JP7035739B2 - Urethane resin composition, thermosetting urethane resin composition and its molded product - Google Patents

Description

The present invention relates to a urethane resin composition, a thermosetting urethane resin composition, and a molded product thereof.

The urethane resin molded body has excellent mechanical properties such as wear resistance, tensile strength, and tear strength, and has good chemical resistance, solvent resistance, and oil resistance, as well as heat resistance and cold resistance. , It is suitably used as various industrial members.

As such a urethane resin molded product, Patent Documents 1 and 2 describe, for example, a reaction of an organic polyisocyanate and a polyol containing a random copolymer of tetrahydrofuran and alkylene oxide having an OH value of 130 or less in the presence of a silicone-based defoaming agent. The molded product obtained by the above-mentioned is described. Further, Patent Document 3 describes a thermosetting resin composition containing a polyisocyanate compound, a hydroxylated polysilicone at both ends, a carboxyl group-containing urethane resin made from a dihydroxy compound having a carboxyl group, and a curing agent. Has been done.

Japanese Unexamined Patent Publication No. 62-101622 Japanese Unexamined Patent Publication No. 62-13424 Japanese Unexamined Patent Publication No. 2007-154134

In the conventionally known urethane resin composition, the smoothness of the surface of the obtained molded product may not be sufficient, and bubbles may be generated when trying to improve the smoothness of the surface, and the surface of the molded product may be generated. It was difficult to suppress the generation of bubbles while improving the smoothness of the resin.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a urethane resin composition capable of suppressing the generation of bubbles while improving the smoothness of the surface of the obtained molded product.

The urethane resin composition of the present invention is a urethane resin composition containing a urethane prepolymer (A) having an isocyanate group and an ether-modified polysiloxane (B), and the degree of molecular weight dispersion (weight average molecular weight) of the ether-modified polysiloxane. / Number average molecular weight) is 1.8 or more and 7 or less.

The urethane resin composition of the present invention or the urethane resin molded body formed from the thermosetting urethane resin composition can suppress the generation of bubbles while improving the smoothness of the surface.

The urethane resin composition of the present invention contains a urethane prepolymer (A) having an isocyanate group and an ether-modified polysiloxane (B). Hereinafter, the urethane resin composition containing the urethane prepolymer (A) and the ether-modified polysiloxane (B) may be referred to as the main agent (i).

The urethane prepolymer can be obtained as a reaction product of the polyol (a1) and the polyisocyanate (a2).

As the polyol (a1), one kind or two or more kinds can be used, and examples thereof include a polyether polyol, a polyester polyol, a polycarbonate polyol, and a polyolefin polyol. Above all, it is preferable to contain a polyether polyol and a polyester polyol, and it is preferable to contain a polyether polyol.

As the polyether polyol, addition polymerization (ring-opening polymerization) of an alkylene oxide is carried out using one or more compounds having two or more groups having two or more active hydrogen atoms (for example, hydroxy group, amino group) as an initiator. Examples thereof include those which have been subjected to ring-opening polymerization of alkylene oxides.

Examples of the initiator include ethylene glycol, diethylene glycol, triethylene glycol, trimethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and 1, , 5-Pentanediol, Neopentyl glycol, 1,6-hexanediol and other linear or branched chain diols; Triols such as glycerin, trimethylolethane, trimethylolpropane, pyrogallol; sorbitol, sucrose, aconit sugar, etc. Polyols; tricarboxylic acids such as aconitic acid, trimellitic acid, hemmellitic acid; phosphoric acid; polyamines such as ethylenediamine and diethylenetriamine; alkanolamines such as triisopropanolamine;phenolic acids such as dihydroxybenzoic acid and hydroxyphthalic acid; 1, Examples thereof include 2,3-propanetriol.

The alkylene oxide has, for example, a halogen atom (for example, a chlorine atom) as a substituent having 2 to 8 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran. Good cyclic ethers and the like can be mentioned.

As the polyether polyol, it is preferable to use polyoxytetramethylene glycol obtained by addition polymerization (ring-opening polymerization) of tetrahydrofuran to the initiator used as needed.

The number average molecular weight of the polyether polyol is preferably 500 or more, more preferably 1,000 or more, still more preferably 1,500 or more, preferably 5,000 or less, more preferably 4,000 or less, still more preferably. Is less than 3,000.
In the present specification, the number average molecular weight of the polyol represents a value calculated based on the hydroxyl value.

The polyester polyol is, for example, a polyester polyol obtained by esterifying a low molecular weight polyol (for example, a polyol having a molecular weight of 50 or more and 300 or less) and a polycarboxylic acid; and ring-opening polymerization of a cyclic ester compound such as ε-caprolactone. The polyester polyol obtained in the above; examples thereof include these copolymerized polyester polyols.

As the low molecular weight polyol, a polyol having a molecular weight of 50 or more and 300 or less can be used, and for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and the like. An aliphatic polyol having 2 or more and 6 or less carbon atoms such as 3-methyl-1,5-pentanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, and 1,3-butanediol; and fats such as cyclohexanediol and cyclohexanedimethanol. Polyols containing a cyclic structure (hereinafter, the inclusion of an alicyclic structure is simply referred to as "alicyclic structure"); bisphenol compounds such as bisphenol A and bisphenol F and alkylene oxide adducts thereof. Examples thereof include polyols containing aromatic structures.

Examples of the polycarboxylic acid include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid; aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid; Examples thereof include an anhydride or an ester-forming derivative of the aliphatic polycarboxylic acid and the aromatic polycarboxylic acid.

The number average molecular weight of the polyester polyol is preferably 500 or more, more preferably 1,000 or more, still more preferably 1,500 or more, preferably 5,000 or less, more preferably 4,000 or less, still more preferably. It is 3,000 or less.

Examples of the polycarbonate polyol include a reaction product of a carbonic acid ester and a polyol; a reaction product of phosgene and bisphenol A and the like.

Examples of the carbonic acid ester include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenylcarbonate and the like.

Examples of the polyol that can react with the carbonic acid ester include the polyol exemplified as the low molecular weight polyol; a high molecular weight polyol (weight) such as a polyether polyol (polyethylene glycol, polypropylene glycol, etc.) and a polyester polyol (polyhexamethylene adipate, etc.). The average molecular weight is 500 or more and 5,000 or less).

Examples of the polyolefin polyol include polyisobutene polyol, hydrogenated (hydrogenated) polybutadiene polyol, hydrogenated (hydrogenated) polyisoprene polyol and the like.

The total content of the polyether polyol, the polyester polyol, the polycarbonate polyol and the polyolefin polyol (preferably the polyether polyol and the polyester polyol, more preferably the polyester polyol) contained in the polyol (a1) is the polyol (a1-1). Among them, it is preferably 30% by mass or more, more preferably 40% by mass or more, and preferably 100% by mass or less.

The polyol (a1) may contain other polyols, if necessary. Examples of the other polyols include ethylene glycol, diethylene glycol, 1,2-propylene glycol, dipropylene glycol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, and 1,4-butanediol. , 1,5-Pentanediol, 3-Methyl-1,5-Pentanediol, 1,4-Cyclohexanediol, 1,6-Hexanediol, Cyclohexanedimethanol and the like with relatively low molecular weight (for example, molecular weight of 50 or more and 300 or less). ) Polyol.

As the polyisocyanate (a2) capable of reacting with the polyol (a1), one kind or two or more kinds can be used, for example, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane. Aromatic polyisocyanates such as diisocyanate, crude diphenylmethane diisocyanate, phenylenediisocyanate, trienediisocyanate, naphthalenediocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; cyclohexanediisocyanate, hydrogenated xyl Examples thereof include alicyclic polyisocyanates such as range isocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate.

The polyisocyanate (a2) preferably contains an aromatic polyisocyanate. The content of the aromatic polyisocyanate is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and preferably 100% by mass or less in the polyisocyanate (a2). be.

The isocyanate group equivalent of the urethane prepolymer (A) is preferably 200 g / eq. As mentioned above, more preferably 500 g / eq. Above, more preferably 800 g / eq. As mentioned above, 1,000 g / eq. Is particularly preferable. The above is preferable, and 5,000 g / eq. Hereinafter, more preferably, 4,000 g / eq. Hereinafter, more preferably 3,500 g / eq. Hereinafter, even more preferably, 3,000 g / eq. Hereinafter, particularly preferably, 2,000 g / eq. It is as follows.

The weight average molecular weight of the urethane prepolymer (A) is preferably 1,000 or more, more preferably 5,000 or more, still more preferably 8,000 or more, preferably 50,000 or less, more preferably 30, It is 000 or less, more preferably 15,000 or less.
The molecular weight dispersion (weight average molecular weight / number average molecular weight) of the urethane prepolymer (A) is preferably 1.5 or more, more preferably 2 or more, still more preferably 3 or more, and preferably 15 or less. It is more preferably 10 or less, still more preferably 8 or less.
In the present specification, the weight average molecular weight and the number average molecular weight of the urethane prepolymer (A) represent the converted values measured by gel permeation chromatography using polystyrene as a standard substance.

The content of the urethane prepolymer (A) is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 98% by mass or more, and preferably 100 in the non-volatile content of the urethane resin composition. It is less than mass%.
In the present specification, the non-volatile component of the urethane resin composition means a portion obtained by removing the solvent from the urethane resin composition.

The urethane prepolymer (A) can be produced by reacting the polyol (a1) with the polyisocyanate (a2) in the presence of a catalyst to be used, if necessary.

As the catalyst, one kind or two or more kinds can be used as the catalyst, for example, a tertiary amine catalyst; an organometal such as an alkyl metal compound (particularly, an alkyl tin and a salt thereof) and a metal acetylacetonate. Examples include catalysts.

The ether-modified polysiloxane (B) represents a compound in which a group represented by the formula (1) is introduced into a side chain or a terminal of a polydialkylsiloxane (preferably polydimethylsiloxane), and the side chain of the polysiloxane and the terminal thereof. At least a part of the methyl group at the terminal may be replaced with a phenyl group or a hydrogen atom.

[In the formula (1), L ¹ represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms. R ¹ represents a divalent hydrocarbon group having 2 to 10 carbon atoms. R ² represents a monovalent hydrocarbon group having 1 to 10 carbon atoms. n represents an integer of 1 or more. However, when two or more R ^1s are included, the plurality of R ^1s may be the same or different. ]

The divalent hydrocarbon group represented by L ¹ is a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms; a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms; a carbon atom. A divalent aromatic hydrocarbon group having a number of 6 to 20; a combination of two or more of the aliphatic hydrocarbon group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group having 20 carbon atoms. The following groups and the like are mentioned, and the aliphatic hydrocarbon group and the alicyclic hydrocarbon group are preferable, the aliphatic hydrocarbon group is more preferable, and the saturated aliphatic hydrocarbon group is further preferable.

The number of carbon atoms of the divalent hydrocarbon group represented by L ¹ is preferably 2 or more, preferably 15 or less, more preferably 12 or less, still more preferably 10 or less.

The divalent hydrocarbon group represented by R ¹ is a divalent aliphatic hydrocarbon group having 2 to 10 carbon atoms; a divalent alicyclic hydrocarbon group having 3 to 10 carbon atoms; a carbon atom. A divalent aromatic hydrocarbon group having a number of 6 to 10; a group that is a combination of two or more of the aliphatic hydrocarbon group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group, and has the number of carbon atoms. Examples thereof include groups of 10 or less, and the aliphatic hydrocarbon group and the alicyclic hydrocarbon group are preferable, the aliphatic hydrocarbon group is more preferable, and the saturated aliphatic hydrocarbon group is further preferable.

The number of carbon atoms of the divalent hydrocarbon group represented by R ¹ is preferably 2 or more, preferably 8 or less, more preferably 6 or less, still more preferably 5 or less.

The monovalent hydrocarbon group represented by R ² is a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms; a monovalent alicyclic hydrocarbon group having 3 to 10 carbon atoms; a carbon atom. Examples thereof include monovalent aromatic hydrocarbon groups having a number of 6 to 10; a group in which two or more of the aliphatic hydrocarbon group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group are combined; and the like. An aliphatic hydrocarbon group and an alicyclic hydrocarbon group are preferable, an aliphatic hydrocarbon group is more preferable, and a saturated aliphatic hydrocarbon group is further preferable.

The number of carbon atoms of the monovalent hydrocarbon group represented by R ² is preferably 2 or more, preferably 8 or less, more preferably 6 or less, still more preferably 5 or less.

n is preferably an integer of 1 or more, more preferably 2 or more, still more preferably 3 or more, preferably 50 or less, more preferably 20 or less, still more preferably 15 or less.

Examples of the group represented by the formula (1) include an alkyloxy-polyalkyloxy-alkyl group such as an alkyloxy-polyethyloxy-alkyl group and an alkyloxy-polypropyloxy-polyethyloxy-alkyl group. Can be mentioned.

The number average molecular weight of the ether-modified polysiloxane (B) is preferably 100 or more, more preferably 200 or more, still more preferably 300 or more, preferably 5,000 or less, more preferably 4,000 or less, still more preferably. Is less than 3,000.
The number average molecular weight of the ether-modified polysiloxane (B) can be measured as a conversion value using polystyrene as a standard sample by using a gel permeation chromatography method.

As the ether-modified polysiloxane (B), a commercially available product may be used.

The content of the ether-modified polysiloxane (B) is preferably 0.001 part by mass or more, more preferably 0.002 part by mass or more, and further preferably 0 with respect to 100 parts by mass of the urethane prepolymer (A). It is .003 parts by mass or more, preferably 0.1 parts by mass or less, more preferably 0.07 parts by mass or less, and further preferably 0.05 parts by mass or less.

The thermosetting urethane resin composition containing the main agent (i) containing the urethane prepolymer (A) having an isocyanate group and the ether-modified polysiloxane (B) and the curing agent (ii) is also included in the scope of the present invention. To.

The curing agent (ii) is a compound having a group having an active hydrogen atom (preferably an amino group) as a group capable of reacting with an isocyanate group, and is, for example, a polyaminochlorophenylmethane compound, a polyaminochlorophenylmethane compound and a polytetramethylene glycol. Examples thereof include 4,4'-diamino-3,3'-dichlorodiphenylmethane (MBOCA), which is a binuclear compound of a polyaminochlorophenylmethane compound. The reactive compound (C) is, for example, Pandex E (manufactured by DIC Corporation, 4,4'-diamino-3,3'-dichlorodiphenylmethane), Pandex E-50 (manufactured by DIC Corporation, polyaminochlorophenylmethane compound). Etc. can be obtained as commercial products. Among these, one or more selected from the group consisting of 4,4'-diamino-3,3'-dichlorodiphenylmethane, which is a dikaryon of a polyaminochlorophenylmethane compound and a polyaminochlorophenylmethane compound, is preferable.

The molar ratio (NH ₂ / OH) of the amino group of the curing agent (ii) to the isocyanate group of the main agent (i) is preferably 0.5 or more, more preferably 0.6 or more, still more preferably 0. It is 0.7 or more, preferably 1.5 or less, more preferably 1.3 or less, still more preferably 1.2 or less, and particularly preferably 1.0 or less.

The thermosetting urethane resin composition may further contain a catalyst. As the catalyst, one kind or two or more kinds can be used, for example, N, N-dimethylaminoethyl ether, Toyocat ET (trade name, manufactured by Toso Co., Ltd., N, N-dimethylaminoethyl ether). Amine-based catalysts such as triethylenediamine, dimethylethanolamine, triethanolamine, N, N, N', N'-tetramethylhexamethylenediamine, N-methylimidazole; and organic metal catalysts such as dioctyltin dilaurate can be mentioned.

The urethane resin composition and the thermosetting urethane resin composition are, if necessary, a leveling agent; a cross-linking agent such as an epoxy cross-linking agent; a plasticizer; a filler; a pigment; It may contain one or more additives such as dyes; stabilizers; flame retardants.

A urethane resin molded product can be produced by molding the thermosetting urethane resin composition, drying it if necessary, and then heat-curing it. Examples of the molding method include coating, injection into a mold, and the like. The drying may be at room temperature, natural drying, or heat drying. The heat drying is usually preferably performed at 40 ° C. or higher and 250 ° C. or lower for 30 minutes or longer and 2 hours or shorter. Further, as a secondary curing step, heat drying may be performed at a temperature of 40 ° C. or higher and 100 ° C. or lower for 8 hours or longer and 17 hours or lower.

The urethane resin molded body may have a sheet shape, a film shape, a columnar shape, a cylindrical shape, or the like, or may have a further molded shape.

The urethane resin molded body formed from the urethane resin composition or the thermosetting urethane resin composition of the present invention can suppress the generation of bubbles while improving the smoothness of the surface.

Hereinafter, the present invention will be described in more detail with reference to examples.

(Preparation of polyester oar (a1))
In a four-necked flask equipped with a nitrogen introduction tube, a thermometer, and a stirrer, 31.5 parts by mass of ethylene glycol, 68.5 parts by mass of adipic acid, and 0.06 parts of tetrabutyl titanate were charged, and the temperature was 220 ° C. under a nitrogen stream. The reaction was carried out for 24 hours to obtain a polyester polyol (a1) having an acid value of 0.12 and a hydroxyl value of 45.6.

(Preparation Examples 1 to 8, Comparative Preparation Examples 1 to 9: Preparation of main agents (i-1) to (i-17))
In a four-necked flask equipped with a nitrogen introduction tube, a thermometer, and a stirrer, 100 parts by mass of polyester polyol (a1) and toluene diisocyanate as aromatic polyisocyanate (a2) (“Coronate T80” manufactured by Tosoh Corporation) are shown. The mixture was mixed in the amount shown in 1 and stirred. The reaction was carried out at 80 ° C. under a nitrogen stream for 5 hours, and the isocyanate group equivalent was 1630 g / eq. Urethane prepolymer (1) was obtained.
The urethane prepolymer (1) and ether-modified polydimethylsiloxane (B) were mixed in the amounts shown in Table 1 to obtain main agents (i-1) to (i-17).

(Examples 1 to 8, Comparative Examples 1 to 9: Preparation of urethane resin composition)
The main agents (i-1) to (i-17) heated to 80 ° C. and 3,3'-dichloro-4,4'-diaminodiphenylmethane (hereinafter referred to as MBOCA) heated to 120 ° C. are added to the urethane. The prepolymer main agent and the curing agent were stirred and mixed so as to have a blending ratio of NH ₂ / NCO = 0.8 (functional group ratio), and vacuum degassed for 2 minutes using a suction bell. Then, it was poured into a drum rotary mold heated to 100 ° C. The molds were primarily cured at 100 ° C. for 1 hour and then secondarily cured at 110 ° C. for 16 hours to form 2 mm thick sheet-shaped urethane resin molded bodies (1) to (8) and comparative molded bodies (C1). ~ (C9) was obtained.

The number average molecular weights of the ether-modified polydimethylsiloxanes (b1) to (b5) used in the examples were as follows, and the molecular weight dispersion was as shown in Table 1.
Ether-modified polydimethylsiloxane (b1): 2,332
Ether-modified polydimethylsiloxane (b2): 1,990
Ether-modified polydimethylsiloxane (b3): 3,655
Ether-modified polydimethylsiloxane (b4): 3,482
Ether-modified polydimethylsiloxane (b5): 2,448

The number average molecular weight and the degree of molecular weight dispersion were measured by a gel permeation chromatography method (GPC method).
Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)
Columns: The following columns (all manufactured by Tosoh Corporation) were connected in series and used.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 This "TSKgel G2000" (7.8 mm ID x 30 cm) x 1 Detector: RI (Differential Refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection amount: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4% by mass)
Standard sample: A calibration curve was prepared using the following standard polystyrene.
(Standard polystyrene)
"TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation

The obtained sheet was evaluated for appearance and defoaming property. The evaluation results are shown in Tables 2 and 3.

[Appearance evaluation]
The surface of the sheet of 10 cm × 10 cm was visually confirmed, and the appearance was evaluated according to the following criteria.
◎ Number of dents is less than 2 ○ Number of dents is 2 or more and less than 4 △ Number of dents is 4 or more and less than 6 × Number of dents is 6 or more

[Evaluation of defoaming property]
MBOCA heated to 120 ° C. was added to the main agent heated to 80 ° C. so that NH ₂ / NCO became 0.8, and immediately stirred and mixed with a hand mixer for 1 minute, and then using a suction bell. The generation of air bubbles during vacuum degassing was visually observed, and the defoaming property was evaluated according to the following criteria.
◎ No bubbles are generated in less than 1 minute.
○ Bubbles disappear in 1 minute or more and less than 3 minutes △ Bubbles disappear in 3 minutes or more and less than 5 minutes.
× The generation of bubbles does not disappear even after 5 minutes or more.

Examples 1 to 8 are examples of the present invention, and both appearance and defoaming property can be achieved at the same time. On the other hand, Comparative Examples 1 to 3 did not contain ether-modified polysiloxane and were inferior in both appearance or appearance and defoaming property. Further, in Comparative Examples 4 to 6, the degree of molecular weight dispersion of the ether-modified polysiloxane was outside the range of the present invention, and the defoaming property was inferior. In Comparative Examples 7 to 9, the polysiloxane was not ether-modified and was inferior in appearance or defoaming property.

Claims (5)

A thermosetting urethane resin composition containing a urethane prepolymer (A) having an isocyanate group and an ether-modified polysiloxane (B).
The degree of molecular weight dispersion (weight average molecular weight / number average molecular weight) of the ether-modified polysiloxane (B) is 1.8 or more and 7 or less.
The isocyanate group equivalent of the urethane prepolymer (A) is 200 g / eq. More than 4000 g / eq. Is below
Further, the curing agent (ii) contains at least one selected from the group consisting of a polyaminochlorophenylmethane compound and a binuclear body of a polyaminochlorophenylmethane compound 4,4'-diamino-3,3'-dichlorodiphenylmethane. A thermosetting urethane resin composition characterized by. The thermosetting urethane resin composition according to claim 1, wherein the urethane prepolymer (A) having an isocyanate group is a reaction product of a polyol and an aromatic polyisocyanate. The thermosetting urethane resin according to claim 1 or 2 , wherein the content of the ether-modified polysiloxane (B) with respect to 100 parts by mass of the urethane prepolymer (A) is 0.001 part by mass or more and 0.1 part by mass or less. Composition. A molded product according to any one of claims 1 to 3, wherein the molded product is a cured product of the thermosetting urethane resin composition. The molded body according to claim 4 , which is an industrial member.