WO2014007505A1 - Pré-imprégné thermoplastique et son procédé de préparation - Google Patents

Pré-imprégné thermoplastique et son procédé de préparation Download PDF

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WO2014007505A1
WO2014007505A1 PCT/KR2013/005844 KR2013005844W WO2014007505A1 WO 2014007505 A1 WO2014007505 A1 WO 2014007505A1 KR 2013005844 W KR2013005844 W KR 2013005844W WO 2014007505 A1 WO2014007505 A1 WO 2014007505A1
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Prior art keywords
thermoplastic resin
resin film
thermoplastic
prepreg
melt flow
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PCT/KR2013/005844
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English (en)
Korean (ko)
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박용민
배성수
박근형
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에스케이케미칼 주식회사
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Publication of WO2014007505A1 publication Critical patent/WO2014007505A1/fr

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • 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
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • B29C43/20—Making multilayered or multicoloured articles
    • 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]
    • B29C70/504—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] using rollers or pressure bands
    • B29C70/506—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] using rollers or pressure bands and impregnating by melting a solid material, e.g. sheet, powder, fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/22—Thermoplastic resins

Definitions

  • the present invention relates to a thermoplastic prepreg and a method of manufacturing the same, and more particularly, to a thermoplastic prepreg impregnated with a reinforced fiber and having excellent impregnation and mechanical strength. And to a method for producing the same.
  • Prepreg is an abbreviation of "Preimpregnated Material,” and refers to a product in the form of a sheet in which a matrix is impregnated with a reinforcing fiber, and is used as an intermediate material for forming a composite material.
  • 1 is a view for explaining a conventional prepreg configuration (A) and a photo (B) showing an example of the prepreg.
  • the reinforcing fibers 12 and the binder 11 are integrated to form a prepreg 13
  • the prepreg 13 is a sheet. It is manufactured in the form of a sheet, wound on a paper roll 14, and cut and used to a desired length in use.
  • the prepreg 13 may be divided into a unidirectional prepreg in which the reinforcing fibers 12 are aligned in one direction, and a woven prepreg in which the reinforcing fibers 12 are formed in a woven form.
  • 1B shows an example of one-way prepreg.
  • thermosetting resins such as epoxy resins, phenol resins, unsaturated polyester resins, melamine resins and cyanate ester resins, polypropylene, polyethylene, polyamides, polystyrenes, polyesters, polycarbonates, thermoplastic polyurethanes, polyacetals, Various thermoplastic resins such as polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, ABS resin, polyetherimide, polyether ether ketone, polyphenylene sulfide, polylactic acid and the like can be used.
  • prepreg is applied to the molding of composite materials.
  • it is possible to precisely control the content and arrangement of reinforcing material (reinforcement fiber), thereby realizing the material properties of the designed material.
  • reinforcement fiber reinforcement fiber
  • the composite material forming process using prepreg uses the intermediate material, so the price of raw material is high, but the molding process is clean and simple, and the process cost can be reduced.
  • the prepreg is mainly in the form of a sheet, so it is easy to handle, saves energy costs during molding, and can reduce the number of parts required for processing due to the nature of cutting molding. It is widely used as an intermediate material for composite molding in many industries.
  • the prepreg may be classified into a thermosetting prepreg to which a thermosetting resin is applied, and a thermoplastic prepreg to which a thermoplastic resin is applied, and a thermosetting prepreg that is relatively easy to manufacture was mainly used in the early stages of prepreg development. Increasingly, thermoplastic prepregs that are compatible with and capable of recycling are being increased.
  • the manufacturing method of the thermoplastic prepreg is a film process, a powder coating process, a co-mingled yarn process, a direct melt process, Various solutions such as a solution process, but in view of economics, ease of production, quality of the molding, etc., the film method is most widely used.
  • FIG. 2 is a view illustrating a conventional thermoplastic prepreg production process.
  • FIG. 2A is a manufacturing process diagram of a woven thermoplastic prepreg 28a
  • FIG. 2B is a manufacturing process diagram of a unidirectional thermoplastic prepreg 28b.
  • the two processes are identical except for the addition of reinforcing fibers. Referring to FIG. 2A, in the roll 20a, the reinforcing fibers 21a in the form of weaved fabric are released, and both sides (upper part) of the reinforcing fibers 21a supplied from the roll 20a are released.
  • the resin films 22a and 22b obtained by processing the thermoplastic resin in the form of a film are supplied through a first feeder ( ⁇ ⁇ , 23a, 23b), and then the second paper feeder Release materials 24a and 24b are supplied from (second feeder, 25a and 25b).
  • the reinforcing fibers 21a in which the resin films 22a and 22b are laminated pass through the heating / pressing device 26.
  • the said heating / pressure apparatus 26 heats the resin films 22a and 22b to the temperature more than melting
  • the release materials 24a and 24b are recovered through separate take-up rolls 27a and 27b, thereby manufacturing the fabric-type thermoplastic prepreg 28a.
  • the fiber-like reinforcing fiber strands 30 are unwound in a warp form unfolded in one direction from a plurality of failures 20b and creel, and are evenly arranged and arranged in one direction.
  • a reinforcing fiber 21b of the form is formed, and the reinforcing fiber 21b is used for producing the unidirectional thermoplastic prepreg 28b, and the rest of the process is the same as that shown in A of FIG.
  • the resin films 22a and 22b in general, a non-stretching film is used, but in some cases, a stretched film, a resin fiber fabric, a resin nonwoven fabric, or the like is used. A modified film of may be used.
  • the release materials 24a and 24b supplied from the second paper feeders 25a and 25b may be used. 24a and 24b are commonly used a release paper made of paper and a release film made of a polymer material.
  • the manufacturing method of the thermoplastic prepreg using the film method is simple in configuration, and when changing the variety of the prepreg, only the film can be selectively changed, which is advantageous for the production of various varieties, the production yield is high, and the resin flushing is performed. Since there is no need for a separate pre / post treatment process such as dissolution of resin and compounding of resin, there is an advantage that the working environment is clean.
  • thermoplastic prepreg manufacturing process using the film method
  • melt viscosity (viscosity, viscosity) of the thermoplastic resin is very high, it is difficult to uniformly impregnate the resin in the reinforcing fibers, and to produce a high quality thermoplastic prepreg with high impregnation degree
  • the production temperature is excessively increased or the production speed is set low.
  • thermoplastic resin in order to lower the melt viscosity of the thermoplastic resin and improve the impregnation, heating to a temperature much higher than the melting point of the resin film or slowing down the production speed to increase the high temperature residence time results in thermal decomposition of the resin, resulting in the prepreg There is a possibility that the physical properties are lowered. Due to this difficulty of impregnation, in spite of the deterioration of physical properties, a low molecular weight resin film having a low melt viscosity may be used, but in this case, the melt viscosity is lower than that of a resin having a large molecular weight, which is advantageous for production. There is a problem that mechanical properties are significantly lowered.
  • thermoplastic prepreg in which a thermoplastic resin is used as a matrix (substrate) and excellent in impregnation degree and mechanical strength, and a method of manufacturing the same.
  • Another object of the present invention is to improve the impregnation with a resin film having a low melt viscosity, and to improve mechanical properties with a resin film having a high melt viscosity, thereby providing a method of easily and economically producing a thermosetting prepreg. It is.
  • a melt flow index (MI) of the first thermoplastic resin film is greater than a melt flow index (MI) of the second thermoplastic resin film in the heating and pressurizing step. to provide.
  • the present invention the sheet-like reinforcing fibers; A first thermoplastic resin film impregnated in the reinforcing fiber; And a second thermoplastic resin film bonded to the first thermoplastic resin film, wherein a melt flow index MI of the first thermoplastic resin film is greater than a melt flow index MI of the second thermoplastic resin film. It provides a thermoplastic prepreg.
  • thermoplastic prepreg and the manufacturing method thereof according to the present invention a thermoplastic prepreg excellent in impregnation and mechanical properties (strength, etc.) can be easily produced even in a simple three step process.
  • thermoplastics excellent in both the degree of impregnation and mechanical properties Prepregs can be prepared.
  • 1 is a view for explaining a conventional prepreg configuration and a photograph showing an example of the prepreg.
  • thermoplastic prepreg is a view showing a method of manufacturing a thermoplastic prepreg according to an embodiment of the present invention.
  • FIG. 4 shows a conventional heating / pressure device that can be used in the present invention.
  • thermoplastic prepreg is a view showing the structure of a thermoplastic prepreg according to an embodiment of the present invention.
  • 6a to 6c is a view showing a thermoplastic prepreg manufacturing method according to an embodiment of the present invention and a comparative example.
  • thermoplastic prepreg produced according to the Examples and Comparative Examples of the present invention.
  • FIG. 8 is a cross-sectional photograph of a hybrid thermoplastic prepreg according to an embodiment of the present invention.
  • thermoplastic prepreg is a view showing a method of manufacturing a thermoplastic prepreg according to an embodiment of the present invention.
  • the first thermoplastic resin films 42a and 42b are supplied to at least one surface of the reinforcing fibers 41 in the form of sheets.
  • the second thermoplastic resin films 44a and 44b are supplied (stacked) on any one or more surfaces of the first thermoplastic resin films 42a and 42b, and any one of the first thermoplastic resin films 42a and 42b is supplied.
  • Second thermoplastic resin films 44a and 44b are laminated on one or both surfaces.
  • the laminated reinforcing fibers 41, the first thermoplastic resin films 42a and 42b, and the second thermoplastic resin films 44a and 44b are heated and pressurized while passing through the heating / pressing device 48, and the first The thermoplastic resin films 42a and 42b are impregnated in the reinforcing fibers 41, and the first thermoplastic resin films 42a and 42b and the second thermoplastic resin films 44a and 44b are bonded to each other.
  • the melt flow index (MI) of the first thermoplastic resin films 42a and 42b is greater than the melt flow index MI of the second thermoplastic resin films 44a and 44b. It is set to.
  • the melt flow index MI of the first thermoplastic resin films 42a and 42b and the second thermoplastic resin films 44a and 44b is impregnated with the reinforcing fibers 41 and the first thermoplastic resin films 42a and 42b.
  • the property is superior to the impregnation of the reinforcing fibers 41 and the second thermoplastic resin films 44a and 44b, and the mechanical properties (strength and the like) of the second thermoplastic resin films 44a and 44b are the first thermoplastic resin film.
  • the ratio ((MI of first thermoplastic resin film) / (MI of second thermoplastic resin film)) is 1.01 times or more, for example, 1.01 to 5,000 times, preferably 1.1 times or more, more preferably 2 times or more. And most preferably at least 5 times.
  • the melt flow index (MI) is a number representing the number of g of the resin passed through the hole having a certain cross-sectional area for 10 minutes at a specific temperature and pressure, the higher the melt flow index (MI), the higher the fluidity of the resin, the higher the melt viscosity Lowers.
  • the melt flow index (MI) is measured according to ASTM D1238, the measurement temperature is the heating / pressure of the first thermoplastic resin film (42a, 42b) and the second thermoplastic resin film (44a, 44b)
  • the temperature of the stage (maximum heating temperature if the heating is done in several stages), measuring load is 2160 g, resin dissolution time is 10 minutes, and measuring unit is grams (g / 10 minutes).
  • the temperature of the heating / pressing step depends on the resin used, but is at least 5 ° C. higher than the melting point of the resin, for example, at a temperature of 10 ° C. to 30 ° C. higher than the melting point of the resin, specifically, high density polyethylene (HDPE).
  • polyethylene such as polyethylene
  • it is about 260 degreeC in polyester, such as 190 degreeC, and polycarbonate (PC), and a polyethylene terephthalate (PET).
  • the melt flow index MI of the first thermoplastic resin films 42a and 42b is 5 or more, preferably 10 or more, more preferably 15 or more. (As long as it can be molded into a prepreg, the higher the value, for example, the upper limit may be 50), and the melt flow index MI of the second thermoplastic resin films 44a and 44b is less than 5, Preferably it is 1 or less, More preferably, it is 0.5 or less (as long as it can be shape
  • melt flow index MI of the first thermoplastic resin films 42a and 42b is too small, impregnation does not occur to the inside of the reinforcing fiber, so that an unimpregnated portion (pores, voids) occurs in the prepreg.
  • melt flow index MI of the second thermoplastic resin films 44a and 44b is too large, there is a possibility that the improvement of physical properties of the prepreg may be insufficient.
  • the reinforcing fibers 41 may be used without limitation, conventional reinforcing fibers used for the production of prepreg, for example, high strength and elastic carbon fibers, glass fibers, aramid fibers ( aramid fibers, basalt fibers, boron fibers, and the like.
  • the reinforcing fibers 41 may be fibers arranged in one direction or may be fibers in the form of a fabric, and the thickness thereof is not particularly limited as long as it can be used as the reinforcing fibers.
  • the reinforcing fiber supply device 40 for supplying the reinforcing fibers 41 is a general supply device for supplying the woven or unidirectional reinforcing fibers 41.
  • the first thermoplastic resin films 42a and 42b supplied (laminated) to the upper and / or lower surfaces of the reinforcing fibers 41 have a melt viscosity such that the reinforcing fibers 41 are easily impregnated when heated and pressed. Made of small resin.
  • the first thermoplastic resin films 42a and 42b may be made of various conventional thermoplastic resins, and preferably polypropylene (PP), polyethylene (PE), polyamide (PA), polystyrene (PS), and polyester (PES), polycarbonate (PC), thermoplastic polyurethane (TPU), polyacetal (POM), polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), ABS (acrylonitrile butadiene styrene resin) resin, polyetherimide (PEI), polyetheretherketon (PEEK), polyphenylene sulfide (PPS) and polylactic acid, PLA) and a resin selected from the group consisting of.
  • PP polypropylene
  • PE polyethylene
  • PA polyamide
  • PS polystyrene
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • ABS acrylonitrile butadiene styrene resin
  • the thickness of the first thermoplastic resin films 42a and 42b is not particularly limited as long as the reinforcing fibers 41 can be impregnated, but is, for example, 0.01 mm to 2 mm.
  • the first thermoplastic resin films 42a and 42b are supplied by the first paper feeders 43a and 43b, and the first paper feeders 43a and 43b are used to feed the raw material in the form of a film. It is a normal paper feeding device which supplies continuously.
  • the second thermoplastic resin films 44a and 44b may also be made of various conventional thermoplastic resins satisfying the melt flow index MI.
  • the first thermoplastic resin films 42a and 42b may be formed. It may be made of various thermoplastic resins as described in the thermoplastic resin to be formed.
  • the thickness of the second thermoplastic resin films 44a and 44b is not particularly limited as long as it can improve the physical properties of the thermoplastic prepreg, but is, for example, 0.01 mm to 2 mm.
  • the first thermoplastic resin films 42a and 42b and the second thermoplastic resin films 44a and 44b have different molecular weights but are made of the same type of resin, or have compatibility or compatibility between resins. It is preferable that it consists of heterogeneous resin which does not fall in physical property at an interface.
  • a heterogeneous resin compatible polycarbonate (PC) and polyethylene terephthalate (PET) can be used. Both PET and PC have similar processing temperatures of around 260 ° C, while PET has a very high melt flow index (MI) of over 100 at 260 ° C, while PC has a relatively low melt flow index (MI) of less than 10 and mechanical Physical properties are superior to PC.
  • prepreg is produced by using PET as the first thermoplastic resin films 42a and 42b which are resins for impregnation, and by using the PC having strong mechanical properties as the second thermoplastic resin films 44a and 44b which are resins for enhancing properties. If it is, it is possible to produce a thermoplastic prepreg excellent in both impregnation degree and mechanical properties. In addition, if necessary, three or more kinds of various thermoplastic resin films may be laminated to produce thermoplastic prepregs having various functions.
  • melt viscosity of the thermoplastic resin can be expressed by the melt flow index (MI), the melt flow index (MI) according to the molecular weight of a representative thermoplastic resin, High Density Poly Ethylene (HDPE), and the Izod impact strength, which is a representative mechanical property value.
  • MI melt flow index
  • HDPE High Density Poly Ethylene
  • Izod Impact Strength is shown in Table 1 below.
  • Table 1 shows that the HDPE # 1 resin having a high molecular weight has excellent impact strength, but has a very low melt flow index (MI) of 0.02.
  • the HDPE # 5 resin has a low impact strength of 3 and a very low impact strength of the molded article to which the resin is applied, but has a high melt flow index (MI) of 20, which is advantageous for impregnation during prepreg manufacture.
  • the second thermoplastic resin films 44a and 44b are supplied by the second paper feeders 45a and 45b, and the second paper feeders 45a and 45b supply the raw material in the form of a film. It is a normal paper feeding device which supplies continuously.
  • the release materials 46a and 46b are supplied (laminated) to at least one surface of the second thermoplastic resin films 44a and 44b from the third feeders 47a and 47b. In the future, a phenomenon in which the molten second thermoplastic resin films 44a and 44b and the heating / pressing device 48 adhere to each other can be prevented. After the heating / pressing process, the release members 46a and 46b are recovered through the take-up rolls 49a and 49b.
  • the temperature and pressure of the heating / pressing device 48 impregnate the reinforcing fibers 41 with the first thermoplastic resin films 42a and 42b, and the first thermoplastic resin films 42a and 42b and the first agent.
  • the 2 thermoplastic resin films 44a and 44b can be bonded together, it will not specifically limit, According to the kind and physical property of the said 1st thermoplastic resin films 42a and 42b and the 2nd thermoplastic resin films 44a and 44b suitably, Can be set.
  • FIG. 4 shows a conventional heating / pressurizing device that can be used in the present invention, a roller-type heating / pressurizing device (A), a double belt type heating / pressurizing device (B), heating / pressurization of the fixed press type The device C is shown.
  • Fig. 4A in the roller type heating / pressing device A, the reinforcing fibers 41 and the resin passing through a set of heating / pressing rollers 31a and 31b provided at the upper and lower portions thereof.
  • the films 42a, 42b, 44a, 44b are heated / pressurized to impregnate the resin in the resin films 42a, 42b, 44a, 44b with the reinforcing fibers 41.
  • the roller type heating / pressing device A only one set of rollers 31a and 31b may be used, but productivity may be improved by using a plurality of roller sets.
  • the double belt type heating / pressing device B is a device capable of continuously applying temperature and pressure by placing the continuous belts 32a and 32b made of metal on the upper and lower sides.
  • the heating / pressing device C of the fixed press type performs heating and pressurization through module presses 33a and 33b in the form of blocks.
  • the heating / pressing device C of the fixed press type may be composed of only one module press 33a, 33b, similarly to the roller-type heating / pressing device A, but using a plurality of module presses, And the impregnation efficiency can be improved.
  • the roller type heating / pressing device (A) and the double belt type heating / pressing device (B) are mainly used for the continuous process, and the fixed press type heating / pressing device (C) is mainly used for the step process. Is used.
  • thermoplastic prepreg is a view showing the structure of a thermoplastic prepreg according to an embodiment of the present invention.
  • the thermoplastic prepreg according to an embodiment of the present invention the first thermoplastic resin film 42a, 42b, which is impregnated in the sheet-like reinforcing fibers 41, the reinforcing fibers 41 ) And second thermoplastic resin films 44a and 44b bonded to the first thermoplastic resin films 42a and 42b.
  • the melt flow index MI of the first thermoplastic resin films 42a and 42b is greater than the melt flow index MI of the second thermoplastic resin films 44a and 44b. If necessary, as shown in FIG.
  • the reinforcing fibers 41 may be partially impregnated not only in the first thermoplastic films 42a and 42b but also in the second thermoplastic films 44a and 44b. .
  • first thermoplastic resin films 42a and 42b having an advantageous impregnation in the reinforcing fibers 41 and the second resin films 44a and 44b having excellent physical properties are impregnated and bonded by heating / pressurizing, impregnation and mechanical properties It is possible to manufacture a thermoplastic prepreg 50 that satisfies all.
  • One-way prepreg 135 was manufactured using the installation with the roller type heating / pressing apparatus 160 (refer FIG. 6A). Using an opening device (100), glass fibers (OCV SE4121, 2400 tex, 101) having a width of 30 cm and a fiber weight of 300 g / m2 per unit area were opened to open the first nip roll (140). Was added.
  • OCV SE4121, 2400 tex, 101 glass fibers having a width of 30 cm and a fiber weight of 300 g / m2 per unit area were opened to open the first nip roll (140).
  • thermoplastic resin films 130a and 130b were introduced into the first paper feeders 104a and 104b
  • High molecular weight HDPE SK General Chemicals 2800, Mw: 190,300, MI: 0.02 at 2O < 0 > C
  • second thermoplastic resin films 131a and 131b were introduced into the second paper feeders 132a and 132b.
  • polyimide release films 105a and 105b subjected to cross-sectional release treatment having a thickness of 50 ⁇ m were introduced.
  • the rollers of the heating / pressure device 160 of the roller type used three sets 107, 108, and 109, and the respective temperatures were 120 ° C. for the first roller 107, 190 ° C. for the second roller 108, and third
  • the roller 109 was set to 190 ° C.
  • the pressure of the roller was set to 20 kg / cm of the first roller 107, 40 kg / cm of the second roller 108, and 40 kg / cm of the third roller 109.
  • the production rate was 1.0 m / min (102).
  • the release films 105a and 105b were recovered by take-up rolls 110a and 110b.
  • the preparation conditions of the thermoplastic prepreg are summarized in Table 2, and the impact strengths are measured and shown in Table 3.
  • the first feeder 104a, 104b is a low-molecular weight HDPE (SK General Chemicals JK910, Mw: 56,400, MI: 20 at 190 ° C.) having a thickness of 80 ⁇ m.
  • a thermoplastic prepreg was produced in the same manner as in Example 1 except that 103a and 103b were added and second feeding devices 132a and 132b were not used.
  • the preparation conditions of the thermoplastic prepreg are summarized in Table 2, and the impact strengths are measured and shown in Table 3.
  • the first thermoplastic feeder 104a, 104b is a high molecular weight HDPE having a thickness of 80 ⁇ m (SK General Chemicals 2800, Mw: 190,300, MI: 0.02 at 190 ° C.).
  • a thermoplastic prepreg was produced in the same manner as in Example 1, except that (113a, 113b) was added and the second paper feeders 132a, 132b were not used.
  • the preparation conditions of the thermoplastic prepreg are summarized in Table 2, and the impact strengths are measured and shown in Table 3.
  • thermoplastic prepreg is a cross-sectional photograph and cross-sectional conceptual view of the thermoplastic prepreg produced according to the Examples and Comparative Examples of the present invention.
  • the thermoplastic resin films 103a and 103b are uniformly impregnated in the reinforcing fiber 101
  • thermoplastic prepreg C of the Comparative Example 2 is The thermoplastic resin films 113a and 113b hardly penetrate the reinforcing fibers 101, are mainly distributed on the surface of the reinforcing fibers 101, and voids (gaps, 64) are formed between the reinforcing fibers 101, and resins It can be seen that the impregnation is insufficient.
  • thermoplastic prepreg A of Example 1 uses the first thermoplastic resin films 130a and 130b and the second thermoplastic resin films 131a and 131b simultaneously, and the first resin films 130a and 130b are used. It can be seen that the reinforcing fibers 101 are sufficiently impregnated, and the second resin films 131a and 131b are positioned in a layer on the outside.
  • the prepreg of Comparative Example 1 has a low impact strength using a relatively low molecular weight resin
  • the prepreg of Comparative Example 2 used a high molecular weight resin having excellent physical properties, but due to poor impregnation
  • the mechanical properties such as the thermoplastic resin films 113a and 113b and the reinforcing fiber 101 are separated from each other.
  • the thermoplastic prepreg of Example 1 has a high impact strength in combination with impregnation and mechanical properties.
  • a double belt heating / pressure device (divided into three sections) was sequentially set to a temperature of 200 ° C. in the first part, 260 ° C. in the second part, and 280 ° C. in the third part. Pressure is 20 kg / cm), and as the reinforcing fiber 101, a woven 3K carbon fiber plain fabric (modern fiber product C120, fiber weight per unit area: 200 g / m2) is used.
  • thermoplastic resin films 130a and 130b As the thermoplastic resin films 130a and 130b, a 40- ⁇ m-thick PET resin film (SKC SKYroll) was used, and as the second thermoplastic resin films 131a and 131b, a 40- ⁇ m-thick PC resin film (Ione Film) IPC-40A) was used, and the remaining conditions were the same as in Example 1, to prepare a thermoplastic prepreg.
  • a cross-sectional photograph of the prepared thermoplastic prepreg is shown in FIG. 8. As shown in FIG. 8, a tow 72 formed of a bundle of carbon fibers 150 constitutes a fabric, and PET resin films 130a and 130b having a low melt viscosity are impregnated between the tows 72.
  • thermoplastic prepreg of the present invention is a PC resin film (131a, 131b) is difficult to be impregnated, while the PET resin film (130a, 130b) is well impregnated in the reinforcing fiber 150, even at a low processing temperature It can be seen that the mechanical properties of can be utilized simultaneously.

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  • Reinforced Plastic Materials (AREA)

Abstract

Cette invention concerne : un pré-imprégné thermoplastique constitué d'une fibre de renfort imprégnée avec une résine thermoplastique, ayant un excellent degré d'imprégnation et une excellente résistance mécanique ; et son procédé de production. Le procédé de préparation du pré-imprégné thermoplastique comprend les étapes suivantes : application d'un premier film de résine thermoplastique à une ou plusieurs surfaces d'une fibre de renfort en forme de feuille ; l'application d'un second film de résine thermoplastique sur le premier film de résine thermoplastique ; et le chauffage et la mise sous pression du premier film de résine thermoplastique et du second film de résine thermoplastique de façon à imprégner le premier film de résine thermoplastique dans la fibre de renfort et à joindre le premier et le second film de résine thermoplastique, l'indice de fluidité à chaud (MI) du premier film de résine thermoplastique étant supérieur à celui à second dans l'étape de chauffage et de mise sous pression.
PCT/KR2013/005844 2012-07-03 2013-07-02 Pré-imprégné thermoplastique et son procédé de préparation WO2014007505A1 (fr)

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KR10-2012-0072278 2012-07-03
KR1020120072278A KR101934059B1 (ko) 2012-07-03 2012-07-03 열가소성 프리프레그 및 그 제조방법

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160057839A (ko) * 2014-11-14 2016-05-24 코오롱글로텍주식회사 완성품 형태의 프리프레그의 제조방법
EP3130452A4 (fr) * 2014-04-08 2017-11-29 Kolon Industries, Inc. Procédé de préparation d'un préimprégné thermoplastique et préimprégné thermoplastique préparé par ce procédé
KR20180130876A (ko) 2017-05-30 2018-12-10 재단법인 한국탄소융합기술원 일방향 시트가 혼합 적층된 열가소성 비굴곡 강화 직물 프리폼 및 프리프레그 제조방법
KR102053632B1 (ko) 2018-09-05 2019-12-09 재단법인 한국탄소융합기술원 이종섬유 ncf 및 이를 제조하는 장치
CN111452438A (zh) * 2020-05-19 2020-07-28 山东大学 一种热塑性复合膜
CN117384400A (zh) * 2023-12-11 2024-01-12 西南石油大学 具有损伤监测功能的玄武岩纤维复合材料及其制备方法

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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KR101713714B1 (ko) 2015-06-29 2017-03-22 현대자동차주식회사 열가소성 수지 복합재 및 이의 제조방법
KR101928847B1 (ko) * 2017-02-21 2019-03-12 이동우 열가소성 프리프레그 제조방법
KR102516146B1 (ko) * 2019-12-31 2023-03-30 코오롱인더스트리 주식회사 프리프레그, 이의 제조 방법 및 이로부터 제조되는 섬유 강화 복합 재료
KR102325446B1 (ko) * 2020-10-05 2021-12-01 김태헌 현무암섬유를 포함한 열경화성 섬유강화 복합소재, 그 제조방법 및 이 복합소재로 형성된 밴딩 구조물
KR102618861B1 (ko) 2021-03-11 2024-01-04 (유)씨앤투영 열가소성 탄소섬유직물 제조시스템

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR920019532A (ko) * 1991-04-23 1992-11-19 이따가끼 히로시 섬유강화 열가소성 시이트 및 그의 제조방법
US5387301A (en) * 1992-11-30 1995-02-07 Tonen Corporation Method of manufacturing a prepreg
US5441590A (en) * 1993-12-10 1995-08-15 Cheil Synthetics Incorporation Method for the preparation of prepreg of thermoplastic composite resin
US7820274B2 (en) * 2006-05-30 2010-10-26 Nof Corporation Prepreg and conductive layer-laminated substrate for printed wiring board
KR20120056027A (ko) * 2010-11-24 2012-06-01 지에스칼텍스 주식회사 복합재 시트 및 이의 제조방법

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6063874A (en) 1998-08-31 2000-05-16 General Electric Co. Polyetherimide resin/polyester resin blends
US6787179B2 (en) 2001-06-29 2004-09-07 Ethicon, Inc. Sterilization of bioactive coatings

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR920019532A (ko) * 1991-04-23 1992-11-19 이따가끼 히로시 섬유강화 열가소성 시이트 및 그의 제조방법
US5387301A (en) * 1992-11-30 1995-02-07 Tonen Corporation Method of manufacturing a prepreg
US5441590A (en) * 1993-12-10 1995-08-15 Cheil Synthetics Incorporation Method for the preparation of prepreg of thermoplastic composite resin
US7820274B2 (en) * 2006-05-30 2010-10-26 Nof Corporation Prepreg and conductive layer-laminated substrate for printed wiring board
KR20120056027A (ko) * 2010-11-24 2012-06-01 지에스칼텍스 주식회사 복합재 시트 및 이의 제조방법

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3130452A4 (fr) * 2014-04-08 2017-11-29 Kolon Industries, Inc. Procédé de préparation d'un préimprégné thermoplastique et préimprégné thermoplastique préparé par ce procédé
KR20160057839A (ko) * 2014-11-14 2016-05-24 코오롱글로텍주식회사 완성품 형태의 프리프레그의 제조방법
KR102170680B1 (ko) 2014-11-14 2020-10-27 코오롱글로텍주식회사 완성품 형태의 프리프레그의 제조방법
KR20180130876A (ko) 2017-05-30 2018-12-10 재단법인 한국탄소융합기술원 일방향 시트가 혼합 적층된 열가소성 비굴곡 강화 직물 프리폼 및 프리프레그 제조방법
KR102053632B1 (ko) 2018-09-05 2019-12-09 재단법인 한국탄소융합기술원 이종섬유 ncf 및 이를 제조하는 장치
CN111452438A (zh) * 2020-05-19 2020-07-28 山东大学 一种热塑性复合膜
CN117384400A (zh) * 2023-12-11 2024-01-12 西南石油大学 具有损伤监测功能的玄武岩纤维复合材料及其制备方法
CN117384400B (zh) * 2023-12-11 2024-02-13 西南石油大学 具有损伤监测功能的玄武岩纤维复合材料及其制备方法

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