JP2017048319A - Composition for forming polyurethane elastomer, and industrial mechanical component using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for forming a thermosetting polyurethane elastomer for an industrial mechanical component that is free from the occurrence of bleed and bloom and has continuously very low friction coefficient even when subjected to cutting work, to provide a member for an industrial mechanical component using the composition and to provide an NCO group-terminated urethane prepolymer and an active hydrogen group-terminated curing agent for producing a thermosetting polyurethane elastomer having high quality stability by improving the compatibility of a lubricant component with an NCO group-terminated urethane prepolymer and an active hydrogen group-terminated curing agent used in the composition.SOLUTION: As a composition for forming a thermosetting polyurethane elastomer for an industrial mechanical component member, at least 0.2 to 8 mass% of at least one kind of compound selected from the group consisting of (C1) a polyoxyethylene alkyl ether, (C2) a 20-40C linear aliphatic alcohol and (C3) an octadecyl isocyanate is included and 0.05 to 0.5 mass% of (C4) a fatty acid amide is contained in the composition to produce a thermosetting polyurethane elastomer for an industrial mechanical component which does not cause bleed nor bloom and has continuously very low friction coefficient even in a surface subjected to cutting work.SELECTED DRAWING: None

Description

  The present invention relates to a thermosetting polyurethane elastomer-forming composition used for industrial machine component parts.

Thermosetting polyurethane elastomers have a very high durability because of their high modulus, high breaking strength, low wear, and low strain, and are suitably used as component parts for industrial machines.
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.

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

For example, as an isocyanate component, diphenyl metadiisocyanate (hereinafter abbreviated as “MDI”) and a polyol, NCO group-terminated urethane prepolymer composed of butylene adipate (hereinafter abbreviated as “PBA”) and a polyol component as 1,4- A hydroxyl group terminal curing agent (hereinafter abbreviated as “OH group terminal curing agent”) using a hydroxyl group obtained by mixing butanediol, trimethylolpropane and PBA as an active hydrogen group is preferably used. In addition, an NCO-terminated urethane prepolymer composed of tolylene diisocyanate (hereinafter abbreviated as “TDI”) and polytetramethylene glycol (hereinafter abbreviated as “PTMG”) and 4,4′-diamino-3,3′-dichlorodiphenylmethane An amino group terminal curing agent (hereinafter abbreviated as “NH ₂ group terminal curing agent”) using an amino group as an active hydrogen group (hereinafter abbreviated as “MOCA”) is preferably used.

  However, the coefficient of friction of the thermosetting polyurethane elastomer molding obtained as described above is very high. 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 lubricant such as liquid and powdery higher fatty acid esters composed of 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).

JP-A-57-194946 JP-A-3-346 Japanese Patent Laid-Open No. 5-133440 JP-A-11-51122 Japanese Patent Laid-Open No. 2005-120216

  However, when a lubricant that does not react with the above-mentioned polyurethane is mixed with the polyurethane elastomer, the compatibility between the lubricant and the NCO group-terminated urethane prepolymer or the active hydrogen group-terminated curing agent is poor, and a non-uniform polyurethane elastomer molding is obtained. In addition, the occurrence of bleeding and bloom of the 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.

  The present invention has been made on the basis of the above circumstances, and as a thermosetting polyurethane elastomer-forming composition for industrial machine component members, at least polyoxyethylene alkyl ether (C1), a straight chain having 20 to 40 carbon atoms. Bleed and bloom are generated by introducing at least one compound selected from the group consisting of a chain aliphatic alcohol (C2) and octadecyl isocyanate (C3) and a minimum amount of fatty acid amide (C4) as a modifier. The object is to provide a thermosetting polyurethane elastomer for industrial machine parts having a very low coefficient of friction. 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.

  The present invention is shown in the following (1) to (9).

(1) A thermosetting polyurethane elastomer-forming composition comprising an isocyanate group-terminated urethane prepolymer (A), an active hydrogen group-end curing agent (B), and a lubricant (C), wherein the lubricant (C) is a polyoxy Including at least one compound selected from the group consisting of ethylene alkyl ether (C1), linear aliphatic alcohol (C2) having 20 to 40 carbon atoms, and octadecyl isocyanate (C3), and fatty acid amide (C4),
The total amount of polyoxyethylene alkyl ether (C1), linear aliphatic alcohol (C2) having 20 to 40 carbon atoms, and octadecyl isocyanate (C3) is 0.2 to 8% by mass in the thermosetting polyurethane elastomer-forming composition. A thermosetting polyurethane elastomer-forming composition comprising 0.05 to 0.5% by mass of a fatty acid amide (C4).

  (2) Polyoxyethylene alkyl ether (C1) has a hydroxyl value of 5 to 70 KOH mg / g, a linear aliphatic alcohol (C2) having 20 to 40 carbon atoms having a melting point of 90 ° C. or lower, and a fatty acid amide (C4) having a melting point of It is 90 degrees C or less, The thermosetting polyurethane elastomer formation composition as described in said (1) characterized by the above-mentioned.

  (3) The isocyanate group-terminated urethane prepolymer (A) is a polyoxyethylene alkyl ether (C1), a linear aliphatic alcohol (C2) having 20 to 40 carbon atoms, an octadecyl isocyanate (C3), and a fatty acid amide (C4). It comprises an isocyanate group-terminated urethane prepolymer (A1) that is modified with at least one compound selected from the group consisting of the above-mentioned (1) or (2) thermosetting polyurethane elastomer-forming properties Composition.

  (4) The active hydrogen group terminal curing agent (B) is at least selected from the group consisting of polyoxyethylene alkyl ether (C1), linear aliphatic alcohol (C2) having 20 to 40 carbon atoms, and fatty acid amide (C4). The thermosetting polyurethane elastomer-forming composition as described in (1) or (2) above, which comprises an active hydrogen group terminal curing agent (B1) modified with one kind of compound.

  (5) Formation of a thermosetting polyurethane elastomer containing the isocyanate group-terminated urethane prepolymer (A) according to any one of (1) to (4), an active hydrogen group-end curing agent (B), and a lubricant (C). A method for producing a thermosetting polyurethane elastomer, which comprises heat-treating a curable composition.

  (6) 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 (4). An industrial machine part having a static friction coefficient of 0.8 or less and a dynamic friction coefficient of 0.6 or less.

  (7) 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 (4). An industrial machine part, wherein the cured product (D1) obtained by cutting has a static friction coefficient of 0.8 or less and a dynamic friction coefficient of 0.6 or less.

  (8) The cured product (D) according to (6) heat-treated at 100 to 200 ° C. for 1 to 60 minutes has a static friction coefficient of 0.8 or less and a dynamic friction coefficient of 0.6 or less. Industrial machine parts.

  (9) The static friction coefficient of the cured product (D1) obtained by cutting the cured product (D) according to (7), which is heat-treated at 100 to 200 ° C. for 1 to 60 minutes, is 0.8 or less, and An industrial machine part having a coefficient of dynamic friction of 0.6 or less.

  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.

  The thermosetting polyurethane elastomer molding composition for industrial machine parts of the present invention comprises an isocyanate group-terminated urethane prepolymer (A), an active hydrogen group-terminated curing agent (B), and a lubricant (C), and at least as a lubricant (C). Introduction of at least one compound selected from the group consisting of polyoxyethylene alkyl ether (C1), linear aliphatic alcohol (C2) having 20 to 40 carbon atoms, and octadecyl isocyanate (C3), and fatty acid amide (C4) By doing so, the friction coefficient can be reduced.

  By introducing polyoxyethylene alkyl ether (C1) and linear aliphatic alcohol (C2) having 20 to 40 carbon atoms, the static friction coefficient and the dynamic friction coefficient can be reduced. Further, 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
The values of m and n in the general formula 1 are not particularly limited, but the hydroxyl value is preferably 5 to 70 KOHmg / g in order to reduce the friction more effectively. 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. As specific examples of commercially available products of polyoxyethylene alkyl ether (C1), polyoxyethylene lauryl ether “NIKKOL BL-2, NIKKOL BL-4.2, NIKKOL BL-21, NIKKOL BL-25 manufactured by Nikko Chemicals”, polyoxy Ethylene cetyl ale "NIKKOL BC-2, NIKKOL BC-5.5, NIKKOL BC-7, NIKKOL BC-10, NIKKOL BC-20, NIKKOL BC-23, NIKKOL BC-25, NIKKOL BC-25, NIKOKL BC-25 , NIKKOL BC-150 ", polyoxyethylene stearyl ether" NIKKOL BS-2, "NIKKOL BS-4," NIKKOL BS-20 ", polyoxyethylene oleyl ether""NIKKOL O-2V, “NIKKOL BO-7V,” NIKKOL BO-10V, “NIKKOL BO-15V,“ NIKKOL BO-20V, “NIKKOL BO-50V”, polyoxyethylene behenyl ether “NIKKOL BB-10L, B , NIKKOL BB-20, NIKKOL BB-40 "and the like can be used.

The straight chain aliphatic alcohol (C2) having 20 to 40 carbon atoms 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 linear aliphatic alcohol having 20 to 40 carbon atoms can be represented by the general formula 2.
[Formula _{2] CH 3 - (CH 2} ) n-OH, n = 19~39
The value of n in the general formula 1 is 19 to 39, but the melting point is preferably 90 ° C. or lower in order to more effectively reduce the friction. When the melting point exceeds 90 ° C., the solubility with the NCO group-terminated urethane prepolymer (A) is generally poor, and even when 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 (B) is also inferior. 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 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-pentatriacontanol (C35), 1 -Hexatriacontanol (C36), 1-heptatriacontanol (C 7), 1-octa triacontanol (C38), 1-nona triacontanol (C39), 1-tetra con methanol (C40) and the like.

  Specific examples of commercially available products of these mixtures having a melting point of 90 ° C. or lower include, for example, behenyl alcohol, behenyl alcohol 65, behenyl alcohol 80R, highsonol 20SS, highsonol 22SS, NIKKOL behenyl alcohol 65, NIKKOL behenyl alcohol manufactured by Nikko Chemicals. 80, 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
As a specific example of a commercially available product of octadecyl isocyanate (C3), Millionate O (manufactured by Hodogaya Chemical Co., Ltd.) can be used.

  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 NCO group-terminated urethane prepolymer (A) is generally poor, and even when 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 (B) is also inferior. 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 fatty acid amide (C4) include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic acid amide, unsaturated fatty acid amide oleic acid amide, erucic acid amide, substituted amide. N-oleylpartic 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 Amides, ethylene bis lauric acid amides, ethylene bis stearic acid amides, ethylene bis hydroxy stearic acid amides, ethylene bis behenic acid amides, hexamethylene bis stearic acid amides, hexamethylene bis bevenic acid Amide, hexamethylene bishydroxystearic acid amide, N, N-distearyl adipic acid amide, N, N-distearyl acetacic acid amide, ethylene bisoleic acid amide of unsaturated fatty acid bisamide, ethylene biserucic acid amide, hexamethylene Bisoleic acid amide, N, N-dioleyl adipic acid amide, N, N-dioleyl sebacic acid amide and the like can be mentioned.

  Moreover, as a specific example of the commercial item of these mixtures whose melting | fusing point is 90 degrees C or less, Nippon Kasei's Diamit Y, Diamit O-200, Diamit L-200, Nikka Amide OP, Nikka Amide SO. Nikka Amide OS, Nikka Amide SE, etc. can be used.

  The lubricant (C) used in the present invention contains fatty acid amide (C4) as an essential component, and is composed of polyoxyethylene alkyl ether (C1), linear aliphatic alcohol (C2) having 20 to 40 carbon atoms, and octadecyl isocyanate (C3). At least one compound selected from the group can be arbitrarily selected and used, among them, polyoxyethylene alkyl ether (C1) and / or linear aliphatic alcohol (C2) having 20 to 40 carbon atoms, A combination of octadecyl isocyanate (C3) is particularly preferred. 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 octadecyl isocyanate (C3) is the thermosetting polyurethane elastomer-forming composition. 0.2-8 mass% is preferable with respect to the whole thing, When it is less than 0.2 mass%, sufficient friction reduction effect is not seen, and when it exceeds 8 mass%, the physical property fall by the fall of an average functional group number Or the quality of the prepolymer is deteriorated.

  The introduction amount of the fatty acid amide (C4) used in combination with these is preferably 0.05 to 0.5% by mass with respect 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.

  If the NCO group terminal prepolymer (A) used for this invention can be prepared from a polyisocyanate (A3) and a polyol (A4), there will be no restriction | limiting in any way. Among these, at least one compound selected from the group consisting of polyoxyethylene alkyl ether (C1), linear aliphatic alcohol (C2) having 20 to 40 carbon atoms, octadecyl isocyanate (C3), and fatty acid amide (C4). It is preferable to use a modified NCO group-terminated urethane prepolymer (A1).

  The modification referred to here is to change the properties of the NCO group-terminated prepolymer (A). For example, the NCO group-terminated urethane prepolymer (A1) modified with octadecyl isocyanate (C3) is a polyisocyanate (A3). And an NCO group-terminated prepolymer prepared from octadecyl isocyanate (C3) in addition to polyol (A4).

  Moreover, you may add reaction inhibitor (E) as needed. The NCO content of the NCO group-terminated urethane prepolymer (A) 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. If it is higher than 25% by mass, the stability of properties during storage and use will be significantly deteriorated, resulting in problems such as difficulty in obtaining stable industrial machine parts and 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 (A) used for this invention, The following manufacturing methods are preferable.

  Polyisocyanate (A3), and if necessary, octadecyl isocyanate (C3) and reaction inhibitor (E) are charged into the stirring vessel, and after stirring, the polyol (A4), while maintaining the temperature in the vessel at 40 to 70 ° C., and If necessary, polyoxyethylene alkyl ether (C1) and linear aliphatic alcohol (C2) having 20 to 40 carbon atoms are added and stirred. If necessary, fatty acid amide (C4) is added and stirred. Subsequently, the NCO group-terminated urethane prepolymer (A) can be obtained by proceeding 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 (A3) 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 kind is preferably selected from aromatic diisocyanates, and 4,4'-diphenylmethane diisocyanate is particularly preferable.

<Polyisocyanate>
Specific examples of polyisocyanates include, for example, hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, cyclohexyl diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated trimethylxylylene diisocyanate, 2-methylpentane-1, Such as 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>
The polyol (A4) 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 glass transition temperature, the average functional group number is 2-3 and the number average molecular weight is 250- It is preferable to select at least one of 5000 polyester polyols and polyether polyols. In addition, a monomer polyol can also be used together as needed.

<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. An acid or one of these anhydrides, and the like, 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-dimethanol , Dimer acid diol, bisphenol A ethylene oxide and propylene oxide adducts, bis (β-hydroxyethyl) benzene, xylylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc. What is obtained from the polycondensation reaction with the above 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 2-3 active hydrogen groups such as diols 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, ethylene oxide or propylene oxide adduct of bisphenol A, 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 a dealcoholization reaction or a dephenol reaction with diaryl carbonates such as phenanthryl carbonate, diindanyl carbonate, and tetrahydronaphthyl carbonate.

  In addition, the polyol (A4) can be used alone or in combination of two or more of polyolefin polyol, acrylic polyol, silicone polyol, castor oil-based polyol, fluorine-based polyol, and monomer polyol 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, which are copolymerized with 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 Examples include alkyl acrylates, esters of (meth) acrylic acid with cycloaliphatic alcohols such as cyclohexyl (meth) acrylate, and (meth) acrylic acid allyl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate. be able to. 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 acrylic acid hydroxy compounds such as 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 3-hydroxy-2,2-dimethylpropyl acrylate, and pentaerythritol triacrylate. Moreover, methacrylic acid hydroxy compounds, such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 3-hydroxy-2,2-dimethylpropyl methacrylate, and pentaerythritol trimethacrylate, are mentioned. These acrylic acid hydroxy compounds and / or 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-butylperoxyisopropylcarbonate. , Peroxyesters such as t-hexylperoxyisopropyl carbonate, di (t-butylperoxy) -2-methylcyclohexane, di (t-butylperoxy) 3,3,5-trimethylcyclohexane and di (t-butylperoxy) cyclohexane Peroxyketals and the like.

  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 ether, Benzoin ethers such as benzoin isopropyl butyl ether, benzophenone, 2-chlorobenzophenone, p, p′-dichlorobenzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone, 4- (2-hydroxy) Ketones such as ethoxy) phenyl (2-hydroxy-2-propyl) ketone, thioxanthones such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, phosphine oxides such as bisacylphosphine oxide and benzoylphosphine oxide And ketals such as benzyldimethyl ketal and quinones such as camphan-2,3-dione and phenanthrenequinone.

<Silicone polyol>
Specific examples of silicone polyols include, for example, 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 And polysiloxanes such as ω-dihydroxypolydiphenylsiloxane.

<Castor oil-based polyol>
Specific examples of the castor oil-based polyol include linear or branched polyester polyols obtained by a reaction between a castor oil fatty acid and a 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 hydroxyalkyl vinyl crotonates. Examples thereof include hydroxyl group-containing vinyl carboxylates such as, monomers having hydroxyl groups such as allyl esters, and the like.

<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 reaction inhibitor (E) used for this invention will not be specifically limited if there exists an effect of this invention. Specific examples of the reaction inhibitor (E) include, for example, phosphite esters, acidic phosphate esters, polyoxyethylene alkyl ether phosphates, and the like. 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.

  As the active hydrogen group terminal curing agent (B) used in the present invention, the aforementioned polyol (A4) can be arbitrarily selected and used. 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, at least one compound selected from the group consisting of polyoxyethylene alkyl ether (C1) used as a lubricant, straight chain aliphatic alcohol (C2) having 20 to 40 carbon atoms, and fatty acid amide (C4) is used. You can also.

  A catalyst (F) can be added to the active hydrogen group terminal curing agent (B) used in the present invention, if 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 polyurethane nurating catalyst (F1), potassium salts and quaternary ammonium salts are used. N, N, N′-trimethylaminoethylethanolamine and N, N-dimethylaminoethoxyethanol are preferred as the allophanatization catalyst for polyurethane (F2). In addition, a urethanization catalyst (F3) can also be used together or can be used alone 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>
The polyurethane nurating catalyst (F1) used in the nurating reaction can be appropriately selected from known catalysts, and specific examples thereof include, for example, triethylamine, N-ethylpiperidine, N, N′-dimethyl. Piperazine, N-ethylmorpholine, tertiary amines such as phenolic Mannich bases, tetramethylammonium hydrogencarbonate, methyltriethylammonium hydrogencarbonate, ethyltrimethylammonium hydrogencarbonate, propyltrimethylammonium hydrogencarbonate, butyltrimethyl Ammonium bicarbonate, pentyltrimethylammonium bicarbonate, hexyltrimethylammonium bicarbonate, heptyltrimethylammonium bicarbonate, octyltrimethylammonium bicarbonate, nonyltrimethylan Monium bicarbonate, decyltrimethylammonium bicarbonate, undecyltrimethylammonium bicarbonate, dodecyltrimethylammonium bicarbonate, tridecyltrimethylammonium bicarbonate, tetradecyltrimethylammonium bicarbonate, heptadecyltrimethylammonium bicarbonate Hexadecyltrimethylammonium hydrogencarbonate, heptadecyltrimethylammonium hydrogencarbonate, octadecyltrimethylammonium hydrogencarbonate, (2-hydroxypropyl) trimethylammonium hydrogencarbonate, hydroxyethyltrimethylammonium hydrogencarbonate, 1-methyl-1- Azania-4-azabicyclo [2.2.2] octanium bicarbonate, or 1,1-dimethyl-4-methylpiperidinium bicarbonate Such as quaternary ammonium bicarbonate, tetramethylammonium carbonate, methyltriethylammonium carbonate, ethyltrimethylammonium carbonate, propyltrimethylammonium carbonate, butyltrimethylammonium carbonate, pentyltrimethylammonium carbonate, hexyltrimethylammonium carbonate Salt, heptyltrimethylammonium carbonate, octyltrimethylammonium carbonate, nonyltrimethylammonium carbonate, decyltrimethylammonium carbonate, undecyltrimethylammonium carbonate, dodecyltrimethylammonium carbonate, tridecyltrimethylammonium carbonate, tetradecyltrimethylammonium carbonate Carbonate, heptadecyltrimethylammonium carbonate, hexadecyltrimethylan Nium carbonate, heptadecyltrimethylammonium carbonate, octadecyltrimethylammonium carbonate, (2-hydroxypropyl) trimethylammonium carbonate, hydroxyethyltrimethylammonium carbonate, 1-methyl-1-azania-4-azabicyclo [2,2 , 2] octanium carbonate, or quaternary ammonium carbonate such as 1,1-dimethyl-4-methylpiperidinium carbonate, hydroxyalkylammonium such as trimethylhydroxypropylammonium, trimethylhydroxypropylammonium, triethylhydroxyethylammonium Of carboxylic acids such as hydroxides, weak organic acid salts, acetic acid, propionic acid, butyric acid, caproic acid, capric acid, valeric acid, octylic acid, myristic acid, naphthenic acid Examples include lithium metal salts. Moreover, these isocyanurate formation catalysts (F1) for polyurethane can be used individually or in combination of 2 or more types. In addition, the usage-amount of an isocyanurate-ized catalyst (F1) is the range of 0.001-0.5 mass% with respect to the total mass of NCO group terminal urethane prepolymer (A) and OH group terminal hardening | 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.

<Allophanatization catalyst for polyurethane>
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 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 polycyclic 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, linoleic acid , Monocarboxylic acids such as linolenic acid, soybean fatty acid, unsaturated fatty carboxylic acid such as 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, glutaric 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, Examples thereof include polycarboxylic acids such as β-diethylsuccinic acid, maleic acid, fumaric acid, trimellitic acid, and pyromellitic acid.

  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, iron, cobalt, Examples include transition metals such as nickel, copper, zinc, and zirconium. These metal carboxylates 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. In addition, the usage-amount of an allophanatization catalyst (F2) is the range of 0.001-0.5 mass% with respect to the total mass of NCO group terminal urethane prepolymer (A) and active hydrogen group terminal hardening | 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.

<Urethane catalyst for polyurethane>
The urethane urethanization catalyst (F3) used in the urethanization reaction can be appropriately selected from known catalysts. Specific examples of the amine catalyst include 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′-tetramethylhexa Methylenediamine, bis (2-dimethylaminoethyl) ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoeth Siethanol, N, N-dimethyl-N ′-(2-hydroxyethyl) ethylenediamine, N, N-dimethyl-N ′-(2-hydroxyethyl) propanediamine, bis (dimethylaminopropyl) amine, bis (dimethylamino) Propyl) 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-hydroxy Propyl) -2-methylimidazole and the like.

  Specific examples of metal catalyst systems include stannous diacetate, stannous dioctoate, stannous dioleate, stannous dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dioctyltin dilaurate, and the like. Examples thereof include a tin catalyst, nickel octylate, nickel naphthenate, cobalt octylate, cobalt naphthenate, bismuth octylate, and bismuth naphthenate. In addition, the usage-amount of a urethanization catalyst (F3) is the range of 0.001-0.5 mass% with respect to the total mass of NCO group terminal urethane prepolymer (A) and an active hydrogen group terminal hardening | 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.

  In the present invention, if necessary, antioxidants, antifoaming agents, ultraviolet absorbers and the like can be introduced and used as additives in the forming composition.

  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, allophanated bonds.

In this case, as a method for producing a thermosetting polyurethane elastomer molded product according to the present invention using the forming composition according to the present invention, it 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 formable composition into a preheated mold, the mold is poured into the mold (casting), and the formable composition is heat-cured in the mold (specifically, cured by heating). Reaction). 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, it is preferable to perform an aging treatment at room temperature for one week after demolding the thermosetting polyurethane elastomer molded product (industrial machine part).

In addition, the blending molar ratio (hereinafter abbreviated as “α value”) determined from the NCO group content of the NCO terminal prepolymer at the time of casting and the OH group (NH ₂ group) content of the active hydrogen group terminal curing agent, 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 in the case of using the polyurethane nurating catalyst (F1) or the polyurethane allophanating catalyst (F2) is preferably 0.2 to 0.8. 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 the ratio exceeds 0.8, the number of crosslinking points due to nurateization or allophanate decreases, leading to a decrease in initial modulus (M100), a large amount of deformation with respect to stress, and insufficient strength against hardness. In addition, 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 of the present invention produced by using the formable composition of the present invention is heat-treated at 100 to 200 ° C. for 1 to 60 minutes after demolding, thereby efficiently reducing the temperature. Can be rubbed. 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. Further, when the heat temperature exceeds 200 ° C. or when the time exceeds 60 minutes, the thermosetting polyurethane molded product leads to an increase in the coefficient of friction due to softening, so the effect is small.

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

Examples 1-8, Comparative Examples 1-8
In the mixing ratio shown in Table 1 and Table 2, in a 5 L stirring vessel filled with nitrogen, various polyisocyanates (A3) and octadecyl isocyanate (C3), reaction inhibitor (E), oxidation according to the mixing ratio as necessary The inhibitor was added and stirred. Then, while maintaining the temperature in the stirring vessel at 40 to 70 ° C., various polyols (A4) and a polyoxyethylene alkyl ether (C1) and a linear aliphatic alcohol having 20 to 40 carbon atoms (C2) as necessary according to the blending ratio. ) Was added and stirred. Subsequently, the urethanization reaction is allowed to proceed for about 2 to 5 hours while adding appropriate amounts of fatty acid amide (C4) and antifoaming agent according to the blending ratio and keeping the temperature in the stirring vessel at 70 to 90 ° C. Various NCO group-terminated urethane prepolymers (A) were obtained. However, for Example 1 and Example 4, fatty acid amide (C4) was added after the urethanization reaction and stirred and mixed for about 0.5 to 1 hour to obtain various NCO group-terminated urethane prepolymers (A). It was.

  In addition, in the mixing ratio shown in Table 1 and Table 2, in a 5 L stirring vessel filled with nitrogen, various polyols (A4) and a polyoxyethylene alkyl ether (C1), 20 to 20 carbon atoms as required according to the mixing ratio 40 linear aliphatic alcohol (C2), fatty acid amide (C4), various catalysts (F) and an appropriate amount of antifoaming agent were added and stirred, and the temperature in the stirring vessel was kept at 40 to 70 ° C. Various active hydrogen group terminal curing agents (B) were obtained by mixing and stirring for about an hour.

  Next, according to the formulations (blending ratios) shown in Table 1 and Table 2, the NCO group-terminated urethane prepolymer (A) previously kept at 70 to 90 ° C. and the catalyst-containing active hydrogen group previously kept at 40 to 120 ° C. The thermosetting polyurethane elastomer-forming composition of the present invention was prepared by mixing the terminal curing agent (B) with a two-component mixed urethane casting machine, and this composition was preheated to a curing temperature of 2 mm. It is poured into a mold for forming a flat sheet with a thickness of 3 mm or thick, and the molded product is heated and cured in the mold for a minimum time that can be taken out (demolded) from the mold. By demolding, a polyurethane elastomer molded product (sheet) of the present invention was obtained.

Abbreviations of raw materials used in Table 1 and Table 2 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 (manufactured by 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 BB-5; polyoxyethylene behenyl ether (manufactured by Nikko Chemicals), hydroxyl value = 106 KOHmg / g
(13) Permacol 350 Alcohol (manufactured by Nikko Chemicals), C20 to C40, melting point = 68 to 89 ° C, hydroxyl value = 129 KOHmg / g
(14) Permacol 425 Alcohol (manufactured by Nikko Chemicals), C20-C40, melting point = 85-99 ° C., hydroxyl value = 100 KOH mg / g
(15) NIKKOL behenyl alcohol 80 (manufactured by Nikko Chemicals), C22 (containing 80%), melting point = 65-75 ° C., hydroxyl value = 171 KOH mg / g
(16) 1-icosanol; manufactured by Tokyo Chemical Industry Co., Ltd., C20, melting point = 64 ° C., hydroxyl value = 188 KOHmg / g
(17) 1-hexadecanol; manufactured by Tokyo Chemical Industry Co., Ltd., C16, melting point = 50 ° C., hydroxyl value = 231 KOH mg / g
(18) Diamit O-200; oleic acid amide (manufactured by Nippon Kasei Co., Ltd.), melting point = 75 ° C.
(19) Nikka Amide OS; N-oleyl stearamide (manufactured by Nippon Kasei Co., Ltd.), melting point = 74 ° C.
(20) Slipak O; ethylenebisoleic acid amide (Nippon Kasei Co., Ltd.), melting point = 119 ° C.
(21) Rico wax E; Montanic acid ester WAX (manufactured by Client Japan), melting point = 79-83 ° C.
"catalyst"
(22) POLYCAT-46; (Air Products), mixture of potassium acetate and ethylene glycol (23) DABCO TMR; (Air Products), mixture of quaternary ammonium salt catalyst and ethylene glycol (24) TOYOCAT RX- 5; (manufactured by Tosoh Corporation), trimethylaminoethylethanolamine (25) TOYOCAT TEDA-L33E; (manufactured by Tosoh Corporation), a mixture of triethylenediamine and ethylene glycol "others and additives"
(26) Reaction inhibitor: Phospholan PS-236 (manufactured by Akzo Nobel), mono-di (C10-12) palace-5 phosphate (27) antioxidant; Irganox 1010 (manufactured by BASF Japan) pentaerythritol tetrakis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate]
(28) Antifoaming agent; BYK-052 (manufactured by Big Chemie Japan).

  The characteristic values of the obtained molded sheet are shown in Tables 3 and 4, and the characteristic value of the molded sheet cut surface is shown in Table 5. The characteristic evaluation method is as follows.

  (1) JIS-A hardness; measured using an A-type hardness meter in accordance with JIS K7312.

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

(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 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 stage value as a sustainability index.
“Measurement conditions” Measurement jig = ball indenter (SUS), load = 50 g, table moving speed = 50 mm / min, table moving distance = 50 mm, number of reciprocations = 1000 times, measurement time = 3 hours 23 minutes.

(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 (product 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 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 stage value as a sustainability index.
“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) Presence / absence of bleed and bloom; the test piece used for the measurement of the dynamic friction coefficient is 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 is visually observed. The presence or absence of bleed and bloom was evaluated.

  The implementation result of this invention is shown in Examples 1-8. In any of the conditions in the claims, further reduction of friction, which is a subject of the present invention, and maintenance of low friction during repeated use are achieved. In addition, the thermosetting polyurethane elastomer-forming composition obtained from these is excellent in compatibility with the lubricant component, the NCO group-terminated urethane prepolymer (A), and the active hydrogen group-terminated curing agent (B). In addition, the mechanical strength was high and tough physical properties could be obtained.

  Comparative Example 1 was an example of molding without adding a lubricant, and showed a higher friction coefficient than that of the Example.

  Comparative Example 2 is an example in which 5.0% of octadecyl isocyanate (C3) was added as a lubricant. Although the coefficient of friction decreased slightly, it was not at a sufficient level for use in industrial machine parts.

  Comparative Example 3 is an example in which 5.0% of polyoxyethylene alkyl ether (C1) was added as a lubricant. Although the dynamic friction coefficient decreased, the late value showed a higher value than the initial value, and the low friction persistence was low.

  In Comparative Example 4, 4.9% polyoxyethylene alkyl ether (C1) and 0.82% fatty acid amide (C4) were added. The coefficient of friction was at a practical level and its sustainability was good, but bleed bloom occurred.

  Comparative Example 5 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 6 is an example in which 4.0% of polyoxyethylene alkyl ether (C1) and 0.5% of montanic acid ester wax (Licowax E) are 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 7 is an example in which 2.5% of 1-hexadecanol, which is an aliphatic alcohol having 20 or less carbon atoms, and 0.3% 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.

  In Comparative Example 8, 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.

  Using a 3 mm-thick sheet produced in the same process according to Table 1, 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 (D2) for checking the coefficient of friction of the surface was prepared. Next, according to Table 5, 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.

  Examples 9 to 12 are examples heated at 100 to 200 ° C. for 1 to 60 minutes, and in all cases, the coefficient of friction was reduced, and a great reduction was observed particularly on the cutting surface. Moreover, in the heating conditions other than the above shown in Examples 13 to 16, although the reduction of the friction coefficient by the heat treatment was extremely small, it was a sufficient level for use in industrial machine parts.

Claims (9)

A thermosetting polyurethane elastomer-forming composition comprising an isocyanate group-terminated urethane prepolymer (A), an active hydrogen group-end curing agent (B), and a lubricant (C), wherein the lubricant (C) is a polyoxyethylene alkyl ether (C1), at least one selected from the group consisting of C20-C40 linear aliphatic alcohol (C2) and octadecyl isocyanate (C3), and fatty acid amide (C4),
The total amount of polyoxyethylene alkyl ether (C1), linear aliphatic alcohol (C2) having 20 to 40 carbon atoms, and octadecyl isocyanate (C3) is 0.2 to 8% by mass in the thermosetting polyurethane elastomer-forming composition. A thermosetting polyurethane elastomer-forming composition comprising 0.05 to 0.5% by mass of a fatty acid amide (C4).   Polyoxyethylene alkyl ether (C1) has a hydroxyl value of 5 to 70 KOHmg / g, a linear aliphatic alcohol (C2) having 20 to 40 carbon atoms having a melting point of 90 ° C. or lower, and a fatty acid amide (C4) having a melting point of 90 ° C. or lower. The thermosetting polyurethane elastomer-forming composition according to claim 1, wherein   Isocyanate group-terminated urethane prepolymer (A) is composed of polyoxyethylene alkyl ether (C1), linear aliphatic alcohol (C2) having 20 to 40 carbon atoms, octadecyl isocyanate (C3), and fatty acid amide (C4). The thermosetting polyurethane elastomer-forming composition according to claim 1 or 2, comprising an isocyanate group-terminated urethane prepolymer (A1) modified with at least one selected compound.   The active hydrogen group terminal curing agent (B) is at least one selected from the group consisting of polyoxyethylene alkyl ether (C1), linear aliphatic alcohol (C2) having 20 to 40 carbon atoms, and fatty acid amide (C4). The thermosetting polyurethane elastomer-forming composition according to claim 1 or 2, comprising an active hydrogen group-end curing agent (B1) modified with a compound.   A thermosetting polyurethane elastomer-forming composition containing the isocyanate group-terminated urethane prepolymer (A), the active hydrogen group-end curing agent (B), and the lubricant (C) according to any one of claims 1 to 4 is heated. A method for producing a thermosetting polyurethane elastomer, comprising performing a curing treatment.   The 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 4 is 0. An industrial machine component having a coefficient of dynamic friction of not more than 8 and a coefficient of dynamic friction of not more than 0.6.   Obtained by cutting 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 4. An industrial machine part characterized in that the cured product (D1) has a static friction coefficient of 0.8 or less and a dynamic friction coefficient of 0.6 or less.   The industrial machine part characterized in that the static friction coefficient of the cured product (D) according to claim 6 heat-treated at 100 to 200 ° C for 1 to 60 minutes is 0.8 or less and the dynamic friction coefficient is 0.6 or less. .   The static friction coefficient of the hardened | cured material (D1) obtained by cutting a hardened | cured material (D) of Claim 7 heat-processed at 100-200 degreeC for 1 to 60 minutes, and a dynamic friction coefficient is 0. Industrial machine parts characterized by being 6 or less.