WO2019128802A1 - 一种热固性树脂成型用薄膜材料及其应用 - Google Patents

一种热固性树脂成型用薄膜材料及其应用 Download PDF

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Publication number
WO2019128802A1
WO2019128802A1 PCT/CN2018/122071 CN2018122071W WO2019128802A1 WO 2019128802 A1 WO2019128802 A1 WO 2019128802A1 CN 2018122071 W CN2018122071 W CN 2018122071W WO 2019128802 A1 WO2019128802 A1 WO 2019128802A1
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layer
thermosetting resin
film material
resin
resin molding
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PCT/CN2018/122071
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English (en)
French (fr)
Inventor
桂宗彦
苏海晖
赵天心
蒋昕楠
荒井崇
郑淼
长田俊一
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东丽先端材料研究开发（中国）有限公司
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Priority to EP18893930.0A priority Critical patent/EP3756883A4/en
Priority to JP2020535249A priority patent/JP7279050B2/ja
Priority to CN201880080976.0A priority patent/CN111511550A/zh
Publication of WO2019128802A1 publication Critical patent/WO2019128802A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
    • B29C33/68—Release sheets
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • 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
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/06—Unsaturated polyesters
    • 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
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/70—Wind energy
    • Y02E10/72—Wind turbines with rotation axis in wind direction

Definitions

  • the invention belongs to the field of polymer materials and relates to a film material for thermosetting resin molding.
  • Thermosetting resin refers to a type of resin that undergoes a chemical reaction and solidifies under certain conditions of temperature, pressure or ultraviolet irradiation to form a crosslinked network structure.
  • Thermosetting resins are closely related to human production and life, and can be processed into various shapes according to design and use requirements.
  • epoxy resin can be used on various shapes of panels such as automotive interiors, brackets, and outer and outer casings.
  • thermosetting resin is generally difficult to meet the requirements for ultra-high mechanical strength.
  • a method of compounding with inorganic materials is required, which not only ensures the material weight and easy molding, but also ensures the mechanical mechanism of the material. performance.
  • the most common is the combination with glass fiber and carbon fiber, which can increase the impact resistance of the material.
  • thermosetting resin Whether it is a thermosetting resin or a composite material, a common vacuum infusion molding process can be employed: a raw material such as a thermosetting resin and a curing agent is vacuum-infused into a set mold and heated to be solidified and then removed from the mold.
  • a raw material such as a thermosetting resin and a curing agent is vacuum-infused into a set mold and heated to be solidified and then removed from the mold.
  • the wind turbine blade As a kind of large-sized molded body, the wind turbine blade has a relatively complicated structure and high mechanical performance. With the innovation of technology, the large-scale blade has become an inevitable trend, which is the shape and size of the blade. Accuracy puts higher demands on it.
  • the forming process of the blade basically adopts the above-mentioned vacuum infusion molding, and its technical difficulties are concentrated in the following aspects: 1. How to efficiently demould and ensure that the mold maintains dimensional accuracy after repeated use; 2. How to efficiently process the blade The surface, while avoiding the subsequent coating process without dust and solvent.
  • the mold release method is generally applied by applying a mold release agent on the inner surface of the mold, and after the organic solvent is volatilized, a mold release layer is formed on the inner surface of the mold to enable curing.
  • the thermosetting resin can be easily separated from the mold.
  • a part of the release agent adheres to the surface of the thermosetting resin molded article, so it is necessary to repair the missing mold release agent, and the multiple repairs may result in the mold.
  • the wear of the surface which causes the surface regularity of the formed blade to decrease, requires the shape of the blade to be trimmed later, which increases the man-hour.
  • a tape which can replace the liquid release coating is used, and the substrate is a polytetrafluoroethylene coated glass fiber cloth, and the other side opposite to the polytetrafluoroethylene is coated.
  • the cloth has silica gel.
  • the tape can be attached to the inner surface of the mold and can be recycled many times, and used for edge sealing, caulking and the like in the blade manufacturing process.
  • the tape can only be applied to the molding part with partial or small curvature, which seriously limits the practical application of the tape.
  • CN106068550A Application No. CN201580012256.7
  • a release film which is easily detached from the mold after molding is proposed, and the film can be used to protect the inner surface of the mold to a certain extent and reduce the wear of the inner surface of the mold.
  • the film is not provided with a coating layer. After the thermosetting resin is molded, the surface of the molded article needs to be polished and painted, the working time cannot be shortened, and a large amount of dust and solvent are generated by grinding and painting, which is not good for the operator.
  • CN101905622A (Application No.: CN200910052388.9)
  • the interlayer structure thereof is a carrier layer, a release layer, a printing layer, and a coating layer.
  • an adhesive layer which can be used to modify the printing layer, the coating layer and the adhesive layer to the wall surface.
  • the conditions of use of this film are different from those of thermosetting resin, and cannot be applied to the high temperature requirements of thermosetting resin molding.
  • the epoxy resin bonding force of the decorative layer cannot meet the bonding force requirement of the surface coating of the wind power blade, so the thermosetting property cannot be applied. Resin molding process.
  • a Chinese patent application publication CN101631674A proposes a film for transfer decorative sheet, the layer structure of which is a base material film, a release layer, a release layer, a pattern layer, a bonding layer, and a transfer.
  • the layer and the transfer decorative sheet are peeled off from the base material film after the molding and demolding process, and a transfer layer such as a decorative layer can be left on the surface of the resin molded body.
  • the film is used for the injection molding process of a thermoplastic resin, and the thermosetting resin molding process is greatly different. Under the thermosetting resin molding process, the transfer layer may not be transferred to the surface of the thermosetting resin, or may be detached from the film of the base material before molding. It is impossible to lay on the mold, so the film for such a transfer decorative sheet cannot be applied to the thermosetting resin molding process.
  • the invention provides a film material for thermosetting resin molding (especially for wind turbine blade molding), which has the advantages of easy operation, easy removal, no damage to the dimensional accuracy of the inner surface of the mold, and film material after the thermosetting resin molding process.
  • the functional layer can be transferred to the surface of the thermosetting resin to impart functional characteristics, thereby improving the volatilization of the organic solvent caused by the liquid release agent, the dust generated by the subsequent grinding of the surface of the molded body, and the difficulty of polishing, and it is difficult to use the mold after repeated use. Maintain design accuracy and other issues.
  • the treatment of the surface roughness and the use of the primer can be omitted, and the process can be reduced and the man-hour can be saved. At the same time, it can still ensure sufficient adhesion between the topcoat and the thermosetting resin.
  • the present invention provides a film material for thermosetting resin molding, the film comprising at least a first layer and a second layer, and at 23 ° C, there is peeling between the first layer and the second layer
  • the interface has an intensity of between 0.02 and 30 N/cm.
  • the main function of the first layer is to provide the film material for thermosetting resin molding with sufficient mechanical strength, workability, and workability, and is a substrate of a film material for thermosetting resin molding.
  • the second layer can be completely or partially detached from the film material for thermosetting resin molding and transferred to the thermosetting resin molded article, it is preferable that peeling occurs between the second layer and the first layer at 23 ° C
  • the interface has an intensity of 0.02 to 30 N/cm. If the peel strength at 23 ° C is more than 30 N/cm, there is a phenomenon that the second layer cannot be transferred to the thermosetting resin; if it is less than 0.02 N/cm, the second layer cannot be stably applied to the surface of the first layer.
  • the first layer contains one of a polyester resin, a polyurethane resin, a polycarbonate resin, a polyolefin resin, an acrylic resin, a polyimide resin, a polyamide resin, an aramid resin, or a fluororesin or A variety.
  • the polyester resin refers to a hetero chain polymer having an ester bond in its main chain.
  • examples thereof include polyethylene terephthalate, polybutylene terephthalate, poly(cyclohexanedimethylene terephthalate), polyethylene trimellitate, and polystyrene trisuccinate.
  • the urethane resin refers to a polymer compound having a urethane bond in the main chain.
  • a polyurethane resin can be produced by a reaction of a polyol and an isocyanate.
  • the polyhydric alcohol include ethylene glycol, diethylene glycol, 1,2-propylene glycol, dipropylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, and 2- Methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, dihydroxy polyoxypropylene ether, trihydroxy polyoxypropylene ether, tetrahydroxypropylethylenediamine or dihydroxypolytetrahydrofuran Ethers and the like contain a plurality of hydroxyl chemical structures.
  • isocyanate examples include aromatic diisocyanate such as toluene diisocyanate, benzene dimethylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, and tolidine diisocyanate, and ⁇ .
  • aromatic diisocyanate such as toluene diisocyanate, benzene dimethylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, and tolidine diisocyanate, and ⁇ .
  • An aliphatic diisocyanate having an aromatic ring such as ⁇ , ⁇ ', ⁇ '-tetramethylbenzenedimethylene diisocyanate, methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethyl six Aliphatic diisocyanate such as methylene diisocyanate or hexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, isopropylidene group
  • An alicyclic diisocyanate such as dicyclohexyl diisocyanate. These may be used singly or in combination of two or more.
  • the polycarbonate resin refers to a high polymer resin having a carbonate bond in its main chain.
  • the polycarbonate resin can be transesterified by a carbonic acid diester or phosgene synthesis.
  • the carbonic acid diester include substituted diphenyl carbonate represented by diphenyl carbonate and dinonyl carbonate, dimethyl carbonate or di-tert-butyl carbonate. These carbonic acid diesters may be used singly or in combination of two or more.
  • Specific examples of the polycarbonate resin include chemical structures such as bisphenol A type polycarbonate, chloro polycarbonate, and allyl diglycol carbonate, or copolymers having the above chemical structure and other chemical structures.
  • the polyolefin resin refers to a resin obtained by polymerizing or copolymerizing one or more olefins, and examples of the olefin include ethylene, propylene, butene, pentene or norbornene. Specific examples of the polyolefin resin include high density polyethylene, low density polyethylene, isotactic polypropylene, syndiotactic polypropylene, polynorbornene, poly-1-butene, poly 4-methyl-1-pentene. a chemical structure such as an ethylene-vinyl acetate copolymer or a copolymer of the above chemical structure and other chemical structures.
  • the acrylic resin is a copolymer synthesized by using a vinyl group such as acrylate, methacrylate or styrene as a main monomer.
  • the monomer may, for example, be methyl methacrylate, ethyl methacrylate, styrene, acrylonitrile, ethyl acrylate, n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate or methyl.
  • the polyimide resin is a polymer containing an imide bond in the main chain, and examples thereof include a polycondensation type aromatic polyimide and a polyaddition type polyimide. Specific examples thereof include a chemical structure such as a homophenylene polyimide, a bismaleimide polyimide, a PMR polyimide, or an acetylene terminal polyimide, or a copolymer having the above chemical structure and other chemical structures.
  • the polyamide resin also referred to as nylon, may be nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 612, nylon 46 or nylon 1010.
  • Aramid resins ie, aromatic polyamides, include para-aramids, meta-aramids or copolymers thereof.
  • the fluororesin refers to a polymer containing a fluorine atom in its molecular structure, and examples thereof include a perfluorinated alkyl vinyl ether copolymer, a polyperfluorinated isopropylene, an ethylene-tetrafluoroethylene copolymer, a polyvinylidene fluoride, and a poly A chemical structure such as chlorotrifluoroethylene or a copolymer of the above chemical structure and other chemical structures.
  • the first layer may contain polyethylene terephthalate, thermoplastic polyurethane, bisphenol A polycarbonate, polytetrafluoroethylene, polyvinylidene fluoride, fluorinated ethylene propylene copolymer, One or more of a copolymer or blend of ethylene-tetrafluoroethylene copolymer, polyethylene, polypropylene, polypropylene/polyethylene.
  • the thickness of the first layer is not particularly limited, and may be 10 to 200 ⁇ m, preferably 20 to 100 ⁇ m from the viewpoint of ease of laying.
  • the first layer can be prepared by a known method, such as by calendering, casting, blow molding or stretching.
  • Calendering refers to a process in which a thermoplastic is continuously formed into a film or sheet by passing it through a series of heated press rolls.
  • the casting method refers to the process of forming a film by melt-plasticizing the resin in an extruder, extruding through a slit die, and adhering the melt to the cooling roll, and then stretching, trimming, and winding.
  • the blow molding method refers to a process in which a resin is inflated in a closed mold by means of fluid pressure to make the resin into a hollow product.
  • the stretching method refers to stretching in the longitudinal or transverse direction of the film at a temperature lower than the melting point of the film material and higher than the glass transition temperature of the film material, or biaxially stretching in the longitudinal and transverse directions, and then appropriately cooling under tension.
  • Membrane process refers to stretching in the longitudinal or transverse direction of the film at a temperature lower than the melting point of the film material and higher than the glass transition temperature of the film material, or biaxially stretching in the longitudinal and transverse directions, and then appropriately cooling under tension.
  • the second layer is a functional layer, and the second layer may be completely or partially detached from the film material for thermosetting resin molding during the thermosetting resin molding process, and transferred to the thermosetting resin molded article.
  • the beneficial effects can be exemplified, such as providing heat resistance, light resistance, ultraviolet resistance, flame resistance, corrosion resistance, solvent resistance, water resistance, aging resistance, fuel resistance, hydraulic oil resistance, wear resistance, Impact resistance or decorative effects.
  • Additional adjacent layers may be added to the outside of the transferred second layer as needed, and the second layer may also serve the purpose of bonding the thermosetting resin and additional adjacent layers.
  • the second layer preferably contains one or more of a polyurethane resin, an epoxy resin, an unsaturated polyester resin, an acrylic resin or a fluororesin.
  • the following may be mentioned as a substance which can be contained in the said 2nd layer.
  • the polyurethane resin include the following cured products of polymers or coatings: WU210A/B series produced by Shanghai Meiga Paint Co., Ltd., WU233A/B series; LT2552/LW7260 series produced by Pompeite Coatings (Shanghai) Co., Ltd.; The 881-FYDM-A/B series produced by Zetiancheng Electronics Co., Ltd.
  • Examples of the epoxy resin include cured products of the following polymers or coatings: LP149 series manufactured by Pompeii Coatings (Shanghai) Co., Ltd.; 670HS-A/B series manufactured by AkzoNobel; EM400 produced by Shuangshi Coating Co., Ltd. -A/B series.
  • Examples of the unsaturated polyester resin include the following polymers or cured products of paints: 191 series produced by Sanhua Chemical Coating Co., Ltd.; TS-817 series produced by Qingyi Chemical Materials Co., Ltd.
  • Examples of the acrylic resin include a cured product of the following polymer or coating: FNUH-606 series manufactured by Renai Technology Development Co., Ltd.; and E0512 series produced by Yoshida Chemical Co., Ltd.
  • fluororesin examples include a cured product of the following polymer or coating: YQ-F-011-I series produced by Shandong Yingqiang New Material Technology Co., Ltd.; HC-0210F-A/B manufactured by Renai Technology Development Co., Ltd. series.
  • the second layer is sufficient for the bonding force of a thermosetting resin (for example, an epoxy resin) having the following properties: at 23 ° C, the epoxy resin binding force of the second layer is 6 MPa or more.
  • the epoxy resin binding force is measured by using the Airstone series 760E/766H epoxy resin manufactured by The Dow Chemical Co., Ltd., and mixing the ratio of 760E to 766H at a mass ratio of 100:32.
  • the film material for thermosetting resin molding of the invention On the second layer of the film material for thermosetting resin molding of the invention, 8 layers of glass fibers (Taishan glass fiber, triaxial, 1200 g/m 2 ) and a release cloth, a porous film, a flow guiding net, a vacuum bag film, and the like are laid. After the auxiliary material, a vacuum infusion operation was performed, and after curing at 80 ° C, 0.1 MPa, and 2 hours, an epoxy resin molded article having a thickness of 6 mm was obtained, and when the film material for thermosetting resin molding of the present invention was removed at 23 ° C, The second layer is transferred from the film material for thermosetting resin molding to the surface of the epoxy resin molded article.
  • glass fibers Teishan glass fiber, triaxial, 1200 g/m 2
  • a release cloth After the auxiliary material, a vacuum infusion operation was performed, and after curing at 80 ° C, 0.1 MPa, and 2 hours, an epoxy resin molded article having a thickness
  • the second layer was subjected to an adhesion test using an adhesion tester to obtain a second layer of epoxy bonding strength. If the epoxy resin bonding strength of the second layer is less than 6 MPa, there is a phenomenon that the second layer can be easily peeled off from the surface of the thermosetting resin and the durability is insufficient.
  • the second layer may further contain one or more of a blocked isocyanate group, an epoxy group, a hydroxyl group, a carboxyl group, an acid anhydride group or an amine compound.
  • a blocked isocyanate group an epoxy group, a hydroxyl group, a carboxyl group, an acid anhydride group or an amine group added to the second layer, and a chemical component, a thermosetting resin and/or a curing agent in the second layer
  • the reaction forms a chemical bond between the second layer and the thermosetting resin, thereby achieving the purpose of improving the bonding force between the epoxy resins of the second layer and improving the bonding force of the second layer with the thermosetting resin.
  • Blocked isocyanate means that an isocyanate group-containing compound is reacted with a blocking agent to form a compound which is stable at room temperature but which can be re-decomposed to an isocyanate at a high temperature.
  • examples of the isocyanate group-containing compound include toluene diisocyanate, benzene dimethylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, naphthalene diisocyanate or tolidine diisocyanate.
  • An aliphatic diisocyanate having an aromatic ring such as an aromatic diisocyanate, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylbenzenedimethylene diisocyanate, methylene diisocyanate, propylene diisocyanate, lysine Aliphatic diisocyanate such as acid diisocyanate, trimethylhexamethylene diisocyanate or hexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl An alicyclic diisocyanate such as methane diisocyanate or isopropylidene dicyclohexyl diisocyanate. These may be used singly or in combination of two or more.
  • the capping agent refers to phenols, pyridinol and corresponding mercapto compounds, alcohols, mercaptans and other hydroxyl-containing compounds, terpenes, amides, cyclic amides and acylamines, imidazoles, imidazolines, hydrazines And related compounds, one or more of pyrazoles, triazoles, amines, active methylene compounds, inorganic acids, and the like. Specific examples thereof include phenol, cresol, catechol, methoxyphenol, p-chlorophenol, 2-hydroxypyridine, 3-hydroxyquinoline, 8-hydroxypyridine, n-butanol, dimethylaminoethanol, and acrylic acid.
  • the blocked isocyanate can be exemplified by the TAKENATE series of Mitsui Chemicals Co., Ltd., the HIBLOCK series of Xiamen Aichem Chemical Co., Ltd., the BL-175 series of Shanghai Yitu Industrial Co., Ltd., and the GT of Jiangyin Getai Chemical Co., Ltd. -5100 series, HR-0325 series of Zhangjiagang Tianyi Chemical Co., Ltd., Trixene series of Basington, UK.
  • the outer surface of the second layer can be tested by infrared spectroscopy at a certain temperature to detect the change in the content of the isocyanate group.
  • the film material for thermosetting resin molding according to the present invention preferably satisfies the content of the isocyanate group by 5 to 20% after heating at 120 ° C for 10 minutes.
  • Specific examples of the compound containing an epoxy group, a hydroxyl group, a carboxyl group, an acid anhydride group or an amine group include glycidol, trimellitic anhydride, 3-hydroxypropionic acid, 2-tetrahydrofurfurylamine, L-aspartic acid, and ⁇ - Aminopropionic acid, diethyl tartrate, and the like.
  • the roughness of the outer surface of the second layer is preferably higher than 0.5 ⁇ m.
  • the outer surface is a surface of the film material in contact with the thermosetting resin when the thermosetting resin is molded. If it is lower than this requirement, the second layer may not be transferred from the first layer to the surface of the thermosetting resin under the molding process conditions, or the second layer may easily fall off from the surface of the thermosetting resin after the transfer.
  • the roughness of the outer surface of the second layer is further preferably higher than 1 ⁇ m.
  • the roughness of the inner surface of the second layer is preferably Above 0.1 ⁇ m.
  • the inner surface is the reverse side of the outer surface of the second layer.
  • the roughness of the inner surface of the second layer is further preferably higher than 0.5 ⁇ m.
  • the surface of the layer directly contacting the inner surface of the second layer may be roughened.
  • Roughening treatment refers to the treatment of the surface to make the surface have a large pitch and unevenness of the micro-peaks.
  • the roughening treatment method may specifically refer to electroplating, electroless plating, hot dip plating, corona treatment, mechanical roughing, coating, vacuum coating, oxidation treatment, decorative coating, oxidation treatment, solvent treatment, or Flame treatment.
  • the roughening of the first layer may be selected from one or more of a corona treatment method, a mechanical roughing method, a coating method, an oxidation treatment method, a solvent treatment method, or a flame treatment method.
  • the second layer can be prepared by spraying, brushing, dipping, roller coating, or shower coating on the first layer.
  • Spraying refers to a coating method in which a paint or a disc atomizer is used to disperse a paint into uniform and fine mist droplets by pressure or centrifugal force, and is applied to the surface of the object to be coated.
  • Brushing refers to a method of manually brushing a paint onto a surface of an object to be coated.
  • the impregnation method refers to immersing a solid powder or a shaped solid of a shape and size in a solution of a soluble compound containing an active component, and separating the residue after a certain period of time, so that the active component is attached as an ion or a compound.
  • Roll coating refers to a method of forming a wet coating of a certain thickness on a roll and then transferring some or all of the wet coating to the workpiece as it passes through the roll.
  • the leaching method refers to a coating method in which a uniform lacquer is applied to the surface of the object by a shower head.
  • the second layer may be subjected to roll coating by a coater equipped with a coating roll such as a comma roll or a micro-concave roll.
  • coating can be carried out using a film coating tool such as a wet film preparation device or a wire rod.
  • the thickness of the second layer is required to be set according to properties such as viscosity and curing time of the second layer and process conditions.
  • the thickness of the second layer is preferably 25 to 250 ⁇ m, and further preferably the thickness of the second layer is 30 to 200 ⁇ m.
  • the film material preferably has the property that the light transmittance of the second layer is 20% or more under the premise of the thickness of the second layer. If the light transmittance is less than 20%, the surface of the inner thermosetting resin is not observed due to the excessive covering effect of the second layer.
  • the light transmittance refers to the percentage of the luminous flux permeating the second layer as measured by the Suga company's HZ-V3 haze meter. Further, in order to pass through the second layer, the effect of the surface of the inner thermosetting resin is clearly observed, and the light transmittance is preferably 40% or more.
  • the film material for thermosetting resin molding has the following properties: the color difference ⁇ E of the second layer and the thermosetting resin is 0.5 the above.
  • the chromatic aberration refers specifically to the difference in color between the second layer and the thermosetting resin.
  • the color difference ⁇ E between the second layer and the thermosetting resin molded article in which the film material for thermosetting resin molding is not used can be measured by an NF333 portable colorimeter of the electrochromic company.
  • the second layer preferably contains a colorant.
  • the colorants include pigments and dyes.
  • a pigment is a series of colored fine-grained powdery substances that are insoluble in water, oil, solvent, resin, etc., but can be dispersed in various media. It may be a natural mineral pigment, a metal oxide pigment, a sulfide pigment, a sulfate pigment, a chromate pigment, a molybdate pigment, a carbon black pigment, an azo pigment, a phthalocyanine pigment, a heterocyclic pigment, a lake pigment, One or more of fluorescent pigments.
  • Dyes are a class of colored organic compounds that are soluble in water or other media to form a solution or dispersion to color the material.
  • a direct dye may be one or more of a direct dye, an acid dye, a metal complex dye, a vat dye, a sulfur dye, a disperse dye, a reactive dye, a cationic dye, a polycondensation dye, an oxidation dye, or a solvent dye.
  • a direct dye an acid dye, a metal complex dye, a vat dye, a sulfur dye, a disperse dye, a reactive dye, a cationic dye, a polycondensation dye, an oxidation dye, or a solvent dye.
  • Specific examples thereof include an anthraquinone dye, an azo dye, indigo, thioindigo, nigrosine, an anthraquinone dye, a polymethine dye, an arylmethane dye, a nitro dye, and a nitroso dye.
  • the surface tension of at least one surface of the first layer is 40 mN/m or less.
  • the surface tension of at least one surface of the first layer is further preferably 35 mN/m or less in view of the need to further increase the transfer ability of the second layer at the time of molding.
  • the surface tension of at least one surface of the first layer is further preferably 10 mN/m or more in view of the operability of the film material.
  • the film material for thermosetting resin molding further comprises a third layer, and a third layer
  • the surface tension of at least one surface of the layer is preferably 40 mN/m or less.
  • the surface tension of at least one surface of the third layer is further preferably 35 mN/m or less in view of further improving the transfer ability of the second layer at the time of molding of the thermosetting resin.
  • the surface tension of at least one surface of the third layer is further preferably 10 mN/m or more in view of the operability of the film material.
  • a third layer may be disposed between the first layer and the second layer for providing release properties.
  • the third layer may be adjusted in surface tension by a known method, such as by providing one or more of compounds containing a silicon-containing element and/or a fluorine element in the third layer.
  • the silicon-containing compound may be a silicone polymer, and examples thereof include polyvinyltriisopropoxysilane, polyvinyltrimethoxysilane, polyvinyltriethoxysilane, and polyvinyltripropoxyl.
  • Polysiloxane such as silane and its derivative (silicone oil).
  • the fluorine-containing compound may be a fluorine-containing polymer, and examples thereof include polytetrafluoroethylene, ethylene-polytetrafluoroethylene copolymer, and fluorine-containing vinyl-modified silicone oil.
  • the third layer can be prepared by reacting a monomer with a crosslinking agent under the action of a catalyst, coating it on the surface of the substrate, or directly by a kneading extrusion method.
  • the first layer is provided with the second layer on one side and the adhesive layer on the other side.
  • the adhesive layer is formed by bonding the film material for thermosetting resin molding and the surface of the thermosetting resin molding die to the effect of fixing the film material for thermosetting resin molding on the surface of the mold, and the film for thermosetting resin molding can be used at the end of use. Thereafter, it is peeled off from the surface of the molding die, and there is little or no adhesive layer remaining on the surface of the molding die.
  • the adhesive layer contains one or more of a natural polymer, a polyvinyl alcohol, a polyamide resin, a polyurethane resin, an acrylic resin, a polyester resin or a silicone resin.
  • a natural polymer such as starches, celluloses, polyvinyl alcohols; solvent-based adhesives such as acrylics and polyurethanes; emulsion-type adhesives such as polyvinyl acetate emulsions; and heat-curing adhesives such as epoxy Resins, silicone resins, unsaturated polyester resins; UV-curable adhesives: such as acrylates; anaerobic curing: such as acrylates; moisture-curing adhesives: such as cyanoacrylates, polyurethanes; polycondensation Reaction type: such as urethane; free radical polymerization type: such as acrylate; hot melt adhesive: such as acrylate, polyamide resin, polyester resin; rewet type adhesive: such as starch; pressure sensitive Adhesives: such as water-
  • the thickness of the adhesive layer can be set according to properties such as viscosity and curing time of the adhesive, process conditions, and the like.
  • the thickness of the adhesive layer is preferably from 1 to 100 ⁇ m, preferably from 2 to 80 ⁇ m.
  • a method of setting the adhesive layer can be carried out by a known method, for example, referring to the setting method of the second layer described above.
  • the thermosetting resin preferably contains one or more of an epoxy resin, a polyurethane resin, an acrylic resin, an unsaturated polyester resin, a phenol resin, a melamine formaldehyde resin or a furan resin.
  • examples of the raw material of the thermosetting resin described above include the following.
  • the epoxy resin the Airstone series 760E/766H produced by The Dow Chemical Company, the 2511-1A/2511-1BC series of Shangwei (Shanghai) Fine Chemical Co., Ltd., and the R-802 of Japan Showa Polymer are mentioned. Series, etc.
  • the polyurethane resin include the 78BD075/44CP20 series of Covestro Polymers (China) Co., Ltd., and the like.
  • Examples of the acrylic resin include the 10031/7662 series of Beijing Junfengyuan Chemical Co., Ltd., and the like.
  • Examples of the vinyl ester resin include MFE-VARTM-200 series from Huachang Polymer Co., Ltd., and AROPOL G300 series from Ashland, USA.
  • Examples of the phenolic resin include HK2506 series of Shandong Yuhua Chemical Co., Ltd. and 2124 series of Wuxi Boruiyu Chemical Technology Co., Ltd.
  • Examples of the furan resin include the NPEL128 series of Wuxi Changgan Chemical Co., Ltd., and the like.
  • thermosetting resin further contains an inorganic substance to enhance its mechanical properties.
  • the inorganic substances include, but are not limited to, glass fiber, asbestos fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium whisker, silicon whisker, wollastonite, sea bubble Stone, asbestos, slag fiber, xonotlite, silica apatite, gypsum fiber, silica fiber, silica/alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber or boron fiber, etc.
  • fibrous inorganic materials or glass flakes, non-swelling mica, swellable mica, graphite, metal foil, ceramic beads, talc, clay, mica, sericite, zeolite, bentonite, alfalfa Stone, montmorillonite, dolomite, kaolin, micronized silicic acid, feldspar powder, potassium titanate, fine hollow glass spheres, calcium carbonate, magnesium carbonate, calcium sulfate, titanium dioxide, silicon oxide, gypsum, fine quartzite, sodium One or more of flake or granular inorganic materials such as alumina or clay.
  • thermosetting resin includes hand lay-up, injection molding, vacuum bag forming, extrusion molding, pressure bag forming, filament winding, resin transfer molding, vacuum assisted resin injection molding, continuous sheet forming, pultrusion, centrifugal casting Molding, lamination or roll forming, sandwich structure forming, compression molding, press forming or spray forming.
  • the thermosetting resin molding according to the present invention may specifically be any one or more of a process such as hand lay-forming, filament winding molding, resin transfer molding, vacuum assisted resin injection molding, pultrusion molding, compression molding or prepreg placement. kind.
  • thermosetting resin molding of the present invention can be used in molding engineering of various thermosetting resins, such as wind turbine blades, automobiles, trains, airplanes, and the like, and the molding engineering application of electronic components, molding and decorative plates, and the like.
  • various thermosetting resins such as wind turbine blades, automobiles, trains, airplanes, and the like
  • the molding engineering application of electronic components, molding and decorative plates, and the like In order to achieve high efficiency production, high dimensional accuracy, low resin surface pollution, and environmentally friendly production process.
  • the present invention also provides the above-mentioned film material for thermosetting resin molding in the fields of automobiles, trains, airplanes and the like, electronic components, molded decorative panels, and the like, in particular, wind turbine blade molding.
  • the present invention also provides a product produced by the above-described film material for thermosetting resin molding, particularly a wind turbine blade.
  • the second layer can be transferred to the surface of the blade (mainly composed of epoxy or polyurethane resin) to act as a primer or primer and topcoat, thus eliminating the need for
  • the process of polishing the surface of the blade and the process of applying the primer (and topcoat) before the primer coating in the prior art process simplifies the process, shortens the process time, saves labor, and reduces VOC emissions.
  • the surface of the inner thermosetting resin can be directly observed through the second layer, which is helpful for detecting and directly observing the defects and positions on the surface of the thermosetting resin, and accurately performing the repairing process.
  • the film material for thermosetting resin molding of the present invention can be directly detached from the blade mold, and there is no or little residual glue, no need to clean the mold, reduce wear on the mold, and prolong the service life of the mold.
  • test methods used in the examples and comparative examples are as follows. For all tests, if the test temperature is not clearly stated, it is tested at 23 °C.
  • the thickness of the sample was measured at three different positions, and the arithmetic mean of the three thicknesses was taken as the thickness of the sample.
  • the peel strength of the film material for thermosetting resin molding refers to the peel strength of the first layer and the second layer in units of N/cm (peel strength): the second layer is reinforced with TESA7475 test tape, and the sample size is 150 mm ⁇ 10 mm, and is used.
  • the stretching machine was subjected to 180° peel strength and a peeling speed of 200 mm/min.
  • the number of test samples was 3, and the arithmetic mean of the test results was taken as the peel strength result.
  • the second layer was completely peeled off from the first layer, and the transmittance of the second layer was measured using a D65 light source using a HZ-V3 haze meter of Suga Corporation. The number of test samples was 3, and the arithmetic mean of the test results was taken as the light transmittance result.
  • an epoxy resin molded article was prepared by laying a film material for thermosetting resin molding on a molding die, and setting an auxiliary material according to a vacuum forming step of the wind power blade, using an Airstone series 760E/766H epoxy resin produced by The Dow Chemical Company. After mixing at a mass ratio of 760E to 766H of 100:32, a vacuum infusion operation was performed, and after vacuum forming at 80 ° C, 0.1 MPa, and 2 hours, the mixture was cooled to 23 ° C, and the mold was removed to obtain a ring having a thickness of 6 mm. Oxygen resin molded product.
  • the surface of the film material for thermosetting resin molding after transfer (the surface to be bonded to the thermosetting resin during molding) and the outer surface of the thermosetting resin molded article (the surface to be bonded to the film material for thermosetting resin molding during molding) are respectively measured by infrared spectroscopy. According to the measurement results of the second layer components on the two surfaces, the following determination is made:
  • the color difference refers to a color difference between the second layer of the film material for thermosetting resin molding and the thermosetting resin.
  • the second layer and the thermosetting resin molded article not using the film material for thermosetting resin molding are respectively placed on a black plate of the same specification, and the NF333 portable colorimeter of the electrochromic company is set to a color difference test mode, The second layer was used as a color difference measurement reference sample, and a reference value was measured. Further, the thermosetting resin molded article in which the film material for thermosetting resin molding was not used was measured, and the color difference ⁇ E between the two was obtained by an instrument. The number of test samples was 3, and the arithmetic mean of the test results was taken as the result of the color difference ⁇ E.
  • the second layer of epoxy resin bonding force in MPa.
  • a molded sample was prepared by the following method: using a Airstone series 760E/766H epoxy resin manufactured by The Dow Chemical Co., Ltd., and mixing the film material of the thermosetting resin molding of the present invention after mixing at a mass ratio of 760E to 766H of 100:32.
  • 8 layers of glass fiber (Taishan glass fiber, triaxial, 1200g/m 2 ) and a release cloth, a porous film, a flow guiding net, a vacuum bag film and the like are laid, and then a vacuum infusion operation is performed.
  • an epoxy resin molded article having a thickness of 6 mm was obtained, and when the film material for thermosetting resin molding of the present invention was removed at 23 ° C, the second layer was obtained from a thermosetting resin.
  • the film material for molding is transferred onto the surface of the epoxy resin molded article.
  • a flat position was selected on the outer surface of the molded article, which was used as a test position, and the test position was lightly ground with a 120-mesh sandpaper to a matte finish.
  • the measuring instrument is the XH-M portable adhesion tester of Beijing Zhongjian Sanyou Technology Co., Ltd., and the 20mm test spindle matched with the tester is bonded to the test position with MC1500 adhesive, and it is tested after being placed for 2 hours. The bonding force at three different positions was tested, and the arithmetic mean of the three results was taken as the result of the epoxy bonding force of the second layer of the sample.
  • thermosetting molding The second layer surface of the film material for thermosetting molding was subjected to FTIR-ATR test by iZ10 Fourier Infrared (FT-IR) spectrometer of Thermo Fisher Scientific (China) Co., Ltd. Then, the same thermosetting film material was heated at 120 ° C for 10 min, and a second FTIR-ATR test was performed on the surface of the second layer, and the alkyl stretching vibration region in the test image before and after the heat treatment was highly normalized. , comparing the height of the -NCO region, gives an increased ratio of isocyanate groups.
  • FT-IR Fourier Infrared
  • the test was carried out using a stylus type roughness profile tester (Xiamen Jinheyuan Technology Co., Ltd., TR200). Set the test speed to 0.5mm/s. The surface roughness of the three different positions was tested, and the arithmetic mean of the three test results was taken as the surface roughness result.
  • the outer surface roughness of the second layer is obtained by testing the outer surface of the second layer.
  • the inner surface roughness of the second layer is obtained by testing the surface of the first layer before the second layer (or the surface on which the second layer is to be disposed).
  • the Hitachi S-3400N scanning electron microscope was used, and the EDX model was Apollo X, and the element contained in the third layer of the film material for thermosetting resin molding was measured.
  • A1 Polyethylene terephthalate release film produced by Toray Industries, Ltd. XD-55YR. The thickness was 50 ⁇ m, the longitudinal tensile strength was 153 MPa, and the elongation at break was 38.6%.
  • the single surface is a release surface, and the surface of the release surface is formed by the EDX element of the scanning electron microscope through the silicon release treatment. The surface tension of the release surface is 20 mN/m; the surface tension of the non-release surface is 30 mN. /m. Both surface roughnesses were 0.1 ⁇ m.
  • the film is a first layer with a release surface (ie, a first layer with a third layer).
  • A2 Polyolefin film produced by Toray Industries, Ltd. 7H55G.
  • the thickness is 30 ⁇ m
  • the self-adhesive surface on one side the surface tension of the self-adhesive surface is 20 mN/m
  • the roughness is 0.1 ⁇ m
  • the surface tension of the non-self-adhesive surface is 25 mN/m
  • the roughness is 0.2 ⁇ m.
  • A3 Dongli Co., Ltd. produces biaxially oriented polypropylene film 50-2500A.
  • the thickness is 50 ⁇ m. Both surfaces have a surface tension of 18 mN/m and a roughness of 0.1 ⁇ m.
  • XB-G282 On the basis of B1, 0.5% of XB-G282 was added to WU233A as a filler, and the others were unchanged.
  • XB-G282 is a TAKENATE series of blocked isocyanate produced by Mitsui Chemicals Co., Ltd., specifically, a blocked hydrogenated phenylmethane diisocyanate, and the blocking agent is an active methylene compound.
  • B5 On the basis of B4, XB-G282 was changed to Sigma-Aldrich to produce glycidol, and the others were unchanged.
  • B6 On the basis of B4, XB-G282 was changed to Aladdin Reagent (Shanghai) Co., Ltd. to produce trimellitic anhydride, and the others were unchanged.
  • B7 On the basis of B4, XB-G282 was changed to 3-hydroxypropionic acid produced by Aladdin Reagent (Shanghai) Co., Ltd., and the others were unchanged.
  • B8 On the basis of B4, XB-G282 was changed to Al-Reagent (Shanghai) Co., Ltd. to produce L-aspartate, and the others were unchanged.
  • B10 On the basis of B4, XB-G282 parts by weight was changed to 0.5 part by weight, and 0.5 part by weight of glycidol was further added, and the others were unchanged.
  • B11 On the basis of B1, 1% of TiO 2 was added to WU233A as a filler, and the others were unchanged.
  • B12 On the basis of B1, 0.5% iron blue pigment was added as filler in WU233A, and the others were unchanged.
  • Y-1210/Y-101 which is an acrylate type adhesive, in which Y-1210 is the main agent and the solid content is 36%; Y-101 is a curing agent with a solid content of 75%.
  • the mass ratio of Y-1210 to Y-101 is 100:0.56.
  • the viscosity was 10,000 CPS at 25 ° C, the drying condition was 100 ° C for 2 minutes, and the curing conditions were 40 ° C for 24 hours.
  • UPSA-933A/B which is a polyurethane adhesive, of which UPSA-933A is the main agent, the solid content of the main component is 65%; UPSA-933B is the curing agent, the solid content is 70%.
  • the mass ratio was 100:6, the drying conditions were 100 ° C, 3 minutes, and the curing conditions were 80 ° C for 24 hours.
  • a second layer of the stock solution was applied to one side of the first layer using a wet film preparation machine, and then cured under the curing conditions of the used second layer to obtain a second layer having a thickness of 100 ⁇ m.
  • the second layer is disposed on the non-release surface of A1; in the embodiment 4-6, the second layer is disposed on the release surface of A1; in the embodiment 7-9, the second layer The layer is disposed on the self-adhesive surface of A2; in Examples 10-12, the second layer is disposed on either side of A3.
  • a second layer of the stock solution was applied onto the self-adhesive side of A2 using a wet film preparation machine, and then cured under the curing conditions of the used second layer to obtain a second layer having a thickness of 100 ⁇ m.
  • a second layer of the stock solution was applied onto the self-adhesive side of A2 using a wet film preparation machine, and then cured under the curing conditions of the used second layer to obtain a second layer having a thickness of 100 ⁇ m.
  • the stock solution of the adhesive layer was applied onto the non-self-adhesive surface of A2 using a wet film preparation machine, and then cured under the curing conditions of the adhesive layer used to obtain an adhesive layer having a thickness of 5 ⁇ m.
  • a second layer of the stock solution was applied to the other side of the first layer using a wet film preparation machine, and then cured under the curing conditions of the second layer used to obtain a thickness of 100 ⁇ m. Second floor.
  • Roughening treatment is performed on the release surface of A1, the self-adhesive surface of A2, and any one of A3, so that the roughness of the roughened surface of A1 is 3 ⁇ m, and the roughness of roughened surface of A2 is 0.6 ⁇ m, A3 The roughness of the roughened surface was 1 ⁇ m.
  • the stock solution of the adhesive layer was applied onto the non-treated surface of the first layer using a wet film preparation machine, and then cured under the curing conditions of the adhesive layer to be used to obtain an adhesive layer having a thickness of 5 ⁇ m.
  • a second layer of the stock solution was applied to the other side of the first layer using a wet film preparation machine, and then cured under the curing conditions of the second layer used to obtain a thickness of 100 ⁇ m. Second floor.
  • the stock solution of the adhesive layer was applied onto the non-self-adhesive surface of A2 using a wet film preparation machine, and then cured under the curing conditions of the adhesive layer to be used to obtain an adhesive layer having a thickness of 5 ⁇ m.
  • a second layer of the stock solution was applied to the other side of A2 using a wet film preparation machine, and then cured under the curing conditions of the second layer used to obtain a second layer B1 having a thickness of 100 ⁇ m. .
  • the outer surface of the second layer B1 was roughened so that the roughness of the roughened surface of B1 was 0.6 ⁇ m (Example 28) and 2 ⁇ m (Example 29).
  • a second layer of the stock solution was applied to the self-adhesive side of A2 using a wet film preparation machine, and then cured under the curing conditions of the second layer used to obtain a second layer having a thickness of 100 ⁇ m. Thereafter, the outer surface of the second layer of Examples 30-32 was subjected to infrared spectrum detection.
  • the film material for thermosetting resin molding was heated at 120 ° C for 10 minutes, and the outer surface of the second layer of the heated Examples 30 to 32 was subjected to infrared spectrum detection.
  • the content of the isocyanate group was measured by two infrared spectroscopy detection results, and the results are shown in Table 7.
  • the second layer of C1 was applied to the non-release surface of the first layer A1 using a wet film preparation machine, and then cured under the curing conditions of the second layer used to obtain a thickness of The second layer of 100 ⁇ m.
  • the peel strength of the first layer and the second layer was found to be 35 N/cm, and the transferability of the second layer was ⁇ , that is, it could not be transferred.
  • the second layer of the film material for thermosetting resin molding of the present invention can be transferred to the surface of the thermosetting resin molded article during the molding of the thermosetting resin to have a beneficial effect.

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Abstract

本发明提供一种热固性树脂成型用薄膜材料，至少含有第一层和第二层，且在23℃下，所述第一层和所述第二层之间存在剥离强度在0.02～30N/cm之间的界面。本发明的热固性树脂成型用薄膜材料具有易于操作、易于移除、不损害模具表面的尺寸精度、在热固性树脂成型后薄膜材料功能层向热固性树脂表面转移，赋予成型品功能性的特点，从而能够改善使用液体脱模剂，所带来的有机溶剂挥发、后续成型体表面打磨带来的粉尘产生与打磨技术难度高、模具经过多次使用后难以保证设计精度等问题。尤其是脱模之后修饰在成型树脂表面的第二层的存在，省去了表面打磨和底涂漆操作步骤，在减少工序、节约工时的情况下，仍能保证面漆的附着能力。

Description

一种热固性树脂成型用薄膜材料及其应用 技术领域
本发明属于高分子材料领域，涉及一种热固性树脂成型用薄膜材料。
背景技术
热固性树脂是指在一定温度、压力或紫外照射等条件下，发生化学反应并固化成型，形成交联网状结构的一类树脂。热固性树脂与人类的生产、生活息息相关，可按照设计与使用需求，被加工成多种形状。比如环氧树脂，可以用于汽车内饰、支架、车门内外侧的外壳等各种形状板材上。
作为高分子材料的一种，热固性树脂一般难以满足对超高机械强度的要求，这时需采用与无机材料复合的方法，既保证了材料轻量化、易成型的特点，又保证了材料的机械性能。最常见的是与玻璃纤维、碳纤维复合，这样可以增加材料的抗冲击性能。
无论是热固性树脂还是其复合材料，都可以采用常见的真空灌注成型工艺：将热固性树脂及固化剂等原料真空灌注到设定的模具内并加热，使之固化成型后脱去模具。为了保证成型品的尺寸精度，在具体的实施过程中，对树脂本身的性能和模具的表面状态、加工条件都有一定的要求。
风力发电机叶片作为大型成型体的一种，其结构一般较为复杂，对机械性能要求较高，而且随着技术的革新，叶片的大型化已经成为必然的趋势，这就对叶片的形状以及尺寸精度提出了更高的要求。叶片的成型工艺基本上采用上述的真空灌注成型，其技术难点集中在以下几个方面：1.如何高效脱 模并保证模具在反复使用后，仍保持尺寸上的精度；2.如何高效处理叶片表面，同时避免后续的涂装过程无粉尘和溶剂产生。
现有技术中，对于上述问题点1，通常采用在模具内表面涂布脱模剂的方法进行脱模，待有机溶剂挥发完后，模具内表面会形成一层脱模剂层，使固化后的热固性树脂与模具能够很容易的分离。但是上述脱模剂层在反复使用3-4次后，会有一部分脱模剂黏附到热固性树脂成型品表面，因此需要对这一部分缺失的脱模剂进行修补，多次修补则会造成模具内表面的磨损，进而造成成型叶片表面规整度的下降，因此需要后期对叶片进行形状上的修整，增加了工时。模具内表面的磨损也会严重缩短模具的使用寿命。为了改善上述问题，作为现有技术，可以列举出一种可以替代液体脱模涂层的胶带，其基材为聚四氟乙烯涂布的玻璃纤维布，与聚四氟乙烯相反的另一面涂布有硅胶。该胶带可以贴附于模具内表面并可以多次循环使用，在叶片制造的工艺中用于封边、填缝等操作。但是，受到玻璃纤维断裂延展度差的限制，该胶带目前只能适用于局部或者曲率不大的成型部位，严重限制了此种胶带的实际应用。中国专利申请公开文本CN106068550A(申请号CN201580012256.7)中提出了一种成型后易于从模具脱离的脱模膜，使用此薄膜可以在一定程度上保护模具内表面，减少模具内表面的磨损。但此薄膜没有设置涂料层，在热固性树脂成型后，需进行成型品表面的打磨与涂装，无法缩短作业工时，且打磨和涂装会产生大量粉尘和溶剂，也不利于操作人员健康。
现有技术中，对于上述问题点2，后期涂装过程的前期准备工作(叶片形状修整、叶片表面粗糙化、底漆涂装)一般是由人工完成，精度难以保证，因此打磨效率较为低下。另外，打磨带来的大量粉尘、底漆涂装所产生的大量有机溶剂都会对工作人员的健康产生不利影响。为了改善上述问题，作为 现有技术，可以列举出一种机器人打磨生产线，虽然可以一定程度上提高打磨效率，但此技术仍无法克服粉尘、有机溶剂大量产生的缺点。作为现有技术，中国专利申请公开文本CN101905622A(申请号：CN200910052388.9)中提出了一种涂层可转移性的薄膜，其层间结构依次为承载层、离型层、印刷层、涂料层和粘着层，利用此薄膜可将印刷层、涂料层和粘着层转移至墙面起到修饰作用。此薄膜的使用条件与热固性树脂成型条件不同，无法适用于热固性树脂成型时的高温要求，装饰层的环氧树脂结合力无法达到风电叶片表面涂层所需的结合力要求，因此不能运用到热固性树脂的成型工艺。此外，中国专利申请公开文本CN101631674A(CN200880007651.6)中提出了一种转印装饰片用薄膜，其层结构依次为基体材料膜、脱模层、剥离层、图案层、粘结层、转印层、转印装饰片，在成型、脱模过程后，剥离除去基体材料膜，可在树脂成型体表面上保留装饰层等转印层。但此种薄膜用于热塑性树脂的注塑成型工艺，与热固性树脂成型工艺差异大，在热固性树脂成型工艺条件下，转印层或无法转移到热固性树脂表面，或在成型前从基体材料膜上脱落，无法在模具上进行铺设，因此此种转印装饰片用薄膜不能运用到热固性树脂成型工艺。
发明内容
本发明提供一种热固性树脂成型用(尤其是风力发电机叶片成型用)的薄膜材料，具有易操作、易移除、不损害模具内表面的尺寸精度、且在热固性树脂成型工艺后，薄膜材料功能层可向热固性树脂表面转移，赋予其功能性的特点，从而能够改善使用液体脱模剂带来的有机溶剂挥发、后续成型体表面打磨产生的粉尘及打磨难度高、模具多次使用后难以维持设计精度等问 题。尤其是脱模之后，修饰在树脂表面的功能性层(本文中后述的第二层)作为底漆存在时，可以省去表面粗糙度的处理和底漆的使用，在减少工序、节约工时的同时，仍能保证面漆与热固性树脂之间具有足够的附着能力。
具体而言，本发明提供一种热固性树脂成型用薄膜材料，所述薄膜至少含有第一层和第二层，且在23℃时，所述第一层和所述第二层之间存在剥离强度在0.02～30N/cm之间的界面。
所述的第一层的主要功能是提供所述的热固性树脂成型用薄膜材料以足够的力学强度、可操作性及可施工性，是热固性树脂成型用薄膜材料的基材。
考虑到第二层能够全部或部分的从所述热固性树脂成型用薄膜材料上脱离并转移到热固性树脂成型品上，因此优选为：在23℃时，第二层与第一层之间存在剥离强度为0.02～30N/cm的界面。在23℃时的剥离强度如果大于30N/cm，则会出现第二层不能转移至热固性树脂的现象；如果小于0.02N/cm，则第二层不能够稳定贴敷在第一层表面。
进一步的，优选在23℃时，第二层和第一层之间存在剥离强度在0.1～15N/cm的界面。
进一步的，所述的第一层含有聚酯树脂、聚氨酯树脂、聚碳酸酯树脂、聚烯烃树脂、丙烯酸树脂、聚酰亚胺树脂、聚酰胺树脂、芳纶树脂或氟树脂中的一种或多种。
所述的聚酯树脂是指主链上有酯键的杂链聚合物。可以举出聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚对苯二甲酸环己二甲醇酯、聚偏苯三酸乙二醇酯、聚苯均三酸丁二醇酯、对羟基苯甲酸乙酯、聚间苯二甲酸新戊二醇酯、聚乳酸、聚对苯二甲酸己二酸丁二醇酯、聚丁二酸丁二醇酯、聚丁二酸己二酸丁二醇酯、聚己内酯、聚丁内酯等化学结构或上述化学结构同 其它化学结构形成的共聚物。
聚氨酯树脂是指主链上具有氨酯键的高分子化合物。通常聚氨酯树脂可以通过多元醇和异氰酸酯的反应来制作。多元醇可以举出乙二醇、一缩二乙二醇、1，2-丙二醇、一缩二丙二醇、1，4-丁二醇、新戊二醇、1，6-己二醇、2-甲基-1，3-丙二醇、3-甲基-1，5-戊二醇、二羟基聚氧化丙醚、三羟基聚氧化丙醚、四羟丙基乙二胺或二羟基聚四氢呋喃氧化丙醚等含有多个羟基化学结构。作为异氰酸酯，可以举出甲苯二异氰酸酯、苯二亚甲基二异氰酸酯、亚甲基二苯基二异氰酸酯、亚苯基二异氰酸酯、萘二异氰酸酯、联甲苯胺二异氰酸酯等芳香族二异氰酸酯、α，α，α’，α’-四甲基苯二亚甲基二异氰酸酯等具有芳香环的脂肪族二异氰酸酯、亚甲基二异氰酸酯、亚丙基二异氰酸酯、赖氨酸二异氰酸酯、三甲基六亚甲基二异氰酸酯、六亚甲基二异氰酸酯等脂肪族二异氰酸酯、环己烷二异氰酸酯、甲基环己烷二异氰酸酯、异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯、异亚丙基二环己基二异氰酸酯等脂环族二异氰酸酯等。这些物质可以单独使用，也可以多种并用。
聚碳酸酯树脂是指主链上含有碳酸酯键的高聚物树脂。聚碳酸酯树脂可以通过碳酸二酯进行酯交换，或者光气法合成。其中碳酸二酯可以举出碳酸二苯酯、碳酸二卞酯所代表的取代碳酸二苯酯、碳酸二甲酯或碳酸二叔丁酯等。这些碳酸二酯可以单独使用，也可以多种并用。具体的，聚碳酸酯树脂可以列举出双酚A型聚碳酸酯、氯代聚碳酸酯、烯丙基二甘醇碳酸酯等化学结构或上述化学结构同其它化学结构形成的共聚物等。
聚烯烃树脂是指由一种或几种烯烃聚合或共聚制得的树脂，其中烯烃可以举出，乙烯、丙烯、丁烯、戊烯或降冰片烯等。具体的，聚烯烃树脂可以列举出高密度聚乙烯、低密度聚乙烯、等规聚丙烯，间规聚丙烯、聚降冰片 烯、聚1-丁烯、聚4-甲基-1-戊烯、乙烯-醋酸乙烯酯共聚物等化学结构或上述化学结构同其它化学结构形成的共聚物等。
丙烯酸树脂是以丙烯酸酯、甲基丙烯酸酯及苯乙烯等乙烯基类为主要单体合成的共聚物。所述的单体可以举出甲基丙烯酸甲酯、甲基丙烯酸乙酯、苯乙烯、丙烯腈、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸月桂酯、丙烯酸-2-乙基己酯、甲基丙烯酸月桂酯、甲基丙烯酸正辛酯、丙烯酸-2-羟基乙酯、丙烯酸-2-羟基丙酯、甲基丙烯酸-2-羟基乙酯、甲基丙烯酸-2-羟基丙酯、甲基丙烯酸缩水甘油酯、丙烯酰胺、N-羟甲基丙烯酰胺、N-丁氧甲基(甲基)丙烯酰胺、二丙酮丙烯酰胺、甲基丙烯酸乙酰乙酸乙酯、二乙烯基苯、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三异丙氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、苯乙烯磺酸、乙烯基磺酸钠等化学结构或上述化学结构同其它化学结构形成的共聚物等。
聚酰亚胺树脂是主链上含有酰亚胺键的聚合物，可以举出缩聚型芳香族聚酰亚胺、加聚型聚酰亚胺。具体可以举出均苯型聚酰亚胺、双马来聚酰亚胺、PMR聚酰亚胺、乙炔端基聚酰亚胺等化学结构或上述化学结构同其它化学结构形成的共聚物等。
聚酰胺树脂，又称尼龙，可以举出尼龙6、尼龙66、尼龙11、尼龙12、尼龙610、尼龙612、尼龙46或尼龙1010等。
芳纶树脂，即芳香族聚酰胺，包括对位芳酰胺、间位芳酰胺或其共聚物。
氟树脂是指分子结构中含有氟原子的聚合物，可以举出，全氟化烷基乙烯基醚共聚物、聚全氟化异丙烯、乙烯-四氟乙烯共聚物、聚偏氟乙烯、聚三氟氯乙烯等化学结构或上述化学结构同其它化学结构形成的共聚物等。
具体而言，所述的第一层可以含有聚对苯二甲酸乙二醇酯、热塑性聚氨 酯、双酚A型聚碳酸酯、聚四氟乙烯、聚偏氟乙烯、氟化乙烯丙烯共聚物、乙烯-四氟乙烯共聚物、聚乙烯、聚丙烯、聚丙烯/聚乙烯的共聚物或共混物中的一种或多种。
所述的第一层，其厚度没有特别的要求，从方便铺设的角度考虑，可以是10～200μm，优选为20～100μm。
所述的第一层可以通过公知的方法进行制备，比如通过压延法、流延法、吹塑法或拉伸等工艺。压延法是指将热塑性塑料通过一系列加热的压辊，使其连续成型为薄膜或片材的成型方法。流延法是指将树脂在挤出机熔融塑化，通过狭缝机头模口挤出，使熔料紧贴在冷却辊上，再经过拉伸、切边、卷取等工序形成薄膜的工艺。吹塑法是指树脂借助流体压力，在闭合模具中进行吹胀，使树脂成为中空制品的工艺。拉伸法是指在低于薄膜材料熔点、高于薄膜材料玻璃化转变温度的温度条件下，对膜纵向或横向拉伸，或纵横双向拉伸，然后在张紧状态下进行适当冷却的成膜工艺。
所述的第二层是功能性层，在热固性树脂成型工艺过程中，所述的第二层可以全部或部分地从所述热固性树脂成型用薄膜材料上脱离，转移到热固性树脂成型品上，从而起到有益效果。所述的有益效果可以举例出，如提供耐热性、耐光性、耐紫外、耐燃性、耐腐蚀性、耐溶剂性、耐水性、耐老化性、耐燃油性、耐液压油、耐磨性、耐冲击性或装饰性等效果。根据需要，转移后的第二层的外侧还可以增加额外相邻层，此时，第二层还可以起到粘结热固性树脂和额外相邻层的目的。
进一步的，考虑到第二层需要有一定的功能性，所述的第二层优选含有聚氨酯树脂、环氧树脂、不饱和聚酯树脂、丙烯酸树脂或氟树脂中的一种或多种。
具体而言，作为所述的第二层中可以含有的物质，可以举出以下这些。作为聚氨酯树脂类，可以列举出以下聚合物或涂料的固化物：上海麦加涂料有限公司产的WU210A/B系列、WU233A/B系列；庞贝捷涂料(上海)有限公司产的LT2552/LW7260系列；鸿泽天诚科贸有限公司产的881-FYDM-A/B系列。作为环氧树脂类，可以列举出以下聚合物或涂料的固化物：庞贝捷涂料(上海)有限公司产的LP149系列；阿克苏诺贝尔产的670HS-A/B系列；双狮涂料有限公司产的EM400-A/B系列。作为不饱和聚酯树脂类，可以列举出以下聚合物或涂料的固化物：三化化工涂料有限公司产的191系列；青衣化工物资有限公司产的TS-817系列。作为丙烯酸树脂类，可以列举出以下聚合物或涂料的固化物：仁爱科技开发有限公司产的FNUH-606系列；吉田化工有限公司产的E0512系列。作为氟树脂类，可以列举出以下聚合物或涂料的固化物：山东应强新材料科技有限公司产的YQ-F-011-I系列；仁爱科技开发有限公司产的HC-0210F-A/B系列。
进一步的，为了实现在热固性树脂成型工艺过程中，所述的第二层具有全部或部分地从所述热固性树脂成型用薄膜材料上脱离、并转移到热固性树脂成型品上这一效果，且需要第二层对热固性树脂(例如环氧树脂)的结合力足够，所述的热固性树脂成型用薄膜材料具有如下性能：23℃时，第二层的环氧树脂结合力为6MPa以上。所述的环氧树脂结合力是通过以下方法进行测定的：使用陶氏化学公司产的Airstone系列760E/766H环氧树脂，以760E与766H的质量比为100∶32的比例混合后，在本发明的热固性树脂成型用薄膜材料的所述第二层上，铺设8层玻璃纤维(泰山玻纤，三轴，1200g/m 2)和脱模布、多孔膜、导流网、真空袋膜等辅材后，进行真空灌注操作，通过80℃、0.1MPa、2小时固化处理后，得到厚度为6mm的环氧树脂成型品，于 23℃下移除本发明的热固性树脂成型用薄膜材料时，所述第二层从热固性树脂成型用薄膜材料上转移到环氧树脂成型品的表面。利用附着力测试仪对第二层进行附着力测试，得到第二层的环氧树脂结合力。如果第二层的环氧树脂结合力低于6MPa，则会出现第二层能够较容易地从所述热固性树脂表面剥离、耐久性不足的现象。
为了提高第二层的环氧树脂结合力，所述的第二层还可含有封端异氰酸酯基、环氧基、羟基、羧基、酸酐基或胺基化合物中的一种或多种。添加到第二层中的含封端异氰酸酯基、环氧基、羟基、羧基、酸酐基或胺基的一种或多种化合物，与第二层中的化学成分、热固性树脂和/或固化剂反应，使第二层与热固性树脂之间形成化学键连接，从而达到提高第二层的环氧树脂间结合力，提高第二层与热固性树脂的结合力的目的。
封端异氰酸酯是指含异氰酸酯基团的化合物与封端剂反应，生成室温稳定、但在高温下可重新分解为异氰酸酯的化合物。
具体而言，含异氰酸酯基团的化合物可以举出：甲苯二异氰酸酯、苯二亚甲基二异氰酸酯、亚甲基二苯基二异氰酸酯、亚苯基二异氰酸酯、萘二异氰酸酯或联甲苯胺二异氰酸酯等芳香族二异氰酸酯、α，α，α’，α’-四甲基苯二亚甲基二异氰酸酯等具有芳香环的脂肪族二异氰酸酯、亚甲基二异氰酸酯、亚丙基二异氰酸酯、赖氨酸二异氰酸酯、三甲基六亚甲基二异氰酸酯、六亚甲基二异氰酸酯等脂肪族二异氰酸酯、环己烷二异氰酸酯、甲基环己烷二异氰酸酯、异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯或异亚丙基二环己基二异氰酸酯等脂环族二异氰酸酯等。这些物质可以单独使用，也可以多种并用。
所述封端剂是指酚类、吡啶酚及相应的巯基化合物，醇类、硫醇类及其 他含羟基的化合物，肟类，酰胺、环酰胺及酰内胺类，咪唑、咪唑啉、脒及相关化合物，吡唑类、三唑类，胺类，活泼亚甲基化合物、无机酸类等的一种或多种。具体可以举出，苯酚、甲酚、邻苯二酚、甲氧基苯酚、对氯苯酚、2-羟基吡啶、3-羟基喹啉、8-羟基吡啶、正丁醇、二甲氨基乙醇、丙烯酸羟乙醇、2-三氟乙醇、三苯硫醇、己硫醇、十二烷基硫醇、N-羟基丁二酰胺、N-吗啉代乙醇、2-羟甲基吡啶、乙二醇单乙醚、二乙二醇单乙醚、丁酮肟、乙酰苯胺、N-甲基乙酰胺、内酰胺、己内酰胺、咪唑、2-乙基-4-甲基咪唑、环脒、二咪唑啉、嘧啶、1，2，4-三唑、N-甲基苯胺、N-甲氧基苯胺、二苯胺、N-苯基萘胺、二叔丁基胺、二异丙基胺、N-甲基己胺、二环己基胺、2，6-二哌啶、丙二酸二乙酯、乙酰乙酸乙酯、β-二羰基化合物、KHSO 3、NaHSO 3、HCl、HCN、乙醇酸、丙基乙酸、异丙基乙醇酸等。
具体而言，封端异氰酸酯可以举出，三井化学株式会社的TAKENATE系列，厦门爱珂玛化工有限公司的HIBLOCK系列，上海宜涂实业有限公司的BL-175系列，江阴格泰化工有限公司的GT-5100系列，张家港市天一化工有限公司的HR-0325系列，英国巴辛顿的Trixene系列。
如果第二层中含有封端异氰酸酯基化合物，可以通过红外光谱在一定温度下对第二层的外表面进行测试，来检测异氰酸酯基含量的变化。进一步的，本发明所述的热固性树脂成型用薄膜材料优选满足在120℃加热10min后，相对于加热前，异氰酸酯基的含量提高5～20％。
作为含有环氧基、羟基、羧基、酸酐基或胺基的化合物，具体可以举出，缩水甘油，偏苯三酸酐，3-羟基丙酸，2-四氢糠胺，L-天门冬氨酸，β-氨基丙酸，酒石酸二乙酯等。
进一步的，为了使第二层对热固性树脂有良好的结合力，所述的第二层 的外表面的粗糙度优选高于0.5μm。所述的外表面是所述热固性树脂成型时薄膜材料同热固性树脂接触的表面。如果低于此要求，成型工艺条件下，第二层可能不会从所述的第一层转移到热固性树脂表面，或第二层在转移后容易从热固性树脂表面脱落。所述的第二层的外表面的粗糙度进一步优选高于1μm。
考虑到在所述的第二层转移到热固性树脂上后，可能需要在第二层的外侧再设置额外的层，为了易于设置额外的层，进一步的，第二层的内表面的粗糙度优选高于0.1μm。所述的内表面为上述第二层的外表面的反面。所述的第二层的内表面的粗糙度进一步优选高于0.5μm。
为了使第二层的内表面的粗糙度高于0.1μm，也可以对第二层内表面直接接触的层的表面进行粗糙化处理。粗糙化处理是指通过对表面处理，使表面具有的较大的间距和微大峰谷的不平度。粗糙化处理方式具体可以指，电镀、化学镀、热浸镀、电晕处理法、机械打毛法、涂层法、真空镀膜、氧化处理、装饰涂层、氧化处理法、溶剂处理法、或火焰处理法。第一层的粗糙化可以选择电晕处理法、机械打毛法、涂层法、氧化处理法、溶剂处理法、或火焰处理法中的一种或多种。
所述的第二层可以通过以下方法进行制备：通过喷涂、刷涂、浸渍法、辊涂、或淋涂等方式涂装在第一层上。喷涂是指通过喷枪或碟式雾化器，借助压力或离心力，将涂料分散成均匀而微细的雾滴，施涂于被涂物表面的涂装方法。刷涂指人工用毛刷蘸取涂料涂刷于被涂物表面的方法。浸渍法是指将固体粉末或一定形状及尺寸的已成型的固体浸泡在含有活性组分的可溶性化合物溶液中，接触一定的时间后分离残液，使活性组分以离子或化合物的形式附着在固体上的方法。辊涂是指在辊上形成一定厚度的湿涂层，随后通 过辊筒时将部分或全部湿涂层转涂到工件上的方法。淋涂是指通过淋头，形成均匀的漆幕淋在被涂物表面的涂装方法。具体而言，在生产条件下，第二层可以通过配置有逗号辊、微凹辊等涂布辊的涂布机进行辊涂。实验室条件下，可以使用湿膜制备器、线棒等涂膜工具进行涂布。
所述的第二层，其厚度要求需要根据第二层的粘度和固化时间等性能、实施工艺条件来设定。第二层的厚度优选为25～250μm，进一步优选第二层的厚度为30～200μm。
为了在所述的第二层全部或部分从所述热固性树脂成型用薄膜材料转移到热固性树脂成型品之后，具有能够透过第二层观察到内侧热固性树脂表面的效果，所述的热固性树脂成型用薄膜材料优选具有如下性能：在上述第二层厚度前提下，所述的第二层的透光率在20％以上。如果透光率低于20％，则由于第二层过高的遮盖作用，观测不到内侧热固性树脂表面。所述的透光率是指利用Suga公司的HZ-V3雾度计测定的透过所述的第二层的光通量占入射光通量的百分率。进一步的，为了能够透过第二层，清楚观察到内侧热固性树脂表面的效果，透光率优选为40％以上。
进一步的，为了能够确认成型后，所述的第二层在热固性树脂表面的转移效果，所述的热固性树脂成型用薄膜材料具有如下性能：所述的第二层与热固性树脂的色差ΔE在0.5以上。所述的色差特指所述的第二层与热固性树脂的颜色差别。可利用电色公司的NF333便携式色度仪，测定所述的第二层与未使用所述的热固性树脂成型用薄膜材料的热固性树脂成型品间的色差ΔE。所述的第二层与热固性树脂的色差ΔE低于0.5时，则第二层与热固性树脂的颜色过于接近，无法准确判断所述的第二层是否转移至热固性树脂表面。
为了调整第二层与热固性树脂的色差，所述的第二层优选含有着色剂。所述的着色剂包括颜料和染料。颜料是指不溶于水、油、溶剂、树脂等介质中，但能分散在各种介质中的一系列有色的细颗粒粉状物质。可以是天然矿物颜料、金属的氧化物颜料、硫化物颜料、硫酸盐颜料、铬酸盐颜料、钼酸盐颜料、炭黑颜料、偶氮颜料、酞菁颜料、杂环颜料、色淀颜料、荧光颜料等一种或多种。具体可以举出，朱砂、红土、雄黄、硅灰石、滑石粉、二氧化钛、氧化铁、氧化铬、镉黄、镉红、铬黄、铬橙、钼红、色素炭黑、颜料黄93、酞菁蓝颜料、喹吖啶酮类颜料、立索尔大红颜料、或荧光黄YG-51颜料等。染料是指能溶于水或其他介质以制成溶液或分散液，从而使材料着色的一类有色有机化合物。可以是直接染料、酸性染料、金属络合染料、还原染料、硫化染料、分散染料、活性染料、阳离子染料、缩聚染料、氧化染料、溶剂染料的一种或多种。具体可以举出，葸醌染料、偶氮染料、靛蓝、硫靛、苯胺黑、酞箐类染料、多甲川类染料、芳甲烷类染料、硝基类染料、亚硝基类染料等。
进一步的，为了使所述第二层在所述热固性树脂的成型时，更好的由第一层转移到热固性树脂上，所述的第一层的至少一个表面的表面张力在40mN/m以下。考虑到需要进一步提高第二层在成型时的转移能力，第一层的至少一个表面的表面张力进一步优选35mN/m以下。考虑到所述的薄膜材料的可操作性，第一层的至少一个表面的表面张力进一步优选10mN/m以上。
进一步的，为了使所述第二层在所述热固性树脂的成型时，更好的由第一层转移到热固性树脂上，所述的热固性树脂成型用薄膜材料还包含第三层，且第三层至少一个表面的表面张力优选在40mN/m以下。考虑到进一步提高第二层在所述热固性树脂的成型时的转移能力，第三层至少一个表面的表面 张力进一步优选35mN/m以下。考虑到所述的薄膜材料的可操作性，第三层的至少一个表面的表面张力进一步优选10mN/m以上。第三层可以设置在第一层与第二层之间，用于提供离型性能。
所述的第三层，可以通过公知的方法调节其表面张力，比如通过在第三层设置含有含硅元素和/或氟元素的化合物中的一种或多种。其中，含硅的化合物可以是有机硅聚合物，可以列举出聚乙烯基三异丙氧基硅烷、聚乙烯基三甲氧基硅烷、聚乙烯基三乙氧基硅烷、聚乙烯基三丙氧基硅烷等聚硅氧烷及其衍生物(硅油)。含氟的化合物可以是含氟聚合物，可以列举出聚四氟乙烯、乙烯-聚四氟乙烯共聚物、或含氟乙烯基改性硅油等。所述的第三层可以通过使单体在催化剂的作用下与交联剂进行反应后，将其涂布在基材表面或者直接通过混炼挤出方法来进行制备。
进一步优选的，所述的第一层的单侧设置有所述第二层，另一侧设置有粘着层。所述的粘着层通过粘接所述的热固性树脂成型用薄膜材料和热固性树脂成型模具表面，达到在模具表面上固定热固性树脂成型用薄膜材料的效果，且能够使热固性树脂成型用薄膜在使用结束后，从成型模具表面上剥离，成型模具表面没有或很少有粘着层残留。
进一步的，所述的粘着层含有天然高分子、聚乙烯醇、聚酰胺树脂、聚氨酯树脂、丙烯酸树脂、聚酯树脂或有机硅树脂中的一种或多种。具体可以举例，水性胶粘剂：如淀粉类、纤维素类、聚乙烯醇类；溶剂型胶粘剂：如丙烯酸类、聚氨酯类；乳液型胶粘剂：如聚乙酸乙烯酯乳液；热固化型胶粘剂：如环氧树脂类、有机硅树脂类、不饱和聚酯树脂类；紫外线固化型胶粘剂：如丙烯酸酯类；厌氧固化型：如丙烯酸酯类；湿固化胶粘剂：如氰基丙烯酸酯类、聚氨酯类；缩聚反应型：如尿烷类；自由基聚合型：如丙烯酸酯 类；热熔型胶粘剂：如丙烯酸酯类、聚酰胺树脂类、聚酯树脂类；再湿型胶粘剂：如淀粉类；压敏型胶粘剂：如丙烯酸酯类。
所述的粘着层，其厚度可以根据胶粘剂的粘度及固化时间等性能、实施工艺条件等来设定。推荐粘着层的厚度为1～100μm，优选为2～80μm。
粘着层的设置方法可以使用公知的方法，例如参考上述第二层的设置方法。
所述的热固性树脂优选含有环氧树脂、聚氨酯树脂、丙烯酸树脂、不饱和聚酯树脂、酚醛树脂、三聚氰胺甲醛树脂或呋喃树脂中的一种或多种。具体而言，作为所述的热固性树脂的原料，可以列举下述这些。例如，作为环氧树脂类，可以举出：陶氏化学公司产Airstone系列760E/766H、上纬(上海)精细化工有限公司的2511-1A/2511-1BC系列、日本昭和高分子的R-802系列等。作为聚氨酯树脂类，可以举出：科思创聚合物(中国)有限公司的78BD075/44CP20系列等。作为丙烯酸树脂类，可以举出：北京骏丰源化工有限公司的10031/7662系列等。作为乙烯基酯树脂类，可以举出：华昌聚合物有限公司的MFE-VARTM-200系列、美国亚什兰AROPOL G300系列等。作为酚醛树脂类，可以举出：山东佰仟化工有限公司的HK2506系列、无锡博瑞宇化工科技有限公司的2124系列等。作为呋喃树脂类，可以举出：无锡长干化工有限公司的NPEL128系列等。
进一步的，所述的热固性树脂中还含有无机物，以增强其力学性能。所述的无机物包括但不限于玻璃纤维、石棉纤维、碳纤维、石墨纤维、金属纤维、钛酸钾晶须、硼酸铝晶须、镁系晶须、硅系晶须、硅灰石、海泡石、石棉、矿渣纤维、硬硅钙石、硅磷灰石、石膏纤维、二氧化硅纤维、二氧化硅/氧化铝纤维、氧化锆纤维、氮化硼纤维、氮化硅纤维或硼纤维等纤维状无机 物中的一种或多种，或玻璃薄片、非膨润性云母、膨润性云母、石墨、金属箔、陶瓷珠粒、滑石、粘土、云母、绢云母、沸石、膨润土、蛭石、蒙脱土、白云石、高岭土、微粉硅酸、长石粉、钛酸钾、微细中空玻璃球、碳酸钙、碳酸镁、硫酸钙、二氧化钛、氧化硅、石膏、均密石英岩、片钠铝石或白土等片状或粒状无机物中的一种或多种。
热固性树脂的成型工艺包括手糊成型、注射成型、真空袋压法成型、挤出成型、压力袋成型、纤维缠绕、树脂传递成型、真空辅助树脂注射成型、连续板材成型、拉挤成型、离心浇铸成型、层压或卷制成型、夹层结构成型、模压成型、冲压成型或喷射成型等。本发明所述的热固性树脂成型具体可以是手糊成型、纤维缠绕成型、树脂传递成型、真空辅助树脂注射成型、拉挤成型、模压成型或预浸料铺放等工艺中的任一种或多种。
本发明的热固性树脂成型用薄膜材料可以在各种热固性树脂的成型工程上使用，比如风力发电机叶片、汽车、火车、飞机等交通工具、电子元器件、成型加饰板等的成型工程上应用，以达到高效生产、尺寸精度高、树脂表面低污染、生产过程环境友好的有益效果。
本发明还提供上述的热固性树脂成型用薄膜材料在汽车、火车、飞机等交通工具、电子元器件、成型加饰板等领域，尤其是风力发电机叶片成型上的应用。
本发明还提供上述的热固性树脂成型用薄膜材料制造的产品，尤其是风力发电机叶片。在风力发电机叶片的真空成型工艺中使用时，第二层可以转移到叶片(主要由环氧树脂或聚氨酯树脂组成)的表面，起到底漆或底漆和面漆的作用，从而省去了现有工艺中底漆涂覆前打磨叶片表面的工序和底漆(以及面漆)涂覆的工序，使得工艺流程简化，缩短工艺时间、节省人工、 降低VOC排放。在第二层转移到叶片表面后，可直接透过第二层观测到内侧热固性树脂的表面，有助于检测和直接观察判断热固性树脂表面存在的缺陷和位置，精确进行修补工艺。另一方面，本发明的热固性树脂成型用薄膜材料能够从叶片模具上直接脱离，没有或很少有残胶，不需对模具进行清理，减少对模具的磨损，延长模具使用期限。
具体实施方式
通过以下实施例对本发明做更详细的描述，但所述实施例不构成对本发明的限制。
实施例与对比例中使用的测试方法如下，对于所有测试，如果没有明确说明测试温度，则在23℃时测试。
1.厚度：
使用测厚仪进行测试。测试样品3个不同位置的厚度，取这3个厚度的算术平均值作为该试样厚度。
2.热固性树脂成型用薄膜材料的剥离强度：
热固性树脂成型用薄膜材料的剥离强度指第一层和第二层的剥离强度，单位N/cm(剥离强度)：用TESA7475测试胶带对第二层进行补强，样品尺寸为150mm×10mm，使用拉伸机进行180°剥离强度、剥离速度为200mm/min。测试样品数量为3，取3次测试结果的算术平均值作为剥离强度结果。
3.透光率：
是指透过第二层的光通量占入射光通量的百分率。将第二层从第一层上完整地剥离，利用Suga公司的HZ-V3雾度计，选择D65光源对第二层进行透光率测定。测试样品数量为3，取3次测试结果的算术平均值作为透光率结果。
4.第二层的转移性：
首先，按照以下方法制备环氧树脂成型品：将热固性树脂成型用薄膜材料铺在成型模具上方，按照风电叶片真空成型步骤设置辅助材料，用陶氏化学公司产的Airstone系列760E/766H环氧树脂，以760E与766H的质量比为100∶32的比例混合后，进行真空灌注操作，通过80℃、0.1MPa、2小时真空成型后，冷却至23℃，脱去模具，得到厚度为6mm的环氧树脂成型品。
继而通过红外光谱法分别测定转移后的热固性树脂成型用薄膜材料表面(成型时与热固性树脂贴合的面)和热固性树脂成型品的外表面(成型时与热固性树脂成型用薄膜材料贴合的面)，根据两个表面上第二层成分的测定结果，进行以下判定：
○：转移性优，仅热固性树脂成型品的外表面上检测出第二层的成分；
△：转移性中，两个表面上都检测出第二层的成分；
×：转移性差，仅热固性树脂成型用薄膜材料表面上检测出第二层成分。
5.色差：
色差指热固性树脂成型用薄膜材料的第二层与热固性树脂间的颜色差异。将所述的第二层和未使用所述热固性树脂成型用薄膜材料的热固性树脂成型品分别垫于同一规格的黑色板上，将电色公司的NF333便携式色度仪设置为色差测试模式，以所述的第二层作为色差测定基准样品，测定得到基准值。再对未使用所述热固性树脂成型用薄膜材料的热固性树脂成型品进行测定，根据仪器显示得到两者间色差ΔE。测试样品数量为3，取3次测试结果的算术平均值作为色差ΔE结果。
6.第二层的环氧树脂结合力：
第二层的环氧树脂结合力，单位MPa。按照下述方法制备成型样品：使 用陶氏化学公司产的Airstone系列760E/766H环氧树脂，以760E与766H的质量比为100∶32的比例混合后，在本发明的热固性树脂成型用薄膜材料的所述第二层上，铺设8层玻璃纤维(泰山玻纤，三轴，1200g/m 2)和脱模布、多孔膜、导流网、真空袋膜等辅材后，进行真空灌注操作，通过80℃、0.1MPa、2小时固化处理后，得到厚度为6mm的环氧树脂成型品，于23℃下移除本发明的热固性树脂成型用薄膜材料时，所述第二层从热固性树脂成型用薄膜材料上转移到环氧树脂成型品的表面。
在成型品的外表面选定平整位置，将其作为测试位置，用120目砂纸轻微打磨测试位置至无光泽。测定仪器为北京中测三友科技有限公司的XH-M便携式附着力测试仪，将测试仪配套的20mm测试锭子用MC1500胶粘剂粘接在测试位置上，放置2小时后测试。测试3个不同位置的结合力，取这3个结果的算术平均值作为该试样的第二层的环氧树脂结合力结果。
7.异氰酸酯基团提高含量测定：
通过赛默飞世尔科技(中国)有限公司的iZ10傅立叶红外(FT-IR)光谱仪对热固性成型用薄膜材料的第二层表面进行FTIR-ATR测试。再将同一热固性成型用薄膜材料在120℃下加热10min，对第二层表面进行第二次FTIR-ATR测试，将加热处理前后的测试图像中的烷基伸缩振动区域进行高度归一化处理后，对比-NCO区域高度，得到异氰酸酯基团提高的比例。
8.表面粗糙度：
使用触针式粗糙度轮廓测试仪(厦门金河源科技有限公司，TR200)进行测试。设定测试速度为0.5mm/s。测试3个不同位置的表面粗糙度，取3次测试结果的算术平均值作为表面粗糙度结果。第二层的外表面粗糙度通过测试第二层的外表面得到。第二层的内表面粗糙度通过测试设置第二层前的第 一层的表面(或将要设置第二层的表面)得到。
9.表面张力测试：
按照ASTM D2578-99a，使用符合标准规格的达因笔或者达因液进行测试。
10.元素测定：
利用日立S-3400N型扫描电镜，EDX型号为Apollo X，测定热固性树脂成型用薄膜材料的第三层所含元素。
实施例和对比例中使用的原料如下：
<第一层(包括带有第三层时的情况)>
A1：东丽株式会社产聚对苯二甲酸乙二醇酯离型膜
Figure PCTCN2018122071-appb-000001
XD-55YR。厚度50μm，纵向拉伸强度为153MPa，断裂伸长率为38.6％。单面为离型表面，通过硅离型处理，通过扫描电镜的EDX元素分析到离型表面有硅元素的存在，离型表面的表面张力为20mN/m；非离型面的表面张力为30mN/m。两表面粗糙度都为0.1μm。本薄膜为带有离型表面的第一层(即，带有第三层的第一层)。
A2：东丽株式会社产聚烯烃薄膜
Figure PCTCN2018122071-appb-000002
7H55G。厚度30μm，单面为自粘性表面，自粘性表面的表面张力为20mN/m，粗糙度为0.1μm；非自粘面表面张力为25mN/m，粗糙度为0.2μm。
A3：东丽株式会社产双向拉伸聚丙烯薄膜
Figure PCTCN2018122071-appb-000003
50-2500A。厚度为50μm。两表面的表面张力都为18mN/m，粗糙度都为0.1μm。
<第二层>
B1：上海麦加涂料有限公司产WU233A/B，其中WU233A为主剂，固含量为97％，主要成份为聚氨酯类化合物；WU233B为固化剂，固含量为99％，主要成 份为六亚甲基二异氰酸酯三聚体。按照WU233A∶WU233B＝3∶2的质量比混合后，待用。该涂层的固化条件为23℃、24小时。
B2：庞贝捷涂料(上海)有限公司产LT255/LW7260：其中LT255为主剂，固含量为72％，主要成分为聚酯多元醇类化合物；LW7260为固化剂，固含量为34％，主要成份为六亚甲基二异氰酸酯三聚体。按照LT255∶LW7260＝4∶1的质量比混合后，待用。干燥条件为100℃、4分钟，固化条件为23℃、24小时。
B3：骏和化工(上海)有限公司产JH-8152/3390：其中JH-8152为主剂，固含量为95％，主要成份为聚天门冬氨酸酯类化合物；3390为固化剂，固含量为98％，主要成分为六亚甲基二异氰酸酯三聚体。按照JH-8152∶3390＝4∶5的质量比混合后，待用。干燥条件为100℃、4分钟，固化条件为23℃、24小时。
B4：在B1的基础上，将WU233A中添加0.5％的XB-G282作为填料，其它不变。XB-G282是三井化学株式会社产的TAKENATE系列封端型异氰酸酯，具体为封闭氢化苯基甲烷二异氰酸酯，封闭剂为活性亚甲基类化合物。
B5：在B4的基础上，将XB-G282改为Sigma-Aldrich产缩水甘油，其它不变。
B6：在B4的基础上，将XB-G282改为阿拉丁试剂(上海)有限公司产偏苯三酸酐，其它不变。
B7：在B4的基础上，将XB-G282改为阿拉丁试剂(上海)有限公司产3-羟基丙酸，其它不变。
B8：在B4的基础上，将XB-G282改为阿拉丁试剂(上海)有限公司产L-天门冬氨酸，其它不变。
B9：在B4的基础上，将XB-G282重量份改为2重量份，其它不变。
B10：在B4的基础上，将XB-G282重量份改为0.5重量份，再添加0.5重量 份的缩水甘油，其它不变。
B11：在B1的基础上，将WU233A中添加1％的TiO 2作为填料，其它不变。
B12：在B1的基础上，在WU233A中添加0.5％的铁蓝颜料作为填料，其它不变。
<粘着层>
C1：安佐化学有限公司产Y-1210/Y-101，为丙烯酸酯型胶粘剂，其中Y-1210为主剂，固含量为36％；Y-101为固化剂，固含量为75％。Y-1210与Y-101质量配比为100∶0.56。粘度在25℃下为10000CPS，干燥条件为100℃，2分钟，固化条件为40℃，24小时。
C2：康利邦科技有限公司产UPSA-933A/B，为聚氨酯型胶粘剂，其中UPSA-933A为主剂，固含量主要成份为65％；UPSA-933B为固化剂，固含量为70％。质量配比为100∶6，干燥条件为100℃，3分钟，固化条件为80℃，24小时。
实施例1-12
按表1所示的组成，使用湿膜制备器在第一层的单面上涂敷第二层的原液后，在所使用第二层的固化条件下固化，得到厚度为100μm的第二层。其中，实施例1-3中，第二层设置在A1的非离型面上；实施例4-6中，第二层设置在A1的离型面上；实施例7-9中，第二层设置在A2的自粘性表面；实施例10-12中，第二层设置在A3的任意一面上。
对得到的样品进行各种性能测定，结果列于表1。
实施例13-15
按表2所示的组成，使用湿膜制备器在A2的自粘面上涂敷第二层的原液后， 在所使用第二层的固化条件下固化，得到厚度为100μm的第二层。
对得到的样品进行各种性能测定，结果列于表2。
实施例16-22
按表3所示的组成，使用湿膜制备器在A2的自粘面上涂敷第二层的原液后，在所使用第二层的固化条件下固化，得到厚度为100μm的第二层。
对得到的样品进行各种性能测定，结果列于表3。
实施例23-24
按表4所示的组成，使用湿膜制备器在A2的非自粘面上涂敷粘着层的原液后，在所使用的粘着层的固化条件下固化，得到厚度为5μm的粘着层。
继而，按表4所示的组成，使用湿膜制备器在第一层的另一面上涂敷第二层的原液后，于所使用的第二层的固化条件下固化，得到厚度为100μm的第二层。
对得到的样品进行各种性能测定，结果列于表4。
实施例25-27
对A1的离型面、A2的自粘面、A3的任意一面进行粗糙化处理，使A1的粗糙化处理面的粗糙度为3μm、A2的粗糙化处理面的粗糙度为0.6μm、A3的粗糙化处理面的粗糙度为1μm。
按表5所示的组成，使用湿膜制备器在第一层的非处理面上涂敷粘着层的原液后，于所使用的粘着层的固化条件下固化，得到厚度为5μm的粘着层。
继而，按表5所示的组成，使用湿膜制备器在第一层的另一面上涂敷第二层的原液后，于所使用的第二层的固化条件下固化，得到厚度为100μm的第二层。
对得到的样品进行各种性能测定，结果列于表5。
实施例28-29
按表6所示的组成，使用湿膜制备器在A2的非自粘面上涂敷粘着层的原液后，于所使用的粘着层的固化条件下固化，得到厚度为5μm的粘着层。
按表6所示的组成，使用湿膜制备器在A2的另一面上涂敷第二层的原液后，于所使用的第二层的固化条件下固化，得到厚度为100μm的第二层B1。对第二层B1外表面进行粗糙化处理，使B1的粗糙化处理面的粗糙度分别为0.6μm(实施例28)、2μm(实施例29)。
对得到的样品进行各种性能测定，结果列于表6。
实施例30-32
按表7所示的组成，使用湿膜制备器在A2的自粘面上涂覆第二层的原液后，于所使用的第二层的固化条件下固化，得到厚度为100μm的第二层后，对实施例30-32的第二层外表面进行红外光谱检测。
继而，将所述的热固性树脂成型用薄膜材料在120℃下加热10min，对加热后的实施例30-32的第二层外表面进行红外光谱检测。
利用两次红外光谱检测结果，测定异氰酸酯基团提高含量，结果列于表7。
对比例1
按表8所示的组成，使用湿膜制备器在第一层A1的非离型面上涂敷第二层C1的原液后，于所使用的第二层的固化条件下固化，得到厚度为100μm的第二层。测试得到第一层和第二层的剥离强度为35N/cm，第二层的转移性为×，即其无法转移。
由各实施例可见，本发明的热固性树脂成型用薄膜材料，其第二层可以在热固性树脂的成型过程中，转移到热固性树脂成型品的表面，起到有益效 果。
表1
Figure PCTCN2018122071-appb-000004
表2
Figure PCTCN2018122071-appb-000005
表3
Figure PCTCN2018122071-appb-000006
Figure PCTCN2018122071-appb-000007
表4
Figure PCTCN2018122071-appb-000008
表5
Figure PCTCN2018122071-appb-000009
表6
Figure PCTCN2018122071-appb-000010
Figure PCTCN2018122071-appb-000011
表7
Figure PCTCN2018122071-appb-000012
表8
项目 对比例1
第一层 A1
第二层 C1
剥离强度(N/cm) 35
转移性 ×
环氧树脂结合力(MPa) ×

Claims (21)

  1. 一种热固性树脂成型用薄膜材料，其特征在于：所述薄膜至少含有第一层和第二层，且在23℃时，所述第一层和所述第二层之间存在剥离强度在0.02～30N/cm之间的界面。
  2. 根据权利要求1所述的热固性树脂成型用薄膜材料，其特征在于：所述的第一层含有聚酯树脂、聚氨酯树脂、聚碳酸酯树脂、聚烯烃树脂、丙烯酸树脂、聚酰亚胺树脂、聚酰胺树脂、芳纶树脂或氟树脂中的一种或多种。
  3. 根据权利要求1所述的热固性树脂成型用薄膜材料，其特征在于：所述的第二层含有聚氨酯树脂、环氧树脂、不饱和聚酯树脂、丙烯酸树脂或氟树脂中的一种或多种。
  4. 根据权利要求1所述的热固性树脂成型用薄膜材料，其特征在于：所述的热固性树脂含有环氧树脂、聚氨酯树脂、丙烯酸树脂、不饱和聚酯树脂、酚醛树脂、三聚氰胺甲醛树脂或呋喃树脂中的一种或多种。
  5. 根据权利要求1所述的热固性树脂成型用薄膜材料，其特征在于：所述的第二层在23℃时的环氧树脂结合力为6MPa以上。
  6. 根据权利要求3所述的热固性树脂成型用薄膜材料，其特征在于：所述的第二层含有封端异氰酸酯基、环氧基、羟基、羧基、酸酐基或胺基化合物中的一种或多种。
  7. 根据权利要求6所述的热固性树脂成型用薄膜材料，其特征在于：在使用红外光谱法检测第二层的外表面的情况下，所述的热固性树脂成型用薄膜材料在120℃加热10min后，相对于加热前，异氰酸酯基的含量提高了5～20％。
  8. 根据权利要求1所述的热固性树脂成型用薄膜材料，其特征在于：所述的 第二层的透光率在20％以上。
  9. 根据权利要求1所述的热固性树脂成型用薄膜材料，其特征在于：所述的第二层与热固性树脂的色差ΔE在0.5以上。
  10. 根据权利要求9所述的热固性树脂成型用薄膜材料，其特征在于：所述的第二层含有着色剂。
  11. 根据权利要求1所述的热固性树脂成型用薄膜材料，其特征在于：所述的第一层的至少一个表面的表面张力在40mN/m以下。
  12. 根据权利要求1所述的热固性树脂成型用薄膜材料，其特征在于：还包含有第三层，且所述的第三层的至少一个表面的表面张力在40mN/m以下。
  13. 根据权利要求12所述的热固性树脂成型用薄膜材料，其特征在于：所述的第三层含有含硅元素和/或氟元素的化合物中的一种或多种。
  14. 根据权利要求1所述的热固性树脂成型用薄膜材料，其特征在于：所述的第二层的厚度在25～250μm之间。
  15. 根据权利要求1所述的热固性树脂成型用薄膜材料，其特征在于：所述的第二层的外表面的粗糙度高于0.5μm。
  16. 根据权利要求1所述的热固性树脂成型用薄膜材料，其特征在于：所述的第二层的内表面的粗糙度高于0.1μm。
  17. 根据权利要求1所述的热固性树脂成型用薄膜材料，其特征在于：所述的第一层的单侧设置有所述的第二层，另一侧设置有粘着层。
  18. 根据权利要求17所述的热固性树脂成型用薄膜材料，其特征在于：所述的粘着层含有聚酰胺树脂、聚氨酯树脂、丙烯酸树脂、聚酯树脂或有机硅树脂中的一种或多种。
  19. 根据权利要求4所述的热固性树脂成型用薄膜材料，其特征在于：所述的 热固性树脂中还含有无机物。
  20. 权利要求1-19中任一项所述的热固性树脂成型用薄膜材料在风力发电机叶片成型上的应用。
  21. 使用权利要求1-19中任一项所述的热固性树脂成型用薄膜材料制造的风力发电机叶片。
PCT/CN2018/122071 2017-12-27 2018-12-19 一种热固性树脂成型用薄膜材料及其应用 WO2019128802A1 (zh)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110588018A (zh) * 2019-09-24 2019-12-20 上海麦加涂料有限公司 一种风力发电机叶片用模内胶衣的涂装成型方法及风力发电机叶片成型方法
CN111173675A (zh) * 2020-02-18 2020-05-19 中材科技风电叶片股份有限公司 一种油漆预制膜、防护结构及其制备方法
CN112238626A (zh) * 2019-07-18 2021-01-19 东丽先端材料研究开发（中国）有限公司 一种灌注成型方法及其成型品
CN112238664A (zh) * 2019-07-18 2021-01-19 东丽先端材料研究开发（中国）有限公司 一种热固性树脂成型用薄膜材料及其成型品
CN112936914A (zh) * 2019-12-11 2021-06-11 东丽先端材料研究开发（中国）有限公司 一种复合薄膜及其应用
CN113733695A (zh) * 2020-05-28 2021-12-03 东丽先端材料研究开发（中国）有限公司 一种热固性树脂成型用复合薄膜及其应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023150439A1 (en) * 2022-02-03 2023-08-10 Prc-Desoto International, Inc. In-mold coating compositions and uses thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101022952A (zh) * 2004-07-20 2007-08-22 通用电气公司 多层膜、片材的制备方法及其制品
CN101631674A (zh) 2007-03-30 2010-01-20 大日本印刷株式会社 转印装饰片、装饰成型品的制造方法以及装饰成型品
CN101905622A (zh) 2009-06-02 2010-12-08 陈武 一种装饰用涂料转移膜
JP2015013465A (ja) * 2013-06-06 2015-01-22 住友ベークライト株式会社 離型フィルムおよび離型フィルムの使用方法
WO2016133092A1 (ja) * 2015-02-18 2016-08-25 リンテック株式会社 離型フィルム
CN106068550A (zh) 2014-03-07 2016-11-02 旭硝子株式会社 脱模膜、以及密封体的制造方法
CN106166863A (zh) * 2016-08-11 2016-11-30 苏州柯创电子材料有限公司 耐高温复合离型膜

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000108149A (ja) * 1998-10-02 2000-04-18 Sekisui Chem Co Ltd 表面に模様を有する熱硬化性樹脂成形品の製造方法
WO2002008318A1 (fr) * 2000-07-21 2002-01-31 Kansai Paint Co., Ltd. Film de resine urethane fonctionnel et film lamelle comprenant ce film
US7666510B2 (en) * 2005-09-07 2010-02-23 Transitions Optical, Inc. Optical elements that include curable film-forming compositions containing blocked isocyanate adhesion promoters
JP5493938B2 (ja) 2009-04-28 2014-05-14 東洋紡株式会社 成型用積層ポリエステルフィルム
JP5577673B2 (ja) 2009-10-26 2014-08-27 大日本印刷株式会社 転写加飾フィルム及びその製造方法並びにそれを用いた加飾成形品及びその製造方法
JP5732779B2 (ja) 2010-08-20 2015-06-10 大日本印刷株式会社 加飾シート
JP5706221B2 (ja) 2011-04-13 2015-04-22 帝人デュポンフィルム株式会社 成形用離型ポリエステルフィルム
JP5910196B2 (ja) 2012-03-14 2016-04-27 東レ株式会社 フィルムおよびそれを用いた積層シート
WO2014068925A1 (ja) * 2012-10-29 2014-05-08 凸版印刷株式会社 転写フィルム、成形品の製造方法及び成形品
JP6083233B2 (ja) * 2012-12-19 2017-02-22 Jnc株式会社 インモールド成形用転写フィルム、インモールド成形体の製造方法および成形体
EP2956498B1 (de) 2013-02-12 2023-10-11 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Silikonbeschichtete trennfolien mit besonderer vakuumtiefziehfähigkeit
JP6184742B2 (ja) 2013-05-16 2017-08-23 株式会社ユポ・コーポレーション インモールド成形用ラベル
EP2942174B1 (en) * 2014-05-07 2016-09-21 Siemens Aktiengesellschaft Method of preparing a mould for vacuum resin transfer moulding

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101022952A (zh) * 2004-07-20 2007-08-22 通用电气公司 多层膜、片材的制备方法及其制品
CN101631674A (zh) 2007-03-30 2010-01-20 大日本印刷株式会社 转印装饰片、装饰成型品的制造方法以及装饰成型品
CN101905622A (zh) 2009-06-02 2010-12-08 陈武 一种装饰用涂料转移膜
JP2015013465A (ja) * 2013-06-06 2015-01-22 住友ベークライト株式会社 離型フィルムおよび離型フィルムの使用方法
CN106068550A (zh) 2014-03-07 2016-11-02 旭硝子株式会社 脱模膜、以及密封体的制造方法
WO2016133092A1 (ja) * 2015-02-18 2016-08-25 リンテック株式会社 離型フィルム
CN106166863A (zh) * 2016-08-11 2016-11-30 苏州柯创电子材料有限公司 耐高温复合离型膜

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3756883A4

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112238626A (zh) * 2019-07-18 2021-01-19 东丽先端材料研究开发（中国）有限公司 一种灌注成型方法及其成型品
CN112238664A (zh) * 2019-07-18 2021-01-19 东丽先端材料研究开发（中国）有限公司 一种热固性树脂成型用薄膜材料及其成型品
CN112238626B (zh) * 2019-07-18 2024-01-30 东丽先端材料研究开发（中国）有限公司 一种灌注成型方法及其成型品
CN112238664B (zh) * 2019-07-18 2024-05-03 东丽先端材料研究开发（中国）有限公司 一种热固性树脂成型用薄膜材料及其成型品
CN110588018A (zh) * 2019-09-24 2019-12-20 上海麦加涂料有限公司 一种风力发电机叶片用模内胶衣的涂装成型方法及风力发电机叶片成型方法
CN112936914A (zh) * 2019-12-11 2021-06-11 东丽先端材料研究开发（中国）有限公司 一种复合薄膜及其应用
CN111173675A (zh) * 2020-02-18 2020-05-19 中材科技风电叶片股份有限公司 一种油漆预制膜、防护结构及其制备方法
CN113733695A (zh) * 2020-05-28 2021-12-03 东丽先端材料研究开发（中国）有限公司 一种热固性树脂成型用复合薄膜及其应用

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