WO2016039485A1 - 繊維強化ポリイミド樹脂成形体及びその製造方法 - Google Patents
繊維強化ポリイミド樹脂成形体及びその製造方法 Download PDFInfo
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- WO2016039485A1 WO2016039485A1 PCT/JP2015/076074 JP2015076074W WO2016039485A1 WO 2016039485 A1 WO2016039485 A1 WO 2016039485A1 JP 2015076074 W JP2015076074 W JP 2015076074W WO 2016039485 A1 WO2016039485 A1 WO 2016039485A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/002—Methods
- B29B7/005—Methods for mixing in batches
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
- B29B7/22—Component parts, details or accessories; Auxiliary operations
- B29B7/28—Component parts, details or accessories; Auxiliary operations for measuring, controlling or regulating, e.g. viscosity control
- B29B7/286—Component parts, details or accessories; Auxiliary operations for measuring, controlling or regulating, e.g. viscosity control measuring properties of the mixture, e.g. temperature, density
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/88—Adding charges, i.e. additives
- B29B7/90—Fillers or reinforcements, e.g. fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
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- 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
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/82—Heating or cooling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2079/00—Use of polymers having nitrogen, with or without oxygen or carbon only, in the main chain, not provided for in groups B29K2061/00 - B29K2077/00, as moulding material
- B29K2079/08—PI, i.e. polyimides or derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/12—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles
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- 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
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Definitions
- the present invention relates to a fiber-reinforced polyimide resin molded body and a method for producing the same. More specifically, the present invention has excellent sliding performance, and functional fibers in the polyimide resin are dispersed, so that shape stability during molding is achieved. The present invention relates to an excellent molded body and a method for producing the same.
- molded products made of fiber reinforced resin made by blending functional fibers such as carbon fibers with resin have excellent properties such as weather resistance, mechanical strength, and durability.
- the following Patent Document 1 describes a carbon fiber reinforced resin molded article composed of a specific pitch-based carbon short fiber mixture and a matrix resin, and describes that it is suitably used for various electronic components.
- Patent Document 2 a friction material comprising a resin composition for a friction material using a specific aromatic polyimide oligomer as a binder such as carbon fiber has been proposed.
- Patent Document 3 proposes a rolling element made of a carbon fiber reinforced synthetic resin containing 10 to 70% by weight of carbon fiber having a specific thermal conductivity.
- an addition reaction type polyimide resin excellent in mechanical strength, heat resistance and durability and excellent in resin impregnation property As an addition reaction type polyimide resin, a highly functional addition reaction type polyimide resin capable of producing a carbon fiber reinforced composite by transfer molding (RTM) and resin injection (RI) has also been proposed (Patent Document 4).
- the addition reaction type polyimide resin that can be suitably used as a matrix resin for functional fibers such as carbon fibers has a low melt viscosity in a prepolymer state.
- an object of the present invention is to provide a fiber-reinforced polyimide resin molded article that has excellent sliding performance, is free from warpage, and has excellent shape stability during molding.
- Another object of the present invention is to provide a production method capable of molding a fiber-reinforced polyimide resin molded article having excellent sliding performance with good shape stability.
- a resin molded body in which functional fibers are dispersed in an addition-reaction type polyimide resin, which has a limit PV value of 3000 kPa ⁇ m / s or more. Is done.
- the matrix of the composition constituting the resin molded body is an addition reaction type polyimide resin, and the functional fiber is impregnated with the polyimide resin, 2.
- the functional fiber is contained in an amount of 5 to 200 parts by weight based on 100 parts by weight of the addition reaction type polyimide; 3.
- the functional fiber is at least one of carbon fiber, glass fiber, aramid fiber, and metal fiber; 4).
- the functional fiber is a carbon fiber having an average fiber length of 50 to 6000 ⁇ m and an average fiber diameter of 5 to 20 ⁇ m; 5. Containing a thickener in an amount of 5 to 40 parts by weight with respect to 100 parts by weight of the addition reaction type polyimide, and the thickener is dispersed in the resin molded body, 6).
- the thickener is at least one of graphite, molybdenum disulfide, PTFE (tetrafluoroethylene resin), fine carbon-based material, and metal powder; Is preferred.
- the prepolymer of the addition reaction type polyimide resin and the functional fiber are kneaded at a temperature not lower than the melting point (160 to 170 ° C.) of the addition reaction type polyimide resin and not higher than the thermosetting start temperature (near 300 ° C.).
- a method for producing a resin molded body comprising at least a dispersion kneading step and a shaping step of shaping the mixture under a temperature condition equal to or higher than a thermosetting start temperature of an addition reaction type polyimide resin.
- the kneaded product obtained in the dispersion kneading step is increased to increase the viscosity of the kneaded product by holding for a certain time at a temperature equal to or higher than the thermosetting start temperature of the addition reaction type polyimide resin. Having a viscous process, 2.
- the functional fiber is contained in an amount of 5 to 200 parts by weight based on 100 parts by weight of the addition reaction type polyimide; 3.
- the mixture obtained through the dispersion kneading step has a melt viscosity of 10 to 5000 Pa ⁇ s under a temperature condition of 300 to 320 ° C., the mixture is cooled, pulverized and mixed, and then pressure-shaped, 4). Adjusting the melt viscosity of the mixture at a temperature of 300 to 320 ° C. to 10 to 5000 Pa ⁇ s in the thickening step; 5.
- the addition reaction type polyimide resin is a polyimide resin having a phenylethynyl group as an addition reaction group; 6).
- the addition reaction type polyimide resin is a polyimide resin having a phenylethynyl group as an addition reaction group
- the thickening step holding at a temperature of 310 ⁇ 10 ° C. for 30 to 60 minutes, Is preferred.
- a method for producing a resin molded article comprising 5 to 200 parts by weight of functional fiber and 5 to 40 parts by weight of a thickener dispersed in 100 parts by weight of an addition reaction type polyimide.
- a method for producing a resin molded body comprising: a shaping step of pressure-molding under a temperature condition equal to or higher than a thermosetting start temperature of an addition reaction type polyimide resin.
- the melt viscosity under the temperature condition of 300 to 320 ° C. of the mixture after the dispersion kneading step is 10 to 5000 Pa ⁇ s.
- the said shaping process is performed by compression molding.
- an addition reaction type polyimide resin excellent in heat resistance, durability and mechanical strength is used as a matrix resin, and 5 functional fibers are added to 100 parts by weight of this addition reaction type polyimide.
- 5 functional fibers are added to 100 parts by weight of this addition reaction type polyimide.
- the functional fibers are uniformly cured and molded in the molded body, they are crosslinked and cured, so that they are free from warping and other distortion and can be suitably used as a slidable member.
- the limit PV value is a value obtained by the product of the surface pressure P and the speed V when the frictional force suddenly increases.
- the limit PV value is used as an index for determining whether the sliding member is suitable for the use environment. It is common to calculate. Under conditions close to the limit PV value, dynamic friction coefficient and sample temperature increase due to melting and seizure of resin due to frictional heat on the sliding surface, abnormal wear of the material, etc. are seen. Higher values indicate higher sliding performance. Means that.
- the fiber-reinforced polyimide resin molded body of the present invention has a functional fiber impregnated with an addition-reactive polyimide and contains a predetermined amount of functional fiber, and is excellent in sliding and used as a sliding member. In addition to being able to maintain stable performance over a long period of time, deformation due to warpage can be prevented, so that productivity is excellent, and changes in PV value due to wear during long-term use can be reduced. Easy to manage devices.
- the viscosity of the prepolymer (imide oligomer) of the polyimide resin in the molten state is added after the dispersion kneading step of the addition reaction type polyimide resin and the functional fiber.
- the functional fiber in an amount of 5 to 200 parts by weight and the amount of 5 to 40 parts by weight with respect to 100 parts by weight of the addition reaction type polyimide.
- the viscosity of the mixture after the dispersion kneading step is adjusted to a high viscosity of 10 to 5000 Pa ⁇ s under a temperature condition of 300 to 320 ° C. without providing a thickening step. It becomes possible to do.
- the thickener suitably used in the present invention is excellent in slidability and can further improve the sliding performance.
- the fiber-reinforced polyimide resin molded body of the present invention is a resin molded body in which functional fibers are dispersed in an addition reaction type polyimide resin described later, and it is important that the limit PV value is 3000 kPa ⁇ m / s or more. It has such features as heat resistance, durability, and mechanical strength, and has a large limit PV value and excellent sliding performance.
- an addition reaction type polyimide resin is used as a polyimide resin to be a matrix of a composition constituting a fiber reinforced polyimide resin molded body.
- the addition reaction type polyimide resin used in the present invention is composed of an aromatic polyimide oligomer having an addition reaction group at the terminal, and those prepared by a conventionally known production method can be used.
- a method for the reaction a method of polymerizing at a temperature of 100 ° C. or lower, preferably 80 ° C.
- a method comprising two steps of heat imidization by heating at a high temperature of about 140 to 270 ° C., or one step of performing a polymerization / imidization reaction at a high temperature of 140 to 270 ° C. for 0.1 to 50 hours from the beginning.
- a method comprising two steps of heat imidization by heating at a high temperature of about 140 to 270 ° C., or one step of performing a polymerization / imidization reaction at a high temperature of 140 to 270 ° C. for 0.1 to 50 hours from the beginning.
- the solvent used in these reactions is not limited to this, but N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, ⁇ -butyllactone, N- An organic polar solvent such as methylcaprolactam can be preferably used.
- the terminal addition reaction group of the aromatic imide oligomer is not particularly limited as long as it is a group that undergoes a curing reaction (addition polymerization reaction) by heating when producing a resin molded body, but preferably performs a curing reaction.
- a curing reaction addition polymerization reaction
- any reactive group selected from the group consisting of a phenylethynyl group, an acetylene group, a nadic acid group, and a maleimide group is preferable.
- the phenylethynyl group is suitable because it does not generate a gas component due to the curing reaction, and is excellent in the heat resistance and mechanical strength of the obtained resin molded body.
- addition-reactive groups are a reaction in which a compound having an anhydride group or amino group together with an addition reactive group in the molecule forms an imide ring, preferably with an amino group or acid anhydride group at the terminal of an aromatic imide oligomer. Is introduced at the end of the aromatic imide oligomer.
- Compounds having an anhydride group or amino group in the molecule together with an anhydride group or an amino group include, for example, 4- (2-phenylethynyl) phthalic anhydride, 4- (2-phenylethynyl) aniline, 4-ethynyl-phthalic anhydride, 4 -Ethynylaniline, nadic acid anhydride, maleic acid anhydride and the like can be preferably used.
- Examples of the tetracarboxylic acid component that forms an aromatic imide oligomer having an addition reactive group at the terminal include 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyl At least selected from the group consisting of tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride
- One tetracarboxylic dianhydride can be exemplified, and in particular, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride can be preferably used.
- the diamine component that forms the aromatic imide oligomer having an addition reactive group at the terminal is not limited to this, but 1,4-diaminobenzene, 1,3-diaminobenzene, 1,2-diaminobenzene, 2,6- Diethyl-1,3-diaminobenzene, 4,6-diethyl-2-methyl-1,3-diaminobenzene, 3,5-diethyltoluene-2,4-diamine, 3,5-diethyltoluene-2,6- Diamine having one benzene ring such as diamine, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone 4,4′-diaminodiphenylmethane, 3,3′-di
- a mixed diamine composed of at least two aromatic diamines selected from the group consisting of methyl) benzidine, particularly 1,3-diaminobenzene and 1,3-bis (4-aminophenoxy) benzene.
- the number of repeating units of the imide oligomer is preferably more than 0 and 20 or less, particularly 1 to 5, and is preferably in terms of styrene by GPC.
- the number average molecular weight is preferably 10,000 or less, particularly 3000 or less.
- Adjustment of the number of repeating units can be performed by changing the ratio of aromatic tetracarboxylic dianhydride, aromatic diamine, and compound having an anhydride group or amino group together with an addition reactive group in the molecule, By increasing the proportion of the compound having an anhydride group or amino group in the molecule and an anhydride group or amino group, the number of repeating units is reduced by lowering the molecular weight. The number of unit repetitions increases.
- resin additives such as flame retardants, colorants, lubricants, heat stabilizers, light stabilizers, ultraviolet absorbers, fillers, etc.
- flame retardants flame retardants
- colorants colorants
- lubricants heat stabilizers
- light stabilizers light stabilizers
- ultraviolet absorbers fillers, etc.
- the functional fiber to be dispersed in the above-described addition reaction type polyimide resin conventionally known materials can be used, and conventionally known functionalities such as carbon fiber, aramid fiber, glass fiber, metal fiber, etc.
- fibers can be used, carbon fibers can be particularly preferably used.
- carbon fibers having an average fiber length of 50 to 6000 ⁇ m and an average fiber diameter of 5 to 20 ⁇ m can be preferably used.
- the average fiber length is shorter than the above range, the effect of carbon fiber as a reinforcing material cannot be sufficiently obtained.
- the average fiber length is longer than the above range, the dispersibility in the polyimide resin becomes poor. .
- the handling property is inferior and expensive
- the average fiber diameter is thicker than the above range
- the settling rate of the functional fiber is increased and the functional fiber is increased. May tend to be unevenly distributed, and the strength of the fiber tends to decrease, and the effect as a reinforcing material may not be sufficiently obtained.
- the content of the functional fiber has a significant influence on the sliding performance of the resin molded body and the occurrence of warpage during molding.
- the functional fiber is added to 100 parts by weight of the addition reaction type polyimide. Containing 5 to 200 parts by weight, particularly 10 to 150 parts by weight, is suitable for obtaining a molded article having excellent sliding performance and excellent shape stability without warping. It is.
- the limit PV value is less than the above value, and the slidability may be lowered.
- the limit PV value may be lowered as compared with the case where the amount is within the above range. In addition, excessive thickening may occur and molding may not be possible.
- inorganic materials such as fine carbon-based materials such as carbon black, metal powders such as aluminum powder and copper powder can be blended.
- the inorganic material is preferably contained in an amount of 5 to 40 parts by weight with respect to 100 parts by weight of the addition reaction type polyimide.
- the viscosity of the prepolymer of the addition reaction type polyamide resin is increased by using the thickener together with the functional fiber in an amount of 5 to 40 parts by weight with respect to 100 parts by weight of the addition reaction type polyimide.
- the functional fibers can be maintained uniformly dispersed in the prepolymer without settling.
- the thickener graphite, molybdenum disulfide, PTFE (tetrafluoroethylene resin), magnesium oxide, magnesium hydroxide, calcium hydroxide, and the like can be used. Among them, graphite, molybdenum disulfide, PTFE, The sliding performance can be further improved, which is particularly preferable.
- the thickener is preferably contained in an amount of 5 to 40 parts by weight based on 100 parts by weight of the addition reaction type polyimide. If the amount of the thickener is less than the above range, the viscosity of the prepolymer does not increase sufficiently, the settling of the functional fibers cannot be sufficiently suppressed, and the warp deformation in which the functional fibers are uniformly dispersed It is not possible to mold a resin molded body without any. Further, if the amount of the thickener is larger than the above range, the sliding performance may be impaired, such as an increase in coefficient of friction and a decrease in wear resistance.
- the first manufacturing method of the resin molded body of the present invention is at least a prepolymer (imide oligomer) of an addition reaction type polyimide resin and a functional fiber at a temperature not lower than the melting point of the addition reaction type polyimide resin and not higher than the thermosetting start temperature.
- the viscosity of the kneaded product is maintained by holding the kneaded product obtained by the dispersion kneading step at a temperature equal to or higher than the thermal curing start temperature of the reactive polyimide resin for a certain period of time. It is characterized by having a thickening step (B) in which the viscosity of the kneaded product is adjusted to an appropriate range by raising the viscosity as necessary.
- the addition reaction type polyimide resin used for molding the resin molded body of the present invention has a low viscosity in the state of the prepolymer before cross-linking and curing, and when functional fibers are contained, it settles. As a result, functional fibers are ubiquitous and warping occurs in the molded body.
- the viscosity of the prepolymer is increased by the thickening step (B) to prevent sedimentation of the functional fiber, and the state thereof is changed. Since it is shaped in the shaping step (C) while being maintained, the functional fibers are uniformly dispersed, and it becomes possible to mold a molded product without warping by shrinking evenly during heat curing.
- the prepolymer and the functional fiber are mixed by heating the prepolymer (imide oligomer) of the addition reaction type polyimide resin and the functional fiber at a temperature equal to or higher than the melting point of the addition reaction type polyimide resin and kneading while melting the prepolymer.
- the functional fiber is used in an amount of 5 to 200 parts by weight, particularly 10 to 150 parts by weight, based on 100 parts by weight of the addition reaction type polyimide. Further, the above-mentioned inorganic materials can be blended in the above-mentioned amounts.
- the above-mentioned thickener can be blended in the above-mentioned amount.
- a conventionally known mixer such as a Henschel mixer, a tumbler mixer, or a ribbon blender can be used.
- a batch type pressure kneader kneader
- the present invention it is desirable to cool and solidify the mixture of prepolymer and functional fiber that has undergone the dispersion-kneading step, and then form a lump of a predetermined size. Thereby, it becomes possible to store the mixture in which the functional fibers are dispersed in the prepolymer with the lapse of time, and the handleability is also improved.
- the melt viscosity of the mixture of the melt-kneaded prepolymer and the functional fiber under a temperature condition of 300 to 320 ° C. is 10 or less
- the temperature of the polyimide resin used in the mixture is about 310 ⁇ 10 ° C. near the thermosetting start temperature.
- the melt viscosity under the temperature condition of 300 to 320 ° C. is adjusted to the range of 10 to 5000 Pa ⁇ s. That is, when the mixture of the prepolymer and the functional fiber is held at a temperature of 310 ⁇ 10 ° C.
- the prepolymer gradually starts to crosslink, so that the viscosity increases.
- the functional fiber impregnated in the prepolymer by the dispersion kneading step can maintain a dispersed state without settling in the prepolymer due to this viscosity increase.
- the reaction start temperature depends on the addition reaction group, and in the polyimide resin having a phenylethynyl group suitable as the addition reaction group in the present invention, 310 ⁇ 10 which is close to the thermosetting start temperature. It is desirable to heat at a temperature of 30 ° C. for 30 to 60 minutes.
- the mixture of the prepolymer and the functional fiber whose melt viscosity is adjusted to the above range through the thickening step is shaped under a temperature condition equal to or higher than the thermosetting start temperature of the polyimide resin to be used as a resin molded body having a desired shape. Molded.
- the mixture is cured by introducing a mixture of the polyimide prepolymer and functional fibers in the above-mentioned viscosity range in the molten state into a mold and heating and pressing at a temperature equal to or higher than the thermosetting start temperature.
- the shaping is preferably performed by compression molding or transfer molding in which the mixture introduced into the molding die is compressed and compressed, but can also be molded by injection molding or extrusion molding.
- the second production method of the resin molded body of the present invention is such that 5 to 200 parts by weight of functional fiber and 5 to 40 parts by weight of thickening agent are added to 100 parts by weight of the prepolymer (imide oligomer) of the addition reaction type polyimide resin.
- a dispersion kneading step in which the agent is kneaded at a temperature not lower than the melting point of the addition reaction type polyimide resin and not higher than the thermosetting start temperature, and the mixture having undergone the dispersion kneading step is subjected to a temperature condition not lower than the thermosetting start temperature of the reaction type polyimide resin. It is characterized by comprising a shaping step for pressure shaping.
- the addition reaction type polyimide resin used for molding the resin molded body of the present invention has a low viscosity in the state of the prepolymer before cross-linking and curing, and when functional fibers are contained, it settles. As a result, functional fibers are ubiquitous and warping occurs in the molded body.
- the second production method of the present invention it is possible to increase the viscosity of the prepolymer without passing through the thickening step by adding a predetermined amount of thickener together with the functional fiber to the prepolymer. As a result, the functional fibers are dispersed without precipitating in the prepolymer, and the functional fibers are formed in the shaping process while maintaining the dispersed state. Thus, it becomes possible to mold a molded body without warping.
- Prepolymer (imide oligomer) of addition reaction type polyimide resin, functional fiber, and thickener are heated at a temperature equal to or higher than the melting point of addition reaction type polyimide resin and kneaded while melting the prepolymer. Mix sex fibers.
- the functional fiber is used in an amount of 5 to 200 parts by weight, particularly 10 to 150 parts by weight, and the thickener 5 to 40 parts by weight with respect to 100 parts by weight of the addition reaction type polyimide.
- the kneading of the prepolymer and the functional fiber can be performed in the same manner as in the first production method described above.
- the temperature of the dispersion kneading step is equal to or higher than the melting point of the prepolymer and equal to or lower than the crosslinking curing temperature, and particularly preferably, the mixture that has undergone the dispersion kneading step has a melt viscosity of 10 at a temperature of 300 to 320 ° C. It is preferably in the range of ⁇ 5000 Pa ⁇ s. The increase in viscosity and the penetration of the prepolymer into the functional fiber are combined, and the functional fiber does not settle and maintains a state dispersed in the prepolymer.
- the mixture of the prepolymer, the functional fiber, and the thickener that has undergone the dispersion kneading step is cooled and solidified and then formed into a lump of a predetermined size. Thereby, it becomes possible to store the mixture in which the functional fibers are dispersed in the prepolymer with the lapse of time, and the handleability is also improved.
- Warpage / Diameter ratio (%) t / D ⁇ 100 t: Test piece warpage (mm), D: Product diameter (mm)
- the quality determination of the warp / diameter ratio was evaluated as ⁇ when less than 1.5% and ⁇ when 1.5% or more.
- the melt viscosity at 310 ° C. was measured with a rheometer (ARES manufactured by TA instrument).
- the measurement mode was dynamic frequency dispersion, the angular frequency was 0.1 to 500 rad / s, and the melt viscosity under the condition of 0.1 rad / s was taken as the measured value.
- Example 1 11.1 parts by weight of pitch-based carbon fiber (K223HM manufactured by Mitsubishi Plastics) with an average single fiber length of 200 ⁇ m is blended with 100 parts by weight of addition-polymerized polyimide (PET-330 manufactured by Ube Industries Co., Ltd.). It was melt-kneaded at 280 ° C. for 30 minutes under atmospheric pressure. Then, the mixture (bulk molding compound, BMC) cooled to room temperature was obtained. The obtained BMC was divided into easy-to-handle sizes, held in an electric furnace at 310 ° C.
- PTT-330 addition-polymerized polyimide
- Example 2 42.9 parts by weight of pitch-based carbon fiber (K223HM, manufactured by Mitsubishi Plastics) with an average single fiber length of 200 ⁇ m is blended with 100 parts by weight of addition-polymerized polyimide (PET-330, manufactured by Ube Industries). It was melt-kneaded at 280 ° C. for 30 minutes under atmospheric pressure. Thereafter, BMC cooled to room temperature was obtained. After dividing the obtained BMC into a size that fits in the mold, the BMC was held in a mold for a compression molding machine at 280 ° C. to 320 ° C. for a certain period of time, and then melted and soaked. While applying pressure, the plate was heated to 371 ° C.
- PKT-330 addition-polymerized polyimide
- Example 3 The same as Example 2 except that the amount of carbon fiber was changed to 100 parts by weight.
- Example 4 It was the same as Example 1 except that 310 ° C. was not maintained in the electric furnace. Since the obtained resin molding was warped, the front and back layers were scraped to a predetermined parallelism, and the limit PV value was measured. Although the limit PV value of the surface before cutting was not measured, when the measured surface was observed, carbon fibers were clearly present more than the surface before cutting. This also shows that a predetermined amount of carbon fiber is necessary on the surface.
- Example 1 The same as Example 2 except that no carbon fiber was blended.
- Example 2 It was the same as Example 2 except having changed the compounding quantity of carbon fiber into 233 weight part.
- the viscosity of the BMC obtained after melt-kneading was high, and in some cases, the elongation in the mold was insufficient in the shaping process, and the limit PV value could not be measured.
- Table 1 shows the results of measuring the limit PV values of the test pieces obtained in Examples 1 to 4 and Comparative Examples 1 and 2, the presence or absence of the thickening step, the quality of fiber dispersion, and the presence or absence of defects in the molded product.
- Example 1 was the same as Example 1 except that BMC was set in an electric furnace at 310 ° C. for 45 minutes.
- Example 6 Example 1 was the same as Example 1 except that BMC was changed to 310 ° C. for 60 minutes in an electric furnace.
- Example 1 was the same as Example 1 except that BMC was changed to 310 ° C. for 15 minutes in an electric furnace. In addition, warpage deformation due to BMC leakage from the mold and non-uniform fiber distribution occurred.
- Example 1 was the same as Example 1 except that BMC was changed to 310 ° C. for 75 minutes in an electric furnace. The resin viscosity was high and it could not be molded without stretching.
- Table 2 shows the measurement results of the shapeability of the test pieces obtained in Examples 1, 5, 6 and Comparative Examples 3, 4, the quality of fiber dispersion, the warp / diameter ratio, and the melt viscosity.
- Example 7 12.5 parts by weight of pitch-based carbon fiber (K223HM manufactured by Mitsubishi Plastics) with an average single fiber length of 200 ⁇ m, graphite powder (Wako Pure Chemical Industries) with respect to 100 parts by weight of addition polymerization type polyimide (PET-330 manufactured by Ube Industries) 070-01325) 12.5 parts by weight were blended and melt kneaded in a kneader at 280 ° C. under atmospheric pressure for 30 minutes. Then, the mixture (bulk molding compound, BMC) cooled to room temperature was obtained. After dividing the obtained BMC into a size that fits in the mold, the BMC was melted and soaked in a mold for a compression molding machine at 280 ° C. to 320 ° C.
- BMC bulk molding compound
- the plate was heated to 371 ° C. at a temperature rising rate of 3 ° C./min, held for 1 hour, and gradually cooled to obtain a plate having a diameter of 40 mm and a thickness of 3 mm.
- the obtained plate was subjected to a curing treatment for 6 hours under the condition of 357 ° C., and then processed into a desired dimension to obtain a test piece.
- Example 7 was the same as Example 7 except that the amount of carbon fiber was changed to 28.6 parts by weight and the amount of graphite powder was changed to 14.3 parts by weight.
- Example 9 28.6 parts by weight of pitch-based carbon fiber (K223HM manufactured by Mitsubishi Plastics) with an average single fiber length of 200 ⁇ m, PTFE powder (manufactured by Kitamura Co., Ltd.) per 100 parts by weight of addition polymerization type polyimide (PET-330 manufactured by Ube Industries) (KT-600M) 14.3 parts by weight was blended and melt kneaded in a kneader at 280 ° C. under atmospheric pressure for 30 minutes. Thereafter, BMC cooled to room temperature was obtained. After dividing the obtained BMC into a size that fits in the mold, the BMC is melted and soaked in the mold for a compression molding machine at 280 ° C. to 320 ° C.
- PTT-330 manufactured by Ube Industries
- the plate was heated to 371 ° C. at a heating rate of 3 ° C./min, held for 1 hour, and gradually cooled to obtain a plate having a diameter of 200 mm and a thickness of 3 mm.
- the obtained plate was subjected to a curing treatment for 6 hours under the condition of 357 ° C., and then processed into a desired dimension to obtain a test piece.
- Example 9 was the same as Example 9 except that the amount of carbon fiber was changed to 14.3 parts by weight and the amount of PTFE powder was changed to 28.6 parts by weight.
- Example 9 was the same as Example 9 except that the amount of carbon fiber was changed to 33.3 parts by weight and the amount of PTFE powder was changed to 33.3 parts by weight.
- Table 3 shows the results of measurement of limit PV values of the test pieces obtained in Examples 4 and 7 to 11 and Comparative Example 5 and the quality of fiber dispersion.
- FIG. 3 shows the fiber dispersion state in the test piece which was the same as that of Example 12 except for the plate thickness of 1.5 mm.
- Example 12 Example 6 was the same as Example 6 except that the amount of carbon fiber was changed to 14.3 parts by weight and the amount of graphite powder was changed to 28.6 parts by weight.
- Example 6 was the same as Example 6 except that the amount of carbon fiber was changed to 16.7 parts by weight and the amount of graphite powder was changed to 50.0 parts by weight.
- Table 4 shows the measurement results of the formability of the test pieces obtained in Examples 4, 7 to 9, 12 and Comparative Example 6, the quality of fiber dispersion, the warp / diameter ratio, and the melt viscosity.
- the state before applying the curing treatment for 6 hours under the condition of 357 ° C. is measured, and the quality is determined. It was.
- the resin molded body of the present invention is excellent in sliding performance with a limit PV value of 3000 kPa ⁇ m / s or more, and therefore can be used for various applications as a sliding member in automobiles, electrical / electronic fields and the like.
Abstract
Description
例えば、下記特許文献1には、特定のピッチ系炭素短繊維混合物及びマトリックス樹脂から成る炭素繊維強化樹脂成形体が記載されており、各種電子部品に好適に使用されることが記載されている。
また下記特許文献2には、炭素繊維等のバインダーとして特定の芳香族ポリイミドオリゴマーを用いた摩擦材用樹脂組成物から成る摩擦材が提案されており、この摩擦材においては、従来、摩擦材のバインダーとして好適に使用されていたフェノール樹脂を用いた場合に比べて、バインダー自身の耐熱性や機械的特性が優れ、成形性が良好であることが記載されている。
更に下記特許文献3には、特定の熱伝導率を有する炭素繊維を10~70重量%含む炭素繊維強化合成樹脂から成る転動体が提案されている。
付加反応型ポリイミド樹脂として、トランスファー成形(RTM)と樹脂圧入(RI)によって炭素繊維強化コンポジットを製造可能な高機能の付加反応型ポリイミド樹脂も提案されている(特許文献4)。
本発明者等がこの原因について鋭意研究した結果、以下の事実が分かった。すなわち、炭素繊維等の機能性繊維のマトリックス樹脂として好適に使用できる付加反応型ポリイミド樹脂は、プレポリマーの状態で溶融粘度が低いことから、プレポリマーに機能性繊維を混合すると、機能性繊維が沈降してプレポリマー中に偏在した状態となり、この状態で樹脂が架橋硬化されることにより、機能性繊維の存在量に応じて成形体の収縮量に差が生じてしまい、得られる繊維強化樹脂成形体に反りを生じてしまうことが分かった。
本発明の他の目的は、優れた摺動性能を有する繊維強化ポリイミド樹脂成形体を、形状安定性よく成形可能な製造方法を提供することである。
本発明の樹脂成形体においては、
1.前記樹脂成形体を構成する組成物のマトリックスが付加反応型ポリイミド樹脂であり、前記機能性繊維に前記ポリイミド樹脂が含浸していること、
2.前記機能性繊維が、付加反応型ポリイミド100重量部に対して5~200重量部の量で含有されていること、
3.前記機能性繊維が、炭素繊維、ガラス繊維、アラミド繊維、金属繊維の何れか1種以上であること、
4.前記機能性繊維が、平均繊維長50~6000μm、平均繊維径5~20μmの炭素繊維であること、
5.前記付加反応型ポリイミド100重量部に対して5~40重量部の量の増粘剤を含有し、該増粘剤が前記樹脂成形体中に分散していること、
6.前記増粘剤が、グラファイト、二硫化モリブデン、PTFE(四フッ化エチレン樹脂)、微細炭素系材料、金属粉の少なくとも1種以上であること、
が好適である。
本発明の樹脂成形体の上記第一の製造方法においては、
1.前記分散混練工程と賦形工程の間に、分散混練工程で得られた混練物を付加反応型ポリイミド樹脂の熱硬化開始温度以上の温度で一定時間保持することにより混練物の粘度を上昇させる増粘工程を有すること、
2.前記機能性繊維が、付加反応型ポリイミド100重量部に対して5~200重量部の量で含有されていること、
3.前記分散混練工程を経て得られた混合物の300~320℃の温度条件下における溶融粘度が10~5000Pa・sであり、該混合物を冷却し粉砕混合した後、加圧賦形すること、
4.前記増粘工程において、混合物の300~320℃の温度条件下における溶融粘度を10~5000Pa・sに調整すること、
5.前記付加反応型ポリイミド樹脂が、付加反応基としてフェニルエチニル基を有するポリイミド樹脂であること、
6.前記付加反応型ポリイミド樹脂が、付加反応基としてフェニルエチニル基を有するポリイミド樹脂である場合には、前記増粘工程おいて、310±10℃の温度で30~60分間保持すること、
が好適である。
本発明の樹脂成形体の上記第二の製造方法においては、前記分散混練工程を経た混合物の300~320℃の温度条件下における溶融粘度が10~5000Pa・sであることが好適である。
また本発明の樹脂成形体の製造方法においては、前記賦形工程が、圧縮成形により行われることが好適である。
また後述するように本発明で好適に用いる増粘剤は摺動性にも優れており、摺動性能を更に向上することができる。
本発明の繊維強化ポリイミド樹脂成形体は、後述する付加反応型ポリイミド樹脂中に機能性繊維が分散して成る樹脂成形体であって、限界PV値が3000kPa・m/s以上であることが重要な特徴であり、耐熱性、耐久性及び機械的強度を有すると共に、限界PV値が大きく、優れた摺動性能を有している。
本発明においては、繊維強化ポリイミド樹脂成形体を構成する組成物のマトリックスとなるポリイミド樹脂として、付加反応型ポリイミド樹脂を用いることが重要な特徴である。
本発明に用いる付加反応型ポリイミド樹脂は、末端に付加反応基を有する芳香族ポリイミドオリゴマーから成り、従来公知の製法により調製したものを使用することができる。例えば、芳香族テトラカルボン酸二無水物、芳香族ジアミン、及び分子内に付加反応基と共に無水物基又はアミノ基を有する化合物を、各酸基の当量の合計と各アミノ基の合計とをほぼ等量となるように使用して、好適には溶媒中で反応させることによって容易に得ることができる。反応の方法としては、100℃以下、好適には80℃以下の温度で、0.1~50時間重合してアミド酸結合を有するオリゴマーを生成し、次いでイミド化剤によって化学イミド化する方法や、140~270℃程度の高温で加熱して熱イミド化する2工程からなる方法、或いは始めから140~270℃の高温で、0.1~50時間重合・イミド化反応を行わせる1工程からなる方法を例示できる。
これらの反応で用いる溶媒は、これに限定されないが、N-メチル-2-ピロリドン、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N,N-ジエチルアセトアミド、γ-ブチルラクトン、N-メチルカプロラクタム等の有機極性溶媒を好適に使用できる。
これらの付加反応基は、分子内に付加反応基と共に無水物基又はアミノ基を有する化合物が、芳香族イミドオリゴマーの末端のアミノ基又は酸無水物基と、好適にはイミド環を形成する反応によって、芳香族イミドオリゴマーの末端に導入される。
分子内に付加反応基と共に無水物基又はアミノ基を有する化合物は、例えば4-(2-フェニルエチニル)無水フタル酸、4-(2-フェニルエチニル)アニリン、4-エチニル-無水フタル酸、4-エチニルアニリン、ナジック酸無水物、マレイン酸無水物等を好適に使用することができる。
繰返し単位の繰返し数の調整は、芳香族テトラカルボン酸二無水物、芳香族ジアミン、及び分子内に付加反応基と共に無水物基又はアミノ基を有する化合物の割合を変えることにより行うことができ、分子内に付加反応基と共に無水物基又はアミノ基を有する化合物の割合を高くすることにより、低分子量化して繰返し単位の繰返し数は小さくなり、この化合物の割合を小さくすると、高分子量化して繰返し単位の繰返し数は大きくなる。
本発明において、上述した付加反応型ポリイミド樹脂中に分散させる機能性繊維としては、従来公知の物を使用することができ、炭素繊維、アラミド繊維、ガラス繊維、金属繊維等、従来公知の機能性繊維を使用することができるが、特に炭素繊維を好適に用いることができる。
中でも、平均繊維長が50~6000μm及び平均繊維径が5~20μmの範囲にある炭素繊維を好適に使用することができる。上記範囲よりも平均繊維長が短い場合には、炭素繊維の強化材としての効果を充分に得ることができず、その一方上記範囲よりも長いとポリイミド樹脂中での分散性に劣るようになる。また上記範囲よりも平均繊維径が細い場合には、取扱い性に劣ると共に高価であり、一方上記範囲よりも平均繊維径が太い場合には機能性繊維の沈降速度が増大して、機能性繊維が偏在しやすくなるおそれがあると共に、繊維の強度が低下する傾向があり、強化材としての効果を充分に得られないおそれがある。
上記無機材料は、付加反応型ポリイミド100重量部に対して5~40重量部の量で含有されていることが好適である。
本発明においては、上記機能性繊維と共に増粘剤を付加反応型ポリイミド100重量部に対して5~40重量部の量で用いることにより、付加反応型ポリアミド樹脂のプレポリマーの粘度を増粘工程を経ることなく増大させることが可能になり、これにより機能性繊維は沈降することなく、プレポリマー中に均一に分散した状態を維持できる。
増粘剤としては、グラファイト、二硫化モリブデン、PTFE(四フッ化エチレン樹脂)、酸化マグネシウム、水酸化マグネシウム、水酸化カルシウム等を使用することができるが、中でもグラファイト、二硫化モリブデン、PTFEは、摺動性能を更に向上させることもできるので特に好適である。
増粘剤は、上述したとおり、付加反応型ポリイミド100重量部に対して5~40重量部の量で含有されていることが好適である。上記範囲よりも増粘剤の量が少ないと、プレポリマーの粘度が十分に増加せず、機能性繊維の沈降を充分に抑制することができず、機能性繊維が均一分散している反り変形のない樹脂成形体を成形することができない。また上記範囲よりも増粘剤の量が多くなると摩擦係数の増大や耐摩耗性の低下等、摺動性能を損なうおそれがある。
本発明の樹脂成形体の第一の製造方法は、少なくとも、付加反応型ポリイミド樹脂のプレポリマー(イミドオリゴマー)と機能性繊維を付加反応型ポリイミド樹脂の融点以上、熱硬化開始温度以下の温度で混練する分散混練工程(A)、分散混練工程を経た混合物を反応型ポリイミド樹脂の熱硬化開始温度以上の温度条件下で加圧賦形する賦形工程(C)、から成り、必要により、前記分散混練工程(A)と賦形工程(C)の間に、分散混練工程により得られた混練物を反応型ポリイミド樹脂の熱硬化開始温度以上の温度で一定時間保持することにより混練物の粘度を必要に応じて上昇させ適正範囲に混練物の粘度を調整する増粘工程(B)を有することを特徴とする。
前述したとおり、本発明の樹脂成形体の成形に用いる付加反応型ポリイミド樹脂は、架橋硬化前のプレポリマーの状態では低粘度であることから、機能性繊維を含有させると沈降してしまい、その結果、機能性繊維が遍在し、成形体に反りが発生する。本発明の第一の製造方法においては、上記分散混練工程(A)後に、上記増粘工程(B)によりプレポリマーの粘度を増大させることにより機能性繊維の沈降を防止して、その状態を維持したまま賦形工程(C)で賦形されることから、機能性繊維が均一に分散し、加熱硬化の際に均等に収縮して反りのない成形体を成形することが可能になる。
付加反応型ポリイミド樹脂のプレポリマー(イミドオリゴマー)と機能性繊維を付加反応型ポリイミド樹脂の融点以上の温度で加熱しプレポリマーを溶融しながら混練することにより、プレポリマーと機能性繊維を混合する。この際、前述したとおり、付加反応型ポリイミド100重量部に対して機能性繊維を5~200重量部、特に10~150重量部の量で用いる。また上述した無機材料を上述した量配合することもできる。また特に必要はないが、上述した増粘剤を上述した量で配合することもできる。
プレポリマー及び機能性繊維の混練は、ヘンシェルミキサー、タンブラーミキサー、リボンブレンダ―等の従来公知の混合機を用いることもできるが、機能性繊維の破断を抑制すると共に均一に分散させることが重要であることから、バッチ式の加圧ニーダー(混練機)を用いることが特に好適である。
次いで、溶融混練されたプレポリマーと機能性繊維の混合物の300~320℃の温度条件下における溶融粘度が10以下である場合、その混合物に用いるポリイミド樹脂の熱硬化開始温度近傍310±10℃の温度で30~60分間保持することにより、300~320℃の温度条件下における溶融粘度を10~5000Pa・sの範囲に調整する。
すなわち、プレポリマーと機能性繊維の混合物を、電気炉等を用いて310±10℃の温度で30~60分間保持することにより、プレポリマーが徐々に架橋し始めることから粘度は上昇する。更に前記分散混練工程によりプレポリマー中に含浸された機能性繊維はこの粘度上昇によりプレポリマー中で沈降することなく分散状態を維持できる。また上記範囲の加熱温度及び保持時間にすることで、プレポリマーを完全に架橋硬化させることなく、粘度のみを上記範囲に上昇させることが可能になる。従って、増粘工程は、プレポリマーの熱硬化開始温度以上、且つ、完全に架橋硬化する温度未満にて行う。
尚、付加反応型ポリイミド樹脂においては、反応開始温度は付加反応基に依存し、本発明において付加反応基として好適なフェニルエチニル基を有するポリイミド樹脂においては、熱硬化開始温度近傍である310±10℃の温度で30~60分間加熱することが望ましい。
増粘工程を経て溶融粘度が上記範囲に調整されたプレポリマー及び機能性繊維の混合物は、用いるポリイミド樹脂の熱硬化開始温度以上の温度条件下で賦形し、所望の形状の樹脂成形体として成形される。
賦形工程を行う場合には、溶融状態にある上記の粘度範囲にあるポリイミドプレポリマーと機能性繊維の混合物を、成形型に導入して熱硬化開始温度以上の温度で加熱加圧することにより硬化させて樹脂成形体を成形する。
尚、賦形は、成形型に導入された混合物を加圧圧縮して成形する圧縮成形やトランスファー成形によることが好適であるが、射出成形や押出成形によっても成形することができる。
本発明の樹脂成形体の第二の製造方法は、付加反応型ポリイミド樹脂のプレポリマー(イミドオリゴマー)100重量部に対して5~200重量部の機能性繊維及び5~40重量部の増粘剤を、付加反応型ポリイミド樹脂の融点以上、熱硬化開始温度以下の温度で混練する分散混練工程、及び前記分散混練工程を経た混合物を反応型ポリイミド樹脂の熱硬化開始温度以上の温度条件下で加圧賦形する賦形工程、とから成ることを特徴とする。
前述したとおり、本発明の樹脂成形体の成形に用いる付加反応型ポリイミド樹脂は、架橋硬化前のプレポリマーの状態では低粘度であることから、機能性繊維を含有させると沈降してしまい、その結果、機能性繊維が遍在し、成形体に反りが発生する。本発明の第二の製造方法においては、機能性繊維と共に所定量の増粘剤をプレポリマーに配合することにより、増粘工程を経ることなく、プレポリマーの粘度を増大させることが可能になり、その結果、プレポリマー中で機能性繊維が沈降することなく分散し、機能性繊維が分散した状態を維持したまま賦形工程で賦形されることから、加熱硬化の際に均等に収縮して反りのない成形体を成形することが可能になる。
付加反応型ポリイミド樹脂のプレポリマー(イミドオリゴマー)と機能性繊維及び増粘剤を、付加反応型ポリイミド樹脂の融点以上の温度で加熱しプレポリマーを溶融しながら混練することにより、プレポリマーと機能性繊維を混合する。この際、前述したとおり、付加反応型ポリイミド100重量部に対して機能性繊維を5~200重量部、特に10~150重量部、増粘剤を5~40重量部の量で用いる。
プレポリマー及び機能性繊維の混練は、前述した第一の製造方法と同様に行うことができる。
この態様において、分散混練工程の温度は、プレポリマーの融点以上、且つ架橋硬化する温度以下、特に好ましくは、分散混練工程を経た混合物が、300~320℃の温度条件下での溶融粘度が10~5000Pa・sの範囲にあることが好ましい。この粘度上昇と機能性繊維にプレポリマーが浸透することとが相俟って、機能性繊維は沈降することなく、プレポリマー中に分散した状態を維持する。
分散混練工程を経たプレポリマーと機能性繊維及び増粘剤の混合物は、冷却固化した後、所定の大きさの塊状にしておくことが望ましい。これにより、機能性繊維がプレポリマーに分散した混合物を経時保管することが可能になり、取扱い性も向上する。
分散混練工程を経て溶融粘度が上記範囲に調整されたプレポリマー、機能性繊維及び増粘剤の混合物の賦形は、前述した第一の製造方法における賦形と同様に行うことができる。
JIS K 7218(プラスチックの滑り摩耗試験方法)に適合したスラスト型摩耗試験機を用い、図1に示すようなリングオンディスク式にて速度一定の条件下で5分又は10分おきに面圧を上昇させ、摩擦力が急激に上昇する或いは著しい変形と摩耗粉が発生したところを限界とし、限界時の1つ前の面圧(P)と速度(V)の積を限界PV値とした。
限界PV値測定条件
試験速度;0.5m/s、初期面圧;0.5MPa
面圧ステップ 0.5MPa/10min(~10MPa)
1MPa/10min(10MPa~)
相手材 :S45Cリング 表面粗さRa0.8μm
外径25.6mm、内径20mm(接触面積2cm2)
試験環境:23±2℃、50%±5%RH
試験機:エー・アンド・デイ社製 摩擦摩耗試験機 EMF-III-F
成形体の断面を観察し、繊維の偏在の有無を目視または走査電子顕微鏡(日立ハイテクテクノロジー社製S-3400N)による観察にて確認した。繊維が分散しているものを○、繊維の沈降がみられるものを×とした。
図2に示す試験片反り量t(mm)、製品直径寸法D(mm)を測定し、反り/直径比を以下の式(1)により算出した。
反り/直径比(%)=t/D×100
t:試験片反り量(mm)、D:製品直径(mm)
なお反り/直径比の良否判定は1.5%未満を○、1.5%以上を×とした。
310℃における溶融粘度をレオメータ(TA instrument社製ARES)により測定した。測定モードを動的周波数分散として、角周波数を0.1~500rad/sとし、0.1rad/sの条件における溶融粘度を測定値とした。
付加重合型ポリイミド(宇部興産社製PETI-330)100重量部に対して、平均単繊維長さ200μmのピッチ系炭素繊維(三菱樹脂社製K223HM)11.1重量部を配合し、ニーダーにより大気圧下280℃、30分で溶融混練した。その後、室温まで冷却された混合物(バルクモールディングコンパウンド、以下BMC)を得た。得られたBMCを扱いが容易なサイズに割ってから310℃、30分電気炉内に保持し、急冷、再度粉砕した樹脂混合体(増粘BMC)を圧縮成形機用金型内で、280℃~320℃で一定時間保持することで溶融および均熱した後、2.4MPaに加圧しながら、昇温速度3℃/minで371℃まで昇温、60分間保持、徐冷してφ40mm厚さ3mmの板を得た。得られた板材を357℃条件下で6時間の硬化処理を施した後、所望の寸法に加工し試験片を得た。
付加重合型ポリイミド(宇部興産社製PETI-330)100重量部に対して、平均単繊維長さ200μmのピッチ系炭素繊維(三菱樹脂社製K223HM)42.9重量部を配合し、ニーダーにより大気圧下280℃、30分で溶融混練した。その後、室温まで冷却されたBMCを得た。得られたBMCを金型内に納まる大きさ程度に割ってから、BMCを圧縮成形機用金型内で、280℃~320℃で一定時間保持することで溶融および均熱した後、11MPaに加圧しながら、昇温速度3℃/minで371℃まで昇温、1時間保持、徐冷してφ100mm厚さ3mmの板を得た。得られた板材を357℃条件下で6時間の硬化処理を施した後、所望の寸法に加工し試験片を得た。
炭素繊維の配合量を100重量部に変更した以外は実施例2と同じとした。
電気炉内に310℃保持しなかった以外は実施例1と同じとした。得られた樹脂成形体は、反りが生じていたため、表裏層を削って所定の平行度とし、限界PV値を測定した。削る前の面の限界PV値は測定していないが、測定した面を観察したところ、削る前の面と比較して炭素繊維が明らかに多く存在していた。このことからも、表面には所定量の炭素繊維が必要であることがわかる。
炭素繊維を配合しなかった以外は実施例2と同じとした。
炭素繊維の配合量を233重量部に変更した以外は実施例2と同じとした。なお、溶融混練後に得られたBMCの粘度が高く、賦形工程にて金型内での伸張不足が一部みられ、限界PV値の測定ができなかった。
BMCを電気炉に310℃の条件下で45分とした以外は実施例1と同じとした。
BMCを電気炉に310℃、60分とした以外は実施例1と同じとした。
BMCを電気炉に310℃、15分とした以外は実施例1と同じとした。なお、金型内からBMC漏れ、及び繊維の不均一な分布による反り変形が生じた。
BMCを電気炉に310℃、75分とした以外は実施例1と同じとした。なお、樹脂粘度が高く伸張せず賦型することができなかった。
付加重合型ポリイミド(宇部興産社製PETI-330)100重量部に対して、平均単繊維長さ200μmのピッチ系炭素繊維(三菱樹脂社製K223HM)12.5重量部、グラファイト粉末(和光純薬製070-01325)12.5重量部を配合し、ニーダーにより大気圧下280℃、30分で溶融混練した。その後、室温まで冷却された混合物(バルクモールディングコンパウンド、以下BMC)を得た。得られたBMCを金型内に納まる大きさ程度に割ってからBMCを圧縮成形機用金型に、280℃~320℃で一定時間保持することで溶融および均熱した後、2.4MPaに加圧しながら、昇温速度3℃/minで371℃まで昇温、1時間保持、徐冷してφ40mm厚さ3mmの板を得た。得られた板材を357℃条件下で6時間の硬化処理を施した後、所望の寸法に加工し試験片を得た。
炭素繊維の配合量を28.6重量部、グラファイト粉末の配合量を14.3重量部に変更した以外は実施例7と同じとした。
付加重合型ポリイミド(宇部興産社製PETI-330)100重量部に対して、平均単繊維長さ200μmのピッチ系炭素繊維(三菱樹脂社製K223HM)28.6重量部、PTFE粉末(喜多村社製 KT-600M)14.3重量部を配合し、ニーダーにより大気圧下280℃、30分で溶融混練した。その後、室温まで冷却されたBMCを得た。得られたBMCを金型内に納まる大きさ程度に割ってからBMCを圧縮成形機用金型に、280℃~320℃で一定時間保持することで溶融および均熱した後、11MPaに加圧しながら、昇温速度3℃/minで371℃まで昇温、1時間保持、徐冷してφ200mm厚さ3mmの板を得た。得られた板材を357℃条件下で6時間の硬化処理を施した後、所望の寸法に加工し試験片を得た。
炭素繊維の配合量を14.3重量部、PTFE粉末の配合量を28.6重量部に変更した以外は実施例9と同じとした。
炭素繊維の配合量を33.3重量部、PTFE粉末の配合量を33.3重量部に変更した以外は実施例9と同じとした。
付加重合型ポリイミド(宇部興産社製PETI-330)を280℃~320℃で一定時間保持することで溶融および均熱した後、11MPaに加圧しながら、昇温速度3℃/minで371℃まで昇温、1時間保持、徐冷してφ100mm厚さ3mmの板を得た。得られた板材を357℃条件下で6時間の硬化処理を施した後、所望の寸法に加工し試験片を得た。
炭素繊維の配合量を14.3重量部、グラファイト粉末の配合量を28.6重量部に変更した以外は実施例6と同じとした。
炭素繊維の配合量を16.7重量部、グラファイト粉末の配合量を50.0重量部に変更した以外は実施例6と同じとした。
Claims (17)
- 付加反応型ポリイミド樹脂中に機能性繊維が分散して成る樹脂成形体であって、限界PV値が3000kPa・m/s以上であることを特徴とする樹脂成形体。
- 前記樹脂成形体を構成する組成物のマトリックスが付加反応型ポリイミド樹脂であり、前記機能性繊維に前記ポリイミド樹脂が含浸している請求項1に記載の樹脂成形体。
- 前記機能性繊維が、付加反応型ポリイミド100重量部に対して5~200重量部の量で含有されている請求項1又は2記載の樹脂成形体。
- 前記機能性繊維が、炭素繊維、ガラス繊維、アラミド繊維、金属繊維の何れか1種以上である請求項1~3の何れかに記載の樹脂成形体。
- 前記機能性繊維が、平均繊維長50~6000μm、平均繊維径5~20μmの炭素繊維である請求項1~4の何れかに記載の樹脂成形体。
- 前記付加反応型ポリイミド100重量部に対して5~40重量部の量の増粘剤を含有し、該増粘剤が前記樹脂成形体中に分散している請求項1~5の何れかに記載の樹脂成形体。
- 前記増粘剤が、グラファイト、二硫化モリブデン、PTFE(四フッ化エチレン樹脂)、微細炭素系材料、金属粉の少なくとも1種以上である請求項1~6の何れかに記載の樹脂成形体。
- 付加反応型ポリイミド樹脂のプレポリマーと機能性繊維を付加反応型ポリイミド樹脂の融点以上、熱硬化開始温度以下の温度で混練する分散混練工程、
該混合物を付加反応型ポリイミド樹脂の熱硬化開始温度以上の温度条件下で賦形する賦形工程、
を少なくとも有することを特徴とする樹脂成形体の製造方法。 - 前記分散混練工程と賦形工程の間に、分散混練工程で得られた混練物を付加反応型ポリイミド樹脂の熱硬化開始温度以上の温度で一定時間保持することにより混練物の粘度を上昇させる増粘工程を有する請求項8記載の製造方法。
- 前記機能性繊維の含有率が付加反応型ポリイミド100重量部に対して5~200重量部である請求項8記載の樹脂成形体の製造方法。
- 前記分散混練工程を経て得られた混合物の300~320℃の温度条件下における溶融粘度が10~5000Pa・sであり、該混合物を冷却し粉砕混合した後、加圧賦形する請求項8又は10記載の製造方法。
- 前記増粘工程において、混合物の300~320℃の温度条件下における溶融粘度を10~5000Pa・sに調整する請求項9又は10記載の製造方法
- 前記付加反応型ポリイミド樹脂が、付加反応基としてフェニルエチニル基を有するポリイミド樹脂である請求項8~12の何れかに記載の製造方法。
- 前記増粘工程おいて、310±10℃の温度で30~60分間保持する請求項13記載の製造方法。
- 付加反応型ポリイミド100重量部に対して、5~200重量部の機能性繊維、5~40重量部の増粘剤が分散して成る樹脂成形体の製造方法であって、
前記付加反応型ポリイミド樹脂のプレポリマー、機能性繊維及び増粘剤を付加反応型ポリイミド樹脂の融点以上、熱硬化開始温度以下の温度で混練する分散混練工程、
分散混練工程を経た混合物を付加反応型ポリイミド樹脂の熱硬化開始温度以上の温度条件下で加圧賦形する賦形工程、とから成ることを特徴とする樹脂成形体の製造方法。 - 前記分散混練工程を経た混合物の300~320℃の温度条件下における溶融粘度が10~5000Pa・sである請求項15記載の製造方法。
- 前記賦形工程が、圧縮成形により行われる請求項8~16の何れかに記載の製造方法。
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EP3467328A4 (en) * | 2016-06-01 | 2020-02-12 | Toyo Seikan Group Holdings, Ltd. | SLIDING STRUCTURE AND METHOD FOR PRODUCING THE SAME |
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CN110520455A (zh) * | 2017-04-12 | 2019-11-29 | 东洋制罐集团控股株式会社 | 具有高填料含量的组合物和成形体的生产方法 |
EP3611201A4 (en) * | 2017-04-12 | 2021-01-06 | Toyo Seikan Group Holdings, Ltd. | COMPOSITION WITH A HIGH LOAD CONTENT AND PROCESS FOR THE PRODUCTION OF A MOLDED ARTICLE |
CN110520455B (zh) * | 2017-04-12 | 2022-05-24 | 东洋制罐集团控股株式会社 | 具有高填料含量的组合物和成形体的生产方法 |
EP3892672A4 (en) * | 2018-12-07 | 2022-08-31 | Toyo Seikan Group Holdings, Ltd. | FIBER-REINFORCED POLYIMIDE RESIN PRECURSOR AND PROCESS FOR THE PRODUCTION THEREOF |
WO2021246532A1 (ja) * | 2020-06-05 | 2021-12-09 | 東洋製罐グループホールディングス株式会社 | ポリイミド樹脂成形体及びその製造方法 |
JP6984804B1 (ja) * | 2020-06-05 | 2021-12-22 | 東洋製罐グループホールディングス株式会社 | ポリイミド樹脂成形体及びその製造方法 |
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CN106715545A (zh) | 2017-05-24 |
EP3192827A4 (en) | 2018-05-30 |
EP3192827A1 (en) | 2017-07-19 |
US20170252986A1 (en) | 2017-09-07 |
CN106715545B (zh) | 2023-06-23 |
BR112017004587B1 (pt) | 2022-04-05 |
BR112017004587A2 (pt) | 2018-03-13 |
EP3192827B1 (en) | 2024-03-06 |
US10406765B2 (en) | 2019-09-10 |
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