CN105073370A - 复合材料的制造方法 - Google Patents

复合材料的制造方法 Download PDF

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Publication number
CN105073370A
CN105073370A CN201380074711.7A CN201380074711A CN105073370A CN 105073370 A CN105073370 A CN 105073370A CN 201380074711 A CN201380074711 A CN 201380074711A CN 105073370 A CN105073370 A CN 105073370A
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CN
China
Prior art keywords
molded article
raw material
step solidification
temperature
article raw
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Granted
Application number
CN201380074711.7A
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English (en)
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CN105073370B (zh
Inventor
服部英敬
林宣也
渡边晃永
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Mitsubishi Heavy Industries Ltd
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Mitsubishi Heavy Industries Ltd
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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
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • B29C43/18—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles incorporating preformed parts or layers, e.g. compression moulding around inserts or for coating articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/90—Measuring or controlling the joining process
    • B29C66/91—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
    • B29C66/919—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges
    • B29C66/9192—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams
    • B29C66/91921—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature
    • B29C66/91941—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature in explicit relation to Tg, i.e. the glass transition temperature, of the material of one of the parts to be joined
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • B29C43/10—Isostatic pressing, i.e. using non-rigid pressure-exerting members against rigid parts or dies
    • B29C43/12—Isostatic pressing, i.e. using non-rigid pressure-exerting members against rigid parts or dies using bags surrounding the moulding material or using membranes contacting the moulding material
    • 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
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • 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
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/022—Particular heating or welding methods not otherwise provided for
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/05—Particular design of joint configurations
    • B29C66/10—Particular design of joint configurations particular design of the joint cross-sections
    • B29C66/11—Joint cross-sections comprising a single joint-segment, i.e. one of the parts to be joined comprising a single joint-segment in the joint cross-section
    • B29C66/112—Single lapped joints
    • B29C66/1122—Single lap to lap joints, i.e. overlap joints
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/05—Particular design of joint configurations
    • B29C66/10—Particular design of joint configurations particular design of the joint cross-sections
    • B29C66/13—Single flanged joints; Fin-type joints; Single hem joints; Edge joints; Interpenetrating fingered joints; Other specific particular designs of joint cross-sections not provided for in groups B29C66/11 - B29C66/12
    • B29C66/131—Single flanged joints, i.e. one of the parts to be joined being rigid and flanged in the joint area
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/47—Joining single elements to sheets, plates or other substantially flat surfaces
    • B29C66/474—Joining single elements to sheets, plates or other substantially flat surfaces said single elements being substantially non-flat
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/50—General aspects of joining tubular articles; General aspects of joining long products, i.e. bars or profiled elements; General aspects of joining single elements to tubular articles, hollow articles or bars; General aspects of joining several hollow-preforms to form hollow or tubular articles
    • B29C66/51—Joining tubular articles, profiled elements or bars; Joining single elements to tubular articles, hollow articles or bars; Joining several hollow-preforms to form hollow or tubular articles
    • B29C66/52—Joining tubular articles, bars or profiled elements
    • B29C66/524—Joining profiled elements
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/72—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined
    • B29C66/721—Fibre-reinforced materials
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/731—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the intensive physical properties of the material of the parts to be joined
    • B29C66/7311—Thermal properties
    • B29C66/73117—Tg, i.e. glass transition temperature
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/737—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined
    • B29C66/7375—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined uncured, partially cured or fully cured
    • B29C66/73753—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined uncured, partially cured or fully cured the to-be-joined area of at least one of the parts to be joined being partially cured, i.e. partially cross-linked, partially vulcanized
    • B29C66/73754—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined uncured, partially cured or fully cured the to-be-joined area of at least one of the parts to be joined being partially cured, i.e. partially cross-linked, partially vulcanized the to-be-joined areas of both parts to be joined being partially cured
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/80—General aspects of machine operations or constructions and parts thereof
    • B29C66/81—General aspects of the pressing elements, i.e. the elements applying pressure on the parts to be joined in the area to be joined, e.g. the welding jaws or clamps
    • B29C66/814—General aspects of the pressing elements, i.e. the elements applying pressure on the parts to be joined in the area to be joined, e.g. the welding jaws or clamps characterised by the design of the pressing elements, e.g. of the welding jaws or clamps
    • B29C66/8145—General aspects of the pressing elements, i.e. the elements applying pressure on the parts to be joined in the area to be joined, e.g. the welding jaws or clamps characterised by the design of the pressing elements, e.g. of the welding jaws or clamps characterised by the constructional aspects of the pressing elements, e.g. of the welding jaws or clamps
    • B29C66/81455—General aspects of the pressing elements, i.e. the elements applying pressure on the parts to be joined in the area to be joined, e.g. the welding jaws or clamps characterised by the design of the pressing elements, e.g. of the welding jaws or clamps characterised by the constructional aspects of the pressing elements, e.g. of the welding jaws or clamps being a fluid inflatable bag or bladder, a diaphragm or a vacuum bag for applying isostatic pressure
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/90—Measuring or controlling the joining process
    • B29C66/91—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
    • B29C66/919—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges
    • B29C66/9192—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams
    • B29C66/91921—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature
    • B29C66/91941—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature in explicit relation to Tg, i.e. the glass transition temperature, of the material of one of the parts to be joined
    • B29C66/91943—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature in explicit relation to Tg, i.e. the glass transition temperature, of the material of one of the parts to be joined higher than said glass transition temperature
    • 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
    • B29C70/44—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using isostatic pressure, e.g. pressure difference-moulding, vacuum bag-moulding, autoclave-moulding or expanding rubber-moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D99/00—Subject matter not provided for in other groups of this subclass
    • B29D99/001—Producing wall or panel-like structures, e.g. for hulls, fuselages, or buildings
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/739—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/7392—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoplastic
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/80—General aspects of machine operations or constructions and parts thereof
    • B29C66/84—Specific machine types or machines suitable for specific applications
    • B29C66/843—Machines for making separate joints at the same time in different planes; Machines for making separate joints at the same time mounted in parallel or in series
    • B29C66/8432—Machines for making separate joints at the same time mounted in parallel or in series
    • 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
    • B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
    • B29K2105/0872—Prepregs
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/001—Profiled members, e.g. beams, sections
    • B29L2031/003—Profiled members, e.g. beams, sections having a profiled transverse cross-section
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29L2031/00—Other particular articles
    • B29L2031/08—Blades for rotors, stators, fans, turbines or the like, e.g. screw propellers
    • B29L2031/082—Blades, e.g. for helicopters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29L2031/3076—Aircrafts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
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    • B29L2031/3082—Fuselages
    • B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract

本发明提供一种复合材料的制造方法，所述复合材料由至少两种以上的被成型品原材料(12、13)构成，该方法包括：使构成所述复合材料的被成型品原材料(12、13)中的至少一种一次固化而准备一次固化了的被成型品原材料(13)，将上述一次固化了的被成型品原材料(13)通过粘接剂或不通过粘接剂与构成所述复合材料的其它被成型品原材料(12)组装来准备组装体(16)，将上述组装体(16)加热至上述一次固化了的至少一种被成型品原材料(13)的玻璃化转变温度以上，使上述至少一种被成型品原材料(13)成为橡胶态，使与该被成型品原材料(13)相接的粘接剂或者与上述被成型品原材料相接的上述其它被成型品原材料(12、13)在固化过程中与上述橡胶态的被成型品原材料共存，使上述一次固化了的至少一种被成型品原材料(13)二次固化，从而使至少一种被成型品原材料(13)与上述其它被成型品原材料(12)一体化。

Description

复合材料的制造方法
技术领域
本发明涉及飞机用加强面板(スティフナ·パネル)等的复合材料的制造方法。
背景技术
以往，已知在飞机的机翼结构或机身结构等中采用加强面板。
作为这样的加强面板的复合材料的制造方法，已知有所谓的一体成型法。
作为这样的一体成型法，已知有本发明人等提出的日本专利第2647530号公报(专利文献1)中涉及的方法。在该成型法中，复合材料的被成型品原材料用复合材料一体成型用形状保持器具保持，使整体一体固化。
该一体成型法由于是将被成型品原材料整体一体固化，因此所得到的复合材料的强度优异。但是，加强原材料液化时保持加强形状所必需的夹具容易变得复杂，工程上的负担容易增大。
另一方面，作为加强面板的复合材料的制造方法，有所谓的复合法(コボンド法)。
在该复合法中，将预先固化成型了的面板或加强物中的任意一者与未进行固化成型的另一者通过粘接剂设置，用热压罐使其固化。
该复合法由于使面板或加强物中的任意一者事先固化，制造过程中，各被成型品原材料的处理性良好。但是，所得到的复合材料的强度依赖于加强物和面板之间的粘接剂的粘结强度，因此有必要提高粘结质量。
现有技术文献
专利文献
专利文献1：日本专利第2647530号公报
发明内容
发明要解决的课题
本发明是鉴于上述情况而完成的，其目的在于提供能以优异的强度获得飞机用加强面板等的复合材料、在制造工序上各被成型品原材料的处理性也良好的复合材料的制造方法。
解决问题的方法
本发明为了实现上述目的，提供一种复合材料的制造方法，所述复合材料由至少两种以上的被成型品原材料构成，该方法包括：将用于构成所述复合材料的至少一种被成型品原材料一次固化而准备一次固化了的被成型品原材料，将上述一次固化了的被成型品原材料通过粘接剂或不通过粘接剂与构成所述复合材料的其它被成型品原材料组装(組み付け)来准备组装体(組付体)，将上述组装体加热至上述一次固化了的至少一种被成型品原材料的玻璃化转变温度以上，使上述至少一种被成型品原材料成为橡胶态，使与该被成型品原材料相接的粘接剂或者与上述被成型品原材料相接的上述其它被成型品原材料在固化过程中与上述橡胶态的被成型品原材料共存，使上述一次固化了的至少一种被成型品原材料二次固化，从而使上述至少一种被成型品原材料与上述其它被成型品原材料一体化。
这里，关于“其它被成型品原材料”，在不通过粘接剂组装的情况下，需要经过与粘接剂同样的反应固化过程而与“至少一种被成型品原材料”一体化。但是，通过粘接剂组装的情况下，不一定有这个必要，此时，“其它被成型品原材料”可以不管其固化状态来采用。例如可以采用固化完成后的材料。另外，材质也可以是金属。
在其它的实施方式中，本发明复合材料的制造方法的特征在于将上述一次固化了的被成型品原材料的玻璃化转变温度Tg和与该被成型品原材料相接的粘接剂或者与上述被成型品原材料相接的上述其它被成型品原材料的反应温度Tr设定为满足以下(i)～(x)中的任意条件。
(i)dT31＝Tr3－Tg1≥30℃、且Tr2－Tg1＞0℃的控制范围。
(ii)满足上述(i)、且dT21＝Tr2－Tg1≥25℃的控制范围。
(iii)满足上述(ii)、且dT11＝Tr1－Tg1≥20℃的控制范围。
(iv)dT32＝Tr3－Tg2≥10℃、且Tr2－Tg1＞0℃的控制范围。
(v)满足上述(iv)、且dT22＝Tr2－Tg2≥5℃的控制范围。
(vi)满足上述(v)、且dT12＝Tr1－Tg2≥0℃的控制范围。
(vii)dT33＝Tr3－Tg3≥0℃、且Tr2－Tg1＞0℃的控制范围。
(viii)dT23＝Tr2－Tg3≥0℃的控制范围。
(ix)dT13＝Tr1－Tg3≥0℃的控制范围。
(x)dT13＝Tr1－Tg3≥10℃的控制范围。
其中，Tg1、Tg2、Tg3、Tr1、Tr2、Tr3是以下的温度。
Tg1：一次固化了的被成型品原材料的储能模量开始下降的点的温度
Tg2：一次固化了的被成型品原材料由玻璃态到橡胶态的相转变中间附近的温度(tanδ(＝损耗模量/储能模量)显示峰值的温度)
Tg3：一次固化了的被成型品原材料的储能模量下降结束的点的温度
Tr1：与一次固化了的被成型品原材料相接的粘接剂或者与一次固化了的被成型品原材料相接的其它被成型品原材料的反应开始点的温度
Tr2：与一次固化了的被成型品原材料相接的粘接剂或者与一次固化了的被成型品原材料相接的其它被成型品原材料的反应温度
Tr3：与一次固化了的被成型品原材料相接的粘接剂或者与一次固化了的被成型品原材料相接的其它被成型品原材料反应结束点的温度
此外，在其它实施方式中，本发明的复合材料的制造方法中上述复合材料可以是加强原材料和面板原材料形成的复合材料。复合材料可以制成飞机的机翼材料或机身材料。并且，在该方式中，可以使加强原材料一次固化。
在其它实施方式中，本发明的复合材料的制造方法中可以由使用了链式固化型树脂的纤维强化树脂构成上述加强原材料。
发明的效果
本发明提供能以优异的强度获得飞机用加强面板等的复合材料、在制造工序上各被成型品原材料的处理性也良好的复合材料的制造方法。
附图说明
[图1]是用于说明本发明的复合材料的制造方法的一个实施方式中在成型夹具中配置型芯盒和纤维基材的状态的剖面图。
[图2]是用于说明本发明的复合材料制造方法的一个实施方式中通过真空泵等使模腔内减压的状态的剖面图。
[图3]是用于说明本发明的复合材料制造方法的一个实施方式中通过树脂注入管道将树脂材料从注射器等注入模腔内的状态的剖面图。
[图4]是用于说明本发明的复合材料制造方法的一个实施方式中关闭真空管道、利用来自树脂注入管道的压力来增加模腔内压力的状态的剖面图。
[图5]是用于说明本发明的复合材料制造方法的一个实施方式中使注入的树脂材料一次固化的状态的剖面图。
[图6]是用于说明本发明的复合材料制造方法的一个实施方式中用水等冷却成型夹具的状态的剖面图。
[图7]是用于说明本发明的复合材料制造方法的一个实施方式中在一次固化后的加强原材料上组装面板原材料的状态的剖面图。
[图8]是用于说明本发明的复合材料制造方法的一个实施方式中使加强原材料二次固化、从而将加强原材料与面板原材料一体化的状态的剖面图。
[图9]是用于说明本发明的复合材料制造方法的一个实施方式中一体化后的加强面板的剖面图。
[图10]是示出一次固化了的被成型品原材料的弹性模量变化和粘接剂的热量变化的曲线图。
[图11]是说明玻璃化转变温度Tg1、Tg2、Tg3的技术意义的曲线图。
[图12]是说明粘接剂的反应温度Tr1、Tr2、Tr3的技术意义的曲线图。
[图13]是说明关于Tg1和Tr的相关关系的控制值(控制范围)的控制范围的曲线图。
[图14]是说明在Tg控制中与Tg1相比更优选以Tg2为指标的Tg2和Tr的相关关系的控制值(控制范围)的曲线图。
[图15]是说明在Tg控制中与Tg2相比更优选以Tg3为指标的Tg3和Tr的相关关系的控制值(控制范围)的曲线图。
[图16]是说明对要达到一次固化(低Tg控制型固化)状态的被成型品原材料所使用的材料实施DSC测定而得到的固化(反应)开始温度Tp1的曲线图。
符号说明
1成型夹具
2型芯盒
3纤维基材
4模腔
5上盖
6下盖
7框模
8密封材料
9脱模材料
10真空管道
11树脂注入管道
12半固化片
13加强原材料
14包装膜
15密封材料
16组装体
17热压罐
18加强面板
具体实施方式
以下，参照附图所示的实施方式对本发明的复合材料的制造方法进行说明。
在优选的实施方式中，本发明的复合材料的制造方法至少实施以下的工序。
(1)准备一次固化了的加强原材料。这里，该一次固化了的加强原材料对应于“至少一种一次固化了的被成型品原材料”。
(2)准备面板原材料。该面板原材料对应于“用于构成上述复合材料的其它被成型品原材料”。可以在准备加强原材料的同时准备面板原材料，或者也可以在准备加强原材料前后的任意时间准备面板原材料。
(3)在一次固化了的加强原材料上通过粘接剂组装面板原材料，制成组装体。
(4)将组装体加热至一次固化了的加强原材料的玻璃化转变温度以上，使加强原材料为橡胶态，在与加强原材料相接的粘接剂的固化过程中使上述橡胶态的原材料共存，使加强原材料二次固化，从而将加强原材料和面板原材料一体化。
需要说明的是，加强原材料有若干个叫法，有时也被称为框、肋、架、纵梁、轮廓(シル)、翼梁(スパー)、纵梁(ロンジロン)、骨架、框模、纵桁(縦通材)等。
另外，面板原材料有时也被称为皮、外板、外皮、表皮、舱壁(压力间壁)用面板等。
首先，关于准备加强原材料的步骤，参照图1～图6对其一种实施方式进行说明。
如图1所示，在成型夹具(成型模)1中配置型芯盒2和纤维基材(预成型体)3。
本发明中，使用成型夹具1通过RTM成型方法成型加强原材料，但不限于RTM成型方法，也可以采用例如热压罐成型法。
如图所示，用于实施RTM成型方法的RTM成型装置在成型夹具1的内部形成用于成型制品的模腔4。RTM成型装置在成型夹具1的上盖5、下盖6的外侧具有将该成型夹具1夹拢、并从外侧施加压力的未图示的一对加压器(プレス)，但也可以是能将成型夹具1闭合并固定的其它装置。加压器由于容易调整合模力而优选。
在成型夹具1的一个端部具有用于向模腔4内注入树脂材料的图1中未示出的树脂注入管道、真空管道。树脂注入管道与用于注入树脂材料的装置连接。例如与注射器连接。用于注入树脂材料的装置优选附带对成型夹具1内加压的功能。真空管道通过真空管线(真空ライン)与真空泵等连接。需要说明的是，为了防止树脂材料被吸入到真空泵中，真空管线中可以设置真空阱等。
在上盖5和模框(枠型)7、下盖6和框模7之间配置有用于密封接合面的密封材料8。
成型夹具1和型芯盒2可以使用通常被用作型材的材料，例如可以是铝、铝合金、铁、不锈钢或因伐合金等合金钢等金属材质，也可以是纤维强化树脂或玻璃材质。另外，它们也可以由隔热材料而不是上述非隔热材料构成。隔热材料没有特别限定，优选导热系数为0.3W/(m·K)以下、进一步优选为0.2W/(m·K)、最优选为0.1W/(m·K)以下的材料。另外，材料优选容积比热小的材料，例如优选容积比热为铝以下的材料。另外，材料优选热容量小的材料，例如优选热容量为铝以下的材料。例如可以使用表面为耐热性的高分子膜、内部为发泡体的材料。
作为配置于模腔4中的纤维基材3，可以广泛使用玻璃纤维、碳纤维、芳纶纤维等纤维强化树脂用纤维。纤维基材3上可以根据需要带有夹具、螺母等部件。
在纤维基材3和下盖6之间配置剥离层等脱模材料9。该脱模材料9是根据需要配置的。需要说明的是，在纤维基材3和上盖5之间也可以配置脱模材料。
此外，根据需要，也可以在型芯盒2和纤维基材3之间配置剥离层等脱模材料(图示省略)。或者，还可以对型芯盒2的表面进行脱模处理。或者，还可以由脱模材料构成型芯盒2。
根据需要，也可以在与纤维基材3相接的型芯盒2及成型夹具1中设置用于将纤维基材3固定在给定位置的构造。例如在图1中，可以设置在上盖5、下盖6、框模7或型芯盒2上。在成型夹具1内配置型芯盒2和纤维基材3后将上盖5和下盖6闭合。另外，在合模后，根据需要通过加压等将成型夹具1夹拢，并从外侧施加压力。
接着，如图2所示，根据需要通过真空管道10和真空管线并利用真空泵等使模腔4内减压。特别优选使模腔4内减压至真空状态。
另外，可以根据需要用热板压机等对成型夹具1加热。加热时，加热至含浸温度或干燥温度等预定的温度。
接着，如图3所示，通过树脂注入管道11将树脂材料从注射器等中注入模腔4内。树脂材料在注入前可以进行预加热。树脂材料通过型芯盒2的端部和下盖6之间的树脂流路、或上盖5、下盖6、框模7和纤维基材3之间的树脂流路、型芯盒2和纤维基材3之间的树脂流路流到成型夹具1内，迅速填满模腔4内。需要说明的是，可以根据需要在上盖5、下盖6、框模7、型芯盒2各部位设置使树脂材料流通的树脂流路。
根据需要，也可以关闭真空管道10，并通过用于注入树脂材料的机构、例如注射器等进行加压。通过利用注射器等进行加压可以促进树脂材料的含浸。
另外，在用树脂材料填满模腔4内之后，根据需要，可以关闭真空管道10，并利用来自树脂注入管道11的压力来增加模腔4内的压力(图4)。加压力优选为3个大气压以上，更优选为5个大气压以上，最优选为10个大气压以上。模腔4内的压力上限没有特别限定，但优选为100个大气压以下。在树脂材料含浸到纤维基材3中之后，根据需要，可以用加压器等进一步将成型夹具1闭合。
然后，使注入的树脂材料固化(图5)。根据所使用的树脂材料来施加热、紫外线(UV)、或者它们两者，由此进行固化。施加热时，可以通过例如热板压机等或组装在成型夹具中的加热器等所具备的加热功能来进行。另外，UV辐射可以用UV灯(图示省略)等来进行。
而且，本发明中的固化进行到一次固化(半固化)为止。在本申请说明书中，“一次固化(半固化)”是指树脂材料变成了固体、但交联反应尚未全部完成的状态的固化，是固化至可以操作状态的状态。固化中利用热时，其温度根据树脂材料的组成及所使用的催化剂的不同而不同。另外，通过成型夹具1及型芯盒2使用非隔热材料，可以容易地进行固化中树脂材料的温度控制。
关于控制到一次固化(半固化)为止这一点，将在后面进一步详细描述。
另外，作为所使用的树脂材料，优选使用链式固化型的树脂组合物。“链式固化型的树脂组合物”是指具有如下特性的树脂：通过热或UV等能量射线的辐射而引发固化，固化时产生固化反应热，利用该固化反应热使固化反应链式进行从而连续地产生固化反应热，不管组合物中是否有能量射线屏蔽性物质，均可利用固化反应本身产生的热使固化反应链式进行而无需能量射线的辐射(日本特开平11-193322号公报、日本专利第3950241号公报、日本专利第3944217号公报)。
作为这样的链式固化型的树脂组合物，可以使用例如在光聚合性低聚物或光聚合性单体等光聚合性树脂成分中配合聚合引发剂成分而得到的树脂组合物，所述聚合引发剂成分由以光聚合引发剂和通过光和热两者引发聚合的光-热聚合引发剂作为成分的2元体系以上构成。作为光聚合性树脂成分，优选阳离子系树脂，更优选环氧树脂，进一步优选脂环式环氧树脂、缩水甘油醚型环氧树脂、环氧化聚烯烃树脂。作为光聚合引发剂，优选重氮盐、碘盐、吡啶盐、盐、锍盐、铁-丙二烯化合物及磺酸酯。作为光-热聚合引发剂，优选芳基系锍盐。相对于光聚合性树脂成分100重量份，优选包含聚合引发剂成分0.5～6.0重量份。光-热聚合引发剂/光聚合引发剂的重量比优选为1～4。
另外，作为链式固化型的树脂组合物，还可以使用例如在光聚合性树脂成分中配合光聚合引发剂成分和用于使光聚合性树脂成分常温固化或加热固化的固化剂成分而得到的树脂组合物(日本特开2001-89639号公报、日本专利第4108094号公报、日本专利第4241721号公报)。该树脂组合物中，作为光聚合性树脂成分，优选分子结构中具有环状醚结构的环氧树脂。作为光聚合引发剂成分，优选铁-丙二烯系化合物、锍盐。作为固化剂成分，优选酸酐。相对于光聚合性树脂成分1摩尔，优选以0.1～1.4摩尔的比率配合固化剂成分。另外，相对于树脂组合物中光聚合引发剂成分以外的其它成分的总重量100重量份，优选以0.1～6.0重量份的比率配合光聚合引发剂成分。
此外，作为链式固化型的树脂组合物，还可以使用例如含有分子内具有2个氧化环己烯的脂环式环氧化合物和改性双酚A型环氧树脂，且以上述2种成分的总量为100质量％时脂环式环氧化合物的含量为25～90质量％的树脂组合物；以及含有分子内具有2个氧化环己烯的脂环式环氧化合物、改性双酚A型环氧树脂及液态双酚型环氧树脂，且以上述3种成分的总量为100质量％时脂环式环氧化合物的含量为25～90质量％的树脂组合物。例如可以使用日本特开2011-079989号公报中公开的树脂组合物。
通过使用这样的链式固化型的树脂组合物，可以通过施加热或UV等能量引发链式固化反应，从而使成型夹具1内的树脂材料固化。即使型芯盒2是难以施加使全部树脂材料均匀固化的能量的形状，链式固化反应也能通过自身产生的热使固化反应链式进行，因此可以在短时间内完成全部树脂材料的固化。固化时间虽然根据成型对象的大小及板厚、树脂的种类等而变化，例如如果是纵横长度为1m、厚度为2mm左右的通常的CFRP的情况下，从链式固化开始到固化完成的时间为1～10分钟左右。固化只要是使树脂材料固化到可以操作的状态、即固化到上述的一次固化为止即可。
需要说明的是，作为树脂材料，除了使用链式固化型的树脂组合物以外，还可以使用固化型树脂。作为固化型树脂，可以列举例如环氧树脂、酚醛树脂、双马来酰亚胺树脂、聚酰亚胺树脂、不饱和聚酯树脂、苯并嗪树脂等。
一次固化后，根据需要，用水等对成型夹具1进行冷却(图6)。通过冷却成型夹具1，能安全且容易地进行成型夹具1的操作、从其中取出型芯盒2和纤维强化树脂，同时一次固化状态的控制也变得容易。
树脂材料固化后，从成型夹具1中取出加强原材料。
例如可以将2～200片厚度为0.1～0.4mm的半固化片叠层来准备面板原材料，但并不限于此。例如可以使基质树脂含浸在碳纤维中来准备半固化片。作为基质树脂，可以采用上述的树脂或定向用于飞机结构的半固化片的树脂。另外，还可以使用热塑性树脂，例如PPS、PEEK、PEKK、PEK、PI、PEI、PA等。
另外，还可以使固化前的基质树脂含浸在将2～200片碳纤维基材叠层而成的叠层体中来准备面板原材料。碳纤维基材可以使用例如碳纤维织物等。另外，也可以使用预先将几层叠层并整理好的(纏められた)预成型品或无褶皱织物。预成型品或无褶皱织物的叠层片数在考虑预先叠层的分量的基础上来决定。本工序也可以是经过与上述加强原材料同样的工序通过RTM成型来进行准备。另外，树脂的含浸工序也可以在将加强原材料组装后进行。
任意情况下均可以不通过粘接剂而组装到加强原材料上。
参照图7说明在一次固化了的加强原材料上组装面板原材料的步骤的一个实施方式。
在该步骤中，将构成面板原材料的半固化片12载置在夹具上。然后，以保持型芯盒2的状态通过粘接剂组装加强原材料13。用包装膜14覆盖被成型原材料，使内部为真空状态。需要说明的是，图中15是密封材料。
将这样得到的组装体16如图8所示导入热压罐(加压加热罐)17内。将组装体16加热至加强原材料13的玻璃化转变温度以上，使加强原材料13成为橡胶态，在与加强原材料13相接的粘接剂的固化过程中使上述橡胶态的加强原材料13共存，使加强原材料13二次固化，从而使加强原材料13和面板原材料12一体化。
通过以上操作，得到了如图9所示一体化了的加强面板18。
需要说明的是，也可以将面板原材料和加强原材料的关系反过来，使面板原材料一次固化来准备一次固化了的面板原材料以实施本发明的复合材料的制造方法。
这里，进一步说明以上进行一体化时的温度条件的关系。
<被成型品原材料的弹性模量的温度依赖性＞
如图10的曲线A所示，通过粘弹性测定来测定上述加强原材料这样的一次固化(半固化)了的材料的弹性模量的温度依赖性时，(从室温起)随着温度上升，储能模量缓慢降低(玻璃态，B部分)。随后，超过某个温度时，随着温度上升，储能模量急剧降低(由玻璃态到橡胶态的状态变化，C部分。将该状态转变点称为玻璃化转变点，将该转变点的温度称为玻璃化转变温度：Tg)。
此外，超过某个温度时，在橡胶态下，随着温度上升，储能模量缓慢降低(橡胶态，D部分)。比较玻璃态下的储能模量和橡胶态下的储能模量，通常橡胶态下的储能模量会降低玻璃态下的储能模量的一半以下～1个数量级以上。
需要说明的是，固化时Tg向高温侧移动。
另外，曲线E示意性地示出了粘接剂一侧的能量曲线。
<一次固化(半固化状态)＞
一般而言，固化性树脂的一次固化[半固化(状态)]通常是指固化未完、不良的状态(固化反应未完成的状态)。
固化未完成的状态都可以叫半固化状态。但是，即使是同一树脂，根据固化程度(固化进展到什么程度)的不同，可以在各种特性方面(物理特性、机械特性、化学特性)表现出完全不同的特性。
<本发明中所谓的一次固化(低Tg控制型固化)状态＞
本发明中使复合材料的被成型品原材料一体化时，其特征在于，一体化时使用如下的被成型品原材料：从Tg的观点考虑来控制一体化所使用的被成型品原材料的固化状态，控制在具有比该被成型品原材料在固化完成状态下本来所具有的Tg更低的Tg的状态，同时是在一体化时的升温过程中树脂不会变成液态而流动的状态，并且是具有被控制在后述的(<一次固化(低Tg控制型固化)状态下的被成型品原材料的Tg和粘接剂反应温度的相关、Tg控制要点＞)的温度范围的Tg的固化状态(低Tg控制型固化状态)。
这虽然在广义上是半固化状态，但绝不是半固化状态＝一次固化(低Tg控制型固化)，仅仅是半固化状态无法实现本发明。
<一次固化(低Tg控制型固化)状态的被成型品原材料的Tg和粘接剂(接合部接触面对偶材料)的反应温度的相关、Tg控制要点＞
在得到一次固化(低Tg控制型固化)状态的被成型品原材料方面重要的是将所述被成型品原材料的Tg控制在何种程度(什么温度)，这是要点。该Tg根据与所使用的粘接剂等接合部接触面对偶材料(粘接剂或其它被成型品原材料)的反应温度的相关性来决定。即，根据所使用的被成型品原材料的种类或粘接剂的种类不同，一次固化完成时的Tg、粘接剂的反应温度也分别不同。但是，作为一次固化(低Tg控制型固化)状态的被成型品原材料的Tg，只要显示与后述粘接剂的反应温度(Tr)的相关，则不管被成型品原材料的种类或粘接剂的种类如何都有效。后述的例子是通过粘接剂的例子来说明。但是，Tr是指一次固化(低Tg控制型固化)状态的被成型品原材料的接合部接触面对偶材料的反应温度。例如接合部接触面对偶材料不是粘接剂、而是半固化片材或RTM用基质树脂时等，可以另读为它们各自的反应温度。
首先，关于一次固化(低Tg控制型固化)状态的被成型品原材料的Tg，定义为以下(1)～(3)的任意内容。
(1)储能模量开始降低的点的Tg1(玻璃态一侧的起始(onset)值)
这是通过测得一次固化状态的被成型品原材料的粘弹性来限定的。测定的一种方式是用夹头将试样(平板)的上下固定，以预定的升温速度施加热。对下部夹头施加扭力，用上部夹头传感扭力。基于上下的差异计算出弹性模量变化。
如图11所示，储能模量开始降低的点是加热初期的平缓B部分的线性外推和弹性模量急剧降低的C部分的线性外推的交点。刚性设计中，由于弹性模量变化影响性能，因此以变化前的值作为指标，可以采用该确定方法。
(2)由玻璃态到橡胶态的相转变的中间附近Tg2(tanδ(＝损耗模量/储能模量)显示峰值的温度)
这也示于图11中。
这也通过测定一次固化状态的被成型品原材料的粘弹性来限定。
(3)储能模量降低结束点Tg3(橡胶态一侧的起始(onset)值、或者储能模量降低峰值)。
这也通过测定一次固化状态的被成型品原材料的粘弹性来限定。
如图11所示，这是弹性模量急剧下降的C部分的线性外推和变平缓了的D部分的线性外推的交点。
本发明中Tg和Tr的相关控制可以通过控制Tg1和Tr的相关来体现。更优选控制Tg2和Tr的相关，最优选控制Tg3和Tr的相关。
另一方面，所使用的粘接剂的Tr定义为以下(1)～(3)的任意内容。
(1)反应开始点的温度Tr1[反应开始一侧的起始(onset)值(DSC测定)]
如图12所示，是平缓部分A和陡峭部分B的外推的交点。
在图12中，纵轴是通过DSC测定(差示扫描量热测定)测得的热量(能量)。
(2)反应温度Tr2[反应峰值温度(DSC测定)]
在图12中，是峰值温度。
(3)反应结束点的温度Tr3[反应结束侧的起始(onset)值(DSC测定)]
如图12所示，是陡峭的C部分和平缓的D部分的外推的交点。
本发明中Tg和Tr的相关的控制可以通过控制Tg和Tr3的相关来体现。更优选控制Tg和Tr2的相关，最优选控制Tg和Tr1的相关。
接着，根据以上的定义，在以下示出Tg和Tr的相关关系的控制值(控制范围)。需要说明得是，关于一次固化(低Tg控制型固化)状态的被成型品原材料的固化状态，其前提是一体化时的升温过程过程中被成型品原材料的基质树脂不会变成液态流动的固化状态。
关于Tg1和Tr的相关关系的控制值(控制范围)的控制范围如以下所示。
(i)dT31＝Tr3－Tg1≥30℃、且Tr2－Tg1＞0℃的控制范围。需要说明的是，“dT”符号用于表示温度间的差异，在以下的叙述中也同样。
(ii)更优选满足上述(i)、且dT21＝Tr2－Tg1≥25℃的控制范围。
(iii)进一步优选满足上述(ii)、且dT11＝Tr1－Tg1≥20℃的控制范围。
上述(i)～(iii)中Tr和Tg的温度差越大越优选。
以下示出Tg控制中与Tg1相比更优选以Tg2为指标的Tg2和Tr的相关关系的控制值(控制范围)。
(iv)dT32＝Tr3－Tg2≥10℃、且Tr2－Tg1＞0℃的控制范围。
(v)更优选满足上述(iv)、且dT22＝Tr2－Tg2≥5℃的控制范围。
(vi)进一步优选满足上述(v)、且dT12＝Tr1－Tg2≥0℃的控制范围。
上述(iv)～(vi)中Tr和Tg的温度差越大越优选。
以下示出Tg控制中与Tg2相比更优选以Tg3为指标的Tg3和Tr的相关关系的控制值(控制范围)。
(vii)dT33＝Tr3－Tg3≥0℃、并且Tr2－Tg1＞0℃的控制范围。
(viii)更优选dT23＝Tr2－Tg3≥0℃的控制范围。
(ix)进一步优选dT13＝Tr1－Tg3≥0℃的控制范围。
(x)最优选dT13＝Tr1－Tg3≥10℃的控制范围。
上述(vii)～(x)中Tr和Tg的温度差越大越优选。
根据本发明，通过如上所述地设定温度相关的控制范围，将组装体加热至一次固化了的至少一种被成型品原材料(例如加强原材料)的玻璃化转变温度以上，使至少一种被成型品原材料成为橡胶态，在固化过程中使与该被成型品原材料相接的粘接剂或者与被成型品原材料相接的其它被成型品原材料共存，使一次固化了的至少一种被成型品原材料二次固化，从而可以将至少一种被成型品原材料和其它被成型品原材料一体化。
<一次固化(低Tg控制型固化)状态的成型条件的确立方法＞
示出一次固化(低Tg控制型固化)状态的成型条件的确立方法的例子。
但是，不限于此例，重要的是得到上述的固化状态。
通过DSC测定来测定粘接剂的反应温度的Tr(Tr1、Tr2、Tr3)。
对想要制成一次固化(低Tg控制型固化)状态的被成型品原材料所使用的材料实施DSC测定，测定固化(反应)开始温度Tp1。
这里，Tp1是固化(反应)开始点[反应开始侧的起始(onset)值(DSC测定)]，如图16所示，定义为平缓部分A和陡峭部分B的外推的交点。
在想要制成一次固化(低Tg控制型固化)状态的被成型品原材料的成型中，使成型温度和保持时间为固化开始温度Tp1和30分钟来进行成型，通过粘弹性来测定该被成型品原材料的Tg(假Tg)。
比较该Tg(假Tg)和对粘接剂测得的上述Tr(Tr1、Tr2、Tr3)，考虑是否进入了对Tg和Tr规定的上述控制值[控制范围(i)～(x)]。是上述Tg(假Tg)不在上述控制值[控制范围(i)～(x)]内的情况、或者上述控制值[控制范围(i)～(x)]没有进入目标范围的情况下，过高时，再次将复合材料成型，成型条件定为固化开始温度－10℃、或者保持时间定为一半即15分钟(或者两种)，并再次计测Tg(假Tg)。在上述Tg计测中发生液化时(和上述Tg(假Tg)过低时)，再次将复合材料成型，成型条件定为固化开始温度+10℃、或者保持时间为一倍即1小时(或者两者)，再次计测Tg(假Tg)。
作为其它方法，在厂商等推荐的成型条件中的成型温度－20℃的成型温度下将被成型品原材料成型后，同样地通过粘弹性测定Tg(假Tg)，基于该结果，与上述同样地，进一步在成型温度+10℃或－10℃的成型温度下将被成型品原材料成型后，同样地再次通过粘弹性测定Tg(假Tg)。
作为其它方法，还有将目标Tg用作成型时的保持温度基准的方法等。
采用任何方法通常都可以通过数次试验确立一次固化(低Tg控制型固化)状态的成型条件。
<其它＞
在为了接合而进行的成型过程中，作为升温条件，在Tg1以上Tr3以下的温度范围设立阶梯(温度保持)也是有用的。作为设立阶梯的温度范围(Tg和Tr)，Tg侧的温度范围优选为Tg2以上，更优选为Tg3以上。另一方面，Tr侧的温度范围优选为Tr2以下，更优选为Tr1以下。
以上参照实施方式说明了本发明，但本发明不限于前文所述的实施方式，可以基于本发明的技术思想进行各种变更和变形。
权利要求书(按照条约第19条的修改)
1.一种复合材料的制造方法，所述复合材料由至少两种以上的被成型品原材料构成，该方法包括：
将用于构成所述复合材料的至少一种被成型品原材料一次固化而准备一次固化了的被成型品原材料，
将所述一次固化了的被成型品原材料通过粘接剂或不通过粘接剂与用于构成所述复合材料的其它被成型品原材料组装来准备组装体，
将所述组装体加热至所述一次固化了的至少一种被成型品原材料的玻璃化转变温度以上，使所述至少一种被成型品原材料成为橡胶态，使与该被成型品原材料相接的粘接剂或者与所述被成型品原材料相接的所述其它被成型品原材料在固化过程中与所述橡胶态的被成型品原材料共存，使所述一次固化了的至少一种被成型品原材料二次固化，从而使至少一种被成型品原材料与所述其它被成型品原材料一体化，
求出以下所述的温度Tg1、Tg2、Tg3、Tr1、Tr2、Tr3，
Tg1：一次固化了的被成型品原材料的储能模量开始下降的点的温度，
Tg2：一次固化了的被成型品原材料由玻璃态到橡胶态的相转变中间附近的温度，
Tg3：一次固化了的被成型品原材料的储能模量下降结束的点的温度，
Tr1：与一次固化了的被成型品原材料相接的粘接剂或者与一次固化了的被成型品原材料相接的其它被成型品原材料的反应开始点的温度，
Tr2：与一次固化了的被成型品原材料相接的粘接剂或者与一次固化了的被成型品原材料相接的其它被成型品原材料的反应温度，
Tr3：与一次固化了的被成型品原材料相接的粘接剂或者与一次固化了的被成型品原材料相接的其它被成型品原材料反应结束点的温度，
将所述一次固化了的被成型品原材料的玻璃化转变温度Tg、和与该被成型品原材料相接的粘接剂或者与所述被成型品原材料相接的所述其它被成型品原材料的反应温度Tr设定为满足以下(i)～(x)的任意条件：
(i)dT31＝Tr3－Tg1≥30℃、且Tr2－Tg1＞0℃的控制范围，
(ii)满足上述(i)、且dT21＝Tr2－Tg1≥25℃的控制范围，
(iii)满足上述(ii)、且dT11＝Tr1－Tg1≥20℃的控制范围，
(iv)dT32＝Tr3－Tg2≥10℃、且Tr2－Tg1＞0℃的控制范围，
(v)满足上述(iv)、且dT22＝Tr2－Tg2≥5℃的控制范围，
(vi)满足上述(v)、且dT12＝Tr1－Tg2≥0℃的控制范围，
(vii)dT33＝Tr3－Tg3≥0℃、且Tr2－Tg1＞0℃的控制范围，
(viii)dT23＝Tr2－Tg3≥0℃的控制范围，
(ix)dT13＝Tr1－Tg3≥0℃的控制范围，
(x)dT13＝Tr1－Tg3≥10℃的控制范围。
2.根据权利要求1所述的复合材料的制造方法，其中，所述复合材料是由加强原材料和面板原材料形成的复合材料，且使加强原材料一次固化。
3.根据权利要求2所述的复合材料的制造方法，其中，由使用了链式固化型树脂的纤维强化树脂构成所述加强原材料。

Claims (4)

1.一种复合材料的制造方法，所述复合材料由至少两种以上的被成型品原材料构成，该方法包括：
将用于构成所述复合材料的至少一种被成型品原材料一次固化而准备一次固化了的被成型品原材料，
将所述一次固化了的被成型品原材料通过粘接剂或不通过粘接剂与用于构成所述复合材料的其它被成型品原材料组装来准备组装体，
将所述组装体加热至所述一次固化了的至少一种被成型品原材料的玻璃化转变温度以上，使所述至少一种被成型品原材料成为橡胶态，使与该被成型品原材料相接的粘接剂或者与所述被成型品原材料相接的所述其它被成型品原材料在固化过程中与所述橡胶态的被成型品原材料共存，使所述一次固化了的至少一种被成型品原材料二次固化，从而使至少一种被成型品原材料与所述其它被成型品原材料一体化。
2.根据权利要求1所述的复合材料的制造方法，其中，将所述一次固化了的被成型品原材料的玻璃化转变温度Tg、和与该被成型品原材料相接的粘接剂或者与所述被成型品原材料相接的所述其它被成型品原材料的反应温度Tr设定为满足以下(i)～(x)的任意条件：
(i)dT31＝Tr3－Tg1≥30℃、且Tr2－Tg1＞0℃的控制范围，
(ii)满足上述(i)、且dT21＝Tr2－Tg1≥25℃的控制范围，
(iii)满足上述(ii)、且dT11＝Tr1－Tg1≥20℃的控制范围，
(iv)dT32＝Tr3－Tg2≥10℃、且Tr2－Tg1＞0℃的控制范围，
(v)满足上述(iv)、且dT22＝Tr2－Tg2≥5℃的控制范围，
(vi)满足上述(v)、且dT12＝Tr1－Tg2≥0℃的控制范围，
(vii)dT33＝Tr3－Tg3≥0℃、且Tr2－Tg1＞0℃的控制范围，
(viii)dT23＝Tr2－Tg3≥0℃的控制范围，
(ix)dT13＝Tr1－Tg3≥0℃的控制范围，
(x)dT13＝Tr1－Tg3≥10℃的控制范围，
其中，Tg1、Tg2、Tg3、Tr1、Tr2、Tr3是以下的温度，
Tg1：一次固化了的被成型品原材料的储能模量开始下降的点的温度，
Tg2：一次固化了的被成型品原材料由玻璃态到橡胶态的相转变中间附近的温度，
Tg3：一次固化了的被成型品原材料的储能模量下降结束的点的温度，
Tr1：与一次固化了的被成型品原材料相接的粘接剂或者与一次固化了的被成型品原材料相接的其它被成型品原材料的反应开始点的温度，
Tr2：与一次固化了的被成型品原材料相接的粘接剂或者与一次固化了的被成型品原材料相接的其它被成型品原材料的反应温度，
Tr3：与一次固化了的被成型品原材料相接的粘接剂或者与一次固化了的被成型品原材料相接的其它被成型品原材料反应结束点的温度。
3.根据权利要求1所述的复合材料的制造方法，其中，所述复合材料是由加强原材料和面板原材料形成的复合材料，且使加强原材料一次固化。
4.根据权利要求1所述的复合材料的制造方法，其中，由使用了链式固化型树脂的纤维强化树脂构成所述加强原材料。
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