CN102108185B - Epoxy matrix resin and prepreg and preparation method thereof and device for preparation thereof - Google Patents
Epoxy matrix resin and prepreg and preparation method thereof and device for preparation thereof Download PDFInfo
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- CN102108185B CN102108185B CN2010106116287A CN201010611628A CN102108185B CN 102108185 B CN102108185 B CN 102108185B CN 2010106116287 A CN2010106116287 A CN 2010106116287A CN 201010611628 A CN201010611628 A CN 201010611628A CN 102108185 B CN102108185 B CN 102108185B
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Abstract
The invention discloses an epoxy matrix resin, a prepreg, a preparation method of the prepreg and a device for preparation of the prepreg, in order to solve the problem of poor performance of an epoxy matrix resin curing substance caused by uneven toughening phase state even no phase separation in the traditional epoxy matrix resin curing product, the problem of complex technique of the traditional preparation method of the prepreg and relatively imprecise control on the resin content in the prepreg, and the problem of high manufacturing cost of the traditional device for preparing the prepreg. The epoxy matrix resin is prepared from a phenolic epoxy resin, a bisphenol A epoxy resin, a core shell polymer, a curing agent and a curing accelerator; the prepreg is prepared from the epoxy matrix resin and fiber woven cloth; and the prepreg is prepared through the device for producing the prepreg by a heat fusion method. After and before the resin is cured, the toughening phase state is not changed and is uniformly dispersed; and the toughening phase state effect is good and stable. The mechanical property of the composite material obtained by curing with the prepreg is high.
Description
Technical field
The present invention relates to the device of epoxy matrix resin, prepreg and preparation method thereof and the employing of preparation prepreg.
Background technology
The epoxy/glass fibre composite has that light weight, intensity are high, modulus is big, good corrosion resistance, electrical property are excellent, starting material extensively, characteristics such as easy, the production efficiency height of good manufacturability, machine-shaping; And have the material designability and reach specific functionality such as characteristics such as shielding electromagnetic wave, noise reduction by force; Become irreplaceable important materials in national economy, national defense construction and the development in science and technology, be to use one of the widest matrix material at present at present.
Solidification value is low because of having for the intermediate temperature setting epoxy matrix resin, shaping cycle is short, can satisfy advantage such as requirements storage period has obtained widely-used in the glass fibre reinforced composion prepreg.But because not toughness reinforcing epoxy matrix resin cured product is more crisp, by its matrix material of processing because the destruction that the premature failure of epoxy matrix resin causes matrix material.Therefore, the toughening modifying of epoxy matrix resin is particularly important.
At present, epoxy matrix resin can carry out toughness reinforcing through rubber elastomer, thermoplastics etc.Also there is latest information to show, epoxy resin carried out the toughness reinforcing good effect that obtained with hyperbranched polymer.No matter traditional fluid rubber or thermoplastics, the blend of they and epoxy resin all can be separated in curing, and under normal circumstances toughner is separated out from blend, and is separated and curing reaction is competitive process.Therefore, the aggregated structure of cured article and performance depend on toughner character and the consumption thereof that solidifies standard, interpolation.Have only strict these factors of control, just can reach optimum toughening effect.
Prepreg is the middle base material of preparation matrix material, and its quality directly has influence on the quality of composite element.The production technique of prepreg mainly contains solution dipping method and hot melt process technology.With respect to solution method, the hot melt process advantage has: 1. prepreg resin content control is accurately higher; 2. volatile content is low; 3. environmental protection, the problem of nonpollution environment; 4. the matrix material wet-hot aging performance that makes is good, and production rate is fast, and efficient is high.Therefore, hot melt process prepreg technology is the developing direction of current prepreg.
Existing hot melt process prepreg mostly adopts glued membrane machine and hot melt preimpregnation machine two portions production equipment; At first with prepreg matrix resin film forming on the glued membrane machine; Then with glued membrane and fibre knitting cloth on the hot melt preimpregnation machine with certain temperature, speed and pressure under compound preimpregnation, can control prepreg resin content through the film thickness adjustment; Also having a kind of technology is that fibre knitting cloth is flooded the matrix resin of hot melt under the transmission mechanism effect, and then is transferred on the removing device and removes on the fibre knitting cloth unnecessary resin and control prepreg resin content.The said apparatus manufacturing cost is high, complex manufacturing, and prepreg resin content is controlled than out of true.
Summary of the invention
The objective of the invention is in order to solve the phenomenon that toughness reinforcing phase state in the existing epoxy matrix resin cured product is inhomogeneous, even be not separated; Cause the epoxy matrix resin condensate performance poor; Satisfied not the composite property requirement; And in the preparing method's complex process of existing prepreg, prepreg resin content control than out of true; And the high problem of device manufacturing cost of existing preparation prepreg, the invention provides epoxy matrix resin, prepreg and preparation method thereof and prepare the device that prepreg adopts.
Epoxy matrix resin of the present invention is processed by 40 parts of phenol aldehyde type epoxy resins, 60 parts of bisphenol A epoxide resins, 2～10 parts of core-shell polymers, 15～24 parts solidifying agent and 3.0～6.0 parts curing catalyst by mass parts; Said solidifying agent is Dyhard RU 100 and 4; The cooperation solidifying agent of 4 '-diaminodiphenylsulfone(DDS); Wherein 4, the mass parts of 4 '-diaminodiphenylsulfone(DDS) and Dyhard RU 100 be respectively 18 parts and 6 parts, 14 parts and 7 parts, 10 parts and 8 parts, or 6 parts and 9 parts; Said curing catalyst is organic ureas or derivatives thereof.
The preparation method of epoxy matrix resin of the present invention realizes through following steps: one, take by weighing 40 parts of phenol aldehyde type epoxy resins, 60 parts of bisphenol A epoxide resins, 2～10 parts of core-shell polymers, 15～24 parts solidifying agent and 3.0～6.0 parts curing catalyst by mass parts; Said solidifying agent is Dyhard RU 100 and 4; The cooperation solidifying agent of 4 '-diaminodiphenylsulfone(DDS); Wherein 4; The mass parts of 4 '-diaminodiphenylsulfone(DDS) and Dyhard RU 100 is respectively 18 parts and 6 parts, 14 parts and 7 parts, 10 parts and 8 parts, perhaps 6 parts and 9 parts, and said curing catalyst is organic ureas or derivatives thereof; Two, 40 parts of phenol aldehyde type epoxy resins that step 1 taken by weighing, 60 parts of bisphenol A epoxide resins and 2～10 parts of core-shell polymers mix and add in the container; Under agitation condition, be heated to 150 ℃ then; Add again that step 1 takes by weighing 4,4 '-diaminodiphenylsulfone(DDS) solidifying agent continues to stir also and is heated to 150 ℃; Insulation 3～5min is cooled to room temperature then and obtains the B b stage resin b; Three, get the B b stage resin b that 30 parts of step 2 obtain and put into three-roll grinder; And then 3.0～6.0 parts curing catalyst taking by weighing of the dicy-curing agent that takes by weighing in the adding step 1 and step 1; In three-roll grinder, grind then 3～6 times; And then with the remaining B b stage resin b adding that step 2 prepares, continue in three-roll grinder, to grind 3～6 times, obtain epoxy matrix resin; The temperature of three-roll grinder described in the step 3 remains on 60～70 ℃.
Adopt the benchmark of umber the same when taking by weighing in the umber in the B b stage resin b that 30 parts of step 2 described in the preparing method's of the epoxy matrix resin of the present invention step 3 obtain and the step 1.
Prepreg of the present invention; Be to process by epoxy matrix resin and fibre knitting cloth; Control fugitive constituent mass content is lower than 1%, and wherein the mass content of epoxy matrix resin is 37%～43%, epoxy matrix resin by mass parts by 40 parts of phenol aldehyde type epoxy resins, 60 parts of bisphenol A epoxide resins, 2～10 parts of core-shell polymers, 15～24 parts solidifying agent; 3.0～6.0 parts curing catalyst is processed; Wherein said solidifying agent is Dyhard RU 100 and 4, the cooperation solidifying agent of 4 '-diaminodiphenylsulfone(DDS), wherein 4; The mass parts of 4 '-diaminodiphenylsulfone(DDS) and Dyhard RU 100 is respectively 18 parts and 6 parts, 14 parts and 7 parts, 10 parts and 8 parts, perhaps 6 parts and 9 parts, and said curing catalyst is organic ureas or derivatives thereof.
The preparation method of prepreg of the present invention realizes through following steps: one, preparation epoxy matrix resin: a, take by weighing 40 parts of phenol aldehyde type epoxy resins, 60 parts of bisphenol A epoxide resins, 2～10 parts of core-shell polymers, 15～24 parts solidifying agent by mass parts; 3.0～6.0 parts curing catalyst; Said solidifying agent is Dyhard RU 100 and 4; The cooperation solidifying agent of 4 '-diaminodiphenylsulfone(DDS); Wherein 4, the mass parts of 4 '-diaminodiphenylsulfone(DDS) and Dyhard RU 100 be respectively 18 parts and 6 parts, 14 parts and 7 parts, 10 parts and 8 parts, or 6 parts and 9 parts, said curing catalyst is organic ureas or derivatives thereof; B, 40 parts of phenol aldehyde type epoxy resins, 60 parts of bisphenol A epoxide resins and 2～10 parts of core-shell polymers that step 1 is taken by weighing mix in the adding container; Under agitation condition, be heated to 150 ℃ then; Add again that step 1 takes by weighing 4,4 '-diaminodiphenylsulfone(DDS) solidifying agent continues to stir also and is heated to 150 ℃; Insulation 3～5min is cooled to room temperature then and obtains the B b stage resin b; C, get the B b stage resin b that 30 parts of step 2 obtain and put into three-roll grinder; And then the curing catalyst of the dicy-curing agent that takes by weighing in the adding step 1 and 3.0～6.0 parts; In three-roll grinder, grind then 3～6 times; And then with the remaining B b stage resin b adding that step 2 prepares, continue in three-roll grinder, to grind 3～6 times, obtain epoxy matrix resin; The temperature of three-roll grinder described in the step 3 remains on 60～70 ℃;
Two, preparation prepreg: a, the single face separate-type paper hung successively twines roll shaft 1, middle roll shaft 5 and the rolling of single face separate-type paper to the single face separate-type paper and twine on the roll shaft 4; Making the single face separate-type paper twine roll shaft 1, middle roll shaft 5 and 4 formation of single face separate-type paper rolling winding roll shaft is in transmission connection; Then two-sided separate-type paper is hung successively to two-sided separate-type paper winding roll shaft 2, middle roll shaft 5 and product rolling winding roll shaft 3; Making two-sided separate-type paper twine roll shaft 2, middle roll shaft 5 and 3 formation of product rolling winding roll shaft is in transmission connection; Again fibre knitting cloth is set in the single face separate-type paper and twines between the single face separate-type paper and two-sided separate-type paper between roll shaft 1 and the two-sided separate-type paper winding roll shaft 2; Wherein the single face separate-type paper contacts with middle roll shaft 5, then the single face separate-type paper is twined roll shaft 1 and is preheated to 75～85 ℃ with two-sided separate-type paper winding roll shaft 2; B, the epoxy matrix resin that step 1 is prepared are poured the single face separate-type paper into and are twined in " V-type " space that roll shaft 1 and fibre knitting cloth form; Starter gear then; Make fibre knitting cloth and epoxy matrix resin twine the slit between roll shaft 1 and the two-sided separate-type paper winding roll shaft 2 through the single face separate-type paper; Obtain the prepreg that both sides are stained with single face separate-type paper and two-sided separate-type paper respectively; Control single face separate-type paper twine roll shaft 1 and and the two-sided separate-type paper distance of twining between the roll shaft 2 be 0.1～2mm, the LV that two-sided separate-type paper is twined roll shaft 2 is 100～300m/h, the temperature of epoxy matrix resin is at 75～85 ℃; C, twine in the rolling of single face separate-type paper under the effect of roll shaft 4 the single face separate-type paper is peeled off, product rolling is simultaneously twined roll shaft 3 side is stained with the prepreg rolling of two-sided separate-type paper, promptly accomplishes the preparation of prepreg.
The device that preparation prepreg of the present invention adopts; Said device comprises that the single face separate-type paper twines roll shaft, two-sided separate-type paper and twine roll shaft, product rolling and twine roll shaft, the rolling of single face separate-type paper and twine that roll shaft, middle roll shaft, the 3rd chain-drive mechanism, first, first chain-drive mechanism, second, second chain-drive mechanism and first gear drive, second gear drive, the 3rd, single face separate-type paper are twined the charging roll shaft, two-sided separate-type paper is twined charging roll shaft, the 4th chain-drive mechanism and frame; First is passed through first chain-drive mechanism and is connected with second shaft drive; Second is passed through second chain-drive mechanism and is connected with the shaft drive of two-sided separate-type paper winding roller; Two-sided separate-type paper is twined roll shaft and is connected with the shaft drive of single face separate-type paper winding roller through first gear drive; The single face separate-type paper is twined roll shaft and is connected through single face separate-type paper and the shaft drive of single face separate-type paper winding feeding roller; Two-sided separate-type paper is twined roll shaft and is connected through two-sided separate-type paper and the shaft drive of two-sided separate-type paper winding feeding roller; First is passed through the 3rd chain-drive mechanism and is connected with the 3rd shaft drive; The 3rd is passed through second gear drive and is connected with the shaft drive of product rolling winding roller; The 3rd is passed through the 4th chain-drive mechanism and is connected with the shaft drive of single face separate-type paper rolling winding roller; It is characterized in that said device comprises that also fibre knitting cloth twines roll shaft, spring and adjusting screw(rod); The fibre knitting cloth that fibre knitting cloth twines roll shaft is arranged in the slit between single face separate-type paper winding roll shaft 1 and the two-sided separate-type paper winding roll shaft; Fibre knitting cloth twines roll shaft and is connected with the shaft drive of two-sided separate-type paper winding roller through fibre knitting cloth; Two-sided separate-type paper is twined roll shaft and is connected with intermediate roll shaft drive through the prepreg moulding product; Middle roll shaft is connected with the shaft drive of product rolling winding roller through the prepreg moulding product, and shaft drive is connected middle roll shaft with single face separate-type paper rolling winding roller through the single face separate-type paper, is provided with spring between the axle head of single face separate-type paper winding roll shaft and two-sided separate-type paper winding roll shaft; Adjusting screw(rod) passes frame and leans in two-sided separate-type paper and twine on the roll shaft, and the single face separate-type paper is twined roll shaft, two-sided separate-type paper and twined roll shaft, product rolling and twine roll shaft, the rolling of single face separate-type paper and twine roll shaft, middle roll shaft, first, second, the 3rd, single face separate-type paper and twine charging roll shaft, two-sided separate-type paper and twine charging roll shaft and fibre knitting cloth and twine roll shaft and all be contained on the frame.
Roll shaft is twined in the product rolling in the device of the present invention, the rolling of single face separate-type paper is twined on roll shaft, fibre knitting cloth winding roll shaft, single face separate-type paper winding charging roll shaft and the two-sided separate-type paper winding charging roll shaft powder clutch all is housed.
The single face separate-type paper is twined on roll shaft and the two-sided separate-type paper winding roll shaft and is equipped with the enclosed cavity that is full of the circulation heating medium in the device of the present invention, and two enclosed cavities pass through pipeline connection.
Also comprise two baffle plates in the device of the present invention, the single face separate-type paper is twined roll shaft and two-sided separate-type paper and is twined the two ends of roll shaft and respectively be provided with one and be used to the baffle plate that stops that matrix resin is excessive.
Bisphenol A epoxide resin described in the present invention is an E-51 epoxy resin, E-44 epoxy resin or E-20 epoxy resin; Said phenol aldehyde type epoxy resin is the F-44 phenol aldehyde type epoxy resin, F-48 phenol aldehyde type epoxy resin or F-51 phenol aldehyde type epoxy resin.Said core-shell polymer is duricrust with the polymethylmethacrylate for being soft nuclear with polybutadiene rubber, styrene-butadiene rubber(SBR) or polymethyl siloxane.
Epoxy matrix resin of the present invention, the second-order transition temperature that under 120 ℃ of conditions, solidifies 2～3 hours cured product is 133～138 ℃, shock strength is 10～22KJ/m
2, tensile strength is 65～85MPa, and tensile modulus is 3.0～3.6GPa, and elongation at break is 2.6～4.6%, flexural strength 100～140MPa, modulus in flexure is 2.6～3.6GPa.Before and after solidifying, toughness reinforcing phase state does not change, and dispersion state is even, and toughening effect is good and stable.
Gelation time under the good stability of prepreg of the present invention, 120 ℃ of conditions is 9～20min.Its preparation method adopts hot melt process to make prepreg technology; Fibre knitting cloth is passed through dip roll under the release paper protects effect; Hot melt matrix resin impregnated fiber woven cloth and control resin content under the deadweight and the pressure effect of dip roll; Form the individual layer prepreg with the automatic winding mode, production technique is simple.
The trilaminar at least prepreg that obtains after the prepreg stack that the present invention is prepared adopts autoclave technology, under 120 ℃ of conditions, solidifies 2～3h, composite material laminated board, wherein the number of plies of prepreg is determined on a case-by-case basis.The tensile strength of the composite material laminated board that obtains is 500～600MPa, and tensile modulus is 22～26GPa; Flexural strength reaches 700～800MPa, and modulus in flexure reaches 24～28GPa; It is 72～82MPa that layer is cut intensity, and mechanical property is good.
The present invention has the following advantages:
1, the present invention adopts core-shell polymer to substitute traditional rubber and the next toughness reinforcing epoxy matrix resin of thermoplastic resin (TP).The result proves that after the pre-designed Core-Shell Polymer Particles and the resin alloy that is modified, its composition, form, size and the distribution in resin are constant before and after solidifying, promptly irrelevant with solidification process.Use core-shell Polymer toughening epoxy resin, the made epoxy matrix resin that obtains and composite material laminated board toughness, tensile strength, flexural strength are greatly improved, and Tg and modulus obviously do not descend.
2, prepreg of the present invention adopts the hot melt one-step technology, and with respect to solvent method, it is low to have a volatile content, environmental protection, the problem of nonpollution environment; With respect to hot melt adhesive film transfer method (earlier matrix resin is rolled into membranaceous, and then with the compound dipping of fibre knitting cloth), its working efficiency is higher, and manufacturing cost is lower.
3, the prepreg tool stability characteristics that make of the present invention, (25 ℃) can be stored 3 months under the normality, can preserve 6 months below-18 ℃.
4, the present invention's device of preparing prepreg is accomplished epoxy matrix resin and fiber all over the impregnation technology of a weaving cotton cloth step; Compare with existing hot melt process prepreg production equipment, the equipment configuration manufacturing cost is lower, and production technique is simpler; Production efficiency is higher, and prepreg resin content control is more accurate.
Description of drawings
Fig. 1 is the device that the preparation prepreg adopts among the present invention.Fig. 2 is the vertical view at A place among Fig. 1.
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the epoxy matrix resin of this embodiment is processed by 40 parts of phenol aldehyde type epoxy resins, 60 parts of bisphenol A epoxide resins, 2～10 parts of core-shell polymers, 15～24 parts solidifying agent and 3.0～6.0 parts curing catalyst by mass parts; Wherein said solidifying agent is Dyhard RU 100 and 4; The cooperation solidifying agent of 4 '-diaminodiphenylsulfone(DDS); Wherein 4, the mass parts of 4 '-diaminodiphenylsulfone(DDS) and Dyhard RU 100 be respectively 18 parts and 6 parts, 14 parts and 7 parts, 10 parts and 8 parts, or 6 parts and 9 parts; Said curing catalyst is organic ureas or derivatives thereof.
The particle diameter of the described core-shell polymer of this embodiment is 100～300nm.Said core-shell polymer is the commercially available prod or adopts existing open preparation method to prepare all can.
The cured product that the epoxy matrix resin of this embodiment was solidified 2～3 hours under 120 ℃ of conditions carries out performance test; Testing method and parameter are following: 1, adopt DMA method (dynamic mechanical analysis method) to survey second-order transition temperature; Adopt the three-point bending loading mode; The batten size (18 ± 0.5mm) * (5 ± 0.2mm) * (1.5 ± 0.2mm), frequency 1Hz, 5 ℃/min of temperature rise rate; 2, press GB/T2568 resin-cast body Erichsen test method test tensile strength, modulus in tension and elongation; 3, press crooked strong intensity of GB/T2570 Test method for flexural properties of resin casting body test and modulus in flexure; 4, press GB/T2571 resin-cast body impact test method test shock strength, the shock strength specimen size is length 80mm ± 2mm, width 10mm ± 0.5mm, thickness 4 ± 0.2mm.
Test result is: the second-order transition temperature of the cured product of the epoxy matrix resin of this embodiment (condition of cure: solidified 2～3 hours under 120 ℃ of conditions) is 133～138 ℃, and shock strength is 10～22KJ/m
2, tensile strength is 65～85MPa, and tensile modulus is 3.0～3.6GPa, and elongation at break is 2.6～4.6%, flexural strength 100～140MPa, modulus in flexure is 2.6～3.6GPa.The epoxy matrix resin of this embodiment is functional.
Embodiment two: what this embodiment and embodiment one were different is that epoxy matrix resin is processed by 40 parts of phenol aldehyde type epoxy resins, 60 parts of bisphenol A epoxide resins, 3～8 parts of core-shell polymers, 18～22 parts solidifying agent and 4.0～5.0 parts curing catalyst by mass parts.Other parameter is identical with embodiment one.
More excellent in this embodiment is that epoxy matrix resin is processed by 40 parts of phenol aldehyde type epoxy resins, 60 parts of bisphenol A epoxide resins, 5 parts of core-shell polymers, 24 parts solidifying agent and 5.0 parts curing catalyst by mass parts.
Embodiment three: this embodiment is different with embodiment one or two be said core-shell polymer for being soft nuclear with polybutadiene rubber, styrene-butadiene rubber(SBR) or polymethyl siloxane, be duricrust with the polymethylmethacrylate.Other parameter is identical with embodiment one.
Embodiment four: this embodiment and embodiment one, two or three are different is that the oxirane value of said phenol aldehyde type epoxy resin is 0.42～0.54, and the oxirane value of bisphenol A epoxide resin is 0.41～0.56.Other parameter is identical with embodiment one, two or three.
Embodiment five: what this embodiment was different with one of embodiment one to four is that said curing catalyst is N; N '-dimethyl diphenyl urea, N; N '-diethyl diphenyl urea, N-are to chlorophenyl-N, N '-dimethyl urea, 3-phenyl 1; 1-dimethyl urea, 3-rubigan 1,1 dimethyl urea (chlorourea) or thiocarbamide.Other parameter is identical with one of embodiment one to four.
Embodiment six: this embodiment is the preparation method of embodiment one described epoxy matrix resin; The preparation method of epoxy matrix resin realizes through following steps: one, take by weighing 40 parts of phenol aldehyde type epoxy resins, 60 parts of bisphenol A epoxide resins, 2～10 parts of core-shell polymers, 15～24 parts solidifying agent and 3.0～6.0 parts curing catalyst by mass parts; Wherein said solidifying agent is Dyhard RU 100 and 4; The cooperation solidifying agent of 4 '-diaminodiphenylsulfone(DDS); Wherein 4; The mass parts of 4 '-diaminodiphenylsulfone(DDS) and Dyhard RU 100 is respectively 18 parts and 6 parts, 14 parts and 7 parts, 10 parts and 8 parts, perhaps 6 parts and 9 parts, and said curing catalyst is organic ureas or derivatives thereof; Two, 40 parts of phenol aldehyde type epoxy resins that step 1 taken by weighing, 60 parts of bisphenol A epoxide resins and 2～10 parts of core-shell polymers mix and add in the container; Under agitation condition, be heated to 150 ℃ then; Add again that step 1 takes by weighing 4,4 '-diaminodiphenylsulfone(DDS) solidifying agent continues to stir also and is heated to 150 ℃; Insulation 3～5min is cooled to room temperature then and obtains the B b stage resin b; Three, get the B b stage resin b that 30 parts of step 2 obtain and put into three-roll grinder; And then 3.0～6.0 parts curing catalyst taking by weighing of the dicy-curing agent that takes by weighing in the adding step 1 and step 1; In three-roll grinder, grind then 3～6 times; And then with the remaining B b stage resin b adding that step 2 prepares, continue in three-roll grinder, to grind 3～6 times, obtain epoxy matrix resin; The temperature of three-roll grinder described in the step 3 remains on 60～70 ℃.
This embodiment preparation method is simple, and is easy to operate.Core-shell polymer described in the step 1 is the commercially available prod or adopts existing open preparation method to prepare all can.Adopt the benchmark of umber the same when taking by weighing in the umber in the B b stage resin b that 30 parts of step 2 described in the step 3 of this embodiment obtain and the step 1.
Performance test methods and parameter that the epoxy resin cure that adopts embodiment one record is; Cured article (condition of cure: solidified 2～3 hours under 120 ℃ of conditions) to the epoxy matrix resin of this embodiment preparation is tested; Recording second-order transition temperature is 133～138 ℃, and shock strength is 10～22KJ/m
2, tensile strength is 65～85MPa, and tensile modulus is 3.0～3.6GPa, and elongation at break is 2.6～4.6%, flexural strength 100～140MPa, modulus in flexure is 2.6～3.6GPa.The epoxy matrix resin of this embodiment is functional.
Embodiment seven: what this embodiment and embodiment six were different is to take by weighing 40 parts of phenol aldehyde type epoxy resins, 60 parts of bisphenol A epoxide resins, 3～8 parts of core-shell polymers, 18～22 parts solidifying agent and 4.0～5.0 parts curing catalyst by mass parts in the step 1.Other parameter and embodiment six phase are together.
Better in this embodiment is to take by weighing 40 parts of phenol aldehyde type epoxy resins, 60 parts of bisphenol A epoxide resins, 5 parts of core-shell polymers, 24 parts solidifying agent and 5.0 parts curing catalyst by mass parts in the step 1.
Embodiment eight: this embodiment is different with embodiment six or seven be core-shell polymer described in the step 1 for being soft nuclear with polybutadiene rubber, styrene-butadiene rubber(SBR) or polymethyl siloxane, be duricrust with the polymethylmethacrylate.Other parameter is identical with embodiment six or seven.
Embodiment nine: this embodiment and embodiment six, seven or eight are different is that the oxirane value of phenol aldehyde type epoxy resin described in the step 1 is 0.42～0.54, and the oxirane value of bisphenol A epoxide resin is 0.41～0.56.Other parameter is identical with embodiment six, seven or eight.
Embodiment ten: what this embodiment was different with one of embodiment six to nine is that curing catalyst described in the step 1 is N; N '-dimethyl diphenyl urea, N; N '-diethyl diphenyl urea, N-are to chlorophenyl-N, N '-dimethyl urea, 3-phenyl 1; 1-dimethyl urea, 3-rubigan 1,1 dimethyl urea (chlorourea) or thiocarbamide.Other parameter is identical with one of embodiment six to nine.
Embodiment 11: this embodiment is a prepreg; Prepreg is to be processed by epoxy matrix resin and fibre knitting cloth; Control fugitive constituent mass content is lower than 1%; Wherein the mass content of epoxy matrix resin is 37%～43%, and epoxy matrix resin is processed by 40 parts of phenol aldehyde type epoxy resins, 60 parts of bisphenol A epoxide resins, 2～10 parts of core-shell polymers, 15～24 parts solidifying agent and 3.0～6.0 parts curing catalyst by mass parts, and said solidifying agent is Dyhard RU 100 and 4; The cooperation solidifying agent of 4 '-diaminodiphenylsulfone(DDS); Wherein 4, the mass parts of 4 '-diaminodiphenylsulfone(DDS) and Dyhard RU 100 be respectively 18 parts and 6 parts, 14 parts and 7 parts, 10 parts and 8 parts, or 6 parts and 9 parts, said curing catalyst is organic ureas or derivatives thereof.
Core-shell polymer described in this embodiment is the commercially available prod or adopts existing open preparation method to prepare all can.Said core-shell polymer is duricrust with the polymethylmethacrylate for being soft nuclear with polybutadiene rubber, styrene-butadiene rubber(SBR) or polymethyl siloxane.
The prepreg stable performance of this embodiment, (25 ℃) can be stored 3 months under the normality, can preserve 6 months below-18 ℃.
This embodiment is measured the fugitive constituent of prepreg by " HB7736.4 matrix material Preblend physical property test method the 4th part: the mensuration of volatile content ", obtains that the fugitive constituent mass content is lower than 1% in the prepreg.
This embodiment is measured prepreg resin content by " HB 7736.5 material prepreg physical property test methods the 5th part: the mensuration of resin content ", and the mass content that obtains epoxy matrix resin in the prepreg is 37%～43%.
This embodiment is pressed the gelation time that " HB 7736.7 material prepreg physical property test methods the 7th part: the mensuration of gel time " measured prepreg, and obtaining the gelation time of prepreg under 120 ℃ of conditions is 9～20min.
The trilaminar at least prepreg that obtains after the prepreg stack with this embodiment adopts autoclave technology, under 120 ℃ of conditions, solidifies 2～3h, gets composite material laminated board.The tensile strength of the composite material laminated board that obtains is 500～600MPa, and tensile modulus is 22～26GPa; Flexural strength reaches 700～800MPa, and modulus in flexure reaches 24～28GPa; It is 72～82MPa that layer is cut intensity.
Embodiment 12: what this embodiment and embodiment 11 were different is that said fibre knitting cloth is fiberglass braided thing or carbon fiber preform.Other parameter is identical with embodiment 11.
Embodiment 13: this embodiment and embodiment 11 are different is that said fibre knitting cloth is that the trade mark of Nanjing Glass Fibre Research and Design Institute production is the fiberglass braided thing of SW110, SW220, SW280, EW110 or EW220.Other parameter is identical with embodiment 11.
This embodiment is not limited to the above-mentioned fiberglass braided thing of enumerating.
Embodiment 14: what this embodiment and embodiment 11 were different is that said fibre knitting cloth is that the trade mark is the carbon fiber woven cloth of G827 or the T300 carbon fiber woven cloth that toray company produces.Other parameter is identical with embodiment 11.
This embodiment is not limited to the above-mentioned carbon fiber woven cloth of enumerating.
Embodiment 15: this embodiment is the preparation method of embodiment 11 described prepregs; The preparation method of prepreg realizes through following steps: one, prepare epoxy matrix resin: a, take by weighing 40 parts of phenol aldehyde type epoxy resins, 60 parts of bisphenol A epoxide resins, 2～10 parts of core-shell polymers, 15～24 parts solidifying agent and 3.0～6.0 parts curing catalyst by mass parts; Said solidifying agent is Dyhard RU 100 and 4; The cooperation solidifying agent of 4 '-diaminodiphenylsulfone(DDS); Wherein 4; The mass parts of 4 '-diaminodiphenylsulfone(DDS) and Dyhard RU 100 is respectively 18 parts and 6 parts, 14 parts and 7 parts, 10 parts and 8 parts, perhaps 6 parts and 9 parts, and said curing catalyst is organic ureas or derivatives thereof; B, 40 parts of phenol aldehyde type epoxy resins, 60 parts of bisphenol A epoxide resins and 2～10 parts of core-shell polymers that step 1 is taken by weighing mix in the adding container; Under agitation condition, be heated to 150 ℃ then; Add again that step 1 takes by weighing 4,4 '-diaminodiphenylsulfone(DDS) solidifying agent continues to stir also and is heated to 150 ℃; Insulation 3～5min is cooled to room temperature then and obtains the B b stage resin b; C, get the B b stage resin b that 30 parts of step 2 obtain and put into three-roll grinder; And then 3.0～6.0 parts curing catalyst taking by weighing of the dicy-curing agent that takes by weighing in the adding step 1 and step 1; In three-roll grinder, grind then 3～6 times; And then with the remaining B b stage resin b adding that step 2 prepares, continue in three-roll grinder, to grind 3～6 times, obtain epoxy matrix resin; The temperature of three-roll grinder described in the step 3 remains on 60～70 ℃;
Two, preparation prepreg: a, the single face separate-type paper hung successively twines roll shaft 1, middle roll shaft 5 and the rolling of single face separate-type paper to the single face separate-type paper and twine on the roll shaft 4; Making the single face separate-type paper twine roll shaft 1, middle roll shaft 5 and 4 formation of single face separate-type paper rolling winding roll shaft is in transmission connection; Then two-sided separate-type paper is hung successively to two-sided separate-type paper winding roll shaft 2, middle roll shaft 5 and product rolling winding roll shaft 3; Making two-sided separate-type paper twine roll shaft 2, middle roll shaft 5 and 3 formation of product rolling winding roll shaft is in transmission connection; Again fibre knitting cloth is set in the single face separate-type paper and twines between the single face separate-type paper and two-sided separate-type paper between roll shaft 1 and the two-sided separate-type paper winding roll shaft 2; Wherein the single face separate-type paper contacts with middle roll shaft 5, then the single face separate-type paper is twined roll shaft 1 and is preheated to 75～85 ℃ with two-sided separate-type paper winding roll shaft 2; B, the epoxy matrix resin that step 1 is prepared are poured the single face separate-type paper into and are twined in " V-type " space that roll shaft 1 and fibre knitting cloth form; Starter gear then; Make fibre knitting cloth and epoxy matrix resin twine the slit between roll shaft 1 and the two-sided separate-type paper winding roll shaft 2 through the single face separate-type paper; Obtain the prepreg that both sides are stained with single face separate-type paper and two-sided separate-type paper respectively, wherein, control single face separate-type paper twine roll shaft 1 and and the two-sided separate-type paper distance of twining between the roll shaft 2 be 0.1～2mm; The LV that two-sided separate-type paper is twined roll shaft 2 is 100～300m/h, and the temperature of epoxy matrix resin is at 75～85 ℃; C, twine in the rolling of single face separate-type paper under the effect of roll shaft 4 the single face separate-type paper is peeled off, product rolling is simultaneously twined roll shaft 3 side is stained with the prepreg rolling of two-sided separate-type paper, promptly accomplishes the preparation of prepreg.
Adopt the benchmark of umber the same when taking by weighing in the umber in the B b stage resin b that 30 parts of step 2 described in the c step in the step 1 of this embodiment obtain and a step.
The fugitive constituent mass content is lower than 1% in the prepreg that this embodiment prepares, and the mass content of epoxy matrix resin is 37%～43%, and the gelation time under 120 ℃ of conditions is 9～20min.
The equipment of preimpregnated material manufacture method of this embodiment adopts the hot melt one-step technology, and with respect to solvent method, it is low to have a volatile content, environmental protection, the problem of nonpollution environment; With respect to hot melt adhesive film transfer method (elder generation rolls into matrix resin membranaceous, and then compound with fibre knitting cloth), its working efficiency is higher, and manufacturing cost is lower.
Matrix resin and fibre knitting cloth that this embodiment twines the hot melt in the slit between roll shaft 1 and the two-sided separate-type paper winding roll shaft 2 in the single face separate-type paper are accomplished compound dipping under certain temperature, rotating speed and pressure effect, twine roll shaft 1 through adjustment single face separate-type paper and can accurately control prepreg resin content with the rotating speed that two-sided separate-type paper is twined roll shaft 2.
Embodiment 16: this embodiment and embodiment 15 are different is to take by weighing 40 parts of phenol aldehyde type epoxy resins, 60 parts of bisphenol A epoxide resins, 3～8 parts of core-shell polymers, 18～22 parts solidifying agent and 4.0～5.0 parts curing catalyst by mass parts in a step of step 1.Other parameter is identical with embodiment 15.
Better in this embodiment is to take by weighing 40 parts of phenol aldehyde type epoxy resins, 60 parts of bisphenol A epoxide resins, 5 parts of core-shell polymers, 24 parts solidifying agent and 5.0 parts curing catalyst by mass parts in a step of step 1.
Embodiment 17: this embodiment is different with embodiment 15 or 16 is that core-shell polymer is duricrust with the polymethylmethacrylate for being soft nuclear with polybutadiene rubber, styrene-butadiene rubber(SBR) or polymethyl siloxane described in a step of step 1.Other parameter and embodiment 15 or ten six phases are together.
Embodiment 18: this embodiment and embodiment 15,16 or 17 are different is that the oxirane value of phenol aldehyde type epoxy resin described in a step of step 1 is 0.42～0.54, and the oxirane value of bisphenol A epoxide resin is 0.41～0.56.Other parameter is identical with embodiment 15,16 or 17.
Embodiment 19: this embodiment is different with one of embodiment 15 to 18 is that curing catalyst is N described in a step of step 1; N '-dimethyl diphenyl urea, N; N '-diethyl diphenyl urea, N-are to chlorophenyl-N, N '-dimethyl urea, 3-phenyl 1; 1-dimethyl urea, 3-rubigan 1,1 dimethyl urea (chlorourea) or thiocarbamide.Other parameter is identical with one of embodiment 15 to 18.
Embodiment 20: combine Fig. 1 and Fig. 2 that the device of this embodiment for the prepreg employing of one of preparation embodiment 11 to 14 is described; Said device comprises that the single face separate-type paper twines roll shaft 1, two-sided separate-type paper and twine roll shaft 2, product rolling and twine roll shaft 3, the rolling of single face separate-type paper and twine that roll shaft 4, middle roll shaft 5, the 3rd chain-drive mechanism 6, first spool 7, first chain-drive mechanism 8, second 9, second chain-drive mechanism 10 and first gear drive 11, second gear drive 14, the 3rd spool 15, single face separate-type paper are twined charging roll shaft 16, two-sided separate-type paper is twined charging roll shaft 17, the 4th chain-drive mechanism 18 and frame 22; Be in transmission connection through first chain-drive mechanism 8 and second 9 for first 7; Twining roll shaft 2 through second chain-drive mechanism 10 and two-sided separate-type paper for second 9 is in transmission connection; Two-sided separate-type paper is twined roll shaft 2 and is in transmission connection through first gear drive 11 and single face separate-type paper winding roll shaft 1; The single face separate-type paper is twined roll shaft 1 and is in transmission connection through single face separate-type paper and single face separate-type paper winding charging roll shaft 16; Two-sided separate-type paper is twined roll shaft 2 and is in transmission connection through two-sided separate-type paper and two-sided separate-type paper winding charging roll shaft 17; Be in transmission connection through the 3rd chain-drive mechanism 6 and the 3rd 15 for first 7; Twining roll shaft 3 through second gear drive 14 and product rolling for the 3rd 15 is in transmission connection; Twining roll shaft 4 through the 4th chain-drive mechanism 18 and the rolling of single face separate-type paper for the 3rd 15 is in transmission connection; It is characterized in that said device comprises that also fibre knitting cloth twines roll shaft 12, spring 13 and adjusting screw(rod) 21; The fibre knitting cloth that fibre knitting cloth twines roll shaft 12 is arranged in the slit between single face separate-type paper winding roll shaft 1 and the two-sided separate-type paper winding roll shaft 2; Fibre knitting cloth twines roll shaft 12 and is in transmission connection through fibre knitting cloth and two-sided separate-type paper winding roll shaft 2; Two-sided separate-type paper is twined roll shaft 2 and is in transmission connection through prepreg moulding product and middle roll shaft 5; Middle roll shaft 5 twines roll shaft 3 through prepreg moulding product and product rolling and is in transmission connection; Middle roll shaft 5 twines roll shaft 4 through single face separate-type paper and the rolling of single face separate-type paper and is in transmission connection; The single face separate-type paper is twined between the axle head that roll shaft 1 and two-sided separate-type paper twine roll shaft 2 and is provided with spring 13, and adjusting screw(rod) 21 passes frame 22 and leans in two-sided separate-type paper and twine on the roll shaft 2, and the single face separate-type paper is twined roll shaft 1, two-sided separate-type paper and twined roll shaft 2, product rolling and twine roll shaft 3, the rolling of single face separate-type paper and twine roll shaft 4, middle roll shaft 5, first 7, second 9, the 3rd 15, single face separate-type paper and twine charging roll shaft 16, two-sided separate-type paper and twine charging roll shaft 17 and fibre knitting cloth and twine roll shaft 12 and all be contained on the frame 22.
This embodiment prepares the device of prepreg employing to be accomplished epoxy matrix resin and fiber all over impregnation technology of weaving cotton cloth and one step of prepreg resin content CONTROL PROCESS; Compare with existing hot melt process prepreg production equipment; The equipment configuration manufacturing cost is lower; Production technique is simpler, and production efficiency is higher, and prepreg resin content control is more accurate.
The single face separate-type paper is twined on roll shaft 1 and the two-sided separate-type paper winding roll shaft 2 and is equipped with the enclosed cavity that is full of the circulation heating medium in this embodiment, and two enclosed cavities pass through pipeline connection.
The said device of this embodiment also comprises two baffle plates 20, and the two ends of single face separate-type paper winding roll shaft 1 and two-sided separate-type paper winding roll shaft 2 respectively are provided with one and are used to stop the excessive baffle plate of matrix resin 20.
Embodiment 21: this embodiment and embodiment 20 are different is that the product rolling is twined roll shaft 3, the rolling of single face separate-type paper and twined roll shaft 4, fibre knitting cloth and twine roll shaft 12, single face separate-type paper and twine charging roll shaft 16 and two-sided separate-type paper and twine on the charging roll shaft 17 powder clutch 19 all is housed.Other compositions and annexation are identical with embodiment 20.
Embodiment 22: this embodiment is an epoxy matrix resin; Epoxy matrix resin by mass parts by 40 parts of F-44 phenol aldehyde type epoxy resins, 60 parts of E-51 epoxy resin, 2 parts of core-shell polymers, 16 part 4; The 3-phenyl 1 of the cooperation solidifying agent of 4 '-diaminodiphenylsulfone(DDS), 8 parts of dicy-curing agents and 5.0 parts; 1-dimethyl urea curing catalyst is processed, and wherein said core-shell polymer is duricrust with the polymethylmethacrylate for being soft nuclear with polybutadiene rubber.
The trade mark that the said core-shell polymer of this embodiment is produced with Japanese Kaneka company is that the form of the masterbatch of Kane Ace MX-125 adds; Wherein the mass content of Kane Ace MX-125 core-shell polymer is 25%; With polybutadiene rubber is soft nuclear; To gather the methylpropanoic acid methyl esters is duricrust, and size of particles is 100nm; The mass content of E-51 epoxy resin is 75%.
The cured product that the epoxy matrix resin of this embodiment was solidified 2 hours under 120 ℃ of conditions carries out performance test, and testing method and parameter adopt the method and the parameter of record in the embodiment one.Test result is: the second-order transition temperature of the cured product of the epoxy matrix resin of this embodiment (condition of cure: solidified 2 hours under 120 ℃ of conditions) is 138.2 ℃; Shock strength is 15.7KJ/m
2Tensile strength is 69.7MPa, and tensile modulus is 3.6GPa; Elongation at break is 3.0%; Flexural strength 118.6MPa, modulus in flexure is 3.5GPa.The epoxy matrix resin of this embodiment is functional.
The preparation method of the epoxy matrix resin of this embodiment is: one, take by weighing masterbatch that the trade mark that the Japanese Kaneka of 40 parts of F-44 phenol aldehyde type epoxy resins, 54 parts of E-51 epoxy resin, 8 parts company produces is Kane Ace MX-125,16 part 4 by mass parts; The 3-phenyl 1 of the cooperation solidifying agent of 4 '-diaminodiphenylsulfone(DDS), 8 parts of dicy-curing agents and 5.0 parts, 1-dimethyl urea curing catalyst; Two, the trade mark that the Japanese Kaneka of 40 parts of F-44 phenol aldehyde type epoxy resins that step 1 taken by weighing, 54 parts of bisphenol A epoxide resins and 8 parts company produces is that the masterbatch of Kane Ace MX-125 mixes and adds in the container; Under agitation condition, be heated to 150 ℃ then; Add 16 part 4 that step 1 takes by weighing again, 4 '-diaminodiphenylsulfone(DDS) solidifying agent continues to stir and be heated to 150 ℃; Insulation 3～5min is cooled to room temperature then and obtains the B b stage resin b; Three, get the B b stage resin b that 30 parts of step 2 obtain and put into three-roll grinder; And then 5 parts 3-phenyl 1 taking by weighing of 8 parts of dicy-curing agents that take by weighing in the adding step 1 and step 1; 1-dimethyl urea curing catalyst grinds 4 times in three-roll grinder then, and then the remaining B b stage resin b of step 2 preparation is added; Continuation is ground in three-roll grinder 4 times, obtains epoxy matrix resin; The temperature of three-roll grinder described in the step 3 remains on 60～70 ℃.Adopt the benchmark of umber the same when wherein, taking by weighing in the umber in the B b stage resin b that obtains of 30 parts of step 2 described in the step 3 and the step 1.
Embodiment 23: this embodiment is a prepreg; Prepreg is processed by the glass fiber woven cloth that the epoxy matrix resin and the trade mark of embodiment 22 is SW110; The fugitive constituent mass content is lower than 1%, and wherein the mass content of epoxy matrix resin is 37%～43%.
The density of the glass fiber woven cloth of SW110 is 110g/m in this embodiment
2
The preparation method of the prepreg of this embodiment is: one, preparation epoxy matrix resin: the preparation method according to record in the embodiment 22 prepares epoxy matrix resin; Two, preparation prepreg: a, the single face separate-type paper hung successively twines roll shaft 1, middle roll shaft 5 and the rolling of single face separate-type paper to the single face separate-type paper and twine on the roll shaft 4; Making the single face separate-type paper twine roll shaft 1, middle roll shaft 5 and 4 formation of single face separate-type paper rolling winding roll shaft is in transmission connection; Then two-sided separate-type paper is hung successively to two-sided separate-type paper winding roll shaft 2, middle roll shaft 5 and product rolling winding roll shaft 3; Making two-sided separate-type paper twine roll shaft 2, middle roll shaft 5 and 3 formation of product rolling winding roll shaft is in transmission connection; Again fibre knitting cloth is set in the single face separate-type paper and twines between the single face separate-type paper and two-sided separate-type paper between roll shaft 1 and the two-sided separate-type paper winding roll shaft 2; Wherein the single face separate-type paper contacts with middle roll shaft 5, then the single face separate-type paper is twined roll shaft 1 and is preheated to 75～85 ℃ with two-sided separate-type paper winding roll shaft 2; B, the epoxy matrix resin that step 1 is prepared are poured the single face separate-type paper into and are twined in " V-type " space that roll shaft 1 and fibre knitting cloth form; Starter gear then; Make fibre knitting cloth and epoxy matrix resin twine the slit between roll shaft 1 and the two-sided separate-type paper winding roll shaft 2 through the single face separate-type paper; Obtain the prepreg that both sides are stained with single face separate-type paper and two-sided separate-type paper respectively, wherein, control single face separate-type paper twine roll shaft 1 and and the two-sided separate-type paper distance of twining between the roll shaft 2 be 0.15～0.2mm; The LV that two-sided separate-type paper is twined roll shaft 2 is 200m/h, and the temperature of epoxy matrix resin is at 75～85 ℃; C, twine in the rolling of single face separate-type paper under the effect of roll shaft 4 the single face separate-type paper is peeled off, product rolling is simultaneously twined roll shaft 3 side is stained with the prepreg rolling of two-sided separate-type paper, promptly accomplishes the preparation of prepreg.Adopt the benchmark of umber the same when wherein taking by weighing in the umber in the B b stage resin b that obtains of 30 parts of step 2 described in the c step of step 1 and a step.
The preparation method of this embodiment adopts the device of record in the embodiment 20.
This embodiment is pressed the gelation time that " HB 7736.7 material prepreg physical property test methods the 7th part: the mensuration of gel time " measured prepreg, and obtaining the gelation time of prepreg under 120 ℃ of conditions is 9～20min.
At least 3 layers of prepreg that the prepreg stack that this embodiment is obtained obtains adopt autoclave technology, under 120 ℃ of conditions, solidify 3h, get composite material laminated board.The tensile strength 540.2MPa of the composite material laminated board that obtains, tensile modulus 24.8GPa; Flexural strength 750MPa, modulus in flexure 25.9GPa; Layer is cut intensity 76.5MPa.
Embodiment 24: this embodiment is an epoxy matrix resin; Epoxy matrix resin by mass parts by 40 parts of F-44 phenol aldehyde type epoxy resins, 60 parts of E-51 epoxy resin, 3 parts of core-shell polymers, 16 part 4; The 3-phenyl 1 of the cooperation solidifying agent of 4 '-diaminodiphenylsulfone(DDS), 8 parts of dicy-curing agents and 5.0 parts; 1-dimethyl urea curing catalyst is processed, and wherein said core-shell polymer is duricrust with the polymethylmethacrylate for being soft nuclear with polybutadiene rubber rubber.
The trade mark that the said core-shell polymer of this embodiment is produced with Japanese Kaneka company is that the content of kana Ace MX-960 core-shell polymer is 25%, is soft nuclear with polymethyl siloxane, is duricrust to gather the methylpropanoic acid methyl esters, and size of particles is 300nm; The content of bisphenol A type epoxy resin is 75% mass parts.
The cured product that the epoxy matrix resin of this embodiment was solidified 2 hours under 120 ℃ of conditions carries out performance test, and testing method and parameter adopt the method and the parameter of record in the embodiment one.Test result is: the second-order transition temperature of the cured product of the epoxy matrix resin of this embodiment (condition of cure: solidified 2 hours under 120 ℃ of conditions) is 137.3 ℃; Shock strength is 16.8KJ/m
2Tensile strength is 75.6MPa, and tensile modulus is 3.5GPa; Elongation at break is 3.2%; Flexural strength 126.4MPa, modulus in flexure is 3.4GPa.The epoxy matrix resin of this embodiment is functional.
The preparation method of the epoxy matrix resin of this embodiment is: one, take by weighing masterbatch that the trade mark that the Japanese Kaneka of 40 parts of F-44 phenol aldehyde type epoxy resins, 51 parts of E-51 epoxy resin, 12 parts company produces is Kane Ace MX-960,16 part 4 by mass parts; The 3-phenyl 1 of the cooperation solidifying agent of 4 '-diaminodiphenylsulfone(DDS), 8 parts of dicy-curing agents and 5.0 parts, 1-dimethyl urea curing catalyst; Two, the trade mark that the Japanese Kaneka of 40 parts of F-44 phenol aldehyde type epoxy resins that step 1 taken by weighing, 51 parts of bisphenol A epoxide resins and 12 parts company produces is that the masterbatch of Kane Ace MX-960 mixes and adds in the container; Under agitation condition, be heated to 150 ℃ then; Add 16 part 4 that step 1 takes by weighing again, 4 '-diaminodiphenylsulfone(DDS) solidifying agent continues to stir and be heated to 150 ℃; Insulation 3～5min is cooled to room temperature then and obtains the B b stage resin b; Three, get the B b stage resin b that 30 parts of step 2 obtain and put into three-roll grinder; And then 5 parts 3-phenyl 1 taking by weighing of 8 parts of dicy-curing agents that take by weighing in the adding step 1 and step 1; 1-dimethyl urea curing catalyst grinds 4 times in three-roll grinder then, and then the remaining B b stage resin b of step 2 preparation is added; Continuation is ground in three-roll grinder 4 times, obtains epoxy matrix resin; The temperature of three-roll grinder described in the step 3 remains on 60～70 ℃.Adopt the benchmark of umber the same when wherein taking by weighing in the umber in the B b stage resin b that obtains of 30 parts of step 2 described in the step 3 and the step 1.
Adopt the preparation method of record in the embodiment 23 to prepare prepreg, wherein the preparation method of epoxy matrix resin adopts the method for putting down in writing in this embodiment to carry out.(density is 110g/m to the glass fiber woven cloth that the prepreg for preparing is SW110 by the epoxy matrix resin and the trade mark of embodiment 24
2) process, the fugitive constituent mass content is lower than 1%, and wherein the mass content of epoxy matrix resin is 37%～43%.Press " HB 7736.7 material prepreg physical property test methods the 7th part: the mensuration of gel time " and measure the gelation time of prepreg, obtaining the gelation time of prepreg under 120 ℃ of conditions is 9～20min.
At least 3 layers of prepreg that obtain after the prepreg stack that this embodiment is obtained adopt autoclave technology, under 120 ℃ of conditions, solidify 3h, composite material laminated board.The tensile strength 570.3MPa of the composite material laminated board that obtains, tensile modulus 24.1GPa; Flexural strength 765MPa, modulus in flexure 25.02GPa; Layer is cut intensity 81.2MPa.
Embodiment 25: this embodiment is an epoxy matrix resin; Epoxy matrix resin by mass parts by 40 parts of F-44 phenol aldehyde type epoxy resins, 60 parts of E-51 epoxy resin, 5 parts of core-shell polymers, 16 part 4; The 3-phenyl 1 of the cooperation solidifying agent of 4 '-diaminodiphenylsulfone(DDS), 8 parts of dicy-curing agents and 5.0 parts; 1-dimethyl urea curing catalyst is processed, and wherein said core-shell polymer is duricrust with the polymethylmethacrylate for being soft nuclear with polybutadiene rubber.
The trade mark that the said core-shell polymer of this embodiment is produced with Japanese Kaneka company is that the form of the masterbatch of Kane Ace MX-125 adds; Wherein the mass content of Kane Ace MX-125 core-shell polymer is 25%; With polyhutadiene is soft nuclear; To gather the methylpropanoic acid methyl esters is duricrust, and size of particles is 100nm; The mass content of E-51 epoxy resin is 75%.
The cured product that the epoxy matrix resin of this embodiment was solidified 2 hours under 120 ℃ of conditions carries out performance test, and testing method and parameter adopt the method and the parameter of record in the embodiment one.Test result is: the second-order transition temperature of the cured product of the epoxy matrix resin of this embodiment (condition of cure: solidified 2 hours under 120 ℃ of conditions) is 137.3 ℃; Shock strength is 16.8KJ/m
2Tensile strength is 83.5MPa, and tensile modulus is 3.4GPa; Elongation at break is 3.5%; Flexural strength 126.4MPa, modulus in flexure is 3.4GPa.The epoxy matrix resin of this embodiment is functional.
Preparing method's the difference of the epoxy matrix resin of record is in the step 1 to take by weighing masterbatch that the trade mark that the Japanese Kaneka of 40 parts of F-44 phenol aldehyde type epoxy resins, 45 parts of E-51 epoxy resin, 20 parts company produces is Kane Ace MX-125,16 part 4 by mass parts in the preparation method of the epoxy matrix resin of this embodiment and the embodiment 22; The 3-phenyl 1 of the cooperation solidifying agent of 4 '-diaminodiphenylsulfone(DDS), 8 parts of dicy-curing agents and 5.0 parts, 1-dimethyl urea curing catalyst; The material of respective quality part that adding above-mentioned steps one takes by weighing in all the other steps gets final product.
Adopt the preparation method of record in the embodiment 23 to prepare prepreg, the difference is that the preparation method of epoxy matrix resin adopts the method for putting down in writing in this embodiment to carry out.(density is 110g/m to the glass fiber woven cloth that the prepreg for preparing is SW110 by the epoxy matrix resin and the trade mark of embodiment 25
2) process, the fugitive constituent mass content is lower than 1%, and wherein the mass content of epoxy matrix resin is 37%～43%.Press " HB 7736.7 material prepreg physical property test methods the 7th part: the mensuration of gel time " and measure the gelation time of prepreg, obtaining the gelation time of prepreg under 120 ℃ of conditions is 9～20min.
Obtain at least 3 layers prepreg after the prepreg stack that this embodiment is obtained, adopt autoclave technology, under 120 ℃ of conditions, solidify 3h, composite material laminated board.The tensile strength 598.3MPa of the composite material laminated board that obtains, tensile modulus 23.5GPa; Flexural strength 785MPa, modulus in flexure 24.2GPa; Layer is cut intensity 81.2MPa.
Embodiment 26: this embodiment is the contrast experiment: epoxy matrix resin by mass parts by 40 parts of F-44 phenol aldehyde type epoxy resins, 60 parts of E-51 epoxy resin, 16 part 4; The 3-phenyl 1 of the cooperation solidifying agent of 4 '-diaminodiphenylsulfone(DDS), 8 parts of dicy-curing agents and 5.0 parts, 1-dimethyl urea curing catalyst is processed.
The cured product that the epoxy matrix resin of this embodiment was solidified 2 hours under 120 ℃ of conditions carries out performance test, and testing method and parameter adopt the method and the parameter of record in the embodiment one.Test result is: the second-order transition temperature of the cured product of the epoxy matrix resin of this embodiment (condition of cure: solidified 2 hours under 120 ℃ of conditions) is 137.8 ℃; Shock strength is 11.5KJ/m
2Tensile strength is 62.5MPa, and tensile modulus is 3.6GPa; Elongation at break is 2.7%; Flexural strength 108.0MPa, modulus in flexure is 3.5GPa.
Preparing method's the difference of the epoxy matrix resin of record is in the step 1 to take by weighing 40 parts of F-44 phenol aldehyde type epoxy resins, 60 parts of E-51 epoxy resin, 16 part 4 by mass parts in the preparation method of the epoxy matrix resin of this embodiment and the embodiment 22; The 3-phenyl 1 of the cooperation solidifying agent of 4 '-diaminodiphenylsulfone(DDS), 8 parts of dicy-curing agents and 5.0 parts, 1-dimethyl urea curing catalyst; The material of respective quality part that adding above-mentioned steps one takes by weighing in all the other steps gets final product.
Adopt the preparation method of record in the embodiment 23 to prepare prepreg, wherein the preparation method of epoxy matrix resin adopts the method for putting down in writing in this embodiment to carry out.(density is 110g/m to the glass fiber woven cloth that the prepreg for preparing is SW110 by the epoxy matrix resin and the trade mark of embodiment 26
2) process, the fugitive constituent mass content is lower than 1%, and wherein the mass content of epoxy matrix resin is 37%～43%.Press " HB 7736.7 material prepreg physical property test methods the 7th part: the mensuration of gel time " and measure the gelation time of prepreg, obtaining the gelation time of prepreg under 120 ℃ of conditions is 9～20min.
At least 3 layers the prepreg that obtains after the prepreg stack that this embodiment is obtained adopts autoclave technology, under 120 ℃ of conditions, solidifies 3h, composite material laminated board.The tensile strength of the composite material laminated board that obtains is 510.5MPa, tensile modulus 25.6GPa; Flexural strength 720MPa, modulus in flexure 26.3GPa; Layer is cut intensity 73.8MPa.
Claims (9)
1. epoxy matrix resin; It is characterized in that epoxy matrix resin processed by 40 parts of phenol aldehyde type epoxy resins, 60 parts of bisphenol A epoxide resins, 2～10 parts of core-shell polymers, 15～24 parts solidifying agent and 3.0～6.0 parts curing catalyst by weight; Wherein said solidifying agent is Dyhard RU 100 and 4; The cooperation solidifying agent of 4 '-diaminodiphenylsulfone(DDS); Wherein 4, the mass parts of 4 '-diaminodiphenylsulfone(DDS) and Dyhard RU 100 be respectively 18 parts and 6 parts, 14 parts and 7 parts, 10 parts and 8 parts, or 6 parts and 9 parts, said promotor is organic ureas;
Said core-shell polymer is duricrust with the polymethylmethacrylate for being soft nuclear with polybutadiene rubber, styrene-butadiene rubber(SBR) or polymethyl siloxane.
2. epoxy matrix resin according to claim 1 is characterized in that epoxy matrix resin processed by 40 parts of phenol aldehyde type epoxy resins, 60 parts of bisphenol A epoxide resins, 3～8 parts of core-shell polymers, 18～22 parts solidifying agent and 4.0～5.0 parts curing catalyst by weight.
3. epoxy matrix resin according to claim 1 and 2, the oxirane value that it is characterized in that said phenol aldehyde type epoxy resin is 0.42～0.54, the oxirane value of bisphenol A epoxide resin is 0.41～0.56.
4. the preparation method of epoxy matrix resin as claimed in claim 1; The preparation method who it is characterized in that epoxy matrix resin realizes through following steps: one, take by weighing 40 parts of phenol aldehyde type epoxy resins, 60 parts of bisphenol A epoxide resins, 2～10 parts of core-shell polymers, 15～24 parts solidifying agent and 3.0～6.0 parts curing catalyst by mass parts; Said solidifying agent is Dyhard RU 100 and 4; The cooperation solidifying agent of 4 '-diaminodiphenylsulfone(DDS); Wherein 4, the mass parts of 4 '-diaminodiphenylsulfone(DDS) and Dyhard RU 100 be respectively 18 parts and 6 parts, 14 parts and 7 parts, 10 parts and 8 parts, or 6 parts and 9 parts, said curing catalyst is organic ureas; Two, 40 parts of phenol aldehyde type epoxy resins that step 1 taken by weighing, 60 parts of bisphenol A epoxide resins and 2～10 parts of core-shell polymers mix and add in the container; Under agitation condition, be heated to 150 ℃ then; Add again that step 1 takes by weighing 4,4 '-diaminodiphenylsulfone(DDS) solidifying agent continues to stir also and is heated to 150 ℃; Insulation 3～5min is cooled to room temperature then and obtains the B b stage resin b; Three, get the B b stage resin b that 30 parts of step 2 obtain and put into three-roll grinder; And then 3.0～6.0 parts curing catalyst taking by weighing of the dicy-curing agent that takes by weighing in the adding step 1 and step 1; In three-roll grinder, grind then 3～6 times; And then with the remaining B b stage resin b adding that step 2 prepares, continue in three-roll grinder, to grind 3～6 times, obtain epoxy matrix resin; The temperature of three-roll grinder described in the step 3 remains on 60～70 ℃.
5. prepreg; It is characterized in that prepreg is to be processed by epoxy matrix resin and fibre knitting cloth; Control fugitive constituent mass content is lower than 1%, and wherein the mass content of epoxy matrix resin is 37%～43%, and epoxy matrix resin is by weight by 40 parts of phenol aldehyde type epoxy resins, 60 parts of bisphenol A epoxide resins, 2～10 parts of core-shell polymers, 15～24 parts solidifying agent; 3.0～6.0 parts curing catalyst is processed; Said solidifying agent is Dyhard RU 100 and 4, the cooperation solidifying agent of 4 '-diaminodiphenylsulfone(DDS), wherein 4; The mass parts of 4 '-diaminodiphenylsulfone(DDS) and Dyhard RU 100 is respectively 18 parts and 6 parts, 14 parts and 7 parts, 10 parts and 8 parts, perhaps 6 parts and 9 parts, and said curing catalyst is organic ureas;
Said core-shell polymer is duricrust with the polymethylmethacrylate for being soft nuclear with polybutadiene rubber, styrene-butadiene rubber(SBR) or polymethyl siloxane.
6. prepreg according to claim 5 is characterized in that said fibre knitting cloth is fiberglass braided thing or carbon fiber preform.
7. the preparation method of prepreg as claimed in claim 5; The preparation method who it is characterized in that prepreg realizes through following steps: one, preparation epoxy matrix resin: a, take by weighing 40 parts of phenol aldehyde type epoxy resins, 60 parts of bisphenol A epoxide resins, 2～10 parts of core-shell polymers, 15～24 parts solidifying agent and 3.0～6.0 parts curing catalyst by weight; Wherein said solidifying agent is Dyhard RU 100 and 4; The cooperation solidifying agent of 4 '-diaminodiphenylsulfone(DDS); Wherein 4, the mass parts of 4 '-diaminodiphenylsulfone(DDS) and Dyhard RU 100 be respectively 18 parts and 6 parts, 14 parts and 7 parts, 10 parts and 8 parts, or 6 parts and 9 parts, said curing catalyst is organic ureas; B, 40 parts of phenol aldehyde type epoxy resins, 60 parts of bisphenol A epoxide resins and 2～10 parts of core-shell polymers that step 1 is taken by weighing mix in the adding container; Under agitation condition, be heated to 150 ℃ then; Add again that step 1 takes by weighing 4,4 '-diaminodiphenylsulfone(DDS) solidifying agent continues to stir also and is heated to 150 ℃; Insulation 3～5min is cooled to room temperature then and obtains the B b stage resin b; C, get the B b stage resin b that 30 parts of step 2 obtain and put into three-roll grinder; And then 3.0～6.0 parts curing catalyst taking by weighing of the dicy-curing agent that takes by weighing in the adding step 1 and step 1; In three-roll grinder, grind then 3～6 times; And then with the remaining B b stage resin b adding that step 2 prepares, continue in three-roll grinder, to grind 3～6 times, obtain epoxy matrix resin; The temperature of three-roll grinder described in the step 3 remains on 60～70 ℃;
Two, preparation prepreg: a, the single face separate-type paper hung to the single face separate-type paper successively twines on roll shaft (1), middle roll shaft (5) and the single face separate-type paper rolling winding roll shaft (4); Making the single face separate-type paper twine roll shaft (1), middle roll shaft (5) and single face separate-type paper rolling winding roll shaft (4) formation is in transmission connection; Then two-sided separate-type paper is hung successively to two-sided separate-type paper winding roll shaft (2), middle roll shaft (5) and product rolling winding roll shaft (3); Making two-sided separate-type paper twine roll shaft (2), middle roll shaft (5) and product rolling winding roll shaft (3) formation is in transmission connection; Again fibre knitting cloth is set between the single face separate-type paper and two-sided separate-type paper that is positioned between single face separate-type paper winding roll shaft (1) and the two-sided separate-type paper winding roll shaft (2); Wherein the single face separate-type paper contacts with middle roll shaft (5), then single face separate-type paper winding roll shaft (1) and two-sided separate-type paper winding roll shaft (2) is preheated to 75～85 ℃; B, the epoxy matrix resin that step 1 is prepared are poured the single face separate-type paper into and are twined in " V-type " space of roll shaft (1) and fibre knitting cloth formation; Starter gear then; Make fibre knitting cloth and epoxy matrix resin twine the slit between roll shaft (1) and the two-sided separate-type paper winding roll shaft (2) through the single face separate-type paper; Obtain the prepreg that both sides are stained with single face separate-type paper and two-sided separate-type paper respectively, wherein, control single face separate-type paper twine roll shaft (1) and and the two-sided separate-type paper distance of twining between the roll shaft (2) be 0.1～2mm; The LV that two-sided separate-type paper is twined roll shaft (2) is 100～300m/h, and the temperature of epoxy matrix resin is at 75～85 ℃; C, twine in the rolling of single face separate-type paper under the effect of roll shaft (4) the single face separate-type paper is peeled off, product rolling is simultaneously twined roll shaft (3) side is stained with the prepreg rolling of two-sided separate-type paper, promptly accomplishes the preparation of prepreg.
8. be used to prepare the device of prepreg as claimed in claim 5; Said device comprises that the single face separate-type paper is twined roll shaft (1), two-sided separate-type paper twines roll shaft (2), product rolling winding roll shaft (3), single face separate-type paper rolling winding roll shaft (4), middle roll shaft (5), the 3rd chain-drive mechanism (6), first (7), first chain-drive mechanism (8), second (9), second chain-drive mechanism (10) and first gear drive (11), second gear drive (14), the 3rd (15), single face separate-type paper are twined charging roll shaft (16), two-sided separate-type paper is twined charging roll shaft (17), the 4th chain-drive mechanism (18) and frame (22); First (7) are in transmission connection through first chain-drive mechanism (8) and second (9); Second (9) are twined roll shaft (2) through second chain-drive mechanism (10) and two-sided separate-type paper and are in transmission connection; Two-sided separate-type paper is twined roll shaft (2) and is in transmission connection through first gear drive (11) and single face separate-type paper winding roll shaft (1); The single face separate-type paper is twined roll shaft (1) and is in transmission connection through single face separate-type paper and single face separate-type paper winding charging roll shaft (16); Two-sided separate-type paper is twined roll shaft (2) and is in transmission connection through two-sided separate-type paper and two-sided separate-type paper winding charging roll shaft (17); First (7) are in transmission connection through the 3rd chain-drive mechanism (6) and the 3rd (15); The 3rd (15) are twined roll shaft (3) through second gear drive (14) and product rolling and are in transmission connection; The 3rd (15) are twined roll shaft (4) through the 4th chain-drive mechanism (18) and the rolling of single face separate-type paper and are in transmission connection; It is characterized in that said device comprises that also fibre knitting cloth twines roll shaft (12), spring (13) and adjusting screw(rod) (21); The fibre knitting cloth that fibre knitting cloth twines roll shaft (12) is arranged in the slit between single face separate-type paper winding roll shaft (1) and the two-sided separate-type paper winding roll shaft (2); Fibre knitting cloth twines roll shaft (12) and is in transmission connection through fibre knitting cloth and two-sided separate-type paper winding roll shaft (2); Two-sided separate-type paper is twined roll shaft (2) and is in transmission connection through prepreg moulding product and middle roll shaft (5); Middle roll shaft (5) twines roll shaft (3) through prepreg moulding product and product rolling and is in transmission connection; Middle roll shaft (5) twines roll shaft (4) through single face separate-type paper and the rolling of single face separate-type paper and is in transmission connection; Be provided with spring (13) between the axle head of single face separate-type paper winding roll shaft (1) and two-sided separate-type paper winding roll shaft (2); Adjusting screw(rod) (21) passes frame (22) and leans on two-sided separate-type paper winding roll shaft (2), and the single face separate-type paper is twined roll shaft (1), two-sided separate-type paper winding roll shaft (2), product rolling winding roll shaft (3), single face separate-type paper rolling winding roll shaft (4), middle roll shaft (5), first (7), second (9), the 3rd (15), single face separate-type paper winding charging roll shaft (16), two-sided separate-type paper twines charging roll shaft (17) and fibre knitting cloth winding roll shaft (12) all is contained on the frame (22).
9. device as claimed in claim 8 is characterized in that roll shaft (3) is twined in the product rolling, the rolling of single face separate-type paper is twined on roll shaft (4), fibre knitting cloth winding roll shaft (12), single face separate-type paper winding charging roll shaft (16) and the two-sided separate-type paper winding charging roll shaft (17) powder clutch (19) all is housed.
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| CN2010106116287A CN102108185B (en) | 2010-12-29 | 2010-12-29 | Epoxy matrix resin and prepreg and preparation method thereof and device for preparation thereof |
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| CN2010106116287A CN102108185B (en) | 2010-12-29 | 2010-12-29 | Epoxy matrix resin and prepreg and preparation method thereof and device for preparation thereof |
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| CN102108185B true CN102108185B (en) | 2012-07-04 |
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Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102675826A (en) * | 2012-04-25 | 2012-09-19 | 北京化工大学常州先进材料研究院 | Temperature-resistant high-strength high-toughness composite epoxy resin and manufacturing method thereof |
| CN102731969B (en) * | 2012-06-18 | 2014-12-17 | 航天材料及工艺研究所 | Flame retardant epoxy prepreg composite material |
| CN103694455B (en) * | 2012-09-28 | 2015-12-02 | 中国石油天然气股份有限公司 | A kind of be applicable in warm molten legal system for the concocting method of the epoxy resin of carbon fiber prepreg |
| CN104119639B (en) * | 2013-04-24 | 2016-08-03 | 台光电子材料(昆山)有限公司 | Non-halogen resin composition and apply its copper clad laminate and printed circuit board (PCB) |
| GB201313420D0 (en) * | 2013-07-26 | 2013-09-11 | Hexcel Composites Ltd | Improvements in or relating to fibre reinforced composites |
| JP6580359B2 (en) * | 2015-03-31 | 2019-09-25 | 三菱重工業株式会社 | Structure manufacturing method and structure |
| CN108368281B (en) * | 2015-12-10 | 2021-10-26 | 三菱化学株式会社 | Tow prepreg, composite material-reinforced pressure vessel, and method for producing composite material-reinforced pressure vessel |
| CN105907040B (en) * | 2016-06-14 | 2018-07-03 | 航天材料及工艺研究所 | Composition epoxy resin that a kind of suitable low temperature uses and preparation method thereof |
| CN106349650A (en) * | 2016-08-29 | 2017-01-25 | 江苏恒神股份有限公司 | Epoxy resin composition, preparing method, preparing method of prepreg and preparing method of composite |
| CN107868400A (en) * | 2016-09-26 | 2018-04-03 | 中国石油化工股份有限公司 | Intermediate temperature setting prepreg resin matrix and preparation method thereof |
| CN107353775B (en) * | 2017-08-01 | 2020-03-24 | 江苏恒神股份有限公司 | Carbon fiber reinforced resin matrix composite flame-retardant surface film and preparation method thereof |
| CN107722897A (en) * | 2017-10-25 | 2018-02-23 | 杭州之江新材料有限公司 | A kind of epoxy joint trimming agent and preparation method thereof |
| CN111320734B (en) * | 2018-12-13 | 2022-06-24 | 航天特种材料及工艺技术研究所 | Method for reducing volatile content in resin |
| CN112280293B (en) * | 2020-10-14 | 2022-10-28 | 航天材料及工艺研究所 | Hot-melt epoxy resin composition, preparation method and hot-melt prepreg thereof |
| CN114230980B (en) * | 2022-01-17 | 2024-02-06 | 武汉本邦复合材料科技有限公司 | Dry-method cold-drawn molding prepreg and preparation method thereof |
| CN114953304A (en) * | 2022-05-13 | 2022-08-30 | 苏州科阳半导体有限公司 | Preparation method of novel resin through hole adapter plate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1946780A (en) * | 2004-02-27 | 2007-04-11 | 东丽株式会社 | Epoxy resin composition for carbon-fiber-reinforced composite material, prepreg, integrated molding, sheet of fiber-reinforced composite material and cabinet for electrical/electronic equipment |
| CN101501132A (en) * | 2006-06-30 | 2009-08-05 | 东丽株式会社 | Epoxy resin composition, prepreg, and fiber-reinforced composite material |
| CN101824205A (en) * | 2004-02-27 | 2010-09-08 | 东丽株式会社 | Integrated molding, fiber-reinforced composite material board and housing for electric/electronic device |
-
2010
- 2010-12-29 CN CN2010106116287A patent/CN102108185B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1946780A (en) * | 2004-02-27 | 2007-04-11 | 东丽株式会社 | Epoxy resin composition for carbon-fiber-reinforced composite material, prepreg, integrated molding, sheet of fiber-reinforced composite material and cabinet for electrical/electronic equipment |
| CN101824205A (en) * | 2004-02-27 | 2010-09-08 | 东丽株式会社 | Integrated molding, fiber-reinforced composite material board and housing for electric/electronic device |
| CN101501132A (en) * | 2006-06-30 | 2009-08-05 | 东丽株式会社 | Epoxy resin composition, prepreg, and fiber-reinforced composite material |
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