CN1139399A - Process and apparatus for resin impregnation of a porous web - Google Patents

Process and apparatus for resin impregnation of a porous web Download PDF

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Publication number
CN1139399A
CN1139399A CN94194689.4A CN94194689A CN1139399A CN 1139399 A CN1139399 A CN 1139399A CN 94194689 A CN94194689 A CN 94194689A CN 1139399 A CN1139399 A CN 1139399A
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CN
China
Prior art keywords
resin
roller
diameter
porous
thermosetting resin
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Granted
Application number
CN94194689.4A
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Chinese (zh)
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CN1043972C (en
Inventor
S.R.伊尔
C.D.施里尔
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Faustel Inc
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Shell Internationale Research Maatschappij BV
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B15/00Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
    • B29B15/08Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
    • B29B15/10Coating or impregnating independently of the moulding or shaping step
    • B29B15/12Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
    • B29B15/122Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2101/00Use of unspecified macromolecular compounds as moulding material
    • B29K2101/10Thermosetting resins
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/02Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

A process and apparatus are described for impregnating a porous web with a thermosettable resin. The process involves the use of resin application means comprising a large-diameter rotating roller (4) on which is deposited a liquid-form thermosettable resin in essentially uncured state; passing a porous web (2) in countercurrent contact with the thermosettable resin so as to transfer the thermosettable resin into the porous web; passing the resin-containing fibrous web in countercurrent contact with at least one small-diameter rotating roller (11, 12); and passing the resin-containing fibrous web to a heating zone (13) to partially cure the resin and form a prepreg. The process is particularly suited for application of a solventless resin formulation to a glass web in the preparation of a prepreg for an electrical laminate. The apparatus includes resin application means comprising a large-diameter rotating roller (4); means for applying a liquid-form thermosettable resin onto the rotatable roller; means for advancing, in a countercurrent direction with respect to the direction of motion of the roller, a fibrous web (2) to the roller and in contact with the thermosettable resin thereon and thence to a resin cure zone; and at least one small-diameter roller (11, 12) between the large-diameter roller and the resin cure zone (13) to apply heat to smooth the surface of the resin-containing web and to promote resin penetration thereof.

Description

The method and apparatus of resin dipping porous net
The present invention relates to thermosetting resin dipping porous net.In specific embodiment, the present invention relates to method and apparatus with solvent-free aathermoset resin system impregnated glass fiber base material.
The manufacturing of cured thermosetting circuit board substrate starts from liquid thermosetting resin system impregnated glass fiber base material.Then " preimpregnation materials and parts " are made in the base material part curing of resin dipping.The preimpregnation materials and parts of one group of stratiform are depressed heating adding, resin is solidified fully and make hard laminate, it is as the substrate of circuit board.
Though existing various thermosetting resins, as at room temperature being the low-molecular-weight epoxy resin of liquid, but now circuit board requires to use at room temperature the high performance resin system as solid or thick liquid, and with resin to be coated on the base material in fusion form or the solution form.But the processing thermosetting resin is difficult under molten condition, because make the required high temperature of resin fusion can make the resin premature setting, makes resin poor to " infiltration " of base material, i.e. saturation deficit.
The commercial run that is used to make the preimpregnation materials and parts now be organic solution with resin with resin-coating to base material.Solwution method must comprise such one usually with the partly solidified step of carrying out of resin, in this step,, solvent is removed from the preimpregnation materials and parts by solvent is heated to volatilization temperature.But this method has many shortcomings: at first, it need handle or discharge organic volatile.Secondly, solvent volatilizees from uncured resin and may produce cavity and inhomogeneities in the preimpregnation materials and parts and then in the laminate that solidifies.In addition, remove solvent step and need a large amount of time.
Having proposed a kind of method, to be used for that solventfree resin is coated to glass fibre online, this method comprise with solventfree resin deposit to the rotation roller on, and make reverse contact of the glass fiber mesh and the resin of deposition pass through the rotation roller so that resin transfer is moving online, then through optional second applicator roll that resin-coating is arrived the reverse side of net, deliver to bringing-up section, make resin partly solidified.This method is open in EP476752.Hope is removed second applicator roll under the condition of not damaging product appearance and quality.
So, the purpose of this invention is to provide a kind of method and apparatus with thermosetting resin impregnation of fibers base material.One concrete aspect, the purpose of this invention is to provide the method for simplifying and the cheap apparatus of the solvent-free aathermoset resin system impregnated glass fiber of a kind of usefulness base material.
So, the present invention relates to a kind ofly by the method for following steps with thermosetting resin dipping porous net, uncured liquid form thermosetting resin has been deposited on the larger-diameter rotation applicator roll; Make the porous net with described roller on the reverse mode that contacts of described resin pass through so that thermosetting resin is transferred on the porous substrate; Make the porous base that contains resin just by the section of being heating and curing, make resin partly solidified.In the method, resiniferous porous substrate is by solidifying before the section, and the one side at least of resiniferous porous substrate has the conditioning roller than minor diameter to contact with at least one.
In exemplary embodiments of the present invention, a kind of like this method with thermosetting resin dipping porous net is provided, this method comprises: the resin-coating equipment that provides the rotation roller; The liquid form thermosetting resin prescription that will contain uncured basically thermosetting resin deposits on the rotation roller; Make the porous net to pass through, so that the thermosetting resin prescription is transferred on the porous substrate with the thermosetting resin of rotation on the roller reverse mode that contacts of filling a prescription; At least the one side of resiniferous fiber base material is contacted with at least one rotation roller than minor diameter; And make resiniferous fiber base material by solidifying section, make resin partly solidified and make the preimpregnation materials and parts that contain porous substrate and partly solidified thermosetting resin.
According to the present invention, also provide a kind of and flood the device that the porous net prepares the preimpregnation materials and parts with thermosetting resin, this device includes the resin-coating equipment of rotation applicator roll; Make the thermosetting resin of liquid form deposit to equipment on the applicator roll; To become reverse the porous net is fed to applicator roll, and contacts, be fed to the equipment of resin solidification section then with thermosetting resin on it with respect to the direction of motion that applies the rotation roller; And at least one rotation roller between applicator roll and described resin solidification section than minor diameter.
The present invention is for providing a kind of technology of suitable simple and inexpensive with the thermosetting resin impregnation of fibers base material of liquid form.This method is particularly suitable for preparing the preimpregnation materials and parts that finally are used for electrical laminated plate with solventfree resin system impregnated glass fiber net.The purpose of resin-coating method of the present invention is the abundant infiltration that reaches base material, so that does not use second applicator roll to make resin-coating arrive the reverse side of base material, from but make high-quality cured layer pressing plate more economically.
In resin-coating method of the present invention, with the hot solids thermoplastic resin-impregnated fibers base material of liquid form.Though the inventive method useable solvents base resin is implemented, for method of the present invention, preferred resin system is the resin system that does not contain organic solvent, as water-based resin system or solventfree resin system.For the solventfree resin system, can at room temperature there be low viscous thermosetting resin to reach liquid form by using, perhaps thermosetting resin is heated to such temperature, reach the abundant just enough low viscosity of base of soaking into.Certainly be that under one situation of back, resin system (thermosetting resin and any curing component that uses with it) must be without any the curing of significance degree in the time range of base material dipping process under its melt temperature.
Can be with reference to figure 1 explanation resin-coating method of the present invention and device, base material 2 (is generally any short fiber, felt or woven porous material, be preferably woven glass fiber mesh) to send to from conveying equipment 1, conveying equipment generally includes and be used for automatic equipment that net is sent under selected speed and institute's network selection tension force.Fleece can be chosen wantonly by for example infrared heater heating before being fed to the resin-coating section.Guide device 3 is installed makes net be sent to resin-coating roller 4 with certain contact angle α radian.Angle α can be with the total structural change of coating scheme, but usually in 30-180 degree scope, preferred 90-150 degree, and 120-150 degree most preferably, so that make resin waste minimum, and that the heat from the roller to the base material is transmitted is maximum.Rotation roller 4 is delivered to liquid resin film 5 basal plane of the reverse net that passes through 2.Applicator roll 4 remains under such temperature, and resin molding 5 is remained under the liquid form that does not solidify basically.This temperature changes with resin, but usually in 50-250 ℃ of scope, preferred 100-200 ℃.The speed that tension force when making rotary speed, the net 2 contact pressure resin films 5 of applicator roll 4 and net 2 are fed to applicator roll is coordinated mutually, so that make Wondertek arrive good infiltration.These specification requirements can be with the variations such as heating efficiency of resin system, net materials type and B-staging unit, downstream.Usually, the rotary speed of applicator roll 4 in the 70-160% of network speed scope, the 100-140% of preferred network speed; The tension force of net 2 usually in 0.4536-1.3608kg (1-3 pound)/2.540cm (liner inch) scope, preferred 0.6804-0.9072kg/2.540cm (1.5-2.0PLI); And the feed rate of resin-coating section is crossed in 0.04064-1.016m/s (8-200ft/min) scope by Netcom, preferred 0.127-0.635m/s (the about 125ft/min of 25-).
By the resin delivery device that is shown nozzle 7 here resin molding 5 is coated on the applicator roll 4, nozzle 7 can be coated to the liquid resin of controlled amounts on the surface of revolution of applicator roll.Nozzle 7 can carry the equipment of the resin of liquid form to link to each other in room temperature or under heating up with any continuously.To under different volumetric rate, carry out resin transfer, synchronous with the speed of mobile network, so that, make the time of staying in the resin transfer system the shortest simultaneously with the resin transfer of predetermined on the net.Resin delivery device for example can comprise static mixing machine, the dynamic mixer that the outlet of temperature control links to each other with nozzle 7 or mix squeezer.
Use measuring equipment with resin delivery device 7, so that control is transported to the quantity of online liquid resin, measuring equipment here is shown decides crack roller 8 between the contact point that is installed in nozzle 7 and resin molding 5 and sends net to.Decide crack roller 8 and be preferably one and roller than minor diameter arranged than applicator roll 4, with respect to the applicator roll counter-rotating, its rotary speed in network speed 1-50% scope, preferred 8-35%.Optional scraper plate 10 can be installed, to prevent that resin from refluxing from coated side, by with the pitch deposition face with decide the crack roller and install forward with respect to applicator roll 4, promptly with the angle β of horizontal radius less than 90 °, so that prevent that by gravity resin from counterclockwise flowing down also and can reach such result from being coated with roller.The slit of deciding between crack roller 8 and the applicator roll 4 by careful setting under first kind of situation that is controlled at of resin-coating speed on the net reaches, to obtain uniform thickness.Secondly, the rotary speed of applicator roll matches with network speed, with resin molding is transferred to mobile on the net.In addition, because do not need film-traying roll to control contacting of mobile net and applicator roll, therefore need control net tension force to guarantee the stable operation of resin-coating process.
Optional resin is removed equipment 9 (scraper plate shown here) and is used for removing at resin molding 5 and sending between the net 2 after the contact from applicator roll, such cull by before 360 ° of rotations of roller on roller residual any resin.Resin is removed equipment and is preferably mounted at roller and the porous net place that sends to, thus at net with before applicator roll contacts, make that directly to deposit to porous from any resin that contacts with scraper plate online.
Resiniferous net 6 is fed to by the conditioning roller 11 and 12 with respect to the feeding direction backwards rotation of netting and solidifies section 13, and optional thermal source (not shown) can be installed, and makes its heating with the resiniferous net of box lunch when the resin-coating face is sent to.Heating steps impels resin to flow in net or by net in the middle of this, by the net of resin pickup and vertical direction are 45 ° at the most (preferably 20-40 °) also can increase mobile, as shown in Figure 1.
Can or can contact with the conditioning roller at the back side (shown in roller 12) of the resin-coating face of netting at the resin-coating face of netting (shown in conditioning roller 11), the both has the required effect that promotes that resin permeates and produce the appearance of smooth rule in the preimpregnation materials and parts.The temperature of conditioning roller remains on and makes resin viscosity effectively in required scope, makes resin solidification minimum again simultaneously, usually in 120-250 ℃ of scope.The number of used conditioning roller is generally 1-10 roller with the variation of operating parameters of prepreg process, preferred 2-6 roller.Usually, along with network speed increases, for the number of the required conditioning roller of the outward appearance that keeps required preimpregnation materials and parts also increases.
The diameter of conditioning roller is usually less than 20.32cm (8in), preferably in 1.27-15.24cm (0.5-6in) scope.The diameter of conditioning roller is littler than applicator roll, and the latter's diameter is usually greater than 25.4cm (10in).In operation, found that such minor diameter conditioning roller " mentions " resin from network, be with it around the roller rotation, and resin is deposited on the net once more that the pressure resin is by netting interior and promoting the effect of required resin web in this process.Usually, the diameter of conditioning roller is littler by 20% than applicator roll, and the diameter of preferably nursing one's health roller is the 20-70% of applicator roll, preferred 30-55%.
The common available Fig. 2 of prepreg process of the present invention describes.The Autonet that fleece 43 usefulness are fit to is sent system 42 to and is transported to resin-coating section 44, and this system has the measurement device of control feed rate and net tension force.The net tension control apparatus is known in this specialty.For example, separating winding up roller 41 can have lock with front end dancer rools combination, and its keeps intending going into to be in the predetermined net tension force into the unit of leading between dancer rools and the resin-coating section.Equally, can keep the downstream net tension force that is fit to by the dancer rools that the speed that makes the variable-ratio that is in the bringing-up section downstream decide the diameter roller is slowed down.
Fleece is sent to by resin-coating section 44, and here the resin-coating segment table is shown and is vertically oriented, and wherein when liquid resin applied with the method that describes in detail above, net passed through by controlled speed with usually up direction.Coated segment 44 comprises resin delivery device, and the blender that has resin to mix with curing system remains on the required temperature control of required viscosity with resin system.
The net that resin is saturated is fed to by conditioning roller 45 and 46 from the resin-coating section and solidifies section 47, in the resin solidification section, the Netcom that resin is saturated crosses to be exposed in thermal source such as convection furnace or the infrared heater and heats, and resin is solidified in the situation lower part of not gelling, and this process is called " B-staging ".The temperature of solidifying section changes with resin system and required resin solidification degree, but usually in 120-250 ℃ of scope, preferred 150-230 ℃.The net that resin is saturated will be subjected to being enough to reaching the B-staging of required state of cure time and handle, and 15% curable groups such as epoxy radicals are solidified, and preferably at the most 10%, more preferably at the most 5%, the time is generally 10s to 8min.Net is sent to from resin solidification section 47 with the form of preimpregnation materials and parts 48, and twists on the draw roll 49, so that store, can directly send in lamination on the other hand.
By being handled to make resin solidification and make the preimpregnation materials and parts force together into laminar structure, one group of stratiform preimpregnation materials and parts makes laminate.Laminate can have been chosen one or more layers conductive material such as copper wantonly.Lamination is generally time 30min to 4hr, preferred 1-2hr, temperature 160-300 ℃, preferred 170-200 ℃, pressure 3.516-35.16kgf/cm 2(50-500psi).Laminate can choose that heating 1-6hr comes " solidify the back " under 200-230 ℃, normal pressure wantonly, to improve hot property.
The lamination composition that contains epoxy resin will contain curing agent.The effective curing agent that becomes known for epoxy resin for example comprises amine, acids, anhydrides, phenols and imidazoles.Also referring to EP476752.At present the preferred consolidation agent of best lamination performance is provided is the phenol degree of functionality greater than 1.75 phenolic compounds for epoxy composite.Preferred phenol curing agent is to react the phenolic aldehyde that makes by dihydric phenol such as resorcinol or bisphenol-A and formaldehyde in acid solution to dye clearly.The preferred clear colorable resin curing agent of phenolic aldehyde is that bisphenol-A dyes clearly, and its each phenolic group heavily be 60-500, and preferred 60-300, each molecule be on average greater than 2 phenolic hydroxyl groups, preferably 3-5 phenolic hydroxyl group.Such phenol dyes clearly and can buy from Shell International Chemical Company by trade name EPIKURE DX-175 (EPIKURE is a trade mark).Phenol dyes the quantity of curing agent in composition clearly should make epoxy resin cure, usually whenever amount epoxy resin has stoichiometry 0.75-1.25 equivalent phenol to dye curing agent clearly.Percentage is by weight pressed total restatement of epoxy resin and curing agent, and the consumption of curing agent is generally 10-70% (weight), preferred 15-50% (weight), most preferably 15-40% (weight).For fire-retardant application, curing agent can be the mixture of the phenolic curing agent of phenolic resin curative and bromination.In order to accelerate in the composition the faster curing of resin Composition and/or more to solidify under the low temperature, can use optional curing accelerator.
Aathermoset resin system must design in some specification requirement scope of resin-coating procedure parameter requirement.Resin formula does not make to the base material under the temperature of resin solidification in resin-coating in required time must be liquid.Resin system must have enough low viscosity, makes Wondertek arrive good infiltration or saturated, and does not use film-traying roll in application point.But in case resin system is coated on the base material, it just must have sufficiently high viscosity, and it is dripped from network in that resiniferous Wondertek is unlikely before the bringing-up section.Viscosity is in 0.05-1.0PaS (0.5-10P) scope, and the resin formula of preferred 0.05-0.6PaS (0.5-6P) is best suited for.At present preferred resin system be have WPE be the bisphenol-A of 175-190 diglycidyl ether, WPE is arranged is the diglycidyl ether, the mixture that phenolic aldehyde dyes curing agent and glyoxal ethyline accelerator clearly of bromination of the bisphenol-A of 310-350 and bromine content 30-50%.
Method of the present invention can be chosen wantonly with such thermosetting resin prescription and implement: it contains organic solvent or diluent, and its quantity can effectively reduce the viscosity of system, so that processing.Polar organic solvent is to be fit to as ketone, alcohols and glycol ether.The boiling point of selected solvent is usually less than 160 ℃.For epoxy resin, preferred solvent is ketone such as acetone, MEK and methyl iso-butyl ketone (MIBK), and the solvent mixture of they and alkylene glycol ether such as propylene glycol monomethyl ether.The ratio of solid constituent can have bigger variation in composition, depends on the quantity of other components and the application of composition, but the solvent in solvent substrate system accounts for the 15-50% (weight) of prescription total amount usually.

Claims (10)

1. method with thermosetting resin dipping porous net, this method comprise uncured liquid form thermosetting resin conveying equipment are deposited on the larger-diameter rotation applicator roll; The porous net is passed through, so that thermosetting resin is transferred on the porous base ability with reverse contact of described resin on the described applicator roll; And make resiniferous porous base just solidify section by adding gesture, so that resin is partly solidified, in the method, before by the curing section, the one side at least of resiniferous porous substrate contacts with at least one conditioning roller than minor diameter.
2. according to the process of claim 1 wherein that the diameter of rotation applicator roll is at least 25.4cm (10in).
3. according to the method for claim 1 or 2, wherein the diameter of rotation conditioning roller is less than 20.32cm (8in).
4. according to the method for claim 3, the diameter of wherein nursing one's health roller is in 1.72-15.24cm (0.5-6in) scope.
5. according to each method among the claim 1-4, wherein nurse one's health roller and remain in the 120-250 ℃ of scope.
6. according to each method among the claim 1-5, wherein the porous net is a glass fiber mesh.
7. according to each method among the claim 1-6, wherein thermosetting resin is an epoxy resin.
8. according to each method among the claim 1-7,, wherein resiniferous porous substrate from applicator roll with respect to vertical direction be about 20 ° to about 40 ° angles by the resin solidification section.
9. with the device of thermosetting resin dipping porous net, comprising:
(a) larger-diameter rotation roller is arranged;
(b) the liquid form thermosetting resin of controlled amounts is deposited to equipment on the described rotation roller;
(c) porous substrate is sent to described rotation roller on reverse contact of thermosetting resin, be fed to the equipment of the section of being heating and curing then; And
(d) be installed in described rotation roller (a) and solidify at least a rotation roller that has than minor diameter between the section.
10. according to the device of claim 9, the diameter that wherein rotates roller be at least 25.4cm (10in) and the diameter of rotation conditioning roller less than 20.32cm (8in).
CN94194689A 1993-12-29 1994-12-27 Process and apparatus for resin impregnation of a porous web Expired - Fee Related CN1043972C (en)

Applications Claiming Priority (2)

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US17473693A 1993-12-29 1993-12-29
US08/174,736 1993-12-29

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CN1139399A true CN1139399A (en) 1997-01-01
CN1043972C CN1043972C (en) 1999-07-07

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EP (1) EP0737127A1 (en)
JP (1) JPH09507175A (en)
KR (1) KR100362097B1 (en)
CN (1) CN1043972C (en)
AU (1) AU1415495A (en)
CA (1) CA2180132A1 (en)
MY (1) MY131661A (en)
WO (1) WO1995018000A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106000768A (en) * 2015-03-25 2016-10-12 株式会社思可林集团 Coating device, coating method and coating film forming system
CN107209158A (en) * 2014-08-06 2017-09-26 路易威登马利蒂公司 Perfume test system

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6245383B1 (en) * 1998-11-25 2001-06-12 Matsushita Electric Works, Ltd. Method for manufacturing prepreg in which reinforcing substrate is impregnated with thermosetting matrix resin
JP5912464B2 (en) * 2011-12-02 2016-04-27 日本バイリーン株式会社 Production method and production apparatus for porous sheet carrying coating component
DE102012003001A1 (en) * 2012-02-15 2013-08-22 Bayerische Motoren Werke Aktiengesellschaft Method for manufacturing fiber composite, particularly carbon fiber composite component for use in automotive industry, involves cutting fiber semi-finished part to form fiber layers with predetermined dimensions

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NL289083A (en) *
DE3345010C2 (en) * 1983-12-13 1986-10-30 Messerschmitt-Bölkow-Blohm GmbH, 8012 Ottobrunn Device for winding cylindrical components made of fiber-reinforced plastic
US4804509A (en) * 1986-12-17 1989-02-14 Amoco Corporation Hot-melt prepreg tow process
ES2056567T5 (en) * 1990-09-17 2003-09-01 Resolution Res Nederland Bv PROCEDURE AND APPARATUS FOR THE IMPREGNATION WITH RESIN OF A FIBROSO SUBSTRATE.

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107209158A (en) * 2014-08-06 2017-09-26 路易威登马利蒂公司 Perfume test system
CN106000768A (en) * 2015-03-25 2016-10-12 株式会社思可林集团 Coating device, coating method and coating film forming system
CN106000768B (en) * 2015-03-25 2019-06-21 株式会社思可林集团 Apparatus for coating, coating method and film form system

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AU1415495A (en) 1995-07-17
EP0737127A1 (en) 1996-10-16
MY131661A (en) 2007-08-30
KR100362097B1 (en) 2003-02-11
CN1043972C (en) 1999-07-07
JPH09507175A (en) 1997-07-22
WO1995018000A1 (en) 1995-07-06
CA2180132A1 (en) 1995-07-06

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