Polyorganosiloxane having long-chain alkyl group and thiourea group or urea group in side chain, and method for producing the same

Abstract

To provide a polyorganosiloxane having a long-chain alkyl group and a thiourea group or urea group in a side chain, and a method for producing the polyorganosiloxane.SOLUTION: There are provided a polyorganosiloxane represented by formula (1), having a long-chain alkyl group and a thiourea group or a urea group in a side chain, and having a polystyrene-converted molecular weight of 1,000-30,000, and a method for producing the same. R is a group selected from an alkyl group, an aryl group, and an aralkyl group; Ra is a linear or branched alkyl group having 3-20 carbon atoms; X1 is a group represented by formula (2) or (3); and Y is a hydrogen atom or the like.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a polyorganosiloxane having a long-chain alkyl group and a thiourea group or urea group in the side chain, and a method for producing the same. [Background technology]

[0002] In general, polyorganosiloxanes having long-chain alkyl groups have mineral oil compatibility, mold releasability, paintability, water repellency, surface slipperiness, etc. Taking advantage of these properties, they are widely used industrially as mold release agents, lubricants, water repellents, fiber treatment agents, etc.

[0003] However, when applying a polyorganosiloxane having a long-chain alkyl group to a substrate, there are cases where a higher level of adhesion to the substrate than conventional methods is required.

[0004] On the other hand, it has been reported that when a coating agent containing a silane coupling agent having a thiourea group is applied to metal, acrylic substrates, glass substrates, and PET substrates, the resulting coating exhibits good rust prevention properties and substrate adhesion (Patent Documents 1 and 2).

[0005] It has also been reported that when a coating agent containing a silane coupling agent having a urea group is applied to an allyl diglycol carbonate resin substrate, a urethane resin substrate, a thiourethane resin substrate, or an episulfide resin substrate, the resulting coating exhibits sufficient film hardness and substrate adhesion (Patent Document 3).

[0006] The high adhesion of the coating to the substrate reported in the above patent is presumably due to hydrogen bonds formed by the thiourea and urea groups. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-031556 [Patent Document 2] Japanese Patent Application Publication No. 2020-196696 [Patent Document 3] Japanese Patent Application Laid-Open No. 2010-30993 Summary of the Invention [Problem to be solved by the invention]

[0008] For this reason, polyorganosiloxanes having a long-chain alkyl group and a thiourea group or urea group in the side chain are expected to have higher adhesion than long-chain alkyl group-modified polyorganosiloxanes not having a thiourea group or urea group. However, polyorganosiloxanes having a long-chain alkyl group and a thiourea group or urea group in the side chain are not known.

[0009] The present invention has been made to solve the above problems, and an object of the present invention is to provide a polyorganosiloxane having a long-chain alkyl group and a thiourea group or urea group in a side chain, and a method for producing the same. [Means for solving the problem]

[0010] In order to solve the above problems, the present invention provides a compound represented by the following formula (1) having a long-chain alkyl group (R a ), and a thiourea group or a urea group, and a polystyrene-equivalent weight-average molecular weight of 1,000 to 30,000. [ka] (In formula (1), R is independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; R a are independently a linear or branched alkyl group having 3 to 20 carbon atoms, and X 1are independently a group represented by the following formula (2) or (3), where p is a number from 10 to 300, q is a number from 3 to 20, and r is a number from 0.1 to 5. The bonding order of the siloxane units bounded by p, q, and r may be block or random. [ka] (In formula (2), * indicates bonding to a silicon atom, and Y is independently a hydrogen atom or a group represented by formula (4) below, with the proviso that the proportion of groups represented by formula (4) below is 25% or more.) [ka] (In formula (3), * indicates bonding to a silicon atom, and Y is independently a hydrogen atom or a group represented by the following formula (4), with the proviso that the proportion of groups represented by the following formula (4) is 25% or more.) [ka] (In formula (4), * indicates bonding to a nitrogen atom, Z is independently a sulfur atom or an oxygen atom, and R b are independently a group selected from an alkyl group having 1 to 18 carbon atoms, an allyl group, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms.

[0011] Furthermore, the present invention provides a polyorganosiloxane characterized in that Z in the above formula (4) is a sulfur atom.

[0012] Furthermore, the present invention provides a polyorganosiloxane characterized in that Z in the above formula (4) is an oxygen atom.

[0013] The above-described polyorganosiloxane has a long-chain alkyl group and a thiourea group or urea group sufficient to have high adhesion in the side chain, and therefore has higher adhesion than a long-chain alkyl group-modified polyorganosiloxane that does not have a thiourea group or urea group.

[0014] In addition, in the present invention, there is provided a method for producing the polyorganosiloxane, which comprises: a The present invention provides a method for producing a polyorganosiloxane having a long-chain alkyl group and a thiourea group in its side chain, which method comprises reacting a polyorganosiloxane (A) having a long-chain alkyl group and an amino group with an isothiocyanate (B) represented by the following formula (8): [ka] (In formula (5), R and R a is the same as above, and X 2 are independently a group represented by the following formula (6) or (7), and p, q, and r are the same as above. The bonding order of the siloxane units bounded by p, q, and r may be block or random. [ka] (In formula (6), * indicates bonding to a silicon atom.) [ka] (In formula (7), * indicates bonding to a silicon atom.) [ka] (In formula (8), R b is a group selected from an alkyl group having 1 to 18 carbon atoms, an allyl group, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms.

[0015] In addition, in the present invention, the method for producing the polyorganosiloxane further comprises adding a long-chain alkyl group (R a The present invention provides a method for producing a polyorganosiloxane having a long-chain alkyl group and a urea group in its side chain, which method comprises reacting a polyorganosiloxane (A) having a long-chain alkyl group and an amino group with an isocyanate (B) represented by the following formula (12): [ka] (In formula (9), R and R a is the same as above, and X 2 are independently a group represented by the following formula (10) or (11), and p, q, and r are the same as above. The bonding order of the siloxane units bounded by p, q, and r may be block or random. [ka] (In formula (10), * indicates bonding to a silicon atom.) [ka] (In formula (11), * indicates bonding to a silicon atom.) [ka] (In formula (12), R b is a group selected from an alkyl group having 1 to 18 carbon atoms, an allyl group, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms.

[0016] This production method makes it possible to introduce sufficient thiourea or urea groups into polyorganosiloxane that has been co-modified with many long-chain alkyl groups to provide high adhesion. [Effects of the Invention]

[0017] As described above, according to the present invention, a thiourea group or a urea group can be introduced into a polyorganosiloxane co-modified with a large number of long-chain alkyl groups, and this can be expected to have higher adhesion than a long-chain alkyl group-modified polyorganosiloxane that does not have a thiourea group or a urea group. [Brief explanation of the drawings]

[0018] [Figure 1] 1 is a 1H-NMR spectrum chart of polyorganosiloxane having a long-chain alkyl group and a thiourea moiety on the side chain, synthesized in Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0019] As described above, there has been a need for the development of a polyorganosiloxane having a long-chain alkyl group and a thiourea group or urea group in the side chain, and a method for producing the same.

[0020] As a result of intensive research to solve the above problems, the present inventors have found that thiourea groups or urea groups can be introduced into polyorganosiloxanes that have been co-modified with many long-chain alkyl groups, and have completed the present invention.

[0021] That is, the present invention provides a compound represented by the following formula (1) having a long-chain alkyl group (R a The present invention relates to a polyorganosiloxane characterized by having a thiourea group or a urea group and a weight average molecular weight in terms of polystyrene of 1,000 to 30,000, and a method for producing the same. [ka] (In formula (1), R is independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; R a are independently a linear or branched alkyl group having 3 to 20 carbon atoms, and X 1 are independently a group represented by the following formula (2) or (3), where p is a number from 10 to 300, q is a number from 3 to 20, and r is a number from 0.1 to 5. The bonding order of the siloxane units bounded by p, q, and r may be block or random. [ka] (In formula (2), * indicates bonding to a silicon atom, and Y is independently a hydrogen atom or a group represented by formula (4) below, with the proviso that the proportion of groups represented by formula (4) below is 25% or more.) [ka] (In formula (3), * indicates bonding to a silicon atom, and Y is independently a hydrogen atom or a group represented by the following formula (4), with the proviso that the proportion of groups represented by the following formula (4) is 25% or more.) [ka] (In formula (4), * indicates bonding to a nitrogen atom, Z is independently a sulfur atom or an oxygen atom, and R b are independently a group selected from an alkyl group having 1 to 18 carbon atoms, an allyl group, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms.

[0022] The present invention will be described in detail below, but the present invention is not limited thereto.

[0023] [Polyorganosiloxane having a long-chain alkyl group and a thiourea group or urea group in the side chain] The present invention relates to a polyorganosiloxane represented by the following formula (1), which has a long-chain alkyl group and a thiourea group or a urea group in the side chain and has a weight average molecular weight in terms of polystyrene of 1,000 to 30,000.

[0024] [ka] In the above formula (1), p is a number from 10 to 300, and preferably a number from 50 to 150. q is a number from 3 to 20, and preferably a number from 8 to 15. r is a number from 0.1 to 5, and preferably a number from 0.5 to 4. The bonding order of the siloxane units bounded by p, q, and r may be block or random.

[0025] In the above formula (1), R is independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms.

[0026] Examples of the alkyl group having 1 to 10 carbon atoms include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, and an octyl group; and cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group.

[0027] Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a p-toluyl group, and a p-ethylphenyl group.

[0028] Examples of the aralkyl group having 7 to 10 carbon atoms include a phenylmethyl group and a 2-phenylethyl group. R is preferably a methyl group or a phenyl group, and more preferably a methyl group.

[0029] In the above formula (1), R a are independently a straight-chain or branched alkyl group having 3 to 20 carbon atoms, and preferably a straight-chain or branched alkyl group having 8 to 18 carbon atoms.

[0030] Examples of the alkyl group include 1-octyl, 2-methyl-1-heptyl, 1-decyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl, and 1-octadecyl. The shorter the alkyl chain length, the poorer the compatibility with mineral oils. The longer the alkyl chain length, the more difficult it is to obtain the raw materials required for production. Therefore, R a is preferably a 1-dodecyl group, a 1-tetradecyl group or a 1-hexadecyl group.

[0031] In the above formula (1), X 1 are independently a group represented by the following formula (2) or (3). In formulas (2) and (3), Y is independently a hydrogen atom or a group represented by the following formula (4). In both formulas (2) and (3), the proportion of groups represented by formula (4) is 25% or more, and preferably 50% or more.

[0032] [ka] (In formula (2), * indicates bonding to a silicon atom.)

[0033] [ka] (In formula (3), * indicates bonding to a silicon atom.)

[0034] [ka] (In formula (4), * indicates bonding to a nitrogen atom.)

[0035] In the above formula (4), Z is independently a sulfur atom or an oxygen atom. b are independently a group selected from an alkyl group having 1 to 18 carbon atoms, an aryl group, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms.

[0036] Examples of alkyl groups having 1 to 18 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, hexyl, heptyl, n-octyl, dodecyl, and octadecyl; and cycloalkyl groups such as cyclopentyl and cyclohexyl.

[0037] Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a p-toluyl group, and a p-ethylphenyl group.

[0038] Examples of the aralkyl group having 7 to 10 carbon atoms include a benzyl group and a 2-phenylethyl group.

[0039] When Z is a sulfur atom, R b is preferably an isopropyl group, an n-butyl group, an isobutyl group, an n-octyl group, or a cyclohexyl group.

[0040] When Z is an oxygen atom, R b is preferably an isopropyl group, an n-butyl group, a hexyl group, a dodecyl group, or a cyclohexyl group.

[0041] In the present invention, the polyorganosiloxane having a long-chain alkyl group and a thiourea group or urea group in the side chain has a polystyrene-equivalent weight average molecular weight of 1,000 to 30,000, preferably 2,000 to 20,000, and more preferably 3,000 to 15,000.

[0042] In the present invention, the weight average molecular weight is a value determined by GPC (gel permeation chromatography) analysis using polystyrene as a standard substance under the following conditions. [Measurement conditions] Developing solvent: tetrahydrofuran (THF) Flow rate: 0.6mL / min Detector: Refractive index detector (RI) Column: TSK Guardcolumn SuperH-H TSKgel SuperHM-N(6.0mmI.D.×15cm×1) TSKgel SuperH2500(6.0mmI.D.×15cm×1) (All manufactured by Tosoh Corporation) Column temperature: 40℃ Sample injection volume: 50 μL (0.3% by mass THF solution)

[0043] [Method for producing polyorganosiloxane] The method for producing a polyorganosiloxane having a long-chain alkyl group and a thiourea group or urea group on the side chain in the present invention involves reacting a polyorganosiloxane (A) having a long-chain alkyl group and an amino group on the side chain, as shown in the following formula (5), with an isothiocyanate (B) shown in the following formula (8). This results in a polyorganosiloxane having a thiourea group on the side chain, as shown in the above formula (1), in which Z in formula (4) is a sulfur atom.

[0044] [ka] (In formula (5), R and R a is the same as above, and X 2are independently a group represented by the following formula (6) or (7), and p, q, and r are the same as above. The bonding order of the siloxane units bounded by p, q, and r may be block or random.

[0045] [ka] (In formula (6), * indicates bonding to a silicon atom.)

[0046] [ka] (In formula (7), * indicates bonding to a silicon atom.)

[0047] [ka] (In formula (8), R b is a group selected from an alkyl group having 1 to 18 carbon atoms, an allyl group, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms.

[0048] Examples of the isothiocyanate represented by the above formula (8) include methyl isothiocyanate, ethyl isothiocyanate, allyl isothiocyanate, 1-propyl isothiocyanate, isopropyl isothiocyanate, n-butyl isothiocyanate, isobutyl isothiocyanate, s-butyl isothiocyanate, cyclohexyl isothiocyanate, n-octyl isothiocyanate, phenyl isothiocyanate, p-toluyl isothiocyanate, and benzyl isothiocyanate. Preferred are isopropyl isothiocyanate, n-butyl isothiocyanate, isobutyl isothiocyanate, n-octyl isothiocyanate, and cyclohexyl isothiocyanate.

[0049] When polyorganosiloxane (A) having a long-chain alkyl group and an amino group on the side chain, as shown in the above formula (5), is reacted with isocyanate (B) shown in the following formula (12), polyorganosiloxane having a urea group on the side chain, as shown in the above formula (1), in which Z in formula (4) is an oxygen atom, is obtained.

[0050] [ka] (In formula (12), R b is a group selected from an alkyl group having 1 to 18 carbon atoms, an allyl group, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms.

[0051] Examples of the isocyanate represented by the above formula (12) include methyl isocyanate, ethyl isocyanate, 1-propyl isocyanate, isopropyl isocyanate, n-butyl isocyanate, t-butyl isocyanate, hexyl isocyanate, heptyl isocyanate, dodecyl isocyanate, octadecyl isocyanate, cyclopentyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, p-toluyl isocyanate, p-ethylphenyl isocyanate, benzyl isocyanate, and 2-phenylethyl isocyanate. Preferred are isopropyl isocyanate, n-butyl isocyanate, hexyl isocyanate, dodecyl isocyanate, and cyclohexyl isocyanate.

[0052] In the production method of the present invention, the ratio of the number of moles of the isothiocyanate of the formula (8) or the isocyanate of the formula (12) to the total number of moles of the amino groups in the formula (5) is preferably 0.25 to 1.0 times, more preferably 0.50 to 1.0 times.

[0053] The catalyst used in the production method of the present invention is not particularly limited. It is preferable to carry out the production method without a catalyst, but a catalyst can also be used. As the catalyst used, a known urethanization catalyst can be used.

[0054] Examples of urethanization catalysts include tertiary amines such as triethylamine and 1,4-diazabicyclo[2.2.2]octane; and organometallic compounds such as iron(III) acetylacetonate, dibutyltin dilaurate, dioctyltin dilaurate, bismuth 2-ethylhexanoate, bismuth n-octanoate, tetrabutyl orthotitanate, titanium diisopropoxide bis(acetylacetonate), zirconium tetrabutoxide, and zirconium tetraacetylacetonate.

[0055] In the production method of the present invention, the reaction conditions such as the reaction temperature, reaction time, and solvent to be used are not particularly limited.

[0056] The reaction temperature is preferably 25°C or higher and 90°C or lower, more preferably 50°C or higher and 70°C or lower.

[0057] The reaction time is preferably 1 to 24 hours, more preferably 1 to 12 hours, and most preferably 2 to 6 hours.

[0058] Although it is preferable to carry out the reaction without using a solvent, a solvent can also be used. Examples of the solvent include aprotic solvents such as hydrocarbon solvents such as hexane, and aromatic hydrocarbon solvents such as toluene and xylene. [Example]

[0059] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0060] As described in the examples 1 H-NMR was performed using an AVANCE-III 400MHz (BRUKER). 29 Si-NMR was measured using a JNM-ECX 500II 500MHz (manufactured by JEOL Ltd.) using deuterated chloroform as a solvent and TMS (tetramethylsilane) as a reference substance. In the following formula, n-Bu refers to an n-butyl group.

[0061] [Example 1] A separable flask equipped with a thermometer, stirrer, and reflux condenser was charged with 200 g (20.2 mmol) of polyorganosiloxane having a long-chain alkyl group and an amino group on the side chain, as shown in the following formula (a), and 2.3 g (20.2 mmol) of n-butyl isothiocyanate, and the mixture was heated and stirred at 60°C for 6 hours. 202 g of polyorganosiloxane having a long-chain alkyl group and a thiourea moiety on the side chain, as shown in the following formula (b), was obtained.

[0062] The structure of the product is as follows: 1 H-NMR spectrum, and 29 This was estimated from the Si-NMR spectrum that the ratio of silicon atoms forming bonds with one oxygen atom to silicon atoms forming bonds with two oxygen atoms was 2:110. [ka] [ka]

[0063] The organopolysiloxane obtained in Example 1 is 1 The H-NMR spectrum is shown (see Figure 1). 1 H-NMR (400MHz, CDCl3): δ -0.15~0.24(m,648H), 0.41~0.55(m,20H), 0.78~0.99(m,20H), 1.11~1.74(m,214H), 3.28~3.49(m,4H)

[0064] [Example 2] Except for adding 2.3 g (20.2 mmol) of cyclohexyl isocyanate to 200 g (20.2 mmol) of the polyorganosiloxane represented by the above formula (a), synthesis was carried out in the same manner as in Example 1. 202 g of the polyorganosiloxane represented by the following formula (c) was obtained.

[0065] The structure of the product is as follows: 1 H-NMR spectrum, and 29This was estimated from the Si-NMR spectrum that the ratio of silicon atoms forming bonds with one oxygen atom to silicon atoms forming bonds with two oxygen atoms was 2:110. [ka]

[0066] The organopolysiloxane obtained in Example 2 is shown below. 1 The H-NMR spectrum is shown. 1 H-NMR(400MHz, CDCl3):δ -0.17~0.24(m,648H), 0.41~0.56(m,20H), 0.78~0.95(m,20H), 1.03~1.97(m,217H), 3.12(t, J=7.1Hz,2H), 3.43~3.54(m,1H)

[0067] [Example 3] Except for using 200 g (19.0 mmol) of polyorganosiloxane represented by the following formula (d) and 2.2 g (19.0 mmol) of n-butyl isothiocyanate, synthesis was carried out in the same manner as in Example 1. 202 g of polyorganosiloxane represented by the following formula (e) was obtained.

[0068] The structure of the product is as follows: 1 H-NMR spectrum, and 29 This was estimated from the Si-NMR spectrum that the ratio of silicon atoms forming bonds with one oxygen atom to silicon atoms forming bonds with two oxygen atoms was 2:110.25. [ka] [ka]

[0069] The organopolysiloxane obtained in Example 3 is shown below. 1 The H-NMR spectrum is shown. 1H-NMR(400MHz, CDCl3):δ -0.16~0.25(m,648.8H), 0.40~0.55(m,20.5H), 0.79~0.98(m,20.5H), 1.05~1.71(m,304H), 2.64(t,J=7.0Hz,0.5H), 3.27~3.49(m,4H)

[0070] [Example 4] Except for using 200 g (20.2 mmol) of polyorganosiloxane represented by the following formula (f) and 2.2 g (20.2 mmol) of n-butyl isothiocyanate, synthesis was carried out in the same manner as in Example 1. 202 g of polyorganosiloxane represented by the following formula (g) was obtained.

[0071] The structure of the product is as follows: 1 H-NMR spectrum, and 29 This was estimated from the Si-NMR spectrum that the ratio of silicon atoms forming bonds with one oxygen atom to silicon atoms forming bonds with two oxygen atoms was 2:80.25. [ka] [ka]

[0072] The organopolysiloxane obtained in Example 4 is shown below. 1 The H-NMR spectrum is shown. 1 H-NMR(400MHz, CDCl3):δ -0.16~0.23(m,468.8H), 0.41~0.55(m,20.5H), 0.78~0.97(m,20.5H), 1.10~1.78(m,214H), 2.62(t,J=7.0Hz,0.5H), 3.28~3.49(m,4H)

[0073] [Example 5] Except for using 200 g (20.2 mmol) of polyorganosiloxane represented by the following formula (h) and 4.7 g (40.3 mmol) of n-butyl isothiocyanate, synthesis was carried out in the same manner as in Example 1. 205 g of polyorganosiloxane represented by the following formula (i) was obtained.

[0074] The structure of the product is as follows: 1 H-NMR spectrum, and 29 This was estimated from the Si-NMR spectrum that the ratio of silicon atoms forming bonds with one oxygen atom to silicon atoms forming bonds with two oxygen atoms was 2:110. [ka] [ka]

[0075] The organopolysiloxane obtained in Example 5 is shown below. 1 The H-NMR spectrum is shown. 1 H-NMR (400MHz, CDCl3): δ -0.17~0.25(m,648H), 0.42~0.57(m,20H), 0.80~0.99(m,20H), 1.12~1.79(m,221H), 3.22~3.55(m,10H)

[0076] This specification includes the following inventions.

[0077] [1]: A compound represented by the following formula (1), having a long-chain alkyl group (R a ) and a polyorganosiloxane having a thiourea group or a urea group and a weight average molecular weight in terms of polystyrene of 1,000 to 30,000. [ka] (In formula (1), R is independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; Ra are independently a linear or branched alkyl group having 3 to 20 carbon atoms, and X 1 are independently a group represented by the following formula (2) or (3), where p is a number from 10 to 300, q is a number from 3 to 20, and r is a number from 0.1 to 5. The bonding order of the siloxane units bounded by p, q, and r may be block or random. [ka] (In formula (2), * indicates bonding to a silicon atom, and Y is independently a hydrogen atom or a group represented by formula (4) below, with the proviso that the proportion of groups represented by formula (4) below is 25% or more.) [ka] (In formula (3), * indicates bonding to a silicon atom, and Y is independently a hydrogen atom or a group represented by the following formula (4), with the proviso that the proportion of groups represented by the following formula (4) is 25% or more.) [ka] (In formula (4), * indicates bonding to a nitrogen atom, Z is independently a sulfur atom or an oxygen atom, and R b are independently a group selected from an alkyl group having 1 to 18 carbon atoms, an allyl group, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. [2]: The polyorganosiloxane according to [1], wherein Z in the above formula (4) is a sulfur atom. [3]: The polyorganosiloxane according to [1], wherein Z in the above formula (4) is an oxygen atom. [4]: A method for producing the polyorganosiloxane according to [1] or [2], wherein the polyorganosiloxane has a long-chain alkyl group (R a A method for producing a polyorganosiloxane having a long-chain alkyl group and a thiourea group in its side chain, comprising reacting a polyorganosiloxane (A) having a long-chain alkyl group and an amino group with an isothiocyanate (B) represented by the following formula (8): [ka] (In formula (5), R and R a is the same as above, and X 2 are independently a group represented by the following formula (6) or (7), and p, q, and r are the same as above. The bonding order of the siloxane units bounded by p, q, and r may be block or random. [ka] (In formula (6), * indicates bonding to a silicon atom.) [ka] (In formula (7), * indicates bonding to a silicon atom.) [ka] (In formula (8), R b is a group selected from an alkyl group having 1 to 18 carbon atoms, an allyl group, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. [5]: A method for producing the polyorganosiloxane according to [1] or [3], wherein the polyorganosiloxane has a long-chain alkyl group (R a A method for producing a polyorganosiloxane having a long-chain alkyl group and a urea group in its side chain, comprising reacting a polyorganosiloxane (A) having an alkyl group and an amino group with an isocyanate (B) represented by the following formula (12): [ka] (In formula (9), R and R a is the same as above, and X 2 are independently a group represented by the following formula (10) or (11), and p, q, and r are the same as above. The bonding order of the siloxane units bounded by p, q, and r may be block or random. [ka] (In formula (10), * indicates bonding to a silicon atom.) [ka] (In formula (11), * indicates bonding to a silicon atom.) [ka] (In formula (12), R b is a group selected from an alkyl group having 1 to 18 carbon atoms, an allyl group, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms.

[0078] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits similar effects is included within the technical scope of the present invention.

Claims

1. A compound represented by the following formula (1) having a long-chain alkyl group (R ａ ), and a polyorganosiloxane having a thiourea group or a urea group and a weight average molecular weight in terms of polystyrene of 1,000 to 30,000. 【Chemical 1】 (In formula (1), R is independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; R ａ are independently a linear or branched alkyl group having 3 to 20 carbon atoms, and X １ are independently a group represented by the following formula (2) or (3), where p is a number from 10 to 300, q is a number from 3 to 20, and r is a number from 0.1 to 5. The bonding order of the siloxane units bounded by p, q, and r may be block or random. 【Chemistry 2】 (In formula (2), * indicates bonding to a silicon atom, and Y's are independently hydrogen atoms or groups represented by the following formula (4), with the proviso that the proportion of groups represented by the following formula (4) is 25% or more.) 【Chemistry 3】 (In formula (3), * indicates bonding to a silicon atom, and Y's are independently hydrogen atoms or groups represented by the following formula (4), with the proviso that the proportion of groups represented by the following formula (4) is 25% or more.) 【Chemistry 4】 (In formula (4), * indicates bonding to a nitrogen atom, Z is independently a sulfur atom or an oxygen atom, and R ｂ are independently a group selected from an alkyl group having 1 to 18 carbon atoms, an allyl group, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms.

2. The polyorganosiloxane according to claim 1, wherein Z in the formula (4) is a sulfur atom.

3. The polyorganosiloxane according to claim 1, wherein Z in the formula (4) is an oxygen atom.

4. The method for producing polyorganosiloxane according to claim 1, wherein the polyorganosiloxane has a long-chain alkyl group (R ａ A method for producing a polyorganosiloxane having a long-chain alkyl group and a thiourea group in a side chain, comprising reacting a polyorganosiloxane (A) having an alkyl group and an amino group with an isothiocyanate (B) represented by the following formula (8): 【Chemistry 5】 (In formula (5), R and R ａ is the same as above, and X ２ are independently a group represented by the following formula (6) or (7), and p, q, and r are the same as above. The bonding order of the siloxane units bounded by p, q, and r may be block or random. 【Chemistry 6】 (In formula (6), * indicates bonding to a silicon atom.) 【Chemistry 7】 (In formula (7), * indicates bonding to a silicon atom.) 【Chemistry 8】 (In formula (8), R ｂ is a group selected from an alkyl group having 1 to 18 carbon atoms, an allyl group, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms.

5. The method for producing polyorganosiloxane according to claim 1, wherein the polyorganosiloxane has a long-chain alkyl group (R ａ A method for producing a polyorganosiloxane having a long-chain alkyl group and a urea group in a side chain, comprising reacting a polyorganosiloxane (A) having an alkyl group and an amino group with an isocyanate (B) represented by the following formula (12): 【Chemistry 9】 (In formula (9), R and R ａ is the same as above, and X ２ are independently a group represented by the following formula (10) or (11), and p, q, and r are the same as above. The bonding order of the siloxane units bounded by p, q, and r may be block or random. 【Chemistry 10】 (In formula (10), * indicates bonding to a silicon atom.) 【Chemistry 11】 (In formula (11), * indicates bonding to a silicon atom.) 【Chemistry 12】 (In formula (12), R ｂ is a group selected from an alkyl group having 1 to 18 carbon atoms, an allyl group, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms.

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