WO2016035865A1

WO2016035865A1 - 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

Info

Publication number: WO2016035865A1
Application number: PCT/JP2015/075125
Authority: WO
Inventors: 野村弘二; 中島雄次
Original assignee: 東ソー株式会社
Priority date: 2014-09-05
Filing date: 2015-09-03
Publication date: 2016-03-10
Also published as: TW201638214A

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°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°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 parts using the same, release agent composition used for resin molding, and polyurethane resin molded product molded using the same

The present invention relates to a thermosetting polyurethane elastomer-forming composition used for industrial machine component members, a release agent composition used for resin molding, and a polyurethane resin molded product produced using the same.

The thermosetting polyurethane elastomer has a very high durability because it has a high modulus, high breaking strength, low wear, and low strain, and is suitably used as a component member of an industrial machine.

In general, thermosetting polyurethane elastomers used for industrial machine component parts are obtained by mixing a main agent composed of an isocyanate group component and a curing agent composed of an active hydrogen-containing component with a mixing head of a casting machine. The liquid can be poured into a mold, and the mixed liquid can be heated and cured (urethane reaction) in the mold.
In order to facilitate removal of the molded product, a mold release agent is applied to the inner surface of the mold in advance. As the mold release agent, polyethylene wax, organopolysiloxane, polyfluorinated ethylene and the like are preferably used.

As a component forming a composition for molding a thermosetting polyurethane elastomer, an isocyanate group-terminated urethane prepolymer (hereinafter abbreviated as “NCO group-terminated urethane prepolymer”) composed of an isocyanate and a polyol and a polyol or a polyamine are used. A method in which an active hydrogen group terminal curing agent is mixed and heat-cured is generally used.

For example, as an isocyanate component, an NCO group-terminated urethane prepolymer comprising diphenyl metadiisocyanate (hereinafter abbreviated as “MDI”) and a polyol component, polybutylene adipate (hereinafter abbreviated as “PBA”), and a polyol component as 1 , 4-butanediol (hereinafter abbreviated as “1,4-BD”), trimethylolpropane (hereinafter abbreviated as “TMP”), and PBA are preferably used. In addition, an NCO-terminated urethane prepolymer comprising tolylene diisocyanate (hereinafter abbreviated as “TDI”) and polytetramethylene glycol (hereinafter abbreviated as “PTMG”), 4,4′-diamino-3,3′-dichloro An amino group terminal curing agent having an amino group as an active hydrogen group such as diphenylmethane (hereinafter abbreviated as “MOCA”) is preferably used.

However, it is known that the coefficient of friction of the thermosetting polyurethane elastomer molding obtained as described above is very large due to its high elastic force. For this reason, in industrial machine parts that are used continuously, heat is generated due to friction caused by driving, and this heat gradually accumulates, resulting in a temperature higher than the design and changes in physical properties. Particularly problematic is a vicious circle in which the elastic force increases and the frictional resistance further increases as the temperature increases. When these thermosetting polyurethane elastomer moldings are used as industrial machine parts, the characteristics change due to the heat storage of the parts, and in a relatively short period of time, defects due to breakage, cracks, wear, etc. of the parts occur. Parts need to be replaced. In particular, in recent years, with the high-speed processing of industrial equipment, the temperature rises due to the heat storage of the part, leading to a decrease in mechanical strength, and the resulting breakage, cracks, wear, etc. of the part frequently occur. Therefore, a conventionally well-known thermosetting polyurethane elastomer molded product cannot be used sufficiently, and a low-friction thermosetting polyurethane elastomer molded product is strongly desired.

For the purpose of reducing the friction coefficient of polyurethane elastomer moldings, such as graphite, tetrafluoroethylene, resin powder, paraffin, disulfide molybdenum, wax, etc., fatty alcohol esters, higher fatty acids having 13 or more carbon atoms and alcohols having 8 or more carbon atoms It has been proposed to mix a liquid elastomer and a powdery lubricant such as higher fatty acid ester, etc., with a polyurethane elastomer (Patent Documents 1 to 3). In addition, a method of incorporating a lubricant component into a polyurethane molecule by introducing a stearic acid having a hydroxyl group or an amino group or an oleic acid ester and a curing agent, or introducing octadecyl isocyanate having an NCO group has been proposed ( Patent Documents 4 to 5).

In addition, a method of forming a polyurethane layer containing a siloxane bond by reacting a silicone compound having active hydrogen with a polyurethane resin has been proposed (Patent Document 6), and by forming a high hardness layer on the surface, low friction is proposed. A technique for realizing this has been proposed (Patent Document 7).

Japanese Unexamined Patent Publication No. 57-194946 Japanese Unexamined Patent Publication No. 3-346 Japanese Patent Laid-Open No. 5-133440 Japanese Unexamined Patent Publication No. 11-51122 Japanese Unexamined Patent Publication No. 2005-120216 Japanese Unexamined Patent Publication No. 4-189114 However, when a lubricant that does not react with the above-mentioned polyurethane is mixed with a polyurethane elastomer, the compatibility of the lubricant with an NCO group-terminated urethane prepolymer or an active hydrogen group-terminated curing agent is high. Unfortunately, not only becomes a non-uniform polyurethane elastomer molded product, but also generation of bleeding and bloom of a lubricant component is observed. In particular, when used for precision industrial machine parts, contamination by these lubricant components may cause problems in the industrial machine. A polyurethane elastomer molded product in which a lubricant with reaction with polyurethane described below is mixed with polyurethane elastomer and the lubricant component is incorporated in the polyurethane molecule is sufficient on the surface of the molded product due to the lack of carbon number of these lubricant components and the inhibition of the degree of freedom. In many cases, the friction cannot be reduced and the friction reduction is insufficient. Also, on the machined surface, the lubricant component cannot be sufficiently transferred, and the friction reduction is often insufficient or does not continue.

Also, the method of forming a silicone polyurethane resin layer on the urethane resin surface was insufficient in reducing the dynamic friction coefficient. In addition, silicones with active hydrogen groups that react with isocyanates are used, which also contain silicones that do not contain active hydrogen functional groups as impurities, which can bleed to the surface and contaminate the parts that come into contact with them. There is sex.

In addition, the method of forming a high hardness layer has a problem that the number of processes increases and productivity decreases because of the two-stage molding in which urethane resin molding is performed after the formation of the high hardness layer.

This invention is made | formed based on the above situations, As a 1st subject, as a thermosetting polyurethane elastomer formation composition for industrial machine component members, polyoxyethylene alkyl ether (C1) and carbon number At least one selected from the group consisting of linear aliphatic alcohols (C2) having a melting point of 20 to 40 and a melting point of 90 ° C. or lower, introducing octadecyl isocyanate (C3) for obtaining a better effect, At least one selected from the group consisting of oxyethylene alkyl ether (C1), linear aliphatic alcohol (C2) having 20 to 40 carbon atoms and a melting point of 90 ° C. or lower, and octadecyl isocyanate (C3), and fatty acid amide (C4 ), The friction coefficient is reduced without causing bleed and bloom. And to provide a consistently low industrial machinery parts thermoset polyurethane elastomer for. Moreover, by improving the compatibility with the NCO group-terminated urethane prepolymer and the active hydrogen group-terminated curing agent for obtaining these thermosetting polyurethane elastomers, a thermosetting polyurethane elastomer whose quality is stabilized is obtained. It is an object of the present invention to provide an NCO group-terminated urethane prepolymer and an active hydrogen group-terminated curing agent.

By using a release agent composition containing organopolysiloxane (A) having at least one carboxylate selected from the group consisting of at least quaternary ammonium and quaternary phosphonium in the molecular structure as a second problem, An object of the present invention is to provide a polyurethane resin molded product for industrial machine parts having a very low coefficient of friction without causing deterioration of physical properties, bleed or bloom, and without impairing productivity.

The present invention includes the following embodiments (1) to (26).
(1) An isocyanate group-terminated urethane prepolymer (A), an active hydrogen group-terminated curing agent (B), and a lubricant (C) are contained, and the lubricant (C) is added to the thermosetting polyurethane elastomer-forming composition in an amount of 0.00. 1 to 8% by mass of polyoxyethylene alkyl ether (C1), or 0.1 to 5% by mass of 20 to 40 carbon atoms in the thermosetting polyurethane elastomer-forming composition and a melting point of 90 ° C. A thermosetting polyurethane elastomer-forming composition comprising the following linear aliphatic alcohol (C2):
(2) The group in which the lubricant (C) is a polyoxyethylene alkyl ether (C1), a linear aliphatic alcohol (C2) having 20 to 40 carbon atoms and a melting point of 90 ° C. or less, and octadecyl isocyanate (C3) The thermosetting according to the above (1), which comprises at least two compounds selected from the group consisting of 0.2 to 8% by mass of the lubricant (C) in the thermosetting polyurethane elastomer-forming composition. -Forming polyurethane elastomer-forming composition.
(3) The group in which the lubricant (C) is a polyoxyethylene alkyl ether (C1), a linear aliphatic alcohol (C2) having 20 to 40 carbon atoms and a melting point of 90 ° C. or less, and octadecyl isocyanate (C3) At least one selected from the group consisting of fatty acid amide (C4), polyoxyethylene alkyl ether (C1), linear aliphatic alcohol (C2) having 20 to 40 carbon atoms and a melting point of 90 ° C. or lower, and octadecyl The total amount of isocyanate (C3) is 0.2 to 8% by mass in the thermosetting polyurethane elastomer-forming composition, and the fatty acid amide (C4) is 0.05 to 0 in the thermosetting polyurethane elastomer-forming composition. The thermosetting polyurethane elastomer-forming composition as described in (1) above, containing 5% by mass.
(4) The thermosetting polyurethane elastomer-forming composition as described in any one of (1) to (3) above, wherein the polyoxyethylene alkyl ether (C1) has a hydroxyl value of 5 to 70 KOHmg / g .
(5) A group consisting of polyoxyethylene alkyl ether (C1), linear aliphatic alcohol (C2) having 20 to 40 carbon atoms and a melting point of 90 ° C. or lower, octadecyl isocyanate (C3), and fatty acid amide (C4) The above-mentioned (1) characterized in that an isocyanate group-terminated prepolymer obtained by modifying an isocyanate group-terminated urethane prepolymer (A0) composed of at least a polyisocyanate (A6) and a polyol (A7) in advance is used as at least one selected from the above (1) The thermosetting polyurethane elastomer-forming composition according to any one of (1) to (4).
(6) at least one selected from the group consisting of polyoxyethylene alkyl ether (C1), linear aliphatic alcohol (C2) having 20 to 40 carbon atoms and a melting point of 90 ° C. or lower, and fatty acid amide (C4); The thermosetting polyurethane elastomer according to any one of the above (1) to (4), characterized by using an active hydrogen group terminal curing agent comprising: an active hydrogen group terminal curing agent (B0) Formable composition.
(7) The thermosetting polyurethane as described in (3) above, wherein the polyoxyethylene alkyl ether (C1) has a hydroxyl value of 5 to 70 KOHmg / g and the fatty acid amide (C4) has a melting point of 90 ° C. or less. Elastomer-forming composition.
(8) A method for producing a thermosetting polyurethane elastomer, comprising subjecting the thermosetting polyurethane elastomer-forming composition according to any one of (1) to (7) to a thermosetting treatment.
(9) A cured product having a JIS-A hardness in the range of 60 to 98 obtained by thermosetting the thermosetting polyurethane elastomer-forming composition according to any one of (1) to (7) above. Industrial machine parts.
(10) A cured product having a JIS-A hardness in the range of 60 to 98 obtained by thermosetting the thermosetting polyurethane elastomer-forming composition according to any one of (1) to (7) (D Industrial machinery parts having a static friction coefficient of 0.8 or less and a dynamic friction coefficient of 0.6 or less.
(11) A cured product (D) having a JIS-A hardness of 60 to 98 obtained by thermosetting the thermosetting polyurethane elastomer-forming composition according to any one of (1) to (7) above An industrial machine part in which a static friction coefficient of a cured product (D1) obtained by cutting is 0.8 or less and a dynamic friction coefficient is 0.6 or less.
(12) The cured product obtained by further heat-treating the cured product (D) according to (10) at 100 to 200 ° C. for 1 to 120 minutes has a static friction coefficient of 0.8 or less and a dynamic friction coefficient of 0.6 or less. Industrial machine parts.
(13) The static friction coefficient of the cured product (D2) obtained by further heat-treating the cured product (D1) obtained by cutting the cured product (D) described in (11) at 100 to 200 ° C. for 1 to 120 minutes. Industrial machine parts with 0.8 or less and a coefficient of dynamic friction of 0.6 or less.
(14) A mold release used for resin molding, comprising an organopolysiloxane (J) having in its molecular structure at least one carboxylate selected from the group consisting of quaternary ammonium and quaternary phosphonium. Agent composition.
(15) The release agent composition used for resin molding, wherein the release agent composition used for resin molding described in (14) above further contains silicone (L) having an active hydrogen group. object.
(16) Organopolysiloxane (J) having at least one carboxylate selected from the group consisting of quaternary ammonium and quaternary phosphonium in the molecular structure is quaternary ammonium (J1), quaternary phosphonium (J2), And a release agent composition for use in resin molding as described in (14) or (15) above, comprising at least one selected from the group consisting of a carboxyl group-containing organopolysiloxane (J3).
(17) The total content of at least one carboxylate selected from the group consisting of quaternary ammonium (J1) and quaternary phosphonium (J2) is at least one selected from the group consisting of quaternary ammonium and quaternary phosphonium. Any one of (14) to (16) above, wherein 0.3 mmol / g or more is contained with respect to the total content of organopolysiloxane (J) having a carboxylate in the molecular structure. Mold release agent composition used for resin molding.
(18) An active hydrogen group is added to 100 parts by mass of an organopolysiloxane (J) having at least one carboxylate selected from the group consisting of quaternary ammonium (J1) and quaternary phosphonium (J2) in the molecular structure. The release agent composition for use in resin molding as described in any one of (15) to (17) above, which comprises 5 to 150 parts by mass of the silicone (L) having the resin.
(19) The release agent composition used for resin molding as described in any one of (15) to (18) above, wherein the silicone (L) having an active hydrogen group is an amino group-containing silicone.
(20) Polyurethane resin-forming composition (K) is molded by a molding die to which a release agent composition used for resin molding according to any one of (14) to (19) is applied. Resin molding.
(21) The mold release agent composition used in the resin molding described in any one of (14) to (19) is applied to a mold, and the polyurethane resin-forming composition (K) is injected into the mold. A method for producing a molded polyurethane resin product obtained by molding.
(22) The polyurethane resin according to (20) above, wherein the polyurethane resin-forming composition (K) comprises an isocyanate group-terminated urethane prepolymer (A0) and an active hydrogen group-terminated curing agent (B0). Molded product.
(23) The polyurethane resin-forming composition (K) is a polyoxyethylene alkyl ether (C1) as a lubricant (C), a linear aliphatic alcohol (C2) having 20 to 40 carbon atoms and a melting point of 90 ° C. or less. The polyurethane resin molded product according to (20) or (22) above, which contains at least one compound selected from the group consisting of: octadecyl isocyanate (C3) and fatty acid amide (C4).
(24) The polyurethane resin molded product according to (22) or (23) above, which contains diphenylmethane diisocyanate or tolylene diisocyanate as an isocyanate component of the isocyanate group-terminated urethane prepolymer (A0).
(25) The isocyanate group / active hydrogen group molar ratio when mixing the isocyanate group-terminated urethane prepolymer (A0) and the active hydrogen group terminal curing agent (B0) is 1.0 to 3.0. The polyurethane resin molded product according to any one of (20), (22), (23), or (24).
(26) The dynamic friction coefficient is 0.8 or less and the JIS-A hardness is in the range of 60 to 98, according to any one of (20), (22), (23), (24), or (25) Industrial machine parts using polyurethane resin moldings.

By using the thermosetting polyurethane elastomer-forming composition for industrial machine parts of the present invention for industrial machines, the NCO group-terminated urethane prepolymer, and active hydrogen have both low contamination and low friction, which could not be achieved in the past. A uniform thermosetting polyurethane elastomer for industrial machine parts can be obtained without impairing the properties (compatibility) of the base terminal curing agent.

Furthermore, by using the release agent of the present invention, the thermosetting polyurethane elastomer has a high elasticity and low friction that could not be achieved in the past, and is a uniform thermosetting polyurethane elastomer for industrial machine parts with the same production method. Can be obtained.

The thermosetting polyurethane elastomer molding composition for industrial machine parts of the present invention that solves the first problem includes an isocyanate group-terminated urethane prepolymer (A), an active hydrogen group-terminated curing agent (B), and a lubricant (C). A thermosetting polyurethane elastomer-forming composition comprising a polyoxyethylene alkyl ether (C1) as a lubricant (C) and a linear aliphatic alcohol (C2) having 20 to 40 carbon atoms and a melting point of 90 ° C. or less At least one compound selected from the group consisting of: introducing octadecyl isocyanate (C3) to obtain a better effect; or polyoxyethylene alkyl ether (C1) having 20 to 40 carbon atoms and a melting point Is a group consisting of a linear aliphatic alcohol (C2) and octadecyl isocyanate (C3) of 90 ° C. or less At least the one selected Ri, it is possible to reduce the friction coefficient by introducing fatty acid amide (C4).

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

Also, the introduction of octadecyl isocyanate (C3) can continuously reduce the dynamic friction coefficient, and the introduction of fatty acid amide (C4) can significantly reduce the static friction coefficient.

The polyoxyethylene alkyl ether (C1) introduced as the lubricant (C) used in the present invention is not particularly limited as long as the effects of the present invention are exhibited. This polyoxyethylene alkyl ether can be represented by the general formula 1.
[General Formula 1]
H _{2m + 1} C _m —O— (CH ₂ CH ₂ O) _n H
Although the values of m and n in the general formula 1 are not particularly limited, the hydroxyl value is preferably 5 to 70 KOHmg / g for more effective reduction of friction. When the hydroxyl value exceeds 70 KOHmg / g, the number of carbon atoms is generally short, and the effect as a lubricant component may be gradually reduced. Specific examples of commercially available products of polyoxyethylene alkyl ether (C1) include, for example, polyoxyethylene lauryl ether “NIKKOL BL-2, NIKKOL BL-4.2, NIKKOL BL-21, NIKKOL BL-25 manufactured by Nikko Chemicals”, Polyoxyethylene cetyl ale "NIKKOL BC-2, NIKKOL BC-5.5, NIKKOL BC-7, NIKKOL BC-10, NIKKOL BC-20, NIKKOL BC-23, NIKKOL BC-25, NIKOL BC-25, NIKOL BC-25, NIKOL BC-25 -40, NIKKOL BC-150 ", polyoxyethylene stearyl ether" NIKKOL BS-2, "NIKKOL BS-4," NIKKOL BS-20 ", polyoxyethylene oleyl ether""NI KOL BO-2V, "NIKKOL BO-7V," NIKKOL BO-10V, "NIKKOL BO-15V," NIKKOL BO-20V, "" NIKKOL BO-50V ", polyoxyethylene behenyl ether" NIKKOLB BKB " 10, NIKKOL BB-20, NIKKOL BB-40 ”and the like can be used.

The linear aliphatic alcohol (C2) having 20 to 40 carbon atoms and a melting point of 90 ° C. or lower introduced as the lubricant (C) used in the present invention is not particularly limited as long as the effects of the present invention are exhibited. The straight chain aliphatic alcohol having 20 to 40 carbon atoms can be represented by the general formula 2.
[General formula 2]
CH ₃ — (CH ₂ ) n—OH, n = 19 to 39
The value of n in the general formula 2 is 19 to 39, and the melting point is 90 ° C. or less. When the melting point exceeds 90 ° C., the solubility with the isocyanate group-terminated urethane prepolymer is generally poor, and even if the temperature during prepolymer synthesis is raised to 100 ° C. or higher, uniform dissolution is difficult, and the reaction temperature increases. , Resulting in a high viscosity due to side reactions such as allophanatization, leading to a decrease in the quality of the prepolymer. Moreover, the solubility with an active hydrogen group terminal hardening | curing agent is also bad. During production, it can be dissolved by heating above the melting point, but when it is filled and stored, it will crystallize at room temperature, so when molding a thermosetting polyurethane elastomer, heat it again above the melting point. However, it is necessary to stir uniformly, and it becomes difficult to handle.

Examples of the linear aliphatic alcohol (C2) having 20 to 40 carbon atoms and a melting point of 90 ° C. or less include 1-icosanol (C20), 1-heneicosanol (C21), 1-docosanol (C22), 1-tricosanol ( C23), 1-tricosanol (C24), 1-pentacosanol (C25), 1-hexacosanol (C26), 1-heptacosanol (C27), 1-octacosanol (C28), 1-nonacosanol (C29), 1 Triacontanol (C30), 1-Hentriacontanol (C31), 1-Dotriacontanol (C32), 1-Tritriacontanol (C33), 1-Tetratriacontanol (C34), 1-Pentatria Contanol (C35), 1-hexatriacontanol (C36), 1-heptato Acon ethanol (C37), 1-octa triacontanol (C38), 1-nona triacontanol (C39), 1-tetra con methanol (C40) can be mentioned.

Specific examples of commercial products of these mixtures having a melting point of 90 ° C. or lower include behenyl alcohol, behenyl alcohol 65, behenyl alcohol 80R, highsonol 20SS, highsonol 22SS manufactured by Higher Alcohol Industry, NIKKOL behenyl alcohol 65, NIKKOL behenyl alcohol 80 manufactured by Nikko Chemicals. Permacol 350 Alcohol, etc. can be used.

The octadecyl isocyanate (C3) introduced as the lubricant (C) used in the present invention can be represented by the general formula 3.
[General formula 3]
CH ₃ (CH ₂ ) ₁₇ NCO
Millionate O (manufactured by Hodogaya Chemical Co., Ltd.) can be used as a specific example of a commercially available product of octadecyl isocyanate (C3).

The fatty acid amide (C4) introduced as the lubricant (C) used in the present invention is not particularly limited as long as the effects of the present invention are exhibited. As this fatty acid amide, a saturated fatty acid amide, an unsaturated fatty acid amide, a substituted amide, a saturated fatty acid bisamide, and an unsaturated fatty acid bisamide can be used, and in order to reduce friction more effectively, the melting point is 90 ° C. or lower. It is preferable. When the melting point exceeds 90 ° C., the solubility with the isocyanate group-terminated urethane prepolymer is generally poor, and even if the temperature during prepolymer synthesis is raised to 100 ° C. or higher, uniform dissolution is difficult, and the reaction temperature increases. In some cases, the viscosity increases due to side reactions such as allophanatization, leading to deterioration of the quality of the prepolymer. In addition, the solubility with the active hydrogen group terminal curing agent is poor, and during the production, it can be dissolved by heating above the melting point. When molding a flexible polyurethane elastomer, it is necessary to heat it to the melting point or higher and stir it uniformly, which makes it difficult to handle.

As fatty acid amide (C4), for example, lauric acid amide of saturated fatty acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxy stearic acid amide, oleic acid amide of unsaturated fatty acid amide, erucic acid amide, substituted amide N-oleyl palmitic acid amide, N-stearyl stearic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide, methylene bis stearic acid amide of saturated fatty acid bisamide, ethylene biscapric acid amide , Ethylene bis lauric acid amide, ethylene bis stearic acid amide, ethylene bis hydroxy stearic acid amide, ethylene bis behenic acid amide, hexamethylene bis stearic acid amide, hexamethylene bis bevenic acid Amide, hexamethylene bishydroxystearic acid amide, N, N-distearyl adipic acid amide, N, N-distearyl acevacic acid amide, ethylene bisoleic acid amide of unsaturated fatty acid bisamide, ethylene biserucic acid amide, hexamethylene Examples thereof include bisoleic acid amide, N, N-dioleyl adipic acid amide, N, N-dioleyl sebacic acid amide and the like. Specific examples of commercial products of these mixtures having a melting point of 90 ° C. or lower include Diamit Y, Diamit O-200, Diamit L-200, Nikka Amide OP, Nikka Amide SO, Nikka Amide manufactured by Nippon Kasei. OS, Nikka Amide SE, etc. can be used.

In the first embodiment, when the content of polyoxyethylene alkyl ether (C1) in the thermosetting polyurethane elastomer molding is less than 0.1% by mass, the friction reducing effect is not seen. Moreover, when it exceeds 8 mass%, although the friction reduction effect is seen, there exists a possibility of causing the physical-property fall of the thermosetting polyurethane elastomer obtained by increase in 1 functional component.

In the second embodiment, when the content of the linear aliphatic alcohol (C2) having 20 to 40 carbon atoms and a melting point of 90 ° C. or less is less than 0.1% by mass, a friction reducing effect is seen. Absent. Moreover, when it exceeds 5 mass%, although the friction reduction effect is seen, there exists a possibility of causing the physical-property value fall of the thermosetting polyurethane elastomer obtained by increase in 1 functional component.

In the third embodiment, polyoxyethylene alkyl ether (C1) and linear aliphatic alcohol (C2) having 20 to 40 carbon atoms and a melting point of 90 ° C. or less in the thermosetting polyurethane elastomer molding. The total amount of at least one compound selected from the group consisting of octadecyl isocyanate (C3) is preferably 0.2 to 8% by mass, and particularly preferably 1 to 6% by mass, in the thermosetting polyurethane elastomer molding. When the total addition amount of the lubricant (C) is less than 0.2% by mass, a sufficient friction-reducing effect is not observed, and when it exceeds 8% by mass, the physical properties decrease due to the decrease in the average functional group number or the prepolymer. There is a risk of quality degradation.

Furthermore, in the fourth embodiment, the lubricant (C) contains fatty acid amide (C4) as an essential component, polyoxyethylene alkyl ether (C1), a straight chain having 20 to 40 carbon atoms and a melting point of 90 ° C. or lower. One or more of aliphatic alcohol (C2) and octadecyl isocyanate (C3) can be arbitrarily selected and used. Among them, polyoxyethylene alkyl ether (C1), carbon number 20 to 40, and melting point A combination of at least one selected from the group consisting of linear aliphatic alcohols (C2) of 90 ° C. or lower and octadecyl isocyanate (C3) is particularly preferable. The amount of lubricant component selected from the group consisting of polyoxyethylene alkyl ether (C1), linear aliphatic alcohol (C2) having 20 to 40 carbon atoms and a melting point of 90 ° C. or lower, and octadecyl isocyanate (C3) is as follows: The content is preferably 0.2 to 8% by mass in the whole thermosetting polyurethane elastomer-forming composition. When the amount is less than 0.2% by mass, a sufficient friction reducing effect is not observed, and when the amount is more than 8% by mass, the physical properties may be lowered due to a decrease in the number of average functional groups or the quality of the prepolymer may be reduced. The introduction amount of the fatty acid amide (C4) used in combination with these is preferably 0.05 to 0.5% by mass relative to the entire thermosetting polyurethane elastomer-forming composition, and considering the bleed (bloom). A small amount of 0.05 to 0.3% by mass is particularly preferred.

As the first embodiment, the NCO group-terminated urethane prepolymer (A) used in the present invention is not limited as long as the NCO group-terminated urethane prepolymer (A0) is included. Among these, an NCO group-terminated urethane prepolymer (A1) to which polyoxyethylene alkyl ether (C1) is further added can be suitably used. The NCO group-terminated urethane prepolymer (A1) uses a reaction inhibitor (E) as necessary, and undergoes urethanation reaction with at least polyisocyanate (A6), polyol (A7), and polyoxyethylene alkyl ether (C1). What is obtained is preferred. Here, the NCO group-terminated urethane prepolymer (A0) is prepared from at least a polyisocyanate (A6) and a polyol (A7) and does not contain a lubricant (C) component.

The NCO content of the NCO group-terminated urethane prepolymer (A) or (A1) 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 flowability of the urethane resin is remarkably deteriorated during casting. When the content is higher than 25% by mass, the stability of properties during storage and use is remarkably deteriorated, and it is difficult to obtain a stable industrial machine part, resulting in molding failure. It may become unsuitable as a terminal urethane prepolymer.

Although there is no restriction | limiting in particular as a manufacturing method of NCO group terminal urethane prepolymer (A1), For example, the following manufacturing methods can be mentioned. The polyisocyanate (A6) and the reaction inhibitor (E) are charged and stirred in the stirring vessel, and then the polyol (A7) and the polyoxyethylene alkyl ether (C1) while maintaining the temperature in the stirring vessel at 40 to 70 ° C. Is stirred. Subsequently, the urethanization reaction can be carried out for about 2 to 5 hours while maintaining the temperature in the stirring vessel at 70 to 90 ° C.

As a second embodiment, the NCO group-terminated urethane prepolymer (A) used in the present invention is not limited as long as at least the NCO group-terminated urethane prepolymer (A0) is included. Among these, an NCO group-terminated urethane prepolymer (A2) further added with a linear aliphatic alcohol (C2) having 20 to 40 carbon atoms and a melting point of 90 ° C. or less can be suitably used. The NCO group-terminated urethane prepolymer (A2) uses a reaction inhibitor (E) as necessary, and at least a polyisocyanate (A6), a polyol (A7), a carbon number of 20 to 40, and a melting point of 90 ° C. or less. Those obtained by a urethanization reaction with a linear aliphatic alcohol (C2) are preferred.

The NCO content of the NCO group-terminated urethane prepolymer (A) or (A2) 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 flowability of the urethane resin is remarkably deteriorated during casting. When the content is higher than 25% by mass, the stability of properties during storage and use is remarkably deteriorated, and it is difficult to obtain a stable industrial machine part, resulting in molding failure. It may become unsuitable as a terminal urethane prepolymer.

Although there is no restriction | limiting in particular as a manufacturing method of NCO group terminal urethane prepolymer (A2), For example, the following manufacturing methods can be mentioned. The polyisocyanate (A6) and the reaction inhibitor (E) are charged into the stirring vessel and stirred, and then the polyol (A7), having 20 to 40 carbon atoms and a melting point while maintaining the temperature in the stirring vessel at 40 to 70 ° C. Is charged with a straight chain aliphatic alcohol (C2) having a temperature of 90 ° C. or less. Subsequently, the urethanization reaction can be carried out for about 2 to 5 hours while maintaining the temperature in the stirring vessel at 70 to 90 ° C.

As a third embodiment, the NCO group-terminated urethane prepolymer (A) used in the present invention is not limited as long as at least the NCO group-terminated urethane prepolymer (A0) is included. Among them, the NCO group-terminated urethane prepolymer (A3) modified by further adding octadecyl isocyanate (C3), or polyoxyethylene alkyl ether (C1), and having 20 to 40 carbon atoms and a melting point of 90 ° C. or less It is preferable to use an NCO group-terminated urethane prepolymer (A4) modified by further adding at least one compound selected from the group consisting of linear aliphatic alcohols (C2) and octadecyl isocyanate (C3).

The modification referred to here is to change the properties of the NCO group-terminated urethane prepolymer (A0). For example, the NCO group-terminated urethane prepolymer (A3) modified with octadecyl isocyanate (C3) is a polyisocyanate (A6). ) And polyol (A7), and an NCO group-terminated prepolymer prepared from octadecyl isocyanate (C3).

Further, a reaction inhibitor (E) may be added as necessary. The NCO content of the NCO-terminated 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 flowability of the urethane resin is remarkably deteriorated during casting. When the content is higher than 25% by mass, the stability of properties during storage and use is remarkably deteriorated, and it is difficult to obtain a stable industrial machine part, resulting in molding failure. It may become unsuitable as a terminal urethane prepolymer.

Although there is no restriction | limiting in particular as a manufacturing method of NCO group terminal urethane prepolymer (A3) or (A4), For example, the following manufacturing methods can be mentioned. After the polyisocyanate (A6), octadecyl isocyanate (C3), and the reaction inhibitor (E) are charged into the stirring vessel and stirred, the polyoxyethylene alkyl ether (C1), while maintaining the temperature in the vessel at 40 to 70 ° C., And a mixture of at least one selected from the group consisting of linear aliphatic alcohols (C2) having 20 to 40 carbon atoms and a melting point of 90 ° C. or less and a polyol (A7), or a polyol (A7) is added and stirred. To do. Subsequently, the isocyanate group-terminated urethane prepolymer (A3) or (A4) can be obtained by proceeding with the urethanization reaction for about 2 to 5 hours while maintaining the temperature in the stirring vessel at 70 to 90 ° C. Further, octadecyl isocyanate (C3) can be added and blended after the urethanization reaction.

As a fourth embodiment, the NCO group-terminated urethane prepolymer (A) used in the present invention is not limited as long as at least the NCO group-terminated urethane prepolymer (A0) is included. Among them, selected from the group consisting of polyoxyethylene alkyl ether (C1), linear aliphatic alcohol (C2) having 20 to 40 carbon atoms and melting point of 90 ° C. or lower, octadecyl isocyanate (C3), and fatty acid amide (C4). It is preferable to use an NCO group-terminated urethane prepolymer (A5) modified with at least one compound.

The modification referred to here is to change the properties of the NCO group-terminated urethane prepolymer (A0). For example, the NCO group-terminated urethane prepolymer (A5) modified with a fatty acid amide (C4) is a polyisocyanate (A6). ) And polyol (A7), and NCO group-terminated prepolymer prepared from fatty acid amide (C4).

Further, a reaction inhibitor (E) may be added as necessary. The NCO content of the NCO group-terminated urethane prepolymer (A) or (A5) 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 flowability of the urethane resin is remarkably deteriorated during casting. When the content is higher than 25% by mass, the stability of properties during storage and use is remarkably deteriorated, and it is difficult to obtain a stable industrial machine part, resulting in molding failure. It will become unsuitable as a terminal urethane prepolymer.

Although there is no restriction | limiting in particular as a manufacturing method of the NCO group terminal urethane prepolymer (A5) used for this invention, For example, the following manufacturing methods can be mentioned. The polyisocyanate (A6) and, if necessary, the octadecyl isocyanate (C3) and the reaction inhibitor (E) are charged into the stirring vessel, and after stirring, the temperature in the vessel is kept at 40 to 70 ° C. At least one selected from the group consisting of ethylene alkyl ether (C1) and linear aliphatic alcohol (C2) having 20 to 40 carbon atoms and a melting point of 90 ° C. or less, and polyol (A7) are added and stirred. . If necessary, fatty acid amide (C4) is added and stirred. Subsequently, the isocyanate group-terminated urethane prepolymer (A5) can be obtained by proceeding with the urethanization reaction for about 2 to 5 hours while maintaining the temperature in the stirring vessel at 70 to 90 ° C. Octadecyl isocyanate (C3) and fatty acid amide (C4) can also be added and blended 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 are exhibited. From the viewpoint of mechanical properties and reaction control, at least one selected from aromatic diisocyanates is preferable, and 4,4'-diphenylmethane diisocyanate is particularly preferable.

<Polyisocyanate (A6)>
Specific examples of the polyisocyanate include hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, cyclohexyl diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated trimethylxylylene diisocyanate, 2-methylpentane-1, 5-diisocyanate, 3-methylpentane-1,5-diisocyanate, 2,2,4-trimethylhexahylene-1,6-diisocyanate, 2,4,4-trimethylhexahylene-1,6-diisocyanate, etc. Aliphatic and alicyclic diisocyanates. 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyldiisocyanate, 1,5-naphthylene diisocyanate Aromatic diisocyanates such as paraphenylene diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate. Difficult yellowing diisocyanates such as orthoxylylene diisocyanate, metaxylylene diisocyanate, paraxylylene diisocyanate, tetramethylxylylene diisocyanate. In addition, urethane-modified products, urea-modified products, carbodiimide-modified products, uretonimine-modified products, uretdione-modified products, isocyanurate-modified products, allophanate-modified products, etc. can be used.

<Polyol (A7)>
The polyol (A7) used in the present invention is not particularly limited as long as the effects of the present invention are exhibited, but from the viewpoint of mechanical properties and glass transition temperature, the average number of functional groups is 2 to 3, and the number average molecular weight is 250 to 5000. It is preferable that at least one kind selected from polyester polyols and polyether polyols. In addition, a monomer polyol can also be used together as needed.

In addition, the following polyols can be arbitrarily selected and used for the active hydrogen group terminal curing agent (B) described later.

<Polyester polyol>
Specific examples of the polyester polyol include, for example, phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, succinic acid, tartaric acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, glutaconic acid, azelaic acid. , Sebacic acid, 1,4-cyclohexyl dicarboxylic acid, α-hydromuconic acid, β-hydromuconic acid, α-butyl-α-ethylglutaric acid, α, β-diethylsuccinic acid, maleic acid, fumaric acid, etc. One or more of acids or their anhydrides, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, , 9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-di 1 of low molecular weight polyols having a molecular weight of 500 or less such as methanol, dimer acid diol, ethylene oxide or propylene oxide adduct of bisphenol A, bis (β-hydroxyethyl) benzene, xylylene glycol, glycerin, trimethylolpropane, pentaerythritol The thing obtained from a polycondensation reaction with more than a kind can be mentioned. In addition, a polyester-amide polyol obtained by replacing a part of the low molecular polyol with a low molecular polyamine such as hexamethylene diamine, isophorone diamine or monoethanolamine or a low molecular amino alcohol can also be used.

<Polyether polyol>
Specific examples of the polyether polyol include ethylene glycol, 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-dimethylolheptane, diethylene glycol, dipropylene glycol , Neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, bisphenol A, bis (β-hydroxyethyl) benzene, xylylene glycol, glycerin, trimethylolpropane, pentaerythritol Small molecules such as Initiates compounds having 2 or more, preferably 2 to 3 active hydrogen groups such as riols or low molecular weight polyamines such as ethylenediamine, propylenediamine, toluenediamine, metaphenylenediamine, diphenylmethanediamine, xylylenediamine, etc. As an agent, polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, etc., or alkyl glycidyl ethers such as methyl glycidyl ether, aryl glycidyl ethers such as phenyl glycidyl ether And polyether polyols obtained by ring-opening polymerization of cyclic ether monomers such as tetrahydrofuran.

<Polycarbonate polyol>
Specific examples of the polycarbonate polyol include, for example, ethylene glycol, 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-dimethylolheptane, diethylene glycol, dipropylene glycol, Neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, bisphenol A ethylene oxide and propylene oxide adducts, bis (β-hydroxyethyl) benzene, xylylene glycol, glycerin The One or more kinds of low molecular polyols such as methylolpropane and pentaerythritol, dialkyl carbonates such as dimethyl carbonate and diethyl carbonate, alkylene carbonates such as ethylene carbonate and propylene carbonate, diphenyl carbonate, dinaphthyl carbonate, dianthryl carbonate, di Examples thereof include those obtained from dealcoholization reaction and dephenol reaction with diaryl carbonates such as phenanthryl carbonate, diindanyl carbonate, and tetrahydronaphthyl carbonate.

In addition, the polyol (A7) may be a polyolefin polyol, an acrylic polyol, a silicone polyol, a castor oil-based polyol, a fluorine-based polyol, or a monomer polyol alone or in combination of two or more, as long as the performance does not deteriorate.

<Polyolefin polyol>
Specific examples of the polyolefin polyol include polybutadiene having two or more hydroxyl groups, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, and the like.

<Acrylic polyol>
Examples of the acrylic polyol include acrylic acid ester and / or methacrylic acid ester (hereinafter referred to as (meth) acrylic acid ester), acrylic acid hydroxy compound having at least one hydroxyl group in the molecule and / or methacrylic acid which can be a reaction point. Examples include an acid hydroxy compound (hereinafter referred to as a (meth) acrylic acid hydroxy compound) and a polymerization initiator obtained by copolymerizing an acrylic monomer using thermal energy, light energy such as ultraviolet rays or electron beams, and the like.

<(Meth) acrylic acid ester>
Specific examples of (meth) acrylic acid esters include alkyl esters having 1 to 20 carbon atoms. Specific examples of such (meth) acrylate esters include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and pentyl (meth) acrylate. (Meth) such as hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate Esters of (meth) acrylic acid with cycloaliphatic alcohols such as alkyl acrylates, cyclohexyl (meth) acrylates, (meth) acrylic acid allyl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate Can be mentioned. Such (meth) acrylic acid esters can be used singly 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 in the molecule that can be a reaction point with the polyisocyanate composition, specifically, 2-hydroxyethyl acrylate, Examples thereof include hydroxy acrylate compounds such as 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 3-hydroxy-2,2-dimethylpropyl acrylate, and pentaerythritol triacrylate. Also, hydroxy methacrylate compounds such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 3-hydroxy-2,2-dimethylpropyl methacrylate, and pentaerythritol trimethacrylate are exemplified. These acrylic acid hydroxy compounds and methacrylic acid hydroxy compounds can be used singly or in combination of two or more.

<Polymerization initiator>
Examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator, and are appropriately selected depending on the polymerization method.

Specific examples of the thermal polymerization initiator include peroxydicarbonates such as di-2-ethylhexyl peroxydicarbonate, t-butylperoxybenzoate, t-butylperoxy-2-ethylhexanoate, and t-butylperoxyisopropyl carbonate. , Peroxyesters such as t-hexylperoxyisopropyl carbonate, di (t-butylperoxy) -2-methylcyclohexane, di (t-butylperoxy) 3,3,5-trimethylcyclohexane and di (t-butylperoxy) cyclohexane And peroxyketals.

Specific examples of the photopolymerization initiator include acetophenone, methoxyacetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, α-hydroxy-α, α Acetophenones such as' -dimethylacetophenone, 2-hydroxy-2-cyclohexylacetophenone, 2-methyl-1 [4- (methylthio) phenyl] -2-montforinopropanone-1, benzoin, benzoin methyl ether, benzoin ethyl Benzoin ethers such as ether and benzoin isopropyl butyl ether, benzophenone, 2-chlorobenzophenone, p, p'-dichlorobenzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone, 4- (2- Ketones such as droxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, thioxanthones such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, phosphines such as bisacylphosphine oxide and benzoylphosphine oxide Examples thereof include oxides, ketals such as benzyldimethyl ketal, and quinones such as camphane-2,3-dione and phenanthrenequinone.

<Silicone polyol>
Specific examples of the silicone polyol include a vinyl group-containing silicone compound obtained by polymerizing γ-methacryloxypropyltrimethoxysilane and the like, and α, ω-dihydroxypolydimethylsiloxane having at least one terminal hydroxyl group in the molecule, α , Ω-dihydroxypolydiphenylsiloxane, and the like.

<Castor oil-based polyol>
Specific examples of the castor oil-based polyol include linear or branched polyester polyols obtained by the reaction of castor oil fatty acid and polyol. Dehydrated castor oil, partially dehydrated castor oil partially dehydrated, hydrogenated castor oil added with hydrogen, and the like can also be used.

<Fluorine-based polyol>
Specific examples of the fluorine-based polyol include linear or branched polyols obtained by a copolymerization reaction using a fluorine-containing monomer and a monomer having a hydroxy group as essential components. Here, the fluorine-containing monomer is preferably a fluoroolefin, for example, tetrafluoroethylene, chlorotrifluoroethylene, trichlorofluoroethylene, hexafluoropropylene, vinylidene fluoride, vinyl fluoride, trifluoromethyl trifluoroethylene. Etc. Examples of the monomer having a hydroxyl group include hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether and cyclohexanediol monovinyl ether, hydroxyalkyl allyl ethers such as 2-hydroxyethyl allyl ether, and vinyl hydroxyalkyl crotonates. Examples thereof include monomers having hydroxyl groups such as hydroxyl group-containing vinyl carboxylate such as allyl ester.

<Monomer polyol>
Specific examples of the monomer polyol include, for example, ethylene glycol, 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-dimethylolheptane, diethylene glycol, dipropylene glycol, neo Pentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, bisphenol A, bis (β-hydroxyethyl) benzene, xylylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc. Can be mentioned.

The active hydrogen group terminal curing agent (B) used in the present invention can be arbitrarily selected from the aforementioned polyols. Among these, it is preferable to use a mixture obtained by adding any one of polyester polyols, polyether polyols, and polycarbonate polyols having an average functional group number of 2 to 3 and a number average molecular weight of 250 to 5000. Further, from the viewpoint of improving mechanical properties and molding processability, monomer polyols can be used alone or in admixture of two or more. As the monomer polyol, a mixture of 1,4-butanediol and trimethylolpropane is preferable.

Furthermore, according to each embodiment, polyoxyethylene alkyl ether (C1) used as a lubricant (C), a linear aliphatic alcohol (C2) having 20 to 40 carbon atoms and a melting point of 90 ° C. or less, fatty acid amide (C4 It is also possible to add and use at least one compound selected from the group consisting of:

Note that an active hydrogen group terminal curing agent that does not contain the lubricant (C) is referred to as an active hydrogen group terminal curing agent (B0).

The catalyst (F) can be added to the active hydrogen group terminal curing agent (B) used in the present invention as necessary.

The catalyst (F) is not particularly limited as long as the effects of the invention are achieved, but from the viewpoint of improving mechanical properties and molding processability, as the nurating catalyst for polyurethane (F1), potassium salt or quaternary ammonium is used. A salt is preferable, and N, N, N′-trimethylaminoethylethanolamine or N, N-dimethylaminoethoxyethanol is preferable as the allophanatization catalyst (F2) for polyurethane. In addition, a urethanization catalyst (F3) can also be used together or used independently as needed. As the urethanization catalyst (F3), known general amine catalysts such as triethylenediamine, imidazole catalysts such as 1-isobutyl-2-methylimidazole, metal catalysts such as dioctyltin dilaurate, and the like can also be used.

<Nuration catalyst for polyurethane (F1)>
As the nurating catalyst for polyurethane (F1) used in the nurating reaction, it can be appropriately selected from known catalysts and used.
Specific examples include, for example, triethylamine, N-ethylpiperidine, N, N′-dimethylpiperazine, N-ethylmorpholine, tertiary amines such as phenolic Mannich bases, tetramethylammonium hydrogen carbonate, methyltriethylammonium carbonate. Hydrogen salt, ethyl trimethylammonium bicarbonate, propyltrimethylammonium bicarbonate, butyltrimethylammonium bicarbonate, pentyltrimethylammonium bicarbonate, hexyltrimethylammonium bicarbonate, heptyltrimethylammonium bicarbonate, octyltrimethylammonium bicarbonate Salt, nonyltrimethylammonium bicarbonate, decyltrimethylammonium bicarbonate, undecyltrimethylammonium bicarbonate, dodecyltri Methylammonium bicarbonate, tridecyltrimethylammonium bicarbonate, tetradecyltrimethylammonium bicarbonate, heptadecyltrimethylammonium bicarbonate, hexadecyltrimethylammonium bicarbonate, heptadecyltrimethylammonium bicarbonate, octadecyltrimethylammonium carbonate Hydrogen salt, (2-hydroxypropyl) trimethylammonium bicarbonate, hydroxyethyltrimethylammonium bicarbonate, 1-methyl-1-azania-4-azabicyclo [2.2.2] octanium bicarbonate, or 1,1 Quaternary ammonium hydrogen carbonates such as dimethyl-4-methylpiperidinium hydrogen carbonate, tetramethylammonium carbonate, methyltriethylammonium carbonate, ethyltrimethyl Ammonium carbonate, propyltrimethylammonium carbonate, butyltrimethylammonium carbonate, pentyltrimethylammonium carbonate, hexyltrimethylammonium carbonate, heptyltrimethylammonium carbonate, octyltrimethylammonium carbonate, nonyltrimethylammonium carbonate, decyltrimethylammonium carbonate Salt, undecyltrimethylammonium carbonate, dodecyltrimethylammonium carbonate, tridecyltrimethylammonium carbonate, tetradecyltrimethylammonium carbonate, heptadecyltrimethylammonium carbonate, hexadecyltrimethylammonium carbonate, heptadecyltrimethylammonium carbonate, Octadecyltrimethylammonium carbonate, (2-hydroxypropyl Pill) trimethylammonium carbonate, hydroxyethyltrimethylammonium carbonate, 1-methyl-1-azania-4-azabicyclo [2.2.2] octanium carbonate, or 1,1-dimethyl-4-methylpiperidinium carbonate Quaternary ammonium carbonates such as salts, hydroxyalkylammonium hydroxides such as trimethylhydroxypropylammonium, trimethylhydroxypropylammonium, triethylhydroxyethylammonium and weak organic acid salts, acetic acid, propionic acid, butyric acid, caproic acid, capric acid, Examples thereof include alkali metal salts of carboxylic acids such as valeric acid, octylic acid, myristic acid and naphthenic acid. Moreover, these isocyanurate-ized catalysts (F1) for polyurethane can be used individually or in combination of 2 or more types.

The amount of the isocyanurate-forming catalyst (F1) used is 0.001 to 0.5% by mass with respect to the total mass of the NCO group-terminated urethane prepolymer (A) and the active hydrogen group-end curing agent (B). It is preferably used in the range, and in particular, it is more preferably used in the range of 0.005 to 0.10% by mass from the viewpoint of easy reaction control.

<Allophanatization catalyst for polyurethane (F2)>
The allophanatization catalyst for polyurethane (F2) used in the allophanatization reaction can be appropriately selected from known catalysts, and for example, a metal salt of a carboxylic acid can be used.

Specific examples of the carboxylic acid include, for example, acetic acid, propionic acid, butyric acid, caproic acid, octylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, 2-ethylhexanoic acid and other saturated aliphatic carboxylic acids, cyclohexanecarboxylic acid , Saturated monocyclic carboxylic acids such as cyclopentanecarboxylic acid, saturated bicyclic carboxylic acids such as bicyclo [4.4.0] decane-2-carboxylic acid, mixtures of the above-mentioned carboxylic acids such as naphthenic acid, oleic acid, linole Monocarboxylic acids such as acid, linolenic acid, unsaturated fatty carboxylic acid such as soybean oil fatty acid and tall oil fatty acid, aromatic aliphatic carboxylic acid such as diphenylacetic acid, aromatic carboxylic acid such as benzoic acid and toluic acid; phthalic acid , Isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, succinic acid, tartaric acid, oxalic acid, malonic acid, Taric acid, adipic acid, pimelic acid, suberic acid, kurtaconic acid, azelaic acid, sebacic acid, 1,4-cyclohexyldicarboxylic acid, α-hydromuconic acid, β-hydromuconic acid, α-butyl-α-ethylglutaric acid , Α, β-diethylsuccinic acid, maleic acid, fumaric acid, trimellitic acid, pyromellitic acid and other polycarboxylic acids.

Examples of the metal constituting the metal salt of carboxylic acid include alkali metals such as lithium, sodium and potassium, alkaline earth metals such as magnesium, calcium and barium, other typical metals such as tin and lead, manganese and iron , Transition metals such as cobalt, nickel, copper, zinc and zirconium. These carboxylic acid metal salts can be used alone or in combination of two or more.

In addition, examples of the alkanolamine include N, N, N, N′-trimethylaminoethylethanolamine, N, N-dimethylaminoethoxyethanol, and the like.

The amount of the allophanatization catalyst (F2) used is in the range of 0.001 to 0.5% by mass with respect to the total mass of the NCO group-terminated urethane prepolymer (A) and the active hydrogen group-terminated curing agent (B). In particular, from the viewpoint of easy reaction control, it is more preferably used in the range of 0.005 to 0.10% by mass.

<Urethaneization catalyst for polyurethane (F3)>
The polyurethane urethanization catalyst (F3) used in the urethanization reaction can be appropriately selected from known catalysts.

Specific examples of the amine catalyst include, for example, triethylenediamine, 2-methyltriethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N ′, N ″, N ″ -pentamethyl- (3-aminopropyl) ethylenediamine, N, N, N ′, N ″, N ″ -Pentamethyldipropylenetriamine, N, N, N ', N'-tetramethylhexamethylenediamine, bis (2-dimethylaminoethyl) ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol, N, N- Dimethyl-N '-(2-hydroxyethyl) ethylenediamine, N, N-dimethyl -N '- (2-hydroxyethyl) propanediamine, bis (dimethylaminopropyl) amine, bis (dimethylaminopropyl) isopropanolamine and the like.

Specific examples of the imidazole-based catalyst include 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethylaminopropylimidazole, N, N-dimethylhexanolamine, N-methyl- N ′-(2-hydroxyethyl) piperazine, 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, dibutyltin dilaurate, dibutyltin dichloride, dioctyltin dilaurate and the like. Organotin catalysts, nickel octylate, nickel naphthenate, cobalt octylate, cobalt naphthenate, bismuth octylate, bismuth naphthenate, and the like.

The amount of the urethanization catalyst (F3) used is in the range of 0.001 to 0.5% by mass with respect to the total mass of the NCO group-terminated urethane prepolymer (A) and the active hydrogen group-terminated curing agent (B). In particular, from the viewpoint of easy reaction control, it is more preferably used in the range of 0.005 to 0.10% by mass.

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

Specific examples of the reaction inhibitor (E) include a phosphite ester system, an acidic phosphate ester system, and a polyoxyethylene alkyl ether phosphate system. Examples of phosphite esters include triphenyl phosphate, tridecyl phosphate, and dibutyl hydrogen phosphate. Examples of the acidic phosphate ester include butyl acid phosphate, 2-ethylhexyl acid phosphate, and isodecyl acid phosphate. Examples of the polyoxyethylene alkyl ether phosphoric acid system include di (C12-15) pares-2 phosphoric acid, di (C12-15) -pares tetraphosphoric acid, di (C12-15) -palace 6 phosphoric acid, di (C12 -15) -Palace 8-phosphate, di (C12-15) -Palace 10-phosphate, phosphoric acid (mono, di) polyethylene glycol (3EO) C10-14 alcohol, polyoxyethylene tridecyl ether phosphate, phosphorus Acid (mono, di) polyethylene glycol (4E0) 4-noniphenyl and the like.

In the present invention, if necessary, an antioxidant, a defoaming agent, an ultraviolet absorber and the like can be introduced into the forming composition as additives.

In the present invention, using the thermosetting polyurethane elastomer-forming composition described so far, a curing process (specifically, a process for promoting curing by heating) is performed in a mold as a process. To produce a thermoset polyurethane elastomer molding having urethanized, nurated, and allophanatized bonds.

In this case, the method for producing a thermosetting polyurethane elastomer molded product using the forming composition of the present invention is preferably produced by a method including the following steps.

Step (1):
NCO group terminal prepolymer (A) and active hydrogen group terminal curing agent (B). However, if the active hydrogen group terminal curing agent (B) does not contain the catalyst (F) in advance, the catalyst (F) is added separately. The forming composition is prepared by mixing uniformly. In addition, when air is involved and bubbles are observed, the bubbles are removed by vacuum defoaming or the like. These steps are preferably performed using a dedicated polyurethane casting machine.

Step (2):
Immediately after mixing the moldable composition into a preheated mold (casting), the moldable composition is cured in the mold (specifically, heated to cure reaction) Promote). In this case, the temperature of the mold is preferably in the range of 80 to 170 ° C. from the viewpoint that the urethanization reaction, the nurateization and the allophanatization reaction are performed easily and reliably.

Step (3):
After the forming composition is cured, the cured product (that is, the thermosetting polyurethane elastomer molded product) is taken out from the mold (demolding). In the present invention, the time required from casting to demolding is not particularly limited. However, from the viewpoint of productivity of the thermosetting polyurethane elastomer intended by the present invention, the amount of catalyst and molding It is preferable that the preheating temperature of the mold is adjusted to be in the range of 30 to 600 seconds.

Step (4):
After curing, the molded product of the thermosetting polyurethane elastomer is removed, and then subjected to aging treatment at room temperature for one week.

The compounding molar ratio (hereinafter abbreviated as “α value”) determined from the NCO group content of the NCO group-terminated prepolymer and the OH group (NH ₂ group) content of the active hydrogen group terminal curing agent at the time of casting, OH group The (NH ₂ group) / NCO group can be selected according to the selected catalyst type and desired physical properties.

For example, the α value is preferably 0.2 to 0.8 when the polyurethane nurating catalyst (F1) or the polyurethane allophanating catalyst (F2) is used. In this case, a urethanization catalyst (F3) can also be used in combination. When it is less than 0.2, nurateization or allophanate formation by excess isocyanate becomes extremely large, and this increase in the cross-linking point may lead to a significant decrease in tensile property values. On the other hand, when it exceeds 0.8, the number of cross-linking points due to nurateization or allophanate decreases, leading to a decrease in initial modulus (M100), a large deformation amount with respect to stress, and a lack of strength with respect to hardness.

Further, the α value when the urethanization catalyst (F3) is used alone is preferably 0.8 to 1.0. If it is less than 0.8, sufficient molecular extension cannot be performed and problems such as insufficient curing occur. Further, when the ratio exceeds 1.0, problems such as deterioration of physical properties and insufficient curing may occur.

The thermosetting polyurethane elastomer molded product produced by using the forming composition of the present invention can be efficiently reduced in friction by heat treatment at 100 to 200 ° C. for 1 to 60 minutes after demolding. it can. When the heating temperature is less than 100 ° C. or when the time is less than 1 minute, the effect is small because the lubricant is difficult to transfer to the outermost surface. Moreover, when a heat temperature exceeds 200 degreeC or time exceeds 60 minutes, it is easy to lead to the increase in a friction coefficient by softening of a thermosetting polyurethane molding, and an effect is small.

The molded product produced using the thermosetting polyurethane elastomer-forming composition of the present invention can be suitably used for industrial machine parts that require a low friction coefficient.

Next, the release agent composition used in the resin molding of the present invention for solving the second problem has a molecular structure containing at least one carboxylate selected from the group consisting of at least quaternary ammonium and quaternary phosphonium. By containing the organopolysiloxane (J) contained therein, the isocyanurate reaction on the mold contact surface is promoted, and only the surface is hardened due to an increase in the crosslink density, and the resulting polyurethane resin molded product retains the conventional physical properties. However, low friction can be achieved. When the organopolysiloxane (J) having in its molecular structure at least one carboxylate selected from the group consisting of quaternary ammonium and quaternary phosphonium is not contained, the resulting molded product does not have low friction. In addition, when the organopolysiloxane (J) and the silicone (L) having an active hydrogen group are used in combination, it is possible to impart slipperiness in addition to increasing the hardness of the surface, and to further reduce friction.

The organopolysiloxane (J) used in the present invention can be obtained, for example, by reacting a carboxyl group-containing organopolysiloxane with at least one hydroxide selected from the group consisting of quaternary ammonium and quaternary phosphonium. In addition to hydroxides of quaternary ammonium and quaternary phosphonium, salts with acids that are weaker than carboxylic acids, such as carbonates, undergo a salt exchange reaction with the carboxylic acids in the organopolysiloxane, promptly. A desired release agent composition can be obtained. Otherwise, it can be obtained by reacting a tertiary amine-containing organopolysiloxane, an alkylene oxide, and an organic carboxylic acid. It can also be obtained by reacting an alkylene oxide-containing organopolysiloxane, a tertiary amine, or an organic carboxylic acid. The organopolysiloxane (J) used in the resin molding of the present invention has a structure in which at least one carboxylate selected from the group consisting of quaternary ammonium and quaternary phosphonium is bonded to the organopolysiloxane molecule. As long as the above effect is exhibited, the structure and the manufacturing method are not limited to those described above. The content of the carboxylate is not particularly limited, but is preferably 0.3 mmol / g or more based on the organopolysiloxane (J) in order to achieve low friction by increasing the hardness of the molding surface. In addition, the release agent composition containing an organopolysiloxane (J) having at least one carboxylate selected from the group consisting of quaternary ammonium and quaternary phosphonium in the molecular structure improves the coatability. These release agent compositions may be diluted with a solvent capable of dissolving, ether compounds such as diethyl ether and tetrahydrofuran (hereinafter abbreviated as “THF”), ester compounds such as ethyl acetate and butyl acetate, benzene and toluene Examples thereof include aromatic hydrocarbon compounds such as hexane, octane, etc., or mixtures thereof. Used in preparing a release agent composition used for resin molding containing organopolysiloxane (J) having at least one carboxylate selected from the group consisting of quaternary ammonium and quaternary phosphonium in the molecular structure. Specific examples of the raw material to be used include the following.

<Reactive functional group-containing organopolysiloxane>
Examples of the organopolysiloxane having a carboxyl group include a dimethylpolysiloxane having a carboxyl group at one end and a molecular weight of 1000 to 2000 (for example, “X-22-3710” manufactured by Shin-Etsu Silicone), and a molecular weight of 4000 having a carboxyl group at both ends. -5000 dimethylpolysiloxane (for example, “X-22-162C” manufactured by Shin-Etsu Silicone), dimethylpolysiloxane having a carboxyl group in the side chain (for example, “X-22-3701E” manufactured by Shin-Etsu Silicone), and the like. It is done.

<Quaternary ammonium, quaternary phosphonium hydroxide>
Tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, 2-hydroxypropyltrimethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrabutylphosphonium hydroxide, benzyltrimethylammonium Examples thereof include hydroxides and mixtures thereof.

The silicone (L) having an active hydrogen group used in the present invention is not particularly limited as long as it is a silicone compound having an amino group, a hydroxyl group, a thiol group, or a carboxyl group, and specifically, dimethyl silicone, methylphenyl silicone, diphenyl silicone. Dimethyl methylphenyl silicone, dimethyl diphenyl silicone, methyl hydrogen silicone, and mixtures thereof. The position and the number of active hydrogen groups are not particularly limited, and one or more active hydrogen groups may be present at the terminal or side chain. Of these, silicone having an amino group is preferred.

The amount of the active hydrogen group-containing silicone (L) used in the present invention is not particularly limited, but is 5 to 150 parts by weight, particularly 10 to 120 parts by weight, based on 100 parts by weight of the organopolysiloxane (J). Is preferred. If the amount is 5 parts by mass or less, the imparting and hardening of the slipperiness to the surface of the molded product is small, and if it is 150 parts by mass or more, the effect of increasing the hardness of the surface is reduced, and the synergistic effect of the slipperiness and the increase in hardness cannot be obtained.

In the present invention, the mold release agent composition is applied to a mold, and the polyurethane resin-forming composition (K) is injected into the mold and molded to obtain a polyurethane resin molded product having low friction. . The polyurethane resin-forming composition (K) used in the present invention preferably comprises an NCO group-terminated prepolymer (A0) and an active hydrogen group-terminated curing agent (B0), and more preferably a polyoxyethylene alkyl ether (C1), It preferably contains at least one lubricant (C) selected from linear aliphatic alcohol (C2), octadecyl isocyanate (C3), and fatty acid amide (C4) having 20 to 40 carbon atoms and a melting point of 90 ° C. or less. .

The NCO group-terminated urethane prepolymer (A0) used in the present invention can be obtained by a urethanization reaction of at least a polyisocyanate (A6), a polyol and (A7) using a reaction inhibitor if necessary. The NCO content of the NCO group-terminated urethane prepolymer 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 flowability of the urethane resin is remarkably deteriorated during casting. When the content is higher than 25% by mass, the stability of properties during storage and use is remarkably deteriorated, and it is difficult to obtain a stable industrial machine part, resulting in molding failure. It will become unsuitable as a terminal urethane prepolymer (A0).

The NCO group-terminated urethane prepolymer (A0) is prepared by adding a polyisocyanate (A6) and, if necessary, a reaction inhibitor to a stirring vessel and stirring the polyol (A7) while maintaining the temperature in the stirring vessel at 40 to 70 ° C. ) Is stirred. Subsequently, the urethanization reaction can be carried out for about 2 to 5 hours while maintaining the temperature in the stirring vessel at 70 to 90 ° C.

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

<Polyisocyanate (A6)>
Examples of the polyisocyanate include the polyisocyanate (A6) described above.

<Polyester polyol>
Examples of the polyester polyol include the above-described polyester polyol.

<Polyether polyol>
Examples of the polyether polyol include the above-described polyether polyol. .

<Polycarbonate polyol>
Examples of the polycarbonate polyol include the above-described polycarbonate polyol.

Also, the polyol may be a polyolefin polyol, an acrylic polyol, a silicone polyol, a castor oil-based polyol, or a fluorine-based polyol alone or in combination of two or more as long as the performance does not deteriorate.

<Polyolefin polyol>
Examples of the polyolefin polyol include the above-described polyolefin polyol.

<Acrylic polyol>
Examples of the acrylic polyol include the above-described acrylic polyol.

<Silicone polyol>
Examples of the silicone polyol include the aforementioned silicone polyols.

<Castor oil-based polyol>
As the castor oil-based polyol, the aforementioned castor oil-based polyol can be exemplified.

<Fluorine-based polyol>
Examples of the fluorine-based polyol include the fluorine-based polyol described above.

<Monomer polyol>
Examples of the monomer polyol include the monomer polyol described above.

The reaction inhibitor used in the present invention is not particularly limited as long as the effects of the present invention are exhibited, and examples thereof include the reaction inhibitor (E) described above.

The active hydrogen group terminal curing agent (B0) used in the present invention is not particularly limited as long as at least the polyol (A7) described above can be used, and the effects of the present invention are exhibited. From the viewpoint of improving mechanical properties and molding processability, monomer polyols can be used alone or in admixture of two or more. Further, a mixture obtained by adding any one of polyester polyols, polyether polyols, and polycarbonate polyols having an average functional group number of 2 to 3 and a number average molecular weight of 250 to 5000 can be used. As the monomer polyol, a mixture of 1,4-butanediol and trimethylolpropane is preferable. Further, a mixture in which a polyester polyol or polyether polyol having an average number of functional groups of 2 and an average molecular weight of 500 to 3000 is added is preferred.

The active hydrogen group terminal curing agent (B0) used in the present invention can be added with a catalyst (F) as required. The catalyst is not particularly limited as long as the effects of the invention are achieved. From the viewpoint of improving mechanical properties and molding processability, the isocyanurate catalyst (F1), the allophanate catalyst (F2), the urethanization catalyst (F3) ) Is used. The urethanization catalyst may be a known general amine catalyst such as triethylenediamine, imidazole catalyst such as 1-isobutyl-2-methylimidazole, metal catalyst such as dioctyltin dilaurate, and the like. The isocyanuration catalyst can be a potassium salt or a quaternary ammonium salt, and the allophanate catalyst can be N, N, N'-trimethylaminoethylethanolamine or N, N-dimethylaminoethoxyethanol. These may be used alone or in admixture of two or more as required.

<Isocyanurate catalyst for polyurethane (F1)>
As the isocyanurate-forming catalyst, it can be appropriately selected from known catalysts, and examples thereof include the above-mentioned isocyanurate-forming catalysts.

The amount of the isocyanurate-forming catalyst is preferably used in a range of 0.001 to 0.5% by mass with respect to the total mass of the NCO group-terminated urethane prepolymer and the OH group-end curing agent. From the viewpoint of easy reaction control, it is more preferably used in the range of 0.005 to 0.10% by mass.

<Allophanatization catalyst for polyurethane (F2)>
The allophanatization catalyst can be appropriately selected from known catalysts, and examples thereof include the allophanatization catalyst for polyurethane described above.
The amount of the allophanatization catalyst used is preferably in the range of 0.001 to 0.5% by mass with respect to the total mass of the NCO group-terminated urethane prepolymer and the active hydrogen group-terminated curing agent, From the viewpoint of easy reaction control, it is more preferably used in the range of 0.005 to 0.10% by mass.

<Urethaneization catalyst for polyurethane (F3)>
The polyurethane urethanization catalyst used in the urethanization reaction can be appropriately selected from known catalysts, and examples thereof include the polyurethane urethanization catalysts described above.

The amount of the urethanization catalyst used is preferably in the range of 0.001 to 0.5% by mass with respect to the total mass of the NCO group-terminated urethane prepolymer and the active hydrogen group-end curing agent, From the viewpoint of easy reaction control, it is more preferably used in the range of 0.005 to 0.10% by mass.

A lubricant (C) can be added to the polyurethane resin-forming composition (K) of the present invention. The lubricant (C) is not particularly limited, but is particularly polyoxyethylene alkyl ether (C1), a linear aliphatic alcohol (C2) having 20 to 40 carbon atoms and a melting point of 90 ° C. or less, octadecyl isocyanate (C3), It is preferable to use at least one lubricant selected from fatty acid amides (C4). The addition amount of the lubricant is not particularly limited, but is preferably 0.1 to 8% by mass, particularly preferably 0.2 to 5% by mass in the polyurethane resin-forming composition (C). If it is less than 0.1% by mass, the effect of reducing friction due to the imparting of slipperiness to the surface of the molded product is small. Specific examples of compounds are given below.

<Polyoxyethylene alkyl ether (C1)>
Examples of the polyoxyethylene alkyl ether (C1) include the polyoxyethylene alkyl ether (C1) described above. In order to reduce friction more effectively, the hydroxyl value is preferably 5 to 70 KOHmg / g. When the hydroxyl value exceeds 70 KOH mg / g, the number of carbon atoms is generally short, and the effect as a lubricant component is gradually reduced. On the other hand, when the hydroxyl value is less than 5 KOHmg / g, the surface may be roughened.

<Linear aliphatic alcohol (C2) having 20 to 40 carbon atoms and a melting point of 90 ° C. or lower>
As the linear aliphatic alcohol (C2) having 20 to 40 carbon atoms and a melting point of 90 ° C. or less, the linear aliphatic alcohol (C2) having 20 to 40 carbon atoms and a melting point of 90 ° C. or less is used. Can be mentioned. In order to effectively reduce friction, the melting point is 90 ° C. or lower. When the melting point exceeds 90 ° C, the solubility with the NCO-terminated urethane prepolymer (A0) is generally poor, and even if the temperature during prepolymer synthesis is raised to 100 ° C or higher, uniform dissolution is not only difficult, but the reaction temperature The increase in viscosity may increase the viscosity due to side reactions such as allophanatization, leading to a decrease in quality of the prepolymer. Moreover, the solubility with an active hydrogen group terminal hardening | curing agent (B0) is also bad. During production, it can be dissolved by heating above the melting point, but when it is filled and stored, it will crystallize at room temperature, so when molding a thermosetting polyurethane elastomer, heat it again above the melting point. However, it is necessary to stir uniformly, and it becomes difficult to handle.

<Octadecyl isocyanate (C3)>
As the octadecyl isocyanate (C3), the above-mentioned octadecyl isocyanate (C3) can be mentioned, and Millionate O (manufactured by Hodogaya Chemical Co., Ltd.) can be used as a specific example of a commercially available product.

<Fatty acid amide (C4)>
Examples of the fatty acid amide (C4) include the fatty acid amide (C4) described above, and are not particularly limited as long as they are amide compounds derived from fatty acids and amines, but with the polyurethane resin-forming composition (K). Higher fatty acid amides having 10 to 20 carbon atoms are preferred from the viewpoint of compatibility.

In the present invention, if necessary, an antioxidant, a defoaming agent, an ultraviolet absorber and the like can be introduced and used as an additive in the forming composition.

In the present invention, using the thermosetting polyurethane elastomer-forming composition of the present invention described so far, curing treatment (specifically, treatment for accelerating curing by heating) in the mold. To produce a thermoset polyurethane elastomer molding having urethane, nurate, and allophanate bonds.

The manufacturing process in this case is preferably manufactured by the method of the above-described steps (1) to (4).

The molar ratio (NCO group / active hydrogen group) between the NCO group content of the NCO group-terminated prepolymer (A0) and the active hydrogen group content of the active hydrogen group terminal curing agent (B0) at the time of casting is determined by the selected catalyst. It can be selected according to the species and the desired physical properties.

For example, when an isocyanurate-forming catalyst or allophanate-forming catalyst is used, 1.2 to 3.0 is preferable. In this case, a urethanization catalyst can be used in combination. In the case of exceeding 3.0, the nucleation or allophanate formation with excess isocyanate proceeds extremely, resulting in an increase in the cross-linking point and a significant decrease in tensile property values. On the other hand, when the ratio is less than 1.2, the number of cross-linking points due to nurateization or allophanate decreases, and sufficient friction reduction does not occur. In addition, the initial modulus (M100) is lowered, the deformation amount with respect to the stress is large, and the strength is insufficient with respect to the hardness. Further, when the urethanization catalyst is used alone, 1.0 to 1.2 is preferable. If it exceeds 1.2, sufficient molecular extension cannot be performed and problems such as insufficient curing occur. Moreover, when it is less than 1.0, problems such as deterioration of physical properties and insufficient curing occur. In particular, in the present invention, since it is important that excess isocyanate is isocyanurate on the mold contact surface, it is preferable that the isocyanate is excessive as long as the physical properties are not impaired.

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. In Examples and Comparative Examples, “%” means “% by mass”, and the unit of blending is “g”.

<Embodiment 1>
Examples 1-7, Comparative Examples 1-7
Various polyisocyanates (A6) and reaction inhibitors (E) were charged and stirred in a 5 L stirring vessel filled with nitrogen at the blending ratios shown in Tables 1 and 2. Thereafter, while maintaining the temperature in the stirring vessel at 40 to 70 ° C., various polyols (A7) and, if necessary, polyoxyethylene alkyl ether (C1) were added and stirred. Subsequently, various NCO group-terminated urethane prepolymers (A0), or () by adding an appropriate amount of antifoaming agent and proceeding the urethanization reaction for about 2 to 5 hours while keeping the temperature in the stirring vessel at 70 to 90 ° C. A1) was obtained.

Further, in the mixing ratios shown in Table 1 and Table 2, various polyols (B0), polyoxyethylene alkyl ether (C1), various catalysts (F) and appropriate amounts in a 5 L stirring vessel filled with nitrogen By adding and stirring the antifoaming agent and mixing and stirring for about 1 to 3 hours while maintaining the temperature in the stirring vessel at 40 to 70 ° C., various active hydrogen group terminal curing agents (B0) or (B1) Obtained.

Next, according to the blending ratios shown in Table 1 and Table 2, the NCO group-terminated urethane prepolymer and the catalyst-containing active hydrogen group-end curing agent are mixed by a two-component mixed urethane casting machine, thereby producing the heat of the present invention. A curable polyurethane elastomer-forming composition was prepared. This formable composition is poured into a mold for forming a flat sheet having a thickness of 2 mm or 3 mm, which has been preheated to a curing temperature in advance, and the molded product can be taken out from the mold (minimum mold removal). The polyurethane elastomer molding (D) of the present invention was obtained by heat-curing in a mold for a period of time and quickly removing the molding.

<Embodiment 2>
Examples 8 to 13 and Comparative Examples 8 to 13
In the mixing ratios shown in Table 3 and Table 4, various polyisocyanates (A6) and reaction inhibitors (E) were charged and stirred into a 5 L stirring vessel filled with nitrogen. Thereafter, while maintaining the temperature in the stirring vessel at 40 to 70 ° C., various polyols (A7), and if necessary, linear aliphatic alcohol (C2) having 20 to 40 carbon atoms and a melting point of 90 ° C. or less are added and stirred. did. Subsequently, various NCO group-terminated urethane prepolymers (A0), or () by adding an appropriate amount of antifoaming agent and proceeding the urethanization reaction for about 2 to 5 hours while keeping the temperature in the stirring vessel at 70 to 90 ° C. A2) was obtained.

In addition, various polyols (B0) in a 5 L stirring vessel filled with nitrogen at the blending ratios shown in Tables 3 and 4, linear fatty acids having 20 to 40 carbon atoms and a melting point of 90 ° C. or less as required. Group alcohol (C2), various catalysts (F) and an appropriate amount of antifoaming agent are added and stirred, and mixed and stirred for about 1 to 3 hours while maintaining the temperature in the stirring vessel at 40 to 70 ° C. Hydrogen group terminal curing agent (B0) or (B2) was obtained.

Next, according to the blending ratios shown in Tables 3 and 4, the NCO group-terminated urethane prepolymer and the catalyst-containing active hydrogen group-end curing agent are mixed by a two-component mixed urethane casting machine, whereby the heat of the present invention. A curable polyurethane elastomer-forming composition was prepared. This composition is poured into a mold for forming a flat sheet having a thickness of 2 mm or 3 mm, which has been preheated to a curing temperature in advance, and the molded product is removed from the mold for a minimum time that can be removed (demolding). The polyurethane elastomer molded product (D) of the present invention was obtained by heat-curing in a mold and quickly removing the molded product.

<Embodiment 3>
Examples 14 to 21, Comparative Examples 14, 15, 18 and Reference Examples 1 to 5
In the mixing ratio shown in Table 5 and Table 6, various polyisocyanate (A6), octadecyl isocyanate (C3), reaction inhibitor (E), antioxidant, antifoaming agent in a 5 L stirring vessel filled with nitrogen Was stirred. Thereafter, while maintaining the temperature in the stirring vessel at 40 to 70 ° C., various polyols (A7), polyoxyethylene alkyl ether (C1) as required according to the blending ratio, and / or carbon number 20 to 40, and melting point Of 90 ° C. or lower was added and stirred. Subsequently, various NCO group-terminated urethane prepolymers (A0), or () by adding an appropriate amount of antifoaming agent and proceeding the urethanization reaction for about 2 to 5 hours while keeping the temperature in the stirring vessel at 70 to 90 ° C. A3) was obtained. However, for Example 14 and Example 17, octadecyl isocyanate (C3) was added after the urethanization reaction and stirred and mixed for about 0.5 to 1 hour.

Further, in the mixing ratios shown in Tables 5 and 6, various polyols (B0) in a 5 L stirring vessel filled with nitrogen, and polyoxyethylene alkyl ether (C1) and / or as required according to the mixing ratio. A linear aliphatic alcohol (C2) having 20 to 40 carbon atoms and a melting point of 90 ° C. or less, various catalysts (F) and an appropriate amount of antifoaming agent are charged and stirred, and the temperature in the stirring vessel is adjusted to 40 to 70 ° C. While maintaining, various active hydrogen group terminal curing agents (B0) or (B2) were obtained by mixing and stirring for about 1 to 3 hours.

Next, according to the blending ratios shown in Tables 5 and 6, NCO group-terminated urethane prepolymer previously kept at 70 to 90 ° C. and catalyst-containing active hydrogen group end curing agent preliminarily kept at 40 to 120 ° C. The thermosetting polyurethane elastomer-forming composition of the present invention was prepared by mixing with a liquid mixing urethane casting machine. This composition is poured into a mold for forming a flat sheet having a thickness of 2 mm or 3 mm, which has been preheated to a curing temperature in advance, and the molded product is removed from the mold for a minimum time that can be removed (demolding). The polyurethane elastomer molded product (D) of the present invention was obtained by heat-curing in a mold and quickly removing the molded product. Tables 10 and 11 show the evaluation results of the obtained molded product, such as the coefficient of friction.

<Embodiment 4>
Examples 22 to 29, Comparative Examples 24 to 27, Reference Examples 6 and 7
In the mixing ratio shown in Table 7 and Table 8, in a 5 L stirring vessel filled with nitrogen, various polyisocyanates (A6) and octadecyl isocyanate (C3), reaction inhibitor (E), oxidation according to the mixing ratio as necessary An inhibitor and an antifoaming agent were added and stirred. Thereafter, while maintaining the temperature in the stirring vessel at 40 to 70 ° C., various polyols (A7) and polyoxyethylene alkyl ether (C1) as necessary according to the blending ratio, 20 to 40 carbon atoms, and melting point of 90 ° C. or less The straight chain aliphatic alcohol (C2) was added and stirred. Subsequently, according to the blending ratio, if necessary, an appropriate amount of fatty acid amide (C4) and an antifoaming agent are added, and the urethanization reaction is advanced for about 2 to 5 hours while maintaining the temperature in the stirring vessel at 70 to 90 ° C. Various NCO group-terminated urethane prepolymers (A5) were obtained. However, in Examples 22 and 25, the fatty acid amide (C4) was added after the urethanization reaction, and the mixture was stirred and mixed for about 0.5 to 1 hour.

Further, in the mixing ratios shown in Tables 7 and 8, various polyols (B0) and a polyoxyethylene alkyl ether (C1) according to the mixing ratio and a carbon number of 20 to 20 in a 5 L stirring vessel filled with nitrogen as required. 40, and a linear aliphatic alcohol (C2), fatty acid amide (C4), various catalysts (F) and an appropriate amount of antifoaming agent having a melting point of 90 ° C. or less are charged and stirred, and the temperature in the stirring vessel is set to 40 to 70. Various active hydrogen group terminal curing agents (B3) were obtained by mixing and stirring for about 1 to 3 hours while maintaining the temperature.

Next, according to the blending ratios shown in Tables 7 and 8, 2 NCO group-terminated urethane prepolymers preliminarily kept at 70 to 90 ° C. and 2 active catalyst-containing hydrogen radical-end curing agents preliminarily kept at 40 to 120 ° C. The thermosetting polyurethane elastomer-forming composition of the present invention was prepared by mixing with a liquid mixing urethane casting machine. This composition is poured into a mold for forming a flat sheet having a thickness of 2 mm or 3 mm, which has been preheated to a curing temperature in advance, and the molded product is removed from the mold for a minimum time that can be removed (demolding). The polyurethane elastomer molded product (D) of the present invention was obtained by heat-curing in a mold and quickly removing the molded product. Tables 13 and 14 show the evaluation results of the obtained molded product, such as the coefficient of friction.

The abbreviations of the raw materials used in Tables 1 to 8 are as follows.

"Isocyanate"
(1) TDI; Coronate T-100 (manufactured by Tosoh Corporation), 2,4-TDI, NCO content = 48.2%
(2) MDI: Millionate MT (manufactured by Tosoh Corporation), 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; Nipponran 3027 (manufactured by Tosoh Corporation), polybutylene adipate, hydroxyl value = 44.9 KOHmg / g
(5) PEA-2000; Nipponran 4040 (manufactured by Tosoh Corporation), polyethylene adipate, hydroxyl value = 56.1 KOHmg / g
(6) PTMG-1000; PTMG-1000 (Mitsubishi Chemical Corporation), polytetramethylene glycol, hydroxyl value = 112.0 KOHmg / g
(7) 1.4-BG; 1,4-butanediol (Mitsubishi Chemical Corporation), hydroxyl value = 1,245 KOHmg / g
(8) TMP: Trimethylolpropane (manufactured by Mitsubishi Gas Chemical Company), hydroxyl value = 1,247 KOHmg / g
(9) MOCA; 4,4′-diamino-3,3′-dichlorodiphenylmethane (manufactured by Ihara Chemical Industry), hydroxyl value (amino group) = 420 KOH mg / g
"Lubricant"
(10) NIKKOL BC-150; polyoxyethylene cetyl ether (manufactured by Nikko Chemicals), hydroxyl value = 9 KOHmg / g
(11) NIKKOL BO-50V; polyoxyethylene oleyl ether (manufactured by Nikko Chemicals), hydroxyl value = 24 KOHmg / g
(12) NIKKOL BL-25; polyoxyethylene lauryl ether (manufactured by Nikko Chemicals), hydroxyl value = 45 KOH mg / g
(13) NIKKOL BB-5; polyoxyethylene behenyl ether (manufactured by Nikko Chemicals), hydroxyl value = 106 KOHmg / g
(14) Permacol 350 Alcohol (Nikko Chemicals), C20 to C40, melting point = 68 to 89 ° C, hydroxyl value = 129 KOHmg / g
(15) Permacol 425 Alcohol (manufactured by Nikko Chemicals), C20 to C40, melting point = 85 to 99 ° C., hydroxyl value = 100 KOHmg / g
(16) Permacol 550 Alcohol (manufactured by Nikko Chemicals), C30 to C50, melting point = 93 to 106 ° C., hydroxyl value = 83 KOHmg / g
(17) NIKKOL behenyl alcohol 80 (manufactured by Nikko Chemicals), C22 (containing 80%), melting point = 65 to 75 ° C., hydroxyl value = 171 KOHmg / g
(18) 1-Icosanol; 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 purpose synthetic WAX (manufactured by Nippon Seiwa)
(21) Riquemar SL-900; stearyl stearate (Riken Vitamin Co., Ltd.)
(22) Diamit O-200; oleic amide (manufactured by Nippon Kasei Co., Ltd.), melting point = 75 ° C.
(23) Nikka Amide OS; N-oleyl stearamide (manufactured by Nippon Kasei Co., Ltd.), melting point = 74 ° C.
(24) Slipak O; ethylenebisoleic acid amide (manufactured by Nippon Kasei Co., Ltd.), melting point = 119 ° C.
(25) Lycowax E; Montanic acid ester WAX (manufactured by Client Japan), melting point = 79-83 ° C.
"catalyst"
(26) POLYCAT-46; (Air Products), mixture of potassium acetate and ethylene glycol (27) DABCO TMR; (Air Products), mixture of quaternary ammonium salt catalyst and ethylene glycol (28) TOYOCAT RX- 5; (manufactured by Tosoh Corp.), trimethylaminoethylethanolamine (29) TOYOCAT TEDA-L33E; (manufactured by Tosoh Corp.), a mixture of triethylenediamine and ethylene glycol "Other additives"
(30) Reaction inhibitor: Phospholan PS-236 (manufactured by Akzo Nobel), mono-di (C10-12) palace-5 phosphate (31) antioxidant; Irganox 1010 (manufactured by BASF Japan) pentaerythritol tetrakis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate]
(32) Antifoaming agent; BYK-052 (manufactured by Big Chemie Japan)
The characteristic evaluation method of the obtained molded sheet is as follows.

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

(2) 100% modulus (M100), tensile strength (TB), elongation rate (EB) using a 2 mm thick molded sheet; measured according to JIS K7312.

(3) Static friction coefficient and dynamic friction coefficient of molded sheet surface: Preparation of test piece: A 3 mm thick molded sheet was cut into a width of 25 mm and a length of 100 mm, and degreased using cyclohexane to prepare a test piece. Thereafter, after standing for 1 day in an environment of room temperature 23 ° C. and humidity 50%, the static friction coefficient and the dynamic friction coefficient were measured under the following conditions. The measurement was continuously repeated 1000 times, and the average value of the 5th to 10th outbound trips was used as the initial value, and the average value of 995 to 1000 outbound trips was used as the late value and used as an indicator of sustainability.
"Measurement conditions" Measuring jig = Ball indenter (SUS), Load = 50 g, Table moving speed = 50 mm / min, Table moving distance = 50 mm, Number of reciprocations = 1000 times, Measuring time = 3 hours and 23 minutes Measuring equipment: Surface property measurement Machine TYPE: 38 (made by Shinto Kagaku)

(4) Static friction coefficient and dynamic friction coefficient of the cutting surface: Using a 3 mm thick molded sheet, a feather shaving blade S single blade (part number: FAS-10) was cut vertically into a 30 mm × 10 mm rectangle, 3 mm (width) × 30 mm A test piece of (length) × 10 mm (height) was prepared. Then, immediately or after heat treatment, the static friction coefficient and dynamic friction coefficient were measured under the following conditions using a surface of 3 mm × 30 mm after being left for 1 day in an environment of room temperature 23 ° C. and humidity 50%. The measurement was continuously repeated 1000 times, and the average value of the 5th to 10th outbound trips was used as the initial value, and the average value of 995 to 1000 outbound trips was used as the late value and used as an indicator of sustainability.
“Measurement conditions” Cutting surface measurement conditions: Ball indenter (SUS), load = 100 g, table moving speed = 150 mm / min, table moving distance = 10 mm, number of reciprocations = 10 times, measuring time = 82 seconds Measuring instrument: surface property measurement Machine TYPE: 38 (manufactured by Shinto Kagaku)

(5) Appearance of molded sheet; Immediately after the measurement of the dynamic friction test, the presence or absence of white turbidity was observed as an indicator of the compatibility of the lubricant component and the urethane component by visual observation using the test piece.

(6) Presence / absence of bleed and bloom: The test piece used for the measurement of the dynamic friction coefficient was left in an environment of room temperature 23 ° C. and humidity 50% for 2 weeks, and then the surface condition of the test piece before and after wiping off the gauze was visually observed. The presence or absence of bleed and bloom was evaluated.

Implementation results are shown in Examples 1 to 29. A tough thermosetting polyurethane elastomer with low friction, high mechanical strength and toughness that does not cause bleed and bloom without impairing the compatibility of the lubricant of the present invention with the NCO group-terminated urethane prepolymer and the active hydrogen group terminal curing agent. I was able to get it.

Comparative Example 1 is a comparative example in which the polyoxyethylene alkyl ether (C1) of the present invention is less than 0.1% by mass, and is not suitable because sufficient friction reduction cannot be achieved.

Comparative Example 2 is a comparative example in which the polyoxyethylene alkyl ether (C1) of the present invention exceeds 8% by mass, and the friction property is sufficiently reduced, but the tensile property value is extremely low and is not suitable. Met.

Comparative Examples 3 to 7 are comparative examples in the case of using a lubricant other than the present invention. Although the friction is reduced, the compatibility with the isocyanate group-terminated urethane prepolymer and the active hydrogen group-end curing agent is low. Unfortunately, bleeding or bloom was seen in the obtained molded product, which was not suitable.

Comparative Example 8 is a comparative example in the case where the linear aliphatic alcohol (C2) having 20 to 40 carbon atoms and a melting point of 90 ° C. or less is less than 0.1% by mass, and sufficient friction reduction cannot be achieved. It was not suitable.

Comparative Example 9 is a comparative example in the case where the linear aliphatic alcohol (C2) having 20 to 40 carbon atoms and a melting point of 90 ° C. or less of the present invention exceeds 5% by mass, and sufficiently reduces friction. However, the tensile properties were extremely low and not suitable.

Comparative Example 10 is a comparative example in which a lubricant other than the present invention is used. Although it contains 20 to 40 carbon atoms, it contains a substance having a melting point exceeding 90 ° C., and low friction is achieved. However, the compatibility with the isocyanate group-terminated urethane prepolymer (A) and the active hydrogen group-terminated curing agent (B) was poor, and the resulting molded product was uneven and unsuitable.

Comparative Example 11 is a comparative example in which a lubricant other than the present invention is used, and contains a substance having a carbon number of 30 to 50 and a melting point exceeding 90 ° C., and a little lower friction is achieved. However, the compatibility with the isocyanate group-terminated urethane prepolymer and the active hydrogen group-terminated curing agent was poor, and the resulting molded product was uneven and unsuitable.

Comparative Example 12 is a comparative example in which a lubricant other than the present invention is used, and since it does not have a hydroxyl group, low friction is achieved, but an isocyanate group-terminated urethane prepolymer, an active hydrogen group-terminated curing agent. The molded product obtained was not uniform and bleeds and blooms were not suitable.

Comparative Example 13 was a comparative example in which a lubricant other than the present invention was used, and the carbon number was as short as C16, which was not suitable because sufficient friction reduction could not be achieved.

Comparative Example 14 was a comparative example in which the lubricant of the present invention was not contained, and was not suitable as a thermosetting polyurethane for industrial machine parts because sufficient friction was not achieved.

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

Reference Examples 1, 3, and 4 are at least one selected from the polyoxyethylene alkyl ether (C1) of the present invention, a linear aliphatic alcohol (C2) having 20 to 40 carbon atoms and a melting point of 90 ° C. or lower. This is a case where more than one kind of compound is contained, and the initial value of the dynamic friction coefficient is low, but it is understood that the friction coefficient may be increased in the continuous repeated friction test.

Reference Example 2 is an example in which the polyoxyethylene alkyl ether (C1) of the present invention and a montanic acid ester WAX (Licowax E) as a general lubricant are contained, and the static friction coefficient and the dynamic friction coefficient are extremely high. However, it is understood that bleed and bloom may be generated from the thermosetting polyurethane elastomer-forming composition.

Comparative Example 18 is at least one compound selected from the polyoxyethylene alkyl ether (C1) of the present invention, a linear aliphatic alcohol (C2) having 20 to 40 carbon atoms and a melting point of 90 ° C. or lower. Is a comparative example in which 1-hexadecanol having 20 or less carbon atoms is contained in place of, and although low friction is somewhat achieved, it is not suitable as a thermosetting polyurethane for industrial machine parts. Met.

Reference Example 5 is a polyoxyethylene alkyl ether (C1) of the present invention, at least one compound selected from linear aliphatic alcohols (C2) having 20 to 40 carbon atoms and a melting point of 90 ° C. or lower. As well as containing octadecyl isocyanate (C3), the content of these lubricants (C) exceeds 8% by mass, and although sufficient friction reduction is achieved, the mechanical strength may be lowered. Is understood.

Reference Example 6 is an example in which 5.0% of polyoxyethylene alkyl ether (C1) was added as a lubricant. Although the coefficient of dynamic friction has decreased, it is understood that the late value is higher than the initial value, and the persistence of low friction may be reduced.

Reference Example 7 is an example in which 4.9% polyoxyethylene alkyl ether (C1) and 0.82% fatty acid amide (C4) were added. Although the coefficient of friction was at a practical level and its sustainability was good, it is understood that bleed and bloom may occur.

Comparative Example 24 is an example in which 0.30% of fatty acid amide (C4) was added. No decrease in the dynamic friction coefficient was observed.

Comparative Example 25 is an example in which 4.0% of polyoxyethylene alkyl ether (C1) is added and 0.51% of montanic acid ester wax (Licowax E) is added instead of fatty acid amide (C4). The coefficient of dynamic friction was at a practical level and its sustainability was good, but bleed bloom occurred.

Comparative Example 26 is an example in which 2.5% of 1-hexadecanol, which is an aliphatic alcohol having less than 20 carbon atoms, and 0.25% of fatty acid amide (C4) are added. Although the coefficient of friction decreased slightly, it was not at a sufficient level for use in industrial machine parts.

Comparative Example 27 is an example in which 11.2% polyoxyethylene alkyl ether (C1) and 0.19% fatty acid amide were added. The coefficient of friction decreased slightly, but the tensile strength and elongation decreased significantly.

Examples 30-37
Using a sheet of 3 mm thickness prepared in the same process according to Tables 1 and 3, cut out to 3 mm (width) x 30 mm (length) x 10 mm (height) with a feather shaving blade S single blade (product number: FAS-10) A test piece (D1) for confirming the friction coefficient of the cutting surface was prepared. Then, according to Table 9, the 2 mm thick sheet (D) and the cut 3 mm thick sheet (D1) were heat-treated, and the static friction coefficient and the dynamic friction coefficient were measured. The results are shown in Table 9.

Examples 38-45
Using a sheet of 3 mm thickness produced in the same process according to Table 5, cut out to 3 mm (width) x 30 mm (length) x 10 mm (height) with a feather shaving blade S single blade (product number: FAS-10) and cut A test piece (D1) for checking the coefficient of friction of the surface was prepared. Next, according to Table 12, the 2 mm thick sheet (D) and the cut 3 mm thick sheet (D1) were heat-treated, and the static friction coefficient and the dynamic friction coefficient were measured. The results are shown in Table 12.

Examples 46-53
Using a sheet of 3 mm thickness produced in the same process according to Table 7, cut and cut into 3 mm (width) x 30 mm (length) x 10 mm (height) with a feather shaving blade S single blade (product number: FAS-10) A test piece (D1) for checking the coefficient of friction of the surface was prepared. Next, according to Table 15, the 2 mm thick sheet (D) and the cut 3 mm thick sheet (D1) were heat-treated, and the static friction coefficient and the dynamic friction coefficient were measured. The results are shown in Table 15.

Next, examples using the release agent of the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. In Examples and Comparative Examples, “%” means “% by mass” unless otherwise specified. Moreover, about carboxyl equivalent, if it is 1000 g / mol, for example, it has having one carboxyl group per 1000 molecular weight silicone units.

<Synthesis of release agent 1>
Organopolysiloxane A (carboxyl group-containing dimethylpolysiloxane one-end modified type “X-22-3710” manufactured by Shin-Etsu Silicone Co., Ltd., carboxyl group equivalent: 1450 g / mol) was added to a 100 ml eggplant-shaped flask equipped with a magnetic stirrer. 25 g and 25 g of tetrahydrofuran (Kishida Chemical Reagent “THF”) were added and stirred at room temperature for 30 minutes to obtain a uniform solution. Subsequently, 10.5 g of an aqueous 15% tetramethylammonium hydroxide solution (Wako Pure Chemical Reagent, hereinafter abbreviated as “TMAH”) (equal moles relative to the carboxyl group of organopolysiloxane A) was added, and the mixture was stirred at room temperature for 1 hour. From this reaction solution, THF and water are removed under reduced pressure, and mineral spirit A (a petroleum solvent manufactured by JX Nippon Mining & Energy Co., Ltd., hereinafter abbreviated as “MSA”) is added to the residue and dissolved, resulting in a non-volatile content of 50%. A release agent 1 was obtained.

<Synthesis of Release Agent 2>
In a 100 ml eggplant-shaped flask equipped with a magnetic stirrer, 25 g of organopolysiloxane A and 25 g of THF were placed and stirred at room temperature for 30 minutes to obtain a uniform solution. Subsequently, 12.7 g (equal moles relative to the carboxyl group of organopolysiloxane A) of 20% tetraethylammonium hydroxide aqueous solution (Wako Pure Chemical Reagent, hereinafter abbreviated as “TEAH”) was added and stirred at room temperature for 1 hour. From this reaction solution, THF and water were removed under reduced pressure, and mineral spirit A was added to the residue to prepare a non-volatile content of 50%, whereby a release agent 2 was obtained.

<Synthesis of release agent 3>
In a 100 ml eggplant-shaped flask equipped with a magnetic stirrer, 25 g of organopolysiloxane A and 25 g of THF were placed and stirred at room temperature for 30 minutes to obtain a uniform solution. Subsequently, 44.7 g (equal moles with respect to the carboxyl group of organopolysiloxane A) of 10% tetrabutylammonium hydroxide aqueous solution (Wako Pure Chemicals Reagents, hereinafter abbreviated as “TBAH”) was added and stirred at room temperature for 1 hour. From this reaction solution, THF and water were removed under reduced pressure, and mineral spirit A was added to the residue to prepare a non-volatile content of 50%, whereby a release agent 3 was obtained.

<Synthesis of Release Agent 4>
In a 100 ml eggplant-shaped flask equipped with a magnetic stirrer, 25 g of organopolysiloxane A and 25 g of THF were placed and stirred at room temperature for 30 minutes to obtain a uniform solution. Subsequently, 7.2 g (equal moles to the carboxyl group of organopolysiloxane A) of 40% benzyltrimethylammonium hydroxide and methanol solution (Wako Pure Chemicals Reagents, hereinafter abbreviated as “BTMAH”) was added and stirred at room temperature for 1 hour. did. From this reaction solution, THF and methanol were removed under reduced pressure, and MSA was added to the residue to prepare a non-volatile content of 50%, whereby a release agent 4 was obtained.

<Synthesis of Release Agent 5>
In a 100 ml eggplant-shaped flask equipped with a magnetic stirrer, 25 g of organopolysiloxane A and 25 g of THF were placed and stirred at room temperature for 30 minutes to obtain a uniform solution. Subsequently, 4.6 g (based on the carboxyl group of organopolysiloxane A) of 45% 2-hydroxyethyltrimethylammonium and methanol solution (Wako Pure Chemicals Reagent “45% choline, methanol solution”, hereinafter abbreviated as “2-HETMAH”) Equimolar) and stirred at room temperature for 1 hour. From this reaction solution, THF and methanol were removed under reduced pressure, and MSA was added to the residue to prepare a non-volatile content of 50%, whereby a release agent 5 was obtained.

<Synthesis of release agent 6>
Release agent 1 and release agent 4 were mixed at a mass ratio of 1: 1 to obtain release agent 6.

<Synthesis of Release Agent 7>
Into a 100 ml eggplant-shaped flask equipped with a magnetic stirrer, organopolysiloxane B (carboxyl group-containing dimethylpolysiloxane modified at both ends “X-22-162C” manufactured by Shin-Etsu Silicone Co., Ltd., carboxyl group equivalent: 2300 g / mol) was added. 25 g and 25 g of tetrahydrofuran (Kishida Chemical Reagent “THF”) were added and stirred at room temperature for 30 minutes to obtain a uniform solution. Subsequently, 6.6 g of TMAH (equal moles relative to the carboxyl group of organopolysiloxane B) was added, and the mixture was stirred at room temperature for 1 hour. From this reaction solution, THF and water were removed under reduced pressure, and MSA was added to the residue to prepare a non-volatile content of 50%, whereby a release agent 7 was obtained.

<Synthesis of Release Agent 8>
In a 100 ml eggplant-shaped flask equipped with a magnetic stirrer, 5.7 g of organopolysiloxane A and organopolysiloxane C (carboxy group-containing dimethylpolysiloxane side chain modified type “X-22-3701E” manufactured by Shin-Etsu Silicone Co., Ltd.), 19.3 g of carboxyl group equivalent: 4000 g / mol) and 25 g of THF were added and stirred at room temperature for 30 minutes to obtain a uniform solution. Subsequently, 5.3 g of TMAH (equimolar to the carboxyl groups of organopolysiloxane A and organopolysiloxane C) was added and stirred at room temperature for 1 hour. From this reaction solution, THF and water were removed under reduced pressure, and MSA was added to the residue to prepare a non-volatile content of 50%, whereby a release agent 8 was obtained.

<Synthesis of Release Agent 9>
In a 100 ml eggplant-shaped flask equipped with a magnetic stirrer, 25 g of organopolysiloxane C and 25 g of THF were placed and stirred at room temperature for 30 minutes to obtain a uniform solution. Subsequently, 6.3 g of TMAH was added and stirred at room temperature for 1 hour. From this reaction solution, THF and water were removed under reduced pressure, and MSA was added to the residue to prepare a non-volatile content of 50%. Thus, a release agent 9 was obtained.

<Synthesis of Release Agent 10>
In a 100 ml eggplant-shaped flask equipped with a magnetic stirrer, 25 g of organopolysiloxane A and 25 g of THF were placed and stirred at room temperature for 30 minutes to obtain a uniform solution. Subsequently, 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 this reaction solution, THF was removed under reduced pressure, and MSA was added to the residue to prepare a non-volatile content of 50%, whereby a release agent 10 was obtained.

<Releasing agent 11>
Organopolysiloxane A was used as the release agent 11.

<Synthesis of Release Agent 12>
In a 100 ml eggplant-shaped flask equipped with a magnetic stirrer, 12.5 g of 2-ethylhexanoic acid and 12.5 g of THF were placed and stirred at room temperature for 30 minutes to obtain a uniform solution. Subsequently, 52.7 g of TMAH was added and stirred at room temperature for 1 hour. From this reaction solution, THF and water were removed under reduced pressure, and MSA was added to the residue to prepare a non-volatile content of 50%, whereby a release agent 11 was obtained.

<Releasing agent 13>
Organopolysiloxane D (unmodified dimethylpolysiloxane “KF-96” manufactured by Shin-Etsu Silicone) was used as the release agent 13.

<Releasing agent 14>
The release agent 12 and the release agent 13 were mixed at a mass ratio of 15:85 to obtain a release agent 14.

<Synthesis of Urethane Prepolymer 1 (UP-1)>
520 g of diphenylmethane diisocyanate (“Millionate MT” manufactured by Nippon Polyurethane Industry Co., Ltd., NCO content: 33.5%), polybutylene adipate (Japan), in a four-necked flask with a capacity of 1000 ml equipped with a stirrer, thermometer and condenser. 480 g of “Nipporan 4010” manufactured by Polyurethane Industry Co., Ltd., hydroxyl value 56.0 KOH mg / g) was charged, and urethanization reaction was performed at 80 ° C. for 3 hours while introducing nitrogen. The obtained urethane prepolymer had an NCO content of 15.4%.

<Synthesis of Urethane Prepolymer 2 (UP-2)>
In a four-necked flask with a capacity of 1000 ml equipped with a stirrer, a thermometer and a cooling tube, 225 g of tolylene diisocyanate (“Coronate T-100” manufactured by Nippon Polyurethane Industry Co., Ltd., NCO content: 48.2%), polytetramethylene 775 g of glycol (“PTMG1000” manufactured by Mitsubishi Chemical Corporation, hydroxyl value 112.0 KOHmg / g) was charged, and urethanization reaction was performed at 80 ° C. for 3 hours while passing nitrogen. The obtained urethane prepolymer had an NCO content of 4.2%.

<Preparation of polyol 1 (PO-1)>
In a four-necked flask with a capacity of 1000 ml equipped with a stirrer, thermometer, and cooling tube, 900 g of Nipponran 4010 and 70 g of 1,4-butanediol (Mitsubishi Chemical Co., Ltd., hereinafter abbreviated as “1,4-BD”) Then, 30 g of trimethylolpropane (manufactured by Mitsubishi Gas Chemical Co., Inc., hereinafter abbreviated as “TMP”) and 0.2 g of triethylenediamine (manufactured by Tosoh Corporation, hereinafter abbreviated as “TEDA”) were charged and mixed with stirring at 80 ° C. for 2 hours. The resulting polyol had a hydroxyl value of 175.0 KOHmg / g.

<Preparation of polyol 2 (PO-2)>
A 1000 ml four-necked flask equipped with a stirrer, a thermometer, and a cooling tube was charged with 750 g of 1,4-BD, 250 g of trimethylolpropane, and 1 g of TEDA, and stirred and mixed at 80 ° C. for 2 hours. The obtained polyol had a hydroxyl value of 1247 KOHmg / g.

<Preparation of polyol 3 (PO-3)>
A 1000 ml four-necked flask equipped with a stirrer, a thermometer, and a condenser, 900 g of Nipponran 4010, 70 g of 1,4-BD, 30 g of trimethylolpropane, N, N, N′-trimethylaminoethylethanol 2.5 g of amine (“TOYOCAT RX-5” manufactured by Tosoh Corporation) was charged, and the mixture was stirred and mixed at 80 ° C. for 2 hours. The resulting polyol had a hydroxyl value of 175.0 KOHmg / g.

Next, according to the blending ratio shown in Table 18 and Table 19, the NCO group-terminated urethane prepolymer and the catalyst-containing active hydrogen group-end curing agent are mixed by a two-component mixed urethane casting machine, thereby forming a polyurethane resin-forming composition. A composition is prepared, and this composition is poured into a mold for forming a flat sheet having a thickness of 2 mm, which has been preheated to the curing temperature and coated with the release agent composition of the present invention, and the molded product is removed from the mold. The polyurethane elastomer molded product (sheet) of the present invention was obtained by heat-curing in a mold for a minimum time (demolding) and quickly demolding the molded product.

The characteristics evaluation method of the obtained molded sheet is as follows.

(1) JIS-A hardness: Measured using an A-type hardness meter according to JIS K7312.

(2) Tensile strength (TB), elongation rate (EB): Measured according to JIS K7312.

(3) Dynamic friction coefficient:
"Preparation of specimen"
The molded sheet was cut into a width of 25 mm and a length of 100 mm and degreased using cyclohexane to prepare a test piece. Then, after leaving in an environment of room temperature 23 ° C. and humidity 50% for 1 day, the dynamic friction coefficient was measured under the following conditions.
"Measurement condition"
Measuring equipment: Surface property measuring machine TYPE: 38 (manufactured by Shinto Kagaku)
Measurement conditions: measurement jig = ball indenter (SUS), load = 20 g, table moving speed = 50 mm / min.

(4) Releasability: When removing the polyurethane resin from the mold for forming the flat sheet, the ease of demolding was evaluated as follows.
○: Peeling is light and can be removed immediately (within 5 seconds)
Δ: Slightly heavy peeling but demolding in a short time (about 10 seconds)
X: Heavy peeling and time required for demolding (30 seconds or more)

Examples 101 to 112 show the implementation results of the present invention. Under any of the conditions in the examples, by using the release agent of the present invention, a tough polyurethane resin having a low dynamic friction coefficient, high mechanical strength, and high strength could be obtained.

Since Comparative Examples 101 to 104 do not contain the organopolysiloxane (J) having a quaternary ammonium and / or quaternary phosphonium carboxylate of the present invention in the molecular structure in the release agent, the dynamic friction coefficient is high. It became a polyurethane resin.

Comparative Example 105 is close to the embodiment of the present invention, but at least one carboxylate selected from the group consisting of quaternary ammonium and quaternary phosphonium is not bonded to organopolysiloxane, that is, quaternary ammonium and 4 Since this is not an organopolysiloxane (J) having in its molecular structure at least one carboxylate selected from the group consisting of secondary phosphoniums, a polyurethane resin having a high dynamic friction coefficient was obtained.

Example 113
After adding 29 g of silicone (I) (single-end hydroxyl group-containing “X-22-170BX”, hydroxyl group equivalent: 2800 g / mol) manufactured by Shin-Etsu Silicone Co., Ltd. to release agent 3, TBAH-modified organopolysiloxane A / one-end hydroxyl group-containing silicone A release agent composition having a content of 50/50 was prepared. A polyurethane elastomer molded article was obtained in the same manner as in Example 103, except that this release agent composition was used. The results are shown in Table 21.

Examples 114-120
A release agent composition was prepared by changing the amount and type of one-end hydroxyl group-containing silicone used in Example 113, and a polyurethane elastomer molded product was obtained in the same manner as in Example 103. The silicone used is shown below.
Silicone (I):
One-end hydroxyl group-containing type “X-22-170BX” manufactured by Shin-Etsu Silicone Co., functional group equivalent: 2800 g / mol
Silicone (II):
One-end hydroxyl group-containing type “X-22-170DX” manufactured by Shin-Etsu Silicone Co., functional group equivalent: 4667 g / mol
Silicone (III)
Hydroxyl group-containing type “X-22-160AS” from Shin-Etsu Silicone Co., functional group equivalent: 470 g / mol
Silicone (IV)
Side chain amino group-containing type “KF-8004” manufactured by Shin-Etsu Silicone Co., Ltd., functional group equivalent: 1500 g / mol
Silicone (V)
Side chain amino group-containing type “KF-8005” manufactured by Shin-Etsu Silicone Co., Ltd., functional group equivalent: 11000 g / mol
Silicone (VI)
Side chain amino group containing type “KF-868” manufactured by Shin-Etsu Silicone Co., functional group equivalent: 8800 g / mol
Silicone (VII)
Amino group-containing type “KF-8008” manufactured by Shin-Etsu Silicone Co., functional group equivalent: 5700 g / mol
Table 21 summarizes the composition in the release agent and the dynamic friction coefficient of the molded product. The dynamic friction coefficient of the molded product was lower than the value of the molded product obtained in Example 103, and the introduction of silicone further reduced the friction.

Comparative Examples 106 and 107
A polyurethane elastomer molded product was obtained in the same manner as in Example 103, except that silicone (I) or silicone (IV) was used as the release agent. The results are shown in Table 21. Even if silicone having an active hydrogen group is used as a release agent, the effect of reducing the dynamic friction coefficient is small.

Example 121
In the synthesis of urethane prepolymer 1 (UP-1), the amount of diphenylmethane diisocyanate was changed to 515 g, and further 5 g of octadecyl isocyanate (“Millionate O” manufactured by Hodogaya Chemical Co., Ltd.) was added to the polyurethane resin-forming composition. 25 mass%) was added to prepare 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 polyol 1 (PO-1), the amount of polybutylene adipate “Niporan 4010” was changed to 880 g, and 20 g of polyoxyethylene cetyl ether (“NIKKOL BC-150” manufactured by Nikko Chemicals Co., Ltd.) was formed. Polyol 4 (PO-4) was prepared by adding 1% by mass in the active composition. 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 “Nippolan 4010” was changed to 840 g, and further 60 g of polyoxyethylene cetyl ether “NIKKOL BC-150” (3% in the polyurethane resin-forming composition). (Mass%) was added to prepare 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 molded polyurethane elastomer was obtained in the same manner as in Example 103, except that urethane prepolymer 3 (UP-3) and polyol 4 (PO-4) were used.

Example 125
In the preparation of polyol 4 (PO-4), instead of polyoxyethylene cetyl ether, 20 g of behenyl alcohol (“NIKKOL behenyl alcohol 80” manufactured by Nikko Chemicals Co., Ltd., melting point: 65 to 75 ° C.) was added to the polyurethane resin-forming composition. (Mass%) was used to prepare polyol (PO-6). 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 polyol 1 (PO-1), 10 g of N-oleyl stearamide (Nikka Amide OS manufactured by Nippon Kasei Co., Ltd.) as a saturated fatty acid amide (0.5% by mass in the polyurethane resin-forming composition) was added. 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.

The results are summarized in Table 22. By molding by adding a lubricant to the urethane prepolymer or polyol, a polyurethane elastomer molded product having a lower dynamic friction coefficient than that obtained when the release agent was used alone (Example 103) was obtained.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.

Japanese Patent Application No. 2014-181777 filed on September 5, 2014, Japanese Patent Application No. 2014-194778 filed on September 25, 2014, Japanese Patent Application filed on September 29, 2014 The entire contents of the specification, claims, and abstract of application 2014-198063 are incorporated herein by reference as the disclosure of the specification of the present invention.

Claims

An isocyanate group-terminated urethane prepolymer (A), an active hydrogen group-terminated curing agent (B), and a lubricant (C), wherein the lubricant (C) is 0.1 to 8 in the thermosetting polyurethane elastomer-forming composition. Containing 0.1% by mass of polyoxyethylene alkyl ether (C1), or 0.1 to 5% by mass of carbon number 20 to 40% and a melting point of 90 ° C. or less in the thermosetting polyurethane elastomer-forming composition. A thermosetting polyurethane elastomer-forming composition comprising a chain aliphatic alcohol (C2).
The lubricant (C) is selected from the group consisting of polyoxyethylene alkyl ether (C1), linear aliphatic alcohol (C2) having 20 to 40 carbon atoms and a melting point of 90 ° C. or less, and octadecyl isocyanate (C3). 2. The thermosetting polyurethane elastomer formation according to claim 1, comprising at least two kinds of compounds, and the lubricant (C) is contained in the thermosetting polyurethane elastomer-forming composition in an amount of 0.2 to 8% by mass. Sex composition.
The lubricant (C) is selected from the group consisting of polyoxyethylene alkyl ether (C1), linear aliphatic alcohol (C2) having 20 to 40 carbon atoms and a melting point of 90 ° C. or less, and octadecyl isocyanate (C3). At least one kind and fatty acid amide (C4), polyoxyethylene alkyl ether (C1), linear aliphatic alcohol (C2) having 20 to 40 carbon atoms and melting point of 90 ° C. or less, and octadecyl isocyanate (C3 ) In the thermosetting polyurethane elastomer-forming composition in an amount of 0.2 to 8% by mass, and the thermosetting polyurethane elastomer-forming composition contains 0.05 to 0.5 mass of the fatty acid amide (C4). The thermosetting polyurethane elastomer-forming composition according to claim 1, comprising:
The thermosetting polyurethane elastomer-forming composition according to any one of claims 1 to 3, wherein the hydroxyl value of the polyoxyethylene alkyl ether (C1) is 5 to 70 KOHmg / g.
Selected from the group consisting of polyoxyethylene alkyl ether (C1), linear aliphatic alcohol (C2) having 20 to 40 carbon atoms and melting point of 90 ° C. or lower, octadecyl isocyanate (C3), and fatty acid amide (C4) The isocyanate group-terminated prepolymer obtained by modifying an isocyanate group-terminated urethane prepolymer (A0) comprising at least a polyisocyanate (A6) and a polyol (A7) in advance is used as at least one kind. The thermosetting polyurethane elastomer-forming composition according to any one of the above.
At least one selected from the group consisting of polyoxyethylene alkyl ether (C1), linear aliphatic alcohol (C2) having 20 to 40 carbon atoms and a melting point of 90 ° C. or lower, and fatty acid amide (C4), and active hydrogen The thermosetting polyurethane elastomer-forming composition according to any one of claims 1 to 4, wherein an active hydrogen group terminal curing agent containing a group terminal curing agent (B0) is used.
4. The thermosetting polyurethane elastomer-forming composition according to claim 3, wherein the polyoxyethylene alkyl ether (C1) has a hydroxyl value of 5 to 70 KOHmg / g and the fatty acid amide (C4) has a melting point of 90 ° C. or less. object.
A method for producing a thermosetting polyurethane elastomer, comprising subjecting the thermosetting polyurethane elastomer-forming composition according to any one of claims 1 to 7 to thermosetting treatment.
An industrial machine part comprising a cured product having a JIS-A hardness in the range of 60 to 98 obtained by thermosetting the thermosetting polyurethane elastomer-forming composition according to any one of claims 1 to 7.
A static friction coefficient of a cured product (D) having a JIS-A hardness of 60 to 98 obtained by thermosetting the thermosetting polyurethane elastomer-forming composition according to any one of claims 1 to 7 is 0. .8 Industrial machinery parts with a coefficient of dynamic friction of 0.6 or less.
A cured product (D) having a JIS-A hardness in the range of 60 to 98 obtained by thermosetting the thermosetting polyurethane elastomer-forming composition according to any one of claims 1 to 7 is obtained by cutting. An industrial machine part in which the cured product (D1) has a static friction coefficient of 0.8 or less and a dynamic friction coefficient of 0.6 or less.
An industrial machine part having a static friction coefficient of 0.8 or less and a dynamic friction coefficient of 0.6 or less of a cured product obtained by further heat-treating the cured product (D) according to claim 10 at 100 to 200 ° C. for 1 to 120 minutes.
The static friction coefficient of a cured product (D2) obtained by further heat-treating the cured product (D1) obtained by cutting the cured product (D) according to claim 11 at 100 to 200 ° C. for 1 to 120 minutes is 0.8 or less. Industrial machinery parts with a coefficient of dynamic friction of 0.6 or less.
A release agent composition used for resin molding, comprising an organopolysiloxane (J) having in its molecular structure at least one carboxylate selected from the group consisting of quaternary ammonium and quaternary phosphonium. .
15. A release agent composition used for resin molding, wherein the release agent composition used for resin molding according to claim 14 further contains silicone (L) having an active hydrogen group.
Organopolysiloxane (J) having at least one carboxylate selected from the group consisting of quaternary ammonium and quaternary phosphonium in the molecular structure is quaternary ammonium (J1), quaternary phosphonium (J2), and carboxyl group The mold release agent composition used for resin molding according to claim 14 or 15, comprising at least one selected from the group consisting of containing organopolysiloxane (J3).
The total content of at least one carboxylate selected from the group consisting of quaternary ammonium (J1) and quaternary phosphonium (J2) is at least one carboxylate selected from the group consisting of quaternary ammonium and quaternary phosphonium. It is used for the resin molding according to any one of claims 14 to 16, wherein 0.3 mmol / g or more is contained with respect to the total content of the organopolysiloxane (J) having in the molecular structure. Release agent composition.
Silicone having an active hydrogen group with respect to 100 parts by mass of organopolysiloxane (J) having at least one carboxylate selected from the group consisting of quaternary ammonium (J1) and quaternary phosphonium (J2) in the molecular structure ( The release agent composition for use in resin molding according to any one of claims 15 to 17, characterized in that it contains 5 to 150 parts by mass of L).
The release agent composition used for resin molding according to any one of claims 15 to 18, wherein the silicone (L) having an active hydrogen group is an amino group-containing silicone.
A polyurethane resin-molded product obtained by molding a polyurethane resin-forming composition (K) with a mold to which a release agent composition used for resin molding according to any one of claims 14 to 19 is applied.
A mold release agent composition used for resin molding according to any one of claims 14 to 19 is applied to a mold, and the polyurethane resin-forming composition (K) is injected into the mold and molded. A method for producing a molded polyurethane resin product.
The polyurethane resin molded product according to claim 20, wherein the polyurethane resin-forming composition (K) comprises an isocyanate group-terminated urethane prepolymer (A0) and an active hydrogen group-terminated curing agent (B0).
The polyurethane resin-forming composition (K) is a polyoxyethylene alkyl ether (C1) as a lubricant (C), a linear aliphatic alcohol (C2) having 20 to 40 carbon atoms and a melting point of 90 ° C. or less, octadecyl isocyanate The polyurethane resin molded article according to claim 20 or 22, comprising at least one compound selected from the group consisting of (C3) and fatty acid amide (C4).
The polyurethane resin molded product according to claim 22 or 23, wherein the isocyanate component of the isocyanate group-terminated urethane prepolymer (A0) contains diphenylmethane diisocyanate or tolylene diisocyanate.
The isocyanate group / active hydrogen group molar ratio when mixing the isocyanate group-terminated urethane prepolymer (A0) and the active hydrogen group terminal curing agent (B0) is 1.0 to 3.0, The polyurethane resin molded product according to any one of claims 20, 22, 23, and 24.
The industrial machine part using the polyurethane resin molded product according to any one of claims 20, 22, 23, 24, or 25 having a dynamic friction coefficient of 0.8 or less and a JIS-A hardness of 60 to 98.