Classifications

• • 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
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
  • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/10—Homopolymers or copolymers of propene
  • C08L23/14—Copolymers of propene
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • 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
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2323/10—Homopolymers or copolymers of propene
  • C08J2323/12—Polypropene
• • 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
  • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
• • 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
  • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
  • C08L2205/16—Fibres; Fibrils

Definitions

• the present invention relates to a unidirectional fiber reinforced resin sheet having excellent vibration fatigue characteristics, a laminate containing a plurality of the sheets, and an automobile member including the sheets.
• a unidirectional fiber reinforced resin sheet is known as a fiber reinforced resin containing reinforcing fibers.
• This unidirectional fiber reinforced resin sheet is a sheet in which a fiber bundle (a bundle composed of a plurality of fibers) aligned in one direction is impregnated with resin. It is lighter than sheet-shaped metal and has better mechanical strength than sheets made entirely of resin. Therefore, this unidirectional fiber reinforced resin sheet may be used, for example, for the purpose of partially reinforcing the resin molded product to improve its strength.
• the resin molded body reinforced in this way is useful as a substitute for, for example, a metal member.
• Patent Document 1 describes a unidirectional fiber-reinforced resin sheet containing acid-modified propylene and non-acid-modified polypropylene as a matrix resin. It is also explained that this sheet may contain an inorganic filler as an optional component.
• the unidirectional fiber reinforced resin sheet described in Patent Document 1 is used for stamping molding, and it is not described that it is used as a reinforcing material in the sheet state.
• Examples of applications for using the seat as a reinforcing material include components of vehicles and aircraft that are required to be lightweight and strong. However, since vehicles and aircraft generate vibration during operation, they are also required to have excellent vibration fatigue characteristics.
• an object of the present invention is to provide a unidirectional fiber reinforced resin sheet having excellent vibration fatigue characteristics, a laminate containing a plurality of the sheets, and an automobile member including the sheets.
• the present inventors first tried adding a general filler such as talc having a relatively small aspect ratio in order to improve the vibration fatigue characteristics of the unidirectional fiber reinforced resin sheet. In this case, the vibration fatigue characteristics were slightly improved, but the level was not yet sufficient. Therefore, this time, when a filler having a relatively large aspect ratio (a filler having an aspect ratio within a specific range) was added, it was found that the vibration fatigue characteristics were remarkably improved, and the present invention was completed. That is, the present invention is specified by the following matters.
• thermoplastic resin contains an unmodified propylene resin (P1) having a melt flow rate of 100 g / 10 minutes or more measured at 230 ° C. and a load of 2.16 kg according to ASTM D1238.
• P1 unmodified propylene resin
• thermoplastic resin contains a modified propylene resin (P2) containing at least a carboxylate bonded to a polymer chain.
• P2 modified propylene resin
• thermoplastic resin contains a polyamide resin having a melt flow rate of 40 g / 10 minutes or more measured at 230 ° C. and a load of 2.16 kg according to ASTM D1238 after drying at 80 ° C. for 5 hours [1].
• the described unidirectional fiber reinforced resin sheet is a polyamide resin having a melt flow rate of 40 g / 10 minutes or more measured at 230 ° C. and a load of 2.16 kg according to ASTM D1238 after drying at 80 ° C. for 5 hours [1].
• the present invention it is possible to provide a unidirectional fiber reinforced resin sheet having excellent vibration fatigue characteristics, a laminate containing a plurality of the sheets, and an automobile member including the sheets.
• the vibration fatigue characteristics largely depend on the material of the surface of the sheet, and the surface of the conventional unidirectional fiber reinforced resin sheet is usually dominated by matrix resin. Therefore, the vibration fatigue characteristics of the conventional sheet largely depend on the strength of the matrix resin.
• the matrix resin contains the filler (S)
• the surface strength is increased and the vibration fatigue characteristics of the matrix resin are improved.
• the vibration fatigue characteristics are remarkably improved as compared with the case where a filler having a small aspect ratio is used.
• the filler having a large aspect ratio tends to be oriented along the same direction as the fibers of the carbon filament (L), and as a result, the filler having a small aspect ratio is used. It is presumed that the area occupied by the filler on the surface of the sheet becomes larger than in the case, and the effect of improving the strength of the filler is more remarkable.
• the numerical range represented by using “-” means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
• the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. Further, in the numerical range described in the present specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples.
• the long carbon fiber (L) used in the present invention is a carbon fiber having a fiber length of 20 mm or more.
• the upper limit of the fiber length is not particularly limited, and any length may be used as long as it corresponds to the size required in the application in which the unidirectional fiber reinforced resin sheet is used.
• the aspect ratio of the long carbon fiber (L) usually exceeds 500.
• the average fiber diameter of the long carbon fiber (L) is not particularly limited, but is preferably 1 to 20 ⁇ m, more preferably 3 to 15 ⁇ m from the viewpoint of the mechanical properties and surface appearance of the obtained molded product.
• the type of long carbon fiber (L) is not particularly limited, and various known carbon fibers can be used. Among them, PAN-based, pitch-based or rayon-based long carbon fibers are preferable from the viewpoint of improving mechanical properties and reducing the weight of molded products. Further, PAN-based carbon filaments are more preferable from the viewpoint of the balance between the strength and elastic modulus of the obtained molded product.
• the upper limit of the surface oxygen concentration ratio is not particularly limited, but 0.5 or less is generally preferable from the viewpoint of the balance between handleability and productivity of carbon fibers.
• the surface oxygen concentration ratio [O / C] of this carbon fiber can be measured by the method described in International Publication No. 2017/183672.
• the method for controlling the surface oxygen concentration ratio [O / C] of the carbon fiber is not particularly limited. For example, it can be controlled by a method such as electrolytic oxidation treatment, chemical solution oxidation treatment, and gas phase oxidation treatment. Above all, electrolytic oxidation treatment is preferable.
• the carbon filaments (L) are preferably those in which carbon fiber bundles bundled with a sizing agent (sizing agent) are opened.
• the number of single yarns of the carbon fiber bundle is not particularly limited, but is usually 100 to 350,000, preferably 1,000 to 250,000, and more preferably 5,000 to 220,000.
• the sizing agent constituting the carbon fiber bundle is, for example, an olefin emulsion, a urethane emulsion, an epoxy emulsion, or a nylon emulsion, preferably an olefin emulsion, and more preferably a propylene emulsion.
• a propylene emulsion containing an unmodified propylene resin and a modified propylene resin is preferable from the viewpoint of improving the adhesiveness between the reinforcing fiber bundle and the matrix resin.
• the unmodified propylene resin and the modified propylene resin used for this sizing agent the same ones as the unmodified propylene resin (P1) and the modified propylene resin (P2) used for the matrix resin (M) described later are preferably used. Can be used.
• thermoplastic resin used in the present invention is mainly a matrix resin (M) of a unidirectional fiber reinforced resin sheet.
• thermoplastic resin examples include polycarbonate resin, styrene resin, polyamide resin, polyester resin, polyphenylene sulfide resin (PPS resin), modified polyphenylene ether resin (modified PPE resin), polyacetal resin (POM resin), and liquid crystal polyester.
• Polyetherlate acrylic resin such as polymethylmethacrylate resin (PMMA), vinyl chloride, polyimide (PI), polyamideimide (PAI), polyetherimide (PEI), polysulfone, polyethersulfone, polyketone, polyetherketone, Examples thereof include polyolefins such as polyetheretherketone (PEEK), polyethylene and polypropylene, modified polyolefins, phenol resins and phenoxy resins.
• the resin having polarity is preferably a polyamide resin or a polyester resin, and the resin having low polarity is preferably a polyolefin resin.
• the thermoplastic resin preferably contains a propylene resin and / or a polyamide resin.
• the type of the propylene-based resin is not particularly limited, and either a propylene homopolymer or a propylene-based copolymer may be used, or they may be used in combination.
• the stereoregularity may be isotactic, syndiotactic, or atactic. In particular, it is preferably isotactic or syndiotactic.
• the mass ratio [(P1) / (P2)] of the two is preferably 99.9 / 0.1 to 80/20, more preferably 99.5 / 0.5 to 85/15, and particularly preferably. It is 99/1 to 90/10.
• the melt flow rate (MFR) measured at 230 ° C. and a load of 2.16 kg according to ASTM D1238 of the unmodified propylene resin (P1) is preferably 100 g / 10 minutes or more, more preferably 130 to 500 g / 10 minutes. is there.
• MFR melt flow rate
• the weight average molecular weight (Mw) of the unmodified propylene resin (P1) is preferably 50,000 to 300,000, more preferably 50,000 to 200,000.
• the unmodified propylene resin (P1) is a resin having a structural unit derived from propylene, and the amount of the structural unit derived from propylene is preferably 50 mol% or more. It may be a copolymer containing a structural unit derived from propylene, at least one olefin (excluding propylene) selected from the group consisting of ⁇ -olefin, conjugated diene and non-conjugated diene, and a structural unit derived from polyene.
• the unmodified propylene resin (P1) is a copolymer
• specific examples of the ⁇ -olefin as a copolymerization component include ethylene, 1-butene, 3-methyl-1-butene, and 4-methyl-1-. Penten, 3-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 1-nonen, 1-octene, 1-hexene, 1-hexene, 1-decene, 1- Examples thereof include ⁇ -olefins having 2 to 20 carbon atoms excluding propylene such as undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.
• 1-butene, ethylene, 4-methyl-1-pentene and 1-hexene are preferable, and 1-butene and 4-methyl-1-pentene are more preferable.
• Specific examples of the conjugated diene and the non-conjugated diene which are copolymerization components include butadiene, ethylidene norbornene, dicyclopentadiene, and 1,5-hexadiene. Two or more kinds of the above ⁇ -olefin, conjugated diene and non-conjugated diene may be used in combination.
• the modified propylene resin (P2) is a propylene resin containing at least a carboxylate bonded to the polymer chain.
• the carboxylate of the modified propylene resin (P2) has an effect of increasing the interfacial adhesive strength between the long carbon fibers (L) and the matrix resin (M).
• the propylene polymer includes, for example, a propylene homopolymer; an ethylene / propylene copolymer, a propylene / 1-butene copolymer, and an ethylene / propylene / 1-butene polymer.
• examples thereof include a polymer typified by a polymer and a copolymer of propylene and ⁇ -olefin alone or in combination of two or more.
• the monomer having a carboxylic acid structure includes, for example, a monomer having a carboxylic acid group that has been neutralized or not neutralized, and a carboxylic acid that has been saponified or has not been saponified.
• Monomers having an ester can be mentioned.
• a method of radical-grafting polymerizing such a propylene-based polymer and a monomer having a carboxylic acid structure is a typical method for producing a modified propylene-based resin (P2).
• Specific examples of the olefin used in the propylene-based polymer are the same as those used in the unmodified propylene-based resin (P1).
• the modified propylene resin (P2) can be obtained by directly polymerizing propylene and a monomer having a carboxylic acid ester by using a special catalyst, or ethylene and propylene if it is a polymer containing a large amount of ethylene. And a monomer having a carboxylic acid structure may be obtained by high-pressure radical polymerization.
• Examples of the monomer having a carboxylic acid group that has been neutralized or not neutralized and the monomer having a carboxylic acid ester that has been sanitized or not sanitized include ethylene-based unsaturated compounds.
• Carboxylic acids, their anhydrides, their esters; compounds having unsaturated vinyl groups other than olefins can be mentioned.
• ethylenically unsaturated carboxylic acid examples include (meth) acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, and isocrotonic acid.
• acid anhydride examples include Nasicic Acid TM (endosis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid), maleic anhydride, and citraconic anhydride.
• compounds having an unsaturated vinyl group other than olefins include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and the like.
• tert-butyl (meth) acrylate n-amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, Dodecyl (meth) acrylate, octadecyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, lauroyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, isobolonyl ( (Meta) acrylic acid esters such as meta) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acryl
• Aromatic vinyls such as acrylamide, methacrylicamide, N-methylolmethacrylate, N-methylolacrylamide, diacetoneacrylamide, maleic acid amide; vinyl esters such as vinyl acetate and vinyl propionate; N, N- Dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-dipropylaminoethyl (meth) acrylate, N, N-dibutylamino Aminoa such as ethyl (meth) acrylate, N, N-dihydroxyethylaminoethyl (meth) acrylate Lucil (meth) acrylates; unsaturated sulfonic acids such as styrene sulfonic acid, sodium styrene sulfonic acid, 2-
• Two or more types of the above monomers may be used in combination. Among them, acid anhydride is preferable, and maleic anhydride is more preferable.
• the modified propylene resin (P2) can be obtained by various methods as described above. More specifically, for example, in the presence of a polymerization initiator, a propylene-based polymer and an ethylene-based unsaturated carboxylic acid having an unsaturated vinyl group or a monomer having an unsaturated vinyl group other than an olefin are mixed in an organic solvent.
• a method of reacting with a propylene-based polymer and then removing the solvent a method of reacting a melt obtained by heating and melting a propylene-based polymer, a carboxylic acid having an unsaturated vinyl group, and a polymerization initiator with stirring; Examples thereof include a method in which a mixture of a carboxylic acid having an unsaturated vinyl group and a polymerization initiator is supplied to an extruder and reacted while being heated and kneaded, and then converted into a carboxylate by a method such as neutralization or saponification.
• polymerization initiator examples include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoate) hexin-3.
• examples thereof include various peroxide compounds such as 1,4-bis (tert-butylperoxyisopropyl) benzene.
• an azo compound such as azobisisobutyronitrile may be used. Two or more kinds of polymerization initiators may be used in combination.
• organic solvent examples include aromatic hydrocarbons such as xylene, toluene and ethylbenzene; aliphatic hydrocarbons such as hexane, heptane, octane, decane, isooctane and isodecane; and fats such as cyclohexane, cyclohexene, methylcyclohexane and ethylcyclohexane.
• aromatic hydrocarbons such as xylene, toluene and ethylbenzene
• aliphatic hydrocarbons such as hexane, heptane, octane, decane, isooctane and isodecane
• fats such as cyclohexane, cyclohexene, methylcyclohexane and ethylcyclohexane.
• Cyclic hydrocarbons include ester solvents such as ethyl acetate, n-butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone ; Can be mentioned. A mixture of two or more kinds of organic solvents may be used. Of these, aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons are preferable, and aliphatic hydrocarbons and alicyclic hydrocarbons are more preferable.
• the method of obtaining the modified propylene resin (P2) through a neutralization or saponification step is a practical and preferable method because it is easy to treat the raw material of the modified propylene resin (P2) as an aqueous dispersion. is there.
• alkali metals such as sodium, potassium, lithium, calcium, magnesium and zinc, alkaline earth metals or other metals; hydroxylamine, water.
• Inorganic amines such as ammonium oxide; organic amines such as ammonia, (tri) methylamine, (tri) ethanolamine, (tri) ethylamine, dimethylethanolamine, morpholine; alkali metals such as zinc such as sodium oxide and sodium peroxide.
• alkali earth metals or other metal oxides, hydroxides or hydrides; alkali metals such as sodium carbonate or alkaline earth metals or weak acid salts of other metals; may be mentioned.
• alkali metal carboxylic acid salts such as sodium carboxylate and potassium carboxylate; ammonium carboxylate are particularly suitable.
• the degree of neutralization or saponification that is, the conversion rate of the carboxylic acid group of the raw material of the modified propylene resin (P2) to a carboxylic acid salt such as a metal salt or an ammonium salt, depends on the stability of the aqueous dispersion and the fiber. From the viewpoint of adhesiveness, it is usually 50 to 100%, preferably 70 to 100%, and more preferably 85 to 100%.
• the carboxylic acid groups in the modified propylene resin (P2) are preferably all neutralized or saponified by a basic substance, but some of the carboxylic acid groups may remain without being neutralized or saponified. ..
• a method for analyzing the salt component of the carboxylic acid group for example, a method for detecting a metal species forming a salt by ICP emission spectrometry, IR, NMR, mass spectrometry or elemental analysis is used to analyze the salt of the acid group. There is a way to identify the structure.
• the weight average molecular weight (Mw) of the modified propylene resin (P2) is preferably 01,000 to 100,000, more preferably 02,000 to 80,000.
• the adhesiveness to the metal tends to be improved.
• the type of the polyamide resin is not particularly limited, and various known polyamide resins can be used. Specific examples include polyamide 6, polyamide 12, polyamide 66, polyamide 11, and aromatic polyamide. Of these, polyamide 6 and polyamide 12 are preferable.
• the melt flow rate (MFR) of the polyamide resin measured at 230 ° C. and a load of 2.16 kg according to ASTM D1238 after drying at 80 ° C. for 5 hours is preferably 40 g / 10 minutes or more, more preferably 40 to 400 g / 10 Minutes.
• MFR melt flow rate
• the weight average molecular weight (Mw) of the polyamide resin is preferably 05,000 to 50,000, more preferably 55,000 to 30,000.
• the aspect ratio of the filler (S) used in the present invention is 5.0 to 500, preferably 5.0 to 200, and more preferably 5.0 to 100. When the aspect ratio is within this range, the vibration fatigue characteristics tend to be remarkably improved.
• the reason why the vibration fatigue characteristics are remarkably improved is not always clear, but when the aspect ratio of the filler (S) is within this specific range, the filler (S) becomes a carbon filament (L). It is presumed that the fibers tend to be oriented along the same direction as the fibers of the above, and as a result, the effect of improving the strength of the filler (S) is more remarkably exhibited.
• the vibration fatigue characteristics are remarkably improved as compared with the case where a filler having a small aspect ratio is used.
• the acid of the modified propylene resin (P2) is generally consumed by the filler, but as described above, the aspect ratio of the filler (S) is within this specific range. Since the vibration fatigue characteristics are improved, it is possible to relatively reduce the amount of the filler compounded, and accordingly, the amount of acid consumed by the filler is reduced, and the matrix resin and carbon filaments (L) due to the consumption of acid It is also considered that the decrease in the interfacial bonding force of the resin is suppressed.
• the type of filler (S) is not particularly limited. Specific examples thereof include carbon short fibers, glass short fibers, carbon nanotubes, wollastonite, sepiolite, mica, basic magnesium sulfate, montmorillonite, basalt fiber, and total aromatic polyamide. In particular, from the viewpoint of improving strength, at least one fiber selected from the group consisting of carbon short fibers and glass short fibers is preferable.
• the length of the filler (S) is preferably 0.01 to 10 mm, more preferably 0.03 to 5 mm.
• the filler (S) tends to easily enter between the carbon filaments (L), and physical properties such as better vibration fatigue characteristics and elastic modulus tend to be exhibited. It is in. Further, when the length is equal to or more than the lower limit of these ranges, physical properties such as vibration fatigue characteristics and elastic modulus tend to be improved.
• the unidirectional fiber reinforced resin sheet of the present invention contains the carbon filaments (L), the thermoplastic resin, and the filler (S) described above, and the carbon filaments (L) are oriented in one direction. It is a sheet.
• the content of the filler (S) is preferably 0.1 to 40.0% by mass, more preferably 0.5 to 20.0% by mass, particularly, in 100% by mass of the total mass of the unidirectional fiber reinforced resin sheet. It is preferably 0.5 to 10.0% by mass, and most preferably 0.5 to 5.0% by mass.
• the matrix resin (M) tends to be modified to further improve the vibration fatigue characteristics while maintaining the impregnation property of the matrix resin (M) with respect to the carbon filaments (L). ..
• the method for measuring the content rate is as described in the column of Examples described later.
• the content of the long carbon fibers (L) is preferably 20 to 80% by mass, more preferably 30 to 75% by mass in the total mass of 100% by mass of the unidirectional fiber reinforced resin sheet.
• the content of the thermoplastic resin is preferably 35 to 70% by mass, more preferably 40 to 65% by mass.
• the fiber volume content (vf) of the long carbon fibers (L) in the unidirectional fiber reinforced resin sheet is preferably 10 to 70%, more preferably 15 to 60%.
• the thickness of the unidirectional fiber reinforced resin sheet is preferably 1 to 500 ⁇ m, more preferably 5 to 400 ⁇ m, and particularly preferably 5 to 300 ⁇ m.
• the method for producing the unidirectional fiber reinforced resin sheet of the present invention is not particularly limited.
• a mixture of a matrix resin (M) and a filler (S) is prepared in advance, and the opened carbon fiber bundles (bundles of long carbon fibers (L)) are aligned in one direction and melted. Can be obtained by contacting with.
• the unidirectional fiber reinforced resin sheet of the present invention may be used as a single sheet as it is, or may be used as a laminate containing a plurality of unidirectional fiber reinforced resin sheets. In particular, it is preferable to use it as a laminate containing a plurality of unidirectional fiber reinforced resin sheets of the present invention. Alternatively, it may be appropriately cut into a tape shape for use.
• the unidirectional fiber reinforced resin sheet of the present invention is preferably used even in the form of compounding or laminating with other materials. Above all, it is useful as a reinforcing material for other structural materials, and in particular, it is useful as a reinforcing material for members constituting vehicles and aircraft in which vibration is continuously generated.
• the use of the unidirectional fiber reinforced resin sheet of the present invention is not limited to the above-mentioned uses, and can be used for various uses.
• primary structural materials such as main wings, vertical and horizontal tail wings, secondary structural materials such as auxiliary wings, directional steering and elevating steering, interior materials such as seats and tables, power units, hydraulic cylinders, composite brakes and other aircraft.
• General air vehicle parts such as helicopters, rocket parts such as nozzle cones and motor cases, antennas, structures, solar cell panels, battery cases, artificial satellite parts such as telescopes, frames, shafts, rollers, Machine parts such as leaf springs, machine tools, robot arms, transport hands, synthetic fiber pots, high-speed rotating parts such as centrifuge rotors and uranium concentrators, parabolic antennas, battery parts, radars, acoustic speaker cones, etc.
• Computer parts, printer parts, electronic electrical parts such as PC housings and tablet housings, skeleton parts, semi-structural parts, outer panel parts, interior / exterior parts, power units, other equipment-hydraulic cylinders, brakes, battery cases, drives Shafts, engine parts, spoilers, racing car bodies, crash cones, chairs, tablets, telephone covers, undercovers, side covers, transmission covers, battery trays, rear steps, spare tire containers, bus body walls, truck body walls, etc.
• Bike parts interior materials, floorboard panels, ceiling panels, linear motor car bodies, Shinkansen / railway bodies, window cleaning wipers, trolleys, seats and other vehicle parts, yachts, cruisers, boats and other ship hulls, masts, rudder, Propellers, hard sails, screws, military hulls, submersible hulls, deep-sea exploration vessels, and other marine parts / aircraft, actuators, cylinders, bombs, hydrogen tanks, CNG tanks, oxygen tanks and other pressure vessel parts, stirring blades, pipes, Scientific equipment parts / members such as tanks, pit floors, plant piping, blades, skins, skeleton structures, wind power generation parts such as ice removal systems, X-ray diagnostic equipment parts, wheelchairs, artificial bones, artificial legs / hands, pine needles, nursing care Auxiliary equipment / robots (power assist suits), pedestrians, medical / nursing equipment parts / supplies such as nursing beds, CF composite cables, concrete reinforcement members, guard rails, bridges, tunnel walls, hoods, cables,
• the automobile member of the present invention includes the unidirectional fiber reinforced resin sheet of the present invention described above.
• automobile parts include, for example, skeleton parts, semi-structural parts, outer panel parts, interior / exterior parts, power units, other equipment-hydraulic cylinders, brakes, battery cases, drive shafts, engine parts, spoilers. , Racing car body, crash cone, chair, tablet, telephone cover, undercover, side cover, transmission cover, battery tray, rear step, spare tire container, bus body wall, truck body wall, etc.
• the aspect ratio, length and content of the filler (S), and the physical properties of the propylene-based resin are values measured by the following methods.
• the aspect ratio and length were determined (this aspect ratio and length are average values).
• the type of dispersion medium used is not particularly limited as long as it can perform dynamic image analysis, but in this example, a 0.05 mass% aqueous solution of a surfactant was used.
• Example 1 (Preparation of long carbon fiber (L)) A carbon fiber bundle (manufactured by Mitsubishi Rayon Co., Ltd., trade name Pyrofil TR50S12L, number of filaments 24,000, strand strength 5000 MPa, strand elastic modulus 242 GPa) is immersed in acetone, ultrasonic waves are applied for 10 minutes, and then the carbon fiber bundle is pulled up. The sizing agent was removed by washing with acetone three times and drying at room temperature for 8 hours.
• a 20% aqueous potassium hydroxide solution was continuously supplied at a rate of 90 g / hour and extruded continuously at a heating temperature of 210 ° C.
• the extruded resin mixture was cooled to 110 ° C. with a static mixer with a jacket installed at the mouth of the extruder, and further poured into warm water at 80 ° C. to obtain an emulsion.
• the solid content concentration of the obtained emulsion was 45%.
• the maleic anhydride-modified propylene resin has 96 parts by mass of a propylene / butene copolymer, 4 parts by mass of maleic anhydride, and 0.4 parts by mass of a polymerization initiator (manufactured by Nippon Oil & Fats Co., Ltd., trade name: Perhex 25B). It is a modified resin obtained by mixing the parts and modifying the mixture at a heating temperature of 160 ° C. for 2 hours.
• the emulsion obtained as described above was attached to long carbon fibers (the above-mentioned carbon fiber bundle manufactured by Mitsubishi Rayon Co., Ltd. from which the sizing agent was removed) by using a roller impregnation method. Then, it was dried online at 130 ° C. for 2 minutes to remove low boiling point components to obtain a carbon fiber bundle. The amount of the emulsion adhered was 0.87% by mass.
• the content of each component in this unidirectional fiber reinforced resin sheet was 56% by mass of carbon filament (L), 4.4% by mass of filler (S), and 39.6% by mass of thermoplastic resin.
• the fiber volume content (vf) of the long carbon fibers (L) was 39%, and the thickness of the unidirectional fiber reinforced resin sheet was 200 ⁇ m.
• the long carbon fiber (L) had a fiber length of 20 mm or more and an aspect ratio of more than 500.
• the content of the filler (S) and the thermoplastic resin can be adjusted by appropriately changing the degree of opening of the long carbon fibers (L) and the contact time with the impregnated roll. Further, the thickness of the unidirectional fiber reinforced resin sheet can be adjusted by appropriately changing the extrusion amount.
• a unidirectional fiber reinforced resin sheet was produced in the same manner as in Example 1 except that the content was changed to the described content. The thickness of the unidirectional fiber reinforced resin sheet was 200 ⁇ m. Further, the long carbon fiber (L) had a fiber length of 20 mm or more and an aspect ratio of more than 500.
• ⁇ Comparative example 1> A unidirectional fiber reinforced resin sheet was produced in the same manner as in Example 1 except that the filler (S) was not used and the content of each of the other components was changed to the content shown in Table 1.
• the obtained laminate was cut to obtain a test piece conforming to ASTM D671-TypeA. Then, a vibration fatigue test is performed using a repeated vibration fatigue tester (B50 type manufactured by Toyo Seiki Co., Ltd.) under the conditions of room temperature, frequency 30 Hz, and pressure 60 MPa, and vibration fatigue is determined by the number of repetitions when the displacement reaches 8 mm. The characteristics were evaluated.
• Comparative Example 1 since the filler (S) was not used, the vibration fatigue characteristics were inferior. Further, in Comparative Example 2, since talc (S-3) having a small aspect ratio was used as the filler (S), the vibration fatigue characteristics were inferior.
• the unidirectional fiber reinforced resin sheet of the present invention and its laminate are excellent in vibration fatigue characteristics, they can be used for various purposes, especially for reinforcing members of vehicle parts such as automobiles and trains, and flying bodies such as aircraft. Suitable for component applications.

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• 2020
  • 2020-06-09 JP JP2021528103A patent/JPWO2020255786A1/ja active Pending
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