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

Abstract

The present invention is 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. As a result of the above, the present invention provides a polyorganosiloxane having a long-chain alkyl group and a thiourea group or urea group in a side chain represented by formula (1); and a method for producing the polyorganosiloxane. 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); Y is is a hydrogen atom or a group of formula (4) and the ratio of the group of formula (4) is 25% or more; and * represents a bond to the silicon atom. Z is a sulfur atom or an oxygen atom; Rb is a group selected from an alkyl group having 1-18 carbon atoms, an allyl group, an aryl group having 6-10 carbon atoms, and an aralkyl group having 7-10 carbon atoms; and * represents a bond to the nitrogen atom.

Description

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

[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.

[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 a metal, acrylic substrate, glass substrate, or PET substrate, 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-based resin substrate, a urethane-based resin substrate, a thiourethane-based substrate, or an episulfide-based 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.

[0007] JP 2014-031556 A JP 2020-196696 A JP 2010-30993 A

[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.

[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 has a weight average molecular weight in terms of polystyrene of 1,000 to 30,000. (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. (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.) (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.) (In formula (4), * indicates bonding to a nitrogen atom, Z is independently a sulfur atom or an oxygen atom, and R ｂare 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, the method for producing the polyorganosiloxane further 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): (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. (In formula (6), * indicates bonding to a silicon atom.) (In formula (7), * indicates bonding to a silicon atom.) (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): (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. (In formula (10), * indicates bonding to a silicon atom.) (In formula (11), * indicates bonding to a silicon atom.) (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.

[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.

[0018] The polyorganosiloxane synthesized in Example 1 having a long-chain alkyl group and a thiourea moiety on the side chain １ 1 is a H-NMR spectrum chart.

[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. (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. (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.) (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.) (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 a Urea Group in the Side Chain] The present invention is 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 polystyrene-equivalent weight average molecular weight of 1,000 to 30,000.

[0024] 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 alkyl groups having 1 to 10 carbon atoms include alkyl groups such as methyl, ethyl, propyl, butyl, and octyl; and cycloalkyl groups such as cyclopentyl and cyclohexyl.

[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, 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 chain length of the long-chain alkyl contained, the poorer the compatibility with mineral oils becomes, and the longer the alkyl chain length, the more difficult it becomes to obtain the raw materials involved in 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). However, in both formulas (2) and (3), the proportion of groups represented by formula (4) is 25% or more, preferably 50% or more. The upper limit of these proportions is not particularly limited, but is about 100% in both formulas (2) and (3).

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

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

[0034] (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 group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, hexyl group, heptyl group, n-octyl group, dodecyl group, and octadecyl group; and cycloalkyl groups such as cyclopentyl group and cyclohexyl group.

[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 polystyrene-equivalent weight average molecular weight of the polyorganosiloxane having a long-chain alkyl group and a thiourea group or urea group in the side chain is 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 obtained by GPC (gel permeation chromatography) analysis using polystyrene as a standard substance under the following conditions: [Measurement conditions] Developing solvent: tetrahydrofuran (THF) Flow rate: 0.6 mL / min Detector: differential refractive index detector (RI) Column: TSK Guard column Super H-H TSKgel Super HM-N (6.0 mm I.D. × 15 cm × 1) TSKgel Super H2500 (6.0 mm I.D. × 15 cm × 1) (all manufactured by Tosoh Corporation) Column temperature: 40°C Sample injection volume: 50 μL (THF solution with a concentration of 0.3% by mass)

[0043] [Method for producing polyorganosiloxane] In the present invention, the method for producing a polyorganosiloxane having a long-chain alkyl group and a thiourea group or urea group on the side chain comprises 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 produces 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] (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.

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

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

[0047] (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, represented by the above formula (5), is reacted with isocyanate (B) represented by the following formula (12), a polyorganosiloxane having a urea group on the side chain, represented by the above formula (1), in which Z in formula (4) is an oxygen atom, is obtained.

[0050] (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 (thio)urea catalyst can be used.

[0054] Examples of the (thio)urea catalyst 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, and 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.

[0059] The present invention will be explained in more detail below by showing 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 400 MHz (manufactured by BRUKER). ２９Si-NMR was measured using a JNM-ECX 500II 500 MHz (manufactured by JEOL Ltd.) using deuterated chloroform as a solvent and TMS (tetramethylsilane) as a reference substance. In the following formula, n-Bu represents an n-butyl group.

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

[0063] The organopolysiloxane obtained in Example 1 is １ The H-NMR spectrum is shown (see Figure 1). １ H-NMR (400MHz, CDCl ３ ): δ -0.15 to 0.24 (m, 648H), 0.41 to 0.55 (m, 20H), 0.78 to 0.99 (m, 20H), 1.11 to 1.74 (m, 214H), 3.28 to 3.49 (m, 4H)

[0064] [Example 2] Synthesis was carried out in the same manner as in Example 1, except that 2.3 g (20.2 mmol) of cyclohexyl isocyanate was added to 200 g (20.2 mmol) of the polyorganosiloxane represented by the above formula (a). 202 g of 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.

[0066] The organopolysiloxane obtained in Example 2 is １ The H-NMR spectrum is shown. １ H-NMR (400MHz, CDCl ３ ): δ -0.17 to 0.24 (m, 648H), 0.41 to 0.56 (m, 20H), 0.78 to 0.95 (m, 20H), 1.03 to 1.97 (m, 217H), 3.12 (t, J = 7.1Hz, 2H), 3.43 to 3.54 (m, 1H)

[0067] [Example 3] Synthesis was carried out in the same manner as in Example 1, except that 200 g (19.0 mmol) of polyorganosiloxane represented by the following formula (d) and 2.2 g (19.0 mmol) of n-butyl isothiocyanate were used. 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.

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

[0070] Example 4 Synthesis was carried out in the same manner as in Example 1, except that 200 g (20.2 mmol) of polyorganosiloxane represented by the following formula (f) and 2.2 g (20.2 mmol) of n-butyl isothiocyanate were used. 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.

[0072] The organopolysiloxane obtained in Example 4 is １ The H-NMR spectrum is shown. １ H-NMR (400MHz, CDCl ３ ):δ -0.16 to 0.23 (m, 468.8H), 0.41 to 0.55 (m, 20.5H), 0.78 to 0.97 (m, 20.5H), 1.10 to 1.78 (m, 214H), 2.62 (t, J = 7.0Hz, 0.5H), 3.28 to 3.49 (m, 4H)

[0073] [Example 5] Synthesis was carried out in the same manner as in Example 1, except that 200 g (20.2 mmol) of polyorganosiloxane represented by the following formula (h) and 4.7 g (40.3 mmol) of n-butyl isothiocyanate were used. 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.

[0075] The organopolysiloxane obtained in Example 5 is shown below. １ The H-NMR spectrum is shown. １H-NMR (400MHz, CDCl ３ ): δ -0.17 to 0.25 (m, 648H), 0.42 to 0.57 (m, 20H), 0.80 to 0.99 (m, 20H), 1.12 to 1.79 (m, 221H), 3.22 to 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. (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. (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.) (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.) (In formula (4), * indicates bonding to a nitrogen atom, Z is independently a sulfur atom or an oxygen atom, and R ｂare independently 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], characterized in that Z in the above formula (4) is a sulfur atom. [3]: The polyorganosiloxane according to [1], characterized in that Z in the above formula (4) is an oxygen atom. [4]: ​​A method for producing the polyorganosiloxane according to [1] or [2], comprising adding 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): (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. (In formula (6), * indicates bonding to a silicon atom.) (In formula (7), * indicates bonding to a silicon atom.) (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 a 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 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): (In formula (9), R and R ａ is the same as above, and X ２are 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. (In formula (10), * indicates bonding to a silicon atom.) (In formula (11), * indicates bonding to a silicon atom.) (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. (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. (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.) (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.) (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): (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. (In formula (6), * indicates bonding to a silicon atom.) (In formula (7), * indicates bonding to a silicon atom.) (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): (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. (In formula (10), * indicates bonding to a silicon atom.) (In formula (11), * indicates bonding to a silicon atom.) (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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