Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
  • B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
  • B29B15/10—Coating or impregnating independently of the moulding or shaping step
  • B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
  • B29B15/122—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex
  • B29B15/125—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex by dipping
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B1/00—Layered products having a non-planar shape
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
  • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
  • B29C70/28—Shaping operations therefor
  • B29C70/40—Shaping or impregnating by compression not applied
  • B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
  • B29C70/52—Pultrusion, i.e. forming and compressing by continuously pulling through a die
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
  • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
  • B29C70/28—Shaping operations therefor
  • B29C70/40—Shaping or impregnating by compression not applied
  • B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
  • B29C70/52—Pultrusion, i.e. forming and compressing by continuously pulling through a die
  • B29C70/525—Component parts, details or accessories; Auxiliary operations
  • B29C70/528—Heating or cooling
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
  • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
  • B32B5/08—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer the fibres or filaments of a layer being of different substances, e.g. conjugate fibres, mixture of different fibres
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2101/00—Use of unspecified macromolecular compounds as moulding material
  • B29K2101/12—Thermoplastic materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
  • B32B2260/02—Composition of the impregnated, bonded or embedded layer
  • B32B2260/021—Fibrous or filamentary layer
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
  • B32B2260/04—Impregnation, embedding, or binder material
  • B32B2260/046—Synthetic resin

Definitions

• the present invention relates to a thermoplastic resin composite reinforced with continuous reinforcing fibers (hereinafter, referred to as a composite), using the composite as a core material, and forming a peripheral surface of the composite using a thermoplastic resin.
• the present invention relates to a long-fiber-reinforced thermoplastic resin-coated composite covered with a covered portion (hereinafter, referred to as a coated composite) and a method for producing the same.
• FRP rods Various types of industrial rods use FRP rods.
• this FRP rod has problems such as difficulty in bending and difficult processing. Therefore, rods that are easy to be added (and easy to bend) are required:
• Japanese Patent Publication No. 1-38668 discloses “Material for forming coated FRP products”: The FRP core material part, a thermoplastic resin covering the core material part, and an intermediate layer straddling both of them, are obtained by shaping before the core material part is hardened. In addition to the limited shaping time, it has the drawback that reshaping is not possible, and the resulting molded article is difficult to bend.
• Japanese Patent Publication No. 63-36964 discloses “Fiber Reinforced Structure and Method for Producing the Same”.
• the content of reinforcing fibers in it is As it increases, it is necessary to bend and break the composite
• the stress (bending resistance) increases, it has the disadvantage that the composite becomes difficult to bend.
• the composite material that constitutes the core material of the coated composite material is generally difficult to become a product by itself.-Because the composite material is difficult to mold, it is a high-quality composite material with good shape accuracy. Therefore, it was difficult to produce a stable product: Therefore, in order to make it a practical product, the obtained composite was cut into berets, and injection molding was performed. At present, it was not possible to make full use of the inherent properties of continuous reinforcing fibers: In such a situation, it was used in a continuous, long shape and within a practical range. A composite having the shape accuracy as possible was desired.
• Japanese Patent Publication No. Sho 63-376694 discloses such a composite and a method for producing the same, but has such a shape accuracy that it can be used within a practical range. At present, no complex was obtained:
• An object of the present invention is to provide a coated composite which is easy to bend and has excellent resistance to bending fracture, a composite whose shape accuracy is remarkably improved, a method for producing the same, and a large number of composites which can be simultaneously coated.
• An object of the present invention is to provide a method for producing a coated composite which is easy to maintain and a production apparatus having a simple structure suitable for the production method:
• the coated composite according to one aspect of the present invention is a coated composite comprising a core material, which is a composite reinforced in the longitudinal direction with reinforcing fibers, and a thermoplastic resin coating that covers the peripheral surface of the core material.
• the core material has a reinforcing fiber content of at least 10% by weight, the core material has an average diameter or average thickness of 3 mm or more, and the coating has an average thickness of 0.3 mir. ! ⁇ 1.5 mm, it is a coated composite.
• a composite according to one aspect of the present invention is a composite reinforced in the longitudinal direction with reinforcing fibers, wherein the content of the reinforcing fiber is 10 to 80% by weight, and the composite is formed in the longitudinal direction.
• the reinforcing fiber is introduced into the fiber-opening impregnation tank, and is impregnated with the molten mature resin.
• the reinforcing fiber impregnated with the thermoplastic resin obtained by pulling it out of the chair is cooled so that the surface temperature is within the crystallization temperature range of the thermoplastic resin, and at least within the temperature range.
• One aspect of the present invention is a method for producing a coated composite, comprising: a molten resin tank for coating a composite reinforced in a longitudinal direction with reinforcing fibers; an inlet nozzle into which the composite is introduced; and a molten resin tank.
• the outlet nozzle from which the coated composite coated with the molten resin filled in is sent out is on a straight line, and the resin pressure in the molten resin tank is about the same as the liquid head pressure of the molten resin. Without forced pressurization, the thickness of the coating is regulated by the size of the outlet nozzle.
• the method of making the overlying composite is:
• one or more inlet nozzles are located horizontally on the side surface of a box-shaped molten resin tank having an open upper part, It is a coated composite manufacturing device with one or more outlet nozzles on its opposite face and in line with the inlet nozzle:
• FIG. 1 is a cross-sectional view of the coated composite cut at right angles to the longitudinal direction, in which FIG. 1A is a schematic perspective view of the coated composite of the present invention, and FIG. IB is a core material.
• FIG. 4 is a schematic enlarged cross-sectional view showing a unit area and a verification area set in a cross section of a part (composite).
• FIG. 2 is an explanatory view of a manufacturing apparatus for obtaining the composite described in the example.
• FIG. 3 is an external view of a manufacturing apparatus of the coated composite of the present invention.
• FIG. 4 is an explanatory cross-sectional view of a coated composite manufacturing apparatus according to the present invention.
• the composite of the present invention, the coated composite and the method for producing them will be specifically described.First, the coated composite of the present invention will be described with reference to FIG. 1-.
• (1) is the coated composite of the present invention, (11) is its coating, (1 2) is its core, and (1 2 ⁇ ′) is reinforcing material penetrating the core.
• (Tzl), (Tz2) and (Tz3) represent three unit areas randomly set in the core section (1 2), respectively.
• (Dzll) and (Dzl2) are two test areas randomly provided in (Tzl)
• (Dz21) and (Dz22) are two test areas randomly provided in (Tz2)
• (Dz31) and (Dz32) represent the two test areas randomly set in (Tz3):
• the plurality of unit areas are congruent with each other, but have the same unit area (for example, (
• test areas (Dzll) and test area (Dzl2) has size similar shapes are different, if usually the former is a 0. 1 mm 2 the latter 1 mm 2 : Of course, vice versa:
• the content C11 of the reinforcing fiber penetrating through this test area (for example, (Dzll)) (the area occupied by the reinforcing fiber Z and the area of the Z test range) is measured by cross-sectional photography, and this procedure is carried out by another test.
• the content C12 of the reinforcing fiber is repeatedly obtained for the region (for example, (Dzl2)), and applied to the test region (for example, (Dz21)) in another unit region (for example, (Tz2)).
• the coated composite of the present invention is excellent in bending fracture resistance because the core is composed of the reinforcing fiber having a high content, and the coating existing on the peripheral surface of the core is relatively soft. Since it is composed of a thermoplastic resin with a large elongation, it is excellent in bendability and cracking resistance: Such bending resistance and bending resistance are contradictory characteristics. In order to maintain a good balance, the following configuration is particularly desirable:
• test areas Dzl, Dz2
• C1, C2 the content of the reinforcing fiber penetrating each test area. This is performed for three unit areas (Tzl, ⁇ 2, and ⁇ 3).
• the calculated six content rates (C1 and C12, C21, C22, C31 and C32) are all Mc ⁇ 3 o [Mc: arithmetic mean, ⁇ : standard deviation], preferably Mc ⁇ 2 Desired to be in the range of a,-
• the effective balance between bendability and bending fracture resistance referred to in the present invention is a value measured by a bending fracture stress test described below, which is a test for examining bending fracture resistance.
• the value of the coated composite is 1.2 times or more the value of the composite (core material), and the value measured by the 1% radius stress test described below, which is a test for examining the bendability. However, the value of the coated composite is 1.2 times or less the value of the composite (core part).
• the content of the reinforcing fiber in the core portion is at least 10% by weight, the average diameter or the average thickness of the core portion is 3 mm or more, and the average thickness of the coated portion.
• the reinforcing fiber content of the core material is considerably less than 10% by weight and the average diameter or average thickness of the core material is significantly less than 3 mm, the bending resistance of the obtained coated composite is reduced. Extremely destructive and impractical. Also, the cladding does not perform as expected:
• the average thickness of the coated portion is considerably less than 0.3 mm, even if the core portion is coated with a thermoplastic resin, the bending resistance of the coated composite is improved only to a small extent.
• the average thickness of the portion is considerably larger than 1.5 mm, the obtained coated composite has improved bending fracture resistance, but is hardly bent.
• the shape of the core material constituting the coating composite of the present invention is not particularly limited: a circle, a triangle, a square, or a hexagon. Any polygon (including not only regular polygons but also inequilateral polygons) can be used.
• the thermoplastic resin constituting the core part (12) used in the present invention includes a polyolefin resin, a polyamide resin, a polyester resin, a polycarbonate resin, and an acrylic resin.
• Resin, polysulfone resin, polyethylene resin, polyurethane resin examples of the resin include a resin, a polyether resin, and a polyacetal resin.
• the term “resin” is not limited to a crystalline polymer, but is generally used in the polymer processing industry for polymer materials. The concept encompasses resinous materials that are traded as such and are subjected to molding or processing:
• thermoplastic resins may be a single resin or a composition in which two or more thermoplastic resins are combined. It is difficult to obtain various properties (properties) with a single thermoplastic resin, but it can be solved by combining two or more thermoplastic resins.
• composition of a polyphenylene ether resin and a polystyrene resin there may be mentioned a composition of a polyphenylene ether resin and a polystyrene resin:
• the polyphenylene ether resin has a melting point and a decomposition point.
• the moldability is poor due to the close proximity, but good moldability can be maintained by combining with the low-melting resin, polystyrene resin:
• thermoplastic resin having compatibility with both thermoplastic resins is blended into both or at least one of them so that the thermoplastic resin can be fused, or the third thermoplastic resin is formed into a layer. And intervene between them:
• thermoplastic resin polyolefin resin
• the core portion is provided with excellent flexural fracture resistance by the reinforcing fiber contained therein, but this performance is effectively used. This is because Bolbropyrene resin is generally dominant:
• the one with the highest rigidity is crystalline poly (vinylene) obtained by homopolymerization of propylene:
• the propylene single weight is used. It is preferable to use a (crystalline) polypropylene copolymer composed of at least one kind of ⁇ -olefin such as ethylene instead of coalescing.
• ⁇ -olefin such as ethylene
• the reinforcing fibers constituting the core part (12) used in the present invention single fibers having an average diameter of 3 to 21 zra, preferably 9 to 21 / zm, are preferably 500 to 500.
• a bundle of about 4.00 bundles (hereinafter sometimes referred to as roving) is desirable.
• the average diameter of the reinforcing fibers is 1 ⁇ m or less, it is difficult to form a composite. The fibers are easily broken, and the impact strength of the molded article tends to be insufficient. If the average diameter of the continuous fibers is 25 ⁇ m or more, the appearance of the composite becomes poor and the mechanical strength tends to deteriorate.
• the average length of the fiber reinforcement is preferably substantially equal to the average length of the composite: obtained by reinforcing fibers reinforcing a continuous body such as a composite.
• the tensile strength in the longitudinal direction of the composite and the flexural fracture resistance of the composite are improved:
• Examples of the above reinforcing fibers include inorganic fibers and organic fibers.
• Examples of the inorganic fibers include artificial fibers such as glass fiber, carbon fiber and metal fiber.
• glass fibers are preferably used because of their excellent physical properties and economy: Hard glass is preferred as the glass fiber, and in particular, in addition to E-glass, which is alkali-free glass, Borosilicate glass (porosilicate glass) is preferably used.
• the inorganic fibers may be, for example, a silane-based cutting agent, a titanium-based cutting agent, a boron-based cutting agent, an aluminum-based cutting agent, and a zirco-aluminum-based cutting agent.
• the inorganic fiber may be used after being subjected to a surface treatment with at least one of surface treatment agents: When the inorganic fiber is subjected to a surface treatment, it has an affinity for a hydrophobic mature plastic resin such as polystyrene or pyrene. Strength is enhanced and the thermoplastic resin is more likely to be impregnated between the reinforcing fiber spreads:
• organic fibers examples include polyolefin fibers, such as polyethylene fibers, polystyrene fibers and poly-4-methyl-tribenten fibers, and polyamide fibers such as 6-polyamide (6- Nylon), 7-polyamide, U-polyamide, 12-polyamide, 6,6-polyamide, 6,7-polyamide, 6,10- Polyamide, 6, 12-Polyamide, Semi-aromatic Polyamide
• Thermoplastic fiber such as nylon fiber MXD 6 (co-condensate of m-xylylene diamine and adipic acid), wholly aromatic polyamide fiber [aramid fiber (trade name: Kepler)], etc.
• Polyester fibers for example, PET (polyethylene terephthalate) fibers, PBT (poly-1,4-butylene terephthalate) fibers, and wholly aromatic polyester fibers, etc .: Preferred because of its high melting point and excellent mechanical strength:
• the above-mentioned inorganic fibers and organic fibers may be used alone or in combination of two or more. Include two or more combinations in inorganic fibers or two or more combinations in organic fibers.
• the coating part constituting the coating composite of the present invention is preferably one whose inner wall surface is firmly adhered to the outer wall surface of the core part, or one which is slidably contacted. : Therefore, the thermoplastic resin used for the core part and the mature resin used for the coating part are those which show mutual adhesion, affinity or compatibility, etc., but do not show Combinations of materials are desirable: In addition, it is important that the composite does not adversely affect the flexural failure resistance of the composite
• polyolefin resin is preferred for both the thermoplastic resin used for the covering part and the mature plastic resin used for the core part.-
• the covering part impairs the bending fracture resistance of the core part.
• the propylene copolymer occupies at least 80 mol%, preferably 85 to 97 mol%, more preferably 90 to 95 mol%, of the propylene unit in the polypropylene copolymer.
• the remaining amount is usually 20 mol% or less, preferably 15 to 3 mol%, more preferably 1 () to 5 mol%, in other ⁇ -olefin units.
• Ethylene is preferred as a comonomer to form this ⁇ -olefin unit:
• the role of the coating in addition to the above, also includes the role of protecting the core against contamination, moisturizing and other undesirable effects: ⁇ this role, but also polyolefin. Fat is useful.
• the composite of the present invention also corresponds to the core part of the coated composite of the present invention. That is, it can be used even without the covering portion.
• thermoplastic resin and the reinforcing fibers that constitute the composite of the present invention are as described above in the ⁇ core part (
• the reinforcing fiber is contained in the range of 10 to 80% by weight:
• the content of the reinforcing fiber is less than 10% by weight, the amount of the ripened resin becomes too large, control of the shape becomes difficult, and it becomes difficult to obtain a product having a smooth surface and a high commercial value. If the content of the fibers for use exceeds 80% by weight, the impregnated fibers are liable to generate fluff at the exit of the die and become unstable in shape, so that not only the external appearance is deteriorated, but also stable continuous production cannot be performed.
• the composite of the present invention has an average cross-sectional diameter of 3 mm or more when cut at a right angle to the longitudinal direction.
• the shape accuracy does not improve even if the impregnated fiber is shaped, and only products with low commercial value can be obtained.
• the composite of the present invention has an average deviation of the cross-sectional diameter when cut at a right angle to the longitudinal direction in a range of 0.10 or less-when the average deviation exceeds 0.10, the composite obtained is obtained.
• the body has poor shape accuracy: preferably less than 0.05, particularly preferably less than 0.02:
• the composite of the present invention has excellent shape accuracy, it is useful for columns for tunnel houses, side guides for automobiles, handrails on boules, and the like.
• the method for producing a composite of the present invention comprises the steps of: 3807 PT / JP98 / 01316
• the impregnated fiber in the shaped cooling slit is At the inlet (opening impregnation tank side entrance), a pool of molten thermoplastic resin will form, making shape control difficult and eventually impossible to manufacture:
• the crystallization temperature range referred to here is the extrapolated crystallization onset temperature (T ic) obtained by differential scanning calorimetry (DSC) of a thermoplastic resin based on JISK-7121-1987. ) And the extrapolated crystallization end temperature (T ec), and in the case of helium at the horizon, about 90 C to 130-C is a guideline.
• T ic extrapolated crystallization onset temperature obtained by differential scanning calorimetry (DSC) of a thermoplastic resin based on JISK-7121-1987.
• T ec extrapolated crystallization end temperature
• about 90 C to 130-C is a guideline.
• a plurality of shaped cooling slits are used, and the diameter of the shaped cooling slit closest to the spread impregnation tank is farthest from the spread impregnation tank. It is desirable that the diameter of the slit is larger than the diameter of the shaped cooling slit.-The diameter of the slit should be determined in consideration of the degree of shrinkage of the thermoplastic resin used.
• the molten resin tank (36) used in the present invention has a box shape with an open top, and one or more inlet nozzles (31) are located horizontally on the side surface. It has one or more exit nozzles (32) on its opposite surface.
• the molten resin (35) is stored in the molten resin tank (36). 807
• the resin (35) is supplied from the existing extruder: the molten resin (35) is marginally separated from the extrusion pressure from the extruder and is almost free of pressure.
• the molten resin is stored in the molten resin tank (36):
• the molten resin is basically the same as the ripened resin described in the above ⁇ Coating part (11)>.
• the molten resin tank (36) is heated by a heater (not shown), so that the internal molten resin (35) can be maintained at the set temperature.
• the upper part is open to prevent the resin pressure from being applied to the molten resin tank (36). If the structure is capable of releasing the pressure, the lid may be attached. Peni
• the positional relationship between the inlet nozzle (31) located on the side surface of the molten resin tank (36) and the outlet nozzle (32) located on the opposite surface of the molten resin tank (36) is such that the composite is broken by both nozzles. It is desirable to connect them with one straight line so that the music does not stick
• the center of the inlet nozzle (31) and the center of the outlet nozzle (32) are positioned so that they are aligned in a straight line in the axial direction of both nozzles.
• the thickness of the part can be made uniform and uneven thickness can be reduced:
• the complex (33) is not placed without completely removing the moisture attached to the surface, the molten resin (35) that has been ripened and melted to about 27O0C in the molten resin tank (36) can be obtained. ) Is present, which causes the attached water to boil and roughen the surface of the coated composite (34):
• the present invention is an improvement on a conventional coating device such as a cross head die, it is possible to replace the composite (33) with a metal wire such as a copper wire, an iron wire, or an aluminum wire.
• a metal wire such as a copper wire, an iron wire, or an aluminum wire.
• the composite (33) may be covered with a monofilament such as resin or polyvinyl chloride resin. The time required for the complex (33) to pass through the molten resin tank (36) is also important.
• the coating will be insufficient, and if the length is too long, the composite (33) will melt and the shape will not be maintained: the temperature (resin viscosity) of the molten resin (35), the coating thickness and the line Depending on the speed, such defects can be adjusted.
• the inlet nozzle (31) located on the side of the molten resin tank (36) facilitates the passage of the complex, and the molten resin (35) in the molten resin tank (36) is filled with the inlet nozzle (3). It must be slightly larger than the cross section of the complex so that it does not seep out of 1): For example, if the complex has a substantially circular cross section, the It is good to make it about 0.2 mm larger
• the coating thickness coated on the composite (33) can be adjusted by considering the size of the exit nozzle (32):
• the composite (33) is In the case of a substantially circular shape, the thickness of the coating is generally obtained by subtracting the radius of the composite (33) from the radius of the exit nozzle (32) and considering the shrinkage of the molten resin (35).
• the coated composite of the present invention has significantly improved flexural fracture resistance of the core, while preserving the flexibility of the coated composite at the same level as that of the core. Almost no fluff is generated, the surface appearance is extremely smooth, and post-processing such as bending is easy.
• the composite of the present invention is very close to a perfect circle, has very good shape accuracy, and is practical and of high commercial value.
• the method for producing a composite of the present invention can stably produce the composite of the present invention with a shape very close to a perfect circle and with extremely excellent shape accuracy:
• a plurality of composites can be simultaneously coated in one molten resin tank, and the thickness of the coated portion can be controlled relatively easily. Variations in volume can also be reduced:
• the apparatus for producing a coated composite of the present invention can carry out the method for producing a coated composite with an apparatus having an extremely simple structure.
• the coating composite of the present invention will be specifically described based on examples and sometimes with reference to useful comparative examples. However, the present invention is not limited to these examples. Not subject to any restrictions :.
• the diameter of each composite and the coated composite was measured according to JIS K69U-1979.
• a glass fiber orifice is introduced into the open fiber impregnation tank from the reinforcing fiber introduction port of the tank:
• a thermoplastic resin is introduced into the tank from the molten resin inlet port formed in the bottom plate of the tank. This thermoplastic resin is usually melt-kneaded in an extruder and then charged into the tank via a pipe or directly.
• All of the reinforcing fibers introduced into the above-mentioned opening and impregnating tank have an average single fiber diameter of 17 ⁇ ! And are used as a mouthpiece having a fiber count of 115 g / km. :
• a pair of two open fiber fins are formed between the left side wall and the right side wall forming the left and right long sides with the flow path of the thermoplastic resin and the reinforcing fiber therebetween.
• the vertical spacing (H) between the two opened fibers constituting each pair is set within the range expressed by the following relational expression with respect to the average diameter (D) of the reinforcing fibers.
• the vertical interval (H) is defined to include the case where the line passing through the center axis of the upper and lower opening bins is inclined with respect to the vertical line. If the line connecting the center of the opening fiber and the center of the lower opening pin is not on the vertical line, one of the opening bins is slid parallel to the flow direction of the reinforcing fiber,
• the vertical interval (H) is the interval when the center of is on the vertical line:
• Fiber reinforcement inlet located upstream of the fiber impregnation tank (perforated on the upstream end wall or upstream end 3807
• the reinforcing fibers are introduced from the top plate, and are passed through the gap between the first opening bin pair at the upstream end in a non-contact manner, and then opened, and then the second opening adjacent to the downstream side is opened.
• the fiber was opened by passing through the pin gap of the bin pair in a non-contact manner, and finally opened by passing through the pin gap of the third spreading bin pair located downstream of the bin in a non-contact manner.
• the molten thermoplastic resin is impregnated between the reinforcing fibers of the spread.
• the composite obtained from the reinforcing fiber and the thermoplastic resin that has passed through the third opening pin is shaped through a shaping nozzle (inside diameter 5.7 O ram) formed in the downstream end wall of the opening and impregnating tank. Cooling after shaping results in a composite (average diameter 5.63 mm) containing longitudinally aligned reinforcing fibers. The content of the reinforcing fiber in this composite was 18.2% by weight. The results of measuring its properties are shown in Table 1.
• the test region was also determined for the other two unit regions ((T z2) and (T z3)).
• the coated composite was obtained basically in the same manner as in Example 1. However, the method of producing the composite, the diameter of the circular die, and the diameter of the coated composite were changed according to each experimental example and comparative example. As a result, the results are different from those in Example 1.
• the content of the reinforcing fiber in the cross-section of the core material of the obtained coated composite such as the conditions in each experimental example and the comparative examples, C mn, and their arithmetic mean values
• Tables 1 and 2 show the deviation ⁇ mn of the difference (M c-C ran) between Mc, ⁇ c and the content C mn of each reinforcing fiber, the standard deviation calculated therefrom, and the property values of the composite. Show. Table 2
• Diameter The diameter of the obtained composite was measured in accordance with JIS K 6911-1979. That is, the diameter of the cross section of the composite when cut at a right angle to the longitudinal direction was measured on the same plane. Four points were measured at intervals of ° (Dll, D12, D13, D14)-This operation was also determined for other sections set for the same complex (D21, D22, D23, D24), and the arithmetic mean ( The MD obtained by measuring the average deviation (roundness MD) from the average diameter Dm) is derived from the following equation. The smaller the MD value, the closer to a perfect circle and the higher the shape accuracy. Do:
• Example 8 a composite was formed by using an apparatus as shown in FIG. 2-that is, 20 gussets (21) of glass fibers as reinforcing fibers were used to form a thermoplastic resin. Opening in which maleic anhydride-modified polyfluorophenyl FR (230-C; 21.18N) 100 g / lOmin] is filled with a melt adjusted to a temperature of 270 ° C Impregnation tank (2
• roving (21) As the roving (21), an average single fiber diameter of 17 ⁇ and a tex number of 1150gZkm was used-and the roving (21) was provided in the opening impregnation tank (22). Opened with fine fiber (23) and impregnated with the melted modified polybrohillene ⁇ Next, roving impregnated with the melted modified polybrohillen ( 2 1) passes through a die (24) with an inner diameter of 6.0 mm provided at the outlet of the opening and impregnating tank (22), and then an air cooling tank ( After passing through 25), the surface temperature is adjusted to 125 : C. ⁇
• the impregnated rovings (21) are made of a 10 mm wide steel, controlled at a temperature of 30 : C, and have an inner diameter of 6 lmm, spaced at 40 mni intervals.
• a composite having an average diameter of 5.85 mm was obtained by sequentially passing through the shaped cooling slit (26) and the second shaped cooling slit (27) with an inner diameter of 5.9 ram. .:
• Table 3 shows the evaluation results of the obtained composites based on the following measurement tests:
• Example 9 is substantially the same as Example 8, but differs in that the number of orifices (21) is different and that three shaped cooling slits are provided. :.
• the impregnated rovings (21) are made of steel with a width of 1 Omra, controlled at a temperature of 30 C, arranged at intervals of 40 mm and 20 mm and having an inner diameter of 6.1 mm.
• Example 10 This example 10 is substantially the same as example 8, except that the number of mouths per bing (2 1) is different, and four shaped cooling slits are provided. In other words, in the same manner as in Example 8, four glass fiber orifices (21) were used, and maleic anhydride-modified polypropylene copolymer having a temperature of 270 : C was used. The fiber was fed to a fiber impregnation tank (22), which was filled with the molten material, and was continuously impregnated at a take-off speed of lOOcra / min:
• the orifice (21) impregnated with the molten modified polypropylene is passed through a die (24) with an inner diameter of 6.0 mm provided at the outlet of the fiber impregnation tank (22). Passing through the air cooling tank (25), the surface temperature is adjusted to 125C:
• one impregnating port bing (21) is made of steel 10 mm in width, controlled at a temperature of 30 : C, and has inner diameters arranged at intervals of 10 mm, 20 mm and 20 mm. 6 ⁇ lmm first shaped cooling slit (26), inner diameter 5.9mm second shaped cooling slit (27), inner diameter 5.8mm third shaped cooling slit (28) and a fourth shaped cooling slit (29) having an inner diameter of 5.7 mra, a composite having an average diameter of 5.65 mm was obtained.
• the obtained composite had extremely small variation in shape.
• the glass fiber content was 18% by weight.
• the evaluation result of the obtained composite based on the following measurement test was obtained. Table 3 shows:
• Example 11 is substantially the same as Example 8, except that the number of the orifices (21), the dies (24) and the diameter of the first shaped cooling slit (26) are smaller.
• the diameter of the second shaped cooling slit (27) is different:
• the impregnating port one bing (21) is made of steel with a width of 10 mm, is controlled at a temperature of 30 : C, and has an inner diameter of 3.6 mm, which is arranged at intervals of 20 mm.
• a composite having an average diameter of 3.46 mm was obtained by sequentially passing through the first shaped cooling slit (26) and the second shaped cooling slit (27) having an inner diameter of 3.5 mm.
• the obtained composite had a very small variation in shape: the glass fiber content was 73% by weight: The evaluation results of the obtained composite based on the following measurement test were shown. 3 Show:
• the roving (21) impregnated with the molten modified polypropylene is passed through a 6. Omrn die (24) having an inner diameter of 6. Omrn provided at the outlet of the fiber impregnation tank (22). After passing through the air cooling tank (25), the surface temperature is adjusted to 125C-.
• the impregnated rovings (2 1) can be made to have an average diameter without using a shaped cooling slit.
• the orifice (21) impregnated with the molten modified polypropylene passes through a die (24) with an inner diameter of 6. Omm provided at the outlet of the fiber impregnation tank (22). After passing through the air cooling bath (25), the surface temperature is adjusted to 14 OC:
• the impregnating port one bing (2 1) is made of 1 Omm wide steel, controlled at a temperature of 30 C, and has a 6.2 mm inner diameter first shaping cooling slit. (26), a molten pool of propylene resin was formed at the slit inlet, the line stopped, and no composite was obtained.
• the evaluation results are shown in Table 3.
• the roving (21) impregnated with the molten modified polypropylene is opened. 6. After passing through the Omra dice (24 :;) at the outlet of the fiber impregnation tank (22), it passes through the air cooling tank (25), and the surface temperature is adjusted to 60 : C. RU:
• the impregnating port one bing (21) is made of a 10mm-wide steel, controlled at a temperature of 30C, and has a 6.2mm inner diameter first shaped cooling slit (21). After passing through 26), the solidified polypropylene resin at the slit entrance caught the entrance and could not be shaped, the line stopped, and no composite was obtained .: Evaluation results Table 3 shows:
• This Example 12 formed a coated composite using an apparatus as shown in FIGS. 3 and 4.
• the melted reforming port The three rovings impregnated with pyrene pass through an inside die with an internal diameter of 2 and Omni, which is provided at the outlet of the fiber opening impregnation tank, and then pass through an air-cooled tank, where the surface temperature rises. Is adjusted below 1 25 : C:
• the three rovings are made of steel with an inner diameter of 2.2mni and 2.0mm, respectively, and a width of Omm, controlled at a temperature of 30 : C, and arranged at intervals of 40mni. By sequentially passing through each of the shaped cooling slits, three composites (33) were obtained.
• a molten resin tank (36) was set up on that line, and three of the obtained composites (33) were passed through a 2.2mm ⁇ inlet nozzle (31), respectively, and heated and melted at 270C.
• the melted resin (35) [Vitrocene 352 (MI 30g / 10min)] was attached to the periphery of the composite (33), and a 3.5mra ⁇ outlet nozzle (32) was attached at 15m / After passing through at a speed of min, the mixture was passed through a cooling bath to obtain a coated composite (34) of 3 ⁇ ⁇ .
• the molten resin tank (36) has a size of 200mmW x 80mm LX lOOmmH, and has 2.2mm ⁇ inlet nozzles (31) on the opposing sides and 3 3.5mm ⁇ outlet nozzles (32) It has three holes and the upper part is opened to prevent resin pressure .: A heater is attached around the molten resin tank (36) so that the resin temperature can be secured. Natsu is—
• the resin supply to the molten resin tank (36) is based on the fact that the liquid level of the molten resin (35) The molten resin (35) was dropped from the open upper part so that it would not be lower than lOmra above (33).
• the obtained coated composite (34) was cut to a fixed size, weighed, and the adhesion amount of the molten resin (35) was determined. As a result, the variation in the coating amount among the three composites (33) was excellent within 5%:
• the composite (33) of Example 12 was replaced with a linear product made of a pyrene resin (33) having a diameter of 4 mm and passed through an inlet nozzle (31) having a diameter of 4.2 ⁇ , and each of the composites (33) was 270 °. While adhering the molten resin (35) [Petrocene 35 2 ( ⁇ . 30 g / 10min)], which was heated and melted, to the periphery of the linear object (33), the outlet nozzle of 5.5 ⁇ (32) ) At a speed of 15 m / min, and then passed through a cooling bath to obtain a coated linear object (34) of Omra ⁇ -The obtained coated linear object (34) was reduced to a fixed size. After cutting, the weight was measured, and the adhesion amount of the molten resin (35) was determined. As a result, the variation in the coating amount among the three linear objects (33) was excellent within 5%.

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• 1998
  • 1998-03-25 WO PCT/JP1998/001316 patent/WO1998043807A1/ja active Application Filing
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