JP2005307030A - Polyurethane foam roller and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a polyurethane foam roller high in liquid fluidity with slow initial reaction, and excellent in compression set properties under high-temperature and high-humidity circumstances. <P>SOLUTION: The polyurethane foam roller provided with at least one polyurethane layer is obtained by injecting into a mold a mixed liquid of a polyisocyanate, a polyol, water and a catalyst followed by expansion molding in the mold; wherein the catalyst contains one or more kinds of compound of the chemical formula:K<SP>+</SP>-RCOO<SP>-</SP>[ wherein, R is C<SB>n</SB>H<SB>2n+1</SB>( n is an integer of ≥1 )]. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polyurethane foam roller, an image forming apparatus component using the same, and an image forming apparatus. More specifically, the present invention relates to a polyurethane foam roller suitable for use in an electrophotographic process having excellent characteristics, an image forming apparatus component using the roller, a charging component, a developing component, and a toner supply component. The present invention relates to an image forming apparatus mounted as a component, a transfer component, or a cleaning component.

  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, and is used in the form of a roller 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 rollers can be manufactured in a mold. For example, a toner supply roller is manufactured by the following method.

  First, polyisocyanate, polyol, water, and a catalyst are mixed and stirred and injected into a toner supply roller molding die. A toner supply roller can be manufactured by foaming this in a mold and then removing the molded product (for example, Patent Document 1).

Examples of general polyurethane foam catalysts used here include amine catalysts and organometallic catalysts. With amine catalysts (including delayed amine catalysts such as carboxylates and borates) and organometallic catalysts, the initial reaction of polyurethane becomes faster and the viscosity of the mixture increases as the amount of the catalyst increases. For this reason, the liquid does not spread uniformly in the mold and the number of defective moldings increases, and the polyurethane may solidify in the mixing chamber. In order to prevent such an undesirable increase in viscosity, 1,8-diazabicyclo (5,4,0) undecene-7 (DBU) and 1,5-diazabicyclo (4,3,0) nonene-5 (DBN) ), A thermosensitive (retarding) catalyst composed of an organic acid salt and an organometallic catalyst having a high resinification activity or F22 (manufactured by Tosoh) have been used in combination (for example, Patent Document 2).
JP-A-9-274373 JP-A-9-327865

  However, when an organic acid salt of 1,8-diazabicyclo (5.4.0) undecene-7 (DBU) or 1,5-diazabicyclo (4,3,0) nonene-5 (DBN) is used, molding is performed. It remains in the later polyurethane foam and accelerates the deterioration reaction of the polyurethane. In particular, the deterioration reaction in a high temperature and high humidity environment was remarkable, and the compression set characteristics in a high temperature and high humidity environment tended to deteriorate.

  The present invention has been made in view of such circumstances, and an object thereof is to provide a polyurethane foam roller having a low initial reaction, excellent liquid flowability, and excellent compression set characteristics in a high temperature and high humidity environment. It is to be.

In order to solve the above-described problems and achieve the object, the polyurethane foam roller according to the present invention injects a mixed solution of polyisocyanate, polyol, water, and catalyst into a mold, and foams in the mold. A polyurethane foam roller comprising at least one or more polyurethane layers produced by molding,
The catalyst is
K ⁺ -RCOO ^-
_{Where, R: -C n H 2n +} 1 (n is an integer of 1 or more)
It contains at least one compound represented by the chemical formula:

  The polyurethane foam roller according to the present invention is characterized in that the catalyst is mixed in an amount of 0.02 to 1 part by mass with respect to the total polyol.

  In the polyurethane foam roller according to the present invention, a polyol containing at least one polyoxyalkylene polyol is used as the polyol.

  In the polyurethane foam roller according to the present invention, the polyol has a molecular weight of 2,000 to 10,000.

  In the polyurethane foam roller according to the present invention, the polyol has 2 to 4 functional groups.

  The polyurethane foam roller according to the present invention is characterized in that diphenylmethane diisocyanate and / or a derivative thereof, toluene diisocyanate and / or a derivative thereof is used alone or in combination as the polyisocyanate.

  In the polyurethane foam roller according to the present invention, the polyisocyanate contains 10 to 50% of isocyanate groups.

  In the polyurethane foam roller according to the present invention, the number of functional groups of the polyisocyanate is 2 or more.

Further, the polyurethane foam roller according to the present invention is produced by injecting a mixed liquid of polyisocyanate, polyol, water and catalyst into a mold and foaming and molding in the mold. A polyurethane foam roller having the above polyurethane layer,
K ⁺ -RCOO ^-
_{Where, R: -C n H 2n +} 1 (n is an integer of 1 or more)
One or more compounds represented by the chemical formula are contained in the polyurethane layer.

Also, the method for producing a polyurethane foam roller according to the present invention includes at least 1 by injecting a mixture of polyisocyanate, polyol, water, and catalyst into a mold, and foaming and molding the mold. A method for producing a polyurethane foam roller comprising more than one polyurethane layer,
In the catalyst,
K ⁺ -RCOO ^-
_{Where, R: -C n H 2n +} 1 (n is an integer of 1 or more)
One or more compounds represented by the chemical formula are contained.

  In the method for producing a polyurethane foam roller according to the present invention, the catalyst is mixed in an amount of 0.02 to 1 part by mass with respect to the total polyol.

  In the method for producing a polyurethane foam roller according to the present invention, a polyol containing at least one polyoxyalkylene polyol is used as the polyol.

  In the method for producing a polyurethane foam roller according to the present invention, the polyol has a molecular weight of 2000 to 10,000.

  In the method for producing a polyurethane foam roller according to the present invention, the polyol has 2 to 4 functional groups.

  In the method for producing a polyurethane foam roller according to the present invention, diphenylmethane diisocyanate and / or a derivative thereof, toluene diisocyanate and / or a derivative thereof is used alone or in combination as the polyisocyanate. .

  In the method for producing a polyurethane foam roller according to the present invention, the polyisocyanate contains 10 to 50% of isocyanate groups.

  In the method for producing a polyurethane foam roller according to the present invention, the polyisocyanate has two or more functional groups.

  According to the present invention, it is possible to provide a polyurethane foam roller having a slow initial reaction and excellent liquid flowability and excellent compression set characteristics in a high temperature and high humidity environment.

  A preferred embodiment of the present invention will be described below with reference to the drawings.

  In the present embodiment, as shown in FIG. 1, a case where a polyurethane foam roller 3 is manufactured by forming a polyurethane foam layer 3 around a metal core portion 2 will be described as an example.

  First, the molding die for the polyurethane foam roller used in the present embodiment may be any molding die conventionally used for molding a polyurethane foam roller.

  Next, in this embodiment, the mixture poured into the molding die for the polyurethane foam roller contains polyisocyanate, polyol, water, and catalyst.

  The polyisocyanate is not particularly limited, and can be appropriately selected from conventionally known various polyisocyanates. Examples of this polyisocyanate include aromatic polyisocyanates and derivatives thereof such as toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and multimeric mixtures thereof, and aliphatic polyisocyanates and derivatives thereof such as hexamethylene diisocyanate (HMDI). And cycloaliphatic polyisocyanates such as isophorone diisocyanate (IPDI) and derivatives thereof.

  Examples of the derivatives include 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, and burettes. Examples include modified products.

  Among these polyisocyanates, by using aromatic polyisocyanates such as toluene diisocyanate and diphenylmethane diisocyanate and derivatives thereof, it is possible to reduce the hardness of the member and improve the durability in a high temperature and high humidity environment.

  Examples of the polyol include polyethylene adipate (PEA), polybutylene adipate (PBA), polyhexylene adipate (PHA), a copolymer of ethylene adipate and butylene adipate, dimer acid polyol, castor oil polyol, polycaprolactone Examples thereof include polyester polyols such as polyols and polyether polyols such as polyoxyalkylene glycols. These polyols are preferably used alone or mixed to adjust the molecular weight to 2000 to 10,000.

  That is, when the molecular weight is less than 2,000, the crosslinking density is insufficient, so that the physical properties of the resulting polyurethane foam tend to be lowered. On the other hand, if it exceeds 10,000, the polyol is thickened and workability is lowered. Of the polyols, the use of polyether polyol is preferable for producing a highly elastic polyurethane foam excellent in durability under a high temperature and high humidity environment. Furthermore, it is preferable to use a polyether polyol containing 5 mol% or more of ethylene oxide because of good moldability. Further, it may be used in advance as a modified urethane with isocyanate or the like.

  At least a part of the polyether polyol can be replaced with a commonly known polymer polyol (trade name: manufactured by Mitsui Takeda Chemical Co., Ltd.) modified by polymerization of an ethylenically unsaturated monomer in the polyether polyol. By using a part of the polymer polyol in combination, it is possible to improve air permeability and hardness without reducing the durability of the polyurethane foam in a high temperature and high humidity environment.

  The ethylenically unsaturated monomer is not particularly limited, and examples thereof include acrylonitrile, styrene, methyl methacrylate, vinylidene chloride, and these polymers are usually dispersed in the form of fine particles having a diameter of 0.1 to 10 μm.

  The value obtained by dividing the total number of isocyanate groups in the polyisocyanate by the total number of active hydrogens that react with hydroxyl groups such as polyols, cross-linking agents, water, and isocyanate groups such as amino groups is defined as the NCO index. That is, when the number of active hydrogens reacting with an isocyanate group and the isocyanate group in the polyisocyanate are stoichiometrically equal, the NCO index is 100. The NCO index in the present embodiment is 60 to 120, preferably 80 to 100.

  Water reacts with the polyisocyanate to generate carbon dioxide gas. The amount usually used is 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyol. The part by weight of polyol referred to here is a converted value, and even when the amount used is less than 100 parts by weight or exceeds 100 parts by weight, the amount of polyol in the entire material is 100 parts by weight (regardless of urethanization in advance). It is to be converted into parts.

  As necessary foam stabilizers, water-soluble polyether siloxane from polydimethylsiloxane and EO / PO copolymer, sodium salt of sulfonated ricinoleic acid, and these with polysiloxane / polyoxyalkylene copolymer And the like. Among these, water-soluble polyether siloxane is preferable as the polyether polyol-based foam stabilizer. Hot mold foams tend to gel faster than slab foams and are overpacked with molds, so the breathability of the foam tends to be low. For this reason, a foam stabilizer that is basically similar to that for slabs but has a slightly weak foam regulating ability and high air permeability is selected. In addition, because high-elastic foam has high system viscosity and high reactivity, if a normal foam stabilizer is used, foam stabilization becomes excessive, and the degree of communication decreases and foam shrinkage occurs. Produce. For this purpose, low molecular weight copolymers are used. What added the organic functional group instead of the polyether chain | strand may be used.

  As other additives, a crosslinking agent, a flame retardant, a colorant, an anti-aging agent, an antioxidant and the like can be used as necessary.

  Furthermore, in this embodiment, the catalyst used with the said polyisocyanate, a polyol, and water contains at least 1 or more types of compounds represented by following Chemical formula (1). In addition, although the detail of the following organic acid potassium is unknown, it turned out that it is excellent in temperature sensitivity and the activity at high temperature is high.

K ⁺ -RCOO ^- ... (1)
Here, R is -C _n H _{2n + 1} (n is an integer of 1 or more)
That is, organic acid potassium is an amine catalyst (triethylenediamine, bis (dimethylaminoethyl) ether, N, N, N ′, N′-tetramethylhexanediamine, 1,2-dimethylimidazole, N-ethylmorpholine, N -Methylmorpholine, etc.) and organometallic catalysts (tin octylate, tin oleate, dibutyltin dilaurate, dibutyltin diacetate, tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy)) Titanium, etc.) has higher temperature sensitivity than conventional general-purpose catalysts, so when used as a catalyst for foaming reaction by mixing polyisocyanate and polyol, it is almost active until the liquid temperature after mixing reaches a predetermined temperature. The initial reaction of the liquid can be suppressed and the initial viscosity can be kept low. Having the characteristics say. Therefore, the initial reaction is slow, the liquid injection operation is good, and there is no occurrence of defective products such as polyurethane residue and air accumulation. Moreover, since the said organic acid potassium has high activity compared with the conventional general purpose catalyst, when it reaches predetermined temperature, the foaming reaction from that time will advance faster than before. Therefore, the molding time after casting can be greatly shortened.

  Further, a temperature sensitivity comprising a conventionally known organic acid salt of 1,8-diazabicyclo (5,4,0) undecene-7 (DBU) or 1,5-diazabicyclo (4,3,0) nonene-5 (DBN). Unlike a reactive (retarding) catalyst, even if the reaction is completed and remains in the foam, the polyurethane deterioration reaction is not promoted. Therefore, the compression set characteristics in a high temperature and high humidity environment are good.

  Examples of the potassium organic acid include commercially available product names DABCO P15 (manufactured by Nippon Emulsifier Co., Ltd.), DABCO K15 (manufactured by Nippon Emulsifier Co., Ltd.), and the like, and are usually used in the same manner as general-purpose catalysts. . The DABCO P15 is represented by the following chemical formula (2). The DABCO K15 is represented by the following chemical formula (3).

K ⁺ —CH ₃ COO ⁻ (2)
_{^{K + -C 7 H 15 COO -}} ... (3)
And it is suitable for the compounding quantity of the said organic acid potassium to set to 0.02-1 mass part with respect to all the polyols. That is, at 0.02 parts by mass or less, the foaming reaction promoting effect is low, and it takes time to complete the foaming reaction, and the effect of improving the production efficiency cannot be expected so much. This is because there is a possibility that a flow failure may occur at the time of injection into the mold.

  In the present embodiment, as the catalyst for promoting the foaming reaction, a conventionally known general-purpose catalyst (the amine catalyst or organometallic catalyst) may be used in combination with the organic acid potassium. In this case, the total amount of the organic acid potassium and the general-purpose catalyst is preferably set to 0.02 to 1 part by mass with respect to the total polyol as in the case of using only the organic acid potassium.

  In this embodiment, a polyurethane foam roller is manufactured as follows, for example.

  First, in accordance with a conventionally known method, a rod-shaped metal core is placed in a predetermined polyurethane foam roller mold. On the other hand, a composition for a polyurethane foam roller is prepared by mixing polyisocyanate, polyol, water and the specific catalyst. And the said composition is inject | poured into the said shaping | molding die, a shaping | molding die is heated at the temperature of 25-80 degreeC, and foam molding is carried out. In some cases, the reaction may be promoted in a heating furnace having a temperature of 80 to 250 ° C. And a polyurethane foam roller can be obtained by taking out a molding from a shaping | molding die.

  According to this production method, since the composition contains the catalyst (potassium organic acid), the initial reaction is slow, and the injection work into the mold is easy, and defective products due to insufficient flow do not occur. And since the foaming reaction proceeds rapidly after the liquid reaches the predetermined temperature, the time from casting to demolding can be as short as 20 minutes or less, and the production efficiency can be improved by shortening the molding cycle. Can be realized.

  In this embodiment, since the temperature sensitivity of the catalyst is very strong, variations in stirring efficiency and the like are unlikely to occur as in conventional general-purpose catalysts, and the reactivity can be easily controlled by the raw material temperature and the mold temperature. It is.

(Example)
Hereinafter, specific examples of the present embodiment will be described, but the present invention is not limited to these examples. In addition, the part and% in an Example represent a mass part and mass%, respectively.

First, the polyisocyanate, polyol, water, catalyst, and other auxiliaries having the compositions shown in FIGS. 4 and 5 were adjusted to a liquid temperature of 25 ° C. These liquids were blended so that the NCO index was 100, stirred for 5 seconds in the mixing chamber, and then poured into a free foaming confirmation mold temperature-controlled at 50 ° C., and the change in foam height was measured. . As a measure of the initial reaction, the time when the foaming height starts to rise from the start of mixing is shown as “Cream Time” and is shown in FIGS. Also, each of the above compositions was poured into a polyurethane foam roll molding mold adjusted to 50 ° C. to produce a polyurethane foam roller having a density of 0.10 g / cm ^3. The fluidity of was evaluated. The results are also shown in FIGS.

In addition, 1) -18 in FIG.4 and FIG.5 represents the following contents.
1) Polyether polyol manufactured by Mitsui Takeda Chemical Co., Ltd. (OH value = 28 mg KOH / g)
2) Polymer polyol manufactured by Mitsui Takeda Chemical Co., Ltd. (OH value = 28 mgKOH / g)
3) Nippon Unicar Co., Ltd. silicone foam stabilizer 4) Kishida Chemical Co., Ltd. diethanolamine (special grade)
5) Polyisocyanate manufactured by Mitsui Takeda Chemical Co., Ltd. (NCO = 45%)
6) Polyisocyanate manufactured by Mitsui Takeda Chemical Co., Ltd. (NCO = 40%)
7) Tosoh Co., Ltd. Amine Catalyst 8) Nippon Emulsifier Co., Ltd. Amine Catalyst 9) Nippon Emulsifier Co., Ltd. Organic Acid Potassium Catalyst (potassium acetate)
10) Organic acid potassium catalyst (potassium octylate) manufactured by Nippon Emulsifier Co., Ltd.
11) Total amount of catalyst used: part by mass 12) Time when foaming height starts to rise from the start of mixing 13) ○: Good, Δ: Partially defective, X: Bad (non-uniform)
14) Time required from casting to demolding 15) As shown in FIGS. 2 (a) and 2 (b), the polyurethane foam roller 1 is supported by the support portions 4 at the cored bar portions 2 at both ends thereof. When the polyurethane foam layer 3 is pressed at a speed of 10 mm / min with a jig 10 having a plate-like pressing surface having a width of 10 mm, a length of 50 mm, and a thickness of 10 mm, a 1 mm displacement (compression) is obtained. The hardness of the molded product is expressed by the load (g). The larger the value, the higher the hardness of the polyurethane foam layer, that is, the harder it is. Further, the measurement points are average values obtained by measuring four locations every 90 degrees in the circumferential direction, as shown in FIG. The hardness is preferably 350 g or less.
16) As shown in FIG. 3 (a) and FIG. 3 (b), the polyurethane foam roller 1 is supported by the support portions 7 at the cored bar portions 2 at both ends thereof, and the polyurethane foam layer 3 has a diameter of 16 mm. With the sleeve 6 displaced (compressed) by 1.5 mm, the sleeve 6 is left for 72 hours under a temperature of 50 ° C. and a humidity of 95%, and after 30 minutes have elapsed after the release and release (the recess indicated by 8 in FIG. 3B). Representing the degree of restoration (JIS K 6202: CS = (t0-t1) /1.5×100, CS: compression set (%), t0: radius of original molded product (mm), t1: test The radius (mm) of the later molded product. The compression set in a high temperature and high humidity environment is preferably 15% or less. ○: 15% or less, ×: more than 15% 17) Comprehensive evaluation of moldability and compression set under high-temperature and high-humidity environment, both excellent: ○, one having a defect: ×
18) Nippon Emulsifier Co., Ltd. Amine Catalyst: Octylate of 1,8-diazabicyclo (5,4,0) undecene-7 (DBU) As described above, in this embodiment, the polyurethane foam roller is In the production, since an organic acid potassium that has not been conventionally used is used as a catalyst to be contained in the composition, the initial reaction is slow, the liquid flowability is good, and a defective product does not occur. Further, when the composition reaches a predetermined temperature, the curing reaction proceeds rapidly from that point, so that the molding time after casting is short, and the production efficiency can be greatly improved.

  Furthermore, when the organic acid potassium is used alone or in combination with another catalyst, when the amount of the catalyst is set to 0.02 to 1 part by mass with respect to the total polyol, a particularly excellent production efficiency improvement effect is obtained. I can do it.

  Moreover, the temperature sensitivity which consists of a conventionally well-known organic acid salt of 1,8-diazabicyclo (5,4,0) undecene-7 (DBU) or 1,5-diazabicyclo (4,3,0) nonene-5 (DBN). Unlike a reactive (retarding) catalyst, even if the reaction is completed and remains in the foam, the polyurethane deterioration reaction is not promoted. Therefore, the compression set characteristics in a high temperature and high humidity environment are good.

  Therefore, it is possible to provide a polyurethane foam roller having a low initial reaction and excellent liquid flow property and no defective product, and a polyurethane foam roller excellent in compression set under a high temperature and high humidity environment.

It is a perspective view which shows the polyurethane foam roller of one Embodiment of this invention. It is explanatory drawing which shows the measuring method of the hardness of a polyurethane foam roller (polyurethane foam layer), Comprising: (a) is plane explanatory drawing, (b) is side explanatory drawing. It is explanatory drawing which shows the measuring method of the compression set in the high temperature, high humidity environment of a polyurethane foam roller (polyurethane foam layer), Comprising: (a) is plane explanatory drawing, (b) is side explanatory drawing. It is a figure which shows the evaluation result of the polyurethane foam roller of the Example of this invention. It is a figure which shows the evaluation result of the polyurethane foam roller of a comparative example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Skin layer 2 Core metal part 3 Polyurethane foam layer 4 Core metal support part 6 Sleeve ((phi) 16mm)
7 Compression permanent jig (Installation of cored bar by inter-axis regulation)
8 Foam dent after release

Claims (17)

A polyurethane foam roller comprising at least one polyurethane layer produced by pouring a mixture of polyisocyanate, polyol, water, and catalyst into a mold and foaming and molding in the mold. And
The catalyst is
K ⁺ -RCOO ^-
_{Where, R: -C n H 2n +} 1 (n is an integer of 1 or more)
A polyurethane foam roller comprising at least one compound represented by the chemical formula:   The polyurethane foam roller according to claim 1, wherein 0.02 to 1 parts by mass of the catalyst is mixed with respect to the total polyol.   The polyurethane foam roller according to claim 1 or 2, wherein a polyol containing at least one polyoxyalkylene polyol is used as the polyol.   The polyurethane foam roller according to any one of claims 1 to 3, wherein the polyol has a molecular weight of 2,000 to 10,000.   The polyurethane foam roller according to any one of claims 1 to 4, wherein the polyol has 2 to 4 functional groups.   3. The polyurethane foam roller according to claim 1, wherein diphenylmethane diisocyanate and / or a derivative thereof, toluene diisocyanate and / or a derivative thereof is used alone or in combination with the polyisocyanate.   The polyurethane foam roller according to any one of claims 1, 2, and 6, wherein the polyisocyanate contains 10 to 50% of an isocyanate group.   The polyurethane foam roller according to any one of claims 1, 2, 6, and 7, wherein the number of functional groups of the polyisocyanate is 2 or more. A polyurethane foam roller comprising at least one polyurethane layer produced by pouring a mixture of polyisocyanate, polyol, water, and catalyst into a mold and foaming and molding in the mold. And
K ⁺ -RCOO ^-
_{Where, R: -C n H 2n +} 1 (n is an integer of 1 or more)
A polyurethane foam roller, wherein the polyurethane layer contains at least one compound represented by the chemical formula: A method for producing a polyurethane foam roller having at least one polyurethane layer by injecting a mixed liquid of polyisocyanate, polyol, water and catalyst into a mold and foaming and molding in the mold Because
In the catalyst,
K ⁺ -RCOO ^-
_{Where, R: -C n H 2n +} 1 (n is an integer of 1 or more)
A process for producing a polyurethane foam roller, comprising one or more compounds represented by the chemical formula:   The method for producing a polyurethane foam roller according to claim 10, wherein the catalyst is mixed in an amount of 0.02 to 1 part by mass with respect to the total polyol.   The method for producing a polyurethane foam roller according to claim 10 or 11, wherein a polyol containing at least one polyoxyalkylene polyol is used as the polyol.   The method for producing a polyurethane foam roller according to any one of claims 10 to 12, wherein the polyol has a molecular weight of 2,000 to 10,000.   The method for producing a polyurethane foam roller according to any one of claims 10 to 13, wherein the number of functional groups of the polyol is 2 to 4.   12. The method for producing a polyurethane foam roller according to claim 10, wherein diphenylmethane diisocyanate and / or a derivative thereof, toluene diisocyanate and / or a derivative thereof is used alone or in combination with the polyisocyanate. .   The method for producing a polyurethane foam roller according to any one of claims 10, 11, and 15, wherein the polyisocyanate contains 10 to 50% of an isocyanate group.   The method for producing a polyurethane foam roller according to any one of claims 10, 11, 15, and 16, wherein the number of functional groups of the polyisocyanate is 2 or more.

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