EP2623667B1 - Courroie de presse à sabot pour la fabrication de papier - Google Patents

Courroie de presse à sabot pour la fabrication de papier Download PDF

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Publication number
EP2623667B1
EP2623667B1 EP13000525.9A EP13000525A EP2623667B1 EP 2623667 B1 EP2623667 B1 EP 2623667B1 EP 13000525 A EP13000525 A EP 13000525A EP 2623667 B1 EP2623667 B1 EP 2623667B1
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EP
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Prior art keywords
polyurethane
shoe press
curing agent
press belt
layer
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EP13000525.9A
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German (de)
English (en)
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EP2623667A1 (fr
Inventor
Takao Yazaki
Shintaro Yamazaki
Yuya Takamori
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Ichikawa Co Ltd
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Ichikawa Co Ltd
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F3/00—Press section of machines for making continuous webs of paper
    • D21F3/02—Wet presses
    • D21F3/0209—Wet presses with extended press nip
    • D21F3/0218—Shoe presses
    • D21F3/0227—Belts or sleeves therefor

Definitions

  • dehydration is performed by passing a transportation felt 3 and a wet web 4 through a press section formed of a press roll 1 and a shoe 5 using a shoe press mechanism in which a loop-like shoe press belt 2 is provided between the press roll 1 and the shoe 5, as shown, for example, in FIG. 3 .
  • the shoe press belt 2 includes a outer peripheral polyurethane layer 21 and a inner peripheral polyurethane layer 22 provided on both surfaces of a reinforcing fiber substrate 6, which is integrated into the polyurethane layers.
  • a large number of concave grooves 24 are formed in the press roll side surface of the outer peripheral polyurethane layer 21. Water squeezed from a wet web 4 during pressing is held in the concave grooves 24, and the held water is further transferred to the outside of the press section by the rotation of the belt. Therefore, it is desired that the concave grooves 24 formed in the press roll side surface of the outer peripheral polyurethane layer 21 should have improved shape retention properties when pressurized by a press roll 1 and the shoe 5.
  • a convex part 25 of the press roll side surface of the outer peripheral polyurethane layer 21 be improved in mechanical properties such as cracking resistance, resistance to fatigue from flexing, and wear resistance against vertical pressing force by the press roll 1, the friction of the shoe press belt in a shoe press region, and fatigue from flexing.
  • Polyurethanes that exhibit excellent cracking resistance and wear resistance are widely used as resin materials to form the outer peripheral polyurethane layer 21 of the shoe press belt 2.
  • JP-A-11-247086 discloses a shoe press belt including an outer peripheral polyurethane layer and an inner peripheral polyurethane layer provided on both surfaces of a reinforcing fiber substrate, which is integrated into the polyurethane layers.
  • the polyurethane of the outer peripheral layer and inner peripheral layer is obtained by heat-curing a urethane prepolymer having a terminal isocyanate group (TAKENATE L2395 manufactured by Takeda Pharmaceutical Company Limited), obtained by reacting toluene-diisocyanate (TDI) with polytetramethylene glycol (PTMG), and 3,3'-dichloro-4,4'-diaminodiphenylmethane (which is a compound commercially available as MBOCA and MOCA and also known as 4,4'-methylene bis-orthochloroaniline or 4,4'-methylene bis-(2-chloroaniline)) as a curing agent (chain extender).
  • TAKENATE L2395 manufactured by Takeda
  • JP-B-3698984 discloses a shoe press belt including an outer peripheral polyurethane layer and an inner peripheral polyurethane layer provided on both surfaces of a reinforcing fiber substrate, which is integrated into the polyurethane layers.
  • the polyurethane of the outer peripheral layer is obtained by heat-curing a urethane prepolymer having a terminal isocyanate group (HIPREN L manufactured by Mitsui Chemicals, Inc.), obtained by reacting toluene-diisocyanate (TDI) with polytetramethylene glycol (PTMG), and dimethylthiotoluenediamine (ETHACURE 300).
  • HIPREN L a terminal isocyanate group
  • PTMG polytetramethylene glycol
  • ETHACURE 300 dimethylthiotoluenediamine
  • Dimethylthiotoluenediamine is used instead of 3,3'-dichloro-4,4'-diaminodiphenylmethane as a curing agent in JP-B-3698984 , U.S. Patent No. 7,374,641 , EP 0 855 414 , JP-B-3803106 , and U.S. Patent No. 7,090,747 because: (i) JP-A-7-292237 points out the toxicity of 4,4'-methylenebis-(2-chloroaniline) and recommends use of diethyltolylenediamine as a curing agent (see paragraph [0006]), (ii) the journal " Polyfile," January 1999, pp.
  • ETHACURE 300 New Curing Agent as Substitute for MOCA
  • ETHACURE 300 has excellent low-temperature curability equivalent to that of MOCA and lower toxicity than MOCA, and thus is used as a substitute for MOCA; and (iii) the journal " POLYMER,” vol. 36, 1995, pp.
  • JP-A-10-212333 describes both 4,4'-methylenebis-(2-chloroaniline) and dimethylthiotoluenediamine as curing agents for a polyurethane constituting a belt.
  • EP 2 169 112 A1 discloses a shoe press belt for papermaking, comprising a reinforcing fiber base and a polyurethane layer which are integral with each other, said reinforcing fiber base being embedded in said polyurethane layer, wherein said polyurethane layer includes a polyurethane produced by curing a mixed composition of an urethane prepolymer (A) and a curing agent (B); said urethane prepolymer (A) is obtained by reacting an isocyanate compound (a) comprising 55 to 100 molar % of p-phenylene-diisocyanate compound with polytetramethylene glycol (b), and has a terminal isocyanate group; and said curing agent (B) is selected from the group consisting of 1, 4-butanediol, hydroquinone bis-ß hydroxyl ethyl ether, 3,5-diethyltoluenediamine and 3.5-dimethylthiotoluenediamine.
  • EP 2 284 314 A1 discloses a papermaking shoe press belt formed of a reinforcing fiber base material and a polyurethane layer integrated with each other, said reinforcing fiber base material being embedded in the polyurethane layer, wherein the papermaking shoe press belt comprises, as the polyurethane layer, a polyurethane layer obtainable by curing a composition of the following urethane prepolymer (A) and the following curing agent (B) having active hydrogen group (H): an urethane prepolymer (A) obtainable by reacting an isocyanate compound, which comprises 55 to 100 mol % of a p-phenylene-diisocyanate compound, with a long-chain polyol and having terminal isocyanate group(s), a curing agent (B) containing 65 to 100 mol% of one or more organic polyamine compound having active hydrogen groups (H) and selected from 4,4'-methylene bis(2,6-diethyl-3-chloroaniline), 4,4'
  • EP 1 338 696 A1 discloses a papermaking belt comprising a reinforcing substrate embedded in a thermosetting polyurethane layer and having an outer peripheral surface and an inner peripheral surface formed by said thermosetting polyurethane layer, wherein a polyurethane layer forming said outer peripheral surface is made of a composition containing a urethane prepolymer having isocyanate groups on ends and a hardener containing dimethylthiotoluenediamine.
  • the present invention is directed to a paper making shoe press belt (also referred to as a shoe press belt) used in a paper making shoe press device.
  • the present invention is directed to a shoe press belt used in a closed type shoe press.
  • Exemplary shoe press belts according to the present invention are excellent in cracking resistance.
  • Exemplary shoe press belts according to the present invention include a reinforcing fiber substrate embedded in one or more adjacent polyurethane layers formed from a urethane prepolymer having specific composition that is heat-cured with a mixed chain extender.
  • Exemplary shoe press belts according to the present invention exhibit excellent results in a crack occurrence resistance test whether the belts include or do not include grooves in an outermost surface.
  • Exemplary shoe press belts according to the present invention may be prepared using both ETHACURE 300 as a main component and another curing agent having excellent low-temperature curability as a subcomponent, as curing agents employed to completely cure a urethane prepolymer.
  • a paper making shoe press belt includes a reinforcing fiber substrate and a polyurethane laminate.
  • the polyurethane laminate is integrally constituted.
  • the reinforcing fiber substrate is embedded in at least one layer of the polyurethane laminate.
  • At least one layer of the polyurethane laminate includes a polyurethane obtained by heat-curing a urethane prepolymer (A) together with a mixed curing agent (B).
  • the urethane prepolymer (A) includes a terminal isocyanate group.
  • the urethane prepolymer (A) is obtained by reacting a diisocyanate compound (a) and a long-chain polyol (b).
  • the diisocyanate compound (a) includes at least one of toluene-diisocyanate (TDI), diphenylmethane-diisocyanate (MDI), and paraphenylene-diisocyanate (PPDI).
  • the mixed curing agent (B) includes 70-99.5 mol% of dimethylthiotoluenediamine (c) and 0.5-30 mol% of a curing agent (d).
  • the curing agent (d) includes at least one of 4,4'-methylenebis(2,6-diethyl-3-chloroaniline), 4,4'-methylenedianiline, and 1,4-butanediol.
  • An equivalent ratio of active hydrogen groups of the mixed curing agent (B) to isocyanate groups of the urethane prepolymer (A) ((-H)/(-NCO)) is from 1.02 to 1.15.
  • a paper making shoe press belt is formed of a polyurethane, wherein a reinforcing fiber substrate is integrated with polyurethane layers and the reinforcing fiber substrate is buried in the polyurethane, wherein the polyurethane is obtained by heat-curing a urethane prepolymer (A) having a terminal isocyanate group obtained by reacting
  • an outer peripheral polyurethane layer of the shoe press belt facing a wet web side is formed from a polyurethane that is completely cured with a mixed curing agent, the shoe press belt exhibits improved results in a crack occurrence resistance test.
  • FIG. 1 is a cross-sectional view of an exemplary shoe press belt 2 according to the present invention, in which a reinforcing fiber substrate 6 is integrated with a polyurethane in an outer peripheral layer 21 and an inner peripheral layer 22.
  • the reinforcing fiber substrate 6 is embedded in the polyurethane, and grooves 24 are formed in the outer peripheral polyurethane layer 21.
  • FIG. 2 illustrates an alternative exemplary embodiment of the present invention, in which grooves 24 are not formed in an outer peripheral polyurethane layer.
  • FIG. 2(a) shows a configuration in which a reinforcing fiber substrate 6 is embedded at the interface of an outer peripheral polyurethane layer 2a and an inner peripheral polyurethane layer 2b, the layers being of like composition.
  • FIG. 2(b) shows a configuration in which a reinforcing fiber substrate 6 is embedded at the interface of an outer peripheral polyurethane layer 2a and an inner peripheral polyurethane layer 2b, the layers being of different composition.
  • FIG. 2(c) shows a configuration in which a reinforcing fiber substrate 6 is embedded in an intermediate polyurethane layer 2c provided between an outer peripheral polyurethane layer 2a and an inner peripheral polyurethane layer 2b.
  • FIG. 3 is a simplified diagram of a shoe press mechanism in a paper making machine.
  • reference numeral 2 denotes a shoe press belt
  • reference numeral 4 denotes a wet web
  • reference numeral 3 denotes a paper-making felt
  • reference numeral 1 denotes a press roll
  • reference numeral 5 denotes a shoe.
  • FIG. 4 is an explanatory drawing showing conduct of a test for crack propagation properties of a polyurethane test piece 61 using a De Mattia flex tester.
  • FIG. 5 is an explanatory drawing of a tester 42 for measuring crack occurrence in a shoe press belt 41.
  • the reinforcing fiber substrate 6 may be a woven fabric as described in JP-A-11-247086 , U.S. Patent No. 7,374,641 , or EP 0 855 414 , or alternative reinforcing fiber substrates described in other documents.
  • the reinforcing fiber substrate 6 may be a grid-like material in which 5000 dtex multifilament twisted yarns of polyethylene terephthalate (PET) fibers are used as warp and weft, the warp is sandwiched in the weft, and the intersections between the weft and the warp are bonded by polyurethane adhesion.
  • PET polyethylene terephthalate
  • polyamide fibers such as fibers of aramid, nylon 6,6, nylon 6,10, and nylon 6 may be used instead of polyethylene terephthalate fibers. Further, fibers made of different materials may be used for the warp and the weft, or warp and weft having different thicknesses like 5000 dtex and 7000 dtex may be used.
  • the polyurethane that forms the outer peripheral polyurethane layer 21 of the shoe press belt is a polyurethane with a JIS-A hardness of 90 to 99, preferably 94 to 97, obtained by heat-curing a urethane prepolymer (A) having a terminal isocyanate group, obtained by reacting (a) a diisocyanate compound selected from toluene-diisocyanate (TDI), diphenylmethane-diisocyanate (MDI), and paraphenylene-diisocyanate (PPDI) with (b) a long-chain polyol, and a mixed curing agent (B) comprising (c) 70-99.5 mol% of dimethylthiotoluenediamine and (d) 0.5-30 mol% of a curing agent selected from 4,4'-methylenebis(2,6-diethyl-3-chloroaniline), 4,4'-methylenedianiline, and 1,4-but
  • the polyurethane that forms the inner peripheral polyurethane layer 22 of the shoe press belt may be identical to the polyurethane that forms the outer peripheral polyurethane layer 21 or may be a polyurethane having different composition.
  • the long-chain polyol which is the raw material of the urethane prepolymer (A) may include one or two or more polyol compounds selected from polyether polyols, polyester polyols, polycaprolactone polyols, and polycarbonate polyols.
  • polyether polyols polyether polyols
  • polyester polyols polycaprolactone polyols
  • polycarbonate polyols polycarbonate polyols.
  • polytetramethylene glycol (PTMG) polyethylene glycol
  • PEG polyethylene glycol
  • PPG propylene glycol
  • the shoe press belt is manufactured by a method in which a mandrel surface coated with a mold release agent is coated and impregnated with a mixture of a urethane prepolymer and a mixed curing agent for forming an inner peripheral polyurethane layer while rotating the mandrel so that the inner peripheral polyurethane layer is formed to a thickness of 0.8-3.5 mm on a mandrel surface.
  • the resulting layer is pre-cured at 85-125°C for 0.5-1 hour.
  • a reinforcing fiber substrate is wound therearound and a mixture of a urethane prepolymer and a curing agent for forming an intermediate layer is then coated to a thickness of 0.5-2 mm.
  • the reinforcing fiber substrate is impregnated with the mixture which also adheres to the inner peripheral polyurethane layer, and the resulting layer is pre-cured at 50-120°C for 0.5-1 hour. Thereafter, the surface of the reinforcing fiber substrate is coated and impregnated with a mixture of a urethane prepolymer and a curing agent for forming an outer peripheral polyurethane layer while rotating the mandrel so that the outer peripheral polyurethane layer is formed to a thickness of 1.5-4 mm. The resulting structure is cured at 100-130°C for 2-20 hours. Thereafter, grooves as illustrated in FIG. 1 are carved into the outer peripheral polyurethane layer.
  • the grooves may be carved into the outer peripheral polyurethane layer by bringing a heated emboss roll having a surface with protrusions having heights of groove depths into pressure contact with the outer peripheral polyurethane layer during curing of the outer peripheral polyurethane layer.
  • the mandrel includes a heating apparatus.
  • the shoe press belt is manufactured by a method in which a mandrel surface coated with a mold release agent is coated with a mixture of a urethane prepolymer and a mixed curing agent for forming an inner peripheral polyurethane layer so that the inner peripheral polyurethane layer is formed to a thickness of 0.8-3 mm.
  • the resulting layer is pre-cured at 70-130°C for 0.5-2 hours.
  • a reinforcing fiber substrate is then wound around the external surface of the inner peripheral polyurethane layer and a mixture of a urethane prepolymer and a curing agent for forming an intermediate layer is coated to a thickness of 0.5-2 mm.
  • the reinforcing fiber substrate is impregnated with the mixture, which also adheres to the inner peripheral polyurethane layer.
  • the resulting layer is pre-cured at 50-120°C for 0.5-1 hour.
  • a mixture of a urethane prepolymer and a mixed curing agent for forming an outer peripheral polyurethane layer is coated so that the outer peripheral polyurethane layer has a thickness of 2-4 mm.
  • the resulting structure is cured at 70-130°C for 12-20 hours. Grooves are cut and processed in the outer peripheral polyurethane layer with a cutting tool, and the outer peripheral polyurethane layer is polished with sandpaper or a polyurethane abrasive cloth.
  • the shoe press belt is manufactured by a method in which a mandrel surface coated with a mold release agent is coated with a mixture of a urethane prepolymer and a curing agent for forming an inner peripheral polyurethane layer so that the inner peripheral polyurethane layer is formed to a thickness of 0.8-3 mm.
  • the resulting layer is pre-cured at 50-140°C for 0.5-2 hours.
  • An intermediate polyurethane layer having a thickness of 1-2 mm in which a reinforcing fiber substrate is embedded (produced beforehand) is wound around the outer surface of the inner peripheral polyurethane layer.
  • the intermediate layer is pressed by a nip roll heated to 50-140°C.
  • a mixture of a urethane prepolymer and a mixed curing agent for forming an outer peripheral polyurethane layer is further coated so that the outer peripheral polyurethane layer is formed to a thickness of 2-4 mm.
  • the resulting structure is cured at 70-140°C for 2-20 hours.
  • the outer peripheral polyurethane layer is polished with sandpaper or a polyurethane abrasive cloth. Grooves are cut and processed in the polished outer peripheral polyurethane layer with a cutting tool.
  • the shoe press belt is manufactured by a method using two rolls instead of a mandrel.
  • an endless reinforcing fiber substrate is extended between two rolls.
  • the surface of the reinforcing fiber substrate is coated with a mixture of a urethane prepolymer and a curing agent.
  • the reinforcing fiber substrate is impregnated with the mixture and the resulting structure is pre-cured at 50-120°C for 0.5-2 hours.
  • a mixture of a urethane prepolymer and a mixed curing agent for forming an inner peripheral polyurethane layer is coated onto the reinforcing fiber substrate so that the inner peripheral polyurethane layer is formed to a thickness of 0.5-3 mm.
  • the resulting structure is pre-cured at 70-140°C for 2-12 hours.
  • a surface of the inner peripheral polyurethane layer is polished with sandpaper or an abrasive cloth.
  • the semifinished product is reversed, hung on the two rolls, and extended.
  • the surface of the extended semifinished product is coated with a mixture of a urethane prepolymer and a mixed curing agent for forming an outer peripheral polyurethane layer to impregnate the reinforcing fiber substrate.
  • the surface of the extended semifinished product is further coated with the mixture so that the outer peripheral polyurethane layer is formed to a thickness of 1.5-4 mm.
  • the resulting structure is cured at 70-140°C for 2-20 hours. After curing, the outer peripheral polyurethane layer is polished to a predetermined thickness, and grooves are cut and processed in the outer peripheral polyurethane layer with a cutting tool.
  • polyurethane test pieces were produced as described below.
  • a urethane prepolymer (percentage of NCO: 6.02%, viscosity at 80°C: 400 cps, preheat temperature: 66°C) obtained by reacting toluene-diisocyanate (TDI) with polytetramethylene glycol (PTMG) and a mixed curing agent consisting of 90 mol% of dimethylthiotoluenediamine (ETHACURE 300) and 10 mol% of 1,4-butanediol (H/NCO ratio of the mixed curing agent to the urethane prepolymer would be 1.05) were poured into a preheated die, heated to 100°C, precured at 100°C for 0.5 hour, then removed from the die, and post-cured at 100°C for 16 hours to obtain a polyurethane sheet. A test piece (thickness of 3.5 mm) was produced from the sheet.
  • a urethane prepolymer (percentage of NCO: 6.02%, viscosity at 80°C: 400 cps, preheat temperature: 66°C) obtained by reacting toluene-diisocyanate (TDI) with polytetramethylene glycol (PTMG) and a curing agent composed of dimethylthiotoluenediamine (ETHACURE 300) (H/NCO ratio of the mixed curing agent to the urethane prepolymer would be 0.95) were poured into a preheated die, heated to 100°C, precured at 100°C for 0.5 hour, then removed from the die, and post-cured at 100°C for 16 hours to obtain a polyurethane sheet. A test piece (thickness of 3.5 mm) was produced from the sheet.
  • Polyurethane sheets were obtained in the same manner as in Reference Example 1 except that urethane prepolymers listed in TABLE 1 and TABLE 2 as urethane prepolymers and curing agents listed in TABLE 1 and TABLE 2 as curing agents were used at H/NCO ratios listed in the tables and under preheating and curing conditions listed in the tables. Test pieces (thicknesses of 3.5 mm) were produced from the sheets.
  • the curing agents listed in TABLE 1 and TABLE 2 are dimethylthiotoluenediamine (ETHACURE 300), 4,4'-methylenebis(2,6-diethyl-3-chloroaniline) (LONZACURE MCDEA), 4,4'-methylenedianiline (CAYTUR 31DA), 1,4-butanediol (1,4-BD), and 4,4'-methylenebis-(2-chloroaniline) (MOCA).
  • CAYTUR 31DA is a complex of 4,4'-methylenedianiline and sodium chloride dispersed in dioctyl adipate (DOA).
  • the polyurethane sheet test pieces obtained in Examples 1-13 were subjected to a De Mattia flex test.
  • a test for crack propagation properties was conducted using a tester, illustrated in FIG. 4 , similar to that in the De Mattia flex test defined in JIS-K-6260 (2005) under an atmosphere at 20°C and a relative humidity of 52% under the following conditions.
  • the test piece 61 had a width of 25 mm, a length of 185 mm (including one side of tong hold of 20 mm), a length of 150 mm between grippers 62, a thickness of 3.4 mm, and a semicircular dimple 61 a having a radius of 1.5 mm in a center.
  • the maximum distance between the grippers was 100 mm, the minimum distance was 35 mm, a motion distance was 65 mm, and a reciprocation speed was 360 reciprocations/min.
  • a slit having a length of about 2 mm was notched in the center of the test piece in a width direction.
  • the right and left grippers were set to be at angles of 45° with respect to a reciprocation direction, respectively. Flexing was repeated under the foregoing conditions and crack length was measured after predetermined increments of strokes.
  • the number of strokes as used herein was a value obtained by multiplying test time by reciprocation speed.
  • the test was finished when the crack length exceeded 15 mm from a measurement value of an early notch length (about 2 mm), an approximate curve of the number of strokes and the crack length was drawn, the number of strokes was read when the crack length was 15 mm, and a value obtained by dividing a growing crack length (15 mm in crack length - measurement value of early notch length) by the number of strokes at this time was regarded as a crack propagation property.
  • the obtained physical properties are summarized in TABLE 1 and TABLE 2.
  • Example 7 Urethane prepolymer Isocyanate TDI TDI MDI PPDI/MDI 9/1 PPDI/TDI 9/1 TDI/MDI 5/5 TDI/PPDI 5/5 Polyol PTMG PTMG PTMG PTMG PTMG PTMG PTMG NCO (%) 6.02 6.02 8.85 5.84 5.56 7.44 5.77 Viscosity (cps) 400 (@80°C) 400 (@80°C) 400 (@100°C) 1800 (@55°C) 1700 (@55°C) 600 (@80°C) 500 (@80°C) Preheat temperature (°C) 66 66 80 80 66 80 66 Curing agent (compound name) ETHACURE 300 ETHACURE 300 ETHACURE 300 ETHACURE 300 ETHACURE 300 ETHACURE 300 ETHACURE 300 ETHACURE 300 ETHACURE 300 ETHACURE 300 ETHACURE 300 ETHACURE 300 ETHACURE 300 ETHACURE 300
  • Shoe press belts were prepared using the polyurethane compositions described above in the manner described below.
  • Step 1 A release agent (KS-61: manufactured by Shin-Etsu Chemical Co., Ltd.) was coated on the surface of a mandrel having a diameter of 1500 mm and that was rotatable by driving means. Then, a composition prepared by mixing the urethane prepolymer (TDI/PTMG-based prepolymer) and the mixed curing agent as specified in Reference Example 1 was spirally coated onto the rotating mandrel to a thickness of 1.4 mm using an injection molding nozzle movable in parallel to the rotation axis of the mandrel, and a urethane resin layer was formed.
  • KS-61 manufactured by Shin-Etsu Chemical Co., Ltd.
  • the layer was left to stand at room temperature for 40 minutes while rotating the mandrel, and the resin was further heated at 115°C for 0.5 hour by a heating apparatus attached to the mandrel and precured to produce a shoe side inner peripheral polyurethane layer.
  • Step 2 A grid-like material was prepared using a 5000 dtex multifilament twisted yarn of polyethylene terephthalate fibers as weft and a 550 dtex multifilament yarn of polyethylene terephthalate fibers as warp. The warp was sandwiched in the weft, and the intersections between the weft and the warp were bonded by urethane-based resin adhesion (warp density of 1 strand/cm; and weft density of 4 strands/cm). One layer of the grid-like material having a plurality of pieces was placed on the outer periphery of the shoe side layer without any gap so that the weft was along the axial direction of the mandrel.
  • 6700 dtex multifilament yarn of polyethylene terephthalate fibers was helically wound around the outer periphery of the grid-like material at a pitch of 30 strands/5 cm to form a spool layer. Then, the polyurethane composition was coated to a thickness of about 1.6 mm and integrated as an intermediate layer to fill the gap between the grid-like material and the spool layer, and a reinforcing fiber substrate polyurethane intermediate layer was formed.
  • Step 3 A composition prepared by mixing the urethane prepolymer and the curing agent as specified in Reference Example 1 was impregnated and coated to a thickness of about 2.5 mm on the intermediate layer by spiral coating, heated at 115°C for 16 hours, and post-cured to produce an outer peripheral layer.
  • the surface of the outer peripheral layer was polished to have an overall thickness of 5.2 mm, and a shoe press belt was obtained by forming a large number of concave grooves (of 1.0 mm in groove width, 1.0 mm in depth, and 3.18 mm in pitch width) in the machine direction of the belt by a rotary blade.
  • a shoe press belt was obtained in the same manner as in Example 1 except that the polyurethane composition used in Reference Example 6 was used instead of the polyurethane composition in Reference Example 1 and the curing conditions of precuring and post-curing were changed to 100°C for 0.5 hour and 100°C for 16 hours, respectively.
  • Shoe press belts were obtained in the same manner as in Example 1 except that the urethane prepolymers listed in TABLE 1 and TABLE 2 as urethane prepolymers and the curing agents listed in TABLE 1 and TABLE 2 as curing agents were used under the preheating and curing conditions listed in the tables.
  • a flexing fatigue test was conducted for the obtained shoe press belts.
  • the flexing fatigue test was conducted by evaluating the grooved belt samples.
  • As the flexing fatigue test a crack occurrence test was conducted under an atmosphere of 20°C and a relative humidity of 52% using the device illustrated in FIG. 5 .
  • the test piece 71 had a width of 60 mm and a length between grippers of 70 mm.
  • an upper gripper 42b and the test piece By subjecting a lower gripper 42a to circular-arc reciprocating motion, an upper gripper 42b and the test piece also reciprocated along a circular-arc path so that the test piece was flexed to cause fatigue on the top of the lower gripper.
  • a distance between the center of the circular arc and the top of the lower gripper was 168 mm, the migration length of the lower gripper was 161 mm, and a reciprocation speed was 162 reciprocations/min.
  • the weight of the upper gripper was 400 g. Flexing was repeated under the conditions specified, and the number of flexings until a crack occurred was measured. All the shoe press belts according to Examples exhibited the results in which 1 million flexings could be born. The results are listed in TABLE 3 and TABLE 4.
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Example 6
  • Example 7 Number of flexings (ten thousand times) 100 (not cracked) 100 (not cracked) 100 (not cracked) 100 (not cracked) 100 (not cracked) 100 (not cracked) 100 (not cracked) 100 (not cracked) TABLE 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Number of flexings (ten thousand times) 20 80 15 56 50 35
  • shoe press belts according to embodiments of the present invention are excellent in low-temperature curing properties, exhibit improved crack occurrence inhibiting effect, and have excellent practical values in comparison with known shoe press belts (e.g., as in the Comparative Examples).
  • the present invention is provided as the following (1) to (13).

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Claims (13)

  1. Courroie de presse à sabot pour la fabrication de papier (2), comprenant :
    un substrat en fibres de renforcement (6), et
    un stratifié en polyuréthanne,
    où :
    le substrat en fibres de renforcement est encastré dans au moins une couche (2a, 2b, 2c, 21, 22) du stratifié en polyuréthanne ;
    au moins une couche (2a, 2b, 2c, 21, 22) du stratifié en polyuréthanne comprend un polyuréthanne obtenu par durcissement à chaud d'un prépolymère d'uréthanne (A) avec un agent de durcissement mixte (B) ;
    le prépolymère d'uréthanne (A) comprend un groupe isocyanate terminal ;
    le prépolymère d'uréthanne (A) est obtenu par réaction d'un composé diisocyanate (a) et d'un polyol à longue chaine (b) ;
    le composé diisocyanate (a) comprend au moins un membre choisi dans le groupe consistant en le diisocyanate de toluène (TDI), le diisocyanate de diphénylméthane (MDI) et le diisocyanate de paraphénylène (PPDI) ;
    l'agent de durcissement mixte (B) comprend 70-99,5% en moles de diméthylthiotoluènediamine (c) et 0,5-30% en moles d'un agent de durcissement (d) ;
    l'agent de durcissement (d) comprend au moins un membre choisi dans le groupe consistant en la 4,4'-méthylènebis(2,6-diéthyl-3-chloroaniline), la 4,4'-méthylènedianiline et le 1,4-butanediol, et
    le rapport d'équivalents des hydrogènes actifs dans l'agent de durcissement mixte (B) aux groupes isocyanate dans le prépolymère d'uréthanne (A) ((-H)/(-NCO)) se situe dans l'intervalle allant de 1,02 à 1,15.
  2. Courroie de presse à sabot pour la fabrication de papier (2) selon la revendication 1, où le stratifié en polyuréthanne comprend une couche en polyuréthanne périphérique interne (2b, 22) et une couche en polyuréthanne périphérique externe (2a, 21).
  3. Courroie de presse à sabot pour la fabrication de papier (2) selon la revendication 2, où la couche en polyuréthanne périphérique interne (2b, 22) comprend le polyuréthanne obtenu par durcissement à chaud du prépolymère d'uréthanne (A) avec l' agent de durcissement mixte (B).
  4. Courroie de presse à sabot pour la fabrication de papier (2) selon la revendication 3, où la couche en polyuréthanne périphérique interne (2b, 22) et la couche en polyuréthanne périphérique externe (2a, 21) comprennent le polyuréthanne obtenu par durcissement à chaud du prépolymère d'uréthanne (A) avec l' agent de durcissement mixte (B).
  5. Courroie de presse à sabot pour la fabrication de papier (2) selon la revendication 2, où la couche en polyuréthanne périphérique externe (2a, 21) comprend le polyuréthanne obtenu par durcissement à chaud du prépolymère d'uréthanne (A) avec l' agent de durcissement mixte (B).
  6. Courroie de presse à sabot pour la fabrication de papier (2) selon la revendication 2, où le substrat en fibres de renforcement est encastré dans la couche en polyuréthanne périphérique interne (2b, 22) et dans la couche en polyuréthanne périphérique externe (2a, 21).
  7. Courroie de presse à sabot pour la fabrication de papier (2) selon la revendication 2, comprenant en outre, une couche en polyuréthanne intermédiaire (2c) entre la couche en polyuréthanne périphérique interne (2b) et la couche en polyuréthanne périphérique externe (2a).
  8. Courroie de presse à sabot pour la fabrication de papier (2) selon la revendication 7, où le substrat en fibres de renforcement (6) est encastré dans la couche en polyuréthanne intermédiaire (2c).
  9. Courroie de presse à sabot pour la fabrication de papier (2) selon la revendication 1, où la au moins une couche (2a, 2b, 2c, 21, 22) du stratifié en polyuréthanne présente une surface comprenant des rainures (24).
  10. Courroie de presse à sabot pour la fabrication de papier (2) selon la revendication 3, où la couche en polyuréthanne périphérique externe (2a, 21) a une surface comprenant des rainures (24).
  11. Courroie de presse à sabot pour la fabrication de papier (2) selon l'une quelconque des revendications 1 à 10, où le rapport d'équivalents des hydrogènes actifs dans l'agent de durcissement mixte (B) aux groupes isocyanate dans le prépolymère d'uréthanne (A) se situe dans l'intervalle allant de 1,05 à 1,12.
  12. Courroie de presse à sabot pour la fabrication de papier (2) selon l'une quelconque des revendications 1 à 10, où le rapport d'équivalents des hydrogènes actifs dans l'agent de durcissement mixte (B) aux groupes isocyanate dans le prépolymère d'uréthanne (A) se situe dans l'intervalle allant de 1,02 à 1,10.
  13. Courroie de presse à sabot pour la fabrication de papier (2) selon l'une quelconque des revendications 1 à 10, où le rapport d'équivalents des hydrogènes actifs dans l'agent de durcissement mixte (B) aux groupes isocyanate dans le prépolymère d'uréthanne (A) se situe dans l'intervalle allant de 1,10 à 1,15.
EP13000525.9A 2012-02-01 2013-02-01 Courroie de presse à sabot pour la fabrication de papier Active EP2623667B1 (fr)

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CN105339546A (zh) * 2013-06-14 2016-02-17 株式会社市川 造纸用靴形压榨带
JP6501537B2 (ja) * 2015-01-16 2019-04-17 イチカワ株式会社 シュープレスベルト及びその製造方法
EP3199700B1 (fr) * 2016-02-01 2018-12-05 Ichikawa Co., Ltd. Courroie de presse à sabot
DE102017117227A1 (de) * 2017-07-31 2019-01-31 Voith Patent Gmbh Pressmantel und dessen Verwendung sowie Presswalze und Schuhpresse
JP6580774B1 (ja) * 2018-05-16 2019-09-25 第一工業製薬株式会社 熱可塑性マトリックス樹脂形成用二液硬化型組成物、繊維強化複合材料用マトリックス樹脂、及び繊維強化複合材料
DE102018122782A1 (de) * 2018-09-18 2020-03-19 Voith Patent Gmbh Pressmantel, dessen Verwendung sowie Presswalze und Schuhpresse

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JPH07292237A (ja) 1994-04-28 1995-11-07 Bando Chem Ind Ltd ベルト用ポリウレタン組成物
US5821316A (en) 1997-01-24 1998-10-13 Air Products And Chemicals, Inc. Polyurethane prepolymers for making elastomers having improved dynamic properties
JP3408416B2 (ja) 1998-02-26 2003-05-19 市川毛織株式会社 シュープレス用ベルト及びその製造法
JP3698984B2 (ja) 2000-11-10 2005-09-21 ヤマウチ株式会社 シュープレス用ベルト
JP3803106B2 (ja) * 2004-11-26 2006-08-02 ヤマウチ株式会社 製紙用ベルトおよび製紙用ベルトの製造方法
JP2006225839A (ja) * 2006-04-03 2006-08-31 Yamauchi Corp シュープレス用ベルト
JP4516583B2 (ja) * 2007-05-18 2010-08-04 イチカワ株式会社 シュープレス用ベルト
WO2009001766A1 (fr) * 2007-06-25 2008-12-31 Ichikawa Co., Ltd. Bande de presse à sabot pour la fabrication de papier
JP2010116652A (ja) * 2008-11-14 2010-05-27 Ichikawa Co Ltd シュープレス用ベルト
JP4444367B1 (ja) * 2009-07-21 2010-03-31 イチカワ株式会社 製紙用シュープレスベルト

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CN103243603A (zh) 2013-08-14
CN103243603B (zh) 2015-12-09
EP2623667A1 (fr) 2013-08-07
US20130192787A1 (en) 2013-08-01
JP2013159860A (ja) 2013-08-19

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