JP2022186609A - Fiber-containing thermoplastic resin composition and molded article of the same - Google Patents

Abstract

To provide a fiber-containing thermoplastic resin composition in which a content of a fibrous filler has small variation.SOLUTION: A fiber-containing thermoplastic resin composition is provided which contains (A) a master batch pellet containing a thermoplastic resin and a fibrous filler having specific gravity of 4.0 or more, and (B) a dilution material pellet, and satisfies the following requirement (I) and requirement (II) or requirement (I) and requirement (III). (I): 1.0≤M1/M2≤4.0. In the requirement (I), M1 and M2 represent the masses of the (A) and the (B), respectively. (II): 0.5≤L1/L2≤1.5. In the requirement (II), L1 and L2 are lengths from one end face to the other end face on an opposite side in a length direction when the (A) and the (B) are columnar molded bodies. (III): 0.5≤D1/D2≤1.0. In the requirement (III), D1 and D2 are central values of a shortest distance (minor axis) and a longest distance (major axis) passing through the center of gravity on the end face or the other end face, when the (A) and the (B) are columnar molded bodies.SELECTED DRAWING: None

Description

The present disclosure relates to fiber-containing thermoplastic resin compositions and molded articles thereof.

Conventionally, when using a fiber-containing thermoplastic resin composition to obtain a molded product with a low fiber content concentration, a method of mixing long fiber pellets containing fibers at a high concentration and a diluent (diluting resin) has been carried out. It is

In Patent Document 1, in a mixed raw material consisting of long fiber reinforced resin pellets and low fiber content pellets with a fiber content smaller than that of the long fiber reinforced resin pellets, the average fiber content of the long fiber reinforced resin pellets and the mixed raw material The difference in fiber content is 50% by weight or less, the pellet length of the long fiber reinforced resin pellet is 5 mm or more and 15 mm or less, and the pellet length of the low fiber content pellet is 1/2 or more of the pellet length of the long fiber reinforced resin pellet. An invention of a mixture of long fiber reinforced resin pellets and low fiber content pellets composed of two or more types of pellets satisfying the conditions of .

JP-A-6-23745

An object of the present disclosure is to provide a fiber-containing thermoplastic resin composition having a small variation in fiber content, and a molded article obtained from the fiber-containing thermoplastic resin composition.

This disclosure is
(A) contains a masterbatch pellet containing a thermoplastic resin and a fibrous filler with a specific gravity of 4.0 or more and (B) a diluent pellet, and the following requirements (I) and requirements (II) or requirements (I ) and requirement (III).
(I): 1.0≤M1/M2≤4.0
(II): 0.8≤L1/L2≤1.5
(III): 0.5≤D1/D2≤1.0
Requirement (I): M1 represents the mass of the masterbatch pellets of component (A), and M2 represents the mass of the diluent pellets of component (B).
Requirement (II): L1 is the length from one end face to the other end face on the opposite side in the length direction when the masterbatch pellet of component (A) is a columnar compact (the one end face and the other end face are the same shape),
L2 is the length from one end face to the other end face on the opposite side in the length direction when the diluent pellet of component (B) is a columnar compact (the one end face and the other end face have the same shape). , indicates the length of the longest portion when the (B) component diluent pellet is a sphere, an elliptical sphere, or a deformed stereomorphic object.
Requirement (III): D1 is the median value of the shortest distance (minor axis) and the longest distance (major axis) passing through the center of gravity of the one end surface or the other end surface when the masterbatch pellet of component (A) is a columnar compact. (the one end face and the other end face have the same shape),
D2 is the median value of the shortest distance (minor axis) and the longest distance (major axis) passing through the center of gravity of the one end face or the other end face when the diluent pellet of the component (B) is a columnar compact (said One end face and the other end face have the same shape), and when the diluent pellet of component (B) is a sphere, an elliptical sphere, or a three-dimensional amorphous object deformed from them, the cut surface when cut at L2 is the maximum Shows the median of the shortest distance (minor axis) and the longest distance (major axis) passing through the center of gravity of the surface. However, L1>D1 and L2>D2.

Molded articles obtained from the fiber-containing thermoplastic resin composition of the present disclosure show little variation in the content of the fibrous filler in a plurality of molded articles.

(a) is a plan view of a three-stage plate test piece manufactured in an example, and (b) is a side view of (a).

<Fiber-containing thermoplastic resin composition>
Component (A) is a masterbatch pellet containing a thermoplastic resin and a fibrous filler having a specific gravity of 4.0 or more.
The fibrous filler having a specific gravity of 4.0 or more is preferably made of a metal, preferably a metal selected from iron, copper, nickel, chromium, zinc, gold, silver, titanium and alloys containing these. Stainless steel can be mentioned as an alloy containing iron.

Thermoplastic resins include polyamide resins, olefin resins, styrene resins, polycarbonate resins, polyvinyl chloride, polyvinylidene chloride, polycarbonate resins, acrylic resins, methacrylic resins, polyester resins, polyacetal resins, and polyphenylene sulfide. One or two or more selected from system resins can be mentioned.
As the thermoplastic resin, one selected from polyamide resins is preferable.

The masterbatch pellet of component (A) is obtained by impregnating and integrating continuous fiber bundles in which continuous fibers having a specific gravity of 4.0 or more are bundled in the length direction with the thermoplastic resin in a molten state. It is preferably in the form of cylindrical resin-impregnated fiber bundles cut to lengths of 3 to 50 mm.
The resin-impregnated fiber bundle can be produced by a known production method using a die. Japanese Patent Application Laid-Open No. 6-2344 (Method for producing resin-coated long fiber bundle and molding method), Japanese Patent Application Laid-Open No. 6-114832 (Fiber-reinforced thermoplastic resin structure and its manufacturing method), Japanese Patent Application Laid-Open No. 6-293023 (Long Method for producing a fiber-reinforced thermoplastic resin composition), JP-A-7-205317 (method for taking out a fiber bundle and method for producing a long-fiber-reinforced resin structure), JP-A-7-216104 (long-fiber-reinforced resin structure product manufacturing method), Japanese Patent Laid-Open No. 7-251437 (Manufacturing method and manufacturing apparatus for long fiber reinforced thermoplastic composite material), Japanese Patent Laid-Open No. 8-118490 (Crosshead die and long fiber reinforced resin structure manufacturing method ), and the manufacturing method described in Japanese Patent No. 5959183 can be applied.

The length of the resin-impregnated fiber bundle (that is, the length of the fibrous filler having a specific gravity of 4.0 or more contained in the resin-impregnated fiber bundle) is preferably 3 to 50 mm, more preferably 3 mm to 40 mm, and 3 mm to 30 mm is more preferred.
Although the diameter of the resin-impregnated fiber bundle is not particularly limited, it can be in the range of 0.5 mm to 5 mm.

The content of the fibrous filler having a specific gravity of 4.0 or more in the (A) component masterbatch pellets is preferably 20 to 60% by mass, more preferably 20 to 55% by mass, and even more preferably 20 to 50% by mass.

Component (B) is a diluent pellet for mixing with component (A) to reduce the content of fibrous filler.
The (B) component diluent pellets include diluent pellets made of the same thermoplastic resin as described above. The thermoplastic resin used in the diluent pellets may be the same thermoplastic resin as component (A), or may be a thermoplastic resin different from component (A).

The content of the fibrous filler having a specific gravity of 4.0 or more in 100% by mass of the total amount of components (A) and (B) is preferably 1 to 10% by mass, more preferably 1 to 8% by mass, and 2 to 10% by mass. 6% by mass is more preferred.

The fiber-containing thermoplastic resin composition of the present disclosure satisfies at least one of the following requirement (I), requirement (II), and requirement (III).
(I): 1.0≤M1/M2≤4.0
(II): 0.8≤L1/L2≤1.5
(III): 0.5≤D1/D2≤1.0
Requirement (I): M1 represents the mass of the masterbatch pellets of component (A), and M2 represents the mass of the diluent pellets of component (B).

Requirement (II): L1 is the length from one end face to the other end face on the opposite side in the length direction when the masterbatch pellet of component (A) is a columnar compact (the one end face and the other end face are the same shape),
L2 is the length from one end face to the other end face on the opposite side in the length direction when the diluent pellet of component (B) is a columnar compact (the one end face and the other end face have the same shape). , indicates the length of the longest portion when the (B) component diluent pellet is a sphere, an elliptical sphere, or a deformed stereomorphic object.
The one end surface and the other end surface (that is, both end surfaces in the length direction) are circular, elliptical, or triangular or more polygonal, preferably circular or elliptical.
Three-dimensional amorphous objects that are deformed spheres or ellipsoids are those that have concaves, convexes or unevenness in part or all of the spheres or ellipsoids, or those that have a part (including multiple places) of the spheres or ellipses. It includes cut objects, spheres and elliptical spheres cut from a part, and those having recesses, protrusions, or unevenness in part or all of them.
When the columnar compacts of components (A) and (B) are cuboids with rectangular end faces, L1 and L2 are the lengths of the cuboids, and when they are cylinders with circular end faces, L1 and L2. is the length of the cylinder.
When the (B) component is a sphere, L2 is the diameter.

Requirement (III): D1 is the median value of the shortest distance (minor axis) and the longest distance (major axis) passing through the center of gravity of the one end surface or the other end surface when the masterbatch pellet of component (A) is a columnar compact. (the one end face and the other end face have the same shape),
D2 is the median value of the shortest distance (minor axis) and the longest distance (major axis) passing through the center of gravity of the one end face or the other end face when the diluent pellets of the component (B) are columnar compacts (the one The end face and the other end face have the same shape), and when the diluent pellet of component (B) is a sphere, an elliptical sphere, or a three-dimensional amorphous object deformed from them, the cut surface when cut at L2 is the maximum. Shows the median of the shortest distance (minor axis) and the longest distance (major axis) passing through the center of gravity of the plane. However, L1>D1 and L2>D2.
The one end face and the other end face (that is, both end faces in the length direction) are a circle, an ellipse, or a triangle or more polygon, preferably a circle, an ellipse, a square, or a rectangle. They are quadrilaterals and regular hexagons that have the same shape and size.
Three-dimensional amorphous objects that are deformed spheres or ellipsoids are those that have concaves, convexes or unevenness in part or all of the spheres or ellipsoids, or those that have a part (including multiple places) of the spheres or ellipses. It includes cut objects, spheres and elliptical spheres cut from a part, and those having recesses, protrusions, or unevenness in part or all of them.
When the columnar compacts of the components (A) and (B) are rectangular parallelepipeds with rectangular end faces, D1 and D2 are the medians of the short sides and long sides of the rectangles, and the cylindrical bodies with circular end faces are Then D1 and D2 are the diameters of the circles.
When the (B) component is a sphere, D2 is the diameter.

The fiber-containing thermoplastic resin composition of the present disclosure satisfies the requirements (I) and (II) or the requirements (I) and (III) to dilute the components (A) and (B). Variation in the content of the fibrous filler can be reduced.

The fiber-containing thermoplastic resin composition of the present disclosure contains powdered fillers, pigments, colorants, flame retardants, heat, light and ultraviolet stabilizers, phase Other ingredients such as solubilizers, lubricants, foaming agents, antimicrobial agents, etc. may be included.
Such other components may be contained in component (A), contained in component (B), or contained separately from components (A) and (B) in the fiber-containing thermoplastic resin composition. can.

The fiber-containing thermoplastic resin composition of the present disclosure can be obtained by dry-blending components (A), (B), and other components as necessary using a mixer, blender, or the like.

<Molded product>
The molded article of the present disclosure is obtained by molding the fiber-containing thermoplastic resin composition by a known resin molding method such as injection molding.
Molded articles of the present disclosure can be shaped and sized according to the application.
The molded article of the present disclosure has a small variation in the content of the fibrous filler for each molded article, and a small variation in quality evaluated by mechanical properties and the like.
Standard deviation (variation in mass of molded articles with 30 samples) is preferably within ±0.5 from the average value, more preferably within ±0.45 from the average value, and more preferably the average value is within ±0.40 from

Each aspect disclosed in this specification may be combined with any other feature disclosed in this specification.
Each configuration and combination thereof in each embodiment is an example, and addition, omission, replacement, and other changes of configuration are possible as appropriate without departing from the gist of the disclosure of the present invention. This disclosure is not limited by the embodiments, but only by the claims.

Production raw materials for component (A) Stainless fiber bundle 1: stainless steel fiber with a diameter of 11 μm, about 7000 fiber bundles Stainless fiber bundle 2: stainless steel fiber with a diameter of 12 μm, about 2000 fiber bundles Stainless fiber bundle 3: stainless steel with a diameter of 11 μm Fiber, about 3000 fiber bundles Stainless fiber bundle 4: Stainless fiber with a diameter of 8 μm, about 7000 fiber bundles Thermoplastic resin: Polyamide 6 "UBE NYLON 1013B" (manufactured by Ube Industries, Ltd.)
(B) Component Diluent pellets (cylindrical): Polyamide 6/ABS (manufactured by Daicel Miraise Co., Ltd.)

Production Examples 1-3
A stainless steel fiber bundle 1 was passed through a crosshead die. At this time, molten polyamide 6 was supplied to the crosshead die from a twin-screw extruder to produce component (A) in which the stainless steel fiber bundles 1 were impregnated with the polyamide resin. The mass ratio was adjusted to stainless fiber bundle 1:polyamide 6=40:60.
After that, it is shaped with a shaping nozzle at the exit of the crosshead die, shaped with a shaping roll, and cut to the length (L1) shown in Table 1 to obtain a cylindrical masterbatch pellet of component (A). (circular with the same size on both ends).

Production example 4
A columnar masterbatch pellet of component (A) was obtained in the same manner as in Production Example 1 except that the fiber bundle of component (A) was changed to stainless steel fiber bundle 2 (both end surfaces of which are circular with the same size).

Production example 5
A columnar masterbatch pellet of component (A) was obtained in the same manner as in Production Example 1 except that the fiber bundle of component (A) was changed to stainless steel fiber bundle 3 (both end surfaces of which are circular with the same size).

Production example 6
A cylindrical masterbatch pellet of component (A) was obtained in the same manner as in Production Example 1 except that the fiber bundle of component (A) was changed to stainless steel fiber bundle 4 (both end surfaces of which are circular with the same size).

Examples 1 to 5, Comparative Examples 1 and 2
For M1 and M2 shown in Table 1, the mass of 10 randomly selected masterbatch pellets was measured, and the average value was obtained.
For L1 and L2 shown in Table 1, the length from one end face to the other end face on the opposite side in the longitudinal direction of 10 randomly selected masterbatch pellets was measured, and the average value was obtained.
D1 and D2 shown in Table 1 measure the median of the shortest distance (minor axis) and the longest distance (long axis) passing through the center of gravity of one end surface or the other end surface of 10 randomly selected masterbatch pellets, and the average value ( The average value of the diameters of the circles on both end faces) was obtained.
Using the masterbatch pellets of component (A) and the diluent pellets of component (B) shown in Table 1, dry blending is performed so that the content of the fibrous filler is the amount shown in Table 1, and the fiber content heat A plastic resin composition was obtained.
The resulting fiber-containing thermoplastic resin composition was injection-molded to obtain a three-stage plate test piece shown in FIG. Thirty three-plate specimens were obtained for each case.
(Injection molding conditions)
Injection molding machine: S-2000i 100B (manufactured by FANUC Co., Ltd.)
Cylinder temperature: 250°C
Injection pressure: 80MPa

The mass of 30 three-stage plate test pieces of each of Examples 1 to 5 and Comparative Examples 1 and 2 was measured to obtain the standard deviation. The measurement was performed with AUX120 (manufactured by Shimadzu Corporation), and the values were obtained to four digits below the decimal point.
Examples 1 and 2 satisfy requirements (I) and (II), Examples 3 to 5 satisfy requirements (I) and (III), and Comparative Examples 1 and 2 satisfy requirements (I) to (III). This is an example that does not satisfy all of
From the comparison between Comparative Example 1 and Examples 1 and 2, and the comparison between Comparative Example 2 and Examples 3-5, the standard deviation is reduced by satisfying any two of the requirements (I) to (III). From this result, it was confirmed that the variation in the content of the fibrous filler in the 30 molded products was small.
Since the variation in the content of the fibrous filler in the molded product is small in this way, the variation in the quality of the molded product can also be reduced.

Molded articles obtained from the fiber-containing thermoplastic resin composition of the present disclosure include fuel caps for agricultural vehicles such as automobiles, motorcycles, combine harvesters, and tractors, automobile parts excluding fuel caps, and sensors used in various sensors. It can be used for housings of electrical and electronic equipment such as covers.

Claims (7)

(A) contains a masterbatch pellet containing a thermoplastic resin and a fibrous filler with a specific gravity of 4.0 or more and (B) a diluent pellet, and the following requirements (I) and requirements (II) or requirements (I )
and a fiber-containing thermoplastic resin composition that satisfies requirement (III).
(I): 1.0≤M1/M2≤4.0
(II): 0.8≤L1/L2≤1.5
(III): 0.5≤D1/D2≤1.0
Requirement (I): M1 represents the mass of the masterbatch pellets of component (A), and M2 represents the mass of the diluent pellets of component (B).
Requirement (II): L1 is the length from one end face to the other end face on the opposite side in the length direction when the masterbatch pellet of component (A) is a columnar compact (the one end face and the other end face are the same shape),
L2 is the length from one end face to the other end face on the opposite side in the length direction when the diluent pellet of component (B) is a columnar compact (the one end face and the other end face have the same shape). , indicates the length of the longest portion when the (B) component diluent pellet is a sphere, an elliptical sphere, or a deformed stereomorphic object.
Requirement (III): D1 is the median value of the shortest distance (minor axis) and the longest distance (major axis) passing through the center of gravity of the one end surface or the other end surface when the masterbatch pellet of component (A) is a columnar compact. (the one end face and the other end face have the same shape),
D2 is the median value of the shortest distance (minor axis) and the longest distance (major axis) passing through the center of gravity of the one end face or the other end face when the diluent pellet of component (B) is a columnar compact (the one The end face and the other end face have the same shape), and when the diluent pellet of component (B) is a sphere, an elliptical sphere, or a three-dimensional amorphous object deformed from them, the cut surface when cut at L2 is the maximum. Shows the median of the shortest distance (minor axis) and the longest distance (major axis) passing through the center of gravity of the plane. However, L1>D1 and L2>D2. The fiber-containing material according to claim 1, wherein the fibrous filler having a specific gravity of 4.0 or more is selected from iron, copper, nickel, chromium, zinc, gold, silver, titanium and alloys containing them. A thermoplastic resin composition. The thermoplastic resin is polyamide resin, olefin resin, styrene resin, polycarbonate resin, polyvinyl chloride, polyvinylidene chloride, polycarbonate resin, acrylic resin, methacrylic resin, polyester resin, polyacetal resin, polyphenylene. 3. The fiber-containing thermoplastic resin composition according to claim 1, which is selected from sulfide resins. (A) The masterbatch pellet of the component is 3 integrated ones in which continuous fiber bundles in which continuous fibers having a specific gravity of 4.0 or more are bundled in the length direction are impregnated with a thermoplastic resin in a molten state. The fiber-containing thermoplastic resin composition according to any one of claims 1 to 3, which is in the shape of a cylinder or an elliptical cylinder cut into lengths of up to 50 mm. The fiber-containing thermoplastic resin composition according to any one of claims 1 to 4, wherein the content of the fibrous filler having a specific gravity of 4.0 or more in the masterbatch pellet of component (A) is 20 to 60% by mass. thing. 6. The content of the fibrous filler having a specific gravity of 4.0 or more in 100% by mass of the total amount of components (A) and (B) is 1 to 10% by mass, according to any one of claims 1 to 5. A fiber-containing thermoplastic resin composition. A molded article comprising the fiber-containing thermoplastic resin composition according to any one of claims 1 to 6.

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