JP2009237465A - Toner supply roller - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner supply roller eliminating a defect caused by the exudation contamination of a foam stabilizer by forming a polyurethane foam layer of polyurethane foam with little transpiration and migration of the foam stabilizer. <P>SOLUTION: The toner supply roller has core metal and one or more polyurethane foam layers formed on the core metal. The polyurethane foam layer is formed of a raw material composition containing at least (A) polyol, (B) polyisocyanate, (C) a foaming agent, (D) a catalyst, and (E) a silicone foam stabilizer, and contains (E) the silicone foam stabilizer at 0.1-5.0 pts.mass based on 100 pts.mass of (A) polyol in the raw material composition. Further, a mass decrease rate after heating at 100°C for 30 minutes is 1.0% or less. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a toner supply roller for an image forming apparatus.

  With the advancement of electrophotographic technology, image forming apparatuses such as dry electrophotographic apparatuses are made of polyurethane foam as parts for parts used for charging, development, transfer, toner supply, cleaning, etc. Is attracting attention. For example, it is used as a member for an image forming apparatus having elasticity such as a charging roller, a developing roller, a transfer roller, a toner supply roller, and a cleaning roller.

  Many of these polyurethane foam members can be manufactured in a mold. For example, a toner supply roller is manufactured by the following method. First, polyol, polyisocyanate, foam stabilizer, water, and catalyst are mixed and stirred and injected into a toner supply roller mold. The toner supply roller can be manufactured by foaming and curing this in a mold and then removing the molded product.

  As the foam stabilizer, the following siloxane compounds are used. Water-soluble polyether siloxanes from polydimethylsiloxane and ethylene oxide / propylene oxide copolymers, mixtures of sodium sulfonated ricinoleic acid and polysiloxane / polyoxyalkylene copolymers. Among them, water-soluble polyether siloxanes are widely used for, for example, slab foam, hot mold, high elasticity (cold) mold, and hard.

  Polyurethane foams used for in-mold molding tend to have a faster gelation than slab foams and are overpacked with molds, so the air permeability of the foam tends to be low. For this reason, a foam stabilizer that is basically similar to a foam stabilizer for slab foam, but has a slightly weak foam regulating ability and increases the air permeability of the foam, has been used.

Furthermore, in the case of a sound absorbing material or packing material for electronic equipment, the evaporation of low molecular components of the foam stabilizer causes an important problem, and thus the foam stabilizer may not be used (for example, see Patent Document 1). In addition, the foam stabilizer in the polyurethane foam may move to another image forming apparatus that contacts the member and cause problems such as discoloration. In order to solve these problems, the use of a foam stabilizer having a reactive group that reacts with polyurethane foam or its raw material has been proposed (see, for example, Patent Document 2), but it is not very effective and is baked for a long time. (Cure) treatment is required.
JP-A-11-288161 JP 2007-145904 A

  An object of the present invention is to provide a toner supply roller in which a polyurethane foam layer is formed from a polyurethane foam in which the foam stabilizer has little transpiration and migration, and the problems due to the foam stabilizer oozing out and contamination are eliminated.

  The above-mentioned subject is achieved by the following.

(1) A toner supply roller having a cored bar and at least one polyurethane foam layer formed on the cored bar, wherein the polyurethane foam layer includes at least (A) a polyol, (B) a polyisocyanate, (C And (E) a raw material composition containing a catalyst and (E) a silicone foam stabilizer, and the content of (E) silicone foam stabilizer in the raw material composition is (A) a polyol. 0.1 to 5.0 parts by mass with respect to 100 parts by mass, and the (E) silicone foam stabilizer has a mass reduction rate of 1.0% or less by heating at 100 ° C. for 30 minutes. A toner supply roller.

(2) The toner supply roller according to (1) above, wherein the (E) silicone foam stabilizer has a mass reduction rate after heating at 100 ° C. for 30 minutes of 0.6% or less.

(3) The (A) polyol contains a polyether polyol having at least a weight average molecular weight (Mw) of 2,000 to 10,000 and containing 5 mol% or more of ethylene oxide at the end, and the (B) polyisocyanate is The toner supply roller according to (1) or (2) above, which contains at least diphenylmethane diisocyanate (MDI) or a derivative thereof.

(4) The toner supply roller according to any one of (1) to (3), wherein the raw material composition has an NCO index of 90 to 120.

  According to the present invention, since the polyurethane foam layer is composed of polyurethane foam with less transpiration and migration of silicone, it is possible to provide a toner supply roller in which the problems caused by the bleeding out of the foam stabilizer are eliminated.

  The present invention is a toner supply roller having a cored bar and at least one polyurethane foam layer formed on the cored bar. The polyurethane foam layer is formed from a raw material composition containing at least (A) polyol, (B) polyisocyanate, (C) foaming agent, (D) catalyst, and (E) silicone foam stabilizer. In addition, the content of (E) silicone foam stabilizer in the raw material composition is 0.1 to 5.0 parts by mass with respect to 100 parts by mass of (A) polyol, and (E) silicone foam stabilizer. The agent has a mass reduction rate of 1.0% or less by heating at 100 ° C. for 30 minutes.

  This will be described in detail below.

  The toner supply roller in the present invention has a cored bar and at least one polyurethane foam layer formed on the cored bar. The polyurethane foam layer contains a raw material composition containing at least (A) polyol, (B) isocyanate, (C) foaming agent, (D) catalyst, and (E) silicone foam stabilizer, for example, a toner supply roller. It is formed by foaming and curing in a mold for moldability.

  In the present invention, the (E) silicone foam stabilizer needs to have a mass reduction rate of 1.0% by mass or less, preferably 0.6% by mass or less, by heating at 100 ° C. for 30 minutes. is there. When the mass reduction rate is larger than 1.0%, the bleeding out of the silicone foam stabilizer component or the scattered component is very likely to cause an important problem.

  The content of the (E) silicone foam stabilizer in the raw material composition is 0.1 to 5.0 parts by weight, preferably 0.1 to 2.0 parts by weight, based on 100 parts by weight of the (A) polyol. Part. (E) When the content of the silicone foam stabilizer is less than 0.1 parts by mass with respect to 100 parts by mass of the polyol (A), the foam foaming power is weak, so that the entire foam is liable to be rough, and in some cases, This is not preferable because a large air pool is generated. On the other hand, when the content is larger than 5.0 parts by mass, even when a silicone foam stabilizer that is difficult to scatter is used, it is excessively added, and the influence of the bleed-out of the silicone foam stabilizer component or the scattered component is observed. Therefore, it is not preferable.

  The silicone foam stabilizer in the present invention is not particularly limited as long as the mass reduction rate after heating at 100 ° C. for 30 minutes is 1.0% by mass or less, and a conventionally known silicone foam stabilizer is used. Can do. For example, a water-soluble polyether siloxane from polydimethylsiloxane and an ethylene oxide / propylene oxide copolymer, a mixture of a sodium salt of sulfonated ricinoleic acid and a polysiloxane / polyoxyalkylene copolymer, and the like are suitable.

  In the present invention, the polyol (A) in the raw material composition includes a polyether polyol having at least a mass average molecular weight (Mw) of 2,000 to 10,000 and containing 5 mol% or more of ethylene oxide at the terminal. preferable. Moreover, it is preferable that (B) isocyanate contains at least diphenylmethane diisocyanate (MDI) or its derivative (s).

  The polyol (A) used in the present invention contains a polyether polyol in which at least 5 mol% or more of ethylene oxide is added to the terminal. Polyether polyols having 5 mol% or more of ethylene oxide added to the terminal are preferable because the terminal is a primary hydroxyl group, and the reaction with polyisocyanate becomes good. As the polyol (A), as long as it contains a polyether polyol in which 5 mol% or more of ethylene oxide is added to the terminal, a polyol used for other toner supply rollers can be used in combination. In addition, it is desirable that the polyether polyol having 5 mol% or more added to the terminal contains at least 50 mass%, preferably 70 mass% or more.

  In addition, the polyether polyol which added 5 mol% or more of this ethylene oxide to the terminal is manufactured as follows, for example. That is, it is produced by adding a compound having two or more active hydrogens as an initiator, adding an alkylene oxide derivative thereto by a known method, and finally adding a predetermined amount of ethylene oxide.

  Examples of compounds having two or more active hydrogens include the following compounds. For example, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, glycerin, Trimethylolpropane, pentaerythritol, sorbitol; sugar alcohols such as sucrose and glucose; bisphenol A; diamines such as ethylenediamine, propylenediamine, diethylenetriamine, toluenediamine, metaphenylenediamine, diphenylmethanediamine, and xylylenediamine.

  Moreover, the following compounds can be mentioned as an alkylene oxide derivative. For example, alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and amylene oxide; glycidyl compounds such as glycidyl ether, methyl glycidyl ether, t-butyl glycidyl ether, and phenyl glycidyl ether.

  In the present invention, the polyether polyol having 5 mol% or more of ethylene oxide added to the terminal has a sufficient strength at the time of demolding because the urethanization reaction is delayed if the amount of ethylene oxide added to the terminal is less than 5 mol%. Polyurethane foam cannot be produced. In addition, it is more preferable that the addition amount to the terminal of ethylene oxide is 10 mol% or more. Addition of ethylene oxide to the terminal increases the proportion of primary hydroxyl groups in the terminal hydroxyl groups, promotes the reaction between the polyol and polyisocyanate (urethanization), and forms a polyurethane foam with sufficient strength during demolding .

  The polyol (A) preferably has an Mw of 2,000 to 10,000. That is, when Mw is less than 2,000, the polyol component is likely to ooze out due to a decrease in reactivity, which may adversely affect other members used in the image forming apparatus. Further, if Mw is greater than 10,000, the reactivity is high and the viscosity is high, so that molding defects are likely to occur. More preferably, Mw is 2,500 to 8,000.

  In the present invention, (B) polyisocyanate preferably contains at least diphenylmethane diisocyanate (MDI), and MDI may be a derivative. Since the polyisocyanate containing MDI and its derivatives is excellent in the reaction (urethanization) with a polyol, it exhibits good moldability in molding.

  There is no restriction | limiting in particular as another polyisocyanate, It can use suitably selecting from conventionally well-known various isocyanate. The following can be mentioned as an example of this isocyanate. Aromatic polyisocyanates and derivatives thereof such as tolylene diisocyanate (TDI); aliphatic isocyanates and derivatives thereof such as hexamethylene diisocyanate (HMDI); alicyclic isocyanates such as isophorone diisocyanate (IPDI) and derivatives thereof. In addition, it is preferable that MDI and its derivative in (B) polyisocyanate are 3 to 80 mass%.

  Derivatives include, for example, polynuclear products, urethane-modified products modified with polyols, dimers formed by uretidione, isocyanurate-modified products, carbodiimide-modified products, uretonimine-modified products, allophanate-modified products, urea-modified products, burette-modified products, etc. It is. Among these polyisocyanates, MDI, TDI, and derivatives thereof (B) The member for an image forming apparatus having a polyurethane foam produced using polyisocyanate as a main component has low hardness and improved wet heat durability. Is preferred.

  The blending amount of these polyisocyanates in the image forming apparatus member is not particularly limited, but it is preferable to set the blending amount with respect to the polyol so that the NCO index is 90 to 120. If the NCO index is less than 90, the polyurethane skeleton is not sufficiently formed and foam breakage or the like is likely to occur at the time of demolding, and unreacted polyol components ooze out and contaminate other members incorporated in the image forming apparatus. Doing so may cause image defects. On the other hand, if the NCO index exceeds 120, the hardness becomes high and sufficient performance as a polymer member for an image forming apparatus may not be obtained. For example, when used as a toner supply roller of the image forming apparatus, the toner supply roller performance such as toner supply and scraping can be sufficiently exhibited by maintaining it within the NCO index range.

  The NCO index is a value obtained by dividing the total number of isocyanate groups in the polyisocyanate by the total number of active hydrogens that react with isocyanate groups such as hydroxyl groups and amino groups in the blended polyol, crosslinking agent, foaming agent and other components. It is. The NCO index is defined as 100 when the number of active hydrogens reacting with an isocyanate group and the isocyanate group in the isocyanate are stoichiometrically equal.

  In the present invention, water is preferably used as the foaming agent (C). A blowing agent other than water, for example, trichloromonofluoromethane, dichlorodifluoromethane, methylene chloride, trichlorofluoromethane, carbon dioxide or the like may be used alone or in combination of two or more.

  In the present invention, the catalyst (D) can be appropriately selected from known amine catalysts and organometallic catalysts. Moreover, the following can be mentioned as an amine catalyst. 1,2-dimethylimidazole, triethylamine, tripropylamine, tributylamine, hexadecyldimethylamine, N-methylmorpholine, N-ethylmorpholine, N-octadecylmorpholine, diethylenetriamine, N, N, N ', N'-tetramethyl Ethylenediamine, N, N, N ′, N′-tetramethylpropylenediamine, N, N, N ′, N′-tetramethylbutanediamine, N, N, N ′, N′-tetramethyl-1,3-butanamine N, N, N ', N'-tetramethylhexamethylenediamine, bis [2- (N.N-dimethylamino) ethyl] ether, N, N-dimethylbenzylamine, N, N-dimethylcyclohexylamine, N , N, N ′, N ′, N ″, N ″ -pentamethyldiethylenetriamine, trie Range amines, salts of triethylenediamine, oxyalkylene adducts of amino groups of primary and secondary amines, 1,8-diazabicyclo (5,4,0) undecene-7, 1,5-diazabicyclo (4,3,0 ) Azacyclo compounds such as nonene-5, N, N-dialkylpiperazines, various N, N ′, N ″ -trialkylaminoalkylhexahydrotriamines, etc. Further examples of organometallic urethanization catalysts include Tin acetate, tin octylate, tin octetate, tin oleate, tin laurate, dibutyltin dichloride, dibutyltin dilaurate, dibutyltin diacetate, tetra-i-propoxytitanium, tetra-n-butoxy Titanium, tetrakis (2-ethylhexyloxy) titanium, lead naphthenate, naphthenic acid nickele , Cobalt naphthenate, etc., organic acid catalyst (carboxylate, borate, etc.) with reduced initial activity of the amine catalyst and organometallic catalyst, etc. These catalysts can be used alone or in combination. Used.

  The toner supply roller of the present invention preferably has a roller shape, and is manufactured, for example, as follows. First, in accordance with a conventionally known method, a rod-shaped metal core is placed in a predetermined toner supply roller mold. On the other hand, a raw material composition for a polyurethane foam roller is prepared by mixing polyol, polyisocyanate, foaming agent, catalyst and foam stabilizer. And this raw material composition is inject | poured into a shaping | molding die, and it heats at 25 thru | or 80 degreeC, and foam-molds. In some cases, the reaction may be promoted in a heating furnace at 80 to 250 ° C. Then, after completion of the reaction (foam curing), the toner supply roller can be obtained by taking it out from the mold. When the polyurethane foam layer needs to be conductive, a conductive agent such as carbon black can be appropriately added to the raw material composition.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not restrict | limited by these Examples.

As raw materials used in the following Examples and Comparative Examples, the following materials used were used.
(A) Polyol / EP553: Polyether polyol “ACTCOL EP-553” (trade name, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.), OH value = 56 mg KOH / g, Mw = 3,000, terminal ethylene oxide bond amount = 7 mol %.
GP3000: Polyether polyol “Sanix GP-3000” (trade name, manufactured by Sanyo Chemical Co., Ltd.), OH value = 56 mgKOH / g, Mw = 3,000, no ethylene oxide bond to the terminal.
-MF16: Polyether polyol "Actol MF-16" (trade name, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.), OH value = 46 mg KOH / g, mW = 2,500, end ethylene oxide bond amount = 15 mol%.
7012: Polyether polyol “Preminol 7012” (trade name, manufactured by Asahi Glass Co., Ltd.), OH number = 17 mg KOH / g, Mw = 10,000, terminal ethylene oxide bond amount = 15 mol%.

(B) Polyisocyanate / TM50: Polyisocyanate mixture “Cosmonate TM-50” (trade name, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.), NCO = 40%, MDI = 50 mol%.
T80: Toluene diisocyanate “Cosmonate T-80” (trade name, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.), NCO = 48%, MDI not contained.

(D) Catalyst / ET: Amine-based catalyst “TOYOCAT ET” (trade name, manufactured by Tosoh Corporation), 70% dipropylene glycol solution of bis (dimethylaminoethyl) ether.
33LV: amine catalyst “Dabco 33LV” (trade name, manufactured by Air Products Japan), 33% dipropylene glycol solution of triethylenediamine.

(E) Silicone foam stabilizer L3640: Silicone foam stabilizer “NIAX SILICON L-3640” (trade name, manufactured by Momentive Performance Materials Japan GK), mass reduction rate of 100 ° C. × 30 minutes = 0 32%.
SZ1336: Silicone foam stabilizer “SZ-1336” (trade name, manufactured by Toray Dow Corning Co., Ltd.), mass reduction rate of 100 ° C. × 30 minutes = 0.69%.
Y10184: silicone-based foam stabilizer “NIAX SILICONY-10184” (trade name, manufactured by Momentive Performance Materials Japan GK), mass reduction rate of 100 ° C. × 30 minutes = 3.55%.

  The mass reduction rate of these foam stabilizers by heating at 100 ° C. for 30 minutes was measured under a nitrogen atmosphere using a differential thermothermal gravimetric simultaneous measurement device “TG / DTA6200” (trade name, manufactured by Seiko Instruments Inc.). About 10 mg of the foam stabilizer was measured by heating at 100 ° C. for 30 minutes.

Example 1
(A) 100 parts by weight of polyol “EP553”, (C) 2 parts by weight of water as a blowing agent, (D) 0.05 part by weight of catalyst “ET”, 0.2 part by weight of “33LV”, and (E) silicone preparation 1 part by mass of foaming agent “L3640” was mixed with stirring. (B) Isocyanate “TM50” was added in an amount to give an NCO index of 100 and stirred for 5 seconds in the mixing chamber, and then poured into a mold for toner supply roller adjusted to 50 ° C. The foam was cured and further cured at 120 ° C. for 30 minutes. As a result, a toner supply roller made of urethane foam having a density of 0.10 g / cm ³ was obtained.

The obtained toner supply roller was incorporated as a toner supply roller in each color cartridge of a full-color laser beam printer “LBP-2510” (trade name, manufactured by Canon Inc.). Using the full-color laser beam printer to which this cartridge was attached, it was allowed to stand for at least one night after installation, and then a halftone image of each color was formed, the density uniformity was examined visually, and the image was evaluated according to the following criteria. The results are shown in Table 1.
(Double-circle): In any color, density unevenness and color omission are not seen, and it is good.
○: There is no problem in using a material with uneven density and slight color loss.
(Triangle | delta): Density unevenness and color omission are seen a little, and it is a grade which is worrisome to use.
X: Density unevenness and color loss are observed and cannot be used.
The density unevenness means that the image is not uniform, and the color loss means that the toner is not supplied to the place where the image exists.

Example 2
(E) A toner supply roller was prepared in the same manner as in Example 1 except that 1 part by weight of “SZ1336” was used as the silicone foam stabilizer. Image evaluation was performed in the same manner as in Example 1 using the obtained toner supply roller, and the results are shown in Table 1.

Example 3
(B) A toner supply roller was prepared in the same manner as in Example 1 except that 50 parts by weight of “EP553” and 50 parts by weight of “GP3000” were used as the polyol. Image evaluation was performed in the same manner as in Example 1 using the obtained toner supply roller, and the results are shown in Table 1.

Example 4
(A) A toner supply roller was prepared in the same manner as in Example 1 except that 100 parts by mass of “MF50” was used as the polyol. Image evaluation was performed in the same manner as in Example 1 using the obtained toner supply roller, and the results are shown in Table 1.

Example 5
(A) A toner supply roller was prepared in the same manner as in Example 1 except that 100 parts by weight of “7012” was used as the polyol. Image evaluation was performed in the same manner as in Example 1 using the obtained toner supply roller, and the results are shown in Table 1.

Example 6
(B) A toner supply roller was prepared in the same manner as in Example 1 except that the amount of polyisocyanate “TM50” used was NCO index 80. Image evaluation was performed in the same manner as in Example 1 using the obtained toner supply roller, and the results are shown in Table 1.

  (B) A toner supply roller was prepared in the same manner as in Example 1 except that the amount of polyisocyanate “TM50” used was NCO index 90. Image evaluation was performed in the same manner as in Example 1 using the obtained toner supply roller, and the results are shown in Table 1.

  (B) A toner supply roller was prepared in the same manner as in Example 1 except that the amount of polyisocyanate “TM50” used was NCO index 120. Image evaluation was performed in the same manner as in Example 1 using the obtained toner supply roller, and the results are shown in Table 1.

Example 9
(B) A toner supply roller was prepared in the same manner as in Example 1 except that the amount of polyisocyanate “TM50” used was NCO index 125. Image evaluation was performed in the same manner as in Example 1 using the obtained toner supply roller, and the results are shown in Table 1.

Example 10
(B) A toner supply roller was prepared in the same manner as in Example 1 except that “T80” was used as the polyisocyanate in an amount to give an NCO index of 100. Image evaluation was performed in the same manner as in Example 1 using the obtained toner supply roller, and the results are shown in Table 1.

Example 11
(E) A toner supply roller was prepared in the same manner as in Example 1 except that the amount of the silicone foam stabilizer “L3640” used was 0.1 part by mass. Image evaluation was performed in the same manner as in Example 1 using the obtained toner supply roller, and the results are shown in Table 1.

Example 12
(E) A toner supply roller was prepared in the same manner as in Example 1 except that the amount of the silicone foam stabilizer “L3640” used was 5.0 parts by mass. Image evaluation was performed in the same manner as in Example 1 using the obtained toner supply roller, and the results are shown in Table 1.

Comparative Example 1
(E) A toner supply roller was prepared in the same manner as in Example 1 except that the amount of the silicone foam stabilizer “L3640” used was 0.05 part by mass. Image evaluation was performed in the same manner as in Example 1 using the obtained toner supply roller, and the results are shown in Table 1.

Comparative Example 2
(E) A toner supply roller was prepared in the same manner as in Example 1 except that the amount of the silicone foam stabilizer “L3640” used was 6 parts by mass. Image evaluation was performed in the same manner as in Example 1 using the obtained toner supply roller, and the results are shown in Table 1.

Comparative Example 3
(E) A toner supply roller was prepared in the same manner as in Example 1 except that 1 part by mass of “Y10184” was used as the silicone foam stabilizer. Image evaluation was performed in the same manner as in Example 1 using the obtained toner supply roller, and the results are shown in Table 1.

  As can be seen from Table 1, the toner supply roller of the present invention (Examples 1 to 12) is excellent in image evaluation. On the other hand, in Comparative Example 1 that deviates from the present invention, cell roughness was observed on the foam surface, and density unevenness was observed due to the influence thereof. Further, in Comparative Examples 2 and 3, the bleeding derived from the foam stabilizer exerted an adverse effect on other members used in the image forming apparatus, and the image evaluation deteriorated.

Claims (4)

A toner supply roller having a cored bar and at least one polyurethane foam layer formed on the cored bar,
The polyurethane foam layer is formed from a raw material composition containing at least (A) polyol, (B) polyisocyanate, (C) blowing agent, (D) catalyst, and (E) silicone foam stabilizer,
In the raw material composition, the content of (E) silicone foam stabilizer is 0.1 to 5.0 parts by mass with respect to 100 parts by mass of (A) polyol, and
The toner supply roller according to (E), wherein the silicone foam stabilizer has a mass reduction rate of 1.0% by mass or less by heating at 100 ° C. for 30 minutes.   2. The toner supply roller according to claim 1, wherein a mass reduction rate of the (E) silicone foam stabilizer after heating at 100 ° C. for 30 minutes is 0.6% by mass or less. The (A) polyol includes a polyether polyol having at least a weight average molecular weight (Mw) of 2,000 to 10,000 and containing 5 mol% or more of ethylene oxide at the end,
The toner supply roller according to claim 1, wherein the (B) polyisocyanate contains at least diphenylmethane diisocyanate (MDI) or a derivative thereof.   4. The toner supply roller according to claim 1, wherein the raw material composition has an NCO index of 90 to 120. 5.