CN110202862A - A kind of unidirectional yarn composite plate and preparation method thereof - Google Patents

A kind of unidirectional yarn composite plate and preparation method thereof Download PDF

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Publication number
CN110202862A
CN110202862A CN201910513784.0A CN201910513784A CN110202862A CN 110202862 A CN110202862 A CN 110202862A CN 201910513784 A CN201910513784 A CN 201910513784A CN 110202862 A CN110202862 A CN 110202862A
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China
Prior art keywords
unidirectional yarn
composite plate
unidirectional
weight
parts
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CN201910513784.0A
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Inventor
曾瑞东
陈华刚
洪机剑
张娣
陈文泉
骆钰栋
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New Materials Co Ltd Zhejiang China Is
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New Materials Co Ltd Zhejiang China Is
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Priority to CN201910513784.0A priority Critical patent/CN110202862A/en
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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
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/02—Layered products comprising a layer of paper or cardboard next to a fibrous or filamentary layer
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/08—Impregnating
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/12—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer characterised by the relative arrangement of fibres or filaments of different layers, e.g. the fibres or filaments being parallel or perpendicular to each other
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/08—Interconnection of layers by mechanical means
    • 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
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B32B2260/023—Two or more layers
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/106—Carbon fibres, e.g. graphite 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/546—Flexural strength; Flexion stiffness
    • 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
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • 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
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica

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  • Manufacturing & Machinery (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Reinforced Plastic Materials (AREA)

Abstract

A kind of unidirectional yarn composite plate is matched by the way that unidirectional yarn prepreg different structure is folded, it is made through hot press molding, unidirectional yarn prepreg used carries out compound preparation using the resin adhesive liquid of special formulation and unidirectional yarn, unidirectional yarn composite plate includes recombiner unit, recombiner unit includes floor level and rotation surface layer, rotation surface layer relative level layer is obliquely installed, structure between adjacent recombiner unit is symmetrical along recombiner unit binding face, plate can be effectively prevented, warping phenomenon occurs, improve the flexural strength of this unidirectional yarn composite plate, further increase the service life of this unidirectional yarn composite plate.

Description

A kind of unidirectional yarn composite plate and preparation method thereof
Technical field
The invention belongs to field of compound material, in particular to a kind of preparation method of unidirectional yarn composite plate.
Background technique
With the development of consumer electronics field technology, people are higher and higher to the security requirement of equipment, especially adjoint Battery of mobile phone explosion accident occur often, mobile phone terminal is also higher and higher to the intensity requirement of cell rear cover plate, common thermosetting Property composite material battery cover board bending strength about 450MPa, can not meet using safety requirements, urgent need develops a kind of bending strength The high-strength composite board of >=800MPa.Meanwhile battery cover board surface needs injection molding, is bonded other materials, and the plate that surface roughness is high Surface be easier to carry out injection molding, bonding process, about 0.5 μm of conventional laminates surface roughness Ra value, thus improve surface roughness (Ra >=3.5 μm) are also a basic demand of cell rear cover plate.
Summary of the invention
Against the above deficiency, technical problem to be solved by the invention is to provide a kind of preparation sides of unidirectional yarn composite plate Method, for improving the flexural strength of battery of mobile phone back shroud, and it is heat-resist, surface adhesiveness is good.
In order to solve the above technical problems, the technical solution adopted by the present invention is that,
Prepreg be with resin adhesive liquid impregnating continuous fibres or fabric under conditions of strict control, be made resin adhesive liquid with The composition of reinforcement, and unidirectional yarn prepreg refers to that reinforcement uses unidirectional fabric.
A kind of unidirectional yarn composite plate is matched by the way that unidirectional yarn prepreg different structure is folded, is made through hot press molding, used Unidirectional yarn prepreg carries out compound preparation using the resin adhesive liquid of special formulation and unidirectional yarn, and the unidirectional yarn composite plate includes two A above recombiner unit, the recombiner unit include floor level and rotation surface layer, and the rotation surface layer relative level layer is in Certain angle setting, adjacent recombiner unit is symmetrical in mirror surface along recombiner unit binding face, and plate can be effectively prevented Warping phenomenon improves the flexural strength of this unidirectional yarn composite plate, further increases the service life of this unidirectional yarn composite plate.
While using above technical scheme, the present invention, which is also further used or combined, uses following technical side Case.
Rotate surface layer relative level layer rotary setting, that is, rotation surface layer can be obliquely installed with relative level surface layer, be rotated Angle α between surface layer and floor level are as follows: 0 ° < α < 180 °., preferably angle α is 90 ° or 45 °, is also possible to other angles Degree rotates the angle that the angle between surface layer and floor level is two adjacent plate machine directions.
Two layers of floor level is equipped between two adjacent rotation surface layers, mutually hot pressing connects between adjacent floor level It connects, by the stacking of at least two surfacess of revolution with the unidirectional yarn composite plate formed, and upper and lower two rotation surface layers are kept in structure It is lower symmetrical, plate can be effectively prevented, warping phenomenon occurs, improves the flexural strength of this unidirectional yarn composite plate, further increase The service life of this unidirectional yarn composite plate.
Be fitted with superficial layer in the side of unidirectional yarn composite plate or two sides, superficial layer using release film, release paper, Any one in release cloth, floor level and rotation surface layer are unidirectional using the common glass impregnated by resin adhesive liquid Any one in the unidirectional yarn of yarn, S grade high-strength fiber glass, the unidirectional yarn of carbon fiber and a variety of combinations, by the setting of superficial layer, to multiple Isolation and protective effect are played in the side or two sides of plywood.
In some preferred modes, unidirectional yarn composite plate with a thickness of 0.1mm-2.0mm, unidirectional yarn is by prepreg Thickness after reason is between 0.05-0.2mm.
A kind of preparation method of unidirectional yarn composite plate, comprising the following steps:
Step 1: prepare unidirectional yarn and resin adhesive liquid；
Step 2: resin adhesive liquid is applied in release paper, and unidirectional yarn is then placed in two panels release paper and is coated with resin glue It is carried out by compounding machine compound between the side of liquid, finally removes release paper, obtain unidirectional yarn prepreg；
Step 3: unidirectional yarn prepreg is cut, and more than two unidirectional yarn prepregs are folded according to preset structure Match, obtains unidirectional yarn composite material；
Step 4: superficial layer is sticked in the unidirectional yarn composite material side or two sides；
Step 5: the compound that step 4 is obtained is hot-forming, after cooling, obtains unidirectional yarn composite plate.
Resin adhesive liquid ingredient in step 1 include 50-80 parts by weight epoxy resin A, 20-50 parts by weight epoxy resin B, 10-20 parts by weight toughener, 2.0-2.6 parts by weight dicyandiamide, 15-20 parts by weight 4,4- diaminodiphenylsulfone, 0.05-0.15 weight Measure part methylimidazole, 2-8 parts by weight fumed silica and 40-60 pbw acetone.
The hot pressing condition of preliminary hot pressing in step 5 is 120 DEG C of -160 DEG C of hot pressing 1-8h.
It includes bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenolic aldehyde that epoxy resin A, which is selected from, It is one or more in epoxy resin.
It includes one of multifunction group epoxy, brominated epoxy resin and phosphorous epoxy resin or more that epoxy resin B, which is selected from, Kind.
It includes macromolecular phenoxy resin, nitrile rubber, poly(aryl ether ketone), acrylic rubber, polyurethane that toughener, which is selected from, It is one or more of.
The preparation step of resin adhesive liquid in step 1 is as follows:
(1) first dicyandiamide, 4,4- diaminodiphenylsulfone, methylimidazole are dissolved into acetone solvent and obtain mixed liquor One；
(2) epoxy resin A, epoxy resin B, toughener, fumed silica are subjected to heating stirring, are mixed after melting Close liquid two；
(3) mixed liquor one and mixed liquor two are uniformly mixed, are vacuumized, after removing solvent, resin glue is made Liquid.
The invention has the advantages that (1) this unidirectional yarn composite plate folds distribution structure design by unidirectional yarn prepreg difference, To improve the bending strength on unidirectional yarn composite plate different directions；By being handled in surface coating surface layer and by prepreg Unidirectional yarn afterwards is hot-forming together, to realize the high roughness of material surface, and protects to the surface of composite board Shield.
(2) structure between adjacent recombiner unit is symmetrical along recombiner unit binding face, and plate can be effectively prevented Warping phenomenon occurs for material, improves the flexural strength of this unidirectional yarn composite plate, further increases the use of this unidirectional yarn composite plate Service life.
Detailed description of the invention
Fig. 1 is the top view of 0 ° of unidirectional yarn, that is, the unidirectional yarn is floor level.
Fig. 2 is the top view of 90 ° of unidirectional yarns, that is, the rotation surface layer that 0 ° of unidirectional yarn is formed after being rotated by 90 °.
Fig. 3 is the top view of 45 ° of unidirectional yarns, that is, the rotation surface layer that 0 ° of unidirectional yarn is formed after rotating 45 °.
Fig. 4 is to rotate unidirectional yarn composite plate when folding with relationship between surface layer and floor level is 0 ° 90 ° 0 ° 0 ° 90 ° 0 ° Top view.
Fig. 5 is to rotate unidirectional yarn composite plate when folding with relationship between surface layer and floor level is 0 ° 45 ° 0 ° 0 ° 45 ° 0 ° Top view.
Fig. 6 is to rotate unidirectional yarn composite plate when folding with relationship between surface layer and floor level is 0 ° 45 ° 90 ° 90 ° 45 ° 0 ° Top view.
Appended drawing reference: floor level 1 rotates surface layer 2, superficial layer 3.
Specific embodiment
The present invention is described further with reference to the accompanying drawing.
Embodiment one
Resin adhesive liquid preparation process is as follows:
1) by the dicyandiamide of 2.3 parts by weight, the dimethyl miaow of the 4,4- diaminodiphenylsulfone of 18 parts by weight, 0.08 parts by weight Azoles is dissolved in the acetone of 50 parts by weight, obtains mixed liquor one；
2) 60 parts by weight of bisphenol A type ring oxygen Resin As, 40 parts by weight polyfunctional epoxy resin B, the big of 10 parts by weight are divided The fumed silica of sub- phenoxy resin, 3 parts by weight is stirred at 120 DEG C, is uniformly dispersed to obtain mixed liquor wait melt Two；
3) mixed liquor one is mixed with mixed liquor two, temperature control at 35-50 DEG C, speed of agitator 600-800 turns/ Min after being uniformly dispersed, is vacuumized, and is removed solvent acetone, is obtained mixed glue solution.
Prepreg manufacturing process is as follows:
4) the above-mentioned resin adhesive liquid prepared is added in the glue groove of film applicator, carries out film, film temperature control exists 60-80 DEG C, in 3-9m/min, film paper is placed on release paper wire velocity control by tension force after the completion of 120-300N, film Thermostatic chamber is spare；
5) 2 coil coating film paper are individually placed to upper film and lower film location, by fiber grammes per square metre 125g/m2S grades of high-strength fiber glass are unidirectional Yarn is placed between upper and lower film paper, carried out on compounding machine it is compound, compound linear velocity be 3-8m/min, tension 120-300N, glue Content control is made the unidirectional yarn prepreg of S grades of high-strength fiber glass, is indirectly smeared resin adhesive liquid by release paper 40 ± 1% On the two sides of unidirectional yarn, unidirectional yarn prepreg is obtained；
6) the unidirectional yarn prepreg of S made from step 5 grades of high-strength fiber glass wound, sealed, being put into freezer preservation.
Unidirectional yarn composite plate preparation is as follows:
The unidirectional yarn prepreg of the S prepared grade high-strength fiber glass is cut into 1280*1000mm, distribution structure is folded and presses 0 ° 90 ° 0 ° 0 ° 90 ° 0 ° (i.e. Fig. 1) carries out folded match, it is preferred that before folded match, needs to remove the release paper table being compounded on unidirectional yarn prepreg Surface layer, and stick one layer of release cloth on surface and do rough surface, it is put into mold steel plate, after 120-160 DEG C of hot pressing 2h is formed The unidirectional yarn composite plate of 0.6mm high bending strength, high surface roughness is made, table 1 is the performance of the composite plate of embodiment preparation Table.
Embodiment two:
Resin adhesive liquid preparation process is as follows:
1) by the dicyandiamide of 2.0 parts by weight, the dimethyl miaow of the 4,4- diaminodiphenylsulfone of 20 parts by weight, 0.08 parts by weight Azoles is dissolved in the acetone of 60 parts by weight, obtains mixed liquor one；
2) 60 parts by weight of bisphenol A type ring oxygen Resin As, 40 parts by weight polyfunctional epoxy resin B, the big of 20 parts by weight are divided The fumed silica of sub- phenoxy resin, 3 parts by weight is stirred at 120 DEG C, is uniformly dispersed to obtain mixed liquor wait melt Two；
3) mixed liquor one is mixed with mixed liquor two, temperature control at 35-50 DEG C, speed of agitator 600-800 turns/ Min after being uniformly dispersed, is vacuumized, and is removed solvent acetone, is obtained mixed glue solution.
Prepreg manufacturing process is as follows:
4) the above-mentioned resin adhesive liquid prepared is added in the glue groove of film applicator, carries out film, film temperature control exists 60-80 DEG C, in 3-9m/min, film paper is placed on release paper wire velocity control by tension force after the completion of 120-300N, film Thermostatic chamber is spare；
5) 2 coil coating film paper are individually placed to upper film and lower film location, by fiber grammes per square metre 125g/m2S grades of high-strength fiber glass are unidirectional Yarn is placed between upper and lower film paper, carried out on compounding machine it is compound, compound linear velocity be 3-8m/min, tension 120-300N, glue Content control is made the unidirectional yarn prepreg of S grades of high-strength fiber glass, is indirectly smeared resin adhesive liquid by release paper 40 ± 1% On the two sides of unidirectional yarn, unidirectional yarn prepreg is obtained；
6) the unidirectional yarn prepreg of S made from step 5 grades of high-strength fiber glass wound, sealed, being put into freezer preservation.
Unidirectional yarn composite plate preparation is as follows:
The unidirectional yarn prepreg of the S prepared grade high-strength fiber glass is cut into 1280*1000mm, distribution structure is folded and presses 0 ° 90 ° 0 ° 0 ° 90 ° 0 ° (i.e. Fig. 1) carries out folded match, it is preferred that before folded match, needs to remove the release paper table being compounded on unidirectional yarn prepreg Surface layer, and stick one layer of release cloth on surface and do rough surface, it is put into mold steel plate, after 120-160 DEG C of hot pressing 2h is formed The unidirectional yarn composite plate of 0.6mm high bending strength, high surface roughness is made, table 1 is the performance of the composite plate of embodiment preparation Table.
Embodiment three:
Resin adhesive liquid preparation process is as follows:
1) by the dicyandiamide of 2.0 parts by weight, the dimethyl miaow of the 4,4- diaminodiphenylsulfone of 20 parts by weight, 0.08 parts by weight Azoles is dissolved in the acetone of 60 parts by weight, obtains mixed liquor one；
2) 60 parts by weight of bisphenol A type ring oxygen Resin As, 40 parts by weight polyfunctional epoxy resin B, the big of 20 parts by weight are divided The fumed silica of sub- phenoxy resin, 3 parts by weight is stirred at 120 DEG C, is uniformly dispersed to obtain mixed liquor wait melt Two；
3) mixed liquor one is mixed with mixed liquor two, temperature control at 35-50 DEG C, speed of agitator 600-800 turns/ Min after being uniformly dispersed, is vacuumized, and is removed solvent acetone, is obtained mixed glue solution.
Prepreg manufacturing process is as follows:
4) the above-mentioned resin adhesive liquid prepared is added in the glue groove of film applicator, carries out film, film temperature control exists 60-80 DEG C, in 3-9m/min, film paper is placed on release paper wire velocity control by tension force after the completion of 120-300N, film Thermostatic chamber is spare；
5) 2 coil coating film paper are individually placed to upper film and lower film location, by fiber grammes per square metre 125g/m2S grades of high-strength fiber glass are unidirectional Yarn is placed between upper and lower film paper, carried out on compounding machine it is compound, compound linear velocity be 3-8m/min, tension 120-300N, glue Content control is made the unidirectional yarn prepreg of S grades of high-strength fiber glass, is indirectly smeared resin adhesive liquid by release paper 40 ± 1% On the two sides of unidirectional yarn, unidirectional yarn prepreg is obtained；
6) the unidirectional yarn prepreg of S made from step 5 grades of high-strength fiber glass wound, sealed, being put into freezer preservation.
Unidirectional yarn composite plate preparation is as follows: the unidirectional yarn prepreg of S grade high-strength fiber glass that will be prepared cuts into 1280* 1000mm, folded distribution structure carry out folded matches by 0 ° 45 ° 0 ° 0 ° 45 ° 0 ° (i.e. Fig. 2), it is preferred that before folding and matching, need to remove and be compounded in Release paper superficial layer on unidirectional yarn prepreg, and stick one layer of release cloth on surface and do rough surface, it is put into mold steel plate, The unidirectional yarn composite plate of 0.6mm high bending strength, high surface roughness is made after 120-160 DEG C of hot pressing 2h is formed, table 1 is real Apply the performance table of the composite plate of example preparation.
Example IV:
Resin adhesive liquid preparation process is as follows:
1) by the dicyandiamide of 2.0 parts by weight, the dimethyl miaow of the 4,4- diaminodiphenylsulfone of 20 parts by weight, 0.08 parts by weight Azoles is dissolved in the acetone of 60 parts by weight, obtains mixed liquor one；
2) 60 parts by weight of bisphenol A type ring oxygen Resin As, 40 parts by weight polyfunctional epoxy resin B, the big of 20 parts by weight are divided The fumed silica of sub- phenoxy resin, 3 parts by weight is stirred at 120 DEG C, is uniformly dispersed to obtain mixed liquor wait melt Two；
3) mixed liquor one is mixed with mixed liquor two, temperature control at 35-50 DEG C, speed of agitator 600-800 turns/ Min after being uniformly dispersed, is vacuumized, and is removed solvent acetone, is obtained mixed glue solution.
Prepreg manufacturing process is as follows:
4) the above-mentioned resin adhesive liquid prepared is added in the glue groove of film applicator, carries out film, film temperature control exists 60-80 DEG C, in 3-9m/min, film paper is placed on release paper wire velocity control by tension force after the completion of 120-300N, film Thermostatic chamber is spare；
5) 2 coil coating film paper are individually placed to upper film and lower film location, by fiber grammes per square metre 125g/m2S grades of high-strength fiber glass are unidirectional Yarn is placed between upper and lower film paper, carried out on compounding machine it is compound, compound linear velocity be 3-8m/min, tension 120-300N, glue Content control is made the unidirectional yarn prepreg of S grades of high-strength fiber glass, is indirectly smeared resin adhesive liquid by release paper 40 ± 1% On the two sides of unidirectional yarn, unidirectional yarn prepreg is obtained；
6) the unidirectional yarn prepreg of S made from step 5 grades of high-strength fiber glass wound, sealed, being put into freezer preservation.
Unidirectional yarn composite plate preparation is as follows:
The unidirectional yarn prepreg of the S prepared grade high-strength fiber glass is cut into 1280*1000mm, distribution structure is folded and presses 0 ° 45 ° 90 ° 90 ° 45 ° 0 ° (i.e. Fig. 3) carry out folded match, it is preferred that before folded match, need to remove the release paper being compounded on unidirectional yarn prepreg Superficial layer, and stick one layer of release cloth on surface and do rough surface, it is put into mold steel plate, is formed through 120-160 DEG C of hot pressing 2h The unidirectional yarn composite plate of 0.6mm high bending strength, high surface roughness is made afterwards, table 1 is the property of the composite plate of embodiment preparation It can table.
Embodiment five:
Resin adhesive liquid preparation process is as follows:
1) by the dicyandiamide of 2.0 parts by weight, the dimethyl miaow of the 4,4- diaminodiphenylsulfone of 20 parts by weight, 0.08 parts by weight Azoles is dissolved in the acetone of 60 parts by weight, obtains mixed liquor one；
2) 60 parts by weight of bisphenol A type ring oxygen Resin As, 40 parts by weight polyfunctional epoxy resin B, the big of 20 parts by weight are divided The fumed silica of sub- phenoxy resin, 3 parts by weight is stirred at 120 DEG C, is uniformly dispersed to obtain mixed liquor wait melt Two；
3) mixed liquor one is mixed with mixed liquor two, temperature control at 35-50 DEG C, speed of agitator 600-800 turns/ Min after being uniformly dispersed, is vacuumized, and is removed solvent acetone, is obtained mixed glue solution.
Prepreg manufacturing process is as follows:
4) the above-mentioned resin adhesive liquid prepared is added in the glue groove of film applicator, carries out film, film temperature control exists 60-80 DEG C, in 3-9m/min, film paper is placed on release paper wire velocity control by tension force after the completion of 120-300N, film Thermostatic chamber is spare；
5) 2 coil coating film paper are individually placed to upper film and lower film location, by fiber grammes per square metre 125g/m2The common unidirectional yarn of glass is put Between upper and lower film paper, carried out on compounding machine it is compound, compound linear velocity be 3-8m/min, tension 120-300N, glue content Control is made the unidirectional yarn prepreg of common glass, resin adhesive liquid is applied to unidirectional yarn indirectly by release paper 40 ± 1% Two sides on, obtain unidirectional yarn prepreg；
6) the unidirectional yarn prepreg of common glass made from step 2 wound, sealed, being put into freezer preservation.
Unidirectional yarn composite plate preparation is as follows: the unidirectional yarn prepreg of the common glass that will be prepared cuts into 1280*1000mm, Folded distribution structure carries out folded matches by 0 ° 90 ° 0 ° 0 ° 90 ° 0 ° (i.e. Fig. 1), it is preferred that before folding and matching, needs to remove and is compounded in unidirectional yarn Release paper superficial layer on prepreg, and stick one layer of thick release paper of height on surface and do rough surface, it is put into mold steel plate, passes through The unidirectional yarn composite plate of 0.6mm high bending strength, high surface roughness is made after 120-160 DEG C of hot pressing 2h molding, table 1 is to implement The performance table of the composite plate of example preparation.
Embodiment six:
Resin adhesive liquid preparation process is as follows:
1) by the dicyandiamide of 2.0 parts by weight, the dimethyl miaow of the 4,4- diaminodiphenylsulfone of 20 parts by weight, 0.08 parts by weight Azoles is dissolved in the acetone of 60 parts by weight, obtains mixed liquor one；
2) 60 parts by weight of bisphenol A type ring oxygen Resin As, 40 parts by weight polyfunctional epoxy resin B, the big of 20 parts by weight are divided The fumed silica of sub- phenoxy resin, 3 parts by weight is stirred at 120 DEG C, is uniformly dispersed to obtain mixed liquor wait melt Two；
3) mixed liquor one is mixed with mixed liquor two, temperature control at 35-50 DEG C, speed of agitator 600-800 turns/ Min after being uniformly dispersed, is vacuumized, and is removed solvent acetone, is obtained mixed glue solution.
Prepreg manufacturing process is as follows:
4) the above-mentioned resin adhesive liquid prepared is added in the glue groove of film applicator, carries out film, film temperature control exists 60-80 DEG C, in 3-9m/min, film paper is placed on release paper wire velocity control by tension force after the completion of 120-300N, film Thermostatic chamber is spare；
5) 2 coil coating film paper are individually placed to upper film and lower film location, by fiber grammes per square metre 125g/m2The unidirectional yarn of carbon fiber is placed on Between upper and lower film paper, carried out on compounding machine compound, compound linear velocity is 3-8m/min, tension 120-300N, glue content control System is made the unidirectional yarn prepreg of carbon fiber, resin adhesive liquid is applied to the two sides of unidirectional yarn indirectly by release paper 40 ± 1% On face, unidirectional yarn prepreg is obtained；
6) the unidirectional yarn prepreg of carbon fiber made from step 2 wound, sealed, being put into freezer preservation.
Unidirectional yarn composite plate preparation is as follows: the unidirectional yarn prepreg of the carbon fiber that will be prepared cuts into 1280*1000mm, folded to match Structure carries out folded matches by 0 ° 90 ° 0 ° 0 ° 90 ° 0 ° (i.e. Fig. 1), it is preferred that before folded match, needs to remove and is compounded in unidirectional yarn preimpregnation Release paper superficial layer on material, and stick one layer of thick release paper of height on surface and do rough surface, it is put into mold steel plate, through 120- The unidirectional yarn composite plate of 0.6mm high bending strength, high surface roughness is made after 160 DEG C of hot pressing 2h moldings, table 1 is embodiment system The performance table of standby composite plate.
Embodiment seven
Resin adhesive liquid preparation process is as follows:
1) by the dicyandiamide of 2.0 parts by weight, the dimethyl miaow of the 4,4- diaminodiphenylsulfone of 20 parts by weight, 0.08 parts by weight Azoles is dissolved in the acetone of 60 parts by weight, obtains mixed liquor one；
2) 60 parts by weight of bisphenol A type ring oxygen Resin As, 40 parts by weight polyfunctional epoxy resin B, the big of 20 parts by weight are divided The fumed silica of sub- phenoxy resin, 3 parts by weight is stirred at 120 DEG C, is uniformly dispersed to obtain mixed liquor wait melt Two；
3) mixed liquor one is mixed with mixed liquor two, temperature control at 35-50 DEG C, speed of agitator 600-800 turns/ Min after being uniformly dispersed, is vacuumized, and is removed solvent acetone, is obtained mixed glue solution.
Prepreg manufacturing process is as follows:
4) the above-mentioned resin adhesive liquid prepared is added in the glue groove of film applicator, carries out film, film temperature control exists 60-80 DEG C, in 3-9m/min, film paper is placed on release paper wire velocity control by tension force after the completion of 120-300N, film Thermostatic chamber is spare；
5) 2 coil coating film paper are individually placed to upper film and lower film location, by fiber grammes per square metre 125g/m2It is the unidirectional yarn of carbon fiber, common The unidirectional yarn of glass is respectively placed between upper and lower film paper, carried out on compounding machine it is compound, compound linear velocity be 3-8m/min, Power 120-300N, glue content are controlled 40 ± 1%, and the unidirectional yarn prepreg of carbon fiber and the unidirectional yarn preimpregnation of common glass are made respectively Material；
6) the unidirectional yarn prepreg of carbon fiber made from step 2 wound, sealed, being put into freezer preservation.
Unidirectional yarn composite plate preparation is as follows: the unidirectional yarn prepreg of the carbon fiber that will be prepared, the unidirectional yarn of common glass are cut into 1280*1000mm folds distribution structure and presses 0 ° 90 ° 0 ° 0 ° 90 ° 0 ° (i.e. Fig. 1), and material is followed successively by carbon fiber, carbon fiber, glass, glass, carbon Fine, carbon fiber, which fold, matches, and sticks the thick embossing release film of one layer of height on surface and do rough surface, is put into mold steel plate, passes through The unidirectional yarn composite plate of 0.6mm high bending strength, high surface roughness is made after 120-160 DEG C of hot pressing 2h molding, table 1 is to implement The performance table of the composite plate of example preparation, in the present embodiment, 0 ° of angle referred between floor level and horizontal plane, 90 ° of fingers Be the angle rotated between surface layer and horizontal plane.
Folded distribution structure in the above-described embodiments is symmetrical above and below.
In the above-described embodiments, for ease of description, the machine direction of prescribed level surface layer be 0 °, it is corresponding, 90 ° or 45 ° refer to floor level be rotated by 90 ° or 45 ° after the rotation surface layer that is formed.
Comparative example one:
Resin adhesive liquid preparation process is as embodiment two；
Prepreg manufacturing process, referring to embodiment two, by 125g/m2S grades of high-strength unidirectional yarns change 125g/m into2Common glass Woven cloth, other processes are the same；
Unidirectional yarn composite plate preparation is as follows:
The common glass woven cloth prepreg prepared is cut into 1280*1000mm, and referring to embodiment (woven cloth without Directionality) carry out it is folded match, and stick common release film in upper and lower surface, be put into mold steel plate, through 120-160 DEG C of hot pressing 2h at The high bending strength of 0.6mm, the unidirectional yarn composite plate of high surface roughness are made after type, table 1 is the composite plate of embodiment preparation Performance table.
The performance data table of the composite plate of 1 embodiment of table preparation
Embodiment two is compared to embodiment seven and comparative example one, it can be seen that same resin adhesive liquid formula is used, The bending strength of conventional sheet about 450MPa, and special unidirectional yarn prepreg of the invention, using the plate after different folded distribution structures All in 800MPa or more, bending strength is obviously improved material bending strength, and reaches design strength requirement；
Embodiment one is compared to embodiment seven and comparative example one, it can be seen that conventional plate made from common release film About 0.5 μm of surface roughness Ra value, the surface roughness Ra value of the composite plate as made from introducing the material of high roughness exists 3.5 μm or more, roughness is obviously improved, and facilitates injection molding, the fitting in plate later period；
Embodiment one is compared with embodiment two, and other conditions are the same, and main difference is the formula of resin adhesive liquid not Equally, bending strength: two < embodiment three of embodiment, finally, the optimization of proper formulation can change plate toughness, into And improve the bending strength of unidirectional yarn composite plate；
Embodiment two, embodiment five, embodiment six compare, it can be seen that identical resin adhesive liquid is used, it is identical Folded distribution structure, the corresponding intensity size of the unidirectional yarn of unlike material is variant, specific bending strength size order: the unidirectional yarn of carbon fiber The unidirectional yarn of the > high-strength fiber glass common glass of single line yarn >；
Embodiment two, embodiment three, example IV compare, it can be seen that the unidirectional yarn prepreg of same material is adopted With the different corresponding bending strengths of folded distribution structure, there is also differences；
Embodiment five, embodiment six, embodiment seven compare, it can be seen that identical resin adhesive liquid is used, it is identical Folded distribution structure, introduces that a variety of unidirectional yarns mixing are folded to match, and corresponding intensity size is by difference, specific bending strength size order: The unidirectional yarn of the unidirectional common common glass of glass single line yarn > of the unidirectional yarn of yarn > carbon fiber of carbon fiber, using the unidirectional yarn of carbon fiber and common glass Unidirectional yarn carries out compound structure, and bending strength is substantially better than the unidirectional yarn of common glass, and can reduce cost (carbon fiber is unidirectional Yarn cost is higher than the unidirectional yarn of common glass), tool has great advantage.
It can be seen that unidirectional yarn prepreg different resins glue formula disclosed by the invention, different folded distribution structures are set Meter and different surface roughness material selection, are made high-strength (bending strength >=800MPa) of the present invention, high surface roughness The unidirectional yarn composite plate of (surface roughness Ra >=3.5 μm).
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, defined in the present invention General Principle can realize in other embodiments without departing from the spirit or scope of the present invention；Therefore, this hair It is bright to be not intended to be limited to the embodiments shown herein, and be to fit to and the principles and novel features disclosed herein phase Consistent widest scope.
Although the corresponding term of appended drawing reference in figure is used more herein, be not precluded using other terms can It can property；The use of these items is only for be more convenient to describe and explain essence of the invention；It is construed as any one The additional limitation of kind is disagreed with spirit of that invention.

Claims (10)

1. a kind of unidirectional yarn composite plate, which is characterized in that the unidirectional yarn composite plate includes more than two recombiner units, described multiple Closing unit includes floor level (1) and rotation surface layer (2), and rotation surface layer (2) the relative level surface layer (1) sets at an angle It sets, adjacent recombiner unit is along recombiner unit binding face in symmetrical above and below.
2. a kind of unidirectional yarn composite plate according to claim 1, which is characterized in that rotation surface layer (2) and floor level (1) Between angle α are as follows: 0 ° < α < 180 °.
3. a kind of unidirectional yarn composite plate according to claim 1, which is characterized in that unidirectional yarn composite plate side or Two sides are fitted with superficial layer (3), and superficial layer (3) is using any one in release film, release paper, release cloth.
4. a kind of unidirectional yarn composite plate according to claim 3, which is characterized in that floor level (1) and rotation surface layer (2) Using any in the unidirectional yarn of common glass, the unidirectional yarn of S grades of high-strength fiber glass, the unidirectional yarn of carbon fiber by resin adhesive liquid dipping A kind of and a variety of combination.
5. a kind of preparation method of unidirectional yarn composite plate, which comprises the following steps:
Step 1: prepare unidirectional yarn and resin adhesive liquid；
Step 2: resin adhesive liquid is applied in release paper, and unidirectional yarn is then placed in two panels release paper and is coated with resin adhesive liquid It is carried out by compounding machine compound between the side, finally removes release paper, obtain unidirectional yarn prepreg；
Step 3: unidirectional yarn prepreg is cut, and more than two unidirectional yarn prepregs fold according to preset structure and are matched, is obtained To unidirectional yarn composite material；
Step 4: superficial layer is sticked in the unidirectional yarn composite material side or two sides；
Step 5: the compound that step 4 is obtained is hot-forming, after cooling, obtains unidirectional yarn composite plate.
6. a kind of preparation method of unidirectional yarn composite plate according to claim 5, which is characterized in that the resin in step 1 The component of glue includes 50-80 parts by weight epoxy resin A, 20-50 parts by weight epoxy resin B, 10-20 weight in parts by weight Part toughener, 2.0-2.6 parts by weight dicyandiamide, 15-20 parts by weight 4,4- diaminodiphenylsulfone, 0.05-0.15 parts by weight diformazan Base imidazoles, 2-8 parts by weight fumed silica and 40-60 pbw acetone.
7. a kind of preparation method of unidirectional yarn composite plate according to claim 6, which is characterized in that epoxy resin A is selected from Including one or more in bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, novolac epoxy resin.
8. a kind of preparation method of unidirectional yarn composite plate according to claim 6, which is characterized in that epoxy resin B is selected from Including one of multifunction group epoxy, brominated epoxy resin and phosphorous epoxy resin or a variety of.
9. a kind of preparation method of unidirectional yarn composite plate according to claim 6, which is characterized in that toughener, which is selected from, includes Macromolecular phenoxy resin, nitrile rubber, poly(aryl ether ketone), acrylic rubber, the one or more of polyurethane.
10. a kind of preparation method of unidirectional yarn composite plate according to claim 6, which is characterized in that the tree in step 1 The preparation step of rouge glue is as follows:
(1) first dicyandiamide, 4,4- diaminodiphenylsulfone, methylimidazole are dissolved into acetone solvent and obtain mixed liquor one；
(2) epoxy resin A, epoxy resin B, toughener, fumed silica are subjected to heating stirring, obtain mixed liquor after melting Two；
(3) mixed liquor one and mixed liquor two are uniformly mixed, are vacuumized, after removing solvent, resin adhesive liquid is made.
CN201910513784.0A 2019-06-14 2019-06-14 A kind of unidirectional yarn composite plate and preparation method thereof Pending CN110202862A (en)

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Application publication date: 20190906