WO2017016436A1 - 预浸纤维布及其制备方法 - Google Patents

预浸纤维布及其制备方法 Download PDF

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Publication number
WO2017016436A1
WO2017016436A1 PCT/CN2016/090901 CN2016090901W WO2017016436A1 WO 2017016436 A1 WO2017016436 A1 WO 2017016436A1 CN 2016090901 W CN2016090901 W CN 2016090901W WO 2017016436 A1 WO2017016436 A1 WO 2017016436A1
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WIPO (PCT)
Prior art keywords
fiber cloth
resin
parts
fiber
prepreg
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Ceased
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PCT/CN2016/090901
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English (en)
French (fr)
Inventor
崔静娜
毛定文
黄小萍
罗文海
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BYD Co Ltd
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BYD Co Ltd
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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
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/248—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using pre-treated fibres
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the present disclosure relates to prepreg fiber cloths and methods of making same.
  • prepreg fiber cloth is usually pre-impregnated with prepreg, and the prepreg used in the prior art usually contains unsaturated polyester resin, vinyl resin, phenylpropazine resin, phenolic resin, The urea resin, the epoxy resin or the melamine resin, the prepreg fiber cloth obtained by pre-impregnating the prepreg is insufficient in interlayer bonding force when it is heat-compressed into a composite sheet by alternately laminating.
  • the inventors of the present disclosure have unexpectedly found that when a resin composition containing a thermosetting binder resin and chopped fibers is impregnated into a fiber cloth, if the length of the chopped fibers is 50 ⁇ m to 2 mm, the effect can be remarkably improved.
  • the present disclosure provides a prepreg fiber cloth comprising a fiber cloth and a resin bonding layer, at least part of a surface of the fiber cloth being coated with the resin bonding layer, wherein the resin bonding layer and The chopped fibers are embedded between the fiber cloths, and the chopped fibers have a length of 50 ⁇ m to 2 mm.
  • the present disclosure also provides a method of preparing the above prepreg fiber cloth, comprising impregnating a resin composition containing a thermosetting binder resin and chopped fibers into a fiber cloth, and heat curing, wherein the chopped fiber The length is 50 ⁇ m-2mm.
  • the prepreg fiber cloth according to the present disclosure has excellent interlayer adhesion when heat pressed into a composite sheet.
  • FIG. 1 is a schematic view of the fiber panels X1, X2, and X3 in Test Example 1.
  • FIG. 2 is a schematic view of the fiber panels Y1, Y2, and Y3 in Test Example 1.
  • Test Example 4 is a schematic view of a sample to be tested in Test Example 1.
  • Fig. 5 is a schematic view showing the test of the sample to be tested in Test Example 1.
  • the prepreg fiber cloth provided by the present disclosure includes a fiber cloth and a resin bonding layer, at least part of the surface of the fiber cloth is coated with a resin bonding layer, wherein the resin bonding layer and the fiber cloth are embedded There are chopped fibers, and the chopped fibers have a length of 50 ⁇ m to 2 mm.
  • all surfaces of the fiber cloth are coated with a resin bonding layer.
  • the present disclosure mainly improves the prepreg fiber cloth by embedding chopped fibers between the resin bonding layer and the fiber cloth. The roughness of the surface, thereby improving the interlayer bonding force when the impregnated fiber cloth is hot pressed into the composite sheet.
  • the length of the chopped fibers described above is optionally from 75 ⁇ m to 1 mm.
  • the diameter of the chopped fibers may vary over a wide range.
  • the chopped fibers may have a cross-sectional diameter of from 0.5 ⁇ m to 20 ⁇ m, for example from 1 ⁇ m to 10 ⁇ m.
  • the chopped fibers are one or more of glass fibers, carbon fibers, and aramid fibers.
  • the fiber cloth is not particularly limited, and the material thereof may be various conventional ones, for example, one or more of glass fiber cloth, carbon fiber cloth, and aramid fiber cloth, or A blended fabric of two or more kinds of glass fibers, carbon fibers, and aramid fibers.
  • the mass per unit area of the fiber cloth is not particularly limited, and may specifically vary within a wide range.
  • the fiber cloth has a mass per unit area of 20-700 g/m 2 , for example, 50-300 g. /m 2 .
  • the resin bonding layer is used to bond each prepreg fiber cloth into one body.
  • the resin adhesive layer may be a layer obtained by curing a resin composition containing a thermosetting binder resin and chopped fibers.
  • thermosetting binder resin is optionally one or more of an acrylic resin, an epoxy resin, a polyurethane resin, a polyester resin, a benzoxazine resin, a phenol resin, a urea resin, and a melamine resin.
  • an acrylic resin an epoxy resin, a polyurethane resin, a polyester resin, a benzoxazine resin, a phenol resin, a urea resin, and a melamine resin.
  • epoxy resin epoxy resin.
  • the resin composition further contains a reactive diluent.
  • the reactive diluent is contained in an amount of 10 to 55 parts by weight with respect to 100 parts by weight of the thermosetting binder resin; alternatively, with respect to 100 parts by weight of the thermosetting binder resin, The reactive diluent is contained in an amount of from 13 to 53 parts by weight.
  • the reactive diluent is optionally propylene glycidyl ether, butyl glycidyl ether, ethylene glycol diglycidyl ether, resorcinol diglycidyl ether, hexanediol diglycidyl ether, butanediol II Shrink
  • the reactive diluent is butyl glycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl One or more of an ether and an alkyl polyglycidyl ether.
  • neopentyl glycol diglycidyl ether is one or more of an ether and an alkyl polyglycidyl ether.
  • the resin composition further contains a curing agent.
  • the curing agent is contained in an amount of 1-55 parts by weight relative to 100 parts by weight of the thermosetting binder resin; alternatively, relative to 100 parts by weight of the thermosetting binder resin, The curing agent is contained in an amount of 2 to 50 parts by weight.
  • the curing agent may be various curing agents for curing which are commonly used in the art.
  • dicyandiamide for example, dicyandiamide.
  • the resin composition may further contain a curing accelerator.
  • the curing accelerator is contained in an amount of 0 to 10 parts by weight with respect to 100 parts by weight of the thermosetting binder resin; alternatively, with respect to 100 parts by weight of the thermosetting binder resin, The curing accelerator is contained in an amount of from 0.9 to 8.8 parts by weight.
  • the curing accelerator may be various curing accelerators commonly used in the art.
  • it may be one or more of an organic quinone compound, an imidazole compound, and a urea compound; for example, an imidazole compound; for example, 1-methylimidazole.
  • the resin composition may further contain one or more of an antifoaming agent, a leveling agent, and a wetting agent.
  • an antifoaming agent e.g., a leveling agent, and a wetting agent.
  • the foaming agent, the leveling agent, and the wetting agent are each contained in an amount of 0 to 12 parts by weight, for example, 1.5 to 11 parts by weight, per 100 parts by weight of the thermosetting binder resin.
  • the antifoaming agent, leveling agent and wetting agent can be various antifoaming agents, leveling agents and wetting agents commonly used in the art.
  • the antifoaming agent is one of a polyacrylic acid-polyether copolymer defoaming agent, a silicone defoaming agent, an organic modified silicone antifoaming agent, and a fluorosilicone defoaming agent.
  • the leveling agent is one or more of an acrylate, a polyether siloxane copolymer, and an organic modified polysiloxane
  • the wetting agent is a nonionic organic surfactant.
  • the resin bonding layer has a thickness of from 0.02 mm to 0.5 mm, for example, from 0.02 mm to 0.2 mm.
  • the chopped fiber surface is coated with a silane coupling agent.
  • a silane coupling agent By coating a surface of the chopped fiber with a silane coupling agent, a reactive group capable of chemically bonding with the surface of the fiber and a reactive group chemically bonded to the organic material, a bridge between the fiber and the prepreg resin can be used. The effect is such that the interlayer bonding force can be further improved.
  • the method of coating the surface of the chopped fiber with a silane coupling agent may be a method known in the art, for example, spraying a solution obtained by mixing a silane coupling agent with a dispersing agent and a solvent on the surface of the chopped fiber to be dried. .
  • the silane coupling agent may be various silane coupling agents commonly used in the art.
  • the silane coupling agent is one or more of an aminosilane, an epoxysilane, a thiosilane, a methacryloxysilane, a vinylsilane, a ureidosilane, and an isocyanatosilane.
  • the silane coupling agent is one or more of an aminosilane and an epoxysilane.
  • the dispersing agent may be various dispersing agents commonly used in the art, and is optionally water glass, sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, triethylhexylphosphoric acid, sodium lauryl sulfate, One or more of methylpentanol, a cellulose derivative, a polyacrylamide, a guar gum, an aliphatic polyethylene glycol ester, and a modified polyalkoxide.
  • the silane coupling agent and the dispersant solvent may be preferably used, and may be, for example, ethanol, xylene, n-butanol, ethylene glycol butyl ether, butyl acetate, isopropanol or a ring.
  • One or more of ketone and methyl isobutyl ketone may be used, for example, ethanol, xylene, n-butanol, ethylene glycol butyl ether, butyl acetate, isopropanol or a ring.
  • One or more of ketone and methyl isobutyl ketone isobutyl ketone.
  • the mixing mass ratio of the silane coupling agent, the dispersing agent and the solvent is optionally from 1:0.5 to 5:50 to 200; for example, 1:3:100.
  • the present disclosure also provides a method of preparing a prepreg fiber cloth, comprising impregnating a resin composition containing a thermosetting binder resin and chopped fibers into a fiber cloth, and heat curing, wherein the chopped fiber The length is 50 ⁇ m-2mm.
  • the content of the chopped fiber is compared with 100 parts by weight of the thermosetting binder resin. It is 5 to 50 parts by weight; alternatively, the chopped fiber is contained in an amount of 8 to 38 parts by weight with respect to 100 parts by weight of the thermosetting binder resin.
  • the length is from 75 ⁇ m to 1 mm.
  • the diameter of the chopped fiber may vary over a wide range.
  • the chopped fiber may have a cross-sectional diameter of from 0.5 ⁇ m to 20 ⁇ m, for example, from 1 ⁇ m to 10 ⁇ m.
  • the chopped fiber is one or more of glass fiber, carbon fiber, and aramid fiber.
  • the resin composition contains a thermosetting binder resin.
  • the thermosetting binder resin may be selected from one or more of an acrylic resin, an epoxy resin, a polyurethane resin, a polyester resin, a benzoxazine resin, a phenol resin, a urea resin, and a melamine resin.
  • epoxy resin for example, epoxy resin.
  • the resin composition further contains a reactive diluent.
  • the reactive diluent may be used in an amount conventionally used in the art, and the reactive diluent is contained in an amount of 10 to 55 parts by weight based on 100 parts by weight of the thermosetting binder resin; alternatively, relative to 100
  • the heat-curable binder resin is contained in an amount of from 13 to 53 parts by weight based on parts by weight.
  • the reactive diluent is used for dissolving and dispersing a film-forming substance, and has a function of participating in a film-forming reaction during film formation of the coating material to form a component which does not exhibit a component remaining in the coating film.
  • a reactive diluent propylene glycidyl ether, butyl glycidyl ether, ethylene glycol diglycidyl ether, resorcinol diglycidyl ether, hexanediol diglycidyl ether, butylene glycol may be selected.
  • the reactive diluent is one or more of butyl glycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and alkyl polyglycidyl ether. .
  • it is neopentyl glycol diglycidyl ether.
  • the resin composition further contains a curing agent.
  • the curing agent may be used in an amount conventionally used in the art.
  • the curing agent is contained in an amount of 1-55 parts by weight relative to 100 parts by weight of the thermosetting binder resin; alternatively, relative The curing agent is contained in an amount of 2 to 50 parts by weight based on 100 parts by weight of the thermosetting binder resin.
  • the curing agent may be various curing agents commonly used in the art for curing, optionally diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone adipate dihydrazide, dicyandiamide Amine, triethylenediamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, montan diamine, isophoronediamine, N-aminoethylpiperazine, bis(4-amino-3- One or more of methylcyclohexyl)methane and bis(4-aminocyclohexyl)methane.
  • dicyandiamide for example, dicyandiamide.
  • the resin composition further contains a curing accelerator.
  • the curing accelerator may be used in an amount conventionally used in the art, and optionally, the curing accelerator is contained in an amount of from 0 to 10 parts by weight, based on 100 parts by weight of the thermosetting binder resin;
  • the content of the curing accelerator is from 0.9 to 8.8 parts by weight based on 100 parts by weight of the thermosetting binder resin.
  • the curing accelerator may be various curing accelerators commonly used in the art.
  • it may be one or more of an organic quinone compound, an imidazole compound, and a urea compound; alternatively, an imidazole compound; for example, 1-methylimidazole.
  • the resin composition may further contain one or more of an antifoaming agent, a leveling agent, and a wetting agent.
  • an antifoaming agent e.g., a leveling agent, and a wetting agent.
  • the foaming agent, the leveling agent, and the wetting agent are each contained in an amount of 0 to 12 parts by weight, for example, 1.5 to 11 parts by weight, per 100 parts by weight of the thermosetting binder resin.
  • the antifoaming agent is one of a polyacrylic acid-polyether copolymer defoaming agent, a silicone defoaming agent, an organic modified silicone antifoaming agent, and a fluorosilicone defoaming agent.
  • the leveling agent is one or more of an acrylate, a polyether siloxane copolymer, and an organic modified polysiloxane; and the wetting agent is a nonionic organic surfactant.
  • the method for preparing the prepreg fiber cloth according to the present disclosure is not particularly limited, and the material thereof may be various conventional ones, for example, one of glass fiber cloth, carbon fiber cloth, and aramid fiber cloth. A plurality of blended fabrics of two or more of the above glass fibers, carbon fibers, and aramid fibers may be used.
  • the thickness of the fiber cloth is not particularly limited, and may specifically vary within a wide range.
  • the mass per unit area of the fiber cloth is 20 g/m 2 - 700 g/m 2 is , for example, 100 g/m 2 to 200 g/m 2 .
  • the chopped fiber surface is coated with a silane coupling agent.
  • a silane coupling agent By coating a surface of the chopped fiber with a silane coupling agent, a reactive group capable of chemically bonding with the surface of the fiber and a reactive group chemically bonded to the organic material, a bridge between the fiber and the prepreg resin can be used. The effect is such that the interlayer bonding force can be further improved.
  • the method of coating the surface of the chopped fiber with a silane coupling agent may be a method known in the art, for example, a solution obtained by mixing a silane coupling agent with a dispersing agent and a solvent is sprayed on the surface of the chopped fiber.
  • the silane coupling agent may be various silane coupling agents commonly used in the art.
  • the silane coupling agent is One or more of aminosilane, epoxysilane, thiosilane, methacryloxysilane, vinylsilane, ureidosilane, and isocyanatosilane; alternatively, the silane coupling agent is Aminosilane and/or epoxysilane.
  • the dispersing agent may be various dispersing agents commonly used in the art, and is optionally water glass, sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, triethylhexylphosphoric acid, sodium lauryl sulfate, One or more of methylpentanol, a cellulose derivative, a polyacrylamide, a guar gum, an aliphatic polyethylene glycol ester, and a modified polyalkoxide.
  • the solvent may be any one of the silane coupling agent and the dispersant solvent, and may be, for example, ethanol, xylene, n-butanol, ethylene glycol butyl ether, butyl acetate, isopropanol or cyclohexane.
  • ethanol xylene
  • n-butanol ethylene glycol butyl ether
  • butyl acetate isopropanol or cyclohexane.
  • One or more of a ketone and a methyl isobutyl ketone isobutyl ketone.
  • the mixing mass ratio of the silane coupling agent, the dispersing agent and the solvent is optionally from 1:0.5 to 5:50 to 200; for example, 1:3:100.
  • the method comprises impregnating a resin composition containing a thermosetting binder resin and chopped fibers into a fiber cloth and heat curing to obtain a prepreg fiber. cloth.
  • a resin composition containing a thermosetting binder resin and chopped fiber into the fiber cloth various methods known in the art can be employed.
  • the resin composition may be mixed and dispersed to obtain a prepreg, and the prepreg is brought into contact with the fiber cloth, and then the contacted fiber cloth is subjected to heat curing treatment.
  • the order of mixing the components in the composition there is no particular requirement for the order of mixing the components in the composition, and it may be any.
  • the epoxy resin and the reactive diluent are mixed and dispersed, and then the chopped fibers are added for dispersion mixing, and then the curing agent, the curing accelerator and the antifoaming agent are added. Dispersion mixing is carried out to obtain a prepreg.
  • the conditions for bringing the prepreg into contact with the fiber cloth may be such that the chopped fibers can be pre-impregnated between the resin bonding layer and the fiber cloth.
  • the contacting can be carried out at room temperature (10 ° C to 40 ° C) for a time of 3 min to 30 min.
  • the conditions for the above heat curing may be specifically selected depending on the composition of the resin composition, but are usually heated at a temperature of from 60 ° C to 98 ° C for 10 min to 100 min.
  • the prepreg fiber cloth obtained by the method for producing a prepreg fiber cloth according to the present disclosure has excellent interlayer adhesion when heat-compressed into a composite sheet.
  • pretreatment agent on the surface of 4kg chopped fiber (glass chopped fiber, length 200 ⁇ m, cross-sectional diameter 10 ⁇ m), and drying to obtain pretreated fiber X;
  • step 2) The pretreated filament X obtained in step 2) is added to the mixture A, and dispersed by a high speed disperser to obtain a mixture B;
  • the cross section of the prepreg fiber cloth is observed by a microscope, and the surface of the fiber cloth is covered with a resin bonding layer, and chopped fibers are embedded between the resin bonding layer and the fiber cloth.
  • the thickness of the adhesive layer was 0.2 mm.
  • pretreatment agent on the surface of 8kg chopped fiber (glass chopped fiber, length 200 ⁇ m, cross-sectional diameter 10 ⁇ m), and drying to obtain pretreated fiber X;
  • step 2) The pretreated filament X obtained in step 2) is added to the mixture A, and dispersed by a high speed disperser to obtain a mixture B;
  • the cross section of the prepreg fiber cloth is observed by a microscope, and the surface of the fiber cloth is covered with a resin bonding layer, and chopped fibers are embedded between the resin bonding layer and the fiber cloth.
  • the thickness of the adhesive layer was 0.25 mm.
  • Preparing a pretreatment agent according to a ratio (mass ratio) of a silane coupling agent: a dispersing agent: ethanol 1:3:100;
  • pretreatment agent on 15kg chopped fiber (glass chopped fiber, length 200 ⁇ m, cross-sectional diameter 10 ⁇ m), and drying to obtain pretreated fiber X;
  • step 2) The pretreated filament X obtained in step 2) is added to the mixture A, and dispersed by a high speed disperser to obtain a mixture B;
  • a fiber cloth (carbon fiber cloth having a mass per unit area of 150 g/m 2 ) was pulled through a fiber prepreg (the contact time of the fiber cloth with the prepreg was 15 min) to obtain a fiber cloth coated with a prepreg.
  • the cross section of the prepreg fiber cloth is observed by a microscope, and the surface of the fiber cloth is covered with a resin bonding layer, and chopped fibers are embedded between the resin bonding layer and the fiber cloth.
  • the thickness of the adhesive layer was 0.15 mm.
  • Example 1 The procedure of Example 1 was carried out except that the length of the glass chopped fibers was 75 ⁇ m and the cross-sectional diameter was 3 ⁇ m, and the prepreg fiber cloth A4 was obtained in the same manner.
  • the cross section of the prepreg fiber cloth was observed by a microscope, and the surface of the fiber cloth was covered with a resin bonding layer, and A chopped fiber is embedded between the resin bonding layer and the fiber cloth.
  • Example 1 The procedure of Example 1 was carried out except that the length of the glass chopped fibers was 500 ⁇ m and the cross-sectional diameter was 5 ⁇ m, and the prepreg fiber cloth A5 was obtained in the same manner.
  • the cross section of the prepreg fiber cloth was observed by a microscope, and the surface of the fiber cloth was covered with a resin bonding layer, and chopped fibers were embedded between the resin bonding layer and the fiber cloth.
  • Example 1 The procedure of Example 1 was carried out except that the length of the glass chopped fibers was 800 ⁇ m and the cross-sectional diameter was 8 ⁇ m, and the prepreg fiber cloth A6 was obtained in the same manner.
  • the cross section of the prepreg fiber cloth was observed by a microscope, and the surface of the fiber cloth was covered with a resin bonding layer, and chopped fibers were embedded between the resin bonding layer and the fiber cloth.
  • Example 1 The procedure of Example 1 was carried out except that the length of the glass chopped fibers was 1000 ⁇ m and the cross-sectional diameter was 10 ⁇ m, and the prepreg fiber cloth A7 was obtained in the same manner.
  • the cross section of the prepreg fiber cloth was observed by a microscope, and the surface of the fiber cloth was covered with a resin bonding layer, and chopped fibers were embedded between the resin bonding layer and the fiber cloth.
  • Example 1 The procedure of Example 1 was carried out except that the surface of the chopped fiber was not sprayed with the pretreatment agent to obtain a prepreg fiber cloth A8.
  • the cross section of the prepreg fiber cloth was observed by a microscope, and the surface of the fiber cloth was covered with a resin bonding layer, and chopped fibers were embedded between the resin bonding layer and the fiber cloth.
  • Example 1 The procedure of Example 1 was carried out except that the length of the chopped fibers was 2.5 mm, and a prepreg fiber D1 was obtained.
  • the cut fiber cloth and aluminum sheet are stacked in the order of aluminum sheets, X1, Y1, X2, Y2, X3, Y3 (as shown in Fig. 3, 1 indicates 6 layers of fiber cloth, 2 indicates 2 mm thick aluminum plate) ) and placed in a hot press to obtain a hot pressed product XY.

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Abstract

一种预浸纤维布及其制备方法，所述预浸纤维布包括纤维布和树脂粘结层，所述纤维布的至少部分表面包覆有所述树脂粘结层，其中所述树脂粘结层和所述纤维布之间包埋有短切纤维，且所述短切纤维的长度为50μm-2mm。

Description

预浸纤维布及其制备方法
相关申请的交叉引用
本申请主张在2015年7月27日在中国提交的中国专利申请号No.201510447814.4的优先权，其全部内容通过引用包含于此。
技术领域
本公开涉及预浸纤维布及其制备方法。
背景技术
目前，预浸纤维布通常是采用预浸料对纤维布进行预浸，现有技术中所使用的预浸料通常含有不饱和聚酯树脂、乙烯基树脂、苯丙噁嗪树脂、酚醛树脂、尿素树脂、环氧树脂或三聚氰胺树脂，通过预浸该预浸料得到的预浸纤维布在通过交替铺层热压成复合板材时，其层间结合力不充分。
发明内容
本公开的目的是提供预浸纤维布及其制备方法，该预浸纤维布在被热压成复合板材时具有优良的层间结合力。
本公开的发明人意外地发现，将含有热固化性粘结剂树脂及短切纤维的树脂组合物浸渗到纤维布中时，如果使短切纤维的长度为50μm-2mm，能够显著提高将得到的预浸纤维布热压成复合板材时的层间结合力。推测其原因为：通过使用上述特定长度的短切纤维能够显著提高预浸纤维布表面的粗糙度，由此增加了层间结合力。
由此，本公开提供了一种预浸纤维布，其包括纤维布和树脂粘结层，所述纤维布的至少部分表面包覆有所述树脂粘结层，其中所述树脂粘结层和所述纤维布之间包埋有短切纤维，且所述短切纤维的长度为50μm-2mm。
本公开还提供了制备上述预浸纤维布的方法，其包括将含有热固化性粘结剂树脂及短切纤维的树脂组合物浸渗到纤维布中，以及加热固化，其中所述短切纤维的长度为50μm-2mm。
根据本公开的预浸纤维布，其在被热压成复合板材时具有优良的层间结合力。
本公开的其它特征和优点将在随后的具体实施方式部分予以详细说明。
附图说明
参照下面的描述和附图，将清楚本发明的实施例的这些和其他方面。在这些描述和附图中，具体公开了本发明的实施例中的一些特定实施方式，来表示实施本发明的实施例的原理的一些方式，但是应当理解，本发明的实施例的范围不受此限制。相反，本发明的实施例包括落入所附加权利要求书的精神和内涵范围内的所有变化、修改和等同物。
图1为测试例1中的纤维布块X1、X2、X3的示意图。
图2为测试例1中的纤维布块Y1、Y2、Y3的示意图。
图3为测试例1中的热压产品XY的示意图。
图4为测试例1中的待测试样品的示意图。
图5为测试例1中的待测试样品进行测试的示意图。
附图标记说明
1：6层纤维布
2：2mm厚铝板
3：4层纤维布
4：2层纤维布
5：施加力部位
6：固定部位
X1、X2、X3：纤维布块
Y1、Y2、Y3：纤维布块
具体实施方式
以下对本公开的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本公开，并不用于限制本公开。
本公开提供的预浸纤维布包括纤维布和树脂粘结层，所述纤维布的至少部分表面包覆有树脂粘结层，其中，所述树脂粘结层和所述纤维布之间包埋有短切纤维，且所述短切纤维的长度为50μm-2mm。
在本公开中，可选地，所述纤维布的所有表面包覆有树脂粘结层。
本公开主要是通过在所述树脂粘结层和纤维布之间包埋有短切纤维，提高预浸纤维布 表面的粗糙度，从而提高浸纤维布热压成复合板材时的层间结合力。
根据本公开，为了进一步提高各层之间结合力，可选地，上述短切纤维的长度为75μm-1mm。
在本公开中，短切纤维的直径可以在较大范围内变动，可选地，所述短切纤维的截面直径为0.5μm-20μm，例如为1μm-10μm。
在本公开中，可选地，所述短切纤维为玻璃纤维、碳纤维和芳纶纤维中的一种或多种。
在本公开中，对于所述纤维布没有特殊限制，其材质可以为常规的各种，例如，具体可以为玻璃纤维布、碳纤维布和芳纶纤维布中的一种或多种，也可以为玻璃纤维、碳纤维和芳纶纤维中的二种以上形成的混纺布。
本公开中，对于上述纤维布的单位面积质量没有特别限制，具体可以在较大范围内变动，可选地，所述纤维布的单位面积质量为20-700g/m2，例如为50-300g/m2。
根据本公开，在将预浸纤维布层压时，所述树脂粘结层用于将各预浸纤维布结合为一体。
上述树脂粘结层可以为由含有热固化性粘结剂树脂及短切纤维的树脂组合物固化而得到层。
所述热固化性粘结剂树脂可选地为丙烯酸树脂、环氧树脂、聚氨酯树脂、聚酯树脂、苯丙噁嗪树脂、酚醛树脂、尿素树脂和三聚氰胺树脂中一种或多种。例如为环氧树脂。
可选地，所述树脂组合物还含有活性稀释剂。可选地，相对于100重量份的热固化性粘结剂树脂，所述活性稀释剂的含量为10-55重量份；可选地，相对于100重量份的热固化性粘结剂树脂，所述活性稀释剂的含量为13-53重量份。
所述活性稀释剂可选地为丙烯基缩水甘油醚、丁基缩水甘油醚、乙二醇双缩水甘油醚、间苯二酚双缩水甘油醚、己二醇二缩水甘油醚、丁二醇二缩
水甘油醚、聚丙二醇二缩水甘油醚、新戊二醇二缩水甘油醚和烷基多缩水甘油醚中的一种或多种。从降低粘度效果更优，对纤维预浸效果更好的方面来考虑，可选地，所述活性稀释剂为丁基缩水甘油醚、丁二醇二缩水甘油醚、新戊二醇二缩水甘油醚和烷基多缩水甘油醚中的一种或多种。例如为新戊二醇二缩水甘油醚。
根据本公开，可选地，所述树脂组合物还含有固化剂。可选地，相对于100重量份的热固化性粘结剂树脂，所述固化剂的含量为1-55重量份；可选地，相对于100重量份的热固化性粘结剂树脂，所述固化剂的含量为2-50重量份。
所述固化剂可以为本领域常用的各种用于固化的固化剂。可选地，为二氨基二苯基甲 烷、间苯二胺、二氨基二苯基砜己二酸二酰肼、双氰胺、三乙烯二胺、三乙烯四胺、四乙烯五胺、二乙氨基丙胺、孟烷二胺、异佛尔酮二胺、N-氨乙基哌嗪、双(4-氨基-3-甲基环己基)甲烷和双(4-胺基环己基)甲烷中的一种或多种。例如为双氰胺。
根据本公开，可选地，所述树脂组合物还可以含有固化促进剂。可选地，相对于100重量份的热固化性粘结剂树脂，所述固化促进剂的含量为0-10重量份；可选地，相对于100重量份的热固化性粘结剂树脂，所述固化促进剂的含量为0.9-8.8重量份。
所述固化促进剂可以本领域常用的各种固化促进剂。例如可以为有机胍类化合物、咪唑类化合物和脲类化合物中的一种或多种；例如为咪唑类化合物；例如为1-甲基咪唑。
根据本公开，可选地，所述树脂组合物还可以含有消泡剂、流平剂和润湿剂中的一种或多种。可选地，相对于100重量份的热固化性粘结剂树脂，所述泡剂、流平剂和润湿剂的含量分别为0-12重量份，例如为1.5-11重量份。
所述消泡剂、流平剂和润湿剂可以本领域常用的各种消泡剂、流平剂和润湿剂。可选地，所述消泡剂为聚丙烯酸-聚醚共聚物消泡剂、有机硅类消泡剂、有机改性聚硅氧烷消泡剂和氟硅氧烷消泡剂中的一种或多种；所述流平剂为丙烯酸酯、聚醚硅氧烷共聚物和有机改性聚硅氧烷中的一种或多种；所述润湿剂为非离子有机表面活性剂。
另外，本公开中，可选地，所述树脂粘结层的厚度为0.02mm-0.5mm，例如为0.02mm-0.2mm。
根据本公开，可选地，所述短切纤维表面包覆有硅烷偶联剂。通过在所述短切纤维表面包覆有硅烷偶联剂，具有能和纤维表面化学结合的反应基团及与有机材料化学结合的反应基团，可以在纤维和预浸树脂间起来桥梁作用的效果，从而能够进一步提高层间结合力。
在所述短切纤维表面包覆硅烷偶联剂的方法可以为本领域所公知的方法，例如将硅烷偶联剂与分散剂和溶剂混合后的溶液喷洒在所述短切纤维的表面后干燥。
所述硅烷偶联剂可以为本领域所常用的各种硅烷偶联剂。可选地，所述硅烷偶联剂为氨基硅烷、环氧基硅烷、硫基硅烷、甲基丙烯酰氧基硅烷、乙烯基硅烷、脲基硅烷和异氰酸酯基硅烷中的一种或多种。可选地，所述硅烷偶联剂为氨基硅烷和环氧基硅烷中的一种或多种。所述分散剂可以为本领域所常用的各种分散剂，可选地为水玻璃、三聚磷酸钠、六偏磷酸钠、焦磷酸钠、三乙基己基磷酸、十二烷基硫酸钠、甲基戊醇、纤维素衍生物、聚丙烯酰胺、古尔胶、脂肪族聚乙二醇酯和改性聚烷氧化物中的一种或多种。作为所述溶剂只要能够很好地将所述硅烷偶联剂和分散剂溶剂即可，例如可以为乙醇、二甲苯、正丁醇、乙二醇丁醚、乙酸丁酯、异丙醇、环己酮和甲基异丁基酮中的一种或多种。
对于硅烷偶联剂、分散剂和溶剂的混合质量比例可选地为1：0.5-5：50-200；例如为＝1：3：100。
本公开还提供一种制备预浸纤维布的方法，其包括将含有热固化性粘结剂树脂及短切纤维的树脂组合物浸渗到纤维布中，以及加热固化，其中所述短切纤维的长度为50μm-2mm。
根据本公开的制备预浸纤维布的方法，为了得到表面的粗糙度高的预浸纤维布，可选地，相对于100重量份的热固化性粘结剂树脂，所述短切纤维的含量为5-50重量份；可选地，相对于100重量份的热固化性粘结剂树脂，所述短切纤维的含量为8-38重量份。
对于上述短切纤维，可选地，其长度为75μm-1mm。
在本公开的制备预浸纤维布的方法中，短切纤维的直径可以在较大范围内变动，可选地，所述短切纤维的截面直径为0.5μm-20μm，例如为1μm-10μm。
在本公开的制备预浸纤维布的方法中，可选地，所述短切纤维为玻璃纤维、碳纤维和芳纶纤维中的一种或多种。
根据本公开的制备预浸纤维布的方法，所述树脂组合物含有热固化性粘结剂树脂。所述热固化性粘结剂树脂可选为丙烯酸树脂、环氧树脂、聚氨酯树脂、聚酯树脂、苯丙噁嗪树脂、酚醛树脂、尿素树脂和三聚氰胺树脂中一种或多种。例如为环氧树脂。
根据本公开的制备预浸纤维布的方法，可选地，所述树脂组合物还含有活性稀释剂。所述活性稀释剂的用量可以为本领域的常规用量，相对于100重量份的热固化性粘结剂树脂，所述活性稀释剂的含量为10-55重量份；可选地，相对于100重量份的热固化性粘结剂树脂，所述活性稀释剂的含量为13-53重量份。
所述活性稀释剂用于溶解和分散成膜物质，具有在涂料成膜过程中参与成膜反应，形成不发挥组分留在涂膜中的作用。作为上述所述活性稀释剂可选为丙烯基缩水甘油醚、丁基缩水甘油醚、乙二醇双缩水甘油醚、间苯二酚双缩水甘油醚、己二醇二缩水甘油醚、丁二醇二缩水甘油醚、聚丙二醇二缩水甘油醚、新戊二醇二缩水甘油醚和烷基多缩水甘油醚中的一种或多种；从降低粘度效果更优，对纤维预浸效果更好的方面来考虑，可选地，所述活性稀释剂为丁基缩水甘油醚、丁二醇二缩水甘油醚、新戊二醇二缩水甘油醚和烷基多缩水甘油醚中的一种或多种。例如，为新戊二醇二缩水甘油醚。
根据本公开的制备预浸纤维布的方法，可选地，所述树脂组合物还含有固化剂。所述固化剂的用量可以为本领域的常规用量，可选地，相对于100重量份的热固化性粘结剂树脂，所述固化剂的含量为1-55重量份；可选地，相对于100重量份的热固化性粘结剂树脂，所述固化剂的含量为2-50重量份。
所述固化剂可以为本领域常用的各种用于固化的固化剂，可选地为二氨基二苯基甲烷、间苯二胺、二氨基二苯基砜己二酸二酰肼、双氰胺、三乙烯二胺、三乙烯四胺、四乙烯五胺、二乙氨基丙胺、孟烷二胺、异佛尔酮二胺、N-氨乙基哌嗪、双(4-氨基-3-甲基环己基)甲烷和双(4-胺基环己基)甲烷中的一种或多种。例如为双氰胺。
根据本公开的制备预浸纤维布的方法，可选地，所述树脂组合物还含有固化促进剂。所述固化促进剂的用量可以为本领域的常规用量，可选地，相对于100重量份的热固化性粘结剂树脂，所述固化促进剂的含量为0-10重量份；可选地，相对于100重量份的热固化性粘结剂树脂，所述固化促进剂的含量为0.9-8.8重量份。
所述固化促进剂可以本领域常用的各种固化促进剂。例如可以为有机胍类化合物、咪唑类化合物和脲类化合物中的一种或多种；可选地为咪唑类化合物；例如为1-甲基咪唑。
所述树脂组合物还可以含有消泡剂、流平剂和润湿剂中的一种或多种。可选地，相对于100重量份的热固化性粘结剂树脂，所述泡剂、流平剂和润湿剂的含量分别为0-12重量份，例如为1.5-11重量份。
作为所述消泡剂、流平剂和润湿剂可以本领域常用的各种消泡剂、流平剂和润湿剂。可选地，所述消泡剂为聚丙烯酸-聚醚共聚物消泡剂、有机硅类消泡剂、有机改性聚硅氧烷消泡剂和氟硅氧烷消泡剂中的一种或多种；所述流平剂为丙烯酸酯、聚醚硅氧烷共聚物和有机改性聚硅氧烷中的一种或多种；所述润湿剂为非离子有机表面活性剂。
根据本公开的制备预浸纤维布的方法，对于所述纤维布没有特殊限制，其材质可以为常规的各种，例如，具体可以为玻璃纤维布、碳纤维布、芳纶纤维布中的一种或多种，也可以为上述玻璃纤维、碳纤维和芳纶纤维中的两种以上形成的混纺布。
本公开的制备预浸纤维布的方法中，对于上述纤维布的厚度没有特殊限制，具体可以在较大范围内变动，可选地，所述纤维布的单位位面积质量为20g/m2-700g/m2，例如为100g/m2-200g/m2。
根据本公开的制备预浸纤维布的方法，可选地，所述短切纤维表面包覆有硅烷偶联剂。通过在所述短切纤维表面包覆有硅烷偶联剂，具有能和纤维表面化学结合的反应基团及与有机材料化学结合的反应基团，可以在纤维和预浸树脂间起来桥梁作用的效果，从而能够进一步提高层间结合力。
在所述短切纤维表面包覆硅烷偶联剂的方法可以为本领域所公知的方法，例如将硅烷偶联剂与分散剂和溶剂混合后的溶液喷洒在所述短切纤维的表面。
所述硅烷偶联剂可以为本领域所常用的各种硅烷偶联剂。可选地，所述硅烷偶联剂为 氨基硅烷、环氧基硅烷、硫基硅烷、甲基丙烯酰氧基硅烷、乙烯基硅烷、脲基硅烷和异氰酸酯基硅烷中的一种或多种；可选地，所述硅烷偶联剂为氨基硅烷和/或环氧基硅烷。所述分散剂可以为本领域所常用的各种分散剂，可选地为水玻璃、三聚磷酸钠、六偏磷酸钠、焦磷酸钠、三乙基己基磷酸、十二烷基硫酸钠、甲基戊醇、纤维素衍生物、聚丙烯酰胺、古尔胶、脂肪族聚乙二醇酯和改性聚烷氧化物中的一种或多种。所述溶剂只要能够很好地将所述硅烷偶联剂和分散剂溶剂即可，例如可以为乙醇、二甲苯、正丁醇、乙二醇丁醚、乙酸丁酯、异丙醇、环己酮和甲基异丁基酮中的一种或多种。
对于硅烷偶联剂、分散剂和溶剂的混合质量比例可选地为1：0.5-5：50-200；例如为＝1：3：100。
如上所述，在本公开的制备预浸纤维布的方法中，其包括将含有热固化性粘结剂树脂及短切纤维的树脂组合物浸渗到纤维布中以及加热固化来得到预浸纤维布。作为具体的将含有热固化性粘结剂树脂及短切纤维的树脂组合物浸渗到纤维布中的方法可以采用本领域所公知的各种方法。例如可以将所述树脂组合物混合分散后得到预浸料，将该预浸料与纤维布进行接触，然后将接触后的纤维布进行加热固化处理。
在上述方法中，对于组合物中各成分的混合顺序没有特别的要求，可以是任意的。但是，从进一步提高层间结合力上来考虑，可选地，将环氧树脂和活性稀释剂混合分散后，再加入短切纤维进行分散混合，然后加入固化剂、固化促进剂和消泡剂后进行分散混合，从而得到预浸料。
另外，对于将该预浸料与纤维布进行接触的条件只要能够使所述短切纤维预浸到所述树脂粘结层和纤维布之间即可。例如，所述接触可以在常温(10℃-40℃)下进行，接触的时间为3min-30min。
对于上述加热固化的条件可以根据树脂组合物的成分具体选择，但通常是在温度为60℃-98℃下加热10min-100min。
根据本公开的制备预浸纤维布的方法得到的预浸纤维布，在被热压成复合板材时具有优良的层间结合力。
以下将通过实施例对本公开进行详细描述。
以下实施例和对比例中，原料为以下公司的市售品。
品种 型号 公司
硅烷偶联剂 A1130 美国康普顿
分散剂 六偏磷酸钠 北京康普汇维科技有限公司
乙醇 乙醇 东莞市兆能化工有限公司
短切纤维 EMG-200 泰山玻璃纤维有限公司
环氧树脂 E44 CYTEC
双氰胺 DICYANEX 1400F 美国气体
咪唑 1-甲基咪唑 天津格瑞恒业科技有限公司
消泡剂 Airex 932 DEGO
活性稀释剂 SM678 江苏三木集团有限公司
纤维布 USN 15000 龙泓复合材料有限公司
实施例1
1)按照硅烷偶联剂：分散剂：乙醇＝1：3：100的比例(质量比)配制预处理剂；
2)在4kg短切纤维(玻璃短切纤维，长度为200μm，截面直径为10μm)表面喷洒预处理剂，烘干得到预处理纤维丝X；
3)称取环氧树脂48kg、活性稀释剂25kg，用高速分散机(购于上海法孚莱能源有限公司，以下相同)分散，得到混合物A；
4)将步骤2)中得到的预处理纤维丝X加入混合物A中，用高速分散机分散，得到混合物B；
5)称取双氰胺15kg(固化剂)、1-甲基咪唑5kg(固化促进剂)、消泡剂3kg，加入混合物B中，用高速分散机分散，得到预浸料，并加入纤维预浸槽；
6)将纤维布(碳纤维布，单位面积质量为150g/m2)拉扯经过纤维预浸槽(纤维布与预浸料的接触时间为25min)，得到涂布有预浸料的纤维布；
7)在温度为80℃下加热具有预浸料的纤维布30min，得到预浸纤维布A1。
将该预浸纤维布的横截面通过显微镜观察可知，纤维布的表面被树脂粘结层包覆，且在所述树脂粘结层和所述纤维布之间包埋有短切纤维，另外，粘着剂层的厚度为0.2mm。
实施例2
1)按照硅烷偶联剂：分散剂：乙醇＝1：3：100的比例(质量比)配制预处理剂；
2)在8kg短切纤维(玻璃短切纤维，长度为200μm，截面直径为10μm)表面喷洒预处理剂，烘干得到预处理纤维丝X；
3)称取环氧树脂75kg、活性稀释剂10kg，用高速分散机分散，得到混合物A；
4)将步骤2)中得到的预处理纤维丝X加入混合物A中，用高速分散机分散，得到混合物B；
5)称取双氰胺5kg(固化剂)、1-甲基咪唑0.7kg(固化促进剂)、消泡剂1.3kg，加入混合物B中，用高速分散机分散，得到预浸料，并加入纤维预浸槽中；
6)将纤维布(碳纤维布，单位面积质量为150g/m2)拉扯经过纤维预浸槽(纤维布与预浸料的接触时间为20min)，得到涂布有预浸料的纤维布；
7)在温度为70℃下加热具有预浸料的纤维布50min，得到预浸纤维布A2。
将该预浸纤维布的横截面通过显微镜观察可知，纤维布的表面被树脂粘结层包覆，且在所述树脂粘结层和所述纤维布之间包埋有短切纤维，另外，粘着剂层的厚度为0.25mm。
实施例3
按照硅烷偶联剂：分散剂：乙醇＝1：3：100的比例(质量比)配制预处理剂；
2)在15kg短切纤维(玻璃短切纤维，长度为200μm，截面直径为10μm)表面喷洒预处理剂，烘干得到预处理纤维丝X；
3)称取环氧树脂40.5kg、活性稀释剂18kg，用高速分散机分散，得到混合物A；
4)将步骤2)中得到的预处理纤维丝X加入混合物A中，用高速分散机分散，得到混合物B；
5)称取双氰胺20kg(固化剂)、1-甲基咪唑3.5kg(固化促进剂)、消泡剂3kg，加入混合物B中，用高速分散机分散，得到预浸料，并加入纤维预浸槽中。
6)将纤维布(碳纤维布，单位面积质量为150g/m2)拉扯经过纤维预浸槽(纤维布与预浸料的接触时间为15min)，得到涂布有预浸料的纤维布。
7)在温度为60℃下加热具有预浸料的纤维布90min，得到预浸纤维布A3。
将该预浸纤维布的横截面通过显微镜观察可知，纤维布的表面被树脂粘结层包覆，且在所述树脂粘结层和所述纤维布之间包埋有短切纤维，另外，粘着剂层的厚度为0.15mm。
实施例4
按照实施例1的方法进行，不同的是玻璃短切纤维的长度为75μm，截面直径为3μm，相同地得到预浸纤维布A4。
将该预浸纤维布的横截面通过显微镜观察可知，纤维布的表面被树脂粘结层包覆，且 在所述树脂粘结层和所述纤维布之间包埋有短切纤维。
实施例5
按照实施例1的方法进行，不同的是玻璃短切纤维的长度为500μm，截面直径为5μm，相同地得到预浸纤维布A5。
将该预浸纤维布的横截面通过显微镜观察可知，纤维布的表面被树脂粘结层包覆，且在所述树脂粘结层和所述纤维布之间包埋有短切纤维。
实施例6
按照实施例1的方法进行，不同的是玻璃短切纤维的长度为800μm，截面直径为8μm，相同地得到预浸纤维布A6。
将该预浸纤维布的横截面通过显微镜观察可知，纤维布的表面被树脂粘结层包覆，且在所述树脂粘结层和所述纤维布之间包埋有短切纤维。
实施例7
按照实施例1的方法进行，不同的是玻璃短切纤维的长度为1000μm，截面直径为10μm，相同地得到预浸纤维布A7。
将该预浸纤维布的横截面通过显微镜观察可知，纤维布的表面被树脂粘结层包覆，且在所述树脂粘结层和所述纤维布之间包埋有短切纤维。
实施例8
按照实施例1的方法进行，不同的是短切纤维表面未喷洒预处理剂，得到预浸纤维布A8。
将该预浸纤维布的横截面通过显微镜观察可知，纤维布的表面被树脂粘结层包覆，且在所述树脂粘结层和所述纤维布之间包埋有短切纤维。
对比例1
按照实施例1的方法进行，不同的是短切纤维的长度为2.5mm，得到预浸纤维布D1。
测试例1(剥离强度测试)
1)加工一片100mm×20mm×2mm的铝片。
2)将实施例1-8和对比例1所得的预浸纤维布，分别按照图1所示纤维排布方向裁制三片100mm×20mm的纤维布块X1、X2、X3。
3)将实施例1-8和对比例1所得的预浸纤维布，分别按照图2所示纤维排布方向裁制三片100mm×20mm的纤维布块Y1、Y2、Y3。
4)将所裁制的纤维布与铝片按照铝片、X1、Y1、X2、Y2、X3、Y3顺序叠在一起(如图3所示，1表示6层纤维布，2表示2mm厚铝板)，并放在热压机中得到热压产品XY。
5)按照图4所示加工XY，得到待测试样品A1-A8和D1(图4中，3表示4层纤维布，4表示2层纤维布)。
6)在万能材料试验机上，按图5所示将4层纤维布加铝板一端6夹于治具中，另一端5按照图示方向进行剥离，剥离速度为10mm/min，使薄端完全脱落，记录下数据，该值即为剥离强度。
其结果如表1所示。
表1
序号 剥离强度(N)
A1 265
A2 291
A3 320
A4 250
A5 330
A6 352
A7 340
A8 218
D1 150
以上详细描述了本公开的可选的实施方式，但是，本公开并不限于上述实施方式中的具体细节，在本公开的技术构思范围内，可以对本公开的技术方案进行多种简单变型，这些简单变型均属于本公开的保护范围。
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的 情况下，可以通过任何合适的方式进行组合为了避免不必要的重复，本公开对各种可能的组合方式不再另行说明。
此外，本公开的各种不同的实施方式之间也可以进行任意组合，只要其不违背本公开的思想，其同样应当视为本公开所公开的内容。

Claims (33)

  1. 一种预浸纤维布，包括纤维布和树脂粘结层，所述纤维布的至少部分表面包覆有所述树脂粘结层，其中所述树脂粘结层和所述纤维布之间包埋有短切纤维，且所述短切纤维的长度为50μm-2mm。
  2. 根据权利要求1所述的预浸纤维布，其中所述短切纤维的长度为75μm-1mm。
  3. 根据权利要求1或2所述的预浸纤维布，其中所述短切纤维的截面直径为0.5μm-20μm。
  4. 根据权利要求1-3中任一项所述的预浸纤维布，其中所述短切纤维的截面直径为1μm-10μm。
  5. 根据权利要求1-4中任一项所述的预浸纤维布，其中所述短切纤维为玻璃纤维、碳纤维和芳纶纤维中的一种或多种。
  6. 根据权利要求1-5中任一项所述的预浸纤维布，其中所述纤维布为玻璃纤维布、碳纤维布和芳纶纤维布中的一种或多种。
  7. 根据权利要求1-6中任一项所述的预浸纤维布，其中所述纤维布的单位面积质量为20-700g/m2。
  8. 根据权利要求1-7中任一项所述的预浸纤维布，其中所述树脂粘结层为由含有热固化性粘结剂树脂及所述短切纤维的树脂组合物固化而得到层。
  9. 根据权利要求1-8中任一项所述的预浸纤维布，其中所述树脂粘结层的厚度为0.02mm-0.5mm。
  10. 根据权利要求1-9中任一项所述的预浸纤维布，其中所述短切纤维表面包覆有硅烷偶联剂。
  11. 一种制备预浸纤维布的方法，包括：
    将含有热固化性粘结剂树脂及短切纤维的树脂组合物浸渗到纤维布中；以及
    加热固化，
    其中所述短切纤维的长度为0.5μm-2mm。
  12. 根据权利要求11所述的方法，其中相对于100重量份的所述热固化性粘结剂树脂，所述短切纤维的含量为5-50重量份。
  13. 根据权利要求11或12所述的方法，其中相对于100重量份的所述热固化性粘结剂树脂，所述短切纤维的含量为8-38重量份。
  14. 根据权利要求11-13中任一项所述的方法，其中所述树脂组合物还含有活性稀释剂。
  15. 根据权利要求14所述的方法，其中相对于100重量份的所述热固化性粘结剂树脂，所述活性稀释剂的含量为10-55重量份。
  16. 根据权利要求14或15所述的方法，其中相对于100重量份的所述热固化性粘结剂树脂，所述活性稀释剂的含量为13-53重量份。
  17. 根据权利要求14-16中任一项所述的方法，其中所述活性稀释剂为丙烯基缩水甘油醚、丁基缩水甘油醚、乙二醇双缩水甘油醚、间苯二酚双缩水甘油醚、己二醇二缩水甘油醚、丁二醇二缩水甘油醚、聚丙二醇二缩水甘油醚、新戊二醇二缩水甘油醚和烷基多缩水甘油醚中的一种或多种。
  18. 根据权利要求11-17中任一项所述的方法，其中所述树脂组合物还含有固化剂。
  19. 根据权利要求18所述的方法，其中相对于100重量份的所述热固化性粘结剂树脂，所述固化剂的含量为1-55重量份。
  20. 根据权利要求18或19所述的方法，其中相对于100重量份的所述热固化性粘结剂树脂，所述固化剂的含量为2-50重量份。
  21. 根据权利要求18-20中任一项所述的方法，其中所述固化剂为二氨基二苯基甲烷、间苯二胺、二氨基二苯基砜己二酸二酰肼、双氰胺、三乙烯二胺、三乙烯四胺、四乙烯五胺、二乙氨基丙胺、孟烷二胺、异佛尔酮二胺、N-氨乙基哌嗪、双(4-氨基-3-甲基环己基)甲烷和双(4-胺基环己基)甲烷中的一种或多种。
  22. 根据权利要求11-21中任一项所述的方法，其中所述树脂组合物还含有固化促进剂。
  23. 根据权利要求22所述的方法，其中相对于100重量份的所述热固化性粘结剂树脂，所述固化促进剂的含量为0-10重量份。
  24. 根据权利要求22或23所述的方法，其中相对于100重量份的所述热固化性粘结剂树脂，所述固化促进剂的含量为0.9-8.8重量份。
  25. 根据权利要求22-24中任一项所述的方法，其中所述树脂组合物还含有消泡剂、流平剂和润湿剂中的一种或多种。
  26. 根据权利要求11-25中任一项所述的方法，其中所述短切纤维的长度为75μm-1mm。
  27. 根据权利要求11-26中任一项所述的方法，其中所述短切纤维的截面直径为0.5μm-20μm。
  28. 根据权利要求11-27中任一项所述的方法，其中所述短切纤维的截面直径为1μm-10μm。
  29. 根据权利要求11-28中任一项所述的方法，其中所述短切纤维为玻璃纤维、碳纤维和芳纶纤维中的一种或多种。
  30. 根据权利要求11-29中任一项所述的方法，其中所述纤维布为玻璃纤维布、碳纤维布和芳纶纤维布中的一种或多种；
  31. 根据权利要求11-30中任一项所述的方法，其中所述纤维布的单位面积质量20g/m2-700g/m2。
  32. 根据权利要求11-31中任一项所述的方法，其中所述热固化性粘结剂树脂为丙烯酸树脂、环氧树脂、聚氨酯树脂、聚酯树脂、苯丙噁嗪树脂、酚醛树脂、尿素树脂和三聚氰胺树脂中一种或多种。
  33. 根据权利要求11-32中任一项所述的方法，其中所述短切纤维表面包覆有硅烷偶联剂。
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CN118322667A (zh) * 2024-03-25 2024-07-12 广东纵胜新材料股份有限公司 一种基于纤维布的多彩手机后盖及其制备工艺
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