CN110551382A - Modified polymer, prepreg and preparation method and application thereof - Google Patents
Modified polymer, prepreg and preparation method and application thereof Download PDFInfo
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- CN110551382A CN110551382A CN201910581878.1A CN201910581878A CN110551382A CN 110551382 A CN110551382 A CN 110551382A CN 201910581878 A CN201910581878 A CN 201910581878A CN 110551382 A CN110551382 A CN 110551382A
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- modified polymer
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- resin
- mass fraction
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- 229920000642 polymer Polymers 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 22
- 239000011256 inorganic filler Substances 0.000 claims abstract description 19
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 19
- 239000000945 filler Substances 0.000 claims abstract description 13
- 239000013032 Hydrocarbon resin Substances 0.000 claims description 12
- 229920006270 hydrocarbon resin Polymers 0.000 claims description 12
- 238000004891 communication Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims description 8
- 239000004815 dispersion polymer Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical group C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 2
- 238000012545 processing Methods 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 229920001955 polyphenylene ether Polymers 0.000 description 4
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention provides a modified polymer, which comprises resin, a curing agent and a filler, wherein the filler comprises an inorganic filler, and is characterized in that: the filler further comprises a cage silsesquioxane; the mass fraction of the resin is 30-70% based on 100% of the mass of the modified polymer; the mass fraction of the curing agent is 2-20%; the mass fraction of the inorganic filler is 25-55%; the weight percentage of the cage-like silsesquioxane is 2-20%. Compared with the prior art, the modified polymer has the advantages of good heat resistance and low dielectric loss, and also has good flexibility and mechanical strength. The prepreg provided by the invention is prepared by simply processing the modified polymer, so that the prepreg has good heat resistance, lower dielectric loss performance, good flexibility and mechanical strength, and lower thermal expansion coefficient.
Description
[ technical field ] A method for producing a semiconductor device
the invention relates to the field of communication materials, in particular to a modified polymer, a prepreg, and preparation methods and applications thereof.
[ background of the invention ]
the 5G communication is to replace 4G to become the latest communication standard, and has superior performance in various aspects compared with 4G and 5G communication, but the development of corollary equipment cannot be separated to realize the performance. The material properties of various parts in the 5G communication equipment also need to be further developed correspondingly to meet new requirements. The basis of the 5G technology is a high-frequency low-loss circuit board, which needs a low-loss dielectric material at high frequency (more than 1GHz), namely a copper-clad plate and a prepreg bonded with the copper-clad plate. The requirements of various communication devices are higher and higher along with the development, and the performance of the prepreg serving as a basic element needs to be improved along with the development, so that the prepreg is suitable for the requirements.
The existing modified polymer material and the prepreg prepared by the existing modified polymer material have large dielectric loss and cannot meet the requirement.
therefore, there is a need for a low dielectric loss prepreg and a method for preparing the same; in order to prepare the low dielectric loss prepreg, it is necessary to provide a low dielectric loss modified polymer as a raw material for preparing the low dielectric loss prepreg.
[ summary of the invention ]
The invention aims to provide a modified polymer, a prepreg and a preparation method thereof, and aims to solve the technical problem that the dielectric loss of the conventional modified polymer and prepreg is too large.
in order to solve the technical problems, the invention provides a modified polymer, which comprises a resin, a curing agent and a filler, wherein the filler comprises an inorganic filler, and the filler also comprises cage-shaped silsesquioxane;
The mass fraction of the resin is 30-70% based on 100% of the mass fraction of the modified polymer;
The mass fraction of the curing agent is 2-20%;
the mass fraction of the inorganic filler is 25-55%;
The weight percentage of the cage-like silsesquioxane is 2-20%.
preferably, the chemical formula of the cage-like silsesquioxane is (SiO 1.5) 8 Ph 8.
Further preferably, the hydrocarbon resin is SBS;
Further preferably, the mass fraction of the polyphenylene ether is 20-40%, and the mass fraction of the hydrocarbon resin is 10-30%.
Preferably, the curing agent is triallyl isocyanurate;
preferably, the inorganic filler is silica.
the invention also provides a prepreg prepared from the modified polymer.
preferably, the thickness of the prepreg is 50 μm.
In another aspect, the present invention provides a method for preparing a prepreg, including the steps of:
Dispersing resin, a curing agent, an inorganic filler and cage-shaped silsesquioxane in an organic solvent to form a modified polymer dispersion liquid, wherein the mass ratio of the resin to the curing agent to the inorganic filler to the cage-shaped silsesquioxane is 3: 0.2: 2.5: 0.2 to 7: 2: 5.5: 2;
And coating and drying the modified polymer dispersion liquid to obtain the prepreg.
the invention also provides an application of the prepreg in the composition of the circuit board in the 5G communication equipment. .
Compared with the prior art, the modified polymer has the advantages of good heat resistance and low dielectric loss, and also has good flexibility and mechanical strength. Firstly, the resin polyphenyl ether with better heat resistance is selected to ensure that the basic heat resistance of the modified polymer is better, and then the heat resistance of the modified polymer is improved by adopting a curing agent, an inorganic filler and polyhedral silsesquioxane; meanwhile, the dielectric loss of the selected polyphenyl ether is low, and the cage-shaped silsesquioxane with zero dielectric loss is doped to further reduce the dielectric loss, so that the dielectric loss of the modified polymer is lower than that of the existing modified polymer; finally, the combination of the polyphenyl ether and the hydrocarbon resin is adopted, and the good mechanical property of the polyphenyl ether and the good flexibility of the hydrocarbon resin are considered.
the prepreg provided by the invention is prepared by simply processing the modified polymer, so that the prepreg has good heat resistance, lower dielectric loss performance, good flexibility and mechanical strength, and lower thermal expansion coefficient.
The preparation method of the prepreg only needs to disperse the components in the solvent, and then the components are coated and dried, the process steps and the operation are very simple, and the preparation method only designs a chemical process of curing and crosslinking, and the rest is physical fusion, so that the yield is very high, and the preparation method is suitable for large-scale production and popularization.
[ detailed description ] embodiments
The present invention will be further described with reference to the following embodiments.
The embodiment of the invention provides a modified polymer, which comprises resin, a curing agent and a filler, wherein the filler comprises an inorganic filler, and the filler also comprises cage-shaped silsesquioxane;
The mass fraction of the resin is 30-70% based on 100% of the mass fraction of the modified polymer;
The mass fraction of the curing agent is 2-20%;
The mass fraction of the inorganic filler is 25-55%;
The weight percentage of the cage-like silsesquioxane is 2-20%.
Specifically, the resin is a matrix component of the modified polymer, and can be crosslinked with other components such as a curing agent or an R substituent of the cage-like silsesquioxane, so that the heat resistance of the modified polymer is improved.
In a preferred embodiment, the resin comprises polyphenylene ether and hydrocarbon resins. Firstly, the polyphenyl ether has good heat resistance and low dielectric loss. The polyphenyl ether has benzene rings, so that the formed modified polymer has a rigid structure and high mechanical strength, but has the defect of poor flexibility, and therefore, hydrocarbon resin is added to improve the flexibility, so that the modified polymer has high mechanical strength and flexibility. In a further preferred embodiment, the hydrocarbon resin is SBS (styrene-butadiene-styrene block copolymer); in a further preferred embodiment, the mass fraction of the polyphenylene ether is 20-40%, and the mass fraction of the hydrocarbon resin is 10-30%. The proportion can be reasonably adjusted to adapt to different application scenes.
The curing agent is used for crosslinking the components of the modified polymer, so that the aim of curing is fulfilled, and the heat resistance and the mechanical strength of the modified polymer are enhanced. Preferably, the curing agent is triallyl isocyanurate; the triallyl isocyanurate can also improve the corrosion resistance and the flame retardant property.
the purpose of adding fillers, which are usually finely ground powders to dope, can significantly alter the properties of the modified polymer. The embodiment of the invention adopts inorganic filler and organic filler. In a preferred embodiment, the inorganic filler is silica. On the one hand, cost can be saved, and on the other hand, the thermal expansion performance can be improved, so that the modified polymer is not easy to deform thermally.
in order to further reduce dielectric loss and improve heat resistance, the polyhedral oligomeric silsesquioxane is further added, and the polyhedral oligomeric silsesquioxane is a highly symmetrical cage-shaped structure, and has a hollow structure and zero vacuum dielectric loss, so that the polyhedral oligomeric silsesquioxane can play a role in reducing the dielectric loss and also can play a role in improving the heat resistance; the chemical formula of the cage-shaped silsesquioxane is as follows:
In a preferred embodiment, the chemical formula of the cage-shaped silsesquioxane is (SiO 1.5) 8 Ph 8. the benzene ring structure of the cage-shaped silsesquioxane is well compatible with the polyphenylene oxide serving as the matrix component, and the uniformity and the mechanical property of the whole modified polymer can be improved after doping.
As described above, the modified polymer provided by the embodiment of the invention adopts polyphenyl ether with good heat resistance and low dielectric loss as a base material, adds the hydrocarbon resin to improve the flexibility of the modified polymer and also serves as a supplementary base material, and adds the curing agent to enable the resin to be crosslinked into a net, so that the mechanical property and the heat resistance of the modified polymer are greatly improved. The added inorganic curing agent mainly plays a role in reducing the thermal expansion coefficient, and simultaneously can save the cost. Compared with the existing modified resin, the modified resin has the advantages that the cage-like silsesquioxane is added, the dielectric loss of the material is zero, the material has good heat resistance, and the overall dielectric loss can be obviously reduced after doping. The components can be controlled by proportion, and the optimization of the types can generate more interaction and technical effects, such as changing the glass transition temperature, the wear resistance, the corrosion resistance and the like, so that the application is wider.
the embodiment of the invention also provides a prepreg prepared from the modified polymer. Therefore, the composite material has good heat resistance, lower dielectric loss performance, good flexibility and mechanical strength, and lower thermal expansion coefficient. In a preferred embodiment, the thickness of the prepreg is 50 μm. The dielectric loss of the overall prepreg is small when the thickness is thin, but the thickness is selected in consideration of the limitation of process conditions and the manufacturing cost.
The prepreg has the advantages of good heat resistance, low dielectric loss, good flexibility and mechanical property and low thermal expansion coefficient, so that the prepreg is suitable for being used as a component of a circuit board in 5G communication equipment.
In another aspect of the embodiments of the present invention, a method for preparing a prepreg includes the following steps:
S01: dispersing resin, a curing agent, an inorganic filler and cage-shaped silsesquioxane in an organic solvent to form a dispersion of a modified polymer, wherein the mass ratio of the resin to the curing agent to the inorganic filler to the cage-shaped silsesquioxane is 3: 0.2: 2.5: 0.2 to 7: 2: 5.5: 2;
s02: and coating and drying the modified polymer dispersion liquid to obtain the prepreg.
Specifically, in step S01, the raw materials are processed, such as crushed, added to an organic solvent for dispersion, and cured and crosslinked by the curing agent to form a modified polymer dispersion. The organic solvent may preferably be toluene, and these resins and cage-type silsesquioxane have a rigid structure such as a benzene ring and a cage structure and therefore have a good solubility in toluene, so that the dispersion system is more uniform.
In step S02, the dispersion is slurried, recoated and dried, if necessary, by concentration before being coated. In order to accelerate the progress, a drying mode can be adopted. And finally obtaining the prepreg.
The present invention will now be described in further detail by taking the modified polymer, the prepreg and the method for preparing the same as examples.
Examples 1 to 5
Examples 1-5 provide a modified polymer, a prepreg, and methods of making the same, respectively. The formulations of the modified polymers provided in the examples are shown in table 1 below.
the prepregs provided in examples 1 to 5 of this embodiment are all prepared by using the above formulation, and the specific preparation method is as follows:
1) Dispersing polyphenylene ether, SBS, TAIC, curing agent, SiO 2 and (SiO 1.5) 8 Ph 8 in toluene at the ratios of, for example, above to form a dispersion of modified polymer;
2) And reasonably concentrating the modified polymer dispersion liquid until slurry is coated and drying to obtain the prepreg.
Prepreg correlation Performance test
The dielectric constant Dk and dielectric loss Df of the prepregs provided in examples 1-5 were measured, and the dielectric constant Dk and dielectric loss Df data of the prepregs of each example are shown in table 1 below.
TABLE 1
It can be seen from the table that the dielectric loss value of the modified polymer gradually decreases as the content of the cage-type silsesquioxane increases.
while the foregoing is directed to embodiments of the present invention, it will be understood by those skilled in the art that various changes may be made without departing from the spirit and scope of the invention.
Claims (10)
1. A modified polymer comprising a resin, a curing agent, a filler, the filler comprising an inorganic filler, wherein: the filler further comprises a cage silsesquioxane;
the mass fraction of the resin is 30-70% based on 100% of the mass fraction of the modified polymer;
the mass fraction of the curing agent is 2-20%;
The mass fraction of the inorganic filler is 25-55%;
The weight percentage of the cage-like silsesquioxane is 2-20%.
2. The modified polymer according to claim 1, wherein the polyhedral oligomeric silsesquioxane has a chemical formula of (SiO 1.5) 8 Ph 8.
3. The modified polymer of claim 1, wherein: the resin comprises polyphenylene oxide and hydrocarbon resin.
4. The modified polymer of claim 3, wherein: the hydrocarbon resin is SBS.
5. the modified polymer of claim 3, wherein: the mass fraction of the polyphenyl ether is 20-40%, and the mass fraction of the hydrocarbon resin is 10-30%.
6. The modified polymer of claim 1, wherein: the curing agent is triallyl isocyanurate; and/or
the inorganic filler is silica.
7. Prepreg, characterized in that it is produced from the modified polymer according to any one of claims 1 to 6.
8. Prepreg according to claim 7, characterized in that: the thickness of the prepreg was 50 μm.
9. The process for the preparation of prepregs according to any of claims 7 to 8, comprising the following steps:
Dispersing resin, a curing agent, an inorganic filler and cage-shaped silsesquioxane in an organic solvent to form a modified polymer dispersion liquid, wherein the mass ratio of the resin to the curing agent to the inorganic filler to the cage-shaped silsesquioxane is 3: 0.2: 2.5: 0.2 to 7: 2: 5.5: 2;
And coating and drying the modified polymer dispersion liquid to obtain the prepreg.
10. use of a prepreg according to any one of claims 7 to 8 for circuit board assembly in a 5G communication device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910581878.1A CN110551382A (en) | 2019-06-30 | 2019-06-30 | Modified polymer, prepreg and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910581878.1A CN110551382A (en) | 2019-06-30 | 2019-06-30 | Modified polymer, prepreg and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
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| CN110551382A true CN110551382A (en) | 2019-12-10 |
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Family Applications (1)
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| CN201910581878.1A Pending CN110551382A (en) | 2019-06-30 | 2019-06-30 | Modified polymer, prepreg and preparation method and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113307541A (en) * | 2021-06-03 | 2021-08-27 | 中国振华集团云科电子有限公司 | Hydrocarbon resin ceramic bonding sheet and batch production process thereof |
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| CN109735088A (en) * | 2019-01-08 | 2019-05-10 | 苏州生益科技有限公司 | A kind of high frequency resin composition and prepreg, laminate and interlayer dielectric using its preparation |
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2019
- 2019-06-30 CN CN201910581878.1A patent/CN110551382A/en active Pending
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| US20050093158A1 (en) * | 2003-10-30 | 2005-05-05 | Chartered Semiconductor Manufacturing Ltd. | Self-patterning of photo-active dielectric materials for interconnect isolation |
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| CN109504062A (en) * | 2018-11-22 | 2019-03-22 | 南亚塑胶工业股份有限公司 | A kind of compositions of thermosetting resin |
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| CN113307541A (en) * | 2021-06-03 | 2021-08-27 | 中国振华集团云科电子有限公司 | Hydrocarbon resin ceramic bonding sheet and batch production process thereof |
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Application publication date: 20191210 |
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