CN115404584A - Glass yarn, method for producing glass cloth, and glass cloth - Google Patents
Glass yarn, method for producing glass cloth, and glass cloth Download PDFInfo
- Publication number
- CN115404584A CN115404584A CN202210589113.4A CN202210589113A CN115404584A CN 115404584 A CN115404584 A CN 115404584A CN 202210589113 A CN202210589113 A CN 202210589113A CN 115404584 A CN115404584 A CN 115404584A
- Authority
- CN
- China
- Prior art keywords
- glass
- yarn
- filaments
- glass cloth
- glass yarn
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- Pending
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- 239000011521 glass Substances 0.000 title claims abstract description 580
- 239000004744 fabric Substances 0.000 title claims abstract description 254
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 66
- 238000009941 weaving Methods 0.000 claims abstract description 56
- 230000007547 defect Effects 0.000 claims abstract description 23
- 238000005259 measurement Methods 0.000 claims description 22
- 230000003287 optical effect Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 57
- 230000000052 comparative effect Effects 0.000 description 31
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 26
- 239000000292 calcium oxide Substances 0.000 description 25
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 25
- 239000000203 mixture Substances 0.000 description 25
- 239000007921 spray Substances 0.000 description 23
- 239000000835 fiber Substances 0.000 description 21
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 20
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000004381 surface treatment Methods 0.000 description 12
- 239000006087 Silane Coupling Agent Substances 0.000 description 11
- 238000005470 impregnation Methods 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000002966 varnish Substances 0.000 description 7
- 239000011575 calcium Substances 0.000 description 6
- 238000007689 inspection Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000004513 sizing Methods 0.000 description 6
- 238000009987 spinning Methods 0.000 description 6
- 229920001940 conductive polymer Polymers 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
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- 239000012756 surface treatment agent Substances 0.000 description 5
- 238000004804 winding Methods 0.000 description 5
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- 239000011324 bead Substances 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 238000004891 communication Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000004993 emission spectroscopy Methods 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 238000011179 visual inspection Methods 0.000 description 3
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 2
- 229920000856 Amylose Polymers 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229920000106 Liquid crystal polymer Polymers 0.000 description 2
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 230000002452 interceptive effect Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 238000009774 resonance method Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- 229920001685 Amylomaize Polymers 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910000435 bromine oxide Inorganic materials 0.000 description 1
- 239000002419 bulk glass Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
- D03D15/242—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads inorganic, e.g. basalt
- D03D15/267—Glass
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
- D02G3/16—Yarns or threads made from mineral substances
- D02G3/18—Yarns or threads made from mineral substances from glass or the like
-
- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/40—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the yarns or threads
- D03D15/41—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the yarns or threads with specific twist
-
- 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
- H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2101/00—Inorganic fibres
- D10B2101/02—Inorganic fibres based on oxides or oxide ceramics, e.g. silicates
- D10B2101/06—Glass
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Ceramic Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Woven Fabrics (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
Abstract
The invention aims to provide glass yarn, a method for manufacturing glass cloth and glass cloth, in particular to provide glass cloth with less defects, a method for manufacturing the glass cloth and the glass yarn for forming the glass cloth. A glass cloth obtained by weaving glass yarns comprising a plurality of glass filaments as warp yarns and weft yarns, wherein 500m in the longitudinal direction of the glass cloth is subjected to irradiation of white LED light along the cloth surface, and when the number of defects per 1m in the longitudinal direction is observed to be 1 in the case where the whole surface of the cloth surface has fluff, the buckling percentage represented by the following formula is 0 to 3.5%. The deduction rate (%) = (total of statistics of defects/500) × 100.
Description
Technical Field
The invention relates to glass yarn, a method for manufacturing glass cloth, and glass cloth.
Background
With the development of the information communication society in recent years,data communication and/or signal processing are increasingly performed at high capacity and high speed. As a result of using printed circuit boards in high-end servers, high-end routers/switches, supercomputers, communication equipment of base stations, measuring instruments, and the like, the printed circuit boards have been advancing to have low dielectric constants. Therefore, low dielectric glass cloth has been proposed as glass cloth constituting a printed wiring board. For example, patent document 1 discloses: in the case of E glass cloth which has been used conventionally, boron trioxide (B) is incorporated in a large amount in the glass composition 2 O 3 ) And adjusting silicon dioxide (SiO) 2 ) And the like, to achieve low dielectric constant of the glass cloth.
In terminal electronic devices such as smartphones, it is also required to cope with large-capacity and high-speed communication, and therefore, in recent years, further low dielectric constant of printed circuit boards used for smartphone applications is also expected. Therefore, there is a strong demand for a low dielectric glass cloth having a small thickness (for example, 10 to 50 μm).
Documents of the prior art
Patent literature
Patent document 1: japanese laid-open patent publication No. 11-292567
Patent document 2: japanese patent laid-open publication No. 2013-112917
Patent document 3: japanese patent laid-open publication No. 2004-115351
Patent document 4: japanese patent laid-open publication No. 2011-140721
Patent document 5: international publication No. 2018/216637
Disclosure of Invention
Problems to be solved by the invention
The inventors of the present invention have conducted studies and found that: the low dielectric glass cloth described in patent document 1 has a variation in performance or quality as compared with the conventionally known E glass cloth. In particular, in a low dielectric glass cloth having a thickness of 10 to 50 μm, since large variation in the quality of the pile tends to occur, it is difficult to stably obtain a glass cloth having excellent pile quality.
As methods for improving the pile quality of glass cloth, patent documents 2 and 3 disclose methods in which a specific starch is used as a sizing agent for glass yarn, patent document 4 discloses a method in which the warp of yarn in a bead ring is reduced in the production of glass yarn, and patent document 5 discloses a method in which a specific composition is used for low dielectric glass.
Patent document 2 discloses: the glass cloth is produced by using glass yarn produced by using a sizing agent containing 25 to 100 mass% of starch composed of amylose and having an average particle diameter of 12 [ mu ] m or less, thereby suppressing the fuzzing of the cloth.
Patent document 3 discloses: the glass yarn is made to have a bundling property improved by producing the glass yarn to which 1.5 to 3.0 mass% of a bundling agent containing etherified high amylose starch having an amylose content of 50% or more is attached, thereby effectively preventing the generation of fuzz.
Patent document 4 discloses: in the twisting process for producing glass yarn, the yarn passing portion of the bead ring is thickened to alleviate the bending of the yarn when passing through the bead ring, thereby preventing quality defects such as fuzz, yarn breakage, knotting and the like.
Patent document 5 discloses: contains 50. Ltoreq. SiO in% by weight by forming the glass composition 2 ≤56、20≤B 2 O 3 ≤30、10≤Al 2 O 3 Not more than 20, not less than 3.5 not more than 10 of MgO + CaO and not more than 0 of R 2 O is less than or equal to 1.0 (in the formula, R is at least 1 element selected from Li, na and K), and further contains Fe 2 O 3 The low dielectric glass of (2) can suppress yarn breakage or fuzz at the time of processing glass yarn.
It is presumed that the low dielectric glass yarn is weaker in strength than the glass yarn of E glass used in the past, and the quality of the pile of the glass cloth produced by using the commercially available low dielectric glass yarn varies greatly, and therefore, the low dielectric glass yarn which can stably obtain a high quality glass cloth has not been obtained at present.
For example, the quality of the glass cloth can be easily improved by using glass yarns with less defects. In recent years, with the background of the improvement in quality required for glass cloth, it has been desired to provide glass cloth that can satisfy expectations for such quality improvement. For example, low dielectric resins tend to have a high molecular weight or a large volume of functional groups, and there is a background that the impregnation property of varnish is inferior to that of conventional resins, and therefore, high impregnation property is required for the glass cloth side.
The present invention has been made in view of the above problems, and an object of the present invention is to provide a glass yarn with less defects; the glass yarn is used for providing glass cloth with high uniformity and good quality; further provides a method for producing the same.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have focused on the fact that fine fluff and the like can be detected first by a predetermined visual observation, and have completed the present invention. One mode of the invention is listed below.
[1] A glass cloth obtained by weaving warp yarns and weft yarns with glass yarns comprising a plurality of glass filaments,
when 500m in the longitudinal direction of the glass cloth is used as an object, white LED light is irradiated along the cloth surface, every 1m in the longitudinal direction is observed, and the number of missing points is 1 when the whole surface of the cloth is provided, the deduction rate represented by the following formula is 0-3.5%.
Deduction rate (%) = (sum of statistics of defects/500) × 100
[2] The glass cloth according to item 1, wherein the whole surface piles include piles of 200 to 1000 μm caused by breakage of the filaments observed on the surface of the cloth with an optical microscope.
[3] The glass cloth according to item 1 or 2, wherein the thickness of the glass cloth is 10 to 50 μm.
[4] The glass cloth according to any one of items 1 to 3, comprising the glass yarn satisfying the following conditions:
(i) TEX is 1-13;
(ii) The breaking strength is 0.50-0.80N/tex; and is
(iii) The number of filaments slipping off at 180m to 2 times or more of the average value of the yarn width was 3 or less.
[5] The glass cloth according to any one of items 1 to 4, comprising the glass yarn having a twist interval length of 1.8 to 10.0cm.
[6] The glass cloth according to any of items 1 to 5, comprising the glass yarn, wherein a value (twist interval length difference index) obtained by dividing a difference between a maximum value of the twist interval length and a minimum value of the twist interval length of the glass yarn by an average value of the twist interval lengths is 0.7 or less.
[7] The glass cloth according to any one of items 1 to 6, wherein,
the glass yarn having a length of 10,000m or more is used as an object,
when the measurement ranges of 180m in the longitudinal direction are selected at 5 points different from each other, the number of filaments slipping off to 2 times or more the average value of the yarn width is 3 or less in each of the measurement ranges at 5 points.
[8] The glass cloth according to any one of items 1 to 6, wherein,
the glass yarn having a length of 50,000m or more is used as an object,
when the measuring ranges of 180m in the longitudinal direction are selected at 7 points different from each other, the number of filaments slipping off to 2 times or more the average value of the yarn width is 3 or less in the measuring ranges at the 7 points, respectively.
[9] The glass cloth according to any one of items 1 to 6, wherein,
the glass yarn having a length of 100,000m or more is used as an object,
when the measuring ranges of 180m in the longitudinal direction are selected at 10 points different from each other, the number of filaments slipping off to 2 times or more the average value of the yarn width is 3 or less in the measuring ranges at 10 points, respectively.
[10] A method for manufacturing glass cloth, comprising a step of using glass yarn comprising a plurality of glass filaments as warp and weft and weaving the glass yarn,
(i) The TEX of the glass yarn is 1-13;
(ii) The breaking strength of the glass yarn is 0.50-0.80N/tex; and is
(iii) The number of filaments slipping off at 180m to 2 times or more of the average value of the yarn width was 3 or less.
[11] The method for producing a glass cloth according to item 10, wherein the glass yarn has a TEX of 1 to 7.
[12] The method for producing glass cloth according to item 10 or 11, wherein the number of glass filaments constituting the glass yarn is 30 to 120.
[13] The method for producing glass cloth according to any one of items 10 to 12, wherein the glass yarn has a twist interval length of 1.8 to 10.0cm.
[14] The method of manufacturing glass cloth according to any of items 10 to 13, wherein a value (twist interval length difference index) obtained by dividing a difference between a maximum value of the twist interval length and a minimum value of the twist interval length of the glass yarn by an average value of the twist interval lengths is 0.7 or less.
[15]The method for producing glass cloth according to any one of items 10 to 14, wherein the glass yarn has a density of 2.2g/cm 3 More than and less than 2.5g/cm 3 。
[16] The method for producing glass cloth according to any one of items 10 to 15, wherein the glass yarn has an elastic coefficient of 50 to 70GPa.
[17] The method for producing glass cloth according to any one of items 10 to 16, wherein the glass yarn has an elastic coefficient of 50 to 63GPa.
[18] The method for producing glass cloth according to any of items 10 to 17, wherein,
the glass yarn having a length of 10,000m or more is used as an object,
when the measuring ranges of 180m in the length direction are selected at 5 points different from each other, the number of filaments slipping to 2 times or more the average value of the yarn width is 3 or less in the measuring ranges of the 5 points, respectively.
[19] The method for producing glass cloth according to any one of items 10 to 17, wherein,
the glass yarn having a length of 50,000m or more is used as an object,
when the measuring ranges of 180m in the length direction are selected at 7 points different from each other, the number of filaments slipping to 2 times or more the average value of the yarn width is 3 or less in the measuring ranges at the 7 points, respectively.
[20] The method for producing glass cloth according to any of items 10 to 17, wherein,
the glass yarn having a length of 100,000m or more is used as an object,
when the measuring ranges of 180m in the longitudinal direction are selected at 10 points different from each other, the number of filaments slipping off to 2 times or more the average value of the yarn width is 3 or less in the measuring ranges at 10 points, respectively.
[21] A glass yarn, wherein,
(i) TEX is 1-13;
(ii) The breaking strength is 0.50-0.80N/tex; and is provided with
(iii) The number of filaments slipping off at 180m to 2 times or more of the average value of the yarn width was 3 or less.
[22] The glass yarn of item 21, wherein the TEX is 1 to 7.
[23] The glass yarn according to item 21 or 22, wherein the number of glass filaments constituting the glass yarn is 30 to 120.
[24] The glass yarn of any one of items 21 to 23, wherein the twist interval length is 1.8 to 10.0cm.
[25] The glass yarn according to any one of items 21 to 24, wherein a value (twist interval length difference index) obtained by dividing a difference between a maximum value of the twist interval length and a minimum value of the twist interval length by an average value of the twist interval lengths is 0.7 or less.
[26]The glass yarn according to any one of items 21 to 25, which has a density of 2.2g/cm 3 More than or less than 2.5g/cm 3 。
[27] The glass yarn according to any one of items 21 to 26, wherein the modulus of elasticity is 50 to 70GPa.
[28] The glass yarn according to any one of items 21 to 27, wherein the modulus of elasticity is 50 to 63GPa.
[29] The glass yarn of any one of items 21 to 28, wherein,
the glass yarn having a length of 10,000m or more is used as an object,
when the measuring ranges of 180m in the length direction are selected at 5 points different from each other, the number of filaments slipping to 2 times or more the average value of the yarn width is 3 or less in the measuring ranges of the 5 points, respectively.
[30] The glass yarn according to any one of items 21 to 28, wherein,
the glass yarn having a length of 50,000m or more is used as an object,
when the measuring ranges of 180m in the length direction are selected at 7 points different from each other, the number of filaments slipping to 2 times or more the average value of the yarn width is 3 or less in the measuring ranges at the 7 points, respectively.
[31] The glass yarn according to any one of items 21 to 28, wherein,
the glass yarn having a length of 100,000m or more is used as an object,
when the measuring ranges of 180m in the length direction are selected at 10 points different from each other, the number of filaments slipping to 2 times or more the average value of the yarn width is 3 or less in the measuring ranges at 10 points, respectively.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a glass yarn with few defects can be provided, and a glass cloth with high uniformity and good quality can be provided using the glass yarn, and a method for producing the glass cloth can also be provided.
Detailed Description
The embodiments of the present invention (hereinafter, referred to as "embodiments") will be described in detail below, but the present invention is not limited thereto, and various modifications can be made within the scope not departing from the gist thereof.
[ glass cloth ]
The first embodiment of the present invention is a glass cloth.
The glass cloth of the present embodiment is:
the glass yarn is obtained by using glass yarn containing a plurality of glass filaments (hereinafter also referred to as simply "filaments") as warp yarn and weft yarn and weaving, and is observed by irradiating white LED light along the cloth surface for every 1m of the cloth surface in the length direction with respect to a specified measurement length 500 (m) in the full length of the glass cloth in the length direction, and when the number of missing points is 1 in the case that the whole surface of the cloth surface has fluff, the knot fraction represented by the following formula is 0 to 3.5%.
Fraction (%) buckled (= total statistics of whole pile)/500 (m) × 100
In the present embodiment, by illuminating white LED light along the surface of the cloth and observing the surface of the cloth, it is possible to detect a filament break (hereinafter also referred to as "fine fluff") having a length of less than 1mm with good sensitivity, as compared with the conventional observation achieved by illuminating light in the vertical direction to the surface of the cloth. Furthermore, since the mark-off rate derived by this detection method is 0 to 3.5%, the glass cloth has few defects and is excellent in various properties. From the same viewpoint, the deduction ratio is preferably 3.0% or less, more preferably 2.9% or less.
In addition, conventional observation (conventional observation performed by irradiating a surface with light in a vertical direction) does not assume observation of fine fluff. Therefore, in the case of the conventional observation method, it is impossible to detect the fine fluff as assumed in the present embodiment with good sensitivity, and it is not easy to conceive of controlling the cut rate to the numerical range as assumed in the present embodiment.
The calculation method of "deduction ratio (%)" is described in detail in examples.
The whole pile includes a pile of 200 to 1000 μm observed on the surface of the cloth by an optical microscope and caused by the breakage of the filament. As described in the present embodiment, the entire pile is easily observed just by observing the surface of the cloth while emitting the white LED light along the surface of the cloth.
The glass cloth of the present embodiment preferably has a thickness described below. The glass yarn used for obtaining the glass cloth of the present embodiment preferably has a structure described below.
(dielectric constant of glass cloth)
The glass cloth has a dielectric constant of preferably 5.0 or less, more preferably 4.9 or less, further preferably 4.8 or less, and particularly preferably 4.6 or less at a frequency of 10 GHz. The dielectric constant of the glass cloth can be measured by a cavity resonance method. In the present specification, the dielectric constant of the glass cloth means a dielectric constant at a frequency of 10GHz unless otherwise specified.
[ glass yarn ]
The second embodiment of the present invention is a glass yarn.
With regard to the glass yarn of the second embodiment,
(i) TEX is 1-13;
(ii) The breaking strength is 0.50-0.80N/tex; and is provided with
(iii) The number of filaments slipping off to 2 times or more the average value of the yarn width at 180m was measured (hereinafter, "the number of filaments slipping off to 2 times or more the average value of the yarn width at 180m" is also referred to simply as "the number of filaments slipping off") was 3 or less.
The glass cloth manufactured by using the low dielectric glass yarn has a quality difference from that of the conventional E glass cloth. Therefore, it is known that it is difficult to stably obtain a high-quality low dielectric glass cloth. Among them, when a glass cloth having poor quality is examined in detail, it is confirmed that a large number of naps are densely present in a band-like "band-like nap defect" in a low dielectric glass cloth made of low dielectric glass yarns having a number of slipping-off filaments out of a specific range in the longitudinal direction. In contrast, the present embodiment is based on the following findings: this disadvantage of the low dielectric glass cloth can be reduced by using low dielectric glass yarns having filaments falling within a specific range. Without wishing to be bound by theory, it is believed that: when a glass yarn having a filament falling off more than a predetermined value (for example, the number of slipping filaments is more than 3) is subjected to interference with a loom member such as a loop guide after being pulled from a bobbin (bobbin) in a weaving process, the yarn is likely to undergo the acceleration of the filament falling off or the filament breakage.
In particular, the weft yarn is carried with a balloon (balloon) motion in the yarn path until the weft yarn is torn off from the bobbin and ejected. Therefore, it is considered that the filament slipping-off portion is likely to be subjected to shear stress to be broken, and the broken filament pieces are likely to be entangled by the rotational motion to grow into coarse fluff. In order to improve productivity, the weaving speed of the weft is preferably high, but it is considered that: the faster the weft yarn is conveyed, the more likely the yarn is to be broken or the more likely the yarn is to be broken.
The glass yarn of E glass used up to now has a higher density and higher strength than low dielectric glass yarn. Therefore, the glass yarn is stably conveyed and the degree of interference with the loom member is small, and therefore, the damage to the glass yarn when the interference occurs is limited. On the other hand, even in a low dielectric glass yarn which is lighter and has lower strength, the variation tends to be large due to tension variation or the like when the glass yarn is conveyed. Therefore, the interference with the loom member is likely to occur, and the interference with the loom member is also likely to be more damaged. Therefore, it is considered that it is liable to promote the progress of the shedding of the filaments or the breakage of the filaments.
Further, when the glass yarn having a filament falling off more than a specific range is subjected to a physical load such as high-pressure spray water in the opening step, the falling off portion is easily moved. It can therefore be considered that: the drop-off portion is likely to receive a load such as interference with a conveying member of the glass cloth, and fluff due to filament breakage or fluff at the broken portion is likely to occur with the drop-off portion as a starting point. In order to improve the in-plane uniformity of the glass cloth and improve the impregnation property, the fiber opening processing force is preferably strong, but it is considered that: the stronger the opening force is, the more likely the defect of the pile caused by the breakage of the filaments or the defect of the coarse pile caused by the entanglement of the filaments is generated.
Further, the glass strength of the low dielectric glass yarn having a lower density and lower strength than the E glass is remarkably reduced in the thermal cleaning step. It can therefore be considered that: when the opening step is performed after the thermal cleaning step, damage due to a physical load such as high-pressure water spray is strongly applied, and fluff or broken filaments are more likely to be generated due to filament breakage. It can be considered that: these effects are expressed in the form of the quality of the glass cloth.
On the other hand, by using the glass yarn of the present embodiment, even when a glass yarn which is light and has low strength through low dielectric constant is used, damage which is received when the glass yarn interferes with a loom member such as a ring guide when the glass yarn is pulled out in a weaving process and is then passed through the loom member can be reduced. In addition, when the glass yarn of the present embodiment is used, the degree of interference between the drop-off portion and the conveying member or damage to be received during the interference can be reduced in the opening step. Thus, by using the glass yarn of the present embodiment, generation of fuzz due to filament breakage in the weaving step and the opening step can be suppressed, and a glass cloth having good quality and uniformity can be obtained. Further, the use of the glass yarn is preferable because the weaving speed (the weaving speed of the glass yarn) and/or the opening force in the opening step tend to be increased.
When the glass yarn according to the present embodiment is used, it is preferable to prevent a defect such as fluff from being generated when rubbed by a yarn path guide or the like in a process of pulling out the glass yarn (for example, warp) from a bobbin base yarn by a creel (creel) and straightening out the glass yarn. Further, the use of the glass yarn is preferable because the warp production speed tends to be increased.
(TEX of glass yarn)
The TEX of the glass yarn is 1 to 13, preferably 1.5 to 12, more preferably 2.0 to 11, even more preferably 2.5 to 10 or 1 to 7. When the TEX of the glass yarn is 13 or less, the strength of the glass yarn is low, and therefore, the following tendency may occur: the glass yarn is likely to cause a fuzz failure by interfering with a loom member such as a ring guide when the glass yarn is pulled out in a weaving step and then passes through the loom member, and by interfering with a glass cloth conveying member in a fiber opening step. On the other hand, by adjusting the degree of shedding of the filaments within the specific range of the present embodiment, the degree of interference or damage to be received at the time of interference can be reduced, and as a result, a high-quality glass cloth can be stably obtained. When the degree of shedding of the filament is within the specific range of the present embodiment, the TEX of the glass yarn is 1 or more, and thus, when the glass yarn is pulled out in the weaving step and then passed through a loom member such as a ring guide, the filament can be prevented from being broken when the glass yarn interferes with the loom member or when the glass yarn interferes with a glass cloth conveying member in the splitting step.
(breaking Strength of glass yarn)
The breaking strength of the glass yarn is 0.50-0.80N/tex. The breaking strength is preferably in the range of 0.53 to 0.79N/tex, more preferably in the range of 0.57 to 0.78N/tex, and still more preferably in the range of 0.60 to 0.77N/tex. If the breaking strength of the glass yarn is not less than the lower limit, the glass yarn is less likely to break and fluff is less likely to be generated when the glass yarn interferes with a loom member such as a ring guide when the glass yarn is pulled out in the weaving step and interferes with a conveying member of the glass cloth in the opening step to receive a shearing stress. On the other hand, if the breaking strength of the glass yarn is not more than the above upper limit, the yarn deviation or balloon motion during the yarn conveyance process until the glass yarn is pulled out from the bobbin and discharged tends to be suppressed small, and as a result, the progress of the yarn dropping and the fluff defect due to the yarn breaking are less likely to occur. This is presumed to be due to the effect of the ductility of the glass yarn.
(number of slip filaments of glass yarn)
The number of slip filaments of the glass yarn is 3 or less. The number of slipping filaments is preferably 2 or less, more preferably 1 or less, and still more preferably 0.
The above "180m" may be any of the following lengths:
1) A length starting from an end (one end or the other end) of the glass yarn in the longitudinal direction;
2) The length of any portion other than the end portion.
Specific examples of the above 2) include:
2-1) a length set with a portion having a distance of 2 to 6m (for example, 5 m) from the end portion in the longitudinal direction as a starting point.
If 2-1) is used, the number of slipping filaments can be accurately determined without being affected by the "looseness" that tends to occur at the ends of the glass yarn.
In the case of a state where the glass yarn is wound on the bobbin, "180m" may be any one of the following lengths:
3) A length comprising at least a portion of an outermost periphery or an innermost periphery of the bobbin;
4) The length of any portion except the outermost periphery and the innermost periphery.
Specific examples of the above-mentioned 4) include, from the viewpoint of easy observation:
4-1) a length set with a start portion of a second turn when an outermost circumference is a first turn as a start point;
4-2) a length set with the start portion of the second turn when the innermost circumference is the first turn as the starting point.
Among them, it can be:
4-3) length set at an arbitrary position other than the above starting point.
When a glass yarn having a length of 10,000m or more is used as a target, and measurement ranges of 180m in the longitudinal direction are selected at 5 points different from each other, the number of slip filaments is preferably 3 or less, more preferably 2 or less, further preferably 1 or less, and most preferably 0, within the measurement range at 5 points.
When a glass yarn having a length of 50,000m or more is used as a target, and measurement ranges of 180m in the longitudinal direction are selected at 7 points different from each other, the number of slip filaments is preferably 3 or less, more preferably 2 or less, further preferably 1 or less, and most preferably 0, within the measurement range of 7 points.
When the glass yarn having a length of 100,000m or more is selected as the measurement range of 180m in the longitudinal direction at 10 points different from each other, the number of slip filaments is preferably 3 or less, more preferably 2 or less, further preferably 1 or less, and most preferably 0, within the measurement range at 10 points.
When the number of the slipping filaments is measured, the conveying speed of the glass yarn can be increased. In order to keep the same as the weft yarn ejection in the weaving step, the glass yarn may be pulled out from the bobbin by air and the measurement may be performed while the glass yarn is conveyed (in this case, a yarn path guide is appropriately provided to prevent the ejected glass yarn from being out of control).
The number of slipping filaments was measured by the method described in examples.
By setting the number of slipping filaments to be equal to or less than the above range and setting the breaking strength to be equal to or less than the above range, the progress of the dropping of the filaments and the coarse fluff due to the winding of the filaments broken or broken are less likely to occur in the course of conveyance from the time when the glass yarn is pulled out from the bobbin to the time when the glass yarn is discharged. Thus, a high-quality glass cloth having less densely piled portions can be stably obtained. This is presumably because: since the degree and frequency of filament slippage are within a certain range, the degree of interference between the slippage part and the loom member such as a ring guide or the resistance due to the interference is reduced, and thus damage due to interference with the loom member can be suppressed to a small extent.
In particular, as described above, the weft yarn is easily broken, and furthermore, the broken filament sheet is easily twisted by the balloon motion. On the other hand, it can be presumed that: by adjusting the number of dropped filaments to the above range, the breakage of filaments or the entanglement of broken filaments is suppressed. Further, it is presumed that this is because: since the degree and frequency of filament slipping are within a certain range, the degree of interference with the conveying member of the glass cloth or the resistance due to the interference is reduced in the opening step, and thus the damage due to the interference with the conveying member can be suppressed to a small extent.
The number of filaments slipping can be adjusted by the following methods alone or in combination:
a method of designing the arrangement of the bushing nozzles so that distances from the plurality of bushing nozzles to the bundling point are equal when the filaments discharged from the plurality of bushing nozzles (weaving nozzles) are bundled into 1 yarn bundle in the spinning step for producing the glass yarn;
a method of adjusting the nozzle shape of the sleeve nozzle based on the distance difference from the sleeve nozzle to the bundling point;
a method of adjusting the temperature of the thimble nozzle based on the difference in distance from the thimble nozzle to the bundling point;
a method of adjusting the cooling temperature in the spinning step for producing glass yarn;
method of adjusting the cake (cake) take-up tension;
a method of adjusting the cake take-up speed;
a method of adjusting the pass (traverse) at the time of spinning cake winding;
a method for adjusting a spinning cake winding method and aging conditions so that the moisture content and the amount of sizing agent attached to the glass yarn become more uniform over the entire length of the glass yarn in an aging step for producing a spinning cake of the glass yarn;
a method of adjusting the shape and weight of the bead ring so that the load when the glass yarn is bent is reduced in the yarn twisting step for producing the glass yarn;
a method of adjusting the range of variation in the number of twists per unit length to a specific range;
a method of adjusting the tension of the glass yarn so that the tension becomes smaller while the glass yarn is pulled out from the spinning cake and wound on the bobbin;
a method of adjusting a balloon at the time of twisting; and
a method of adjusting the winding edge angle of the glass yarn on the spool.
(Density of glass yarn)
The density of the glass yarn is preferably 2.2g/cm 3 More than and less than 2.5g/cm 3 More preferably 2.2g/cm 3 More than or equal to less than 2.45g/cm 3 More preferably 2.2g/cm 3 Above and 2.40g/cm 3 The lower, more preferably 2.25g/cm 3 Above and 2.4g/cm 3 The following.
If the glass yarn has a density of less than 2.5g/cm 3 In the course of transportation until the glass yarn is pulled out from the bobbin and discharged, the following tendency may occur: the deviation in the direction perpendicular to the transport direction and the balloon motion tend to be large, and the pile defect tends to occur due to interference with the loom member. However, by making the slippage longerThe number of threads is adjusted to fall within the specific range described in the present embodiment, and the generation of fuzz due to interference with the loom members is suppressed, whereby high-quality glass cloth can be stably obtained.
In addition, if the density of the glass yarn is less than 2.5g/cm 3 When a physical load such as a high-pressure water spray pressure is applied in the fiber opening step, the following tendency may occur: the slack of the glass cloth becomes large, and the glass cloth easily interferes with the conveying member, and a fluff defect is easily generated due to the interference with the conveying member. However, by adjusting the number of slip filaments to fall within the specific range in the present embodiment, generation of fuzz due to interference with the conveying member is suppressed, and thus, a high-quality glass cloth can be stably obtained.
On the other hand, by making the density of the glass yarn 2.2g/cm 3 As described above, the conveyance path of the glass yarn can be kept stable. Further, by making the density of the glass yarn 2.2g/cm 3 This can reduce the slack of the glass cloth. The density of the glass strands may be in the order of 1cm 3 The density of the bulk glass (c) is determined.
(filament and diameter)
The glass yarn is obtained by bundling a plurality of filaments and twisting them as necessary. In this case, the glass yarn is classified into glass multifilaments, and the filaments (glass filaments) contained in the glass yarn are classified into glass monofilaments, respectively.
Here, the "slippage" of the filament means not only slippage of the glass monofilament in 1 piece, slippage of the glass monofilament in several pieces, but also the case where the filament is broken. The number of slip filaments can be determined by the method described in the examples.
The glass yarn is preferably a glass yarn obtained by bundling 40 to 240 glass filaments having an average diameter of 3.5 to 5.5 μm or a glass yarn having 30 to 120 glass filaments. By using glass yarns having an average diameter and a number of filaments within the above-mentioned ranges, glass cloth having a thickness equivalent to 1000, 1017, 1015, 1012, 1027, 1024, 1020, 1030, 1037, 1035, 106, 1067, 1078 of conventional E glass cloth (IPC standard (IPC-4412B): style1000, 1017, 1015, 1012, 1027, 1024, 1020, 1030, 1037, 1035, 106, 1067, 1078) can be easily produced.
(coefficient of elasticity of glass yarn)
The modulus of elasticity of the glass yarn is preferably 50 to 70GPa, more preferably 50 to 63GPa, and still more preferably 53 to 63GPa. When the modulus of elasticity is 50GPa or more, the glass yarn tends to have high rigidity and to be less likely to have fuzz in the production process. Further, by setting the modulus of elasticity to 70GPa or less, the glass yarn tends to have improved brittleness resistance and to be less likely to have fuzz in the production process. Further, when the elastic modulus is within the above range, the following tendency is exhibited: the glass yarn has moderate flexibility, and when a mechanical load is applied, breakage of the filament and the like are not easily generated, and fluff and weaving defects are not easily generated.
(constitution of composition of glass yarn)
Examples of the constituent elements of the glass yarn include silicon (Si), boron (B), aluminum (Al), calcium (Ca), magnesium (Mg), phosphorus (P), sodium (Na), potassium (K), titanium (Ti), zinc (Zn), iron (Fe), fluorine (F), and the like.
Si content of the glass yarn is in accordance with SiO 2 The amount is preferably 40 to 60% by mass, more preferably 45 to 55% by mass, still more preferably 47 to 53% by mass, and yet more preferably 48 to 52% by mass.
Si is a component forming the skeleton structure of the glass yarn, and the strength of the glass yarn is more easily improved by making the Si content 40 mass% or more. As a result, the glass cloth tends to be further prevented from being broken in the subsequent steps such as the production process of the glass cloth and the production of a prepreg using the glass cloth. In addition, when the Si content is 40 mass% or more, the dielectric constant of the glass cloth tends to be further lowered. On the other hand, when the Si content is 60 mass% or less, the viscosity at the time of melting is further reduced in the process of producing the filament, and thus glass fibers having a more uniform glass composition tend to be obtained. Therefore, the obtained filament is less likely to have a portion where partial devitrification is likely to occur or a portion where partial removal of bubbles is difficult to occur, and therefore, a portion where partial strength is low is less likely to occur in the filament, and as a result, the glass cloth composed of the glass yarn obtained using the filament is less likely to break. The Si content can be adjusted depending on the amount of raw material used to make the filaments.
B content of the glass strands is in accordance with B 2 O 3 In terms of conversion, it is preferably 15 to 40% by mass, more preferably 17 to 30% by mass or 20 to 40% by mass, even more preferably 18 to 28% by mass, even more preferably 19 to 26% by mass, even more preferably 20 to 25% by mass, most preferably 20.5 to 24% by mass.
When the B content is 15 mass% or more, the dielectric constant tends to be further lowered. Further, by setting the B content to 15 mass% or more, the brittleness resistance of the glass cloth is improved, and appropriate flexibility and ductility are provided, so that the glass yarn tends to be less likely to generate fuzz when contacting a loom member such as a yarn path guide or a reed. On the other hand, the B content is preferably 40 mass% or less in order to maintain the strength of the glass yarn. Further, the moisture absorption resistance is improved by setting the B content to 40 mass% or less. The B content can be adjusted depending on the amount of raw material used to make the filaments. In the case where conditions, amounts, or contents may vary during the production of filaments, the amounts may be estimated in advance, and the amounts of the raw materials may be adjusted.
Al content of glass yarn is in terms of alumina (Al) 2 O 3 ) In terms of conversion, it is preferably 11 to 18% by mass, more preferably 11 to 16% by mass, and still more preferably 12 to 16% by mass. When the Al content is in the above range, the electrical characteristics and strength tend to be further improved. The Al content can be adjusted according to the amount of raw material used to make the filaments.
The Ca content of the glass yarn is preferably 5 to 10 mass%, preferably 5 to 9 mass%, more preferably 5 to 8.5 mass% in terms of calcium oxide (CaO). When the Ca content is 5 mass% or more, the viscosity at the time of melting tends to be further reduced in the process of producing filaments, and glass fibers having a more uniform glass composition tend to be obtained. In addition, when the Ca content is 10 mass% or less, the dielectric constant tends to be further improved. The Ca content can be adjusted according to the amount of raw material used to make the filaments.
The glass yarn may have various excellent properties by containing predetermined amounts of Mg, P, na, K, ti, zn, fe, and F. These amounts can be adjusted depending on the amount of raw materials used to make the filaments.
The above contents can be measured by ICP emission spectrometry. Specifically, the Si content and the B content can be obtained by melting a weighed glass cloth sample with sodium carbonate, dissolving with dilute nitric acid, fixing the volume, and measuring the obtained sample by an ICP emission spectrometry. In addition, the Fe content can be obtained by dissolving a weighed glass cloth sample by an alkali dissolution method and fixing the volume, and measuring the obtained sample by an ICP emission spectrometry. Further, the Al content, ca content and Mg content can be obtained by subjecting a weighed glass cloth sample to thermal decomposition with sulfuric acid, nitric acid and hydrogen fluoride, dissolving with dilute nitric acid and fixing the volume, and measuring the obtained sample by ICP emission spectrometry. The ICP emission spectrometer may be PS3520VDD II manufactured by hitachi high-tech company.
(dielectric constant of glass yarn)
The glass yarn preferably has a dielectric constant of 5.0 or less, more preferably 4.9 or less, further preferably 4.8 or less, and particularly preferably 4.6 or less at a frequency of 10 GHz. The dielectric constant of the glass yarn can be measured by, for example, a cavity resonance method. In the present specification, the dielectric constant of the glass yarn means the dielectric constant at a frequency of 10GHz unless otherwise specified.
(twist interval length of glass yarn and twist interval length difference index)
The length of the space between the glass yarns is preferably 1.8 to 10.0cm, more preferably 1.9 to 9.9cm, still more preferably 1.95 to 4.0cm, and most preferably 2.0 to 3.5cm. The minimum value of the twist interval length is preferably 1.8cm, more preferably 1.9cm, further preferably 1.95cm, and most preferably 2.0cm. The maximum value of the twist interval length is preferably 10.0cm, more preferably 9.9cm, further preferably 4.0cm, and most preferably 3.5cm.
The difference between the maximum value of the twist interval length and the minimum value of the twist interval length of the glass yarn is divided by the average value of the twist interval lengths (twist interval length difference index) and is preferably 0.7 or less, more preferably 0.6 or less, still more preferably 0.5 or less, most preferably 0.4 or less, and may exceed 0. When the twist interval length of the glass yarn and/or the twist interval length difference index is within the above numerical range, the following tendency is present: when the glass yarn is wound around the bobbin, the number of slipping filaments evaluated at the outer layer portion of the bobbin is likely to be 3 or less, and/or the number of slipping filaments over the entire length of the bobbin is reduced. Although not wishing to be bound by theory, the reason for the reduced number of slipping filaments is considered to be three reasons:
(i) If the length of the twist interval is greater than the lower limit value, the torsional shear stress is suppressed to be small, so that the filament is not easy to slip;
(ii) If the length of the twist interval is less than the upper limit value, the binding force between the filaments constituting the glass yarn is increased, and therefore, the filaments are not easy to slip;
(iii) If the twist interval length difference index is smaller than the upper limit value, the variation in twist angle in the longitudinal direction of the glass yarn is suppressed to be small, and therefore, the slip of the filament is less likely to occur.
The standard deviation of the number of twists of the glass yarn is preferably 0.05 to 0.20, and more preferably 0.09 to 0.18.
[ method for producing glass cloth ]
The third embodiment of the present invention is a method for manufacturing a glass cloth.
The present embodiment is a method for manufacturing a glass cloth, including a step of using a glass yarn including a plurality of filaments for a warp and a weft and weaving the same.
The glass yarn used is as described above.
(i) TEX is 1-13;
(ii) The breaking strength is 0.50-0.80N/tex; and is
(iii) The number of slipping-off filaments (the number of filaments slipping off to 2 times or more of the average value of the yarn width at 180m measurement) is 3 or less.
Specifically, the production method includes the following steps: a glass yarn adjusting step of adjusting the glass yarn so that the number of slipping filaments is equal to or less than a predetermined number; a weaving step of weaving the glass yarn adjusted to obtain a glass cloth; and a fiber opening step for opening the glass yarns of the glass cloth. The method for producing the glass cloth may include a degumming step of removing the sizing agent attached to the glass yarn of the glass cloth, if necessary; and a surface treatment process based on a silane coupling agent.
Hereinafter, each step in the method for producing the glass cloth will be described in more detail.
(glass yarn adjusting step)
The glass yarn adjusting step is a step of adjusting the glass yarns so that the number of slip filaments is 3 or less. More specifically, in the glass yarn adjusting step, if the number of slip filaments is within the above range, the glass yarn is used in the weaving step, and if the number is out of the range, the use of the glass yarn in the glass yarn is prohibited.
The method for measuring the number of slipping filaments includes: a method of observing the yarn width and the slipped filament by using a displacement meter of a light projection mode such as laser and LED light while conveying the glass yarn; a method of conveying the glass yarn and observing the yarn width and the slipped filament while observing the shape of the glass yarn in the image, and the like.
(weaving Process)
The weaving step is a step of weaving glass yarns to obtain a glass cloth. Examples of the woven structure of the glass cloth include a plain weave, a basket weave, a satin weave, and a twill weave. Of these, the plain structure is more preferable.
In an example of the weaving step in the manufacturing method of the present embodiment, the warp yarns pulled in parallel are opened in the upper and lower directions by the air jet loom system, and the yarn discharged from the weft storage device is sent out as a weft by the jet flow of the nozzle and passed through the opening, whereby weaving can be performed.
In the weaving step, in the glass yarn ejecting process of winding out the glass yarn as the weft yarn from the bobbin and ejecting the weft yarn via the storage device,
the glass yarn is conveyed with a balloon motion or the like in a direction different from the advancing direction and with interference with a loom member such as a yarn guide; or
Since the weft is repeatedly ejected and stopped in units of a length of 1 weft, the weft is conveyed with a fluctuation in tension and interference with a loom member such as a yarn guide;
therefore, it is difficult to suppress the damage caused by the above interference to a small extent by the weft having a large number of slipping-off filaments, and the resultant glass cloth may be fluffy or have weaving defects.
In contrast, in the present embodiment, the glass yarn having the number of slip filaments within a specific range is used, thereby suppressing the occurrence of fuzz or weaving defects when the weft is woven in, and thus improving the in-plane uniformity and the batch-to-batch uniformity of the quality of the glass cloth. The weaving method is not limited to the air jet loom method, and may be a water jet loom method or a shuttle method.
The beating-up density of the warp and weft constituting the glass cloth is preferably 30 to 120 pieces/25 mm, more preferably 40 to 110 pieces/25 mm, and further preferably 45 to 105 pieces/25 mm. The beating-up density of the warp yarn can be controlled by adjusting the interval of the warp yarns pulled in parallel, and the beating-up density of the weft yarn can be controlled by the number of times of ejection of the weft yarn per unit time from the nozzle and the flow rate of the warp yarn.
(fiber opening step)
The opening step is a step of opening glass yarns of the glass cloth. Examples of the fiber-opening method include a method of performing fiber-opening processing using, for example, water spray (high-pressure water-opening), a vibration washer, ultrasonic water, a mangle, or the like.
The thickness of the glass cloth finally obtained through the fiber-opening step or the like is preferably 5 to 60 μm, more preferably 7 to 55 μm, and still more preferably 9 to 50 μm or 10 to 50 μm. When the thickness of the glass cloth is within the above range, the glass cloth tends to be thin and strong. The weight of the glass cloth finally obtained after the fiber opening processThe amount (weight per unit area) is preferably 5 to 55g/m 2 More preferably 6 to 50g/m 2 More preferably 7 to 48g/m 2 。
(degumming Process)
The degumming step is a step of removing the sizing agent attached to the glass yarn of the glass cloth. As the degumming method, for example, a method of removing the sizing agent by heating can be mentioned.
(surface treatment Process)
The surface treatment step is a step of performing surface treatment of the glass cloth with a silane coupling agent. Further, as the surface treatment method, there may be mentioned: a method of bringing a surface treatment agent containing a silane coupling agent into contact with a glass cloth and drying the same. The contact between the surface treatment agent and the glass cloth includes: a method of impregnating a glass cloth with a surface treatment agent; a method of applying a surface treatment agent to a glass cloth using a roll coater, die coater, gravure coater, or the like. The method of drying the surface treatment agent is not particularly limited, and examples thereof include hot air drying and drying using electromagnetic waves.
[ prepreg ]
The prepreg includes the glass cloth obtained in the above-described manner and a base resin composition impregnated into the glass cloth. The prepreg having the glass cloth has less variation in quality, and the yield of the final product is increased.
The prepreg can be manufactured according to a conventional method. For example, the resin composition can be produced by impregnating a glass cloth with a varnish prepared by diluting a base resin such as an epoxy resin with an organic solvent, and then curing the thermosetting resin to a B-stage state (semi-cured state) by volatilizing the organic solvent in a drying furnace.
Examples of the base resin composition include, in addition to the epoxy resin, thermosetting resins such as bismaleimide resin, cyanate ester resin, unsaturated polyester resin, polyimide resin, BT resin, and functionalized polyphenylene ether resin; thermoplastic resins such as polyphenylene ether resins, polyether imide resins, liquid Crystal Polymers (LCP) of wholly aromatic polyesters, polybutadiene, and fluorine resins; and mixed resins thereof. From the viewpoint of improving dielectric properties, heat resistance, solvent resistance, and press moldability, a resin obtained by modifying a thermoplastic resin with a thermosetting resin can be used as the base resin composition.
The base resin composition may contain an inorganic filler such as silica and aluminum hydroxide; flame retardants such as bromine, phosphorus, and metal hydroxides; and a silane coupling agent; a heat stabilizer; an antistatic agent; an ultraviolet absorber; a pigment; a colorant; lubricants, and the like.
[ printed circuit board ]
The printed wiring board preferably includes the prepreg. The printed wiring board provided with the prepreg has less quality variation, and the yield of the final product is increased. In addition, the printed circuit board provided with the prepreg can also achieve the following effects: since the dielectric properties are excellent and the moisture absorption resistance is excellent, the influence of the use environment, particularly the fluctuation of the dielectric constant in a high humidity environment is small.
Examples
Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples.
[ physical Properties of the glass yarn and glass cloth ]
The physical properties of the glass yarn and the glass cloth, specifically, the thickness of the glass cloth, the average diameter of filaments constituting the glass yarn, the TEX of the glass yarn, the breaking strength (tensile strength) of the glass yarn, and the beating density (weaving density) of the warp and weft were measured in accordance with JIS R3420.
[ twist interval length, twist interval length difference index ]
The number of twists of the 50cm glass yarn was measured using a twist tester (manufactured by TEKNOS corporation), and the length of each 1 interval of the twist was calculated by dividing the 50cm length measured by the number of twists. By this method, the length of each twist at 1 interval is calculated by repeating the measurement at 30 points for each twist number of 50cm, and the length data for each twist at 1 interval is calculated at 30 points. The length data of 1 interval of the twist at 30 points obtained were averaged to determine the twist interval length.
Further, using the average value, the maximum value and the minimum value of the twist interval length data at 30 points obtained, as a ratio of the difference between the maximum value and the minimum value of the twist interval length to the average value of the twist interval length, a twist interval length difference index was obtained by the following expression (1).
Twist interval length difference index = { (maximum value of twist interval length-minimum value of twist interval length)/average value of twist interval length }. Times 100. Cndot. (1)
[ Standard deviation of twist number ]
The number of twists of the 50cm glass yarn was measured using a twist tester (manufactured by TEKNOS Co., ltd.) and converted into the number of twists per 25mm. By this method, the number of twists per 25mm at 30 positions was repeatedly measured, and the standard deviation of the twist number data at 30 positions was obtained.
[ coefficient of elasticity ]
The modulus of elasticity of the glass yarn was measured by a pulse-echo superposition method (pulse-echo-overlap method) using a glass block obtained by melting and cooling the glass yarn as a test piece.
[ number of filaments slipping ]
While the glass yarn was conveyed at a speed of 1 m/min, the projected shape of the glass yarn was observed by a monitor using a size measuring instrument of an LED camera system (manufactured by HIGH ACCURACY CMOS MICROMETER LS-9006 MR/KINYS Co., ltd.) to continuously measure the yarn width. The yarn width of 180m of the glass yarn was measured, and the average value of the yarn width of the glass yarn was calculated from the obtained yarn width data. The yarn width observed at a position 2 times or more the center of the yarn width was counted, and the total of the yarn widths was defined as "the number of filaments slipped", that is, "the number of filaments slipped at 180m to 2 times or more the average value of the yarn width measured".
Here, the yarn width measurement by the LED camera type sizer is performed under the condition that 1934 measurement values can be obtained per 1m, and when an error occurs due to, for example, the focus of the LED being out of focus (value of-9999 is displayed), the measurement values are deleted and the average value of the yarn width and/or the number of slipping filaments are calculated.
The tension applied to the glass yarn during conveyance of the glass yarn was a value measured by a tensiometer (Conrol instruments ETPB-100-C0585 manufactured by SCHMIDT Co.) and was 0.12 to 0.18N.
[ bobbin appearance inspection (fluff inspection) ], manufacturing method thereof, and electronic component
The appearance of the bobbin on which the glass yarn was wound was visually checked, and the number of detected fluffs (number of piles) was counted. This examination was performed 50 times, and the average of the number of piles was calculated.
[ fluff inspection of glass yarn by applying load to glass yarn and evaluating it ]
While the glass yarn was conveyed at a speed of 1 m/min by using a fluff inspection apparatus manufactured by NIHON KAGAKU ENG, the glass yarn was passed through a model reed having a reed interval of 0.35mm, which reciprocated 450 times for 1 min, and after giving a fluff, the number of generation of the fluff per 180m was counted by a sensor. The number of piles generated per 180m was counted by the sensor in the same manner as the model reed with a round trip speed of 100 rounds per minute.
[ evaluation: quality of glass cloth nap ]
The effect of glass yarn quality (e.g., number of filaments slipping off) on the pile quality of the glass cloth was investigated. As a standard condition for glass cloth production, the fiber opening treatment was performed by high-pressure water spraying with a loom rotation speed of 450 rpm. Further, the loom rotation speed (550, 600 rpm) was increased for improving productivity, and the high-pressure water spray intensity was increased for improving characteristics.
The glass cloths obtained in examples, comparative examples and reference examples were evaluated for the pile quality by visual inspection. The quality of the nap of the glass cloth was evaluated visually by using a cloth inspecting machine for glass cloth while conveying the glass cloth at a speed of 10 m/min. In the conventional visual inspection, fuzz and weaving defects were observed in a portion where the glass cloth was irradiated with halogen lamp light in a right angle direction and light was reflected. However, in order to observe broken fuzz of filaments having a length of less than 1mm with good sensitivity, white LED light was irradiated from the end portion side of the glass cloth in a direction parallel to the surface of the glass cloth, and visual inspection was performed. Since the glass cloth on the cloth inspection plate had fluffs scattered over the entire surface, the generation of fluffs observed when the glass cloth was shiny over the entire surface was regarded as a fluffy defect over the entire surface. Fluffing at the whole fluff-generating site was observed by an optical microscope, and as a result, a large amount of fluffing due to filament breakage of about 200 to 1000 μm was generated.
With a measurement length of 500m as an object, when the whole surface of the glass cloth is fluffy within 1m in the longitudinal direction, the number of missing points is counted as 1, and the deduction rate is calculated according to the following formula:
the deduction rate (%) = (total of statistics of defects/500) × 100.
[ evaluation: impregnation Property evaluation of glass cloth
A bisphenol A epoxy resin was dissolved in benzyl alcohol at 23. + -. 2 ℃ to prepare a varnish for evaluation of impregnation property having a viscosity of 230. + -.5 mPas. Next, the glass cloth test piece was immersed in the varnish for evaluation of impregnation property, and the impregnation of the varnish for evaluation of impregnation property into the glass cloth was observed by an optical microscope while irradiating light from the lateral direction. Then, the number of voids (portions not impregnated with the varnish for impregnation evaluation) after 5 minutes from the time when the glass cloth test piece was immersed in the varnish for impregnation evaluation was counted. In this case, the range of the field of view of the glass cloth observed by the optical microscope was: about 6.5mm in the warp direction and about 9mm in the weft direction.
[ examples and comparative examples; glass yarn ]
[ test example 1]
Glass yarns A to N (low dielectric glass yarn, density 2.3 g/cm) in a state of being wound on a bobbin 3 An elastic coefficient of 61 GPa), O to Q (low dielectric glass yarn, density of 2.3 g/cm) 3 56GPa in modulus of elasticity and 2.6g/cm in density of R (E glass yarn) 3 74 GPa) was pulled out, and a portion 5m away from the end in the longitudinal direction was set as a starting point T 0 And measuring the number of slipping filaments.
[ test example 2]
Then, a portion of the glass yarn was further pulled out 500m from the bobbin, that is, a portion separated from the starting point T in the longitudinal direction 0 A part of 500m as a starting point T 500 And measuring the number of slipping filaments.
[ test example 3]
According to the above test examples 1 and 2, the glass yarn was further pulled from the bobbin,
will be spaced from the starting point T in the length direction 0 A site of 1,000m as a starting point T 1,000 ；
Will be spaced from the starting point T in the length direction 0 A site of 2,000m as a starting point T 2,000 ；
Will be spaced from the starting point T in the length direction 0 A site of 5,000m as a starting point T 5,000 ；
Will be spaced from the starting point T in the length direction 0 A site of 7,000m as a starting point T 7,000 ；
Will be spaced from the starting point T in the length direction 0 A site of 9,000m as a starting point T 9,000 ；
Will be spaced from the starting point T in the length direction 0 A site of 10,000m as a starting point T 10,000 ；
Will be spaced from the starting point T in the length direction 0 A site of 20,000m as a starting point T 20,000 ；
Will be spaced from the starting point T in the length direction 0 A site of 30,000m as a starting point T 30,000 ；
Will be spaced from the starting point T in the length direction 0 A site of 40,000m as a starting point T 40,000 ；
Will be spaced from the starting point T in the length direction 0 A site of 50,000m as a starting point T 50,000 ；
Will be spaced from the starting point T in the length direction 0 A site of 60,000m as a starting point T 60,000 ；
Will be spaced from the starting point T in the length direction 0 A site of 70,000m as a starting point T 70,000 ；
Will be spaced from the starting point T in the length direction 0 A site of 80,000m as a starting point T 80,000 ；
Will be spaced from the starting point T in the length direction 0 The site of 100,000m is taken as the starting point T 100,000 ；
Will be spaced from the starting point T in the length direction 0 A portion of 120,000m as a starting point T 120,000 ；
The number of filaments slipping off was determined. The results are shown in Table 1.
[ Table 1-1]
[ tables 1-2]
The number of slip filaments evaluated at the outer layer portion of the bobbin was 3 or less for the glass yarns A to C, G, H, J, K, O and P of examples in which the difference in twist interval length index was small and the glass yarns were twisted uniformly and gently.
And, at the starting point T 0 Starting point T 500 Starting point T 1,000 Starting point T 2,000 Starting point T 5,000 Starting point T 7,000 Starting point T 9,000 When the number of slip filaments is 3 or less in the case of measurement at any starting point in (2). This confirmed that: when a glass yarn having a length of 10,000m or more is used as a target, and measurement ranges of 180m in the longitudinal direction are selected at 5 points different from each other, the number of slip filaments is 3 or less within the measurement ranges at the 5 points.
Even when a glass yarn having a length of 50,000m or more is used, in the same manner as described above, when measuring ranges of 180m in the longitudinal direction are selected at 7 points different from each other, the number of slip filaments is 3 or less in each of the measuring ranges at 7 points.
It can be confirmed that: even when a glass yarn having a length of 100,000m or more is used, in the same manner as described above, when measuring ranges of 180m in the longitudinal direction are selected at 10 points different from each other, the number of slip filaments is 3 or less in each of the 10 measuring ranges.
On the other hand, the number of slip filaments of the glass yarns D to F, I, L to N, Q and R of the comparative examples having a large twist interval length difference index was 4 or more within a predetermined measurement range.
[ example 1]
Low dielectric glass yarns (TEX 4.9, filament number 100, elastic modulus 61GPa, glass composition: siO) 2 Converted into 51.2 mass% of Al 2 O 3 14.3% by mass as converted, 8.1% by mass as converted CaO, 0.3% by mass as converted MgO, and B 2 O 3 Converted into 23.3 mass% of P 2 O 3 Converted to 0.1 mass%) was used for the warp and the weft, and a glass cloth fabric having a warp weaving density of 65 pieces/25 mm and a weft weaving density of 67 pieces/25 mm was obtained under the condition that the loom rotation speed of the air jet loom was 450rpm (the weft weaving speed was 450 pieces/minute).
In tables, e.g. "at start T 0 The item of the measured number of slipping filaments "used in example 1 was the distance T from the starting point 0 And a glass yarn having a number of filaments of 0 which is slipped out of the glass yarn at a length of 180m or more which is 2 times or more the average value of the yarn width.
Then, degumming was carried out by heating the glass cloth with the water pressure adjusted to 5.0. + -. 0.1kg/cm 2 The glass cloth of (2) was subjected to high-pressure water opening and then to surface treatment with a silane coupling agent to prepare a 29 μm thick glass cloth.
[ example 2]
Low dielectric glass yarns (TEX 4.9, filament number 100, modulus of elasticity 61GPa, glass composition: siO) described in the following Table were used 2 Converted into 51.2 mass% of Al 2 O 3 14.3% by mass as converted, 8.1% by mass as converted CaO, 0.3% by mass as converted MgO, and B 2 O 3 Converted into 23.3 mass% of P 2 O 3 In the same manner as in example 1 except that the conversion was 0.1% by mass), a glass cloth having a thickness of 29 μm was produced.
[ example 3]
Low dielectric glass yarns (TEX 4.9, filament number 100, modulus of elasticity 61GPa, glass composition: siO) described in the following Table were used 2 Converted into51.2 mass% of Al 2 O 3 14.3% by mass as converted, 8.1% by mass as converted CaO, 0.3% by mass as converted MgO, and B 2 O 3 Converted into 23.3 mass% of P 2 O 3 In the same manner as in example 1 except that the conversion was 0.1% by mass), a glass cloth having a thickness of 29 μm was produced.
[ example 4]
Low dielectric glass yarns (TEX 4.9, filament number 100, elastic modulus 61GPa, glass composition: siO) described in the following Table were used 2 Converted into 51.2 mass% of Al 2 O 3 14.3% by mass in terms of CaO, 8.1% by mass in terms of CaO, 0.3% by mass in terms of MgO, and B 2 O 3 Converted into 23.3 mass% of P 2 O 3 In the same manner as in example 1 except that the conversion was 0.1% by mass), a glass cloth having a thickness of 29 μm was produced.
[ comparative example 1]
Low dielectric glass yarns (TEX 4.9, filament number 100, elastic modulus 61GPa, glass composition: siO) described in the following Table were used 2 Converted into 51.2 mass% of Al 2 O 3 14.3% by mass in terms of CaO, 8.1% by mass in terms of CaO, 0.3% by mass in terms of MgO, and B 2 O 3 Converted into 23.3 mass% of P 2 O 3 In the same manner as in example 1 except that the conversion was 0.1% by mass), a glass cloth having a thickness of 29 μm was produced.
[ comparative example 2]
Low dielectric glass yarns (TEX 4.9, filament number 100, modulus of elasticity 61GPa, glass composition: siO) described in the following Table were used 2 Converted into 51.2 mass% of Al 2 O 3 14.3% by mass in terms of CaO, 8.1% by mass in terms of CaO, 0.3% by mass in terms of MgO, and B 2 O 3 Converted into 23.3 mass% of P 2 O 3 In the same manner as in example 1 except that the conversion was 0.1% by mass), a glass cloth having a thickness of 29 μm was produced.
[ comparative example 3]
Low dielectric glass yarns (TEX 4.9, V) described in the following Table were used the number of the filaments is 100,The elastic coefficient is 61GPa, and the glass composition is as follows: siO 2 2 Converted into 51.2 mass% of Al 2 O 3 14.3% by mass as converted, 8.1% by mass as converted CaO, 0.3% by mass as converted MgO, and B 2 O 3 Converted into 23.3 mass% of P 2 O 3 In the same manner as in example 1 except that the conversion was 0.1% by mass), a glass cloth having a thickness of 29 μm was produced.
[ example 5]
A glass cloth having a thickness of 29 μm was produced in the same manner as in example 1, except that the rotational speed of the air jet loom was set to 550 rpm.
[ example 6]
A glass cloth having a thickness of 29 μm was produced in the same manner as in example 3, except that the rotational speed of the air jet loom was set to 550 rpm.
[ comparative example 4]
Glass cloth having a thickness of 29 μm was produced in the same manner as in comparative example 1, except that the rotational speed of the air jet loom was set to 550 rpm.
[ example 7]
A glass cloth having a thickness of 29 μm was produced in the same manner as in example 1, except that the rotational speed of the air jet loom was set to 600 rpm.
[ example 8]
A glass cloth having a thickness of 29 μm was produced in the same manner as in example 3, except that the rotational speed of the air jet loom was set to 600 rpm.
[ comparative example 5]
Glass cloth having a thickness of 29 μm was produced in the same manner as in comparative example 1, except that the rotational speed of the air jet loom was set to 600 rpm.
[ example 9]
By increasing the water pressure of the high-pressure water spray in the fiber opening treatment to 12.0 + -0.1 kg/cm 2 Glass cloth having a thickness of 29 μm was produced in the same manner as in example 1, except that the opening strength was increased.
[ example 10]
By using high-pressure water in the fiber opening treatmentThe water pressure of the spray is increased to 12.0 +/-0.1 kg/cm 2 Glass cloth having a thickness of 29 μm was produced in the same manner as in example 3, except that the opening strength was increased.
[ comparative example 6]
By increasing the water pressure of the high-pressure water spray in the fiber opening treatment to 12.0 + -0.1 kg/cm 2 Glass cloth having a thickness of 29 μm was produced in the same manner as in comparative example 1, except that the splitting strength was improved.
[ comparative example 7]
By increasing the water pressure of the high-pressure water spray in the fiber opening treatment to 12.0 + -0.1 kg/cm 2 Glass cloth having a thickness of 29 μm was produced in the same manner as in comparative example 2, except that the opening strength was increased.
[ comparative example 8]
By increasing the water pressure of the high-pressure water spray in the fiber opening treatment to 12.0 + -0.1 kg/cm 2 Glass cloth having a thickness of 29 μm was produced in the same manner as in comparative example 3, except that the opening strength was increased.
[ example 11]
Low dielectric glass yarns (TEX 2.9, number of filaments 100, elastic modulus 61GPa, glass composition: siO) 2 Converted into 51.2 mass% of Al 2 O 3 14.3% by mass in terms of CaO, 8.1% by mass in terms of CaO, 0.3% by mass in terms of MgO, and B 2 O 3 Converted into 23.3 mass% of P 2 O 3 Converted to 0.1 mass%) was used for the warp and the weft, and a glass cloth having a warp weaving density of 74 pieces/25 mm and a weft weaving density of 74 pieces/25 mm was obtained under the condition that the loom rotation speed of the air jet loom was 450rpm (the weft weaving speed was 450 pieces/minute).
Then, degumming was carried out by heating the glass cloth fabric, and adjusting the water pressure to 4.0. + -. 0.1kg/cm 2 The glass cloth was prepared to have a thickness of 21 μm by performing high-pressure water opening by spraying and then performing surface treatment using a silane coupling agent.
[ example 12]
Low dielectric glass yarn (TEX 2.9, length) described in the following Table was usedThe number of the filaments is 100, the elastic coefficient is 61GPa, and the glass composition is as follows: siO 2 2 Converted into 51.2 mass% of Al 2 O 3 14.3% by mass in terms of CaO, 8.1% by mass in terms of CaO, 0.3% by mass in terms of MgO, and B 2 O 3 Converted into 23.3 mass% of P 2 O 3 In the same manner as in example 11 except that the conversion was changed to 0.1% by mass), a glass cloth having a thickness of 21 μm was produced.
[ comparative example 9]
Low dielectric glass yarns (TEX 2.9, filament number 100, modulus of elasticity 61GPa, glass composition: siO) described in the following Table were used 2 Converted into 51.2 mass% of Al 2 O 3 14.3% by mass as converted, 8.1% by mass as converted CaO, 0.3% by mass as converted MgO, and B 2 O 3 Converted into 23.3 mass% of P 2 O 3 In the same manner as in example 11 except that the conversion was changed to 0.1% by mass), a glass cloth having a thickness of 21 μm was produced.
[ example 13]
By increasing the water pressure of the high-pressure water spray in the fiber opening treatment to 10.0 + -0.1 kg/cm 2 A glass cloth having a thickness of 21 μm was produced in the same manner as in example 11, except that the opening strength was increased.
[ comparative example 10]
By increasing the water pressure of the high-pressure water spray in the fiber opening treatment to 10.0 + -0.1 kg/cm 2 A glass cloth having a thickness of 21 μm was produced in the same manner as in comparative example 9, except that the splitting strength was improved.
[ example 14]
The low dielectric glass yarn (TEX 9.8, filament number 200, elastic coefficient 61GPa, glass composition: siO) described in the following table 2 Converted into 51.2 mass% of Al 2 O 3 14.3% by mass in terms of CaO, 8.1% by mass in terms of CaO, 0.3% by mass in terms of MgO, and B 2 O 3 Converted into 23.3 mass% of P 2 O 3 Converted to 0.1 mass%) was used for the warp and weft yarns, and the warp yarn weaving density was obtained under the condition that the loom rotation speed of the air jet loom was 450rpm (the weft yarn weaving speed was 450 pieces/minute)The degree is 52.5 strips/25 mm, and the weft weaving density is 52.5 strips/25 mm.
Then, degumming was carried out by heating the glass cloth fabric with adjusting the water pressure to 6.0. + -. 0.1kg/cm 2 The glass cloth was prepared to have a thickness of 46 μm by performing high-pressure water opening and then performing surface treatment using a silane coupling agent.
[ example 15 ]
Low dielectric glass yarns (TEX 9.8, filament number 200, modulus of elasticity 61GPa, glass composition: siO) described in the following Table were used 2 Converted into 51.2 mass% of Al 2 O 3 14.3% by mass in terms of CaO, 8.1% by mass in terms of CaO, 0.3% by mass in terms of MgO, and B 2 O 3 Converted into 23.3 mass% of P 2 O 3 In the same manner as in example 14 except that the conversion was changed to 0.1% by mass), a glass cloth having a thickness of 46 μm was produced.
[ comparative example 11]
Low dielectric glass yarns (TEX 9.8, number of filaments 200, elastic modulus 61GPa, glass composition: siO) described in the following Table were used 2 Converted into 51.2 mass% of Al 2 O 3 14.3% by mass as converted, 8.1% by mass as converted CaO, 0.3% by mass as converted MgO, and B 2 O 3 Converted into 23.3 mass% of P 2 O 3 In the same manner as in example 14 except that the conversion was changed to 0.1% by mass), a glass cloth having a thickness of 46 μm was produced.
[ example 16]
By increasing the water pressure of the high-pressure water spray in the fiber opening treatment to 12.0 + -0.1 kg/cm 2 Glass cloth having a thickness of 46 μm was produced in the same manner as in example 14, except that the opening strength was increased.
[ comparative example 12]
By increasing the water pressure of the high-pressure water spray in the fiber opening treatment to 12.0 + -0.1 kg/cm 2 Glass cloth having a thickness of 46 μm was produced in the same manner as in comparative example 11, except that the opening strength was increased.
[ example 17]
Low dielectric glass yarns (TEX 4.8, filament number 100, elastic modulus 56GPa, glass composition: siO) 2 Converted into 49.8 mass% of Al 2 O 3 Calculated as 16.8 mass%, caO calculated as 3.1 mass%, mgO calculated as 0.1 mass%, B 2 O 3 Converted into 23.9 mass% of P 2 O 3 Converted to 4.0 mass%) was used for the warp and the weft, and a glass cloth fabric having a warp weaving density of 65/25mm and a weft weaving density of 67 pieces/25 mm was obtained under the condition that the loom rotation speed of the air jet loom was 450rpm (the weft weaving speed was 450 pieces/minute).
Then, degumming was carried out by heating the glass cloth fabric with adjusting the water pressure to 5.0. + -. 0.1kg/cm 2 The glass cloth was prepared to have a thickness of 31 μm by performing high-pressure water opening by spraying and then performing surface treatment using a silane coupling agent.
[ example 18]
Low dielectric glass yarn (TEX 4.8, filament number 100, elastic modulus 56GPa, glass composition: siO) described in the following Table was used 2 Converted into 49.8 mass% of Al 2 O 3 Calculated as 16.8 mass%, caO calculated as 3.1 mass%, mgO calculated as 0.1 mass%, B 2 O 3 Converted into 23.9 mass% of P 2 O 3 In the same manner as in example 17 except that the conversion was changed to 4.0 mass%), a glass cloth having a thickness of 31 μm was produced.
[ comparative example 13]
Low dielectric glass yarn (TEX 4.8, filament number 100, elastic modulus 56GPa, glass composition: siO) described in the following Table was used 2 Converted into 49.8 mass% of Al 2 O 3 Calculated as 16.8 mass%, caO calculated as 3.1 mass%, mgO calculated as 0.1 mass%, B 2 O 3 Converted into 23.9 mass% of P 2 O 3 In the same manner as in example 15 except for converting the thickness to 4.0 mass%), a glass cloth having a thickness of 31 μm was produced.
[ example 19]
By increasing the water pressure of the high-pressure water spray in the fiber opening treatment to 12.0±0.1kg/cm 2 Glass cloth having a thickness of 31 μm was produced in the same manner as in example 17, except that the opening strength was increased.
[ comparative example 14]
By increasing the water pressure of the high-pressure water spray in the fiber opening treatment to 12.0 + -0.1 kg/cm 2 Glass cloth having a thickness of 31 μm was produced in the same manner as in comparative example 13, except that the opening strength was increased.
[ reference example 1a ]
Low dielectric glass yarn (TEX 14.6, filament number 200, elastic coefficient 61GPa, glass composition: siO 5-10 filaments) 2 Converted into 51.2 mass% of Al 2 O 3 14.3% by mass in terms of CaO, 8.1% by mass in terms of CaO, 0.3% by mass in terms of MgO, and B 2 O 3 Converted into 23.3 mass% of P 2 O 3 Converted to 0.1 mass%) was used for the warp and the weft, and a glass cloth having a warp weaving density of 59 pieces/25 mm and a weft weaving density of 61 pieces/25 mm was obtained under the condition that the loom rotation speed of the air jet loom was 450rpm (the weft weaving speed was 450 pieces/minute).
Then, degumming was carried out by heating the glass cloth fabric with the water pressure adjusted to 7.0. + -. 0.1kg/cm 2 The glass cloth was prepared to have a thickness of 73 μm by performing high-pressure water opening by spraying and then performing surface treatment using a silane coupling agent.
[ reference example 1b ]
By increasing the water pressure of the high-pressure water spray in the fiber opening treatment to 12.0 + -0.1 kg/cm 2 Glass cloth having a thickness of 73 μm was produced in the same manner as in reference example 1a, except that the opening strength was increased.
[ reference example 2a ]
Low dielectric glass yarn (TEX 19.4, filament number 200, elastic coefficient 61GPa, glass composition: siO 5-10 filaments 2 Converted into 51.2 mass% of Al 2 O 3 14.3% by mass as converted, 8.1% by mass as converted CaO, 0.3% by mass as converted MgO, and B 2 O 3 Converted into 23.3 mass% of P 2 O 3 Converted to 0.1 mass%) was used for the warp and the weft, and a glass cloth having a warp weaving density of 60 pieces/25 mm and a weft weaving density of 57 pieces/25 mm was obtained under the condition that the loom rotation speed of the air jet loom was 450rpm (the weft weaving speed was 450 pieces/minute).
Then, degumming was carried out by heating the glass cloth fabric with the water pressure adjusted to 7.0. + -. 0.1kg/cm 2 The glass cloth was prepared to have a thickness of 89 μm by performing high-pressure water opening and then performing surface treatment using a silane coupling agent.
[ reference example 2b ]
By increasing the water pressure of the high-pressure water spray in the fiber opening treatment to 12.0 + -0.1 kg/cm 2 A glass cloth having a thickness of 89 μm was produced in the same manner as in reference example 2a, except that the splitting strength was improved.
[ reference example 3a ]
E glass yarn (TEX is 5.5, filament number is 100, elastic coefficient is 74GPa, and glass composition is SiO 2 Converted into 53.1 mass% of Al 2 O 3 15.3% by mass as converted, 21.0% by mass as converted CaO, 1.9% by mass as converted MgO, and B 2 O 3 Converted into 8.0 mass% of P 2 O 3 Converted into<0.1 mass%) was used for the warp and the weft, and a glass cloth having a warp weaving density of 65 pieces/25 mm and a weft weaving density of 67 pieces/25 mm was obtained under the condition that the loom rotation speed of the air jet loom was 450rpm (the weft weaving speed was 450 pieces/minute).
Then, degumming was carried out by heating the glass cloth fabric with adjusting the water pressure to 5.0. + -. 0.1kg/cm 2 The glass cloth was prepared to have a thickness of 29 μm by performing high-pressure water opening and then performing surface treatment using a silane coupling agent.
[ reference example 3b ]
By increasing the water pressure of the high-pressure water spray in the fiber opening treatment to 12.0 + -0.1 kg/cm 2 A glass cloth having a thickness of 89 μm was produced in the same manner as in reference example 3a, except that the opening strength was increased.
The evaluation results of the glass yarn and the glass cloth in the above examples, comparative examples and reference examples are shown in the following table. In the table, "water pressure (kg/cm) at the time of high-pressure water opening 2 ) In the item of "+ -. 0.1 (kg/cm)" is omitted 2 ) "is used herein.
[ Table 2-1]
TABLE 2-1
[ tables 2-2]
Tables 2 to 2
[ tables 2 to 3]
Tables 2 to 3
[ tables 2 to 4]
Tables 2 to 4
[ tables 2 to 5]
Tables 2 to 5
[ tables 2 to 6]
Tables 2 to 6
[ tables 2 to 7]
Tables 2 to 7
[ tables 2 to 8]
Tables 2 to 8
[ tables 2 to 9]
Tables 2 to 9
In examples 1 to 4, 11 to 12, 14 to 15, and 17 to 18, glass cloths having excellent pile quality were obtained. The glass yarns used in these examples are drawn from the starting point T 0 The number of slip filaments measured was 3 or less, so it can be presumed: the number of slip filaments of the entire glass yarn wound around the bobbin is small. It can be confirmed that: by using such glass yarn, glass cloth having excellent pile quality can be obtained.
In examples 5 to 8, even when the loom rotation speed was increased from 450rpm to 550rpm or 600rpm in order to improve productivity in the weaving step, the quality of the pile was not significantly deteriorated, and glass cloth having relatively good pile quality was obtained.
Examples 9, 10, 13, 16, and 19 obtained low dielectric glass cloths having improved impregnation properties while maintaining relatively good fluff quality by increasing the water pressure of the high-pressure water spray.
On the other hand, the glass cloths obtained in comparative examples 1 to 3, 9, 11 and 13 had poor pile quality.
Further, in comparative examples 4 to 8, 10, 12, and 14, when the rotational speed of the loom was increased from 450rpm to 550rpm or 600rpm in the weaving step or the water pressure of the high-pressure water spray was increased in the opening step, glass cloths with significantly deteriorated pile quality were obtained.
In reference examples 1 (a, b) and 2 (a, b), the thicknesses were 73 μm and 89 μm, respectively, and the glass cloths of examples 1 to 16 were not thin.
In reference examples 3 (a, b) using the E glass yarn, glass cloth having relatively good pile quality was obtained. In the low dielectric glass yarn having the same TEX, if the number of slip filaments is large, the fluff quality tends to be deteriorated due to the increase of the spray pressure of the high-pressure water spray (comparative examples 1 to 3 and 6 to 8), whereas in the result of reference example 3, the E glass yarn does not have such a tendency.
The following results were obtained in examples 1 to 4 and comparative examples 1 to 3: the "number of slip filaments" more reflects the pile quality of the glass cloth than "bobbin appearance inspection" and "number of piles generated by applying a load to the glass yarn".
Claims (31)
1. A glass cloth obtained by weaving warp yarns and weft yarns with glass yarns comprising a plurality of glass filaments,
when 500m in the length direction of the glass cloth is used as an object, white LED light is irradiated along the cloth surface, every 1m in the length direction is observed, the deduction rate represented by the following formula is 0-3.5% when the number of missing points is 1 when the whole surface of the cloth surface has fluff,
the deduction rate (%) = (total of statistics of defects/500) × 100.
2. The glass cloth according to claim 1, wherein the whole-face pile comprises 200 to 1000 μm of fuzz caused by breakage of the filaments observed on the cloth face with an optical microscope.
3. The glass cloth according to claim 1, wherein the thickness of the glass cloth is 10 to 50 μm.
4. Glass cloth according to claim 1, comprising the glass yarns satisfying the following conditions:
(i) TEX is 1-13;
(ii) The breaking strength is 0.50-0.80N/tex; and is
(iii) The number of filaments slipping off at 180m to 2 times or more of the average value of the yarn width was 3 or less.
5. The glass cloth according to claim 1, comprising the glass yarn having a twist interval length of 1.8 to 10.0cm.
6. The glass cloth according to claim 1, comprising the glass yarn having a twist interval length difference index of 0.7 or less, which is a value obtained by dividing a difference between a maximum value of twist interval lengths and a minimum value of twist interval lengths of the glass yarn by an average value of twist interval lengths.
7. Glass cloth according to any of claims 1 to 6, wherein the glass yarn having a length of 10,000m or more is targeted,
when the measuring ranges of 180m in the length direction are selected at 5 points different from each other, the number of filaments slipping to 2 times or more the average value of the yarn width is 3 or less in the measuring ranges of the 5 points, respectively.
8. Glass cloth according to any of claims 1 to 6, wherein the glass yarn having a length of 50,000m or more is targeted,
when the measuring ranges of 180m in the length direction are selected at 7 points different from each other, the number of filaments slipping to 2 times or more the average value of the yarn width is 3 or less in the measuring ranges at the 7 points, respectively.
9. Glass cloth according to any of claims 1 to 6, wherein the glass yarn having a length of 100,000m or more is targeted,
when the measuring ranges of 180m in the longitudinal direction are selected at 10 points different from each other, the number of filaments slipping off to 2 times or more the average value of the yarn width is 3 or less in the measuring ranges at 10 points, respectively.
10. A method for manufacturing glass cloth, comprising a step of using glass yarn comprising a plurality of glass filaments as warp and weft and weaving the glass yarn,
(i) The TEX of the glass yarn is 1-13;
(ii) The breaking strength of the glass yarn is 0.50-0.80N/tex; and is provided with
(iii) The number of filaments slipping out at 180m to 2 times or more the average value of the yarn width was 3 or less.
11. The method for producing glass cloth according to claim 10, wherein the TEX of the glass yarn is 1 to 7.
12. The method for manufacturing glass cloth according to claim 10, wherein the number of glass filaments constituting the glass yarn is 30 to 120.
13. The method for manufacturing glass cloth according to claim 10, wherein the glass yarn has a twist interval length of 1.8 to 10.0cm.
14. The method for producing glass cloth according to claim 10, wherein a twist interval length difference index of the glass yarn is 0.7 or less, and the twist interval length difference index is a value obtained by dividing a difference between a maximum value of the twist interval length and a minimum value of the twist interval length by an average value of the twist interval lengths.
15. The method for manufacturing glass cloth according to claim 10, wherein the density of the glass yarn is 2.2g/cm 3 More than and less than 2.5g/cm 3 。
16. The method for producing glass cloth according to claim 10, wherein the glass yarn has an elastic modulus of 50 to 70GPa.
17. The method for producing glass cloth according to claim 10, wherein the glass yarn has an elastic modulus of 50 to 63GPa.
18. The method for producing glass cloth according to any one of claims 10 to 17, wherein the glass yarn having a length of 10,000m or more is used as the target,
when the measurement ranges of 180m in the longitudinal direction are selected at 5 points different from each other, the number of filaments slipping off to 2 times or more the average value of the yarn width is 3 or less in each of the measurement ranges at 5 points.
19. The method for manufacturing glass cloth according to any of claims 10 to 17, wherein the glass yarn having a length of 50,000m or more is used as an object,
when the measuring ranges of 180m in the length direction are selected at 7 points different from each other, the number of filaments slipping to 2 times or more the average value of the yarn width is 3 or less in the measuring ranges at the 7 points, respectively.
20. The method for manufacturing glass cloth according to any of claims 10 to 17, wherein the glass yarn having a length of 100,000m or more is used as an object,
when the measuring ranges of 180m in the length direction are selected at 10 points different from each other, the number of filaments slipping to 2 times or more the average value of the yarn width is 3 or less in the measuring ranges at 10 points, respectively.
21. A glass yarn, wherein,
(i) TEX is 1-13;
(ii) The breaking strength is 0.50-0.80N/tex; and is
(iii) The number of filaments slipping off at 180m to 2 times or more of the average value of the yarn width was 3 or less.
22. The glass yarn of claim 21, wherein said TEX is 1 to 7.
23. The glass yarn as claimed in claim 21, wherein the number of glass filaments constituting the glass yarn is 30 to 120.
24. The glass yarn of claim 21, wherein the twist interval length is from 1.8 to 10.0cm.
25. The glass yarn according to claim 21, wherein the twist interval length difference index is 0.7 or less, which is a value obtained by dividing the difference between the maximum value of the twist interval length and the minimum value of the twist interval length by the average value of the twist interval lengths.
26. The glass yarn as claimed in claim 21 having a density of 2.2g/cm 3 More than and less than 2.5g/cm 3 。
27. The glass yarn as claimed in claim 21, having a coefficient of elasticity of 50-70 GPa.
28. The glass yarn as claimed in claim 21, having a modulus of elasticity of 50-63 GPa.
29. The glass yarn as claimed in any one of claims 21 to 28, wherein said glass yarn having a length of 10,000m or more is targeted,
when the measuring ranges of 180m in the length direction are selected at 5 points different from each other, the number of filaments slipping to 2 times or more the average value of the yarn width is 3 or less in the measuring ranges of the 5 points, respectively.
30. The glass yarn according to any one of claims 21 to 28, wherein said glass yarn having a length of 50,000m or more is targeted,
when the measuring ranges of 180m in the longitudinal direction are selected at 7 points different from each other, the number of filaments slipping off to 2 times or more the average value of the yarn width is 3 or less in the measuring ranges at the 7 points, respectively.
31. The glass yarn according to any one of claims 21 to 28, wherein said glass yarn having a length of 100,000m or more is targeted,
when the measuring ranges of 180m in the longitudinal direction are selected at 10 points different from each other, the number of filaments slipping off to 2 times or more the average value of the yarn width is 3 or less in the measuring ranges at 10 points, respectively.
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| JP2021089446 | 2021-05-27 | ||
| JP2021-089446 | 2021-05-27 |
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Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001048596A (en) * | 1999-08-05 | 2001-02-20 | Nippon Electric Glass Co Ltd | Sizing agent and glass fiber coated with the agent |
| US6322888B1 (en) * | 1997-05-14 | 2001-11-27 | Vetrotex France | Method for producing sized glass fibers and resulting products |
| CN1449983A (en) * | 2002-04-05 | 2003-10-22 | 日本电气硝子株式会社 | Organdy, organdy package, and organdy relaxation method |
| CN102249556A (en) * | 2011-04-25 | 2011-11-23 | 重庆国际复合材料有限公司 | Glass fiber spun yarn impregnation agent and preparation method thereof |
| CN102249555A (en) * | 2011-04-25 | 2011-11-23 | 重庆国际复合材料有限公司 | Electronic yarn sizing agent and preparation method thereof |
| CN103880300A (en) * | 2014-01-29 | 2014-06-25 | 巨石集团有限公司 | Impregnating compound for alkali-free glass fiber direct roving for thermoplastic glass fiber reinforced pipeline |
| CN105254189A (en) * | 2015-10-30 | 2016-01-20 | 陕西华特新材料股份有限公司 | Waterborne epoxy resin emulsion for glass fibers and preparation method of waterborne epoxy resin emulsion |
| CN107709642A (en) * | 2015-08-28 | 2018-02-16 | 尤尼吉可株式会社 | Glass cloth |
| CN107896498A (en) * | 2016-08-03 | 2018-04-10 | 日东纺绩株式会社 | Glass cloth |
| CN108411446A (en) * | 2017-02-10 | 2018-08-17 | 旭化成株式会社 | Glass cloth, prepreg and printed circuit board |
| JP2018197411A (en) * | 2017-05-24 | 2018-12-13 | 信越石英株式会社 | Glass yarn, glass cloth, prepreg and printed wiring board |
| CN210604438U (en) * | 2019-07-12 | 2020-05-22 | 建滔（连州）玻璃纤维有限公司 | Electronic cloth appearance inspection device |
| CN111379063A (en) * | 2018-12-25 | 2020-07-07 | 旭化成株式会社 | Method for producing glass cloth and glass yarn |
| CN111535029A (en) * | 2020-04-17 | 2020-08-14 | 安徽工程大学 | Sizing glass filament yarn and sizing method thereof |
| CN111684117A (en) * | 2018-11-22 | 2020-09-18 | 信越石英株式会社 | Quartz glass yarn and quartz glass cloth |
-
2022
- 2022-04-26 JP JP2022072715A patent/JP2022183025A/en active Pending
- 2022-05-26 CN CN202210589113.4A patent/CN115404584A/en active Pending
- 2022-05-27 TW TW111119807A patent/TW202300742A/en unknown
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6322888B1 (en) * | 1997-05-14 | 2001-11-27 | Vetrotex France | Method for producing sized glass fibers and resulting products |
| JP2001048596A (en) * | 1999-08-05 | 2001-02-20 | Nippon Electric Glass Co Ltd | Sizing agent and glass fiber coated with the agent |
| CN1449983A (en) * | 2002-04-05 | 2003-10-22 | 日本电气硝子株式会社 | Organdy, organdy package, and organdy relaxation method |
| CN102249556A (en) * | 2011-04-25 | 2011-11-23 | 重庆国际复合材料有限公司 | Glass fiber spun yarn impregnation agent and preparation method thereof |
| CN102249555A (en) * | 2011-04-25 | 2011-11-23 | 重庆国际复合材料有限公司 | Electronic yarn sizing agent and preparation method thereof |
| CN103880300A (en) * | 2014-01-29 | 2014-06-25 | 巨石集团有限公司 | Impregnating compound for alkali-free glass fiber direct roving for thermoplastic glass fiber reinforced pipeline |
| CN107709642A (en) * | 2015-08-28 | 2018-02-16 | 尤尼吉可株式会社 | Glass cloth |
| CN105254189A (en) * | 2015-10-30 | 2016-01-20 | 陕西华特新材料股份有限公司 | Waterborne epoxy resin emulsion for glass fibers and preparation method of waterborne epoxy resin emulsion |
| CN107896498A (en) * | 2016-08-03 | 2018-04-10 | 日东纺绩株式会社 | Glass cloth |
| CN108411446A (en) * | 2017-02-10 | 2018-08-17 | 旭化成株式会社 | Glass cloth, prepreg and printed circuit board |
| JP2018197411A (en) * | 2017-05-24 | 2018-12-13 | 信越石英株式会社 | Glass yarn, glass cloth, prepreg and printed wiring board |
| CN111684117A (en) * | 2018-11-22 | 2020-09-18 | 信越石英株式会社 | Quartz glass yarn and quartz glass cloth |
| CN111379063A (en) * | 2018-12-25 | 2020-07-07 | 旭化成株式会社 | Method for producing glass cloth and glass yarn |
| CN210604438U (en) * | 2019-07-12 | 2020-05-22 | 建滔（连州）玻璃纤维有限公司 | Electronic cloth appearance inspection device |
| CN111535029A (en) * | 2020-04-17 | 2020-08-14 | 安徽工程大学 | Sizing glass filament yarn and sizing method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 宗亚宁、张海霞主编: "《纺织材料学（3版）》", 东华大学出版社, pages: 253 - 254 * |
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| TW202300742A (en) | 2023-01-01 |
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