CN1940179A - Shoe press belt - Google Patents
Shoe press belt Download PDFInfo
- Publication number
- CN1940179A CN1940179A CN 200510136138 CN200510136138A CN1940179A CN 1940179 A CN1940179 A CN 1940179A CN 200510136138 CN200510136138 CN 200510136138 CN 200510136138 A CN200510136138 A CN 200510136138A CN 1940179 A CN1940179 A CN 1940179A
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- China
- Prior art keywords
- mdi
- prepolymer
- tdi
- shoe
- polyurethane resin
- Prior art date
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- Granted
Links
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 42
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920005862 polyol Polymers 0.000 claims abstract description 18
- 150000003077 polyols Chemical class 0.000 claims abstract description 18
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011159 matrix material Substances 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 18
- 239000012948 isocyanate Substances 0.000 claims description 8
- KQNHJIJHVJCPOH-UHFFFAOYSA-N C(C1=CC=CC=C1)(N)N.CSC Chemical compound C(C1=CC=CC=C1)(N)N.CSC KQNHJIJHVJCPOH-UHFFFAOYSA-N 0.000 claims description 3
- 238000005336 cracking Methods 0.000 abstract description 24
- 229920002635 polyurethane Polymers 0.000 description 28
- 239000004814 polyurethane Substances 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 21
- 239000010410 layer Substances 0.000 description 16
- 238000005299 abrasion Methods 0.000 description 14
- 239000012530 fluid Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 208000034189 Sclerosis Diseases 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000004744 fabric Substances 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000007598 dipping method Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 229920000742 Cotton Polymers 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 150000005846 sugar alcohols Polymers 0.000 description 5
- 241001112258 Moca Species 0.000 description 4
- QMMFVYPAHWMCMS-UHFFFAOYSA-N dimethylsulfide Substances CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- -1 polytetramethylene Polymers 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 238000009941 weaving Methods 0.000 description 3
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- VPSXHKGJZJCWLV-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-(1-ethylpiperidin-4-yl)oxypyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)OC1CCN(CC1)CC VPSXHKGJZJCWLV-UHFFFAOYSA-N 0.000 description 1
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical class NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 241000293001 Oxytropis besseyi Species 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000120 polyethyl acrylate Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
Images
Landscapes
- Paper (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
In a shoe press belt composed of a basal body and polyurethane resin, the polyurethane resin is obtained by(1)reacting a mixed prepolymer containing TDI prepolymer and MDI prepolymer with a curing agent, wherein the TDI prepolymer is obtained by reacting toluene diisocynate(TDI)with polyol and the terminal of which has a isocyanate group; or(2)reacting urethane prepolymer with curing agent, wherein the urethane prepolymer is obtained by reacting a mixture containing TDI and MDI with polyol and the terminal of which has a isocyanate group. The containing ratio of TDI and MDI in the mixed prepolymer or the mixed diisocynate is that the MDI mol content in the polyurethane resin of the shoe side is more than that of the hair felt side, preferred, the MDI mol content of the shoe side is 60~95% and the MDI mol content of the hair felt side is 5~50%. Thus a shoe press belt for a paper machine with well wear resistance, cracking resistance, and workability is provided.
Description
Technical field
The present invention relates to the shoe press belt (Japanese: シ ュ one プ レ ス ベ Le ト) that papermaking equipment is used.
Background technology
In machine hand's preface of papermaking, what l Water Paper was carried out that the pressures partially of pressurizing and dehydrating uses is to add pressure zone.As adding pressure zone, be to use mostly from the anvil pressurization band of pressurization shoe side to pressure roll pushing rotation, anvil pressing mechanism by paper machine pressurizes to the pressure roll of papermaking equipment and belt and mounting felt and the l Water Paper in the above that moves between the anvil that pressurize, the water transport that makes l Water Paper is to felt, and the moisture of l Water Paper is drained.
Shoe press belt is by the matrix that constitutes by weaving cotton cloth etc. in order to embody the belt bulk strength and on the two sides of matrix or the stacked polyurethane of single face and constituting basically.
The manufacture method of polyurethane is by the vulcabond and terminal polyalcohol generation addition polymerization reaction with a plurality of hydroxyls that makes end have 2 isocyanate group, produces the urethane prepolymer with isocyanate group at first endways.The aqueous urethane prepolymer that so obtains is low molecule, by heating then to wherein adding curing agent (chain elongation agent), can obtain the high molecular polyurethane of solid shape after the sclerosis.
When making this belt that is laminated with polyurethane, employing be the aqueous urethane prepolymer that a kind of coating on matrix, dipping comprise curing agent, by operation dry or that heating is hardened.
Above-mentioned vulcabond as the raw material of urethane prepolymer was to use toluene di-isocyanate(TDI) (hereinafter referred to as TDI) in the past mostly, also used methyl diphenylene diisocyanate (hereinafter referred to as MDI).And, also have a kind of urethane raw of shoe side to use the polyurethane of MDI, felt side to use the motion (patent documentation 1) of TDI system.
[patent documentation 1] Japan Patent spy opens 2002-146694
Because shoe press belt uses under the rigor condition of anvil and the formed high pressure high-speed cruising of pressure roll that is being subjected on one side pressurize, so cause easily and wear and tear and cracking.Again, owing to discharge for the moisture that will be gone by press for extracting juice, shoe press belt is provided with a plurality of rhones in the felt side along traffic direction usually, but can cause the damaged of the distortion of this rhone and turning (flanged lip end) thereof.Therefore, in order to bear use over a long time,, require to have ABRASION RESISTANCE and anti-cracking under this condition for polyurethane resin as the shoe press belt material.
Summary of the invention
The present inventor has found: the polyurethane resin on the two sides (shoe side and felt side) by making base cloth is all simultaneously and with TDI and MDI, the MDI prepolymer that uses TDI prepolymer that (1) obtained by TDI and polyol reaction and obtain by MDI and polyol reaction mix the polyurethane resin that urethane prepolymer obtains, the perhaps polyurethane resin that obtains of (2) urethane prepolymer of obtaining by mixture and the polyol reaction of TDI and MDI, as making raw material is vulcabond, and make the cooperation ratio of vulcabond of the polyurethane of belt both sides be adjusted to best ratio respectively, can improve the rerum natura of ABRASION RESISTANCE and anti-cracking etc. significantly, can obtain being suitable for the belt that papermaking equipment is used, thereby realize the present invention.
Promptly, the 1st embodiment of the present invention is, by matrix, be stacked in the shoe press belt that the shoe side of this matrix and the polyurethane resin on the felt side two sides constitute with impregnate layer, described polyurethane resin is all by the mixed prepolymer of TDI prepolymer and MDI prepolymer and curing agent reaction and obtain, described TDI prepolymer is obtained by toluene di-isocyanate(TDI) (TDI) and polyol reaction, its end has isocyanate group, described MDI prepolymer is obtained by methyl diphenylene diisocyanate (MDI) and polyol reaction, its end has isocyanate group, and the blending ratio of described TDI prepolymer and MDI prepolymer is that the mole containing ratio of MDI of shoe side polyurethane resin is than the mole containing ratio height of the MDI of felt side polyurethane resin.
Again, the 2nd embodiment of the present invention is, by matrix, be stacked in the shoe press belt that the shoe side of this matrix and the polyurethane resin on the felt side two sides constitute with impregnate layer, described polyurethane resin is all reacted by urethane prepolymer and curing agent and obtains, described urethane prepolymer is obtained by the mixture and the polyol reaction of toluene di-isocyanate(TDI) (TDI) and methyl diphenylene diisocyanate (MDI), its end has isocyanate group, and the mixture of described TDI and MDI is that the mole containing ratio of MDI of shoe side polyurethane resin is than the mole containing ratio height of the MDI of felt side polyurethane resin.
State the method (1) of TDI prepolymer and the mixed prepolymer of MDI prepolymer in the use and use in arbitrary embodiment of TDI and the method for mixing vulcabond (2) of MDI, MDI in the mixture and the ratio of TDI be preferably: the mole containing ratio 60～95% of the MDI of shoe side polyurethane resin, particularly 70～90%, the mole containing ratio 5～50% of the MDI in the felt side polyurethane resin, particularly 10～40%.
Have in the shoe press belt of layer of polyurethane on the two sides of matrix, used the mixture of the TDI prepolymer/MDI prepolymer that has specific mole containing ratio respectively as prepolymer at shoe side and felt side, perhaps used the TDI/MDI mixture that has specific mole containing ratio respectively to make the vulcabond of raw material as urethane prepolymer at shoe side and felt side, thus, anti-cracking, ABRASION RESISTANCE and the good in the past shoe press belt of processability geometric ratio of shoe press belt can be provided in the present invention.
Description of drawings
Fig. 1 is the profile of expression shoe press belt of the present invention.
Fig. 2 is the profile of rhone.
Fig. 3 represents shoe press belt of the present invention manufacturing process.
Fig. 4 represents shoe press belt of the present invention manufacturing process.
Fig. 5 represents anti-cracking experimental rig.
Fig. 6 represents the abrasion test device.
Symbol description
10 belts
20 polyurethane
21 felt side resins
22 shoe side resins
23 rhones
24 bottoms
25 flange parts
30 matrixes
The wire rod of 31 MD directions
The wire rod of 32 CMD directions
40,41 rollers
42 resins coating mouth
43 thermals source
51 test pieces
52 clampers
53 rotation rollers
54 pressurization anvils
55 force fit plates
56 rotation rollers
57 friction members
The specific embodiment
Shoe press belt of the present invention has the lit-par-lit structure at the two sides of matrix dipping, stacked polyurethane.Mainly be to use as matrix and weave cotton cloth.
When being layered in layer of polyurethane on the matrix, the aqueous urethane prepolymer coating by will containing curing agent, be immersed on the matrix dry or heating and harden the high molecular polyurethane of stacked solid shape.
Among the present invention, as simultaneously and with the method for TDI and MDI, can adopt in following two kinds of methods any to implement: the method that (1) uses TDI and MDI both to be mixed the mixture of resulting TDI prepolymer/MDI prepolymer with the synthetic TDI prepolymer of polyol reaction and MDI prepolymer, with specific mole containing ratio separately respectively; Perhaps (2) raw material of using the mixture of the TDI/MDI with specific mole containing ratio to be used as the prepolymer manufacturing is the method for vulcabond.
The two sides of the matrix of shoe press belt (shoe side and felt side) all is laminated with layer of polyurethane, but since shoe side and the desired rerum natura of felt side have nothing in common with each other, so must select the material of the best respectively.On the other hand, make the prepolymer sclerosis generate the very big influence that the required firm time of high molecular polyurethane also can be subjected to diisocyanate, so to its comprehensive judgement, select the mole containing ratio of TDI prepolymer/MDI prepolymer of layer of polyurethane on matrix two sides or the mole containing ratio of TDI/MDI.
Among the present invention, at first at the shoe side of matrix, by dipping, the stacked layer of polyurethane that forms.Because of matrix has the liquid permeability, so must consider the vertical phenomenon of fluid drips.That is, when the aqueous urethane prepolymer that will contain curing agent was coated on shoe side, the firm time that shortens shoe side seemed very important to eliminate the vertical phenomenon of fluid drips, and it is effective therefore adding MDI.The TDI firm time is longer, so when being laminated in the shoe side of matrix, fluid drips is hung down and is difficult to stacked easily.Among the present invention, in the scope of the mole containing ratio of the mole containing ratio or the TDI/MDI that adjust TDI prepolymer/MDI prepolymer, just can improve this defective by adding MDI or MDI prepolymer.At this moment,, then after having applied the aqueous urethane prepolymer that contains curing agent, enter sclerosis immediately if the blending ratio of MDI prepolymer or MDI is too much, and new thereafter stacked urethane prepolymer between enough interlayer adhesion that just can not obtain.
Next is to the dipping of the felt side enforcement layer of polyurethane of matrix, stacked, after the layer of polyurethane intensive drying of shoe side is solidified, will reverse inside the table of the belt in the manufacturing process, then passes through dipping, the stacked layer of polyurethane that forms the felt side of matrix.Owing to formed layer of polyurethane at shoe side, the matrix no liquid permeability of this belt, thus need mole containing ratio of the special MDI of adjustment, with the desired function of the resin that satisfies the felt side, be the requirement of anti-cracking and ABRASION RESISTANCE.If the mole containing ratio of MDI is many,, when the mole containing ratio of MDI is too much, can make the ABRASION RESISTANCE variation, so bad though can improve anti-cracking.That is to say that among the present invention, key is, and layer of polyurethane stacked, formation should further have both the good anti-cracking of MDI composition on TDI composition ABRASION RESISTANCE good basis.
Consider each above rerum natura, in shoe press belt of the present invention, the mole containing ratio of TDI in the layer of polyurethane on matrix two sides and MDI is different, and TDI is that shoe side is more than the mole containing ratio of felt side with the blending ratio of MDI.
In general, the felt side all has requirement to the both sides of anti-cracking and ABRASION RESISTANCE.For this reason, among the present invention, by when making felt side polyurethane resin, use the mixed prepolymer or the TDI/MDI mixing vulcabond of TDI prepolymer/MDI prepolymer, making the mole containing ratio of MDI is 5～50%, more preferably 10～40%, just can improve the anti-cracking and the ABRASION RESISTANCE both sides of felt side.If the mole containing ratio of MDI is too much, then can make the ABRASION RESISTANCE variation, but the mole containing ratio of MDI then causes cracking when very few easily.
Again, at the shoe side of matrix by dipping, stacked when forming layer of polyurethane, it is very important to eliminate the vertical phenomenon of fluid drips to shorten firm time, and therefore adding MDI is effectively, among the present invention, in the shoe side polyurethane resin, also use mixed prepolymer or mixed vulcabond, but the mole containing ratio of MDI is bigger than felt side, and the mole containing ratio of MDI is advisable preferably 70～90% with 60～95%, therefore shorten the firm time of shoe side, can eliminate the vertical phenomenon of fluid drips.If the mole containing ratio of MDI is few, can cause that then fluid drips is vertical, the infringement processability, and when the mole containing ratio of MDI is too much, cause splitting easily.
There are various isomers in MDI, preferably 4,4 ' isomer.
As with the polyalcohol of the mixture reaction of TDI and MDI, can use any of polyether polyol, polyester polyol.Can list polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene glycol etc. as polyether polyol.Can list phthalic acid polyester polyalcohol, PEA, polycaprolactam ester, Merlon, PEA, poly-adipic acid butene esters etc. as polyester polyol again.The mean molecule quantity of these polyalcohols is advisable with 200～10000, and preferably 400～4000.These materials both can use separately, and the mixture that also can be used as more than 2 kinds uses.
Made in the reaction of urethane prepolymer by polyalcohol and vulcabond, both mixing ratios should be defined as 1.3/1～4/1 with isocyanate group/OH base equivalent proportion, preferably 1.4/1～1.6/1 scope.
The urethane prepolymer that the end that so obtains has an isocyanate group is low viscosity normally, by using curing agent (chain elongation agent) to make its chain elongation, can obtain the polyurethane of high molecular, but when making the belt for papermaking machine that constitutes by polyurethane of the present invention and matrix, with the impregnation mixture of urethane prepolymer and curing agent in the belt matrix of weaving cotton cloth etc., by heating, sclerosis can obtain as shown in Figure 1, at the two sides of matrix dipping, be laminated with the belt of polyurethane resin.
Among Fig. 1, belt 10 is made of matrix 30 that plays the intensity effect and polyurethane 20, and polyurethane 20 clips matrix 30 by the felt side resin 21 that contacts with l Water Paper or paper with the shoe side resin 22 of papermaking equipment side contacts such as anvil and is stacked.Among Fig. 1, matrix 30 has used weaving cotton cloth that the wire rod 32 by the wire rod 31 of MD direction and CMD direction is made into, and in addition, also can not be made into both, but adopts spiral structure that the shoestring of superimposed structure or film and braided fabric, the narrow width of cloth is rolled into etc.Preferably on the surface of felt side resin 21 (belt outer peripheral face), make the structure that is formed with rhone 23 again.
When this rhone is set, in the use of belt for papermaking machine, from slot part be full of cracks and cracking take place easily.In order to prevent cracking, effective method is the mole containing ratio that strengthens MDI, but from experiment as can be seen, can damage ABRASION RESISTANCE if the mole containing ratio of MDI is crossed at most.Among the present invention, by having made specific to the mole containing ratio of the MDI in the felt side polyurethane resin by the present invention, just can comprehensive raising two rerum naturas, so, use that to mix isocyanates also be extremely effective even for shoe press belt with this rhone.
As the rhone shape, except structure with rectangular channel, also can suitably use USP 6,296,738 and Japanese Utility Model login the 3rd, structure, the structure that extends laterally or the trench bottom of the curved shape of being put down in writing in 104, No. 830 communiques of the sort of groove sidewall is plane and its end is the structure of round bottom shape etc.Among the present invention, preferably using Fig. 1, section shown in Figure 2 is the shape of trapezoidal round bottom as the shape or the section of rectangle round bottom, and the end of the flange part of preferred described rhone is through chamfered.
Fig. 2 is the shape of this rhone of expression in detail.Among Fig. 2, the 23rd, the rhone of rectangle, the moving direction of itself and belt has been set up in parallel many abreast.This bottom has made the shape of round bottom shown in 24.The end of flange part 25 can prevent the scarce limit phenomenon of the damaged and flange part of end thus through chamfered.
As the size of rhone, preferably groove width a is 1～4mm, and groove depth c is 0.5mm～5mm, and the interval b between the adjacent rhone is 1～4mm.By the mole containing ratio that rhone is made this shape and size and adjust the MDI in the felt side polyurethane resin, improved the rerum natura of felt side polyurethane resin.
The present invention is not particularly limited employed curing agent, can list diamines is curing agent, particularly dimethyl sulfide toluenediamine (DMTDA) and methylene two o-chloranilines (MBOCA), for example 3,3 '-dichloro-4,4,4 '-diaminodiphenylmethane etc., but DMTDA preferably.Though there are the different various isomers of diformazan sulfenyl and amino the position of substitution, for example 3 in DMTDA, 5-dimethyl sulfide 2,4-toluenediamine, 3,5-dimethyl sulfide 2,6-toluenediamine etc., but can use with the form of these admixture of isomeric compound, can be available from the Ethacure300 (trade name) of U.S. A Erbeimaer (ア Le ベ マ-Le) corporate system.
Use the sclerous reaction of curing agent to be undertaken by known method.The temperature of sclerous reaction normally 20～150 ℃ be advisable, preferably 90～140 ℃, should react more than 30 minutes at least.Urethane prepolymer mixes with curing agent, and hope is that the reactive hydrogen base with curing agent becomes 0.9～1.10 such mixing recently with the equivalent proportion of the isocyanate group of urethane prepolymer and carries out.
As matrix can use weave cotton cloth, nonwoven fabric, film etc., but preferably weave cotton cloth.Matrix also can or be constructed different stacked uses of the matrix more than 2 kinds with material.
Shoe press belt is laminated with urethane resin layer on the two sides of matrix, and is for example shown in Figure 3 in the method for the stacked polyurethane resin in the two sides of matrix, by matrix 30 crossbearers between roller 40,41.Make the roller rotation on one side, at first will be coated in as the urethane prepolymer of shoe side resin 22 on the matrix 30 from coating mouth 42 on one side, with the table the inside counter-rotating of matrix, coating makes its dry solidification as the urethane prepolymer of felt side resin 21 on the side overleaf behind shoe side resin 22 dry solidifications.
As shown in Figure 4, the crossbearer that obtains thus is impregnated with under the state of urethane prepolymer 22,21 in the both sides of matrix 30 (shoe side and felt side) in the belt between the roller 40,41, carries out a few hours by the thermal source 43 of being located at the top and add thermal response and make its sclerosis.Grind the belt surface sclerosis back, is to form rhone 33 on the felt side resin 21 at outer peripheral face further as required.Among the present invention, the section of rhone 23 be preferably rectangle and the end of the flange part of the shape of round bottom and described rhone through chamfered, perhaps section be trapezoidal and the end of the flange part of the shape of round bottom and described rhone through chamfered.The shape of this rhone can be set according to the shape of grooving cutter.Again, the groove width of rhone, groove depth, also can become required numerical value with interval between the adjacent rhone according to the shape set of grooving cutter.
[embodiment]
According to the present invention, the mixed prepolymer or the TDI/MDI mixing vulcabond of TDI prepolymer/MDI prepolymer produced shoe press belt as raw material, its rerum natura has been made evaluation.Fig. 1 represents the structure of the employed shoe press belt of embodiment.
(manufacturing of urethane prepolymer)
TDI and MDI are mixed with NCO/OH equivalent proportion 1.5/1 with polytetramethylene glycol respectively, it is filled in the reaction vessel of nitrogen replacement, reacted 3 hours down while stirring at 50 ℃, from reaction product, unreacted isocyanates distillation is removed, then residue is filtered, produce TDI prepolymer and MDI prepolymer, both are mixed, obtain the mixed prepolymer of TDI prepolymer/MDI prepolymer with the molar ratio of stipulating.
On the other hand, TDI is cooperated with MDI, itself and polytetramethylene glycol are produced the urethane prepolymer of being made up of TDI/MDI mixing vulcabond the samely with above-mentioned TDI prepolymer, MDI prepolymer with the molar ratio of stipulating.
(interpolation curing agent)
As curing agent, prepared DMTDA (U.S. A Erbeimaer corporate system " Ethacure300 " (3,5-dimethyl sulfide 2,4-toluenediamine/3,5-dimethyl sulfide 2,80 parts/20 parts mixture of 6-toluenediamine), with the mixed prepolymer that obtains in the above-mentioned operation or mix the equivalent proportion 0.97 that prepolymer that vulcabond obtains is mixed into H/NCO.
(coating prepolymer)
As shown in Figure 3, with matrix 30 crossbearers between roller 40,41.Make the roller rotation on one side, from resin coating mouth 42 at first will as the urethane prepolymer of shoe side resin 22 be coated in matrix 30 on one side, make shoe side resin 22 dry solidifications.Then, with the table the inside counter-rotating of matrix, coating makes its dry solidification as the urethane prepolymer of felt side resin 21 on the side overleaf.
(sclerosis)
As shown in Figure 4, make the belt of crossbearer between roller 40,41 that obtains thus, be impregnated with under the state of urethane prepolymer 22,21 in the both sides of matrix 30 (shoe side and felt side), by being located at the thermal source 43 of top, carry out reaction in 3 hours under 100 ℃, heating made its sclerosis in 5 hours under 130 ℃ again.Grind the belt surface polyurethane sclerosis back, be on the felt side resin 21 further as required at outer peripheral face, the rectangular channel 33 that cuts into groove width 1mm, spacing 2.5mm is processed into tape thickness 5mm as rhone, obtains the belt sample that is made of polyurethane and matrix.
For resulting belt sample, carried out following evaluation of physical property.
(1) processability (fluid drips is hung down)
(2) splitting
(3) cracking test
(4) wear test
The evaluation of physical property method is as follows.
Processability (fluid drips is hung down)
Matrix is positioned on the roller of rotation, a vertical property of the resin liquid when face is observed the coating urethane prepolymer is from it made following evaluation.
Do not cause that fluid drips is vertical: processability is good
Cause that fluid drips is vertical: processability is bad
Splitting
On the boundary face of resin that constitutes shoe side and the resin that constitutes the felt side, draw crackle, it is torn, estimate the maximum of this moment with the degree of drawing test instrument.
Anti-cracking test
Use device shown in Figure 5 to measure.The two ends of test piece 51 are held device 52,52 clampings, and clamper 52,52 can move back and forth on left and right directions linkedly.The tension force that puts on test piece 51 is 3kg/cm, and reciprocating speed is 40cm/ second.
Again, test piece 51 is rotated roller 53 and clamps with pressurization anvil 54, moves towards rotation roller direction by making the pressurization anvil, with 36kg/cm
2Pressurize.
By using this device, in test piece, move back and forth repeatedly, the reciprocal time when mensuration cracking occurs on the surface of the rotation roller side of test piece 51 is made 4 kinds of following evaluations.
More than 200,000 times: excellent
10～200,000 times: good
2～100,000 times: poor slightly
Below 20,000: poor
ABRASION RESISTANCE
Use device shown in Figure 6 to measure.Among Fig. 6, test piece 51 is installed in the bottom of force fit plate 55, and its lower surface (determination object face) contacts and is urged with rotation roller 56.On the periphery of rotation roller 56, be provided with friction part 57, under pressure 6kg/cm and 100m/ minute condition of rotation roller rotation rate, carry out contacting friction with 10 minutes that add the rotation roller depressed, the thickness reduction of the test piece 51 behind the determination test is made 4 kinds of following evaluations.
Below the wear extent 0.05mm: excellent
Wear extent 0.05～0.5mm: good
Wear extent 0.5～0.8mm: poor slightly
More than the wear extent 0.8mm: poor
[embodiment 1～embodiment 5 and comparative example 1～comparative example 5] (mixed prepolymer)
As the urethane prepolymer of shoe side and felt side, used the mixed prepolymer of the TDI prepolymer/MDI prepolymer that mixes with the molar ratio shown in the table 1, make various belt samples, the rerum natura of shoe side, felt side has been made evaluation.The result sees table 1 for details.
Table 1
| Shoe side | The felt side | ||||||||||
| The mixture of TDI prepolymer and MDI prepolymer | (*) changes agent firmly | Processability (fluid drips is hung down) | Splitting | The mixture of TDI prepolymer and MDI prepolymer | (*) changes agent firmly | Anti-cracking | Mar proof | ||||
| TDI content | MDI content | TDI content | MDI content | ||||||||
| Mole % | Mole % | ||||||||||
| Embodiment 1 | 40 | 60 | DMTDA | Well | Well | 90 | 10 | DMTDA | Very | Very | |
| | 30 | 70 | DMTDA | Well | Well | 90 | 10 | DMTDA | Very | Very | |
| Embodiment 3 | 20 | 80 | DMTDA | Well | Well | 90 | 10 | DMTDA | Very | Very | |
| Embodiment 4 | 40 | 60 | DMTDA | Well | Well | 95 | 5 | DMTDA | Poor slightly | Very | |
| Embodiment 5 | 40 | 60 | DMTDA | Well | Well | 50 | 50 | DMTDA | Poor slightly | Poor slightly | |
| Comparative example 1 | 100 | 0 | DMTDA | Difference | Well | 100 | 0 | DMTDA | Difference | Excellent | |
| Comparative example 2 | 50 | 50 | DMTDA | Poor slightly | Poor slightly | 90 | 10 | DMTDA | Very | Very | |
| Comparative example 3 | 20 | 80 | DMTDA | Well | Well | 97 | 3 | DMTDA | Difference | Very | |
| Comparative example 4 | 20 | 80 | | Well | Well | 40 | 60 | DMTDA | Excellent | Difference | |
| Comparative example 5 | 20 | 80 | MOCA | Well | Difference | 80 | 20 | DMTDA | Excellent | Very | |
[embodiment 6～embodiment 10 and comparative example 6～comparative example 11] (mixing vulcabond)
Table 2 represents to make as the urethane prepolymer of shoe side and felt side the blending ratio of the vulcabond of raw material respectively, makes the belt sample, and the rerum natura of shoe side, felt side has been made evaluation.The result sees table 2 for details.
Table 2
| Shoe side | The felt side | |||||||||||
| The mixture of TDI prepolymer and MDI prepolymer | (*) changes agent firmly | Processability (fluid drips is hung down) | Splitting | The mixture of TDI prepolymer and MDI prepolymer | (*) changes agent firmly | Anti-cracking | Mar proof | |||||
| TDI content | TDI content | TDI content | MDI content | |||||||||
| Mole % | Mole % | |||||||||||
| Embodiment 6 | 40 | 60 | DMTDA | Well | Well | 90 | 10 | DMTDA | Very | Very | ||
| Embodiment 7 | 20 | 80 | DMTDA | Well | Well | 90 | 10 | DMTDA | Very | Very | ||
| Embodiment 8 | 10 | 90 | DMTDA | Well | Well | 90 | 10 | DMTDA | Very | Very | ||
| Embodiment 9 | 5 | 95 | DMTDA | Well | Well | 95 | 5 | DMTDA | Excellent | Very | ||
| | 2 | 98 | DMTDA | Poor slightly | Well | 85 | 15 | DMTDA | Poor slightly | Excellent | ||
| Comparative example 6 | 100 | 0 | DMTDA | Difference | Well | 100 | 0 | DMTDA | Difference | Excellent | ||
| Comparative example 7 | 0 | 100 | DMTDA | Well | Difference | 80 | 20 | DMTDA | Very | Very | ||
| Comparative example 8 | 50 | 50 | DMTDA | Difference | Well | 80 | 20 | DMTDA | Very | Very | ||
| Comparative example 9 | 10 | 90 | DMTDA | Well | Well | 98 | 2 | DMTDA | Difference | Excellent | ||
| Comparative example 10 | 10 | 90 | | Well | Well | 40 | 60 | DMTDA | Excellent | Difference | ||
| Comparative example 11 | 10 | 90 | MOCA | Well | Difference | 80 | 20 | MOCA | Poor slightly | Very | ||
* curing agent
DMTDA: dimethyl sulfide toluenediamine
MOCA:4,4 '-methylene two-(2-chloroaniline)
From the result of table 1 as can be seen, the blending ratio of TDI prepolymer and MDI prepolymer be shoe side belt one side is set for more than the mole containing ratio of the MDI of felt side belt, the processability of the mole of the present invention shoe press belt (embodiment 1～embodiment 5) of containing ratio in specific scope of the MDI of shoe side, felt side is good in addition, and the result of the anti-cracking of the splitting of shoe side, felt side and ABRASION RESISTANCE is also good.
Again, from the result of table 2 as can be seen, in the raw material vulcabond of polyurethane prepolymer, used the mixing vulcabond of TDI/MDI, and the processability at the of the present invention shoe press belt (embodiment 6～embodiment 10) of mole containing ratio in particular range of the MDI of shoe side, felt side is good, though it is poor slightly that the anti-cracking of the splitting of shoe side, felt side and an ABRASION RESISTANCE part demonstrate, use in the compass but belong to, total result is good.Otherwise (comparative example 8) processability is bad after a little while for the mole containing ratio of (comparative example 6) or MDI when shoe side list usefulness TDI, and again, (comparative example 7) causes splitting during singly with MDI.And the felt side single during with TDI mole containing ratio (comparative example 9) anti-cracking after a little while of (comparative example 6) and MDI poor, again, mole containing ratio of MDI (comparative example 10) has for a long time obtained the result that wears no resistance.
Industrial applicibility
The present invention is in the shoe press belt that the polyurethane resin that is stacked in this substrate two sides by matrix and impregnate layer consists of, the polyurethane resin that polyurethane resin has used the mixture of the MDI prepolymer that TDI prepolymer that (1) obtained by TDI and polyol reaction and MDI and polyol reaction obtain to obtain, perhaps (2) are the polyurethane resin that the urethane prepolymer that is obtained by TDI/MDI mixing di-isocyanate reaction of vulcabond obtains as the manufacturing raw material of urethane prepolymer, which kind of embodiment no matter, it is more than the mole containing ratio of the MDI of felt side polyurethane resin that the blending ratio of TDI prepolymer and MDI prepolymer all is made as the shoe side polyurethane resin, preferably the mole containing ratio of the MDI of shoe side is decided to be 60～95%, particularly 70～90%, the mole containing ratio of the MDI of felt side is decided to be 5～50%, particularly 10～40%, thereby the good shoe press belts such as wearability, resistance to cracking voltinism and processability are provided.
Thus, even under high pressure, under the rigor condition of high-speed cruising, also can reduce the belt damage that causes because of cracking and wearing and tearing, increase durability, can use for a long time belt, thus Cost reduction, shorten the running intermission that transposing causes, be expected to improve productivity.
Claims (11)
1. shoe press belt, by matrix, the shoe side and the polyurethane resin on the felt side two sides that are stacked in this matrix with impregnate layer constitute, it is characterized in that, described polyurethane resin is all by the mixed prepolymer of TDI prepolymer and MDI prepolymer and curing agent reaction and obtain, described TDI prepolymer is obtained by toluene di-isocyanate(TDI) (TDI) and polyol reaction, its end has isocyanate group, described MDI prepolymer is obtained by methyl diphenylene diisocyanate (MDI) and polyol reaction, its end has isocyanate group, and the blending ratio of described TDI prepolymer and MDI prepolymer is that the mole containing ratio of MDI of shoe side polyurethane resin is than the mole containing ratio height of the MDI of felt side polyurethane resin.
2. shoe press belt as claimed in claim 1 is characterized in that, the mole containing ratio of the MDI of felt side polyurethane resin is 60～95%.
3. shoe press belt as claimed in claim 1 is characterized in that, the mole containing ratio of the MDI of shoe side polyurethane resin is 5～50%.
4. shoe press belt, be stacked in the shoe side of this matrix and the polyurethane resin on the felt side two sides constitutes by matrix and impregnate layer, it is characterized in that, described polyurethane resin is all reacted by urethane prepolymer and curing agent and obtains, described urethane prepolymer by the mixture and the polyol reaction of toluene di-isocyanate(TDI) (TDI) and methyl diphenylene diisocyanate (MDI) obtain, its end has isocyanate group, the mixture of described TDI and MDI is that the mole containing ratio of MDI of shoe side polyurethane resin is than the mole containing ratio height of the MDI of felt side polyurethane resin.
5. shoe press belt as claimed in claim 4, it is characterized in that, the shoe side polyurethane resin is by the reaction of urethane prepolymer and curing agent and obtain, and described urethane prepolymer is that 60～95% mixing vulcabond and polyol reaction obtain, its end has isocyanate group by the mole containing ratio of MDI.
6. shoe press belt as claimed in claim 4, it is characterized in that, felt side polyurethane resin is by the reaction of urethane prepolymer and curing agent and obtain, and described urethane prepolymer is that 5～50% mixing vulcabond and polyol reaction obtain, its end has isocyanate group by the mole containing ratio of MDI.
7. as each described shoe press belt in the claim 1～6, it is characterized in that described curing agent is the dimethyl sulfide toluenediamine.
8. as each described shoe press belt in the claim 1～7, it is characterized in that the surface of described felt side resin is formed with rhone.
9. shoe press belt as claimed in claim 8 is characterized in that, the section of described rhone is rectangle and the shape of round bottom, and the end of the flange part of described rhone is through chamfered.
10. shoe press belt as claimed in claim 8 is characterized in that, the section of described rhone is trapezoidal and the shape of round bottom, and the end of the flange part of described rhone is through chamfered.
11. as shoe press belt as described in each in the claim 8～10, it is characterized in that the groove width of described rhone is 1～4mm, groove depth is 0.5mm～5mm, and is spaced apart 1～4mm between the adjacent rhone.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005280103 | 2005-09-27 | ||
| JP2005-280103 | 2005-09-27 | ||
| JP2005280103 | 2005-09-27 |
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| CN1940179A true CN1940179A (en) | 2007-04-04 |
| CN1940179B CN1940179B (en) | 2010-05-26 |
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| JP3698984B2 (en) * | 2000-11-10 | 2005-09-21 | ヤマウチ株式会社 | Shoe press belt |
| US20040014383A1 (en) * | 2002-07-19 | 2004-01-22 | Atsushi Ishino | Belt for papermaking machine and manufacturing method therefor |
| CN1833070B (en) * | 2003-08-07 | 2010-12-29 | 山内株式会社 | Press belt, process for producing the same and shoe press roll using the press belt |
| JP2005290358A (en) * | 2004-03-08 | 2005-10-20 | Ichikawa Co Ltd | Belt for papermaking machine and its producing method |
| JP4325512B2 (en) * | 2004-08-24 | 2009-09-02 | トヨタ自動車株式会社 | Internal combustion engine control unit inspection system, and automatic determination model automatic generation tool implemented in the inspection system |
| JP3803106B2 (en) * | 2004-11-26 | 2006-08-02 | ヤマウチ株式会社 | Papermaking belt and method for producing papermaking belt |
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