JP2011162905A - Fiber material for reinforcing molding material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fiber material for reinforcing a molding material, exhibiting improved dispersibility/mixability and a high reinforcement effect upon blending it with a hydraulic material such as mortar and concrete, or with various molding materials such as a resin and rubber. <P>SOLUTION: There is disclosed a resin-impregnated fiber bundle made to have an uneven surface, including a fiber material (A) selected from an organic fiber and an inorganic fiber integrally impregnated with a thermoplastic resin (B), which resin-impregnated fiber bundle is to be used as a fiber material for reinforcing a molding material. The molding material is selected from a hydraulic material, a synthetic resin, a natural resin, synthetic rubber, natural rubber, and a ceramic material. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a reinforcing fiber material used by blending it with various molding materials such as hydraulic materials such as concrete and mortar, resins and rubbers.

  Various fiber materials made of natural fibers and synthetic fibers for reinforcing various molding materials such as concrete, mortar, resin, rubber and the like are known.

  Patent Document 1 discloses that an organic synthetic fiber selected from polyvinyl alcohol, polyacrylonitrile, polyamide, polyolefin, and aramid is fixed with a hydrophobic polymer sizing agent and then has an aspect ratio of 20 to 300. The invention of a cement mortar or concrete reinforcing fiber cut into two pieces is disclosed.

  Patent Document 2 discloses an invention of a concrete structure composed of a fiber-reinforced high-toughness cement board having cement as a main component and high-strength vinylon fibers as reinforcing fibers.

  Patent Document 3 discloses an invention of a fiber reinforced mortar or fiber reinforced concrete using polyvinyl alcohol fiber or the like ([0018]) as a reinforcing fiber.

  In Patent Document 4, by dry blasting a fiber, particles having an average particle diameter of 7 to 500 μm were partially embedded in the fiber surface (and a recess was also present), rubber, An invention of resin reinforcing fibers is disclosed.

Japanese Patent Publication No. 5-43654 JP 2004-36253 A JP 2007-302528 A JP 2009-249787 A

  When various fibers are used as reinforcing materials for mortar and concrete, it is important that the fiber is highly dispersible and mixed. However, the inventions of Patent Documents 1 to 3 are improved in terms of the dispersible and mixed properties of cement and mortar and fibers. There is room for.

  In the invention of Patent Document 4, since the manufacturing method is complicated and the fiber is treated with dry brass, it is difficult to obtain a constant quality as can be understood from FIG. There is also a risk that the strength is reduced due to damage.

  It is an object of the present invention to provide a reinforcing fiber material that has good dispersion and mixing properties when blended with various molding materials such as hydraulic materials such as mortar and concrete, resins, and rubbers, and has a high reinforcing effect. .

  The present invention is a resin-impregnated fiber bundle in which (A) a fiber material selected from organic fibers and inorganic fibers is impregnated with (B) a thermoplastic resin and has irregularities formed on the surface thereof. A resin-impregnated fiber bundle used as a fiber material is provided.

  The resin-impregnated fiber bundle of the present invention is used as a reinforcing fiber material for various molding materials selected from hydraulic materials such as cement, mortar and natural hydraulic lime, synthetic and natural resins, synthetic and natural rubber, ceramic materials and the like. Is.

  Since the resin-impregnated fiber bundle of the present invention has irregularities on the surface (that is, because the surface area is large), the contact area when mixed with the molding material can be increased. Dispersibility is improved, and when the molding material is solidified, the bondability with the molding material is also improved.

It is a flowchart for demonstrating the manufacturing method of the resin impregnation fiber bundle used as a reinforcing fiber material of this invention. Explanatory drawing of the one part process in the flow shown in FIG. Explanatory drawing of the one part process of embodiment different from FIG. Explanatory drawing of the test method of an Example.

  The resin-impregnated fiber bundle of the present invention is one in which irregularities are formed on the surface of a bundle obtained by impregnating a large number of (A) component fiber materials with the (B) component thermoplastic resin.

  The component (A) contained in the resin-impregnated fiber bundle of the present invention is a fiber material selected from organic fibers and inorganic fibers.

  As the organic fiber of the component (A), those selected from aramid fibers, polyamide fibers (excluding aramid fibers), wholly aromatic polyester fibers, cellulose fibers, and rayon fibers can be used.

  As the inorganic fiber (A), those selected from glass fiber, carbon fiber, basalt fiber, silicon carbide fiber, and boron fiber can be used.

  The diameter and length of the fiber material (organic fiber and inorganic fiber) as the component (A) are not particularly limited, but preferably have a diameter in the range of 5 to 24 μm. In addition, since the length of the fiber material of the component (A) constituting the resin-impregnated fiber bundle coincides with the length of the resin-impregnated fiber bundle, the length is also the length of the resin-impregnated fiber bundle. The length of the fiber material of the component (A) used for the production of the resin-impregnated fiber bundle of the present invention is longer as described in the explanation of the production method.

  The number of (A) component fiber materials contained in the resin-impregnated fiber bundle of the present invention is not particularly limited, but is preferably in the range of 1000 to 24,000, more preferably in the range of 1000 to 12,000.

  As the thermoplastic resin of the component (B) contained in the resin-impregnated fiber bundle of the present invention, polyamide resin (polyamide 6, polyamide 66, polyamide 12, etc.), olefin resin (polypropylene, high density polyethylene, acid-modified polypropylene, etc.), Polyphenylene sulfide resin, polyester (polyethylene terephthalate, polybutylene terephthalate, etc.), thermoplastic urethane resin (TPU), polyoxymethylene resin (POM), ABS resin, polycarbonate resin, alloy of polycarbonate resin and ABS resin, etc. Can be used. (B) The thermoplastic resin of a component can also use the alloy which consists of 2 or more types, In that case, a suitable compatibilizer can also be contained.

  The resin-impregnated fiber bundle of the present invention may contain other components as necessary in addition to the above-described components (A) and (B). As said other component, according to the kind of molding material used as the application object of a reinforcing fiber material, it can select from a well-known additive suitably and can contain.

  In the resin-impregnated fiber bundle of the present invention, the content of the fiber material (A) is preferably 5 to 90% by mass in the total amount of the fiber material (A) and the thermoplastic resin (B). -80 mass% is more preferable, and 20-70 mass% is further more preferable.

  The resin-impregnated fiber bundle of the present invention can be adjusted in dimensions according to the use of various molding materials used as reinforcing fibers, the required mechanical strength, etc., for example, the diameter is 0.5 to 4.0 mm The length can be 4-50 mm.

  Next, a method for producing a resin-impregnated fiber bundle used as a reinforcing fiber material of the molding material of the present invention will be described with reference to FIG. 1 showing a production flow.

  The resin-impregnated fiber bundle of the present invention is one in which unevenness is formed on the surface by applying a production method having an unevenness forming step. A method for producing a resin-impregnated fiber bundle having no irregularities on its surface is known, and is described in, for example, Japanese Patent No. 4302929 (more specifically, paragraph number 0035, paragraph number 0046, FIG. 1). The manufacturing method described in the above-mentioned patent invention does not include an unevenness forming step (irregularity forming means), and therefore cannot obtain a resin-impregnated fiber bundle having unevenness formed on the surface.

  FIG. 1 is the same as FIG. 1 in Japanese Patent No. 4302929, but the molding roll or pelletizer is provided with means for forming irregularities on the surface of the resin-impregnated fiber bundle.

  First, a long fiber bundle 10a in which the fiber materials of the component (A) are bundled in the length direction (for example, about 1000 to 24,000 fiber materials having a fiber diameter of about 5 to 24 μm were bundled). A long fiber bundle is sent into the preheating device 11 and preheated.

  The preheating is a process for easily impregnating the fiber material with a molten resin in the next step. The preheating temperature is a temperature lower than the melting point, and varies depending on the type of fiber material used. For example, the aramid fiber is heated to about 100 to 400 ° C, and the basalt fiber is heated to about 100 to 500 ° C. To do.

  Next, the preheat-treated fiber bundle 10 b is sent to the crosshead die 12. As shown in the figure, an extruder 13 is connected to the crosshead die 12, and the molten thermoplastic resin (B) component is supplied from the extruder 13 via the resin supply path 14, and a long fiber bundle. 10b is contacted. The interior of the cross head die 12 is maintained at least at a temperature equal to or higher than the melting point of the thermoplastic resin, and the long fiber bundle 10b is impregnated with the resin.

  Next, the resin-impregnated fiber bundle 10c is sent from the crosshead die 12 to the molding (shaping) roll 15 and molded (shaping). In one embodiment of the present invention, in the forming (shaping) roll 15, irregularities are formed on the outer surface of the long resin-impregnated fiber bundle. The forming (shaping) roll 15 shown in FIG. 1 is a combination of three rolls, but may be a combination of two or four or more rolls.

  When forming irregularities on the surface of the resin-impregnated fiber bundle by the forming (shaping) roll 15, the forming (shaping) roll 15 combining the two rolls 21 and 22 shown in FIGS. 2 (a) and 2 (b). Can be used.

  On the outer surfaces 21a and 22a of the two rolls 21 and 22, concave portions 21b and 22b are formed at a plurality of positions at equal intervals in the length direction, and the concave portions 21b and 22b are also equally spaced in the circumferential direction. A plurality (eight in the drawing) are formed. It is to be noted that the resin-impregnated fiber bundle is formed by appropriately adjusting the formation position and the formation state (for example, independent depressions and continuous depressions of a certain length) of depressions (or projections) on the roll surface. The state of unevenness (for example, continuous or discontinuous linear or spiral unevenness with respect to a specific direction) can be adjusted to a desired state.

  When the long resin-impregnated fiber bundle 10c passes between the forming (shaping) rolls 15 (the two rolls 21, 22), it comes into contact with a large number of concave portions formed on the outer surface, thereby forming irregularities on the surface. Is formed.

  Next, the forming (shaping) roll 15 is passed through, and the long resin-impregnated fiber bundle 10 d having unevenness is sent to the take-up machine 16.

  Next, the resin-impregnated fiber bundle 10d on which long unevenness formed by passing through the take-up machine 16 is sent to a pelletizer (cutting machine) 17, cut into a predetermined length, and resin with unevenness formed on the surface. An impregnated fiber bundle 10e is obtained.

  In another embodiment of the present invention, the unevenness can be formed by the pelletizer (cutting machine) 17 without forming the unevenness by the forming (shaping) roll 15.

  When forming irregularities with the pelletizer (cutting machine) 17, as shown in FIG. 3A, as the take-up roll 31 for introducing the resin-impregnated fiber bundle 10c into the pelletizer (cutting machine) 17, FIG. ), Two rolls 31a having a mesh (grolet) 32 formed in a mesh shape on the roll surface, or two having a groove (lateral groove) 33 formed at right angles to the take-up direction on the roll surface. A combination of rolls 31b can be used.

  When the resin-impregnated fiber bundle 10c passes through the take-up roll 31, irregularities are formed on the surface by coming into contact with many grooves formed on the outer surface.

As a preferable example of the irregularities formed in the resin-impregnated fiber bundle of the present invention,
(I) Concavities and convexities formed linearly or continuously in the length direction,
(II) Concavities and convexities formed continuously or discontinuously in the circumferential direction,
(III) Concavities and convexities formed spirally continuously or discontinuously in the length direction,
(IV) Independent multiple irregularities,
In addition to the above, it is also possible to make irregularities combining (IV) with any one selected from (I) to (III).

  Of the unevenness, the depth of the concave portion and the height of the convex portion can be in the range of 0.05 to 2 mm, preferably in the range of 0.05 to 1.5 mm, based on the surface on which the unevenness is not formed. Can be.

  The resin-impregnated fiber bundle having irregularities formed on the surface of the present invention is used as a reinforcing fiber material for a molding material selected from hydraulic materials, synthetic and natural resins, synthetic and natural rubber, and ceramic materials.

  Examples of the hydraulic material include known various cements, mortar and concrete containing the various cements, and known materials that are hardened by adding water. For example, natural hydraulic lime (NHL; Natural Hydraulic Lime ).

  The content of the resin-impregnated fiber bundle is preferably 0.1 to 50 parts by mass, more preferably 0.1 to 30 parts by mass, and still more preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of cement.

  When the hydraulic material is mortar, cement, water, fine aggregate, admixture (added as necessary), the above resin-impregnated fiber bundle, and the like can be included.

  When the hydraulic material is concrete, cement, water, fine aggregate, coarse aggregate, admixture (added as necessary), the above resin impregnated fiber bundle, and the like can be included.

  The fine aggregates, coarse aggregates, admixtures and the like described above are known, and examples include those described in paragraph 21 of Patent Document 3 (Japanese Patent Laid-Open No. 2007-302528).

  When used as a reinforcing fiber material for synthetic and natural resins, it is used for a resin having a lower melting point than the resin constituting the resin-impregnated fiber bundle.

Example 1
A resin-impregnated fiber bundle having irregularities formed on the surface was manufactured by the flow shown in FIGS.

  A long fiber bundle consisting of about 1300 aramid (Kevlar) fibers (diameter 14 μm) shown in Table 1 was preheated at about 300 ° C. through a preheating device.

  Next, the preheated fiber bundle is introduced into a crosshead die and brought into contact with a molten resin (a mixture of polypropylene and maleic acid-modified polypropylene) supplied from an extruder (a mixture of polypropylene and maleic acid-modified polypropylene). The fiber bundle was impregnated with resin.

  Next, the long fiber bundle impregnated with the resin was passed through a forming roll shown in FIG. 3 to form a large number of irregularities on the surface.

  Next, after passing through a take-up machine, it was cut with a pelletizer to obtain a resin-impregnated fiber bundle having a diameter of about 2 mm and a length of 25 mm.

Examples 2 and 3
Using about 4000 basalt (basalt) fibers (diameter 13 μm) shown in Table 1 and having the irregularities formed on the surface in the flow shown in FIG. 1, 2 or 3, the diameter is about 2 mm and the length is 25 mm. A resin-impregnated fiber bundle was obtained.

Comparative Examples 1 and 2
Using the aramid fiber and Kevlar fiber shown in Table 1 (the same as in Examples 1 to 3), the surface shown in FIG. A resin-impregnated fiber bundle having a diameter of about 2 mm and a length of 25 mm was produced.

Test example 1
A measurement sample for the pull-out test shown in FIG. 4 was prepared.
1 kg of dry mortar manufactured by Hane Sangyo Co., Ltd. and 15 ml of water were mixed thoroughly to obtain a test mortar.

Next, the test mortar was filled in the inside of the cylinder 50 (made of PP, diameter D = about 6 mm, length L = about 25 mm) whose one end opening was sealed. Thereafter, as shown in the drawing, the l ₁ length (10 mm) portion of the resin-impregnated bundle (length 25 mm) obtained in the examples and comparative examples was inserted and left until the mortar solidified.

ＰＰ：ポリプロピレン（ノーブレンZ101A 住友化学株式会社製）
変性ＰＰ：マレイン酸変性ポリプロピレン（OREVAC CA100 アルケマ製）
アラミド繊維：Kevler49 （東レ・デュポン株式会社製）
玄武岩繊維：バサルトファイバーBCF13（Kamenny Vek社製） In the pull-out test, the cylinder 50 shown in FIG. 4 was fixed, the l ₂ length of the rod 52 was fixed, and the pull-out load (N) when pulled at a pull-out speed of 2 mm / min was measured. Shimadzu Autograph AG2000G (manufactured by Shimadzu Corporation) was used as a measuring instrument. The results are shown in Table 1.

PP: Polypropylene (Noblen Z101A manufactured by Sumitomo Chemical Co., Ltd.)
Modified PP: Maleic acid modified polypropylene (OREVAC CA100 Arkema)
Aramid fiber: Kevler49 (manufactured by Toray DuPont)
Basalt fiber: Basalt fiber BCF13 (Kamenny Vek)

  The resin-impregnated fiber bundle of the example in which irregularities are formed on the surface is used as apparent from the comparison of the extraction load of Example 1 and Comparative Example 1 and the comparison of the extraction load of Examples 2, 3 and Comparative Example 2. The pull-out load was larger. This result is considered to be because the resin-impregnated fiber bundle having unevenness on the surface is better bonded to the mortar.

Claims (9)

  (A) A resin-impregnated fiber bundle in which a fiber material selected from organic fibers and inorganic fibers is impregnated with (B) a thermoplastic resin and has irregularities formed on the surface thereof, and is used as a reinforcing fiber material for a molding material Resin-impregnated fiber bundle.   The resin-impregnated fiber bundle according to claim 1, wherein the fiber material of component (A) has a diameter of 5 to 24 µm, and the number of organic fibers or inorganic fibers forming the resin-impregnated fiber bundle is 1000 to 24,000.   The resin-impregnated fiber bundle of hydraulic material according to claim 1 or 2, wherein the resin-impregnated fiber bundle has a cylindrical shape, a diameter of 0.5 to 4.0 mm, and a length of 4 to 50 mm. (A) component organic fiber is selected from aramid fiber, polyamide fiber (excluding aramid fiber), wholly aromatic polyester fiber, cellulose fiber, rayon fiber,
The resin-impregnated fiber bundle according to any one of claims 1 to 3, wherein the inorganic fiber (A) is selected from glass fiber, carbon fiber, basalt fiber, silicon carbide fiber, and boron fiber.   The resin-impregnated fiber bundle according to any one of claims 1 to 4, wherein the unevenness on the surface of the resin-impregnated fiber bundle is an unevenness formed linearly continuously or discontinuously in the length direction.   The resin-impregnated fiber bundle according to any one of claims 1 to 4, wherein the unevenness on the surface of the resin-impregnated fiber bundle is an unevenness formed continuously or discontinuously in the circumferential direction.   The resin-impregnated fiber bundle according to any one of claims 1 to 4, wherein the unevenness on the surface of the resin-impregnated fiber bundle is an unevenness formed in a spiral shape continuously or discontinuously in the length direction.   The resin-impregnated fiber bundle according to any one of claims 1 to 4, wherein the unevenness on the surface of the resin-impregnated fiber bundle comprises a plurality of independent unevennesses.   The resin-impregnated fiber bundle according to any one of claims 1 to 8, wherein the molding material is selected from hydraulic materials, synthetic and natural resins, synthetic and natural rubber, and ceramic materials.

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