WO2017155009A1 - Faisceau de fibres imprégné de résine, article moulé par compression et son procédé de production - Google Patents

Faisceau de fibres imprégné de résine, article moulé par compression et son procédé de production Download PDF

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Publication number
WO2017155009A1
WO2017155009A1 PCT/JP2017/009353 JP2017009353W WO2017155009A1 WO 2017155009 A1 WO2017155009 A1 WO 2017155009A1 JP 2017009353 W JP2017009353 W JP 2017009353W WO 2017155009 A1 WO2017155009 A1 WO 2017155009A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
fiber bundle
impregnated fiber
impregnated
molded article
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2017/009353
Other languages
English (en)
Japanese (ja)
Inventor
高坂繁行
柴田悟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daicel Polymer Ltd
Original Assignee
Daicel Polymer Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2016074008A external-priority patent/JP6739210B2/ja
Application filed by Daicel Polymer Ltd filed Critical Daicel Polymer Ltd
Priority to US16/078,178 priority Critical patent/US10703019B2/en
Priority to EP17763349.2A priority patent/EP3427913B1/fr
Priority to CN201780016661.5A priority patent/CN108778655B/zh
Publication of WO2017155009A1 publication Critical patent/WO2017155009A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • 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
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B29B9/14—Making granules characterised by structure or composition fibre-reinforced
    • 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
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/32—Component parts, details or accessories; Auxiliary operations
    • B29C43/34—Feeding the material to the mould or the compression means
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

  • the present invention relates to a resin-impregnated fiber bundle containing a thermoplastic resin and reinforcing fibers, a compression molded article, and a method for producing the same.
  • Patent Document 1 Japanese Patent No. 3631994
  • Patent Document 2 Japanese Patent No. 4743592
  • a wire made of a unidirectional long fiber reinforced thermoplastic resin (hereinafter referred to as L-FRTP) having a width of 0.2 to 5 mm and a length of 10 to 150 mm is randomly oriented, and a contact between the wires is fixed.
  • L-FRTP sheet having a basis weight of 30 to 500 g / m 2 , an opening, and a thickness of 0.1 to 1 mm; and the L-FRTP sheet is at least one side of a specific base material Or the invention of the composite molded body arranged inside is described (Claims).
  • the surface rigidity of the L-FRTP sheet can be improved.
  • the cross-sectional shape of L-FRTP is a circle or an ellipse, and it is described that the major axis / minor axis of the cross section is 3 or less (paragraph number 0016). However, what is used in the examples is only a circle. (Embodiment 1) Since an elliptical shape is not used, it is disclosed that a circular shape is preferable in order to obtain the effects of the invention.
  • Patent Document 2 describes an invention of a method for producing a long fiber reinforced thermoplastic resin linear molding material and a long fiber reinforced thermoplastic resin molded product (claims).
  • the cross-sectional shape of the long fiber reinforced thermoplastic resin linear molding material “(a) it has a cross-sectional shape close to a circle or an ellipse. This allows the linear molding material to be distributed in a three-dimensional orientation. It becomes easy to obtain a sheet material or a molded article in which the reinforcing fibers are three-dimensionally oriented by press molding what is spread in this way (paragraph number 0028). Since there is no description of the cross-sectional shape in the reference example and the comparative example, it is considered that the reference example and the comparative example are circular like the invention of Patent Document 1. Summary of the Invention
  • An object of the present invention is to provide a resin-impregnated fiber bundle from which a molded article having high surface impact strength is obtained, a compression-molded article obtained from the resin-impregnated fiber bundle, and a method for producing the same.
  • the present invention (A) A resin-impregnated fiber bundle in which 25 to 300 parts by mass of a thermoplastic resin are impregnated with 100 parts by mass of a bundle of fiber materials,
  • the resin-impregnated fiber bundle has a flat shape in which the cross-sectional shape in the width direction has a major axis and a minor axis (major axis length> minor axis length), An average length (D1) of the major axis is 0.5 to 2.0 mm;
  • An average aspect ratio (D1 / D2) determined from an average length (D1) of the major axis and an average length (D2) of the minor axis is 1.2 to 8.0;
  • the resin-impregnated fiber bundle has a length (L) of 11 to 50 mm, and the ratio of L to D1 (L / D1) is 10 to 50,
  • a resin-impregnated fiber bundle having a bulk density of 0.1 to 0.4 g / cm 3 , a compression molded product obtained therefrom
  • the compression molded product obtained from the resin-impregnated fiber bundle of the present invention has particularly high surface impact strength. Moreover, since the compression-molded article manufacturing method of the present invention combines a preheating step using a non-contact heater and a subsequent compression step, the density of the obtained compression-molded product can be easily adjusted.
  • the fiber material used in the bundle of component (A) fiber materials is preferably selected from carbon fibers, glass fibers, and aramid fibers, but is not limited thereto.
  • the number of fiber material bundles is adjusted in consideration of the outer diameter (major axis length and minor axis length) of the resin-impregnated fiber bundle, and can be selected from a range of, for example, 100 to 30,000. .
  • thermoplastic resin of component (B) polyamide resins (polyamide 6, polyamide 66, polyamide 12 etc.), olefin resins (polypropylene, high density polyethylene, acid-modified polypropylene etc.), polyphenylene sulfide resins, polyesters (polyethylene terephthalate, poly Butylene terephthalate or the like), thermoplastic urethane resin (TPU), polyoxymethylene resin (POM), ABS resin, polycarbonate resin, an alloy of polycarbonate resin and ABS resin, or the like can be used.
  • 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 content ratio of the bundle of the fiber material of component (A) and the thermoplastic resin of component (B) is 25 to 300 parts by weight, preferably 30 to 150 parts by weight, for 100 parts by weight of component (A). Part by mass, more preferably 40 to 100 parts by mass.
  • the resin-impregnated fiber bundle may contain a known resin additive depending on the application.
  • the resin additive include a flame retardant, a heat stabilizer, a light stabilizer, a colorant, an antioxidant, an antistatic agent, and a lubricant.
  • the resin-impregnated fiber bundle has a flat shape in which the cross-sectional shape in the width direction has a major axis and a minor axis (major axis length> minor axis length).
  • the average length (D1) of the major axis of the resin-impregnated fiber bundle is 0.5 to 2.0 mm, preferably 0.5 to 1.5 mm.
  • the average aspect ratio (D1 / D2) obtained from the average length (D1) of the major axis of the resin-impregnated fiber bundle and the average length (D2) of the minor axis is 1.2 to 8.0, 1.5 to 5.0 is preferable, and 1.5 to 3.0 is more preferable.
  • the length (L) of the resin-impregnated fiber bundle is 11 to 50 mm, preferably 15 to 40 mm.
  • the ratio of L to D1 (L / D1) is 10 to 50, preferably 15 to 50, more preferably 20 to 40.
  • Resin-impregnated fiber bundle has a bulk density of 0.1 ⁇ 0.4g / cm 3, preferably 0.1 ⁇ 0.3g / cm 3, more preferably 0.1 ⁇ 0.2g / cm 3.
  • the bulk density is the packing density
  • the weighed resin-impregnated glass fiber bundle (mass m) is gently put into a measuring container such as a female cinder without being compacted, and the loose bulk volume in a state where it is not tapped (loosened) ( v 0) by reading the, it is possible to calculate the bulk density (m / v 0).
  • the resin-impregnated fiber bundle includes those having a cross-sectional shape in the width direction that is elliptical and those that are not elliptical.
  • the cross-sectional shape in the width direction is elliptical, all surfaces are curved surfaces, but when the cross-sectional shape in the width direction is not elliptical, some surfaces are flat surfaces. All or part of the surface facing the axis is planar.
  • the major axis of the resin-impregnated fiber bundle is the same, the one with a shorter minor axis (having a flat surface) is preferable because it easily enters a narrow gap.
  • JP 2013-109779 A Manufacturing of a resin-impregnated glass long fiber bundle of Production Example 1
  • JP 2013-121988 A Publication Manufacture of resin-impregnated glass long fiber bundle of Production Example 1
  • Japanese Patent Application Laid-Open No. 2012-52093 Examples 1 to 9
  • 2012-131104 Production of Resin-impregnated glass long fiber bundle of Production Example 1) Production, production of resin-impregnated carbon fiber long fiber bundle of production example 2), JP 2012-131918 (production of resin-impregnated carbon fiber bundle of production example 1, production of resin-impregnated glass fiber bundle of production example 2), It can be produced according to the methods described in JP 2011-162905 A (Example 1) and JP 2004-14990 A (Examples 1 to 7).
  • a method of adjusting the outlet shape of the crosshead die, and the two arranged vertically at the stage after exiting from the outlet of the crosshead die and before cooling. A method of passing between the rollers (shaping rolls) of the book can be applied.
  • the compression molded product of the present invention is a state in which the resin impregnated fiber bundles in contact with each other are fused with each other in a state where required amounts of the resin impregnated fiber bundles are randomly arranged.
  • the required amount of the resin-impregnated fiber bundle is the total number of resin-impregnated fiber bundles used according to the size (volume) and density of the target compression molded product.
  • the required amount of the resin-impregnated fiber bundle is calculated by determining the size (volume) and density of a compression-molded product as a reference, and obtaining the total number of resin-impregnated fiber bundles necessary for the trial production in advance. be able to.
  • the size (volume) and density of the target compression molded product can be determined according to the application.
  • the compression molded product of the present invention is (I) The resin-impregnated fiber bundles in contact with each other in a state where the required amount of the resin-impregnated fiber bundle is randomly arranged (two-dimensionally arranged) only in the plane direction (for example, a horizontal plane or a vertical plane) In the form of being fused together, (II) The resin in contact in a state where the required amount of the resin-impregnated fiber bundle is randomly arranged so as to be oblique to the surface direction and the surface direction (state arranged in three dimensions) The impregnated fiber bundles can be in the form of being fused together.
  • the cross-section of the resin-impregnated fiber bundle is larger than the shape of (I) and (II)
  • the adjacent resin-impregnated fiber bundles are easily brought into contact with each other, and the contact area is also increased. For this reason, the resin-impregnated fiber bundles are easily fused together when placed in a heated atmosphere.
  • the resin-impregnated fiber bundle of the present invention has a flatness ratio in the range of 1.2 to 8.0, the cross section is likely to be in the form of (II) when compared with a circle or an ellipse close thereto. This is preferable.
  • the resin-impregnated fiber bundle of the present invention having a flat surface because the form (II) is more easily obtained.
  • the compression molded product of the present invention preferably has a thickness of 1.5 to 10 mm and a density of 1.10 to 1.80 g / cm 3 .
  • the compression molded product of the present invention includes not only a planar shape but also a curved shape. Since the compression molded product of the present invention has a particularly high surface impact strength, the service life can be greatly extended when it is formed into a flat plate.
  • the manufacturing method of the compression molded product of this invention is demonstrated.
  • the resin-impregnated fiber bundle of a required amount is randomly arranged in the heating container, preferably in a three-dimensional manner so as to be in a plane direction and an oblique direction with respect to the plane direction. Input in the state. Since the resin-impregnated fiber bundle has a bulk density as small as 0.1 to 0.4 g / cm 3 , the thickness of the resin-impregnated fiber bundle charged into the heating container is small and can be made almost uniform. In addition, the thickness of the resin-impregnated fiber bundle after charging can be smoothed by applying vibration to the heating container as necessary.
  • the vibration When applying the vibration, three methods of the vertical direction, the horizontal direction, the vertical direction and the horizontal direction can be applied to the heating container, but the thickness of the resin-impregnated fiber bundle can be adjusted in a shorter time, so the vertical direction, Or the method of applying a vibration to an up-down and left-right direction is preferable.
  • the resin-impregnated fiber bundle in the heating container is preheated with a non-contact heater.
  • a non-contact type heater a heat source selected from infrared rays, near infrared rays, induction heating (IH) and hot air is preferable.
  • the preheating is performed until the resin-impregnated fiber bundles charged in the heating container are fused and integrated so that the whole does not move.
  • the resin-impregnated fiber bundle used in the previous process has a small bulk density of 0.1 to 0.4 g / cm 3 and there are many gaps between the resin-impregnated fiber bundles. Even if it exists, since heat spreads quickly with respect to the whole resin impregnated fiber bundle in a heating container, it can be integrated by a short process.
  • the pre-heated resin-impregnated fiber bundle is compressed while being heated to obtain a compression molded product.
  • the resin impregnated fiber bundle integrated product obtained in the previous step is put into a pressing mold and then compressed while being heated.
  • the heating temperature at the time of compression is lower than the softening point of the thermoplastic resin contained in the resin-impregnated fiber bundle, and is preferably lower than the preheating temperature.
  • a heat and cool molding method can be applied in order to shorten the molding cycle time or enhance the surface appearance.
  • the heat and cool molding method is a method of rapidly cooling after molding in a state where the mold temperature is rapidly increased before compression molding.
  • the fiber dispersibility in the molded product is improved and the uniformity of the molded product is enhanced by compression molding again. Therefore, a more stable product (because the dispersibility of the fiber in the molded product is good, the mechanical properties of the molded product are stabilized) can be obtained.
  • the thickness of the compression molded product is 1.5 to 10 mm, and the density is 1.10 to 1.80 g / cm 3 .
  • Example 1 (Production of resin-impregnated glass fiber bundle) A fiber bundle (glass fiber 1: a bundle of about 1600 glass fibers having a diameter of 13 ⁇ m) bundled with a sizing agent composed of the long glass fiber (A) was passed through a crosshead die. At that time, the melt of the component (B) polypropylene (PMB02A, manufactured by Sun Allomer Co., Ltd.) is supplied to the crosshead die from another twin-screw extruder (cylinder temperature 290 ° C.) to impregnate the long glass fiber bundle. I let you.
  • PMB02A polypropylene
  • the average length (D1) of the long axis and the average length (D2) of the short axis were measured by the following method. Ten resin-impregnated glass fiber bundles were taken out, and the average value was obtained by measuring the major axis length and minor axis length of the cross section (end face) using a scanning electron microscope. Specifically, the longest axis is the straight line that intersects the cross section and the length of the two intersections between the outer periphery of the cross section and the straight line is the longest axis, and the straight line that intersects the long axis perpendicularly The longest of the two intersection points was defined as the short axis.
  • the integrated product of the resin-impregnated glass fiber bundle was pressed for 10 seconds by a press (STI-1.6-220VF manufactured by Mitomo Co., Ltd.) (press temperature 170 ° C., press pressure 2 t). Then, it cooled to room temperature and obtained the compression molded object (200 mm in length, 200 mm in width, 2 mm in thickness, the density 1.50 g / cm ⁇ 3 >) in the planar shape.
  • a press STI-1.6-220VF manufactured by Mitomo Co., Ltd.
  • the compression molded product obtained from the resin-impregnated fiber bundle of the present invention is thin and has high surface impact strength, it is used for automobile parts, machine parts, building materials, household and commercial tableware and trays, and various daily necessities. It can be used for safety shoe parts.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)

Abstract

L'invention concerne un faisceau de fibres imprégné de résine qui permet d'obtenir un article moulé ayant une résistance élevée aux impacts de surface. Un faisceau de fibres imprégné de résine est obtenu en imprégnant et en intégrant (A) 100 parties en masse d'un faisceau de matériaux fibreux avec (B) 25 à 300 parties en masse d'une résine thermoplastique. Le faisceau de fibres imprégné de résine a une forme aplatie qui présente un profil en coupe transversale ayant un axe majeur et un axe mineur (longueur de l'axe majeur > longueur de l'axe mineur) dans le sens de la largeur ; la longueur moyenne de l'axe majeur (D1) va de 0,5 à 2,0 mm ; le taux d'aplatissement moyen (D1/D2) calculé à partir de la longueur moyenne de l'axe majeur (D1) et de la longueur moyenne de l'axe mineur (D2) va de 1,2 à 8,0 ; la longueur (L) du faisceau de fibres imprégné de résine va de 11 à 50 mm et le rapport de L sur D1 (L/D1) va de 10 à 50 ; et la densité apparente du faisceau de fibres imprégné de résine va de 0,1 à 0,4 g/cm3.
PCT/JP2017/009353 2016-03-11 2017-03-09 Faisceau de fibres imprégné de résine, article moulé par compression et son procédé de production Ceased WO2017155009A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US16/078,178 US10703019B2 (en) 2016-03-11 2017-03-09 Resin-impregnated fiber bundle, compression molded article, and a method for producing the same
EP17763349.2A EP3427913B1 (fr) 2016-03-11 2017-03-09 Faisceau de fibres imprégné de résine, article moulé par compression et son procédé de production
CN201780016661.5A CN108778655B (zh) 2016-03-11 2017-03-09 浸渗有树脂的纤维束、压缩成型品及其制造方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2016-048232 2016-03-11
JP2016048232 2016-03-11
JP2016-074008 2016-04-01
JP2016074008A JP6739210B2 (ja) 2016-03-11 2016-04-01 樹脂含浸繊維束、圧縮成形品およびその製造方法

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WO2017155009A1 true WO2017155009A1 (fr) 2017-09-14

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000210933A (ja) * 1999-01-21 2000-08-02 Nitto Boseki Co Ltd 樹脂被覆繊維束及びその製造方法
JP2012153109A (ja) * 2011-01-28 2012-08-16 Mitsubishi Heavy Ind Ltd 繊維強化プラスチック板及びその製造方法
JP2013107979A (ja) * 2011-11-21 2013-06-06 Daicel Polymer Ltd 樹脂組成物
WO2014030633A1 (fr) * 2012-08-21 2014-02-27 株式会社 豊田自動織機 Composite renforcé par des fibres tridimensionnelles
JP2015147428A (ja) * 2006-05-25 2015-08-20 三菱エンジニアリングプラスチックス株式会社 繊維強化熱可塑性樹脂成形品
JP2016020465A (ja) * 2014-06-18 2016-02-04 ダイセルポリマー株式会社 繊維強化樹脂組成物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000210933A (ja) * 1999-01-21 2000-08-02 Nitto Boseki Co Ltd 樹脂被覆繊維束及びその製造方法
JP2015147428A (ja) * 2006-05-25 2015-08-20 三菱エンジニアリングプラスチックス株式会社 繊維強化熱可塑性樹脂成形品
JP2012153109A (ja) * 2011-01-28 2012-08-16 Mitsubishi Heavy Ind Ltd 繊維強化プラスチック板及びその製造方法
JP2013107979A (ja) * 2011-11-21 2013-06-06 Daicel Polymer Ltd 樹脂組成物
WO2014030633A1 (fr) * 2012-08-21 2014-02-27 株式会社 豊田自動織機 Composite renforcé par des fibres tridimensionnelles
JP2016020465A (ja) * 2014-06-18 2016-02-04 ダイセルポリマー株式会社 繊維強化樹脂組成物

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