TW201734075A - Elastomer member and sealing member for machine tools - Google Patents

Abstract

Provided are: an elastomer member which is suitable for use in a machine tool; and a sealing member for machine tools, which uses this elastomer member. This elastomer member is characterized by: being formed of a cured product of a thermosetting polyurethane composition; having a JIS-A hardness of 67 DEG or more; and being used for a machine tool. This elastomer member is also characterized in that: the thermosetting polyurethane composition contains a polyol component, an isocyanate component and a crosslinking agent; and the polyol component is a polyethylene adipate ester polyol (PEA).

Description

Elastomer member and sealing member for working machine

The present invention relates to an elastomer member and a sealing member for a work machine.

Work machines such as lathes or machining centers are the most basic mechanical devices commonly used in the manufacturing industry. In these working machines, in order to protect the driving mechanism and the like from chips or coolant (cutting oil), for example, a lip seal, a slide seal, a telescopic seal, a lid seal are used. (cover seal) and other sealing members. As a sealing member for a working machine, a sealing member including a supporting member and an elastic member integrated with the supporting member is known.

It has been proposed that the sealing member as described above uses: chloroprene rubber (CR), nitrile butadiene rubber (NBR), hydrogenated nitrile butadiene rubber (H-NBR), styrene A rubber material such as styrene butadiene rubber (SBR), ethylene/propylene diene monomer (EPDM), or an elastic material such as polyurethane as a material of an elastic member (for example) Refer to Patent Document 1). [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2014-8575

[Problems to be Solved by the Invention] As described above, the sealing member for a working machine is a member that protects the drive mechanism from being affected by a coolant or the like. Therefore, when the sealing member for a working machine is used, the elastic member is exposed to the coolant. The elastic member exposed to the coolant is gradually swollen by the coolant. As a result, the sealing member for the working machine no longer functions and must be replaced. Further, in the case where the elastic member containing the additive is exposed to the coolant, there is a case where the additive is eluted. As a result, there is a case where the physical properties of the elastic member are changed, and the function of the sealing member for the working machine is no longer exhibited. The coolant is roughly classified into a water-insoluble cutting oil and a water-soluble cutting oil, and their characteristics are different. On the other hand, the conventional elastic member for the working machine sealing member is only: (a) it is difficult to swell and dissolve in the water-insoluble cutting oil, but is easily swollen or dissolved in the water-soluble cutting oil; or (b) is soluble in water. It is difficult to swell and dissolve in the cutting oil, but it is easy to swell or dissolve in the water-insoluble cutting oil. That is, an elastic member which is hard to swell and dissolve in any of the water-insoluble cutting oil and the water-soluble cutting oil has not been known.

[Means for Solving the Problems] The inventors of the present invention conducted intensive studies to solve the above problems, and found that it is difficult for one of the water-insoluble cutting oil and the water-soluble cutting oil to swell or the additive is difficult to be eluted, and is suitable. The elastomer member for a working machine using a coolant, thereby completing the present invention.

The elastomer member of the present invention is characterized by comprising a cured product of a thermosetting polyurethane composition containing a polyol component, an isocyanate component, and a crosslinking agent. And the polyol component is polyethylene adipate ester polyol (PEA), Japanese Industrial Standards (JIS)-A hardness is 67° or more, and the elastomer member is used for Working machinery.

Since the elastomer member contains a cured product of a thermosetting urethane composition having a JIS-A hardness of 67° or more, it is difficult for any of the water-insoluble cutting oil and the water-soluble cutting oil. Swelling is also difficult to dissolve. Therefore, it can be suitably used for a working machine using a coolant.

The sealing member for a working machine according to the present invention is a working machine sealing member including a supporting member and an elastic member integrated with the supporting member, and the working machine sealing member is characterized in that the elastic member includes the present invention. Elastomeric component. According to the sealing member for a working machine, the elastic member includes the elastic member of the present invention which is hard to swell and hardly eluted by the coolant. Therefore, the sealing member for a working machine is hard to be deteriorated even when exposed to a coolant, and excellent sealing performance can be maintained over a long period of time.

[Effects of the Invention] The elastomer member of the present invention has excellent durability against cutting oil (coolant), regardless of water-insoluble cutting oil or water-soluble cutting oil. Since the sealing member for a working machine of the present invention contains the elastic member of the present invention, it can maintain excellent sealing performance over a long period of time.

Hereinafter, embodiments of the present invention will be described. <Elastomer Member> The elastomer member according to the embodiment of the present invention contains a cured product of a thermosetting urethane composition. The thermosetting urethane composition contains a polyol component, an isocyanate component, and a crosslinking agent, and the polyol component is a polyethylene adipate polyol (PEA). Since the elastomer member is a cured product of a thermosetting urethane composition having a polyol component of PEA, it is difficult to cause swelling or elution by a coolant. Therefore, when used in a working machine using a coolant, even if it is exposed to a coolant, it can satisfy its required characteristics over a long period of time.

The PEA preferably has a number average molecular weight of from 1,000 to 3,000. The use of an elastomer member having a number average molecular weight of PEA within the above range can more reliably prevent entry of cutting powder, coolant, or the like at the time of contact with the target material. The number average molecular weight is a measured value in terms of polystyrene measured by gel permeation chromatograph (GPC).

The thermosetting urethane composition contains an isocyanate component and a crosslinking agent in addition to PEA (polyol component). The isocyanate component is not particularly limited, and examples thereof include an aliphatic isocyanate, an alicyclic isocyanate, and an aromatic isocyanate. Among these isocyanate components, aromatic isocyanates are preferred in terms of good abrasion resistance.

Examples of the aliphatic isocyanate include 1,6-hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, and lysine II. Isocyanate, etc. Further, examples thereof include an isocyanurate body, a biuret body, an adduct, and the like of hexamethylene diisocyanate or isophorone diisocyanate. Examples of the alicyclic isocyanate include isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, and norbornane diisocyanate. (Norbornane diisocyanate, NBDI) and other alicyclic diisocyanates. Examples of the aromatic isocyanate include tolylene diisocyanate (TDI); phenyl diisocyanate; 4,4'-diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, diphenyl a mixture of methane diisocyanate and polymethylene polyphenylene polyisocyanate (hereinafter, collectively referred to as MDI), 1,5-naphthalene diisocyanate (NDI); xylylene Xylylene diisocyanate (XDI); carbodiimide modified MDI; urethane modified MDI and the like. These isocyanate components may be used singly or in combination of two or more.

The isocyanate component is preferably MDI or NDI. The reason for this is that aromatic aromatic isocyanate exhibits particularly good abrasion resistance.

The crosslinking agent may, for example, be 1,4-butanediol (1,4-BD), 1,4-bis(β-hydroxyethoxy)benzene (1,4-bis). (β-hydroxy ethoxy)benzene, BHEB), ethylene glycol, propylene glycol, hexanediol, diethylene glycol, trimethylol propane (TMP), glycerin, 4,4'-methylene double ( 2-Chloroaniline), hydrazine, ethylenediamine, diethylenetriamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodicyclohexylmethane, N,N-bis ( 2-hydroxypropyl)aniline, water, and the like. Among these crosslinking agents, 1,4-butanediol, TMP, and BHEB are preferable in terms of easily exhibiting appropriate rubber hardness and rubber rigidity. Further, the thermosetting urethane composition containing 1,4-butanediol, TMP or BHEB has a long pot life and can be formed by manual casting. These crosslinking agents may be used singly or in combination of two or more.

The thermosetting urethane composition may further contain a reinforcing agent such as a chain extender, a crosslinking accelerator or a crosslinking retarder, a hydrolysis preventing agent, an inorganic fiber or an inorganic filler, etc., as needed. Various additives such as a coloring agent, a light stabilizer, a heat stabilizer, an antioxidant, an antifungal agent, a flame retardant, and a filler (extender).

The isocyanate group concentration in the thermosetting urethane composition is preferably from 5.50% by weight to 10.0% by weight. When the concentration of the isocyanate group is less than 5.50% by weight, when the elastic member is used as an elastic member of a sealing member for a working machine to be described later, the abrasion resistance of the elastic member may be insufficient. On the other hand, when the isocyanate group concentration exceeds 10.0% by weight, the cured product may be excessively hard, and the sliding resistance may increase. The isocyanate group concentration (% by weight) refers to the weight ratio of the isocyanate groups contained in the total amount of the isocyanate component, the polyol component, and the crosslinking agent.

The JIS-A hardness (value measured by a spring type A hardness tester according to JIS K 7312) of the cured product of the thermosetting urethane composition was 67° or more. When the JIS-A hardness of the cured product is less than 67°, the cured product has a small number of crosslinking points, and swelling due to exposure to the coolant cannot be sufficiently avoided. On the other hand, the upper limit of the JIS-A hardness of the cured product is not particularly limited, and may be appropriately selected in consideration of the use portion of the elastic member.

In the case where the elastic member is used as an elastic member of a sealing member for a working machine to be described later, the JIS-A hardness of the cured product is preferably from 67 to 90. When the JIS-A hardness of the cured product is less than 67°, as described above, there is a case where the resistance to the coolant is not exhibited. On the other hand, when the JIS-A hardness of the cured product exceeds 90°, the stress (compression force) of the sealing portion is excessively increased, and as a result, the sliding resistance is excessively increased. The JIS-A hardness is more preferably from 70 to 85.

The elastomer member is obtained by curing the thermosetting urethane composition under predetermined conditions. The curing conditions of the thermosetting urethane composition are not particularly limited, and may be appropriately set depending on the composition of the thermosetting urethane composition. The hardening conditions can be generally carried out under the conditions of heating at 100 ° C to 160 ° C for 30 minutes to 90 minutes. Further, after the curing treatment is carried out under the above conditions, the mold may be subjected to post-hardening at 100 ° C to 160 ° C for 3 hours to 48 hours.

The isocyanate component and the polyol component contained in the thermosetting urethane composition may be formed by reacting before the thermosetting urethane composition is cured under predetermined conditions. Prepolymer.

The molding method for obtaining the thermosetting urethane composition of the elastomer member is not particularly limited. Examples of the molding method include normal pressure casting molding, vacuum casting molding, centrifugal molding, continuous rotary molding, extrusion molding, injection molding, reaction injection molding (RIM), and spin coating. Among these methods, centrifugal molding and continuous rotary molding are preferred. The elastomer member as described above can be suitably used for a working machine using a coolant.

<The sealing member for the working machine> The elastic member of the embodiment of the present invention can be suitably used as the elastic member in the working machine sealing member including the supporting member and the elastic member integrated with the supporting member. Fig. 1 (a) is a plan view showing an example of a sealing member for a working machine according to an embodiment of the present invention, and Fig. 1 (b) is a side view of Fig. 1 (a).

As shown in FIGS. 1(a) and 1(b), the work machine sealing member 10 includes a support member 11 and an elastic member 12. The support member 11 includes a machined metal plate which is bent along a longitudinal direction of a substantially rectangular metal plate. The elastic member 12 is a plate-shaped member 12 that is fixed via the adhesive layer 13 along the longitudinal direction of the support member 11. The elastic member 12 includes the elastomer member. The edge portion 12a of the elastic member 12 of the working machine sealing member 10 is slidably brought into contact with the target member, whereby the predetermined portion of the working machine can be surely sealed.

The support member 11 usually contains a metal material such as steel or aluminum in terms of durability or strength. The support member 11 may also be made of ceramic or rigid plastic. The support member 11 may be a steel sheet which has been subjected to surface treatment such as zinc phosphate treatment, chromate treatment or rust-preventive resin treatment, and an elastic metal plate such as phosphor bronze or spring steel. In order to improve the compatibility with the adhesive layer 13, the support member 11 may be subjected to surface treatment in advance using an urethane-based primer, a decane-based primer, or the like. Further, the surface of the support member 11 (particularly the region in contact with the elastic member 12 via the adhesive layer 13) may be subjected to a roughening treatment. Thereby, the anchoring effect can be utilized to improve the adhesion of the support member 11 and the adhesive layer 13.

The elastic member 12 includes the elastic member formed into a plate shape. The elastic member 12 is fixed to the support member 11 via the adhesive layer 13. The elastomeric member is as described. The JIS-A hardness of the elastic member 12 is as described above, and is preferably from 67 to 90.

The impact resilience of the elastic member 12 is preferably from 10% to 50%. The elastic member 12 is, for example, a member that slides on a contact surface on the working machine side. In this case, the elastic member 12 is required to have an adaptability for following the surface unevenness of the contact surface, and a performance for causing no out-of-sound sound (beat noise) when sliding. These two properties are properties in a trade-off relationship, but the two properties can coexist by setting the impact resilience of the elastic member 12 to the range. The impact rebound rate is preferably from 20% to 40%. The impact rebound rate is a value measured in accordance with JIS K 7312.

The adhesive layer 13 has a function of joining the support member 11 and the elastic member 12. The adhesive layer 13 is not particularly limited as long as it can bond the elastic member 12 and the support member 11 with a sufficient adhesive force. Examples of the adhesive layer 13 include an ethylene-vinyl acetate (EVA)-based, a polyamide-based or a polyurethane-based hot-melt adhesive or a curing adhesive. The former is formed by a double-sided tape or the like.

The adhesive layer 13 is preferably formed of a urethane-based hot-melt adhesive in terms of excellent bonding strength between the support member 11 and the elastic member 12. The adhesive layer 13 is particularly preferably formed of a moisture-curing urethane-based hot-melt adhesive. The adhesive layer 13 formed of the moisture-curable urethane-based hot-melt adhesive does not melt or soften even when the working machine sealing member 10 reaches a high temperature during use. Maintains stable adhesion.

The moisture-curable urethane-based hot-melt adhesive is moisture applied to the surface of the elastic member and/or the support member after application and adhesion in a molten state, or environmental moisture. The binder which reacts slowly and undergoes a crosslinking reaction contains a urethane prepolymer. Specific examples include, for example, 30% by weight to 50% by weight of a urethane prepolymer (for example, a polycarbonate urethane prepolymer) and 0% by weight to 70% by weight of a thermoplastic resin. A resin, and a moisture-curable urethane-based hot-melt adhesive of 0 to 50% by weight of an adhesion-imparting agent. The urethane prepolymer is one which has two or more isocyanate groups in a molecule and is hardened by reaction with moisture or the like in the environment. The thermoplastic resin may, for example, be a saturated polyester or the like. The thermoplastic resin has an action of improving the adhesion by imparting crystallinity and a temperature of about 120 ° C to 140 ° C in the moisture-curable urethane-based hot-melt adhesive. The role of the coated plasticizer. The thermoplastic resin imparts excellent low-temperature workability to the moisture-curable urethane-based hot-melt adhesive.

Commercially available products can also be used as the moisture-curable urethane-based hot melt adhesive. The commercially available products include, for example, TiForce H-810, TiForce H-850, TiForce PUR-1S, TiForce H-910, and Thai. TiForce FH-445, TiForce FH-315SB, TiForce FH-430, TiForce FH-00SB (all manufactured by Dickson (DIC)), RHC-101, 5921 (manufactured by No-tape INDUSTRIAL CO., LTD.), Hibon 4836M, Hibon 4836S, Hibon 4836W (Hitachi Chemical Co., Ltd.) Manufacturing) and so on. Among these commercial products, TiForce H-810 and TiForce H-850 are preferred.

The thickness of the adhesive layer 13 is not particularly limited, but is preferably 50 μm to 500 μm. In the case where the adhesive layer 13 contains a hot melt adhesive, the thickness thereof is preferably from 50 μm to 200 μm. If it is less than 50 μm, sufficient adhesion strength cannot be ensured. On the other hand, when it exceeds 200 μm, temperature and time may be required to melt excess of the hot-melt adhesive.

The work machine sealing member 10 can be manufactured, for example, by the following method. (1) A steel plate or the like is used as a starting material, and after being cut into a predetermined size, a bending process or the like is performed as necessary to produce a support member 11. (2) Separately from the production of the support member 11 in the above (1), a sheet-shaped elastic member including a cured product of the thermosetting urethane composition is prepared. Then, the obtained elastic member is cut into a predetermined size using an ultrasonic cutter or the like to fabricate the elastic member 12. Further, the forming method of the elastic member is as described above. (3) After applying an adhesive to at least one of the support member 11 and the elastic member 12 using an applicator or the like, the two are bonded to each other at a predetermined position. Then, pressurization and/or aging is performed as needed. By the above steps, the sealing member 10 for a working machine can be manufactured.

In the sealing member 10 for a machine tool shown in Fig. 1 (a) and (b), the shape of the elastic member 12 is a plate shape having a rectangular cross section, but in the sealing member for a working machine according to the embodiment of the present invention, The shape of the elastic member is not limited to the shape. The shape of the elastic member may be, for example, a shape in which the edge portion is C-chamfered or R-chamfered. Further, the elastic member may have a shape in which the cross-sectional shape (the shape of the surface perpendicular to the longitudinal direction) is continuously or intermittently tapered toward the edge portion.

The working machine sealing member according to the embodiment of the present invention may be a working machine sealing member as shown in Figs. 2(a) and 2(b). Fig. 2 (a) is a rear view showing another example of the sealing member for a working machine according to the embodiment of the present invention, and Fig. 2 (b) is a side view of Fig. 2 (a).

As shown in FIGS. 2(a) and 2(b), the work machine sealing member 20 includes a support member 21 including a plate-shaped metal plate, and an elastic member 22 integrally formed with the support member 21. The elastic member 22 includes a body portion 22A that is joined to the support member, and a lip portion 22B that extends from the body portion 22A and has an edge portion 22a that is in contact with the target material. The elastic member 22 contains the elastomer member. The edge portion 22a of the elastic member 22 of the working machine sealing member 20 is slidably brought into contact with the target member, and the predetermined portion of the working machine can be surely sealed. As described above, the sealing member for a machine tool according to the embodiment of the present invention may be such that the support member and the elastic member are integrated without passing through the adhesive layer.

In the work machine sealing member 20, the material of the support member 21 is the same as that of the support member 11 in the work machine sealing member 10, and metal, ceramic, rigid plastic or the like can be used. In the working machine sealing member 20, the elastic member 22 is the elastic member, and its preferable physical properties are the same as those of the elastic member 12 in the working machine sealing member 10. Further, in the sealing member for work machine 20, a primer layer may be interposed between the support member 21 and the elastic member 22. Thereby, the adhesion of the support member 21 and the elastic member 22 can be further improved.

The work machine sealing member 20 can be produced by arranging the support member 21 at a predetermined position in the mold, casting the uncured thermosetting urethane composition, and curing it under predetermined curing conditions. Here, the curing conditions of the thermosetting urethane composition are as described above.

The shape of the working machine sealing member according to the embodiment of the present invention is not limited to the shapes shown in Figs. 1(a) and 1(b) and Figs. 2(a) and 2(b). The working machine sealing member may have the same shape as a conventional working machine sealing member such as a lip seal, a sliding seal, a stretch seal, or a lid seal.

The working machine sealing member according to the embodiment of the present invention can be used as a sliding portion or a sliding mechanism for protecting a working machine from being affected by cutting powder or coolant (cutting oil) in various working machines such as a lathe or a cutting machine. A sealing member (wiper member) is used. Specifically, it can be used, for example, as a sliding seal, a stretch seal, a lid seal, a lip seal, and the like.

In the following, a case where the sealing member for a working machine according to the embodiment of the present invention is used as a stretch seal is taken as an example, and an example of use thereof will be described. FIG. 3 is a cross-sectional view schematically showing a part of a telescopic cover 100 to which the working machine sealing member 10 according to the embodiment of the present invention is attached. As shown in FIG. 3, the work machine sealing member 10 is fixed by screwing (not shown) the support member 11 on the lower surface of the outer end portion of each of the cover members 15 constituting the telescopic cover 100. At this time, the work machine sealing member 10 is attached to a position where the outer surface 15a of the lower cover member 15 and the end portion of the elastic member 12 are surely slidably contacted. Further, a through hole (not shown) for a bolt is formed in advance on the support member 11. The telescopic cover 100 in which the work machine sealing member 10 is attached to the outer front end portion of each of the cover members 15 can prevent the cutting powder or the like existing on the outer side of the telescopic cover 100 from entering the cover during expansion and contraction of the telescopic cover 100. Needless to say, the use of the sealing member for a working machine according to the embodiment of the present invention is not limited to the stretch seal.

The elastic member according to the embodiment of the present invention may be used in addition to the elastic member of the sealing member for a work machine. Specifically, for example, it can also be used for a drive belt provided in a work machine or the like. In the working machine, various members are constructed by driving with a drive belt. Among the transmission belts used in the working machine, there are also transmission belts disposed at positions exposed to the coolant. Such a transmission belt may be deteriorated (swelling, or elution of the additive) due to exposure to the coolant, or may be broken as appropriate. On the other hand, in the case of using the transmission belt of the elastic member, deterioration due to the coolant can be suppressed. [Examples]

Hereinafter, embodiments of the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples.

(Example 1) Into 100.00 parts by weight of an MDI-PEA prepolymer (manufactured by Sanyo Chemical Industries, Ltd., trade name "Sanprene P-6814") heated to 110 ° C, 5.60 parts by weight of 1 was added. 4-BD (manufactured by Mitsubishi Chemical Corporation) and 0.76 parts by weight of TMP (manufactured by Mitsubishi Gas Corporation) were stirred and mixed to prepare a urethane composition. The urethane composition obtained immediately was placed in a centrifugal molding machine, and crosslinked by a mold temperature of 150 ° C and a crosslinking time of 60 minutes to form a cylindrical cured product with a thickness of 1.5 mm. After that, demolding is performed. Then, one of the cylindrical hardened materials was cut into a plate shape, and post-crosslinked in a blowing oven at 110 ° C for 24 hours to obtain a whole polyurethane-made product. sheet. Then, the entire sheet was cut into a length of 12 mm × a width of 49 mm to form a long strip of urethane sheet. The urethane sheet had a JIS-A hardness of 70°. Further, the JIS-A hardness of the urethane sheet was measured by superposing 10 sheets of a urethane sheet having a thickness of 1.5 mm in accordance with JIS K 7312.

(Example 2) An elongated amine group was obtained in the same manner as in Example 1 except that the amount of the 1,4-BD was changed to 6.36 parts by weight and the amount of TMP was changed to 0.20 part by weight. Acid tablet. The urethane sheet had a JIS-A hardness of 80°.

(Example 3) 10.50 parts by weight of BHEB was added to 100.00 parts by weight of MDI-PEA prepolymer (manufactured by Sanyo Chemical Industries, Ltd., trade name "Sanprene P-6814") heated to 110 ° C (manufactured by Mitsubishi Fine Chemical Co., Ltd.) and 1.59 parts by weight of 1,4-BD (manufactured by Mitsubishi Chemical Corporation), and stirred and mixed to prepare a urethane composition. The urethane composition obtained immediately was placed in a centrifugal molding machine, and crosslinked by a mold temperature of 150 ° C and a crosslinking time of 60 minutes to form a cylindrical cured product with a thickness of 1.5 mm. After that, demolding is performed. Then, one of the cylindrical hardened materials was cut into a plate shape, and post-crosslinked in a blowing oven at 110 ° C for 24 hours to obtain a whole polyurethane-made product. sheet. Then, the entire sheet was cut into a length of 12 mm × a width of 49 mm to form a long strip of urethane sheet. The urethane sheet had a JIS-A hardness of 90°.

(Example 4) 100.00 parts by weight of PEA (manufactured by Sumitomo Bayer Polyurethane Co., Ltd., trade name "Vulkollan 2000MM") and 19.00 parts by weight of NDI (manufactured by Sumitomo Bayer Polyurethane Co., Ltd., trade name "Dessmore" (Desmodur) 15"), reacted in a vacuum reaction vessel at 125 ° C for 15 minutes while stirring to obtain a prepolymer. Then, 2.50 parts by weight of 1,4-BD (manufactured by Mitsubishi Chemical Corporation) was added to the obtained prepolymer, stirred and mixed, and then placed in a centrifugal molding machine at a mold temperature of 130 ° C and a crosslinking time of 60. The conditions of the minute were cross-linked, and the cylindrical cured product was molded to a thickness of 1.5 mm, and then demolded. Then, one of the cylindrical hardened materials was cut into a plate shape, and post-crosslinked in a blowing oven at 110 ° C for 24 hours to obtain a whole polyurethane-made product. sheet. Then, the entire sheet was cut into a length of 12 mm × a width of 49 mm to form a long strip of urethane sheet. The urethane sheet had a JIS-A hardness of 80°.

(Example 5) An elongated amine group was obtained in the same manner as in Example 4 except that the amount of NDI was changed to 25.00 parts by weight and the amount of 1,4-BD was changed to 5.00 parts by weight. Acid tablet. The urethane sheet had a JIS-A hardness of 90°.

(Example 6) An elongated amine group was obtained in the same manner as in Example 4 except that the amount of NDI was changed to 40.00 parts by weight and the amount of 1,4-BD was changed to 11.00 parts by weight. Acid tablet. The urethane sheet had a JIS-A hardness of 96°.

(Example 7) An elongated amine group was obtained in the same manner as in Example 1 except that the amount of the 1,4-BD was changed to 4.58 parts by weight and the amount of TMP was changed to 1.79 parts by weight. Acid tablet. The urethane sheet had a JIS-A hardness of 67°.

The urethane sheets produced in Examples 1 to 7 are shown in Table 1 in terms of the formulation and JIS-A hardness.

[Table 1]

(Comparative Example 1) 100.00 parts by weight of NBR (manufactured by Zeon Corporation, trade name "Nipol 1031"), and 5.00 parts by weight of bis(2-ethylhexyl) phthalate (manufactured by Mitsubishi Chemical Corporation), 84.00 parts by weight of carbon black (manufactured by Tokai Carbon Co., Ltd., trade name "ISAF"), and 5.00 parts by weight of zinc oxide (manufactured by Nippon Chemical Industry Co., Ltd., trade name "zinc oxide" 5.00 parts by weight of zinc oxide (manufactured by Inoue Lime Industries Co., Ltd., trade name "META ZL-50"), and 0.40 parts by weight of sulfur (manufactured by Hosei Chemical Industry Co., Ltd., trade name "Oil Sulfur"), The mixture was kneaded by a rubber kneading machine for about 120 seconds until reaching the limit temperature of 135 ° C at the time of kneading, and the obtained mixture was molded in the following manner, and then cut to obtain an elongated rubber sheet having the same size as that of Example 1. . The rubber sheet had a JIS-A hardness of 80°. As a forming method, a raw rubber having a thickness of 1.6 mm is processed into a raw rubber sheet having a thickness of 1.6 mm by a calender calender, and the raw rubber is placed in a stamper having a thickness of 1.5 mm × 400 mm × 100 mm. After the sheet, extrusion crosslinking was carried out at 130 ° C for 30 minutes to obtain a rubber crosslinked sheet.

(Comparative Example 2) 100.00 parts by weight of hydrogenated NBR (manufactured by Zeon Corporation, trade name "Zetpol 2021") and 6.00 parts by weight of organic peroxide (manufactured by NOF Corporation, trade name "Peroxymon F40"), 3.00 parts by weight of trimethylolpropane trimethacrylate (manufactured by Seiko Chemical Co., Ltd., trade name "Hi-Cross M"), and 1.00 part by weight Zinc stearate (manufactured by Kawamura Chemical Industry Co., Ltd., trade name "stearic acid"), 60.00 parts by weight of carbon black (manufactured by Showa Cabot Co., Ltd., trade name "IP200"), and 10.00 parts by weight Zinc oxide (manufactured by Nippon Chemical Industry Co., Ltd., trade name "zinc oxide") was kneaded by a rubber kneading machine for about 120 seconds until the limit temperature at the time of kneading was 135 ° C, and the obtained mixture was molded in the following manner. Then, it was cut to obtain an elongated rubber sheet of the same size as in Example 1. The rubber sheet had a JIS-A hardness of 80°. The forming method is a method in which the raw rubber after the kneading is processed into a raw rubber sheet having a thickness of 1.6 mm by a calender calender, and the raw rubber sheet is placed in a stamper having a thickness of 1.5 mm × 400 mm × 100 mm. Thereafter, extrusion crosslinking was carried out at 130 ° C for 30 minutes to obtain a rubber crosslinked sheet.

(Comparative Example 3) 100.00 parts by weight of EPDM (manufactured by Mitsui Chemicals, Inc., trade name "EPT4045M"), 3.00 parts by weight of diethylene glycol (manufactured by Mitsubishi Chemical Corporation), and 3.00 parts by weight of ethylene glycol (Kyoeisha) Manufactured by the chemical company, "Light Ether EG", 5.00 parts by weight of paraffin oil (manufactured by Idemitsu Kosan Co., Ltd., trade name "paraffin oil H"), and 50.00 parts by weight of cerium oxide (manufactured by Tosoh Corporation) The product name "Nipsil VN3"), 5.00 parts by weight of zinc oxide (manufactured by Nippon Chemical Industry Co., Ltd.), and 5.00 parts by weight of titanium oxide (manufactured by Nippon Chemical Industry Co., Ltd.) were kneaded by a rubber kneading machine. After 180 seconds, until the limit temperature at the time of kneading was reached at 155 ° C, the obtained mixture was molded in the following manner, and then cut to obtain an elongated rubber sheet having the same size as in Example 1. The rubber sheet had a JIS-A hardness of 70°. The forming method is a method in which the raw rubber after the kneading is processed into a raw rubber sheet having a thickness of 1.6 mm by a calender calender, and the raw rubber sheet is placed in a stamper having a thickness of 1.5 mm × 600 mm × 100 mm. Thereafter, extrusion crosslinking was carried out at 160 ° C for 30 minutes to obtain a rubber crosslinked sheet.

(Comparative Example 4) MDI-PCL-based thermoplastic polyurethane (manufactured by Miractran Co., Ltd., trade name "E595PNAT") was molded by the following method, and then cut to obtain the same size as in Example 1. Long strips of urethane tablets. The urethane sheet had a JIS-A hardness of 93°. The forming was carried out by extrusion molding a sheet having a thickness of 1.5 mm and a width of 200 mm by using an extruder using a T die having an injection width of 200 mm. At this time, the temperature of the mold was set to 190 °C.

(Comparative Example 5) 4.41 parts by weight of 1,4 parts by weight of MDI-PTMG prepolymer (manufactured by Tosoh Corporation, trade name "Coronate 4362"), which was heated to 110 ° C, was added. 4-BD (manufactured by Mitsubishi Chemical Corporation) and 1.10 parts by weight of TMP (manufactured by Mitsubishi Gas Corporation) were stirred and mixed to prepare a urethane composition. The urethane composition obtained immediately was placed in a centrifugal molding machine, and crosslinked by a mold temperature of 150 ° C and a crosslinking time of 60 minutes to form a cylindrical cured product with a thickness of 1.5 mm. After that, demolding is performed. Then, one of the cylindrical hardened materials was cut into a plate shape, and post-crosslinked in a blowing oven at 110 ° C for 24 hours to obtain a whole polyurethane-made product. sheet. Then, the entire sheet was cut into a length of 12 mm × a width of 49 mm to form a long strip of urethane sheet. The urethane sheet had a JIS-A hardness of 70°.

(Comparative Example 6) Into 100.00 parts by weight of an MDI-PCL prepolymer (manufactured by Sanyo Chemical Industries, Ltd., trade name "Sanprene P-6903") heated to 110 ° C, 6.17 parts by weight of 1 was added. 4-BD (manufactured by Mitsubishi Chemical Corporation) and 1.54 parts by weight of TMP (manufactured by Mitsubishi Gas Corporation) were stirred and mixed to prepare a urethane composition. The urethane composition obtained immediately was placed in a centrifugal molding machine, and crosslinked by a mold temperature of 150 ° C and a crosslinking time of 60 minutes to form a cylindrical cured product with a thickness of 1.5 mm. After that, demolding is performed. Then, one of the cylindrical hardened materials was cut into a plate shape, and post-crosslinked in a blowing oven at 110 ° C for 24 hours to obtain a whole polyurethane-made product. sheet. Then, the entire sheet was cut into a length of 12 mm × a width of 49 mm to form a long strip of urethane sheet. The urethane sheet had a JIS-A hardness of 77°.

(Comparative Example 7) 100.00 parts by weight of DEG-PES (manufactured by Tosoh Corporation, trade name "Nippollan 4706") and 22.20 parts by weight of carbodiimide modified MDI (manufactured by Mitsui Chemicals, Inc.) The product name "Takenate LSI-14P" was mixed using a stirrer. Then, 6.70 parts by weight of BHEB (manufactured by Mitsubishi Fine Chemical Co., Ltd.) and 0.50 parts by weight of TMP (manufactured by Mitsubishi Gas Chemical Co., Ltd.) were added to the obtained mixture, and the mixture was stirred and mixed to prepare a urethane composition. Then, the obtained urethane composition was placed in a centrifugal molding machine, and crosslinked by a mold temperature of 150 ° C and a crosslinking time of 60 minutes to harden a cylindrical shape with a thickness of 1.5 mm. After the material is formed, demolding is performed. Then, one of the cylindrical hardened materials was cut into a plate shape, and post-crosslinked in a blowing oven at 110 ° C for 24 hours to obtain a whole polyurethane-made product. sheet. Then, the entire sheet was cut into a length of 12 mm × a width of 49 mm to form a long strip of urethane sheet. The urethane sheet had a JIS-A hardness of 67°.

(Comparative Example 8) A strip shape was obtained in the same manner as in Comparative Example 7, except that the amount of the carbodiimide-modified MDI was changed to 32.20 parts by weight and the amount of BHEB was changed to 13.00 parts by weight. A urethane tablets. The urethane sheet had a JIS-A hardness of 85°.

(Comparative Example 9) An elongated amine group was obtained in the same manner as in Example 1 except that the amount of the 1,4-BD was changed to 3.82 parts by weight and the amount of TMP was changed to 2.54 parts by weight. Acid tablet. The urethane sheet had a JIS-A hardness of 65°.

The rubber sheet and the urethane sheet produced in Comparative Examples 1 to 9 are shown in Table 2 in terms of the formulation and the JIS-A hardness.

[Table 2]

[Evaluation of Cooling Resistance] The sheets (urethane sheets or rubber sheets) produced in the examples and the comparative examples were evaluated for durability against the coolant. Here, the durability of the coolants was evaluated using the following three types of coolants. Coolant A (oil system): trade name "Daphne Marg Plus MP10" (manufactured by Idemitsu Kosan Co., Ltd.) Coolant B (water system): trade name "Clear Cut RH-1K" (Neos 10 times dilution of the company's manufactured coolant C (water system): 10 times dilution of the product name "Neocool Bio-60E" (manufactured by Moresco)

(Evaluation Method) The sheets prepared in the examples and the comparative examples were each immersed in the coolant A to the coolant C for a predetermined period of time (0 hours, 72 hours, and 520 hours), and the weight increase rate of the sheet during immersion was calculated ( %). Here, in the 0 hour immersion, the sheet was immersed in a coolant, and then the sheet was pulled out immediately. Further, the coolant A to the coolant C were used as a coolant at room temperature and 50 ° C, respectively. Further, the weight was measured by pulling out the sheet from the coolant, and quickly using a paper towel to wipe the coolant. The results are shown in Tables 3 and 4 and Figs. 4(a) to 6(b).

4(a) and 4(b) are graphs showing the immersion time and the weight increase rate when the sheet is immersed in the coolant A (50 ° C). The evaluation results of Examples 1 to 7 are shown in Fig. 4(a). The evaluation results of Comparative Example 1 to Comparative Example 9 are shown in Fig. 4(b). 5(a) and 5(b) are graphs showing the immersion time and the weight increase rate when the sheet is immersed in the coolant B (50 ° C). The evaluation results of Examples 1 to 7 are shown in Fig. 5(a). The evaluation results of Comparative Example 1 to Comparative Example 9 are shown in Fig. 5 (b). 6(a) and 6(b) are graphs showing the immersion time and the weight increase rate when the sheet is immersed in the coolant C (50 ° C). The evaluation results of Examples 1 to 7 are shown in Fig. 6(a). The evaluation results of Comparative Example 1 and Comparative Example 2 are shown in Fig. 6(b).

Then, based on the weight increase rate, the sheets produced in the examples and the comparative examples were classified into "good", "swelled", and "dissolved" on the basis of the following basis. The results are shown in Tables 3 and 4.

Good: The weight increase rate is -5% to +5%. Swelling: The weight increase rate is greater than 5%. Dissolution: The weight reduction rate is more than 5% (weight increase rate <-5%).

In addition, as an index of the coolant resistance, the "weight increase rate (%) in 520 h / weight increase rate (%) in 72 h" was calculated. The results are shown in Tables 3 and 4. According to this index, the coolant resistance of the sheet can also be evaluated. In this index, the closer the calculated value is to 1.0, the better the coolant resistance is.

[table 3]

[Table 4]

As shown in Table 3, Table 4, and Figs. 4(a) to 6(b), the polyol component is a polyethylene adipate polyol (PEA) and the JIS-A hardness is 67° or more. The elastomer member of Example 7 is excellent in coolant resistance to any of the water-insoluble cutting oil and the water-soluble cutting oil. On the other hand, the elastomer member (or the rubber member) of Comparative Examples 1 to 9 was confirmed to be swollen or eluted by any of the coolants.

[Evaluation] An elastomer member (rubber member) having the same composition as that of the urethane sheet of Example 2 and the rubber sheet of Comparative Example 1 was used as the sealing member for the working machine of the elastic member. Specifically, regarding the urethane sheet of Example 2, first, the crosslinked sheet was cut into 20 mm × 600 mm, and bonded to a metal support having a thickness of 1.2 mm and a length of 900 mm. Then, the end portion is cut into a necessary length and angle, and the mounting hole is opened to form a sealing member. On the other hand, regarding the rubber sheet of Comparative Example 1, first, a raw rubber sheet and a metal support were placed in a lip-sealed mold heated to 150 ° C (about 2 mm thickness × 32 mm width × 1200 mm length). The mixture was extruded and crosslinked by pressurization for 30 minutes to obtain an integrally molded product of the rubber and the support. Then, the end portion is cut to a necessary length and angle, and the mounting hole is opened to form a sealing member.

The obtained working machine sealing member was mounted as a lip seal (the amount of front end extrusion: 3 mm) was placed on a CNC lathe (DMX Mori Seiki Co., Ltd., NLX3000) and operated for 800 hours. The edge portion of the sealing member for the working machine was observed before and after the operation. The results are shown in Fig. 7 and Fig. 8. 7 is a photograph (left side) and a schematic view (right side) of photographing a state of an edge portion when a sealing member for a working machine including the urethane sheet of Example 2 is used as an elastic member, and the upper section is before operation and the lower section. After the operation. 8 is a photograph (left side) and a schematic view (right side) of a state in which an edge portion is used when a sealing member for a working machine including a rubber sheet of Comparative Example 1 is used as an elastic member, and the upper portion is before operation and the lower portion is after operation.

As shown in Fig. 8, the elastomer member having the same composition as the urethane sheet of Example 2 as the elastic member has only a small amount of wear. On the other hand, as shown in FIG. 9, the rubber member having the same composition as the rubber sheet of Comparative Example 1 as the elastic member was largely worn (about 1 mm). From these circumstances, it is clear that the elastomer member (elastic member) using PEA as the polyol component is excellent in durability.

10, 20‧‧‧Working machine sealing members
11, 21‧‧‧ Supporting components
12, 22‧‧‧ elastic members
12a, 22a‧‧‧ edge
13‧‧‧Adhesive layer
15‧‧‧Cover components
15a‧‧‧ outer surface of the cover member 15
22A‧‧‧ Body Department
22B‧‧‧Lip
100‧‧‧Retractable cover

Fig. 1 (a) is a plan view showing an example of a sealing member for a working machine according to an embodiment of the present invention, and Fig. 1 (b) is a side view of Fig. 1 (a). Fig. 2 (a) is a rear view showing another example of the sealing member for a working machine according to the embodiment of the present invention, and Fig. 2 (b) is a side view of Fig. 2 (a). 3 is a cross-sectional view schematically showing a part of a telescopic cover to which a sealing member for a machine tool according to an embodiment of the present invention is attached. Fig. 4 (a) is a graph showing the immersion time and the weight increase rate when the sheet produced in the example was immersed in the coolant A (50 ° C), and Fig. 4 (b) is a view showing the preparation of the comparative example. A graph of the immersion time and the weight increase rate when the sheet was immersed in the coolant A (50 ° C). Fig. 5 (a) is a graph showing the immersion time and the weight increase rate when the sheet produced in the example was immersed in the coolant B (50 ° C), and Fig. 5 (b) is a view showing the preparation of the comparative example. A graph of the immersion time and the weight increase rate when the sheet was immersed in the coolant B (50 ° C). Fig. 6(a) is a graph showing the immersion time and the weight increase rate when the sheet produced in the example was immersed in the coolant C (50 ° C), and Fig. 6 (b) is a view showing the preparation of the comparative example. A graph of the immersion time and the weight increase rate when the sheet was immersed in the coolant C (50 ° C). FIG. 7 is a photograph and a schematic view of a state in which an edge portion is used when the urethane sheet of Example 2 is used as an elastic member for a working machine sealing member. FIG. 8 is a photograph and a schematic view of a state in which an edge portion is used when a rubber sheet of Comparative Example 1 is used as a sealing member for a working machine of an elastic member.

no

Claims (2)

An elastomer member comprising a cured product of a thermosetting polyurethane composition, wherein the thermosetting polyurethane composition contains a polyol component, an isocyanate component, and a crosslinking agent. And the polyol component is a polyethylene adipate polyol (PEA), the Japanese Industrial Standard-A hardness is 67° or more, and the elastomer member is used for a working machine. A sealing member for a working machine, comprising: a supporting member, and an elastic member integrated with the supporting member, wherein the working member sealing member is characterized in that the elastic member comprises the one described in claim 1 Elastomeric component.