CN1926188A - Epoxy resin composition for fiber-reinforced composite material, prepreg and fiber-reinforced composite material - Google Patents

Abstract

Disclosed is an epoxy resin composition containing at least an epoxy resin (a) having an oxazolidone ring and a glycidylamine epoxy resin (b). This epoxy resin composition contains 1-20 parts by weight of a solid rubber per 100 parts by weight of the total epoxy resin, and it also contains an aromatic amine as a curing agent. When the composition is heated and cured at 180 1/2 C for 2 hours, the glass transition temperature of the resulting cured product is 160-220 1/2 C.

Description

Epoxy resin composition for fiber-reinforced composite material, prepreg and fibre reinforced composites

Technical field

The present invention relates to composition epoxy resin, prepreg and the laminar composite of suitable light weight and high strength, the cellular laminar composite of high inflexible.

Background technology

Contain fortifying fibre and matrix resin fibre reinforced composites since its excellent mechanics rerum natura etc. be widely used in flyer, automobile, the industry purposes.In the past, as the aircraft construction material, used following layered product, this layered product has used and contained the unidirectional pre-immersion material base that resin pickup forms in the fortifying fibre of unidirectional doubling, and it is excellent especially in hot and humid environment lower compression characteristic.

On the other hand, in recent years from light-weighted viewpoint, fibre reinforced composites are increased as the example that skin panel is used for cellular sandwich panel.As the honeycomb core of these cellular sandwich panel, use aramid honeycomb, glass honeycomb, aluminium honeycomb.In the manufacturing of cellular sandwich panel, when bonding prepreg and honeycomb core, use will be processed into membranaceous adhesive clip between the layered product of honeycomb core and prepreg, carried out co-curing and the adherent method thereafter in the past.But, the requirement that reduces along with cost in flyer purposes field strengthens, and recently, prepreg is laminated to the honeycomb core two sides, by heating, thereby make the sclerosis of prepreg and the bonding autoadhesion honeycomb fashion co-curing moulding method of carrying out simultaneously of prepreg and honeycomb core become main flow.In this autoadhesion honeycomb fashion co-curing moulding method, require to do one's utmost to improve the prepreg that becomes skin panel and the binding property of honeycomb core.But, because it is bonding to utilize the resin that oozes out to carry out, therefore must consider the complicated factors such as affinity of used resin and honeycomb core etc. from prepreg, all be difficult to fully guarantee binding property always.

So, relative therewith even at first require under hot and humid degree environment, also to bring into play the high compression characteristic with matrix resin for the unidirectional pre-immersion material base, to the matrix resin that uses in being shaped with prepreg at the honeycomb fashion co-curing then strong request have self adhesion.For example, in order to improve cellular sandwich panel self adhesion, attempt to improve binding property (for example with reference to patent documentation 1) with honeycomb core by the acrylonitrile butadiene rubber that cooperates weak bridging property with prepreg.In addition, also proposed to have the Resins, epoxy of  oxazolidone ring structure and the self adhesion prepreg of the outward appearance excellence that thermoplastic resin obtains (for example with reference to patent documentation 2) by combination.

In addition, as with the matrix modification of prepreg and improve other method of self adhesion, disclose in matrix resin or prepreg surface engagement thermoplastic resin particle (for example with reference to patent documentation 3,4).

In general, in autoadhesion honeycomb fashion co-curing method, the sclerosis because the matrix resin that joins with honeycomb core flows has formed glue knurl (Off イ Star ト) at the bonding part of surface and honeycomb core.In patent documentation 1, patent documentation 4 disclosed methods, make its high tenacityization by in this glue knurl, flowing into the thermoplastic resin particle, obtain self adhesion.But, must in matrix resin, cooperate a large amount of thermoplastic resin particles in order to obtain enough autoadhesion intensity in this method, have the tackiness that significantly loses prepreg, the property handled reduction, perhaps the characteristic of matrix resin is produced detrimentally affect, easily produce the problems such as mechanical characteristic, hole of forming board.In addition, on the approaching position of the fortifying fibre of honeycomb core wall and prepreg, because amount of resin reduces, the effect that therefore also has high tenacityization is little, because factors such as molding condition can not form glue knurl and the extreme problem that reduces of autoadhesion intensity well.

The matrix resin that uses in these self adhesion prepreg has self adhesion, but when the matrix resin of described unidirectional pre-immersion material base uses before conduct, has the inadequate problem of compressive strength under hot and humid degree.That is, because with respect to the desired characteristic difference of matrix resin, therefore at present use different resin combinations respectively, can't be met both require characteristic, can be general resin combination, this is a present situation.Therefore, because the difference of this resin properties, unidirectional pre-immersion material base and honeycomb fashion co-curing there is being restriction in prepreg hybrid shaping, appropriate combination.

And with regard to cellular sandwich panel was shaped, following characteristic also enjoyed attention.At first, in order to ensure the plastic property of prepreg, require the tackiness and the drape of prepreg to 3 dimension curved surfaces.Defectives such as requirement internal void are few, so that can appear as the stable mechanical characteristic of body.And, also require surface smoothing, so that can be simplified to surface working, the reparation step of body.

Be conceived to the erosion resistance of fibre reinforced composites excellence, attempt used as the integral body of the transportation machine of motions such as flyer, automobile, electric car, blimp, ship, boats and ships, the outside plate of various industrial machines.In such purposes, special strict demand takes into account raising intensity and rigidity (security), is used to suppress the lightweight of consumed energy (environmental cure) and 3 characteristics of outward appearance grade.Particularly, the outward appearance grade is not only apparent problem, knows that also its fluid impedance to air, water has great effect, requires more level and smooth.

But therefore fibre reinforced composites are difficult to satisfy the outward appearance grade that can be applicable to such use owing to produce concavo-convex that fortifying fibre causes on its surface.Particularly, when improving fortifying fibre that intensity and rigidity use fabric shape as fortifying fibre, this tendency is more remarkable.

For this problem, disclose on the basis of matrix resin modification, the improvement of the fiber reinforcement fabrics such as order Fu Liang by cover factor, enhanced fabrics improves the technology (for example with reference to patent documentation 5,6) of the surperficial grade etc. of fibre reinforced composites such as skin panel.But, in these disclosed technology, being used for requirement more during the outside plate purposes of high precision, smoothness, surface smoothing is insufficient.

In addition, disclosing by using matrix resin content is the prepreg of the high prepreg of 90～98 weight % and resin content as the formation top layer, improves the technology (for example with reference to patent documentation 7) of skin panel surface smoothing.But, the prepreg that resin content is high like this, operational problems such as the property handled is poor, interlayer entrained air, gauffer are arranged.

In addition,, often use lamination prepreg, paste the method that membranaceous tackiness agent (hereinafter referred to as bonding film) carries out the heating and pressurizing shaping that is processed at the outermost layer of this prepreg as the additive method that improves lamination material surface smoothing.But this bonding film is owing to use as tackiness agent, and is therefore not only different with the composition of matrix resin, and order pay greatly, very thick, worry can cause the weight of lamination material to increase or the mechanics rerum natura reduces.In addition, also have air, gauffer is blended into operational problems such as adhesive interface.

And as additive method, also known in advance after tool surfaces is coated on the surperficial coating material (hereinafter referred to as gel coat) that modification distortion does not take place under the forming temperature, lamination prepreg is carried out heating and pressurizing hardened method (for example with reference to patent documentation 8).Because this method can be omitted surface grinding, coating, be therefore in industrial advantageous method, the superficiality of gained lamination material is also excellent.But in order to obtain excellent surface smoothing, the thickness of gel coat often reaches more than the 200 μ m, not only gains in weight, but also has outside plate when being subjected to external force deformation, the shortcoming that gel coating resin ruptures, peels off.In addition, different with the composition of the matrix resin of prepreg as the resin that gel coat uses, when heat hardening, because the difference of their linear expansivity, distortion such as warpage take place in the whole meeting of molding, therefore have the problem of the outside plate that can not be used for precision prescribed.

Patent documentation 1: Japanese kokai publication hei 6-025446 communique

Patent documentation 2: TOHKEMY 2003-261744 communique

Patent documentation 3: United States Patent (USP) 2002/0079052 A1 communique

Patent documentation 4: Japanese spy is the 1999-002586 communique again

Patent documentation 5: TOHKEMY 2000-238154 communique

Patent documentation 6: TOHKEMY 2003-147103 communique

Patent documentation 7: No. 2767329 communique of patent

Patent documentation 8: Japanese kokai publication hei 8-112864 communique

Summary of the invention

The object of the present invention is to provide and have sufficient tackiness, drape and self adhesion when being used for prepreg, when the gained molding has surperficial grade and inner grade, can under hygrothermal environment, have the composition epoxy resin of high compression-strength and use its prepreg and fibre reinforced composites.

Other purposes of the present invention are to provide and satisfy the desired all characteristics of skin-material, simultaneously with the prepreg of the self adhesion excellence of honeycomb with use the cellular laminar composite of its light weight and mechanical characteristic excellence.

Other purposes of the present invention also are to provide and satisfy outside plate and require all characteristics, simultaneously laminate structures that the subsurface defect of surface smoothing excellence is few and the prepreg that is used for it.

Composition epoxy resin of the present invention has following formation in order to reach above-mentioned purpose.

(1) the present invention is a composition epoxy resin, at least contain following Resins, epoxy (a) and Resins, epoxy (b) as Resins, epoxy, the vulcanite that contains 1～20 weight part with respect to 100 weight part total epoxies, contain aromatic amine as stiffening agent, and the second-order transition temperature at the hardening thing of 180 ℃ of following heat hardenings after 2 hours is 160～220 ℃

(a) have the Resins, epoxy of  oxazolidone ring,

(b) glycidyl amine type epoxy resin.

(2) prepreg of the present invention with this composition epoxy resin and fortifying fibre as integrant.

(3) fibre reinforced composites of the present invention are shaped this prepreg and form.

(4) in addition, the present invention is the prepreg that comprises following integrant [A], [B] and [C],

[A]: comprise long stapled fortifying fibre,

[B]: matrix resin,

[C]: the thermoplastic resin that has the space and have continuous morphology.

(5) the present invention is for comprising following integrant [A], [C], [D] and [E], and integrant [C] is configured in the laminar composite that forms between honeycomb core [E] and the integrant [A],

[A]: comprise long stapled fortifying fibre,

[C]: have the space and have continuous morphology thermoplastic resin,

[D]: the matrix resin hardening thing,

[E]: honeycomb core.

(6) in addition, the present invention is for comprising following integrant [A], [C] and [D], and integrant [C] is configured in the laminar composite outside plate of the outside surface side of integrant [A],

[A]: comprise long stapled fortifying fibre,

[C]: have the space and have continuous morphology thermoplastic resin,

[D]: matrix resin hardening thing.

(7) prepreg of the present invention is above-mentioned (4) described prepreg, and wherein integrant [B] is the composition epoxy resin of above-mentioned (1) item.

(8) laminar composite of the present invention is above-mentioned (5) described laminar composite, and wherein integrant [D] is the hardening thing of the composition epoxy resin of above-mentioned (1) item.

(9) laminar composite outside plate of the present invention is above-mentioned (6) described laminar composite outside plate, and wherein integrant [D] is the hardening thing of the composition epoxy resin of above-mentioned (1) item.

Composition epoxy resin of the present invention is suitable for as the prepreg resin combination.The prepreg of using this resin combination to obtain has excellent tackiness and drape, and is also excellent with the self adhesion of honeycomb core.In addition, the surperficial grade and the inner grade excellence of the fibre reinforced composites of the present invention that obtain by this prepreg.On the basis of these features, when composition epoxy resin of the present invention is used for the unidirectional pre-immersion material base, can access the fibre reinforced composites that under hygrothermal environment, have high compression-strength.And, because composition epoxy resin of the present invention can be applicable in any of Fabric prereg base and unidirectional pre-immersion material base, therefore can carry out the hybrid shaping of Fabric prereg base and unidirectional pre-immersion material base etc., improve the design freedom of structural member greatly.

As described below, the present invention can provide and satisfy all characteristics that surfacing requires, simultaneously with the prepreg of the self adhesion excellence of honeycomb, and the cellular laminar composite that utilizes its light weight that obtains, mechanical characteristic excellence.

Following explanation, the present invention can be provided at when satisfying the desired all characteristic of outside plate, the laminar composite of surface smoothing excellence.

Description of drawings

Fig. 1 utilizes DSC to carry out the synoptic diagram that hardening thing Tg measures.

Fig. 2 is utilize DMA to absorb water a synoptic diagram that post-hardening thing Tg measures.

Nomenclature

1: endothermic side to

2: the heat release direction

3: glass transition temperature Tg _DSC

4: temperature

5: rigidity modulus G

6: the tangent line of vitrifying zone line

7: the tangent line of glass transition zone line

8: glass transition temperature Tg _DMA

9: temperature

Embodiment

The contriver furthers investigate in view of above-mentioned problem, and the result is when combination cooperates the Resins, epoxy that contains  oxazolidone ring and rubber constituent in the composition epoxy resin, unexpectedly to have solved at one stroke this problem attempting to the aromatic amine sclerosis.Particularly find to obtain the tackiness, drape, self adhesion, the surperficial grade of gained fibre reinforced composites, inner grade of prepreg and at the composition epoxy resin of hygrothermal environment lower compression intensity balance excellence with honeycomb core.

Composition epoxy resin among the present invention is the resin combination that contains Resins, epoxy and stiffening agent.For modification, can also cooperate thermosetting resin beyond the Resins, epoxy, thermoplastic resin, filler, other additives etc.

In the present invention, must contain following 2 kinds of Resins, epoxy at least as Resins, epoxy:

(a) have  oxazolidone ring Resins, epoxy,

(b) glycidyl amine type epoxy resin.

Resins, epoxy with  oxazolidone ring has the effect of raising to the self adhesion of honeycomb core, in the total epoxy of 100 weight %, preferably contains 10～60 weight %, more preferably contains 20～50 weight %, especially preferably contains 25～40 weight %.When having the Resins, epoxy less than 10 weight % of  oxazolidone ring, insufficient, the poor heat resistance of self adhesion sometimes then.And when containing the Resins, epoxy with  oxazolidone ring and surpassing 60 weight %, tackiness and drape reduce sometimes.This Resins, epoxy that contains  oxazolidone ring can generate  oxazolidone ring at intramolecularly and obtain by making the reaction of various Resins, epoxy and polyisocyanate compounds.As the Resins, epoxy of raw material, can preferably utilize the polyfunctional epoxy resin of 2 functionality Resins, epoxy, glycidyl amine or the phenolic resin varnish type epoxy resin representative of bisphenol A type epoxy resin representative.In addition, as polyisocyanate compounds,, can also use polyfunctional isocyanates such as poly-MDI except with the vulcabond headed by TDI (tolylene diisocyanate), the MDI (diphenylmethanediisocyanate).In addition, from stable on heating viewpoint, optimization aromatic class polymeric polyisocyanate.It should be noted that as being the Resins, epoxy with  oxazolidone ring of raw material, can use ア ラ Le ダ イ De (registered trademark) AER4152, XAC4151 (エ of Asahi Chemical Industry Port キ シ (strain) production) etc. with the bisphenol A type epoxy resin.

Glycidyl amine type epoxy resin that must composition as another has the stable on heating effect of raising, preferably contains 10～60 weight % in 100 weight % total epoxies, more preferably contains 20～50 weight %, further preferably contains 25～40 weight %.During glycidyl amine type epoxy resin less than 10 weight %, insufficient, the poor heat resistance of self adhesion sometimes.In addition, when containing glycidyl amine type epoxy resin, resin toughness arranged, climb the situation that bulging stripping strength (CDP) reduces above 60 weight %.As this glycidyl amine type epoxy resin, can use four glycidyl group diaminodiphenyl-methane, triglycidyl group amino-phenol, the amino cresols of triglycidyl group, diglycidylaniline, diglycidyl Tolylamine etc.

As above-mentioned four glycidyl group diaminodiphenyl-methane, can use ELM434 (Sumitomo Chemical (strain) production), YH434L (Dongdu changes into (strain) and produces), MY720 (Ha Application Star マ Application ア De バ Application ス ト マ テ リ ア Le ズ (strain) production), エ ピ コ one ト 604 (registered trademark, oiling シ エ Le エ Port キ シ (strain) produce) etc.As triglycidyl group amino-phenol or the amino cresols of triglycidyl group, can use ELM100 (Sumitomo Chemical (strain) production), MY0510 (production of チ バ ガ イ ギ one company), エ ピ コ one ト 630 (registered trademark, oiling シ エ Le エ Port キ シ (strain) produce) etc.As diglycidylaniline, can use GAN (Japanese chemical drug (strain) production) etc.As the diglycidyl Tolylamine, can use GOT (Japanese chemical drug (strain) production) etc.

As Resins, epoxy, except Resins, epoxy and glycidyl amine type epoxy resin with  oxazolidone ring, can also use for example bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, humidity resistance is good and give the biphenyl type epoxy resin of inflexible resin, naphthalene type Resins, epoxy, dicyclopentadiene-type epoxy resin, diphenylfluorene type Resins, epoxy, phenolic novolac, the cresols lacquer resins, the phenol aralkyl-type epoxy resin, four (glycidyl oxygen base phenyl) ethane, three (glycidyl oxygen base) methane etc., or their mixture.

With respect to 100 weight part total epoxies, must contain 1～20 weight part vulcanite in the composition epoxy resin of the present invention.Also can preferably contain 2～15 weight parts, more preferably contain 3～10 weight parts.Vulcanite is during less than 1 weight part, and self adhesion, tackiness, drape and surperficial grade are insufficient sometimes.When vulcanite surpassed 20 weight parts, thermotolerance reduced sometimes.

Described vulcanite is meant do not have mobile rubber under the room temperature.For example, can use the various rubber of excellent heat resistances such as hard acrylonitrile butadiene rubber, its hydride and acrylic rubber, ethylene-acrylic rubber, styrene butadiene rubbers, epichloro hydrin rubber, isoprene-isobutylene rubber, ethylene-propylene rubber, ethylene-vinyl acetate rubber.In addition, as these vulcanites, can preferably use to have functional group in the chemical structure.As functional group, preferred carboxyl, anhydride group, epoxy group(ing), amino, amide group, hydroxyl, isocyanate group, phosphate, sulfydryl, halogen etc.

Wherein, consider the carboxy-modified acrylonitrile butadiene rubber of preferred especially use from the aspect of consistency and self adhesion.As this acrylonitrile butadiene rubber can use hydrogenant, unhydrided any, perhaps also can use two kinds.If the use hydrogenant, then the weathering resistance of gained composition of the present invention and thermotolerance are good.In addition, as acrylonitrile butadiene rubber, can be a kind in the various compositions, also can be the mixture more than 2 kinds.Consider that from the viewpoint of consistency it is that 20 weight %～40 weight %, carboxyl amount are the carboxy-modified hydrogenated acrylonitrile divinyl rubber of 0.5 weight %～6 weight % that the hydrogenated acrylonitrile divinyl rubber preferably uses the itrile group amount.

In addition, consider that from the inside grade of raising molding and the viewpoint of surperficial grade at least a portion of preferred rubber composition is reacted with the epoxy composition in advance, form key.

Composition epoxy resin of the present invention contains aromatic amine as stiffening agent.This aromatic amine preferably contains stoichiometric 50～120% with respect to total epoxy, more preferably contains 60～120%, further preferably contains 70～120%.During aromatic amine stiffening agent less than 50%, the thermotolerance of gained hardening of resin thing is not enough sometimes.The aromatic amine stiffening agent surpasses at 120% o'clock, and the toughness of gained hardening of resin thing reduces sometimes.As this aromatic amine stiffening agent, so long as the aromatic amine that uses as epoxy resin hardener gets final product, be not particularly limited, can preferably use diaminodiphenylsulfone(DDS) (DDS), diaminodiphenyl-methane (DDM), diamino-diphenyl ether (DADPE), dianiline (ゼ ス ア ニ リ Application), benzyl dimethyl aniline, 2-(dimethylaminomethyl) phenol (DMP-10), 2 particularly, 4, three-2-ethylhexoate of 6-three (dimethylaminomethyl) phenol (DMP-30), DMP-30 etc., and their isomer or derivative.They can use separately, also can use mixing more than 2 kinds.

In addition, as required, can also and with stiffening agent, hardening catalyst beyond the aromatic amine.Can use carboxylic acid anhydride, carboxylic acid hydrazides, carboxylic acid amide, polyphenolic substance, novolac resin, polythiols etc. such as fatty amine, imdazole derivatives, Dyhard RU 100, tetramethyl guanidine, thiocarbamide addition amine, methyl hexahydro phthalic anhydride particularly.In addition, can use for example 3-(3, the 4-dichlorophenyl)-1, so-called Lewis acid complex compound such as 1-dimethyl urea urea derivativess such as (DCMU), imdazole derivatives, tertiary amine, boron trifluoride ethylamine complex compound, sulfonium salt, sulphonate etc. as hardening catalyst.Therefore it should be noted that owing to the storage stability of base material raising in the middle of the prepreg etc. can preferably use the material that these stiffening agents, hardening catalyst micro encapsulation are obtained.

In order to improve the rerum naturas such as toughness of gained hardening of resin thing, composition epoxy resin of the present invention can cooperate thermoplastic resin.As this thermoplastic resin, can preferably use to have the thermoplastic resin that is selected from the key in carbon-carbon bond, amido linkage, imide bond (polyetherimide etc.), ester bond, ehter bond, siloxane bond, carbonic acid ester bond, ammonia ester bond, urea key, thioether bond, sulfone key, imidazoles key, the ketonic linkage on the main chain.For example can preferably use polysulfones, polyethersulfone, polyetherimide, polyimide, polymeric amide, polyamidoimide, polyphenylene oxide, phenoxy resin, vinylic polymers etc. to have both thermotolerance and flexible.

Especially preferably use polyethersulfone, polyetherimide, because their effect of performance under the stable on heating condition can damaged hardly.As polyethersulfone, can use ス ミ カ エ Network セ Le (registered trademark) PES3600P, ス ミ カ エ Network セ Le (registered trademark) PES5003P, ス ミ カ エ Network セ Le (registered trademark) PES5200P, ス ミ カ エ Network セ Le (registered trademark more than is Sumitomo Chemical (strain) production) PES7200P; As polyetherimide, can use ウ Le テ system (registered trademark) 1000, ウ Le テ system (registered trademark more than is Japanese ジ one イ one プ ラ ス チ Star Network ス (strain) production) 1010 etc.

This thermoplastic resin especially preferably solves homogeneously in the composition epoxy resin or with the particle shape differential and looses, and is the prepreg production process at center so that do not hinder with the impregnation.

In addition, in the time of in being dissolved in composition epoxy resin, with respect to 100 weight part Resins, epoxy, the use level of this thermoplastic resin is preferably 1～10 weight part, more preferably 1～7 weight part, more preferably 1～5 weight part.On the other hand, when it is disperseed to use, be preferably 10～40 weight parts with respect to 100 weight part Resins, epoxy, more preferably 15～30 weight parts.If not enough this use level, then toughness raising effect becomes insufficient sometimes.And surpassing above-mentioned scope, then impregnation, tackiness, drape and thermotolerance are not enough sometimes.

For optimization viscosity, composition epoxy resin of the present invention can use the thixotropy imparting agent.As this thixotropy imparting agent, can enumerate inorganic particulates such as talcum, pure aluminium silicate, microparticulate silica, lime carbonate, mica, montmorillonite, terre verte, carbon black, silicon carbide, hydrated alumina.Wherein, known microparticulate silica in joining resin combination the time thixotropy expression effect big, moreover, also reduced the temperature dependency of the visco-elasticity function of resin combination, even handle the operating environment temperature of prepreg change has been arranged, the property handled also is difficult for variation, and prepreg place the tackiness cause through the time change little, improved surface smoothing, and the effect that makes with the self adhesion excellence of honeycomb core has been arranged as the skin panel of hardening thing, therefore preferred.With the micropartical silicon-dioxide of silicon-dioxide as basic framework, for example once the mean value of particle diameter is sold on market with the trade mark of ア エ ロ ジ Le (Japanese ア エ ロ ジ Le (strain) production) in 5～40nm scope.Primary particle size is carefully to 40nm, owing to investing sufficient tackify effect, therefore preferably.Particle diameter uses electron microscope to estimate.Preferred specific surface area is 50～400m ²/ g scope.The general silica sphere that uses is covered by the silanol base, but consider from the raising aspect of the mechanics rerum natura of the water tolerance of the tackify effect, thixotropy stabilization aspect and the molding that improve resin, compressive strength representative, be more preferably the hydrophobic particulate shape silicon-dioxide that the hydrogen that uses the silanol base has been replaced by methyl, octyl group, dimethyl siloxane etc.When cooperating this thixotropy imparting agent, preferably add with the scope of 0.1～8 weight % with respect to composition epoxy resin integral body.Less than 0.1 weight % then easily produces indenture or starved (Trees fat ガ The れ) on the skin panel of cellular sandwich panel; On the other hand, when surpassing 8 weight %, then resin viscosity too high, to the impregnation of the fortifying fibre difficulty that becomes easily.Preferred addition is the scope of 0.2～5 weight %, more preferably the scope of 0.3～3 weight %.

The MV minium viscosity of composition epoxy resin of the present invention is preferably in the scope of 1～50Pas, more preferably in the scope of 2～50Pas, particularly preferably in the scope of 3～50Pas.If not enough 1Pas, when then being shaped with the adhesive face of honeycomb core on can not fully to form glue knurl, self adhesion not enough sometimes.And when surpassing 50Pas, then tackiness and drape are not enough sometimes.This MV minium viscosity is a value of utilizing the dynamic viscoelastic analysis to obtain, as described later, and by being that the temperature under 2 ℃/minute the condition and the relation curve of viscosity are tried to achieve at heat-up rate.This MV minium viscosity can perhaps be controlled by the cooperation of various particles, thermoplastic resin by the use level control of above-mentioned vulcanite.In addition,, consider, also use stiffening agent, the hardening catalyst that can react at low temperatures more preferred than aromatic amine from improving the MV minium viscosity aspect as stiffening agent.

As the composition epoxy resin of the present invention that so obtains, by the glass transition temperature Tg of the hardening of resin thing that obtained in 2 hours 180 ℃ of following heat hardenings _DSCBe the value of utilizing differential scanning calorimetry (DSC) to measure, be necessary for 160～220 ℃.From taking into account the compressive strength under hygrothermal environment and climbing aspect the bulging stripping strength (CDP) and consider, be preferably 170～220 ℃, more preferably 175～220 ℃ scope.This glass transition temperature Tg _DSCAs less than 160 ℃, then the strength characteristics of gained fibre reinforced composites under hot environment reduces sometimes.When surpassing 220 ℃, then toughness becomes insufficient sometimes.

Composition epoxy resin of the present invention is immersed in the glass transition temperature Tg after 2 days in the boiling water at 180 ℃ of hardening things that obtained in 2 hours that harden down _DMAPreferably 110～150 ℃ scope, more preferably 120～150 ℃ scope, particularly preferably in 125～150 ℃ scope.If 110 ℃ of less thaies, then the strength characteristics of gained matrix material under hygrothermal environment reduces sometimes.And when surpassing 150 ℃, it is insufficient that toughness becomes sometimes.Here said glass transition temperature Tg _DMAIt is the value of measuring by dynamic viscoelastic analysis (DMA).

The pattern I energy release rate G of the described composition epoxy resin of the present invention hardening of resin thing that sclerosis obtained in 2 hours under 180 ℃ _ICPreferably at 200～1000J/m ²Scope, more preferably at 230～1000J/m ²Scope, particularly preferably in 250～1000J/m ²Scope.If not enough 200J/m ², then the self adhesion with honeycomb core is not enough sometimes.And above 1000J/m ²The time, it is insufficient that thermotolerance becomes sometimes.As described later, the G of the hardening thing of this composition epoxy resin _ICBe to measure the value that obtains, as toughness index according to JIS K7161 (1994).

Then, prepreg is described.Prepreg of the present invention contains the composition epoxy resin and the fortifying fibre of the invention described above.

Glass transition temperature Tg when this prepreg is unhardened is the same measuring method of glass transition temperature Tg of the hardening thing of utilization and above-mentioned composition epoxy resin, uses differential scanning calorimetry (DSC) to try to achieve.This Tg is preferably-5～10 ℃ scope, more preferably-3～5 ℃ scope.As not enough-5 ℃, then tackiness became strong, sometimes laminating operation was made troubles.And when surpassing 10 ℃, then tackiness, drape are not enough sometimes.

In addition, the volatile amount of prepreg is preferably in the scope of 0.01～1 weight %, more preferably in 0.01～0.7% scope.When volatile amount surpassed 1 weight %, surperficial grade and inner grade when making fibre reinforced composites reduced sometimes.The volatile amount of this prepreg is by the sample prepreg (values that 100mm * 100mm) obtains 180 ℃ of changes in weight after placing 2 hours down.

Prepreg of the present invention can have following formation.That is, be the prepreg that comprises following integrant [A], [B] and [C],

[A]: contain long stapled fortifying fibre,

[B]: matrix resin,

[C]: the thermoplastic resin that has the space and have continuous morphology.

This prepreg can be used as cellular autoadhesion and uses with prepreg.

In addition, this prepreg can also be used with prepreg as outside plate.

Integrant [C] preferred disposition is in the outside surface side as the integrant [A] of fortifying fibre.Here, the outside surface side for example is meant when prepreg and honeycomb core are bonded shape, with contacted that side of honeycomb core.Thus, integrant [C] is configured between integrant [A] and the honeycomb core.Perhaps, the outside surface side is meant prepreg being loaded in when being shaped on the tool palette, with contacted that side of tool palette.Thus, integrant [C] is disposed between integrant [A] and the tool palette, when becoming molding, is positioned at the outermost layer side.

Like this, when prepreg is contacted with honeycomb core, prepreg positively is clipped between integrant [A] and the honeycomb core disposes, strengthened the bond strength of the contact part of skin panel and honeycomb core.And in the time of the cellular veneer sheet of skin-material after sclerosis will being peeled off, fracture is configured key element [C] and stops, so bond strength significantly improves.

Among the present invention, integrant [C] is the thermoplastic resin that has the space and have continuous morphology.Here, have the space and be meant integrant [C] for for example spongy or fibrous, integrant [B] is containing the meaning that can see through when being dipped between the integrant [C].As non-woven fabrics, the form with a plurality of continuous gaps in the perforation table is the preference with impregnability.

Thus, resin can pass through integrant [C] to the honeycomb core side shifting from integrant [A] side of prepreg, forms the glue knurl.Integrant [C] is not when having the space, and resin flow diminishes, and resin can not abundant wetting honeycomb core wall, and the glue tumorigenesis on the gained sandwich panel is insufficient, and particularly the bond strength of tool side skin panel and honeycomb core is not enough easily.In addition, when being shaped, when prepreg is contacted with tool-face, integrant [C] positively is clipped in integrant [A] and tool-face and disposes, laminate surface formation resin layer that can be after sclerosis, so surface smoothing becomes good.

In addition, owing to have the space, integrant [B] also can see through integrant [C] on the direction in face, also can keep integrant [B] on the sunk part from prepreg surface integrant [A] shape.That is, can keep resin, can obtain the good laminate structures of surface smoothing of forming board on the surface of prepreg.

Because integrant [C] has the space, the whole surface that is not covered, therefore matrix resin becomes tackiness, drape etc. and handles excellent prepreg easily by, impregnation when the making of prepreg.And, has the integrant [C] in space owing to have the function that keeps a certain amount of resin on the prepreg surface, therefore compare with common prepreg, not only the adjusting range of tackiness is big, and have the tackiness of making through the time become minimum effect, have the unusual effect of the good laminate structures of the surface smoothing that can access forming board.

That continuous morphology of the present invention is meant is netted, successive form on the direction in laminate surface such as random shape.If integrant [C] has continuous morphology,, also can keep the area density of integrant [C], i.e. the weight of unit surface (paying) when being shaped hereinafter referred to as order even then integrant [B] flows.Thus, on the contact part of honeycomb core wall and prepreg integrant [A], even matrix resin [B] also can dispose the integrant [C] of high concentration because the contact pressure is excluded on contact part.Like this, the bond strength of skin panel and honeycomb core is enhanced.When integrant [C] does not have continuous morphology for particle shape etc., be accompanied by resin flow integrant [C] dissipation, the bond strength of the contact part of skin panel and honeycomb core can not be strengthened fully.In addition, owing to can not fully obtain keeping the effect of resin, so integrant [B] the whole molding surface that can not be covered, produce indenture, starved on the skin panel surface from integrant [A] shape on prepreg surface.In the scope of not damaging above-mentioned effect because the existence of seam etc., integrant [C] but continuity also part is discontinuous, but consider from the viewpoint of the above-mentioned effect of effective expression, at least must be continuous greater than the scope of used honeycomb core cell size.

As this integrant [C], promptly have the space and have the preference of the thermoplastic resin of continuous morphology, can enumerate non-woven fabrics, fabric, cloth, reticulate body, apertured film etc.

The apparent thickness of preferred integrant [C] is variable.Apparent thickness is meant that resin contains the thickness that is dipped in after hardening in the integrant [C], and the variable thickness of sclerosis back gained molding that is meant of apparent thickness is dipped in the meaning of the quantitative changeization of integrant [C] along with matrix resin contains.Thus, even also keep resin in a large number by sunk part in the integrant that comes from the prepreg surface [A] shape, there is the very thick integrant of apparent thickness [C], forms resin layer, can access the good laminate structures of surface smoothing of forming board on the prepreg surface.

In addition, integrant [C] is preferably random form when being continuous morphology.Random form is meant and is not to repeat isomorphic structure (for example, monofilament or multifilament is arranged in parallel or the fabric structure of rules such as fabric, cloth, braid) at some cycles.Thus, the inplane shear of integrant [C] distortion restriction to some extent, the retentivity that order is paid increases.And, this form can be only to scatter or to spray and realize, the special devices such as loom when not needing to make regular fabric.Consider from above aspect, as integrant [C], most preferably non-woven fabrics.Particularly, non-woven fabrics is compared with fabric, delustring fabric, does not need material resin is made monofilament, and can directly obtain fabric by resin, and productivity is also excellent.

Integrant [C] can only be provided in the one side in the two sides in the table of prepreg, also can all set on the two sides.When being equipped on one side, because the unnecessary integrant that sets [C] minimizing is therefore efficient.On the other hand, when being equipped on the two sides, even because the difference in the table of prepreg when not paying special attention to lamination, also integrant [C] positively can be provided on the adhesive face and/or tool-face with honeycomb core, therefore the lamination number reduces, prevent the lamination mistake, and then can cut down manufacturing cost.

Prepreg of the present invention, the scope of the voidage of preferred integrant [C] (be meant here and have the space and have the shared ratio (%) in space in the thermoplastic resin plane of continuous morphology) 15%～90%, more preferably in 20～85% scope, the scope particularly preferably in 30～80%.The voidage of integrant [C] was less than 15% o'clock, and resin flow is little when cellular sandwich panel is shaped, and the glue tumorigenesis in the gained sandwich panel is insufficient sometimes.In addition, if the voidage of integrant [C] surpasses 90%, then be difficult to obtain necessary order and pay, it is big that the deviation that order is paid becomes.The voidage of integrant [C] is the ratio that the space part shadow area when seeing through the thickness direction observation accounts for the total area, for example can obtain according to following steps.Prepreg is cut into any size (integrant [C] is when having regular texture, greater than the scope of its structure size), makes integrant [B] stripping but do not make the solvent etc. of integrant [C] stripping extract integrant [C].Then, except that desolvating.Use microscope (for example digital HD microscope VB-6010 (デ ジ Le HD マ イ Network ロ ス コ one プ VB-6010) of キ one エ Application ス (strain) production) to observe, identify space part, obtain its area by image analysis.For the influence of exclusive segment voidage deviation, this evaluation can be carried out same evaluation to 5 above positions choosing arbitrarily, gets its mean value.

In addition, preferred integrant [C] is configured in the surface of prepreg as far as possible equably.Preferred 1cm on the prepreg single face ²The minimum order of unit pay for average order pay more than 20%, more preferably more than 30%.1cm ²The minimum order of unit is for example paid and can be obtained according to following steps.Cut out the test sample of 10 10mm * 10mm arbitrarily, make integrant [B] stripping but do not make the solvent etc. of integrant [C] stripping extract integrant [C].Then, except that desolvating and fortifying fibre.Measure the weight of integrant [C], obtain its order and pay.Pay the influence of deviation for the exclusive segment order, this evaluation can be carried out same evaluation to 5 above positions choosing arbitrarily, preferred 10 above positions, wherein minimum order is paid as minimum order paid.Pay comparison with itself and the average order that the test sample that uses 100mm * 100mm is in kind measured, minimum order pay be preferably that average order pays more than 20%.

The order of preferred integrant [C] is paid at 2g/m ²～20g/m ²Scope, more preferably at 3g/m ²～10g/m ²Scope.If the order of integrant [C] is paid less than these scopes, when then using as the skin-material of honeycomb core, the tendency that the autoadhesion undercapacity is arranged, if it is opposite greater than these scopes, then not only surperficial grade is not along with the increase of weight obviously improves, and desired other characteristics of skin-material reduce sometimes.

The weight ratio of each integrant of prepreg of the present invention preferably satisfies following formula (1).

1＜[A]/([B]+[C])＜1.5 (formula 1)

[A]/([B]+[C]) if value less than this scope, then the effect of the reinforcing fiber of skin panel reduces, and the trend of its mechanical characteristic of infringement is arranged.On the contrary, [A]/([B]+[C]) if value greater than this scope, then not only have the glue tumorigenesis insufficient, or with the trend that toughness reduces, autoadhesion intensity reduces of the adhesive face of honeycomb core, and have the surface resin amount of prepreg not enough, the trend of the surface smoothing reduction of gained molding.More preferably 1.1＜[A]/([B]+[C])＜1.4.

The material of integrant [C] is a thermoplastic resin.As thermoplastic resin, be typically the thermoplastic resin that on main chain, has the key that is selected from carbon-carbon bond, amido linkage, imide bond, ester bond, ehter bond, carbonic acid ester bond, ammonia ester bond, thioether bond, sulfone key, imidazoles key, ketonic linkage.Particularly polymeric amide, polycarbonate, polyacetal, polyphenylene oxide, polyphenylene sulfide, aromatic polyester, polyester, polyamidoimide, polyimide, polyetherimide, polysulfones, polyethersulfone, polyetherketone, polyether-ether-ketone, aromatic poly, polybenzimidazole are because tenacity excellent, can improve self adhesion, therefore suitable.Wherein therefore polymeric amide, polyacetal, polyphenylene oxide, polyimide, polyetherimide, polyethersulfone, polyether-ether-ketone, aromatic poly are suitable for the present invention because high tenacity and thermotolerance are good.The toughness of polymeric amide is excellent especially, belongs to the material of amorphousness transparent nylon by use, can also have thermotolerance concurrently.Nylon 12 in the polymeric amide has the desired shape that is easy to get, structure, and toughness is very high, and the characteristic that suction causes reduces advantages such as little, and is preferred especially.As integrant [C], can be used in combination the macrofiber of multiple thermoplastic resin, perhaps use the macrofiber that multiple thermoplastic resin conjugate spinning is obtained.These methods can improve the characteristic of matrix material by the combination of optimization material, and are therefore preferred.

When the Young's modulus of the material of integrant [C] and yield strength are lower than the Young's modulus of the hardening thing that the hardening of resin that makes integrant [B] obtains and yield strength, effective as the opposing material when skin panel is peeled off, therefore preferred.But, on the other hand, when the Young's modulus of the material of integrant [C] is low as elastomerics, because the conditions such as pressure, temperature or heat-up rate in composite formed change and easy deformation, the thickness deviation of veneer sheet interlayer, easily change along with the variation of molding condition, the rerum natura of matrix material becomes unstable as a result.Therefore, the bending elastic modulus of the material monolithic of preferred integrant [C] is in the scope of 0.8～4Gpa, and reason is to obtain molding condition is changed insensitive stable high tenacity.In addition since with above-mentioned same reason, preferably integrant [C] is made modulus in tension when fibrous in the scope of 0.4～50GPa.

In addition, the pattern I energy release rate G of the material of integrant [C] _ICBe preferably 1500J/m ²More than.G _IC2000J/m more preferably ²More than.G _ICLess than 1500J/m ²The time, when making matrix material the raising of shock-resistance often insufficient, also become insufficient sometimes with the binding property of skin panel.G _ICEvaluation use and will make the tabular forming board that obtains as the thermoplastic resin heating fusion of the material of integrant [C], compact tension specimen method or two torsional technique by ASTM E399-83 (model A4) defined carry out.

The tension fracture elongation rate of the material of preferred integrant [C] is more than 10%.Tension fracture elongation rate was less than 10% o'clock, and a little less than the effect of shock absorption, the shock-resistance when making matrix material is not enough sometimes, became insufficient sometimes with the binding property of skin panel.The evaluation of tension fracture elongation rate is that be used as the material of integrant [C] thermoplastic resin formed is to carry out plate according to ASTMD638-97.

In addition, preferred integrant [C] is not had a solvability for integrant [B].If integrant [C] is dissolved in the integrant [B], then when resin flows, integrant [C] is scattered and disappeared, and can not fully obtain keeping on the prepreg surface effect of resin, and the effect that therefore improves laminar composite surface grade diminishes sometimes.And because integrant [C] is dissolved in the integrant [B], resin properties changes, and the thermotolerance of gained laminar composite, mechanics rerum natura might reduce.

The fusing point of integrant [C] preferably is higher than the stiffening temperature of integrant [B].Integrant [C] if fusing point be higher than the stiffening temperature of integrant [B], then not fusion of integrant [C] in the sclerosis of integrant [B] can keep form, therefore improves the surface smoothing of gained skin panel, so show above-mentioned effect effectively, therefore preferred.

The MV minium viscosity that the matrix resin that uses as integrant [B] among the present invention is preferably in the shaping is the thermosetting resin of 0.1～1000Pas.During deficiency 0.1Pas, in the process of setting of prepreg, resin flows can't obtain the sandwich panel of required fibre content or inner core crushing (コ ア Network ラ Star シ ユ) takes place.And during greater than 1000Pas, resin flow is little, and the glue tumorigenesis of gained sandwich panel is insufficient sometimes.Here, the glue knurl is meant from the thickness direction of prepreg lamination body towards honeycomb core, and resin is with the state that hangs down along the honeycomb core wall or with up state hardened part.As the MV minium viscosity of matrix resin more preferably 0.5～100Pas, more preferably 0.5～50Pas.

As the matrix resin that is used as integrant [B] in the present invention, will be by the sclerosis of external energies such as heat, light or electron beam, the resin that forms three-dimensional hardening thing to small part uses as principal constituent.The preferred especially so-called thermosetting resin that utilizes heat embrittlement that uses.Thermosetting resin preferably uses Resins, epoxy, resol, vinyl ester resin, benzoxazine resin, cyanate ester resin, bimaleimide resin etc., mixing more than 2 kinds of these can be used.Wherein, owing to be shaped easily, preferably use the Resins, epoxy of physical properties excellent.

As integrant [B] also two or more kinds may be used thermosetting resin.For example, use [B-1] and [B-2], impregnation [B-1] in integrant [A] respectively, impregnation [B-2] in integrant [C] as different integrant [B].But the integrant [B] that preferably is connected in integrant [A] is a same integrant [B] with the integrant [B] that is connected in integrant [C].If the integrant [B] of the integrant of being connected in [A] is different with the resin composition of the integrant that is connected in integrant [C] [B], then the mechanics rerum natura of gained laminar composite reduces.In addition, when heat hardening, because the difference of their linear expansivity, distortion such as warpage all take place in molding, are unsuitable for the outside plate of precision prescribed sometimes.

Conduct is as the Resins, epoxy of integrant [B] among the present invention, be not particularly limited, the above-mentioned matrix resin that contains 2 kinds of Resins, epoxy of Resins, epoxy that (a) have  oxazolidone ring, (b) glycidyl amine type epoxy resin at least, because the self adhesion excellence of itself and honeycomb core, therefore by making up with integrant [C], has significant more effect, so preferred.

Contain long stapled fortifying fibre as what integrant [A] was used among the present invention, can use various corresponding to the matrix material application target.As the object lesson of fortifying fibre, can enumerate carbon fiber, graphite fibre, aromatic arginyl amine fiber, silicon carbide fiber, sapphire whisker, boron fibre, wolfram varbide fiber, glass fibre etc.Fortifying fibre can also make up multiple use.Wherein, specific tenacity and carbon fiber, graphite fibre better than Young's modulus, that lightweight is had a great role are fit to the present invention.According to purposes, carbon fiber, graphite fibre can use carbon fiber, the graphite fibre of all kinds, but consider from the original tensile strength of fiber, aspect that shock-resistance when making cellular sandwich panel is high, preferably all high-strength carbon fibers.That is, the line drawing intensity in the preferred line drawing test is preferably above, the above high-strength carbon fiber of 4.6GPa more preferably of 4.4GPa.The line drawing intensity of fortifying fibre is high more preferred more, but in most cases is promptly enough about 4.9GPa.If surpass 10GPa, the processibility of gained matrix material variation sometimes then.In addition, the tension fracture elongation rate of fortifying fibre is preferably more than 1.7%, more preferably more than 1.8%.This tension fracture elongation rate is high more preferred more, as long as but be about 2.0%, then as the object of the invention, in most cases promptly enough.It should be noted that line drawing described here test is meant the resin of the following composition of impregnation in the carbon fiber of pencil, 130 ℃ of sclerosis after 35 minutes down, the test of carrying out according to JIS R7601 (1986).

^*Resin is formed

3,4-epoxycyclohexyl methyl-3,4-epoxy-cyclohexyl-carboxylicesters (ERL-4421, ユ ニ オ Application カ one バ イ De company produce) 100 weight parts

Boron trifluoride mono aminoethane (production of ス テ ラ ケ ミ Off ア Co., Ltd.) 3 weight parts

Acetone (Wako Pure Chemical Industries, Ltd.'s production) 4 weight parts

In addition, the preferred modulus in tension of fortifying fibre is more than the 200GPa.Use the high spandex fiber of modulus in tension in as the bulging stripping strength of climbing of one of self adhesion evaluation (CDP), to obtain high strength.The modulus in tension of fortifying fibre is more preferably more than the 210GPa, more preferably more than the 220GPa.This modulus in tension is high more preferred more, and is as long as about 230GPa, then as the object of the invention, in most cases promptly enough.If surpass 700GPa, then the gained matrix material becomes fragile sometimes, and shock-resistance reduces.

The present invention uses contains long stapled fortifying fibre and carbon fiber, graphite fibre can be mixed use with other fortifying fibres.For the shape of fortifying fibre, arrange without limits, for example can use unidirectional, random direction, sheet, cushion, textile-like, braid shape, wherein can preferably use two-dimensional fabric.When using two-dimensional fabric, the effect that surperficial grade improves is big especially.Its reason is, can effectively suppress the surface imperfection that produces at the intersection point place of warp and parallel easily by taking formation of the present invention.At this moment, be not particularly limited fabrics such as preferred plain goods, twilled fabric, leno cellular fabric, satin weave as texture of fabric.Particularly plain weave structure is owing to be easy to make thin molding, thereby preferred.Weaving with silk of fabric contains fibrous bundle, and the single fiber dimension in fibrous bundle is preferably 2500～50000 scope.Be lower than 2500, then fibre array becomes easily snakelike, easily becomes the reason that intensity reduces.Surpass 50000, then be difficult to contain resin pickup when prepreg is made or during shaping.More preferably 2800～25000 scope.Particularly, consider that preferred single fiber dimension is more than 5000 from the viewpoint of the surface smoothing raising of cellular skin panel.Preferred use will comprise the flat carbon fiber multifilament of not twisting basically of many carbon fibers as the fabric of weaving with silk, its reason is, even place the Fabric prereg base for a long time, the depression that moving of fabric fibre to be also little, be difficult to take place surface resin, suppressed the prepreg tackiness through the time change, thereby preferred.In addition, in the prepreg in shaping fabric fibre move also for a short time, be difficult to take place the depression of surface resin, make the surface smoothing raising of the cellular sandwich panel after the sclerosis thus, thereby preferred.Here, so-called " not twisting basically " is meant that the filament length of every 1m does not have the state of the above twisting of 1 rotation.From fabric fibre mobile little, easily keep weave with the silk flat form, suppress the prepreg tackiness through the time change and improve the surface smoothing of cellular sandwich panel viewpoint consider that preferred especially multifilament not have twisting, convergency to fall (Off Star Network De ロ プ) value at 100～1000mm, preferably at the fabric of the multifilament formation of 100～500mm scope in hook substantially.Here, so-called hook drop-away value is meant the carbon fiber bundle of vertically slinging under the atmosphere of 23 ℃ of temperature, humidity 60%RH, the upper and lower bending 20～30mm of the stainless steel metal line about diameter 1mm, long 100mm, the weight of 12g is suspended on the bottom, upper hook is used the value of representing through weight drop after 30 minutes on fibrous bundle.If twisting is arranged, reverse, then this value diminishes.When making the reinforcing textile that uses carbon fiber wire,, the ultimate fibre of precursor fiber bundle is interweaved, give carbon fiber wire with convergency usually in order to prevent that the ultimate fibre that ruptures is wound up into the operation fault that causes in the roller in carbon fiber manufacturing process.In addition, by the adhesion amount of sizing agent, the bonding carbon fiber wire of giving between the ultimate fibre with convergency.Control convergency by the adhesion amount of the interlacing degree between the ultimate fibre, sizing agent and the bondability between the ultimate fibre.The hook drop-away value below 100mm, convergency crosses when strong, then is difficult to increase the cover factor of above-mentioned fabrics prepreg sometimes.At this moment, the prepreg tackiness through the time change to become greatly, in addition, the resin impregnation of prepreg is also variation sometimes.As a result, skin panel is easy to generate surface pitting, internal void.If the hook drop-away value is more than 1000mm, then the convergency of carbon fiber wire is poor, easily fluffing, and weaving has the trend of variation, in addition, as the intensity reduction of matrix material.

Use fabric when comprising long stapled fortifying fibre, preferred especially cover factor is the fabric more than 95%.Here, cover factor is meant the ratio that exists area to account for of weaving with the silk part in the prepreg total area.When to set area on fabric be S1 regional, by this area S1 and be present in the zone in knit the eye (be formed on weave with the silk between the space) area summation S2, on any 10 positions according to Cf=[(S1-S2)/S1] * 100 obtain Cf, its simple average value is a cover factor.Cover factor is big more, then weave with silk to open fibre, expanding and flattening good more, it is more little to knit eye.By use cover factor at the Fabric prereg base 95% or more as skin panel because few, so become the skin panel of rigidity and excellent strength as the hole of skin panel subsurface defect.In addition, by use cover factor at the Fabric prereg base more than 95% as skin panel, can access the cellular sandwich panel of the self adhesion excellence of skin panel and honeycomb core.In addition, by use cover factor at the Fabric prereg base more than 95% as skin panel, because fabric evenly spreads, therefore can access the good cellular sandwich panel of surface smoothing of skin panel, be easy to simultaneously resin is remained on the prepreg surface, thus the tackiness of prepreg through the time diminish.

In addition, if cover factor is big, then obtain burning the forming board of excellent.Here, burning characteristic is meant when using as built-in material when fire disaster etc. and hinders the effect that flame connects.Promptly burn excellent and be meant that resistivity against fire is good.When cover factor is insufficient, indenture, the inner hole that produces of skin panel taking place on the skin panel surface of molding sometimes then, climbs bulging stripping strength (CDP) and diminish.In addition, when cover factor is insufficient, then as the tackiness of prepreg through the time change sometimes greatly.Particularly preferred cover factor scope is more than 97.5% among the present invention.

In addition, use among the present invention when comprising long stapled enhanced fabrics, the order of enhanced fabrics is paid and is preferably 150～550g/m ²Thus, can access skin panel with excellent mechanical strength.The order of enhanced fabrics is paid not enough 150g/m ²The time, physical strength is insufficient sometimes, surpasses 550g/m ²The time, the operability when the infringement laying is shaped (レ イ ア Star プ).More preferably to pay be 170～500g/m to the order of enhanced fabrics ²In addition, the weight fraction of enhanced fabrics is during with respect to the overall less than 40 weight % of prepreg, and the rigidity of gained fibre reinforced composites skin panel is not enough sometimes, as surpassing 85 weight %, often easily produces hole on the gained skin panel.

Then, the manufacture method to prepreg describes.Be immersed in the fortifying fibre by above-mentioned composition epoxy resin is contained, can make prepreg.Be not particularly limited, but can be by matrix resin being dissolved in the damp process that reduces viscosity and impregnation in methylethylketone, the methyl alcohol equal solvent; Perhaps reduce the method manufacturings such as hot melt process of viscosity and impregnation by heating.

In the damp process, be immersed in fortifying fibre in the liquid that contains matrix resin after, mention, use baking oven etc. to make solvent evaporation, can obtain prepreg.

For hot melt process, can by will be by heating the matrix resin of lowering viscousity directly contain the method that is dipped in the fortifying fibre, perhaps at first make resin combination is coated on the film that obtains on release paper etc., then, contain the prepreg that is soaked with resin by the heating and pressurizing making from both sides or one-sided laminated this film of fortifying fibre.Owing in prepreg, do not have residual solvent, therefore preferred hot melt process.

For the processing that makes prepreg at proper range, preferably in fortifying fibre, contain in the operation of resin pickup, the top temperature that resin combination arrives is 70 ℃～150 ℃ scope.More preferably 80～130 ℃.When this top temperature surpassed 150 ℃, then the reactive moieties of Resins, epoxy and stiffening agent ground carried out in resin combination, and unhardened resin Tg rises, and can not obtain suitable drape sometimes.In addition, during 70 ℃ of top temperature less thaies, be difficult to abundant impregnation.

In the prepreg, composition epoxy resin there is no need necessarily to contain the inside that is immersed in carbon fiber bundle, can make the composition epoxy resin part be present in the carbon fiber of unidirectional doubling slabbing, the near surface of carbon fibre fabric.

When using the having the space and make prepreg of integrant [C], can use following method as the thermoplastic resin of continuous morphology.

[method 1]

The surperficial random configuration integrant [C] of the material that impregnation integrant [B] obtains in integrant [A] becomes plane, forms prepreg thus.Under this state, integrant [C] is exposed to the prepreg surface, and tackiness is insufficient, and heating and pressurizing such as therefore preferred use warming mill contain integrant [B] and are immersed in the integrant [C].As the accommodation of this method, surperficial random configuration integrant [C] that can also the material that impregnation integrant [B] obtains in integrant [A] become plane after, paste the integrant [B] that is coated on the release paper etc., heating and pressurizing makes its impregnation.

[method 2]

Making and become planely by being coated on the surface that is configured as membranaceous integrant [B] on the supporter such as release paper random configuration integrant [C], paste integrant [A], heating and pressurizing, thus form prepreg.

[method 3]

Go up random configuration integrant [C] in integrant [A] and make and become planely, then contain dipping integrant [B], form prepreg thus.

[method 4]

Paste the non-woven fabrics of integrant [C] on the material that impregnation integrant [B] obtains in integrant [A], form prepreg thus.At this moment, because under this state, integrant [C] is exposed to the prepreg surface, therefore the insufficient possibility of tackiness is arranged, so preferably use heating and pressurizing such as warming mill after stickup, integrant [B] is contained be immersed in the integrant [C].As the accommodation of this method, can also be in the non-woven fabrics of integrant [C] impregnation integrant in advance [B].

[method 5]

To paste simultaneously according to random order by being coated on the non-woven fabrics, the integrant [A] that are configured as membranaceous integrant [B], integrant [C] on the supporter such as release paper,, form prepreg by heating and pressurizing.At this moment, be that the non-woven fabrics of integrant [C] is clipped in integrant [A] and is configured as between the membranaceous integrant [B] if close laminated position, then integrant [B] contains in the non-woven fabrics that is immersed in integrant [C] easily, thereby preferably.

When using prepreg shaped fibers matrix material, can use after lamination prepreg, on one side laminate is exerted pressure, one side is with the method for resin heat hardening.

The method that applies heat and pressure has press molding method, autoclave moulding method, pack moulding method, looping band method, interior pressure moulding method etc.Particularly preferably adopt looping band method, interior pressure moulding method for sports goods.For the flyer purposes of, high performance laminar composite more high-quality, preferably adopt autoclave to be shaped for requiring.In various vehicle exterior equipments, preferably use press molding.

Looping band method be with prepreg twist in plug etc. metal-cored on, the method for shaping tubular body arranged inside, preferred when making rhoptry such as golf club, Veronicastrum Herb.Specifically, prepreg is wound on the plug, for fixing prepreg and exert pressure, to comprise the outside of the looping tape wrapping of thermoplastic resin film in prepreg, after the heating resin makes its sclerosis in baking oven, remove metal-coredly, can obtain tubular body arranged inside thus.

In press in the moulding method, preform is wound up into to press in the thermoplastic resin pipe etc. invests the stock that obtains on the body and be contained in the mould, then inwardly press to invest to import high pressure gas in the body, exert pressure, heating of metal mould simultaneously, thereby can form tubular body arranged inside.

As the method that obtains fibre composite, except the method that can use prepreg, can also make laying shaping by hand, RTM (resin die casting), SCRIMP (registered trademark), long filament twine moulding methodes such as method, pultrusion, resin molding dip mold according to purpose.

The second-order transition temperature of these fibre reinforced composites is preferably 160～220 ℃, more preferably 170～220 ℃, more preferably during 175～220 ℃ scope, particularly takes into account aspect compressive strength and the impact characteristics useful under hygrothermal environment.This second-order transition temperature is during less than 160 ℃, and the strength characteristics of gained fibre reinforced composites under hot environment reduces sometimes.When surpassing 220 ℃, shock-resistance is not enough sometimes.

This second-order transition temperature is measured according to differential scanning calorimetry (DSC).At first, cut out fibre reinforced composites as working sample.With 10 ℃/minute speed this sample that heats up, obtain the DSC curve.Then,, as shown in Figure 1, obtain the temperature of intersection point of tangent line of the tangent line of baseline and endotherm and the terminal temperature of heat absorption for this DSC curve, with this mid point of 2 as Tg.Use the DSC2910 (model) of TA イ Application ス Star Le メ Application Star company production etc. as determinator.

The fiber direction compressive strength of these fibre reinforced composites under hot and humid condition is preferably more than the 1000MPa.This fiber direction compressive strength is during less than 1000MPa, takes place sometimes in use to destroy or tired, can not be applicable to structural member.But this value is that fibre weight content is 65 ± 1% and the value of fibre orientation when being essentially a direction in the fibre reinforced composites that use in mensuration.For these fibre reinforced composites, be determined at fiber direction compressive strength under the high temperature sucting wet state (in 71 ℃ of warm water 2 week of dipping back, 82 ℃ of atmosphere gas in) according to JIS K7076 (1991).

Cellular sandwich panel of the present invention contains the fibre reinforced composites and the honeycomb core of the invention described above.

Then, the manufacture method to cellular sandwich panel of the present invention describes.Cellular sandwich panel of the present invention can preferably use the prepreg of the invention described above to make.For example, can be in many prepreg of the two sides of honeycomb core lamination, while form by the co-curing method that hardening of resin is connected with honeycomb core.In addition, cellular sandwich panel can be shaped, use the autoclave shaping, press molding of vacuum bag etc. to form by vacuum bag, but more high-quality in order to obtain, high performance cellular sandwich panel, preferred autoclave is shaped.

The bulging stripping strength (CDP) of climbing of cellular sandwich panel is preferably more than the 25Nm/m.This CDP is during less than 25Nm/m, and when applying crooked equal stress on panel, skin panel is peeled off from honeycomb core sometimes.

Other modes of laminar composite of the present invention are for comprising following integrant [A], [C], [D] and [E], and integrant [C] is configured in the laminar composite between honeycomb core [E] and the integrant [A],

[A]: contain long stapled fortifying fibre,

[C]: have the space and have continuous morphology thermoplastic resin,

[D]: the matrix resin hardening thing,

[E]: honeycomb core.

This cellular laminar composite can be shaped by autoadhesion honeycomb fashion co-curing moulding method, promptly, above-mentioned prepreg is directly contacted with the one side at least of honeycomb core carry out lamination, on this contact part, exert pressure, under this state, use means such as heat, light to make integrant [B] hardened be adhered to honeycomb core simultaneously.As the matrix resin hardened method that under the state of exerting pressure, makes prepreg to the contact part of prepreg and honeycomb core, can use vacuum bag shaping, the autoclave shaping of using vacuum bag, press molding etc., but more high-quality in order to obtain, high performance laminar composite, preferred autoclave is shaped.

The integrant of cellular laminar composite of the present invention [E] is not particularly limited so long as honeycomb core gets final product, and for example uses graphite honeycomb, paper wasp nest, aramid honeycomb, glass honeycomb, aluminium honeycomb.The aspect that can form the high-strength structure body is considered from light weight, simultaneously, ノ one メ Star Network ス (registered trademark) honeycomb core of aramid paper of resol that preferably contained impregnation.The cell size that can preferably use honeycomb core is the honeycomb core of 3～19mm.Special preferred cell size is the honeycomb core of 3.2mm (1/8in), 4.8mm (3/16in), 6.4mm (1/4in) in the cellular laminar composite of flyer purposes.

In this cellular laminar composite, the integrant of prepreg [B] sclerosis becomes the matrix resin hardening thing [D] of skin panel.Integrant [C] is configured in honeycomb core and is adjacent between the integrant [A] that connects, and when wanting the overburden removing panel, the integrant of high tenacity [C] has been blocked the carrying out of fracture, has showed higher autoadhesion intensity.In the cellular laminating material that obtains like this, preferably can access and climb bulging stripping strength (CDP) above for 33Nm/m, more preferably can access and high self adhesion suitable more than the 35Nm/m.This CDP can measure according to ASTM D1781-98.

The another one mode of laminar composite of the present invention is for comprising following integrant [A], [C] and [D], and integrant [C] is configured in the laminar composite outside plate that integrant [A] outside surface side forms,

[A]: comprise long stapled fortifying fibre,

[C]: have the space and have continuous morphology thermoplastic resin,

[D]: matrix resin hardening thing.

In this cellular laminar composite, the integrant of prepreg [B] sclerosis becomes the matrix resin hardening thing [D] of skin panel.Owing to begin to dispose integrant [D], [C], [A] from skin, therefore can access the good laminate structures of skin panel surface smoothing.

On the outermost layer of laminar composite, the above surface pitting number of the degree of depth 50 μ m is preferably every 10cm ²Be below 2.If the above surface pitting of the degree of depth 50 μ m is arranged, then can not be directly used in automobile purposes etc. and require in the purposes of surface smoothing, often need this surface pitting removed etc.

The degree of depth of surface pitting described here and number can be measured by the method that is called non-contact type 3D measuring shape method.

Porosity in the cellular sandwich panel preferred surface layer is below 0.5%.As described later, the porosity in the upper layer quantitatively can use opticmicroscope to measure.If this porosity surpasses 0.5%, then the mechanical strengths such as bending of panel reduce sometimes.

Embodiment

Below, be described more specifically the present invention by embodiment.For each embodiment, comparative example, utilize following method to carry out the making of the making of prepreg, matrix material etc., the mensuration of various rerum naturas.

The making of＜resin combination 〉

In each embodiment, comparative example, use material resin shown below, it is mixing to utilize kneader to carry out by composition shown in table 1, the table 2, resin composition modulation.

[Resins, epoxy]

AER4152 (エ of Asahi Chemical Industry Port キ シ (strain), contain the Resins, epoxy of  oxazolidone ring)

MY720 (Ha Application Star マ Application ア De バ Application ス ト マ テ リ ア Le ズ (strain), four glycidyl group diaminodiphenyl-methane)

ELM434 (Sumitomo Chemical (strain) system, four glycidyl group diaminodiphenyl-methane)

エ ピ コ one ト (registered trademark) 825 (ジ ヤ パ Application エ Port キ シ レ ジ Application (strain) is produced, bisphenol A type epoxy resin)

エ ピ コ one ト (registered trademark) 828 (ジ ヤ パ Application エ Port キ シ レ ジ Application (strain) is produced, bisphenol A type epoxy resin)

[rubber constituent]

Zetpol (registered trademark) 2020 (Japanese ゼ オ Application (strain) is produced, the hydrogenated acrylonitrile divinyl rubber)

Nipol (registered trademark) 1072 (Japanese ゼ オ Application (strain) is produced, and contains the acrylonitrile butadiene rubber of carboxyl)

[aromatic amine stiffening agent]

3,3 '-DDS (the Wakayama industry (strain) of refining is produced, and 3,3 '-diaminodiphenylsulfone(DDS))

ス ミ キ ユ ア (registered trademark) S (Sumitomo Chemical (strain) is produced, and 4,4 '-diaminodiphenylsulfone(DDS))

[other]

PES (Sumitomo Chemical (strain) is produced, polyethersulfone, ス ミ カ エ Network セ Le PES5003P)

YP-50 (Dongdu changes into (strain) and produces, phenoxy resin)

DICY (ジ ヤ パ Application エ Port キ シ レ ジ Application (strain) is produced, Dyhard RU 100, DICY7)

DCMU (protect native ケ paddy chemistry (strain) production, 3-(3, the 4-dichlorophenyl)-1, the 1-dimethyl urea, DCMU99)

SP-500 (east beautiful (strain) produces, nylon 12 resin particles)

The viscosimetric analysis of＜resin combination 〉

Viscosity by dynamic viscoelastic assay determination resin combination.Under the condition of 2 ℃/minute of heat-up rates, vibrational frequency 0.5Hz, parallel plate (diameter 40mm), obtain MV minium viscosity by the relation curve of temperature and viscosity.

Here, the determination of viscoelasticity system expanding " ARES " (model) that uses Rheometric Scientific company to produce as determinator.

The glass transition temperature Tg of＜hardening of resin thing _DSC

Utilize differential scanning calorimetry (DSC) to measure the glass transition temperature Tg of hardening of resin thing _DSCWill 180 ℃ down the hardening thing that obtained in 2 hours of heating resin combinations heat up with 10 ℃/minute speed as working sample, obtain the DSC curve.Then,, as shown in Figure 1, obtain the intersection point temperature and the heat absorption terminal temperature of the tangent line of the tangent line of baseline and endotherm to this DSC curve, with this mid point of 2 as Tg.Here, the DSC2910 (model) that uses TA イ Application ス Star Le メ Application Star company to produce as determinator.

Hardening of resin thing glass transition temperature Tg after the＜suction _DMA

By the dynamic viscoelastic analysis, measure the hardening of resin thing glass transition temperature Tg after absorbing water _DMA

Will 180 ℃ down the tabular hardening thing that obtained in 2 hours of the above-mentioned resin combinations of heating (thickness 2 ± 0.1mm, wide 10 ± 0.5mm, long 50 ± 5mm) are immersed in the boiling water 2 days, and it is used as working sample.Under the condition of spacing 40mm, 5 ℃/minute of heat-up rates, torsional frequency 1.0Hz, dependent variable 0.1%, heat up, by the DMA method, measure this sample.

In this evaluation assessment, as shown in Figure 2, obtain the temperature of intersection point of the tangent line of the tangent line of vitrifying zone line and glass transition zone line, with this intersection point temperature as Tg.Here, the determination of viscoelasticity system expanding " ARES " (model) that uses Rheometric Scientific company to produce as determinator.

The pattern I energy release rate G of＜hardening of resin thing _IC

(thickness 2 ± 0.1mm, wide 10 ± 0.5mm, long 120 ± 10mm) use as test film the tabular hardening thing that will obtain in 2 hours at 180 ℃ of above-mentioned resin combinations of following heating.According to the method for JIS K7161 (1994) record, obtain modulus in tension E and Poisson's ratio υ by this test film.According to ASTM D5045-99, (thickness 6 ± 0.3mm, wide 12.7 ± 0.3mm, long 80 ± 10mm) obtain K to the tabular hardening thing that is obtained by same heat hardening _ICHere, as determinator, the イ Application ス ト ロ Application material-testing machine (model 5565) of using イ Application ス ト ロ Application ジ ヤ パ Application カ Application パ ニ イ リ ミ テ Star De company to produce.

G _ICBe to use this modulus in tension E, Poisson's ratio υ and K _IC, according to G _IC=(1-υ ²) K _IC ²The calculating formula of/E derives.Measure 10 times, with mean value as G _IC

＜have the space and have the mensuration of voidage of the thermoplastic resin of continuous morphology

At first, the Fabric prereg base that 300mm is wide with wide vertical direction on be cut into 100mm, obtain the sample of 2 300mm * 100mm.This sample evenly is divided into 3 parts on the width of original Fabric prereg base, makes the observation sample of 6 100mm * 100mm.The sample of making is immersed in the methylethylketone, extracts the thermoplastic resin [C] that has the space and have continuous morphology out.The use Vacuumdrier is dried, and removes methylethylketone.Digital HD microscope (the デ ジ Le HD マ イ Network ロ ス コ one プ) VB-6000 that uses キ one エ Application ス (strain) to produce observes with the central part of sample observing, and video recording obtains image.At this moment, the VB-G25 (contact-type) that lens use キ one エ Application ス (strain) to produce, then use picture processing software (AdobeSystems, Inc. the Adobe Photoshop Elemetnts (Japanese version) of Sheng Chaning), from " image " menu, select " tone adjustment ", and then select " look Jie (2 Bands Toneization) ", threshold value to be made as 128, with the binarization of gained image.Then, selecting from " image " menu " histogram ", passage is made as " brightness ", is histogram with the graphical representation of binarization.Read the pointer that makes on the picture " ratio " value when static, make that " level (the レ ベ Le) " by histogram graph representation reaches 128, as voidage.6 observations are obtained this voidage with sample, obtain its mean value.

＜have the space and have the mensuration that the order of the thermoplastic resin of continuous morphology is paid

(1) the average order mensuration of paying

At first, the prepreg that 300mm is wide with the vertical direction of width on cut out 100mm, obtain the sample of 2 300mm * 100mm.This sample evenly is divided into 3 parts on the width of original Fabric prereg base, makes the test sample of 6 100mm * 100mm.The sample that cuts out is immersed in the methylethylketone, beyond solution heat plastic resin and the carbon fiber.The use Vacuumdrier is dried, and removes methylethylketone, removes carbon fiber.Utilize electronic balance to measure the weight of the thermoplastic resin that so obtains.6 samples are measured, obtained its average order and pay.

(2) small part (every 1cm ²) minimum order pay the mensuration of ratio

At first, the Fabric prereg base that 300mm is wide with the vertical direction of width on cut 10mm, obtain the sample of 300mm * 10mm.On the width of original Fabric prereg base, cut out the test sample of 10 10mm * 10mm arbitrarily by this sample.The sample that cuts out is immersed in the methylethylketone, except that thermoplastic resin and carbon fiber, dissolves.The use Vacuumdrier is dried, and removes methylethylketone, removes carbon fiber.Utilize electronic balance to measure the weight of the thermoplastic resin that so obtains.10 samples are measured, the value of minimum weight is wherein paid as minimum order.It is paid with average order remove, pay ratio as the minimum order of small part.

The making of＜prepreg 〉

In embodiment 1～5, comparative example 1～5, the thermosetting resin composition that table 1 is put down in writing is coated on the release paper, makes the resin molding that regulation resin order is paid.This resin molding is laminated from the two sides of fortifying fibre, on one side heating and pressurizing, resin combination contained be immersed in the fortifying fibre on one side, make prepreg.

During for the unidirectional pre-immersion material base, as fortifying fibre, the fiber order that uses carbon fiber " ト レ カ (registered trademark) " T700G-12K (several 12000 of fiber, tensile strength 4.9GPa, modulus in tension 240GPa, tensile elongation 2.1%) that east beautiful (strain) produced to make is paid and is 190g/m ²Unidirectional sheet material, making resin content is the prepreg of 36 weight %.

During for the Fabric prereg base, as fortifying fibre, use the plain goods CF6273H contain carbon fiber " ト レ カ (the registered trademark) " T700G-12K (several 12000 of fiber, tensile strength 4.9GPa, modulus in tension 240GPa, tensile elongation 2.1%) that east beautiful (strain) produces (fabric thickness 0.22mm, silk be loose/silk thickness rate 69.2, cover factor 99.7%, fiber order pay 193g/m ²), making resin content is the prepreg of 40 weight %.

In embodiment 6～11, the comparative example 6～8,, thermosetting resin composition is coated on the release paper resin molding that the resin order that making table 2 is put down in writing is paid with above-mentioned same.Use above-mentioned plain goods CF6273H as fortifying fibre.The integrant [C] that the sticky table 2 resin order of putting down in writing is paid on the surface of resin molding with its both sides that are laminated in enhanced fabrics, makes integrant [C] become the inboard.On one side heating and pressurizing contains resin combination on one side and is immersed in integrant [C] and the enhanced fabrics making prepreg.

It should be noted that and use following substances as the thermoplastic resin (integrant [C]) that has the space and have continuous morphology.

Non-woven fabrics (Japanese バ イ リ one Application (strain) is produced, nylon 12 fabric nonwoven cloths)

Cloth (cloths of nylon 66 multifilament (16.5dtex (15 DENIER), 7 ultimate fibres) that the MODEL CR-B that uses Xiao Chi machinery system to be produced makes)

(use contains nylon 12 to reticulate body, applies cut channel on film, extends the material of making by twin shaft then according to the method for Japanese Patent Publication 40-155 communique, in order to improve the binding property with matrix resin, uses after the Corona discharge Treatment implementing.Corona discharge Treatment is to carry out according to the method for Japanese kokai publication hei 1-87246 communique.)

Apertured film (whole mask has the polyetherimde films of the communicating pores of diameter 2mm φ)

(polyetherimde films, film order are paid 7.5g/m to film ²)

The glass transition temperature Tg of＜prepreg 〉

For presclerotic prepreg,, utilize with above-mentioned same method and obtain second-order transition temperature by differential scanning calorimetry (DSC).

＜volatile amount 〉

Above-mentioned unidirectional pre-immersion material base blocked be 100mm * 100mm, make test film.With this test film weigh the back (W ₁), the prepreg that will be loaded on the aluminium sheet in being set at 180 ℃ thermostatted was kept 2 hours with the state that leaves standstill, and put in moisture eliminator and was chilled to room temperature, weighing test film (W ₂).Calculate volatile amount (weight %) by following formula.Measure number n=5, with mean value as volatile amount.

PVC＝(W ₁-W ₂)×100/W ₁

PVC: the volatile component of prepreg (weight %)

Volatile amount (weight %)=PVC * 100/RC

RC: the resin content of prepreg (weight %)

The evaluation of＜tackiness 〉

Above-mentioned unidirectional pre-immersion material base blocked be 100mm * 100mm, as test film.Under 25 ± 2 ℃, the atmosphere of 50%RH, laminated prepreg, even whether confirm can fix fully peels off, the form of prepreg can turmoil yet, can paste once more.As decision metrics, A is for very possibility, B are impossible for possibility, C for problem, D are arranged slightly.

The evaluation of＜drape 〉

Above-mentioned unidirectional pre-immersion material base blocked be 100mm * 100mm, as test film.Under 25 ± 2 ℃, the atmosphere of 50%RH, confirm whether can be shaped to the compound curved surface of the SUS system of R=100mm.As decision metrics, A for do not have fully moulding of gauffer, B for do not have gauffer can moulding, gauffer produces C in order to have slightly, D is for producing gauffer.

The making of＜sandwich panel 〉

(1) lamination of sample

As honeycomb core, use ノ one メ Star Network ス (registered trademark) honeycomb SAH1/8-8.0 (clear and aircraft (strain) company produces model: SAH1/8-8.0, thickness 12.7mm).Prepreg is used the above-mentioned fabrics prepreg, is formed in 2 layers of symmetrical lamination structure that are (± 45 °)/(± 45 °) up and down of honeycomb core.Here, honeycomb core and prepreg are of a size of 40cm (width) * 50cm (length direction), prepreg according to width become band (L) direction of honeycomb core, the organizine direction of prepreg is carried out lamination.

(2) shaping of sample

Step according to following (a)～(d) is carried out.

(a) with lamination the unshaped body of above-mentioned honeycomb core and prepreg be positioned in be coated with releasing agent, for example on the aluminium tool palette of " Off リ コ one ト " (registered trademark) 44-NC (THE DEXTERCORPORATION production).

(b) with behind the nylon membrane covering unshaped body, in nylon membrane, (be designated hereinafter simply as in the system) under the state that remains on vacuum state, directly put in the autoclave.

(c) pressure in the autoclave is risen to 0.15MPa, then with the pressure recovery in the system to normal pressure, begin to heat up after then the pressure in the autoclave being risen to 0.30MPa.

(d) pressure in the autoclave is remained on 0.30MPa always finishes, be warming up to 180 ℃ with 1.5 ℃/minute, then placed 2 hours down at 180 ℃ until shaping, when making in the prepreg contained hardening of resin and honeycomb core bonding., with 2 ℃/minute be cooled to room temperature, obtain honeycomb core co-curing molding, promptly cellular sandwich panel thereafter.

＜climb the mensuration of bulging stripping strength (CDP) 〉

(skin panel of aluminium tool palette side and the CDP between the honeycomb core according to ASTMD1781-98, are measured in 76 ± 0.5mm * 355 ± 1mm) to cut out sample by above-mentioned molding.Measure number n=4 or 5, mean value is as CDP.Here, the イ Application ス ト ロ Application material-testing machine (model 5565) of using イ Application ス ト ロ Application ジ ヤ パ Application カ Application パ ニ イ リ ミ テ Star De company to produce as determinator.

＜porosity 〉

Grind the cross section of cellular sandwich panel, use the percentage of mesoporosity, the top layer sectional area of the opticmicroscope unit of obtaining top layer sectional area, as the porosity in the top layer.Measurement range is 10mm, measures number n=3, as voidage.

The mensuration of＜surface roughness value (A) 〉

In embodiment 1～5, comparative example 1～5, surface for the aluminium tool palette side of sandwich panel, with the central part of cellular sandwich panel as the center, band (L) direction along honeycomb core, by the length of contact pilotage meter scanning 95mm, obtain the poor of 5 simple average height that is selected from therebetween peak dot and 5 the simple average height that is selected from the valley point.Here, the surfaceness meter サ one Off テ ス ト 301 that uses ミ Star ト ヨ (strain) company to produce as the contact pilotage meter.It should be noted that gained surface roughness value (μ m) is more little here, then the presentation surface smoothness is excellent more.

The mensuration of＜surface roughness value (B) 〉

In embodiment 6～11, comparative example 6～8,5 10cm are chosen on the surface of a side of joining for the aluminium tool palette with sandwich panel arbitrarily ²The zone, the evaluation table surface roughness.The evaluation of surfaceness uses 3D measuring shape system (production of コ system ス (strain) company) to carry out.Finding speed is 5000 μ m/s, measure the pitch X-axis, Y-axis is 254 μ m.Here gained surface roughness value (surface pitting is in the degree of depth of Z-direction) is more little, and then the presentation surface smoothness is excellent more.Obtain the number of surface roughness value more than 50 μ m.Obtain the average of 5 position finding values, as the value of surfaceness.

0 ° of compressive strength of the fibre reinforced composites of＜unidirectional pre-immersion material base 〉

Make the fiber direction unanimity of the unidirectional pre-immersion material base of making by aforesaid method, 6 layers of laminations, in autoclave, under the pressure of 0.59MPa, be warming up to 180 ℃ with 1.5 ℃/minute, then place down and formed in 2 hours, make fibre reinforced composites at 180 ℃.

For these fibre reinforced composites, obtain 0 ° of compressive strength according to JIS K7076 (1991).Measure in addition also and under high temperature sucting wet state (after flooding for 2 weeks in 71 ℃ of warm water, under 82 ℃ of atmosphere), carry out.Here, the イ Application ス ト ロ Application material-testing machine (model 4208) of using イ Application ス ト ロ Application ジ ヤ パ Application カ Application パ ニ イ リ ミ テ Star De company to produce as determinator.

0 ° of compressive strength of the fibre reinforced composites of＜Fabric prereg base 〉

Make the fiber direction unanimity of the Fabric prereg base of making by aforesaid method, measure under the drying at room temperature state be 6 layers, what measure under the high temperature sucting wet state is 4 to press layer by layer, in autoclave under the pressure of 0.59MPa, be warming up to 180 ℃ with 1.5 ℃/minute, then place down and formed the making layered product in 2 hours at 180 ℃.For this layered product, obtain 0 ° of compressive strength according to JIS K7076 (1991).5 samples are measured this compressive strength, obtain its average 0 ° of compressive strength.In addition, be determined at drying at room temperature state and high temperature sucting wet state (in 98 ℃ of warm water the dipping 2 days after, 82 ℃ of heating) under carry out.Here, the イ Application ス ト ロ Application material-testing machine (model 4208) of using イ Application ス ト ロ Application ジ ヤ パ Application カ Application パ ニ イ リ ミ テ Star De company to produce as determinator.

(embodiment 1～5, comparative example 1～5)

According to aforesaid method, make composition epoxy resin, prepreg, fibre reinforced composites and cellular sandwich panel, estimate various physics values.The content of each embodiment is shown in table 1.

Among the embodiment 1～5, compare with comparative example 1～5, the compressive strength when climbing bulging stripping strength (CDP) raising, high temperature moisture absorption is also abundant, other characteristics are also comparatively excellent.

Comparative example 5 is same composition with the embodiment 5 of above-mentioned patent documentation 1.Though CDP is satisfied level, the compressive strength during the high temperature moisture absorption has problem.

Table 1

		Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4	Comparative example 5
												Composition epoxy resin
(A) Resins, epoxy	·AER4152	40	20	40	30	30		50	30	30	20
												·MY720	40	50	20	30	30	50		30	30
	エ ピ コ one ト 825	20	30	40	40	40	50	50	40	40
												エ ピ コ one ト 828										80
	(B) rubber constituent	·Zetpol2020	3	4	4	5		6	4		5
·Nipol1072																5
		(C) aromatic amine stiffening agent	·3，3-DDS		40				40
·スミキユアS	35												30	35	35		25	35		30
			(D) other	·PES																	7
·YP-50																			27
				·DICY																	6
·DCMU																		3
				Resin properties	70 ℃ of viscosity (Pas)	52	41	36	48	51	28									61	120	43	283
MV minium viscosity (Pas)	1.2	2.1	5.5									3.9	5.7	1.1	1.5	0.3	16	1.3
					Hardening thing Tg (℃)	187	192	175	181	183	191								165	188	147	175
Hardening thing Tg after the suction (℃)	129	130	112									125	127	130	100	130	90	127
					G IC(J/m 2)	230	200	390	280	330	110								410	160	250	280
The unidirectional pre-immersion material base
				The prepreg specification	The carbon fiber kind	T700G	T700G	T700G	T700G	T700G	T700G								T700G	T700G	T700G	T700G
Resin content (weight %)	36	36	36									36	36	36	36	36	36	36
					The prepreg characteristic	Prepreg Tg (℃)	7	5	3	0	0								-3	5	7	0	0
Volatile amount (weight %)	0.7	0.7	0.7	0.4								0.4	0.5	0.7	0.7	0.7	0.4
						Tackiness	B	B	A	A	A							B	C	D	A	C
Drape	B	B	B	A								A	B	C	D	A	C
						Layered product (matrix material)	0 ° of compressive strength (MPa) high temperature sucting wet state	1100	1150	1050	1100							1100	1000	850	1150	750	800
The Fabric prereg base
						The prepreg specification	The carbon fiber kind	T700G	T700G	T700G	T700G							T700G	T700G	T700G	T700G	T700G	T700G
Resin content (weight %)	40	40	40	40	40							40	40	40	40	40
							Cellular sandwich panel	CDP(N·m/m)	25	26	31						28	30	15	23	17	18	25
Porosity (%)	0.5	0.3	0.2	0.3	0.1	0.9						0.7	1.5	0.9	1.5
								Surfaceness (A) (μ m)	48	31	23					19	12	103	71	147	85	98

(embodiment 6～11, comparative example 6～8)

According to aforesaid method, make composition epoxy resin, prepreg, fibre reinforced composites and cellular sandwich panel, estimate various physics values.The content of each embodiment is shown in table 2.

Embodiment 6～11 is compared as can be known with comparative example 6～8, is the surface smoothing of the skin panel of index for climbing bulging stripping strength (CDP) for the binding property of the skin panel of index and honeycomb core and with the surfaceness, and prepreg of the present invention is greatly excellent.

Table 2

			Embodiment 6	Embodiment 7	Embodiment 8	Embodiment 9	Embodiment 10	Embodiment 11	Comparative example 6	Comparative example 7	Comparative example 8
												Fortifying fibre (kind of integrant [A])			T700G	T700G	T700G	T700G	T700G	T700G	T700G	T700G	T700G
Matrix resin (integrant [B])	Resins, epoxy	″スミエポキシ″ELM434	40	40	40	40	40	40	40	40	40
												" エ ピ コ one ト 828 "	30	30	30	30	30	30	30	30	30
		″AER4152″	30	30	30	30	30	30	30	30	30
												Stiffening agent	″スミキユア″S	34.8	34.8	34.8	34.8	34.8	34.8	34.8	34.8	34.8
	Vulcanite	″Nipol1072″	4	4	4	4	4	4	4	4	4
												The thermoplasticity particulate	″SP-500″	0	0	0	0	0	0	0	0	10
	Other (integrant [C])	Kind		Non-woven fabrics	Non-woven fabrics	Non-woven fabrics	Cloth	Reticulate body	Apertured film	-	Film												-
Voidage (%)												55	46	31	48	58	35	-		-
		Average order is paid (g/m 2)		5	7.5	10	6.5	5	7.5	-	7.5										-
Every 1cm 2Order pay * 100/ average order pays (%)												93	95	95	90	15		-	97	-
		The prepreg specification	Fortifying fibre	Order is paid (g/m 2)	193	193	193	193	193	193	193										193	193
Resin molding	Order is paid (g/m 2)											80.6	76.4	64.3	78.6	80.6	76.4	64.3	76.4	64.3
			Weight ratio [A]/([B]+[C])		1.13	1.11	1.29	1.13	1.13	1.11	1.50										1.29	1.50
Laminar composite	0 ° of compressive strength (MPa)											The drying at room temperature state	677	655	633	660	672	648	720	650			666
		The high temperature sucting wet state	566	516	482	555	560	632	612	530	542
												Cellular sandwich panel	Climb bulging stripping strength (Nm/m)		38.7	41.4	48.5	38.2	38.0	40.2	26.9		28.6
The indenture number that surfaceness (B) 50 μ m are above		1	0	0	0	2		10	8	8

Industrial applicability

Composition epoxy resin of the present invention is suitable as the prepreg resin combination. The prepreg of using this resin combination to obtain has excellent adhesivity and drapability, and is also excellent with the self adhesion of honeycomb core. In addition, the fibre reinforced composites of the present invention excellence on surperficial grade and inner grade that is obtained by this prepreg. Except these features, when composition epoxy resin of the present invention is used for the unidirectional pre-immersion material base, can obtain under hygrothermal environment, having the fibre reinforced composites of high compression-strength. And, because composition epoxy resin of the present invention is applicable in any of for example Fabric prereg base and unidirectional pre-immersion material base, therefore can carry out the hybrid shaping of Fabric prereg base and unidirectional pre-immersion material base etc., the design freedom of structure member improves greatly.

In addition, the present invention can provide satisfy the desired all characteristics of skin-material, simultaneously with the prepreg of the self adhesion excellence of honeycomb, and the cellular laminar composite that the quality of utilizing it to obtain is light, mechanical characteristic is excellent.

In addition, the present invention can also provide the composite laminates that satisfies the desired all characteristics of outside plate, while surface smoothness excellence.

Claims (28)

1. composition epoxy resin, at least contain following Resins, epoxy (a) and Resins, epoxy (b) as Resins, epoxy in the said composition, contain 1～20 weight part vulcanite with respect to 100 weight part total epoxies, contain aromatic amine as stiffening agent, and the second-order transition temperature at the hardening thing of 180 ℃ of following heat hardenings after 2 hours is 160～220 ℃

(a) have  oxazolidone ring Resins, epoxy,

(b) glycidyl amine type epoxy resin.

2. composition epoxy resin as claimed in claim 1 wherein in the total epoxy of 100 weight %, contains the above-mentioned Resins, epoxy of 10～60 weight % (a), the above-mentioned Resins, epoxy of 10～60 weight % (b).

3. composition epoxy resin as claimed in claim 1 or 2, wherein above-mentioned vulcanite is the hard acrylonitrile butadiene rubber.

4. as each described composition epoxy resin of claim 1～3, the second-order transition temperature that wherein above-mentioned hardening thing is flooded this hardening thing after 2 days in boiling water is 110～150 ℃.

5. as each described composition epoxy resin of claim 1～4, the pattern I energy release rate G of above-mentioned hardening thing wherein _ICAt 200～1000J/m ²Scope.

6. as each described composition epoxy resin of claim 1～5, wherein, the MV minium viscosity when carrying out viscosimetric analysis with 2 ℃/minute of heat-up rates is in the scope of 1～50Pas.

7. prepreg, it contains claim 1～6 each described composition epoxy resin and fortifying fibre.

8. prepreg as claimed in claim 7, wherein volatile amount is 0.1～1 weight %.

9. prepreg, it comprises following integrant [A], [B] and [C]:

[A]: contain long stapled fortifying fibre,

[B]: matrix resin,

[C]: the thermoplastic resin that has the space and have continuous morphology.

10. prepreg as claimed in claim 9, wherein integrant [C] is configured in the outside surface side of integrant [A].

11. as claim 9 or 10 described prepreg, wherein the voidage of integrant [C] is 15%～90%.

12. as each described prepreg of claim 9～11, wherein integrant [C] is a non-woven fabrics.

13. as each described prepreg of claim 9～12, wherein the weight per unit area of integrant [C] is 2g/m on the prepreg single face ²～20g/m ²Scope.

14. as each described prepreg of claim 9～13, wherein integrant [A] is a fabric.

15. as each described prepreg of claim 9～14, wherein on the prepreg single face, every 1cm of integrant [C] ²Minimum weight be more than 20% of weight in average of unit surface.

16. as each described prepreg of claim 9～15, wherein the weight ratio of integrant [A], [B] and [C] is expressed from the next:

1＜[A]/([B]+[C])＜1.5。

17. as each described prepreg of claim 9～16, wherein the thermoplastic resin of integrant [C] comprises the resin more than a kind that is selected from polymeric amide, polyacetal, polyphenylene oxide, polyimide, polyetherimide, polyethersulfone, polyether-ether-ketone and the aromatic poly.

18. as each described prepreg of claim 9～17, this prepreg is used for the honeycomb fashion autoadhesion.

19. as each described prepreg of claim 9～17, this prepreg is that outside plate is used.

20. fibre reinforced composites, it is that each described prepreg of shaping claim 9～19 forms.

21. the cellular sandwich panel of fibre reinforced composites, it contains described fibre reinforced composites of claim 20 and honeycomb core.

22. a laminar composite, this material comprise following integrant [A], [C], [D] and [E], integrant [C] is configured between honeycomb core [E] and the integrant [A],

[A]: contain long stapled fortifying fibre,

[C]: have the space and have continuous morphology thermoplastic resin,

[D]: the matrix resin hardening thing,

[E]: honeycomb core.

23. laminar composite as claimed in claim 22, this material is more than the 33Nm/m according to the bulging stripping strength of climbing of ASTMD1781-98.

24. a laminar composite outside plate, this outside plate comprise following integrant [A], [C] and [D], integrant [C] is configured in the outside surface side of integrant [A],

[A]: contain long stapled fortifying fibre,

[C]: have the space and have continuous morphology thermoplastic resin,

[D]: matrix resin hardening thing.

25. laminar composite outside plate as claimed in claim 24, wherein on the surface of laminar composite, every 10cm ²The above surface pitting number of the degree of depth 50 μ m be below 2.

26. as each described prepreg of claim 9～19, wherein integrant [B] is each described composition epoxy resin of claim 1～6.

27. as claim 22 or 23 described laminar composites, wherein integrant [D] is the hardening thing of each described composition epoxy resin of claim 1～6.

28. as claim 24 or 25 described laminar composite outside plates, wherein integrant [D] is the hardening thing of each described composition epoxy resin of claim 1～6.

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