CN100591713C - Epoxy resin composition for carbon-fiber-reinforced composite material, prepreg, integrated molding, sheet of fiber-reinforced composite material and cabinet for electrical/electronic equipment - Google Patents

Abstract

A lightweight fiber-reinforced composite material that exhibits excellent flame resistance and mechanical properties and does not emit any halogen gas at combustion; an epoxy resin composition and prepreg suitable for obtaining the above fiber-reinforced composite material; and an integrated molding suitable to electrical/electronic equipment cabinet, in which use is made of the above fiber-reinforced composite material. There is provided an epoxy resin composition for carbon-fiber-reinforced composite material, comprising: [A] epoxy resin, [B] amine curing agent, and [C] phosphorus compound,the component [C] contained in an amount, in terms of concentration of phosphorus atoms, of 0.2 to 15 wt.%.

Description

Epoxy resin composition for carbon-fiber-reinforced composite material, prepreg, integrated molding, fiber-reinforced composite material board and electric/electronic device shell

Technical field

The present invention relates to be suitable as the composition epoxy resin of the matrix resin of carbon fibre reinforced composite.Particularly, the present invention relates to provide composition epoxy resin with good flame retardancy, mechanical characteristic and light-weight resin cured matter and the prepreg that contains this composition epoxy resin, also relate to the fiber-reinforced composite material board that constitutes by this epoxy resin cured product and carbon fiber.

In addition, the invention further relates to the integrated molding that is applicable to electric/electronic device usefulness shell that contains above-mentioned fiber-reinforced composite material board.

Background technology

Fibre reinforced composites, especially the carbon fibre reinforced composite that constitutes of carbon fiber and matrix resin, because its mechanical characteristic is good, not only be applied to sports goodss such as golf club, tennis racket, fishing rod, but also be used for the wide spectrum such as structured material, consolidation of concrete structure of flyer, vehicle etc.Recently, because carbon fiber has electroconductibility, this matrix material has good electromagnetic wave shielding performance or has good mechanical characteristic, so also be used for shell of electric/electronic devices such as notebook computer or pick up camera etc., has brought into play and made the shell thin-walled property, alleviated effects such as weight of equipment.

Wherein, in special structured material, the material of construction etc., because because of fire causes the structured material catching fire, generation toxic gas etc. is breakneck, so the strong request material has flame retardancy at flyer or vehicle etc.

In addition, in the electric/electronic device purposes, in order to prevent also to require the difficult burning of material because of from installing inner heating or suffering outside high temperature that the accident of catching fires such as shell or parts takes place.

Up to now, in the difficult burning of fibre reinforced composites, be extensive use of the halogen incombustible agent.Disclose particularly and used brominated epoxy resin or in brominated epoxy resin, add the difficult combustible epoxy resin composition (for example, referring to following patent documentation 1～4) of ANTIMONY TRIOXIDE SB 203 99.8 PCT as incombustible agent.In addition, difficult combustible epoxy resin composition or the prepreg (for example, referring to following patent documentation 5) as incombustible agent such as the Organohalogen compounds that use hexabromobenzene also disclosed.

Above-mentioned halogen incombustible agent has more high-leveled and difficult combustion effect, but exists the situation that generates obnoxious flavoures such as hydrogen halide or Organohalogen compounds during extremely fire extinguishing on fire on the contrary.In addition, when also known burning disposal contains the plastic material of halogen incombustible agent,, then can produce carinogenicity material dioxins if it is fully burnt.In addition,, must be noted that in use, so requirement does not recently use halogen incombustible agent or ANTIMONY TRIOXIDE SB 203 99.8 PCT can reach certain flame retardancy yet because the ANTIMONY TRIOXIDE SB 203 99.8 PCT of using simultaneously with the halogen incombustible agent has hazardous propertyes such as pungency.

Therefore the halogen incombustible agent is about 1.2 with respect to common epoxy resin cured product proportion owing to have halogen atom in the molecule, and the proportion of incombustible agent itself is bigger, be about 1.9 (below, proportion all is the value under 25 ℃).And and the ANTIMONY TRIOXIDE SB 203 99.8 PCT of usefulness to have be 5.2 very high proportion.Therefore, if in resin combination, add above-mentioned incombustible agent as incombustible agent, the proportion of the resin cured matter that obtains after then it being solidified is compared with the resin cured matter that does not add above-mentioned incombustible agent and is become big, generally speaking, be that the proportion of the fibre reinforced composites of matrix resin also increases with this resin combination.Thus, the lightweight that fibre reinforced composites have and the problem of high inflexible feature have appearred can't having given play in material.

On the other hand; as the difficult burning technology that does not conform to the composition epoxy resin that halogen is arranged, the fibre reinforced composites that are made of at the thermoplastic resin more than 120 ℃ Resins, epoxy and metal oxide and the vitrification point technology (for example patent documentation 6) with matrix resin is disclosed.Though this technology has the advantage that does not generate halogenation gas, metal oxide just is difficult to obtain sufficient flame retardancy more than 20 parts if do not add.The resin combination that contains this incombustible agent in a large number is because the viscosity height, so, the usability of prepreg is caused detrimentally affect, or generates the space in the matrix material after moulding to the impregnation of the fortifying fibre difficulty that becomes, easily cause descending as the rerum natura of matrix material, particularly tensile properties descends.

In addition, because the same proportion with the halogen incombustible agent of metal oxide is bigger, for example magnesium oxide has the proportion more than 3.2, thus exist with this compound identical as resin combination and the fibre reinforced composites that incombustible agent obtains with the halogen incombustible agent, the problem that exists proportion to increase.

As mentioned above, present situation is and is difficult to obtain giving the good mechanical characteristic of fibre reinforced composites and be the light-weight difficult combustible epoxy resin composition of non-halogen.

At present just in the shell of notebook computer, portable phone, portable information terminal or digital camera and so on electric/electronic device, information equipment or parts, use thermoplastic resin material.In recent years, along with popularizing rapidly of aforesaid device and parts, strong request is developed slim and the light-weight product in market.Accompany with it, the shell of requirement formation product or internal part thin-walled, light-weight also require high strength, high rigidity simultaneously.

For satisfying above-mentioned requirements, adopted magnesium alloy.High inflexible requires further to improve, so consideration utilizes the higher metallic substance of rigidity such as aluminium alloy.But be to use this metallic substance to be difficult to the easily parts or the product of mass production complicated shape, because proportion of metal material is big, the result can't satisfy lightweight simultaneously.

On the other hand, the fibre reinforced composites (FRP) that obtain of configuration continuous reinforcing fiber in matrix resin, the carbon fibre reinforced composite (CFRP) that especially in fortifying fibre, uses carbon fiber owing to can form various parts as mechanical characteristic, lightweight excellent material, structure is widely used.But above-mentioned FRP is not suitable for making parts or the structure with complicated shape in single molding procedure, therefore, in such use, must make the parts that are made of this FRP, carries out integrated with miscellaneous part then.

, in electric/electronic device, information equipment purposes, exist following situation herein: in order to prevent because of heating or the outside accident that suffers high temperature that catching fires such as shell or parts take place, also strong request flame retardancy from device interior.Generally well-known thermoplastic resin material is for being combined with the material of various incombustible agents in resin, for example, electronics that resin combination spray up n. that the red phosphorus that to add in carbon fiber, semiaromatic polyamide composition, fatty polyamide as incombustible agent obtains obtains is disclosed with electroconductibility housing (shell) (for example, referring to following patent documentation 7).

As mentioned above, in the difficult burning of fibre reinforced composites, be extensive use of the halogen incombustible agent.For example, use brominated epoxy resin and the ANTIMONY TRIOXIDE SB 203 99.8 PCT carbon fibre reinforced composite (for example, referring to patent documentation 4) as incombustible agent is disclosed.But there is the problem that is restricted because of the uses in such use such as hazardous property to environment, human body in this incombustible agent.

In addition, also disclose being used as the fibre reinforced composites (for example, referring to patent documentation 6) of the composition epoxy resin of incombustible agent as magnesium oxide, the aluminum oxide of non-halogen incombustible agent as matrix resin.But there is following problems in this known technology: must add a large amount of incombustible agents in order to obtain sufficient flame retardancy, thereby the viscosity that causes resin combination rises, forming defects such as space take place in the result, mechanical properties decrease, or since incombustible agent than great, so destroy good lightweight etc.

As mentioned above, present situation is with the parts that are made of FRP moulding product after integrated when being used for such use, not only can't satisfy mechanical property and lightweight, also can't satisfy good flame retardancy.

Patent documentation 1: special public clear 59-2446 communique

Patent documentation 2: special public clear 59-52653 communique

Patent documentation 3: the spy opens flat 6-206980 communique

Patent documentation 4: the spy opens flat 9-278914 communique

Patent documentation 5: No. the 3216291st, patent

Patent documentation 6: the spy opens flat 11-147965 communique

Patent documentation 7: the spy opens flat 10-120798 communique

Patent documentation 8: the spy opens flat 3-177418 communique

Patent documentation 9: the spy opens flat 3-296525 communique

Patent documentation 10: the spy opens clear 64-70523 communique

Non-patent literature 11:R.F.Fedors.Polym.Eng.Sci., 14 (2), 147 (1974)

Summary of the invention

The present invention is in view of above-mentioned prior art problems, the light-weight fibre reinforced composites that do not generate halogen gas when having good flame retardancy and mechanical characteristic and burning are provided, the prepreg and the composition epoxy resin that are suitable for obtaining these fibre reinforced composites also are provided.

Other purposes of the present invention not only have high mechanical characteristic, lightweight for providing, and do not use the halogen incombustible agent also can obtain good flame retardancy, are applicable to that electric/electronic device is with the integrated molding of shell.

In order to address the above problem, the invention provides:

A kind of epoxy resin composition for carbon-fiber-reinforced composite material contains following compositions [A], [B], [C], and the content of composition [C] is counted 0.2～15 weight % with phosphorus atom concentration.

[A] Resins, epoxy

[B] amine curing agent

[C] phosphorus compound

A kind of prepreg, described prepreg are to make to contain the prepreg that above-mentioned epoxy resin composition for carbon-fiber-reinforced composite material obtains in the carbon fiber.

The serve as reasons fibre reinforced composites of the resin cured matter that above-mentioned epoxy resin composition for carbon-fiber-reinforced composite material solidified obtain and carbon fiber formation of a kind of fibre reinforced composites, described fibre reinforced composites.

The invention provides a kind of integrated molding, described integrated molding by connection contain by (a) continuous reinforcing fiber, (b) with the thermosetting resin be the matrix resin composition of main component and (c) parts (I) and the miscellaneous part (II) of the fiber reinforced compound board that forms of incombustible agent form, above-mentioned parts (I) be determined as V-1 or V-0 based on the flame retardancy of UL-94 with the test film of its essence thickness.

The invention provides a kind of fiber-reinforced composite material board, serve as reasons (a) continuous reinforcing fiber, (b) of described fiber-reinforced composite material board is the matrix resin composition of main component and (c) fiber-reinforced composite material board (A) that constitutes of incombustible agent with the thermosetting resin, it is characterized in that, comprise (d) thermoplastic resin that on part surface, has jog at least, be determined as V-1 or V-0 with the test film of its essence thickness based on the flame retardancy of UL-94.

According to the present invention, as following illustrated, do not produce in the time of can obtaining having good flame retardancy and mechanical characteristic, burning halogen gas the light-weight fibre reinforced composites, be applicable to the prepreg and the composition epoxy resin that obtain these fibre reinforced composites.

In addition, integrated molding of the present invention or fiber-reinforced composite material board not only help thin lightization owing to having good mechanical characteristic and lightweight, and are preferred for notebook computer or portable information terminal etc. because of having good flame retardancy concurrently.

Description of drawings

Fig. 1 is the profile schema diagram of one of fiber-reinforced composite material board of the present invention example.

Fig. 2 is that vertical bonding strength is estimated sample.

Fig. 3 is the mode chart of vertical bonding strength evaluating apparatus.

Fig. 4 is the mode chart of the integrated molding of the computer casing of use fiber-reinforced composite material board of the present invention.

Fig. 5 is the mode chart of the cellular phone display shell of use composite panel of the present invention.

Fig. 6 is that vertical bonding strength is estimated sample.

Nomenclature

1: fortifying fibre

1-in: the most inboard fortifying fibre that connects thermoplastic resin coating 3

1-out: the outermost fortifying fibre that connects thermoplastic resin coating 3

2: thermosetting resin

3: the thermoplastic resin coating

4: the fiber-reinforced composite material board surface

5: the interface between thermosetting resin and the thermoplastic resin coating

Tpf: the maximum ga(u)ge of the concaveconvex shape of coating

Distance between Tsur:1-out and the surface 4

6: vertical bonding strength evaluation sample

7: fiber-reinforced composite material board

8: miscellaneous part (II)

9a: stretching clamp

9b: stretching clamp

10: adhesive face

11a: draw direction arrow

11b: draw direction arrow

12: notebook computer casing

13: the fiber-reinforced composite material board that constitutes notebook computer casing

14: the miscellaneous part (II) that constitutes notebook computer casing

15: the cellular phone display shell

16: the fiber-reinforced composite material board that constitutes the cellular phone display shell

17: the miscellaneous part (II) that constitutes the cellular phone display shell

18: the length of test film

19: the width of test film

20: test film

21: connection section

22: the length of connection section

Embodiment

Composition epoxy resin of the present invention contains following compositions [A], [B], [C].

[A] Resins, epoxy

[B] amine curing agent

[C] phosphorus compound

The phosphorus atom concentration that contains in the Resins, epoxy is necessary for 0.2～15 weight %.

The difficulty combustion effect of phosphorus atom is thought to be obtained by the effect that phosphorus atom promotes carbide to form, and is subjected to the influence of the phosphorus atom concentration in the resin combination largely.If phosphorus atom concentration less than 0.2 weight %, then is difficult to fully obtain difficult combustion effect,, then can bring detrimentally affect to mechanical characteristics, particularly tensile strength or the charpy impact value of the matrix material that obtains if surpass 15 weight %.Being preferably 0.3～13 weight %, more preferably is 0.4～11 weight %, more preferably 0.5～10 weight %.

,,, be not particularly limited herein, preferably use phosphoric acid ester, condensed phosphoric acid esters, phospho hetero phenanthrene compounds etc. to contain the compound or the red phosphorus of phosphorus as long as contain phosphorus atom in the molecule as phosphorus compound.Above-mentioned phosphorus compound can be caught, also can disperse or be dissolved in the composition epoxy resin by epoxy backbone in curing reaction.

Red phosphorus is because proportion is 2.2, and is littler than metal oxide, and the phosphorus atom containing ratio of the performance incombustible agent effect that contains in the red phosphorus is very high, so the addition of the incombustible agent of having to add in order to obtain difficult fully combustion effect can be on a small quantity.Thus, the proportion that adds resin cured matter that red phosphorus obtains as incombustible agent and fibre reinforced composites is little, can give full play of the advantage of lighting.In addition, be a small amount of by suppressing addition, can control the rheology of composition epoxy resin easily, therefore preferred especially.This is because when obtaining fibre reinforced composites via the prepreg as intermediates, or when adopting the method for injection resin such as the resin metaideophone method of forming to obtain fibre reinforced composites, the rheology of this composition epoxy resin influences formability etc.

The surface that red phosphorus more preferably uses red phosphorus is by metal hydroxides and/or resin-coatedly improved stable red phosphorus.As metal hydroxides, can enumerate aluminium hydroxide, magnesium hydroxide, zinc hydroxide, titanium hydroxide etc.Kind and amount of coating to resin are not particularly limited, as resin, preferably with as the high resol of the Resins, epoxy affinity of base resin, Resins, epoxy, polymethylmethacrylate etc.Amount of coating is more than the 1 weight % with respect to red phosphorus preferably.During less than 1 weight %, the lining effect is insufficient, can produce phosphine gas during at high temperature mixing etc.Though above-mentioned amount of coating multistability more is good more, consider preferably to be no more than 20 weight % with respect to red phosphorus from the viewpoint of lighting of difficulty combustion effect or fibre reinforced composites and so on.

Phosphoric acid ester and condensed phosphoric acid esters since the containing ratio of phosphorus atom lack than red phosphorus, so how much increased addition for the flame retardancy that obtains same degree.But, because the proportion of phosphoric acid ester and condensed phosphoric acid esters is about 1.2, substantially be equal to or less than the proportion of the cured article that adds the composition epoxy resin before the incombustible agent, give flame retardancy so can not increase the proportion of the resin cured matter that obtains and fibre reinforced composites.In addition, because most of commercially available phosphoric acid ester and condensed phosphoric acid esters be liquid at normal temperatures, so the mechanical characteristics decline of the matrix material that takes place can suppress the use metal hydroxides time can obtain keeping the fibre reinforced composites of higher characteristic.

When using the phosphorus compound powder, preferably its maximum particle diameter is below the 200 μ m.If particle diameter is worth greater than this, then exist following situation:, or the trafficability characteristic of the manufacturing process of prepreg brought detrimentally affect to the dispersed variation of resin.More preferably maximum particle diameter is below the 150 μ m.Said herein maximum particle diameter is meant the maximum particle diameter that detects in the particle size distribution, can utilize the laser diffraction type particle size distribution device to measure in the particle size distribution.

In addition, preferably to use median size be particle in 0.1～70 mu m range to the phosphorus compound powder.Thus, can improve dispersiveness, reduce the uneven of formability, flame retardancy etc., in addition, promptly can show the flame retardancy of effect on a small quantity Resins, epoxy.0.5～50 μ m more preferably.Need to prove that said median size is meant volume averaging herein, can utilize the laser diffraction type particle size distribution device to measure.

As the concrete example of phosphoric acid ester, can enumerate triaryl phosphate, alkyl aryl phosphate, alkyl phosphate, phosphonic acid ester etc.As triaryl phosphate, triphenylphosphate, tricresyl phosphate (o-toluene ester), trixylyl phosphate, tricresyl phosphate biphenyl ester, tricresyl phosphate 22 are arranged, 6-diformazan phenyl ester, phosphoric acid hydroxyl diphenyl ester etc.As alkyl aryl phosphate, octyl diphenyl phosphate etc. is arranged.As alkyl phosphate, trimethyl phosphite 99, triethyl phosphate, TRI N BUTYL PHOSPHATE, three iso-butyl ester of phosphoric acid, tricresyl phosphate (2-methyl hexyl) ester etc. are arranged.As phosphonic acid ester, dimethyl methyl phosphonate etc. is arranged.

As condensed phosphoric acid esters, Resorcinol two (bisphosphate), dihydroxyphenyl propane two (diphenyl phosphoester) etc. are arranged.

Wherein, preferably use the high as far as possible compound of phosphorus atom weight containing ratio in the molecule.

Need to prove that operable phosphoric acid ester, condensed phosphoric acid esters are not limited to concrete example.

In addition, above-mentioned phosphorus compound may be used alone, can also be used in combination multiple, can also use in advance and the mixing material that becomes the master batch shape such as resin.

As being used for Resins, epoxy of the present invention (composition [A]), as long as be the compound that has 2 above epoxy group(ing) in the compound, be not particularly limited, for example, can use bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenolic resin varnish type epoxy resin, naphthalene type Resins, epoxy, phenolic resin varnish type epoxy resin, Resins, epoxy with fluorene skeleton, multipolymer with oxybenzene compound and Dicyclopentadiene (DCPD) is the Resins, epoxy that raw material obtains, diepoxy propyl group Resorcinol, four (epoxypropyl oxygen base phenyl) ethane, three (epoxypropyl oxygen base phenyl) methane and so on glycidyl ethers type composition epoxy resin, Fourth Ring oxygen propyl group diaminodiphenyl-methane, three epoxypropyl amino-phenols, the amino cresols of three epoxypropyl, Fourth Ring oxygen propyl group dimethylphenylene diamine and so on epoxypropyl amine type Resins, epoxy, biphenyl type epoxy resin, the mixture of isocyanic ester denaturation loop epoxy resins and above-mentioned resin.Resins, epoxy can use above-mentioned resin separately, also can mix use.When particularly needing to have the equilibrated matrix material of thermotolerance, mechanical characteristics, the preferred material that combination 2 officials can Resins, epoxy obtain in polyfunctional epoxy resin, for example preferably combination as the phenol novolak type epoxy resin of polyfunctional epoxy resin and as 2 officials can Resins, epoxy bisphenol A type epoxy resin or bisphenol f type epoxy resin.

The solidifying agent that the present invention uses is amine curing agent (composition [B]).Amine curing agent is meant the solidifying agent that has nitrogen-atoms in the solidifying agent molecule.As this solidifying agent, as long as contain nitrogen-atoms in the molecule, be not particularly limited, for example, can use 4,4 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenylsulfone(DDS), 3,3 '-diaminodiphenylsulfone(DDS), mphenylenediamine, between two methylene diamines, diethyl toluene diamine and so on has the aromatic series polyamino compound of active hydrogen, diethylenetriamine, Triethylenetetramine (TETA), isophorone diamine, two (amino methyl) norbornane, two (4-aminocyclohexyl) methane, polyethylene imine based dimeric dibasic acid ester and so on has the fatty amine of active hydrogen, make above-mentioned amine and epoxy compounds with active hydrogen, vinyl cyanide, phenol and formaldehyde, the sex change amine that the reaction of compounds such as thiocarbamide obtains, xylidine, dimethyl benzyl amine, 2,4,6-three (dimethylaminomethyl) phenol or 1 substituted imidazole and so on do not have the tertiary amine of active hydrogen, the dicyano diamide, tetramethyl guanidine, hexanodioic acid hydrazides or naphthalic acid hydrazides and so on poly carboxylic acid hydrazides, boron trifluoride ethylamine coordination compound and so on Lewis acid coordination compound etc.

Wherein, when being used for the purposes of high heat resistance must be arranged, especially preferably use the aromatic series polyamine.If use the aromatic series polyamine, though need about 180 ℃ high temperature when solidifying, can obtain spring rate, cured article that thermotolerance is high, be the structured material that the fiber-resin composite of matrix resin is applicable to flyer or vehicle etc. with it.Wherein, use 3,3 '-diaminodiphenylsulfone(DDS), 4,4 '-diaminodiphenylsulfone(DDS) can obtain having the stable on heating fibre reinforced composites of thermotolerance, particularly moisture-proof, and are mixing-liquefying and have good storage stability under the situation in Resins, epoxy and preferred especially.

In order to improve curing activity, can appropriate combination use curing catalyst in the above-mentioned solidifying agent.For example, can be in Dyhard RU 100 appropriate combination as the 3-phenyl-1 of curing catalyst, 1-dimethyl urea, 3-(3, the 4-dichlorophenyl)-1,1-dimethyl urea (DCMU), 3-(3-chloro-4-aminomethyl phenyl)-1,1-dimethyl urea, 2,4-two (3,3-dimethyl urea groups) toluene and so on urea derivatives or imdazole derivatives use.Sclerosis needs about 170～180 ℃ temperature during separately for Dyhard RU 100, and is relative with it, uses the resin combination of aforesaid combination to solidify about 80～150 ℃.The combination of compounds that has 2 above urea keys in preferred especially Dyhard RU 100 and 1 molecule.As the compound that has 2 above urea keys in 1 molecule, preferred 1,1 '-4 (methyl-metaphenylene) two (3, the 3-dimethyl urea) or 4,4 '-methylene radical two (phenyl dimethyl urea) is when using above-claimed cpd, can be promptly curable through 2～10 minutes under 150～160 ℃, in addition, can also increase substantially the flame retardancy of the plate of thinner thickness, preferred especially when being used for situations such as electric and electronic material applications.

In addition, can also enumerate in aromatic amine combination as the example of the boron trifluoride ethylamine coordination compound of curing catalysts etc.

Also must have in the purposes of curability at low temperatures, can preferably use solidifying agent at 70～125 ℃ of following activatory potentiality solidifying agent.Herein, activation is meant that reaction beginning temperature is in 70～125 ℃ scope under 70-125 ℃.Described reaction begins temperature (hereinafter referred to as activation temperature) and can try to achieve according to differential scanning calorimetric analysis (DSC).Particularly, to being to add the composition epoxy resin that 10 weight parts obtain as the solidifying agent of evaluation object in about 184～194 the bisphenol A type epoxy resin at 100 weight part epoxy equivalent (weight)s, can try to achieve by the intersection point of the tangent line of the tangent line of the flex point of the heating curve that utilizes the differential scanning calorimetric analysis to obtain and baseline.If, then there is the inadequate situation of storage stability less than 70 ℃ in above-mentioned activation temperature,, then there is the situation that can not get desired rapidly-curable if surpass 125 ℃.

As at 70～125 ℃ of following activatory potentiality solidifying agent, as long as have above-mentioned activation temperature, be not particularly limited, for example can enumerate amine-adduct type potentiality solidifying agent, microcapsule-type potentiality solidifying agent, aminimide, blocked isocyanate, make epoxy group(ing) Cheng the carbaminate, salt etc. of salt, amine of compound, vinyl ether end-blocking carboxylic acid, imidazoles and carboxylic acid of oxazolidone ring with urethane reaction Xing.

Herein, as amine-adduct type potentiality solidifying agent be meant by making have primary, the compound of the second month in a season or uncle's amino or various imidazolium compounds isoreactivity composition with can quantize with some compounds reaction carrying out polymers of this compound reaction, thereby be thawless material under storage temperature.As amine-adduct type potentiality solidifying agent, can use " AMICURE " (registered trademark) PN-23, MY-24 (above is aginomoto fine chemistry (strain) system), " AdekaHardner " (registered trademark) EH-3293S, EH-3615S, EH-4070S (above is rising sun electrochemical industry (strain) system), " FUJICURE " (registered trademark) FXE1000, FXR-1020 (above change into industry (strain) system for Fuji) etc., as microcapsule-type potentiality solidifying agent, can use " Novacure " (registered trademark) HX-3271, HX-3722 (Asahi Chemical Industry's industry (strain) system) etc.In these solidifying agent, particularly the amine-adduct type potentiality solidifying agent of " AMICURE " PN-23 and so on has at room temperature good storage stability and significantly and preferably use of rapidly-curable.

Microcapsule-type potentiality solidifying agent is meant by being nuclear with the solidifying agent, being covered as shell with polymer substance such as Resins, epoxy, urethane resin, polystyrene type, polyimide or cyclodextrin etc. that this is examined and reduces the solidifying agent that contacts between Resins, epoxy and the solidifying agent.

If in 70～125 ℃ of following activatory potentiality solidifying agent, make up specific solidifying agent to solidifying agent, then at low temperatures also can fast setting.For example, made up in the potentiality solidifying agent such as " AMICURE " PN-23 organic acid dihydrazides such as Xie Ansuan two hydrazides the solidifying agent class, in the potentiality solidifying agent, made up solidifying agent class behind the curing catalysts such as DCMU curable through about 10 minutes under 110 ℃, so preferred the use.

In addition, also can use following solidifying agent: the curative compound that heating amine compound, Resins, epoxy and the urea of record obtain its reaction in the above-mentioned patent documentation 8; 9 records of above-mentioned patent documentation make N, N-dialkyl aminoalkyl amine with have active hydrogen and have the cyclic amine of nitrogen-atoms and isocyanic ester or the solidified nature compound that further obtains with epoxide reaction; Being nuclear, being the master batch type solidifying agent that becomes of hull shape etc. of above-mentioned patent documentation 10 records with itself and the reaction product of Resins, epoxy with specific amine compound.Above-mentioned solidifying agent may be used alone, can also be used in combination multiple.

Composition epoxy resin of the present invention, in expectation can the purposes such as shell of mass-produced at short notice industry material applications, particularly electric/electronic device, preferably can 150 ℃ following 30 minutes with interior curing.More preferably at 10 minutes with interior curing.Herein, can solidify be meant that above-mentioned resin combination solidifies behind the certain hour resin cured matter at a certain temperature can the demoulding, be meant that particularly internal diameter on being placed on the punch press (press) that is heated to 150 ℃ is that 31.7mm, thickness are to inject the 1.5ml resin combination in the tetrafluoroethylene system O shape ring of 3.3mm, cure under pressure can not make the degree of resin cured matter shifting ground with its taking-up after 10 minutes.

In order to control visco-elasticity or to give toughness, can in composition epoxy resin of the present invention, be used thermoplastic resin.

As the example of above-mentioned thermoplastic resin, can enumerate polymethylmethacrylate, polyvinyl formal, polyvinyl butyral acetal, polyethylene acetal, Polyvinylpyrolidone (PVP), will be selected from least 2 kinds of polymkeric substance in the aromatic vinyl monomer vinyl cyanide monomer gelatinous polymer, polymeric amide, polyester, polycarbonate, polyarylether, polysulfones, polyethersulfone, polyimide etc. as constituent.As at least 2 kinds of examples that are selected from aromatic vinyl monomer vinyl cyanide monomer gelatinous polymer, can enumerate acrylonitrile-styrene-butadienecopolymer (ABS resin), acrylonitritrile-styrene resin (AS resin) etc. as the polymkeric substance of constituent.Polysulfones, polyimide can contain ehter bond, amido linkage on main chain.

Polymethylmethacrylate, polyvinyl formal, polyvinyl butyral acetal, Polyvinylpyrolidone (PVP) have the good intermiscibility with multiple Resins, epoxy such as bisphenol A type epoxy resin, phenolic resin varnish type epoxy resins, the effect of the flowability of control compositions of thermosetting resin is obvious and preferred, special preferably polyethylene alcohol formal.If enumerate the commercially available product of above-mentioned thermoplastic resin, then there be " Denka Butyral " to reach " Denka Formal " (registered trademark, electrochemical industry (strain) system), " Vinylec " (registered trademark, intelligence rope (strain) system) etc.

Polysulfones, polyethersulfone, the resin of polyimide itself has good thermotolerance, in addition, have and require stable on heating purposes as being widely used in, the Fourth Ring oxygen propyl group diaminodiphenyl-methane of the Resins, epoxy in structure unit of flyer etc. for example, three epoxypropyl amino-phenols, the amino cresols of three epoxypropyl, Fourth Ring oxygen propyltoluene diamines and so on epoxypropyl amine type Resins, epoxy has the polymkeric substance of the resin matrix of suitable intermiscibility, if use above-mentioned polymkeric substance, then the effect of the flowability of resin combination control is obvious, in addition also has the effect of the shock-resistance that can increase fiber-resin composite and preferred.Example as above-mentioned polymkeric substance, polysulfones has " RADEL " (registered trademark, Solvay Advanced Polymers society system) A, " Sumika Excel " (registered trademark) PES (Sumitomo Chemical (strain) system) etc., polyimide has " Ultem " (registered trademark, General Electric's plastic cement corporate system), " Matrimid " (registered trademark) 5218 (the general chemical company's system that reaches) etc.

In the composition epoxy resin of the present invention, thermoplastic resin preferably contains 1～60 weight part with respect to 100 weight part Resins, epoxy.If less than 1 weight part, then can't show effect, if be more than 60 weight parts, then the lining of prepreg is destroyed, or aspect such as water-absorbent is affected.

Composition epoxy resin of the present invention can contain the compound beyond the above-claimed cpd.For example, in order to improve flame retardancy, can contain metal oxide or metal hydroxides.But when containing above-claimed cpd, preferably the content in composition epoxy resin is below the 10 weight %.More preferably be below the 5 weight %, 0 weight % more preferably.If surpass above-mentioned use level, then consider to have inapplicable situation from the viewpoint of lighting.

In addition, solidify the proportion of the cured article that resin combination of the present invention obtains, be preferably below 1.35.By being set at above-mentioned scope, can provide more light-weight fibre reinforced composites.The proportion of composition epoxy resin more preferably is below 1.33, more preferably below 1.32.

Make up above-mentioned composition epoxy resin and fortifying fibre, can obtain fibre reinforced composites.Method as making fibre reinforced composites has following method: stacked heating contains in fortifying fibre and is soaked with composition epoxy resin and makes the prepreg of sheet material shape and the method for moulding; Do not use prepreg, directly impregnation composition epoxy resin post-heating solidified method in fortifying fibre, for example methods of forming such as hand pasting forming method, fiber winding method, pultrusion method, resin spray up moulding, the resin metaideophone method of forming.

Wherein, composition epoxy resin of the present invention is suitable for obtaining via prepreg the method for matrix material.

The viscosity of resin combination of the present invention under 60 ℃ is preferably in the scope of 10～700Pas.If viscosity is less than 10Pas, when then making fortifying fibre contain resin pickup to make prepreg, resin sinks in the fortifying fibre, and the resin on prepreg surface tails off so the surface can not get sufficient viscosity is binding property, or resin flows is big during moulding, and the confusion of fortifying fibre takes place.In addition, if surpass 700Pas, then the impregnation to fortifying fibre becomes difficult or brings detrimentally affect for forming process and moulding product quality.This viscosity can be tried to achieve by using the viscosity of rotary viscosity design determining under 60 ℃.

Composition epoxy resin of the present invention is especially in the demanding purposes of the lighting of material or high strength, and preferably combination is used than spring rate, carbon fiber that specific tenacity is good.As fortifying fibre, except that carbon fiber, can also use fibers such as glass fibre, aromatic polyamide fibre, boron fibre, pbo fiber, high-tenacity polyethylene fibre, sapphire whisker and silicon carbide fiber, can be mixed with two or more above-mentioned fiber.

When having intensity and high rigidity concurrently, can further use spring rate to be the carbon fiber more than the 300GPa as the requirements such as structured material of flyer.In addition, when the shell of electric/electronic device etc. is paid attention to more thin-walled property lighting, require high rigidity, use spring rate as more than the 300GPa, further be the carbon fiber more than the 400GPa.The tensile strength of said carbon fiber, spring rate refer to the wire stretching intensity, the wire stretching spring rate that record according to JIS R7601 herein.

Form or assortment to fortifying fibre are unqualified, for example can use doubling to arrive fiber structures such as unidirectional macrofiber, single rescutched tow, fabric, knitted fabrics, non-woven fabrics, unglazed fabric and braid.

The unidirectional pre-immersion material base, in the direction set because of fortifying fibre, fiber bending is few, thus the rate of utilization of strength height of fiber direction, so preferred especially.If with the stacked a plurality of prepreg aftershapings of suitable stepped construction, the spring rate, intensity that then can freely control all directions of carbon fibre reinforced composite are so preferred especially unidirectional pre-immersion material base.

The Fabric prereg base because can obtain the few material of the anisotropy of intensity, spring rate, pattern, appearance design that the surface can show carbon fibre fabric are good and preferred.Can the multiple prepreg of moulding, for example, use unidirectional pre-immersion material base and Fabric prereg base to carry out moulding simultaneously.

Composition epoxy resin can be contained the inside that is dipped into reinforcing fiber bundles, can make the resin combination part be present in its near surface under the situations such as the prepreg of sheet.

The intensity of the fibre reinforced composites that obtain and spring rate depend on the fortifying fibre amount more greatly.When promptly containing a certain amount of fortifying fibre, the amount of the matrix resin of combination is few more, can reduce the weight of product more in the performance of roughly keeping fibre reinforced composites or the finished product definitely.To achieve these goals, preferably the content with respect to the fortifying fibre of prepreg of the present invention and fibre reinforced composites gross weight is 30～95 weight %, more preferably 50～90 weight %, more preferably 60～90 weight %.The content of fortifying fibre is during less than 30 weight, and the lighting effect is insufficient, if surpass 95 weight %, then exists amount of resin to cause residual clearance in the matrix material less, the situation that mechanical characteristics descends.

Prepreg of the present invention can be carried out making behind the lowering viscousity it to contain the wet method that is immersed in the fortifying fibre or undertaken making behind the lowering viscousity it to contain hot melt process of being immersed in the fortifying fibre etc. by heating and make by resin combination is dissolved in methyl ethyl ketone, the methyl alcohol equal solvent.

Wet method is after being impregnated into fortifying fibre in the solution of resin combination, to take out, and uses baking oven etc. to make solvent evaporation obtain the method for prepreg.

Hot melt process is to make the method for the direct impregnation of fortifying fibre by the resin combination of heating lowering viscousity, or make in advance resin combination is coated in the resin molding that obtains on interleaving paper etc., from both sides or one-sided overlapping this film of fortifying fibre, make it contain the method that resin pickup obtains prepreg then by heating and pressurizing.This hot melt process is because of residual solvent is not preferred in fact in prepreg.

When adopting hot melt process to obtain prepreg, the temperature of resin combination is preferably 30～80 ℃ in the operation of application of resin film, more preferably is 40～70 ℃.If less than 30 ℃, have then that viscosity uprises, the unsettled situation of the weight per unit area of resin molding, if surpass 80 ℃ then have that resin solidifies the situation that viscosity significantly rises in the coating.

In addition, can use prepreg of the present invention, the limit applies heat or the pressure limit makes manufacturing fibre reinforced composites such as resin is heating and curing.

As the method that applies heat and pressure, can adopt extrusion forming method, autoclave molding method, flexible bag moulding method (bag molding), abrasive belt moulding (lapping tape molding) method, internally pressuring shaping method etc.

As the temperature of shaping fiber reinforced composite,, be preferably 80～220 ℃ though depend on the kind of the solidifying agent that contains in the composition epoxy resin.If this mold temperature is less than 80 ℃, then there is the situation that can't obtain sufficient rapidly-curable, if surpass 220 ℃, then there is the situation of the warpage that the Yi Fashengyin thermal distortion causes.Particularly preferred extrusion forming in order to shorten the moulding circulation.The flexible bag moulding that moulding is at low temperatures preferably carried out in a vacuum.

Carbon fibre reinforced composite of the present invention is 60% o'clock with respect to the volume (following table is shown Vf) that contains of the carbon fiber of fibre reinforced composites cumulative volume, and preferred specific gravity is below 1.7.If be more than 1.7, when for example being used for the shell of electronics, can't bring into play the characteristic of " light and solid " of fibre composite, and can't fully obtain the advantage of " gently ".

Herein, the Vf of carbon fibre reinforced composite is greater than 60% o'clock, and the proportion of carbon fibre reinforced composite increases, if but compare with the material of same thickness then can obtain the bigger moulding product of intensity, so, can reduce the thickness of necessary material in order to obtain identical intensity.Thus, for example Vf is 85% o'clock, and preferred specific gravity is below 1.9.

On the other hand, the Vf of carbon fibre reinforced composite was less than 60% o'clock, and proportion diminishes, and the strength degradation of the material of same thickness therefore in order to obtain same intensity, has to increase the thickness of material.Thus, for example Vf is 40% o'clock, and proportion is preferably below 1.6.

When using with composition epoxy resin of the present invention to the fibre composite of matrix resin, because the shock absorption of material is big when wishing to fall, so preferably use the but high material of shellfish (sharpy) impact value as the shell of electronics.When prepreg was the unidirectional pre-immersion material base, preferred charpy impact value was 100J/m ²More than.More preferably be 150J/m ², 200J/m more preferably ²The charpy impact value can be measured according to the method for JIS K7077 record.

When using, wish the tensile strength height as structured material.When prepreg was the unidirectional pre-immersion material base, preferred tensile strength was more than the 1000MPa, more preferably 1300MPa, more preferably 1500MPa.Tensile strength can be measured according to the method for ASTM D3039 record.

Adopting fiber-resin composite that aforesaid method obtains being that test film below the 2mm is measured the flame retardancy that obtains and is preferably more than the V-1 based on the UL94 standard to thickness, more preferably is V-0.In addition, when using as the shell of electric/electronic device, when supposing that can be designed to thinner wall thickness uses, preferably to thickness be test film below the 1.5mm to measure the flame retardancy that obtains be more than the V-1, more preferably be V-0.More preferably thickness is the following test film of 1.2mm, more preferably thickness is that the following test film of 0.8mm, special preferred thickness are that the flame retardancy that the following test film mensuration of 0.5mm obtains is more than the V-1, especially is V-0.

Herein, V-0 and V-1 flame retardancy are represented to satisfy in UL-94 standard (U.S.'s combustion test method that designs among the UnderwritersLabratories Inc.), the having or not or the flame retardancy of the condition of V-0 that the incendivity of its burning molten drop etc. is stipulated and V-1 of the molten drop (drip) that has or not, burn that spreads according to combustion time or its state, burning.

Integrated molding of the present invention as one of its textural element, has fiber-reinforced composite material board.

Fiber-reinforced composite material board is the plate object that is formed by fortifying fibre and matrix resin composition.

As fortifying fibre, for example can enumerate steel fibers such as aluminium, brass, stainless steel; Or polypropylene nitrile, regenerated fiber class, lignin, pitch-based carbon fiber or insulativity fibers such as graphite fibre, glass fibre; Organic fibres such as aromatic polyamide, PBO, polyphenylene sulfide, polyester, vinylformic acid, nylon, polyethylene; Inorganic fibre such as silicon carbide, silicon nitride.In addition, can implement surface treatment to above-mentioned fiber.As surface treatment, except the processing of lining as the metal of electrical conductor, what also have coupling agent treatment, adhesive treated, additive adheres to processing etc.Above-mentioned fortifying fibre can be used alone or two or more kinds may be used.

Wherein, consider, preferably use carbon fiber, especially consider and realize cheap cost aspect, preferably use the polyacrylonitrile based carbon fiber from the equilibrated viewpoint of specific tenacity, specific rigidity, lightweight or electroconductibility.

As the form of fortifying fibre, consider effectively to show the reinforcing effect aspect of fortifying fibre and preferred mean length is the fortifying fibre that the above fibre lay-up of 10mm becomes the stratiform configuration.As the form of fortifying fibre layer, preferably use cloth or unidirectional form is arrived in doublings such as macrofiber, cloth, macrofiber bundle, textile yarn.Stacked doubling is during to the layer of unidirectional form because the anisotropy of the intensity of duplexer is diminished preferred every layer all stacked towards different directions ground.The form of above-mentioned layer can be used a kind separately, and two or more kinds may be used.

The intensity of the fibre reinforced composites that obtain and spring rate depend on the fortifying fibre amount more greatly.When promptly containing a certain amount of fortifying fibre, the amount of the matrix resin of combination is few more, can alleviate the weight of product more in the performance of roughly keeping fibre reinforced composites or the finished product definitely.To achieve these goals, preferably the content with respect to the fortifying fibre of prepreg of the present invention and fibre reinforced composites gross weight is 30～95 weight %, more preferably is 50～90 weight %, more preferably 60～90 weight %.The content of fortifying fibre is during less than 30 weight %, and lighting effect sometimes is insufficient, if surpass 95 weight %, then has the situation that causes residual clearance in the matrix material, mechanical property decline owing to amount of resin is few.

The preferred formation at least of above-mentioned matrix resin composition mainly contains the compositions of thermosetting resin layer of thermosetting resin and obtains with mainly containing thermoplastic resin composition's layer of thermoplastic resin.

Consider more preferably to use thermosetting resin from the easiness viewpoint of mechanical characteristic, moulding.

As the thermosetting resin that constitutes fiber-reinforced composite material board of the present invention, for example, unsaturated polyester, vinyl acetate, epoxy, phenol (first rank phenol aldehyde type), urea aldehyde trimeric cyanamide, polyimide, bismaleimides, cyanate etc. are arranged, the multipolymer of above-mentioned resin, sex change body and at least 2 kinds of resins that above-mentioned resin obtains of blending.In order to improve impact, can add elastomerics or rubber constituent.Particularly consider preferred epoxy from the viewpoint of the mechanical characteristic of moulding product.And, preferably contain Resins, epoxy as main component in order to demonstrate good mechanical characteristic, preferably contain particularly more than the 60 weight %.

Consider that from the viewpoint that improves flame retardancy the vitrification point Tg of preferred thermosetting resin satisfies Tmax-Tg≤50.Tmax is meant and carries out after fixing, is in and do not observe the vitrification point of thermosetting resin of fiber-reinforced composite material board of state of being estimated the residual thermal value of the thermosetting resin obtain by DSC herein.As the after fixing condition, preferably before after fixing, estimate vitrification point Tg in advance as the thermosetting resin of the fiber-reinforced composite material board of object, in the temperature range of this vitrification point Tg+30, carry out.By being set at this temperature range, deterioration or thermolysis ground that thermosetting resin can not take place correctly carry out the evaluation of Tmax.

By being set at Tmax-Tg≤50, the lower molecular weight body in the thermosetting resin is tailed off, suppress the generation of decomposition gas, improve flame retardancy.

Via thermoplastic resin composition's layer integrated can the accessing than the known tackiness agent of use of fiber-reinforced composite material board and miscellaneous part is connected more firm connection.

As being the thermoplastic resin that uses in the layer of main component with the thermoplastic resin, for example can be polyester such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), Poly(Trimethylene Terephthalate) (PTT), PEN (PENP), liquid crystal polyester; Polyolefine such as polyethylene (PE), polypropylene (PP), polybutene; Styrene resin, polyoxymethylene (POM), polyamide (PA), polycarbonate (PC), polymethylmethacrylate (PMMA), polyvinyl chloride (PVC), polyphenylene sulfide (PPS), polyphenylene oxide (PPE), sex change PPE, polyimide (PI), polyamidoimide (PAI), polyetherimide (PEI), polysulfones (PSU), sex change PSU, polyethersulfone (PES), polyketone (PK), polyetherketone (PEK), polyether-ether-ketone (PEEK), PEKK (PEKK), polyarylester (PAR), polyethers nitrile (PEN), phenolic resinoid, phenoxy resin, fluorine-type resins such as tetrafluoroethylene, or the multipolymer of above-mentioned resin, the sex change body, and the resin that blending obtains more than 2 kinds etc.Wherein, polyamide resin is because mechanical characteristic is good and preferred.

In addition, in order to improve shock-resistance, can add other elastomericss or rubber constituent.Can contain other packing materials or additive in the scope of not destroying purpose of the present invention according to purposes etc.For example, can enumerate inorganic filling material, incombustible agent, electroconductibility imparting agent, nucleator, UV light absorber, antioxidant, vibration damping agent, antiseptic-germicide, insect-proof agent, deodorizer, anti-coloring agent, thermo-stabilizer, releasing agent, anti-live agent, softening agent, lubricant, tinting material, pigment, dyestuff, whipping agent, defoamer, coupling agent etc.

As incombustible agent, can select according to the idea identical with above-mentioned incombustible agent (c).

In addition, the solubility parameter δ (SP value) that preferably constitutes the thermoplastic resin of thermoplastic resin composition's layer is 9～16, more preferably is 10～15, more preferably 11～14.Solubility parameter (SP value) is meant the value of the repeating unit of the polymkeric substance of being measured by the Fedors method under 25 ℃.This method is documented in the above-mentioned non-patent literature 11.By solubility parameter δ (SP value) is set in the above-mentioned scope, it is big that the cohesive force of the molecular chain of thermoplastic resin becomes, and thermoplastic resin composition self becomes survivable, also can improve with the avidity of fortifying fibre, so can show firm bounding force.

As the thermoplastic resin that can reach above-mentioned solubility parameter δ, for example, can enumerate have amido linkage, the resin of ester bond, amino-formate bond, ehter bond, amino, hydroxyl, carboxyl, key, functional group or structure that aromatic nucleus geometric ratio hydrocarbon skeleton polarity is higher.As above-mentioned thermoplastic resin composition, contain the thermoplastic resin composition of amido linkage, ester bond, amino-formate bond, hydroxyl etc., can enumerate polyamide-based resin, polyester resin, polycarbonate resin, ethylene-vinyl alcohol copolymerization resinoid etc.The thermoplastic resin composition of containing aromatic nucleus can enumerate styrene resin or PPS resinoid etc.Above-mentioned resin not only can use with monomer, also can use resin that the multipolymer, sex change body of above-mentioned resin and at least 2 kinds of above-mentioned resins that mix obtain etc.

As the mark of compositions of thermosetting resin layer and thermoplastic resin composition's layer, consider the mechanical property that improves moulding product and preferably the weight fraction of compositions of thermosetting resin layer greater than the weight fraction of thermoplastic resin composition's layer.

In addition, in order to improve shock-resistance, can in matrix resin composition, add other elastomericss or rubber constituent.Can contain other packing materials or additive in the scope of not destroying purpose of the present invention according to purposes etc.For example, can enumerate inorganic filling material, electroconductibility imparting agent, nucleator, UV light absorber, antioxidant, vibration damping agent, antiseptic-germicide, insect-proof agent, deodorizer, anti-coloring agent, thermo-stabilizer, releasing agent, anti-live agent, softening agent, lubricant, tinting material, pigment, dyestuff, whipping agent, defoamer, coupling agent etc.

As described later, burying in thermosetting resin to the small part group of fibers in the preferred fortifying fibre buries in the layer that with the thermoplastic resin is main component to other group of fibers of small part.According to such scheme, can obtain firm bonding.

The maximum ga(u)ge Tpf that buries the concaveconvex shape in the zone that exists of fortifying fibre group in the layer that with the thermoplastic resin is main component is preferably 10～100 μ m, more preferably is 20～80 μ m, more preferably 40～60 μ m.By aforesaid operations, can obtain more firm bonding.This maximum ga(u)ge Tpf is defined as follows: on the thickness direction of layer that with the thermoplastic resin is main component, from being that the surface (among Fig. 1 4) of the layer (Fig. 1 3) of main component is observed with the thermoplastic resin, the fortifying fibre (1-out among the figure) that buries in the fortifying fibre in the layer that with the thermoplastic resin is main component the most approaching surface with, burying at the position of deep thickness maximum from the surface that with the thermoplastic resin is the layer of main component is being the layer of main component with the thermoplastic resin or the distance on thickness direction between the fortifying fibre middle distance surface fortifying fibre (1-in among Fig. 1) farthest that is connected with this layer.If the Tpf maximum value is 100 μ m, then can obtain fully firm bonding.In addition, from being that the surface 4 of the layer of main component is preferably 10～200 μ m to fortifying fibre 1-out apart from Tsur with the thermoplastic resin.More preferably be 20～100 μ m.By being set at this scope, be that the layer of main component can be effective as bonding coat and plays a role with the thermoplastic resin.Crossing and cause the bounding force deficiency when thin, when blocked up is that the layer of main component is destroyed easily with the thermoplastic resin.

With thermosetting resin and thermoplastic resin is that the layer of main component is preferably formed the interface of concaveconvex shape.Increase two-layer contact area thus, bonding securely, at interval with the thermoplastic resin to be that layer bonding of main component also becomes firm bonding thereby make.On this interface, same fiber buries in layer two-layer that with thermosetting resin and thermoplastic resin is main component, can be described as the effect reinforcement adhesive interface that utilizes spike, obtains firm bonding.

With thermosetting resin and thermoplastic resin be main component the layer between interfacial configuration and Tpf can observe by scanning electron microscope (SEM) or infiltration type electron microscope (TEM).The test film of observing is for downcutting the thin-walled section that the skin section branch obtains from fiber-reinforced composite material board.For under observation adjust with thermosetting resin and thermoplastic resin be main component the layer between contrast gradient, test film can be dyeed.

Contained incombustible agent (c) in the fiber-reinforced composite material board, for example, can enumerate Phosphorus incombustible agents such as Triphenyl phosphate (TPP), tricresyl phosphate (o-toluene ester), tricresyl phosphate biphenyl ester, trioctyl phosphate, ammonium polyphosphate, polyphosphonitrile, phosphoric acid ester, phosphonic acid ester, phosphinate, phosphine oxide, condensed phosphoric acid esters, the luxuriant and rich with fragrance compounds of phosphine, red phosphorus; Mineral-type such as calcium aluminate, zirconium white incombustible agent; Nitrogen such as melamine cyanurate, polyphosphoric acid melamine class; The silicon class; Metal hydroxides classes such as aluminium hydroxide, magnesium hydroxide, calcium hydroxide, stannic hydroxide; Incombustible agents such as phenols.

Wherein, if at high temperature do not burn, may produce dioxin when then burning, so be preferably non-halogen class incombustible agent.Consider especially preferably Phosphorus, nitrogen class, silicon class incombustible agent from the lightweight aspect.The high Phosphorus incombustible agent of more preferably awkward combustion effect.If is 0.2～15 weight % with respect to the Phosphorus incombustible agent of fiber-reinforced composite material board with phosphorus atom densitometer content, then can fully show difficult combustion effect and preferred.Wherein, even the big red phosphorus addition of phosphorus atom content is preferred for also playing a role effectively on a small quantity.

Red phosphorus more preferably uses through metal hydroxides and/or resin-coated surface and has improved stable red phosphorus.As metal hydroxides, can enumerate aluminium hydroxide, magnesium hydroxide, zinc hydroxide, titanium hydroxide etc.The kind of resin and the thickness of lining are not particularly limited, as resin, preferably with as the high resol of the affinity of the Resins, epoxy of substrate resin, Resins, epoxy, plexiglass etc.In addition, amount of coating is more than the 1 weight % with respect to red phosphorus preferably.If less than 1 weight %, the effect that then is covered is insufficient, the situation that produces phosphine gas such as have when at high temperature mixing.Though consider preferred more amount of coating from stable aspect, consider that from the lighting viewpoint of difficulty combustion effect or fibre reinforced composites amount of coating preferably is no more than 20 weight %.

Preferably use the phosphorus compound powder of median size in 0.1～70 mu m range when using the phosphorus compound powder.Thus, can improve dispersiveness, reduce the inequality of formability, flame retardancy etc., in addition, can bring into play flame retardancy effectively on a small quantity Resins, epoxy.More preferably be 0.5～50 μ m.Need to prove that the implication of said median size is a volume average particle size herein, can utilize the laser diffraction type particle size distribution device to measure.

Consider from the mechanical characteristic of fiber-reinforced composite material board and flame retardancy two aspect viewpoints, the content of above-mentioned incombustible agent preferably in fiber-reinforced composite material board proportion be 1～20 weight %.More preferably be 3～12 weight %.

As the form of fiber-reinforced composite material board, preferred inside accompanies the sandwich structure of core.Can further improve lightweight thus.As core, consider foaies such as preferred phenols, polyimide, PPS class from the viewpoint of flame retardancy, lightweight.

Fiber-reinforced composite material board of the present invention is based on the flame retardancy of UL-94, is expressed as V-1 or V-0 is important with the test film measurement result with essence thickness, is preferably V-0.Herein, said " test film with essence thickness " is meant with the thickness of the fiber-reinforced composite material board that the uses thickness as the sample that is used to measure.By making flame retardancy is V-1 or V-0, is applicable in the product that requires flame retardancy.Essence thickness is preferably 0.05～2mm, considers more preferably to be 0.1～1.0mm, more preferably 0.2～0.8mm from the viewpoint of light thin-wall.

As the density of fiber-reinforced composite material board, consider to be preferably 1.8g/cm from the viewpoint of lightweight ³Below, more preferably be 1.7g/cm ³Below, 1.6g/cm more preferably ³Below.Consider from the viewpoint of intensity, with 0.05g/cm ³Be actual lower limit.

The crooked elastic rate of fiber-reinforced composite material board is preferably more than the 35GPa, more preferably is more than the 40GPa.By setting crooked elastic rate is more than the 35GPa, goes for the electric/electronic device parts.The upper limit of the crooked elastic rate of fiber-reinforced composite material board is not particularly limited, and in most cases is to get final product about 350GPa.Further describe this measuring method with embodiment.

Constituting electric/electronic device of the present invention fiber-reinforced composite material board with parts, based on the flame retardancy of UL-94, is that the measurement result of the test film below the 1.6mm is expressed as V-1 or V-0 is important with thickness, is preferably V-0.Herein, " thickness is the following test film of 1.6mm " has following implication: when the thickness of determination object surpasses 1.6mm, prune equably from the two sides, the sample of promptly selecting for use the 1.6mm central part conduct on the thickness direction to be used to measure, the thickness of determination object is that 1.6mm is when following, directly as the sample that is used to measure.If flame retardancy is V-2, then exist the situation that requires characteristic of the flame retardancy that is not suitable for product.

Fiber-reinforced composite material board, the electric wave shielding when adopting the frequency 1GHz that Advantest (advantest) method measures is more than the 40dB, more preferably is more than the 45dB, more preferably more than the 50dB.The back further describes this measuring method with embodiment.

Integrated molding of the present invention can form by further connect miscellaneous part on above-mentioned fiber-reinforced composite material board.

As this " miscellaneous part (II) ", for example can form by the metallic substance such as alloy of aluminium, iron, magnesium, titanium and above-mentioned metal, also can form by above-mentioned fibre reinforced composites, can also constitute by the thermoplastic resin composition.

If use through fortifying fibre enhanced thermoplastic resin composition conduct " miscellaneous part (II) ", the lightweight that can't realize in the time of then can obtaining adopting metallic substance is so preferred.

As the thermoplastic resin that is used for " miscellaneous part (II) ", for example can enumerate polyester such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), Poly(Trimethylene Terephthalate) (PTT), PEN (PENP), liquid crystal polyester; Polyolefine such as polyethylene (PE), polypropylene (PP), polybutene; Styrene resin, polyoxymethylene (POM), polyamide (PA), polycarbonate (PC), polymethylmethacrylate (PMMA), polyvinyl chloride (PVC), polyphenylene sulfide (PPS), polyphenylene oxide (PPE), sex change PPE, polyimide (PI), polyamidoimide (PAI), polyetherimide (PEI), polysulfones (PSU), sex change PSU, polyethersulfone, polyketone (PK), polyetherketone (PEK), polyether-ether-ketone (PEEK), PEKK (PEKK), polyarylester (PAR), polyethers nitrile (PEN), phenolic resinoid, phenoxy resin, fluorine-type resins such as tetrafluoroethylene, the multipolymer of above-mentioned resin, the sex change body, and the resin that obtains more than 2 kinds of blending etc.

In addition, in order to improve shock-resistance, can add other elastomericss or rubber.Can contain other packing materials or additive in the scope of not destroying the object of the invention according to purposes etc.For example, can enumerate inorganic filling material, incombustible agent, electroconductibility imparting agent, nucleator, UV light absorber, antioxidant, vibration damping agent, antiseptic-germicide, insect-proof agent, deodorizer, anti-coloring agent, thermo-stabilizer, releasing agent, anti-live agent, softening agent, lubricant, tinting material, pigment, dyestuff, whipping agent, defoamer, coupling agent etc.

Particularly, preferably in the thermoplastic resin composition of above-mentioned " miscellaneous part (II) ", add incombustible agent in order to improve flame retardancy.As incombustible agent, it is Phosphorus to enumerate Triphenyl phosphate (TPP), tricresyl phosphate (o-toluene ester), tricresyl phosphate biphenyl ester, trioctyl phosphate, ammonium polyphosphate, polyphosphonitrile, phosphoric acid ester, phosphonic acid ester, phosphinate, phosphine oxide, red phosphorus etc.; Mineral-type such as calcium aluminate, zirconium white; Nitrogen such as melamine cyanurate, polyphosphoric acid melamine class; The silicon class; Metal hydroxides classes such as aluminium hydroxide, magnesium hydroxide, calcium hydroxide, stannic hydroxide; Incombustible agents such as phenols.

" miscellaneous part (II) " for example uses flame retardancy film lining fiber-reinforced composite material board in order further to improve flame retardancy; Or use that with the binding property of miscellaneous part bonding film is covered etc. in order further to improve.When " miscellaneous part (II) " formed integrated molding, when being used for the not direct affected position of the flame retardancys such as inboard of product, the 2nd parts can have flame retardancy, also can not have flame retardancy, but the parts that preferably have flame retardancy.

" miscellaneous part (II) " when having flame retardancy, represents to be preferably V-1 or V-0 based on the flame retardancy of UL-94 standard with the measurement result of test film with essence thickness.Identical with above-mentioned fiber-reinforced composite material board, be that the measurement result of the test film of 0.1～2.0mm is expressed as V-1 or V-0 more preferably with thickness.

Above-mentioned thermoplastic resin composition considers that from the balance of mechanical characteristic, flame retardancy, mechanical characteristic preferred fortifying fibre is 5～35 weight %, and polyamide resin is that 45～94 weight %, incombustible agent are 1～20 weight %.

Integrated molding of the present invention, preferred interval thermoplastic resin composition's layer connect above-mentioned fibre reinforced composites and form with " miscellaneous part (II) ".Can connect by this thermoplastic resin composition's layer of interval and obtain good integraty.

The vertical bonding strength of preferred this connection portion is down more than the 6MPa at 25 ℃.By being set at more than the 6MPa, can make the firm connection of being connected to of integrated molding.The upper limit of vertical bonding strength is not particularly limited, and just can be useful for fully in the purposes of the present invention as long as reach 40MPa.

In order to show that fiber-reinforced composite material board of the present invention has good strength of joint, the ISO4587 bonding strength between the preferred laminated fiber-reinforced composite material board is down more than the 6MPa at 25 ℃.By being set at more than the 6MPa, can obtain the connection of firm integrated molding.The upper limit of vertical bonding strength is not particularly limited, and just can be useful for fully in the purposes of the present invention as long as reach 40MPa.

As connecting the method for above-mentioned fiber-reinforced composite material board with " miscellaneous part (II) " manufacturing integrated molding, can enumerate following method: utilize the above treatment temp bonding " miscellaneous part (II) " of fusing point of the thermoplastic resin of the thermoplastic resin composition's layer that constitutes fibre reinforced composites, connect fibre reinforced composites and other structured materials by cooling then.As making the melt bonded method of thermoplastic resin, for example, can enumerate that hot melt applies, vibration is deposited, spray up n. on the ultrasonic wave coating, laser cladding, embedding spray up n., inserts.

In addition, " miscellaneous part (II) " is when being made of metallic substance, and be preferred in advance to the priming paint processing of this parts enforcement as bonding pre-treatment.

In addition, the integrated preferred complementary ground of fiber-reinforced composite material board and " miscellaneous part (II) " and form with mechanical connections such as chimeric or embedding, bolt or screw etc.

As the purposes of integrated molding of the present invention, be applicable in the moulding product of desired strength, lightweight and flame retardancy.For example, various gears, various housings, inductor block, the LED lamp, connector, socket, resistor, relay cabinet, switch, coil bobbin, electrical condenser, optical pick-up, vibrator, various terminal strips, transformer, plug, printed-wiring board (PWB), tuner, speaker, microphone, earphone, miniature motor, head suspension (magnetic head base), power pack, semi-conductor, indicating meter, the FDD carriage, the chassis, HDD, MO, the electric motor brush carrier, notebook computer, portable phone, digital still camera (digital still cameras), PDA, electric/electronic devices such as portable MD, information equipment, electronic storage medium, the shell of acoustics etc. or parts.Wherein, especially preferably as the electric/electronic device shell.

Embodiment

Illustrate composition epoxy resin of the present invention, prepreg and carbon fibre reinforced composite with embodiment.In addition, the characteristic of the resin of each embodiment composition, the resin combination that obtains, prepreg, fibre reinforced composites is shown in table 1 and table 2 summary.

1. the making of composition epoxy resin, prepreg, carbon fibre reinforced composite

(1) uses raw material

＜Resins, epoxy 〉

" Epicoat " 807 (bisphenol f type epoxy resins, japan epoxy resin (strain) system), " Epicron " 830 (bisphenol f type epoxy resins, big Japanese ink chemical industry (strain) system), " Epicoat " 825, " Epicoat " 828, " Epicoat " 834, " Epicoat " 1001, (above be bisphenol A type epoxy resin to " Epicoat " 1002, japan epoxy resin (strain) system), (above be phenol novolak type epoxy resin to " Epicoat " 154, japan epoxy resin (strain) system), " Epicron " 152 (brominated bisphenol a type epoxy resin, epoxy equivalent (weight) is 360, brominated amount is 47%, big Japanese ink (strain) system), " Epicoat " 604 (4 officials energy epoxypropyl amine type Resins, epoxy, japan epoxy resin (strain) system), " Sumi " (registered trademark) epoxy ELM-434 (4 officials energy epoxypropyl amine type Resins, epoxy, Sumitomo Chemical (strain) system), " AER " (registered trademark) XAC4151 (isocyanic ester denaturation loop epoxy resins, Asahi Chemical Industry's (strain) system), " Sumi " (registered trademark) epoxy ESCN-220F (o-cresol phenolic epoxy varnish, Sumitomo Chemical (strain) system), " Adekaresin " (registered trademark) EPU-6 (carbamate denaturation loop epoxy resins, Asahi Chemical Industry's (strain) system)

＜solidifying agent 〉

DICY7 (Dyhard RU 100; japan epoxy resin (strain) system), " AMICURE " PN-23 (aginomoto fine chemistry (strain) system), ADH-4S (adipic dihydrazide, big tomb chemistry (strain) system), " Sumicure " (registered trademark) S (4; 4 '-diaminodiphenylsulfone(DDS); Sumitomo Chemical (strain) system), TD2131 (phenolic varnish type phenol cured agent; big Japanese ink chemical industry (strain) system), " PLYOPHEN " (registered trademark) VH-4150 (bisphenol A-type novolac resin, big Japanese ink chemical industry (strain) system)

＜curing catalyst 〉

DCMU-99 (3,4-dichlorophenyl-1, the 1-dimethyl urea, hodogaya chemical industry (strain) system), " OMICURE " (registered trademark) 24 (2,4-toluene two (dimethyl urea), PTI Japan (strain) system), " OMICURE " (registered trademark) 52 (4,4 '-methylene radical two (phenyl dimethyl urea), PTI Japan (strain) system), 2E4MZ (2-ethyl-4-methylimidazole, four countries change into (strain) system)

＜thermoplastic resin 〉

" Vinylec " K (registered trademark) (polyvinyl formal, intelligence rope (strain) system), " Sumicaexcel " (registered trademark) PES5003P (polyethersulfone, Sumitomo Chemical (strain) system), " Ultem " (registered trademark) 1000 (polyetherimide) (General Electric society system)＜surface-coated red phosphorus 〉

" NOVARED " 120 (registered trademarks, median size is 25 μ m, phosphorus content is 85%), " NOVAEXCEL " 140 (registered trademarks, median size is 28 μ m, phosphorus content is 92%), " NOVAEXCEL " F5 (registered trademark, median size is 5 μ m, and phosphorus content is 92%) (above is phosphorus chemistry industry (strain) system).Need to prove that the median size of surface-coated red phosphorus is measured by laser diffraction formula particle size distribution device SALD-200A ((strain) Shimadzu Seisakusho Ltd. system).

＜phosphoric acid ester 〉

CDP (tricresyl phosphate biphenyl ester, phosphorus content is 9.1%, and is liquid), CR-733S (resorcinol diphosphate, phosphorus content is 10.9%, and is liquid) (above is big eight chemical industry (strain) systems)

＜other incombustible agents 〉

ANTIMONY TRIOXIDE SB 203 99.8 PCT, aluminium hydroxide, magnesium oxide (Aldrich society system)

＜carbon fiber 〉

" TORAYCA " (registered trademark) T700SC-12K-50C (tensile strength is 4900MPa, and tensile elasticity rate is 235Gpa, and fiber proportion is 1.80)

(3) cured article of composition epoxy resin is made

Under reduced pressure with after the composition epoxy resin deaeration, be injection moulding in the mould of 2mm at thickness, in the hot air dryer of the solidification value that is preheated to table 1, be heating and curing.In advance thermopair is inserted in the resin in the mould, the hold-time that reaches after the solidification value with its temperature is set time.

(4) making of prepreg

Use reverse roll coater that the resin combination that modulates is coated on the interleaving paper, make resin molding.The amount of resin of resin molding per unit area is 25g/m ²

Then, becoming the fibre weight of tabular per unit area in unidirectional array is 100g/m ²Carbon fiber TORAYCA (registered trademark) T700SC-12K-50C (Dongli Ltd.'s system, tensile strength is 4900MPa, and tensile elasticity rate is 230GPa) go up two sides overlay tree adipose membrane from carbon fiber, and heating and pressurizing, make its impregnation resin combination, make the unidirectional pre-immersion material base.

(5) making of fiber-reinforced composite material board (plywood)

A. (0/90/45) s plywood

With the stacked unidirectional pre-immersion material base of the structure of (0/90/45) s, carry out heating and pressurizing by heat press with the pressure of 0.6MPa, obtain the carbon fiber-reinforced resin composite materials plate that thickness is about 0.6mm.Temperature-time is as shown in table 1.

B. (0/90) s plywood

With the stacked unidirectional pre-immersion material base of the structure of (0/90) s, carry out heating and pressurizing by heat press with the pressure of 0.6MPa, obtain the carbon fiber-reinforced resin composite materials plate that thickness is about 0.4mm.Temperature-time is as shown in table 1.

C. (0/0) plywood

With the stacked unidirectional pre-immersion material base of the structure of (0/0), carry out heating and pressurizing by heat press with the pressure of 0.6MPa, obtain the carbon fiber-reinforced resin composite materials plate that thickness is about 0.2mm.Temperature-time is as shown in table 1.

D. unidirectional ply lamination

Stacked unidirectional pre-immersion material base makes the fiber orientation equidirectional, carries out heating and pressurizing by heat press with the pressure of 0.6MPa, and making thickness respectively is the unidirectional carbon fiber reinforced composite material plate (plywood) of 1mm, 3mm.Temperature-time is as shown in table 1.

2. evaluating characteristics

(1) proportion

Based on the method for JIS 7112 records, measure the cured article of composition epoxy resin and the proportion of plywood by substitution method in the water down at 25 ℃.

(2) fiber volume fraction

Try to achieve from the proportion of the cured article of plywood, carbon fiber, composition epoxy resin.The proportion of carbon fiber is 1.8.

(3) vitrification point (Tg)

Based on the method for JIS K7121 record, use Pyris 1DSC (Perkinelmer Instruments LLC's system differential scanning calorimetry), measure the vitrification point (following province is Tg slightly) of (0/90/45) s plywood.Heat-up rate is set at 10 ℃/minute, and the intermediate point of the part of the stepped variation of DSC curve is a vitrification point.

(4) flame retardancy

Based on the UL94 standard, estimate flame retardancy by testing vertical flammability.

Be that to cut out 5 width be that 12.7 ± 0.1mm, length are the test film of 127 ± 1mm to length direction with 45 ° of directions of (0/90/45) s, (0/90) s plywood, (0/0) plywood respectively.The flame height of burner is adjusted to 19mm, will keep that end in contact flame left flame after 10 seconds under the vertical test film central authorities, record combustion time.After flame disappeared, the flame of catalytic combustion device was once more removed flame after 10 seconds immediately, measures combustion time.The molten drop (drip) if do not burn, the 1st time, the 2nd time time to fire extinguishing was in 10 seconds, and adding up in 50 seconds of 5 combustion times of test film behind 10 contact flame, then be judged to be V-0, if be to add up to 250 seconds with interior then be judged to be V-1 with the combustion time behind interior and 10 contacts of the 5 test films flame in 30 seconds combustion time.In addition,, but there is the situation of burning molten drop to be judged to be V-2, was longer than combustion time 250 seconds or burnt to test film and keep the situation at position to be judged to be defective even identical combustion time with V-1.

(5) tension test

Method based on ASTM D3039 record is carried out.

Be that bond length is after 56mm, thickness are the glass fin of 1.5mm on the two sides of unidirectional ply lamination of 1 ± 0.05mm at thickness, cutting out width is that 12.7 ± 0.1mm, length are the test film of 250 ± 5mm, test with the draw speed that 2.0mm/ divides, measure 0 ° of tensile strength.Measure number of times and be set at n=6, with mean value as 0 ° of tensile strength.

(6) Charpy impact test

Method based on JIS K7077 record is tested.From thickness is on the unidirectional ply lamination of 3 ± 0.2mm, with 0 ° of direction is that to cut out width be that 10 ± 0.2mm, length are the test film of 80 ± 1mm to length direction, making the distance between the test film supporting station is that 60mm, the moment of hammering the wraparound rotating shaft into shape are that 300kgfcm, lifting angle are 134.5 °, central authorities apply impact to test film, and the anti-angle angle of raising of the hammer after breaking from test film is obtained the charpy impact value.Need to prove,, use the rice storehouse to make Co., Ltd. of institute system Charpy impact tester as Charpy impact tester.

(7) the resin combination solidified nature is estimated

To place internal diameter on 150 ℃ the pressing machine be that 31.7mm, thickness are that (Viton (registered trademark) O shape is encircled for the tetrafluoroethylene system O shape ring of 3.3mm being heated to, E.I.Du Pont Company's system), after in O shape ring, injecting the 1.5ml resin combination, put down press, make its cure under pressure.During the adherence pressure machine, the situation that the resin cured matter shifting ground is taken out is judged to be zero after 10 minutes and 30 minutes, and the situation of distortion is judged to be *.

(8) binding property evaluation

Estimate the binding property of prepreg by contact.Suitable and the situation very easy use of binding property is 00, and binding property is big slightly or slightly little but situation that do not influence use is zero, the excessive or too small unworkable situation of binding property is judged to be *.

[comparative example 2-1]

With stirrer the raw material shown in the table 1 is mixed according to order shown below, obtain the composition epoxy resin of polyvinyl formal uniform dissolution.The numeral weight part (following identical) that resin in the table 1 is formed.

(a) each Resins, epoxy raw material and polyvinyl formal limit are heated to 150～190 ℃ of limits stirrings 1～3 hour, uniform dissolution polyvinyl formal.

(b) resin temperature is reduced to 90～110 ℃, stirred 20～40 minutes behind the interpolation phosphorus compound.

(c) resin temperature is reduced to 55～65 ℃, add Dyhard RU 100 and 3-(3, the 4-dichlorophenyl)-1, the 1-dimethyl urea after under this temperature mixing 30～40 minutes, takes out from stirrer, obtains resin combination.

Resin viscosity when this resin combination is determined at 60 ℃ according to the method described above, the result is 145Pas, the result who estimates formability be under 150 ℃, 30 minutes curable.

Use this resin combination, make the resin cured matter plate according to the method described above, measuring proportion is 1.25.

Use this resin combination, make prepreg, shown suitable binding property by aforesaid method.

Further use this prepreg to make fiber-reinforced composite material board according to the method described above.The characteristic of above-mentioned fiber-reinforced composite material board is as shown in table 1.The test film that plywood thickness is about 0.6mm is measured and is found that flame retardancy reaches V-0, obtains sufficient flame retardancy, and vitrification point is about 140 ℃, enough height, and proportion is 1.57.In addition, mechanical characteristics such as 0 ° of tensile strength and charpy impact value is good.

[comparative example 2-2～2-5]

The amount of red phosphorus incombustible agent " NOVARED " 120 is changed into 6 weight parts, 10 weight parts, 15 weight parts, 2 weight parts from 3 weight parts, in addition, with comparative example 2-1 modulating epoxy resin composition in the same manner.The characteristic of the composition epoxy resin that evaluation obtains, the viscosity of resin combination, the proportion of resin cured matter almost do not have difference.In addition, the solidified nature of resin combination is a same degree with comparative example 2-1 all.The binding property of prepreg, except that adding 15 weight parts, all the other are suitably, though it is inadequate slightly to add the binding property of 15 weight parts, are the degree that does not influence use.

Make prepreg and fiber-reinforced composite material board according to the method described above.The flame retardancy of the fiber-reinforced composite material board that obtains is measured with the test film that plywood thickness is about 0.6mm, and comparative example 2-2～2-4 reaches V-0, and comparative example 2-5 reaches V-1, and other matrix material characteristics are all well mutually with comparative example 2-1.

[comparative example 1]

Add 30 weight part red phosphorus incombustible agents " NOVARED " 120, in addition, adopt the method identical to carry out the resin modulation with comparative example 2-1, the proportion of evaluating resin viscosity and resin cured matter, arbitrary value all is higher than comparative example 2-1.Make prepreg according to the method described above, obtain binding property deficiency, unworkable prepreg.In addition, use the evaluating combined according to the method described above material behavior of prepreg obtain, mechanical characteristicies such as 0 ° of tensile strength and charpy impact value descend.

[comparative example 2～3]

Do not add or add 0.2 weight part red phosphorus incombustible agent " NOVARED " 120, in addition, adopt the method identical to make resin combination, prepreg and fiber-reinforced composite material board with comparative example 2-1.Carry out the evaluation of various characteristics according to the method described above, the flame retardancy evaluation of the plywood of arbitrary thickness is defective.

[embodiment 6～7]

Use OMICURE24 to replace DCMU, in addition, adopt the method identical to make resin combination, prepreg and fibre reinforced composites with comparative example 2-1 as curing catalyst.Carry out the evaluation of various characteristics according to the method described above, the resin combination that obtains is curable through 3 minutes under 150 ℃, and the mechanical characteristics of matrix material and comparative example 2-1～2-4 are all well.In addition, about flame retardancy, not only plywood thickness is about the test film of 0.6mm, and the test film that plywood thickness is about 0.4mm, be about 0.2mm has also reached V-0.

[comparative example 4～6]

Do not add phosphorus compound, in addition, adopt the method identical to make resin combination, prepreg and fiber-reinforced composite material board with embodiment 11,12, comparative example 2-13.Carry out the evaluation of various characteristics according to the method described above, difficult combustion is evaluated as defective.

[embodiment 8～9]

Use " NOVAEXCEL " F5 to replace red phosphorus incombustible agent " NOVARED " 120, in addition, adopt method making resin combination, prepreg and the fibre reinforced composites identical with embodiment 6,7.Carry out the evaluation of various characteristics according to the method described above, for flame retardancy, not only plywood thickness is about the test film of 0.6mm, and the test film that plywood thickness is about 0.4mm, be about 0.2mm also reaches V-0, and mechanical characteristics and embodiment 6,7 are equal.

[embodiment 10～11]

Use " NOVAEXCEL " 140 as the red phosphorus incombustible agent, in addition, adopt the method identical to make resin combination, prepreg, reach fiber-reinforced composite material board with embodiment 6,7.Carry out the evaluation of various characteristics according to the method described above, for flame retardancy, not only plywood thickness is about the test film of 0.6mm, and the test film that plywood thickness is about 0.4mm, be about 0.2mm also reaches V-0, and mechanical characteristics and embodiment 6,7 are equal good.

[embodiment 12]

The composition of change Resins, epoxy as shown in table 2, interpolation is as " OMICURE " 24,3 weight parts of curing catalyst red phosphorus incombustible agent " NOVAEXCEL " 140 as phosphorus compound, in addition, adopt the method identical to make resin combination, prepreg and fiber-reinforced composite material board with comparative example 2-1.Carry out the evaluation of various characteristics according to the method described above, 0 ° of tensile strength and charpy impact value have shown the value that is higher than comparative example 2-1.In addition, for flame retardancy, not only plywood thickness is about the test film of 0.6mm, and the test film that plywood thickness is about 0.4mm, be about 0.2mm also reaches V-0, obtains good product.

[comparative example 2-13]

In addition the composition of change composition epoxy resin as shown in table 2, adopts the method identical with comparative example 2-1 to make resin combination, prepreg and fiber-reinforced composite material board.Carry out the evaluation of various characteristics according to the method described above, 0 ° of tensile strength and charpy impact value have shown the value that is higher than comparative example 2-1, and other characteristics and comparative example 2-1 are good on an equal basis.

[comparative example 2-14]

Proportioning according to table 2, use CDP (tricresyl phosphate biphenyl ester) to replace red phosphorus incombustible agent " NOVARED " 120 as phosphorus compound, in addition, adopt the method identical to make resin combination, prepreg, fiber-reinforced composite material board with comparative example 2-1.Carry out the evaluation of various characteristics according to the method described above, the binding property of prepreg is big slightly, but for not influencing the degree of use, the Tg of matrix material and charpy impact value descend slightly, in addition, obtain the equal characteristic with comparative example 2-1.For flame retardancy, the measurement result when plywood thickness is about 0.6mm is V-0, and the measurement result when plywood thickness is about 0.4mm is V-1.

[comparative example 2-15]

Proportioning according to table 2, use CR-733S (resorcinol diphosphate) to replace red phosphorus incombustible agent " NOVARED " 120 as phosphorus compound, in addition, adopt the method identical to make resin combination, prepreg, fiber-reinforced composite material board with comparative example 2-1.Carry out the evaluation of various characteristics according to the method described above, the Tg of matrix material and charpy impact value descend slightly, in addition, obtain the equal characteristic with comparative example 2-1.For flame retardancy, the measurement result when plywood thickness is about 0.6mm is V-0, and the measurement result when plywood thickness is about 0.4mm is V-1.

[comparative example 2-16]

In addition the composition of change Resins, epoxy as shown in table 2, adopts the method identical with comparative example 2-2 to make resin combination, prepreg, fiber-reinforced composite material board.Carry out the evaluation of various characteristics according to the method described above, the viscosity of resin combination is up to 850Pas, and the binding property of the prepreg that obtains is low slightly, but for not influencing the degree of use.The matrix material characteristic, 2-2 compares with comparative example, and 0 ° of tensile strength and charpy impact value are shown as low slightly value, but for flame retardancy, the measurement result when plywood thickness is about 0.6mm is V-0, the measurement result when plywood thickness is about 0.4mm is V-1.

[comparative example 2-17]

The composition of change Resins, epoxy as shown in table 2, add the red phosphorus incombustible agent " NOVAEXCEL " 140 of 6 weight parts as phosphorus compound, in addition, estimate according to the method identical with comparative example 2-1, the viscosity of resin combination is reduced to 1.6Pas, can be observed resin and sink in the prepreg that obtains, binding property is low slightly but for not influencing the degree of use.The matrix material characteristic, 2-2 compares with comparative example, and 0 ° of tensile strength and charpy impact value are shown as low slightly value, but for flame retardancy, the measurement result when plywood thickness is about 0.6mm is V-0, the measurement result when plywood thickness is about 0.4mm is V-1.

[comparative example 7]

Add 30 weight part magnesium oxide and replace red phosphorus incombustible agent " NOVARED " 120, in addition, adopt the method identical to make resin combination, prepreg, fiber-reinforced composite material board with comparative example 2-1.Estimate various characteristics according to the method described above, the binding property deficiency of prepreg, for flame retardancy, when promptly using plywood thickness to measure as the test film of 0.6mm, the result also is V-2, and is insufficient, other thickness then are defective.And the proportion of resin cured matter is 1.43, and the proportion of matrix material is up to 1.65, and in addition, 0 ° of tensile strength and charpy impact value have shown the value that is lower than comparative example 2-1.

[comparative example 8]

Replace red phosphorus incombustible agent " NOVARED " 120, brominated epoxy resin " Epicron " 152 instead of part " Epicoat " 1001 with ANTIMONY TRIOXIDE SB 203 99.8 PCT, adopt the method identical to make resin combination, prepreg, fiber-reinforced composite material board with comparative example 2-1.Estimate various characteristics according to the method described above, though 0 ° of mechanical characteristics such as crooked elastic rate is equal, flame retardancy is V-0 for the measurement result of the test film of the about 0.6mm of plywood thickness, the measurement result that plywood thickness is about the test film of 0.4mm is V-1, but, although the resin viscosity under 60 ℃ is and the proximate value of comparative example 2-14, but the binding property surplus of prepreg, be unworkable degree.In addition, the proportion of resin cured matter is 1.37, and the proportion of matrix material is up to 1.63.

[comparative example 2-18]

Change resin combination as shown in table 4, the temperature that drops into solidifying agent is set at 55 ℃, in addition, adopts the method resin composition modulation identical with comparative example 2-1, and the viscosity of the resin combination that obtains under 60 ℃ is 63Pas.The proportion that resin combination is solidified the resin cured matter that obtained in 2 hours under 80 ℃ is 1.25.Use this resin combination to make prepreg according to the method described above, shown high slightly but the last no problem binding property of use.Stacked prepreg, 80 ℃ of moulding 2 hours, the characteristic of the composite panel that obtains was, and flame retardancy reaches V-0, obtains sufficient flame retardancy, and vitrification point is 83 ℃, and proportion is 1.58.In addition, mechanical characteristics such as 0 ° of tensile strength and charpy impact value is good.

[comparative example 2-19]

Change Resins, epoxy as shown in table 4 after interpolation " AMICURE " PN-23 stirs, further adds adipic dihydrazide and stirred 15 minutes as amine curing agent, in addition, adopts the method resin composition modulation identical with comparative example 2-18.The proportion that makes above-mentioned resin combination solidify the resin cured matter that obtained in 10 minutes under 110 ℃ is 1.25.Use this resin combination to make prepreg, binding property is big slightly but for not influencing the degree of use.The characteristic of the composite panel that stacked prepreg was obtained 110 ℃ of moulding in 10 minutes is estimated, and Tg is 105 ℃, and in addition, 2-18 is equal with comparative example.

[comparative example 9～10]

Do not add red phosphorus incombustible agent " NOVARED " 120, in addition, adopt the method identical to make resin combination, prepreg, fiber-reinforced composite material board with comparative example 2-18 and 2-19.Estimate various characteristics, difficult combustion is evaluated as defective.

[comparative example 2-20]

Use SUMICURE S as amine curing agent, " SUMICAEXCEL " PES5003P as thermoplastic resin, be set at composition as shown in table 4, in addition, adopt the method resin composition modulation identical with comparative example 2-1, the viscosity of the resin combination that obtains under 60 ℃ is 245Pas.In addition, be 1.29 at 180 ℃ of proportions that down this resin combination solidified the resin cured matter that obtained in 2 hours, use this resin combination to adopt aforesaid method to make prepreg, shown suitable binding property.The characteristic of the composite panel that stacked prepreg was obtained at 180 ℃ of compacted unders in 2 hours is estimated, and flame retardancy reaches V-0, obtains sufficient flame retardancy, and Tg is 203 ℃, and proportion is 1.59.In addition, mechanical characteristics such as 0 ° of tensile strength and charpy impact value is good.

[comparative example 2-21]

Use SUMICURE S as amine curing agent, " Ultem " 1000 as thermoplastic resin, be set at ratio of components as shown in table 4, in addition, adopt the method resin composition modulation identical with comparative example 2-1, the viscosity of the resin combination that obtains under 60 ℃ is 433Pas.In addition, be 1.25 at 125 ℃ of proportions that down this resin combination solidified the resin cured matter that obtained in 2 hours, use this resin combination to make prepreg, shown suitable binding property.The characteristic of the composite panel that stacked prepreg was obtained at 125 ℃ of compacted unders in 2 hours is estimated, and flame retardancy reaches V-0, obtains sufficient flame retardancy, and vitrification point is 130 ℃, and proportion is 1.58.In addition, mechanical characteristics such as 0 ° of tensile strength and charpy impact value is good.

[comparative example 11]

Do not add red phosphorus incombustible agent " NOVARED " 120, in addition, adopt the method identical to make resin combination, prepreg, fiber-reinforced composite material board with comparative example 2-20.Estimate various characteristics according to the method described above, difficult combustion is evaluated as defective.

[comparative example 12]

Change according to the resin ratio of components shown in the table 4, use bisphenol A-type novolac resin " PLYOPHEN " VH-4150 to replace amine curing agent, itself and red phosphorus are dropped into simultaneously, in addition, adopt the method identical to carry out the resin modulation with comparative example 2-1.The viscosity of the resin combination that obtains under 60 ℃ is 1250Pas, and is very high.Therefore can't use this resin combination to make resin molding, thereby be difficult to make prepreg.The characteristic of resin solidification plate is that proportion is up to 1.40.

[comparative example 13]

In addition the composition of change resin combination as shown in table 5, adopts the method identical with comparative example 2-1 to make resin combination, prepreg, fiber-reinforced composite material board.Carry out the evaluation of various characteristics according to the method described above, the flame retardancy of matrix material reaches V-0, but the ratio of resin cured matter and matrix material is great, and the binding property of prepreg has insufficient tendency.In addition, tensile strength, charpy impact value are low.

[comparative example 14]

With phenolic varnish type phenol cured agent TD2131 in Resins, epoxy, dissolve stir after, near 60 ℃, add tricresyl phosphate biphenyl ester as phosphorus compound, 2E4MZ as curing catalyst, mixing 30 minutes, resin composition modulation, the viscosity of the resin combination that obtains under 60 ℃ is 1090Pas, and is very high.Use this resin combination to make prepreg, the prepreg surface irregularity does not have binding property fully, and influence is used.Stacked prepreg is as shown in table 5 in the characteristic of the composite panel that 180 ℃ of moulding obtained in 3 hours, and flame retardancy reaches V-0, and vitrification point is 130 ℃, and proportion is 1.57, but the space is more in the matrix material, and 0 ° of tensile strength and charpy impact value are lower.

Provide following embodiment 22～27, comparative example 2-28, comparative example 15,16 employed evaluating and measuring methods below.

[embodiment 22]

Use OMICURE52 to replace DCMU, in addition, adopt the method identical to make resin combination, prepreg and fiber-reinforced composite material board with comparative example 2-2 as curing catalyst.Carry out the evaluation of various characteristics according to the method described above, the resin combination that obtains is promptly curable through 3 minutes under 150 ℃, and the flame retardancy mechanical characteristics and the comparative example 2-2 of matrix material are good equally.In addition, the measurement result that about flame retardancy, test film, the plywood thickness that plywood thickness is about 0.6mm is about 0.4mm, be about the test film of 0.2mm all can reach V-0.

[embodiment 23]

The red phosphorus incombustible agent is changed into NOVAEXCEL140 from NOVARED120, and increase addition, in addition, adopt method making resin combination, prepreg and the fiber-reinforced composite material board identical with embodiment 22.Carry out the evaluation of various characteristics according to the method described above, the resin combination that obtains is curable through 3 minutes under 150 ℃, and the flame retardancy mechanical characteristics of matrix material is good similarly to Example 22.

[comparative example 15]

Except that not adding phosphorus compound, adopt method making resin combination, prepreg and the fiber-reinforced composite material board identical with embodiment 22,23.Carry out the evaluation of various characteristics according to the method described above, difficult combustion is evaluated as defective.

[embodiment 24～26]

Use OMICURE24 or OMICURE52 to replace DCMU as curing catalyst, proportioning according to table 6 cooperates phosphorus compound CR-733S (resorcinol diphosphate), in addition, adopt the method identical to make resin combination, prepreg and fiber-reinforced composite material board with comparative example 2-15.Carry out the evaluation of various characteristics according to the method described above, the resin combination that obtains is curable through 3 minutes under 150 ℃, and the mechanical characteristics of matrix material obtains identical good characteristic with comparative example 2-15.In addition, the measurement result that about flame retardancy, test film, the plywood thickness that plywood thickness is about 0.6mm is about 0.4mm, be about the test film of 0.2mm all can reach V-0.

[embodiment 27]

To heat to 60 ℃ according to the resin combination of the prescription dispensing of table 6, use the resin implanter, it was injected the carbon fibre fabric (CB6343 that is heated to 150 ℃ in advance, is provided with necessary number through 1 minute, the beautiful system in east) in the metal pattern, solidified 3 minutes, adopt resin metaideophone method of forming making layer lamination, the matrix material that obtains is compared with the matrix material of the prepreg of using embodiment 24, though tensile strength, charpy impact intensity are relatively poor, but be V-0 during the stacked thickness of flame retardancy in office, good.

[comparative example 16]

With red phosphorus incombustible agent " NOVARED " 120 be changed to ANTIMONY TRIOXIDE SB 203 99.8 PCT, partly " Epicoat " 1001 is changed to brominated epoxy resin " Epicron " 152, adopts method making resin combination, prepreg, the fiber-reinforced composite material board identical with embodiment 6.Estimate various characteristics according to the method described above, 0 ° of mechanical characteristics such as crooked elastic rate is equal, for flame retardancy, measurement result when plywood thickness is about 0.6mm is V-1, V-0, but, although the resin viscosity under 60 ℃ is the value approaching with comparative example 2-14, but the binding property surplus of prepreg, and use difficulty.In addition, the proportion of resin cured matter is 1.4, and the proportion of matrix material is up to 1.64.

Below provide the method for the evaluating and measuring that adopts in following embodiment 30,36,38, comparative example 2-28,2-29,2-31～2-35,2-37,2-39,2-40, the comparative example 17～19.

(1) solubility parameter δ (SP value)

According to the data decision of following formula by the evaporation energy and the molecular volume of atom in the structural formula of resulting compound and atomic group.

δ＝(∑Δe _i/∑Δv _i) ^1/2

Δ e in the formula _iAnd Δ v _iEvaporation energy and the molecular volume of representing atom or atomic group respectively.

Need to prove that the structural formula of the compound that obtains can utilize structure analysis method commonly used such as IR, NMR, mass spectrum to determine usually.

(2) the phosphorus atom content in the matrix resin composition

Measure by combustion method-colorimetry.That is, make fiber-reinforced composite material board burning, make the gas that absorbing pure water generates with the form of ortho-phosphoric acid or various condensed phosphoric acids after, the various condensed phosphoric acids that contain in this solution are carried out becoming ortho-phosphoric acid after the oxide treatment, use colorimetric determination.Colorimetric adopts phosphovanadomolybdic acid with reagent.

(3)Tpf

With the section of tem observation fiber-reinforced composite material board, measure according to above-mentioned definition.

(4) density

Based on the method for JIS K 7112 records, 25 ℃ of density that adopt substitution method mensuration fortifying fibre composite panel in the water down.

(5) crooked elastic rate

Estimate based on ASTM D790.Fiber orientation directions with the upper layer of fiber-reinforced composite material board is a length direction, cuts out 4 test films with the different angles of 0 degree, 45 degree, 90 degree, 135 degree from the almost plane position of fiber-reinforced composite material board.Test film cut out the part that shapes such as flange part, hinge portion, jog are avoided having in the position as far as possible, if comprise above-mentioned position then be used for test after it is pruned.Maximum value in the crooked elastic rate that will can access in above-mentioned test film is as said crooked elastic rate herein.

(6) flame retardancy

Estimate flame retardancy based on the UL-94 standard by testing vertical flammability.It is that 12.7 ± 0.1mm, length are the test film of 127 ± 1mm that fiber-reinforced composite material board after the moulding cuts out 5 width.The direction that cuts out is a length direction for the fiber orientation directions with the upper layer of fiber-reinforced composite material board.About the processing of thickness, as mentioned above, in each embodiment comparative example, because the thickness of any determination object is below the 1.6mm, so directly measure with its thickness.With the altitude mixture control of the blue flame that does not have yellow internal flame of burner is 19.5mm (3/4inch), and the central part contact flame of lower end that keeps vertical test film after 10 seconds, is left flame, the time of record fray-out of flame.After the fray-out of flame, identical with the 1st time, the 2nd contact flame 10 seconds leaves flame again, measures combustion time, according to the grade of the following division flame retardancy of incendiary situation.

V-0:5 opens the time that every of test film contact flame amounts to for 2 times behind 10 contact flame till disappearing to flame and adds up in 50 seconds, and the time till disappearing to flame of contacting respectively behind the flame is in 10 seconds, and the molten drop (drip) that do not burn.

V-1: though do not reach above-mentioned V-0, the time till but every contact of 5 test films flame amounts to for 2 times behind 10 contact flame and to disappear to flame added up in 250 seconds, the time that contacts respectively behind the flame till disappearing to flame is in 30 seconds, and the molten drop (drip) that do not burn.

V-2:5 opens the time that every of test film contact flame amounts to for 2 times behind 10 contact flame till disappearing to flame and adds up in 250 seconds, and the time that contacts respectively behind the flame till disappearing to flame is in 30 seconds, and burning molten drop (drip) is arranged.

OUT:5 opens the time that every of test film contact flame amounts to for 2 times behind 10 contact flame till disappearing to flame and totals over 250 seconds, or the time that contacts respectively behind the flame till disappearing to flame surpass 30 seconds, or burn to the test film maintaining part.

Be that flame retardancy is in proper order for the order of V-0＞V-1＞V-2＞OUT.

" miscellaneous part (II) " carried out same operation.

(7) electromagnetic wave shielding performance

Estimate according to Advantest (advantest) method.Cut out the flat board of 120mm * 120mm as test film from fiber-reinforced composite material board.During evaluation, make test film be in absolute dry condition (moisture content is below 0.1%), four limits coating conductive paste (Teng Cang changes into (strain) system DOTITE), thorough drying conductive paste.

Test film is clipped in the shielded cell, utilize spectrum analyzer measure frequency for the electromagnetic wave shielding performance of 1GHz (unit: dB), as electromagnetic wave shielding performance.This numerical value is high more, shows that electromagnetic wave shielding performance is good more.

(8) vertical bonding strength

From the fiber-reinforced composite material board of integrated molding and the connecting portion of " miscellaneous part (II) ", cut out 10mm * 10mm size and estimate sample (Fig. 3) as vertical bonding strength.

Then, sample is fixed in the anchor clamps (9a, 9b among Fig. 3) of determinator.As determinator, use " INSTRON " (registered trademark) 5565 type universal testing machines (INSTRONJAPAN (strain) system).In addition, about fixing of test portion, can directly be clipped in by the moulding product that the chuck of INSTRON is controlled and carry out tension test on the chuck, can not control can be on formed body coating adhesive (Three bond1782, Three bond Co., Ltd. system), under 23 ± 5 ℃, 50 ± 5%RH, place and made itself and anchor clamps bonding in 4 hours.

Tension test is carried out under 25 ℃ atmosphere temperature in the testing laboratory that can regulate atmosphere temperature.Before on-test, test film is put in the testing laboratory, keeps the state at least 5 minutes that does not apply tension test load, then, on test film, dispose thermopair, carry out tension test after confirming it and atmosphere temperature being identical.

The draw speed that tension test divides with 1.27mm/ stretches from 90 ° of directions of both adhesive faces, removes value that this maximum load obtains as vertical bonding strength (unit: MPa) with bond area.In addition, the test portion number is set at n=5.

(9) Tmax estimates

At first estimate the vitrification point of fiber-reinforced composite material board according to (3), after fixing is 1 hour under the temperature of its vitrification point+20 ℃.Fiber-reinforced composite material board behind the after fixing is confirmed residual thermal value through DSC, confirms not have residual heating back to estimate vitrification point according to (3), is Tmax.

(10) ISO4587 bonding strength

The test film that is used to carry out determining bonding strength is prepared as described below.

The shape of test film and size are based on the regulation of ISO4587 as shown in Figure 6.The length 18 of test film is that 100mm, width 19 are 25mm.Make 2 test films 20.When being difficult to cut out the test film of above-mentioned size, can replace with the test film that the size that shape shown in Figure 6 is scaled forms from fiber-reinforced composite material board.

Ready 2 test films 20 are overlapped, make separately be that the coating of main component becomes connection section with the thermoplastic resin.The length 22 of this connection section 21 is 12.5mm.The abundant fused temperature of resin with two test films 20 are heated to coating connects both, the cooling of limit gripper edge, and the connector that both are connected to form is the tension test sheet.Particularly, the pressure with 0.6MPa keeps connecting in 1 minute under than the high 50 ℃ high temperature of the fusing point of coating resin.This tension test sheet is used for tension test.Near affirmation (boundary vicinity) link position is destroyed, with this breaking tenacity (kN) with the connection section surface-area remove value as strength of joint (MPa).

In addition, the mode chart of the computer casing that the embodiment of the invention is made as shown in Figure 4, the mode chart of the indicating meter of portable phone is as shown in Figure 5.

[comparative example 2-28]

(parts (I))

The prepreg of using comparative example 2-1 to make is made as followsly.

Prepare many above-mentioned prepreg, be laminated into the structure of (0 °/90 °/0 °/0 °/90 °/0 °).

In the superiors of the duplexer of above-mentioned prepreg, as the coating thermoplastic resin, the thickness that stacked 1 terpolyamide resin by polyamide 6/66/610 (east beautiful (strain) system CM4000,150 ℃ of fusing points) forms is the film of 40 μ m.

With this duplexer with heat press 160 ℃ of following preheatings 5 minutes, the molten thermoplastic resin, again the pressure limit that applies 0.6MPa, limit 150 ℃ down heating made its curing in 30 minutes.After solidifying end, cooling at room temperature, the demoulding obtains the fiber-reinforced composite material board that thickness is 0.63mm.

The Tmax of this fiber-reinforced composite material board is 142 ℃, and Tmax-Tg is 2 ℃.

In addition, the flame retardancy of this fiber-reinforced composite material board is V-0, and the maximum ga(u)ge Tpf of the concaveconvex shape of coating is 25 μ m.In addition, Tsur is 20 μ m.The ISO4587 bonding strength is 25MPa.

(" miscellaneous part (II) and integrated ")

Above-mentioned fiber-reinforced composite material board is cut into the size of regulation, be inserted into the computer casing spray up n. with in the metal pattern, by spray up n. east beautiful (strain) system macrofiber particle TLP 1146 (polyamide resin base materials, carbon fiber content is 20 weight %) at the surface forming with thermoplastic resin coating and integrated " miscellaneous part (II) " of fiber-reinforced composite material board, obtain the integrated molding of computer casing.Spray-moulding machine uses the system J350EIII of JSW's (strain), and spray up n. is that 60rpm, cylinder temperature are that 280 ℃, jet velocity are that 90mm/sec, spraying pressure are that 200MPa, back pressure are that 0.5MPa, metal pattern temperature are to carry out under 55 ℃ at the spiral revolution.In addition, adopt other approach, ground same as described above molding thickness is the 2nd parts of 1.0mm, and the result who estimates flame retardancy is V-0.Trial is to the evaluation of the vertical bonding strength of the integrated molding that obtains, and the result is under 6MPa, and the part through adhesive between test materials and the anchor clamps is peeled off prior to the connection portion, and hence one can see that, and vertical bonding strength is more than the 6MPa.

[comparative example 2-29]

(parts (I))

The prepreg of using comparative example 2-2 to make is according to making fiber-reinforced composite material board with comparative example 2-28 identical operations.

The thickness of this fiber-reinforced composite material board is 0.62mm, and Tmax is 142 ℃, and Tmax-Tg is 2 ℃.

In addition, the flame retardancy of this fiber-reinforced composite material board is V-0, and the maximum ga(u)ge Tgf of the concaveconvex shape of coating is 25 μ m.Tsur is 20 μ m.The ISO4587 bonding strength is 25MPa.

(" miscellaneous part (II) " and integrated)

Use above-mentioned fiber-reinforced composite material board, make the integrated molding of computer casing according to the method identical with comparative example 2-28.

Trial is estimated the vertical bonding strength of the integrated molding that obtains, and the result is under 6MPa, and the part through adhesive between test materials and the anchor clamps is peeled off prior to stick portion, and hence one can see that, and vertical bonding strength is more than the 6MPa.

[embodiment 30]

(parts (I))

The prepreg of using embodiment 7 to make is made fiber-reinforced composite material board according to the method identical with comparative example 2-28.

The thickness of this fiber-reinforced composite material board is 0.60mm, and Tmax is 142 ℃, and Tmax-Tg is 4 ℃.

In addition, the flame retardancy of this fiber-reinforced composite material board is V-0, and the maximum ga(u)ge Tpf of the concaveconvex shape of coating is 25 μ m.Tsur is 20 μ m.The ISO4587 bonding strength is 25MPa.

(" miscellaneous part (II) " and integrated)

Use above-mentioned fiber-reinforced composite material board,, make the integrated molding of computer casing according to the method identical with comparative example 2-28.

Trial is estimated the vertical bonding strength of the integrated molding that obtains, and the result is under 6MPa, and the part through adhesive between test materials and the anchor clamps is peeled off prior to the connection portion, and hence one can see that, and vertical bonding strength is more than the 6MPa.

[comparative example 2-31]

(" parts (I) ")

The prepreg of using comparative example 2-3 to make is made fiber-reinforced composite material board according to the method identical with comparative example 2-28.

The thickness of this fiber-reinforced composite material board is 0.61mm, and Tmax is 142 ℃, and Tmax-Tg is 2 ℃.

In addition, the flame retardancy of this fiber-reinforced composite material board is V-0, and the maximum ga(u)ge Tpf of the concaveconvex shape of coating is 25 μ m.Tsur is 20 μ m.The ISO4587 bonding strength is 25MPa.

(" miscellaneous part (II) " and integrated)

Use above-mentioned fiber-reinforced composite material board,, make the integrated molding of computer casing according to the method identical with comparative example 2-28.

Trial is estimated the vertical bonding strength of the integrated molding that obtains, and the result is under 6MPa, and the part through adhesive between test materials and the anchor clamps is peeled off prior to the connection portion, and hence one can see that, and vertical bonding strength is more than the 6MPa.

[comparative example 2-32]

(parts (I))

The fiber-reinforced composite material board that uses comparative example 2-1 to make.

The thickness of fiber-reinforced composite material board is 0.63mm, and Tmax is 142 ℃, and Tmax-Tg is 2 ℃.In addition, the flame retardancy of this fiber-reinforced composite material board is V-0.

(" miscellaneous part (II) " and integrated)

The metal spacer that is processed into the regulation shape is embedded the spray up n. metal pattern be used for computer casing, after this till spray up n. all according to carrying out with comparative example 2-28 identical operations, make the 2nd parts.With the 2nd parts that obtain and the fiber-reinforced composite material board that above-mentioned fiber-reinforced composite material board is set at the regulation shape identical with above-mentioned metal spacer by coating as the Three Bond (strain) of tackiness agent system binary liquid shape acrylic adhesives 3921/3926 carry out bonding after, place 24hr at normal temperatures, make the integrated molding of computer casing.

The vertical bonding strength of the connection portion of the computer casing that obtains is 5MPa.

[comparative example 2-33]

(parts (I))

The prepreg of using comparative example 2-1 to make, the structure of stratification (0 °/90 °/0 °/90 °/0 °/0 °/90 °/0 °/90 °/0 °), later and comparative example 2-28 makes fiber-reinforced composite material board in the same manner.

The thickness of fiber-reinforced composite material board is 1.05mm, and Tmax is 142 ℃, and Tmax-Tg is 2 ℃.

In addition, the flame retardancy of this fiber-reinforced composite material board is V-0.The maximum ga(u)ge Tpf of the concaveconvex shape of coating is 25 μ m.The ISO4587 bonding strength is 25MPa.

(" miscellaneous part (II) " and integrated)

Use above-mentioned fiber-reinforced composite material board,, make the integrated molding of computer casing according to the method identical with comparative example 2-28.

Trial is estimated the vertical bonding strength of the integrated molding that obtains, and the result is under 6MPa, and the part through adhesive between test materials and the anchor clamps is peeled off prior to the connection portion, and therefore vertical as can be known bonding strength is more than the 6MPa.

[comparative example 2-34]

(parts (I))

At first, will utilize 2 extrusion machines to mix the particle extrusion forming that 95 weight part terpolymer polyamide resin CM4000 and 5 weight part melamine cyanurates (MC-440 produces chemical society system daily) obtain, obtain the film that thickness is 40 μ m.In addition the film that use obtains, operates the making fiber-reinforced composite material board with comparative example 2-28 in the same manner as coating.

The thickness of this fiber-reinforced composite material board is 0.64mm, and Tmax is 142 ℃, and Tmax-Tg is 2 ℃.

In addition, the flame retardancy of this fiber-reinforced composite material board is V-0.The maximum ga(u)ge Tpf of the concaveconvex shape of coating is 25 μ m.Tsur is 20 μ m.The ISO4587 bonding strength is 20MPa.

(" miscellaneous part (II) " and integrated)

Use above-mentioned fiber-reinforced composite material board,, make the integrated molding of computer casing according to the method identical with comparative example 2-28.

Trial is estimated the vertical bonding strength of the integrated molding that obtains, and the result is under 6MPa, and the part through adhesive between test materials and the anchor clamps is peeled off prior to the connection portion, and therefore vertical as can be known bonding strength is more than the 6MPa.

[comparative example 2-35]

(parts I)

Prepare the prepreg that many comparative example 2-1 make, be laminated into the structure of (0 °/90 °/0 °/0 °/90 °/0 °).

In the superiors of the stacked body of above-mentioned prepreg, as the coating thermoplastic resin, the thickness that stacked 1 terpolymer polyamide resin by polyamide 6/66/610 (east beautiful (strain) system CM4000, fusing point is 150 ℃) forms is the film of 40 μ m.Further be used to prevent that in stacked 1 conduct of reverse side (orlop) thickness that is formed by Sumitomo Chemical (strain) system " Bond fast " (VC-40, fusing point are 95 ℃) of the 3rd parts of wildness from being the film of 40 μ m.

With this duplexer with heat press 160 ℃ of following preheatings 5 minutes, the molten thermoplastic resin, again the pressure limit that applies 0.6MPa, limit 150 ℃ down heating made its curing in 30 minutes.After solidifying end, cooling at room temperature, the demoulding obtains the fiber-reinforced composite material board that thickness is 0.64mm.

The Tmax of this fiber-reinforced composite material board is 142 ℃, and Tmax-Tg is 2 ℃.

In addition, the flame retardancy of this fiber-reinforced composite material board is V-0, and the maximum ga(u)ge Tpf of the concaveconvex shape of coating is 25 μ m.Tsur is 20 μ m.The ISO4587 bonding strength is 25MPa.

(" miscellaneous part (II) " and integrated)

Above-mentioned fiber-reinforced composite material board is embedded spray up n. with in the metal pattern, utilize spray up n. east beautiful (strain) system macrofiber particle TLP 1146 (polyamide resin base material, carbon fiber content 20 weight %), at the surface forming with thermoplastic resin coating (aramid layer) and integrated " miscellaneous part (II) " of fiber-reinforced composite material board, make the integrated molding of computer casing.

Trial is estimated the vertical bonding strength of the integrated molding that obtains, and the result is under 6MPa, and the part through adhesive between test materials and the anchor clamps is peeled off prior to the connection portion, and therefore vertical as can be known bonding strength is more than the 6MPa.

[embodiment 36]

(parts (I))

Use the fiber-reinforced composite material board of the thickness of comparative example 8 making as 0.62mm.

The Tmax of this fiber-reinforced composite material board is 150 ℃, and Tmax-Tg is 4 ℃.In addition, the flame retardancy of this fiber-reinforced composite material board is V-0.

(" miscellaneous part (II) " and integrated)

Use above-mentioned fiber-reinforced composite material board,, make the integrated molding of computer casing according to the method identical with comparative example 2-32.The vertical bonding strength of the connection portion of the computer casing that obtains is 5MPa.

[comparative example 2-37]

(parts (I))

The fiber-reinforced composite material board that uses comparative example 2-15 to make.

The thickness of this fiber-reinforced composite material board is 0.6mm, and Tmax is 142 ℃, and Tmax-Tg is 3 ℃.

In addition, the flame retardancy of this fiber-reinforced composite material board is V-0.

(" miscellaneous part (II) " and integrated)

Use above-mentioned fiber-reinforced composite material board,, make the integrated molding of computer casing according to the method identical with comparative example 2-32.The vertical bonding strength of the connection portion of the computer casing that obtains is 5MPa.

[embodiment 38]

(parts (I))

The fiber-reinforced composite material board that uses embodiment 27 to make.

The thickness of this fiber-reinforced composite material board is 0.62mm, and Tmax is 136 ℃, and Tmax-Tg is 5 ℃.

In addition, the flame retardancy of this fiber-reinforced composite material board is V-0.

(" miscellaneous part (II) " and integrated)

Use above-mentioned fiber-reinforced composite material board,, make the integrated molding of computer casing according to the method identical with comparative example 2-32.The vertical bonding strength of the connection portion of the computer casing that obtains is 5MPa.

[comparative example 2-39]

(parts (I))

Make fiber-reinforced composite material board in the same manner with comparative example 2-28.

The thickness of fiber-reinforced composite material board is 0.63mm, and Tmax is 142 ℃, and Tmax-Tg is 2 ℃.

In addition, the flame retardancy of this fiber-reinforced composite material board is V-0, and the maximum ga(u)ge Tpf of the concaveconvex shape of coating is 25 μ m.Tsur is 20 μ m.The ISO4587 bonding strength is 25MPa.

(" miscellaneous part (II) " and integrated)

Above-mentioned fiber-reinforced composite material board is cut into prescribed level, embeds the spray up n. metal pattern that is used for the cellular phone display shell, after this make the integrated molding of cellular phone display shell in the same manner with comparative example 2-28.

Trial is estimated the vertical bonding strength of the integrated molding that obtains, and the result is under 6MPa, and the part through adhesive between test materials and the anchor clamps is peeled off prior to the connection portion, and therefore vertical as can be known bonding strength is more than the 6MPa.

[comparative example 2-40]

(parts (I))

Make fiber-reinforced composite material board in the same manner with comparative example 2-28.

The thickness of this fiber-reinforced composite material board is 0.63mm, and Tmax is 142 ℃, and Tmax-Tg is 2 ℃.

In addition, the flame retardancy of this fiber-reinforced composite material board is V-0, and the maximum ga(u)ge Tpf of the concaveconvex shape of coating is 25 μ m.Tsur is 20 μ m.The ISO4587 strength of joint is 25MPa.

(" miscellaneous part (II) " and integrated)

Adopt additive method, use east beautiful (strain) system macrofiber particle TLP 1146, form the 2nd parts through spray up n..Above-mentioned fiber-reinforced composite material board is cut into the size of regulation, use the ultrasonic wave fusion machine frequency as 20kHz, pressure as the condition of 1MPa under with the 2nd parts carry out integrated, as the cellular phone display shell.At this moment, the 2nd parts are connected with the thermoplastic resin coating of fiber-reinforced composite material board and are integrated.

Trial is estimated the vertical bonding strength of the integrated molding that obtains, and the result is under 6MPa, and the part through adhesive between test materials and the anchor clamps is peeled off prior to the connection portion, and therefore vertical as can be known bonding strength is more than the 6MPa.

[comparative example 17]

(parts (I))

The prepreg of using comparative example 3 to make is made fiber-reinforced composite material board in the same manner with comparative example 2-28.

The thickness of this fiber-reinforced composite material board is 0.63mm, and Tmax is 142 ℃, and Tmax-Tg is 2 ℃.

In addition, the flame retardancy of this fiber-reinforced composite material board is defective, and the maximum ga(u)ge Tpf of the concaveconvex shape of coating is 25 μ m.Tsur is 20 μ m.The ISO4587 bonding strength is 25MPa.

(" miscellaneous part (II) ")

Use above-mentioned fiber-reinforced composite material board, make the integrated molding of computer casing in the same manner with comparative example 2-28.

Trial is estimated the vertical bonding strength of the integrated molding that obtains, and the result is under 6MPa, and the part through adhesive between test materials and the anchor clamps is peeled off prior to the connection portion, and therefore vertical as can be known bonding strength is more than the 6MPa.

[comparative example 18]

(parts (I))

The prepreg of using comparative example 3 to make is made fiber-reinforced composite material board in the same manner with comparative example 2-28.

The thickness of this fiber-reinforced composite material board is 0.63mm, and Tmax is 142 ℃, and Tmax-Tg is 2 ℃.

In addition, the flame retardancy of this fiber-reinforced composite material board is defective.

(" miscellaneous part (II) " and integrated)

2-40 operates in the same manner with comparative example, makes the 2nd parts in addition.

With above-mentioned fiber-reinforced composite material board and the 2nd parts that obtain by coating as the Three Bond (strain) of tackiness agent make binary liquid shape acrylic adhesives 3921/3926 carry out bonding after, place 24hr at normal temperatures, make the integrated molding of cellular phone display shell.

The vertical bonding strength of the connection portion of the cellular phone display shell that obtains is 5MPa.

[comparative example 19]

(parts (I))

Curing and molding time are 2 minutes, in addition, operate in the same manner with embodiment 11, make fiber-reinforced composite material board.

The thickness of this fiber-reinforced composite material board is 0.64mm, and Tmax is 142 ℃, and Tmax-Tg is 63 ℃.

In addition, the flame retardancy of this fiber-reinforced composite material board is defective.

(" miscellaneous part (II) " and integrated)

Use above-mentioned fiber-reinforced composite material board, 2-32 operates in the same manner with comparative example, makes the computer casing integrated molding.The vertical bonding strength of the connection portion of the computer casing that obtains is 5MPa.

As implied above, the result at embodiment 30,36,38, comparative example 2-28,2-29,2-31～2-35,2-37,2-39,2-40, middlely can obtain good flame retardancy, and flame retardancy is poor in the comparative example 17～19.

Claims (29)

1, a kind of epoxy resin composition for carbon-fiber-reinforced composite material contains following compositions [A], [B], [C], [D], and the content of composition [C] counts 0.2～15 weight % with phosphorus atom concentration,

[A] Resins, epoxy,

[B] as the Dyhard RU 100 of amine curing agent,

[C] phosphorus compound,

The compound that contains 2 above urea keys in [D] 1 molecule as curing catalyst.

2, epoxy resin composition for carbon-fiber-reinforced composite material as claimed in claim 1 is characterized in that, the viscosity under 60 ℃ is 10～700Pas.

3, epoxy resin composition for carbon-fiber-reinforced composite material as claimed in claim 1 or 2 is characterized in that, [C] contains red phosphorus as composition.

4, epoxy resin composition for carbon-fiber-reinforced composite material as claimed in claim 3 is characterized in that, described red phosphorus is by metal hydroxides and/or resin-coated red phosphorus.

5, epoxy resin composition for carbon-fiber-reinforced composite material as claimed in claim 1 or 2, it is characterized in that above-mentioned [D] curing catalyst is 1,1 '-4 (methyl-metaphenylene) two (3, the 3-dimethyl urea) and/or 4,4 '-methylene radical two (phenyl dimethyl urea).

6, epoxy resin composition for carbon-fiber-reinforced composite material as claimed in claim 3, it is characterized in that above-mentioned [D] curing catalyst is 1,1 '-4 (methyl-metaphenylene) two (3, the 3-dimethyl urea) and/or 4,4 '-methylene radical two (phenyl dimethyl urea).

7, epoxy resin composition for carbon-fiber-reinforced composite material as claimed in claim 4, it is characterized in that above-mentioned [D] curing catalyst is 1,1 '-4 (methyl-metaphenylene) two (3, the 3-dimethyl urea) and/or 4,4 '-methylene radical two (phenyl dimethyl urea).

8, epoxy resin composition for carbon-fiber-reinforced composite material as claimed in claim 1 or 2 is characterized in that, the proportion of described epoxy resin composition for carbon-fiber-reinforced composite material is below 1.35.

9, epoxy resin composition for carbon-fiber-reinforced composite material as claimed in claim 3 is characterized in that, the proportion of described epoxy resin composition for carbon-fiber-reinforced composite material is below 1.35.

10, epoxy resin composition for carbon-fiber-reinforced composite material as claimed in claim 4 is characterized in that, the proportion of described epoxy resin composition for carbon-fiber-reinforced composite material is below 1.35.

11, epoxy resin composition for carbon-fiber-reinforced composite material as claimed in claim 5 is characterized in that, the proportion of described epoxy resin composition for carbon-fiber-reinforced composite material is below 1.35.

12, epoxy resin composition for carbon-fiber-reinforced composite material as claimed in claim 6 is characterized in that, the proportion of described epoxy resin composition for carbon-fiber-reinforced composite material is below 1.35.

13, epoxy resin composition for carbon-fiber-reinforced composite material as claimed in claim 7 is characterized in that, the proportion of described epoxy resin composition for carbon-fiber-reinforced composite material is below 1.35.

14, epoxy resin composition for carbon-fiber-reinforced composite material as claimed in claim 1 or 2 is characterized in that, described epoxy resin composition for carbon-fiber-reinforced composite material can 150 ℃ following 30 minutes with interior curing.

15, epoxy resin composition for carbon-fiber-reinforced composite material as claimed in claim 3 is characterized in that, described epoxy resin composition for carbon-fiber-reinforced composite material can 150 ℃ following 30 minutes with interior curing.

16, epoxy resin composition for carbon-fiber-reinforced composite material as claimed in claim 4 is characterized in that, described epoxy resin composition for carbon-fiber-reinforced composite material can 150 ℃ following 30 minutes with interior curing.

17, epoxy resin composition for carbon-fiber-reinforced composite material as claimed in claim 5 is characterized in that, described epoxy resin composition for carbon-fiber-reinforced composite material can 150 ℃ following 30 minutes with interior curing.

18, epoxy resin composition for carbon-fiber-reinforced composite material as claimed in claim 6 is characterized in that, described epoxy resin composition for carbon-fiber-reinforced composite material can 150 ℃ following 30 minutes with interior curing.

19, epoxy resin composition for carbon-fiber-reinforced composite material as claimed in claim 7 is characterized in that, described epoxy resin composition for carbon-fiber-reinforced composite material can 150 ℃ following 30 minutes with interior curing.

20, epoxy resin composition for carbon-fiber-reinforced composite material as claimed in claim 8 is characterized in that, described epoxy resin composition for carbon-fiber-reinforced composite material can 150 ℃ following 30 minutes with interior curing.

21, epoxy resin composition for carbon-fiber-reinforced composite material as claimed in claim 9 is characterized in that, described epoxy resin composition for carbon-fiber-reinforced composite material can 150 ℃ following 30 minutes with interior curing.

22, epoxy resin composition for carbon-fiber-reinforced composite material as claimed in claim 10 is characterized in that, described epoxy resin composition for carbon-fiber-reinforced composite material can 150 ℃ following 30 minutes with interior curing.

23, epoxy resin composition for carbon-fiber-reinforced composite material as claimed in claim 11 is characterized in that, described epoxy resin composition for carbon-fiber-reinforced composite material can 150 ℃ following 30 minutes with interior curing.

24, epoxy resin composition for carbon-fiber-reinforced composite material as claimed in claim 12 is characterized in that, described epoxy resin composition for carbon-fiber-reinforced composite material can 150 ℃ following 30 minutes with interior curing.

25, epoxy resin composition for carbon-fiber-reinforced composite material as claimed in claim 13 is characterized in that, described epoxy resin composition for carbon-fiber-reinforced composite material can 150 ℃ following 30 minutes with interior curing.

26, a kind of prepreg is characterized in that, described prepreg makes that the described epoxy resin composition for carbon-fiber-reinforced composite material of each in the impregnation claim 1～25 obtains in the carbon fiber.

27, prepreg as claimed in claim 26 is characterized in that, the fiber volume containing ratio is 30～95%.

28, a kind of fiber-reinforced composite material board, it is characterized in that resin cured matter and carbon fiber that described fiber-reinforced composite material board obtains by making each the described epoxy resin composition for carbon-fiber-reinforced composite material curing in the claim 1～25 constitute.

29, a kind of fiber-reinforced composite material board is characterized in that, described fiber-reinforced composite material board makes claim 26 or 27 described prepreg curing and obtains.

Images