the fibers of the sheet material, and then at room temperature. It was left to cure to obtain a polymer material composite.
[0049]
FIG. 1 is a schematic cross-sectional view of the composite 10 of Reference Example 1 . The polymer blend material 22 is filled and cured in the voids 20 formed between the fibers in the flexible sheet material 18, and the polymer blend is mixed in all the voids 20 in the horizontal direction and thickness direction of the flexible sheet material 18. A polymer material composite 24 having a thickness of 5 mm and filled with the material 22 was formed.
( Example 1 )
A polymer material composite was obtained in the same manner as in Reference Example 1 , except that a flexible sheet material was placed in the mold and the polymer blend material was injected into the mold to a height of 8 mm.
[0050]
FIG. 2 is a schematic cross-sectional view showing the composite 24 of the first embodiment. Thus, by increasing the injection amount of the polymer blend material, all of the voids 20 formed between the fibers in the flexible sheet material 18 are filled with the polymer blend material 22, and further, the flexibility A 8 mm thick polymer in which a surface layer 26 made of only the polymer blend material 22 is formed on one surface of the sheet-like material 18, that is, the surface covered with the injected polymer blend material. A cushion material 24 made of a material composite was formed.
(Example 2)
The surface of the flexible sheet material is the same as in Example 1 except that the flexible sheet material is placed in the mold and the polymer blend material is injected into the mold to a height of 10 mm. A cushion material made of a polymer material composite having a thickness of 10 mm was obtained, in which a surface layer having a thickness of about 5 mm made only of the polymer blend material was formed.
(Evaluation of spring characteristics)
A cushion material made of the polymer material composite obtained in Reference Example 1 and Examples 1 and 2 and, as a control, a cushion material made of a 5 mm thick sheet made of the polymer blend material used in Reference Example 1. FIG. 3 shows the result of measuring the spring characteristics in the direction perpendicular to the surface for the control example.
[0051]
The spring characteristic is the force and displacement when a composite or flexible sheet material cut to 40 mm × 40 mm is used as a sample and a cylindrical tip with a diameter of 50 mm is pressed against the sample surface at 10 mm / min. This is a measurement of the relationship. FIG. 3 is a graph showing the vertical spring characteristics of the cushion material made of the polymer material composite obtained in Reference Example 1 and Examples 1 and 2 and the cushion material made of the flexible sheet-like material of the control example. is there. As is clear from FIG. 3, the composite of the present invention exhibited excellent spring characteristics suitable for a cushioning material or the like with respect to the flexible sheet material of the control example. Also, a thin cushion material with easily controlled compression spring characteristics is provided by controlling the thickness of one surface layer by changing the injection condition of the polymer blend material by comparing Example 1 and Example 2. I understand that it is possible.
[0052]
【The invention's effect】
The polymer material composite of the present invention is easy to control the spring characteristics, has good workability during handling, has excellent stability without causing harmful effects such as settling and creep during use, It has the effect that it can be used suitably for a vehicle material, a vehicle interior material, a vehicle seat, an electrical product, and the like.
[Brief description of the drawings]
1 is a schematic cross-sectional view showing a polymer material composite of Reference Example 1. FIG.
FIG. 2 is a schematic cross-sectional view showing a polymer material composite of Example 1 having a polymer blend material layer on the surface.
FIG. 3 is a graph showing spring characteristics in the vertical direction of a sheet made of the polymer material composite obtained in Reference Example 1 and Examples 1 and 2 and a polymer blend material of a control example.

Claims (4)

A cushion material composed of a flexible sheet-like material having voids in the interior constituted by fibers, and a polymer material composite made of a polymer blend material,
(1) The polymer blend material includes a low molecular material and a high molecular organic material, and the weight ratio of the low molecular material and the high molecular organic material is 1.0 or more,
(2) The polymer blend material is filled in all the voids formed in the flexible sheet-like material,
(3) surface layer made of the one surface of the flexible sheet-like material only the polymeric blend material is formed,
A cushioning material comprising a polymer material composite. The flexible sheet-like material is a three-dimensional fiber sheet in which at least two knitted or woven fiber layers are connected to each other via a cushion yarn structure. Cushion material made of polymer material composite.   3. The polymer material composite according to claim 1, wherein the flexible sheet-like material is a nonwoven fabric having a three-dimensional structure formed by partially bonding fibers. 4. The high molecular organic material is a thermoplastic elastomer selected from a hydrogenated butadiene polymer or a hydrogenated butadiene-styrene copolymer. Cushion material made of polymer material composite.

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