WO2017122740A1 - プリプレグ、その製造方法および繊維強化成形品 - Google Patents
プリプレグ、その製造方法および繊維強化成形品 Download PDFInfo
- Publication number
- WO2017122740A1 WO2017122740A1 PCT/JP2017/000864 JP2017000864W WO2017122740A1 WO 2017122740 A1 WO2017122740 A1 WO 2017122740A1 JP 2017000864 W JP2017000864 W JP 2017000864W WO 2017122740 A1 WO2017122740 A1 WO 2017122740A1
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- WIPO (PCT)
- Prior art keywords
- fluororesin
- mass
- group
- thermoplastic resin
- resin
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
-
- 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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Definitions
- the present invention relates to a prepreg, a manufacturing method thereof, and a fiber-reinforced molded article using the prepreg.
- Fiber reinforced molded products are used in a wide range of applications such as transportation equipment (vehicles (automobiles, railcars, etc.), airplanes, etc.), building components, and electronic equipment.
- transportation equipment vehicles (automobiles, railcars, etc.), airplanes, etc.
- building components and electronic equipment.
- a cured product of a thermosetting resin has been often used as a matrix resin for fiber-reinforced molded products.
- a fiber reinforced molded product using a cured product of a thermosetting resin as a matrix resin has the following problems. -Since the cured product of the thermosetting resin is brittle, the impact resistance of the fiber reinforced molded product is insufficient. -In the prepreg which is a precursor of a fiber reinforced molded article, since the thermosetting resin before hardening will harden
- Patent Documents 1 and 2 Therefore, prepregs and fiber reinforced molded products using a thermoplastic resin as a matrix resin have been proposed (for example, Patent Documents 1 and 2).
- Patent Document 2 describes that the fiber-reinforced molded article may contain polytetrafluoroethylene particles. Polytetrafluoroethylene is excellent in chemical resistance but has low affinity with other materials. Therefore, fiber reinforced molded products (laminates) formed using prepregs containing polytetrafluoroethylene particles and other members (other prepregs, metal members, etc.) have adhesion between members (interlayers). Insufficient.
- the present invention can obtain a fiber reinforced molded article excellent in impact resistance, chemical resistance and adhesion between members (interlayers), and has excellent storage stability, a method for producing the same, and impact resistance.
- the present invention provides a fiber reinforced molded article excellent in chemical resistance and adhesion between members (interlayers).
- the present invention has the following aspects. ⁇ 1> A reinforcing fiber and a matrix resin; wherein the matrix resin has a melting point of 100 ° C. or higher and 325 ° C. or lower as a resin component, and includes a carbonyl group-containing group, a hydroxy group, an epoxy group, and an isocyanate group. Including only a melt-moldable fluororesin having at least one functional group selected from: or including the fluororesin and a thermoplastic resin (excluding the fluororesin); the fluororesin and the thermoplastic The prepreg whose ratio of the said fluororesin is 70 to 100 mass% among the total 100 mass% with resin, and whose ratio of the said thermoplastic resin is 0 to 30 mass%.
- the ratio of the fluororesin is 70% by mass or more and less than 100% by mass, and the ratio of the thermoplastic resin is more than 0% by mass to 30% by mass.
- the matrix resin has a sea-island structure composed of a sea part containing the fluororesin and an island part containing the thermoplastic resin; and the average diameter of the island part is 0.01 ⁇ m or more and 200 ⁇ m or less.
- a ⁇ 1> prepreg. ⁇ 3> The prepreg according to ⁇ 1> or ⁇ 2>, wherein the fluororesin has a melting point of 100 ° C. or higher and lower than 260 ° C.
- Resin comprising a melt-moldable fluororesin having a melting point of 100 ° C. or more and 325 ° C. or less and having at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, and an isocyanate group Powder (X) made of material ( ⁇ ) and powder (Y) made of resin material ( ⁇ ) containing a thermoplastic resin (excluding the fluororesin), the fluororesin and the thermoplastic Powder formed by mixing such that the ratio of the fluororesin is 70% by mass or more and less than 100% by mass and the ratio of the thermoplastic resin is more than 0% by mass and 30% by mass or less in the total 100% by mass with the resin.
- a method for producing a prepreg comprising: melting a body mixture in the presence of a reinforcing fiber sheet, and impregnating the reinforcing fiber sheet with the resin material ( ⁇ ) and the resin material ( ⁇ ).
- a resin component or less as a resin component and having at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, and an isocyanate group
- a resin component having at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, and an isocyanate group
- Powder (Z) composed of a resin material ( ⁇ ) that is 70% by mass or more and 100% by mass or less and the ratio of the thermoplastic resin is 0% by mass or more and 30% by mass or less; melted in the presence of the reinforcing fiber sheet
- the powder (Z) has an average particle size of 0.02 ⁇ m or more and 200 ⁇ m or less; of the total 100% by mass of the fluororesin and the thermoplastic resin, the proportion of the fluororesin is 70% by mass Is less than 100% by mass, and the ratio of the thermoplastic resin is more than 0% by mass and not more than 30% by mass; the island containing the thermoplastic resin in the resin material ( ⁇ ) before impregnating the reinforcing fiber sheet.
- ⁇ 8> Fluorine having a melting point of 100 ° C.
- the ratio of the fluororesin is 70% by mass or more and less than 100% by mass, and the ratio of the thermoplastic resin is more than 0% by mass to 30% by mass.
- % Of the island part containing the thermoplastic resin in the resin material ( ⁇ ) before impregnated in the reinforcing fiber sheet is 0.01 ⁇ m or more and 8 ⁇ m or less and less than the thickness of the resin film.
- the prepreg of the present invention it is possible to obtain a fiber reinforced molded article excellent in impact resistance, chemical resistance and adhesion between members (interlayers). Moreover, the prepreg of the present invention is excellent in storage stability. According to the prepreg manufacturing method of the present invention, it is possible to obtain a fiber reinforced molded article having excellent impact resistance, chemical resistance and adhesion between members (interlayers), and manufacturing a prepreg excellent in storage stability. it can.
- the fiber-reinforced molded article of the present invention is excellent in impact resistance, chemical resistance and adhesion between members (interlayers).
- melting point is a temperature corresponding to the maximum value of the melting peak measured by the differential scanning calorimetry (DSC) method.
- Melt moldable means exhibiting melt fluidity.
- Melowing melt flowability means that there is a temperature at which the melt flow rate is 0.1 to 1000 g / 10 minutes at a temperature higher than the melting point of the resin by 20 ° C. or more under the condition of a load of 49 N. .
- the “melt flow rate” is a melt mass flow rate (MFR) defined in JIS K 7210: 1999 (ISO 1133: 1997).
- the “unit” means a portion (polymerized unit) derived from the monomer formed by polymerization of the monomer.
- the unit may be a unit directly formed by a polymerization reaction, or may be a unit in which a part of the unit is converted into another structure by treating the polymer.
- the “average diameter of the island portion” is obtained by measuring the area of five island portions in the electron microscope image of the resin material or the matrix resin, calculating a circle-converted diameter from the area, and averaging these.
- the “average particle diameter of powder” is a volume-based cumulative 50% diameter (D50) determined by a laser diffraction / scattering method. That is, the particle size distribution is measured by the laser diffraction / scattering method, the cumulative curve is obtained with the total volume of the group of particles being 100%, and the particle diameter is the point at which the cumulative volume is 50% on the cumulative curve.
- the prepreg of the present invention has reinforcing fibers and a matrix resin. Specifically, it is a sheet-like material in which reinforcing fibers are impregnated with a matrix resin, and is also referred to as a sheet-like material in which reinforcing fibers are embedded in a matrix resin. In addition, not only those completely impregnated but also what is called a semi-preg in which matrix resin powder is adhered to the surface of the reinforcing fiber and melted and semi-impregnated into the reinforcing fiber is included.
- the reinforcing fiber is preferably a continuous long fiber having a length of 10 mm or more from the viewpoint of the mechanical properties of the fiber-reinforced molded product.
- the reinforcing fibers do not need to be continuous over the entire length in the length direction or the entire width in the width direction of the reinforcing fiber sheet, and may be divided in the middle.
- the reinforcing fiber sheet includes a reinforcing fiber bundle composed of a plurality of reinforcing fibers, a cloth formed by weaving the reinforcing fiber bundle, a unidirectional reinforcing fiber bundle in which a plurality of reinforcing fibers are aligned in one direction, and the unidirectional reinforcement. Examples thereof include a unidirectional cloth composed of fiber bundles, a combination thereof, and a stack of a plurality of reinforcing fiber bundles.
- Examples of reinforcing fibers include inorganic fibers, metal fibers, and organic fibers.
- Examples of the inorganic fiber include carbon fiber, graphite fiber, glass fiber, silicon carbide fiber, silicon nitride fiber, alumina fiber, silicon carbide fiber, and boron fiber.
- Examples of the metal fiber include aluminum fiber, brass fiber, and stainless steel fiber.
- Examples of the organic fiber include aromatic polyamide fiber, polyaramid fiber, polyparaphenylene benzoxazole (PBO) fiber, polyphenylene sulfide fiber, polyester fiber, acrylic fiber, nylon fiber, polyethylene fiber, and the like.
- the reinforcing fiber may be subjected to a surface treatment. Reinforcing fibers may be used alone or in combination of two or more.
- carbon fiber is preferable from the viewpoint of low specific gravity, high strength, and high elastic modulus. Examples of the carbon fiber include those described in WO2013 / 129169, and those described in paragraphs 0018 to 0026 are particularly preferable. Examples of the carbon fiber production method include those described in paragraphs 0028 to 0033.
- a matrix resin contains only a fluororesin (A) as a resin component, or contains a fluororesin (A) and a thermoplastic resin (B) (however, except a fluororesin (A)).
- the matrix resin may contain components other than the fluororesin (A) and the thermoplastic resin (B) as long as the effects of the present invention are not impaired.
- the matrix resin contains the thermoplastic resin (B)
- the matrix resin is a fluororesin (from the point of adhesion between members (interlayers) in the fiber reinforced molded product and the chemical resistance of the fiber reinforced molded product. It is preferable to have a sea-island structure including a sea part including A) and an island part including the thermoplastic resin (B).
- the average diameter of the island is preferably 0.01 ⁇ m or more and 200 ⁇ m or less, and more preferably 0.01 ⁇ m or more and 100 ⁇ m or less. If the average diameter of the islands is equal to or greater than the lower limit of the above range, the fiber-reinforced molded product is remarkably excellent in impact resistance. If the average diameter of the island portion is equal to or less than the upper limit of the above range, the adhesion between members (interlayers) in the fiber reinforced molded product and the chemical resistance of the fiber reinforced molded product are remarkably excellent.
- the fluororesin (A) is a fluororesin having at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, and an isocyanate group (hereinafter referred to as a functional group (f)). is there.
- a functional group (f) By having fluorine atoms, the chemical resistance of the fiber reinforced molded product is excellent.
- the adhesive functional group (f) the adhesiveness between members (interlayers) in the fiber reinforced molded article is excellent.
- the functional group (f) is excellent in adhesion between members (interlayers) in the fiber reinforced molded article, the functional group (f) is either one or both of the end group of the main chain of the fluororesin (A) and the pendant group of the main chain. Preferably it is present.
- the functional group (f) may be one type or two or more types.
- the fluororesin (A) preferably has at least a carbonyl group-containing group as the functional group (f) from the viewpoint of adhesion between members (interlayers) in the fiber reinforced molded product.
- the carbonyl group-containing group include a group having a carbonyl group between carbon atoms of a hydrocarbon group, a carbonate group, a carboxy group, a haloformyl group, an alkoxycarbonyl group, an acid anhydride group, and the like.
- Examples of the hydrocarbon group in the group having a carbonyl group between carbon atoms of the hydrocarbon group include alkylene groups having 2 to 8 carbon atoms.
- carbon number of this alkylene group is carbon number in the state which does not contain carbon which comprises a carbonyl group.
- the alkylene group may be linear or branched.
- the haloformyl group is represented by —C ( ⁇ O) —X (where X is a halogen atom).
- Examples of the halogen atom in the haloformyl group include a fluorine atom and a chlorine atom, and a fluorine atom is preferable.
- the haloformyl group is preferably a fluoroformyl group (also referred to as a carbonyl fluoride group).
- the alkoxy group in the alkoxycarbonyl group may be linear or branched and is preferably an alkoxy group having 1 to 8 carbon atoms, particularly preferably a methoxy group or an ethoxy group.
- the content of the functional group (f) in the fluororesin (A) is preferably 10 to 60000, more preferably 100 to 50000, with respect to 1 ⁇ 10 6 main chain carbon atoms of the fluororesin (A). More preferably, 10000 is preferable, and 300 to 5000 is particularly preferable. If content of a functional group (f) is more than the lower limit of the said range, the adhesiveness between the members (interlayer) in a fiber reinforced molded product will be remarkably excellent. If content of a functional group (f) is below the upper limit of the said range, even if the temperature at the time of shape
- the content of the functional group (f) can be measured by methods such as nuclear magnetic resonance (NMR) analysis and infrared absorption spectrum analysis. For example, as described in Japanese Patent Application Laid-Open No. 2007-314720, using a method such as infrared absorption spectrum analysis, the proportion of units having the functional group (f) (mol) in all units constituting the fluororesin (A) %) And the content of the functional group (f) can be calculated from the ratio.
- NMR nuclear magnetic resonance
- infrared absorption spectrum analysis the proportion of units having the functional group (f) (mol) in all units constituting the fluororesin (A) %)
- the content of the functional group (f) can be calculated from the ratio.
- the melting point of the fluororesin (A) is 100 ° C. or higher and 325 ° C. or lower, preferably 100 ° C. or higher and lower than 260 ° C., more preferably 120 ° C. or higher and 220 ° C. or lower. If the melting point of the fluororesin (A) is at least the lower limit of the above range, the heat resistance of the fiber reinforced molded product is excellent. If the melting point of the fluororesin (A) is not more than the upper limit of the above range, a general-purpose apparatus can be used for producing a fiber reinforced molded product, and adhesion between members (interlayers) in the fiber reinforced molded product Excellent.
- the melting point of the fluororesin (A) is preferably 120 ° C. or higher and 220 ° C. or lower, and more preferably 120 ° C. or higher and 200 ° C. or lower.
- the fluororesin (A) having a relatively high melting point it is preferable because a fiber reinforced molded product having high heat resistance can be obtained.
- the melting point of the fluororesin (A) is preferably 260 to 320 ° C, more preferably 280 to 320 ° C.
- the melting point of the fluororesin (A) can be adjusted by the type and ratio of units constituting the fluororesin (A), the molecular weight of the fluororesin (A), and the like. For example, the melting point tends to increase as the proportion of the unit (u1) described later increases.
- the fluororesin (A) a material that can be melt-molded is used because it is easy to produce a powder, a resin film, and a prepreg.
- the fluororesin (A) that can be melt-molded known fluororesins that can be melt-molded (tetrafluoroethylene / fluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, ethylene / tetrafluoroethylene) Copolymer, polyvinylidene fluoride, polychlorotrifluoroethylene, ethylene / chlorotrifluoroethylene copolymer, etc.), a fluororesin in which a functional group (f) is introduced; a fluoropolymer (A11) described later, etc. .
- the fluororesin (A) has a temperature at which the melt flow rate is 0.1 to 1000 g / 10 min at a temperature higher than the melting point of the fluororesin (A) by 20 ° C. or more under a load of 49 N. Use.
- the melt flow rate is preferably 0.5 to 100 g / 10 minutes, more preferably 1 to 30 g / 10 minutes, and further preferably 5 to 20 g / 10 minutes.
- the melt flow rate is at least the lower limit of the above range, the moldability of the fluororesin (A) is excellent. If the melt flow rate is not more than the upper limit of the above range, the mechanical properties of the fiber-reinforced molded product are excellent.
- Fluororesin (A1) Fluorine-containing heavy having a functional group (f) derived from at least one selected from the group consisting of a monomer, a chain transfer agent and a polymerization initiator used in the production of the fluorinated polymer Coalescence.
- the fluororesin (A1) is also referred to as a fluoropolymer (A1).
- Fluororesin (A2) A fluororesin in which a functional group (f) is introduced into a fluororesin having no functional group (f) by surface treatment such as corona discharge treatment or plasma treatment.
- Fluororesin (A3) A fluororesin obtained by graft polymerization of a monomer having a functional group (f) to a fluororesin having no functional group (f).
- the fluororesin (A) is preferably a fluoropolymer (A1) for the following reasons. -In the fluoropolymer (A1), since the functional group (f) is present in either one or both of the end group of the main chain and the pendant group of the main chain of the fluoropolymer (A1), fiber reinforced molding The adhesiveness between members (interlayers) in the product is remarkably excellent.
- the functional group (f) in the fluororesin (A2) is unstable because it is formed by the surface treatment, and tends to disappear with time.
- the fluoropolymer (A1) is prepared by the following method (i): Can be manufactured.
- the functional group (f) is present in a unit derived from the monomer formed by polymerization of the monomer during production.
- the fluoropolymer (A1) is prepared by the following method (ii) Can be manufactured.
- the functional group (f) exists as a terminal group of the main chain of the fluoropolymer (A1).
- the fluoropolymer (A1) is prepared by the following method (iii) Can be manufactured.
- the functional group (f) exists as a terminal group of the main chain of the fluoropolymer (A1).
- Method (iii): The fluoropolymer (A1) is produced by polymerizing monomers in the presence of a polymerization initiator such as a radical polymerization initiator having a functional group (f).
- radical polymerization initiator having a functional group (f) examples include di-n-propyl peroxydicarbonate, diisopropyl peroxycarbonate, tert-butyl peroxyisopropyl carbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, di-2 -Ethylhexyl peroxydicarbonate and the like.
- the fluoropolymer (A1) can be produced by using two or more of the above methods (i) to (iii) in combination.
- the fluorine-containing polymer (A1) As the fluorine-containing polymer (A1), the content of the functional group (f) can be easily controlled. Therefore, the method (i) is easy to adjust the adhesion between members (interlayers) in a fiber reinforced molded product. ) -Containing fluoropolymer (A1) having a functional group (f) derived from a monomer is preferable.
- a monomer having a functional group (f) a monomer having a carboxy group (maleic acid, itaconic acid, citraconic acid, undecylenic acid, etc.); a monomer having an acid anhydride group (itaconic anhydride (hereinafter referred to as “itaconic acid anhydride”)) , "IAH”), citraconic anhydride (hereinafter also referred to as "CAH”), 5-norbornene-2,3-dicarboxylic acid anhydride (hereinafter also referred to as "NAH”), maleic anhydride, etc. ), Monomers having a hydroxyl group and an epoxy group (such as hydroxybutyl vinyl ether and glycidyl vinyl ether).
- Fluoropolymer (A11) As the fluorine-containing polymer (A1) having a functional group (f) derived from a monomer, the following fluorine-containing polymer (F1) has the following advantages since the adhesion between members (interlayers) in the fiber reinforced molded product is remarkably excellent. A11) is particularly preferred.
- TFE tetrafluoroethylene
- CTFE chlorotrifluoroethylene
- the acid anhydride group of the unit (u2) corresponds to the functional group (f).
- Examples of the acid anhydride group-containing cyclic hydrocarbon monomer constituting the unit (u2) include IAH, CAH, NAH, and maleic anhydride.
- the acid anhydride group-containing cyclic hydrocarbon monomer one type may be used alone, or two or more types may be used in combination.
- the acid anhydride group-containing cyclic hydrocarbon monomer is preferably at least one selected from the group consisting of IAH, CAH and NAH.
- acid anhydride can be used without using a special polymerization method required when maleic anhydride is used (see JP-A-11-193132).
- a fluorine-containing polymer (A11) having a physical group can be easily produced.
- IAH or NAH is preferable from the viewpoint of remarkably excellent adhesion between members (interlayers) in a fiber-reinforced molded product.
- the fluorine-containing monomer at least one selected from the group consisting of HFP, PAVE and FAE is preferable from the viewpoint of excellent moldability of the fluorine-containing polymer (A11), bending resistance of the fiber-reinforced molded product, and the like.
- One or both of FAE and HFP are more preferred.
- the preferable ratio of each unit of the fluoropolymer (A11) is as follows.
- the proportion of the unit (u1) is preferably 90 to 99.89 mol%, more preferably 95 to 99.47 mol%, based on the total of the unit (u1), the unit (u2) and the unit (u3). 96 to 98.95 mol% is more preferable.
- the proportion of the unit (u2) is preferably 0.01 to 3 mol%, more preferably 0.03 to 2 mol%, based on the total of the unit (u1), the unit (u2) and the unit (u3). 0.05 to 1 mol% is more preferable.
- the proportion of the unit (u3) is preferably from 0.1 to 9.99 mol%, preferably from 0.5 to 9.97 mol%, based on the total of the unit (u1), the unit (u2) and the unit (u3). Is more preferably 1 to 9.95 mol%.
- the fluorinated polymer (A11) is a unit derived from a monomer having no fluorine (excluding an acid anhydride group-containing cyclic hydrocarbon monomer).
- (U4) may be included.
- the monomer having no fluorine a compound having no polymerizable fluorine having one polymerizable carbon-carbon double bond is preferable, and examples thereof include olefins (ethylene (hereinafter also referred to as “E”), propylene, 1- Butene and the like) and vinyl esters (vinyl acetate and the like).
- Monomers having no fluorine may be used alone or in combination of two or more.
- ethylene, propylene, and 1-butene are preferable, and ethylene is particularly preferable from the viewpoint of excellent mechanical properties of the fiber-reinforced molded product.
- the proportion of the unit (u1) is preferably 25 to 80 mol%, preferably 40 to 65 mol%, out of a total of 100 mol% of the unit (u1), the unit (u2), the unit (u3) and the unit (u4). More preferred is 45 to 63 mol%.
- the proportion of the unit (u2) is preferably from 0.01 to 5 mol% out of a total of 100 mol% of the unit (u1), the unit (u2), the unit (u3) and the unit (u4), preferably 0.03 to 3 mol% is more preferable, and 0.05 to 1 mol% is more preferable.
- the proportion of the unit (u3) is preferably 0.2 to 20 mol% out of a total of 100 mol% of the unit (u1), the unit (u2), the unit (u3) and the unit (u4), 0.5 to 15 mol% is more preferable, and 1 to 12 mol% is more preferable.
- the proportion of the unit (u4) is preferably from 20 to 75 mol%, preferably from 35 to 50 mol%, based on the total of 100 mol% of the unit (u1), the unit (u2), the unit (u3) and the unit (u4). Is more preferable, and 37 to 55 mol% is more preferable.
- the fiber reinforced molded product is extremely excellent in flame retardancy, chemical resistance, and the like.
- the ratio of the unit (u2) is within the above range, the amount of the acid anhydride group in the fluoropolymer (A11) is appropriate, and the adhesion between members (interlayers) in the fiber reinforced molded product is remarkably excellent.
- the ratio of the unit (u3) is within the above range, the fluoropolymer (A11) is remarkably excellent in moldability, the flex resistance of the fiber reinforced molded product, and the like.
- the proportion of each unit can be calculated by melt NMR analysis, fluorine content analysis, infrared absorption spectrum analysis, etc. of the fluoropolymer (A11).
- a part of the acid anhydride group in the unit (u2) is hydrolyzed, and as a result, a dicarboxylic acid (itaconic acid, Units derived from citraconic acid, 5-norbornene-2,3-dicarboxylic acid, maleic acid, etc.) may be included.
- a dicarboxylic acid (itaconic acid, Units derived from citraconic acid, 5-norbornene-2,3-dicarboxylic acid, maleic acid, etc.) may be included.
- the ratio of the unit is included in the ratio of the unit (u2).
- fluoropolymer (A11) examples include TFE / NAH / PPVE copolymer, TFE / IAH / PPVE copolymer, TFE / CAH / PPVE copolymer, TFE / IAH / HFP copolymer, TFE / CAH / HFP copolymer, TFE / IAH / CH 2 ⁇ CH (CF 2 ) 4 F / E copolymer, TFE / CAH / CH 2 ⁇ CH (CF 2 ) 4 F / E copolymer, TFE / IAH / CH 2 ⁇ CH (CF 2 ) 2 F / E copolymer, TFE / CAH / CH 2 ⁇ CH (CF 2 ) 2 F / E copolymer, TFE / IAH / HFP / CH 2 ⁇ CH ( CF 2 ) 4 F / E copolymer and the like.
- a fluororesin (A) can be manufactured by a conventional method.
- the polymerization method is preferably a polymerization method using a radical polymerization initiator.
- Polymerization methods include bulk polymerization, solution polymerization using organic solvents (fluorinated hydrocarbons, chlorinated hydrocarbons, fluorinated chlorohydrocarbons, alcohols, hydrocarbons, etc.), aqueous media and appropriate organic solvents as required.
- suspension polymerization methods using an aqueous medium and an emulsion polymerization method using an emulsifier and a solution polymerization method are preferred.
- thermoplastic resin (B) examples include a crystalline resin, an amorphous resin, a thermoplastic elastomer, and others (except for the fluororesin (A)).
- polyester resins polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, liquid crystal polyester, etc.
- polyolefin resins polyethylene, polypropylene, polybutylene, acid-modified polyethylene, acid-modified polypropylene, acid) Modified polybutylene, etc.
- polyoxymethylene polyamide, polyarylene sulfide resin (polyphenylene sulfide, etc.)
- polyketone polyetherketone, polyetheretherketone, polyetherketoneketone, polyethernitrile, fluororesin other than fluororesin (A) (Polytetrafluoroethylene and the like), liquid crystal polymers and the like.
- Amorphous resins include styrene resins (polystyrene, acrylonitrile styrene resin, acrylonitrile butadiene styrene resin, etc.), polycarbonate, polymethyl methacrylate, polyvinyl chloride, unmodified or modified polyphenylene ether, thermoplastic polyimide, polyamideimide, Examples include polyetherimide, polysulfone, polyethersulfone, and polyarylate.
- thermoplastic elastomers polystyrene elastomers, polyolefin elastomers, polyurethane elastomers, polyester elastomers, polyamide elastomers, polybutadiene elastomers, polyisoprene elastomers, fluorine elastomers (except for fluororesin (A)). And acrylonitrile-based elastomer.
- Other examples include phenolic resins and phenoxy resins.
- thermoplastic resin (B) from the viewpoint of improving the heat resistance of the prepreg, polyamide, polyarylene sulfide resin (polyphenylene sulfide, etc.), polyketone, polyetherketone, polyetheretherketone, polyetherketoneketone, polyethernitrile, Modified polyphenylene ether, thermoplastic polyimide, polyamideimide, polyetherimide, polysulfone, polyethersulfone, polyarylate and the like are preferable.
- Other ingredients contained in the matrix resin include inorganic fillers, organic fillers, organic pigments, metal soaps, surfactants, ultraviolet absorbers, lubricants, silane coupling agents, organic compounds (for example, organic monomers, polymerization degree of 50 or less) And the like, and an inorganic filler is preferable.
- Ratio of each component Of the total 100% by mass of the fluororesin (A) and the thermoplastic resin (B), the ratio of the fluororesin (A) is 70 to 100% by mass, preferably 70 to less than 100% by mass, and 80 to 100%. Less than mass% is more preferable. If the ratio of a fluororesin (A) is more than the lower limit of the said range, it will be excellent in the adhesiveness between the members (interlayer) in a fiber reinforced molded product, and the chemical resistance of a fiber reinforced molded product. If the ratio of a fluororesin (A) is less than 100 mass%, an expensive fluororesin (A) can be reduced and the cost of a prepreg and a fiber reinforced molded product will fall.
- the ratio of the thermoplastic resin (B) in the total 100% by mass of the fluororesin (A) and the thermoplastic resin (B) is 0-30% by mass, preferably more than 0-30% by mass, more than 0 More preferable is 20% by mass. If the ratio of a thermoplastic resin (B) exceeds 0 mass%, expensive fluororesin (A) can be reduced and the cost of a prepreg and a fiber reinforced molded product will fall. If the ratio of a thermoplastic resin (B) is below the upper limit of the said range, the effect exhibited by a fluororesin (A) will not be impaired.
- the total proportion of the fluororesin (A) and the thermoplastic resin (B) in 100% by mass of the matrix resin is preferably 80 to 100% by mass, more preferably 85 to 100% by mass, and 90 to 100% by mass. Further preferred. When the total ratio of the fluororesin (A) and the thermoplastic resin (B) is within the above range, the effects of the present invention are hardly impaired.
- the total proportion of the other components in 100% by mass of the matrix resin is preferably more than 0 to 20% by mass, more preferably more than 0 to 15% by mass, more than 0 to 10 mass% is more preferable. It is also preferred that no other ingredients are included. If the total ratio of the other components is within the above range, the effects of the present invention are not easily impaired.
- the matrix resin contains only the fluororesin (A) having a melting point of 325 ° C. or less and having an adhesive functional group (f) as the resin component, or the fluororesin (A) and the thermoplastic resin (B), and the proportion of the fluororesin (A) is 1 to less than 70 mass% of the total 100 mass% of the fluororesin (A) and the thermoplastic resin (B).
- the ratio of the thermoplastic resin (B) is more than 30 to 99% by mass, a fiber-reinforced molded article excellent in chemical resistance and adhesion between members (interlayers) can be obtained.
- thermoplastic prepreg containing a fluororesin (A) that can be melt-molded as a matrix resin and, if necessary, a thermoplastic resin (B), it is a thermosetting prepreg.
- A fluororesin
- B thermoplastic resin
- a fiber-reinforced molded article having excellent impact resistance can be obtained, and the storage stability is excellent.
- the prepreg of the present invention can be produced, for example, by impregnating a reinforcing fiber sheet with at least a fluororesin (A).
- Method (I) Specific examples of the method (I) include, for example, n-layer (where n is an integer of 1 or more) reinforcing fiber sheets obtained by alternately stacking reinforcing fiber sheets and powder mixture layers, and (n + 1) ) The stack of the powder mixture layers is hot-pressed with a hot press to melt the powder mixture and impregnate the reinforcing fiber sheet with the resin material ( ⁇ ) and the resin material ( ⁇ ).
- n-layer where n is an integer of 1 or more reinforcing fiber sheets obtained by alternately stacking reinforcing fiber sheets and powder mixture layers
- n + 1 The stack of the powder mixture layers is hot-pressed with a hot press to melt the powder mixture and impregnate the reinforcing fiber sheet with the resin material ( ⁇ ) and the resin material ( ⁇ ).
- the temperature at the time of hot pressing is not less than the melting point of the fluororesin (A) and not less than the melting point of the thermoplastic resin (B), and the higher of the melting point of the fluororesin (A) and the melting point of the thermoplastic resin (B).
- the melting point of + 5 ° C. or higher and the melting point + 100 ° C. or lower is preferable.
- the pressure during hot pressing is preferably from 0.1 MPa to 50 MPa, more preferably from 0.5 MPa to 30 MPa.
- the time for hot pressing is preferably 3 seconds or more and 180 minutes or less, and more preferably 5 seconds or more and 60 minutes or less.
- the powder mixture is a mixture of powder (X) and powder (Y).
- the powder mixture may contain powders other than the powder (X) and the powder (Y) as long as the effects of the present invention are not impaired.
- the powder (X) and the powder (Y) are mixed so that the ratio of the fluororesin (A) and the ratio of the thermoplastic resin (B) are a preferable ratio in the matrix resin described above. It is prepared by.
- Powder (X) consists of resin material ((alpha)) containing a fluororesin (A). Resin material ((alpha)) may contain other components other than a fluororesin (A) in the range which does not impair the effect of this invention.
- the proportion of the fluororesin (A) in 100% by mass of the resin material ( ⁇ ) is preferably 80 to 100% by mass, more preferably 85 to 100% by mass, and further preferably 90 to 100% by mass. If the ratio of a fluororesin (A) is in the said range, the effect of this invention will be hard to be impaired.
- the total proportion of the other components in the resin material ( ⁇ ) of 100% by mass is preferably more than 0 to 20% by mass, more than 0 to 15% by mass. Is more preferable, and more than 0 to 10% by mass is even more preferable. It is also preferable that the resin material ( ⁇ ) does not contain other components. If the total ratio of the other components is within the above range, the effects of the present invention are not easily impaired.
- the average particle size of the powder (X) is preferably 0.02 to 200 ⁇ m, more preferably 1 to 100 ⁇ m. When the average particle diameter is not less than the lower limit of the above range, the workability of the powder is excellent. If the average particle size is not more than the upper limit of the above range, the reinforcing fiber sheet can be easily impregnated with the resin material ( ⁇ ).
- the powder (X) can be produced, for example, by the following procedure.
- the fluororesin (A) and other components are melt-kneaded as necessary.
- the melt of the resin material ( ⁇ ) is extruded into a strand shape.
- the strand is cut with a pelletizer and pelletized.
- the pellet is mechanically pulverized.
- the pulverized product is classified to obtain powder (X).
- Equipment that can mechanically pulverize pellets includes hammer mill, pin mill, disc mill, rotary mill, jet mill, fluidized bed air jet mill, jaw crusher, gyrate leak crusher, cage mill, pan crusher, ball mill, pebble mill, rod mill, A tube mill, a disc attrition mill, an attritor, a disc refiner, etc. are mentioned.
- the pulverization of the pellet is preferably performed by cooling the pellet to a temperature of ⁇ 40 ° C. or less from the viewpoint of easily reducing the average particle size of the pulverized product.
- the cooling temperature is more preferably ⁇ 100 ° C. or less, and further preferably ⁇ 160 ° C. or less.
- Examples of the cooling method include a method using dry ice or liquid nitrogen.
- the powder (Y) is made of a resin material ( ⁇ ) containing a thermoplastic resin (B).
- the resin material ( ⁇ ) may contain components other than the thermoplastic resin (B) as long as the effects of the present invention are not impaired.
- the ratio of the thermoplastic resin (B) in 100% by mass of the resin material ( ⁇ ) is preferably 80 to 100% by mass, more preferably 85 to 100% by mass, and further preferably 90 to 100% by mass. If the ratio is within the above range, the effects of the present invention are hardly impaired.
- the total proportion of the other components in the resin material ( ⁇ ) of 100% by mass is preferably more than 0 to 20% by mass, more than 0 to 15% by mass. Is more preferable, and more than 0 to 10% by mass is even more preferable. It is also preferable that the resin material ( ⁇ ) does not contain other components. If the total ratio of the other components is within the above range, the effects of the present invention are not easily impaired.
- the average particle size of the powder (Y) is preferably 0.02 to 200 ⁇ m, more preferably 1 to 100 ⁇ m.
- the average particle diameter is not less than the lower limit of the above range, the workability of the powder is excellent.
- the average particle size is not more than the upper limit of the above range, the reinforcing fiber sheet can be easily impregnated with the resin material ( ⁇ ).
- this average particle diameter is in the said range, the average diameter of the island part of matrix resin can be made into the preferable range mentioned above.
- the powder (Y) can be produced, for example, by the same procedure as the procedure for producing the powder (X) described above.
- Method (II) Specific examples of the method (II) include, for example, a reinforcing fiber sheet of n layers (where n is an integer of 1 or more) in which reinforcing fiber sheets and powder (Z) layers are alternately stacked, The stack of (n + 1) layers of powder (Z) is hot-pressed with a hot press to melt the powder (Z) and impregnate the reinforcing fiber sheet with the resin material ( ⁇ ).
- n is an integer of 1 or more
- the stack of (n + 1) layers of powder (Z) is hot-pressed with a hot press to melt the powder (Z) and impregnate the reinforcing fiber sheet with the resin material ( ⁇ ).
- a method is mentioned. The temperature, pressure and time during hot pressing are the same as in method (I).
- the powder (Z) is made of a resin material ( ⁇ ) containing a fluororesin (A) and, if necessary, a thermoplastic resin (B).
- the resin material ( ⁇ ) may contain other components other than the fluororesin (A) and the thermoplastic resin (B) as long as the effects of the present invention are not impaired.
- the range of the ratio of the fluororesin (A) and the ratio of the thermoplastic resin (B) in the total 100 mass% of the fluororesin (A) and the thermoplastic resin (B) in the resin material ( ⁇ ) is the matrix described above. This is the same as the specific range in the resin.
- the range of the ratio of the fluororesin (A), the ratio of the thermoplastic resin (B), and the total ratio of the other components in 100% by mass of the resin material ( ⁇ ) is the same as the specific range in the matrix resin described above. It is.
- the average diameter of the island portion containing the thermoplastic resin (B) in the resin material ( ⁇ ) before impregnating the reinforcing fiber sheet is preferably 0.01 to 8 ⁇ m and less than the average particle diameter of the powder (Z), More preferably, it is 0.01 to 5 ⁇ m and less than the average particle diameter of the powder (Z). If the average diameter of the island portion is within the above range, the average diameter of the island portion of the matrix resin can be within the above-described preferable range.
- the average particle size of the powder (Z) is preferably from 0.02 to 200 ⁇ m, more preferably from 1 to 100 ⁇ m. When the average particle diameter is not less than the lower limit of the above range, the workability of the powder is excellent. When the average particle diameter is not more than the upper limit of the above range, the reinforcing fiber sheet can be easily impregnated with the resin material ( ⁇ ).
- the powder (Z) can be produced, for example, by the same procedure as the procedure for producing the powder (X) described above.
- Method (III) As a specific example of the method (III), for example, a reinforcing fiber sheet and a resin film that are alternately stacked, n layers (where n is an integer of 1 or more), and (n + 1) layers A method of melting the resin film and impregnating the reinforcing fiber sheet with a resin material ( ⁇ ) by hot pressing a stack of the resin film with a hot press machine. The temperature, pressure and time during hot pressing are the same as in method (I).
- the resin film is made of a resin material ( ⁇ ) containing a fluororesin (A) and, if necessary, a thermoplastic resin (B).
- the resin material ( ⁇ ) include the same materials as the resin material ( ⁇ ) in the powder (Z), and preferred forms are also the same.
- the average diameter of the island part containing the thermoplastic resin (B) in the resin material ( ⁇ ) before impregnating the reinforcing fiber sheet is preferably less than the thickness of the resin film.
- the resin film may be obtained by melting and kneading the fluororesin (A), the thermoplastic resin (B) as necessary, and other components as necessary, and converting the melt of the resin material ( ⁇ ) into a film from the T die. Can be manufactured by extruding.
- the fiber-reinforced molded product of the present invention is formed using the prepreg of the present invention.
- the fiber-reinforced molded article of the present invention may be formed using only the prepreg of the present invention; a laminate formed using the prepreg of the present invention and a prepreg other than the prepreg of the present invention. It may be a body; it may be a laminate formed using the prepreg of the present invention and, if necessary, another prepreg and another member other than the prepreg.
- prepregs include prepregs in which the matrix resin contains the thermoplastic resin (B) and does not contain the fluororesin (A).
- Examples of the member other than the prepreg include a metal member, a resin film containing a thermoplastic resin (B), and a resin film containing a fluororesin (A).
- Examples of the metal member include metal foil and various metal parts. Examples of the metal include iron, stainless steel, aluminum, copper, brass, nickel, and zinc.
- the shape of the metal member is not particularly limited, and can be appropriately selected according to the fiber reinforced molded product to be obtained.
- the fiber-reinforced molded product of the present invention is, for example, a stack of two or more of the prepregs of the present invention, or one or more of the prepregs of the present invention and other prepregs and prepregs. It can obtain by shape
- the molding method include a press molding method using a mold.
- Examples of the use of the fiber reinforced molded product include the following. Electrical / electronic devices (PCs, displays, OA devices, mobile phones, personal digital assistants, facsimiles, compact discs, portable MDs, portable radio cassettes, PDAs (mobile information terminals such as electronic notebooks), video cameras, digital still cameras, Optical equipment, audio equipment, air conditioners, lighting equipment, entertainment goods, toy goods, other household appliances, etc.) casings, internal members (tray, chassis, etc.), internal member cases, mechanical parts, etc. Building materials (panels) etc.
- Automobiles, motorcycle-related parts, parts and outer plates motor parts, alternator terminals, alternator connectors, IC regulators, light-depot potentiometer bases, suspension parts, various valves (exhaust gas valves, etc.), fuel-related, exhaust system or various intake systems Pipe, air intake nozzle snorkel, intake manifold, various arms, various frames, various hinges, various bearings, fuel pump, gasoline tank, CNG tank, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor , Oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad Wear sensor, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, distributor, starter switch, starter relay, transmission wire harness, window Washer nozzle, air conditioner panel switch board, coil for fuel related electromagnetic valve, connector for fuse, battery tray, AT bracket, headlamp support, pedal housing, handle, door beam, protector, chassis,
- Aircraft related parts, components and skins landing gear pods, winglets, spoilers, edges, ladders, elevators, failings, ribs, etc.
- Other Windmill blades, etc.
- the fiber reinforced molded article is particularly preferably used for aircraft members, windmill blades, automobile outer plates, casings of electronic devices, trays, chassis, and the like.
- Examples 1, 3, and 4 are examples, and example 2 is a comparative example.
- the laminate (fiber reinforced molded product) was cut using a contour machine (manufactured by Amada, V-400) to obtain a sample having a height of 63 mm, a width of 13 mm, and a thickness of 2.8 mm.
- a test piece was obtained by notching the sample at a height of 32 mm.
- Izod test device manufactured by Toyo Seiki Co., Ltd.
- hammer capacity 2.75 J
- hammer weight 13.97 N
- distance from the axis to the center of gravity 10.54 cm
- distance from the axis to the impact point Izod impact strength was measured under the condition of 33.5 cm.
- Fluororesin (A) Fluororesin (A-1): Fluororesin having functional group (f) (manufactured by Asahi Glass Co., Ltd., type of functional group (f): carbonyl group-containing group, content of functional group (f): fluororesin (A-1) ) 3000 per 1 ⁇ 10 6 main chain carbon atoms, melting point: 245 ° C., melt flow rate (297 ° C., load 49 N): 22 g / 10 min).
- the resin was produced in the same manner as in Example 1 of WO2015 / 182702, and the molar ratio of TFE / IAH / CH 2 ⁇ CH (CF 2 ) 2 F / E was 58.5 / 0.1 / It was 2.4 / 39.
- Fluororesin (A′-2) ethylene / tetrafluoroethylene copolymer having no functional group (f) (Asahi Glass Co., Ltd., Fluon (registered trademark) LM-ETFE LM-730AP, melting point: 225 ° C., melt flow rate (297 ° C., load 49 N): 24 g / 10 minutes).
- Fluororesin (A′-3) ethylene / tetrafluoroethylene copolymer having no functional group (f) (Asahi Glass Co., Ltd., Fluon (registered trademark) LM-ETFE LM-720AP, melting point: 226 ° C., melt flow rate (297 ° C., load 49 N): 17.2 g / 10 min).
- Thermoplastic resin (B) Thermoplastic resin (B-1): Polyamide 6 (manufactured by Ube Industries, UBE nylon 1024B).
- Example 1 For the fluororesin (A-1), using a single screw extruder (manufactured by Tanabe Plastics Machinery Co., Ltd., VS-30), 150 mm wide T die, set resin temperature: 280 ° C., line speed: 0.5 m / min A fluororesin film having a thickness of 100 ⁇ m was produced.
- Carbon cloth manufactured by Sunlight, plain weave CF3000, thickness 0.25 mm
- a fluororesin film were cut into dimensions of 10 cm ⁇ 10 cm.
- the fluororesin film and the carbon cloth were alternately stacked to form a stack of one layer of carbon cloth and two layers of fluororesin film.
- press molding was performed using a melt heat press machine (manufactured by Tester Sangyo Co., Ltd.) under the conditions of temperature: 280 ° C., preheating: 10 minutes, pressure: 10 MPa (absolute pressure, the same applies hereinafter), pressing time: 3 minutes
- prepreg (a-1) was obtained.
- thermoplastic resin (B-1) using a single screw extruder (manufactured by Tanabe Plastics Machinery Co., Ltd., VS-30), 150 mm wide T die, set resin temperature: 260 ° C., line speed: 0.5 m / min Thus, a thermoplastic resin film having a thickness of 100 ⁇ m was produced.
- a carbon cloth (manufactured by Sunlight, plain weave CF3000) and a thermoplastic resin film were cut into a size of 10 cm ⁇ 10 cm.
- a thermoplastic resin film and a carbon cloth were alternately stacked to form a stack of one layer of carbon cloth and two layers of thermoplastic resin film.
- the stacked product was press-molded using a melt heat press machine (manufactured by Tester Sangyo Co., Ltd.) under the conditions of temperature: 240 ° C., preheating: 10 minutes, pressure: 10 MPa, pressing time: 3 minutes, and prepreg (b-1) Got.
- the prepreg (a-1) / prepreg (b-1) / prepreg (a-1) were stacked in this order to obtain a stack.
- the stacked product is press-molded under the conditions of temperature: 280 ° C., preheating: 10 minutes, pressure: 10 MPa, press time: 3 minutes, using a melt heat press machine (manufactured by Tester Sangyo Co., Ltd.), and a laminate (fiber reinforced molding).
- Table 1 shows the Izod impact strength and adhesion of the laminate.
- Example 2 A prepreg (a′-2) was obtained in the same manner as in Example 1 except that the fluororesin (A′-2) was used in place of the fluororesin (A-1).
- a laminate fiber reinforced molded product was obtained in the same manner as in Example 1 except that the prepreg (a'-2) was used instead of the prepreg (a-1). Table 1 shows the adhesion of the laminate. In addition, since this sample had insufficient adhesiveness, Izod impact strength was not measured.
- the example 1 containing the fluororesin (A) having the functional group (f) in the upper layer and lower layer matrix resins is different from the example 2 in which the upper layer and lower layer matrix resins contain the fluororesin having no functional group (f). Excellent adhesion between layers.
- Example 3 The fluororesin (A-1) was pulverized by a freeze pulverizer TPH-01 manufactured by AS ONE to obtain a powder having an average particle size of 57 ⁇ m.
- a carbon cloth manufactured by Sunlight, plain weave CF3000, thickness 0.25 mm
- heat exposure was performed at 260 ° C. for 3 minutes in a hot air circulation dryer to obtain a prepreg (a-1P) impregnated with a powder of the fluororesin (A-1).
- the Vf was calculated by the following formula.
- Vf (%) (volume of carbon cloth / (volume of carbon cloth + volume of coated powder (Z))) ⁇ 100
- thermoplastic resin (B-1) was pulverized by a freeze pulverizer TPH-01 manufactured by AS ONE to obtain a powder having an average particle diameter of 122 ⁇ m.
- Example 3 except that the thermoplastic resin (B-1) powder was used in place of the fluororesin (A-1) powder, and heat exposure was performed at 240 ° C. for 3 minutes in a hot air circulation dryer.
- a prepreg (b-1P) impregnated with powder of the thermoplastic resin (B-1) was obtained.
- the obtained prepreg (b-1P) and the prepreg (a-1P) described in Example 3 were alternately stacked to make a stack.
- the stacked product was press-molded in the same manner as in Example 3 to obtain a laminate (fiber-cured molded product) having a thickness of 2.3 mm ( ⁇ 0.05).
- Table 2 shows the Izod impact strength and adhesiveness of the obtained laminate.
- the fiber-reinforced molded product of the present invention is useful as a member constituting transportation equipment (vehicles (automobiles, railway vehicles, etc.), aircrafts, etc.), architecture, electrical / electronic equipment, and the like.
- transportation equipment vehicles (automobiles, railway vehicles, etc.), aircrafts, etc.), architecture, electrical / electronic equipment, and the like.
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Abstract
Description
・熱硬化性樹脂の硬化物が脆いため、繊維強化成形品の耐衝撃性が不充分である。
・繊維強化成形品の前駆体であるプリプレグにおいて、硬化前の熱硬化性樹脂が、プリプレグの保存中に硬化してしまうため、プリプレグの寿命が短い。
なお、特許文献2には、繊維強化成形品がポリテトラフルオロエチレンの粒子を含んでいてもよいことが記載されている。ポリテトラフルオロエチレンは、耐薬品性に優れているものの、他の材料との親和性が低い。そのため、ポリテトラフルオロエチレンの粒子を含むプリプレグおよび他の部材(他のプリプレグ、金属部材等)を用いて形成された繊維強化成形品(積層体)は、部材間(層間)での接着性が不充分である。
<1>強化繊維と、マトリックス樹脂とを有し;前記マトリックス樹脂が、樹脂成分として、融点が100℃以上325℃以下であり、カルボニル基含有基、ヒドロキシ基、エポキシ基およびイソシアネート基からなる群から選ばれる少なくとも1種の官能基を有する溶融成形可能なフッ素樹脂のみを含む、または前記フッ素樹脂と熱可塑性樹脂(ただし、前記フッ素樹脂を除く。)とを含み;前記フッ素樹脂と前記熱可塑性樹脂との合計100質量%のうち、前記フッ素樹脂の割合が70質量%以上100質量%以下であり、前記熱可塑性樹脂の割合が0質量%以上30質量%以下である、プリプレグ。
<2>前記フッ素樹脂と前記熱可塑性樹脂との合計100質量%のうち、前記フッ素樹脂の割合が70質量%以上100質量%未満であり、前記熱可塑性樹脂の割合が0質量%超30質量%以下であり;前記マトリックス樹脂が、前記フッ素樹脂を含む海部と、前記熱可塑性樹脂を含む島部とからなる海島構造を有し;前記島部の平均径が、0.01μm以上200μm以下である、<1>のプリプレグ。
<3>前記フッ素樹脂の融点が、100℃以上260℃未満である、<1>または<2>のプリプレグ。
<4>融点が100℃以上325℃以下であり、カルボニル基含有基、ヒドロキシ基、エポキシ基およびイソシアネート基からなる群から選ばれる少なくとも1種の官能基を有する溶融成形可能なフッ素樹脂を含む樹脂材料(α)からなる粉体(X)と、熱可塑性樹脂(ただし、前記フッ素樹脂を除く。)を含む樹脂材料(β)からなる粉体(Y)とを、前記フッ素樹脂と前記熱可塑性樹脂との合計100質量%のうち、前記フッ素樹脂の割合が70質量%以上100質量%未満となり、前記熱可塑性樹脂の割合が0質量%超30質量%以下となるように混合してなる粉体混合物を;強化繊維シートの存在下に溶融させ、前記樹脂材料(α)および前記樹脂材料(β)を強化繊維シートに含浸させる、プリプレグの製造方法。
<5>前記粉体(X)の平均粒子径が、0.02μm以上200μm以下であり;前記粉体(Y)の平均粒子径が、0.02μm以上200μm以下である、<4>のプリプレグの製造方法。
<6>樹脂成分として、融点が100℃以上325℃以下であり、カルボニル基含有基、ヒドロキシ基、エポキシ基およびイソシアネート基からなる群から選ばれる少なくとも1種の官能基を有する溶融成形可能なフッ素樹脂のみを含む、または前記フッ素樹脂と熱可塑性樹脂(ただし、前記フッ素樹脂を除く。)とを含み、前記フッ素樹脂と前記熱可塑性樹脂との合計100質量%のうち、前記フッ素樹脂の割合が70質量%以上100質量%以下であり、前記熱可塑性樹脂の割合が0質量%以上30質量%以下である樹脂材料(γ)からなる粉体(Z)を;強化繊維シートの存在下に溶融させ、前記樹脂材料(γ)を強化繊維シートに含浸させる、プリプレグの製造方法。
<7>前記粉体(Z)の平均粒子径が、0.02μm以上200μm以下であり;前記フッ素樹脂と前記熱可塑性樹脂との合計100質量%のうち、前記フッ素樹脂の割合が70質量%以上100質量%未満であり、前記熱可塑性樹脂の割合が0質量%超30質量%以下であり;前記強化繊維シートに含浸される前の前記樹脂材料(γ)における前記熱可塑性樹脂を含む島部の平均径が、0.01μm以上8μm以下、かつ前記粉体(Z)の平均粒子径未満である、<6>のプリプレグの製造方法。
<8>樹脂成分として、融点が100℃以上325℃以下であり、カルボニル基含有基、ヒドロキシ基、エポキシ基およびイソシアネート基からなる群から選ばれる少なくとも1種の官能基を有する溶融成形可能なフッ素樹脂のみを含む、または前記フッ素樹脂と熱可塑性樹脂(ただし、前記フッ素樹脂を除く。)とを含み、前記フッ素樹脂と前記熱可塑性樹脂との合計100質量%のうち、前記フッ素樹脂の割合が70質量%以上100質量%以下であり、前記熱可塑性樹脂の割合が0質量%以上30質量%以下である樹脂材料(γ)からなる樹脂フィルムを;強化繊維シートの存在下に溶融させ、前記樹脂材料(γ)を強化繊維シートに含浸させる、プリプレグの製造方法。
<9>前記フッ素樹脂と前記熱可塑性樹脂との合計100質量%のうち、前記フッ素樹脂の割合が70質量%以上100質量%未満であり、前記熱可塑性樹脂の割合が0質量%超30質量%以下であり;前記強化繊維シートに含浸される前の前記樹脂材料(γ)における前記熱可塑性樹脂を含む島部の平均径が、0.01μm以上8μm以下、かつ前記樹脂フィルムの厚さ未満である、<8>のプリプレグの製造方法。
<10>前記<1>~<3>のいずれかのプリプレグを用いた、繊維強化成形品。
「融点」は、示差走査熱量測定(DSC)法で測定した融解ピークの最大値に対応する温度である。
「溶融成形可能」であるとは、溶融流動性を示すことを意味する。
「溶融流動性を示す」とは、荷重49Nの条件下、樹脂の融点よりも20℃以上高い温度において、溶融流れ速度が0.1~1000g/10分となる温度が存在することを意味する。
「溶融流れ速度」は、JIS K 7210:1999(ISO 1133:1997)に規定されるメルトマスフローレート(MFR)である。
「単位」とは、単量体が重合することによって形成された該単量体に由来する部分(重合単位)を意味する。単位は、重合反応によって直接形成された単位であってもよく、重合体を処理することによって該単位の一部が別の構造に変換された単位であってもよい。
「島部の平均径」は、樹脂材料またはマトリックス樹脂の電子顕微鏡像における5個の島部について面積を測定し、該面積から円換算直径を算出し、これらを平均したものである。
「粉体の平均粒子径」は、レーザー回折・散乱法によって求められる体積基準累積50%径(D50)である。すなわち、レーザー回折・散乱法により粒度分布を測定し、粒子の集団の全体積を100%として累積カーブを求め、その累積カーブ上で累積体積が50%となる点の粒子径である。
本発明のプリプレグは、強化繊維と、マトリックス樹脂とを有する。具体的には、強化繊維にマトリックス樹脂を含浸したシート状の材料であり、マトリックス樹脂に強化繊維が埋め込まれたシート状の材料ともいう。なお、完全に含浸したものだけでなく、マトリックス樹脂粉体を強化繊維表面に付着させ溶融させて強化繊維に半含浸させたセミプレグと呼ばれるものも含む。
強化繊維としては、繊維強化成形品の機械的特性の点から、長さが10mm以上の連続した長繊維が好ましい。強化繊維は、強化繊維シートの長さ方向の全長または幅方向の全幅にわたり連続している必要はなく、途中で分断されていてもよい。
強化繊維シートとしては、複数の強化繊維からなる強化繊維束、該強化繊維束を織成してなるクロス、複数の強化繊維が一方向に引き揃えられた一方向性強化繊維束、該一方向性強化繊維束から構成された一方向性クロス、これらを組み合わせたもの、複数の強化繊維束を積み重ねたもの等が挙げられる。
無機繊維としては、炭素繊維、黒鉛繊維、ガラス繊維、シリコンカーバイト繊維、シリコンナイトライド繊維、アルミナ繊維、炭化珪素繊維、ボロン繊維等が挙げられる。
金属繊維としては、アルミニウム繊維、黄銅繊維、ステンレス繊維等が挙げられる。
有機繊維としては、芳香族ポリアミド繊維、ポリアラミド繊維、ポリパラフェニレンベンズオキサゾール(PBO)繊維、ポリフェニレンスルフィド繊維、ポリエステル繊維、アクリル繊維、ナイロン繊維、ポリエチレン繊維等が挙げられる。
炭素繊維としては、例えば、WO2013/129169号公報に記載されたものが挙げられ、特に段落0018~0026に記載されたものが好ましい。また、炭素繊維の製法としては、段落0028~0033に記載されたものが挙げられる。
マトリックス樹脂は、樹脂成分として、フッ素樹脂(A)のみを含む、またはフッ素樹脂(A)と熱可塑性樹脂(B)(ただし、フッ素樹脂(A)を除く。)とを含む。マトリックス樹脂は、本発明の効果を損なわない範囲においてフッ素樹脂(A)および熱可塑性樹脂(B)以外の他の成分を含んでいてもよい。
マトリックス樹脂が熱可塑性樹脂(B)を含む場合、マトリックス樹脂は、繊維強化成形品における部材間(層間)での接着性の点、および繊維強化成形品の耐薬品性の点から、フッ素樹脂(A)を含む海部と、熱可塑性樹脂(B)を含む島部とからなる海島構造を有することが好ましい。
フッ素樹脂(A)は、カルボニル基含有基、ヒドロキシ基、エポキシ基およびイソシアネート基からなる群から選択される少なくとも1種の官能基(以下、官能基(f)と記す。)を有するフッ素樹脂である。フッ素原子を有することによって、繊維強化成形品の耐薬品性に優れる。接着性の官能基(f)を有することによって、繊維強化成形品における部材間(層間)での接着性に優れる。
カルボニル基含有基としては、たとえば、炭化水素基の炭素原子間にカルボニル基を有する基、カーボネート基、カルボキシ基、ハロホルミル基、アルコキシカルボニル基、酸無水物基等が挙げられる。
ハロホルミル基は、-C(=O)-X(ただし、Xはハロゲン原子である。)で表される。ハロホルミル基におけるハロゲン原子としては、フッ素原子、塩素原子等が挙げられ、フッ素原子が好ましい。すなわちハロホルミル基としてはフルオロホルミル基(カルボニルフルオリド基ともいう。)が好ましい。
アルコキシカルボニル基におけるアルコキシ基は、直鎖状であってもよく、分岐状であってもよく、炭素数1~8のアルコキシ基が好ましく、メトキシ基またはエトキシ基が特に好ましい。
融点が比較的高いフッ素樹脂(A)を用いた場合、高い耐熱性を有する繊維強化成形品が得られるので好ましい。したがって、該場合においては、フッ素樹脂(A)の融点は260~320℃が好ましく、280~320℃がより好ましい。
フッ素樹脂(A)の融点は、フッ素樹脂(A)を構成する単位の種類や割合、フッ素樹脂(A)の分子量等によって調整できる。たとえば、後述する単位(u1)の割合が多くなるほど、融点が上がる傾向がある。
溶融成形が可能なフッ素樹脂(A)としては、公知の溶融成形が可能なフッ素樹脂(テトラフルオロエチレン/フルオロアルキルビニルエーテル共重合体、テトラフルオロエチレン/ヘキサフルオロプロピレン共重合体、エチレン/テトラフルオロエチレン共重合体、ポリフッ化ビニリデン、ポリクロロトリフルオロエチレン、エチレン/クロロトリフルオロエチレン共重合体等)に官能基(f)を導入したフッ素樹脂;後述する含フッ素重合体(A11)等が挙げられる。
フッ素樹脂(A1):含フッ素重合体の製造の際に用いた単量体、連鎖移動剤および重合開始剤からなる群から選ばれる少なくとも1種に由来する官能基(f)を有する含フッ素重合体。以下、フッ素樹脂(A1)を含フッ素重合体(A1)ともいう。
フッ素樹脂(A2):コロナ放電処理、プラズマ処理等の表面処理によって官能基(f)を有しないフッ素樹脂に官能基(f)を導入したフッ素樹脂。
フッ素樹脂(A3):官能基(f)を有しないフッ素樹脂に、官能基(f)を有する単量体をグラフト重合して得られたフッ素樹脂。
・含フッ素重合体(A1)においては、含フッ素重合体(A1)の主鎖の末端基および主鎖のペンダント基のいずれか一方または両方に官能基(f)が存在するため、繊維強化成形品における部材間(層間)での接着性が著しく優れる。
・フッ素樹脂(A2)における官能基(f)は、表面処理によって形成されたため不安定であり、時間とともに消失しやすい。
方法(i):単量体の重合によって含フッ素重合体(A1)を製造する際に、官能基(f)を有する単量体を用いる。
方法(ii):官能基(f)を有する連鎖移動剤の存在下に、単量体の重合によって含フッ素重合体(A1)を製造する。
官能基(f)を有する連鎖移動剤としては、酢酸、無水酢酸、酢酸メチル、エチレングリコール、プロピレングリコール等が挙げられる。
方法(iii):官能基(f)を有するラジカル重合開始剤等の重合開始剤の存在下に、単量体の重合によって含フッ素重合体(A1)を製造する。
官能基(f)を有するラジカル重合開始剤としては、ジ-n-プロピルペルオキシジカーボネート、ジイソプロピルペルオキシカーボネート、tert-ブチルペルオキシイソプロピルカーボネート、ビス(4-tert-ブチルシクロヘキシル)ペルオキシジカーボネート、ジ-2-エチルヘキシルペルオキシジカーボネート等が挙げられる。
官能基(f)を有する単量体としては、カルボキシ基を有する単量体(マレイン酸、イタコン酸、シトラコン酸、ウンデシレン酸等);酸無水物基を有する単量体(無水イタコン酸(以下、「IAH」とも記す。)、無水シトラコン酸(以下、「CAH」とも記す。)、5-ノルボルネン-2,3-ジカルボン酸無水物(以下、「NAH」とも記す。)、無水マレイン酸等)、水酸基およびエポキシ基を有する単量体(ヒドロキシブチルビニルエーテル、グリシジルビニルエーテル等)等が挙げられる。
単量体に由来する官能基(f)を有する含フッ素重合体(A1)としては、繊維強化成形品における部材間(層間)での接着性が著しく優れる点から、下記の含フッ素重合体(A11)が特に好ましい。
テトラフルオロエチレン(以下、「TFE」とも記す。)またはクロロトリフルオロエチレン(以下、「CTFE」とも記す。)に由来する単位(u1)と、酸無水物基を有する環状炭化水素単量体(以下、「酸無水物基含有環状炭化水素単量体」とも記す。)に由来する単位(u2)と、含フッ素単量体(ただし、TFEおよびCTFEを除く。)に由来する単位(u3)とを有する含フッ素重合体(A11)。
ここで、単位(u2)の有する酸無水物基が官能基(f)に相当する。
酸無水物基含有環状炭化水素単量体としては、繊維強化成形品における部材間(層間)での接着性が著しく優れる点から、IAHまたはNAHが好ましい。
PAVEとしては、CF2=CFOCF2CF3、CF2=CFOCF2CF2CF3、CF2=CFOCF2CF2CF2CF3、CF2=CFO(CF2)6F等が挙げられ、CF2=CFOCF2CF2CF3(以下、「PPVE」とも記す。)が好ましい。
FAEとしては、CH2=CH(CF2)q1X4(ただし、q1は、2~6であり、2~4が好ましい)が好ましく、CH2=CH(CF2)2F、CH2=CH(CF2)3F、CH2=CH(CF2)4F、CH2=CF(CF2)3H、CH2=CF(CF2)4Hがより好ましく、CH2=CH(CF2)4FまたはCH2=CH(CF2)2Fが特に好ましい。
単位(u1)の割合は、単位(u1)と単位(u2)と単位(u3)との合計に対して、90~99.89モル%が好ましく、95~99.47モル%がより好ましく、96~98.95モル%がさらに好ましい。
単位(u2)の割合は、単位(u1)と単位(u2)と単位(u3)との合計に対して、0.01~3モル%が好ましく、0.03~2モル%がより好ましく、0.05~1モル%がさらに好ましい。
単位(u3)の割合は、単位(u1)と単位(u2)と単位(u3)との合計に対して、0.1~9.99モル%が好ましく、0.5~9.97モル%がより好ましく、1~9.95モル%がさらに好ましい。
フッ素を有しない単量体としては、重合性炭素-炭素二重結合を1つ有するフッ素を有しない化合物が好ましく、たとえば、オレフィン(エチレン(以下、「E」とも記す。)、プロピレン、1-ブテン等)、ビニルエステル(酢酸ビニル等)等が挙げられる。フッ素を有しない単量体は、1種を単独で用いてもよく、2種以上を併用してもよい。
フッ素を有しない単量体としては、繊維強化成形品の機械的特性等に優れる点から、エチレン、プロピレン、1-ブテンが好ましく、エチレンが特に好ましい。
単位(u1)の割合は、単位(u1)と単位(u2)と単位(u3)と単位(u4)との合計100モル%のうち、25~80モル%が好ましく、40~65モル%がより好ましく、45~63モル%がさらに好ましい。
単位(u2)の割合は、単位(u1)と単位(u2)と単位(u3)と単位(u4)との合計100モル%のうち、0.01~5モル%が好ましく、0.03~3モル%がより好ましく、0.05~1モル%がさらに好ましい。
単位(u3)の割合は、単位(u1)と単位(u2)と単位(u3)と単位(u4)との合計100モル%のうち、0.2~20モル%が好ましく、0.5~15モル%がより好ましく、1~12モル%がさらに好ましい。
単位(u4)の割合は、単位(u1)と単位(u2)と単位(u3)と単位(u4)との合計100モル%に対して、20~75モル%が好ましく、35~50モル%がより好ましく、37~55モル%がさらに好ましい。
単位(u2)の割合が前記範囲内であれば、含フッ素重合体(A11)における酸無水物基の量が適切になり、繊維強化成形品における部材間(層間)での接着性が著しく優れる。
単位(u3)の割合が前記範囲内であれば、含フッ素重合体(A11)の成形性、繊維強化成形品の耐屈曲性等に著しく優れる。
各単位の割合は、含フッ素重合体(A11)の溶融NMR分析、フッ素含有量分析、赤外吸収スペクトル分析等により算出できる。
フッ素樹脂(A)は、常法により製造できる。単量体の重合によってフッ素樹脂(A)を製造する場合、重合方法としては、ラジカル重合開始剤を用いる重合方法が好ましい。
重合方法としては、塊状重合法、有機溶媒(フッ化炭化水素、塩化炭化水素、フッ化塩化炭化水素、アルコール、炭化水素等)を用いる溶液重合法、水性媒体と必要に応じて適当な有機溶媒とを用いる懸濁重合法、水性媒体と乳化剤とを用いる乳化重合法が挙げられ、溶液重合法が好ましい。
熱可塑性樹脂(B)としては、結晶性樹脂、非晶性樹脂、熱可塑性エラストマー、その他が挙げられる(ただし、フッ素樹脂(A)を除く)。
その他としては、フェノール系樹脂、フェノキシ樹脂等が挙げられる。
マトリックス樹脂に含まれる他の成分としては、無機フィラー、有機フィラー、有機顔料、金属せっけん、界面活性剤、紫外線吸収剤、潤滑剤、シランカップリング剤、有機化合物(たとえば有機モノマー、重合度50以下の有機オリゴマー等。)等が挙げられ、無機フィラーが好ましい。
フッ素樹脂(A)と熱可塑性樹脂(B)との合計100質量%のうち、フッ素樹脂(A)の割合は、70~100質量%であり、70~100質量%未満が好ましく、80~100質量%未満がより好ましい。フッ素樹脂(A)の割合が前記範囲の下限値以上であれば、繊維強化成形品における部材間(層間)での接着性、および繊維強化成形品の耐薬品性に優れる。フッ素樹脂(A)の割合が100質量%未満であれば、高価なフッ素樹脂(A)を減らすことができ、プリプレグおよび繊維強化成形品のコストが低下する。
また、以上説明した本発明のプリプレグにあっては、マトリックス樹脂として溶融成形可能なフッ素樹脂(A)および必要に応じて熱可塑性樹脂(B)を含む熱可塑性プリプレグであるため、熱硬化性プリプレグに比べ、耐衝撃性に優れた繊維強化成形品を得ることができ、また、保存安定性に優れる。
本発明のプリプレグは、たとえば、少なくともフッ素樹脂(A)を強化繊維シートに含浸させることによって製造できる。
方法(I):フッ素樹脂(A)を含む樹脂材料(α)からなる粉体(X)と、熱可塑性樹脂(B)を含む樹脂材料(β)からなる粉体(Y)とを、特定の割合で混合してなる粉体混合物を、強化繊維シートの存在下に溶融させ、樹脂材料(α)および樹脂材料(β)を強化繊維シートに含浸させる方法。
方法(II):フッ素樹脂(A)と必要に応じて熱可塑性樹脂(B)とを特定の割合で含む樹脂材料(γ)からなる粉体(Z)を、強化繊維シートの存在下に溶融させ、樹脂材料(γ)を強化繊維シートに含浸させる方法。
方法(III):フッ素樹脂(A)と必要に応じて熱可塑性樹脂(B)とを特定の割合で含む樹脂材料(γ)からなる樹脂フィルムを、強化繊維シートの存在下に溶融させ、樹脂材料(γ)を強化繊維シートに含浸させる方法。
方法(I)の具体例としては、たとえば、強化繊維シートと粉体混合物層とを交互に積み重ねた、n層(ただし、nは1以上の整数である。)の強化繊維シートと、(n+1)層の粉体混合物層とからなる積重物を、熱プレス機で熱プレスすることによって、粉体混合物を溶融させ、樹脂材料(α)および樹脂材料(β)を強化繊維シートに含浸させる方法が挙げられる。
熱プレスの際の圧力は、0.1MPa以上50MPa以下が好ましく、0.5MPa以上30MPa以下がより好ましい。
熱プレスの際の時間は、3秒以上180分以下が好ましく、5秒以上60分以下がより好ましい。
粉体混合物は、粉体(X)と粉体(Y)との混合物である。粉体混合物は、本発明の効果を損なわない範囲において粉体(X)および粉体(Y)以外の他の粉体を含んでいてもよい。
粉体(X)は、フッ素樹脂(A)を含む樹脂材料(α)からなる。樹脂材料(α)は、本発明の効果を損なわない範囲においてフッ素樹脂(A)以外の他の成分を含んでいてもよい。
フッ素樹脂(A)および必要に応じて他の成分を溶融混練する。樹脂材料(α)の溶融物をストランド状に押し出す。ストランドをペレタイザで切断してペレット化する。ペレットを機械的に粉砕する。粉砕物を分級し、粉体(X)を得る。
粉体(Y)は、熱可塑性樹脂(B)を含む樹脂材料(β)からなる。樹脂材料(β)は、本発明の効果を損なわない範囲において熱可塑性樹脂(B)以外の他の成分を含んでいてもよい。
粉体(Y)は、たとえば、上述した粉体(X)を製造する手順と同様の手順にて製造できる。
(方法(II))
方法(II)の具体例としては、たとえば、強化繊維シートと粉体(Z)層とを交互に積み重ねた、n層(ただし、nは1以上の整数である。)の強化繊維シートと、(n+1)層の粉体(Z)層とからなる積重物を、熱プレス機で熱プレスすることによって、粉体(Z)を溶融させ、樹脂材料(γ)を強化繊維シートに含浸させる方法が挙げられる。
熱プレスの際の温度、圧力および時間は、方法(I)と同様である。
粉体(Z)は、フッ素樹脂(A)と必要に応じて熱可塑性樹脂(B)とを含む樹脂材料(γ)からなる。樹脂材料(γ)は、本発明の効果を損なわない範囲においてフッ素樹脂(A)および熱可塑性樹脂(B)以外の他の成分を含んでいてもよい。
粉体(Z)は、たとえば、上述した粉体(X)を製造する手順と同様の手順にて製造できる。
方法(III)の具体例としては、たとえば、強化繊維シートと樹脂フィルムとを交互に積み重ねた、n層(ただし、nは1以上の整数である。)の強化繊維シートと、(n+1)層の樹脂フィルムとからなる積重物を、熱プレス機で熱プレスすることによって、樹脂フィルムを溶融させ、樹脂材料(γ)を強化繊維シートに含浸させる方法が挙げられる。熱プレスの際の温度、圧力および時間は、方法(I)と同様である。
樹脂フィルムは、フッ素樹脂(A)と必要に応じて熱可塑性樹脂(B)とを含む樹脂材料(γ)からなる。
樹脂材料(γ)としては、粉体(Z)における樹脂材料(γ)と同様のものが挙げられ、好ましい形態も同様である。なお、強化繊維シートに含浸される前の樹脂材料(γ)における熱可塑性樹脂(B)を含む島部の平均径は、樹脂フィルムの厚さ未満が好ましい。
本発明の繊維強化成形品は、本発明のプリプレグを用いて形成されたものである。
本発明の繊維強化成形品は、本発明のプリプレグのみを用いて形成されたものであってもよく;本発明のプリプレグと、本発明のプリプレグ以外の他のプリプレグとを用いて形成された積層体であってもよく;本発明のプリプレグおよび必要に応じて他のプリプレグと、プリプレグ以外の他の部材とを用いて形成された積層体であってもよい。
金属部材としては、金属箔、各種金属製部品等が挙げられる。金属としては、鉄、ステンレス鋼、アルミニウム、銅、黄銅、ニッケル、亜鉛等が挙げられる。金属部材の形状は、特に限定されず、得ようとする繊維強化成形品に合わせて適宜選択できる。
本発明の繊維強化成形品は、たとえば、本発明のプリプレグの1つのみ、本発明のプリプレグの2つ以上を積み重ねた積重物、または本発明のプリプレグの1つ以上と他のプリプレグおよびプリプレグ以外の他の部材のいずれか一方または両方の1つ以上とを積み重ねた積重物を、加熱しながら成形することによって得ることができる。
成形方法としては、金型を用いたプレス成形法等が挙げられる。
繊維強化成形品の用途としては、たとえば、下記のものが挙げられる。
電気・電子機器(パソコン、ディスプレイ、OA機器、携帯電話、携帯情報端末、ファクシミリ、コンパクトディスク、ポータブルMD、携帯用ラジオカセット、PDA(電子手帳等の携帯情報端末)、ビデオカメラ、デジタルスチルカメラ、光学機器、オーディオ、エアコン、照明機器、娯楽用品、玩具用品、その他家電製品等)の筐体、内部部材(トレイ、シャーシ等)、内部部材のケース、機構部品等。建材(パネル)等。
自動車、二輪車関連部品、部材および外板:モーター部品、オルタネーターターミナル、オルタネーターコネクター、ICレギュレーター、ライトディヤー用ポテンショメーターベース、サスペンション部品、各種バルブ(排気ガスバルブ等)、燃料関係、排気系または吸気系各種パイプ、エアーインテークノズルスノーケル、インテークマニホールド、各種アーム、各種フレーム、各種ヒンジ、各種軸受、燃料ポンプ、ガソリンタンク、CNGタンク、エンジン冷却水ジョイント、キャブレターメインボディー、キャブレタースペーサー、排気ガスセンサー、冷却水センサー、油温センサー、ブレーキパットウェアーセンサー、スロットルポジションセンサー、クランクシャフトポジションセンサー、エアーフローメーター、ブレーキパッド磨耗センサー、エアコン用サーモスタットベース、暖房温風フローコントロールバルブ、ラジエーターモーター用ブラッシュホルダー、ウォーターポンプインペラー、タービンべイン、ワイパーモーター関係部品、ディストリビュター、スタータースィッチ、スターターリレー、トランスミッション用ワイヤーハーネス、ウィンドウォッシャーノズル、エアコンパネルスィッチ基板、燃料関係電磁気弁用コイル、ヒューズ用コネクター、バッテリートレイ、ATブラケット、ヘッドランプサポート、ペダルハウジング、ハンドル、ドアビーム、プロテクター、シャーシ、フレーム、アームレスト、ホーンターミナル、ステップモーターローター、ランプソケット、ランプリフレクター、ランプハウジング、ブレーキピストン、ノイズシールド、ラジエターサポート、スペアタイヤカバー、シートシェル、ソレノイドボビン、エンジンオイルフィルター、点火装置ケース、アンダーカバー、スカッフプレート、ピラートリム、プロペラシャフト、ホイール、フェンダー、フェイシャー、バンパー、バンパービーム、ボンネット、エアロパーツ、プラットフォーム、カウルルーバー、ルーフ、インストルメントパネル、スポイラー、各種モジュール等。
航空機関連部品、部材および外板:ランディングギアポッド、ウィングレット、スポイラー、エッジ、ラダー、エレベーター、フェイリング、リブ等。その他:風車の羽根等。
繊維強化成形品は、特に、航空機部材、風車の羽根、自動車外板および電子機器の筐体、トレイ、シャーシ等に好ましく用いられる。
下記の赤外吸収スペクトル分析によって、フッ素樹脂(A)における、官能基(f)を有するIAHに由来する単位の割合を求めた。
フッ素樹脂(A)をプレス成形して200μmのフィルムを得た。赤外吸収スペクトルにおいて、フッ素樹脂(A)中のIAHに由来する単位における吸収ピークは、1778cm-1に現れる。該吸収ピークの吸光度を測定し、IAHのモル吸光係数20810mol-1・l・cm-1を用いて、IAHに由来する単位の割合(モル%)を求めた。
前記割合をa(モル%)とすると、主鎖炭素数1×106個に対する官能基(f)(酸無水物基)の個数は、[a×106/100]個と算出される。
示差走査熱量計(DSC装置、セイコーインスツル社製)を用い、重合体を10℃/分の速度で昇温したときの融解ピークを記録し、極大値に対応する温度(℃)を融点とした。
メルトインデクサー(テクノセブン社製)を用い、297℃、荷重49Nの条件下で直径2mm、長さ8mmのノズルから、10分間に流出する重合体の質量(g)を測定した。
コンターマシン(アマダ社製、V-400)を用いて積層体(繊維強化成形品)を切断し、高さ:63mm、幅:13mm、厚さ:2.8mmのサンプルを得た。サンプルの高さ32mmの位置にノッチを入れ、試験片を得た。
試験片について、アイゾッド試験装置(東洋精機社製)を用い、ハンマー容量:2.75J、ハンマー重量:13.97N、軸心から重心までの距離:10.54cm、軸心から打撃点までの距離:33.5cmの条件にてアイゾット衝撃強度を測定した。
積層体(繊維強化成形品)の各層間の接着性を下記の基準で評価した。
〇(良好):繊維強化成形品の各層を引き剥がせない。
×(不良):繊維強化成形品の各層を容易に引き剥がせる。
フッ素樹脂(A-1):官能基(f)を有するフッ素樹脂(旭硝子社製、官能基(f)の種類:カルボニル基含有基、官能基(f)の含有量:フッ素樹脂(A-1)の主鎖炭素数1×106個に対し3000個、融点:245℃、溶融流れ速度(297℃、荷重49N):22g/10分)。該樹脂は、国際公開第2015/182702号の実施例1と同様に製造し、TFE/IAH/CH2=CH(CF2)2F/Eのモル比は、58.5/0.1/2.4/39であった。
フッ素樹脂(A’-3):官能基(f)を有しないエチレン/テトラフルオロエチレン共重合体(旭硝子社製、Fluon(登録商標)LM-ETFE LM-720AP、融点:226℃、溶融流れ速度(297℃、荷重49N):17.2g/10分)。
熱可塑性樹脂(B-1):ポリアミド6(宇部興産社製、UBEナイロン 1024B)。
フッ素樹脂(A-1)について、単軸押出機(田辺プラスチックス機械社製、VS-30)、150mm幅Tダイを用い、設定樹脂温度:280℃、ライン速度:0.5m/分にて厚さ100μmのフッ素樹脂フィルムを作製した。
フッ素樹脂(A-1)の代わりにフッ素樹脂(A’-2)を用いた以外は、例1と同様にしてプリプレグ(a’-2)を得た。
含フッ素樹脂(A-1)をアズワン社製冷凍粉砕機TPH-01により粉砕し、平均粒子径57μmの粉体を得た。
一方、カーボンクロス(サンライト社製、平織CF3000、厚み0.25mm)を縦10cm×横10cmの寸法に切断した。かかるカーボンクロス表面に前記フッ素樹脂(A-1)の粉体を、炭素繊維含有率:Vf=50%となるように静電塗装により均一にコーティング処理を実施した。その後、熱風循環式乾燥機にて260℃、3分間の熱暴露を行い、フッ素樹脂(A-1)の粉体を含浸させたプリプレグ(a-1P)を得た。
なお、前記Vfは以下の式により算出した。
Vf(%)=(カーボンクロスの体積/(カーボンクロスの体積+コートされた粉体(Z)の体積))×100
熱可塑性樹脂(B-1)をアズワン社製冷凍粉砕機TPH-01により粉砕し、平均粒子径122μmの粉体を得た。フッ素樹脂(A-1)の粉体の代わりに前記熱可塑性樹脂(B-1)の粉体を用い、熱風循環式乾燥機にて240℃、3分間の熱暴露を行った他は例3と同様にして、熱可塑性樹脂(B-1)の粉体を含浸させたプリプレグ(b-1P)を得た。
得られたプリプレグ(b-1P)と例3に記載のプリプレグ(a-1P)とを交互に合計10枚積み重ね、積重物とした。積重物について、例3と同様にプレス成形を行い、厚さ2.3mm(±0.05)の積層体(繊維硬化成形品)を得た。得られた積層体のアイゾット衝撃強度および接着性を表2に示す。
なお、2016年1月13日に出願された日本特許出願2016-4492号の明細書、特許請求の範囲、図面、及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
Claims (10)
- 強化繊維と、マトリックス樹脂とを有し、
前記マトリックス樹脂が、樹脂成分として、融点が100℃以上325℃以下であり、カルボニル基含有基、ヒドロキシ基、エポキシ基およびイソシアネート基からなる群から選ばれる少なくとも1種の官能基を有する溶融成形可能なフッ素樹脂のみを含む、または前記フッ素樹脂と熱可塑性樹脂(ただし、前記フッ素樹脂と同じものを除く。)とを含み、前記フッ素樹脂と前記熱可塑性樹脂との合計100質量%のうち、前記フッ素樹脂の割合が70~100質量%であり、前記熱可塑性樹脂の割合が0~30質量%である、プリプレグ。 - 前記フッ素樹脂と前記熱可塑性樹脂との合計100質量%のうち、前記フッ素樹脂の割合が70~100質量%未満であり、前記熱可塑性樹脂の割合が0超~30質量%であり、前記マトリックス樹脂が、前記フッ素樹脂を含む海部と、前記熱可塑性樹脂を含む島部とからなる海島構造を有し、前記島部の平均径が0.01~200μmである、請求項1に記載のプリプレグ。
- 前記フッ素樹脂の融点が100~260℃未満である、請求項1または2に記載のプリプレグ。
- 融点が100~325℃であり、カルボニル基含有基、ヒドロキシ基、エポキシ基およびイソシアネート基からなる群から選ばれる少なくとも1種の官能基を有する溶融成形可能なフッ素樹脂を含む樹脂材料(α)からなる粉体(X)と、熱可塑性樹脂(ただし、前記フッ素樹脂を除く。)を含む樹脂材料(β)からなる粉体(Y)とを、前記フッ素樹脂と前記熱可塑性樹脂との合計100質量%のうち、前記フッ素樹脂の割合が70~100質量%未満となり、前記熱可塑性樹脂の割合が0超~30質量%となるように混合してなる粉体混合物を、
強化繊維シートの存在下に溶融させ、前記樹脂材料(α)および前記樹脂材料(β)を強化繊維シートに含浸させる、プリプレグの製造方法。 - 前記粉体(X)の平均粒子径が0.02~200μmであり、前記粉体(Y)の平均粒子径が0.02~200μmである、請求項4に記載のプリプレグの製造方法。
- 樹脂成分として、融点が100~325℃であり、カルボニル基含有基、ヒドロキシ基、エポキシ基およびイソシアネート基からなる群から選ばれる少なくとも1種の官能基を有する溶融成形可能なフッ素樹脂のみを含む、または前記フッ素樹脂と熱可塑性樹脂(ただし、前記フッ素樹脂を除く。)とを含み、前記フッ素樹脂と前記熱可塑性樹脂との合計100質量%のうち、前記フッ素樹脂の割合が70~100質量%であり、前記熱可塑性樹脂の割合が0~30質量%である樹脂材料(γ)からなる粉体(Z)を、
強化繊維シートの存在下に溶融させ、前記樹脂材料(γ)を強化繊維シートに含浸させる、プリプレグの製造方法。 - 前記粉体(Z)の平均粒子径が、0.02~200μmであり、前記フッ素樹脂と前記熱可塑性樹脂との合計100質量%のうち、前記フッ素樹脂の割合が70~100質量%未満であり、前記熱可塑性樹脂の割合が0超~30質量%であり、
前記強化繊維シートに含浸される前の前記樹脂材料(γ)における前記熱可塑性樹脂を含む島部の平均径が、0.01~8μm、かつ前記粉体(Z)の平均粒子径未満である、請求項6に記載のプリプレグの製造方法。 - 樹脂成分として、融点が100~325℃であり、カルボニル基含有基、ヒドロキシ基、エポキシ基およびイソシアネート基からなる群から選ばれる少なくとも1種の官能基を有する溶融成形可能なフッ素樹脂のみを含む、または前記フッ素樹脂と熱可塑性樹脂(ただし、前記フッ素樹脂を除く。)とを含み、前記フッ素樹脂と前記熱可塑性樹脂との合計100質量%のうち、前記フッ素樹脂の割合が70~100質量%であり、前記熱可塑性樹脂の割合が0~30質量%である樹脂材料(γ)からなる樹脂フィルムを、
強化繊維シートの存在下に溶融させ、前記樹脂材料(γ)を強化繊維シートに含浸させる、プリプレグの製造方法。 - 前記フッ素樹脂と前記熱可塑性樹脂との合計100質量%のうち、前記フッ素樹脂の割合が70~100質量%未満であり、前記熱可塑性樹脂の割合が0超~30質量%であり、
前記強化繊維シートに含浸される前の前記樹脂材料(γ)における前記熱可塑性樹脂を含む島部の平均径が、0.01~8μmであり、かつ前記樹脂フィルムの厚さ未満である、請求項8に記載のプリプレグの製造方法。 - 請求項1~3のいずれか一項に記載のプリプレグを用いた、繊維強化成形品。
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US15/997,004 US10836877B2 (en) | 2016-01-13 | 2018-06-04 | Prepreg, method for its production and fiber-reinforced molded product |
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JP2019065061A (ja) * | 2017-09-28 | 2019-04-25 | Agc株式会社 | プリント基板用樹脂組成物および製造方法 |
JP2019183069A (ja) * | 2018-04-16 | 2019-10-24 | Agc株式会社 | 樹脂付き強化繊維基材及びその製造方法、プリプレグの製造方法、繊維強化成形品の製造方法 |
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WO2020246440A1 (ja) * | 2019-06-07 | 2020-12-10 | 倉敷紡績株式会社 | 繊維強化樹脂成形体 |
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JP7259834B2 (ja) * | 2018-02-23 | 2023-04-18 | Agc株式会社 | 積層体及びその製造方法、ならびに成形体及びその製造方法 |
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Also Published As
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US10836877B2 (en) | 2020-11-17 |
JP6766827B2 (ja) | 2020-10-14 |
JPWO2017122740A1 (ja) | 2018-11-01 |
KR20180102547A (ko) | 2018-09-17 |
TWI719114B (zh) | 2021-02-21 |
CN108473700A8 (zh) | 2018-10-19 |
US20180282500A1 (en) | 2018-10-04 |
TW201741378A (zh) | 2017-12-01 |
CN108473700A (zh) | 2018-08-31 |
DE112017000363T5 (de) | 2018-09-27 |
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