CN105625041A - Shape-finalized polyimide fabric and manufacturing method thereof - Google Patents
Shape-finalized polyimide fabric and manufacturing method thereof Download PDFInfo
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- CN105625041A CN105625041A CN201511002527.9A CN201511002527A CN105625041A CN 105625041 A CN105625041 A CN 105625041A CN 201511002527 A CN201511002527 A CN 201511002527A CN 105625041 A CN105625041 A CN 105625041A
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- China
- Prior art keywords
- polyimide
- cloth
- glass
- yarn
- polyamic acid
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- 239000004744 fabric Substances 0.000 title claims abstract description 123
- 229920001721 polyimide Polymers 0.000 title claims abstract description 73
- 239000004642 Polyimide Substances 0.000 title claims abstract description 65
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 239000003292 glue Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 51
- 239000009719 polyimide resin Substances 0.000 claims abstract description 8
- 239000011521 glass Substances 0.000 claims description 98
- 239000007788 liquid Substances 0.000 claims description 49
- 238000005470 impregnation Methods 0.000 claims description 46
- 229920005575 poly(amic acid) Polymers 0.000 claims description 44
- 238000004026 adhesive bonding Methods 0.000 claims description 20
- 229920000742 Cotton Polymers 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 13
- 238000005491 wire drawing Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 150000004985 diamines Chemical class 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000009954 braiding Methods 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229940113088 dimethylacetamide Drugs 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 abstract description 12
- 238000007598 dipping method Methods 0.000 abstract description 11
- 239000004952 Polyamide Substances 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 7
- 229920002647 polyamide Polymers 0.000 abstract description 7
- 230000005012 migration Effects 0.000 abstract description 4
- 238000013508 migration Methods 0.000 abstract description 4
- 230000032683 aging Effects 0.000 abstract description 3
- 238000009941 weaving Methods 0.000 abstract description 3
- 238000004377 microelectronic Methods 0.000 abstract description 2
- 238000004513 sizing Methods 0.000 abstract 2
- 238000005260 corrosion Methods 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- 238000012681 fiber drawing Methods 0.000 abstract 1
- 238000003825 pressing Methods 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 0 *c(cc1)ccc1S(c(cc1)ccc1N)(=O)=O Chemical compound *c(cc1)ccc1S(c(cc1)ccc1N)(=O)=O 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000007601 warm air drying Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000009955 starching Methods 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 2
- HVUVNKBPSFOCLB-UHFFFAOYSA-N C=Nc1cccc(N)c1 Chemical compound C=Nc1cccc(N)c1 HVUVNKBPSFOCLB-UHFFFAOYSA-N 0.000 description 1
- ZYEDGEXYGKWJPB-UHFFFAOYSA-N CC(C)(c(cc1)ccc1N)c(cc1)ccc1N Chemical compound CC(C)(c(cc1)ccc1N)c(cc1)ccc1N ZYEDGEXYGKWJPB-UHFFFAOYSA-N 0.000 description 1
- IATKVIZVOBHQJS-UHFFFAOYSA-N CCc1cc(N)ccc1-c(c(C)c1)ccc1N Chemical compound CCc1cc(N)ccc1-c(c(C)c1)ccc1N IATKVIZVOBHQJS-UHFFFAOYSA-N 0.000 description 1
- KAWCEDACAFGLKU-UHFFFAOYSA-N Cc1cc(N)ccc1-c(c(C(F)(F)F)c1)ccc1N Chemical compound Cc1cc(N)ccc1-c(c(C(F)(F)F)c1)ccc1N KAWCEDACAFGLKU-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N Nc(cc1)ccc1Oc1cc(N)ccc1 Chemical compound Nc(cc1)ccc1Oc1cc(N)ccc1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- GMLBORVZBUHWHQ-UHFFFAOYSA-N Nc(cc1)ccc1Sc(cc1)ccc1[IH2] Chemical compound Nc(cc1)ccc1Sc(cc1)ccc1[IH2] GMLBORVZBUHWHQ-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 229910001423 beryllium ion Inorganic materials 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- -1 phenolic aldehyde Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/59—Polyamides; Polyimides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Woven Fabrics (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention relates to the technical field of glass fiber fabrics, in particular to a shape-finalized polyimide fabric and a manufacturing method thereof. The manufacturing method includes the following steps that fiber drawing is performed, gum dipping and fabric weaving is performed, and glass fiber is immersed in a polyamide acid glue solution to perform sizing treatment, is taken out and dried and then is woven into a glass fiber fabric blank; baking and curing are performed to enable the polyamide acid glue solution to be completely aminated so as to obtain the shape-finalized polyimide fabric, wherein the polyimide resin weight content in the shape-finalized fabric is no more than 30%. According to the manufacturing method, the polyamide acid glue solution is adopted to directly conduct shape finalizing on the glass fiber, weft skewing and other problems of the glass fiber during weaving can be prevented, and the weft skewing problem of traditional glass fiber fabrics in the dipping, sizing treatment and pressing process is also avoided. In addition, the shape-finalized polyimide fabric is applied to PCB, has better ageing resistance, heat resistance, corrosion resistance, ion migration resistance and the like and can meet the requirements of the industry of modern microelectronics.
Description
Technical field
The present invention relates to glass cloth technical field, particularly relate to a kind of polyimide setting cloth and making method thereof.
Background technology
Glass fibre (glassfiber or fiberglass), also known as glass yarn, is the ceramic of a kind of excellent performance, and composition is silicon-dioxide, aluminum oxide, calcium oxide, boron oxide, magnesium oxide, sodium oxide etc. It is made into glass cloth by raw material of glass sphere or discarded glass through high temperature melting, wire drawing, doff, the technique such as weave cotton cloth, and finally form various product, wherein, the diameter of glass fiber single filament is from several microns to twenties microns, be equivalent to the 1/20-1/5 of a hairline, every bundle fiber precursor all by hundreds of even thousands of monofilament form. Strongthener, electrically insulating material and the heat-insulating material that glass cloth is typically used as in matrix material, and the substrate etc. of printed circuit board (PCB) (that is, pcb board), be widely used in national economy every field.
When glass cloth is applied to printed circuit board (PCB), existing technique is that glass cloth is carried out gluing, solidification, forms bonding sheet, just can be made into copper-clad plate at this bonding sheet coated with Copper Foil etc.; And at present traditionally, after glass yarn starching, braiding being processed, then to glass cloth, particularly slim glass cloth that glass cloth blank carries out destarch smoldering and obtain, when it is applied to printed circuit board (PCB), there is following defect:
(1) glass cloth is due to the braiding structure of itself, when gluing, glass yarn wherein is easy to the small ununiformity of the tension force because being subject to, and skew of weft phenomenon occurs after causing glass cloth gluing, and then makes the glass cloth poor dimensional stability after gluing, the serious and apparent unfairness of warpage; And glass cloth is when being slim, also easily it is subject to physical abuse, and then causes the visual defects of the glass cloth after gluing, seriously affect the usability of product, even scrap;
(2) the glass cloth after weaving is due to warp and weft interweaving, make yarn and yarn (namely, warp thread and weft yarn, warp thread and warp thread, weft yarn and weft yarn) between space occurs, this kind of space is bigger and more by what become when skew of weft, owing to the existence in these spaces makes the pcb board made of this glass cloth serious ion migration (CAF) problem occur, cause pcb board defective, time serious, the electrical equipment using this pcb board will be burnt; And at the slim pcb board of making and ultra fine-line pcb board, above-mentioned defect is exaggerated, affects the usability of product time serious, even scrap; Even if glass cloth that prior art makes must be utilized when making slim pcb board and ultra fine-line pcb board, bring great difficulty.
In order to solve the problem, the applicant, through long-term investigation and production practice, have developed the brand-new making method utilizing frit to make glass cloth.
Summary of the invention
For above-mentioned the deficiencies in the prior art, it is an object of the invention to provide the making method of a kind of new polyimide setting cloth;
The two of the object of the present invention are to provide a kind of polyimide setting cloth adopting above-mentioned making method to prepare.
In order to realize above-mentioned purpose, the technical scheme of the present invention is as follows:
A making method for polyimide setting cloth, comprises the steps:
Wire drawing, will carry out wire drawing after frit melting, form glass yarn;
Impregnation is weaved cotton cloth, and is immersed in polyamic acid glue liquid by described glass yarn and carries out gluing, takes out after drying, removes the organic solvent in polyamic acid glue liquid, be woven into glass cloth blank subsequently; Wherein, described polyamic acid glue liquid is less than 200CPS the viscosity of 25 DEG C;
Baking-curing, toasts described glass cloth blank, makes the described polyamic acid complete imidization of glue liquid, obtains polyimide setting cloth; Wherein, in described setting cloth, polyimide resin weight content is no more than 30%.
Relative to prior art, the present invention weaves after described glass yarn directly carries out impregnation, and on the one hand, the various problems that the starching in replacement tradition glass cloth making, destarch smoldering bring, have saved operation; On the other hand, adopt polyamic acid glue liquid directly glass yarn to be carried out heat treatment, the problems such as the skew of weft that glass yarn occurs in braiding can be prevented, it also avoid the problem that skew of weft occurs in dipping gluing and bonding processes in tradition glass cloth. In addition, the present invention adopts poly-acyl polyamic acid glue liquid impregnated glass, for the series plastics such as existing ring oxygen, phenolic aldehyde glue system, the aspects such as its ageing resistance, thermotolerance, resistance to ion transport all relatively conventional resins glue system want high, it is possible to meet the requirement of modern microelectronic industry.
Specifically, described impregnation is weaved cotton cloth and is comprised the steps:
(1) at least two described glass yarn are carried out doubling, form glass filament bundle;
(2) described glass filament bundle is immersed in described polyamic acid glue liquid and carry out gluing, take out after drying, form impregnation glass filament bundle;
(3) carry out successively twisting with the fingers yarn, warping and braiding to described impregnation glass filament bundle, form described glass cloth blank.
In addition, described impregnation is weaved cotton cloth and is not limited to aforesaid method, and it can also be adopted with the following method, comprises step:
(1) at least two described glass yarn are carried out doubling successively, twist with the fingers yarn and warping, form warping yarn;
(2) described warping yarn is immersed in described polyamic acid glue liquid carry out gluing, take out, after oven dry, form impregnation warping yarn;
(3) described impregnation warping yarn is woven, form described glass cloth blank.
In above-mentioned two kinds of impregnations are weaved cotton cloth, glass filament bundle is directly carried out impregnation by one, warping yarn is carried out impregnation by one, namely processed and solidifying and setting with polyimide precursor (polyamic acid glue liquid) in advance in doubling or warping by glass fibre, prevent, in the braiding process of glass cloth, skew of weft problem occurs, avoid simultaneously flood between glass filament bundle bad or ORGANDY hollow etc. cause make printed circuit board (PCB) (PCB) ion migration (CAF) problem occurs.
Specifically, the preparation method of described polyamic acid glue liquid is as follows:
Diamine monomer being dissolved in organic solvent and obtains diamine monomer solution, in a water bath after cooling, add dianhydride monomer under nitrogen flowing in diamine monomer solution, control temperature of reaction is 15��25 DEG C, and reaction 7��10h, obtains described polyamic acid glue liquid; In wherein said polyamic acid glue liquid, solid content is 7%��15%.
Wherein, the polyimide in described polyimide setting cloth is the copolymerization of different diamine monomer, and specifically, described diamine monomer is two or more in following compound:
Described dianhydride monomer is one or both in following compound:
Specifically, described organic solvent is one or both in DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone.
Goodly, the temperature of described polyamic acid glue liquid imidization is 280��350 DEG C.
A kind of polyimide setting cloth, adopts the making method of polyimide setting cloth described above to produce and obtain.
The polyimide setting cloth that the present invention makes, under the polyimide being closely covered in glass yarn (glass fibre) surface supports, being fixed through broadwise wherein, the polyimide setting cloth dimensional stabilizing obtained like this, apparent smooth, solve the skew of weft that tradition glass cloth occurs when making copper-clad plate, the problems such as warpage, conveniently it is applied to making ultra-thin PCB, and this setting cloth avoids space problem that is bad and that cause of flooding between ORGANDY hollow or glass filament bundle, the pcb board using this setting cloth to make there will not be ion migration (CAF) problem, ensure that quality product, in addition, the present invention adopts setting cloth that polyimide is prepared to glass yarn of shaping when for making copper clad laminate CCL, can effectively improve its thermotolerance, electrical property and ageing-resistant performance.
Embodiment
The specific embodiment of the present invention will be described in further detail below.
Polyimide setting cloth of the present invention is when making, first to be prepared polyamic acid glue liquid and frit, polyimide adopts polyamic acid glue liquid hot imidization and obtains, wherein the temperature of hot imidization is 280 DEG C��350 DEG C, specifically, now first the synthetic method of polyamic acid glue liquid is described in detail.
Synthesis example 1
The there-necked flask of 1L adds organic solvent DMAc (N, N-N,N-DIMETHYLACETAMIDE) 500g, the PDA (Ursol D) of weighing 8.652g, the ODA (diaminodiphenyl ether) of 4.005g are dissolved in DMAc to form solution, cooled in a water bath by this solution; The PMDA (pyromellitic acid anhydride) of the BPDA (bibenzene tetracarboxylic dianhydride) and 10.906g of 14.711g is added subsequently under nitrogen flowing in above-mentioned solution, control temperature of reaction is 15��25 DEG C, react after 8 hours, prepare thermosetting polyamide acid glue liquid, wherein solid content is 7%, and described polyamic acid glue liquid is less than 200CPS the viscosity of 25 DEG C.
Synthesis example 2
The there-necked flask of 1L adds organic solvent NMP (N-Methyl pyrrolidone) and DMAc (N, N-N,N-DIMETHYLACETAMIDE) 800g, the PDA (Ursol D) of weighing 16.006g, the ODA (diaminodiphenyl ether) of 6.505g are dissolved in NMP and DMAc to form solution, cooled in a water bath by this solution; The BPDA (bibenzene tetracarboxylic dianhydride) of 53.104g is added subsequently under nitrogen flowing in above-mentioned solution, control temperature of reaction is 15��25 DEG C, react after 8 hours, prepare thermosetting polyamide acid glue liquid, wherein solid content is 8%, and described polyamic acid glue liquid is less than 200CPS the viscosity of 25 DEG C.
Synthesis example 3
Adding NMP (N-Methyl pyrrolidone) 1000g in the there-necked flask of 2L, the TFDB (2,2-bis trifluoromethyl p-diaminodiphenyl) weighing 38.428g is dissolved in NMP to form solution, cooled in a water bath by this solution; The BTDA (benzophenone two acid anhydride) of the 6FDA (hexafluorodianhydride) and 11.168g of 37.911g is added subsequently under nitrogen flowing in above-mentioned solution, control temperature of reaction is 15��25 DEG C, react after 8 hours, prepare thermosetting polyamide acid solution, wherein solid content is 8%, and described polyamic acid glue liquid is less than 200CPS the viscosity of 25 DEG C.
After synthesizing polyamides acid glue liquid, can starting to make polyimide setting cloth, compared to glass cloth of the prior art, the present invention no longer carries out starching and destarch smoldering technique, and glass yarn is directly carried out impregnation by it; The preparation method of the present invention is simple, relative to prior art, saved operation, it is to increase make efficiency; Its concrete technique is as follows:
First wire drawing, will carry out wire drawing after frit melting, form glass yarn;
Impregnation is weaved cotton cloth subsequently, is immersed in above-mentioned synthesis example by the glass yarn obtained in the polyamic acid glue liquid obtained and carries out gluing, and gluing is taken out after completing and dried, and the glass braid of oven dry becomes glass cloth blank; Wherein, described polyamic acid glue liquid is less than 200CPS the viscosity of 25 DEG C;
Finally toast imidization (baking-curing), above-mentioned glass cloth blank is processed at high temperature oven, make the polyamic acid glue liquid complete imidization of dipping on glass cloth blank, namely obtain the polyimide setting cloth of the present invention; Further, in the polyimide setting cloth obtained, polyimide resin weight content is no more than 30%.
The technique that wherein impregnation is weaved cotton cloth specifically comprises two kinds, and the key distinction is that the technical process that concrete impregnation is weaved cotton cloth will explanation in following word at different stage impregnations.
The method that wherein impregnation is weaved cotton cloth is, after doubling, glass filament bundle is carried out a dipping process, specifically comprises the steps:
(1) at least two described glass yarn are carried out doubling, form glass filament bundle;
(2) described glass filament bundle is immersed in described polyamic acid glue liquid and carry out gluing, take out after drying, form impregnation glass filament bundle;
(3) carry out successively twisting with the fingers yarn, warping and braiding to described impregnation glass filament bundle, form described glass cloth blank.
The method that another kind of impregnation is weaved cotton cloth is, after warping, warping yarn is carried out dipping process, specifically comprises the steps:
(1) at least two described glass yarn are carried out doubling successively, twist with the fingers yarn and warping, form warping yarn;
(2) described warping yarn is immersed in described polyamic acid glue liquid carry out gluing, take out, after oven dry, form impregnation warping yarn;
(3) described impregnation warping yarn is woven, form described glass cloth blank.
The method that above-mentioned two kinds of impregnations are weaved cotton cloth is applied in the making processes of polyimide setting cloth, specific as follows.
Embodiment 1
A kind of polyimide setting cloth, its making method comprises the steps:
First wire drawing, will carry out wire drawing after frit melting, form glass yarn;
Impregnation is weaved cotton cloth subsequently, and dipping process method after employing doubling, specifically comprises (1) and at least two glass yarn are carried out doubling, forms glass filament bundle; (2) glass filament bundle is immersed in synthesis example 1 in the polyamic acid glue liquid made and carry out gluing, take out after drying, form impregnation glass filament bundle; (3) carry out successively twisting with the fingers yarn, warping and braiding to impregnation glass filament bundle, form glass cloth blank;
Finally toast imidization (baking-curing), above-mentioned glass cloth blank is processed process in some minutes respectively with 160 DEG C, 180 DEG C, 200 DEG C, 240 DEG C, 300 DEG C in high temperature oven, make the polyamic acid glue liquid complete imidization of dipping on glass cloth blank, namely obtain polyimide setting cloth; Further, in the polyimide setting cloth obtained, polyimide resin weight content is no more than 30%.
The preparation of polyimide curing sheet: above-mentioned polyimide setting cloth adopts the method for manual gluing immerse in synthesis example 1 in the polyamic acid glue liquid made, and the polyimide setting cloth after being completed by impregnation subsequently is dried 160 DEG C of warm air dryings for some minutes; Finally impregnation polyimide setting cloth is placed in high temperature oven and processes some minutes respectively with 160 DEG C, 180 DEG C, 200 DEG C, 240 DEG C, 300 DEG C, complete imidization, obtained polyimide curing sheet.
Embodiment 2
A kind of polyimide setting cloth, its making method comprises the steps: first wire drawing, will carry out wire drawing after frit melting, forms glass yarn;
Impregnation is weaved cotton cloth subsequently, dipping process method after employing warping, specifically comprises (1) and is carried out doubling successively, twists with the fingers yarn and warping by least two glass yarn, forms warping yarn; (2) warping yarn is immersed in the polyamic acid glue liquid of making in synthesis example 3 and carry out gluing, take out after drying, form impregnation warping yarn; (3) described impregnation warping yarn is woven, form described glass cloth blank;
Finally toast imidization (baking-curing), above-mentioned glass cloth blank is processed some minutes respectively with 160 DEG C, 180 DEG C, 200 DEG C, 240 DEG C, 300 DEG C in high temperature oven, make the polyamic acid glue liquid complete imidization of dipping on glass cloth blank, namely obtain polyimide setting cloth; Further, in the polyimide setting cloth obtained, polyimide resin weight content is no more than 30%.
The preparation of polyimide curing sheet: above-mentioned polyimide setting cloth is carried out dipping process by with adhesive applicator, immersing in synthesis example 3 in the polyamic acid glue liquid made, the polyimide setting cloth after being completed by impregnation subsequently is dried 160 DEG C of warm air dryings for some minutes; Finally impregnation polyimide setting cloth is placed in high temperature oven and processes some minutes respectively with 160 DEG C, 180 DEG C, 200 DEG C, 240 DEG C, 300 DEG C, complete imidization, obtained polyimide curing sheet.
Embodiment 3
A kind of polyimide setting cloth, its making method is identical with embodiment 1, and its difference is, it adopts polyamic acid glue liquid obtained in synthesis example 2; In the polyimide setting cloth that it obtains, polyimide resin weight content is no more than 30%. The preparation method of polyimide curing sheet is also identical with embodiment 1, and difference is that it adopts polyamic acid glue liquid obtained in synthesis example 2.
Embodiment 4
A kind of polyimide setting cloth, its making method is identical with embodiment 2, and its difference is, it adopts polyamic acid glue liquid obtained in synthesis example 1; In the polyimide setting cloth that it obtains, polyimide resin weight content is no more than 30%. The preparation method of polyimide curing sheet is also identical with embodiment 2, and difference is that it adopts polyamic acid glue liquid obtained in synthesis example 1.
Comparative example 1
The making method of cured sheets is as follows: first adopting the method for manual gluing that glass cloth (7628 series) is carried out an impregnation, the resin adhesive liquid adopted is polyamic acid glue liquid obtained in synthesis example 1; Glass cloth after being completed by impregnation subsequently is dried 160 DEG C of warm air dryings for some minutes; Finally it is arranged in high temperature oven by impregnation glass with 160 DEG C, 180 DEG C, 200 DEG C, 240 DEG C, 300 DEG C to process some minutes respectively, complete imidization, obtained polyimide curing sheet.
Comparative example 2
The making method of cured sheets is as follows: first adopting adhesive applicator that glass cloth (1080 series) is carried out an impregnation, the resin adhesive liquid adopted is polyamic acid glue liquid obtained in synthesis example 2; Glass cloth after being completed by impregnation subsequently is dried 160 DEG C of warm air dryings for some minutes; Finally it is arranged in high temperature oven by impregnation glass with 160 DEG C, 180 DEG C, 200 DEG C, 240 DEG C, 300 DEG C to process some minutes respectively, complete imidization, obtained polyimide curing sheet.
The polyimide setting cloth that the present invention obtains is as shown in table 1 with comparing of conventional cloth:
Table 1
The cured sheets that the various performance data of the polyimide curing sheet that the embodiment of the present invention is obtained obtains with comparative example be compared as follows shown in table 1:
Table 2
As can be seen from table 1 and 2, the polyimide setting cloth that the present invention makes, under the polyimide being closely covered in glass yarn (glass fibre) surface supports, being fixed through broadwise wherein, the polyimide setting cloth dimensional stabilizing that obtains like this, apparent smooth, and solve the skew of weft problem that tradition glass cloth occurs when making copper-clad plate.
Above-described embodiment, the just better embodiment of the present invention, be not used for restriction the scope of the present invention, therefore all equivalence changes of doing with the structure described in the claims in the present invention, feature and principle or modify, all should be included within the claims in the present invention scope.
Claims (9)
1. the making method of a polyimide setting cloth, it is characterised in that, comprise the steps:
Wire drawing, will carry out wire drawing after frit melting, form glass yarn;
Impregnation is weaved cotton cloth, and is immersed in polyamic acid glue liquid by described glass yarn and carries out gluing, takes out after drying, be woven into glass cloth blank;
Baking imidization, toasts described glass cloth blank, makes the described polyamic acid complete imidization of glue liquid, obtain polyimide setting cloth; Wherein, in described setting cloth, polyimide resin weight content is no more than 30%.
2. the making method of polyimide setting cloth according to claim 1, it is characterised in that, described impregnation is weaved cotton cloth and is comprised the steps:
(1) at least two described glass yarn are carried out doubling, form glass filament bundle;
(2) described glass filament bundle is immersed in described polyamic acid glue liquid and carry out gluing, take out after drying, form impregnation glass filament bundle;
(3) carry out successively twisting with the fingers yarn, warping and braiding to described impregnation glass filament bundle, form described glass cloth blank.
3. the making method of polyimide setting cloth according to claim 1, it is characterised in that, described impregnation is weaved cotton cloth and is comprised the steps:
(1) at least two described glass yarn are carried out doubling successively, twist with the fingers yarn and warping, form warping yarn;
(2) described warping yarn is immersed in described polyamic acid glue liquid carry out gluing, take out, after oven dry, form impregnation warping yarn;
(3) described impregnation warping yarn is woven, form described glass cloth blank.
4. the making method of polyimide setting cloth according to claim 1, it is characterised in that, the preparation method of described polyamic acid glue liquid is as follows:
Diamine monomer being dissolved in organic solvent and obtains diamine monomer solution, in a water bath after cooling, add dianhydride monomer under nitrogen flowing in diamine monomer solution, control temperature of reaction is 15��25 DEG C, and reaction 7��10h, obtains described polyamic acid glue liquid; In wherein said polyamic acid glue liquid, solid content is 7%��15%.
5. the making method of polyimide setting cloth according to claim 4, it is characterised in that, described diamine monomer is two or more in following compound:
6. the making method of polyimide setting cloth according to claim 4, it is characterised in that: described dianhydride monomer is one or both in following compound:
7. the making method of polyimide setting cloth according to claim 4, it is characterised in that: described organic solvent is one or both in DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone.
8. the making method of polyimide setting cloth according to claim 1, it is characterised in that: the temperature of described polyamic acid glue liquid imidization is 280��350 DEG C.
9. a polyimide setting cloth, adopts the making method of polyimide setting cloth as described in item as arbitrary in claim 1��8 to produce and obtain.
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| CN105625041B (en) | 2018-10-09 |
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