CN116732678A - glass cloth - Google Patents
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- Publication number
- CN116732678A CN116732678A CN202310214200.6A CN202310214200A CN116732678A CN 116732678 A CN116732678 A CN 116732678A CN 202310214200 A CN202310214200 A CN 202310214200A CN 116732678 A CN116732678 A CN 116732678A
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- China
- Prior art keywords
- glass
- glass cloth
- mass
- less
- loss tangent
- Prior art date
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- 239000011521 glass Substances 0.000 title claims abstract description 99
- 239000004744 fabric Substances 0.000 title claims abstract description 82
- 239000003365 glass fiber Substances 0.000 claims abstract description 36
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 30
- 229910008051 Si-OH Inorganic materials 0.000 claims abstract description 15
- 229910006358 Si—OH Inorganic materials 0.000 claims abstract description 15
- 230000005540 biological transmission Effects 0.000 abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 31
- 238000000034 method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 11
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 238000004891 communication Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229910000077 silane Inorganic materials 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- -1 alkyl silicate Chemical compound 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000001308 synthesis method Methods 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000004071 soot Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 238000009941 weaving Methods 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 239000011043 treated quartz Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
- BZCWFJMZVXHYQA-UHFFFAOYSA-N 3-dimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[SiH](OC)CCCOC(=O)C(C)=C BZCWFJMZVXHYQA-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GLTDLAUASUFHNK-UHFFFAOYSA-N n-silylaniline Chemical compound [SiH3]NC1=CC=CC=C1 GLTDLAUASUFHNK-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000001028 reflection method Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 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
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
-
- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D13/00—Woven fabrics characterised by the special disposition of the warp or weft threads, e.g. with curved weft threads, with discontinuous warp threads, with diagonal warp or weft
- D03D13/008—Woven fabrics characterised by the special disposition of the warp or weft threads, e.g. with curved weft threads, with discontinuous warp threads, with diagonal warp or weft characterised by weave density or surface weight
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
- D06M13/5135—Unsaturated compounds containing silicon atoms
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
- Glass Compositions (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Woven Fabrics (AREA)
Abstract
Provided is a glass cloth which has a low dielectric loss tangent at 10-40 GHz, a low transmission loss, and easy workability. A glass cloth which is formed by adhering a silane coupling agent in an amount of 0.001 mass% or more and less than 1.0 mass% relative to the glass cloth, the silane coupling agent being formed by glass fibers having a softening point of 1000-1600 ℃ and an Si-OH group content of less than 1000 ppm.
Description
Technical Field
The present application relates to a glass cloth having excellent dielectric characteristics and workability.
Background
With the recent increase in performance and high-speed communication of information terminals such as smart phones, printed wiring boards used have been remarkably developed in terms of low dielectric constant, particularly low dielectric loss tangent, along with high densification and extremely thin printed wiring boards.
As an insulating material of the printed wiring board, widely used are: a laminated board obtained by laminating prepregs obtained by impregnating glass cloth with a thermosetting resin such as an epoxy resin (hereinafter referred to as "matrix resin") and curing the laminated board under heat and pressure. The dielectric constant of the matrix resin used for the high-speed communication substrate is about 3, whereas the dielectric constant of a general E-glass cloth is about 6.7, which is a problem of high dielectric constant when laminated boards are more remarkable.
The transmission loss of the signal is as described in Edward a.wolff formula: the material having a small dielectric constant (epsilon) and dielectric loss tangent (tan delta) is known to be improved as shown by the transmission loss ≡epsilon×tan delta, and in particular, it is known from the above formula that the contribution of dielectric loss tangent (tan delta) to the transmission loss is large.
Accordingly, glass cloths having improved dielectric characteristics such as D glass, NE glass, and L glass, which have glass compositions different from E glass, have been proposed (patent documents 1 to 3).
However, in future 5G communication applications and the like, there is a need for improvement in low dielectric glass cloths having excellent low dielectric constants and low dielectric loss tangents from the viewpoint of achieving sufficient transmission speed performance. Therefore, by making SiO in the glass composition 2 The amount of SiO was made to be approximately 100% by mass, and further reduction of dielectric constant and low dielectric loss tangent was achieved 2 Development of glass cloth with a blending amount of approximately 100 mass% (patent document 4). However, patent document 4 discloses a low dielectric constant, but does not disclose a dielectric loss tangent which contributes more to transmission loss, and the low dielectric loss tangent is an problematic problem.
Regarding transmission loss, it is known that if si—oh groups are present, absorption of harmonics of vibration of si—oh is located at 1.4 μm, and thus transmission efficiency is significantly reduced, and reduction of si—oh groups is a technique effective for reduction of transmission loss.
As a method for reducing the dielectric loss tangent, a method using synthetic quartz glass has been developed (patent document 5). However, patent document 5 describes up to 10GHz, but does not describe dielectric loss tangent in the millimeter wave region of 30GHz to 300GHz, which has been recently demanded. In addition, the cost of synthetic quartz glass is high, and this causes a problem of cost when the synthetic quartz glass is used for 5G communication applications expected to be widespread in the future.
Further, patent document 5 describes, as an advantage of using synthetic quartz glass, easiness of workability in the case of producing a multilayer substrate, and a disadvantage of poor workability is pointed out for a natural quartz glass material.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 5-170483
Patent document 2: japanese patent laid-open No. 2009-263569
Patent document 3: japanese patent laid-open No. 2009-19150
Patent document 4: japanese patent laid-open publication No. 2018-197411
Patent document 5: japanese patent No. 4336086
Disclosure of Invention
Problems to be solved by the application
The present application has been made in view of the above-described problems, and an object of the present application is to provide a glass cloth having a low dielectric loss tangent at 10 to 40GHz, a low transmission loss, and easy processing.
Means for solving the problems
The present inventors have intensively studied to achieve the above object, and as a result, have found that: the present application has been accomplished by solving the above problems by attaching a glass cloth having a specific amount of a silane coupling agent to a glass cloth using glass fibers having a softening point of 1000 to 1600 ℃ and an Si-OH group content of less than 1000 ppm. More specifically, it is used for suppressing high-speed communication such as 5G and the like which are increasing in the future
Further improvement of dielectric loss tangent characteristics of glass cloths used for substrates is demanded, and for example, a significant effect is obtained in that the dielectric loss tangent of 10GHz to 40GHz can be set to 0.002 or less and the ratio of 40GHz to 10GHz can be set to 2.0 or less, and transmission loss due to dielectric loss tangent characteristics can be suppressed.
Accordingly, the present application provides a glass cloth.
1. A glass cloth which is obtained by adhering a silane coupling agent to a glass cloth (or a glass cloth comprising the glass cloth) comprising glass fibers having a softening point of 1000-1600 ℃ and an amount of Si-OH groups of less than 1000ppm, wherein the silane coupling agent is 0.001 mass% or more and less than 1.0 mass% relative to the glass cloth.
2. The glass cloth according to claim 1, wherein a dielectric loss tangent of 10GHz to 40GHz is 0.002 or less, and a dielectric loss tangent ratio of 40GHz/10GHz is 2.0 or less.
3. The glass cloth according to 1 or 2, wherein SiO in the glass fiber 2 The amount is 99.9 mass% or more.
4. The glass cloth according to any one of 1 to 3, wherein the thickness is 200 μm or less.
5. The glass cloth according to any one of 1 to 4, wherein the mass per unit area is 4 to 300g/m 2 。
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present application, a glass cloth excellent in dielectric loss tangent characteristics and workability can be obtained.
Detailed Description
The present application will be described in detail below, with the exception of these embodiments, but of course, various modifications can be made without departing from the technical spirit of the present application. The glass cloth of the present application is a glass cloth comprising glass fibers having a softening point of 1000 to 1600 ℃ and an amount of si—oh groups of less than 1000ppm, and a silane coupling agent is attached at an attachment rate of 0.001 mass% or more and less than 1.0 mass% (hereinafter, may be referred to as an attached glass cloth of the present application).
[ glass fiber ]
The glass fiber of the application has a softening point of 1000-1600 ℃ and an Si-OH group content of less than 1000 ppm.
Even if the glass has the same composition, the structure and physical properties are different due to the heat treatment and the cooling rate during the treatment. Which is affected by the process of cooling the glass from a completely molten state, the fictive temperature differs if the cooling rate differs. If the cooling rate is low, the cooling rate has a sufficient time for the structure to be relaxed, and the virtual temperature is lowered following the actual temperature. On the other hand, when the cooling rate is high, the virtual temperature increases as the actual temperature of the glass is kept away. In addition, as a change caused by the increase of the virtual temperature, the softening point is lowered. The glass fibers of the present application have a softening point of 1000 to 1600 ℃, preferably 1000 to 1400 ℃, more preferably 1050 to 1200 ℃. The softening point is a value obtained by stretching glass fibers in the radial direction (diameter direction) using a thermo-mechanical analysis device (TMA) and measuring the softening point.
The glass fiber of the present application has a Si-OH group content of less than 1000ppm by mass. The method for measuring the content of Si-OH groups was the method described in the examples. Regarding the correlation between the viscosity (pa·s) of glass and the OH amount, it is known that the viscosity decreases as the OH content increases. The softening point is also lowered by the decrease in viscosity, and the OH content can increase the heat-treated elongation in oxyhydrogen flame, but if it is excessively increased, there is a problem that the dielectric loss tangent is deteriorated. The softening point and the amount of Si-OH groups can be adjusted by the method for producing glass fibers.
SiO of glass fiber 2 The content is preferably 99.9 mass% or more, and may be 100 mass%. Examples of the method for producing a raw material ingot of quartz glass include an electric melting method, a flame melting method, a direct synthesis method, a plasma synthesis method, a soot method, a sol-gel method, and the like, which use quartz as a raw material, and a direct synthesis method, a plasma synthesis method, a soot method, and a sol-gel method, which use alkyl silicate as a raw material, which use quartz as a raw material, so long as SiO 2 The blending amount is 99.9 mass%, and is not limited to these production methods. In particular, the electric melting method using crystal as a raw material, the plasma synthesis method using silicon tetraoxide as a raw material, and the soot method are preferable because silanol groups (si—oh) are not easily contained as impurities.
The fiber diameter phi of the glass fiber is preferably 3 to 10. Mu.m, more preferably 3.5 to 10. Mu.m. The dielectric loss tangent of the glass fiber from 10GHz to 40GHz is preferably 0.002 or less, more preferably 0.0015 or less. In addition, it is required that the variation of dielectric loss tangent is small, and the ratio of 40GHz/10GHz is preferably 2.0 or less.
In order to achieve both the processability and the dielectric loss tangent, the glass material is drawn at a speed of 300m/min or more, more preferably 400m/min or more by a factor of 10 or more, more preferably 20 or more, than the target fiber diameter, whereby a glass fiber having a low dielectric loss tangent and easy processability can be obtained.
Glass as a substitute for being stretchedPreparation of glass materials, e.g. as 200.+ -.100. Mu.m, siO 2 A method for producing a quartz glass strand having a content of 99.0 mass% or more, which comprises electric melting. Specifically, glass having a diameter of 50 to 200mm is melted at 1700 to 2300℃and the resultant filaments are wound, whereby glass filaments having a diameter of 200.+ -.100 μm can be obtained. If the melting temperature is less than 1700 ℃, the quartz glass may not be melted, and if it exceeds 2300 ℃, the viscosity may be excessively lowered, and stable stretching may not be performed.
The glass fiber is coated to obtain the strength required for winding because the strength is very weak. The coating agent is preferably a UV-curable resin having an acrylate functional group excellent in curability, and the coating thickness is preferably 5 μm or more. If the thickness is less than 5. Mu.m, the coating thickness may be insufficient, and the reinforcing effect may not be obtained.
In order to improve productivity, it is preferable to perform cooling between melting and coating of the quartz glass. The cooling is water-cooled, air-cooled, or the like, and both are effective. The softening point can be reduced even in this step by heating the quartz glass having a diameter of 50 to 200mm to 1700 to 2300℃and cooling the quartz glass.
[ glass fiber bundles ]
The glass fibers are bundled to obtain a glass fiber bundle. For example, the filament bundle can be obtained by melting 20 to 400 quartz glass fibers by using a mixed flame of oxygen and hydrogen. In the production of glass strands, a bundling agent is used to bundle the glass strands. The composition using starch as a main material is used as a binder, and a softener and a lubricant may be blended to impart functionality.
Glass yarn
The glass yarn can be obtained by twisting the glass yarn bundles. The frequency of twisting is preferably 0.1 to 5.0 times per 25mm, more preferably 0.1 to 4.0 times.
[ glass cloth (before attachment) ]
The glass yarn is woven to obtain glass cloth. The weave and the fabric density of the glass cloth are not particularly limited, and examples of the weave include plain weave, satin weave, basket weave, and twill weave. The fabric density may be, for example, 10 to 150 pieces/25 mm.
The thickness of the glass cloth is preferably 200 μm or less, more preferably 180 μm or less. The mass per unit area of the glass cloth is preferably 4 to 300g/m 2 More preferably 10 to 200g/m 2 。
The weaving method of the glass cloth is not particularly limited, and examples thereof include an air jet loom, a water jet loom, a rapier loom, a shuttle loom, and the like.
In weaving the glass cloth, a paste can be used for the purpose of stability of weaving and suppression of fuzzing. The paste preferably contains 1 or more selected from polyvinyl alcohol, polyethylene oxide, starch, polyester, polyamide, and the like. The glass cloth can be subjected to fiber opening treatment according to the requirement.
As the glass cloth, for example, a glass cloth made of SiO 2 99.9 mass% or more of filament-made silica glass cloth (1078: IPC-4412B appindix I), and the like.
[ glass cloth (after attachment) ]
The attached glass cloth of the present application is a glass cloth having a silane coupling agent attached thereto at an attachment ratio of 0.001 mass% or more and less than 1.0 mass%, and can be obtained by surface-treating the glass strands, glass yarns, and glass cloth with the silane coupling agent.
In the attached glass cloth of the present application, in order to exhibit the impregnability of the resin and the adhesion of the interface between the resin and the glass cloth, the attached glass cloth is treated with a silane compound and a silane coupling agent (treating agent). The silane coupling agent may be selected according to the glass cloth used, and can be used singly or in combination of 2 or more. As the silane coupling agent, for example, a silane coupling agent having a functional group such as a vinyl group, a styryl group, a methacryloyl group, an acryl group, or the like is preferable. Specific examples of the silane coupling agent include γ -methacryloxypropyl dimethoxy silane, γ -methacryloxypropyl trimethoxy silane, γ -methacryloxypropyl triethoxy silane, vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tris (β -methoxyethoxy) silane, and p-styryl trimethoxy silane. The conventionally used silane coupling agents for epoxy resins include epoxy silane coupling agents and cationic silane coupling agents. In addition, a phenylaminosilane treatment agent excellent in solder heat resistance, moisture absorption resistance, copper-attached heat resistance, and insulation reliability can also be used. Among them, the unsaturated group-containing functional group having a stable surface and having a functional group capable of chemically bonding to the organic resin is preferably treated, and for example, vinyl-based, (meth) acrylic-based, and styrene-based silane coupling agents are preferable. As the silane coupling agent, for example, a silane coupling agent having a methacryloyl group (manufactured by Xinyue chemical Co., ltd.: KBM-503: methacryloxypropyl trimethoxysilane) or the like can be used.
The silane coupling treatment method is not particularly limited as long as the silane coupling agent is brought into contact with the glass cloth to give a specific adhesion amount, and the temperature and the like are not particularly limited. The amount of the treating agent to be adhered is 0.001 mass% or more and less than 1.0 mass% (adhering rate) to the glass cloth, preferably 0.01 mass% or more and 0.3 mass% or less. If the amount of the adhesive agent is 1.0 mass% or more, it becomes a cause of deterioration of the dielectric loss tangent, and if it is less than 0.001 mass%, wettability with the resin is deteriorated.
The dielectric loss tangent of the glass cloth of the present application at 10 to 40GHz is preferably 0.002 or less, more preferably 0.0015 or less. In addition, the variation of the dielectric loss tangent is required to be small, and the ratio of 40GHz/10GHz is preferably 2.0 or less, more preferably 1.6 or less. In particular, glass cloth for substrates used for high-speed communications such as 5G is required to have a low dielectric loss tangent.
The mass per unit area of the glass cloth of the present application is preferably 4 to 300g/m 2 More preferably 4 to 260g/m 2 。
The glass cloth for adhesion of the present application can be suitably used as a prepreg for a printed board and a printed wiring board for which low dielectric loss tangent is required, and is particularly suitable as a multilayer printed board for high frequency of 10GHz or more.
Examples
The present application will be specifically described below by way of examples and comparative examples, but the present application is not limited to the following examples.
The dielectric loss tangent, silanol (Si-OH) content, adhesion amount of the silane coupling agent, softening point and processability were measured in the following manner.
[ measurement of dielectric loss tangent ]
The dielectric constant was measured using SPDR (Spl i t pos t dielectric resonators) dielectric resonator frequencies of 10GHz and 40 GHz.
The dielectric tangents of examples and comparative examples represent the dielectric tangents of the glass cloths attached.
[ measurement of silanol (Si-OH) content ]
The silanol content of the glass fiber and glass cloth is measured and calculated by the following method.
For infrared absorption spectra of glass fiber and glass cloth, 3680cm due to silanol was measured by using a Fourier transform infrared spectrometer (IRAfforesity-1S) and a diffuse reflection measuring device (DRS-8000A) and a diffuse reflection method -1 Transmittance T of the nearby peak. Based on the obtained transmittance value, absorbance A was obtained by applying the Lambert-Beer law shown below.
Absorbance a= -Log10T (t=3680 cm -1 Transmittance in the vicinity of
Next, from the absorbance obtained by the above formula, the molar concentration C (mol/L) of silanol was obtained by the following formula.
C＝A/εL
Epsilon: molar absorptivity (molar absorptivity of silanol epsilon=77.5 dm) 3 /mol·cm)
C: molar concentration (mol/L)
L: thickness of sample (light path length)
From the absorbance A obtained, the molar concentration C was determined using the above formula.
Using the molar concentration C obtained, the silanol content (ppm) in the glass fiber was determined using the following formula.
Silanol content (ppm) = { (c×m (Si-OH))/(d×1000) } ×106 specific gravity d=2.2 g/cm of glass fiber 3
Molecular weight of silanol M (Si-OH) =45 g/mol
[ measurement of adhesion Rate of silane coupling agent ]
The glass cloth was heated and attached using an electric furnace at 625℃for 4 hours, and the mass change before and after heating was measured. The adhesion rate (mass%) was calculated based on the following formula.
Attachment ratio (mass%) = (mass of attached glass cloth before heating-mass of attached glass cloth after heating)/mass of attached glass cloth before heating×100
[ determination of softening Point ]
The glass fiber was drawn in the radial direction using a thermo-mechanical analysis apparatus (TMA), and the softening point was measured.
[ evaluation of processability ]
A prepreg was prepared by impregnating an adhesive glass cloth with an epoxy resin, and wettability (unevenness) and drill life were evaluated.
There was no problem in wettability (unevenness) and the drill life was 100 times or more: o (circle)
There are problems in wettability (non-uniformity) or bit life less than 100 times: x-shaped glass tube
Examples 1 to 3
For SiO shown in Table 1 2 A silica glass strand composed of 200 silica glass filaments having a diameter of 5.0 μm was prepared by applying a sizing agent to silica glass fibers having a softening point and stretching them at a high temperature. Next, 0.4 times of twisting per 25mm was applied to the obtained silica glass strand to prepare a silica glass yarn.
The obtained quartz glass yarn was set in an air jet loom, and a plain-woven quartz glass cloth having a warp density of 54 yarns/25 mm and a weft density of 54 yarns/25 mm was woven. Then, the bundling agent was removed by heat washing, and then a silane coupling agent (KBM-503: methacryloxypropyl trimethoxysilane) was used so that the amount of the bundling agent attached became 0.1 mass%And (5) processing. The thickness of the treated quartz glass cloth was 45. Mu.m, and the cloth mass was 42.5g/m 2 . The evaluation results are shown in the following table.
Example 4
A glass cloth was prepared in the same manner as in example 1, and treated with a silane coupling agent (KBM-503) so as to give an adhesion amount of 0.2% by mass, to give a treated silica glass cloth.
Example 5
A glass cloth was prepared in the same manner as in example 1, and treated with a silane coupling agent (KBM-503) so as to give an adhesion amount of 0.05% by mass, to give a treated silica glass cloth.
Comparative example 1
Except that a softening point of 800 ℃ and SiO 2 A glass cloth was prepared in the same manner as in example 1 except that the E glass fiber was contained in an amount of 53% by mass, and the glass cloth was treated with a silane coupling agent (KBM-503) so as to give an adhesion amount of 0.1% by mass, to obtain a treated quartz glass cloth.
Comparative example 2
In addition to using SiO 2 A glass cloth was produced in the same manner as in example 1 except that a silica glass fiber having a content of 99.9 mass% and an Si-OH content of more than 1000ppm was treated with a silane coupling agent (KBM-503) so as to give an adhesion amount of 0.1 mass%, to obtain a treated silica glass cloth.
Comparative example 3
In addition to using SiO 2 A glass cloth was produced in the same manner as in example 1 except that a silica glass fiber having a content of 99.9 mass% and an Si-OH content of less than 1000ppm was treated with a silane coupling agent (KBM-503) so as to give an adhesion amount of 1.0 mass%, to obtain a treated silica glass cloth.
Comparative example 4
The same SiO as in example 1 was used 2 Quartz glass having a content of 99.9 mass% and an Si-OH content of less than 1000ppm was used to prepare glass cloth (untreated with a silane coupling agent).
[ Table 1]
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| SiO 2 Amount (mass%) | 99.9 | 99.9 | 99.9 | 99.9 | 99.9 |
| Silanol amount (ppm) | Less than 1000 | Less than 1000 | Less than 1000 | Less than 1000 | Less than 1000 |
| Adhesion amount of silane treatment agent (%) | 0.1 | 0.1 | 0.1 | 0.2 | 0.05 |
| Softening point (. Degree. C.) | 1200 | 1050 | 1125 | 1200 | 1200 |
| Workability and workability of the product | ○ | ○ | ○ | ○ | ○ |
| Dielectric tangent (10 GHz) | 0.0007 | 0.0010 | 0.0009 | 0.0010 | 0.0008 |
| Dielectric tangent (40 GHz) | 0.001 | 0.0014 | 0.0013 | 0.0014 | 0.0011 |
| Dielectric loss tangent ratio (40 GHz/10 GHz) | 1.4 | 1.4 | 1.4 | 1.4 | 1.4 |
[ Table 2]
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| SiO 2 Amount (mass%) | 53 | 99.9 | 99.9 | 99.9 |
| Silanol amount (ppm) | - | Greater than 1000 | Less than 1000 | Less than 1000 |
| Adhesion amount of silane treatment agent (%) | 0.1 | 0.1 | 1.0 | 0 |
| Softening point (. Degree. C.) | 800 | 990 | 1200 | 1200 |
| Workability and workability of the product | ○ | ○ | ○ | × |
| Dielectric tangent (10 GHz) | 0.0050 | 0.0014 | 0.0015 | 0.0007 |
| Dielectric tangent (40 GHz) | 0.0083 | 0.0022 | 0.0022 | 0.0010 |
| Dielectric loss tangent ratio (40 GHz/10 GHz) | 1.7 | 1.6 | 1.5 | 1.4 |
As shown in examples 1 to 5, the glass cloth of the present application composed of glass fibers has a dielectric loss tangent of less than 0.002 at 10GHz to 40GHz and a ratio of 40GHz to 10GHz of less than 2.0.
As shown in comparative example 1, when glass fibers having a softening point of 800℃are used, the dielectric loss tangent of 10GHz to 40GHz is larger than 0.002.
As shown in comparative example 2, when glass fibers having a softening point of 990℃and a silanol amount of more than 1000ppm were used, the dielectric loss tangent at 10GHz was less than 0.002, but the dielectric loss tangent at 40GHz was more than 0.002.
As shown in comparative example 3, when glass fibers having a softening point of 1200℃and a silanol amount of less than 1000ppm were used and the silane treating agent was adhered in an amount of 1.0 mass%, the dielectric loss tangent at 10GHz was less than 0.002, but the dielectric loss tangent at 40GHz was greater than 0.002.
As shown in comparative example 4, when glass fibers having a softening point of 1200℃and a silanol amount of less than 1000ppm were used, the adhesion amount of the silane treatment agent was 0%, and the processability was poor.
Claims (5)
1. A glass cloth comprising glass fibers having a softening point of 1000-1600 ℃ and an Si-OH group content of less than 1000ppm, and a silane coupling agent having a mass% of 0.001-1.0% relative to the glass cloth.
2. The glass cloth according to claim 1, wherein a dielectric loss tangent of 10GHz to 40GHz is 0.002 or less, and a dielectric loss tangent ratio of 40GHz/10GHz is 2.0 or less.
3. The glass cloth according to claim 1 or 2, wherein the SiO in the glass fibers 2 The amount is 99.9 mass% or more.
4. The glass cloth according to claim 1 or 2, wherein the thickness is 200 μm or less.
5. The glass cloth according to claim 1 or 2, wherein the mass per unit area is 4 to 300g/m 2 。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022035820A JP2023131220A (en) | 2022-03-09 | 2022-03-09 | Glass cloth |
| JP2022-035820 | 2022-03-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116732678A true CN116732678A (en) | 2023-09-12 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310214200.6A Pending CN116732678A (en) | 2022-03-09 | 2023-03-08 | glass cloth |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2023131220A (en) |
| KR (1) | KR20230132699A (en) |
| CN (1) | CN116732678A (en) |
| TW (1) | TW202344730A (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05170483A (en) | 1991-12-25 | 1993-07-09 | Asahi Glass Co Ltd | Glass fiber for fiber reinforced plastics and fiber reinforced plastic product |
| JP2009019150A (en) | 2007-07-13 | 2009-01-29 | Panasonic Corp | Heat transfer prepreg and method for producing the same and heat transfer printed circuit board using the same |
| JP4613977B2 (en) | 2008-04-28 | 2011-01-19 | 日立化成工業株式会社 | Prepreg including thin-layer quartz glass cloth and wiring board using the same |
| JP6837385B2 (en) | 2017-05-24 | 2021-03-03 | 信越石英株式会社 | Glass yarn, glass cloth, prepreg and printed wiring board |
-
2022
- 2022-03-09 JP JP2022035820A patent/JP2023131220A/en active Pending
-
2023
- 2023-02-16 TW TW112105555A patent/TW202344730A/en unknown
- 2023-02-28 KR KR1020230026775A patent/KR20230132699A/en unknown
- 2023-03-08 CN CN202310214200.6A patent/CN116732678A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JP2023131220A (en) | 2023-09-22 |
| TW202344730A (en) | 2023-11-16 |
| KR20230132699A (en) | 2023-09-18 |
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