TW201638214A - Polyurethane elastomer-forming composition, industrial machine component using same, mold release agent composition used for resin molding, and polyurethane resin molded article which is molded using said mold release agent composition - Google Patents

Abstract

To provide a thermosetting polyurethane elastomer which is free from the occurrence of bleeding and blooming, and which has extremely low coefficient of friction. The present invention solves a problem by introducing, into a thermosetting polyurethane elastomer-forming composition, at least one substance selected from the group consisting of polyoxyethylene alkyl ethers and linear aliphatic alcohols having 20-40 carbon atoms and a melting point of 90 DEG C or less, and additionally octadecyl isocyanate in order to achieve a better effect, or alternatively, by introducing an aliphatic amide and at least one substance selected from the group consisting of polyoxyethylene alkyl ethers, linear aliphatic alcohols having 20-40 carbon atoms and a melting point of 90 DEG C or less and octadecyl isocyanate. The present invention solves another problem by using, for resin molding, a mold release agent composition which contains an organopolysiloxane having at least one carboxylate selected from the group consisting of quaternary ammonium and quaternary phosphonium in the molecular structure.

Description

Polyurethane elastomer-forming composition, industrial machine part using the same, release agent composition for resin molding, and polyurethane resin molding molded using the composition

The present invention relates to a thermosetting polyurethane elastomer-forming composition which can be used for industrial machine parts and a release agent composition for resin molding, and a polyurethane resin molded article produced using the same.

The thermosetting polyurethane elastomer has high durability due to high modulus, high breaking strength, low abrasion, and low distortion, and can be suitably used as a component member of an industrial machine.

A thermosetting polyurethane elastic system generally used for industrial machine parts is obtained by mixing a main component composed of an isocyanate-based component and a hardener composed of an active hydrogen-containing component in a mixing head of an injection molding machine. The mixed solution is injected into a mold, and the mixture is heated and hardened (urethane reaction) in the mold to produce.

Further, in order to facilitate the removal of the molded article, the release agent is applied to the inner surface of the mold in advance. As the release agent, polyethylene wax, organopolyoxyalkylene, polyvinyl fluoride or the like can be preferably used.

Then, a component which is a composition for forming a thermosetting polyurethane elastomer, which is composed of an isocyanate and a polyol, is generally used. A cyanate-based terminal urethane prepolymer (hereinafter abbreviated as "NCO-based terminal urethane prepolymer"), which is heated and mixed with an active hydrogen-based terminal hardener composed of a polyhydric alcohol or a polyamine to harden it. Methods.

For example, an active hydrogen-based terminal hardener which is made of diphenylmethane diisocyanate (hereinafter abbreviated as "MDI") as an isocyanate component and polybutene adipate (hereinafter abbreviated as "PBA") can be suitably used. ) an NCO-based terminal urethane prepolymer composed of a polyhydric alcohol; and 1,4-butanediol (hereinafter abbreviated as "1,4-BD") or trimethylolpropane (hereinafter abbreviated as "TMP" ") and PBA are mixed as a polyol component. Further, an amine-based terminal hardener can be preferably used, and NCO-based terminal amino group composed of toluene diisocyanate (hereinafter abbreviated as "TDI") and polytetramethylene glycol (hereinafter abbreviated as "PTMG") can be suitably used. An acid ester prepolymer; and an amine group such as 4,4'-diamino-3,3'-dichlorodiphenylmethane (hereinafter abbreviated as "MOCA") is used as an active hydrogen group.

However, the friction coefficient of the thermosetting polyurethane elastomer molded article obtained as described above is known to be extremely large due to its high elastic force. Therefore, in the industrial machine parts that are continuously used, heat is generated by the friction of the drive, and the heat is gradually stored in the heat to become a temperature above the design to change the physical properties. A special problem is a vicious cycle in which the elastic force is increased due to the increase in temperature and the frictional resistance is further increased to increase the temperature. When these thermosetting polyurethane elastomer molded articles are used as industrial machine parts, the characteristics are changed by the heat storage of the parts, and it is necessary to cause defects such as breakage, cracking, and abrasion of the parts in a short period of time. Replace the part. In particular, in recent years, with the high-speed processing of industrial equipment, it has been found that the mechanical strength of the part is lowered due to an increase in the heat storage temperature, and defects such as breakage, cracking, and abrasion of the parts frequently occur, as previously known. Thermosetting polyurethane elastomer moldings are not sufficient Correspondingly, a low-friction heat-curing polyurethane elastomer molded article is strongly desired.

In order to reduce the friction coefficient of the polyurethane elastomer molded article, it is proposed to use graphite, tetrafluoroethylene, resin powder, paraffin, molybdenum disulfide, wood wax, etc. as a fatty alcohol ester or a higher fatty acid having a carbon number of 13 or more and a carbon number. A lubricant such as a liquid or powdery higher fatty acid ester composed of an alcohol of 8 or more is mixed with a polyurethane elastomer molded article (Patent Documents 1 to 3). Further, there is also a proposal to introduce a lubricant component into a polyurethane molecule by introducing a stearic acid or an oleic acid ester and a hardener having a hydroxyl group or an amine group; or introducing an octadecyl isocyanate having an NCO group; (Patent Documents 4 to 5).

Further, there is a proposal for a method of forming a polyurethane layer containing a siloxane coupling by reacting an anthrone compound having an active hydrogen with a urethane resin (Patent Document 6), and forming a high hardness layer on the surface to make it low. Proposal for the method of friction (Patent Document 7).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. Sho 57-194946

[Patent Document 2] Japanese Patent Laid-Open No. 3-346

[Patent Document 3] Japanese Patent Laid-Open No. 5-134340

[Patent Document 4] Japanese Patent Laid-Open No. Hei 11-51122

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2005-120216

[Patent Document 6] Japanese Patent Laid-Open No. 4-189114

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2001-75451

However, the polyurethane elastomer does not react with the above polyurethane. In the case of a slip agent, these slip agents are inferior in compatibility with the NCO-based terminal urethane prepolymer and the active hydrogen-based terminal hardener, and are not only non-uniform polyurethane elastomer molded articles, but can be seen to ooze out of the slip agent component. Or dusting. In particular, when it is used for parts of a sophisticated industrial machine, there is a problem that an abnormality occurs in an industrial machine due to contamination of these slip components. A polyurethane elastomer molded product in which a slip agent which reacts with a polyurethane and a polyurethane elastomer described later is mixed and reacted with a lubricant component in a polyurethane molecule is not sufficiently transferred to the molding because the carbon content of the slip agent component is insufficient or the degree of freedom is hindered. On the surface of the product, there are many cases where the low friction is insufficient or the case cannot be sustained. Further, in the machined surface, there is a case where the lubricant component is not sufficiently transferred, and there is a case where the amount of low friction is insufficient or it is not sustainable.

Further, in the method of forming the fluorenone urethane resin layer on the surface of the urethane resin, the reduction in the dynamic friction coefficient is not sufficient. Further, although an anthrone having an active hydrogen group reactive with isocyanate is used, since it contains an anthrone having no active hydrogen functional group, there is a possibility that the surface is bleed out and the contacted parts are contaminated.

Further, in the method of forming the high-hardness layer, the formation of the high-hardness layer is followed by the two-stage molding of the urethane resin molding, and the number of steps is increased, which reduces the productivity.

The present invention has been accomplished in view of the above circumstances, and the first object is to introduce a linear aliphatic alcohol selected from the group consisting of polyoxyethylene alkyl ether (C1) and having a carbon number of 20 to 40 and a melting point of 90 ° C or lower ( C2) at least one of the group consisting of, and introducing octadecyl isocyanate (C3) for better effect; or introducing At least one selected from the group consisting of a polyoxyethylene alkyl ether (C1), a linear aliphatic alcohol (C2) having a carbon number of 20 to 40 and a melting point of 90 ° C or less, and octadecyl isocyanate (C3) And a fatty acid decylamine (C4), which is a thermosetting polyurethane elastomer-forming composition for industrial machinery parts, and provides a thermosetting polyurethane for industrial machinery parts which does not bleed, dust, and has a very low friction coefficient. Elastomer. In addition, in order to obtain these thermosetting polyurethane elastomers, the compatibility with the NCO-based terminal urethane prepolymer and the active hydrogen-based terminal curing agent is improved, and thermal hardening for stabilizing the quality is provided. The NCO-based terminal urethane prepolymer of the polyurethane elastomer and the active hydrogen-based terminal hardener.

A second object is to use a release agent composition comprising an organopolyoxane (A) having at least one carboxylate selected from the group consisting of 4- toluene and 4- toluene in a molecular structure. A polyurethane resin molded article for industrial machinery parts which does not reduce physical properties or bleeds, dusting, and which does not impair productivity, and has a very low friction coefficient.

The present invention includes the following embodiments (1) to (26).

(1) A thermosetting polyurethane elastomer-forming composition comprising: an isocyanate group-terminated urethane prepolymer (A), an active hydrogen-based terminal hardener (B), and a lubricant (C) The slip agent (C) is contained in the thermosetting polyurethane elastomer-forming composition in an amount of 0.1 to 8% by mass of the polyoxyethylene alkyl ether (C1) or in the thermosetting polyurethane elastomer-forming composition. 0.1 to 5% by mass of a linear aliphatic alcohol (C2) having a carbon number of 20 to 40 and a melting point of 90 ° C or less.

(2) The thermosetting polyurethane elastomer-forming composition according to the above (1), wherein the lubricant (C) comprises a polyoxyethylene alkyl ether (C1) selected from carbon atoms. a compound of at least two of a group consisting of a linear aliphatic alcohol (C2) having a melting point of 90 ° C or less and an octadecyl isocyanate (C3), and a slip agent (C) in a thermosetting polyurethane The elastomer-forming composition contains 0.2 to 8% by mass.

(3) The thermosetting polyurethane elastomer-forming composition according to the above (1), wherein the lubricant (C) comprises a polyoxyethylene alkyl ether (C1) having a carbon number of 20 to 40 and a melting point. At least one of a group consisting of a linear aliphatic alcohol (C2) and an octadecyl isocyanate (C3) at 90 ° C or lower, and a fatty acid decylamine (C4) in a thermosetting polyurethane elastomer-forming composition The total amount of the linear aliphatic alcohol (C2) and the octadecyl isocyanate (C3) having a polyoxyethylene alkyl ether (C1), a carbon number of 20 to 40, and a melting point of 90 ° C or less is 0.2 to 8 In the thermosetting polyurethane elastomer-forming composition, the fatty acid decylamine (C4) is contained in an amount of 0.05% by mass to 0.5% by mass.

(4) The thermosetting polyurethane elastomer-forming composition according to any one of the above (1), wherein the polyoxyethylene alkyl ether (C1) has a hydroxyl group value of 5 to 70 KOHmg/g.

(5) The thermosetting polyurethane elastomer-forming composition according to any one of the above (1), wherein the polyoxyethylene alkyl ether (C1) is selected from the group consisting of a polyoxyethylene alkyl ether (C1) having a carbon number of 20 to 40. And at least one of a group consisting of a linear aliphatic alcohol (C2), an octadecyl isocyanate (C3), and a fatty acid decylamine (C4) having a melting point of 90 ° C or less, used at least one of polyisocyanate (A6) and An isocyanate-based terminal prepolymer of a pre-denatured isocyanate-terminated urethane prepolymer (A0) composed of a polyol (A7).

(6) The thermosetting polyurethane elastomer-forming composition according to any one of the above (1), wherein the use comprises a polyoxyethylene alkyl ether selected from the group consisting of polyoxyethylene alkyl ethers (C1), at least one of a group consisting of a linear aliphatic alcohol (C2) having a carbon number of 20 to 40 and a melting point of 90 ° C or less, and a fatty acid decylamine (C4), and an active hydrogen-based terminal hardener (B0) An active hydrogen-based terminal hardener characterized by.

(7) The thermosetting polyurethane elastomer-forming composition according to the above (3), wherein the polyoxyethylene alkyl ether (C1) has a hydroxyl group value of 5 to 70 KOHmg/g, and a melting point of the fatty acid decylamine (C4) It is below 90 °C.

(8) A method of producing a thermosetting polyurethane elastomer according to any one of the above (1) to (7), wherein the thermosetting polyurethane elastomer-forming composition according to any one of the above (1) to (7).

(9) A JIS-A hardness obtained by thermally hardening the thermosetting polyurethane elastomer-forming composition according to any one of the above (1) to (7). It is composed of a hardened material in the range of 60 to 98.

(10) A JIS-A hardness obtained by thermally hardening the thermosetting polyurethane elastomer-forming composition according to any one of the above (1) to (7). The cured product (D) in the range of 60 to 98 has a static friction coefficient of 0.8 or less and a dynamic friction coefficient of 0.6 or less.

(11) An industrial machine part obtained by thermosetting the thermosetting polyurethane elastomer-forming composition according to any one of the above (1) to (7), wherein the JIS-A hardness is The cured product (D1) obtained by cutting the cured product (D) in the range of 60 to 98 has a static friction coefficient of 0.8 or less and a dynamic friction coefficient of 0.6 or less.

(12) An industrial machine part characterized in that the cured product (D) according to the above (10) is further heat-treated at 100 to 200 ° C for 1 to 120 minutes, and the static friction coefficient is 0.8 or less, and The dynamic friction coefficient is 0.6 or less.

(13) An industrial machine part characterized in that the cured product (D1) obtained by cutting the cured product (D) according to the above (11) is further heat-treated at 100 to 200 ° C for 1 to 120 minutes. The cured product has a static friction coefficient of 0.8 or less and a dynamic friction coefficient of 0.6 or less.

(14) A release agent composition for resin molding, characterized by comprising an organopolyoxane having at least one carboxylate selected from the group consisting of 4- toluene and 4- toluene in a molecular structure (J).

(15) A release agent composition for resin molding, characterized in that the release agent composition for resin molding described in the above (14) further comprises an anthrone (L) having an active hydrogen group. .

(16) The release agent composition for resin molding according to the above (14) to (15), which comprises at least one carboxylic acid having a group selected from the group consisting of 4- toluene and 4- toluene in a molecular structure. The organic polyoxyalkylene (J) of the acid ester contains at least one selected from the group consisting of 4- toluene (J1), 4-grade ruthenium (J2), and a carboxyl group-containing organopolyoxane (J3).

(17) The release agent composition for resin molding according to any one of the above (14) to (16), wherein the group consisting of a group of ammonium (J1) and a group of cesium (J2) The total content of at least one of the carboxylic acid esters, based on the total content of the organopolyoxane (J) having at least one carboxylic acid ester selected from the group consisting of 4- toluene and 4- toluene in the molecular structure, 0.3 mmol/g or more.

(18) The release agent composition for resin molding according to any one of the above (15) to (17), wherein, in the molecular configuration, it is selected from the group consisting of 4-grade ammonium (J1) and grade 4 (J2) 100 parts by mass of the organopolyoxane (J) of at least one of the carboxylate groups, and 5 to 150 parts by mass of the anthrone (L) having an active hydrogen group.

(19) The release agent composition for resin molding according to any one of (15) to (18) above, wherein the anthracene (L) having an active hydrogen group is an anthracene-containing anthrone.

(20) A polyurethane resin molded article, characterized in that the polyurethane resin-forming composition (K) is coated with a release agent composition for resin molding as described in any one of the above (14) to (19). The forming mold of the object is formed.

(21) A method for producing a urethane resin, wherein the release agent composition for resin molding according to any one of the above (14) to (19) is applied to a molding die to form a urethane resin. It is obtained by injecting the composition (K) into the forming mold.

(22) The polyurethane resin molded article according to the above (20), wherein the urethane resin-forming composition (K) is composed of an isocyanate-based terminal urethane prepolymer (A0) and an active hydrogen-based terminal hardener ( B0) is composed.

(23) The polyurethane resin molded article according to the above (20), wherein the urethane resin-forming composition (K) comprises a polyoxyethylene alkyl ether (C1) having a carbon number of 20 to 40. At least one compound of a group consisting of a linear aliphatic alcohol (C2) having a melting point of 90 ° C or less, octadecyl isocyanate (C3), and a fatty acid decylamine (C4) is used as a lubricant (C).

(24) The polyurethane resin molded article according to the above (22) to (23), wherein the isocyanate component of the isocyanate-based terminal urethane prepolymer (A0) comprises diphenylmethane diisocyanate or toluene diisocyanate.

(25) The polyurethane resin molded article according to any one of the above (20), wherein the isocyanate-terminated urethane prepolymer (A0) and the active compound are mixed Isocyanate group / active hydrogen group at the hydrogen-based terminal hardener (B0) The molar ratio is 1.0~3.0.

(26) An industrial machine component characterized by using the above (20), (22), (23), (24), or (the range of a dynamic friction coefficient of 0.8 or less and a JIS-A hardness of 60-98. 25) The polyurethane resin molded article according to any one of the preceding claims.

By using the thermosetting polyurethane elastomer forming composition for industrial machine parts of the present invention in an industrial machine, it is possible to achieve both low contamination and low friction which have not been obtained before, and which does not damage the NCO-based terminal amino group. The characteristics (compatibility) of the acid ester prepolymer and the active hydrogen group terminal hardener can provide a thermosetting polyurethane elastomer for uniform industrial machine parts.

Further, by using the release agent of the present invention, it is possible to obtain both high elasticity and low friction which were not previously formed, and to obtain a uniform thermosetting polyurethane elasticity for industrial machine parts by the same production method as before. body.

The industrial machine part thermosetting polyurethane elastomer molding composition of the present invention which solves the first problem includes an isocyanate group-terminated urethane prepolymer (A), an active hydrogen group terminal hardener (B), and a lubricant. The thermosetting polyurethane elastomer-forming composition of (C) is a linear agent selected from the group consisting of polyoxyethylene alkyl ether (C1) and having a carbon number of 20 to 40 and a melting point of 90 ° C or less as a lubricant (C). At least one compound of the group consisting of aliphatic alcohols (C2) has a good effect to introduce octadecyl isocyanate (C3); or is introduced from a polyoxyethylene alkyl ether (C1) having a carbon number of 20~ 40 and a linear aliphatic alcohol having a melting point of 90 ° C or less At least one of the group consisting of (C2) and octadecyl isocyanate (C3), and the fatty acid decylamine (C4), can reduce the friction coefficient.

By introducing a polyoxyethylene alkyl ether (C1), a linear aliphatic alcohol (C2) having a carbon number of 20 to 40 and a melting point of 90 ° C or lower, a reduction in the static friction coefficient and the dynamic friction coefficient can be achieved.

Further, by introduction of octadecyl isocyanate (C3), a continuous friction coefficient can be lowered, and the introduction of the fatty acid guanamine (C4) can greatly reduce the static friction coefficient.

The polyoxyethylene alkyl ether (C1) introduced as the slip agent (C) to be used in the present invention is not particularly limited as long as the effects of the present invention can be exhibited. The polyoxyethylene alkyl ether is represented by Formula 1.

[Formula 1] H _2m+1 C _m -O-(CH ₂ CH ₂ O)nH

The values of m and n in the general formula 1 are not particularly limited, and in order to reduce friction more effectively, the valence of the hydroxyl group is preferably 5 to 70 KOH mg/g. When the hydroxyl value is higher than 70 KOHmg/g, in general, the carbon number is short, and the effect as a slip component is gradually reduced. Specific examples of the commercial product of the polyoxyethylene alkyl ether (C1) include polyoxyethylene lauryl ether "NIKKOL BL-2, NIKKOL BL-4.2, NIKKOL BL-21, NIKKOL BL-25 manufactured by Nikko CHEMICALS". ; polyoxyethylene cetyl ether "NIKKOL BC-2, NIKKOL BC-5.5, NIKKOL BC-7, NIKKOL BC-10, NIKKOL BC-20, NIKKOL BC-23, NIKKOL BC-25, NIKKOL BC-30 , NIKKOL BC-40, NIKKOL BC-150"; polyoxyethylene stearyl ether "NIKKOL BS-2, "NIKKOL BS-4, "NIKKOL BS-20"; polyoxyethylene oleyl ether "NIKKOL BO-2V, "NIKKOL BO-7V, "NIKKOL BO-10V, "NIKKOL BO-15V, "NIKKOL BO-20V, "NIKKOL BO-50V"; Polyoxyethylene Twenty Diether Ether" NIKKOL BB- 5. NIKKOL BB-10, NIKKOL BB-20, NIKKOL BB-40, etc.

The linear aliphatic alcohol (C2) having a carbon number of 20 to 40 and a melting point of 90 ° C or less to be introduced into the slip agent (C) of the present invention is not particularly limited as long as the effects of the present invention can be exhibited. The linear aliphatic alcohol having a carbon number of 20 to 40 can be represented by the formula 2.

[Formula 2] CH ₃ -(CH ₂ )n-OH, n19~39

The value of n of the formula 2 is 19-39, and the melting point is 90 ° C or lower. When the melting point exceeds 90 ° C, in general, the solubility with the isocyanate-based terminal polyurethane prepolymer is inferior, and even if the temperature at the time of synthesizing the prepolymer is increased to 100 ° C or more, it is difficult to uniformly dissolve, and the reaction temperature rises due to the urea. A side reaction such as formic acidification causes high viscosity, which leads to a decrease in the quality of the prepolymer. Further, the solubility with the active hydrogen-based terminal hardener is also inferior. At the time of production, it can be dissolved by heating at a melting point or higher, and then crystallized at room temperature during filling and storage. When the thermosetting polyurethane elastomer is molded, it is necessary to reheat to a temperature equal to or higher than the melting point, and it is difficult to handle.

a linear aliphatic alcohol (C2) having a carbon number of 20 to 40 and a melting point of 90 ° C or less, and examples thereof include 1-eicosanol (C20), 1-tertiyl alcohol (C21), and 1-treondiol ( C22), 1-tristriol (C23), 1-tetracosyl alcohol (C24), 1-pentadecanol (C25), 1-hexadecanol (C26), 1-tetradecyl alcohol ( C27), 1-octacosanol (C28), 1-terp-nonanol (C29), 1-triacontanol (C30), 1-triacontanol (C31), 1-triacondiol (C32), 1-tritriol (C33), 1-tridecanol (C34), 1-tripentyl alcohol (C35), 1-trisyl alcohol (C36), 1-trityl alcohol (C37), 1-trisyl alcohol (C38), 1-trisyl alcohol (C39), 1-tetradecyl alcohol (C40).

Further, as a specific example of a commercially available product having a melting point of 90 ° C or less, BEHENYL ALCOHOL, BEHENYL ALCOHOL 65, BEHENYL ALCOHOL 80R, HAINOL 20SS, HAINOL 22SS or NIKKOL BEHENYL ALCOHOL 65 manufactured by Nikko CHEMICALS can be used. NIKKOL BEHENYL ALCOHOL 80, Performacol 350 Alcohol, etc.

The octadecyl isocyanate (C3) introduced as the slip agent (C) used in the present invention can be represented by the formula 3.

[Formula 3] CH ₃ (CH ₂ ) ₁₇ NCO

A specific example of a commercially available product of octadecyl isocyanate (C3) can be, for example, MILLIONATEO (manufactured by Hodogaya Chemical Co., Ltd.).

The fatty acid guanamine (C4) to be introduced into the slip agent (C) of the present invention is not particularly limited as long as the effects of the present invention are exerted. The fatty acid decylamine can be used as a saturated fatty acid decylamine, an unsaturated fatty acid decylamine, a substituted decylamine, a saturated fatty acid bis- decylamine, or a saturated fatty acid bis decylamine for more effective mapping to reduce friction, and the melting point is preferably below 90 ° C. . When the melting point exceeds 90 ° C, in general, the solubility of the isocyanate-based terminal polyurethane prepolymer is poor, and even if the temperature at the time of synthesizing the prepolymer is increased to 100 ° C or higher, it is difficult to uniformly dissolve, and the reaction temperature rises due to the increase in the reaction temperature. A side reaction such as an allotphanate is highly viscous, resulting in a decrease in the quality of the prepolymer. Also, dissolved with an active hydrogen-based terminal hardener The solution is also poor. At the time of production, it can be dissolved by heating at a temperature equal to or higher than the melting point. However, when it is filled and stored, it is crystallized at normal temperature. When the thermosetting polyurethane elastomer is molded, it is necessary to reheat it to a temperature equal to or higher than the melting point, and it is difficult to handle.

The fatty acid guanamine (C4) may, for example, be a lauric acid amide of a saturated fatty acid guanamine, decyl palmitate, decylamine citrate, decyl decyl amide, hydroxystearic acid amide, or an unsaturated fatty acid guanamine. Oleic acid decylamine, succinic acid decylamine, N-oleyl palmitate, substituted decylamine, N-stearyl stearate, N-stearyl oleate, N-oleyl stearate Acid decylamine, N-stearyl succinic acid decylamine, saturated fatty acid bis decylamine methylene bis stearate amide, ethylene bis octyl decylamine, ethylene bismuth laurate oxime, ethylene Ammonium bis-stearate, decylamine bishydroxystearate, decylamine bis-bisanthanate, decyl hexamethylene bis-stearate, decyl hexamethylene bis-decanoate, Hexamethylene bishydroxy decylamine, N,N-distearate decanoate, N,N-distearoyl sebacate, and unsaturated fatty acid bisamine The acid amide, ethylene bismuth amide, hexamethylene bis oleate, N,N-dioleyl adipate, N,N-dioleyl sebacate and the like. Further, as a specific example of a commercially available product having a melting point of 90 ° C or less, DIAMID Y, DIAMID O-200, DIAMID L-20, Nikka Amide OP, Nikka Amide SO, Nikka Amide OS, Nikka can be used. Amide SE and so on.

In the first embodiment, when the content of the polyoxyethylene alkyl ether (C1) in the thermosetting polyurethane elastomer molded article is less than 0.1% by mass, the effect of reducing friction cannot be seen. Moreover, when it exceeds 8% by mass, the effect of reducing friction can be seen, but the increase in the monofunctional component may cause a decrease in the physical properties of the obtained thermosetting polyurethane elastomer.

In the second embodiment, the carbon number is 20 to 40 and the melting point is 90 ° C. When the content of the lower linear aliphatic alcohol (C2) is less than 0.1% by mass, the effect of reducing friction cannot be seen. Moreover, when it exceeds 5% by mass, the effect of reducing friction can be seen, but the increase in the monofunctional component may cause a decrease in the physical properties of the obtained thermosetting polyurethane elastomer.

In the third embodiment, the polyoxyethylene alkyl ether (C1) selected from the thermosetting polyurethane elastomer molded article and the linear aliphatic alcohol (C2 having a carbon number of 20 to 40 and a melting point of 90 ° C or less) are used. The total amount of at least one compound and the octadecyl isocyanate (C3) is preferably 0.2 to 8% by mass in the thermosetting polyurethane elastomer molded article, and particularly preferably 1 to 6% by mass. . When the total amount of the lubricant (C) is less than 0.2% by mass, the effect of sufficiently reducing the friction cannot be seen. When the amount is more than 8% by mass, the physical properties are lowered or the quality of the prepolymer is lowered due to a decrease in the average number of functional groups. Hey.

Further, in the fourth embodiment, the lubricant (C) is a fatty acid decylamine (C4) as an essential component, and the polyoxyethylene alkyl ether (C1) may have a carbon number of 20 to 40 and a melting point of 90 ° C or less. One or more selected from the group consisting of a linear aliphatic alcohol (C2) and an octadecyl isocyanate (C3), wherein the epoxy group is selected from the group consisting of polyoxyethylene alkyl ether (C1) and a carbon number of 20 to 40. The combination of at least one of the linear aliphatic alcohols (C2) having a temperature of 90 ° C or less and the octadecyl isocyanate (C3) is particularly preferable. A slip composition of a group consisting of a linear polyhydric alcohol alkyl ether (C1), a linear aliphatic alcohol (C2) having a carbon number of 20 to 40 and a melting point of 90 ° C or less, and octadecyl isocyanate (C3) The amount of introduction is preferably 0.2 to 8% by mass of the entire thermosetting polyurethane elastomer-forming composition. When the amount is less than 0.2% by mass, the effect of sufficiently reducing the friction cannot be seen. When the amount is more than 8% by mass, the physical properties are lowered or the quality of the prepolymer is lowered due to a decrease in the average number of functional groups. Use with these The introduction amount of the fatty acid decylamine (C4) to be used is preferably 0.05 to 0.5% by mass based on the total amount of the thermosetting polyurethane elastomer-forming composition, in consideration of the minimum amount of 0.05 to 0.3% by mass of the bleed (dusting). Especially good.

In the first embodiment, the NCO-based terminal urethane prepolymer (A) used in the present invention is not particularly limited as long as it contains the NCO-based terminal urethane prepolymer (A0). Among them, an NCO-based terminal urethane prepolymer (A1) further containing a polyoxyethylene alkyl ether (C1) is preferably used. NCO-based terminal urethane prepolymer (A1), if necessary, using reaction inhibitor (E) via at least polyisocyanate (A6), polyol (A7), and polyoxyethylene alkyl ether (C1) The urethanization reaction is preferred. Here, the NCO-based terminal urethane prepolymer (A0) is prepared by at least a polyisocyanate (A6) and a polyhydric alcohol (A7), and does not contain a slip agent (C) component.

The NCO-based terminal urethane prepolymer (A) or (A1) preferably has an NCO content of 5 to 25% by mass. When the NCO content is lower than 5% by mass, the viscosity of the prepolymer is mainly increased, and the fluidity of the urethane resin is remarkably deteriorated at the time of injection molding. When the temperature is higher than 25% by mass, the stability of the characteristics during storage and use is remarkably deteriorated, and it is difficult to obtain stable industrial machine parts, and it is related to problems such as molding failure, so that it is not suitable as an industrial machine parts. The case of the NCO-based terminal urethane prepolymer.

The method for producing the NCO-based terminal urethane prepolymer (A1) is not particularly limited, and examples thereof include the following production methods. The polyisocyanate (A6) and the reaction inhibitor (E) are stirred in a stirred vessel, and then the temperature in the stirred vessel is maintained at 40 to 70 ° C, and the polyol (A7) and polyoxyethylene alkyl ether (C1) are charged. ) Stir. Next, the temperature in the stirring vessel is maintained at 70 to 90 ° C. It is obtained by a carbamate reaction in about 2 to 5 hours.

In the second embodiment, the NCO-based terminal urethane prepolymer (A) used in the present invention is not particularly limited as long as it contains at least the NCO-based terminal urethane prepolymer (A0). Among them, an NCO-based terminal urethane prepolymer (A2) having a linear aliphatic alcohol (C2) having a carbon number of 20 to 40 and a melting point of 90 ° C or less may be suitably used. NCO-based terminal urethane prepolymer (A2), if necessary, using reaction inhibitor (E), at least polyisocyanate (A6), polyol (A7), and carbon number 20-40, melting point 90 The urethanization reaction of a linear aliphatic alcohol (C2) below °C is preferred.

The NCO-based terminal urethane prepolymer (A) or (A2) NCO content is preferably 5 to 25% by mass. When the NCO content is lower than 5% by mass, the viscosity of the prepolymer is mainly increased, and the fluidity of the urethane resin is remarkably deteriorated at the time of injection molding. When the temperature is higher than 25% by mass, the stability of the characteristics during storage and use is remarkably deteriorated, and it is difficult to obtain stable industrial machine parts, and it is related to problems such as molding failure, so that it is not suitable as an industrial machine parts. The case of the NCO-based terminal urethane prepolymer.

The method for producing the NCO-based terminal urethane prepolymer (A2) is not particularly limited, and examples thereof include the following production methods. The polyisocyanate (A6) and the reaction inhibitor (E) are stirred in a stirred vessel, and then the temperature in the stirred vessel is maintained at 40 to 70 ° C, and the polyol (A7) and the carbon number are 20 to 40 and the melting point is The linear aliphatic alcohol (C2) below 90 ° C is stirred. Next, the temperature in the stirring vessel is maintained at 70 to 90 ° C, and a urethanization reaction is carried out for about 2 to 5 hours.

The third embodiment is used for the NCO-based terminal amino group of the present invention. The formate prepolymer (A) is not particularly limited as long as it contains the NCO-based terminal polyurethane prepolymer (A0). Wherein, an NCO-based terminal urethane prepolymer (A3) denatured by further adding octadecyl isocyanate (C3) is used, or a further addition is selected from a polyoxyethylene alkyl ether (C1) having a carbon number of 20~ 40 at least one compound of a group consisting of a linear aliphatic alcohol (C2) having a melting point of 90 ° C or less, and an NCO-based terminal urethane prepolymer (A4) denatured with octadecyl isocyanate (C3) It is better.

Further, the term "denaturation" as used herein refers to a change in the properties of the NCO-based terminal urethane prepolymer (A0), such as an NCO-based terminal urethane prepolymer denatured with octadecyl isocyanate (C3) (A3). The NCO-based terminal prepolymer prepared by adding polyisocyanate (A6) and polyol (A7) plus octadecyl isocyanate (C3).

Further, a reaction inhibitor (E) may be added as needed. The NCO content of the NCO-based terminal urethane prepolymer (A), (A3), or (A4) is preferably 5 to 25% by mass. When the NCO content is lower than 5% by mass, the viscosity of the prepolymer is mainly increased, and the fluidity of the urethane resin is remarkably deteriorated at the time of injection molding. When the temperature is higher than 25% by mass, the stability of the characteristics during storage and use is remarkably deteriorated, and it is difficult to obtain stable industrial machine parts, and it is related to problems such as molding failure, so that it is not suitable as an industrial machine parts. The case of the NCO-based terminal urethane prepolymer.

The method for producing the NCO-based terminal urethane prepolymer (A3) or (A4) is not particularly limited, and examples thereof include the following production methods. In the mixing container, the polyisocyanate (A6), octadecyl isocyanate (C3), and the reaction inhibitor (E) are charged, and then the temperature in the container is maintained at 40 to 70 ° C. a mixture of at least one of a group consisting of polyoxyethylene alkyl ether (C1) and a linear aliphatic alcohol (C2) having a carbon number of 20 to 40 and a melting point of 90 ° C or less, and a polyol (A7), Or the polyol (A7) is stirred up. Next, the temperature in the stirring vessel is maintained at 70 to 90 ° C, and a urethanization reaction is carried out for about 2 to 5 hours to obtain an isocyanate group-terminated urethane prepolymer (A3) or (A4). Further, octadecyl isocyanate (C3) may be added after the urethanization reaction.

In the fourth embodiment, the NCO-based terminal urethane prepolymer (A) used in the present invention is not particularly limited as long as it contains the NCO-based terminal polyurethane prepolymer (A0). Wherein, a linear aliphatic alcohol (C2) selected from the group consisting of polyoxyethylene alkyl ether (C1), having a carbon number of 20 to 40 and a melting point of 90 ° C or lower, octadecyl isocyanate (C3), and fatty acid decylamine are used. (C4) It is preferred that the NCO-based terminal urethane prepolymer (A5) is denatured by at least one compound of the group consisting of.

Further, the term "denaturation" as used herein refers to a property of changing the NCO-based terminal urethane prepolymer (A0), for example, an NCO-based terminal urethane prepolymer (A5) denatured with a fatty acid decylamine (C4), It is an NCO-based terminal prepolymer prepared by polyisocyanate (A6) and polyol (A7) plus fatty acid decylamine (C4).

Further, a reaction inhibitor (E) may be added as needed. The NCO-based terminal urethane prepolymer (A) or (A5) preferably has an NCO content of 5 to 25% by mass. When the NCO content is lower than 5% by mass, the viscosity of the prepolymer is mainly increased, and the fluidity of the urethane resin is remarkably deteriorated at the time of injection molding. When the temperature is higher than 25% by mass, the stability of the characteristics during storage and use is remarkably deteriorated, and it is difficult to obtain stable industrial machine parts, and it is related to problems such as molding failure, so that it is not suitable as an industrial machine parts. The case of the NCO-based terminal urethane prepolymer.

NCO-based terminal urethane prepolymer for use in the present invention The production method of (A5) is not particularly limited, and examples thereof include the following production methods. In the mixing vessel, the polyisocyanate (A6), optionally octadecyl isocyanate (C3) and the reaction inhibitor (E) are added, and then the temperature in the vessel is maintained at 40 to 70 ° C, if necessary. At least one selected from the group consisting of polyoxyethylene alkyl ether (C1) and a linear aliphatic alcohol (C2) having a carbon number of 20 to 40 and a melting point of 90 ° C or less is mixed with a polyol (A7). It. In addition, the fatty acid guanamine (C4) is added as needed. The isocyanate-based terminal urethane prepolymer (A5) can be obtained by maintaining the temperature in the stirring vessel at 70 to 90 ° C for a urethanization reaction for about 2 to 5 hours. Further, octadecyl isocyanate (C3) and fatty acid decylamine (C4) may be mixed after the urethanization reaction.

The polyisocyanate (A6) used in the present invention is not particularly limited as long as the effects of the present invention can be exerted. From the viewpoint of mechanical properties or reaction control, at least one selected from the group consisting of aromatic diisocyanates and 4,4'-diphenylmethane diisocyanate are particularly preferred.

<polyisocyanate (A6)>

Specific examples of the polyisocyanate include hexamethylene isocyanate, lysine diisocyanate, isophorone diisocyanate, cyclohexyl diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and hydrogenated xylene Diisocyanate, hydrogenated trimethyl benzene diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, 2,2,4- An aliphatic group such as trimethylhexamethylene-1,6-diisocyanate or 2,4,4-trimethylhexamethylene-1,6-diisocyanate is an alicyclic diisocyanate. 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate 4,4'-dibenzyl diisocyanate, 1,5-naphthyl diisocyanate An aromatic diisocyanate such as ester, p-phenylene diisocyanate, toluene-2,4-diisocyanate or toluene-2,6-diisocyanate. Difficult yellowing diisocyanate such as o-xylylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate or tetramethyl dimethyl diisocyanate. Further, any of the isocyanate urethane denatured body, the urea denatured body, the carboxydiimide denatured body, the urinary imide denatured body, the urethane diketone denatured body, the isocyanurate denatured body, the urea form can also be used. Acid ester denatured body and the like.

<Polyol (A7)>

The polyol (A7) to be used in the present invention is not particularly limited as long as it exhibits the effects of the present invention, and is selected from the viewpoints of mechanical properties and glass transition temperature, and is selected from the group consisting of an average functional group number of 2 to 3 and a number average molecular weight of 250 to 5,000. At least one of a polyester polyol and a polyether polyol is preferred. Further, a monomer polyol may be used in combination as needed.

Further, any active polyol may be used as the active hydrogen-based terminal curing agent (B) to be described later.

<polyester polyol>

Specific examples of the polyester polyol include phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, succinic acid, tartaric acid, oxalic acid, malonic acid, glutaric acid, and adipic acid. Pimelic acid, suberic acid, glutaconic acid, azelaic acid, sebacic acid, 1,4-cyclohexyl dicarboxylic acid, α-hydrogenated muconic acid, β-hydrogenated acid, α-butyl- One or more kinds of dicarboxylic acids such as α-ethylglutaric acid, α,β-diethyl succinic acid, maleic acid, and fumaric acid, or these acid anhydrides, and ethylene glycol and 1,2-propanediol; 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8- Octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3- Dimethylol heptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid glycol, bisphenol A Low molecular weight polyol having a molecular weight of 500 or less, such as ethylene oxide or propylene oxide adduct, bis(β-hydroxyethyl)benzene, benzenedimethanol, glycerin, trimethylolpropane or isovaerythritol One or more kinds of polycondensation reactions are obtained. Further, a polyester-guanamine polyol can also be obtained by substituting a part of a low molecular polyol with a low molecular polyamine such as hexamethylenediamine, isophoronediamine or monoethanolamine.

<Polyether polyol>

Specific examples of the polyether polyol include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol. 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3- Dimethylol heptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid glycol, bisphenol A , low molecular polyols such as bis(β-hydroxyethyl)benzene, benzenedimethanol, glycerin, trimethylolpropane, and isoamyl alcohol; or ethylene diamine, propylene diamine, toluenediamine, isophthalic acid a compound having two or more, preferably 2 to 3 active hydrogen groups, such as a low molecular polyamine such as a diamine, dimethylmethanediamine or benzodimethyldiamine, as a starter a polyether polyol obtained by addition polymerization of an alkenyl oxide such as ethylene oxide, propylene oxide or butylene oxide, or an alkyl glycidyl ether such as methyl glycidyl ether or a phenyl shrinkage A polyether polyol obtained by ring-opening polymerization of an aryl glycidyl ether such as glyceryl ether or a cyclic ether monomer such as tetrahydrofuran.

<polycarbonate polyol>

Specific examples of the polycarbonate polyol include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butane. Alcohol, 1,5-pentane Alcohol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylol heptane, Diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid glycol, ethylene oxide or ring of bisphenol A One or more kinds of low molecular weight polyols such as oxypropylene adduct, bis(β-hydroxyethyl)benzene, benzenedimethanol, glycerin, trimethylolpropane, and isovaerythritol, and dimethyl carbonate, a dialkyl carbonate such as diethyl carbonate; an alkyl carbonate such as ethylene carbonate or propylene carbonate; diphenyl carbonate, dinaphthyl carbonate, dinonyl carbonate, diphenanthrene carbonate, and diphenocene carbonate. A dearylation reaction or a dephenolization reaction of a diaryl carbonate such as an ester or a tetrahydronaphthyl carbonate.

Further, the polyol (A7) may be a polyolefin polyol, an acrylic polyol, an anthrone polyol, a castor oil polyol, a fluorine polyol, or a monomer polyol, alone or in a range not degrading performance. Use two or more types.

<polyolefin polyol>

Specific examples of the polyolefin polyol include, for example, polybutadiene having two or more hydroxyl groups, hydrogenated polybutadiene, polyisoprene, and hydrogenated polyisoprene.

<Acrylic polyol>

The acrylic polyol, for example, an acrylate and/or methacrylate (hereinafter referred to as (meth) acrylate), an acryl hydroxy compound having at least one or more hydroxyl groups which can serve as a reaction point in the molecule, and/or Further, a methacrylic acid hydroxy compound (hereinafter referred to as a (meth)acrylic acid hydroxy compound) and a polymerization initiator are used to copolymerize an acrylic monomer using thermal energy, ultraviolet light, or light energy such as an electron beam.

<(Meth)acrylate>

Specific examples of the (meth) acrylate include alkyl esters having 1 to 20 carbon atoms. in this way Specific examples of the acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and amyl (meth)acrylate. Hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, decyl (meth)acrylate, (meth)acrylic acid An alkyl (meth)acrylate such as dodecyl ester; an ester of (meth)acrylic acid and an alicyclic alcohol such as (meth)cyclohexyl ester; phenyl (meth)acrylate or benzyl (meth)acrylate; An aryl (meth) acrylate or the like. These (meth)acrylates may be used alone or in combination of two or more.

<(Meth)acrylic acid hydroxy compound>

Specific examples of the (meth)acrylic acid hydroxy compound include, for example, at least one hydroxyl group which can be a reaction point with the polyisocyanate composition in the molecule, specifically, 2-hydroxyethyl acrylate or acrylic acid- Acrylic acid hydroxy compound such as 2-hydroxypropyl ester, 4-hydroxybutyl acrylate, 3-hydroxy-2,2-dimethylpropyl acrylate or isoamyl tetrapropylate. Further, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 3-hydroxy-2,2-dimethylpropyl methacrylate, A methacrylic acid hydroxy compound such as trimethylisopentyl glycol ester. These acryl hydroxy compounds and methacrylic acid hydroxy compounds may be used alone or in combination of two or more.

<Polymerization initiator>

The polymerization initiator may, for example, be a thermal polymerization initiator or a photopolymerization initiator, and may be appropriately selected depending on the polymerization method.

Specific examples of the thermal polymerization initiator include peroxycarbonates such as di-2-ethylhexyl peroxydicarbonate; tert-butyl peroxybenzoate; and 2-ethylhexanoic acid peroxide. Tributyl ester, butyl isopropyl peroxycarbonate, a peroxyester such as oxidized third hexyl isopropyl carbonate; di(t-butylperoxy)-2-methylcyclohexane, bis(t-butylperoxy)-3,3,5- Peroxy ketals such as trimethylcyclohexane and di(t-butylperoxy)cyclohexane.

Further, specific examples of the photopolymerization initiator include acetophenone, methoxyacetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, and 2,2. -dimethoxy-2-phenylacetophenone, α-hydroxy-α,α'-dimethylacetophenone, 2-hydroxy-2-cyclohexylacetophenone, 2-methyl-1-[ Acetophenones such as 4-(methylthio)phenyl]-2-morpholinyl-1-propanone; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl butyl Benzoyl ethers such as ethers; benzophenone, 2-chlorobenzophenone, p-, p-dichlorobenzophenone, N, N'-tetramethyl-4,4'-diamine Ketones such as benzophenone and 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl) ketone; thioxanthone, 2-chlorothioxanthone, 2-methylthiophene a thioxanthone such as a ketone; a phosphine oxide such as a bis-decylphosphine oxide or a benzhydrylphosphine oxide; a ketal such as a benzyldimethylketal; a camphor-2,3-dione; , cockroaches and other cockroaches.

<Anthrone polyol>

Specific examples of the fluorenone polyol include, for example, a vinyl group-containing fluorenone compound obtained by polymerizing γ-methacryloxypropyltrimethoxy decane or the like; and α, ω having at least one terminal hydroxyl group in the molecule. a polyoxynonane such as dihydroxypolydimethyloxane or α,ω-dihydroxypolydiphenyloxane.

<castor oil-based polyol>

Specific examples of the castor oil-based polyol include a linear or branched polyester polyol obtained by reacting a castor oil fatty acid with a polyol. Further, dehydrated castor oil, partially dehydrated partially dehydrated castor oil, hydrogenated castor oil, or the like can also be used.

<Fluoropolyol>

Specific examples of the fluorine-based polyol include a linear or branched polyol obtained by a copolymerization reaction using a fluorine-containing monomer and a monomer having a hydroxyl group as essential components. Here, the fluorine-containing monomer is preferably a fluoroolefin, and examples thereof include tetrafluoroethylene, chlorotrifluoroethyl, trichlorofluoroethylene, hexafluoropropylene, vinylidene fluoride, vinyl fluoride, and trifluoromethyltrifluoroethylene. Wait. Further, examples of the monomer having a hydroxyl group include a hydroxyalkyl vinyl ether such as hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether or cyclohexanediol monovinyl ether; 2-hydroxyethyl A hydroxyalkyl allyl ether such as a allylic ether; a hydroxy group-containing carboxylic acid vinyl ester such as a hydroxyalkyl crotonic acid vinyl ester; or a hydroxy group-containing monomer such as an allyl ester.

<Monomer polyol>

Specific examples of the monomer polyol include, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butane. Alcohol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3 - dimethylol heptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, bisphenol A, bis(β-hydroxyethyl)benzene, benzenedimethanol, glycerin, trimethylolpropane, isovalerol, and the like.

The active hydrogen-based terminal hardener (B) used in the present invention can be optionally used from among the above polyols. Among them, a mixture of a polyester polyol having an average number of functional groups of 2 to 3 and a number average molecular weight of 250 to 5,000, a polyether polyol, and a polycarbonate polyol is preferably used. Moreover, the monomer polyol can be used singly or in combination of two or more kinds from the viewpoint of improving mechanical properties or moldability. The monomer polyol is preferably a mixture of 1,4-butanediol and trimethylolpropane.

Further, it may be added as a lubricant (C) according to each embodiment. At least one compound selected from the group consisting of polyoxyethylene alkyl ether (C1), a linear aliphatic alcohol (C2) having a carbon number of 20 to 40 and a melting point of 90 ° C or less, and a fatty acid decylamine (C4) is used. .

Further, an active hydrogen-based terminal hardener containing no slip agent (C) was used as an active hydrogen-based terminal hardener (B0).

For use in the active hydrogen-based terminal hardener (B) of the present invention, a catalyst (F) may be added as needed.

The catalyst (F) is not particularly limited as long as the effect of the present invention can be exerted, and the isocyanurate catalyst (F1) for polyurethane is used as a potassium salt or a grade 4 from the viewpoint of improving mechanical properties or moldability. Ammonium salt is preferred; polyureidoate catalyst (F2) is preferably N,N,N'-trimethylaminoethylethanolamine or N,N-dimethylaminoethoxyethanol . In addition, a polyurethaneizing catalyst (F3) may be used as needed, or may be used alone. As the polyurethane-based catalyst (F3), an amine catalyst such as a general triethylenediamine or an imidazole catalyst such as 1-isobutyl-2-methylimidazole can be used, and the laurel is used. A metal-based catalyst such as dioctyltin acid.

<Isocyanurate Catalytic Catalyst (F1) for Polyurethane>

The isocyanurate-catalyzed catalyst (F1) for the isocyanurate-catalyzed catalytic reaction can be suitably selected and used by a conventional catalyst, and specific examples thereof include, for example, triethyl. Tertiary amine such as amine, N-ethylpiperidine, N,N'-dimethylpiperazine, N-ethylmorpholine, Mannich base of phenolic compound, tetramethylammonium hydrogencarbonate, methyl Triethylammonium hydrogencarbonate, ethyltrimethylammonium hydrogencarbonate, propyltrimethylammonium hydrogencarbonate, butyltrimethylammonium hydrogencarbonate, pentyltrimethylammonium hydrogencarbonate, hexyl three Methylammonium hydrogencarbonate, heptyl ammonium hydrogencarbonate, octyltrimethylammonium hydrogencarbonate, decyltrimethylammonium hydrogencarbonate, decyltrimethylammonium hydrogencarbonate a salt, undecyltrimethylammonium hydrogencarbonate, dodecyltrimethylammonium hydrogencarbonate, tridecyltrimethylammonium hydrogencarbonate, tetradecyltrimethylammonium hydrogencarbonate, Pentadecyltrimethylammonium hydrogencarbonate, cetyltrimethylammonium hydrogencarbonate, heptadecyltrimethylammonium hydrogencarbonate, octadecyltrimethylammonium hydrogencarbonate, (2 -hydroxypropyl)trimethylammonium hydrogencarbonate, hydroxyethyltrimethylammonium hydrogencarbonate, 1-methyl-1-aza-4-azabicyclo[2.2.2]octane hydrogencarbonate, Or quaternary ammonium hydrogencarbonate such as 1,1-dimethyl-4-methylpiperidine hydrogencarbonate, tetramethylammonium carbonate, methyltriethylammonium carbonate, ethyltrimethylammonium carbonate Salt, propyltrimethylammonium carbonate, butyltrimethylammonium carbonate, pentyltrimethylammonium carbonate, hexyltrimethylammonium carbonate, heptyltrimethylammonium carbonate, octyltrimethyl Alkyl ammonium carbonate, decyl trimethyl ammonium carbonate, decyl trimethyl ammonium carbonate, undecyl trimethyl ammonium carbonate, dodecyl trimethyl ammonium carbonate, tridecyl three Methyl ammonium carbonate, tetradecyl trimethyl ammonium carbonate Pentadecyltrimethylammonium carbonate, cetyltrimethylammonium carbonate, heptadecyltrimethylammonium carbonate, octadecyltrimethylammonium carbonate, (2-hydroxypropyl) Trimethylammonium carbonate, hydroxyethyltrimethylammonium carbonate, 1-methyl-1-aza-4-azabicyclo[2.2.2]octane carbonate, or 1,1-dimethyl Hydrogenation of hydroxyalkylammonium such as quaternary ammonium carbonate, trimethylhydroxypropylammonium, trimethylhydroxypropylammonium or triethylhydroxyethylammonium such as 4-methylpiperidine carbonate An alkali metal salt of a carboxylic acid such as an organic weak acid salt, an ester acid, a propionic acid, a butyric acid, a caproic acid, a citric acid, a oxalic acid, a caprylic acid, a tetradecanoic acid or a naphthenic acid. Further, these isocyanurate-forming catalysts (F1) for polyurethane may be used alone or in combination of two or more.

Further, the amount of the isocyanurate catalyst (F1) used is the sum of the NCO-based terminal urethane prepolymer (A) and the active hydrogen-based terminal hardener (B). The mass is preferably used in the range of 0.001 to 0.5% by mass, and it is more preferably used in the range of 0.005 to 0.10% by mass from the viewpoint of easiness of reaction control.

<Urea allophanate catalyst for polyurethane (F2)>

The polyurethane allophanation catalyst (F2) used in the allophanate reaction can be suitably used by a conventional catalyst, and for example, a metal salt of a carboxylic acid can be used.

Specific examples of the carboxylic acid include saturated aliphatic carboxylic acids such as acetic acid, propionic acid, butyric acid, caproic acid, octanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and 2-ethylhexanoic acid. a mixture of a saturated monocyclic carboxylic acid such as cyclohexanecarboxylic acid or cyclopentanecarboxylic acid, a saturated heterocyclic carboxylic acid such as bicyclo[4.4.0]non-2-carboxylic acid or the like, or a carboxylic acid such as naphthenic acid; An unsaturated aliphatic carboxylic acid such as oleic acid, linoleic acid, linolenic acid, soybean oil fatty acid or tar fatty acid, an aromatic aliphatic carboxylic acid such as diphenylacetic acid, an aromatic carboxylic acid such as benzoic acid or toluic acid, or the like. Monocarboxylic acids; phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, succinic acid, tartaric acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid , glutaconic acid, sebacic acid, sebacic acid, 1,4-cyclohexyl dicarboxylic acid, α-hydrogenated muconic acid, β-hydrogenated muconic acid, α-butyl-α-ethylglutaric acid And polycarboxylic acids such as α,β-diethyl succinic acid, maleic acid, fumaric acid, trimellitic acid, and pyromellitic acid.

Further, examples of the metal constituting the metal salt of the carboxylic acid include an alkali metal such as lithium, sodium or potassium, an alkaline earth metal such as magnesium, calcium or barium, another main group metal such as tin or lead, manganese or iron, and the like. Transition metals such as cobalt, nickel, copper, zinc, and zirconium. These metal carboxylate salts can be used individually or in combination of 2 or more types.

Other examples of the alkanolamines include N,N,N'-trimethylaminoethylethanolamine, N,N-dimethylaminoethoxyethanol, and the like.

Further, the amount of the allophanate catalyst (F2) used is 0.001 to 0.5 for the total mass of the NCO-based terminal urethane prepolymer (A) and the active hydrogen-based terminal hardener (B). The range of the mass % is preferably used, and it is more preferably used in the range of 0.005 to 0.10% by mass from the viewpoint of easiness of reaction control.

<urethane-based catalyst for polyurethane (F3)>

The urethane-forming catalyst (F3) for the polyurethane used in the urethanization reaction can be suitably selected and used by a conventional catalyst.

Specific examples of the amine-based catalyst include, for example, triethylenediamine, 2-methyltriethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N'. , N'-tetramethyl propylene diamine, N, N, N', N", N"-pentamethyldiethylene triamine, N, N, N', N", N"-pentamethyl (3-Aminopropyl)ethylenediamine, N,N,N',N",N"-pentamethyldipropenetriamine, N,N,N',N'-tetramethylhexamethylene Diamine, bis(2-dimethylaminoethyl)ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol, N,N-dimethyl-N' -(2-hydroxyethyl)ethylenediamine, N,N-dimethyl-N'-(2-hydroxyethyl)propanediamine, bis(dimethylamino)amine, bis(dimethylamine) Propyl) isopropanolamine and the like.

Specific examples of the imidazole-based catalyst include 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethylaminopropylimidazole, and N. , N-dimethylhexanolamine, N-methyl-N'-(2-hydroxyethyl) piperidine, 1-(2-hydroxyethyl)imidazole, 1-(2-hydroxypropyl)imidazole, 1-(2-hydroxyethyl)-2-methylimidazole, 1-(2-hydroxypropyl)-2-methylimidazole, and the like.

Specific examples of the metal catalyst system include stannous diacetate, stannous dioctoate, stannous dioleate, stannous dilaurate, dibutyltin oxide, dibutyltin diacetate, and dibutyltin dilaurate. , dichlorodibutyltin, dilaurin, dioctyl tin, etc. Machine tin catalyst, or nickel octoate, nickel naphthenate, cobalt octoate, cobalt naphthenate, bismuth octoate, bismuth naphthenate.

Further, the amount of the urethane-based catalyst (F3) used is 0.001 to 0.5 by mass for the total mass of the NCO-based terminal urethane prepolymer (A) and the active hydrogen-based terminal hardener (B). The range of % is preferably used, and it is more preferably used in the range of 0.005 to 0.10% by mass from the viewpoint of easiness of reaction control.

The reaction inhibitor (E) used in the present invention is not particularly limited as long as the effects of the present invention can be exerted.

Specific examples of the reaction inhibitor (E) include a phosphite type, an acid phosphate type, and a polyoxyethylene alkyl ether phosphate type. The phosphite system is triphenyl phosphate, tridecyl phosphate, dibutyl phosphate or the like. The acidic phosphate ester is butyl citrate, 2-ethylhexyl acid phosphate, isodecyl phosphate. Polyoxyethylene alkyl ether phosphate system, is di(C12-15)alkanol ether-2 phosphate, di(C12-15)-alkanol ether-4 phosphate, di(C12-15)-alkane Alcohol ether-6 phosphate, di(C12-15)-alkanol ether-8 phosphate, di(C12-15) alkanol ether-10 phosphate, phosphoric acid (mono, di) polyethylene glycol (3EO C10-14 alcohol, polyoxyethylene tridecyl ether phosphate, phosphoric acid (mono, di) polyethylene glycol (4E0) 4-nonylphenyl ester.

In the present invention, an antioxidant, a defoaming agent, an ultraviolet absorber or the like may be introduced as an additive into the formable composition as needed.

In the present invention, the thermosetting polyurethane elastomer-forming composition described above is subjected to a step of performing a curing treatment (specifically, a treatment for promoting hardening by heating) in a molding die, and the production has a urethane formation and a different A heat-curable polyurethane elastomer molded article which is cyanurated and allophanated.

At this time, thermosetting is produced using the forming composition of the present invention. The method of molding a polyurethane elastomer is preferably carried out by a method comprising the following steps.

step 1):

When the NCO-based terminal prepolymer (A) and the active hydrogen-based terminal hardener (B) are not contained in the active hydrogen-based terminal hardener (B), a catalyst (F) is additionally added. The composition is prepared by uniformly mixing. Further, when air is caught and bubbles are observed, bubbles are removed by vacuum defoaming or the like. For these steps, a dedicated polyurethane injection molding machine is preferred.

Step (2):

After the composition for forming is mixed, the composition for forming is injected into a molding die (injection molding), and the composition for forming is subjected to a curing treatment (specifically, a heating-promoting hardening reaction) in the molding die. In this case, the temperature of the molding die can be easily and surely subjected to the conditions of urethanization, isocyanuration, and allophanation reaction, and it is preferably in the range of 80 to 170 °C. .

Step (3):

After the forming composition is cured, the cured product (i.e., the thermosetting polyurethane elastomer molded article) is taken out (released) from the forming mold. Further, in the present invention, the time required from the above injection molding to demolding is not particularly limited, and the amount of the catalyst and the preheating of the molding die are adjusted from the viewpoint of productivity of the thermosetting polyurethane elastomer to which the present invention is intended. The temperature is preferably in the range of 30 to 600 seconds.

Step (4):

After the hardening, the thermosetting polyurethane elastomer molded product was released from the mold, and then subjected to one-week aging treatment at room temperature.

Further, the molar ratio of the NCO group content of the NCO-based terminal prepolymer to the OH group (NH ₂ group) of the active hydrogen-based terminal hardener at the time of injection molding is hereinafter referred to as "α value". ”, OH group (NH ₂ group) / NCO group, can be selected according to the type of catalyst or the physical properties of the target.

For example, when an isocyanurate catalyst (F1) for polyurethane or an allophanate catalyst (F2) for polyurethane is used, the α value is preferably 0.2 to 0.8. In this case, a urethane-forming catalyst (F3) may also be used in combination. When it is lower than 0.2, the amount of isocyanurate or allophanation is extremely increased due to an excessive amount of isocyanate, and the bridging point is increased, which causes a significant decrease in the properties of the stretched material. Further, when it exceeds 0.8, the bridging point due to isocyanuration or allophanation decreases, and the initial modulus (M100) decreases, and the amount of deformation to stress is large, which causes hardness. Insufficient strength.

Further, when the urethanized catalyst (F3) is used alone, the α value is preferably 0.8 to 1.0. When the temperature is lower than 0.8, the molecular elongation cannot be sufficiently performed, and there is a problem that the hardening occurs. Further, when it exceeds 1.0, there are cases in which physical properties are lowered or insufficient hardening occurs.

The thermosetting polyurethane elastomer molded article produced by using the composition for forming of the present invention is heat-treated at 100 to 200 ° C for 1 to 60 minutes after demolding, whereby the friction can be effectively reduced. When the heating temperature is lower than 100 ° C, or when the time is lower than 1 minute, the effect is small because the lubricant is not easily transferred to the outermost surface. Further, when the heating temperature exceeds 200 ° C or the time exceeds 60 minutes, the softening of the thermosetting polyurethane molded article is easily linked to increase the friction coefficient, and the effect is small.

The molded article produced by using the thermosetting polyurethane elastomer-forming composition of the present invention can be suitably used in industrial machinery requiring a low coefficient of friction Components.

Next, the resin-molding release agent composition used in the present invention for solving the second problem is characterized by comprising at least one carboxylic acid having at least a group selected from the group consisting of 4- toluene and 4- toluene in a molecular structure. The ester organic polyoxane (J) promotes the isocyanuration reaction on the contact surface of the mold, and the surface density is increased only by the increase in the bridging density, and the obtained polyurethane resin molded article can maintain the previous physical properties and seek low friction. Chemical. When the organopolysiloxane (J) having at least one carboxylic acid ester selected from the group consisting of 4- toluene and 4-grade fluorene in the molecular structure is not contained, the obtained molded article does not have low friction. Further, in combination with the organic polydecane (J) and the anthrone (L) having an active hydrogen group, in addition to imparting high hardness to the surface, it is also possible to impart slip properties and further reduce friction.

The organopolyoxane (J) used in the present invention is obtained, for example, by reacting a carboxyl group-containing organopolyoxane with at least one hydroxide selected from the group consisting of a grade 4 ammonium and a grade 4 ruthenium. In addition to the hydroxide of the fourth-order ammonium and the fourth-order hydrazine, as long as it is a salt which can exhibit a weaker acidity than the carboxylic acid such as a carbonate, it can be subjected to a salt exchange reaction with the carboxylic acid in the organopolyoxane. The desired release agent composition is obtained quickly. In addition to this, an organopolyoxane, an alkenyl oxide or an organic carboxylic acid containing a tertiary amine can be obtained by reacting. Further, an alkenyl oxide-containing organopolyoxane, a tertiary amine or an organic carboxylic acid may be reacted. Further, the resin-molded organopolyoxane (J) which can be used in the present invention is a carboxylate selected from at least one of a group consisting of a 4- toluene and a 4- toluene-bonded to an organopolyoxane molecule. The structure in the middle is not limited to the above structure and manufacturing method as long as the desired effect can be exhibited. The content of the carboxylic acid ester is not particularly limited, and in order to achieve low friction by surface hardness, the organopolyoxane (J) is 0.3 mmol/g. The above is better. Further, the release agent composition containing an organopolysiloxane (J) having at least one carboxylate selected from the group consisting of 4- toluene and 4- toluene in a molecular structure is excellent in coatability. Further, the solvent may be dissolved by dissolving the solvent of the release agent composition, and examples thereof include ether compounds such as diethyl ether and tetrahydrofuran (hereinafter abbreviated as "THF"); ester compounds such as ethyl acetate and butyl acetate; and benzene, toluene, and the like. An aromatic hydrocarbon compound; an aliphatic hydrocarbon compound such as hexane or octane, or a mixture of these or the like. When used to prepare a resin-formed release agent composition containing an organopolyoxane (J) having at least one carboxylate selected from the group consisting of 4- toluene and 4- toluene in a molecular structure Specific examples of the raw materials to be used include the following.

<Organic Polyoxane Containing Reactive Functional Group>

The organic polyoxane having a carboxyl group may be a dimethyl polyoxyalkylene having a carboxyl group having a carboxyl group at a molecular weight of 1,000 to 2,000 (for example, "X-22-3710" manufactured by Shin-Etsu Silicone Co., Ltd.). a dimethylpolysiloxane having a carboxyl group having a molecular weight of from 4,000 to 5,000 (for example, "X-22-162C" manufactured by Shin-Etsu Silicone Co., Ltd.) and a dimethyl polyoxyalkylene having a carboxyl group in a side chain (for example) "X-22-3701E" manufactured by Shin-Etsu Silicone Co., Ltd.).

<4 grade ammonium, 4 grade ruthenium hydroxide>

Examples thereof include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, 2-hydroxypropyltrimethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylene. Ammonium hydroxide, tetrabutylphosphonium hydroxide, benzyltrimethylammonium hydroxide, a mixture of these, and the like.

The anthrone (L) having an active hydrogen group to be used in the present invention is not particularly limited as long as it is an anthrone compound having an amine group, a hydroxyl group, a thiol group or a carboxyl group. Specifically, dimethyl fluorenone, methyl phenyl fluorenone, diphenyl fluorenone, dimethyl. Methyl phenyl fluorenone, dimethyl. Diphenyl fluorenone, methyl hydroquinone, a mixture of these, and the like. The position and number of the active hydrogen group are not particularly limited, and may be one or several at the terminal or side chain. Among them, an anthrone having an amine group is preferred.

The amount of the anthrone (L) having an active hydrogen group to be used in the present invention is not particularly limited. It is preferably 5 to 150 parts by mass, and 10 to 120 parts by mass per 100 parts by mass of the organopolysiloxane (J). The quality is particularly good. When the amount is 5 parts by mass or less, the effect of imparting slip property to the surface of the molded article is small, and when it exceeds 150 parts by mass, the effect of increasing the hardness of the surface is small, and the synergistic effect of the smoothness and the high hardness cannot be obtained.

In the present invention, the release agent composition can be applied to a molding die, and the polyurethane resin-forming composition (K) can be injected into the molding die to obtain a polyurethane resin molded article having low friction properties. The composition (K) for forming a polyurethane resin to be used in the invention is preferably composed of an NCO-based terminal prepolymer (A0) and an active hydrogen-based terminal hardener (B0), and further comprising a polyoxyethylene alkyl ether selected from the group consisting of C1) at least one slip agent (C) of a linear aliphatic alcohol (C2), an octadecyl isocyanate (C3), or a fatty acid decylamine (C4) having a carbon number of 20 to 40 and a melting point of 90 ° C or less is good.

The NCO-based terminal urethane prepolymer (A0) used in the present invention can be obtained by reacting at least a polyisocyanate (A6) with a polyhydric alcohol (A7) by a urethanization reaction, if necessary, using a reaction inhibitor. The NCO-based terminal urethane prepolymer preferably has an NCO content of 5 to 25% by mass. When the content of NCO is less than 5% by mass, the viscosity of the prepolymer is mainly increased, and the fluidity of the urethane resin is remarkably deteriorated during injection molding. When the temperature is higher than 25% by mass, the stability of the characteristics during storage and use is remarkably deteriorated, and it is difficult to obtain stable industrial machine parts, and it is related. In the case of a problem such as poor molding, there is a case where the NCO-based terminal urethane prepolymer (A0) which is not suitable as an industrial machine component member is used.

The NCO-based terminal urethane prepolymer (A0) is placed in a stirred vessel, and the polyisocyanate (A6) and optionally the reaction inhibitor are charged. Thereafter, the temperature in the stirred vessel is maintained at 40 to 70 ° C. The polyol (A7) was charged. Next, the temperature in the stirring vessel is maintained at 70 to 90 ° C, and a urethanization reaction is carried out for about 2 to 5 hours.

The polyisocyanate (A6) to be used for molding the polyurethane resin of the present invention is not particularly limited as long as the effects of the present invention can be exhibited. From the viewpoint of mechanical properties and reaction control, at least one selected from the group consisting of aromatic diisocyanates and 4,4'-diphenylmethane diisocyanate are particularly preferred.

<polyisocyanate (A6)>

The polyisocyanate may, for example, be the above polyisocyanate (A6).

<Polyol (A7)>

The polyol (A7) to be used in the present invention is not particularly limited as long as it exhibits the effects of the present invention, and is selected from the viewpoints of mechanical properties and glass transition temperature, and is selected from the group consisting of an average functional group number of 2 to 3 and a number average molecular weight of 250 to 5,000. At least one of a polyester polyol and a polyether polyol is preferred. In addition, monomeric polyols may also be used in combination.

<polyester polyol>

As the polyester polyol, the above polyester polyol can be mentioned.

<Polyether polyol>

As the polyether polyol, the above polyether polyol can be mentioned.

<polycarbonate polyol>

The polycarbonate polyol may, for example, be a polycarbonate polyol as described above.

Further, the polyhydric alcohol may be used alone or in combination of two or more kinds of polyolefin polyols, acrylic polyols, anthrone polyols, castor oil polyols, and fluorine polyols.

<polyolefin polyol>

As the polyolefin polyol, the above polyolefin polyol can be mentioned.

<Acrylic polyol>

As the acrylic polyol, the above-mentioned acrylic polyol can be mentioned.

<Anthrone polyol>

The fluorenone polyol may, for example, be the above fluorenone polyol.

<castor oil-based polyol>

The castor oil-based polyol may, for example, be a castor oil-based polyol.

<Fluoropolyol>

The fluorine-based polyol may, for example, be the above-mentioned fluorine-based polyol.

<Monomer polyol>

The monomer polyol may, for example, be the above-mentioned monomer polyol.

The reaction inhibitor to be used in the present invention is not particularly limited as long as it exhibits the effects of the present invention, and the above-mentioned reaction inhibitor (E) can be mentioned.

At least the above-mentioned polyol (A7) can be used as the active hydrogen-based terminal curing agent (B0) of the present invention, and is not particularly limited as long as the effects of the present invention can be exerted. The monomer polyol can be used singly or in combination of two or more kinds from the viewpoint of improving mechanical properties and moldability. Further, a mixture of a polyester polyol having an average functional group number of 2 to 3 and a number average molecular weight of 250 to 5,000, a polyether polyol, and a polycarbonate polyol may be further added. More monomer The alcohol is preferably a mixture of 1,4-butanediol and trimethylolpropane. Further, it is preferred to further add a mixture of a polyester polyol having an average functional group number of 2 and an average molecular weight of 500 to 3,000, and a polyether polyol.

For use in the active hydrogen-based terminal hardener (B0) of the present invention, a catalyst (F) may also be added as needed. The catalyst is not particularly limited as long as the effect of the present invention is exerted, and an isocyanurate catalyst (F1) or an allophanate catalyst can be used from the viewpoint of improving mechanical properties and moldability ( F2), urethane-forming catalyst (F3). As the urethane catalyst, an amine catalyst such as a general triethylenediamine or an imidazole catalyst such as 1-isobutyl-2-methylimidazole or dioctyl dilaurate may be used. A metal such as tin is a catalyst or the like. For isocyanurate catalyst, potassium salt, grade 4 ammonium salt; allophanate catalyst, N, N, N'-trimethylaminoethanolamine or N, N-dimethyl Alkyl ethoxyethanol. These can be used individually or in mixture of 2 or more types as needed.

<Isocyanurate Catalyst for Polyurethane (F1)>

The isocyanurate catalyst can be suitably selected and used by a conventional catalyst, and the above-mentioned isocyanurate catalyst can be mentioned.

Further, the amount of the isocyanurate catalyst used is preferably in the range of 0.001 to 0.5% by mass based on the total mass of the NCO-based terminal urethane prepolymer and the OH-based terminal hardener. The viewpoint of the ease of reaction control is preferably in the range of 0.005 to 0.10% by mass.

<Urea allophanate catalyst for polyurethane (F2)>

The allophanate catalyst can be suitably selected and used by a conventional catalyst, and the above-mentioned polyurethane allophanate catalyst can be mentioned.

Furthermore, the amount of allophanate catalyst used, on the basis of NCO The total mass of the terminal urethane prepolymer and the active hydrogen group terminal hardener is preferably 0.001 to 0.5% by mass, and is used in the range of 0.005 to 0.10% by mass from the viewpoint of ease of reaction control. Better.

<urethane-based catalyst for polyurethane (F3)>

The urethane-based catalyst for the urethanization reaction can be suitably used by a conventional catalyst, and the urethane-based catalyst for polyurethane described above can be used.

Further, the amount of the urethanization catalyst used is preferably in the range of 0.001 to 0.5% by mass based on the total mass of the NCO-based terminal urethane prepolymer and the active hydrogen-based terminal curing agent, wherein The viewpoint of the ease of reaction control is preferably in the range of 0.005 to 0.10% by mass.

A slip agent (C) can be added to the composition (K) for forming a polyurethane resin of the present invention. The lubricant (C) is not particularly limited, and is particularly selected from the group consisting of polyoxyethylene alkyl ethers (C1), linear aliphatic alcohols (C2) having a carbon number of 20 to 40 and a melting point of 90 ° C or less, and eighteen At least one type of slip agent is used for the alkyl isocyanate (C3) and the fatty acid decylamine (C4). The amount of the lubricant to be added is not particularly limited, and is preferably from 0.1 to 8% by mass in the urethane resin-forming composition (C), and preferably from 0.2 to 5% by mass. When the amount is less than 0.1% by mass, the effect of imparting low friction to the surface of the molded article is small, and when it is 8 parts by mass or more, the molded surface is sticky or the appearance is poor. Specific compound examples are given below.

<Polyoxyethylene alkyl ether (C1)>

The polyoxyethylene alkyl ether (C1) may, for example, be the above polyoxyethylene alkyl ether (C1). In order to reduce friction more effectively, the hydroxyl value is preferably 5 to 70 KOH mg/g. When the hydroxyl value is higher than 70 KOHmg/g, the total carbon number will become shorter and become a slip agent. The effect of the points will gradually become smaller. On the other hand, when the valence of the hydroxyl group is less than 5 KOHmg/g, there is a problem that the surface is rough.

<Linear aliphatic alcohol (C2) having a carbon number of 20 to 40 and a melting point of 90 ° C or less>

The linear aliphatic alcohol (C2) having a carbon number of 20 to 40 and a melting point of 90 ° C or less may be a linear aliphatic alcohol (C2) having a carbon number of 20 to 40 and a melting point of 90 ° C or less. In order to reduce friction more effectively, the melting point is 90 ° C or less. When the melting point exceeds 90 ° C, the solubility in the NCO-based terminal urethane prepolymer (A0) is inferior, and even if the temperature at the time of synthesizing the prepolymer is increased to 100 ° C or more, it is difficult to uniformly dissolve, because of the reaction temperature. It rises and is highly viscous due to side reactions such as urea acidification, which leads to a decrease in the quality of the prepolymer. Further, the solubility with the active hydrogen-based terminal hardener (B0) is also inferior. At the time of production, it can be dissolved by heating at a melting point or higher. However, when it is filled and stored, it is crystallized at normal temperature. When the thermosetting polyurethane elastomer is molded, it is necessary to reheat to a temperature equal to or higher than the melting point, and it is difficult to handle.

<octadecyl isocyanate (C3)>

The octadecyl isocyanate (C3) is octadecyl isocyanate (C3), and a commercially available product is exemplified by MILLIONATE O (manufactured by Hodogaya Chemical Co., Ltd.).

<Fatty acid guanamine (C4)>

The fatty acid decylamine (C4) is not particularly limited as long as it is an amine compound derived from a fatty acid and an amine, and is compatible with the urethane resin-forming composition (K). It is preferred to use a higher fatty acid decylamine having a carbon number of 10 to 20.

In the present invention, an antioxidant, a defoaming agent, an ultraviolet absorber or the like may be further introduced as an additive into the form-forming composition as needed.

In the present invention, the thermosetting polyurethane elastomer-forming composition described above is subjected to a step of performing a curing treatment (specifically, a treatment for promoting hardening by heating) in a molding die to produce a urethane and isocyanide. A urethane, and allophanate-bonded thermosetting polyurethane elastomer molded article.

The manufacturing steps at this time are preferably carried out by the methods (1) to (4) described above.

Further, the molar ratio (NCO group/active hydrogen group) of the NCO group content of the NCO-based terminal prepolymer (A0) at the time of injection molding to the active hydrogen content of the active hydrogen-based terminal hardener (B0) may be Select the type of catalyst and the physical choice of the target.

For example, when an isocyanurate catalyst or an allophanate catalyst is used, it is preferably 1.2 to 3.0. In this case, a urethane-based catalyst may also be used in combination. When the ratio is higher than 3.0, the isocyanuration or allophanation of the excess isocyanate is extremely progressed to increase the crosslinking point, resulting in a significant decrease in tensile properties. Further, when it is lower than 1.2, the crosslinking point is reduced by isocyanuration or allophanation, and sufficient low friction cannot be caused. Further, the initial modulus (M100) is lowered and the amount of deformation to stress is large, resulting in insufficient strength against hardness. Further, when the urethanized catalyst is used alone, it is preferably 1.0 to 1.2. When it is higher than 1.2, the molecular elongation cannot be sufficiently performed, and there is a problem that insufficient hardening occurs. Further, when it is less than 1.0, there is a problem that the physical properties are lowered or the hardening is insufficient. In particular, in the present invention, it is essential that the isocyanurate of the excess isocyanate is formed on the contact surface of the mold, and the excess of isocyanate is preferably in the range which does not impair the physical properties.

[Examples]

The present invention will be described in more detail by way of examples and comparative examples, but the invention should not be limited thereto. In the examples and comparative examples, "%" means "% by mass", and the unit of the formula is "g".

<Embodiment 1>

Examples 1 to 7 and Comparative Examples 1 to 7

The polyisocyanate (A6) and the reaction inhibitor (E) were stirred in a nitrogen-filled 5 L stirred vessel in the first table and the formulation ratio shown in the second table. Thereafter, the temperature in the stirring vessel was maintained at 40 to 70 ° C, various polyols (A7) were charged, and further, polyoxyethylene alkyl ether (C1) was added as needed to stir. Next, an appropriate amount of defoaming agent is added, and the temperature in the stirring vessel is maintained at 70 to 90 ° C, and a urethanization reaction is carried out for about 2 to 5 hours to obtain various NCO-based terminal urethane prepolymers (A0). ), or (A1).

Further, various polyols (B0), optionally polyoxyethylene alkyl ethers (C1), and various catalysts were placed in a nitrogen-filled 5 L stirred vessel in the first table and the formulation ratio shown in the second table. (F) and an appropriate amount of defoaming agent are stirred, the temperature in the stirring vessel is maintained at 40 to 70 ° C, and the mixture is stirred for about 1 to 3 hours to obtain various active hydrogen-based terminal hardeners (B0) or (B1).

Next, according to the formulation ratios shown in Tables 1 and 2, the NCO-based terminal urethane prepolymer and the catalytically active hydrogen-based terminal hardener are mixed in a 2-liquid mixed urethane injection molding machine. The thermosetting polyurethane elastomer-forming composition of the present invention is prepared. The forming composition is injected into a metal mold for forming a flat sheet having a thickness of 2 mm or 3 mm thick which is preheated to a curing temperature, and the minimum time for taking out the molded product (release) by the metal mold is made. The polyurethane elastomer molded product (D) of the present invention is obtained by heat-hardening in a mold and demolding the molded product rapidly.

<Embodiment 2>

Examples 8 to 13 and Comparative Examples 8 to 13

The polyisocyanate (A6) and the reaction inhibitor (E) were stirred in a nitrogen-filled 5 L stirred vessel at a formulation ratio shown in Tables 3 and 4. After that, the temperature in the stirred vessel is maintained at 40 to 70 ° C, and various polyols are charged. (A7), further, if necessary, a linear aliphatic alcohol (C2) having a carbon number of 20 to 40 and a melting point of 90 ° C or less is stirred. Next, an appropriate amount of defoaming agent is added, and the temperature in the stirring vessel is maintained at 70 to 90 ° C, and a urethanization reaction is carried out for about 2 to 5 hours to obtain various NCO-based terminal urethane prepolymers (A0). ), or (A2).

In addition, in the 5 L stirred container filled with nitrogen, various polyols (B0), if necessary, having a carbon number of 20 to 40 and a melting point of 90 ° C or less are used in the third table and the formulation ratio shown in the fourth table. The linear aliphatic alcohol (C2), various catalysts (F) and an appropriate amount of defoaming agent are stirred, and the temperature in the stirring vessel is maintained at 40 to 70 ° C, and the mixture is stirred for about 1 to 3 hours to obtain various active hydrogen radicals. Hardener (B0), or (B2).

Next, according to the formulation ratios shown in Tables 3 and 4, the NCO-based terminal urethane prepolymer and the active hydrogen-based terminal hardener doped with the catalyst are mixed in a two-liquid mixing polyurethane injection molding machine. The thermosetting polyurethane elastomer-forming composition of the present invention is prepared. The forming composition is injected into a metal mold for forming a flat sheet having a thickness of 2 mm or 3 mm thick which is preheated to a curing temperature, and the minimum time for taking out the molded product (release) by the metal mold is made. The polyurethane elastomer molded product (D) of the present invention is obtained by heat-hardening in a mold and demolding the molded product rapidly.

<Embodiment 3>

Examples 14 to 21, Comparative Examples 14, 15, and 18, and Reference Examples 1 to 5

In the fifth table and the formulation ratio shown in the sixth table, various polyisocyanates (A6), octadecyl isocyanate (C3), and reaction inhibitor (E), and antioxidants were charged in a nitrogen-filled 5 L stirred vessel. Defoaming agent oxidation. After that, it will stir The temperature in the vessel is maintained at 40 to 70 ° C, and various polyols (A7), further optional polyoxyethylene alkyl ethers (C1), and/or carbons having a carbon number of 20 to 40 and a melting point of 90 ° C or less are charged. The chain aliphatic alcohol (C2) is stirred. Next, an appropriate amount of defoaming agent is added, and the temperature in the stirring vessel is maintained at 70 to 90 ° C, and a urethanization reaction is carried out for about 2 to 5 hours to obtain various NCO-based terminal urethane prepolymers (A0). ), (A3). However, in Example 14 and Example 17, octadecyl isocyanate (C3) was added after the urethanization reaction, and the mixture was stirred for about 0.5 to 1 hour.

In addition, in the 5 L stirred container filled with nitrogen, various polyols (B0), polyoxyethylene alkyl ether (C1) according to the formulation ratio, and, if necessary, the ratio of the formulation shown in the fifth table and the sixth table, And/or a linear aliphatic alcohol (C2) having a carbon number of 20 to 40 and a melting point of 90 ° C or less, various catalysts (F) and an appropriate amount of defoaming agent are stirred, and the temperature in the stirring vessel is maintained at 40 to 70. At ° C, the mixture was stirred for about 1 to 3 hours to obtain various active hydrogen-based terminal hardeners (B0) or (B2).

Next, in accordance with the formulation ratios shown in Tables 5 and 6, the NCO-based terminal urethane prepolymer pre-incubated at 70-90 ° C and the catalyst-incorporated activity pre-incubated at 40-120 ° C. The hydrogen-based terminal hardener was mixed in a two-liquid mixing polyurethane injection molding machine to prepare a thermosetting polyurethane elastomer-forming composition of the present invention. The forming composition is injected into a metal mold for forming a flat sheet having a thickness of 2 mm or 3 mm thick which is preheated to a curing temperature, and the minimum time for taking out the molded product (release) by the metal mold is made. The polyurethane elastomer molded product (D) of the present invention is obtained by heat-hardening in a mold and demolding the molded product rapidly. The evaluation results of the friction coefficient and the like of the obtained polyurethane elastomer molded article are shown in Tables 10 and 11.

<Embodiment 4>

Examples 22 to 29, Comparative Examples 24 to 27, and Reference Examples 6 and 7

Various polyisocyanates (A6) and octadecyl isocyanate (C3) and reaction inhibitor (E) according to the formulation ratio were placed in a nitrogen-filled 5 L stirred vessel at a formulation ratio shown in Tables 7 and 8. ), anti-oxidant, defoamer stirred. Thereafter, the temperature in the stirred vessel is maintained at 40 to 70 ° C, and various polyols (A7) are introduced, and further, according to the formulation ratio, polyoxyethylene alkyl ether (C1), carbon number 20 to 40, and melting point of 90 are required. The linear aliphatic alcohol (C2) below °C is stirred. Connect Further, according to the formulation ratio, the fatty acid decylamine (C4) and an appropriate amount of defoaming agent are added as needed, and the temperature in the stirring vessel is maintained at 70 to 90 ° C for about 2 to 5 hours of carbamate reaction. Thus, various NCO-based terminal urethane prepolymers (A5) were obtained. However, in Example 22 and Example 25, the fatty acid decylamine (C4) was added after the urethanization reaction, and the mixture was stirred and mixed for about 0.5 to 1 hour.

In addition, in the 5 L stirred container filled with nitrogen, various polyols (B0) and polyoxyethylene alkyl ether (C1), which are required according to the formulation ratio, are used in the seventh table and the formulation ratio shown in the eighth table. A linear aliphatic alcohol (C2) having a carbon number of 20 to 40 and a melting point of 90 ° C or less, a fatty acid decylamine (C4), various catalysts (F), and an appropriate amount of a defoaming agent are stirred to maintain the temperature in the stirred vessel. The mixture was stirred at 40 to 70 ° C for about 1 to 3 hours to obtain various active hydrogen-based terminal hardeners (B3).

Next, in accordance with the formulation ratios shown in Tables 7 and 8, the NCO-based terminal urethane prepolymer pre-incubated at 70-90 ° C and the catalyst-incorporated activity pre-incubated at 40-120 ° C. The hydrogen-based terminal hardener was mixed in a two-liquid mixing polyurethane injection molding machine to prepare a thermosetting polyurethane elastomer-forming composition of the present invention. The forming composition is injected into a metal mold for forming a flat sheet having a thickness of 2 mm or 3 mm thick which is preheated to a curing temperature, and the minimum time for taking out the molded product (release) by the metal mold is made. The polyurethane elastomer molded product (D) of the present invention is obtained by heat-hardening in a mold and demolding the molded product rapidly. The evaluation results of the friction coefficient and the like of the obtained polyurethane elastomer molded article are shown in Tables 13 and 14.

The abbreviations of the raw materials used in the first to eighth tables are as follows.

"Isocyanate"

(1) TDI: Coronate T-100 (manufactured by TOSOH), 2,4-TDI, NCO content = 48.2%

(2) MDI: Millionate MT (manufactured by TOSOH), 4, 4'-MDI, NCO content = 33.5%

(3) ODI: Millionate O (manufactured by Hodogaya Chemical Co., Ltd.), octadecyl isocyanate, NCO content = 14.2%

"Polyol"

(4) PBA-2500: NIPPOLLAN 3027 (manufactured by TOSOH Co., Ltd.), polybutylene adipate, hydroxyl value = 44.9 KOHmg/g

(5) PEA-2000: NIPPOLLAN 4040 (manufactured by TOSOH Co., Ltd.), polyethylene adipate, hydroxyl value = 56.1 KOH mg/g

(6) PTMG-1000: PTMG-1000 (manufactured by Mitsubishi Chemical Corporation), polytetramethylene glycol, hydroxyl value = 112.0 KOHmg/g

(7) 1.4-BG: 1,4-butanediol (manufactured by Mitsubishi Chemical Corporation), hydroxyl value = 1,245 KOHmg/g

(8) TMP: trimethylolpropane (manufactured by Mitsubishi Gas Chemical Co., Ltd.), hydroxyl value = 1,247 KOHmg/g

(9) MOCA: 4,4'-diamino-3,3'-dichlorodiphenylmethane (manufactured by IHARA CHEMICAL INDUSTRY), hydroxyl value (amine group) = 420 KOHmg/g

"slip agent"

(10) NIKKOL BC-150: hexadecyl polyoxyethylene ether (manufactured by Nikko Chemical Co., Ltd.), hydroxyl value = 9 KOHmg/g

(11) NIKKOL BO-50V: oil-based polyoxyethylene ether (manufactured by Nikko Chemical Co., Ltd.), hydroxyl value = 24 KOHmg/g

(12) NIKKOL BL-25: Lauryl polyoxyethylene ether (manufactured by Nikko Chemical Co., Ltd.), hydroxyl value = 45 KOHmg/g

(13) NIKKOL BB-5: Behenyl polyoxyethylene ether (manufactured by Nikko Chemical Co., Ltd.), hydroxyl value = 106 KOHmg/g

(14) Performacol 350 Alcohol (manufactured by Nikko Chemical Co., Ltd.), C20 to C40, melting point = 68 to 89 ° C, hydroxyl value = 129 KOH mg / g

(15) Performacol 425 Alcohol (manufactured by Nikko Chemical Co., Ltd.), C20~C40, melting point = 85~99 °C, hydroxyl value = 100 KOHmg/g

(16) Performacol 550 Alcohol (manufactured by Nikko Chemical Co., Ltd.), C30~C50, melting point = 93~106 °C, hydroxyl value = 83 KOHmg/g

(17) NIKKOL icosdiol 80 (manufactured by Nikko Chemical Co., Ltd.), C22 (80%), melting point = 65 to 75 ° C, hydroxyl value = 171 KOH mg / g

(18) 1-Eicosanol: manufactured by Tokyo Chemical Industry Co., Ltd., C20, melting point = 64 ° C, hydroxyl value = 188 KOH mg / g

(19) 1-hexadecanol: manufactured by Tokyo Chemical Industry Co., Ltd., C16, melting point = 50 ° C, hydroxyl value = 231 KOH mg / g

(20) FT-0070: Paraffin-based general synthetic wax (made by Nippon Seiko Co., Ltd.)

(21) Rikemal SL-900: stearyl stearate (RIKEN VITAMIN)

(22) DIAMID O-200: decyl oleate (manufactured by Nippon Kasei Co., Ltd.), melting point = 75 ° C

(23) Nikka Amide OS: N-oleyl stearate (made by Nippon Kasei Co., Ltd.), melting point = 74 ° C

(24) SLIPACKS O: ethylene bismuth oleate (manufactured by Nippon Kasei Co., Ltd.), melting point = 119 ° C

(25) Licowax E; montanic acid ester wax (manufactured by CLARIANT JAPAN Co., Ltd.), melting point = 79 to 83 ° C

"catalyst"

(26) POLYCAT-46: (made by Air Products), a mixture of potassium acetate and ethylene glycol

(27) DABCO TMR: (made by Air Products), a mixture of a quaternary ammonium salt catalyst and ethylene glycol

(28) TOYOCAT RX-5: (manufactured by TOSOH Co., Ltd.), trimethylaminoethylethanolamine

(29) TOYOCAT TEDA-L33E: (manufactured by TOSOH), a mixture of triethylenediamine and ethylene glycol

"Other additives"

(30) Reaction inhibitor: Phospholan PS-236 (manufactured by Akzo Nobel Co., Ltd.), single. Di(C10~12) alkanol ether-5 phosphate

(31) Antioxidant: IRGANOX 1010 (manufactured by BASF Japan), isopentanol tetrakis[3-(3',5'-di-t-butylt-4'-hydroxyphenyl)propionate]

(32) Defoaming agent: BYK-052 (BYK JAPAN company)

The method for evaluating the characteristics of the obtained formed sheet is shown below.

(1) JIS-A hardness: Measured using a type A durometer in accordance with JIS K7312.

(2) Using a molded sheet having a thickness of 2 mm, 100% modulus (M100), tensile strength (TB), and elongation (EB) were measured in accordance with JIS K7312.

(3) Static friction coefficient and dynamic friction coefficient of the surface of the formed sheet; preparation of test piece; cut sheet of 3 mm thick was cut into a width of 25 mm × a length of 100 mm, and a test piece was prepared by degreasing with cyclohexane. Thereafter, the mixture was allowed to stand in an environment of room temperature of 23° C. and a humidity of 50% for one day, and then the static friction coefficient and the dynamic friction coefficient were measured under the following conditions. The measurement system is continuously applied back and forth 1000 times, and the average value of the 5th to 10th rounds is used as the initial value, and the average value of 995~1000 is used as the late value. Renewal indicator.

"Measurement conditions" measurement jig = ball pressure (SUS), load weight = 50g, stage movement speed = 50mm / min, stage movement distance = 50mm, round trip times = 1000 times, measurement time = 3 hours 23 minutes

Measuring machine: Surface measuring machine TYPE: 38 (New East Scientific System)

(4) Static friction coefficient and dynamic friction coefficient of the cutting surface: 3 mm thick molded plate, feather unilateral S razor blade (item number: FAS-10), vertical cut 30 mm × 10 mm rectangle, prepare 3 mm (width) ) Test piece of × 30 mm (length) × 10 mm (height). Thereafter, immediately after the heat treatment, the mixture was allowed to stand in an environment of room temperature of 23° C. and a humidity of 50% for one day, and then a static friction coefficient and a dynamic friction coefficient were measured under the following conditions using a surface of 3 mm×30 mm. The measurement system was continuously subjected to repeated back and forth 1000 times, and the average value of the 5th to 10th round trips was used as the initial value, and the average value of 995 to 1000 was used as the late value as the continuous index.

"Measurement conditions" measurement fixture = ball pressure (SUS), load weight = 100g, stage movement speed = 150mm / min, stage movement distance = 10mm, round trip times 10 times, measurement time = 82 seconds

Measuring machine: Surface measurement TYPE: 38 (New East Scientific System)

(5) Appearance of molded piece: After the measurement of the dynamic friction test, the same test piece was used, and the index of the compatibility of the lubricant component and the polyurethane component was visually observed for the presence or absence of white turbidity.

(6) Whether there is oozing or dusting: The test piece used for measuring the dynamic friction coefficient is placed in an environment of room temperature 23 ° C and a humidity of 50% for 2 weeks, and then the test piece before and after wiping with gauze is visually observed. The surface state was evaluated for the presence or absence of bleeding and dusting.

Examples 1 to 29 show the results of the implementation. The compatibility of the slip agent with the NCO-based terminal urethane prepolymer and the active hydrogen-based terminal hardener without causing the problems of the present invention is obtained, and bleeding, dusting, low friction, high mechanical strength and toughness are not caused. Thermosetting polyurethane elastomer.

In the comparative example when the polyoxyethylene alkyl ether (C1) of the present invention is less than 0.1% by mass, it is not possible to achieve sufficient low friction and is not suitable.

In the comparative example 2, when the polyoxyethylene alkyl ether (C1) of the present invention is higher than 8% by mass, a sufficiently low friction can be obtained, but the tensile property value is extremely low and it is uncomfortable.

In Comparative Examples 3 to 7, the comparative examples in the case of using a slip agent other than the present invention have low friction, but have poor compatibility with the isocyanate-based terminal urethane prepolymer and the active hydrogen-based terminal hardener. The obtained molded product was found to be oozing or dusting and was unsuitable.

In Comparative Example 8, a comparative example in which the linear aliphatic alcohol (C2) having a carbon number of 20 to 40 and a melting point of 90 ° C or less is less than 0.1% by mass cannot be sufficiently low-friction and is not suitable.

Comparative Example 9 is a comparative example in which the linear aliphatic alcohol (C2) having a carbon number of 20 to 40 and a melting point of 90 ° C or less is more than 5% by mass in the present invention, and sufficient tensile strength can be obtained, but tensile properties are obtained. The value is extremely low and is uncomfortable.

In Comparative Example 10, a comparative example in which a slip agent other than the present invention was used, although a carbon number of 20 to 40 was satisfied, but a substance having a melting point of more than 90 ° C was obtained, and although a low friction was achieved, the isocyanate-based terminal carbamate was obtained. The prepolymer (A) and the active hydrogen-based terminal hardener (B) have poor compatibility, and the obtained molded article becomes uneven and is unsuitable.

Comparative Example 11 is a comparative example in which a slip agent other than the present invention is used, and a substance having a carbon number of 30 to 50 and a melting point of more than 90 ° C, although having a low friction, is bonded to an isocyanate-terminated urethane prepolymer. (A) The active hydrogen-based terminal hardener (B) has poor compatibility, and the obtained molded article becomes uneven and is unsuitable.

Comparative Example 12 is a comparative example in which a slip agent other than the present invention is used, and since it has no hydroxyl group, it has low friction, but is compatible with an isocyanate-terminated urethane prepolymer and an active hydrogen-based terminal hardener. Poor, the obtained molded article became uneven, and it was found that oozing or dusting was uncomfortable.

In Comparative Example 13, in the comparative example when the lubricant other than the present invention was used, the carbon number was as short as C16, and it was not possible to achieve sufficient low friction and was uncomfortable.

In Comparative Example 14, a comparative example in which the lubricant of the present invention is not contained is not sufficiently reduced in friction, and it is not suitable as a thermosetting polyurethane for industrial machine parts.

Comparative Example 15 is a comparative example in which only the octadecyl isocyanate (C3) of the present invention is contained, and although it is slightly low in friction, it is not suitable as a thermosetting polyurethane for industrial machine parts.

Reference Examples 1, 3, and 4 contain at least one selected from the group consisting of polyoxyethylene alkyl ether (C1) of the present invention, a high-fat aliphatic alcohol (C2) having a carbon number of 20 to 40 and a melting point of 90 ° C or lower. In the case of the compound, although the initial value of the friction coefficient is very low, in the continuous repeated friction test, an increase in the friction coefficient can be seen.

Reference Example 2 is an example in which the polyoxyethylene alkyl ether (C1) of the present invention and the general lubricant lignite-based ester wax (Licowax E) are contained, and the static friction coefficient and the dynamic friction coefficient are extremely low values, but In the case of the thermosetting polyurethane elastomer-forming composition, bleed out and dusting can be seen.

Comparative Example 18 contains 1-hexadecanol having a carbon number of 20 or less to substitute a linear aliphatic group selected from the polyoxyethylene alkyl ether (C1) of the present invention, having a carbon number of 20 to 40 and a melting point of 90 ° C or lower. A comparative example of at least one or more compounds of the alcohol (C2) is not suitable for use as a thermosetting polyurethane for industrial machine parts, although it is slightly low in friction.

Reference Example 5 is a compound containing at least one selected from the group consisting of a polyoxyethylene alkyl ether (C1) of the present invention, a linear aliphatic alcohol (C2) having a carbon number of 20 to 40 and a melting point of 90 ° C or lower, and When the content of the octadecyl isocyanate (C3) exceeds 8% by mass, the friction can be sufficiently reduced, but the mechanical strength may be lowered.

Reference Example 6 is an example in which 5.0% of polyoxyethylene alkyl ether (C1) was added as a slip agent. Although the dynamic friction coefficient is lowered, the late value shows a value higher than the initial value, and the low friction persistence is lowered.

Reference Example 7 is an example in which 4.9% of polyoxyethylene alkyl ether (C1) and 0.82% of fatty acid decylamine (C4) were added. Although the friction coefficient is at a practical level and its persistence is good, there are cases where oozing and dusting occur.

Comparative Example 24 is an example in which 0.30% of fatty acid decylamine (C4) was added. The decrease in the dynamic friction coefficient cannot be confirmed.

Comparative Example 25 is an example in which 4.0% of polyoxyethylene alkyl ether (C1) and a substituted fatty acid decylamine (C4) were added with 0.51% of montanic acid ester wax (Licowax E). Although the dynamic friction coefficient is at a practical level and the continuity is good, there are cases where oozing and dusting occur.

Comparative Example 26 is an example of adding 1-hexadecanol of 2.5% of an aliphatic alcohol having less than 20 carbon atoms and 0.25% of a fatty acid decylamine (C4). Although the friction coefficient is slightly There is a drop, but it is not a sufficient standard for use as an industrial machine part.

Comparative Example 27 is an example in which 11.2% of polyoxyethylene alkyl ether (C1) and 0.19% of fatty acid decylamine were added. Although the friction coefficient is slightly lowered, the tensile strength and elongation are remarkably lowered.

Example 30~37

Make a 3 mm thick plate in the same procedure according to Tables 1 and 3, and use a feather single-side S shaving blade (item number: FAS-10), and cut out 3 mm (width) × 30 mm (length) × 10 mm (height). Prepare the test piece (D1) for the friction coefficient confirmation of the cutting surface. Next, according to the ninth table, the 2 mm thick plate (D) and the 3 mm thick plate (D1) were heat-treated to measure the static friction coefficient and the dynamic friction coefficient. The results are shown in Table 9.

Example 38~45

Prepare a 3 mm thick plate in the same procedure according to the fifth table, and use a feather unilateral S razor blade (item number: FAS-10), and cut out 3 mm (width) × 30 mm (length) × 10 mm (height), and prepare. The friction coefficient of the cutting surface was confirmed by the test piece (D1). Next, according to the 12th table, the 2 mm thick plate (D) and the 3 mm thick plate (D1) were heat-treated, and the static friction coefficient and the dynamic friction coefficient were measured. The results are shown in Table 12.

Examples 46 to 53

Prepare a 3 mm thick plate in the same procedure according to the seventh table, and use a feather unilateral S razor blade (item number: FAS-10), cut out 3 mm (width) × 30 mm (length) × 10 mm (height), and prepare The test piece (D1) for confirming the friction coefficient of the cutting surface. Next, according to the fifteenth table, the 2 mm-thick sheet (D) and the 3 mm-thick sheet (D1) were heat-treated to measure the static friction coefficient and the dynamic friction coefficient. Will knot The results are shown in Table 15.

Next, examples of the release agent to be used in the present invention will be described in more detail by way of examples and comparative examples, but the invention should not be limited thereto. In the examples and comparative examples, unless otherwise mentioned, "%" means "% by mass", and the unit of the formula is "g". Further, the carboxyl group equivalent, for example, 1000 g/mol means that the fluorenone has a molecular weight of 1,000 equivalents and has a carboxyl group having one molecule.

<Synthesis of Release Agent 1>

For a 100 ml eggplant flask with magnetic stirrer, put 25g of organic polypethane Oxystane A (manufactured by Shin-Etsuketone Co., Ltd., carboxy-containing dimethyl polyoxane, terminal-denatured type "X-22-3710", carboxyl equivalent: 1450 g/mol), 25 g of tetrahydrofuran (KISHIDA chemical reagent "THF") Stir at room temperature for 30 minutes to make a homogeneous solution. Next, 10.5 g of a 15% tetramethylammonium hydroxide aqueous solution (Wako Pure Chemical Reagent, hereinafter abbreviated as "TMAH") (mole such as a carboxyl group of the organopolyoxane A) was added, and the mixture was stirred at room temperature for 1 hour. From the reaction liquid, THF and water were removed under reduced pressure, and the residue was dissolved in mineral oil concentrate A (JS Nippon Mining Co., Ltd. petroleum solvent, hereinafter abbreviated as "MSA") to prepare a volatile matter of 50%. , release agent 1 was obtained.

<Synthesis of Release Agent 2>

In a 100 ml eggplant type flask equipped with a magnetic stirrer, 25 g of organopolyoxane A and 25 g of THF were placed, and stirred at room temperature for 30 minutes to prepare a homogeneous solution. Next, 12.7 g of a 20% aqueous solution of tetraethylammonium hydroxide (Wako Pure Chemical Reagent, hereinafter abbreviated as "TEAH") (mole such as a carboxyl group of the organopolyoxane A) was added, and the mixture was stirred at room temperature for 1 hour. From the reaction liquid, THF and water were removed under reduced pressure, and the residue was added with mineral spirit A to prepare a volatile matter of 50% to obtain a release agent 2.

<Synthesis of Release Agent 3>

In a 100 ml eggplant type flask equipped with a magnetic stirrer, 25 g of organopolyoxane A and 25 g of THF were placed, and stirred at room temperature for 30 minutes to prepare a homogeneous solution. Next, 44.7 g of a 10% tetrabutylammonium hydroxide aqueous solution (Wako Pure Chemical Reagent, hereinafter abbreviated as "TBAH") (mole such as a carboxyl group of the organopolyoxane A) was added, and the mixture was stirred at room temperature for 1 hour. From the reaction liquid, THF and water were removed under reduced pressure, and the residue was added with mineral spirit A to prepare a volatile matter of 50% to obtain a release agent 3.

<Synthesis of Release Agent 4>

In a 100 ml eggplant type flask equipped with a magnetic stirrer, 25 g of organopolyoxane A and 25 g of THF were placed, and stirred at room temperature for 30 minutes to prepare a homogeneous solution. Next, 7.2 g of 40% tetrabenzyltrimethylammonium hydroxide, methanol solution (Wako Pure Chemical Reagent, hereinafter abbreviated as "BTMAH") (for the carboxyl group of the organopolyoxane A, etc.) was added to the chamber. Stir for 1 hour. From the reaction liquid, THF and water were removed under reduced pressure, and the residue was added to MSA to obtain a volatile matter of 50% to obtain a release agent 4.

<Synthesis of Release Agent 5>

In a 100 ml eggplant type flask equipped with a magnetic stirrer, 25 g of organopolyoxane A and 25 g of THF were placed, and stirred at room temperature for 30 minutes to prepare a homogeneous solution. Next, 4.6 g of 45% 2-hydroxyethyltrimethylammonium and methanol solution (Wako Pure Chemical Reagent "45% choline, methanol solution", hereinafter, hereinafter abbreviated as "2-HETMAH") (for organic The carboxyl group of the polyoxyalkylene A or the like was stirred at room temperature for 1 hour. From the reaction liquid, THF and water were removed under reduced pressure, and the residue was added to MSA to prepare a volatile matter of 50% to obtain a release agent 5.

<Synthesis of Release Agent 6>

The release agent 1 and the release agent 4 were mixed at a mass ratio of 1:1 as a release agent 6.

<Synthesis of Release Agent 7>

In a 100 ml eggplant type flask equipped with a magnetic stirrer, 25 g of an organic polyoxane B (manufactured by Shin-Etsu Chemical Co., Ltd., a carboxyl group-containing dimethyl polyoxyalkylene-terminated "X-22-162C", Carboxyl equivalent: 2300 g/mol), 25 g of tetrahydrofuran (KISHIDA Chemical "THF"), and stirred at room temperature for 30 minutes to prepare a homogeneous solution. Next, add 6.6 g of TMAH (for the carboxyl group of the organopolyoxane B, etc. Mohr), stirred at room temperature for 1 hour. From the reaction liquid, THF and water were removed under reduced pressure, and the residue was added to MSA to obtain a volatile matter of 50% to obtain a release agent 7.

<Synthesis of Release Agent 8>

In a 100 ml eggplant type flask equipped with a magnetic stirrer, 5.7 g of an organic polyoxane and 19.3 g of an organic polyoxane C (manufactured by Shin-Etsu Chemical Co., Ltd., a carboxyl group-containing dimethyl polyoxyalkylene side chain denatured) The type "X-22-3701E", carboxyl equivalent: 4000 g/mol), 25 g of THF was stirred at room temperature for 30 minutes to prepare a homogeneous solution. Next, 5.3 g of TMAH (mole such as carboxyl group of organopolyoxane A or organopolyoxyalkylene C) was added, and the mixture was stirred at room temperature for 1 hour. From the reaction liquid, THF and water were removed under reduced pressure, and the residue was added to MSA to prepare a volatile matter of 50% to obtain a release agent 8.

<Synthesis of Release Agent 9>

In a 100 ml eggplant type flask equipped with a magnetic stirrer, 25 g of an organic polyoxane C and 25 g of THF were placed, and the mixture was stirred at room temperature for 30 minutes to prepare a homogeneous solution. Then 6.3 g of TMAH was added and stirred at room temperature for 1 hour. From the reaction liquid, THF and water were removed under reduced pressure, and MSA was added to the residue to obtain a volatile matter of 50% to obtain a release agent 9.

<Synthesis of Release Agent 10>

In a 100 ml eggplant type flask equipped with a magnetic stirrer, 25 g of organopolyoxane A and 25 g of THF were placed, and stirred at room temperature for 30 minutes to prepare a homogeneous solution. Next, 4.8 g of tetrabutylammonium chloride (Wako Pure Chemical Reagent, hereinafter abbreviated as "TBAC") was added, and the mixture was stirred at room temperature for 1 hour. From the reaction liquid, THF and water were removed under reduced pressure, and the residue was added to MSA to prepare a volatile matter of 50% to obtain a release agent 10.

<release agent 11>

The organopolyoxyalkylene A was used as the release agent 11.

<Synthesis of Release Agent 12>

In a 100 ml eggplant type flask equipped with a magnetic stirrer, 12.5 g of 2-ethylhexanoic acid and 12.5 g of THF were placed, and the mixture was stirred at room temperature for 30 minutes to prepare a homogeneous solution. Next, 52.7 g of TMAH was added and stirred at room temperature for 1 hour. From the reaction liquid, THF and water were removed under reduced pressure, and the residue was added to MSA to obtain a volatile matter of 50% to obtain a release agent 1.

<release agent 13>

As the release agent 13, an organopolysiloxane D (manufactured by Shin-Etsu Chemical Co., Ltd., non-denaturing dimethyl polyoxyalkylene "KF-96") was used.

<release agent 14>

The release agent 12 and the release agent 13 were mixed at a mass ratio of 15:85 as a release agent 14.

<Carbamate Prepolymer 1 (UP-1) Synthesis>

In a four-necked bottle of 1000 ml capacity equipped with a stirrer, a thermometer, and a condenser, 520 g of diphenylmethane diisocyanate (Millionate MT, manufactured by Nippon Polyurethane Industry Co., Ltd., NCO content: 33.5%), 480 g of polybutene The acid ester (NIPPOLLAN 4010, manufactured by Nippon Polyurethane Industry Co., Ltd., hydroxyl group: 56.0 KOHmg/g) was passed through a nitrogen gas, and subjected to a urethanization reaction at 80 ° C for 3 hours. The resulting urethane prepolymer had an NCO content of 15.4%.

<Synthesis of Urethane Prepolymer 2 (UP-2)>

225 g of tolyl diisocyanate ("Coronate T-100" manufactured by Nippon Polyurethane Industry Co., Ltd., NCO content: 48.2%) and 775 g of poly 1,4 were placed in a four-necked bottle equipped with a stirrer, a thermometer, and a condenser tube having a capacity of 1000 ml. - Butanediol ("MGMG1000" manufactured by Mitsubishi Chemical Corporation, hydroxyl group: 112.0 KOHmg/g), and subjected to a urethanization reaction at 80 ° C for 3 hours under nitrogen gas. The resulting urethane prepolymer had an NCO content of 4.2%.

<Modulation of Polyol 1 (PO-1)>

In a four-necked bottle equipped with a mixer, a thermometer, and a condenser with a capacity of 1000 ml, 900 g of NIPPOLLAN 4010 and 70 g of 1,4-butanediol (manufactured by Mitsubishi Chemical Corporation, hereinafter referred to as "1,4-BD") 30g of trimethylolpropane (three It is abbreviated as "TMP" by 0.2% of polyethylene triacetate (hereinafter referred to as "TEDA" by TOSHO Co., Ltd.), and was stirred and mixed at 80 ° C for 2 hours. The resulting polyol had a hydroxyl group value of 175.0 KOHmg/g.

<Modulation of Polyol 2 (PO-2)>

A four-necked flask having a capacity of 1000 ml of a condenser, a thermometer, and a condenser was placed, and 750 g of 1,4-BD, 250 g of trimethylolpropane, and 1 g of TEDA were placed, and the mixture was stirred and mixed at 80 ° C for 2 hours. The resulting polyol had a hydroxyl group value of 1247 KOH mg/g.

<Modulation of Polyol 3 (PO-3)>

In a four-necked flask with a mixer, a thermometer, and a 1000 ml capacity with a condenser, 900 g of NIPPOLLAN 4010, 70 g of 1,4-BD, 30 g of trimethylolpropane, and 2.5 g of N, N, N'-three were placed. Methylaminoethylethanolamine ("TOYOCATRX-5" manufactured by TOSHO Co., Ltd.) was stirred and mixed at 80 ° C for 2 hours. The resulting polyol had a hydroxyl group value of 175.0 KOHmg/g.

Next, according to the formulation ratio shown in Tables 18 and 19, the NCO-based terminal urethane prepolymer and the active hydrogen-based terminal hardener having a catalyst are mixed by a two-liquid mixing injection molding machine to prepare a polyurethane resin. The composition is injected into a mold for forming a flat sheet of 2 mm thick pre-heated to a curing temperature of the release agent composition of the present invention, so that the molded product can be taken out from the mold ( The minimum time of demolding is heat-hardened in a mold, and the molded article is quickly released from the mold to obtain a polyurethane elastomer molded article (sheet) of the present invention.

The method for evaluating the characteristics of the obtained formed sheet is shown below.

(1) JIS-A hardness: It was measured using a type A durometer in accordance with JIS K7312.

(2) Tensile strength (TB), elongation (EB): Measured in accordance with JIS K7312.

(3) Dynamic friction coefficient:

"Preparation of test strips"

The formed sheet was cut out to have a width of 25 mm × a length of 100 mm, and degreased with cyclohexane to prepare a test piece. Thereafter, the mixture was allowed to stand in an environment of a room temperature of 23° C. and a humidity of 50% for one day, and then the dynamic friction coefficient was measured under the following conditions.

"Measurement conditions"

Measuring machine: Surface measuring machine type: 38 (New East Scientific System)

Measurement conditions: measurement jig = ball pressure (SUS), load weight = 20 g, stage moving speed = 50 mm/min.

(4) Release property: When the polyurethane resin was released from the flat sheet forming mold, the ease of demolding was evaluated as follows.

○: The peeling is very light and can be demolded immediately (within 5 seconds)

△: The peeling is slightly heavier but can be released in a short time (about 10 seconds)

×: It takes time to release the mold and take off (30 seconds or more)

The results of the practice of the present invention are shown in Examples 101 to 112. In any of the examples, by using the release agent of the present invention, a polyurethane resin having a low dynamic friction coefficient, high mechanical strength and toughness can be obtained.

In Comparative Examples 101 to 104, since the release agent does not contain the organopolyoxane (J) having a carboxylic acid ester having a quaternary ammonium and/or quaternary oxime in the molecular structure of the present invention, it is a dynamic friction coefficient. High polyurethane resin.

In Comparative Example 105, although it is close to the embodiment of the present invention, at least one carboxylate selected from the group consisting of 4- toluene and 4- toluene is not bonded to the organopolyoxane, that is, because it is not attached to the molecular structure. An organopolyoxane (J) having at least one carboxylic acid ester selected from the group consisting of a grade 4 ammonium and a grade 4 ruthenium It is a polyurethane resin with high dynamic friction coefficient.

Example 113

To the release agent 3, 29 g of anthrone (I) (manufactured by Shin-Etsu Chemical Co., Ltd., having a hydroxyl group "X-22-170BX" at one end, and a hydroxyl equivalent: 2800 g/mol) was added to prepare a TBAH-denatured organopolyoxane. A release agent composition having a ketone content of a hydroxyl group of 50/50 at the end of A/single side. A polyurethane elastomer molded product was obtained in the same manner as in Example 103 except that the present release agent composition was used. The results are shown in Table 21.

Examples 114~120

The amount and type of the fluorenone containing a hydroxyl group at the one-side terminal of Example 113 were changed to prepare a release agent composition, and a polyurethane elastomer molded article was obtained in the same manner as in Example 103. The anthrone used is expressed as follows.

Anthrone (I): The unilateral end of the company has a hydroxyl group "X-22-170BX", and the functional group equivalent: 2800g/mol

Anthrone (II):

The unilateral end of the company has a hydroxyl group "X-22-170DX", and the functional group equivalent: 4667g/mol

Anthrone (III):

The two ends of the company have a hydroxyl group "X-22-160AS" and the functional group equivalent: 470g/mol

Anthrone (IV):

The side chain made by Shin-Etsuketone Co., Ltd. contains the amine type "KF-8004", and the functional group equivalent: 150g/mol

Anthrone (V):

The side chain made by Shin-Etsu Chemical Co., Ltd. contains an amine type "KF-8005", and the functional group is Amount: 11000g/mol

Anthrone (VI):

The side chain made by Shin-Etsu Chemical Co., Ltd. contains the amine type "KF-868", and the functional group equivalent: 8800g/mol

Anthrone (VII):

The two ends of the company are containing the amine type "KF-8008" and the functional group equivalent: 5700g/mol

The combination of the release agent and the dynamic friction coefficient of the molded article was compiled in Table 21. The dynamic friction coefficient of the molded article was lower than that of the molded article obtained in Example 103, and the introduction of the anthrone was further reduced in friction.

Comparative Examples 106, 107

A polyurethane elastomer molded product was obtained in the same manner as in Example 103 except that the oxime (I) or fluorenone (IV) was used as the release agent. The results are shown in Table 21. Even if an anthrone having an active hydrogen group is used as the release agent, the effect of lowering the coefficient of dynamic friction is small.

Example 121

In the synthesis of urethane prepolymer 1 (UP-1), diphenylmethane diisocyanate The amount of the acid ester was changed to 515 g, and 5 g of octadecyl isocyanate ("Millionate O" manufactured by Hodogaya Chemical Co., Ltd.) (0.25 mass% in the composition for forming a polyurethane resin) was further added to prepare a urethane prepolymer 3 ( UP-3). A polyurethane elastomer molded product was obtained in the same manner as in Example 103 except that UP-1 was changed to UP-3.

Example 122

In the preparation of the polyol 1 (PO-1), the amount of the polybutylene adipate "NIPPOLLAN 4010" was changed to 880 g, and 20 g of polyoxyethylene cetyl ether ("NIKKOL BC-" manufactured by Nikko Chemical Co., Ltd. was further added. 150") (1 mass% in the composition for forming a urethane resin) Polyol 4 (PO-4) was prepared. A polyurethane elastomer molded product was obtained in the same manner as in Example 103 except that PO-1 was changed to PO-4.

Example 123

In the preparation of polyol 1 (PO-1), the amount of polybutylene adipate "NIPPOLLAN 4010" was changed to 840 g, and 60 g of polyoxyethylene cetyl ether "NIKKOL BC-150" (in polyurethane) was further added. 3 mass% of the resin-forming composition was added with polyol 5 (PO-5). A polyurethane elastomer molded product was obtained in the same manner as in Example 103 except that PO-1 was changed to PO-5.

Example 124

A polyurethane elastomer molded product was obtained in the same manner as in Example 103 except that the urethane prepolymer 3 (UP-3) and the polyol 4 (PO-4) were used.

Example 125

In the preparation of the polyol 4 (PO-4), the polyoxyethylene cetyl ether was replaced, and 20 g of eicosyl glycol ("NIKKOL Twendiol 80" manufactured by Nikko Chemical Co., Ltd.) was used. Melting point: 65 to 75 ° C) (1 mass% in the composition for forming a urethane resin) The polyol (PO-6) was prepared. A polyurethane elastomer molded product was obtained in the same manner as in Example 103 except that PO-1 was changed to PO-6.

Example 126

In the preparation of the polyol 1 (PO-1), 10 g of N-oil stearic acid decylamine (Nikka Amide OS, manufactured by Nippon Kasei Co., Ltd.) (0.5% by mass in the urethane resin-forming composition) was added as a saturated fatty acid guanamine. Polyol 7 (PO-7) was prepared. A polyurethane elastomer molded product was obtained in the same manner as in Example 103 except that PO-1 was changed to PO-7.

Organize the results in Table 22. By molding a urethane prepolymer or a polyol in a slip agent, a polyurethane elastomer molded article having a lower coefficient of friction can be obtained than when the release agent is used alone (Example 103).

Claims (26)

A thermosetting polyurethane elastomer-forming composition comprising: an isocyanate-based terminal urethane prepolymer (A), an active hydrogen-based terminal hardener (B), and a slip agent (C), a slip agent (C) The polyoxyethylene alkyl ether (C1) is contained in the thermosetting polyurethane elastomer-forming composition in an amount of 0.1 to 8% by mass, or 0.1 to 5% by mass in the thermosetting polyurethane elastomer-forming composition. Hong Cheng, the director of the Carbon Number 20~40 Crown Group International Patent and Trademark Joint Office, acts as a linear aliphatic alcohol (C2) like Wang Meichun. The thermosetting polyurethane elastomer-forming composition according to claim 1, wherein the lubricant (C) comprises a polyoxyethylene alkyl ether (C1) having a carbon number of 20 to 40 and a melting point of At least two compounds of a group consisting of a linear aliphatic alcohol (C2) and an octadecyl isocyanate (C3) at 90 ° C or lower, and the slip agent (C) in a thermosetting polyurethane elastomer-forming composition It contains 0.2 to 8 mass%. The thermosetting polyurethane elastomer-forming composition according to claim 1, wherein the lubricant (C) comprises a polyoxyethylene alkyl ether (C1) having a carbon number of 20 to 40 and a melting point. At least one of a group consisting of a linear aliphatic alcohol (C2) having 90 ° C or less and octadecyl isocyanate (C3), and a fatty acid decylamine (C4) in a thermosetting polyurethane elastomer-forming composition The total amount of the linear aliphatic alcohol (C2) and the octadecyl isocyanate (C3) having a polyoxyethylene alkyl ether (C1), a carbon number of 20 to 40, and a melting point of 90 ° C or less is 0.2 to 8 In the thermosetting polyurethane elastomer-forming composition, 0.05 to 0.5% by mass of fatty acid decylamine (C4) is contained in the mass%. The thermosetting polyurethane according to any one of claims 1 to 3 An elastomer-forming composition in which the polyoxyethylene alkyl ether (C1) has a hydroxyl group value of 5 to 70 KOHmg/g. The thermosetting polyurethane elastomer-forming composition according to any one of claims 1 to 4, which is selected from the group consisting of polyoxyethylene alkyl ether (C1) having a carbon number of 20 to 40 and a melting point of 90 At least one of a group consisting of a linear aliphatic alcohol (C2), an octadecyl isocyanate (C3), and a fatty acid decylamine (C4) below °C, using at least a polyisocyanate (A6) and a polyol (A7) An isocyanate-based terminal prepolymer of a pre-denatured isocyanate-terminated urethane prepolymer (A0). The thermosetting polyurethane elastomer-forming composition according to any one of claims 1 to 4, wherein the use comprises a polyoxyethylene alkyl ether (C1) selected from the group consisting of a polyoxyethylene alkyl ether (C1) having a carbon number of 20 to 40 and a melting point of At least one of a group consisting of a linear aliphatic alcohol (C2) at 90 ° C or lower and a fatty acid decylamine (C4), and an active hydrogen-based terminal hardener characterized by an active hydrogen-based terminal hardener (B0). The thermosetting polyurethane elastomer-forming composition according to claim 3, wherein the polyoxyethylene alkyl ether (C1) has a hydroxyl group value of 5 to 70 KOHmg/g, and the fatty acid decylamine (C4) has a melting point of Below 90 °C. A thermosetting polyurethane elastomer-forming composition according to any one of claims 1 to 7, wherein the thermosetting polyurethane elastomer-forming composition according to any one of claims 1 to 7 is a heat-curable polyurethane elastomer. An industrial machine part obtained by thermosetting a thermosetting polyurethane elastomer-forming composition according to any one of claims 1 to 7 to have a JIS-A hardness of 60~ A range of 98 hardened materials. An industrial machine part characterized by being thermally hardened by a thermosetting polyurethane elastomer-forming composition according to any one of claims 1 to 7 which has a JIS-A hardness of 60 to 98. The cured product (D) in the range has a static friction coefficient of 0.8 or less and a dynamic friction coefficient of 0.6 or less. An industrial machine part characterized by being thermally hardened by a thermosetting polyurethane elastomer-forming composition according to any one of claims 1 to 7 which has a JIS-A hardness of 60 to 98. The cured product (D) in the range of the cured product (D) has a static friction coefficient of 0.8 or less and a dynamic friction coefficient of 0.6 or less. An industrial machine part characterized in that the cured product (D) according to claim 10 is further heat-treated at 100 to 200 ° C for 1 to 120 minutes, and the static friction coefficient is 0.8 or less, and The dynamic friction coefficient is 0.6 or less. An industrial machine part characterized in that the cured product (D1) obtained by cutting the hardened material (D) according to claim 11 of the patent application is further heat-treated at 100 to 200 ° C for 1 to 120 minutes. The object (D2) has a static friction coefficient of 0.8 or less and a dynamic friction coefficient of 0.6 or less. A release agent composition for resin molding, characterized by comprising an organopolyoxane (J) having at least one carboxylate selected from the group consisting of 4- toluene and 4- toluene in a molecular structure . A release agent composition for resin molding, characterized in that the release agent composition for resin molding as described in claim 14 of the patent application further comprises an anthrone (L) having an active hydrogen group . Resin molding used as described in paragraphs 14 to 15 of the patent application a composition composition, wherein the organic polydecane (J) having at least one carboxylate selected from the group consisting of 4- toluene and 4- toluene in a molecular configuration, comprising selected from the group 4 ammonium (J1), At least one of Group 4 (J2) and a group of organopolyoxyalkylenes (J3) having a carboxyl group. The release agent composition for resin molding according to any one of claims 14 to 16, wherein at least one carboxylic acid selected from the group consisting of 4-grade ammonium (J1) and 4-grade lanthanum (J2) is used. The total content of the acid ester is 0.3 mmol/g based on the total content of the organopolyoxane (J) having at least one carboxylate selected from the group consisting of 4- toluene and 4- toluene in the molecular structure. the above. The release agent composition for resin molding according to any one of claims 15 to 17, which has a molecular structure selected from the group consisting of a grade 4 ammonium (J1) and a grade 4 (J2). 100 parts by mass of the organopolyoxane (J) of at least one of the carboxylic acid esters of the composition includes 5 to 150 parts by mass of an anthrone (L) having an active hydrogen group. The release agent composition for resin molding according to any one of claims 15 to 18, wherein the anthracene (L) having an active hydrogen group is an amino group-containing anthrone. A urethane resin molded article, characterized in that the urethane resin-forming composition (K) is formed by forming a release agent composition for resin molding as described in any one of claims 14 to 19; Mold forming. A method for producing a polyurethane resin molded article, which comprises applying a release agent composition for resin molding according to any one of claims 14 to 19 to a molding die, and forming a composition for forming a polyurethane resin. (K) Injection molding of the forming mold. The urethane resin molded article according to claim 20, wherein the urethane resin-forming composition (K) is composed of an isocyanate-based terminal urethane prepolymer (A0) and an active hydrogen-based terminal hardener (B0). ) composed of. The urethane resin molded article according to claim 20, wherein the urethane resin-forming composition (K) comprises a polyoxyethylene alkyl ether (C1) having a carbon number of 20 to 40 and a melting point of 90. At least one compound of a group consisting of a linear aliphatic alcohol (C2), an octadecyl isocyanate (C3), and a fatty acid decylamine (C4) below °C is used as a slip agent (C). The polyurethane resin molded article according to claim 22, wherein the isocyanate component of the isocyanate-terminated urethane prepolymer (A0) comprises diphenylmethane diisocyanate or toluene diisocyanate. The polyurethane resin molded article according to any one of claims 20, 22, 23, or 24, wherein the isocyanate-terminated terminal urethane prepolymer (A0) and the active hydrogen-based terminal hardener (B0) are mixed. The molar ratio of the isocyanate group/active hydrogen group is 1.0 to 3.0. An industrial machine part characterized by using a dynamic friction coefficient of 0.8 or less and a JIS-A hardness of 60 to 98, as described in any one of claims 20, 22, 23, 24, or 25. Polyurethane resin molded article.