CN102712168A - Carbon fiber laminated molded product, and method for producing same - Google Patents
Carbon fiber laminated molded product, and method for producing same Download PDFInfo
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- CN102712168A CN102712168A CN2011800067434A CN201180006743A CN102712168A CN 102712168 A CN102712168 A CN 102712168A CN 2011800067434 A CN2011800067434 A CN 2011800067434A CN 201180006743 A CN201180006743 A CN 201180006743A CN 102712168 A CN102712168 A CN 102712168A
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D1/00—Casings; Linings; Walls; Roofs
- F27D1/0003—Linings or walls
- F27D1/0006—Linings or walls formed from bricks or layers with a particular composition or specific characteristics
Abstract
Provided are a carbon fiber laminated molded product and a method for producing same wherein it is possible to improve processability and to reduce the cost of the carbon fiber laminated molded product which can be used as a heat insulating material for high temperature furnaces. The carbon fiber laminated molded product is characterized by comprising a carbon fiber paper, a carbon fiber felt laminate, and a woven layer formed from at least one carbon fiber woven fabric in which a carbon fiber spun yarn is woven. The method for producing the carbon fiber laminated molded product involves: a step (a) for laminating by coating an adhesive and for compression molding at least one carbon fiber woven fabric in which a hybrid carbon fiber spun yarn is woven, a laminate of a carbon fiber felt which is impregnated with a thermosetting resin, and a carbon fiber paper; and a step (b) for firing the compression molded laminate thus obtained.
Description
Technical field
The present invention relates to carbon fiber layer and be pressed into body and preparation method thereof.Carbon fiber layer according to the present invention is pressed into body, can reduce the cost that the carbon fiber layer that can be used as high temperature furnace used heat-barrier material is pressed into body, improves processability.In addition, preparation in accordance with the present invention can be simplified preparation section.
Background technology
Carbon fiber layer is pressed into body and is widely used as high temperature furnace used heat-barrier materials such as single crystal pulling stove, vacuum evaporation stove or ceramic post sintering stove owing to having the excellent heat-proof quality and the characteristic of heat capacity.Be pressed into body as above-mentioned carbon fiber layer, for example known have in carbon fiber felt a high resin of infiltration carbonation rate, with the product compression molding that lamination forms, processes the layered product of carbon fiber felt, and carbon fiber layer that its calcining is obtained is pressed into body.Such carbon fiber layer is pressed into body and under inert atmosphere, has high-fire resistance, can stand to reach the use about 3000 ℃.
But, in actual environment for use, often in high temperature furnace, producing the gas of oxidisability or the metal of gasification, carbon fiber layer is pressed into body and their reactions cause consumption and deterioration.For addressing this problem; Proposition has the composite carbonaceous heat insualtor (patent documentation 1) of carbonaceous protective layer on the surface that carbon fiber layer is pressed into body, or on the layered product of carbon fiber felt, be bonded with the tissue layer that is made into by the carbon fiber yarn carbon fiber-containing be laminated into body (patent documentation 2).Particularly the latter's carbon fiber-containing is laminated into the tissue layer in the body; Except that having the protective effect that makes its metal that avoids oxidizing gas or gasification; Also have with respect to using defencive function from the impact of outside and the breakage-proof of stress; The two sides of the layered product through being adhered to carbon fiber felt, can obtain to have simultaneously enough intensity and anti-fissility carbon fiber-containing be laminated into body (patent documentation 2).
But, be pressed into body for carbon fiber layer, the requirement of the processability when the reduction preparation cost being arranged and improving etc. as heat-barrier material, expectation is improvement further.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2000-327441 communique
Patent documentation 2: No. 2008/023777 communique of International Publication.
Summary of the invention
Invent problem to be solved
The inventor attempts in the layered product of carbon fiber felt, only the bonding tissue layer that comprises a kind of fabric on the face of contact with oxygen voltinism gas or gasified metal for cutting down preparation cost.But, since when calcining tissue layer and bonding its degree of shrinkage of bonding agent be higher than the degree of shrinkage of carbon fiber felt layered product, can know that bonding plane one side of tissue layer is shunk biglyyer, carbon fiber layer is pressed into the body warpage.
The inventor furthers investigate for addressing this problem, and the result finds: on the face of the opposition side of the face through carbon fiber paper being adhered to the bonding textiles layer, can eliminate the warpage that carbon fiber layer is pressed into body.
In addition; The inventor furthers investigate the simplification of preparation section in carbon fiber layer is pressed into the preparation method of body; The result finds: compression molding and carbon fiber felt laminate, tissue layer and carbon fiber paper bonding that can carry out the carbon fiber felt laminate simultaneously; Can reduce preparation section thus, cut down preparation cost.Promptly; In the embodiment of patent documentation 2; The operation of compression molding and calcining is carried out respectively 2 times: carry out as the compression molding of the carbon fiber felt laminate (base material) of base material and calcining subsequently; Through bonding agent tissue layer is adhered to the two sides of the base material of acquisition, further carries out compression molding and calcining.In the method for the invention, the operation of compression molding and calcining is 1 time, prepares simplification, and preparation cost obtains cutting down.
What need explanation is that the inventor attempts in preparation method of the present invention, using tissue layer to replace carbon fiber paper.That is, attempt tissue layer is adhered to the two sides of carbon fiber felt laminate (base material), carry out the operation of compression molding and calcining 1 time.At this moment owing to carry out the compression molding and subsequently the calcining of carbon fiber felt laminate as in the past in advance, so the carbon fiber felt laminate above be in soft state.In addition; Can know because tissue layer is soft, so if, then often particularly on the carbon fiber felt laminate, form fold in the tissue layer of lamination tissue layer and carbon fiber felt laminate coating adhesive, together compression molding; Commodity value reduces, the yield rate variation.In the present invention, owing to the higher carbon fiber paper of use hardness on the carbon fiber felt laminate, so do not form fold on the carbon fiber paper, commodity value does not reduce, and does not see that yield rate reduces.
The present invention is based on such opinion and accomplish.
Solve the means of problem
Therefore, the present invention relates to carbon fiber layer and be pressed into body, it is characterized in that comprising: the tissue layer, carbon fiber felt layered product and the carbon fiber paper that comprise at least a kind of carbon fibre fabric that is made into by the carbon fiber yarn.
Be pressed in the preferred implementation of body at carbon fiber layer of the present invention, with above-mentioned tissue layer, carbon fiber felt layered product and the carbon fiber paper that comprises at least a kind of carbon fibre fabric that is made into by the carbon fiber yarn according to this order lamination.
Be pressed in the preferred implementation of body at carbon fiber layer of the present invention, above-mentioned carbon fiber yarn is to contain the core of fiber diameter below 12 μ m to surpass the mixed carbon fibre yarn of the sheath material of 12 μ m with carbon fiber with carbon fiber and fiber diameter.
In addition, the present invention relates to comprise the high temperature furnace used heat-barrier material that above-mentioned carbon fiber layer is pressed into body.
In addition; The present invention relates to the preparation method that carbon fiber layer is pressed into body; Said preparation method comprises: at least a kind of carbon fibre fabric that (a) will be made into by the mixed carbon fibre yarn, infiltration have laminate and the carbon fiber paper of carbon fiber felt of thermosetting resin through the operation of coating adhesive lamination, compression molding and (b) operation of the compression molding layered product that obtains of calcining.
Be pressed in preparation method's the preferred implementation of body at carbon fiber layer of the present invention, in above-mentioned operation (a), tissue layer, carbon fiber felt layered product and the carbon fiber paper that will comprise at least a kind of carbon fibre fabric that is made into by the carbon fiber yarn are according to this order lamination.
The effect of invention
Carbon fiber layer according to the present invention is pressed into body, is pressed into body with existing carbon fiber layer that two sides at the carbon fiber felt layered product has a tissue layer and compares, and replaces the tissue layer of one side through using carbon fiber paper, but cutting down cost.
In addition, with regard to the preparation method that carbon fiber layer of the present invention is pressed into body, compression molding operation and calcination process only need 1 time can prepare, and the preparation method who is pressed into body with existing general carbon fiber layer compares, and can reduce preparation section, cuts down preparation cost.
In addition, in the method for the invention, when using tissue layer to replace carbon fiber paper; Promptly; Do not carry out the compression molding operation and the calcination process of carbon fiber felt layered product, and with tissue layer be adhered to the two sides of carbon fiber felt layered product, when carrying out the compression molding operation, in the particularly superincumbent tissue layer; Form fold, the yield rate variation.In preparation method of the present invention, owing to use carbon fiber paper, do not see the generation of fold, commodity value does not reduce, and does not see that yield rate reduces.
Description of drawings
[Fig. 1] illustrates the sectional view that carbon fiber layer of the present invention is pressed into 1 embodiment of body.
[Fig. 2] illustrates the sectional view (sketch map) of 1 embodiment of compression molding operation among the preparation method that carbon fiber layer of the present invention is pressed into body.
The specific embodiment
1. carbon fiber layer is pressed into body
Carbon fiber layer of the present invention is pressed into body and is characterised in that and comprises: the tissue layer, carbon fiber felt layered product and the carbon fiber paper that comprise at least a kind of carbon fibre fabric that is made into by the mixed carbon fibre yarn; Preferably with tissue layer, carbon fiber felt layered product and carbon fiber paper according to this order lamination.
[tissue layer]
Constitute the carbon fibre fabric of tissue layer among the present invention so long as the carbon fibre fabric that is made into by the carbon fiber yarn does not then have particular determination.For example; As the carbon fiber yarn; Can enumerate out yarn, the yarn that comprises pitch class anisotropy carbon fiber, the yarn that comprises the artificial silk based carbon fiber that comprise polypropylene nitrile (PAN class) carbon fiber, comprise the yarn of pitch class isotropic carbon fiber or comprise the mixed carbon fibre yarn of their combination, preferred especially mixed carbon fibre yarn.As the mixed carbon fibre yarn, for example can enumerate out the carbon fiber yarn of putting down in writing in the mixed carbon fibre yarn put down in writing in No. 2006/090643 communique of International Publication and No. 2008/023777 communique of International Publication.
The carbon fiber yarn of putting down in writing in No. 2008/023777 communique of International Publication for containing fiber diameter is below the 12 μ m, the core of preferred 5 ~ 12 μ m with carbon fiber and fiber diameter surpass 12 μ m, preferably above 12 μ m but the following sheath material of 20 μ m with the mixed carbon fibre yarn of carbon fiber.If core is with the fiber diameter less than 5 μ m of carbon fiber, then production efficiency reduces.In addition, if the sheath material surpasses 20 μ m with the fiber diameter of carbon fiber, then hot strength reduces, or when twisting thread easy the broken string.
Spendable in the present invention mixed carbon fibre yarn is preferably following yarn: core uses carbon fiber to be the anisotropy carbon fiber, and the sheath material uses carbon fiber to be isotropic carbon fiber.Can realize high tensile and high elastic modulus through core with carbon fiber, can be by the good bonding property of bonding agent realization through the sheath material with the heat treatment thing with carbon fiber.
In this manual, " anisotropy carbon fiber " refers to that the hot strength of carbon fiber is that the above or tensile modulus of elasticity of 1000MPa is more than the 100GPa, have carbon plane on the fiber axis direction selective fixed to the fiber of tissue.Particularly, can enumerate out polypropylene nitrile (PAN class) carbon fiber, pitch class anisotropy carbon fiber or artificial silk based carbon fiber, special optimization polypropylene nitrile (PAN class) carbon fiber.
In this manual, " isotropic carbon fiber " refers to not enough 1000MPa of the hot strength of carbon fiber or the not enough 100GPa of tensile modulus of elasticity, has the fiber of the nondirectional tissue of carbon plane, preferred especially pitch class isotropic carbon fiber.
Above-mentioned core has the longest fiber length below the 20m usually with carbon fiber in formed body.As constituting the raw material fiber of core with carbon fiber, be preferably the above average fiber length of 500mm usually, more preferably more than the 1000mm, further be preferably more than the 3m.The formation core does not have the special upper limit with the average fiber length of the raw material fiber of carbon fiber, can from the fibre length that can obtain, select according to purposes is suitable, but usually at the continuous fiber that can obtain in the industry below the 5000m.In yarn, because employed fibre length is long more, reduce at fiber abutment each other, so can improve the intensity of yarn.In addition, just constitute the sheath material with regard to the average fiber length of the raw material fiber of carbon fiber, retrievable curtailment 500mm in industry is preferably below the 300mm, more preferably below the 200mm usually.In addition, the average fiber length that especially preferably contains 3 ~ 30% quality, preferred 5 ~ 20% quality is more than the 150mm and the carbon fiber of not enough 500mm, and contains the carbon fiber of the not enough 150mm of 97 ~ 70% quality, preferred 95 ~ 80% quality.Above carbon fiber is very few if average fiber length is 150mm, and then the hot strength of carbon fiber yarn reduces, if too much, then in spinning process, be prone to cause broken string, the deviation of fiber number occurs, and easy generation is called as the bulk portion of slubbing, flyings, and quality reduces.
Core is preferably 1.65 ~ 2.30g/cm with the density of carbon fiber
3Scope, 1.70 ~ 2.00g/cm more preferably
3Scope, be preferably 1.70 ~ 1.90g/cm especially
3Scope.If core is too small with the density of carbon fiber, then carbonization is insufficient, as if excessive, and excessive crystallizationization then, intensity all reduces under arbitrary situation, is difficult to reach as the core of the reinforcement fabric intensity function with carbon fiber.
In addition, the sheath material is preferably 1.50 ~ 1.80g/cm with the density of carbon fiber
3Scope, 1.50 ~ 1.70g/cm more preferably
3Scope, be preferably 1.55 ~ 1.70g/cm especially
3Scope.If the sheath material is too small with the density of carbon fiber, then carbonization is insufficient, and the intensity of carbon fiber reduces, if excessive, then with the wetability variation of resin (bonding agent), be difficult to reach conduct and make the function of the sheath material of adhering fabric on the carbon fiber felt layered product with carbon fiber.
With regard to core with carbon fiber and sheath material with regard to the ratio of carbon fiber, core is preferably 5% quality ~ 50% quality with the blending amount of carbon fiber, more preferably 10% quality ~ 30% quality further is preferably 15% quality ~ 25% quality.If with blending quantity not sufficient 5% quality of carbon fiber, then there is the situation of the undercapacity of yarn in core, if surpass 50% quality, then there is the cementability reduction of yarn and carbon fiber felt layered product, cause guaranteeing the situation of (bending) intensity of formed body.
The quality (fiber number) of every 1000m of the carbon fiber yarn that is made up of with carbon fiber with carbon fiber and sheath material core is preferably 30 ~ 1000tex, more preferably 30 ~ 750tex.If be less than above-mentioned scope, then expend the preparation cost of yarn, if more than above-mentioned scope, then exist to knit and make the situation of difficult that becomes.The preparation method of carbon fiber yarn does not have particular determination, can adopt the conventional method of preparation mixed carbon fibre yarn, for example can adopt the method for putting down in writing in the method put down in writing in No. 2006/090643 communique of International Publication and No. 2008/023777 communique of International Publication.
Can use above-mentioned carbon fiber yarn, be made into the carbon fibre fabric that uses in the present invention.For example can use loom or rapier loom, process fabrics such as plain cloth, twills, satin fabric or hopsack.
The weight per unit area of carbon fibre fabric (FAW) preferably is made as 300 ~ 1200g/m
2, further preferably be made as 400 ~ 1000g/m
2, most preferably be made as 600 ~ 800g/m
2High from the viewpoint preferred unit area weight of protection carbon fiber felt layered product, but because the carbon fibre fabric thickening, processability reduces, so preferably be made as in the above-mentioned scope.
In carbon fibre fabric, yarn count density! Da ち Write body density) on warp-wise and broadwise, all be preferably 15 ~ 20 pieces/inch, more preferably 16 ~ 19 pieces/inch.The yarn count density of warp-wise and broadwise also can be different, but preferably have identical yarn count density.From the viewpoint of protection carbon fiber felt layered product, the same with weight per unit area, also preferred yarn count density is high, but because the carbon fibre fabric thickening, processability reduces, so preferably be made as in the above-mentioned scope.
The thickness of carbon fibre fabric is preferably 0.3 ~ 2.0mm, and more preferably 0.6 ~ 1.5mm most preferably is 0.8 ~ 1.3mm.The thickness of carbon fibre fabric is by the fiber number (tex) of carbon fiber yarn and the decisions such as yarn count density of carbon fibre fabric.Therefore, from the viewpoint of protection carbon fiber felt layered product, the same with weight per unit area, also preferred thickness is thick, but if blocked up, then processability reduces, so preferably be made as in the above-mentioned scope.
The tissue layer that carbon fiber layer of the present invention is pressed in the body comprises a kind of carbon fibre fabric at least.Can contain the carbon fibre fabric more than 2 kinds though carbon fiber layer is pressed into body, preferably comprise the tissue layer of a kind of carbon fibre fabric from the viewpoint of cutting down cost.The thickness of tissue layer is preferably 0.3 ~ 2.0mm, and more preferably 0.6 ~ 1.5mm most preferably is 0.8 ~ 1.3mm.
[carbon fiber felt layered product]
Carbon fiber layer of the present invention is pressed in the body, and the carbon fiber felt layered product is for to form the carbon fiber felt lamination more than a kind.Particularly, infiltration there is the carbon fiber felt lamination of resin, after compression molding, calcines and form.The number of plies of carbon fiber felt does not have particular determination, can confirm according to its purposes is suitable, for example when as high temperature furnace used heat-barrier material, is preferably 1 ~ 30 layer, more preferably 2 ~ 20 layers, further is preferably 4 ~ 10 layers.
In addition, the thickness of carbon fiber felt layered product is also according to purposes and difference, no particular determination, but when using formed body of the present invention as high temperature furnace used heat-barrier material, the scope of preferred 5 ~ 300mm, the further scope of preferred 10 ~ 150mm usually.Its reason is: if the thickness of carbon fiber felt layered product is blocked up, then production capacity reduces, if thin excessively, then thermal insulation reduces.
Preferred 0.05 ~ the 0.40g/cm of the bulk density of carbon fiber felt layered product
3Scope, further preferred 0.10 ~ 0.30g/cm
3Scope.If not enough 0.05g/cm
3, then thermal insulation reduces, if surpass 0.40g/cm
3, then forming pressure increases, so production capacity reduces.
The carbon fiber that constitutes carbon fiber felt preferably has the fiber diameter of 5 ~ 20 μ m, can more preferably use the carbon fiber with 8 ~ 18 μ m.If less than 5 μ m, the situation that then exists production efficiency to reduce, if surpass 20 μ m, the situation that then exists thermal insulation to reduce.In addition, the scope of the preferred 30 ~ 500mm of fibre length of the carbon fiber of formation carbon fiber felt, the further scope of preferred 50 ~ 250mm.As if not enough 30mm, then there is the weak situation of bending strength of carbon fiber felt layered product, if surpass 500mm, then exist fiber to be difficult to even dispersion, be difficult to prepare the situation of uniform felt.As the carbon fiber that constitutes carbon fiber felt, can enumerate out pitch class isotropic carbon fiber, polypropylene nitrile (PAN class) carbon fiber, artificial silk based carbon fiber or Ji Nuoer (Kynol, カ イ ノ ー Le) carbon fiber etc., but preferred pitch class isotropic carbon fiber.
Carbon fiber felt can be through obtaining above-mentioned carbon fiber acupuncture.The thickness of carbon fiber felt is preferably 5 ~ 30mm, more preferably 10 ~ 30mm.The carbon content rate of carbon fiber felt is preferably more than 80%, more preferably more than 90%, most preferably is more than 95%.
[carbon fiber paper]
Can use in carbon chopped fiber to add adhesive and copy the carbon fiber paper that paper forms, or in the carbon fiber paper that obtains further infiltration resin, the carbon fiber paper that the adhesive carbonization is formed through calcining.
As the carbon chopped fiber that uses in the carbon fiber paper, can not have particular restriction ground and use polyacrylonitrile based carbon fiber, pitch-based carbon fiber or artificial silk based carbon fiber, but preferred pitch-based carbon fiber.
The average fiber length of carbon chopped fiber is preferably 1 ~ 10mm.If the average fiber length of carbon chopped fiber is shorter than 1mm, then often the fiber of the protrusion in machine hand's preface increases, and product yield reduces.If the average fiber length of carbon chopped fiber is longer than 10mm, then, produce bulk portion, so quality reduces often owing in dispersion step, disperse variation.The fiber diameter of carbon chopped fiber is preferably 5 ~ 20 μ m.If the fiber diameter of carbon chopped fiber is less than 5 μ m, then often preparation cost raises.If the fiber diameter of carbon chopped fiber is greater than 20 μ m, then often owing to paper intensity reduces, so quality reduces.
As adhesive, for example can enumerate out polyvinyl alcohol, polyacrylonitrile, cellulose or polyvinyl acetate, but polyvinyl alcohol (PVA) is preferred because of coming off less of the excellence of the cohesive force in machine hand's preface, carbon chopped fiber.Adhesive with respect to the carbon fiber of 100 mass parts, preferably uses 5 ~ 50 mass parts.
The copying the paper method and can enumerate out of carbon fiber paper: make carbon chopped fiber be scattered in the wet method of the system of copying in the liquid medium and carbon chopped fiber is scattered in make it in the air dry method that deposits; But for even mixed adhesive, preferred wet method.
As the resin that uses in the carbon fiber paper, can enumerate out phenolic resins, furane resins, epoxy resin, melamine resin, imide resin, polyurethane resin, aromatic polyamide resin, pitch etc. separately, or enumerate out their mixture.
With regard to regard to the amount of the resin of carbon fiber paper, with respect to the carbon chopped fiber of 100 mass parts, 1 ~ 120 the resin of preferably infiltrating is calcined.
The weight per unit area of carbon fiber paper is preferably 20 ~ 60g/m
2, be preferably 30 ~ 50g/m
2Its reason is: if not enough 20g/m
2, the situation that then exists the intensity under the l Water Paper state (state before dry adhesive solidifies) to reduce is if surpass 60g/m
2, have then that weight increases the weight of under the l Water Paper state, finally because of the damaged situation of deadweight.
2. carbon fiber layer is pressed into the preparation method of body
The preparation method that carbon fiber layer of the present invention is pressed into body comprises: carbon fiber felt laminate and the carbon fiber paper that at least a kind of carbon fibre fabric that (a) will be made into by the mixed carbon fibre yarn, infiltration have a thermosetting resin is through the operation of coating adhesive lamination, compression molding and (b) operation of the compression molding layered product that obtains of calcining; Preferably with carbon fibre fabric, carbon fiber felt laminate and carbon fiber paper according to this order lamination.
Be pressed among the preparation method of body at carbon fiber layer of the present invention, the carbon fibre fabric of employed carbon fibre fabric for being made into by above-mentioned mixed carbon fibre yarn can use the carbon fibre fabric more than a kind or 2 kinds.When the carbon fibre fabric that uses more than 2 kinds, with bonding each carbon fibre fabric of bonding agent.
Carbon fiber felt can infiltrate in the carbon fiber felt more than a kind thermosetting resin through carbon fiber acupuncture is obtained, and carries out lamination, processes laminate and uses.
In addition, carbon fiber paper can use as stated and in carbon chopped fiber, to add adhesive and copy the organic bond carbon fiber paper that paper forms, or the resin that further infiltrates, the carbon binder carbon fiber paper that obtains through calcining.
Therefore the bonding agent that uses among the preparation method of the present invention carbonization through calcining preferably contains a large amount of carbon components, but does not make special restriction according to carbon content.
Particularly, can use the following composition adhesive composite that forms of mixed and dispersed equably: the thermosetting resin of the thermoset prepolymer of 60 ~ 100 mass parts, 20 ~ 60 mass parts; Staple length carbon fiber, carbon black, carbon dust or the graphite powder of 5 ~ 20 mass parts; The solvent of 5 ~ 20 mass parts; Water with 5 ~ 20 mass parts.
As thermoset prepolymer, can preferably enumerate out: the urea resin prepolymer; Melamine resin prepolymer, urea-modified melamine resin prepolymer; The guanamine resin prepolymer; Guanamines modified melamine resin prepolymer; The furane resins prepolymer; The alkyd resins prepolymer; The phenolic resins prepolymer; For example phenolic varnish type phenolic resins prepolymer, solvable novolac type phenolic resin prepolymer, phenolic varnish type alkyl phenolic resin prepolymer, solvable phenol aldehyde type alkyl phenolic resin prepolymer and their xylenes/formaldehyde condensation products, toluene/formaldehyde condensation products, or utilize the modified resin prepolymer of melamine resin, guanamine resin or urea resin; Epoxy prepolymer, for example two (the Alpha-Methyl glycidol ether) of the diglycidyl ether of bisphenol A diglycidyl ether, ester ring type glycol, bisphenol-A two (Alpha-Methyl glycidol ether), ester ring type glycol etc.Also mixed curing agent, curing catalysts etc. as required.Wherein, The preferred high resin prepolymer of carbonization yield rate can especially preferably use phenolic varnish type phenolic resins prepolymer, solvable novolac type phenolic resin prepolymer, phenolic varnish type alkyl phenolic resin prepolymer, solvable phenol aldehyde type alkyl phenolic resin prepolymer.
As thermosetting resin, can preferably enumerate out: urea resin; Melamine resin; Urea-modified melamine resin; Guanamine resin; The guanamines modified melamine resin; Alkyd resins; Furane resins; Unsaturated polyester resin; Phenolic resins, for example phenolic varnish type phenolic resins, solvable novolac type phenolic resin, phenolic varnish type alkyl phenolic resin, solvable phenol aldehyde type alkyl phenolic resin; Epoxy resin, for example two (the Alpha-Methyl glycidol ether) of the diglycidyl ether of bisphenol A diglycidyl ether, ester ring type glycol, bisphenol-A two (Alpha-Methyl glycidol ether), ester ring type glycol etc.Wherein, the preferred high resin of carbonization yield rate can especially preferably use phenolic varnish type phenolic resins, solvable novolac type phenolic resin, phenolic varnish type alkyl phenolic resin, solvable phenol aldehyde type alkyl phenolic resin.
As solvent, can preferably use acetone, MEK, methyl iso-butyl ketone (MIBK), methyl alcohol, ethanol, 2-furancarbinol, toluene, xylenes or methyl-sulfoxide etc.
Bonding carbon fibre fabric of bonding agent and carbon fiber felt laminate, and bonding carbon fiber felt laminate and carbon fiber paper.The use amount of the bonding agent separately with respect to carbon fibre fabric or carbon fiber felt laminate, is preferably 500 ~ 3000g/m
2, further be preferably 1000 ~ 2500g/m
2, most preferably be 1200 ~ 2200g/m
2Its reason is: if not enough 500g/m
2, then bonding force dies down, if surpass 3000g/m
2, then bonding agent solidifies after calcining, and carbon fiber layer is pressed into the processability variation of body.
The coating process of bonding agent can adopt usual way, coatings such as for example available scraper, brush or roller.
As the thermosetting resin that infiltrates in the above-mentioned carbon fiber felt; Can enumerate out urea resin, melamine resin, phenolic resins, epoxy resin, unsaturated polyester resin, alkyd resins, polyurethane resin, furane resins etc., but the preferred high phenolic resins of carbonization yield rate.
Make above-mentioned resin impregnated in carbon fiber felt, the sheet that obtains purpose purposes desired thickness is counted lamination, modulation carbon fiber felt laminate.With respect to the carbon fiber felt of 100 mass parts, the infiltration amount of resin is preferably 10 ~ 100 mass parts, more preferably 15 ~ 50 mass parts.
[compression molding operation]
According to Fig. 2 the compression molding operation among the preparation method of the present invention is described.
In the compression molding operation, carbon fibre fabric (12) is placed on the following corrosion resistant plate (23) of compression molding device (2) bonding agent (25) of coating ormal weight on carbon fibre fabric.When the carbon fibre fabric that uses more than 2 kinds,, also be coated with the bonding agent of ormal weight in the above with the 2nd carbon fibre fabric lamination.In the infiltration of above-mentioned carbon fibre fabric laminated the carbon fiber felt more than a kind (14) of thermosetting resin is arranged, form carbon fiber felt laminate (13).At the bonding agent (25) of the top of this carbon fiber felt laminate coating ormal weight, with carbon fiber paper (10) lamination.The laminate that comprises carbon fibre fabric, carbon fiber felt laminate and carbon fiber paper that obtains, the thermosetting resin cured pressure and temperature lower compression that can in the carbon fiber felt laminate, infiltrate is shaped, and thermosetting resin and bonding agent are solidified, and obtains to be compressed into body.
Process the body that is compressed into of target thickness for the laminate that will comprise carbon fibre fabric, carbon fiber felt laminate and carbon fiber paper; Through around above-mentioned laminate, disposing the dividing plate (22) of target thickness, the method for compression molding then, scalable shortens the thickness of body into.In addition, be compressed into the thickness of body, can adjust the bulk density of carbon fiber felt layered product through adjustment.
Pressure in the compression molding operation for example can carry out under 0.1 ~ 1MPa so long as the use aforementioned barriers does not then have particular determination.In addition, the temperature of above-mentioned heating platen is so long as the thermosetting resin cured temperature of infiltrating in the carbon fiber felt, and then indefinite for example can be carried out in 150 ~ 200 ℃.In addition, the time of compression molding also can suit to stipulate, for example can under 10 minutes ~ 5 hours, carry out.
What need explanation is, in this manual, the laminate that the carbon fiber felt laminate refers to infiltrate and has resin and lamination to form means laminate and the laminate after the compression molding before the compression molding.
[calcination process]
Calcination process among the preparation method of the present invention can be in carrying out below 3000 ℃ in nonoxidizing atmosphere.As nonoxidizing atmosphere, for example can enumerate out under vacuum state, the blanket of nitrogen or under the argon atmospher.Temperature is not so long as the temperature of generation carbonization then has particular determination.
Embodiment
Followingly the present invention is specified, but they not delimit the scope of the invention according to embodiment.
In an embodiment, the various rerum naturas of yarn woven fabric are measured through following method.
[hot strength of yarn woven fabric]
To use Tensilon (テ Application シ ロ Application) universal testing machine [Orientec Co.; Ltd. ((strain) オ リ エ Application テ ッ Network) made; " RTC-1310 type "] fracture strength when the condition stretched yarn woven fabric that the specified 10kN of force cell, the long 150mm of sample, the wide 50mm of sample, draw speed 200mm/ divide is converted into the wide value of every 1cm sample, with its hot strength as this yarn woven fabric.
[thickness of yarn woven fabric]
Sample in that to go out 100mm * 100mm apart from the medial cuts more than the yarn woven fabric edge 30mm square, is measured its central portion the value that the obtains thickness as yarn woven fabric with micrometer [(strain) ミ Star ト ヨ system, U font micrometer " PMU 150-2 "].
" embodiment 1 "
[preparation of carbon fibre fabric]
The carbon fiber yarn that will be made up of the sheath portion that comprises pitch-based carbon fiber of the core that comprises the PAN based carbon fiber of 20% quality and 80% quality is tiltedly knitted as warp thread and weft yarn, and (tiltedly knit, FAW is 700g/m to obtain yarn woven fabric
2, yarn count density is 17.0 pieces/inch of warp-wises and 17.0 pieces/inch of broadwises, hot strength is 0.32kN, thickness is 1.0mm).
[modulation of bonding agent]
The adhesive and carbon fiber yarn fabric mat laminate and laminate bonding of carbon fiber felt and carbon fiber paper of the adhesive, the following materials were mixed and dispersed uniformly to thereby prepare an adhesive agent: 15 parts by mass of the phenolic resin impregnation liquid [Showa Polymer (Ltd.), "Shonol? (Shin ョ ウ Bruno ー Hikaru)? BRS-3897"], 25 parts by mass of powder of phenolic resin [Cashew? Co.,? Ltd.? (grades Shin Rue ウ ー (strain)) system, "Cashew ? (grades Shin Rue have) resin No.05 "], 10 parts by mass of carbon short fiber [Kureha? Corporation? ((strain) Kureha) system, Curecachop? (CLEA grades チ ョ ッ plastic)? M-107T, average fiber length 0.7mm, ?
], 10 parts by mass 2 - furanmethanol [Pure Chemical (strains) system, the pure 1], 40 parts by weight of ethanol mixed solution [Japan? Alcohol? Trading? Co.,? Ltd.? (Japan Asia Hikaru co ー Hikaru Sales (strain)) system. " Solmix? (ソ Hikaru mini ッ ku su)? H-23 "].
" compression molding operation "
Make phenolic resins class infiltration liquid [clear and macromolecule (strain) system of 44 mass parts; " Shonol (シ ョ ウ ノ ー Le) BRS-3896 "] infiltrate in pitch-based carbon fiber felt [Kureha Corporation ((strain) Network レ Ha) system of 100 mass parts; " Curecafelt (Network レ カ Off ェ Le ト) F-110 "] in; Lamination is a tabular for 6 layers, preparation carbon fiber felt laminate.
On the compression molding device, lay above-mentioned carbon fibre fabric, with 1200g/m
2The basic weight of ratio is coated with above-mentioned bonding agent with brush.Ground lamination carbon fiber felt laminate does not pressurize on this carbon fibre fabric.And then, in the top of carbon fiber felt laminate with 1200g/m
2The basic weight of ratio is coated with above-mentioned bonding agent with brush.With the phenolic resins class infiltration liquid that is immersed in 15 mass parts [clear and macromolecule (strain) system; " Shonol (シ ョ ウ ノ ー Le) BRS-3896 "] in carbon fiber paper [Kureha Corporation ((strain) Network レ Ha) system, " Curecapaper (Network レ カ ペ ー パ ー) E-204 "] lamination.
Around the formed laminate that comprises carbon fibre fabric, carbon fiber felt laminate and carbon fiber paper, configuration is adjusted into the dividing plate of 40mm in order to the thickness with the targeted compression formed body, compresses then and heat, makes resin solidification, and acquisition is compressed into body.
" calcination process "
With obtain be compressed into body in the vacuum nitrogen atmosphere in 2000 ℃ of graphitization processing of carrying out 1 hour, obtaining has tissue layer, another side lamination to have the tabular carbon fiber layer of carbon fiber paper to be pressed into body at a lamination of carbon fiber felt layered product.
" embodiment 2 "
(tiltedly knit, FAW is 785g/m to remove the use yarn woven fabric
2, yarn count density is 18.0 pieces/inch of warp-wises and 18.0 pieces/inch of broadwises, hot strength is 0.34kN, thickness is 1.1mm) outside, operate equally with embodiment 1, the acquisition carbon fiber-containing be laminated into body.
" embodiment 3 "
(tiltedly knit, FAW is 700g/m to remove the use yarn fabric
2, yarn count density is 16.0 pieces/inch of warp-wises and 18.0 pieces/inch of broadwises, hot strength is 0.32kN, thickness is 1.0mm) outside, operate equally with embodiment 1, the acquisition carbon fiber-containing be laminated into body.
The yarn woven fabric layer that is laminated into body of the arbitrary carbon fiber-containing among the embodiment 1 ~ 3 is all smooth, does not see the generation of fold.In addition, do not find that warpage etc. is unusual yet.
Utilizability on the industry
The body that is laminated into of carbon fiber-containing of the present invention can be used as high temperature furnace used heat-barrier materials such as crystal lifting furnace, vacuum evaporation stove or ceramic post sintering stove.
The present invention will be described for the specific embodiment of above foundation, but conspicuous variant of those skilled in the art or improvement are also contained in the scope of the present invention.
Symbol description
1 carbon fiber layer is pressed into body;
10 carbon fiber papers;
11 carbon fiber felt layered products;
12 carbon fibre fabrics;
13 carbon fiber felt laminates;
14 carbon fiber felts;
2 compression molding devices;
21 heating platens (top);
22 dividing plates;
23 corrosion resistant plates;
24 heating platen plates (following);
25 binding agents.
Claims (6)
1. carbon fiber layer is pressed into body, it is characterized in that comprising: the tissue layer, carbon fiber felt layered product and the carbon fiber paper that comprise at least a kind of carbon fibre fabric that is made into by the carbon fiber yarn.
2. the carbon fiber layer of claim 1 is pressed into body, and wherein, above-mentioned tissue layer, carbon fiber felt layered product and the carbon fiber paper that comprises at least a kind of carbon fibre fabric that is made into by the carbon fiber yarn is according to this order lamination.
3. claim 1 or 2 carbon fiber layer are pressed into body; Wherein, Above-mentioned carbon fiber yarn is the mixed carbon fibre yarn, and said mixed carbon fibre yarn contains the core of fiber diameter below 12 μ m uses carbon fiber with the sheath material that carbon fiber and fiber diameter surpass 12 μ m.
4. high temperature furnace used heat-barrier material, said material comprise that each carbon fiber layer is pressed into body in the claim 1 ~ 3.
5. carbon fiber layer is pressed into the preparation method of body, and said preparation method comprises:
Laminate and the carbon fiber paper of carbon fiber felt that at least a kind of carbon fibre fabric that (a) will be made into by the mixed carbon fibre yarn, infiltration have a thermosetting resin through coating adhesive lamination, compression molding operation and
(b) operation of the compression molding layered product of calcining acquisition.
6. the carbon fiber layer of claim 5 is pressed into the preparation method of body, and wherein, in above-mentioned operation (a), tissue layer, carbon fiber felt layered product and the carbon fiber paper that will comprise at least a kind of carbon fibre fabric that is made into by the carbon fiber yarn are according to this order lamination.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-012295 | 2010-01-22 | ||
| JP2010012295 | 2010-01-22 | ||
| PCT/JP2011/051053 WO2011090151A1 (en) | 2010-01-22 | 2011-01-21 | Carbon fiber laminated molded product, and method for producing same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102712168A true CN102712168A (en) | 2012-10-03 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2011800067434A Pending CN102712168A (en) | 2010-01-22 | 2011-01-21 | Carbon fiber laminated molded product, and method for producing same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPWO2011090151A1 (en) |
| CN (1) | CN102712168A (en) |
| TW (1) | TW201139151A (en) |
| WO (1) | WO2011090151A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104339730A (en) * | 2013-08-01 | 2015-02-11 | 甘肃郝氏炭纤维有限公司 | Sandwich cured carbon felt |
| CN105339721A (en) * | 2013-06-04 | 2016-02-17 | 霓佳斯株式会社 | Heat insulation material and method of manufacturing heat insulation material |
| CN112424523A (en) * | 2018-09-21 | 2021-02-26 | 大阪燃气化学株式会社 | Carbon fiber forming heat insulation material and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102570076B (en) * | 2012-02-02 | 2014-09-24 | 中国科学院电工研究所 | Hough-type transition connection device for large-current high-temperature superconducting cable terminal |
| JP6187753B2 (en) * | 2012-08-22 | 2017-08-30 | 王子キノクロス株式会社 | Method for producing carbon fiber nonwoven fabric for heat insulating material precursor and method for producing heat insulating material |
| US20150354897A1 (en) * | 2013-02-05 | 2015-12-10 | Sach Sisolar ,Inc. | Crucible liner |
| CN114773080A (en) * | 2022-05-10 | 2022-07-22 | 吉林联科特种石墨材料有限公司 | Preparation method of three-in-one heat-insulating material with graphene as heat reflecting layer |
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| JPS6348763A (en) * | 1986-08-14 | 1988-03-01 | Kureha Chem Ind Co Ltd | Composite electrode substrate bonded with teflon and its manufacture |
| JP2005133032A (en) * | 2003-10-31 | 2005-05-26 | Kureha Chem Ind Co Ltd | Adhesive for heat insulating material and carbonized laminated product for use in heat insulating material using the same |
| WO2008023777A1 (en) * | 2006-08-22 | 2008-02-28 | Kureha Corporation | Laminated molded article containing carbon fiber and method for production thereof |
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- 2011-01-21 TW TW100102328A patent/TW201139151A/en unknown
- 2011-01-21 JP JP2011550965A patent/JPWO2011090151A1/en active Pending
- 2011-01-21 WO PCT/JP2011/051053 patent/WO2011090151A1/en active Application Filing
- 2011-01-21 CN CN2011800067434A patent/CN102712168A/en active Pending
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| JPS6348763A (en) * | 1986-08-14 | 1988-03-01 | Kureha Chem Ind Co Ltd | Composite electrode substrate bonded with teflon and its manufacture |
| JP2005133032A (en) * | 2003-10-31 | 2005-05-26 | Kureha Chem Ind Co Ltd | Adhesive for heat insulating material and carbonized laminated product for use in heat insulating material using the same |
| WO2008023777A1 (en) * | 2006-08-22 | 2008-02-28 | Kureha Corporation | Laminated molded article containing carbon fiber and method for production thereof |
| JP2008165038A (en) * | 2006-12-28 | 2008-07-17 | Fujifilm Corp | Optical element and its manufacturing method |
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Cited By (4)
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| CN105339721A (en) * | 2013-06-04 | 2016-02-17 | 霓佳斯株式会社 | Heat insulation material and method of manufacturing heat insulation material |
| CN111457194A (en) * | 2013-06-04 | 2020-07-28 | 霓佳斯株式会社 | Thermal insulation material and method for manufacturing thermal insulation material |
| CN104339730A (en) * | 2013-08-01 | 2015-02-11 | 甘肃郝氏炭纤维有限公司 | Sandwich cured carbon felt |
| CN112424523A (en) * | 2018-09-21 | 2021-02-26 | 大阪燃气化学株式会社 | Carbon fiber forming heat insulation material and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2011090151A1 (en) | 2013-05-23 |
| WO2011090151A1 (en) | 2011-07-28 |
| TW201139151A (en) | 2011-11-16 |
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