JP6389922B1 - Resin roll for calendering - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a calendering resin roll having an appropriate surface layer hardness and high durability. A resin roll for calendering comprising a cored bar and a surface layer containing a urethane resin disposed on the outer periphery of the cored bar, wherein the urethane resin is a urethane having dicyclohexylmethane diisocyanate groups at both ends. A resin roll for calendering, which is a polymer of a prepolymer and a curing agent that is a diamine or a diol, and the Shore D hardness of the surface layer is 60 ° or more and 90 ° or less. [Selection] Figure 1

Description

  The present invention relates to a calendering resin roll.

  Generally, a calendar processing apparatus includes a metal roll having a heating mechanism and an elastic roll having an elastic layer as a surface layer. In the calendering apparatus, these rolls are brought into contact with each other substantially in parallel, and while applying temperature and pressure, the calendered material is passed through the gaps to impart smoothness and gloss to the surface of the calendered material.

  Currently, a resin roll covered with a surface layer made of urea resin is used as an elastic roll (Patent Document 1). Since the surface layer of such a resin roll has an appropriate hardness, the surface of the woven or non-woven fabric is calendered using the resin roll to give the surface an appropriate glossiness that gives a soft texture. Can do.

JP-A-8-41796

  In general, a resin roll is obtained by installing a cored bar in a casting mold, injecting a liquid resin in which a main agent and a curing agent are mixed into the casting mold, and thermosetting the resin. .

  However, in the case of a high hardness urea resin or urethane resin, since the pot life is short, the curing proceeds while the liquid resin is injected into the casting mold. If the curing progresses during the injection of the liquid resin, a large number of pinholes and flow pattern defects may occur on the outer peripheral surface of the surface layer. Defects in the surface layer of the resin roll may be transferred to the surface of the calendar material during use, and it is necessary to polish and remove it before use, thereby reducing the service life of the resin roll.

  An object of the embodiment is to provide a calendering resin roll having an appropriate surface layer hardness and high durability.

  In order to solve the above problems, the present invention is a resin roll for calendering comprising a cored bar and a surface layer containing a urethane resin disposed on the outer periphery of the cored bar, wherein the urethane resin is disposed at both ends. A calendar comprising a urethane prepolymer having a dicyclohexylmethane diisocyanate (HMDI) group and a curing agent comprising a diamine or a diol, and the surface layer has a Shore D hardness of 60 ° to 90 °. A resin roll for processing is provided.

It is sectional drawing which shows an example of the resin roll for calendar processing which concerns on embodiment. It is sectional drawing which shows the other example of the resin roll for calendar processing which concerns on embodiment. It is the schematic which shows an example of the calendar processing apparatus which uses the resin roll for calendar processing which concerns on embodiment.

  Hereinafter, the resin roll for calendar processing which concerns on embodiment is demonstrated in detail.

  The calendering resin roll is used for calendering a calendared material. Examples of the material to be calendered include paper, woven fabric or nonwoven fabric made of natural fibers, or woven fabric or nonwoven fabric made of synthetic fibers.

  When the calendering resin roll according to the embodiment is calendered by applying it to a woven or non-woven fabric made of natural fibers or synthetic fibers, it can give a soft texture to the surface.

  In addition, since the calendering resin roll according to the embodiment has high heat resistance, when applied to a woven or nonwoven fabric made of synthetic fibers such as polyester and nylon and calendered at a high temperature, the synthetic fibers are melted. The air permeability can be reduced and the water pressure resistance can be improved.

  The resin roll for calendering includes a cored bar and a surface layer disposed on the outer periphery of the cored bar. The core bar and the surface will be described in detail below.

(1) Core metal The core metal is not particularly limited as long as it is a material having sufficient strength to withstand high temperature and continuous pressurization during calendering. For example, carbon steel pipe for machine structure (STKM), stainless steel Alternatively, aluminum can be used.

(2) Surface layer The surface layer is composed of a polymer (urethane resin) of a urethane prepolymer (A) having dicyclohexylmethane diisocyanate groups at both ends and a curing agent (B) made of diamine or diol. When the curing agent is a diamine, the urethane prepolymer and the diamine are polycondensed by a urea bond. When the curing agent is a diol, the urethane prepolymer and the diol are polycondensed by a urethane bond.

<Urethane prepolymer (A)>
The urethane prepolymer (A) has dicyclohexylmethane diisocyanate (HMDI) groups (following formula (a1)) at both ends.

The urethane prepolymer (A) preferably has a polyether diol skeleton (a2-1) or a polycarbonate diol skeleton (a2-2). The urethane prepolymer is a kind of diisocyanate because it has HMDI groups at both ends. The urethane prepolymer (A) is represented by the structural formulas of the following formulas (A1) and (A2), for example.

  The urethane prepolymer (A1) having a polyether diol skeleton (a2-1) has a structure in which two hydroxyl groups of polyether diol and two isocyanate groups of HMDI are reacted to form a urethane bond.

R ₁ in the polyether diol skeleton (a2-1) is, for example, a linear, branched or alicyclic hydrocarbon having 2 to 15 carbon atoms, a linear or branched chain having 2 to 15 carbon atoms, Alternatively, it is an alicyclic ether or an aromatic ring-containing hydrocarbon having 8 to 20 carbon atoms. R ₁ may be one type or two or more types. Specifically, the polyether diol constituting the polyether diol skeleton (a2-1) includes an alkylene oxide adduct of a dihydric alcohol having 2 to 20 carbon atoms.

  Examples of the dihydric alcohol having 2 to 20 carbon atoms include aliphatic diols having 2 to 15 carbon atoms [ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6 Linear alcohols such as hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol or diethylene glycol; 1,2-, 1,3- or 2 , 3-butanediol, 2-methyl-1,4-butanediol, neopentyl glycol, 2,2-butylethyl-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-1,5 -Pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,6-hexanediol, 3-methyl-1 6-hexanediol, 2-methyl-1,7-heptanediol, 3-methyl-1,7-heptanediol, 4-methyl-1,7-heptanediol, 2-methyl-1,8-octanediol, 3 -Branched alcohol such as methyl-1,8-octanediol or 4-methyloctanediol]; alicyclic dihydric alcohol having 6 to 15 carbon atoms [1,4-cyclohexanediol, 1,4-bis (hydroxymethyl)] Cyclohexane or 2,2-bis (4-hydroxycyclohexyl) propane, etc.]; C8-20 aromatic ring-containing dihydric alcohol [m- or p-xylylene glycol, bis (hydroxyethyl) benzene, bis (hydroxyethoxy) ) Ethylene oxide adduct of benzene or bisphenol A, etc.]; A dihydric alcohol may be used independently or may use 2 or more types together.

  N of the polyether diol skeleton (a2-1) is, for example, an integer of 1 to 4.

  The urethane prepolymer (A2) having a polycarbonate diol skeleton (a2-2) has a structure in which two hydroxy groups of polycarbonate diol and two isocyanate groups of HMDI are reacted to form a urethane bond.

Examples of R ₂ and R ₃ in the polycarbonate diol skeleton (a2-2) include the same as R ₁ in the polyether diol skeleton (a2-1) described above. R ₂ and R ₃ may be the same or different. R ₂ and R ₃ may be one type or two or more types. Specifically, the polycarbonate diol constituting the polycarbonate diol skeleton (a2-2) has a structure in which a divalent alcohol is polymerized by a carbonate group. As the dihydric alcohol, the same ones as mentioned in the above-mentioned polyether diol skeleton (a2-1) can be used. As the polycarbonate diol constituting the polycarbonate diol skeleton (a2-2), for example, DURANOL (registered trademark) T5650E manufactured by Asahi Kasei Chemicals Corporation having a number average molecular weight of 500 can be used.

  N of the polycarbonate diol skeleton (a2-2) is, for example, an integer of 1 to 4.

  The isocyanate group content (NCO%) of the urethane prepolymer (A) is related to the Shore D hardness of the surface layer. As the NCO% of the urethane prepolymer increases, the shore D hardness of the surface layer increases because the number of crosslinking points in the urethane resin increases. NCO% is defined by the following equation.

Isocyanate group content (NCO%)
= (Formula weight of isocyanate group (—NCO) of urethane prepolymer) / (Molecular weight of urethane prepolymer) × 100
The NCO% of the urethane prepolymer is preferably 7% to 16%, more preferably 9% to 14%. If the NCO% of the urethane prepolymer is less than 7%, it will be difficult to increase the hardness of the surface layer. If the NCO% of the urethane prepolymer exceeds 16%, the hardness of the surface layer will be too high. It may be difficult to make the hardness range as follows. When the NCO% of the urethane prepolymer is 9% to 14%, when the woven fabric or the nonwoven fabric is calendered, it becomes easy to adjust the Shore D hardness suitable for giving a soft texture to the surface.

  NCO% can be measured by the test method described in JIS K 7301-1995. For example, NCO% is prepared by first dissolving a sample in dehydrated toluene and then adding an excess of di-normal butylamine solution to cause the reaction. Subsequently, the residual dinormal butylamine is back titrated with hydrochloric acid, and the inflection point of the titration curve is taken as the end point, and the end point can be calculated from the titration amount at that end point.

  The number average molecular weight of the urethane prepolymer is preferably 525 to 1150, more preferably 600 to 944. If the number average molecular weight of the urethane prepolymer is less than 525, the crosslinking point of the urethane resin increases, and the hardness of the surface layer may increase excessively. If the number average molecular weight of the urethane prepolymer exceeds 1150, the hardness of the surface layer is lowered, and it may be difficult to achieve the target hardness range.

<Curing agent (B)>
The curing agent (B) is a diamine or diol. The curing agent made of diamine is not particularly limited, and known ones can be used. For example, 4,4′-methylenebis (2-chloroaniline) (MOCA), diaminodiphenylmethane (MDA) and the like can be used. The curing agent made of diol is not particularly limited, and known ones can be used. For example, 1,4-butanediol or 1,2-propanediol can be used. When a curing agent that is a diamine is used, it is preferable to use a diamine because it tends to improve the heat resistance of the surface layer, reduce the dynamic heat generation, and hardly reduce the hardness even when used at high temperatures.

  The Shore D hardness of the surface layer is 60 ° or more and 90 ° or less. The appropriate range of the Shore D hardness of the surface layer varies depending on the type of calendar material to be calendered and its application.

  For example, when calendering a woven fabric or a nonwoven fabric, the Shore D hardness of the surface layer is suitably 60 ° to 90 °. The preferred Shore D hardness is 75 ° to 85 °. When the Shore D hardness of the surface layer is less than 60 °, the linear pressure on the calendar material is reduced during calendering, so that the calendar material is not properly crushed, and an appropriate gloss can be imparted to the surface. It becomes difficult. When the Shore D hardness of the surface layer exceeds 90 °, when calendering the calendered material, the linear pressure on the calendered material increases, so the calendered material may be crushed and the surface may become highly glossy. There is. When the Shore D hardness of the surface layer is 75 ° to 85 °, it is particularly suitable for giving a soft texture to the surface when calendering a woven fabric or a non-woven fabric.

  As an example only, Shore D of the surface layer when a urethane prepolymer having the structural formula of (A1) is cured using 4,4′-methylenebis (2-chloroaniline) (MOCA) as a curing agent. The hardness is 60 ° when the NCO% of the urethane prepolymer is 7%, 75 ° when the NCO% is 9%, 85 ° when the NCO% is 14%, and 90 ° when the NCO% is 16%. Thus, the Shore D hardness of the surface layer can be easily adjusted by adjusting the NCO% of the urethane prepolymer. The Shore D hardness of the surface layer varies depending on the structural formula of the urethane prepolymer, the type of the curing agent, the presence or absence of additives, the curing conditions, etc., in addition to the NCO% of the urethane prepolymer.

  The urethane resin constituting the surface layer may be one obtained by adding a diisocyanate different from the urethane prepolymer and curing. That is, the urethane resin constituting the surface layer may be a polymer of a urethane prepolymer, another diisocyanate, and a curing agent made of diamine or diol. Moreover, the urethane resin which comprises a surface layer may mix the polymer which consists of another diisocyanate and a hardening | curing agent with respect to the polymer which consists of a urethane prepolymer and a hardening | curing agent.

  Thus, by adding another diisocyanate in addition to the urethane prepolymer, the Shore D hardness and pot life of the surface layer can be adjusted. Another diisocyanate can be added up to 12% by weight or less based on the total amount of the urethane prepolymer and another diisocyanate. As an example, when adding another diisocyanate Mc115 (manufactured by Tosoh Corporation) to Samprene (registered trademark) P-870 (NCO%: 12%, manufactured by Sanyo Chemical Industries), which is a urethane prepolymer. , Up to 12% by weight based on the total amount thereof. If the amount of the additional diisocyanate exceeds 12% by weight, the pot life of the urethane resin is shortened, and thus there is a possibility that defects such as pinholes and flow patterns may occur on the surface layer.

  As another diisocyanate, diphenylmethane diisocyanate (MDI) system, toluene diisocyanate (TDI) system, dicyclohexylmethane diisocyanate (HMDI) system can be used. As the MDI-based diisocyanate, Millionate (registered trademark) MT (pure MDI) (manufactured by Hodogaya Chemical Co., Ltd.) and Millionate (registered trademark) MTL (modified MTL) (manufactured by Hodogaya Chemical Industry Co., Ltd.) can be used. As the TDI-based diisocyanate, Coronate (registered trademark) T-100 (2,4-TDI) (manufactured by Tosoh Corporation), Coronate (registered trademark) T-65 (2,4-TDI / 2,6-TDI = 65/35) can be used.

  The thickness of the surface layer is preferably 5 mm to 25 mm. If the thickness of the surface layer is less than 5 mm, the performance of calendering may be affected by the influence of the cored bar disposed below the surface layer. On the other hand, when the thickness of the surface rubber layer exceeds 25 mm, curing shrinkage when the urethane resin is cured increases, so that there is a possibility that a defect occurs in the adhesion of the end portion of the surface layer.

  The surface layer may contain various compounding agents such as pigments, plasticizers and fillers, and catalysts in addition to the urethane resin. As the catalyst, for example, adipic acid, N, N-dimethylethanolamine, or dibutyltin dilaurate is used.

  The surface layer has high heat resistance that can withstand up to 200 ° C. When the material to be calendared is paper, it preferably has a heat resistance of 90 ° C to 140 ° C. Moreover, when a calendar material is a woven fabric or a nonwoven fabric, it is preferable to have the heat resistance of 140 to 200 degreeC.

  The surface layer has a high pressure resistance that can withstand a linear pressure of 350 kg / cm. When the calendar material is paper, it is preferable to withstand a linear pressure of 100 kg / cm to 350 kg / cm. Further, when the calendar material is a woven fabric or a non-woven fabric, it is preferable to withstand a linear pressure of 150 kg / cm to 250 kg / cm.

  The surface layer has high wear resistance. When the material to be calendared is paper, the material to be calendared of about 260000 km is calendered for 6 months, and it is preferable that the wear of the surface layer is small during this period. In addition, when the calendar material is a woven fabric or a nonwoven fabric, the calendar material is calendered for about 3200 km in three months, and therefore it is preferable that the wear of the surface layer is small during this period.

  In addition, the surface layer can be configured by stacking one or two or more layers containing the above-described urethane resin. The desirable surface layer is composed of one layer of the specific urethane resin described above. The surface layer may contain additives in addition to the urethane resin. Examples of the additive include a vulcanizing agent, a vulcanization accelerator, an anti-aging agent, a reinforcing agent, a filler, a colorant, and a plasticizer.

(3) Filament winding layer (FW layer)
The calendering resin roll may further include a filament winding layer (FW layer) between the core metal and the surface layer. The FW layer is a layer obtained by impregnating a certain fiber with a resin and continuously winding the fiber on a roll and curing. The fiber used for the FW layer is not particularly limited as long as it has high mechanical strength. For example, glass fiber or carbon fiber is used. The resin used for the FW layer is not particularly limited as long as it is a thermosetting resin or a thermoplastic resin excellent in heat resistance and pressure resistance. For example, vinyl ester resin, epoxy resin, polyvinyl chloride, or polyethylene is used. .

  The thickness of the FW layer is preferably 2.5 mm to 15 mm, more preferably 2.5 mm to 10 mm. If the thickness of the FW layer is less than 2.5 mm, the cushioning property is reduced, which is not preferable. On the other hand, if the thickness of the FW layer exceeds 15 mm, the pressure resistance of the FW layer is reduced, and cracking is likely to occur during use.

  The calendering resin roll may further include an adhesive layer between the surface layer and the core metal, between the surface layer and the FW layer, or between the FW layer and the core metal. An adhesive layer is not specifically limited, A conventionally well-known adhesive agent can be used suitably.

  An example of the resin roll for calendar processing which concerns on embodiment is demonstrated with reference to FIG. A calendering resin roll 10 shown in FIG. 1 includes a cored bar 11 and a surface layer 12 containing a urethane resin laminated on the outer peripheral surface of the cored bar 11. The urethane resin is a polymer of a specific urethane prepolymer and a curing agent that is a diamine or a diol. The specific urethane prepolymer has, for example, dicyclohexylmethane diisocyanate (HMDI) groups at both ends of the polytetramethylene glycol skeleton, and the NCO% is 7% to 16%. The Shore D hardness of the surface layer 12 is 60 ° or more and 90 ° or less.

  In the calendering resin roll 10, since the surface layer 12 includes the urethane resin described above, the pot life is long, and the curing is difficult to proceed while being poured into a casting mold for a liquid resin. As a result, the calendering resin roll 10 is less prone to defects such as a large number of pinholes and flow patterns on the surface of the surface layer 12. Therefore, there is little possibility that the roll is cracked due to the pinhole, and there is less possibility that the flow pattern is transferred.

  In addition, the calendering resin roll 10 has higher heat resistance than a conventional urethane resin and hardly melts even at high temperatures. Therefore, by using a calendar material that is a woven or non-woven fabric made of synthetic fibers that require high heat resistance and calendering the calendar material, the air permeability can be reduced and the water pressure resistance can be improved. . Moreover, since the surface layer has an appropriate hardness, a soft texture can be imparted to the surface by calendering a woven fabric or a non-woven fabric.

  Therefore, according to the embodiment, a calendering resin roll having appropriate hardness, high heat resistance, and high durability can be provided.

  Another example of the calendering resin roll according to the embodiment will be described with reference to FIG. A calendering resin roll 20 shown in FIG. 2 includes a core bar 21, a filament winding (FW) layer 22 stacked on the outer peripheral surface of the core bar 21, and a surface layer stacked on the outer peripheral surface of the FW layer 22. 23. The FW layer 22 is formed by winding a roving, which is a glass fiber impregnated with, for example, a vinyl ester resin, which is a thermosetting resin, around the outer peripheral surface of the cored bar 21 and thermosetting it. The surface layer 23 is formed of, for example, the same material as that described with reference to FIG.

  The calendering resin roll 20 shown in FIG. 2 can obtain the same effects as the calendering resin roll 10 shown in FIG. In the calendering resin roll 20 shown in FIG. 2, the pressure resistance can be improved because the FW layer 22 serves as a cushion during use. In the calendering resin roll shown in FIG. 2, the thickness of the calendering resin roll can be easily adjusted by the FW layer 22.

  FIG. 3 is a schematic diagram illustrating an example of a calendar processing apparatus 100 for the calendar target material 40 using the calendar processing resin rolls 10a and 10b according to the embodiment. In this apparatus, two calendering resin rolls 10 a and 10 b are in contact with each other substantially in parallel with the metal roll 30 between the upper and lower sides of one metal roll 30. In this apparatus 100, the calendering resin roll 10a, the metal roll 30, and the calendering resin roll 10b are aligned in this order. The metal roll 30 has a heating mechanism and is heated to a temperature suitable for the calendar material 40. The calendar material 40 is conveyed in this order from the delivery roll 50a to the gap between the calendering resin roll 10a and the metal roll 30, and to the gap between the metal roll 30 and the calendering resin roll 10b, and is wound around the winding roll 50b. Taken. At this time, the calendar material 40 is heated by the heat from the metal roll 30 and continuously pressed by the linear pressure between the calendering resin rolls 10 a and 10 b and the metal roll 30. By this heating and pressurization, the calendar material 40 is calendered so as to have an appropriate thickness and an appropriate glossiness.

  The metal roll 30 is heated to a temperature suitable for the material of the calendar target material 40 and its use by a heating mechanism. When the calendar material 40 is paper, the surface temperature of the metal roll 30 is heated to 90 ° C to 140 ° C. When the calendar material 40 is a woven fabric or a non-woven fabric, the surface temperature of the metal roll 30 is heated to 140 ° C to 200 ° C.

  The conveyance speed of the calendar material 40 is adjusted to a speed suitable for the material of the calendar material 40. When the calendar material 40 is paper, for example, the conveyance speed is adjusted to be 1000 m / min. When the calendar material 40 is a woven fabric or a non-woven fabric, for example, the conveyance speed is adjusted to 25 m / min.

  The calendering resin rolls 10a and 10b are preferably subjected to internal cooling and / or surface cooling during operation in which heat accumulation increases. Although it does not specify as a cooling means, it can carry out by passing liquid media, such as cooling water, inside as an example. Moreover, as a method of surface cooling, it can carry out by making it contact with the roll for air cooling or cooling.

  Hereinafter, Examples 1-2 of the present embodiment and Comparative Examples 1-4 will be described in detail.

<Preparation of Resin Roll for Calendar Processing of Example 1>
The calendering resin roll of Example 1 was manufactured to have the configuration shown in FIG. As the metal core 21, a tube having an outer diameter of 300 mm made of STKM was used. Next, an adhesive layer (Konap (registered trademark) 1146, manufactured by Cytec Industries Inc.) was applied to the outer peripheral surface of the core metal 21 by a conventional method. Next, a glass fiber impregnated with a thermosetting resin (Glass Roving No. 4450, manufactured by Asahi Fiber Glass Co., Ltd.) was wound around the outer peripheral surface of the cored bar 21 on which the adhesive layer was formed. Examples of the thermosetting resin include pentaerythritol polyether polyol (Sanix (registered trademark) HD402, manufactured by Sanyo Chemical Industries), pure MDI (Millionate (registered trademark) MT, Hodogaya Chemical Co., Ltd.). Mixture) was used. Then, after heating at 90 degreeC for 10 hours, the thermosetting resin was hardened, it cooled and grind | polished and the filament winding layer (FW layer) 22 was formed.

Subsequently, Samprene (registered trademark) P-870 (manufactured by Sanyo Chemical Industries, Ltd.), which is a urethane prepolymer, was temperature-controlled at 60 ° C. This urethane prepolymer has a polytetramethyl glycol skeleton (a2-1) which is a polyether diol skeleton, has dicyclohexylmethane diisocyanate (a1) groups at both ends thereof, and has an NCO% of 12%. This urethane prepolymer has a structural formula represented by the following formula (A3).

  On the other hand, methylene bis (2-chloroaniline) (Cuamine (registered trademark) MT, manufactured by Ihara Chemical Industry Co., Ltd.), which is a diamine curing agent, was temperature-controlled at 120 ° C. Then, as shown in Table 1, it mix | blended so that it might become 34.3 weight part of hardening | curing agents with respect to 100 weight part of defoamed urethane prepolymer, and it fully stirred and obtained the liquid resin composition.

  Next, the casting mold in which the FW layer 22 is laminated on the outer peripheral surface of the cored bar 21 is placed, and the liquid resin composition is injected. Next, the casting mold into which the resin composition was injected was temperature-controlled at 60 ° C. for 16 hours, and then heated at 180 ° C. for 10 hours to cure the resin composition. Subsequently, the resin roll was taken out from the casting mold, and the surface of the surface layer 23 was polished until the thickness became 12.5 mm. As a result, a calendering resin roll 20 having an outer diameter of 335 mm having the structure shown in FIG. 2 was obtained.

<Preparation of Resin Roll for Calendar Processing of Example 2>
Except for the material of the urethane prepolymer, a calendering resin roll of Example 2 was produced in the same amount as shown in Table 1 in the same manner as in Example 1. The urethane prepolymer has a polycarbonate diol skeleton (a2-2) in which R ₂ is a straight-chain hydrocarbon having 6 carbon atoms and R ₃ is a straight-chain hydrocarbon having 5 carbon atoms. A compound having a dicyclohexylmethane diisocyanate group (a1) at the terminal and an NCO% of 12% was used. This urethane prepolymer has a structural formula represented by the following formula (A4).

<Preparation of Resin Roll for Calendar Processing of Comparative Example 1>
Except for the material of the urethane prepolymer, a calendering resin roll of Comparative Example 1 was prepared with the formulation shown in Table 1 as in Example 1 described above. Adiprene (registered trademark) LF750D (manufactured by Chemtura Corporation) was used as the urethane prepolymer. This urethane prepolymer has a polyether diol skeleton which is a polyether diol skeleton, and has toluene diisocyanate (TDI) groups at both ends thereof.

<Preparation of Resin Roll for Calendar Processing of Comparative Example 2>
Except for the material of the urethane prepolymer, a calendering resin roll of Comparative Example 2 was prepared with the formulation shown in Table 1 in the same manner as in Example 1 described above. As the urethane prepolymer, Adiprene (registered trademark) LF600D (manufactured by Chemtura Corporation) was used. This urethane prepolymer has a polyether diol skeleton which is a polyether diol skeleton, and has toluene diisocyanate (TDI) groups at both ends thereof.

<Preparation of Resin Roll for Calendar Processing of Comparative Example 3>
A calendering resin roll of Comparative Example 3 was prepared with the formulation shown in Table 1 in the same manner as in Example 1 described above except that urea resin was used as the surface layer 23. Liquid A of Porea (registered trademark) R300 (manufactured by Ihara Chemical Industry Co., Ltd.), which is a solvent-free thermosetting polyurea elastomer, was temperature-controlled at 30 ° C., and liquid B was temperature-controlled at 30 ° C. Thereafter, the urethane prepolymer and the curing agent were charged into a mixing stirrer at the ratio shown in Table 1, and after sufficiently stirring, defoaming was performed under reduced pressure to obtain a resin composition. Next, a casting mold in which the FW layer 22 is laminated on the outer peripheral surface of the cored bar 21 is placed, and the resin composition is injected. Next, this casting mold was temperature-controlled at 100 ° C. for 20 minutes and then heat-cured at 180 ° C. for 4 hours.

<Preparation of Resin Roll for Calendar Processing of Comparative Example 4>
A calendering resin roll of Comparative Example 4 was prepared with the formulation shown in Table 1 in the same manner as in Example 1 described above except that an ester resin was used as the surface layer 23. 75 parts by weight of 2,2 ′-(1,3-phenylene) -bis (2-oxazoline), 25 parts by weight of adipic acid and 1 part by weight of triphenyl phosphite were mixed and temperature-controlled. After sufficiently stirring, defoaming was performed under reduced pressure to obtain a resin composition. Next, a casting mold in which the FW layer 22 is laminated on the outer peripheral surface of the cored bar 21 is placed, and the resin composition is injected. Next, the casting mold was temperature-controlled at 100 ° C. for 20 minutes, and then cured at 200 ° C. for 30 minutes.

  For the resin rolls for calendering according to Examples 1 and 2 and Comparative Examples 1 to 4, pot life, Shore D hardness, surface layer condition, gloss of calendar material, surface layer cracking, surface layer wear The results of measuring are shown in Table 1.

  Below, the measuring method of each measurement is demonstrated.

<Shore D hardness>
For each calendering resin roll, Shore D hardness [°] was measured based on JIS6253. As a measuring machine, it measured using the Asker rubber hardness meter D type made from Kobunshi Keiki Co., Ltd.

<Glossiness of calendar material>
Each calendering resin roll was calendered using the calendering apparatus shown in FIG. 3 to determine the glossiness of the calendared material. As the calendar material 40, a plain woven fabric of nylon having a width of 30 cm and a thickness of 0.5 mm was used. The surface temperature of the metal roll 30 was heated to 180 ° C. The linear pressures between the calendering resin rolls 10a and 10b and the metal roll 30 were adjusted to 200 kg / cm, respectively, and the conveying speed of the calendar material 40 was adjusted to 25 m / min. The calendar material 40 was calendered by passing between the calendering resin rolls 10a and 10b and the metal roll 30 twice. Next, the glossiness of the calendared material after calendar processing was visually determined.

<Surface layer cracks and wear>
Each calendering resin roll was calendered using the calendering apparatus shown in FIG. 3 to determine whether the surface layer was cracked or worn. As the calendar material 40, cardboard having a width of 30 cm and a thickness of 0.2 mm was used. The metal roll 30 was heated so that the surface temperature was 180 ° C. The linear pressure between the calendering resin rolls 10a and 10b and the metal roll 30 was adjusted to a maximum of 280 kg / cm, and the conveyance speed of the calendar material 40 was adjusted to 50 m / min. This calendered material was calendered for 1000 m, and this was repeated three times. Subsequently, the state of the surface layer of each calendering resin roll after the calendar test was visually determined.

<Pot life>
In each calendering resin roll, 200 g of the used resin (for example, urethane prepolymer) is collected in a metal container, and the temperature is adjusted to 90 ± 1 ° C. with an oil bath. Subsequently, after adding each hardening | curing agent with respect to each resin and stirring for 1 minute, a viscosity is measured with a tuning fork vibration type viscometer VIBRO VISCOMETER SV-100 (made by A & D Co., Ltd.), and viscosity is 50 Pas. The time to reach is defined as pot life [minutes].

  As is apparent from Table 1, the urethane resin constituting the surface layer is a polymer of a urethane prepolymer having HMDI groups at both ends and a curing agent made of diamine, and the Shore D hardness of the surface layer is 60 °. It can be seen that the calendering resin rolls of Examples 1 and 2 having an angle of 90 ° or less have excellent performance in any item. According to the test results of the glossiness of the calendered material, according to the calendering resin rolls of Examples 1 and 2, the synthetic fiber as the calendered material is melted to reduce the air permeability and improve the water pressure resistance. A soft texture could be given to the surface of the material.

  On the other hand, in the calendering resin rolls of Comparative Examples 1 to 3 in which the surface layer is composed of a conventional urethane resin or urea resin, the pot life is as short as 1 to 6 minutes. A flow pattern defect occurred. In the calendering resin rolls of Comparative Examples 1 to 3, cracks occurred from the internal pinholes in the surface layer cracking test, and the durability was low. Further, in the calendering resin rolls of Comparative Examples 1 and 3, there was a problem that a defect in the flow pattern of the surface layer was transferred to the calendar material in the test result of the glossiness of the calendar material. In the calendering resin roll of Comparative Example 2, since the Shore D hardness of the surface layer is as low as 59 ° in the test result of the glossiness of the calendar material, the glossiness of the surface of the calendar material is weak. A soft texture could not be imparted to the surface.

  On the other hand, in the calendering resin roll of Comparative Example 4, since the Shore D hardness of the surface layer is as high as 92 ° in the gloss test result of the calendar material, the surface gloss of the calendar material is high. A soft texture could not be imparted to the surface of the calendar material.

  From the above results, it was shown that the calendering resin roll according to the embodiment has an appropriate surface layer hardness and high durability.

  In addition, although some embodiment was described, these embodiment is an illustration and does not limit the scope of the invention. These embodiments can be implemented in various other forms, and various changes can be made without departing from the spirit of the invention. These embodiments and modifications thereof are included in the scope and gist of the invention, and are included in the invention described in the claims and the equivalents thereof.

  10, 20, 10a, 10b ... resin roll for calendering, 11, 21 ... core metal, 12, 23 ... surface layer, 22 ... filament winding layer (FW layer), 30 ... metal roll, 40 ... calendar material, 50a ... Sending roll, 50b ... Winding roll, 100 ... Calendar processing device

Claims (5)

A calendering resin roll comprising a cored bar and a surface layer containing a urethane resin disposed on the outer periphery of the cored bar,
The urethane resin is a polymer of a urethane prepolymer having a dicyclohexylmethane diisocyanate group at both ends and a curing agent that is a diamine or a diol,
A calendering resin roll, wherein the surface layer has a Shore D hardness of 60 ° or more and 90 ° or less.   The resin roll for calendering according to claim 1, wherein the urethane prepolymer has a polyether diol skeleton and NCO% is 7% to 16%.   The resin roll for calendering according to claim 1, wherein the urethane prepolymer has a polycarbonate diol skeleton and NCO% is 7% to 16%.   The calendering resin roll according to any one of claims 1 to 3, further comprising a filament winding layer between the core metal and the surface layer. 5. The calendering resin roll according to claim 1, wherein the curing agent is 4,4′-methylenebis (2-chloroaniline) (MOCA).

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