CN101327673B - Metal composite board for injection moulding - Google Patents
Metal composite board for injection moulding Download PDFInfo
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- CN101327673B CN101327673B CN200710123446A CN200710123446A CN101327673B CN 101327673 B CN101327673 B CN 101327673B CN 200710123446 A CN200710123446 A CN 200710123446A CN 200710123446 A CN200710123446 A CN 200710123446A CN 101327673 B CN101327673 B CN 101327673B
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Abstract
The invention provides a metal composite plate used for injection which comprises a metal substrate, and a first resin layer and a second resin layer which are successively adhered on at least one surface of the metal substrate. The first resin layer is made of non-crystallizing polyester. The second resin layer comprises polyester and polycarbonate. With the metal composite plate for injection provided by the invention adopted, the resin of the metal composite plate and the injection is provided with good adhesion. At the same time, the metal composite plate is provided with good processing adhesion between the resin layer and the metal substrate and good impact resistance.
Description
Technical field
The present invention relates to a kind of composite metal plate that is used for injection moulding.
Background technology
Usually, resin is injected into the surface of metal base, both can have obtained the intensity of metal, can obtain good resistance to impact and insulating properties again, thereby the use amount that can also reduce metal simultaneously reduces the cost of materials used, and the weight of the product that alleviates.
When especially this composite being used for electronic product shell, resin is injected into the inboard of metal pre-punching shell molds, thereby can obtains the high-quality shell of metal-like.But the resin of common required injection moulding and the tack of metal base are bad, often directly injection moulding.
CN1033255A discloses a kind of metallic plate and production method thereof of lamination; The metallic plate of this lamination is the bonding laminated metal sheet of polymer film on each main surface at it; Polymer film is adhered on the metallic plate through the while lamination methods; Each the main lip-deep polymer film that is adhered to metallic plate is a kind of compound polyester film (A); It comprises an internal layer (A1) and a skin (A2), and internal layer (A1) is higher than 150 ℃ but be lower than 250 ℃ the linear polyester that is essentially noncrystalline shape for softening temperature is lower than 200 ℃ of fusing points, and outer (A2) is higher than the linear polyester of two orientations of 250 ℃ for fusing point.Wherein, the polyester of internal layer (A1) is the copolymer of ethylene glycol terephthalate and isophthalic acid glycol ester, or the copolymer of being made up of terephthalic acid (TPA) and two kinds of alcohol (being generally ethylene glycol and cyclohexane-dimethanol); Outer (A2) is the PETG of two orientations.
In the metallic plate of the disclosed lamination of above-mentioned patent application, the tack of polymer film and metallic plate is fine.But if with resin, when for example polycarbonate resin was injected on the metallic plate of this lamination, though better than the tack that directly resin is injected on the metallic plate, tack was still relatively poor.
Summary of the invention
The objective of the invention is to overcome the relatively poor defective of metallic plate tack of the resin and the lamination of injection moulding in the above-mentioned prior art, provide a kind of and resin tack injection moulding to be used for the composite metal plate of injection moulding preferably.
The invention provides a kind of composite metal plate that is used for injection moulding; This composite metal plate comprises metal base and successively attached to said metal base at least one lip-deep first resin bed and second resin bed; Said first resin bed is a non-crystalline polyester; Wherein, said second resin bed contains polyester and Merlon.
The composite metal plate that is used for injection moulding provided by the present invention; Can make the resin tack of this composite metal plate and injection moulding fine; The resin bed of this composite metal plate and the processing tack between the metal base are fine simultaneously, and the resistance to impact of this composite metal plate is also fine.
The specific embodiment
The composite metal plate that is used for injection moulding provided by the invention comprises; Metal base and successively attached to said metal base at least one lip-deep first resin bed and second resin bed; Said first resin bed is a non-crystalline polyester, and wherein, said second resin bed contains polyester and Merlon.
Term used herein " polyester " refers to, the general name of the polymer that binary or polyacid and binary or polyalcohol polycondensation obtain.
According to composite metal plate provided by the invention, general according to the concrete needs in the practical application, with first and second resin beds successively attached on a surface of metal base, another surface or two surfaces.For example; When being applied to electronic product shell, then with first and second resin beds successively attached to a surface of metal base, then with the punch process moulding at normal temperatures of this composite metal plate; Put into mould again; At the enclosure interior casting resin of moulding, promptly process the shell that has metal decking, thereby obtain high-quality electronic product casing.The resin of the injection moulding of wanting is a Merlon.
According to composite metal plate provided by the invention, the fusing point of said non-crystalline polyester is 150-250 ℃, and being preferably 180-200 ℃, number-average molecular weight is 31000-34000; The fusing point of said polyester is that to be preferably 180-200 ℃, number-average molecular weight be 31000-34000 to 150-265; The fusing point of said polyester is that 150-265 ℃, number-average molecular weight are 31000-34000; The fusing point of said Merlon is that 220-230 ℃, number-average molecular weight are 28000-32000.
According to composite metal plate provided by the invention, said first resin bed is a non-crystalline polyester, can make the tack of first resin bed and metal base fine, incrust.
According to composite metal plate provided by the invention; Said second resin bed contains polyester and Merlon; And be the blend of polyester and Merlon, so both can have made the tack of second resin bed and first resin bed fine, also can make the resin tack of second resin bed and injection moulding fine.Good and good for both with the resin tack of required injection moulding with the tack of first resin bed, improve resistance to impact simultaneously, therefore in second resin bed, the weight ratio of preferred polyester and Merlon is 1: 99 to 99: 1, more preferably 1: 1 to 20: 1.
According to composite metal plate provided by the invention; For the resin tack that makes composite metal plate of the present invention and injection moulding better; And impact strength is higher, under the preferable case, in said second resin bed, also contains bulking agent; The weight ratio 1 of this bulking agent and Merlon: 10-2: 1, said bulking agent can be selected maleic anhydride graft copolymer and/or (methyl) acrylic acid graft copolymer for use.
According to composite metal plate provided by the invention, the example of available maleic anhydride graft copolymer has maleic anhydride grafted ethene copolymer, maleic anhydride graft ethylene-propylene copolymer, maleic anhydride grafted ethene-octene copolymer, maleic anhydride graft vinyl acetate copolymer etc.The example of available (methyl) acrylic acid graft copolymer has hydroxyethyl methacrylate graft polymers, glycidyl methacrylate graft styrol copolymer, glycidyl methacrylate graft ethylene copolymer.Wherein, preferred maleic anhydride graft copolymer, more preferably maleic anhydride grafted ethene copolymer.
According to composite metal plate provided by the invention,, reach economic purpose simultaneously in order to make first and second resin beds be laminated on the metal base equably and to guarantee that tack is good and be difficult for generation of cracks; Under preferable case, the thickness of first resin bed of said composite metal plate is the 5-50 micron, is preferably the 15-35 micron; The thickness of second resin bed is the 5-50 micron; Be preferably the 15-35 micron, the thickness of metal base is the 0.1-10 millimeter, is preferably the 0.1-1.0 millimeter.
According to composite metal plate provided by the invention, said polyester comprises crystalline polyester and non-crystalline polyester.
This paper employed " crystalline polyester " refers to the polyester of partially crystallizable, and the strand marshalling has nucleus to arrive the generative process of geode in process of setting, and accordings to fixed pattern arranged macromolecular chain.The characteristic of crystalline plastic be opaque, in chain orientation and the uneven physical property of arranged vertical direction, and have obvious and narrow phase change region.
This paper employed " non-crystalline polyester " is commonly referred to as complete non crystallized polyester; The strand random arrangement is tangled; Not forming well-regulated arrangement architecture, in process of setting, do not have nucleus and grain growth process, only is the phenomenon " freezed " of macromolecular chain freely.Many tools transparent appearance, all directions nature difference is little, physical property is comparatively even.
According to composite metal plate provided by the invention; Said non-crystalline polyester is for well known to a person skilled in the art various non-crystalline polyesters, and the example of said non-crystalline polyester is polyethylene glycol isophthalate, gathers the M-phthalic acid butanediol ester, gathers the copolyester of M-phthalic acid terephthalic acid (TPA) ethylene glycol or the copolyester of poly terephthalic acid ethylene glycol cyclohexanedimethanol.Wherein, in the copolyester of poly terephthalic acid ethylene glycol cyclohexanedimethanol, the mol ratio of cyclohexanedimethanol and ethylene glycol is 3: 7-4: 6; In the copolyester of M-phthalic acid terephthalic acid (TPA) ethylene glycol; The mol ratio of M-phthalic acid and terephthalic acid (TPA) is 1: 9-4: 6, and the mol ratio of preferred M-phthalic acid and terephthalic acid (TPA) is the copolyester of 2: 8 M-phthalic acid terephthalic acid (TPA) ethylene glycol.
According to composite metal plate provided by the invention; Said crystalline polyester is for well known to a person skilled in the art various crystalline polyesters, and the example of said crystalline polyester is PETG, polybutylene terephthalate (PBT), PTT, PEN or PBN.
According to composite metal plate provided by the invention; Said Merlon is the Merlon of fatty poly-ester carbonate, fat-aromatic copolycarbonate, aromatic copolycarbonate or modification; The Merlon of modification for example, PC/ABS (PC triblock copolymer), PC/PE (Merlon/polyethylene), PC/POM (Merlon/polyformaldehyde), PC/PS (Merlon/polystyrene), PC/PMMA (Merlon/polymethyl methacrylate).Wherein, the optimization aromatic Merlon is considered from resistance to impact, hear resistance, processability and economy aspect, more preferably bisphenol A polycarbonate.
According to composite metal plate provided by the invention, in said first resin bed and/or in second resin bed, also contain additive, for example one or more in stabilizing agent, anti-oxidant, antistatic additive, pigment, antilubricant and the anticorrisive agent.Above-mentioned additive and addition thereof are conventionally known to one of skill in the art.
According to composite metal plate provided by the invention; To the not special restriction of the metal base that this composite metal plate adopted; Can adopt the various metal bases that adhere to resin bed; For example steel plate, aluminium sheet or aluminium alloy plate, steel plate for example, heat is prolonged steel plate, cold steel plate, galvanized steel plain sheet, tin plate or the corrosion resistant plate of prolonging.
The two layers of resin layer attached on the metal base time, is preferably adhered to the metal base heat bonding securely.Heat bonding can be laminated to resin bed on the metal base that is heated to 260-280 ℃ with laminating roll, makes the resin fusion of metallic substrate surface part at least and bonding.Therefore making composite metal plate of the present invention can adopt following method.
The non-crystalline polyester that (1) will constitute first resin bed and the polyester that constitutes second resin bed and the blend heating and melting and the coextrusion of Merlon directly overlay on the metal base of heating, the roll-in applying.
The non-crystalline polyester that (2) will constitute first resin bed is processed laminated film with the polyester that constitutes second resin bed and the blend heating and melting and the coextrusion of Merlon, covers then on the metal base of heating, and roll-in is fitted.
(3) will constitute the non-crystalline polyester of first resin bed and the blend difference heating and melting of polyester that constitutes second resin bed and Merlon, and extrude respectively then and process film, and be laminated to successively on the metal base of heating again, roll-in is fitted.
After processing composite metal plate with laminating roll laminated resin layer, then cool off.The method of cooling can adopt and well known to a person skilled in the art the whole bag of tricks, for example natural air cooling, forced air-cooling or water-cooled.Consider speed of production, preferably adopt water cooling.
Above-mentioned metal base preferably carries out chemical treatment and makes the tack of resin bed and metal base better adhering to before the resin bed, and chemically treated method is conventionally known to one of skill in the art, handles like phosphatization.
Give an example below to the chemical treatment of stainless steel substrate; Because stainless steel is in carbon steel, to add the steel alloy that chromium, molybdenum, nickel, manganese and titanium elements constitute; Thereby on stainless steel surfaces, formed fine and close continuous passivating film; And make stainless steel have very high corrosion resistance, also have one deck grease to play antirust and corrosion resistant effect simultaneously on the stainless steel surfaces usually.This passivating film and grease can be influential to the adhesive property of stainless steel and resin bed, so preferably carry out the chemical treatment on stainless steel substrate surface.Concrete grammar comprises:
(1) oil removing degreasing.Can adopt the method for electrochemical deoiling, electrochemical degreasing or ultrasonic wave oil removing.The method of these oil removings is conventionally known to one of skill in the art.(2) etch.The content of the method for etch and the composition of etchant and each composition is conventionally known to one of skill in the art; For example the method for etch does; Stainless steel substrate after the oil removing is immersed in concentration is not more than in 20% the etchant, can remove the passivating film on stainless steel substrate surface through etch.(3) phosphatization is handled.It is that stainless steel substrate is immersed in the phosphatization liquid that phosphatization is handled, and on the stainless steel substrate surface, forms phosphating coat, to improve the tack of stainless steel substrate and resin bed.The prescription of parkerized method and phosphatization liquid is conventionally known to one of skill in the art.
Adopt the mode of instance to describe the present invention in more detail below.
Embodiment 1
Being heated on 270 ℃ the SUS 301 banded steel plates (0.15 millimeter of thickness of slab is through the oil removing degreasing), with laminating roll lamination two layers of resin layer, after the lamination, the steel plate that will be attached with the two layers of resin layer immediately immerses chilling in the water, can obtain composite metal plate of the present invention.
First resin bed that adheres to this band shape steel plate is poly terephthalic acid M-phthalic acid ethylene glycol copolyester (Mitsubishi Chemical's polyester Company products; Trade name: BK-2180); Wherein, the mol ratio of terephthalic acid (TPA) and M-phthalic acid is 8: 2, and the thickness of first resin bed is 20 microns; Second resin bed that adheres to first resin bed is the blend that contains Resin A and resin B and bulking agent, and thickness is 30 microns.Bisphenol-a polycarbonate (the Dupont product, trade name: Lexan 141R), the content in blend is 5 weight %; PETG (the Dupont product, trade name: Rynite530), the content in blend is 90 weight %; Bulking agent is that (Dalian Hai Zhou chemical industry Co., Ltd product, trade name: HZEA203), the content in blend is 5 weight % for the polyethylene of maleic anhydride graft copolymerization.
Embodiment 2
Adopt the method for embodiment 1 to process composite metal plate of the present invention; Different is; In second resin bed; The content of resin B bisphenol-a polycarbonate in blend is 20 weight %, and Resin A is that its content in blend of polybutylene terephthalate (PBT) (AM General electrical equipment Plastics Company product, trade name: Valox 310) is 75 weight %; And the thickness of first resin bed is 15 microns, and the thickness of second resin bed is 35 microns.
Embodiment 3
Adopt the method for embodiment 1 to process composite metal plate of the present invention; Different is; In second resin bed, the content of resin B bisphenol-a polycarbonate is 30 weight %, and Resin A is a PTT (U.S. shell chemical company product; Trade name: Corterra), its content in blend is 65 weight %; And the thickness of first resin bed is 35 microns, and the thickness of second resin bed is 15 microns.
Embodiment 4
Adopt the method for embodiment 1 to process composite metal plate of the present invention; Different is; First resin bed be poly terephthalic acid ethylene glycol cyclohexanedimethanol copolyester (Eastman Chemical Company's product, trade name: Eastar GN071), in second resin bed; The content of resin B bisphenol-a polycarbonate in blend is 50 weight %, and the content of Resin A PETG in blend is 45 weight %.
Embodiment 5
Adopt the method for embodiment 1 to process composite metal plate of the present invention; Different is; In second resin bed; The poly content of the bulking agent maleic anhydride graft copolymerization in the blend is 10 weight %, and the content of resin B bisphenol-a polycarbonate in blend is 5 weight %, and the content of Resin A PETG in blend is 85 weight %.
Embodiment 6
Adopt the method for embodiment 2 to process composite metal plate of the present invention; Different is; In second resin bed; The poly content of the bulking agent maleic anhydride graft copolymerization in the blend is 10 weight %, and the content of resin B bisphenol-a polycarbonate in blend is 20 weight %, and the content of Resin A PETG in blend is 70 weight %.
Embodiment 7
Adopt the method for embodiment 3 to process composite metal plate of the present invention; Different is; In second resin bed; The poly content of the bulking agent maleic anhydride graft copolymerization in the blend is 10 weight %, and the content of resin B Merlon in blend is 30 weight %, and the content of Resin A polybutylene terephthalate (PBT) in blend is 60 weight %.
Embodiment 8
Adopt the method for embodiment 4 to process composite metal plate of the present invention; Different is; In second resin bed; The poly content of the bulking agent maleic anhydride graft copolymerization in the blend is 10 weight %, and the content of resin B Merlon in blend is 50 weight %, and the content of Resin A PETG in blend is 40 weight %.
Comparative example 1
Adopt the method for embodiment 1 to process composite metal plate of the present invention, different is that second resin bed is a Merlon.
Comparative example 2
Adopt the method for embodiment 1 to process composite metal plate of the present invention, different is that second resin bed is a PETG.
Comparative example 3
Adopt the method for embodiment 2 to process composite metal plate of the present invention, different is in second resin bed, not contain bulking agent.
Performance evaluation
To embodiment 1-8, the resulting composite metal plate of Comparative Examples 1-3 is estimated by following method, and gained is the result list in the table 1.
1, the processing tack of resin bed
It is 50 millimeters that composite metal plate is struck out diameter, highly is 30 millimeters circular cylindrical shell, makes resin bed be positioned at the inboard of housing.
On above-mentioned circular cylindrical shell medial surface, cut out the crossed grid spirte with drawing the lattice device, otch is deeply until base material; Respectively brush five times with the hairbrush diagonal, be attached on the otch with adhesive tape and draw back again; Observe the situation of grid area, available magnifying glass is observed; Adhesive force is divided according to following standard class:
0 grade: the edge of otch is smooth fully, and the grid edge has no and peels off.
1 grade: have small pieces to peel off in the intersection of otch, actual spoilage is no more than 5% in stroke lattice district.
2 grades: the edge of otch and/or intersection have is peeled off, and its area is greater than 5%, but less than 15%.
3 grades: have part to peel off or whole sheet peels off along notching edge, and/or person's part grid peeled off by full wafer, the area that is peeled off surpasses 15%, but less than 35%.
4 grades: the notching edge sheet peels off/or some grids parts partly or entirely peel off, its area is greater than drawing 35% of lattice district, but is no more than 65%.
5 grades: surpass a last grade.
2, the resistance to impact of resin bed
At the wide sample that is 30 millimeters of cylinder bottom centre place's next block length of cutting of above-mentioned circular cylindrical shell, from the steel plate side of 1 meter height ball falling impact sample.Sample be attached with resin bed one side since ball falling impact cause the prominence place and to be soaked with the sponge that concentration is 1% NaCl solution, this sample is applied 6 volts voltage, the electric current that mensuration is passed through.Current value is low more, shows that the crackle of resin bed generation is more little, and its resistance to impact is good more.The standard of estimating is following:
A level: less than 0.05mA
B level: more than the 0.05mA, below the 0.1mA
C level: more than the 0.1mA, below the 0.3mA
D level: greater than 0.3mA.
3, with the tack of casting resin
The barrel shrond of above-mentioned gained is put into the injection machine mould of size and barrel shrond coupling, is 200 ℃ with mould and die preheating to temperature, and polycarbonate resin is injected the inboard that barrel shrond is attached with resin bed.
The sample of above injection formed is fallen 2 meters eminences, and each sample test is done 50 times; Whether then, observe the Merlon of metallic plate and injection moulding and peel off, available magnifying glass, what do not peel off is good if observing; What slightly peel off is relatively poor; What obviously peel off is poor.
Table 1
Can find out that from the result of table 1 it is fine that the present invention is used for the resin tack of composite metal plate and injection moulding of injection moulding, resistance to impact is fine, and the tack of resin bed and metal base is also fine.
Claims (11)
1. composite metal plate that is used for injection moulding; This composite metal plate comprises metal base and successively attached to said metal base at least one lip-deep first resin bed and second resin bed, said first resin bed is a non-crystalline polyester, it is characterized in that; Said second resin bed contains polyester and Merlon; In said second resin bed, the weight ratio of polyester and Merlon is 1: 99 to 99: 1, and said second resin bed also contains bulking agent; The weight ratio of bulking agent and Merlon is 1: 10-2: 1, and said bulking agent is maleic anhydride graft copolymer and/or (methyl) acrylic acid graft copolymer.
2. composite metal plate according to claim 1, wherein, the fusing point of said non-crystalline polyester is that 150-250 ℃, number-average molecular weight are 31000-34000; The fusing point of said polyester is that 150-265 ℃, number-average molecular weight are 31000-34000; The fusing point of said Merlon is that 220-230 ℃, number-average molecular weight are 28000-32000.
3. composite metal plate according to claim 1, wherein, in said second resin bed, the weight ratio of polyester and Merlon is 1: 1 to 20: 1.
4. composite metal plate according to claim 1, wherein, said bulking agent is a maleic anhydride graft copolymer.
5. composite metal plate according to claim 1, wherein, the thickness of first resin bed of said composite metal plate is the 5-50 micron, and the thickness of second resin bed is the 5-50 micron, and the thickness of metal base is the 0.1-10 millimeter.
6. composite metal plate according to claim 5, wherein, the thickness of first resin bed of said composite metal plate is the 15-35 micron, and the thickness of second resin bed is the 15-35 micron, and the thickness of metal base is the 0.1-1.0 millimeter.
7. composite metal plate according to claim 1, wherein, said polyester comprises crystalline polyester and non-crystalline polyester.
8. according to claim 1 or 7 described composite metal plates; Wherein, said non-crystalline polyester is polyethylene glycol isophthalate, gathers the copolyester of M-phthalic acid butanediol ester, poly terephthalic acid ethylene glycol cyclohexanedimethanol or gather the copolyester of M-phthalic acid terephthalic acid (TPA) ethylene glycol.
9. composite metal plate according to claim 8, wherein, said non-crystalline polyester is the copolyester that gathers M-phthalic acid terephthalic acid (TPA) ethylene glycol, in this copolyester, the mol ratio of M-phthalic acid and terephthalic acid (TPA) is 1: 9-4: 6.
10. composite metal plate according to claim 7; Wherein, said crystalline polyester is PETG, polybutylene terephthalate (PBT), PTT, PEN or PBN.
11. according to any described composite metal plate among the claim 1-3, wherein, said Merlon is an aromatic copolycarbonate.
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| Application Number | Priority Date | Filing Date | Title |
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| CN200710123446A CN101327673B (en) | 2007-06-22 | 2007-06-22 | Metal composite board for injection moulding |
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| CN200710123446A CN101327673B (en) | 2007-06-22 | 2007-06-22 | Metal composite board for injection moulding |
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| CN101327673B true CN101327673B (en) | 2012-09-05 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106243507A (en) * | 2016-08-25 | 2016-12-21 | 芜湖市天雄新材料科技有限公司 | A kind of degredation plastic Masterbatch |
| CN112934966A (en) * | 2021-02-24 | 2021-06-11 | 山东济钢鲍德金属复合板科技有限公司 | Rolling method for improving bonding strength of bimetal composite plate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1033255A (en) * | 1987-10-15 | 1989-06-07 | Mb集团公司 | The metallic plate of lamination |
| CN1228057A (en) * | 1996-07-05 | 1999-09-08 | 东洋钢钣株式会社 | Composite resin film and metallic sheet coated with same |
-
2007
- 2007-06-22 CN CN200710123446A patent/CN101327673B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1033255A (en) * | 1987-10-15 | 1989-06-07 | Mb集团公司 | The metallic plate of lamination |
| CN1228057A (en) * | 1996-07-05 | 1999-09-08 | 东洋钢钣株式会社 | Composite resin film and metallic sheet coated with same |
Non-Patent Citations (3)
| Title |
|---|
| JP特开2002-225073A 2002.08.14 |
| JP特开平10-109391A 1998.04.28 |
| JP特开平7-80992A 1995.03.28 |
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