WO1999028126A1 - Preimpregne pour cartes de circuits imprimes multicouches et leur procede de fabrication - Google Patents

Preimpregne pour cartes de circuits imprimes multicouches et leur procede de fabrication Download PDF

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Publication number
WO1999028126A1
WO1999028126A1 PCT/JP1998/005372 JP9805372W WO9928126A1 WO 1999028126 A1 WO1999028126 A1 WO 1999028126A1 JP 9805372 W JP9805372 W JP 9805372W WO 9928126 A1 WO9928126 A1 WO 9928126A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass
resin
nonwoven fabric
prepreg
printed wiring
Prior art date
Application number
PCT/JP1998/005372
Other languages
English (en)
Japanese (ja)
Inventor
Michio Konno
Shin Kasai
Original Assignee
Nitto Boseki Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nitto Boseki Co., Ltd. filed Critical Nitto Boseki Co., Ltd.
Publication of WO1999028126A1 publication Critical patent/WO1999028126A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
    • B29C70/504—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC] using rollers or pressure bands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
    • B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
    • B29B15/10—Coating or impregnating independently of the moulding or shaping step
    • B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
    • B29B15/122—Coating 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus 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
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates

Definitions

  • the present invention relates to a pre-preda for a multilayer printed wiring board using a glass nonwoven fabric and a method for producing the same.
  • glass cloth has been mainly used as an insulating base material of a laminate for a printed wiring board.
  • a method of manufacturing a laminated board for a printed wiring board using the glass cloth first, a glass cloth is impregnated with a matrix resin such as a liquid epoxy resin whose viscosity has been reduced with a solvent, using a squeezing apparatus. After the excess resin is squeezed and adjusted to the specified resin impregnation amount, it is passed through a dryer and heated to remove the solvent and produce a prepreg in which the resin curing stage is adjusted. After cutting to the prescribed size suitable for the copper-clad laminate, arranging copper foil for circuit on one or both sides, or laminating the number of sheets according to the configuration, printing by heating and pressing with a press A method of manufacturing a wiring laminate II has been adopted.
  • glass cloth is expensive, so instead, glass cloth is used for only one layer on each of the front and back sides, and the core is laminated with prepreg made of glass non-woven fabric.
  • Printed wiring called CEM-3 There are also fields in which ⁇ laminates are used.
  • the amount of the matrix resin impregnated in a laminated board composed of only glass cloth as the insulating base material is about 40% by weight, whereas the use of an insulating base material made of glass non-woven fabric results in the use of a matrix resin.
  • glass fiber In comparison with glass fiber and resin by volume, glass fiber is about 25%, resin is about 75%, and the volume occupied by resin is overwhelming.
  • glass nonwoven fabric was used as the insulating base material, glass fibers could not be contained in a high proportion.
  • a pre-zero pre-printer used for a printed wiring board is required to have further thinner and smoother properties.
  • the glass non-woven fabric obtained by papermaking a small amount of glass fiber chopped strands dispersed in water as the raw material has a straight glass fiber and a smooth surface. It is difficult to obtain a sufficient tensile strength as a non-woven fabric using only glass fiber as a raw material, such as a paper made from an organic raw material without entanglement. Therefore, in order to secure sufficient tensile strength, a method of impregnating a paper-made glass nonwoven fabric with a binder such as a water-soluble acryl resin or epoxy resin and curing it is adopted.
  • a binder such as a water-soluble acryl resin or epoxy resin
  • Glass nonwoven fabric cannot be used, and in order to have sufficient strength, a thick nonwoven fabric with a large basis weight must be used as the glass nonwoven fabric, and a resin binder to be impregnated Because of the necessity of increasing the impregnation amount of prepreg, it was not possible to produce a prepreg having a high glass fiber content and a small thickness.
  • an increase in the amount of resin used for impregnation leads to an increase in the amount of a surfactant for dispersing such a resin in water. In addition to deteriorating the water, it has caused long-term deterioration in insulation performance.
  • the solvent contained in the resin impregnated into the glass fiber is removed, but when the solvent is removed, the volume of the resin part decreases and the resin moves from the surface to the inside. Due to the phenomenon of sink marks, when copper foil is laminated using a non-woven glass surface and press-molded, the surface becomes 10 / m Near intense irregularities may occur. Therefore, when the copper foil is removed by etching or the like on the laminated plate existing on the surface, the copper foil is likely to remain in the concave portion, and the copper foil in the convex portion is easily removed. There was a problem such as disconnection of a circuit or connection of the circuit by mistake due to the remaining copper foil. In addition, if such irregularities are present, spots are generated at the time of bonding the copper foil, which causes disconnection and the like as described above.
  • the present invention is directed to a prepreg using a glass nonwoven fabric impregnated with a resin as an insulating substrate, to prevent bubbles remaining when cutting the glass nonwoven fabric substrate and impregnating the resin, and to reduce the glass fiber content.
  • An object of the present invention is to provide a glass nonwoven fabric prepreg for a multilayer printed wiring board which is high, has excellent surface smoothness, and is thin. It is another object of the present invention to continuously and efficiently manufacture such a pre-preda.
  • the present inventors have studied various methods for impregnating a glass nonwoven fabric substrate with a resin in order to solve the above-mentioned problems.
  • a liquid resin is applied to one side of a specific carrier sheet, and then a glass non-woven fabric made of highly flat glass fiber is supplied thereon to impregnate the resin, thereby cutting the glass non-woven fabric base and cutting the resin.
  • the present inventors have found that bubbles can be prevented from remaining when the resin is impregnated, and that the resin impregnation amount can be reduced, and the present invention has been completed.
  • the present invention relates to a prepreg for a multilayer printed wiring board using a glass nonwoven fabric impregnated with a resin as an insulating base material, wherein the insulating base material has a heat-resistant temperature of 150 ° C. or higher.
  • the present invention relates to a multi-layer printed pre-preparator for a torii wire plate, which is laminated on a carrier sheet made of a copper foil, and wherein the glass nonwoven fabric is made of a highly flat glass fiber.
  • the present invention provides a method for applying a liquid matrix resin to one side of a carrier sheet made of a synthetic resin film or a copper foil for a circuit having a heat resistance temperature of 150 ° C. or more, and then forming a highly flat glass fiber on the liquid matrix resin.
  • the present invention relates to a method for producing a pre-preda for a multilayer printed wiring board, comprising laminating a glass non-woven fabric composed of a resin, impregnating with a resin, and drying and semi-curing the resin.
  • FIG. 1 is a schematic side view of a laminating apparatus used in an embodiment of the method of the present invention.
  • FIG. 2 is a schematic view of the process of the conventional method.
  • the ratio of the major axis to the minor axis of the high flat glass fiber must be 3. : 1 to 8: 1, more preferably 3: 1 to 5: 1, most preferably 3.5: 1 to 4.5: 1.
  • the conventional cross-sectional shape is likely to occur in glass fiber having a circular shape, and bubbles occupy a large amount of space in the nonwoven fabric. The problem can be avoided, and the content of glass fibers in the laminate can be increased.
  • the resin content of the laminate can be reduced to the same level as glass cloth. .
  • the glass nonwoven fabric comprising a conventional cross-sectional shape of a glass fiber is circular, than the tensile strength point, its weight per unit area weight is 5 0 g / m 2 ⁇ 1 0 0 g / m 2 and is commercially available glass nonwoven It was used for composite copper-clad laminates such as CEM-III, but in the present invention, since highly flat glass fiber is used as the glass nonwoven, a glass nonwoven made of glass fiber having a circular cross-sectional shape has hitherto been used. Glass non-woven fabrics having a basis weight in the range of 10 g / m 2 to 50 g / m 2 , which is rarely used in the above, can be used.
  • the ratio of the major axis to the minor axis of the glass fiber is 3: 1 to 5: 1, and the equivalent diameter is 9 to 15 (where the equivalent diameter is the dimension representing the cross-section of the flat glass fiber, the same weight, A value expressed in terms of the diameter when converted to a round glass fiber of the same length.)
  • a nonwoven glass nonwoven fabric with a basis weight of 10 gZm 2 to 50 gZ m 2 using a chopped strand of highly flat glass fiber is density 0. 3 ⁇ 0. 4 5 gr / cm 3 resin content of the laminate is reduced as large as, also, since also have a good dimensional stability of the glass cloth and the same degree, the multilayer of the present invention It is suitable as a pre-preda for printed wiring boards.
  • the carrier sheet used in the present invention needs to be one that does not deform at the heating temperature when the solvent of the resin impregnated in the glass nonwoven fabric is removed from the viewpoint of securing the tensile strength of the glass nonwoven fabric during the manufacturing process.
  • the matrix resin used for the impregnation is an epoxy thermosetting resin FR-4
  • a thermoplastic polyester resin film or the like which does not deform at a heating temperature of 150 ° C. for removing the solvent.
  • PEN polyallyl ether nitrile resin
  • a heat-resistant continuous sheet having a smooth surface such as a copper foil for a circuit to be bonded can also be used as a carrier sheet.
  • the thickness of the carrier sheet is preferably about 0.02 to 1 mm.
  • the synthetic resin carrier sheet is removed during actual use, and a glass non-woven fabric base or a copper non-foiled glass non-woven fabric base is laminated and used as a prepreg for a multilayer printed wiring board.
  • those using a circuit copper foil as a carrier sheet can be used as it is for the surface of a double-sided copper-clad printed wiring board or a copper-clad laminate for a multilayer printed wiring board.
  • the resin to be impregnated into the glass nonwoven fabric that can be used in the present invention is not particularly limited as long as it is a resin that can be dissolved in a solvent and impregnated into the glass nonwoven fabric, but an epoxy resin, an unsaturated polyester resin, or the like is preferable. .
  • the prepreg of the present invention As a method for producing the prepreg of the present invention using these carrier sheets, such a sheet material is sent out onto a flat conveyor that moves as a carrier sheet, and one surface thereof is impregnated with a glass nonwoven fabric in advance. There is a method in which the required resin amount is continuously and uniformly applied, and a glass nonwoven fabric or the like is sequentially laminated thereon. Also, a method of laminating a glass nonwoven fabric on a carrier sheet and supplying a resin from above to impregnate the resin, or a method of applying a resin to the rear surface of the carrier sheet to adjust the amount of adhesion, and then forming a glass nonwoven fabric or the like.
  • the prepreg of the present invention may be manufactured by a method of sequentially supplying and stacking.
  • a well-known liquid application method such as a kiss roll coater, a knife coater, or a rod coater is used.
  • a well-known liquid application method such as a kiss roll coater, a knife coater, or a rod coater is used.
  • the glass nonwoven fabric is sequentially impregnated so as not to trap air bubbles from one side on the resin surface, air bubbles can be greatly reduced as compared with the conventional one.
  • the copper foil can be laminated on the glass nonwoven fabric.
  • a single-sided copper-foiled glass nonwoven fabric impregnated with resin or a resin-impregnated glass nonwoven fabric without copper foil is brought into contact with a heating roller to remove the solvent of the resin impregnated into the glass nonwoven fabric. Remove and pre-cure. Further, if necessary, a glass nonwoven fabric prepreg can be manufactured more stably and continuously by passing the resin through a pair of heating / pressing ports to ensure the impregnation of the resin into the glass nonwoven fabric substrate. It becomes possible.
  • a carrier sheet is present in the impregnation step to the partial curing step, so that the tensile strength required for handling in the production step can be secured.
  • the glass nonwoven fabric can sufficiently withstand a lamination process in a continuous line, and a multi-layer printed wiring board pre-preda can be stably obtained.
  • the basis weight of the glass nonwoven fabric is desirably 100 g / m 2 or less from the viewpoint that the resin is uniformly and completely impregnated.
  • the basis weight is 1 g / m 2.
  • the 0 gZm 2 ⁇ 5 0 gZ m 2 of tensile strength weak nonwoven may also be used.
  • the manufacturing process of the prepreg for a glass-nonwoven copper-clad laminate shown in Fig. 1 consists of a carrier sheet feeder, a resin coating device, a glass nonwoven fabric feeder, a copper foil feeder, a heating roller unit, a trimming device, and a winding device. .
  • the carrier sheet 1 starts moving by operating the feeding device and the winding device. After supplying the resin to the resin coating device, the kiss coater roller 3 is rotated to form a resin layer, and the carrier sheet 1 is brought into contact with the resin layer 4 on the roller 13 to apply the resin to the carrier sheet.
  • the amount of application is adjusted by calculating the required amount of resin of the base material in advance, adjusting the rotation speed of the kiss coater 3 and the clearance of the guide roller 2, and managing the resin viscosity. . Furthermore, the thickness is made more uniform by squeeze barco 1-5.
  • Carrier sheet 1 is in a state where resin is evenly applied, and the moving carrier sheet
  • the glass nonwoven fabric 7 is fed out onto the sheet 1 by a glass nonwoven fabric sending device, and is laminated on the resin layer 4 on the carrier sheet 1.
  • the glass nonwoven fabric 7 is sequentially impregnated with the resin from one side, bubbles are less likely to be generated.
  • bubbles generated when impregnating a glass nonwoven fabric with a resin are trapped in the glass nonwoven fabric.
  • the generation of bubbles itself is unlikely to occur, and the bubbles are further reduced. Even if it occurs, it is not trapped in the glass nonwoven fabric, so that uniform impregnation can be performed.
  • the preheater 6 is an auxiliary heating device when it is necessary to promote the removal of the solvent in the resin.
  • the laminated sheet 9 is brought into a semi-cured state by bringing the impregnated resin into a semi-cured state by bringing the laminated sheet 9 into contact with a heating roller 10 and a heating / pressing roller 11 at 150 to 180 ° C. Trimming to the required width by 2 and winding by a winding device 13 give a continuous glass nonwoven prepreg.
  • a high-flat glass fiber with a major diameter: minor diameter of 4: 1 and an equivalent diameter of 13 / zm is used as the glass non-woven fabric, and an epoxy adhesive is applied at a solid content of 6% by weight. It was used in m 2.
  • composition (FR-4 formulation) of the epoxy resin varnish used for impregnation is as follows.
  • a film of a 50 zm polyallyl ether nitrile resin was used as the carrier sheet. Using these materials, a prepredder was manufactured using the apparatus shown in FIG. 1 described above. The results are shown in Table 1.
  • the obtained prepreg was cut into 50 cm squares, 10 sheets were laminated, and copper foil with a thickness of 18 m was stacked on both sides, sandwiched between mirror plates, and pressed. It was produced by pressing at a force of 50 kg / cm 2 and a temperature of 170 ° C. for 60 minutes.
  • the surface smoothness was measured using a universal shape measuring instrument (manufactured by Kosaka Laboratory Co., Ltd .; trade name: SEF-1A) based on “Surface Roughness Measurement Method” of JISB-0601. Was.
  • a prepreg was produced under the same production conditions as in Example 1 except that a circuit copper foil of 18 / zm was used as a carrier sheet and the basis weight of the glass nonwoven fabric was 20 g / m 2 .
  • the results are shown in Table 1.
  • the preparation of the surface smoothness measurement sample and the method for measuring the same are the same as in Example 1.
  • a prepreg was manufactured in the same manner as in Example 1 except that a glass nonwoven fabric having a basis weight of 50 g / m 2 made of glass fiber having a round cross section was used. The results are shown in Table 1. The preparation of the surface smoothness measurement sample and the measurement method thereof are the same as those in Example 1. (Comparative Example 2)
  • the glass nonwoven fabric prepreg for a multilayer printed wiring board of the present invention is a prepreg having a high glass fiber content, excellent surface smoothness, and a small thickness as compared with conventional ones.
  • the resin is sequentially laminated on the glass nonwoven fabric on the moving carrier sheet, and the resin is impregnated from one side of the glass nonwoven fabric. Even if it occurs, the impregnation can be performed under conditions where air bubbles can easily escape.
  • the impregnation can be performed under conditions where air bubbles can easily escape.
  • the amount of emulsion type lumber impregnated in the glass nonwoven fabric can be reduced, the amount of surfactant added to convert the emulsion type resin into an emulsion can be reduced. It is possible to do.
  • this surfactant has an adverse effect on the water resistance and heat resistance of the printed wiring board, etc., and in order to make up for the lack of strength, which has conventionally been desired to reduce the amount thereof.
  • the amount of the emulsion resin had to be increased, so that the amount of the surfactant could not be reduced to less than 10% by weight in the past.
  • the amount of the surfactant can be significantly reduced to 6% by weight or less.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Reinforced Plastic Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention porte sur un préimprégné pour cartes de circuits imprimés multicouches dont le substrat isolant comprend un tissu de verre non tissé, imprégné de résine. Ce préimprégné se caractérise en ce que le tissu de verre non tissé est appliqué sous forme de couche sur une feuille de support fabriquée dans un film de résine synthétique ayant une température égale ou supérieure à 150 °C ou un tracé métallique à base de cuivre, le tissu étant constitué de fibres de verre extrêmement plates. Le préimprégné a une très grande teneur en fibres de verre, présente une excellente stabilité dimensionnelle et une excellente planéité de surface, et est d'épaisseur réduite. On obtient ainsi un préimprégné comprenant un tissu de verre non tissé et qui est approprié pour être utilisé dans les cartes de circuits imprimés multicouches.
PCT/JP1998/005372 1997-12-01 1998-11-30 Preimpregne pour cartes de circuits imprimes multicouches et leur procede de fabrication WO1999028126A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP9/330411 1997-12-01
JP33041197 1997-12-01

Publications (1)

Publication Number Publication Date
WO1999028126A1 true WO1999028126A1 (fr) 1999-06-10

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Application Number Title Priority Date Filing Date
PCT/JP1998/005372 WO1999028126A1 (fr) 1997-12-01 1998-11-30 Preimpregne pour cartes de circuits imprimes multicouches et leur procede de fabrication

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001315123A (ja) * 2000-03-03 2001-11-13 Hitachi Chem Co Ltd プリプレグの製造方法、プリプレグ、金属張り積層板及び印刷配線板
WO2020071483A1 (fr) * 2018-10-03 2020-04-09 株式会社カネカ Stratifié non durci, matériau composite de fibres de renforcement, procédé de production de stratifié non durci et procédé de production de matériau composite de fibres de renforcement
CN111186138A (zh) * 2020-04-13 2020-05-22 北京化工大学 一种连续纤维熔融浸渍的3d打印装置及工艺

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52106467A (en) * 1976-03-05 1977-09-07 Chuo Meiban Kougiyou Kk Flexible printed circuit substrate and method of producing same
JPS63132044A (ja) * 1986-11-25 1988-06-04 新神戸電機株式会社 金属箔張積層板
JPH07144390A (ja) * 1993-11-25 1995-06-06 Matsushita Electric Works Ltd コンポジット積層板及びその製造方法
JPH07122235B2 (ja) * 1986-01-16 1995-12-25 日東紡績株式会社 積層板用ガラス繊維紙
JPH08127994A (ja) * 1994-10-28 1996-05-21 Honshu Paper Co Ltd 多層プリント配線基板用不織布

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52106467A (en) * 1976-03-05 1977-09-07 Chuo Meiban Kougiyou Kk Flexible printed circuit substrate and method of producing same
JPH07122235B2 (ja) * 1986-01-16 1995-12-25 日東紡績株式会社 積層板用ガラス繊維紙
JPS63132044A (ja) * 1986-11-25 1988-06-04 新神戸電機株式会社 金属箔張積層板
JPH07144390A (ja) * 1993-11-25 1995-06-06 Matsushita Electric Works Ltd コンポジット積層板及びその製造方法
JPH08127994A (ja) * 1994-10-28 1996-05-21 Honshu Paper Co Ltd 多層プリント配線基板用不織布

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001315123A (ja) * 2000-03-03 2001-11-13 Hitachi Chem Co Ltd プリプレグの製造方法、プリプレグ、金属張り積層板及び印刷配線板
WO2020071483A1 (fr) * 2018-10-03 2020-04-09 株式会社カネカ Stratifié non durci, matériau composite de fibres de renforcement, procédé de production de stratifié non durci et procédé de production de matériau composite de fibres de renforcement
JPWO2020071483A1 (ja) * 2018-10-03 2021-09-24 株式会社カネカ 未硬化積層板、強化繊維複合材料、およびそれらの製造方法
CN111186138A (zh) * 2020-04-13 2020-05-22 北京化工大学 一种连续纤维熔融浸渍的3d打印装置及工艺
CN111186138B (zh) * 2020-04-13 2021-04-23 北京化工大学 一种连续纤维熔融浸渍的3d打印装置及工艺

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