Patent Application
20170072596
The present invention relates to a fiber-reinforced resin composition, which can provide a lightweight molded article with good mechanical properties; and a molded article obtained therefrom.
Resin molded articles are used as a metal substitute for the purpose of weight reduction, and in order to enhance their mechanical strengths, molding of a resin composition having a fiber blended therewith is known.
JP-A 2008-013693 discloses an invention on a long fiber-reinforced thermoplastic resin composition for automobile outer plate members obtained by blending 25 to 200 parts by weight of a reinforcement fiber relative to 100 parts by weight of a composition containing a thermoplastic polyurethane resin (TPU) and a styrene-based resin (SR) in a weight ratio (TPU/SR) of 20/80 to 90/10.
It discloses to contain, as a reinforcement fiber, at least one kind of fibers selected from the group consisting of inorganic fibers made of glass, carbon, silicon carbide, basalt or boron; metal fibers made of stainless steel; and organic fibers made of aramid, rayon, nylon, polynaphthalate, polyester, or cellulose, but in its Example, a filament glass fiber is used in a urethane-based resin.
JP-A 2008-202012 discloses an invention on a long fiber-reinforced thermoplastic resin composition obtained by blending 11 to 200 parts by weight of a reinforcement fiber relative to 100 parts by weight of a composition composed of a polycarbonate resin (PC) and a styrene-based resin (SR).
It discloses to contain, as a reinforcement fiber, at least one kind of fibers selected from the group consisting of inorganic fibers made of glass, carbon, silicon carbide, basalt or boron; metal fibers made of stainless steel; organic fibers made of aramid, rayon, nylon, polynaphthalate, or polyester; and cellulose fibers, but in its Example, a glass fiber is used.
JP-A 2013-91775 (WO-A1 2013/051369) discloses an invention on a fiber-reinforced resin composition, which includes a resin-impregnated fiber bundle of a thermoplastic resin and a rayon fiber, and it discloses that a molded article with a good mechanical strength can be obtained.
An object of the present invention is to provide a fiber-reinforced resin composition, which can provide a lightweight molded article with good mechanical properties, and a molded article obtained therefrom.
The present invention provides, in one aspect thereof, a fiber-reinforced resin composition, which contains a resin-adhered long fiber bundle including (A) a thermoplastic resin and (B) a rayon fiber, wherein:
the rayon fiber of the component (B) satisfies the following requirements (b1) and (b2); and
the resin-adhered long fiber bundle is obtained by adhering and integrating the thermoplastic resin of the component (A) in a molten state to and with a strand of longitudinally-arranged rayon fibers of the component (B), and then cutting the strand into a length of 3 to 30 mm,
Further, the present invention provides, in another aspect thereof, a fiber-reinforced resin composition, which contains a resin-adhered long fiber bundle including (A) a thermoplastic resin and (B) a rayon fiber, wherein:
Furthermore, the present invention provides, in yet another aspect thereof, a fiber-reinforced resin composition, which contains a resin-adhered long fiber bundle including (A) a thermoplastic resin and (B) a rayon fiber, wherein:
the rayon fiber as the component (B) satisfies the following requirements (b1), (b2) and (b3); and
the resin-adhered long fiber bundle is obtained by adhering and integrating the thermoplastic resin of the component (A) in a molten state to and with a strand of longitudinally-arranged rayon fibers of the component (B), and then cutting the strand into a length of 3 to 30 mm,
A molded article obtained from the composition of the present invention is lightweight and has an excellent mechanical property.
The present invention may be more completely understood by the following detailed description and the accompanying drawings, which are given only for explanation and do not limit the present invention.
The composition of the present invention contains a resin-adhered long fiber bundle (resin-adhered rayon long fiber bundle) containing a component (A) and a component (B), and may be composed only of the resin-adhered long fiber bundle, or may contain other component as necessary.
The resin-adhered long fiber bundle contained in the composition of the present invention is preferably either of the following (I) and (II),
Examples of the thermoplastic resin of the component (A) include a polyolefin-based resin, a polyamide-based resin, a styrene-based resin, a polycarbonate resin, polyvinyl chloride, polyvinylidene chloride, a polycarbonate-based resin, an acrylic resin, a methacrylic resin, a polyester-based resin, a polyacetal-based resin, and a polyphenylene sulfide-based resin.
As the thermoplastic resin of the component (A), preferable are those containing a resin selected from polyolefin-based resins and polyamide-based resins; and more preferable are those selected from polyolefin-based resins and polyamide-based resins.
As the polyolefin-based resin, usable are polypropylene; high-density, low-density and linear low-density polyethylenes; poly-1-butene; polyisobutylene; a copolymer of ethylene and propylene; ethylene-propylene-diene terpolymer (the diene component as a raw material being in an amount of 10% by mass or less); polymethylpentene; random, block, and graft copolymers of ethylene or propylene (50% by mole or more) with other copolymerizable monomer (vinyl acetate, an alkyl ester of methacrylic acid, an alkyl ester of acrylic acid, aromatic vinyl, etc.), and the like. Among these, preferable is polypropylene.
When a polyolefin-based resin is used as the component (A), an acid-modified polyolefin is preferably used together for easy impregnation into the rayon fiber strand of the component (B).
As the acid-modified polyolefin, preferable are maleic acid-modified polyolefin (maleic acid-modified polypropylene), and maleic anhydride-modified polyolefin (maleic anhydride-modified polypropylene).
When an acid-modified polyolefin is used together as the component (A), it is preferably blended such that an acid amount (amount of an acid contained in the acid-modified polyolefin in the component (A)) in the component (A) is in the range of 0.005 to 0.5% by mass on average in terms of maleic anhydride.
As the polyamide-based resin, preferable is one selected from aliphatic polyamides and aromatic polyamides.
Examples of the aliphatic polyamides include polyamide 6, polyamide 66, polyamide 69, polyamide 610, polyamide 1010, polyamide 612, polyamide 46, polyamide 11, polyamide 12, and the like.
Examples of the aromatic polyamides include those obtained from an aromatic dicarboxylic acid and an aliphatic diamine, and those obtained from an aliphatic dicarboxylic acid and an aromatic diamine, such as Nylon MXD (metaxylylenediamine and adipic acid), Nylon 6T (hexamethylenediamine and terephthalic acid), Nylon 61 (hexamethylenediamine and isophthalic acid), Nylon 9T (nonanediamine and terephthalic acid), Nylon M5T (methylpentadiamine and terephthalic acid), and Nylon 10T (decamethylenediamine and terephthalic acid).
Among these, preferable is an aliphatic polyamide such as polyamide 6, polyamide 69, polyamide 610, polyamide 612, polyamide 11, polyamide 12 and polyamide 1010.
The rayon fiber of the component (B) satisfies any combination selected from combinations of: requirements (b1) and (b2); requirements (b1) and (b3); and requirements (b1), (b2) and (b3).
When a rayon fiber satisfying the above requirements is used as the rayon fiber of the component (B), a molded article obtained from the composition has an improved mechanical strength.
With respect to the requirement (b1), the fiber diameter is 5 to 30 μm, preferably 6 to 20 μm, more preferably 7 to 15 μm. In this connection, when the rayon fiber of the component (B) has a cross section of a flat shape, the fiber diameter may be a number average fiber diameter obtained by converting the flat shape of cross section into a perfect circle with the same area as the shape of cross section. The fiber diameter can be calculated by an image analyzer from an image observed by an optical microscope.
With respect to the requirement (b2), the tensile elongation is preferably 10% or more, more preferably 10 to 20%, and further preferably 10 to 16%. The tensile elongation is measured by a method described in Examples.
With respect to the requirement (b3), the ratio between a major axis length and a minor axis length (major axis length/minor axis length) in a width-directional cross section is 1.1 or more, preferably 1.1 to 3.0, and more preferably 1.2 to 1.8. Major and minor axis lengths are measured by a method described in Examples.
In addition to each of the above requirements, a rayon fiber of the component (B) satisfying each of the following requirements may be used.
A rayon fiber has a tensile strength of preferably 35 MPa or more, more preferably 40 to 80 MPa, and further preferably 40 to 60 MPa.
A rayon fiber has a wettability of preferably 20 to 80%, more preferably 30 to 60%, and further preferably 40 to 55%.
A rayon fiber having an X-ray orientation degree of 90% or more is preferred.
As the rayon fiber of the component (B), the above rayon fiber [(B1)] and a rayon fiber [(B2)] satisfying the following requirements (b11) to (b13) may be used together.
The requirement (b11) pertains to a fiber diameter, which is 5 to 30 μm, preferably 6 to 20 μm, and more preferably 7 to 15 μm.
The requirement (b12) pertains to an X-ray orientation degree, which is 86% or more, and preferably 90% or more.
The X-ray orientation degree is calculated from equations described in paragraph numbers 0012 and 0013 of JP-A 9-31744, and paragraph numbers 0020 and 0021 of JP-A 9-256216; and the disclosure of paragraph number 0038 of JP-A 2013-91775.
The requirement (b13) pertains to a tensile elongation, which is from 2% to less than 10%.
In addition to the requirements (b11) to (b13), a rayon fiber satisfying a requirement for tensile modulus (Young's modulus), which is preferably 10 GPa or more, more preferably 13 GPa or more, and further preferably 15 GPa or more, may be used. The Young's modulus is obtained from the disclosure of paragraph number 0038 of JP-A 2013-91775.
When the rayon fiber (B1) and other rayon fiber (B2) are contained as the rayon fiber of the component (B), the content of the component (B1) relative to the total amount of (B1) and (B2) is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more.
As the rayon fiber of the component (B), usable are those described in Lenzinger Berichte 87 (2009), pages 98 to 105, for example, viscose rayon, polynosic, modal, cupra, lyocell (Tencel), and Bocell or FORTIZAN (manufactured by CELANESE Co., Ltd.; a fiber obtained by expanding a cellulose acetate and then saponifying with alkali).
The rayon fiber of the component (B) has a stronger activity of the fiber surface and a higher reactivity than a natural cellulose fiber or the like having a high crystallinity. Therefore, in order to further enhance the effect obtained by including the component (B), it is preferable to use together an acid-modified polyolefin as the component (A). Containing the acid-modified polyolefin as the component (A) enhances the interface strength between the rayon fiber and the resin of the component (A), further enhancing its physical properties and simultaneously further increasing improvement effects of physical properties obtained by making the fiber long.
The resin-adhered long fiber bundle can be obtained by adhering the thermoplastic resin of the component (A) in a molten state to a strand of the 2,000 to 30,000 longitudinally-arranged rayon fibers of the component (B) and integrating them with each other.
The resin-adhered long fiber bundle can be produced by a well-known production method using a die, and applicable production methods are disclosed in, for example, paragraph number 7 of JP-A 6-313050, paragraph number 23 of JP-A 2007-176227, and others such as JP-B 6-2344 (Method for manufacturing resin-coated long fiber bundle and molding method), JP-A 6-114832 (Fiber-reinforced thermoplastic resin structure and manufacturing method thereof), JP-A 6-293023 (Method for manufacturing long fiber-reinforced thermoplastic resin composition), JP-A 7-205317 (Method for taking out fiber bundle and producing long fiber-reinforced resin structure), JP-A 7-216104 (Method for manufacturing long fiber-reinforced resin structure), JP-A 7-251437 (Method and device for manufacturing long fiber-reinforced thermoplastic composite material), JP-A 8-118490 (Crosshead die and method for manufacturing long fiber-reinforced resin structure), and the like.
The above-described resin-adhered long fiber bundles (I) and (II) can be each produced by adjusting an amount of molten resin to be supplied and a time period for processing.
The length of the resin-adhered long fiber bundle (namely, the length of the rayon fiber of the component (B) contained in the resin-adhered long fiber bundle) is in the range of 3 to 30 mm, preferably 5 mm to 30 mm, and more preferably 6 mm to 25 mm. A length of 3 mm or more can enhance the mechanical strength of a molded article obtained from the composition, and a length of 30 mm or less provides a good moldability.
As to a ratio between the amounts of the component (A) and the component (B) in the resin-adhered long fiber bundle,
The fiber-reinforced resin composition of the present invention may contain other known fire retardant and fire-resistant aid, a thermostabilizer, a lubricant, a light stabilizer, an antioxidant, a colorant, a mold lubricant, an antistatic agent within such a range that can solve the problem of the present invention.
Those components may be contained in the resin-impregnated long fiber bundle, or may be contained separately from the resin-impregnated long fiber bundle.
The molded article of the present invention is obtained by molding the fiber-reinforced resin composition including the aforementioned resin-adhered long fiber bundle.
In obtaining the molded article of the present invention, further to the fiber-reinforced resin composition including the aforementioned resin-adhered long fiber bundle, the thermoplastic resin of the above-mentioned component (A) can be added as necessary.
Since the resin-adhered long fiber bundle included in the fiber-reinforced resin composition of the present invention has a good dispersibility to a molten resin, the rayon fiber of the component (B) can be uniformly dispersed in the obtained molded article.
When molding the fiber-reinforced resin composition including the resin-adhered long fiber bundle of the present invention, it is inevitable that a force applied at the time of molding breaks and shortens the rayon fiber contained in the resin-adhered long fiber bundle. However, the present invention uses a rayon fiber having a good tensile elongation, thereby providing high fiber strength and preventing the rayon fiber from being shortened by the above-mentioned breakage.
In addition, the fiber itself has high strength and elastic modulus, thereby increasing the mechanical strength (bending modulus or the like) of the obtained molded article.
Furthermore, since the molded article obtained from the fiber-reinforced resin composition of the present invention is lightweight in comparison with one containing an inorganic fiber such as glass fiber (namely, being able to lower its density), a molded article having a large specific modulus (bending modulus/specific gravity) can be obtained.
In addition, for example, when a comparison between a rayon long fiber-containing polypropylene molded article and a glass long fiber-containing polypropylene molded article is made, a specific modulus becomes larger as the blending amount of the rayon fiber or glass fiber becomes larger, and a degree of specific modulus of the rayon long fiber-containing polypropylene molded article is larger.
With respect to the molded article obtained from the fiber-reinforced resin composition of the present invention, the molded article with a thickness of 4 mm preferably has a specific modulus of 4,000 MPa or more, more preferably 4,500 MPa or more, and further preferably 5,000 MPa or more.
The molded article of the present invention can be made into a desired shape depending on the intended use, and the specific modulus can be increased as mentioned above. Thus, when an article is molded into a thin plate-like shape, a molded article which is lightweight and has high mechanical strength can be obtained.
In the case that the molded article of the present invention is formed into a thin plate shape, even when the article has a thickness of 1 to 5 mm, for example, the article can provide a high mechanical strength.
In addition, as the molded article obtained from the fiber-reinforced resin composition of the present invention contains the rayon fiber, no combustion residue like glass fiber remains when the article is burnt.
Since the molded article of the present invention is lightweight and has a high mechanical strength (especially specific modulus), it is usable as substitutes of metal parts used in the various fields of electric and electronic equipment, communication equipment, automobile, building material, daily needs, etc., and is especially suitable for housings of various devices and plate-like sheathing materials.
Resin-impregnated long fiber bundles used in Examples 1 to 3 and Comparative Examples 1 and 2 shown in Table 1 were produced.
A strand of fibers made of long rayon fibers (having a fineness shown in Table 1) was passed through a crosshead die. At this time, a molten component (A) shown in Table 1 was supplied to the crosshead die from a biaxial extrusion machine (cylinder temperature of 250° C.) in an amount shown in Table 1, and the rayon fiber strand was impregnated with the molten component.
Thereafter, the resultant product was shaped by a shaping nozzle at an exit of the crosshead die and a shape thereof was adjusted by shaping rolls, and then, cut into a predetermined length (length of the fiber bundle in Table 1) by a pelletizer, so that a resin-impregnated long fiber bundle [long fiber bundle (I)] in a pellet shape (cylindrical shape) was obtained.
When resin-impregnated long fiber bundles thus obtained were cut and checked, Examples 1 to 3 and Comparative Examples 1 and 2 had rayon fibers substantially parallel in the length direction and impregnated up to their center portions with the resin.
A composition composed of the resin-impregnated long fiber bundles obtained by the Production Example 1 was obtained.
Rayon fiber 1 (CR500TEX manufactured by Cordenka GmbH & Co.) and rayon fibers 2 and 3 shown in Table 1 were used.
The rayon fiber 1 had a width-directional cross section of a flat shape (
In Comparative Examples 3 and 4, wood pulp (Pulp NDP-T manufactured by Nippon Paper Industries Co., Ltd.; fiber diameter of 25 μm, average fiber length of 1.8 mm) was used instead of the rayon fibers 1 to 3 in amounts (% by mass) shown in Table 2, so that granular particles containing wood pulp (cellulose fiber) were obtained in the same manner as in Comparative Example 2 of International Publication No. WO2013/051369. However, polyamide shown in Table 2 was used instead of polypropylene or MPP (acid-modified PP).
A rayon fiber was embedded in an epoxy resin, a cross section thereof was obtained by a microtome and an SEM photograph was taken (
When a flat shape is elliptical, lengths of major and minor axes shown in
When a flat shape is indefinite, the longest portion was taken as the major axis and the shortest portion of a line (axis) perpendicular to the major axis was taken as the minor axis as shown in
Major axis lengths and minor axis lengths of 100 rayon fibers were measured, and a number average thereof was used to calculate a ratio between a major axis length and a minor axis length (major axis length/minor axis length).
After 1-week humidity adjustment at 23° C. and 50% RH, a tensile strength was measured at a sample fiber length of 2.5 cm and a crosshead speed of 2.5 cm/min.
After 1-week humidity condition at 23° C. and 50% RH, a tensile elongation was measured at a sample fiber length of 2.5 cm and a crosshead speed of 2.5 cm/min.
0.03 to 0.06 g of rayon fiber was used as a sample fiber.
The sample fiber was dried in vacuum at 50° C., and weighed by an electronic balance.
The sample fiber was soaked into pure water in a petri dish at room temperature (20 to 25° C.) for one minute.
The sample fiber was taken out from the pure water and centrifuged (10,000 r/m, 10 minutes), and then, weighed by an electronic balance. The wettability was calculated based on the following equation.
Wettability (%)=(Mass after centrifugation−mass after vacuum
drying)/mass after vacuum drying×100
Under the following conditions, an ISO multi-purpose test specimen of Type A (2 mm thickness) was prepared, and used as a test specimen for each of the following measurements.
Since Examples 1 to 5 used the rayon fiber 1 with a good tensile elongation, they were good particularly in the tensile strength, elongation, bending strength and impact strength.
The present invention has been described as above. It is natural that various modifications are included within the scope of the present invention, and these modifications are not departed from the scope of the present invention. In addition, all that is obviously taken as modifications of the present invention by those skilled in the art is within the scope of Claims described below.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2014-124978 | Jun 2014 | JP | national |
| 2014-155712 | Jul 2014 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2015/063053 | 5/1/2015 | WO | 00 |
