CN1944026B - Epoxy resin for prepreg, prepreg, fiber-reinforced composite material, and processes for producing these - Google Patents
Epoxy resin for prepreg, prepreg, fiber-reinforced composite material, and processes for producing these Download PDFInfo
- Publication number
- CN1944026B CN1944026B CN2006101267157A CN200610126715A CN1944026B CN 1944026 B CN1944026 B CN 1944026B CN 2006101267157 A CN2006101267157 A CN 2006101267157A CN 200610126715 A CN200610126715 A CN 200610126715A CN 1944026 B CN1944026 B CN 1944026B
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- China
- Prior art keywords
- composition
- prepreg
- epoxy resin
- fiber
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000000463 material Substances 0.000 title claims abstract description 158
- 239000003733 fiber-reinforced composite Substances 0.000 title claims abstract description 16
- 239000003822 epoxy resin Substances 0.000 title claims description 172
- 229920000647 polyepoxide Polymers 0.000 title claims description 172
- 238000000034 method Methods 0.000 title abstract description 54
- 230000008569 process Effects 0.000 title abstract description 10
- 239000000835 fiber Substances 0.000 claims abstract description 152
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- 239000000203 mixture Substances 0.000 claims description 259
- 238000000465 moulding Methods 0.000 claims description 47
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- 229920000049 Carbon (fiber) Polymers 0.000 claims description 40
- 239000004917 carbon fiber Substances 0.000 claims description 40
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 40
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 39
- 238000013459 approach Methods 0.000 claims description 33
- 239000000047 product Substances 0.000 claims description 28
- 239000012783 reinforcing fiber Substances 0.000 claims description 20
- 150000001412 amines Chemical class 0.000 claims description 18
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 14
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Abstract
The invention provides a superior method for producing fiber-reinforced composite material product with high strength and excellent appearance by compression forming in a short time. The method for producing the fiber-reinforced composite material product comprises the following steps: preliminarily adjusting a temperature of a mold to be equal to or more than the curing temperature of a thermosetting resin; putting a molding material (one side surface area S1) which is impregnated with the thermosetting resin in a substantially continuous reinforced fiber, in the temperature-adjusted mold (one side surface area S2); fastening the mold following the former process and then filling the whole inside of the mold with a molding material; and being subjected to compression molding in a manner that S1/S2 is 0.8 to 1.
Description
The application is to be on November 28th, 2003 applying date of original application, and application number is 200380104284.9, and denomination of invention is divided an application for the one Chinese patent application of " epoxy resin for prepreg, prepreg, fibre reinforced composites and manufacturing approach thereof ".
Technical field
The present invention relates to composition epoxy resin, compositions of thermosetting resin, prepreg, fibre reinforced composites and manufacturing approach thereof.The application's epoxy resin is the composition epoxy resin that is suitable for prepreg especially, in the lower following short time of temperature, just can solidify.Thus, use it can obtain mechanical properties superior prepreg superior, that at room temperature can preserve for a long time.And then compositions of thermosetting resin of the present invention is suitable for high-rate forming, can show high mechanical properties for the fibre reinforced composites (also being recited as FRP among later the present invention sometimes) after being shaped.Thereby, can obtain superior prepreg and formed product of fiber-reinforced composite material through using said composition.Superior prepreg provided by the present invention can be used for obtaining aptly can be as the sheet material of the fibre reinforced composites of the outside plate of means of transport or industrial machine.And then, the method for easily making the superior FRP of high strength and aesthetic appearance, the method for particularly using compression forming method to make with the short time are provided among the present invention.
In addition; The application puts down into 14 years No. 346198, Japan's patent application with Japan's patent application and puts down into 14 years No. 347650, Japan's patent application and put down into 14 years No. 353760, Japan's patent application and put down into 14 years No. 362519 and be the basis, and its content is enrolled among the application.
Background technology
FRP has light weight, high strength, high rigid characters, is widely used to industry purposes such as automobile, aircrafts from motion such as fishing rod, golf clubs and leisure purposes.
Use is the method for prepreg to the intermediate materials of the supporting material impregnated with resin that is made up of long fibres such as fortifying fibres, because the content of control fortifying fibre in prepreg easily, and can design its content high, therefore be suitable as the manufacturing approach of FRP.
As the concrete grammar that obtains FRP by prepreg, have method, spy that the spy drives the use autoclave that discloses in the flat 10-128778 communique and open the method for utilizing vacuum bag, the spy that disclose in the 2002-159613 communique and open the compression forming method that discloses in the flat 10-95048 communique etc.
But, in these any one method, when being heating and curing, under approximately more than or equal to 160 ℃ condition, all need about about 2～6 hours time by solidifying when the lamination prepreg and after with the target shape typing.Promptly need high temperature and processing for a long time.
Yet, can produce in a large number in order to make goods, require in the lower temperature about 100～130 ℃ and just can be shaped in the short time about a few minutes to dozens of minutes.Can enumerate for one of method of realizing this problem, use the composition epoxy resin that under a spot of heat, just begins curing reaction, the time method that finishes with the curing of shortening by composition epoxy resin.But if reactivity is too high, then curing reaction is out of control easily, hazardous.Yet when using the curing agent that in the past adopted, if increase the amount of this curing agent, mechanical properties may reduce.And, but such composition epoxy resin is also short between its operating period, at room temperature only preserves and just may solidify in several days.The exploitation that just waiting in expectation like this, at present has desirable reactive composition epoxy resin.
Then, if, can enumerate following condition from the desired suitable condition of prepreg is considered.The drapability operability such as (flexibilities) of near the good viscosity room temperature (state is clamminess), appropriateness is superior;
Can keep this operability for a long time, promptly near room temperature, have the long life-span, and then its mechanical properties of FRP and hot rerum natura after being shaped are superior.
Fortifying fibre is soaked into the prepreg that matrix resins such as composition epoxy resin formed, were widely used as the intermediate materials of fibre reinforced composites and can be applied to various fields; But for the situation of above-mentioned industry purposes, the special demands formability is superior.
Now, need about 1 hour being heating and curing for common prepreg, as stated; If comprise the time of the cooling that heats up; Then need about 2 or 3 hours～6 hours based on the condition once-forming, its time is very long, becomes one of reason of shaping cost increase.
But if shorten the needed heat time heating time that is shaped, then near the life-span room temperature can shorten, and must make the high such disadvantage of forming temperature thereby tend to produce.Giving the exploitation of the compositions of thermosetting resin of prepreg superior characteristic is also carrying out.
Then, characteristic and the FRP sheet material to SMC and prepreg describes.
For the material that is used for FRP beyond the prepreg, be mostly to adopt moulding material such as sheet-shaped moulding material (below be called SMC) to form.But; In the manufacturing of FRP, using in a direction and draw neat continuous reinforcing fiber in fact and the prepreg that forms (below be called the UD prepreg) and Fabric prereg etc. use the SMC with the place that described several places at the back should improve, is being favourable aspect the intensity of FRP particularly.
But in order to obtain more superior FRP expeditiously, the prepreg that uses now also needs new improvement etc.
The sheet material of FRP is because corrosion resistance is superior, and just attempting being used as with the automobile is the means of transport of representative and the outside plate of various industrial machines.The FRP sheet material that for example is called SMC is widely used in the hood of automobile, dashboard off-grade plate.
SMC (for example opening flat 6-286008 communique with reference to the spy) is the middle base material with mixed pasty states such as the fortifying fibre of the short fiber of carbon fiber or glass fibre and mylar.Exert pressure with high pressure to its heating and in mould and (to be generally more than or equal to 50kg/cm
2) and finalize the design, make the base plate that becomes outside plate.Then, cut the surface of this base plate and make it smooth, level and smooth with sand paper or rasion, the covering with paint of painting then, thus form the FRP system outside plate that automobile is for example used.
The outside plate that is formed by SMC is short fiber (discontinuous fiber) owing to fortifying fibre; Thereby with fortifying fibre be continuous fiber situation mutually specific rigidity low (being not only short fiber is fortifying fibre; The elastic modelling quantity of glass is 70GPa, be low to moderate steel elastic modelling quantity 210GPa 1/3).Thereby the thickness ratio metal outer panel of outside plate is all big, and comparing with metal outer panel sometimes may not light weight, though simultaneously can lightweight also mostly be the situation that alleviate a little.And then SMC system outside plate is discontinuous owing to fiber, thereby low as the intensity of the key property beyond the rigidity of outside plate, is particularly impacted the such local assault of outside plate by sudden thing easily and runs through damage.Thereby, need further to increase thickness for the outside plate that uses outside the room of means of transport etc., perhaps take to paste shock-resistant protection countermeasures such as rubber.Can not be formed on the light weight outside plate that the weight aspect can replace metal system outside plate like this, the means of transport that promptly helps environment is used outside plate.
But the outside plate that is much formed by SMC is through irregularly (roughly even) dispersion of short fiber, to obtain roughly surface quality uniformly in the base plate before above-mentioned grinding easily by the main reason of practicability.When using continuous fiber, because Fiber Distribution inhomogeneous and inhomogeneous by the complications of fiber, fluctuation, the fiber concavo-convex and thickness that causes such as staggered each other, the surface undulation of base plate is big than short fiber.Thereby, for this situation, can produce following problem:
1) labour of above-mentioned grinding operation is big;
2) also continuous reinforcing fiber be can grind off during grinding, thereby the machinery and the functional rerum natura of above-mentioned outside plate further reduced.
Yet the situation of continuous fiber has higher rerum natura, and can make the FRP sheet material of light weight, thereby is being desirable aspect rigidity and the intensity.But,, all do not reach practicability though the form of continuous fiber is complicated various to prepreg, fabric, three dimensional fabric etc. for folk prescription.
On the other hand, be that the research of the parts of fortifying fibre is also carried out with the continuous fiber.These parts are with manufacturings such as resin transfer mouldings (RTM); This RTM is the prepreg that lamination is formed by continuous fiber of arranging in one direction and resin on mould; Be cured with autoclave etc., perhaps the preform with fabric etc. is placed in the mould again, and resin reinjects.But, because the complications of the intrinsic fiber of above-mentioned continuous fiber, fluctuation, fiber staggered etc. caused concavo-convex and thickness each other is inhomogeneous, cause surface quality low, actual state is that the outside plate as means of transports such as automobiles does not have practicability.
In order to improve surface quality, adopt the rubbing method that is called gel coat.So-called gel coat method (opening flat 11-171942 communique with reference to the spy) is that the inner face at mould is pre-formed the resin material coatings such as polyester that can become outer plate surfaces, on this coating, disposes reinforcing-fiber substrate again, and close die; Then, inject resin and make its curing, the demoulding is in this coating of surface transfer of FRP outside plate.This method thereby is of value to industrialization owing to can omit the grinding and the covering with paint on surface.But, when being heating and curing, because the difference of the linear expansion coefficient of FRP and gel coat can produce distortion such as whole formed body warpage.Thereby, be not suitable for the outside plate of precision prescribed, and, owing to gel coat breaks or the wrinkling outside plate that is not suitable for.
And then owing to exist concavo-convexly as stated as the surface of the FRP of fortifying fibre with continuous fiber, thereby the thickness of gel coat is thick for the covering with paint films of the situation of covering with paint, lacquer, colour wash, etc. more than or equal to 200 microns.Therefore the defective that exists is, not only weight can increase, and outside plate receives external force and when being out of shape, gel coat can break or peel off, thereby is not suitable for outside plate.
Because the breaking or peel off of gel coat, for the situation of the gel coat of the outside plate that uses without, moisture such as rainwater can be invaded FRP inside, thereby damage light weight, durability as the FRP characteristics sometimes.And the situation of gel coat is compared with covering with paint, and the selection branch of color is few, can't produce the outward appearance that is rich in metal sense and fashion.Thereby the problem of existence is, because the value of whole commodity can reduce, it can not be applicable to that automobile exterior panel etc. needs the outside plate of matching colors with miscellaneous part.Also considered on gel coat, to implement to cover with paint, lacquer, colour wash, etc., further weight increases, cost increases such problem but this situation can produce.
In order to improve surface quality, also carried out other trial (opening the 2001-322179 communique) with reference to the spy through the blanketing fctor of adjusting the carbon fibre fabric that is used as fortifying fibre.
But because carbon fibre fabric will be passed through after weaving and be processed into intermediate materials, severing lamination preformization, be configured as the so various processing of FRP, thereby blanketing fctor to be remained on suitable scope be difficult.If through moving of joint filling constraint carbon fiber, blanketing fctor can remain on suitable scope, but because carbon fiber is restrained, the defective of existence is the unusual difficulty of FRP that obtains curve form.
As stated, actual state is to be that fortifying fibre is few in the example of outside plate as the special practicability of FRP sheet material of the prepreg of continuous fiber with having used prepreg, has the structure of the FRP sheet material of practicality, the quantitative target of surface quality is not established.
The linear expansion coefficient of the thickness direction of FRP wants big than metal.Thereby, if the flatness on surface is poor,, thereby because the lens effect that light such as ultraviolet ray cause, covers with paint, lacquer, colour wash, etc. deterioration and produce spot then because along with the distortion of variations in temperature, rainwater etc. can stop, become the outside plate of spot apperance.
The surface quality of outside plate is except above-mentioned commodity with the long durability, knownly also can produce material impact to the fluid resistance to empty G&W.Thereby, be not only automobile, the whole means of transports for electric car, baby plane, canoe, boats and ships etc. move are necessary to improve surface quality in order to save the energy.If for lightweight outside plate is made the FRP system usually, then, can produce big distortion to the air drag that receives in the means of transport high-speed mobile because the modular ratio metal is low, flow resistance can produce bigger variation.Thus, should independently set the standard different to the surface of FRP sheet material with metal material.
Repeat, in order to have used the FRP sheet material practicability of continuous fiber, the eager such complex art of quantitative target that requires to establish the structure that is suitable for FRP sheet material, material, surface quality.
Then describe to manufacturing approach.
As the method that is obtained FRP by moulding material, known as stated have the method for using autoclave, the method for utilizing vacuum bag, a compression forming method etc.Especially, compression forming method is compared with the forming process of utilizing autoclave and vacuum bag, and curring time is relatively short just can be accomplished, thus be suitable for having good surface appearance, a large amount of productions of high-intensity FRP.And this method is also easy owing to processing mold, thereby also has the also easy advantage of the FRP that makes complicated shape.
But when using with continuous reinforcing fiber as the moulding material of reinforcing material through compression molding manufactured FRP, the resin that viscosity reduces is inner or the surface is sharply mobile at FRP because of pressurization.And owing to should flow, the arrangement of fortifying fibre is upset, and produces so-called coil bending.So not only aesthetic appearance can worsen owing to the coil bending of surface portion, and because the arrangement of the fortifying fibre of this part can cause inner coil bending in a jumble, the mechanical properties of FRP can reduce.Therefore, adopt the manufacturing of the FRP of compression forming method to be limited to the situation that the spy opens the use SMC that discloses in the flat 10-95048 communique etc.
Summary of the invention
The result that the inventor carries out lucubrate provides 4 kinds of modes that realize the problem of following record.
One of problem of the present invention provides with composition epoxy resin in the past and compares, even even but also can accomplish curing at low temperatures in the short time and at room temperature preserve the composition epoxy resin that also can guarantee between the sufficient operating period; And, show the fibre reinforced composites of superior mechanical properties according to the prepreg that uses this resin to obtain.It is realized through the first following invention.
It is first mode of the present invention; A kind of composition epoxy resin; It is the composition epoxy resin that is formed by following A composition, B composition, C composition and D composition, and the content of sulphur atom in the composition epoxy resin and C composition is respectively 0.2～7 quality % and 1～15 quality %.
A composition: epoxy resin
B composition: have the reaction product (B-2 composition) that has the amines of at least one sulphur atom in amines (B-1 composition) and/or the epoxy resin and the molecule of at least one sulphur atom in the molecule
C composition: urea compounds
D composition: dicyandiamide
In above-mentioned composition epoxy resin, can especially preferably use gel time to be composition epoxy resin smaller or equal to 200 seconds at 130 ℃.
In addition; The inventor provides the composition epoxy resin that is associated with first mode; It is the composition epoxy resin that is made up of B-2 composition, C composition and D composition as the reaction product of the amines that has at least one sulphur atom in epoxy resin and the molecule, and the content of sulphur atom in the composition epoxy resin and C composition is respectively 0.2～7 quality % and 1～15 quality %.
B-2 composition: the reaction product that has the amines of at least one sulphur atom in epoxy resin and the molecule
C composition: urea compounds
D composition: dicyandiamide
And then; The inventor provides the manufacturing approach of the composition epoxy resin that is associated with first mode; Wherein, 100 mass parts A compositions and 0.2～7 mass parts B-1 composition are mixed and after obtaining resin combination, further mixed C composition and D composition and when obtaining composition epoxy resin, the content that makes the C composition in the composition epoxy resin is 1～15 quality %.
A composition: epoxy resin
B composition: the amines (B-1 composition) that has at least one sulphur atom in the molecule
C composition: urea compounds
D composition: dicyandiamide
Another problem of the present invention provides the compositions of thermosetting resin that is suitable for prepreg; Said prepreg except have as the characteristics of in the past prepreg promptly the operability of room temperature and superior in the long-life property of room temperature, and can keep shaping after the characteristics of good physical properties, also have the desired characteristics that can high-rate forming of industry purposes.In addition, the prepreg that soaks into this compositions of thermosetting resin and form is provided, and then also provides and use the manufacturing approach of this prepreg with the superior FRP of high-rate forming machinery intensity and hot rerum natura.
This problem realizes through the second following mode.
Be the application's second mode, a kind of compositions of thermosetting resin, it is to be 5 * 10 50 ℃ viscosity
1～1 * 10
4Pasec and under 120 ℃ atmosphere, reach 1 * 10 with interior meeting at 1000 seconds or its
6The compositions of thermosetting resin of Pasec, its after 30 ℃ were placed for 3 weeks 50 ℃ 2 times of viscosity increases or below it.
The application's another problem be solve used continuous fiber FRP sheet material particularly as the synthtic price index on the structure of outside plate, material, surface.That is, following FRP sheet material is provided, it not only has light weight, high rigidity, the high strength that is suitable for means of transport etc., can stand the long-term surface quality that uses but also have, and has structure, material, the superficiality of the outside plate that is of value to the FRP of environment system.This problem realizes through following Third Way.
Be the application's Third Way, (1) with forming pressure more than or equal to 10kg/cm
2, curring time is the prepreg smaller or equal to 0.5 μ m at the center mean roughness (Ra) on the surface of 15 minutes or its FRP sheet material that obtains with interior being heating and curing; (2) with forming pressure more than or equal to 10kg/cm
2, curring time is at 15 minutes or its FRP sheet material that obtains with internal heating curing, it is that the center mean roughness (Ra) on the surface of FRP sheet material is the FRP sheet material smaller or equal to 0.5 μ m.
Another problem of the present invention makes high strength at short notice through compression forming method and aesthetic appearance is superior, with continuous reinforcing fiber in fact as the FRP of reinforcing material.This problem realizes through following mode.
Be the application's cubic formula, a kind of manufacturing approach of formed product of fiber-reinforced composite material, it comprises:
Prepare the step of shaping dies and prepreg; This shaping dies has common edge structure or the rubber sealing structure that keeps sealing; And constituted by mold and bed die, the mould inside when close die has the long-pending S of being of monoplanar surface of one of thickness 2 equal in fact faces at interval
2,
Said prepreg is the prepreg that substantially soaks into composition epoxy resin on the continuous reinforcing fiber; Said composition epoxy resin has following A composition, B composition, C composition and D composition to constitute; The content of sulphur atom in the composition epoxy resin and C composition is respectively 0.2～7 quality % and 1～15 quality %
A composition: epoxy resin
The B composition: the B-1 composition, have the amines and/or the B-2 composition of at least one sulphur atom in the molecule, have the reaction product of the amines of at least one sulphur atom in epoxy resin and the molecule
C composition: urea compounds
D composition: dicyandiamide
The long-pending S of being of monoplanar surface with one of thickness 2 equal in fact faces at interval of this prepreg
1Single face satisfy S
1/ S
2=0.8～1;
With the solidification temperature of said shaping dies temperature adjustment in advance to said epoxy resin or the step more than it;
Said prepreg is put into this step of the shaping dies of temperature adjustment; And
Closed shaping dies carries out compression molding, makes prepreg be full of the inner step of whole shaping dies.
Description of drawings
Figure 1A is that expression has been placed the sectional view of the state of moulding material at mould inside before the close die;
Figure 1B is the sectional view of the state of expression close die;
Fig. 2 is a sectional view of representing preferably to be used to the total marginal texture of the part mould that uses in the cubic formula of the present invention, that upper die and lower die (formpiston and former) contact during close die;
Fig. 3 is a sectional view of representing preferably to be used to the hole to be opened/closed mould, that be located at mould inside of using in the cubic formula of the present invention.Also can be used in the demoulding of FRP through blowing from this hole.
The specific embodiment
Below carry out detailed explanation to the cubic formula of first mode to the of the present invention.
First mode
Following explanation first mode of the present invention, the prepreg that obtains to each composition and additive, manufacturing approach and then by epoxy resin etc. carries out detailed explanation.
Through this mode following composition epoxy resin is provided, its with in the past composition epoxy resin relatively, solidify even also can accomplish in the short time at low temperatures, even and at room temperature preserve and also can guarantee the sufficient up time.According to the prepreg that uses this resin to obtain, can obtain showing the fibre reinforced composites of superior mechanical properties.
(A composition)
A composition in first mode is an epoxy resin.As its example, two functionality epoxy resin can be enumerated the epoxy resin behind these materials of bisphenol A type epoxy resin, bisphenol f type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene-type epoxy resin or modification etc.Example as trifunctional or the multi-functional epoxy resin more than it; Can enumerate such glycidol ether type epoxy of such glycidyl amine type epoxy resin, four (the glycidyl oxygen phenyl) ethane and three (glycidyl oxygen methylmethane) of phenolic resin varnish type epoxy resin, cresols type epoxy resin, four glycidol MDAs, triglycidyl group amino-phenol, four glycidyl amines and the epoxy resin behind these materials of modification, bromination is handled the brominated epoxy resin behind these epoxy resin, but is not limited to this.In addition, as the A composition, also can these epoxy resin combinations be used more than a kind.
Especially, can especially preferably use bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenolic resin varnish type epoxy resin, cresols varnish type epoxy resin.If these epoxy resin, the situation of the epoxy resin high with for example using the rigidity such as epoxy resin that have the naphthalene skeleton in the molecule is compared, the effect of the mechanical strength in the time of can playing further raising and process formed products.This be because, if the high epoxy resin of rigidity is solidified at short notice, then because crosslink density increase is easy to generate strain, on the contrary, if use above-mentioned epoxy resin, the possibility that then produces such problem is low.
On the other hand,, bisphenol-s epoxy resin and the epoxy resin with sulphur skeleton are arranged, also can they be used for the present invention as the epoxy resin that has sulphur atom in the molecule.But, in the present invention,, need the content of the sulphur atom in the composition epoxy resin be carried out quantitatively in order to use these materials effectively.Method for the content of the sulphur atom in the prior quantitatively composition epoxy resin can be used atomic absorption spectrography (AAS) etc.
(B composition)
The B composition of first mode is the reaction product (B-2 composition) that has the amines of at least one sulphur atom in the amines (B-1 composition) that has at least one sulphur atom in the molecule and/or epoxy resin and the molecule.
The B-1 composition is so long as have the just not special qualification of the amines of at least one sulphur atom in the molecule; For example preferably use 4; 4 '-DADPS, 3; 3 '-DADPS, 4,4 '-diamino-diphenyl sulfide, two (4-(4-amino-benzene oxygen) benzene) sulfone, two (4-(3-amino-benzene oxygen) benzene) sulfone, 4,4 '-diamino-diphenyl sulfide, o-tolidine sulfone, and the derivative of these materials etc.
On the other hand, the B-2 composition is the reaction product that has the amines reaction of at least one sulphur atom in above-mentioned epoxy resin and the molecule.In the composition epoxy resin of this mode, through mixing A composition and B-1 composition and make its reaction can obtain containing the B-2 mixture of ingredients, but do not need specially from wherein isolating the B-2 composition separately.
In addition, in the process of the composition epoxy resin of making this mode, the some or all of of material that adds as A composition and B-1 composition can be changed to the B-2 composition.
At this moment, one in A composition and the B-1 composition or both can all be consumed and are changed to into the B-2 composition.
In this mode, can use any of B-1 composition and B-2 composition, but when being to use B-2 composition or B-1 composition and B-2 mixture of ingredients, can improve storage-stable.
(C composition)
C composition in this mode is a urea compounds.
The C composition is not special to be limited, but the preferred urea compounds such as dichloro-dimethyl urea, phenyl dimethyl urea that use.Especially, in molecule, do not have the material of halogen atom, its reactive height and toxicity are also low, thereby can be suitable for as C composition especially.
Can also contain the amide of carbonic acid, carbamic amide among the present invention in the said urea compounds.Generally can make phosgene, chloro-formate, hydrargyrum amidochloratum formyl, carbonic ester, isocyanates, cyanic acid etc. and the amine of ammonia etc. be used for obtaining.
The compound that alkane urea (ureine) that makes uride (acylureas) that urea and acyl chlorides effect obtain and obtain with the hydrogen of hydrocarbyl substituted urea etc. is commonly referred to the urea class is also contained in this mode in the said urea compounds.
In addition, said urea compounds also comprises urea adduct in this mode.
If urea adduct is enumerated an example and described, then be meant at the saturated solution of lower alcohols such as the saturated aqueous solution of hydrocarbon mixture and urea or methyl alcohol and imported the material of hydrocarbon in the crystalline texture of the urea that obtains.
The content of the C composition in the composition epoxy resin need be 1～15 quality %.Be preferably more than and equal 3 quality %, and be preferably smaller or equal to 12 quality %.If less than 1 quality %, then curing reaction can fully not accomplished sometimes; If surpass 15 quality %, but then short between the operating period, near room temperature, possibly can't preserve for a long time.
And then when using the material of solid as the C composition, average grain diameter is preferably smaller or equal to 150 μ m, more preferably smaller or equal to 50 μ m.If average grain diameter surpasses 150 μ m,, might can't realize the i.e. curing at short notice of most important effect of the present invention then because dispersion of nano-particles speed reduces, and consequently the speed of curing reaction reduces.
(D composition)
D composition in first mode is a dicyandiamide.This dicyandiamide plays the effect of curing agent for epoxy resin, through with this mode in the combination of other compositions use can be in lower temperature-curable.
In this mode, the content of the D composition in the composition epoxy resin is preferably 0.1～10 quality %.In addition, if the average grain diameter of D composition smaller or equal to 150 μ m, particularly smaller or equal to 50 μ m, favorable dispersibility then, reaction speed accelerates, thereby is preferred.
(other additives)
In the composition epoxy resin of first mode, can also add in right amount micronized inorganic particles such as silica, pigment, elastomer, as the aluminium hydroxide of fire retardant and bromide or phosphorus series compound, defoamer, with improve the such thermoplastic resin that is dissolved in epoxy resin of polyvinyl acetal resin that operability and flexibility are purpose and phenoxy resin, as imdazole derivatives, metallic complex salt or the tertiary amine compound etc. of the catalyst of curing reaction.
(content of the sulphur atom in the composition epoxy resin)
In the composition epoxy resin of first mode, the content of the sulphur atom in the composition epoxy resin is necessary for 0.2～7 quality %.If less than 0.2 quality % then is difficult to accomplish curing in the short time at low temperatures; If surpass 7 quality %, but then might shorten between the operating period.
(gel time)
The composition epoxy resin of first mode is smaller or equal to 200 seconds at 130 ℃ gel time preferably.In this mode, when so-called gel time is meant the temperature that raises specific to uncured composition epoxy resin, by the time of accomplishing gelation.At this, so-called gelation is meant the state that composition epoxy resin loses flowability at intermolecular formation three-dimensional net structure.
At the composition epoxy resin of 130 ℃ gel times, especially can realize at short notice solidifying smaller or equal to 200 seconds.
(manufacturing approach of composition epoxy resin)
The manufacturing approach of the composition epoxy resin of this mode for example can be added above-mentioned A composition, B-1 composition, C composition, D composition and other additive and mixing in right amount.At this moment, as stated, the A composition of interpolation and part or all reaction of B-1 composition and to be changed to the B-2 composition also passable.
And, also can be pre-mixed A composition and B-1 composition, after modulation contains the resin combination of B-2, mixed C composition and D composition again.
In addition, the temperature during mixing is preferably 50～180 ℃, more preferably 60～160 ℃.
(prepreg)
Through being impregnated in the fortifying fibre as matrix resin, obtain the prepreg that can be shaped at short notice in lower temperature with above-mentioned composition epoxy resin.The manufacturing of prepreg can be carried out through known device and manufacturing approach.
The fortifying fibre that can be applicable to first mode can use various fibers according to the application target of composite, not special the qualification.For example preferably use carbon fiber, graphite fibre, aramid fibre, silicon carbide fibre, alumina fibre, boron fibre, tungsten carbide fiber, glass fibre etc.And, can make up and use these multiple fortifying fibres.
In these fortifying fibres, carbon fiber and graphite fibre because better than elastic modelling quantity, lightweight is had important result, thereby be suitable for the present invention.In addition, can use the carbon fiber and the graphite fibre of all kinds, but special preferred tensile strength be to be more than or equal to 190GPa more than or equal to 3500Ma, tensile modulus of elasticity according to purposes.
In addition, not limiting as the form of the fortifying fibre in the prepreg is special, can be that fortifying fibre is drawn the form of neat form and braiding or used the nonwoven etc. of the fortifying fibre of cutting out weak point in a direction.Particularly draw the situation of the form of neat form and braiding in a direction, so far by being configured as of compression forming method, if spended time, then resin can flow in mould, thereby can not get the good fibre reinforced composites of outward appearance by solidifying.But, if the composition epoxy resin of this mode of use then solidifies at short notice owing to composition epoxy resin, thereby can obtain the good fibre reinforced composites of outward appearance.
Second mode
Below describe to second mode of the present invention, that has at length put down in writing each specifies with the preferred example of this mode etc.
Through second mode; The superior compositions of thermosetting resin that is suitable for prepreg is provided; Said prepreg is in the operability of room temperature and superior in the long-life property of room temperature, and when keeping the good physical properties after the shaping, can carry out the desired high-rate forming of industry purposes.
[mensuration of viscosity]
The inventor carries out the result of lucubrate in order to solve above-mentioned problem, confirmed compositions of thermosetting resin viscosity, heated condition (being specially 120 ℃) arrive target viscosities time, and place after viscosity be important.In second mode, the mensuration of viscosity uses the RDS-200 (the dynamic viscosity determinator with equal performance also can) of Rheometrics manufactured to carry out, and the value that obtains is to use the value of the parallel-plate of 25mm φ with the frequency measurement of 1Hz.Intensification condition to the temperature of heated condition (being specially 120 ℃) specifies in its part.
[50 ℃ viscosity is 5 * 101～1 * 10
4Pasec]
The compositions of thermosetting resin of second mode need be 5 * 10 50 ℃ viscosity
1～1 * 10
4Pasec.
In this viscosity less than 5 * 10
1During Pasec, near the viscosity when processing prepreg room temperature is strong excessively, can become to be very difficult to operation.On the contrary, this viscosity surpasses 1 * 10
4During Pasec, the drapability of prepreg will disappear and become hard, still become to be difficult to operation.
[under 120 ℃ atmosphere, reach 1 * 10 with interior at 1000 seconds or its
6Pasec]
Then, compositions of thermosetting resin must reach 1 * 10 at 1000 seconds or its with interior at 120 ℃ in second mode
6Pasec.
Reach 1 * 10 by viscosity
6The time of Pasec is when surpassing 1000 seconds, and is long at the curring time of high temperature.In the time of in 800 seconds or its, because short, thereby be preferred at the curring time of high temperature, more preferably 600 seconds or it is with interior situation.
Assay method uses in the method described in [mensuration of viscosity], is following enforcement to the intensification condition of the temperature of heated condition (being specially 120 ℃).That is, after 50 ℃ of stationary heat thermosetting resin composition sample, be warming up to 120 ℃, and measure isothermal viscosity at 120 ℃ with 10 ℃/minute programming rates.The time point that reaches 120 ℃ from temperature picks up counting, to reaching 1 * 10 by viscosity
6The time of Pasec is carried out timing.By 1 * 10
6The viscosimetric analysis of Pasec can be measured minimum by 1 * 10 at need
2Viscosity about Pasec, 2 last points of extrapolation are calculated and are reached 1 * 10
6The time of Pasec.Even but the minimum viscosimetric analysis that also need implement more than 1 figure place or 1 figure place.That is to say, through being inserted in 1 * 10 outward
2The data of Pasec obtain 1 * 10
6During the viscosity of Pasec, the viscosity when arriving 120 ℃ must be smaller or equal to 1 * 10
1Pasec.
[placing 3 all backs 50 ℃ 2 times of viscosity increases or below it] at 30 ℃
And, the compositions of thermosetting resin of second mode 30 ℃ place 3 week the back be necessary for 2 times or below it 50 ℃ viscosity increases.
The assay method of viscosity is identical with [mensuration of viscosity].This viscosity increases when surpassing 2 times, near the bad stability of prepreg room temperature.
[resin composition]
Raw material as the compositions of thermosetting resin of second mode; Not special restriction; Can illustration epoxy resin, phenolic resins, vinylester resin, unsaturated polyester resin, bimaleimide resin, bismaleimide-triazine resin, cyanate ester resin, benzoxazine colophony, acrylic resin etc.; But consider from operability, solidfied material rerum natura; The preferred cohesive of epoxy resin, bimaleimide resin, bismaleimide-triazine resin, cyanate ester resin, especially epoxy resin and supporting material of using is superior, thereby especially preferably uses.
For rerum naturas such as the operability that improves prepreg, the outward appearance that improves the FRP after being shaped and raising resistances to impact, also can add thermoplastic resin and other additives in the compositions of thermosetting resin of this mode.
Make an addition to the thermoplastic resin in second mode as suiting, can enumerate like aromatic polyamides, polyester, polyacetals, Merlon, polyphenylene oxide, polyphenylene sulfide, polyarylate, polyimides, PEI, polysulfones, polyamide, polyamidoimide, polyether-ether-ketone etc.
In addition, as other additive, can enumerate as as natural rubbers such as synthetic rubber such as elastomeric butyl rubber, isoprene rubber, acrylonitrile-butadiene rubber, silicon rubber and latex etc.
[interpolation of filler]
Good for the surface smoothing property that makes the FRP that obtains, in the compositions of thermosetting resin of second mode, preferably add fillers such as filler.As the preferred calcium carbonate of filler, preferred 3～10 μ m of the particle diameter of calcium carbonate.
The addition of filler because of the kind of the resin of compositions of thermosetting resin is different, but is 10～300 mass parts with respect to 100 mass parts compositions of thermosetting resin preferably.
In addition, needless to say, in the compositions of thermosetting resin of this mode, add the situation of aforesaid additive, the compositions of thermosetting resin that finally is impregnated into prepreg also must satisfy above-mentioned viscosities.
[prepreg]
The prepreg of second mode is that compositions of thermosetting resin of the present invention is impregnated into supporting material and the prepreg that forms.The not special restriction of the material of the supporting material that uses in the prepreg as this mode; Can enumerate like carbon fiber, glass fibre, aramid fibre, high-strength polyethylene fiber, boron fibre, steel fibre etc., but preferred use can obtain carbon fiber, the glass fibre of the mechanical properties of the performance of superior FRP, particularly light weight and high strength, high rigidity.
The form of the supporting material that uses in the prepreg as second mode is not special yet to be limited; Can enumerate as to a direction or change angle and lamination plain cloth, twills, satin fabric or the fibre bundle object of state sew up; Make its sutural lamina as no crooked fabric (non-crimpfabric) that can not untie or nonwoven, shim-like object; Also have a direction draw neat fortifying fibre and the folk prescription that forms to material etc., but preferred superior fabric or the sutural lamina of operability that use.
The resin content of the prepreg of this mode is not special to be limited, but resin content is few more, and the outward appearance of the FRP that obtains is good more, and the reinforcing effect of supporting material is big more, thereby is preferred.Specifically, the volume content of the compositions of thermosetting resin in the prepreg is preferably smaller or equal to 45 volume %, more preferably smaller or equal to 40 volume %, is preferably especially smaller or equal to 35 volume %.
Lower limit about the volume content of the compositions of thermosetting resin in the prepreg if the content of compositions of thermosetting resin is very few, then can produce the situation that compositions of thermosetting resin can not be filled into each corner of FRP, so bad.Specifically, the content of compositions of thermosetting resin is preferably more than and equals 20 volume %, more preferably more than or equal to 25 volume %.
[manufacturing approach of FRP]
The manufacturing approach of the FRP of second mode is that the prepreg with this mode is placed in the shaping dies manufacturing approach of the FRP that close die heats, pressurizes and is shaped.As the not special restriction of shaping dies, even but metal shaping dies also is difficult to distortion because it applies high pressure, thereby be preferred.
For the also not special restriction of the temperature of heating, but high temperature can shorten curring time more, thereby is preferred.Be preferably more than specifically and equal 120 ℃, more preferably more than or equal to 140 ℃.But, if temperature is too high, then reduce the temperature of shaping dies will be very spended time, perhaps do not reduce temperature and when placing prepreg, owing to begin to solidify, resin does not arrive each corner of final shaping thing sometimes.Therefore heating is preferably smaller or equal to 200 ℃, more preferably smaller or equal to 180 ℃.For the also not special restriction of the degree of pressurization, but the situation of carrying out high-pressure forming can reduce the pin hole and the inner space of FRP on surface, thereby is preferred.Specifically, the pressure that puts on prepreg is preferably more than and equals 0.5MPa, more preferably more than or equal to 1MPa.On to be limited to 100MPa then enough.
Equipment, pattern for being shaped have no particular limits, but are to use its efficient of method of heating and pressurizing equipment of hydraulic type best, are suitable for the manufacturing approach of FRP of the present invention.The shaping dies that preferably has the enclosed system of common edge structure for the shaping dies of this moment.
Third Way
Below describe to Third Way of the present invention.
In the Third Way, provide can solve used continuous fiber FRP sheet material particularly as the superior prepreg and the FRP sheet material of the synthtic price index on the structure of outside plate, material, surface.
< prepreg >
[forming pressure]
For the prepreg of Third Way, for center line average roughness (Ra) with FRP sheet material smaller or equal to the surface of good quality of 0.5 μ m and have and can stand the long-term surface quality that uses, need be with more than or equal to 10kg/cm
2Forming pressure be shaped and continuous reinforcing fiber in fact soaked into the prepreg of matrix resin.
Insufficient pressure 10kg/cm during shaping
2The time, be difficult to form the surface of good quality.
[curring time]
In Third Way, in order to obtain being used for the FRP sheet material of the extra high means of transport purposes of cost consciousness, need be that 15 minutes or its are heating and curing with interior at curring time, and then be preferably 10 minutes or its in.In the present invention, so-called curring time is meant that prepreg is placed on the time of the state that applies the shaping temperature and pressure.
[fortifying fibre]
The fortifying fibre that can in Third Way, use is so long as continuous reinforcing fiber in fact, and its kind is just not special to be limited, and can use carbon fiber, glass fibre, aramid fibre, polyester fiber, boron fibre etc.Wherein, as the parts of airborne vehicle and automobile etc., can use the specific strength carbon fiber higher by optimum than elasticity.
The form of the fortifying fibre in the moulding material can use a direction draw neat fortifying fibre form, woven the form of fortifying fibre etc., not special the qualification.For example, in order to improve the aesthetic appearance of FRP, can the moulding material on the surface of the FRP fabric with fortifying fibre be strengthened, neat fortifying fibre etc. is then drawn in a direction in inside, and with a plurality of enhancing forms.
In addition, in this manual, so-called continuous reinforcing fiber in fact is meant the fiber that does not have the end in the inside of moulding material in fact.
In the prepreg of this mode, preferably use carbon fiber as fortifying fibre.Carbon fiber can use any that PAN (acrylonitrile) is, pitch is.The carbon fiber of PAN system is considered from the balance aspect of intensity, elastic modelling quantity, percentage elongation, and is more preferred aspect the making fabric.As the outside plate purposes, intensity and elastic modelling quantity are high more unreasonablely to be thought, but in order to make it have resistance to impact, preferred percentage elongation is the carbon fiber more than or equal to 1.4%.The percentage elongation of FRP is obtained according to JISK-7054, thereby is meant the tension failure strain strictly speaking.
[carbon fibre fabric]
Carbon fibre fabric forms fabric shapes such as plain cloth, twills, satin fabric with the continuous fiber state.Wherein, mass area ratio (the W g/m of the preferred carbon fibre fabric of fabric among the present invention
2) with the ratio (W/t) of thickness (tmm) in 700～1700 scope.
The fabric that is in this scope is called flimsy material, and is thinner by mass area ratio, has the structure of fiber diffusion.Because the fluctuating of the thickness direction of fiber is little, it can show high intensity and rigidity, makes outside plate lightweight more.And because fabric face concavo-convex little, thereby the surface quality of outside plate also improves, and the durability of FRP sheet material also can improve.In addition, the mass area ratio of fabric and thickness are measured according to JIS R7602.
And then when the blanketing fctor of carbon fibre fabric was in 90～100% the scope, the part that is only formed by resin was few; Face impacts characteristic outward when uprising; Resin shrinks and the concave-convex surface or the concavo-convex spot that cause disappear to thickness direction, obtains high mapping vividness, from but preferred.In running through impact, if also the sudden thing of imagination is the situation of small pieces, then preferred blanketing fctor is in 95～100% the scope.
The blanketing fctor Cf of carbon fibre fabric; Such as the spy open flat 7-118988 communique record, definition; Be the key element relevant with the size that is formed on the space part between textile yarn; When on fabric, setting area S regional, if the area that is formed on the space part between yarn for weaving purpose in the area S is set at s, it is meant the value by the following formula definition.
Blanketing fctor Cf (%)=(S-s)/S} * 100
In addition, because this fabric helps the surface rigidity and the surface quality of particular importance in the rerum natura of outside plate, thereby the position of this fabric preferably is near the superficial layer of plate.Have the carbon fiber of high rigidity through the top layer at outside plate, the surface rigidity of outside plate further improves, and lightweight becomes possibility.
Most preferred position is an outermost layer.And, if twin shaft then can also give outside plate unique appearance of fabrics property to perhaps three axially waiting multi-axial fabrics to be in outermost layer.And then the fabric that ties up to above-mentioned scope through the pass that makes mass area ratio and thickness is positioned at outermost layer, and it is very level and smooth that the surface of outside plate becomes, and is also very level and smooth when being provided with thin filming.
That is the mass area ratio of carbon fibre fabric (W g/m,
2) be in the above-mentioned flimsy material in 700～1700 the scope with the ratio (W/t) of thickness (tmm); Because concavo-convex, tortuous little along the thickness direction of fiber; Thereby the varied in thickness of the resin bed on make outside plate time surface is little, can obtain more level and smooth surface before covering with paint, lacquer, colour wash, etc., after covering with paint, lacquer, colour wash, etc.
In addition; If blanketing fctor is in 90～100% the scope, then the thickness direction at outside plate does not have the place that only is made up of resin, thereby this characteristic very important aspect durability of mapping vividness is improved; Practicality increases, thereby is preferred.
[fortifying fibre beyond the carbon fiber]
Among the present invention, except carbon fiber, can also be also with organic fibers such as inorfils such as glass fibre, alumina fibre, silicon nitride fiber, aromatic polyamides series fiber and nylon.Long fibre, short fiber, textile-like, the object of shim-like or the amalgam of these forms etc. through in carbon fiber or resin, disposing them regularly or brokenly can improve resistance to impact, shock absorbing characteristics etc.
Especially, its low price of glass fibre, the strength balance of compression/stretching is good.Glass fibre is meant with silica (SiO
2) as fibrous glass such as the so-called E glass of principal component, C glass, S glass, the optimum fiber diameter is the glass fibre about 5～20 μ m.Glass cloth can keep resin, thereby formability is good when improving rigidity.Suitable is that Measurement of Quality in Unit Area of Fabric is 20～400g/m
2Glass cloth.When being used for the top layer, if be 20～50g/m
2, then can not damage the aesthetic appearance of fabric, and can keep the transparency yet, thereby be preferred.
The consumption of glass fibre, when needing rigidity preferably smaller or equal to 50 weight % of carbon fiber, when needing resistance to impact preferably smaller or equal to 80 weight %.
In addition, organic fiber and be fragility, but toughness unlike carbon fiber and glass fibre that kind, it is a disturbing property, even have the crooked such characteristics that rupture that also are not easy.And synthetic fibers and carbon fiber be relatively the time and since have not can galvano-cautery like this, thereby it has the advantage that does not need the galvano-cautery countermeasure such.
Moreover, when organic fiber and glass fibre compare, owing to can burn, thereby have easily discarded such advantage; And then because proportion is the only about half of of glass fibre, thereby also has and to make the extremely such advantage of lightweight of parts.
[matrix resin]
The resin that constitutes the FRP sheet material of Third Way comprises thermosetting resin such as epoxy resin, vinylester resin, unsaturated polyester resin, phenolic resins, benzoxazine colophony, acrylic resin and these resins of modification and the modified resin that obtains.
The modified resin of epoxy resin, mylar, vinylester resin and these resins that wherein, preferred resistance to chemical reagents, weatherability etc. are superior.In addition, phenolic resins, its anti-flammability of benzoxazine colophony are superior, are preferred for requiring stable on heating outside plate.
Moreover transparent resins such as acrylic resin are preferred aspect aesthetic appearance.Wherein, its weatherability of acrylic resin is superior, thereby is preferred.And then, through in these transparent resins, adding 3～20% ultra-violet absorber or sunshine absorbent, antioxidant, can further improve weatherability.
[resin combination (1)]
And then, can enumerate composition epoxy resin as first mode of the present invention (with reference to the record of first mode, below be recited as resin combination (1) sometimes) as the preferred matrix resin that uses in the Third Way.In addition, short of specific questions such as the material of in the resin combination of first mode, putting down in writing, condition and preferred example also are preferred in Third Way.
When using this resin combination (1); Can solidify at short notice in lower temperature; Thereby use this composition epoxy resin and even but the prepreg that obtains is at room temperature preserved and also had between the sufficient operating period, and show superior mechanical properties by the FRP sheet material that this prepreg obtains.And then, through using this prepreg, in the shaping of fibre reinforced composites, can shorten process time, thereby can low-costly make.
(other additives)
In resin combination (1), can use and the same additive described in first mode.
(content of the sulphur atom in the resin combination (1))
Resin combination (1) can have with first mode in the content of the same sulphur atom put down in writing.
(gel time)
Resin combination (1) preferably has the gel time same with first mode.
(manufacturing approach of resin combination (1))
Resin combination (1) can be used the method manufacturing same with first mode.Optimum condition in first mode is preferred too in Third Way.
(prepreg)
In Third Way and first mode same, can be impregnated into above-mentioned resin combination (1) in the fortifying fibre as matrix resin and obtain.The kind of fortifying fibre and form etc. also can be used with first mode same, and preferred example is similarly preferred.
Not limiting as the form of the fortifying fibre in the prepreg is special, can be that fortifying fibre is drawn neat form and the form that is woven or uses the nonwoven of cutting out short fortifying fibre etc. in a direction.Particularly draw neat form and by the situation of the form that woven, in the past by being configured as of compression forming method, if by solidifying spended time in a direction; Then resin can flow in mould; Thereby can not get the good fibre reinforced composites of outward appearance, still, if the composition epoxy resin of this mode of use; Then can solidify at short notice, thereby can obtain the good fibre reinforced composites of outward appearance owing to composition epoxy resin.
Like above detailed description, resin combination (1) can solidify in lower temperature at short notice.Thereby, even use this composition epoxy resin and but the prepreg that obtains is at room temperature preserved and also had between the sufficient operating period, and show superior mechanical properties by the composite that this prepreg obtains, can access such effect.And then, through using this prepreg, in the shaping of fibre reinforced composites, can shorten process time, thereby can low-costly make.
[resin combination (2)]
Also have, the preferred matrix resin that uses in the prepreg of Third Way, if consider from its curing characteristics, it also is preferred then using the compositions of thermosetting resin (with reference to second mode, below be recited as resin combination (2) sometimes) of the application's second mode.In addition, short of specific questions such as the material of in the resin combination of second mode, putting down in writing, condition and preferred example also are preferred in Third Way.
This compositions of thermosetting resin suitable as maintain the operability of room temperature, in long-life of room temperature and in the good rerum natura after being shaped, can carry out the matrix resin of the prepreg of the desired high-rate forming of industry purposes.And, prepreg maintain the operability of room temperature, in long-life of room temperature and in the good rerum natura after being shaped, can carry out the desired high-rate forming of industry purposes, therefore can carry out the desired high-rate forming of industry purposes.
Then, to resin combination (2) explanation at length.
(mensuration of viscosity)
Likewise measure with second mode.
(50 ℃ viscosity is 5 * 10
1～1 * 10
4Pasec)
With the explanation in second mode be same.
(under 120 ℃ atmosphere 1000 seconds its reach 1 * 10 with interior
6Pasec)
With the explanation in second mode be same.
(placing 3 all backs in 2 times of the increases of 50 ℃ viscosity or below it) at 30 ℃
With the explanation in second mode be same.
(resin composition)
Can use the resin of putting down in writing in second mode to form equally.
(interpolation of filler)
Can use the record in second mode equally.
(prepreg)
Can likewise make according to the record in second mode.Preferred example such as amount and material is preferred too in Third Way in second mode.
(manufacturing approach of FRP)
Can likewise in Third Way, make FRP with second mode.In second mode, preferably create conditions with examples such as method, equipment in Third Way too for preferred.
Resin combination (2) can provide suitable as maintain the operability of room temperature, in long-life of room temperature and in the good rerum natura after being shaped, can carry out the compositions of thermosetting resin of matrix resin of the prepreg of the desired high-rate forming of industry purposes.
And, the prepreg that obtains by resin combination (2) maintain the operability of room temperature, in long-life of room temperature and in the good rerum natura after being shaped, can carry out the desired high-rate forming of industry purposes.And then, can carry out the desired high-rate forming of industry purposes.Resin combination (2) is very suitable for high-rate forming, goes a long way greatly to reduce the shaping processing charges as the greatest drawback of FRP.
[ratio of the matrix resin in the prepreg]
The ratio of the matrix resin in the prepreg preferably is in 20～45% the scope by quality ratio.This be because, if surpass 45%, then in order to make FRP dull and stereotyped rigidity, resistance to impact and metal system outside plate similar, the lightweight of might having to sacrifice.
In addition, the reason more than or equal to 20% be because, if less than 20%, then matrix resin soak into the difficulty that becomes, produce the space and may be bad aspect rerum natura.
The ratio of the matrix resin in the prepreg is 20～30%, when using epoxy resin as matrix resin, also can obtain sufficient anti-flammability even in epoxy resin, do not add fire retardant, thereby be preferred.
[surface roughness-center mean roughness (Ra)]
Its center mean roughness (Ra) with the surface of the above-mentioned resulting FRP of molding condition of the prepreg of this mode is smaller or equal to 0.5 μ m, and this low and low aspect of durability for the concavo-convex outward appearance that causes of FRP plate surface is necessary.Center mean roughness (Ra) is more preferred during smaller or equal to 0.5 μ m.Concavo-convexly can not eliminate through covering with paint, lacquer, colour wash, etc., can be more remarkable.And, not only damage outward appearance, corresponding its size is concentrated at the stress on the top of recess can become big, destroy thereby advance, thereby concavo-convex little situation can improve the durability of outside plate.
In this mode; The roughness tester 178-368 (resolution unit 178) that the center mean roughness (Ra) on FRP surface is to use Japanese Mitsutoyo K.K. to make, with intercepting value: 2.5mm, measure interval: 2.5 * 5mm, scope: 5 μ m measure.Certainly, the FRP surface produces caused by the damage of metal die face concavo-convex sometimes, thereby will be with except such part and measure in above-mentioned mensuration.
[manufacturing process]
The prepreg of this mode for example through being cured as follows, can obtain the FRP flat board.
To have in advance when close die from mould inside can eluting gas but can suppress structure that resin flows out, surface accuracy is for more than or equal to the solidification temperature of mould temperature adjustment to the compositions of thermosetting resin of #800 or more than it; In this mould, put into the laminate of the prepreg that the above-mentioned carbon fiber by continuous constitutes; Close die makes the laminate of prepreg be full of the whole inside of mould and compression molding then.
And " can the eluting gas from mould inside when close die but can suppress the structure that resin flows out " that mould has generally can be enumerated the structure and the rubber sealing structure that are called as the common edge structure.
In addition, mould preferably has when close die or can make the structure of the inner degassing during just in close die.
As this degassing structure, have at mould inside hole to be opened/closed is set, it is open in the mould outside, is communicated with above-mentioned hole and with the container of pump to the inside degassing, opens valve when close die is inner, with methods such as mould inside one qi exhaustion gas through valve.
And then, after the shaping of FRP sheet material finishes,, also the mechanism with the demoulding of FRP sheet material such as ejector pin and air valve can be installed on mould in order to take out FRP sheet material easily.Thus, do not wait mold cools down just can easily take out FRP sheet material, thereby be suitable for a large amount of productions.In addition, the mechanism of the demoulding can be ejector pin, air valve or mechanism in addition, also can be known in the past any mechanism.
With S
1/ S
2Be that (monoplanar surface is long-pending to be S in this mould for 0.8～1 state
2) (monoplanar surface is long-pending to be S to put into the laminate of the above-mentioned prepreg that is made up of continuous carbon fibre
1), depress can be extremely not mobile adding for matrix resin, thereby be preferred.The mobile meeting of matrix is flowed fortifying fibre, thereby it is concavo-convex that the FRP plate surface is produced.Concavo-convexly can not eliminate through covering with paint, lacquer, colour wash, etc., can be more remarkable.And, not only damage outward appearance, corresponding its size is concentrated at the stress on the top of recess can become big, destroy thereby advance, thereby concavo-convex little situation can improve the durability of outside plate.
FRP sheet material can obtain through even covering with paint methods such as curing and demolding and then enforcement spray guns.Shaping contraction, the thermal contraction of the resin during owing to be shaped also can influence surface quality, thereby the shaping of preferred resin is shunk the circlet epoxy resins, sneaked into the low shrink resin of fillers such as talcum, glass granules and calcium carbonate.
Forming temperature is preferably high 10 ℃ or more than it than outside plate institute serviceability temperature, for automobile exterior panel, is 90 ℃ or more than it, and more preferably 110 ℃ or more than it is preferred from curring time shortening aspect when 130 ℃ or its are above.
[FRP sheet material]
The thickness of FRP sheet material is different because of purposes, but the situation of the outside plate of the means of transport that automobile etc. move on the ground preferably is in the scope of 0.5～8mm.If below this scope, anti-penetrability possibly have problem; If more than this scope, then light weight is insufficient.
Aloft the situation of the means of transport of operation because speed is faster, thereby is preferably the scope of 1～10mm.
In addition, sandwich structure, ripple struction or also be preferred scheme in the structure that the part of outside plate is provided with framework.
FRP sheet material for Third Way; Through using continuous carbon fiber as fortifying fibre; The high elastic modulus and the intensity of one of characteristics as carbon fiber be can show, can resistance, rigidity sense, intensity be realized with light weight as the necessary corresponding depression of outside plate.And owing to be continuous fiber, can obtain as the very important characteristic of outside plate is the anti-impact characteristics that runs through.That is, can obtain with the irrealizable lightweight of short fiber, rigidity and impact characteristics.Certainly, deformation drag, maximum load, addendum modification, energy absorption are also big.
And then continuous fiber has fabric shape, therefore with lamination the situation of the prepreg arranged a direction compare, though be the fortifying fibre of same amount, the anti-impact characteristics that runs through can be higher.Its principle is that fabric is the staggered similar netted structure of fiber, thereby can catch sudden thing.
And, fabric with lamination equate and the situation of the prepreg arranged a direction is compared in the rerum natura of 2 directions of one deck (individual layer) quadrature, just can constitute outside plate with few sheet number, thus more lightweight.For example, the outside plate of lamination if make 2 prepreg quadratures is then because the thermal contraction when solidifying can produce the outer torsional deformation of face that is called as saddle type.The outer distortion of this face is not from external force, can be produced by variations in temperature yet.Also can produce when in-plane stress acts on outside plate, thereby the outside plate distortion is lost shape, not preferred from outward appearance aspect, air force aspect.
And then, through with light weight and high elastic modulus, high-intensity carbon fiber as fortifying fibre, can make the outside plate light weight and have high mechanical properties, and, also superior aspect environment resistant.
[covering with paint]
FRP sheet material of the present invention can be implemented on the surface to cover with paint, lacquer, colour wash, etc.Covering with paint will approach (being generally smaller or equal to 150 microns) than gel coat, and light weight.Through covering with paint, lacquer, colour wash, etc., not only the selection branch of color but also characteristic is also many.Through selected suitable coating, can give characteristic or function that gloss or concavo-convex, low temperature and hot environment, resistance to water, the UV resistant environment etc. on surface only depend on FRP sheet material then can't have, produce practicality first as outside plate.
For example, be divided into the such situation of resin a little less than the UV resistant,, can give UV resistant characteristic as outside plate through implementing the superior covering with paint of UV resistant for the resin portion of FRP sheet material.Certainly, various outward appearances (cosmetic) also are fine, and it also is preferred from the outward appearance aspect, covering with paint, lacquer, colour wash, etc.For outside plate, match colors from needs such as consideration grade and miscellaneous part to safety, can carry out delicate color matching through covering with paint, lacquer, colour wash, etc.In addition, through covering with paint, lacquer, colour wash, etc., moisture and light can not be directly incident on FRP, thereby can obtain environment resistant superior high durable outside plate.And covering with paint, lacquer, colour wash, etc. also is preferred from the fluid resistance aspect.
In addition, cover with paint, lacquer, colour wash, etc. thickness and be preferably 20～200 μ m.If surpass 200 μ m, then film and peel off easily, also not preferred aspect mechanical property and outward appearance.If less than 20 μ m, then light such as sunshine can direct incident, causes deterioration, and be easy to generate the coating spot, and is also not preferred from the aesthetic appearance aspect.The FRP outside plate of needn't gain in weight through being in this scope, both can forming, the durability aspect is also desirable.40～100 μ m more preferably.
Coating can be selected from following coating, and for example silicon/epoxy is synthetic resin coating and water-soluble resin coating such as cold coating, acrylic resin paint, ammonia ester resin paint, Polyester resin lacquer, epoxy coating, fluorine resin coating, cashew resin coating, phthalic resin coating, amino alkyd resin coating, phenolic resin coating, oil paint, oil varnish, NC Nitroncellulose nitrate paint, comprises the coating of priming paint surfacer, priming paint surfacer putty etc.
Coating roughly is divided into air dry or air drying coating, baking vanish, ultraviolet curing coating, electron ray curing coating of a liquid type, two-liquid type, mulit liquid type etc.And, according to coating method, can be divided into spraying with coating, roller coat with coating, flow coat with coating, brushing with coating etc.
In addition, for selecting of coating, preferably select with the good coating of the resin-bonding property of FRP and form.And, because FRP and its ultra-violet resistance of compared with metal are poor, thereby the preferred superior coating of weatherability.Specifically; Be the coating that is called sunshine barrier coating and ultraviolet isolating paint, have in the vehicle of pure acid acrylic acid ammonia ester with carbon black as pigment and to cooperate ultra-violet absorber or reduce telomer polyacid etc. and the coating that obtains, acrylic acid ammonia ester epoxy organosilicon coating, the fluorine that has added black pigments such as cobalt oxide, cupric oxide, iron oxide black be coating etc.Particularly for the situation of transparent coating, above-mentioned additive is indispensable.
Also have, preferably be dispersed with the electrically-conducting paint of conductive fillers such as carbon black or graphite, metal dust.Added the coating of the electric conductor of tin oxide or antimony oxide system; Owing to can form transparent conductive coat; Therefore; Situation or the purpose of utilizing the aesthetic appearance of carbon fibre fabric is that it is preferred electrically-conducting paint when giving the anti-static effect of the outside plate that the dust that can suppress to be caused by static and dirt be attached to automobile etc.
In addition, for the outside plate that is starved of the means of transport that arouses attention at night etc., externally to implement the luminous paint (luminescent coating) that JISK5671 put down in writing also be effective for a slab integral or a part.
Coating method covers with paint, lacquer, colour wash, etc. except spraying (blow and attach) that (air gun with no air mode etc.), static are covered with paint, lacquer, colour wash, etc. (electrostatic spray mode and spray gun mode etc.), electroplate and cover with paint, lacquer, colour wash, etc. (cationic with anionic etc.), powder is covered with paint, lacquer, colour wash, etc. (molten method, mobile impregnating method, the static powder covering with paint method etc. of penetrating), can also be suitable for known special covering with paint method.
Wherein, the FRP sheet material of this mode is because hear resistance is lower than metal, thus baking temperature smaller or equal to 120 ℃, with FRP as the static of anode cover with paint, lacquer, colour wash, etc. be coated with aspect the attaching property superior, from but preferred.And because carbon fiber is an electric conductivity, thereby the static covering with paint also is the high preferred covering with paint method of coating service efficiency.
In addition, when implementing certain thickness covering with paint, preferred degreasing or the polishing of implementing in order to remove releasing agent in the surface of FRP sheet material.Through using non-silicon is that material can not need or reduce degreasing or polishing operation as releasing agent.The temperature of covering with paint, lacquer, colour wash, etc. and the heat resisting temperature of outside plate are closely related, preferably near heat resisting temperature, cover with paint, lacquer, colour wash, etc. drying.Automobile is with the situation of outside plate, and heat resisting temperature is about 100 ℃, and the baking temperature of coating is preferably 60～110 ℃ scope.And be about 3 minutes～60 minutes drying time.
The color of covering with paint, lacquer, colour wash, etc. is determined by the color matching with miscellaneous part, but for the FRP outside plate of carbon fibre fabric as this mode of reinforcement base material, preferably carries out using the deterioration state of visual observations FRP part, the transparent coating of internal injury state.Owing to be transparent,, also have and make the effect that only the experienced third party of metal outer panel is produced the chance of use FRP outside plate so can hold the state of FRP exactly.Certainly, transparent coating also has the aesthetic appearance of utilizing fabric construction and the effect that improves commodity value.In addition, transparent coating can be all of outside plate, also can be a part.
In addition, the representative substances of clear dope is that silicon/epoxy is coating, acrylic acid series coating, but also can be amalgam, the alloy system of ammonia ester system or these coating, can also be colored transparent.
For carbon fibre fabric, the fabric of the structure that the ratio of mass area ratio and thickness is big suits.Covering with paint employing spray gun etc. can form the covering with paint method of filming of uniform and thin.The too thin or too thick tendency that the mapping vividness exist to be reduced if film, thereby to be preferably formed be suitable thickness.
[purposes of FRP sheet material]
The FRP sheet material of this mode can be used as the inside and outside plate of means of transports such as cart, automobile, hot-short, high-speed vessel, bicycle, bicycle, airborne vehicle.
Specifically; Be following purposes: cart panels such as motorbike frame, radome fairing, dashboard; Car panel such as car door, hood, tail gate, side mudguard, side panel, dashboard, trunk lid, top cover, side mirror lid, spoiler, diffuser, luggage carrier; Automobile component purposes such as engine cylinder cover, hood, chassis; Vehicles such as vehicle headstock, top cover, side panel, car door, chassis lid, side skirt are used the outside plate purposes ahead, and vehicles such as goods canopy, seat are with the aerofoil profile inner panel in indoor utensil, the aerofoil profile truck, outside plate, top cover, base plate etc., are installed in the gas components purposes of air disturbance device and side skirt on automobile or the bicycle etc.; Airborne vehicle purposes such as window frame, goods canopy, seat, base plate, wing, screw, body; The framework purposes of notebook computer, mobile phone etc., medical usages such as X ray box, top board, audio and video products purposes such as dynamic planar loudspeakers panel, diffuser; Golf balls, floral disc, skis, aquaplane, backplate (rugby, baseball, hockey, skiing etc.) sports goods purposes, plate clockwork spring, air vane, elevator general industry purposes such as (frame panel, doors).In addition, said sheet material is not only flat board among the present invention, also comprises the sheet material with curvature certainly.
Cubic formula
Below at length explain, and then the explanation of sentence and preferably creating conditions etc. is described to cubic formula of the present invention.
Provide in the cubic formula and used compression forming method can make the superior method of the superior formed product of fiber-reinforced composite material of high strength and aesthetic appearance at short notice.
(continuous reinforcing fiber is in fact soaked into compositions of thermosetting resin and the moulding material that forms)
The fortifying fibre that can in this mode, use can use at the fortifying fibre described in the Third Way, and its preferred example equally also is preferred in this mode.
The compositions of thermosetting resin that in cubic formula, uses gets final product so long as can be used as the known thermosetting resin of the matrix resin of FRP, can use any one of epoxy resin, unsaturated ethylene ester resin, bimaleimide resin etc. aptly.Wherein, if consider the mechanical properties of formed products, the mechanical property after the curing high and with the superior epoxy resin of the cohesive of fortifying fibre can the use of optimum ground.
In this mode; Also can replace above-mentioned moulding material, use the material that continuous reinforcing fiber is in fact soaked into thermosetting resin and at least one side surface and have that material that fortifying fibre to the short fiber shape soaks into thermosetting resin overlaps and the moulding material that forms.Soak into the material of thermosetting resin as fortifying fibre, can suit to use a material that becomes the fortifying fibre of 12～50mm to soak into to the severing that is commonly called SMC with above-mentioned thermosetting resin to the short fiber shape.
The fortifying fibre of short fiber shape is soaked into the material behind the thermosetting resin; Because the orientation of fortifying fibre is random; Thereby compare with the moulding material that only forms by continuous reinforcing fiber in fact; Have the advantage that FRP is easy to carry over the complicated shape with rib structure or bulge-structure, but have the shortcoming of mechanical properties difference.Therefore, compression molding can obtain having concurrently FRP both strong points, that mechanical properties is superior, that have complicated shapes such as rib structure or bulge-structure through overlapping both.
At this, soak into the thermosetting resin in the material behind the thermosetting resin as fortifying fibre to the short fiber shape, can use and the same resin of material that continuous reinforcing fiber is in fact soaked into behind the thermosetting resin, also can use different resins.
(mould)
In the manufacturing approach of the FRP of cubic formula, the preferred use has the mould that when close die, can keep the structure of mould inside airtightly.In this mode, mould is desired airtightly to be meant the moulding material of in mould, putting into abundant amount and to be full of mould that the thermosetting resin that when pressurization, constitutes moulding material in fact can not spill from mould yet.As the structure that keeps mould inside airtightly, the part that upper die and lower die in the time of can making close die (formpiston and former) contact adopts common edge structure (with reference to Fig. 2) or rubber sealing structure.So long as can keep the structure of mould inside airtightly, also can adopt known any structure.
In addition; The air that remains in mould inside during close die becomes the reason in the space of surperficial pin hole of FRP and FRP inside sometimes; But, if use mould, when the whole inside of mould is full of with moulding material with deaerating mechanism as mould; Through using deaerating mechanism to outgas, then can remove the air that remains in mould inside effectively.
As deaerating mechanism, can hole to be opened/closed (with reference to Fig. 3) be set at mould inside, open to the mould outside, pump perhaps further is set, reduce pressure.The degassing is through when pressurizeing, closing and carry out in the moment perforate that is full of the whole inside of mould with moulding material.
And then the shaping of FRP in order easily to take out FRP, also can be installed the mechanism that ejector pin and air valve (with reference to Fig. 3) etc. make the FRP demoulding after finishing on mould.Thus, do not wait mold cools down just can easily take out FRP, thereby be suitable for a large amount of productions.In addition, the mechanism that carries out the demoulding can be ejector pin, air valve or mechanism in addition, also can be known in the past any mechanism.
(manufacturing approach of FRP)
The method that obtains FRP to using above-mentioned moulding material and mould in conjunction with the accompanying drawings.
Figure 1A is that expression has been placed the figure of the state of moulding material at mould inside before the close die.In addition, 1 shown in a plurality of figure of this mode represent former, 2 expression formpistons; 3 expression common edge structures, 4 expressions hole to be opened/closed, the 5 expression tips (up and down) through air; 6 expression sealing gaskets, the air when A representes perforate flows into, and the air when B representes closed pore flows into.At first, with the solidification temperature of the thermosetting resin of mould temperature adjustment to moulding material or after more than it, put into moulding material at mould inside.
Subsequently, form through close die press molding material.Figure 1B is the figure of the state of expression close die.As shown in the drawing, thermosetting resin flows out to mould outside hardly, and moulding material is pressurized and be full of the whole inside of mould.
As noted earlier, the coil bending that produces during prepreg that compression molding is formed by continuous reinforcing fiber mainly is because the surplus of matrix resin flows.Therefore; In this mode, find; In order to suppress resin flow, (monoplanar surface of FRP is long-pending) the approaching long-pending moulding material of monoplanar surface that be to use the monoplanar surface of the inside when being formed with close die long-pending can obtain good effect; Specifically, can make continuous reinforcing fiber is in fact soaked into thermosetting resin and the long-pending S of monoplanar surface of the moulding material that forms
1The monoplanar surface of the mould inside during with close die is amassed S
2Ratio S
1/ S
2Become 0.8～1.If S
1/ S
2Less than 0.8, then fierce in the resin flows of mould inside, be easy to generate coil bending.On the other hand, S
1/ S
2Surpass at 1 o'clock,, then can cause the moulding material in closed mold obstacle or the formed products not enough if the circumference of moulding material exposes from mould; If moulding material is folding, then can produce the mixed and disorderly of fiber orientation.At this, so-called monoplanar surface is long-pending to be the surface area that has one of thickness 2 equal in fact faces at interval basically that constitutes formed products.
In addition, particularly obtain the situation of high-quality FRP, volume and height for moulding material also can use near formed products (shape of the mould inside during close die) person.Put into mould inside moulding material volume and volume that thickness is preferably formed products respectively 100～120% with 100～150% of thickness.
If put into mould inside moulding material the not enough formed products of volume volume 100%, then can not apply sufficient pressure to moulding material.On the other hand, if surpass 120%, then moulding material can flow out before obtaining the air-tightness of mould, thereby and not preferred.
The thickness of moulding material then is difficult to whole faces of moulding material are pressurizeed equably with respect to the thickness less than 100% of FRP, above 150% o'clock, thereby and not preferred.At this, the thickness of so-called moulding material and the thickness of FRP are average thickness separately.
In this mode, need be with the temperature adjustment in advance of above-mentioned mould to the solidification temperature of thermosetting resin or more than it.At this moment, the temperature of temperature adjustment is so long as by the solidification temperature of forming decision of thermosetting resin or more than it, can select better temperature according to the molding condition beyond composition and the temperature.
In the manufacturing approach of the FRP of this mode, the pressure when carrying out compression molding can be known pressure when carrying out compression molding, not special the qualification.Can be according to the decisions aptly such as shape of FRP.
Embodiment
Followingly 4 kinds of modes of the present invention are described particularly according to embodiment.
The embodiment of first mode
In present embodiment and comparative example, used following with being called for short the material of representing.Average grain diameter is the value of measuring with the laser diffraction and scattering method.In addition, this mode is not limited to following embodiment.
< epoxy resin >
EP828: japan epoxy resin (strain) system ェ ピ コ-ト 828 (registration mark, bisphenol A type epoxy resin, 120p/25 ℃)
EP807: japan epoxy resin (strain) system ェ ピ コ-ト 807 (registration mark, bisphenol f type epoxy resin, 30p/25 ℃)
EP604: japan epoxy resin (strain) system ェ ピ コ-ト 604 (registration mark, glycidyl amine type epoxy resins)
N740: big Japanese ink chemical industry (strain) system EPICLON N-740 (phenolic resin varnish type epoxy resin, semisolid)
YCDN701: Dongdu changes into (strain) system Off ェ ノ ト-ト YCDN701 (cresols varnish type epoxy resin)
Off レ Star プ 50: eastern Li Juliuxiangjiaoshe system epoxy resin, registration mark
EXA1514: the EPICLON EXA1514 of Dainippon Ink. & Chemicals Inc bisphenol-s epoxy resin
< amines that in molecule, has at least one sulphur atom >
DDS: Wakayama refine (strain) system セ イ カ キ ユ ア-S (DADPS, registration mark, sulphur atom content are 12.9 quality %)
BAPS: Wakayama refine (strain) system BAPS (4,4 '-diamino-diphenyl sulfide, sulphur atom content are 7.4 quality %)
BAPS-M: Wakayama refine (strain) system BAPS-M (two (4-(3-amino-benzene oxygen) benzene) sulfone, sulphur atom content are 7.4 quality %)
ASD: Wakayama refine (strain) system ASD (4,4 '-diamino-diphenyl sulfide, sulphur atom content are 14.8 quality %)
TSN: Wakayama refine (strain) system TSN (o-tolidine sulfone, sulphur atom content are 11.7 quality %)
<urea compounds >
PDMU: phenyl dimethyl urea (average grain diameter is 50 μ m)
DCMU:3,4-dichlorophenyl-N, N-dimethyl urea (average grain diameter is 50 μ m)
< dicyandiamide >
DICY7: dicyandiamide (average grain diameter is 7 μ m)
DICY15: dicyandiamide (average grain diameter is 15 μ m)
DICY1400: dicyandiamide (average grain diameter is 20 μ m)
< additive >
PVF: チ Star ソ (strain) system PVC two レ Star Network E (polyvinylformal)
YP50: Dongdu changes into (strain) system 7 ェ ノ ト-ト YP50
Aerosil: Japanese ア ェ ロ ジ Le (strain) system, ア ェ ロ ジ Le 300
(evaluation method)
The resin combination of this mode of use with after the method stated make prepreg, but measure its gel time between the operating period, mechanical properties.Assay method is as follows.
(1) gel time
Cut out the square sample of length of side 2mm from prepreg, clamp with 2 sheet glass cover plates.Place it on the heating plate that is controlled to 130 ℃ ± 0.5 ℃.Measure zero-time as gel time placing in an instant behind the sample.Push prepreg repeatedly with tweezers etc. every now and then, confirm the state of composition epoxy resin, measure time that gelation accomplishes fully and with it as gel time.The immobilising state of composition epoxy resin when said here complete gelation is meant and pushes with tweezers etc.
(2) but between the operating period
Prepreg is put into 30 ± 1 ℃ thermostatic drier, observes every day, length is the cohesive of the prepreg after 21 days, lose cohesive (prepreg is not bonded to each other) but fate as between the operating period.
(3) mechanical properties
By the vacuum bag shaping prepreg is formed, make the flat fibre reinforced composites of vertical 200mm * horizontal 200mm * thick 150mm.Measure 0 ° of bending strength and 90 ° of bending strengths of this flat board according to ASTM D 790.
(content of sulphur atom)
When the A composition does not have sulphur atom; Count the summation of the mass parts of the A composition, C composition, D composition and the additive that add X, count the mass parts of the B-1 composition that in the manufacturing of composition epoxy resin, uses Y and count p (quality %) to the content of the sulphur atom in the B-1 composition that in the manufacturing of composition epoxy resin, uses, then the content S of sulphur atom can be obtained by following formula.
S (quality %)=pY/ (X+Y)
When the A composition has sulphur atom, directly measure from composition epoxy resin with following atomic absorption spectrography (AAS).That is, make after the composition epoxy resin, in aqueous solution of nitric acid, decompose this composition epoxy resin of 50mg, utilize this solution of ion exchange water dilution again to 50ml, with this aqueous solution as working sample.
Use high frequency plasma apparatus for analyzing luminosity (Japanese ジ ャ-レ Le ア Star シ ユ society system, ICAP-575 MK-II) to carry out mensuration (condition determination: plasma gas is 180.7nm as 16L/min, carrier gas as 0.48L/min, mensuration wavelength as 0.8L/min, cooling medium gas) for this working sample through the sulphur atom concentration of atomic absorption spectrography (AAS).Use the calibration curve of making in advance to obtain the concentration of the sulphur atom in the aqueous solution, and then calculate the sulphur atom content (quality %) this composition epoxy resin from the concentration of this sulphur atom.
Embodiment 1～10
Be mixed to evenly the modulating epoxy resin composition with the ratio of components shown in the table 1.Use the simple type roll to be 33.7g/m with the resin mass area ratio
2This composition epoxy resin is coated on the processing release paper equably, forms resin bed.Attaching to this resin bed with the fiber mass area ratio is 125g/m
2Mode at the carbon fiber of a beautiful sun of direction La Qi Mitsubishi (strain) system (TR50S, tensile modulus of elasticity: 240GPa) and after the two sides of the board that forms; With roller with 100 ℃, line pressure 2kg/cm heats and pressurize; Composition epoxy resin is impregnated in the carbon fiber, and making the fiber mass area ratio is 125g/m
2The prepreg of (resin content is 35 quality %).
But the prepreg that the composition epoxy resin by embodiment 1～10 is obtained at 130 ℃ gel time and estimate between the operating period; Consequently; Gel time is all smaller or equal to 200 seconds; But and between the operating period, also can keep cohesive during through 21 days, but thereby can confirm more than or equal between 21 days operating period.
Flat plate composite rerum natura (FRP sheet material rerum natura) also is that 0 ° of bending strength is all above 160kg/mm
2, 90 ° of bending strengths are all above 10kg/mm
2, demonstrate good rerum natura.
Embodiment 11～20
Except be mixed to evenly with the ratio of components shown in the table 2, complete and embodiment 1 likewise makes prepreg, and has implemented evaluation.
The prepreg that is obtained by the composition epoxy resin of embodiment 11～20 also is, gel time is all smaller or equal to 200 seconds, but and can confirm more than or equal between 21 days operating period.
Flat plate composite rerum natura (FRP sheet material rerum natura) also is that 0 ° of bending strength is all above 160kg/ mm
2, 90 ° of bending strengths are all above 10kg/mm
2, demonstrate good rerum natura.
Embodiment 21
In the composition shown in the embodiment 21 of table 3, at the epoxy resin of mixed at room temperature B composition and amine component (DDS) afterwards, heat at 150 ℃ that to make part reaction, the viscosity that is modulated into 90 ℃ be 30～90 pools (B-2 composition).This reactant and A composition and C, D composition are mixed to evenly the modulating epoxy resin composition with the ratio of components shown in the embodiment 21 of table 3.Use the simple type roll to be 33.7g/m with the resin mass area ratio
2This composition epoxy resin is coated on the processing release paper equably, forms resin bed.Attaching to this resin bed with the fiber mass area ratio is 125g/m
2Mode at the carbon fiber of a beautiful sun of direction La Qi Mitsubishi (strain) system (TR50S, tensile modulus of elasticity: 240GPa) and after the two sides of the board that forms; With roller with 100 ℃, line pressure 2kg/cm heats and pressurize; Composition epoxy resin is impregnated in the carbon fiber, and making the fiber mass area ratio is 125g/m
2The prepreg of (resin content is 35 quality %).
But the prepreg that the composition epoxy resin by embodiment 21 is obtained at 130 ℃ gel time and estimate between the operating period; Consequently; Gel time is all smaller or equal to 200 seconds; But and between the operating period, also can keep cohesive during through 21 days, but thereby can confirm more than or equal between 21 days operating period.
Flat plate composite rerum natura (FRP sheet material rerum natura) also is that 0 ° of bending strength is all above 160kg/mm
2, 90 ° of bending strengths are all above 10kg/mm
2, demonstrate good rerum natura.
Embodiment 22～31
With the ratio of components shown in the table 3 afterwards, heat at 150 ℃ and to make part reaction, and to be modulated into 90 ℃ viscosity be 30～90 pools at the epoxy resin of mixed at room temperature A composition and amine component (DDS).Except being mixed to evenly with the ratio of components shown in the table 3 this reactant and B composition and C composition, fully and embodiment 21 likewise make prepreg, and implemented evaluation.
The prepreg that is obtained by the composition epoxy resin of embodiment 22～31 also is, gel time is all smaller or equal to 200 seconds, but and also can confirm more than or equal between 21 days operating period.
Flat plate composite rerum natura (FRP sheet material rerum natura) also is that 0 ° of bending strength is all above 160kg/mm
2, 90 ° of bending strengths are all above 10kg/mm
2, demonstrate good rerum natura.
Embodiment 32～45
, after the epoxy resin and amine component of mixed at room temperature A composition, heat at 150 ℃ and to make a part of reaction with the ratio of components shown in the table 4, and to be modulated into 90 ℃ viscosity be 30～90 pools.Except being mixed to evenly with the ratio of components shown in the table 4 this reactant and B composition and C composition, fully and embodiment 21 likewise make prepreg, and implemented evaluation.
The prepreg that is obtained by the composition epoxy resin of embodiment 32～45 also is, gel time is all smaller or equal to 200 seconds, but and also can confirm more than or equal between 21 days operating period.
Comparative example 1～8
Except be mixed to evenly with the ratio of components shown in the table 5, complete and embodiment 1 likewise makes prepreg, and has implemented evaluation.
Consequently, except comparative example 2,4,6, gel time did not perhaps solidify with interior also the end at several hours all above 200 seconds.Comparative example 2,4,6 has shown gel time smaller or equal to 200 seconds rapidly-curable, but but short between the operating period, for smaller or equal to 5 days.
Comparative example 9～10
Except be mixed to evenly with the ratio of components shown in the table 3, complete and embodiment 21 likewise makes prepreg, and has implemented evaluation.
Consequently; For the comparative example that does not contain dicyandiamide 9 and 10; Although cooperated the amount identical with embodiment 21 and embodiment 24 as the total amount of curing agent; But compare with the flat plate composite of in each embodiment, making, only can obtain the flat plate composite of 0 ° of bending strength low about 10%.And then weak point is the prepreg below 5 days between the operating period but in comparative example 10, become.
Specify as above, the composition epoxy resin of this mode just can solidify in lower temperature at short notice.Thereby, even but the prepreg that can obtain using this composition epoxy resin to obtain also have between the sufficient operating period in room temperature preservation, and show this effect of superior mechanical properties by the composite that this prepreg obtains.And then proved, can in the shaping of fibre reinforced composites, shorten process time through using this prepreg, thereby can low-costly make.
The embodiment of second mode
Below, based on embodiment second mode of the present invention is described at length.In addition, this mode is not limited to following embodiment.
As the raw material of compositions of thermosetting resin, epoxy resin and curing agent below preparing.
< epoxy resin >
EP828：
The system liquid bisphenol A of japan epoxy resin society type epoxy resin, ェ ピ コ-ト 828 (registration mark)
EP1009：
The solid-state bisphenol A-type epoxy resin of japan epoxy resin society system, ェ ピ コ-ト 1009 (registration mark)
AER4152：
Society of Asahi Chemical Industry system epoxy resin, ア ラ Le ダ イ ト AER4152 (registration mark)
N740：
Big Japanese ink chemical industry society system phenolic resin varnish type epoxy resin, ェ ピ Network ロ Application N-740 (registration mark)
< curing agent >
HX3722：
Society of Asahi Chemical Industry system microcapsule-type potentiality curing agent, ノ バ キ ユ ア HX3722 (registration mark)
FXE1000：
Fuji changes into society's system used for epoxy resin potentiality curing agent, 7 ジ キ ユ ア FXE1000
PDMU：
PTI Japan society system phenyl dimethyl urea, just ミ キ ユ ア 94 (registration marks)
DCMU：
Protect the chemical society of native ケ paddy system 3,4-dichlorophenyl-N, N-dimethyl urea, DCMU99
Dicy：
Japan epoxy resin society system dicyandiamide, Dicy7
2P4MZ：
Four countries change into the system 2-of society phenyl-4-methylimidazole
< viscosimetric analysis >
Device: Rheometrics corporate system RDS-200
Mode determination: parallel-plate (25mm φ, interval 0.5mm)
Frequency: 1Hz
Temperature is set: from 50 ℃ with 10 ℃ of/minute intensification, reach 120 ℃ after mensuration isothermal viscosity
Determination data: surpass 10 by viscosity 50 ℃ viscosity, after reaching 120 ℃
2The time of Pasec.In the present embodiment, can confirm that the viscosity of whole compositions of thermosetting resin when reaching 120 ℃ is smaller or equal to 10
1Pasec.
< tackifies after 30 ℃ * 3 weeks >
Sample at once after having modulated compositions of thermosetting resin, be determined at 50 ℃ viscosities il through above-mentioned viscosimetry
0, same compositions of thermosetting resin was placed for 3 weeks in 30 ℃ drying machine, through after receiving thermal process, likewise implement viscosimetric analysis, be determined at 50 ℃ viscosities il
1Tackify passes through η
1/ η
0Obtain.
< modulation of prepreg >
Compositions of thermosetting resin is warming up to 50 ℃ to reduce viscosity, is coated on thinly again and modulates the heat fusing film on the processing release paper, the system carbon fibre fabric TR3110 of Li Yang society of Mitsubishi is soaked into this heat fusing film and obtains prepreg.Resin content is adjusted into 30 quality %.
< shaping >
11 layers of prepreg of lamination on equidirectional use to have the metal die of common edge with the forming pressure of 2MPa, form with hot press.The thickness of forming board is roughly 2mm.
< mechanical properties mensuration >
Use Instron corporate system universal testing machine, bend test is implemented interlayer shear test (ILSS) according to ASTMD2344 according to ASTM D790.
Embodiment 46～50
With the modulation of the composition shown in the table 6 compositions of thermosetting resin, carry out 50 ℃ viscosimetric analysis, 50 ℃ viscosimetric analysis after 30 ℃ * 3 weeks.After reaching 120 ℃, mensuration surpasses 10 by viscosity
2The time of Pasec.Process the sense of prepreg armrest and implement the evaluation of operability.Suitable and easy operating is designated as " zero ", unworkable be designated as " * " viscosity, drapability.And, the prepreg after the modulation was placed for 3 weeks at 30 ℃, likewise estimate to operability subsequently.And then through above-mentioned method shaping prepreg.Shaping is under 3 conditions of 120 ℃ * 15 minutes, 120 ℃ * 10 minutes, 140 ℃ * 4 minutes, to implement, and measures mechanical properties respectively.Conclusion is the result be shown in Table 6.Compositions of thermosetting resin in an embodiment, soon operability, the modulation back of prepreg is well 30 ℃ of operability through the prepreg after 3 weeks after the modulation.Appearance after the shaping is also beautiful, and mechanical properties is also good.
Comparative example 13 (at the low example of 50 ℃ viscosity)
With the modulation of the composition shown in the table 7 compositions of thermosetting resin.Because 50 ℃ viscosity less than 5 * 10
1Pasec, thereby soon its viscosity of prepreg is very strong, slimy after the modulation, is difficult to operation.
Comparative example 14 (at the high example of 50 ℃ viscosity)
With the modulation of the composition shown in the table 7 compositions of thermosetting resin.Because 50 ℃ viscosity surpasses 1 * 10
4Pasec, thereby compositions of thermosetting resin is stone, can not filmization.
Comparative example 15 (tackify of the viscosity after 30 ℃ * 3 weeks surpasses 2 times example)
With the modulation of the composition shown in the table 7 compositions of thermosetting resin.This compositions of thermosetting resin after 30 ℃ * 3 weeks is stone, can not measure viscosity.In addition, soon the operability of prepreg is good after the modulation, but places the back hardening of 3 weeks in room temperature, becomes the state of end-of-life.
Comparative example 16 (120 ℃ 10
6Surpass Pasec time of advent 1000 seconds example)
With the modulation of the composition shown in the table 7 compositions of thermosetting resin.120 ℃ 10
6Pasec reaches 1300 seconds the time of advent, compares with embodiment, can know that obviously curable is poor.In addition, bend test is because not fracture, thereby is decided to be " can not measure ".
As stated; The compositions of thermosetting resin of this mode can provide the compositions of thermosetting resin of the matrix resin that is suitable for prepreg; Said prepreg is in the operability of room temperature and good in the long-life property of room temperature; And when keeping the good physical properties after the shaping, can carry out the desired high-rate forming of industry purposes.
As stated, the prepreg of this mode is in the operability of room temperature and superior in the long-life property of room temperature, and when keeping the good physical properties after the shaping, can carry out the desired high-rate forming of industry purposes.
Can prove by above, the compositions of thermosetting resin of this mode, prepreg, and the manufacturing approach of FRP all be suitable for very much high-rate forming, go a long way greatly and reduce shaping processing charges as the greatest drawback of FRP.
The embodiment of Third Way
Below through embodiment Third Way of the present invention is described particularly.In addition, this mode is not limited to following embodiment.
[based on the embodiment of resin combination (1)]
Embodiment 1～20 shown in first mode satisfies desired condition in this mode.The superior result that embodiment 1～20 demonstrates has proved thus that for as described in the embodiment of first mode composition epoxy resin and prepreg that this mode provides have superior characteristic.In addition, the condition that requires in 1～8 discontented unabridged version mode of the comparative example shown in first mode.Proved that thus comparative example 1～8 all can not demonstrate the superior characteristic as embodiment 1～20.
Embodiment 51
Use the simple type roll to be 26.8g/m with the resin mass area ratio
2The composition epoxy resin that obtains among the embodiment 3 with first mode is coated on the processing release paper equably, forms resin bed.Being bonded in this resin bed with the fiber mass area ratio is 125g/m
2Mode at the carbon fiber of a beautiful sun of direction La Qi Mitsubishi (strain) system (TR50S, tensile modulus of elasticity: 240GPa) and after the two sides of the board that forms; With roller with 100 ℃, line pressure 2kg/cm heats and pressurize; Composition epoxy resin is impregnated in the carbon fiber, and making the fiber mass area ratio is 125g/m
2The prepreg of (resin content is 30 quality %).
On the other hand, use the simple type roll to be 164g/m with the resin mass area ratio
2The composition epoxy resin that obtains among the embodiment 3 is coated on the processing release paper equably, forms resin bed.This resin bed is bonded in the carbon fibre fabric TR3110 of the beautiful sun of Mitsubishi (strain) system, and ((mass area ratio is 200g/m to the fabric that forms with 12.5 pieces/inch plain weave TR30S3L of weaving density (the long filament number is 3000)
2)) on face after, with roller with 100 ℃, line pressure 2kg/cm heats and pressurize, and composition epoxy resin is impregnated in the carbon fiber, making the fiber mass area ratio is 200g/m
2The Fabric prereg of (resin content is 45 quality %).
Prepreg and Fabric prereg are cut into 200 * 200mm; Is 0 °/90 °/0 °/90 °/0 °/90 °/0 °/90 °/0 °/90 °/0 °/90 °/0 °/90 °/0 °/90 ° 16 prepregs of lamination altogether with prepreg with machine direction; 1 Fabric prereg of (on 0 ° of layer) lamination prepares the prepreg laminate more above that.
(operable metal die face is 210 * 210mm) to be heated to 130 ℃ to be placed with the metal die of 220 * 220mm of butyl rubber gasket of wide 10mm, thick 3mm with the L font on will 2 limits in 4 limits.
In the part used of metal die with respectively apart from metal die end or butyl rubber gasket 5mm and place the prepreg laminate of previous preparation.And closed immediately metal die also applies 15 minutes 10kg/cm
2Pressure, obtain FRP sheet material.
At random cut out the test film of 3 30 * 30mm by FRP sheet material, obtain the volume content (Archimedes's method) of carbon fiber, consequently average out to 60.6 volume %.Using the density 1.25 of matrix resin, the result that the averag density 1.82 of carbon fiber is calculated resin content is 30.9 weight %.
It is concavo-convex that the FRP sheet material that obtains can see sporadicly that the damage owing to metal die surface produces, and is used in device, the method put down in writing in the detailed description and measures the center line average roughness that does not have concavo-convex part, and its result is 0.27 μ m.
Proof as stated can provide the FRP sheet material of suitable outside plate as means of transport and industrial machine and can be suitable for the prepreg that obtains FRP sheet material through this mode.
The embodiment of cubic formula
Below through embodiment cubic formula of the present invention is described particularly.In addition, this mode is not limited to following embodiment.
Embodiment 52
As the structure that keeps mould inside airtightly, the part of upper die and lower die contact adopts common edge structure (with reference to Fig. 2) during close die, will be 900cm except the FRP thickness partly surface area partly of counterdie
2Mould, upper die and lower die are heated to 140 ℃ simultaneously.
As moulding material; Preparation will draw the prepreg TR390E125S (the beautiful sun of Mitsubishi (strain) system) that neat carbon fiber has soaked into composition epoxy resin to cut into 285 * 285mm to a direction, again so that the differently-oriented directivity of fiber is that (thickness is that 2mm, cumulative volume are 162cm for 0 ° and 90 ° of 18 of staggered mode laminations
3, monoplanar surface is long-pending is 812cm
2) and the material that obtains.S
1/ S
2Be 812/900=0.9.In addition, the epoxy resin that in prepreg TR390E125S, uses is for composition epoxy resin following manufacturing approach manufacturing, that be equivalent to the composition epoxy resin of first mode.
That is, make the mixture (mass ratio is 92: 8) of EP828 and DDS react interpolation 15 mass parts EP828,6 mass parts PDMU, 9 mass parts dicyandiamides in the resin combination that obtains at 150 ℃, be mixed to uniform composition epoxy resin again to 100 mass parts.
On counterdie, place above-mentioned moulding material, and put down patrix at once and close die applies 10 minutes 9.8 * 10
2After the pressure of KPa, open mould, the temperature of mould is remained on 140 ℃, take out formed products (thickness is that 1.6mm, volume are 144cm through being installed in ejector pin on the mould
3).Its surface of this formed products, the back side and cross section all do not have pin hole and space, and outward appearance is superior.
Embodiment 53
As moulding material, use the moulding material that uses among the embodiment 1 (is 812cm with the epoxy resin SMC Lytex4149 (QUANTUM COMPOSITES society system) that contains carbon fiber except the single side surface of thickness part is long-pending
2) (gross thickness is that 4mm, cumulative volume are 325cm for moulding material after the attaching
3).S
1/ S
2Be 0.9.
On counterdie, place above-mentioned moulding material, and put down patrix at once and close die applies 10 minutes 3.0 * 10
3After the pressure of kPa, open mould, the temperature of mould is remained on 140 ℃, take out formed products (thickness 3.2mm, volume 288cm through the ejector pin that is installed on the mould
3).This formed products obtains other goods of level that the surface does not have outward appearance transitivity aspect problem yet.
Proof as stated, the manufacturing approach of the FRP through using this mode is used and is suitable for mass-produced compression forming method, can obtain high strength and aesthetic appearance FRP superior, that formed by continuous reinforcing fiber in fact.
Comparative example 17
Except use as moulding material will to a direction draw prepreg TR390E125S (the beautiful sun of Mitsubishi (strain) system) that neat carbon fiber has soaked into composition epoxy resin cut into 250 * 250mm, again so that the alignment direction of fiber is that (thickness is 162cm as 2.6mm, cumulative volume for 0 ° and 90 ° of 24 of staggered mode laminations
3, monoplanar surface is long-pending is 625cm
2) and beyond the material that obtains and embodiment 1 the same terms form.S
1/ S
2Be 625/900=0.7.
Formed products is because the mixed and disorderly severity, particularly peripheral part of the fiber orientation that the resin flow in being shaped causes significantly mixed and disorderly.
Comparative example 18
Except using and to draw the prepreg TR390E125S (the beautiful sun of Mitsubishi (strain) system) that neat carbon fiber has soaked into composition epoxy resin to cut into 320 * 320mm to a direction, again so that the differently-oriented directivity of fiber is that (thickness is that 1.6mm, cumulative volume are 162cm for 0 ° and 90 ° of 14 of staggered mode laminations as moulding material
3, monoplanar surface is long-pending is 1024cm
2) and beyond the material that obtains and embodiment 1 the same terms form.S
1/ S
2Be 1024/900=1.1.
Owing to constitute the fortifying fibre of moulding material and expose from mould, thereby fiber is drawn out in the shaping, and produces the mixed and disorderly of fiber orientation.Therefore, the formed products bad order that obtains also can not get the goods of surface smoothing.
The possibility of utilizing on the industry
Through the present invention, can easily provide and give quantitative target, can solidify at short notice, mechanical properties is superior and the FRP of the superior prepreg that at room temperature can preserve for a long time and light weight and high strength, high rigidity in lower temperature.It can extensively be suitable for purposes to industry purposes such as automobile and airborne vehicles from moving and lying fallow.
Claims (8)
1. the manufacturing approach of a formed product of fiber-reinforced composite material, it comprises the steps:
Prepare the step of shaping dies and prepreg; This shaping dies has common edge structure or the rubber sealing structure that keeps sealing; And constituted by mold and bed die, the mould inside when close die has the long-pending S of being of monoplanar surface of one of thickness 2 equal in fact faces at interval
2,
Said prepreg is the prepreg that substantially soaks into composition epoxy resin on the continuous reinforcing fiber; Said composition epoxy resin has following A composition, B composition, C composition and D composition to constitute; The content of sulphur atom in the composition epoxy resin and C composition is respectively 0.2～7 quality % and 1～15 quality %
A composition: epoxy resin
The B composition: the B-1 composition, have the amines and/or the B-2 composition of at least one sulphur atom in the molecule, have the reaction product of the amines of at least one sulphur atom in epoxy resin and the molecule
C composition: urea compounds
D composition: dicyandiamide
The long-pending S of being of monoplanar surface with one of thickness 2 equal in fact faces at interval of this prepreg
1Single face satisfy S
1/ S
2=0.8～1;
With the solidification temperature of said shaping dies temperature adjustment in advance to said epoxy resin or the step more than it;
Said prepreg is put into this step of the shaping dies of temperature adjustment; And
Closed shaping dies carries out compression molding, makes prepreg be full of the inner step of whole shaping dies.
2. the manufacturing approach of formed product of fiber-reinforced composite material according to claim 1; Wherein, continuous reinforcing fiber is in fact soaked into composition epoxy resin and the volume of the prepreg that forms and volume that thickness is respectively formed products 100～120% with 100～150% of thickness.
3. the manufacturing approach of formed product of fiber-reinforced composite material according to claim 1, wherein, close die is full of entire die when inner at prepreg, uses deaerating mechanism to outgas.
4. the manufacturing approach of formed product of fiber-reinforced composite material according to claim 1 wherein, does not reduce the temperature of mould and just takes out formed product of fiber-reinforced composite material.
5. the manufacturing approach of formed product of fiber-reinforced composite material according to claim 1 wherein, as mould, is used the mould with the mechanism that makes the formed product of fiber-reinforced composite material demoulding.
6. the manufacturing approach of formed product of fiber-reinforced composite material according to claim 1, wherein, fortifying fibre is a carbon fiber.
7. according to the manufacturing approach of any described formed product of fiber-reinforced composite material in the claim 1～6; Wherein, Replacement is soaked into composition epoxy resin to continuous reinforcing fiber in fact and the prepreg that forms; As moulding material, use to have fortifying fibre to the short fiber shape to the material that continuous reinforcing fiber is in fact soaked into composition epoxy resin and at least one side surface and soak into the moulding material that the material of composition epoxy resin overlaps.
8. the manufacturing approach of formed product of fiber-reinforced composite material according to claim 1, wherein, said prepreg be shaped as the shape that when shaping dies cuts out, is contained in the shaping dies.
Applications Claiming Priority (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002-346198 | 2002-11-28 | ||
| JP2002346198 | 2002-11-28 | ||
| JP2002346198 | 2002-11-28 | ||
| JP2002347650 | 2002-11-29 | ||
| JP2002347650 | 2002-11-29 | ||
| JP2002-347650 | 2002-11-29 | ||
| JP2002353760 | 2002-12-05 | ||
| JP2002353760 | 2002-12-05 | ||
| JP2002-353760 | 2002-12-05 | ||
| JP2002-362519 | 2002-12-13 | ||
| JP2002362519 | 2002-12-13 | ||
| JP2002362519 | 2002-12-13 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003801042849A Division CN100341916C (en) | 2002-11-28 | 2003-11-28 | Epoxy resin for prepreg, prepreg, fiber-reinforced composite material, and processes for producing these |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1944026A CN1944026A (en) | 2007-04-11 |
| CN1944026B true CN1944026B (en) | 2012-03-21 |
Family
ID=35822526
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| CN 200610126713 Pending CN1944527A (en) | 2002-11-28 | 2003-11-28 | Epoxy resin for prepreg, prepreg, fiber-reinforced composite material, and processes for producing same |
| CNB2003801042849A Expired - Lifetime CN100341916C (en) | 2002-11-28 | 2003-11-28 | Epoxy resin for prepreg, prepreg, fiber-reinforced composite material, and processes for producing these |
| CN2006101267142A Expired - Lifetime CN1944528B (en) | 2002-11-28 | 2003-11-28 | Epoxy resin for prepreg, prepreg, fiber-reinforced composite material, and processes for producing same |
| CN2006101267157A Expired - Lifetime CN1944026B (en) | 2002-11-28 | 2003-11-28 | Epoxy resin for prepreg, prepreg, fiber-reinforced composite material, and processes for producing these |
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| CN 200610126713 Pending CN1944527A (en) | 2002-11-28 | 2003-11-28 | Epoxy resin for prepreg, prepreg, fiber-reinforced composite material, and processes for producing same |
| CNB2003801042849A Expired - Lifetime CN100341916C (en) | 2002-11-28 | 2003-11-28 | Epoxy resin for prepreg, prepreg, fiber-reinforced composite material, and processes for producing these |
| CN2006101267142A Expired - Lifetime CN1944528B (en) | 2002-11-28 | 2003-11-28 | Epoxy resin for prepreg, prepreg, fiber-reinforced composite material, and processes for producing same |
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| JP5572390B2 (en) * | 2008-08-28 | 2014-08-13 | 三菱レイヨン株式会社 | Epoxy resin composition, prepreg using the same, fiber reinforced composite resin tubular body manufactured from the prepreg, manufacturing method thereof, and fiber reinforced composite resin molded body |
| CN102134373A (en) * | 2010-01-25 | 2011-07-27 | 核工业第八研究所 | High-performance carbon central mounting plate for robots and manufacturing method thereof |
| WO2011122179A1 (en) * | 2010-03-29 | 2011-10-06 | 三菱電機株式会社 | Fiber-reinforced plastic molding, production method therefor, and elevator |
| EP2787028B1 (en) * | 2011-11-29 | 2018-01-03 | Mitsubishi Chemical Corporation | Prepreg, fiber-reinforced composite material, method for producing same, and epoxy resin composition |
| CN104023979B (en) * | 2011-12-23 | 2015-08-05 | 东丽株式会社 | The preparation method of prepreg, fibre reinforced composites and fibre reinforced composites |
| GB201206885D0 (en) * | 2012-04-19 | 2012-06-06 | Cytec Tech Corp | Composite materials |
| JP5768893B2 (en) * | 2012-08-20 | 2015-08-26 | 三菱レイヨン株式会社 | Epoxy resin composition and film, prepreg, fiber reinforced plastic using the same |
| CN103042702B (en) * | 2012-11-13 | 2015-01-07 | 中国科学院宁波材料技术与工程研究所 | Method capable of reducing the surface defects of fiber reinforced thermoplastic composite products |
| TWI591109B (en) * | 2015-06-11 | 2017-07-11 | Mitsubishi Rayon Co | Epoxy resin composition, molded article, prepreg, fiber reinforced Composites and structures |
| CN105038244A (en) * | 2015-07-31 | 2015-11-11 | 苏州天健竹业科技有限公司 | Reinforced composite for bicycle and preparation method thereof |
| CN105038131A (en) * | 2015-07-31 | 2015-11-11 | 苏州天健竹业科技有限公司 | Impact-resistant composite for bicycle and preparation method thereof |
| EP3388474B1 (en) | 2015-12-10 | 2019-10-30 | Mitsubishi Chemical Corporation | Tow prepreg, composite material-reinforced pressure vessel, and method of producing composite material-reinforced pressure vessel |
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| CN109414887B (en) * | 2016-07-27 | 2021-02-19 | 三菱化学株式会社 | Preform manufacturing device and preform manufacturing method |
| CN107474485A (en) * | 2017-09-03 | 2017-12-15 | 安徽天裕汽车零部件制造有限公司 | A kind of composite of auto parts and components rapid shaping and preparation method thereof |
| CN108016054A (en) * | 2017-11-20 | 2018-05-11 | 刘长喜 | Carbon fibre composite is molded membranous disc manufacturing process |
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| CN113574100A (en) * | 2019-02-28 | 2021-10-29 | 陶氏环球技术有限责任公司 | Method for producing a fiber composite |
| CN113631356B (en) * | 2019-03-26 | 2023-01-10 | 日产自动车株式会社 | Method for manufacturing closed cross-section structural member |
| CN113573885A (en) * | 2019-03-27 | 2021-10-29 | 松下知识产权经营株式会社 | Fiber sheet, and laminate, circuit board, and electronic board using same |
| CN113646164B (en) * | 2019-04-02 | 2023-06-06 | 日本制铁株式会社 | Metal-carbon fiber reinforced resin material composite |
| JP6656702B1 (en) * | 2019-08-15 | 2020-03-04 | 株式会社Ｔｈｅ ＭＯＴ Ｃｏｍｐａｎｙ | Manufacturing method of fiber-reinforced resin molded product |
| CN115023329B (en) * | 2020-01-27 | 2024-04-12 | 帝人株式会社 | Cold press molded article comprising carbon fiber and glass fiber, and method for producing same |
| CN111907086A (en) * | 2020-06-10 | 2020-11-10 | 宁波葆尔新材料有限公司 | Preparation method of SMC composite material containing fireproof heat-insulation ceramic silicone rubber |
| CN111570192A (en) * | 2020-06-16 | 2020-08-25 | 河北顺天电极有限公司 | High-pressure impregnation pressurization carbonization process and equipment for carbon fiber preform |
| CN113736218B (en) * | 2021-11-08 | 2022-02-18 | 山东江山纤维科技有限公司 | Prepreg resin for reinforcing ship body and preparation method and application thereof |
| TWI818690B (en) * | 2022-08-23 | 2023-10-11 | 友達光電股份有限公司 | Solar module |
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- 2003-11-28 CN CNB2003801042849A patent/CN100341916C/en not_active Expired - Lifetime
- 2003-11-28 CN CN2006101267142A patent/CN1944528B/en not_active Expired - Lifetime
- 2003-11-28 CN CN2006101267157A patent/CN1944026B/en not_active Expired - Lifetime
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| CN1242792A (en) * | 1997-10-14 | 2000-01-26 | 东丽株式会社 | Epoxy resin composition for fiber-reinforced composite material, prepreg, and fiber-reinforced composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1944528B (en) | 2011-06-22 |
| CN1944527A (en) | 2007-04-11 |
| CN1944528A (en) | 2007-04-11 |
| CN100341916C (en) | 2007-10-10 |
| CN1717429A (en) | 2006-01-04 |
| CN1944026A (en) | 2007-04-11 |
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