Novel co-modified silicone, co-modified silicone composition containing same, liquid detergent containing same, and method for producing same

Abstract

[Problem] To provide a co-modified silicone, and the like, having, in a molecule, an amino / amide / two types of polyether groups, and being highly useful as a liquid detergent raw material that has stable quality, can be obtained at high purity, and is able to maintain low viscosity. [Solution] Provided are a co-modified silicone compound and a composition thereof, said co-modified silicone compound being represented by the following average structural formula: (1) MDpD(AM) qD(AMD) rD(PE1) sD(PE2) wMOR'Tx [In the formula, M is an R3SiO1 / 2 unit, D(AM) is an RR1SiO unit, D(AMD) is an RR2SiO unit, D(PE1) is an RR3SiO unit, D(PE2) is an RR8SiO unit, MOR' is an R2(OR')SiO1 / 2 unit, 50 ≤ p + q + r + s + w ≤ 160, x is 0-1, the molar ratio M:MOR' is 1.7:0.3-1.2:0.8, R is an alkyl group, R1 is an aminoalkyl group, R2 is a group represented by -R4-NHCO-(CH2)b-O(C2H4O)c-R5, R3 is a first polyether group, R8 is a second polyether group, and when the total number of moles of M and MOR' is established at 2.0, the total number of moles of carboxylate groups and acyloxy groups in a molecule is 1.0 or less.]

Description

Novel co-modified silicone, co-modified silicone composition containing same, liquid detergent containing same, and method for producing same

[0001] The present invention relates to a novel co-modified silicone containing a high-purity amino / amide / two different polyether groups, which exhibits excellent viscosity and appearance stability; a co-modified silicone composition containing the same; a liquid detergent containing the same; and a method for producing the co-modified silicone and its composition. When incorporated into liquid detergents with a particularly clear appearance, the silicone does not significantly impair the detergent's transparency, making it suitable for use as a fabric softener, fabric lubricant, texture-improving component, or fabric surface coating component. Furthermore, the composition has a low viscosity, making it easy to handle when producing clear liquid detergents. Additionally, because the co-modified silicone and its composition according to the present invention are highly pure and contain few impurities derived from raw materials, the amount of the silicone incorporated into clear liquid detergents can be increased, thereby enhancing the commercial appeal of the clear liquid detergents.

[0002] There have been several reports to date regarding amide polyether group-containing silicones, their analogs, and their applications. However, none of them have mentioned the quality issues of amide polyether group-containing silicones, and no practical, quality-stable silicones or methods for producing quality-stable silicones have been known. Furthermore, no methods for producing high-purity silicones have been known.

[0003] Patent Document 1 reports a fiber treatment composition consisting of (A) an amino group-containing organopolysiloxane (amino-modified silicone) and (B) a polyether group-containing carboxylic acid in a specific ratio. The composition can be prepared by simply mixing (A) and (B) uniformly, but it is preferable to mix them while heating at 40 to 180°C. It also describes that component (B) forms a salt with the amino group of component (A), or, depending on the heating conditions, an amide bond.

[0004] Patent Document 2 reported a cleaning composition containing (a) 5 to 70 wt. % of a surfactant and (b) 0.05 to 5 wt. % of an amide polyether group-containing silicone. In the examples, the document disclosed a cleaning composition containing a secondary amino / amide polyether co-modified silicone [Silicone (1)] in which both ends of the polysiloxane main chain are capped with trimethylsilyl groups. However, there was no description of a method for producing component (b).

[0005] Patent Document 3 reported a specific liquid detergent composition comprising (a) 0.05 to 5 wt % of a specific amino-modified silicone derivative containing an amide polyether group and another polyether group, and (b) 5 to 70 wt % of a surfactant (of which 95 to 75 wt % is (i) a specific nonionic surfactant having an HLB value of 12 to 15, and 5 to 15% is (ii) a specific nonionic surfactant having an HLB value of 7 to 10 and a narrow ethylene oxide addition mole distribution), with a specified (a) / (b) weight ratio. In the examples, the composition disclosed a liquid detergent composition containing a primary amino / amide polyether / polyether hybrid-modified silicone [silicone (1)] in which both ends of the polysiloxane main chain are capped with trimethylsilyl groups. However, there was no description of a method for producing the silicone.

[0006] Patent Document 4 reports that the light-duty detergent containing the amino-modified silicone amidation product described in Patent Document 2 was not sufficient in terms of stability, as the detergent composition yellowed and separated during storage.

[0007] Patent Document 5 reports a composition containing (A) an amide polyether-modified organopolysiloxane (amino-free amide polyether-modified silicone) and (B) a polyoxyethylene alkyl ether fatty acid (polyether group-containing carboxylic acid) in a specified ratio. In producing this composition, component (B) is used in an amount equal to or greater than the reaction equivalent during the amidation reaction. In Reference Example 1, a mixture of an amino-modified organopolysiloxane with both ends capped with trimethylsilyl groups and polyoxyethylene (4) lauryl ether acetic acid [component (B)] was reacted at 150°C for 2 hours to obtain a composition consisting of a trimethylsilyl-terminated amide polyether-modified silicone and 5.4 wt% of component (B). However, there was no report on the quality stability, appearance, viscosity, etc. of the composition of Reference Example 1 itself.

[0008] Patent Document 6 reported a detergent composition for delicate fabrics containing (a) a nonionic surfactant, (b) monoethanolamine, (c) a specific carboxylic acid having a molecular weight of 100 to 500, and (d) an amino-modified silicone, with the mass ratio of (a), (b), and (c) and the pH specified. In the examples, the detergent composition for delicate fabrics was disclosed, incorporating a primary amino / amide polyether / polyether hybrid-modified silicone [amino-modified silicone 1] in which both ends of the polysiloxane main chain are capped with trimethylsilyl groups. However, there was no description of a method for producing this silicone.

[0009] Patent Document 7 disclosed a wipe treatment agent containing an amide polyether group-containing polyorganosiloxane. While the composition may further contain a surfactant, a polyhydric alcohol, water, etc., the surfactant is primarily used in small amounts to emulsify the polyorganosiloxane, and the resulting composition is different from a cleaning agent. There is no mention or suggestion of its application to cleaning agents. In Reference Example 1, a mixture of an amino group- and polyether group-containing organopolysiloxane and polyoxyethylene (4.5) lauryl ether acetic acid was reacted at 130°C for 2 hours to obtain a primary amino / amide polyether / polyether composite-modified silicone [amide polyether group-containing organopolysiloxane (viscosity 1000 mPa·s)] in which both ends of the polysiloxane main chain were capped with trimethylsilyl groups. However, there was no report on the quality stability or appearance of the polysiloxane in Reference Example 1.

[0010] Patent Documents 8 and 9 reported transparent laundry detergent compositions using a quaternary ammonium cationic surfactant as a softening agent component. Patent Document 11 reported a liquid detergent composition with improved transparency that contains a specific organic cationic polymer having a quaternary ammonium salt structure as a softening agent component.

[0011] Patent Document 10 reported a liquid detergent composition characterized by containing (A) a specific nonionic surfactant, (B) 1 to 40 mass% of an anionic surfactant (excluding higher fatty acid salts) containing linear alkylbenzene sulfonic acid and polyoxyethylene ether sulfate, and (C) a silicone having at least one modified group selected from an amino-modified group and an amide-modified group and a polyether-modified group in its structure. The liquid detergent composition obtained in the examples was described as having a uniform appearance, but it was unclear whether it was transparent. Furthermore, details regarding the manufacturing method and chemical structure of component (C) were unknown.

[0012] That is, although Patent Documents 1, 5, and 7 briefly describe methods for producing amide polyether group-containing silicones, no information other than simply heating and mixing the raw materials, amino group-containing silicone and polyether group-containing carboxylic acid, for a certain period of time was known. Furthermore, Patent Documents 1 to 11 did not mention any quality issues with the amide polyether group-containing silicones themselves. Patent Documents 2 to 4 and Patent Document 6 disclose detergent compositions containing amide polyether group-containing silicones in which both ends of the polysiloxane main chain are capped with trimethylsilyl groups, but it was unclear how these silicones were specifically produced.

[0013] The present inventors have discovered that amide polyether group-containing silicones produced by previously reported production methods have numerous unreported problems, including: (i) only low-purity compositions are obtained; (ii) they contain a high cyclic dimethylsiloxane content; (iii) the properties or appearance of the compositions are unstable, and even if they are clear liquids immediately after production, they become opaque during storage; and (iv) the viscosity of the compositions increases significantly during storage. Furthermore, the present inventors have discovered that it is extremely difficult to accurately produce amide polyether group-containing silicones in which both ends of the polysiloxane main chain are capped with trimethylsilyl groups. In other words, the cleaning compositions of Patent Documents 2 to 4 and Patent Document 6 suffer from the problem that the raw material amide polyether group-containing silicone cannot be accurately produced, or that a method for accurately reproducing this structure using practical means is unknown.

[0014] As described above, past related literature fails to recognize the quality issues of amide polyether group-containing silicones. Accordingly, there is no description or suggestion of such silicones that are practical and have stable quality, or of methods for producing such silicones with stable quality. Furthermore, there is no description or suggestion of methods for producing such silicones with high purity. Furthermore, these literatures do not disclose co-modified silicones and compositions thereof that have two different polyether groups in one molecule in addition to amino groups and amide polyether groups, and these compositions are therefore novel, and these literatures do not describe or suggest any technical effects or advantages derived from their structure, etc.

[0015] Japanese Patent Publication No. 7-122222 (U.S. Patent No. 4973620) Japanese Patent Publication No. 3-207798 Patent No. 2863137 Patent No. 3299865 Japanese Patent Publication No. 11-5903 (U.S. Patent No. 5965649) Patent No. 41665 No. 64 Patent No. 5702926 (U.S. Patent No. 8802239) U.S. Patent No. 5622925 (Patent No. 2968340) European Patent No. 862609 Patent No. 6956712 U.S. Patent No. 11505766

[0016] As mentioned above, amide polyether group-containing silicones have a number of unreported problems, such as (i) they can only be obtained as low-purity compositions, (ii) they contain a large amount of cyclic dimethylsiloxane, (iii) the properties or appearance of the composition are unstable, and even if they are a clear liquid immediately after production, they become opaque during storage, and (iv) the viscosity of the composition increases significantly during storage. Furthermore, clear liquid detergent compositions containing, as a softener component or texture-improving component, an amide polyether group-containing silicone in which both ends of the polysiloxane main chain are capped with trimethylsilyl groups have been disclosed in examples in past related literature, but this silicone cannot be produced industrially with good reproducibility, and co-modified silicones having such molecular chain ends do not fully solve the above problems, so further improvements are strongly desired.

[0017] The present invention has been made to solve the above-mentioned problems, and its object is to provide a novel co-modified silicone that is practical and has stable quality and has amino / amide / two different polyether-modified groups in the molecule. Another object is to provide a co-modified silicone composition that is highly pure with few impurities and is practical and has stable quality. Another object of the present invention is to provide a liquid detergent containing the co-modified silicone or its composition, particularly a clear concentrated liquid laundry detergent or clear liquid detergent with excellent transparency, and to provide a method for producing the co-modified silicone or its composition. It is desirable that the co-modified silicone or its composition be used as a softener component, fabric lubricant component, texture-improving component, or fabric surface coating component in the clear concentrated liquid laundry detergent or clear liquid detergent.

[0018] In order to solve the above problems, the present inventors have conducted extensive research and have found that the two terminals of the polysiloxane main chain are M [RSiO 1 / 2 ] Units and M OR’ [ R2(OR')SiO 1 / 2 ] units (wherein R represents an alkyl group (having 1 to 12 carbon atoms), and OR′ represents a group selected from a hydroxyl group, an alkoxy group-containing group, and an acyloxy group-containing group), and the molar ratio M:M OR’ is in the range of 1.7:0.3 to 1.2:0.8, and M and M OR’ The present inventors have discovered that a specific amino / amide / two-polyether hybrid-modified silicone composition, in which the total number of moles of carboxylate groups and acyloxy groups is 1.0 or less when the total number of moles of (a) and (b) is taken as 2.0, has improved transparency in appearance and is less susceptible to deterioration over time, and shows significantly less increase in viscosity during storage than amide polyether group-containing silicones obtained by previously reported production methods. The viscosity of the composition can be maintained at a low level even after removal of the cyclic dimethylsiloxane by heating and decompression treatment, and furthermore, the viscosity is highly reproducible between batches. This means that high purity, easy handling, and stable production can be achieved simultaneously, making the composition particularly excellent as an additive product for clear liquid detergents, and capable of solving all of the multiple and complex problems mentioned above.

[0019] More specifically, the problem to be solved by the present invention is as follows: "[1] A compound having the following average structural formula: MD p D (AM) q D (AMD) r D (PE1) s D (PE2) w M OR’ Tx (1) (wherein M is R3SiO 1 / 2 units, D is R2SiO units, D (AM) is RR 1 SiO units, D (AMD) is RR 2 SiO units, D (PE1) is RR 3 SiO units, D (PE2) is RR 8 SiO units, M OR’ is R2(OR')SiO 1 / 2 Unit, T is R3SiO 3 / 2 where p, q, r, s, and w are positive numbers and satisfy the relationship 50≦p+q+r+s+w≦160, x is a number ranging from 0 to 1, and the molar ratio M:M OR’ is in the range of 1.7:0.3 to 1.2:0.8, R is an alkyl group having 1 to 12 carbon atoms, and R 1 is an aminoalkyl (1 to 6 carbon atoms) group, and R 2 is -R 4 -NHCO-(CH2) b -O(C2H4O) c -R 5 (In the formula, R 4 is an alkylene group having 1 to 6 carbon atoms, and R 5 is a monovalent hydrocarbon group having 1 to 18 carbon atoms, b is a number ranging from 1 to 6, and c is a number ranging from 2 to 20; R 3 is -R 6 -O-(C2H4O) d (C3H6O) e -R 7 group (in the formula, R 6is an alkylene group having 2 to 8 carbon atoms, and R ７ is an alkyl group having 1 to 12 carbon atoms, d is a number in the range of 3 to 25, e is a number in the range of 0 to 10, and when e is not 0, the molar ratio of d and e satisfies the relationship d / e ≧ 7 / 3), R 8 is -R 6 -O-(C2H4O) f (C3H6O) g -R 7 (In the formula, R 6 , R ７ are the same groups as defined above, f and g are each a number from 0 to 4, and satisfy the relationship 1≦f+g≦4), OR′ is a group selected from a hydroxyl group, an alkoxy group-containing group, and an acyloxy group-containing group, and further M and M OR’ [2] A co-modified silicone according to [1], wherein in the average structural formula (1), the number x of siloxy units represented by T is in the range of 0.01 to 0.70. [3] A co-modified silicone according to [1], further comprising a co-modified silicone represented by the following average structural formula: ZO-(C2H4O) d (C3H6O) e -R 7 (2) [wherein Z is a group selected from an alkenyl group having 2 to 8 carbon atoms or a hydrogen atom, and R 7, d, and e are as defined above)] in an amount of 5 parts by mass or less, when the sum of the co-modified silicone compound and the polyether compound is 100 parts by mass. [4] The co-modified silicone composition according to [3], wherein the ratio of the number of moles of oxyethylene (C2H4O) groups to 1 mole of Si-R groups in the composition is within the range of 0.2 to 0.6. [5] The co-modified silicone composition according to [3], wherein the content of aminoalkyl groups in the composition is within the range of 0.1 to 0.6 mass%. [6] The co-modified silicone composition according to [3], wherein the content of cyclic dimethylsiloxanes that are tetramers to hexamers is each 0.1 mass% or less of the total composition. [7] A liquid detergent comprising the co-modified silicone according to any one of [1] to [2] or the co-modified silicone composition according to any one of [3] to [6]. [8] The liquid detergent according to claim 7, which is a transparent concentrated liquid laundry detergent or a transparent liquid detergent, and which contains the co-modified silicone according to any one of [1] to [2] or the co-modified silicone composition according to any one of [3] to [6] as one or more of a softener component, a fiber lubricant component, a texture improving component, and a fiber surface coating component.[9] (I) Detergent organic nonionic surfactants having a polyoxyethylene group (the average number of oxyethylene repeats is within the range of 3 to 16): within the range of 10 to 60% by mass of the entire liquid detergent. (II) At least one anti-freeze agent selected from the following (II-1) to (II-3): within the range of 2 to 20% by mass of the entire liquid detergent. (II-1) Saturated monohydric alcohols having 2 to 4 carbon atoms. (II-2) Glycol ethers mono-substituted with alkyl groups having 1 to 6 carbon atoms (provided that the glycol ethers contain an oxyethylene group and / or an oxypropylene group, and the number of repeats is within the range of 1 to 3). (II-3) Diol or triol compounds selected from propylene glycol, dipropylene glycol, tripropylene glycol, triethylene glycol, tetraethylene glycol, trimethylene glycol, and glycerin. (III) Water: within the range of 20 to 85% by mass of the entire liquid detergent. (IV) The liquid detergent according to [7], further comprising the co-modified silicone according to any one of [1] to [2] or the co-modified silicone composition according to any one of [3] to [6], in a range of 0.3 to 3 mass % of the total liquid detergent.

[10] The liquid detergent according to [9], further comprising 0.1 to 15 mass % (wherein the total amount of the components (I) to (V) is taken as 100 mass %) of a stabilizer (V) selected from antibacterial agents (preservatives), hydrotropes, antioxidants, and water softeners (chelating agents).

[11] The liquid detergent according to

[10] , further comprising: (VI) 0.1 to 5% by mass of at least one anti-resoiling agent (anti-redeposition agent or dispersant); (VII) 0.1 to 6% by mass of a pH adjuster; (VIII) 0.1 to 2% by mass of a preparation of at least one enzyme selected from protease, lipase, amylase, cellulase, esterase, pectinase, and mannanase; (IX) 1 to 150 ppm of a colorant; and (X) 5 to 6,000 ppm of a fragrance, the total amount of which is taken as 100% by mass.

[12] A method for producing a liquid detergent according to any one of [9] to

[11] , which contains the components (I) to (IV) and, optionally, the components (V) to (X), characterized in that the components (I) to (VII) are dissolved by heating and mixing at 40 to 80°C, and then cooled to 30°C or below, and one or more components selected from the group consisting of components (VIII), (IX) and (X) are added and mixed uniformly.

[13] A compound having the following average structural formula: MD. ｔ D (AM) ｕ D (PE1) ｖ D (PE2) ｚ M OR’ Tx (3) (wherein M is R3SiO 1 / 2 , D is R2SiO, D (AM) is RR 1 SiO, D (PE1) is RR 3 SiO units, D (PE2) is RR 8 SiO units, M OR’ is R2(OR')SiO 1 / 2 , T is R3SiO 3 / 2 where t, u, v, and z are positive numbers and satisfy the relationship 50≦t+u+v+z≦160, and x is a number ranging from 0 to 1, and the molar ratio M:M OR’ is in the range of 1.7:0.3 to 1.2:0.8, R is an alkyl group having 1 to 12 carbon atoms, and R 1 is an aminoalkyl group having 1 to 12 carbon atoms, and R 3 is -R 6 -O-(C2H4O) d (C3H6O) e -R 7 (In the formula, R 6 is an alkylene group having 2 to 8 carbon atoms, and R ７ is an alkyl group having 1 to 12 carbon atoms, d is a number in the range of 3 to 25, e is a number in the range of 0 to 10, and when e is not 0, the molar ratio of d and e satisfies the relationship d / e ≧ 7 / 3), R 8 is -R 6-O-(C2H4O) f (C3H6O) g -R 7 (In the formula, R 6 , R ７ are the same groups as above, f and g are each a number from 0 to 4, and the relationship 1≦f+g≦4 is satisfied; and OR′ is a group selected from a hydroxyl group, an alkoxy group-containing group, and an acyloxy group-containing group; and an amino / two-type polyether co-modified silicone represented by the following average structural formula: HOOC-(CH2) b -O(C2H4O) c -R 5 (4) [In the formula, R 5 a is a monovalent hydrocarbon group having 1 to 18 carbon atoms, b is a number in the range of 1 to 6, and c is a number in the range of 2 to 20], and a polyether group-containing carboxylic acid represented by the formula (3) is reacted by heating and mixing at 80 to 180°C under reduced pressure and in an inert gas flow, and the reaction is carried out so that the molar ratio (reaction ratio) of the aminoalkyl group in the amino-polyether co-modified silicone represented by formula (3) to the carboxyl group in the polyether group-containing carboxylic acid represented by formula (4) is within the range of 0.1≦carboxyl group / aminoalkyl group≦1.0.

[14] A method for producing the co-modified silicone according to any one of items [1] to [2] or the co-modified silicone composition according to any one of items [3] to [6], wherein in the average structural formula (3), the number x of siloxy units represented by T is in the range of 0.01 to 0.70.

[15] The problem is solved by the production method according to

[13] , which is characterized by reacting the polyether group-containing carboxylic acid represented by the average structural formula (4) in an aqueous solution or in the co-presence of water.

[0020] The novel co-modified silicone and composition thereof according to the present invention are of higher purity than amide polyether-modified silicones prepared by previously reported production methods, and because their quality is stabilized at a low viscosity and with a reduced cyclic dimethylsiloxane content, they offer excellent handleability and production stability. Specifically, the transparency of the appearance is improved, with little deterioration of transparency over time, and the amount of impurities is reduced, so the appearance of the composition remains a stable clear liquid immediately after production and even during storage, and no increase in viscosity occurs during storage, or if it does occur, it is only to a small extent.

[0021] The co-modified silicone and composition thereof according to the present invention are excellent in quality and production stability, making them suitable for commercial transactions, and in particular, when blended into liquid detergents with a clear appearance, they have little effect on the transparency and stability of the detergent, making them suitable for use as a fabric softener component, textile lubricant component, texture-improving component, textile surface coating component, etc. Furthermore, because the co-modified silicone composition according to the present invention has a low impurity content, it is possible to increase the amount blended into clear liquid detergents, which has the advantage of increasing the commercial appeal of the clear liquid detergents.

[0022] In addition, the co-modified silicone and composition thereof according to the present invention can be produced industrially in a stable manner, solving the multiple and complex problems inherent in existing methods for producing co-modified silicones, and also achieving excellent quality reproducibility. Therefore, by utilizing the production method according to the present invention, it is possible to improve both the industrial production and quality of co-modified silicones, and further improve their commercial applicability. In other words, it is believed that the invention according to this production method also exhibits a high degree of originality over the prior art, and an unpredictable and extremely significant technical effect, particularly in terms of the design of the production conditions.

[0023] The co-modified silicone of the present invention and a composition containing the same are described below. The co-modified silicone of the present invention has an aminoalkyl group (R 1 ), an amide polyether group (R ２ ) and two different polyether groups (R ３ and R 8) and the terminal of the polysiloxane main chain is M [RSiO 1 / 2 ] Units and M OR’ [ R2(OR')SiO 1 / 2 ] units, and the terminal groups M : M OR’ The molar ratio of M and M is in the range of 1.7:0.3 to 1.2:0.8, OR’ is 2.0, the total number of moles of carboxylate groups and acyloxy groups is 1.0 or less, and optionally may contain a small amount of T units. Furthermore, the co-modified silicone composition of the present invention preferably contains the co-modified silicone with a high purity, and is preferably a high-purity composition in which the content of the raw material polyether compound having hydrosilylation-reactive terminals is 5 parts by mass or less when the sum of the co-modified silicone compound and the polyether compound is 100 parts by mass.

[0024] More specifically, the co-modified silicone according to the present invention has the following average structural formula: MD p D (AM) q D (AMD) r D (PE1) s D (PE2) w M OR’ Tx (1) (wherein M is R3SiO 1 / 2 units, D is R2SiO units, D (AM) is RR 1 SiO units, D (AMD) is RR 2 SiO units, D (PE1) is RR 3 SiO units, D (PE2) is RR 8 SiO units, M OR’ is R2(OR')SiO 1 / 2 Unit, T is R3SiO 3 / 2where p, q, r, s, and w are positive numbers and satisfy the relationship 50≦p+q+r+s+w≦160, x is a number ranging from 0 to 1, and the molar ratio M:M OR’ is in the range of 1.7:0.3 to 1.2:0.8, R is an alkyl group having 1 to 12 carbon atoms, and R 1 is an aminoalkyl (1 to 6 carbon atoms) group, and R 2 is -R 4 -NHCO-(CH2) b -O(C2H4O) c -R 5 (In the formula, R 4 is an alkylene group having 1 to 6 carbon atoms, and R 5 is a monovalent hydrocarbon group having 1 to 18 carbon atoms, b is a number ranging from 1 to 6, and c is a number ranging from 2 to 20; R 3 is -R 6 -O-(C2H4O) d (C3H6O) e -R 7 group (in the formula, R 6 is an alkylene group having 2 to 8 carbon atoms, and R ７ is an alkyl group having 1 to 12 carbon atoms, d is a number in the range of 3 to 25, e is a number in the range of 0 to 10, and when e is not 0, the molar ratio of d and e satisfies the relationship d / e ≧ 7 / 3), R 8 is -R 6 -O-(C2H4O) f (C3H6O) g -R 7 (In the formula, R 6 , R ７ are the same groups as defined above, f and g are each a number from 0 to 4, and satisfy the relationship 1≦f+g≦4), OR′ is a group selected from a hydroxyl group, an alkoxy group-containing group, and an acyloxy group-containing group, and further M and M OR’ When the total number of moles of carboxylate groups and acyloxy groups in the molecule is taken as 2.0, the total number of moles of carboxylate groups and acyloxy groups in the molecule is 1.0 or less.

[0025] In the formula, R is an alkyl group having 1 to 12 carbon atoms, and industrially preferred is a methyl group. 1 is an aminoalkyl group having 1 to 12 carbon atoms, preferably 2 to 6 carbon atoms, which may be a primary or secondary aminoalkyl group, and is preferably an aminopropyl group.

[0026] R 2 Ha-R 4 -NHCO-(CH2) b -O(C2H4O) c -R 5 The functional group contains an amide structure and a polyether structure. 4 is an alkylene group having 1 to 6 carbon atoms, preferably a propylene group or a methylpropylene group. 5 is a monovalent hydrocarbon group having 1 to 18 carbon atoms, preferably an alkyl group having 8 to 16 carbon atoms; b is a number ranging from 1 to 6; and c is a number ranging from 2 to 20.

[0027] R 3 is -R 6 -O-(C2H4O) d (C3H6O) e -R 7 In the functional group, the number (d) of oxyethylene units (C2H4O) and the number (e) of oxypropylene units (C3H6O) satisfy a specific relationship, and the functional group may be a functional group that does not contain an oxypropylene unit (e=0). 3 The oxyethylene units and oxypropylene units in R may have a random addition structure or a block addition structure. 3 may be one type of polyether group, may be a mixture of a plurality of different polyether groups, or may be a functional group represented by an average structural formula of a plurality of polyether groups.

[0028] In the formula, R 6 is an alkylene group having 2 to 8 carbon atoms, preferably a propylene group or a methylpropylene group. ７is an alkyl group having 1 to 12 carbon atoms, preferably a methyl group. d and e are such that d is a number ranging from 3 to 25, and e is a number ranging from 0 to 10. When e is not 0, d and e satisfy the relationship of a molar ratio d / e ≧ 7 / 3, from the viewpoint of blend stability of the co-modified silicone composition of the present invention in a clear liquid detergent. If the molar ratio (d / e) is less than 7 / 3, the proportion of oxypropylene units (C3H6O) in the polyether structure will be excessive, which may cause the liquid detergent to become cloudy due to the cloud point phenomenon when the storage temperature is high, such as in summer, after blending into a clear liquid detergent. As mentioned above, e may be 0, in which case R 3 is a functional group containing only oxyethylene units in the polyether structure, and is one of the preferred forms in the present invention.

[0029] R 8 is -R 6 -O-(C2H4O) f (C3H6O) g -R 7 and the sum (f) of the number of oxyethylene units (C2H4O) and the number (g) of oxypropylene units (C3H6O) in the functional group and the relationship therebetween are the same as those of the first polyether group (R 3 ). Specifically, f and g are each a number from 0 to 4, and satisfy the relationship 1 ≦ f + g ≦ 4. The coexistence of these two different types of polyether groups within the molecule is a structural feature of the co-modified silicone of the present invention.

[0030] In the formula, p, q, r, s, x, and w represent the number of siloxy units, and their sum corresponds to the degree of siloxane polymerization of the co-modified silicone compound of the present invention, satisfying the relationship 50 ≦ p + q + r + s + w ≦ 160, and x is a number in the range of 0 to 1. If p + q + r + s is less than 50, when incorporated into a clear liquid detergent, it may be difficult to realize the effects as a softener component, fiber lubricant component, texture-improving component, or fiber surface coating component. On the other hand, if p + q + r + s + w exceeds 160, blend stability in the clear liquid detergent tends to decrease, and measures such as increasing the amount of component (II) described below or selecting a component (I) with a compatibilizing effect and using it in the formulation may be necessary to improve solubility, which may result in problems such as increased difficulty and cost in formulating the clear liquid detergent.

[0031] x is an arbitrary structural unit of the co-modified silicone compound according to the present invention, T(RSiO 3 / 2 ) as a structural unit, and is a number in the range of 0 to 1, preferably a number in the range of 0 to 0.7. In particular, when a siloxy unit represented by T is contained, it is preferable that x is in the range of 0.01 to 0.70. The co-modified silicone compound according to the present invention contains a structural unit represented by T(RSiO 3 / 2 ) in excess of the upper limit, it may be difficult to control the process and quality to adjust the viscosity of the composition containing the co-modified silicone compound or its raw materials to fall within the target range, and there may be an increased risk of thickening / gelling during the process of producing the composition of the present invention, making stable industrial production difficult.

[0032] The co-modified silicone compound of the present invention has a polysiloxane main chain whose terminal is M [RSiO 1 / 2 ] Units and M OR’ [ R2(OR')SiO 1 / 2 ] units, and the terminal groups M : M OR’The molar ratio of M to M is within the range of 1.7:0.3 to 1.2:0.8, preferably 1.40:0.60 to 1.20:0.80. Structures in which the ratio of terminal M units exceeds the upper limit are difficult to produce by a practical method. OR’ Structures with a ratio of units exceeding the above lower limit are unstable, and may cause a decrease in transparency (i.e., opacity) or a significant increase in viscosity of the co-modified silicone composition of the present invention during storage, making it impossible to achieve the technical effects intended by the present invention. OR’ The molar ratio of 29 It can be determined by Si NMR analysis.

[0033] In the above average structural formula, M and M OR’ When the total number of moles of carboxylate groups and acyloxy groups is taken as 2.0, the total number of moles of carboxylate groups and acyloxy groups in the molecule must be 1.0 or less. This is because if the total number of moles of carboxylate groups and acyloxy groups exceeds 1.0, the co-modified silicone having amino / amide / two types of polyether modifying groups or its composition will tend to become unstable, and may become opaque or experience a significant increase in viscosity during storage. The total number of moles of carboxylate groups and acyloxy groups is 13 It can be determined by C NMR analysis.

[0034] The composition containing the co-modified silicone of the present invention preferably contains the co-modified silicone in high purity, and preferably contains a certain amount or less of the raw material polyether compound having a hydrosilylation-reactive terminal. Specifically, the polyether compound has the following average structural formula: ZO-(C2H4O) d (C3H6O) e -R 7 (2) [wherein Z is a group selected from an alkenyl group having 2 to 8 carbon atoms or a hydrogen atom, and R 7, d, and e are defined as above)], when the sum of the co-modified silicone compound and the polyether compound is taken as 100 parts by mass, the content of the raw material polyether compound having a hydrosilylation reactive terminal in the composition is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less. If the content of the polyether compound exceeds the above upper limit, separation from the co-modified silicone composition of the present invention or the resulting turbidity is more likely to occur, and care may be needed in product management.

[0035] Similarly, the composition containing the co-modified silicone according to the present invention preferably contains a certain amount or less of the raw material polyether compound having a hydrosilylation reactive terminal. Specifically, the polyether compound has the following average structural formula: ZO-(C2H4O) f (C3H6O) g -R 7 (2') [wherein Z is a group selected from an alkenyl group having 2 to 8 carbon atoms or a hydrogen atom, and R 7 , f, and g are as defined above)], when the sum of the co-modified silicone and the polyether compound is taken as 100 parts by mass, the content of the raw material polyether compound having a hydrosilylation reactive terminal in the composition is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less.

[0036] It is particularly preferred that, when the sum of the co-modified silicone and the two types of polyether compounds represented by the average structural formula (2) or (2') is taken as 100 parts by mass, the content of the two types of polyether compounds having hydrosilylation reactive ends as raw materials in the composition is 5 parts by mass or less, more preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less.

[0037] When the co-modified silicone and composition containing it according to the present invention are formulated as ingredients in a clear concentrated liquid laundry detergent or a clear liquid detergent, the ratio of the number of moles of oxyethylene (C2H4O) groups to 1 mole of Si-R groups in the composition is preferably in the range of 0.2 to 0.6, and particularly preferably in the range of 0.35 to 0.45. If the ratio of the number of moles of oxyethylene groups to Si-R groups is below the lower limit, blending stability may decrease. On the other hand, if this ratio exceeds the upper limit, blending stability will be excellent, but effects such as flexibility, fiber lubricity, and texture may decrease. Note that this ratio is 13 It can be determined by C NMR analysis.

[0038] When the co-modified silicone and composition containing it according to the present invention are incorporated as ingredients in a clear concentrated liquid laundry detergent or a clear liquid detergent, the aminoalkyl group content (—NH2%) in the composition is preferably in the range of 0.10 to 0.60% by mass, and particularly preferably in the range of 0.20 to 0.50% by mass. The mass % of the aminoalkyl group can be calculated by neutralization titration.

[0039] If the mass % of the aminoalkyl group is less than the lower limit, the viscosity of the composition tends to increase, which may be disadvantageous in terms of handling and solubility in a clear liquid detergent. Here, when blending an amino group-containing silicone into a clear liquid detergent, it is generally considered effective to neutralize it with a pH adjuster or the like in order to improve solubility in the system or blend stability.

[0040] When the mass % of aminoalkyl groups exceeds the upper limit, the hydrophilic effect due to neutralization is increased, and therefore, in liquid detergent formulations that do not contain anionic surfactants, both solubility and stability are improved. However, in liquid detergent formulations that contain anionic surfactants, the higher the mass % of amino groups in the silicone, the lower the formulation stability in the detergent, which is likely to cause a decrease in transparency and separation, and there is also concern about adverse effects on detergency. Furthermore, when the mass % of aminoalkyl groups exceeds the upper limit, transparent liquid detergents containing this tend to discolor easily during storage under adverse conditions such as high temperatures in summer, and repeated washing with this detergent may cause quality problems such as gradual discoloration of the laundry itself.

[0041] In the co-modified silicone and composition containing it according to the present invention, the content of the impurities cyclic dimethylsiloxane tetramer, pentamer, and hexamer is preferably reduced to 0.1% by mass or less of the total composition, and more preferably each is 0.01% by mass or less, and particularly preferably below the detection limit by conventional methods. Co-modified silicones with a reduced content of cyclic dimethylsiloxane tetramers to hexamers and compositions containing them can be easily produced by the method described below.

[0042] [Regarding the technical significance of the present invention] As mentioned above, the co-modified silicone and composition thereof according to the present invention contain technical elements that partially overlap with the definitions of the amino-modified silicone derivative disclosed as general formula (I) in Patent Document 3 and the amino-modified silicone disclosed as general formula (II) in Patent Document 6, but these documents make no mention of co-modified silicones that have two different polyether groups in one molecule in addition to an amino group and an amide polyether group, nor do they state or suggest any of the technical benefits thereof. Furthermore, the "amide polyether group-containing silicone having a structure in which both ends of the polysiloxane main chain are blocked with trimethylsilyl groups" disclosed in these documents does not specifically disclose a method for producing it, making it difficult to produce by practical means. Similarly, Patent Document 7 (Reference Example 1) reports that when a mixture of an amino group- and polyether group-containing organopolysiloxane and polyoxyethylene (4.5) lauryl ether acetic acid was reacted at 130°C for 2 hours, the resulting reaction mixture was "an amide polyether group-containing organopolysiloxane in which both ends of the polysiloxane main chain were blocked with trimethylsilyl groups." However, when the present inventors conducted a follow-up experiment under similar conditions, they found that the specified structure could not be obtained under the above production conditions. Furthermore, the actual product had a number of previously unreported and complex problems: (i) it was a low-purity composition, (ii) it contained a high amount of cyclic dimethylsiloxane, (iii) the properties or appearance of the composition were unstable, and even though it was a clear liquid immediately after production, it became opaque during storage, and (iv) the viscosity of the composition increased significantly during storage.

[0043] On the other hand, the co-modified silicone and composition thereof according to the present invention, by virtue of having the above-described structural structure as a co-modified silicone, maintains its appearance transparency for a long period of time, unlike similar compounds disclosed in the prior art, and significantly suppresses viscosity increases during storage compared to amide polyether group-containing silicone compositions obtained by previously reported production methods. Furthermore, the co-modified silicone and composition thereof according to the present invention can maintain the viscosity of the composition at a low level even after removing the cyclic dimethylsiloxane by heating and decompression treatment, thereby achieving both high purity, good handleability, and production stability. Therefore, the co-modified silicone and composition thereof according to the present invention have particularly excellent properties from a commercial perspective as an additive to clear liquid detergents, and achieve an extremely significant technical effect of fully resolving the multiple and complex problems inherent in the prior art.

[0044] [Production of Co-Modified Silicone and Composition Thereof] The co-modified silicone and composition thereof according to the present invention are represented by the following average chemical structural formula: MD ｔ D (AM) ｕ D (PE1) ｖ D (PE2) ｚ M OR’ Tx (3) and the following average chemical structure: HOOC-(CH2) b -O(C2H4O) c -R 5 and a polyether group-containing carboxylic acid represented by formula (4), and react them under reduced pressure and in an inert gas flow at 80 to 180°C, so that the molar ratio (reaction ratio) of the aminoalkyl group in the amino-polyether co-modified silicone represented by formula (3) to the carboxyl group in the polyether group-containing carboxylic acid represented by formula (4) falls within the range of 0.1≦carboxyl group / aminoalkyl group≦1.0. The compounds of formulas (3) and (4) are further described below.

[0045] In formula (3), M is RSiO 1 / 2 , D is R2SiO, D (AM) is RR1 SiO, D (PE1) is RR 3 SiO units, D (PE2) is RR 8 SiO units, M OR’ is R2(OR')SiO 1 / 2 , T is R3SiO 3 / 2 wherein t, u, v, and z are positive numbers and satisfy the relationship 50≦t+u+v+z≦160, x is a number ranging from 0 to 1, and the molar ratio M:M OR’ is in the range of 1.7:0.3 to 1.2:0.8, R is an alkyl group having 1 to 12 carbon atoms, and R 1 is an aminoalkyl group having 1 to 12 carbon atoms, and R 3 is -R 6 -O-(C2H4O) d (C3H6O) e -R 7 (In the formula, R 6 is an alkylene group having 2 to 8 carbon atoms, and R ７ is an alkyl group having 1 to 12 carbon atoms, d is a number in the range of 3 to 25, e is a number in the range of 0 to 10, and when e is not 0, the molar ratio of d and e satisfies the relationship d / e ≧ 7 / 3), R 8 is -R 6 -O-(C2H4O) f (C3H6O) g -R 7 (In the formula, R 6 , R ７ is the same group as above, f and g are each a number from 0 to 4 and satisfy the relationship 1 ≦ f + g ≦ 4), and OR' is a group selected from a hydroxyl group, an alkoxy group-containing group, and an acyloxy group-containing group.

[0046] In formula (3), R is preferably a methyl group, and R 1 is preferably an aminopropyl group but may also be a secondary aminoalkyl group, R 3 , R 8The oxyethylene moiety and the oxypropylene moiety of R may have a random addition structure or a block addition structure. 3 , R 8 R may be a mixture of multiple different polyether groups. 6 is preferably a propylene group or a methylpropylene group, R 7 is preferably a methyl group.

[0047] In formula (3), each of t, u, and v is a positive number, and in order to obtain a co-modified silicone represented by the corresponding average structural formula, it is preferable that the relationship 50 ≦ t + u + v ≦ 160 is satisfied. Similarly, the molar ratio M : M OR’ It is preferable that the ratio of M units is in the range of 1.7:0.3 to 1.2:0.8. It is considered that it is difficult to manufacture a structure having a ratio of M units exceeding 1.7 by a practically advantageous method. OR’ The molar ratio of 29 It can be determined by Si NMR analysis.

[0048] The amino-two-polyether co-modified silicone represented by formula (3) contains M and M OR’ When the total number of moles is 2.0, the structural unit is the T unit (RSiO 3 / 2 It is preferable that the content of T units (x) is 0.7 moles or less (i.e., x is in the range of 0 to 0.7). If the amount of T units exceeds 0.7 moles, it becomes difficult to control the process and quality to adjust the viscosity of the amino / two-type polyether co-modified silicone and its composition, which are raw materials, to the target range, and there may be an increased risk of abnormal thickening or gelation during the manufacturing process.

[0049] In formula (4), R 5 is a monovalent hydrocarbon group having 1 to 18 carbon atoms, b is a number ranging from 1 to 6, and c is a number ranging from 2 to 20, preferably from 4 to 10.

[0050] In producing the co-modified silicone and composition thereof of the present invention, the polyether group-containing carboxylic acid represented by formula (4) may be used as a raw material as is, but from the standpoints of economy and productivity, it is preferable to use an aqueous solution of a polyether group-containing carboxylic acid that is readily commercially available as a raw material.

[0051] The molar ratio (reaction ratio) of the aminoalkyl group in the amino / two-type polyether co-modified silicone represented by formula (3) to the carboxyl group in the polyether group-containing carboxylic acid represented by formula (4) can vary depending on the relationship between their average chemical structures. In the production method of the present invention, it is necessary for the ratio to be within the range of 0.1 ≦ carboxyl group / aminoalkyl group ≦ 1.0, preferably within the range of 0.2 ≦ carboxyl group / aminoalkyl group ≦ 0.8, and particularly preferably within the range of 0.3 ≦ carboxyl group / aminoalkyl group ≦ 0.6.

[0052] The temperature at which the aminoalkyl group in the amino / two-type polyether co-modified silicone represented by formula (3) and the polyether group-containing carboxylic acid represented by formula (4) are heated, mixed, and reacted is preferably within the range of 90 to 150°C, and more preferably within the range of 100 to 130°C. If the reaction temperature is below 80°C, the amidation reaction may be extremely slow and may not proceed at a practical rate. On the other hand, at high temperatures, particularly above 180°C, side reactions tend to proceed significantly, and care may be needed to avoid a decrease in the yield of the target compound.

[0053] An important feature of the production method of the present invention is that the reaction between the aminoalkyl group in the amino-polyether co-modified silicone represented by formula (3) and the polyether group-containing carboxylic acid represented by formula (4) is carried out under reduced pressure and in an inert gas flow, at the molar ratio and reaction temperature range described above. The inventors of the present invention have newly discovered that selecting such reaction conditions efficiently removes water derived from the raw materials or produced as a by-product in the condensation reaction, and the impurity cyclic dimethylsiloxane tetramer to hexamer, allows the amidation reaction to proceed more efficiently than under atmospheric pressure, and stabilizes the chemical structure and quality of the target co-modified silicone having amino, amide, and two different polyether modifying groups. Meanwhile, it is also possible to initially proceed with the amidation reaction under atmospheric pressure, and then transition to reduced pressure midway to achieve the target reaction rate.

[0054] Furthermore, Patent Documents 1, 5, and 7 do not describe or suggest any technique for carrying out the reaction of an amino group-containing silicone with a polyether group-containing carboxylic acid under reduced pressure or any advantages thereof, and it would be difficult to obtain the co-modified silicone and composition thereof of the present invention using the production methods described in these documents.

[0055] The time for the reduced pressure amidation reaction depends on the reaction temperature, but for example, when the temperature is 120 to 130° C., the amidation rate reaches the target level after 4 to 6 hours as a guideline. In the case of industrial production, when an atmospheric pressure amidation step is included first, it may be possible to select a reduced pressure amidation step of less than 4 hours.

[0056] The degree of vacuum during the reduced-pressure amidation reaction is variable because the pressure must be gradually reduced from atmospheric pressure to vacuum while avoiding bumping, since the reaction mixture foams in the reactor during the reduced pressure. For example, it is preferable to reduce the pressure stepwise, such as atmospheric pressure => 380 Torr => 250 Torr => 180 Torr => 120 Torr => 80 Torr => 50 Torr => 30 Torr => 15 Torr => 5 Torr => 1 Torr or less.

[0057] As the inert gas used in producing the co-modified silicone and composition thereof of the present invention, argon gas and the like can be used, but from an economical standpoint, nitrogen gas is most suitable. These inert gases can be passed through the upper space in the reaction vessel, or through the system while being bubbled through the raw material liquid in the reaction vessel, with the latter being more advantageous as it makes it easier to remove impurities and water.

[0058] The above production method makes it possible to efficiently produce the co-modified silicone and composition thereof according to the present invention, which is characterized by the content of cyclic dimethylsiloxane tetramer, pentamer, and hexamer each being 0.1% by mass or less.

[0059] [Filtration Step] If the intermediates (amino-two-type polyether co-modified silicone and composition thereof) and reaction raw materials (polyether carboxylic acid, etc.) used in the production of the co-modified silicone and composition thereof of the present invention contain neutralized salts, these will migrate into the final product and cause a cloudy appearance or the formation of precipitates. In such cases, filtration must be carried out after the amidation reaction. Filtration may be carried out using any filter, etc., depending on the cloudy appearance and the type and size of the precipitate, and multiple filtrations may be carried out. This makes it possible to obtain the co-modified silicone and composition thereof of the present invention, which have high purity and excellent quality stability, even when low-cost intermediates and raw materials are used.

[0060] [Production of Intermediate (Amino / Two-Polyether Co-Modified Silicone Composition)] The method for producing the intermediate composition containing the amino / two-polyether co-modified silicone represented by formula (3) above is not particularly limited, but an industrially advantageous method is preferred. For example, there is a method in which calculated amounts of a dimethylpolysiloxane having a polyether group, a hydrolysis condensate of an aminoalkyldialkoxymethylsilane, and, if necessary, a cyclic dimethylsiloxane or a dimethylpolysiloxane, etc. are charged into a reactor and subjected to an equilibration reaction in the presence of an alkali catalyst. The conditions for the equilibration reaction should be similar to those used when producing a general amino-modified silicone.

[0061] For example, potassium hydroxide or its aqueous solution, tetramethylammonium hydroxide aqueous solution or methanol solution, potassium silanolate, tetramethylammonium silanolate, etc. are easily used as alkaline catalysts. When potassium hydroxide or potassium silanolate is used, it is preferable to neutralize the catalyst by adding acetic acid or the like after the equilibration reaction. When tetramethylammonium hydroxide or tetramethylammonium silanolate is used, it is preferable to perform a thermal decomposition treatment. Thereafter, it is desirable to remove or reduce low-boiling point components present in the reaction system by a stripping treatment. Furthermore, filtration may be performed as desired.

[0062] In addition, the composition containing the amino / two-type polyether co-modified silicone represented by the above formula (3) further contains T units (RSiO 3 / 2 To produce a composition containing T units (siloxy units represented by the formula (3)), one method is to use an appropriate amount of a polysiloxane compound or alkoxysilane compound having T units as one of the raw materials. Alternatively, for example, if an appropriate amount of aminoalkyltrialkoxysilane is intentionally or as an impurity contained in the raw material, such as a hydrolysis condensation product of aminoalkyldialkoxymethylsilane, an equilibration reaction to obtain an amino-two-polyether co-modified silicone represented by formula (3) can generate a predetermined amount of T units within the molecule. Another route for generating T units occurs when a dimethylpolysiloxane having two different polyether groups contains a small amount of -SiMe(OR'')- structural units (where OR'' is a group selected from hydroxyl groups, alkoxy group-containing groups, and acyloxy group-containing groups). Dimethylpolysiloxanes containing two different polyether groups are generally produced by the hydrosilylation reaction of a Si-H group-containing dimethylpolysiloxane with two different vinyl-terminated polyethers in the presence of a platinum catalyst. However, moisture present in the reaction system or the alcohol solvent for the platinum catalyst can cause a slight dehydrogenation reaction, resulting in the formation of the -SiMe(OR'')- structural unit. When such raw materials are used in an equilibration reaction to obtain the amino-two-polyether-modified silicone composition of formula (3), a small amount of T units is generated.

[0063] [Production of Raw Material (Polyether Group-Containing Carboxylic Acid)] The method for producing the polyether group-containing carboxylic acid represented by the formula (4) is not particularly limited. For example, a polyether group-containing carboxylic acid represented by the following average chemical structural formula: HOOC-CH-O(CHO) c -C 12 H 25 (5) When producing a polyether group-containing carboxylic acid represented by the following average chemical structural formula: HO(C2H4O) c -C 12 H 25 A method can be used in which polyoxyethylene lauryl ether represented by the formula (6) and monochloroacetic acid represented by the average chemical structural formula: HOOC-CH2-Cl (7) are etherified in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. During this process, salts such as NaCl or KCl are by-produced. Therefore, the polyether group-containing carboxylic acid of the formula (5) is often obtained in the form of a solution containing water and salts with a main component concentration of 90 to 96% by mass, and is often commercially available in this form. Such solution-form raw materials can also be used in the production method of the present invention.

[0064] Other impurities contained in the polyether group-containing carboxylic acid of the formula (5) include, for example, impurities represented by the following average chemical structure: HOOC-CH2-OC 12 H 25 This compound is produced by reacting lauryl alcohol, a raw material that may remain in small amounts in the formula (6), with the formula (7).

[0065] Another possible impurity contained in the polyether group-containing carboxylic acid of formula (5) is diglycolic acid, which has the following average chemical structural formula: HOOC-CH2-O-CH2-COOH. This compound is produced when glycolic acid, which is produced by hydrolysis of monochloroacetic acid of formula (7) in the presence of an alkali metal hydroxide, and another molecule of monochloroacetic acid undergo an etherification reaction.

[0066] By selecting the production method of the present invention, it is possible to obtain a highly pure, co-modified silicone and a composition thereof according to the present invention that has excellent quality stability, even when a polyether group-containing carboxylic acid containing impurities such as those described above is used as a raw material.

[0067] [Production of Starting Material (Dimethylpolysiloxane Having Two Types of Polyether Groups)] The two-type polyether-modified silicone and its composition, which are one of the starting materials used to produce the amino / two-type polyether co-modified silicone represented by formula (3) and the composition containing it (intermediate), can be designed to correspond to the target structure of the co-modified silicone and its composition according to the present invention, which are the final products, and are preferably produced by an industrially advantageous method. A typical example is a compound represented by the following average chemical structural formula: MD m D (PE1) n D (PE2) j M (10) (wherein M is (CH3)3SiO 1 / 2 Units, D is (CH3)2SiO Units, D (PE1) is RR 3 SiO units, D (PE2) is RR 8 SiO units, m is 0 or a positive number, n and j are positive numbers, R 3 is -R 6 -O-(C2H4O) d (C3H6O) e -R 7 is represented by the group R 6 is an alkylene group (having 2 to 8 carbon atoms), R 7 is an alkyl group (1 to 12 carbon atoms), and R 8 is -R 6 -O-(C2H4O) f (C3H6O) g -R 7 where d is a number between 3 and 25, e is a number between 0 and 25, f and g are each a number between 0 and 4, and satisfy 1 ≦ f + g ≦ 4, and further, the molar ratio d / e ≧ 7 / 3, and R 3The oxyethylene moiety and the oxypropylene moiety of R may have a random addition structure or a block addition structure. 3 and R 8 The general method for producing polyether-modified silicones and compositions thereof will now be briefly described.

[0068] The polyether-modified silicone and its composition represented by the above formula (10) have the average chemical structural formula: MD m D H (n+j) M (11) (wherein M, D, m, n, and j are as defined above, and D H represents a H(CH3)SiO unit], and preferably a dimethylpolysiloxane containing Si-H groups represented by the average chemical structural formula: H2C=CH(R 8 )-(CH2) k -O(C2H4O) d (C3H6O) e -R 7 (12) [In the formula, R 8 is hydrogen or a methyl group, R 7 is an alkyl group (having 1 to 12 carbon atoms), k is a number from 0 to 6, d is a number from 3 to 25, and e is a number from 0 to 25, where the molar ratio d / e is 7 / 3 or more, and the oxyethylene moiety and the oxypropylene moiety may have a random addition structure or a block addition structure; and 8 )-(CH2) k -O(C2H4O) f (C3H6O) g -R 7 (1k) [In the formula, R 8 , R 7 , k has the same meaning as above, f and g each are a number from 0 to 4 and satisfy 1≦f+g≦4, the oxyethylene portion and the oxypropylene portion may be either a random addition structure or a block addition structure, R 3The vinyl-terminated polyether can be produced by subjecting a second vinyl-terminated polyether, typified by the formula (II) above, to a hydrosilylation reaction in the presence of a platinum catalyst under known conditions, and then removing or reducing the amount of the second vinyl-terminated polyether, preferably by a method such as stripping treatment under heating and reduced pressure.

[0069] It is known that during the hydrosilylation reaction, isomerization of terminal vinyl groups (internal double bond rearrangement renders some of the compounds represented by formulas (12) and (1k) inert to hydrosilylation) occurs. To completely consume the Si-H groups, the first polyether represented by formula (12) is used in excess relative to the Si-H groups to be reacted, at a molar ratio of HC=CH / Si-H of approximately 1.1 to 1.4. The second polyether represented by formula (1k) can be used in excess relative to the remaining Si-H groups, at a molar ratio of HC=CH / Si-H of approximately 1.3 to 2.0. Since the second polyether can be removed by stripping after the reaction, its dosage can be increased. Therefore, a corresponding amount of unreacted polyether, primarily derived from the first polyether, is typically present in the two-polyether-modified silicone composition represented by formula (10).

[0070] The polyether of formula (12) has the following average chemical structure: H2C=CH(R 8 )-(CH2) k -O(C2H4O) d (C3H6O) e -H (13) [wherein, R 8 , k, d, and e are as defined above], or a polyether having a terminal hydroxyl group represented by the following average chemical structural formula: HO(C2H4O) d (C3H6O) e -R 7 (14) [wherein, R 7 , d and e are as defined above] are often contained as impurities in small amounts. Therefore, these polyethers may also be contained in the two-type polyether-modified silicone composition represented by formula (10) above.

[0071] In the production method of the present invention, the two-type polyether-modified silicone represented by formula (10) and its composition may optionally be subjected to further purification treatments such as hydrolysis in the presence of an acidic inorganic salt by the method described in Japanese Patent No. 5,491,152, hydrogenation by the method described in Japanese Patent Laid-Open No. 07-330907, removal of low boiling points, or filtration. Furthermore, the polyether-modified silicone represented by formula (10) and its composition may have an antioxidant added or dissolved therein in the range of 10 to 1,000 ppm by mass. Examples of antioxidants include vitamin E and BHT (2,6-di-t-butyl-p-cresol).

[0072] In the above-described method for producing a co-modified silicone and a composition thereof, it is preferable to use intermediates, raw material compounds, and starting materials that are less susceptible to deterioration over time after production, in order to prevent side reactions.

[0073] The liquid detergent of the present invention preferably contains: (I) a cleansing organic nonionic surfactant having a polyoxyethylene group (the average number of oxyethylene repeats is within the range of 3 to 16): within a range of 10 to 60% by mass of the entire clear liquid detergent; (II) at least one anti-freeze agent selected from the following (II-1) to (II-3): within a range of 2 to 20% by mass of the entire clear liquid detergent; (II-1) a saturated monohydric alcohol having 2 to 4 carbon atoms; (II-2) a glycol ether mono-substituted with an alkyl group having 1 to 6 carbon atoms (provided that the glycol ether contains an oxyethylene group and / or an oxypropylene group, and the number of repeats is within a range of 1 to 3); (II-3) a di- or triol compound selected from propylene glycol, dipropylene glycol, tripropylene glycol, triethylene glycol, tetraethylene glycol, trimethylene glycol, and glycerin; (III) water: within a range of 20 to 85% by mass of the entire liquid detergent; and (IV) the co-modified silicone composition: within a range of 0.3 to 3% by mass of the entire liquid detergent.

[0074] The liquid detergent may further contain (V) 0.1 to 15 mass % of a stabilizer selected from antibacterial agents (preservatives), hydrotropes, antioxidants, and water softeners (chelating agents) (where the total amount of the above components (I) to (V) is 100 mass %). Similarly, the liquid detergent may further contain (VI) 0.1 to 5% by weight of at least one anti-resoiling agent (anti-redeposition agent or dispersing agent), (VII) 0.1 to 6% by weight of a pH adjuster, (VIII) 0.1 to 2% by weight of a preparation of at least one enzyme selected from protease, lipase, amylase, cellulase, esterase, pectinase, and mannanase, (IX) 1 to 150 ppm of a colorant, and (X) 5 to 6,000 ppm of a fragrance, (where the total amount of (I) to (VIII) is 100% by weight).

[0075] [(I) Organic Nonionic Surfactant] Component (I) is a cleansing organic nonionic surfactant containing a polyoxyethylene group (the average number of oxyethylene repeats is within the range of 3 to 16). Multiple surfactants that fall under (I) may be used in combination. Component (I) is preferably selected from those with excellent supply properties. Representative examples include alkyl polyethoxylate (AE) and fatty acid polyethoxylate methyl ether (FEM). However, polyoxyethylene / polyoxypropylene alkyl ether (AEP) can also be used as an AE that also has anti-foaming properties. The HLB, which is generally considered to be an indicator of good cleansing properties, is approximately 12 to 14.

[0076] AEs have the advantage of being less affected by water hardness and electrolytes and can be used in combination with all other surfactants. There are many types of AEs with different functional characteristics, such as penetration, emulsification / dispersibility, and detergency, due to the combination of differences in the structure and carbon number distribution of the alkyl lipophilic group and differences in the chain length of the polyoxyethylene hydrophilic group. Therefore, they also have the advantage of being able to finely adjust the balance of these diverse functions to suit the design objectives of the liquid detergent. Generally, alkyl groups that can impart good detergency are those having 10 to 16 carbon atoms, and more preferably those having 11 to 15 carbon atoms. Among these, AEs having a linear primary alkyl group are highly crystalline and tend to gel and thicken significantly at high concentrations in aqueous media. Therefore, when incorporating them into concentrated clear liquid detergents, care must be taken to avoid excessive amounts, and measures must be taken to increase the amount of hydrotrope or antifreeze. When an AE having a linear primary alkyl group is incorporated into the clear liquid detergent composition of the present invention, the amount is preferably within the range of 0 to 10% by mass, with 0 to 5% by mass being particularly preferred. AEs having branched alkyl groups and AEs derived from secondary (sec) alcohols tend to be less prone to gelation or thickening at high concentrations in aqueous media, which is advantageous in this respect. However, when biodegradability is also taken into consideration, AEs derived from linear secondary (sec) alcohols are considered more suitable, and are one of the most preferred as component (I) constituting the clear liquid detergent composition of the present invention. When an AE derived from a linear secondary (sec) alcohol is incorporated as the primary nonionic surfactant in the clear liquid detergent composition of the present invention, its amount is preferably within the range of 10 to 35% by mass, with 15 to 30% by mass being particularly preferred. However, when it is treated as an auxiliary surfactant component, its amount may be less than 10%. On the other hand, AEPs have reduced cohesion even when they contain linear primary alkyl groups, allowing them to be incorporated at higher concentrations than ordinary AEs. The amount of AEP blended in the transparent liquid detergent composition of the present invention is preferably within the range of 0 to 30% by mass, and particularly preferably within the range of 10 to 20% by mass.

[0077] FEM also allows for control of functional characteristics such as penetration, emulsification / dispersibility, and detergency by combining differences in the carbon number distribution in the fatty alkyl group with differences in the chain length of the polyoxyethylene hydrophilic group. Generally, alkyl groups with 10 to 16 carbon atoms are considered to be able to impart good detergency, with 11 to 15 carbon atoms being more preferred. Unlike AE and AEP, FEM does not contain hydroxyl groups in its molecule, thereby suppressing hydrogen bonding interactions. As a result, it is characterized by extremely low gelation and thickening at high concentrations in aqueous media. Therefore, FEM is one of the preferred components (I) constituting the clear liquid detergent composition of the present invention. When FEM is used as the primary nonionic surfactant in the clear liquid detergent composition of the present invention, its amount is preferably within the range of 10 to 50% by mass, with 20 to 40% by mass being particularly preferred. However, when FEM is used as an auxiliary surfactant component, its amount may be less than 10%. Like AE and AEP, FEM has the advantage that its detergency is less affected by water hardness. However, because it contains an ester group in its molecule, it may undergo hydrolysis depending on conditions such as pH and temperature after being incorporated into liquid detergent, resulting in a gradual decline in performance and quality. When incorporating FEM, the pH of the liquid detergent should preferably be controlled within the range of 6.0 to 8.0, and more preferably within the range of 6.5 to 7.5. It is also important to note that when incorporating FEM into a clear liquid detergent formulation, it is best to avoid incorporating esterases and lipases.

[0078] In the clear concentrated liquid detergent composition for home laundry of the present invention, the total amount of component (I) is preferably within the range of 10 to 60% by mass of the total clear liquid detergent. Although the preferred range of the amount of AE, FEM, or AEP as component (I) is as described above, when a highly concentrated clear liquid detergent is desired, the total amount of component (I) may be within the range of 10 to 60% by mass, 20 to 60% by mass, or 30 to 60% by mass.

[0079] [(II) Antifreeze Agent] Component (II) is at least one antifreeze agent selected from the following (II-1) to (II-3), and is blended in the clear liquid detergent composition of the present invention in an amount of 2 to 20% by mass. These may be used in combination. The preferred blend amount of (II) is 4 to 15% by mass, more preferably 6 to 10% by mass. If the blend amount of (II) is less than 2%, the fluidity of the clear liquid detergent decreases, resulting in a problem of increased susceptibility to freezing in winter depending on the geographical environment. While blending in an amount exceeding 20% ​​is possible, the relative reduction in the amount of water in component (III) leads to a poor cost-effectiveness balance.

[0080] (II-1) is a saturated monohydric alcohol having 2 to 4 carbon atoms, examples of which include ethanol, denatured alcohol, 1-propanol, 2-propanol, 1-butanol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, and any mixture thereof. Ethanol and low-odor denatured alcohol are preferred in terms of low odor. 1-butanol may be slightly more advantageous in terms of foam suppression.

[0081] (II-2) is a glycol ether monosubstituted with an alkyl group having 1 to 6 carbon atoms (provided that the glycol ether contains an oxyethylene group and / or an oxypropylene group, and the number of repetitions is within the range of 1 to 3). (II-2) is preferably selected from those with excellent supplyability, and examples of such glycol ethers include propylene glycol methyl ether, propylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol methyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol n-butyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, triethylene glycol n-butyl ether, ethylene glycol n-hexyl ether, diethylene glycol n-hexyl ether, and compounds in which 1 to 2 moles of propylene oxide are added to diethylene glycol n-butyl ether. In general, glycols with a repetition number of 2 offer a good balance between safety and cost and are easy to use. On the other hand, in terms of compatibility with other components, n-butyl ether and n-hexyl ethers, which have a large number of carbon atoms in the alkyl substituent, are preferred, and therefore, from a comprehensive viewpoint, diethylene glycol n-butyl ether, diethylene glycol n-hexyl ether, and dipropylene glycol n-butyl ether are particularly suitable.

[0082] (II-3) is a diol or triol compound selected from propylene glycol, dipropylene glycol, tripropylene glycol, triethylene glycol, tetraethylene glycol, trimethylene glycol, and glycerin, of which propylene glycol, dipropylene glycol, tripropylene glycol, and trimethylene glycol are more preferred, and propylene glycol or dipropylene glycol is most preferred.

[0083] [(III) Water] Component (III) is water, and is incorporated into the clear liquid detergent composition of the present invention in an amount ranging from 20 to 85% by mass. While (III) is not particularly limited as long as it is clean, ion-exchanged water, sterilized water, distilled water, purified water, pure water, etc. are preferred, and tap water or well water may also be usable. If the amount of (III) is less than 20% by mass, not only does the cost of the liquid detergent increase, but it also tends to be difficult to stably incorporate enzymes. If the amount of (III) is more than 85% by mass, there is less room to incorporate effective amounts of various essential ingredients, making it difficult for consumers to realize the intended effects and making it difficult to design a practical clear liquid detergent product. Furthermore, if the proportion of water in the detergent is high, the transportation costs for water during detergent transportation increase, leading to wasteful logistics costs.

[0084] [(IV) Co-modified Silicone and Composition Thereof] Component (IV) is the co-modified silicone and composition thereof according to the present invention, as described above, and is typically incorporated within a range of 0.3 to 3 mass% of the total clear liquid detergent. Within this range, it is cost-effective and easily soluble in existing light-duty clear liquid detergent formulations that use nonionic surfactants as the main cleaning ingredient. A content of less than 0.3 mass% makes it difficult to achieve softening effects, fiber lubrication effects, texture-improving effects, or fiber surface coating effects. A content of more than 3 mass% tends to reduce formulation stability in clear liquid detergents, necessitating measures such as increasing the amount of component (II) to improve solubility or selecting a component (I) with a compatibilizing effect for use in the formulation, which can result in poor economic efficiency. In particular, because the co-modified silicone composition according to the present invention is highly pure, when incorporated within the above range, it has the advantage of being able to efficiently incorporate the main co-modified silicone in terms of quantity, and of having minimal impact on transparency and stability in concentrated clear liquid detergents, thereby enhancing the commercial appeal of the clear liquid detergent.

[0085] [(V) Stabilizer] Component (V) is a stabilizer selected from antibacterial agents (preservatives), hydrotropes, antioxidants, and water softeners (chelating agents), and its amount is 0.1 to 15% by mass of the clear liquid detergent composition of the present invention (where the total amount of (I) to (V) is taken as 100% by mass).

[0086] The antibacterial agent (antiseptic) of component (V) is not particularly limited as long as it can be incorporated into household laundry detergents, and examples include phenoxyethanol, phenoxypropanol, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, saturated alkanediols having 4 to 8 carbon atoms, monoalkyl or alkenyl ethers of glycerin, borates, benzoic acid, parabens, sodium benzoate, sodium dehydroacetate, formic acid, glutaraldehyde, benzyl alcohol, isopropylmethylphenol, diclosan, triclosan, chlorophene, parachlorometaxylenol, chlorthymol, carvacrol, dichlorophene, hexachlorophene, chlorocresol, methylisothiazolinone / methylchloroisothiazolinone mixture, isothiazolinone / benzisothiazolinone mixture, 5-chloro-2-methyl-4-isothiazolin-3-one, 1,2-benzothiazolone, and 2-(4-methylaminomethylthio)benzimidazole. Of these, phenoxyethanol, phenoxypropanol, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, saturated alkanediols having 4 to 8 carbon atoms, and monoalkyl or alkenyl ethers of glycerin are often liquid at room temperature and relatively inexpensive among preservatives and antibacterial agents, so the blending amount can be increased up to 10% by mass. Other preservatives are highly effective and many are expensive, so it is usually preferable to blend them in the range of 0.1 to 2% by mass.

[0087] Examples of the hydrotrope agent related to component (V) include toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, and their sodium or potassium salts. In the present invention, the amount of the hydrotrope agent blended is preferably within the range of 0 to 4 mass%, more preferably 0 to 2 mass%.

[0088] The antioxidant for component (V) is typically preferably incorporated in the range of 0.01 to 1% by mass, and is selected from those that have minimal impact on the design color of the liquid detergent. Multiple types of antioxidants may be used in combination. Examples include sodium sulfite, sodium bisulfite, and phenolic antioxidants. Examples of phenolic antioxidants include dibutylhydroxytoluene, butylhydroxyanisole, 2,2'-methylenebis(4-methyl-6-t-butylphenol), distyrenated cresol, dl-α-tocopherol, d-δ-tocopherol, and natural vitamin E, with dibutylhydroxytoluene being particularly preferred.

[0089] The water softener (chelating agent) for component (V) is not particularly limited as long as it is compatible with household laundry detergents. However, it is generally preferred to incorporate it in a range of 0.1 to 3% by mass, and multiple types may be used in combination. In geographical environments where the water used for washing is highly hard, the amount of chelating agent added to a clear liquid detergent may need to be increased to approximately 5% by mass. Specific examples include polycarboxylic acids and their salts, such as malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid, and citric acid. Other usable salts include ethylenediaminetetraacetic acid (salts), diethylenetriaminepentaacetic acid (salts), methylglycine diacetic acid (salts), ethylglycine diacetic acid (salts), nitrilotriacetic acid (salts), iminodisuccinic acid (salts), iminodiacetic acid (salts), tetrasodium aspartate-N,N-diacetate, trisodium serine diacetate, and tetrasodium glutamate diacetate. Also usable are 1-hydroxyethane-1,1-diphosphonic acid, aminotri(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), 2-phosphono-1,2,4-butanetricarboxylic acid, and their sodium, potassium, ammonium, and alkanolamine salts. Citric acid, malic acid, trisodium methylglycine diacetate, and 1-hydroxyethane-1,1-diphosphonic acid salts are preferred.

[0090] [(VI) Anti-Redeposition Agent] The amount of the anti-redeposition agent (anti-redeposition agent or dispersant) related to component (VI) is usually preferably in the range of 0.1 to 5% by mass. It has functions such as adsorbing to fibers and soiling components to increase the electrical repulsion between them, and stably dispersing soiling components in the cleaning solution to prevent redeposition to fibers. Generally, polymers such as polyalkylene glycols, polyacrylic acids, celluloses, polyvinylpyrrolidones, and ethoxylated polyethyleneimines are commonly used, and multiple types may be used in combination. Specific examples include polyacrylic acid, polymaleic acid, acrylic acid / maleic acid copolymers, carboxymethylcellulose, polyvinylpyrrolidone, polyethylene glycol, polypropylene glycol, propylene oxide adducts of polyhydric alcohols, ethoxylated polyethyleneimine, and propoxylated polyethyleneimine.

[0091] [(VII) pH Adjuster] Component (VII) is a pH adjuster. The amount of component (VII) used varies depending on the target pH value of the clear liquid detergent, but is typically used in the range of 0.1 to 6% by mass, preferably 0.5 to 3% by mass. Examples of component (VII) include acidic compounds such as sulfuric acid, hydrochloric acid, lactic acid, glycolic acid, glutamic acid, aspartic acid, and sulfamic acid; alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, and methylethanolamine; and alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate. Two or more pH adjusters may be used in combination. From the perspective of the stability of the liquid detergent over time, sulfuric acid, sodium hydroxide, potassium hydroxide, and alkanolamines are preferred, with monoethanolamine being particularly preferred due to its ability to prevent deformation and deterioration of the objects being cleaned and to prevent discoloration.

[0092] [(VIII) Enzyme] Component (VIII) is a preparation of at least one enzyme selected from protease, lipase, amylase, cellulase, esterase, pectinase, and mannanase, and is typically incorporated in an amount of 0.1 to 2% by mass. When incorporating component (VIII) into a clear liquid detergent composition, techniques introduced or cited in Japanese Patent No. 5,436,199 (JP 2011-137074 A), Japanese Patent No. 6,188,239 (JP 2016-017133 A), and Japanese Patent No. 6,732,424 (JP 2017-071664 A) may be utilized to prevent a decrease in enzyme activity.

[0093] Aesthetic quality improvers: (IX) colorant and (X) fragrance. The liquid detergent of the present invention may further contain aesthetic quality improvers from the standpoint of usability and the appearance / fragrance of the formulation. Specifically, component (IX) is 1 to 150 ppm of colorant, and component (X) is 5 to 6,000 ppm of fragrance. Preferably, at least one aesthetic quality improver selected from (IX) and (X) is blended in a range of 10 to 6,000 ppm (where the total of (I) to (VIII) is taken as 100% by mass). Representative examples of fragrance formulations are shown in JP-A-2002-146399 and JP-A-2021-134324. Components (IX) and (X) may be omitted depending on the formulation, appearance, and fragrance of the desired liquid detergent.

[0094] [Combination of Components] The liquid detergent (particularly a clear liquid detergent) according to the present invention, which contains the components (I) to (IV) and, optionally, the components (V) to (X), can be produced by dissolving the components (I) to (VII) by heating and mixing at 40 to 80°C, cooling to 30°C or below, and then adding one or more components selected from components (VIII), (IX) and (X) and mixing to homogenize. Depending on the formulation of the desired liquid detergent, some or all of the components (V) to (X) may be omitted in the production process.

[0095] The liquid detergent of the present invention (particularly including a clear concentrated liquid laundry detergent or a clear liquid detergent) may optionally contain other optional components that can be incorporated into a clear liquid detergent for home laundry, in particular, and that do not fall under the above-mentioned components (I) to (X), within a range that does not impair the technical effects of the present invention.

[0096] Examples of other optional components include organic surfactants other than component (I), oils, softeners, or texture-improving components other than component (IV) that are known to be incorporated into household liquid detergents (e.g., organic oils, polyether-modified silicones, amide polyether group-containing silicones produced by previously reported methods, organic cationic polymers for imparting firmness or stiffness or reducing wrinkles, etc.), agents for enzyme stabilization, fluorescent brighteners, appropriate amounts of inorganic salts, polyethylene glycol phenyl ether detergency enhancers, fatty acids (salts), foam suppressors, etc. Foam suppressors that can be used in the liquid detergents of the present invention explicitly include the components disclosed by the present inventors in Japanese Patent Application No. 2023-47481 and the priority application therefor.

[0097] The organic surfactants other than component (I) may be blended in an appropriate amount, taking into consideration the basic formulation framework of each detergent manufacturer's light-duty transparent liquid detergent (a balanced product that can provide not only moderate detergency but also softening and texture-improving effects on items such as clothing). Examples of such surfactants include anionic surfactants, amphoteric surfactants, cationic surfactants, and weakly cationic surfactants. Since these are not essential components in the present invention, their content in the transparent liquid detergent is usually 5% by mass or less, and preferably 10% by mass or less when it is desired to emphasize these effects.

[0098] [Incorporation of Ionic Surfactants] In order to formulate a light-duty transparent liquid detergent containing the co-modified silicone and its composition according to the present invention so that it can be used on almost all clothing materials, such as wool, silk, cotton, linen, and synthetic fibers, without adversely affecting them, it is considered convenient and efficient to use multiple specific organic nonionic surfactants as cleansing surfactants and not include ionic surfactants, as reported in Patent Documents 3 and 6. On the other hand, this does not preclude the detergent manufacturer from optionally using a small amount of an ionic surfactant in combination, depending on its convenience, etc. In this case, it is considered best to design the liquid detergent so that the pH is neutral, around 7.0, so as not to damage wool or silk, and to incorporate lipase or esterase as the enzyme.

[0099] When a light-duty, transparent liquid detergent containing the co-modified silicone and its composition of the present invention is primarily intended for clothing and other materials made of relatively durable, durable synthetic fibers such as cotton or polyester, its detergency can be enhanced by incorporating an appropriate amount of a specific anionic surfactant, such as those described in Patent Documents 8, 10, and 11, in addition to component (I). In this design concept, it is preferable to further incorporate a protease as an enzyme in the aforementioned component (VIII), thereby enhancing the detergency against proteinaceous stains. In this case, it is preferable to design the liquid detergent so that its pH is neutral, around 7.0, in order to maintain enzyme function.

[0100] When it is desired to add texture, softening effects, static electricity suppression, or antibacterial effects to a clear liquid detergent containing the co-modified silicone and its composition of the present invention by using a cationic surfactant, an appropriate amount of a specific quaternary ammonium salt as described in Patent Documents 8 and 9, WO 1994 / 06899, etc., may be blended. Among these, highly biodegradable ester quaternary salts are preferred, and examples include TEAQ (triethanolamine quaternary salt), DEEDMAC (diethyloxyethyldimethyl ammonium chloride), HEQ ((Z)-2-hydroxy-3-[(1-oxo-9-octadecenyl)oxy]propyltrimethylammonium chloride), bis[2-(stearoyloxy)ethyl]dimethylammonium chloride, bis[2(hexadecanoyloxy)ethyl]dimethylammonium chloride, and the quaternized dimethyl sulfate of the reaction product of octadecenoic acid and triethanolamine. Amide-type alkylammonium salts such as stearamidopropyldimethyl-β-hydroxyethylammonium salt may also be used. When a quaternary ester salt is used, it is preferable to design the liquid detergent so that its pH is neutral, around 7.0.

[0101] [Use, Advantages, and Other Applications of the Co-Modified Silicone and Its Composition of the Present Invention in Clear Liquid Detergents] As described above, the co-modified silicone and its composition of the present invention can be incorporated into concentrated clear liquid laundry detergents or clear liquid detergents. When incorporated into liquid detergents with a clear appearance, the composition does not impair or only slightly impairs the transparency of the detergent, and can be used as a fabric softener, fabric lubricant, texture-improving component, or fabric surface coating component. Furthermore, the composition has a low viscosity and does not thicken or change in appearance during storage, or if it does, it only does so to a small extent. This simplifies quality control, makes it highly practical, and makes it easy to handle when producing liquid detergents. Because the composition contains few impurities, it can be incorporated in larger amounts into clear liquid detergents, which has the advantage of enhancing the retroactive effect of the clear liquid detergent.

[0102] The co-modified silicone and composition thereof according to the present invention may also be used in applications other than liquid detergents, and may be used, for example, in the field of fiber treatment agents as described in Patent Document 1, the field of treatment agents for wiping paper as described in Patent Document 7, the field of personal care products such as hair cleansers and hair treatment agents, and fabric softener applications. Furthermore, the co-modified silicone and composition thereof may also be used by adding it to liquid detergents or solid detergents that are opaque in appearance, and there are no particular limitations on the application.

[0103] The present invention will be explained in more detail below with reference to comparative examples and examples, but the present invention is not limited thereto. In the experimental examples, "%" means mass % unless otherwise specified. For simplicity, in the following reference examples, comparative examples, and examples, M is (CH3)3SiO 1 / 2 Units, D is (CH3)2SiO Units, D H is H(CH3)SiO unit, T is CH3SiO 3 / 2 Unit, D (AM) is (CH3)(C3H6NH2)SiO unit, D (AMD) is (CH3){C3H6NHCO-CH2O(EO) 4.5 -C 12 H 25}SiO units, D (PE1) is (CH3){C3H6O(EO) 11 -CH3}SiO units, D (PE2) means (CH3){C3H6O(EO)3-CH3}SiO unit, EO means CH2CH2O unit, PO means C3H6O unit {mainly CH2(CH3)CHO unit}, Me means CH3 group, IPA means 2-propanol, CPA means chloroplatinic acid H2[PtCl6].(H2O)6, D4 means octamethylcyclotetrasiloxane, and POE(4.5) means polyoxyethylene (addition mole number of oxyethylene group: 4.5). The average chemical structure of each compound is ２９ Si, １３ The compositions were identified by NMR analysis using C as a nuclide. The viscosity (mPa·s) of each composition was measured at 25° C. using a rotational viscometer.

[0104] Reference Example 1 Preparation of Two Types of Polyether-Modified Silicone Composition (Base Material) Designed Average Chemical Structural Formula MD 51.3 D H 6.3 134.1g of Si-H group-containing dimethylpolysiloxane represented by M, designed average chemical structure H2C=CH-CH2-O(EO) 11 103.1 g of a first allyl-terminated polyether represented by the formula H2C=CH-CH2-O(EO)3-Me was placed in a 500 mL reactor and heated with stirring under a nitrogen gas flow. 0.33 mL of an IPA solution of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex (Pt concentration: 0.75 wt%) was added to the mixture, and the mixture was aged at 40-82°C for 1.5-2.5 hours, at which point the target reaction rate was reached. Next, 14.8 g of a second allyl-terminated polyether represented by the designed average chemical structure H2C=CH-CH2-O(EO)3-Me and 0.33-0.88 mL of the platinum catalyst solution were added, and the mixture was aged at approximately 80°C for 3-3.5 hours, at which point the reaction was complete. The system is depressurized, and the stripping process is carried out for 1.5 to 5 hours at 130 to 138°C and 1 to 10 Torr. After that, the system is cooled to 55°C or less, the pressure is restored, and the system is filtered through a depth filter. The average chemical structure of the system is MD 51.3 D (PE1) 5.2 D (PE2) 1.1 M { (PE1) = -C3H6O(EO) 11 -Me, (PE2) This yielded 217 g of a two-type polyether-modified silicone composition represented by {H₂C═CH₆=-C₃H₆O(EO)₃-Me} as a nearly colorless, transparent liquid. Because the H₂C═CH / Si-H molar ratio with respect to the first polyether during the hydrosilylation reaction was 1.15, the excess polyether content in the two-type polyether-modified silicone composition was calculated to be 5.5 mass %.

[0105] Reference Example 2: Preparation of two-type polyether-modified silicone composition (raw material) The same experiment as Reference Example 1 was carried out later. The reactivity of the first polyether was slightly reduced, but this was not a problem. 51.3 D (PE1)5.0 D (PE2) 1.3 M { (PE1) = -C3H6O(EO) 11 -Me, (PE2) = -C3H6O(EO)3-Me} was obtained as a pale brown, transparent liquid. Back-calculation from the reactivity of the first polyether revealed that the H2C=CH / Si-H molar ratio with respect to the first polyether during the first hydrosilylation reaction was 1.20. Based on this, the excess polyether content in the two-polyether-modified silicone composition was calculated to be 6.9 mass%.

[0106] [Reference Example 3] Preparation of a single polyether-modified silicone composition Designed average chemical structure MD 72.8 D H 4.8 253.53g of Si-H group-containing dimethylpolysiloxane represented by M, designed average chemical structure H2C=CH-CH2-O(EO) 11 A 500 mL reactor was charged with 146.48 g of an allyl-terminated polyether represented by -Me, and heating was initiated while stirring under a nitrogen gas flow. To this mixture was added 0.48 mL of an IPA solution of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex (Pt concentration 0.75 wt%). The mixture was aged at 54-98°C for a total of 5 hours, with sampling to check the reaction rate. The reaction was nearly complete, yielding 385.3 g of a light brown hazy liquid. 220 g of this was filtered through an activated carbon-loaded depth filter, revealing the average chemical structure MD 72.8 D (PE1) 4.8 M { (PE1) = -C3H6O(EO) 11 A single polyether-modified silicone composition represented by {-Me} was obtained as a colorless, transparent liquid in an amount of 197 g {582 mPa s (25 C)}. Because the H2C=CH / Si-H molar ratio during the hydrosilylation reaction was 1.30, the excess polyether content in the polyether-modified silicone composition was calculated to be 8.5 mass%.

[0107] Reference Example 4: Preparation of a Single Polyether-Modified Silicone Composition The same experiment as in Reference Example 3 was repeated using 90% of the total amount of the main raw materials charged. However, 0.30 mL of a 5% by mass CPA solution in IPA was used as the hydrosilylation catalyst, and the reaction was completed after a total of 4 hours of aging at a reaction temperature of 60 to 102°C, yielding 344.3 g of a light brown hazy liquid. This was filtered in the same manner as in Reference Example 3, and the average chemical structure of the liquid was determined to be MD 72.8 D (PE) 4.8 M { (PE) = -C3H6O(EO) 11 As a result, 317 g of a single polyether-modified silicone composition represented by {-Me} was obtained as a colorless, transparent liquid.

[0108] [Reference Example 5] Preparation of a single polyether-modified silicone composition Designed average chemical structure MD 108.4 D H 8.1 40.93 parts by mass of Si-H group-containing dimethylpolysiloxane represented by M, designed average chemical structure H2C=CH-CH2-O(EO) 11 A reactor was charged with 59.07 parts by mass of an allyl-terminated polyether represented by -Me, and heating was initiated while stirring under a nitrogen gas flow. 200 ppm by mass of a 5% by mass CPA solution in IPA was added, and the mixture was aged at 60 to 85°C for 2 hours, at which point the reaction was nearly complete. The mixture was filtered through a 1 μm pore filter, and the average chemical structure of the product was determined to be MD 108.4 D (PE) 8.1 M { (PE) = -C3H6O(EO) 11 This yielded 99 parts by mass of a single polyether-modified silicone composition represented by {—Me} as a pale yellow-brown, nearly transparent liquid. Because the H₂C═CH / Si—H molar ratio during the hydrosilylation reaction was 1.33, the excess polyether content in the polyether-modified silicone composition was calculated to be 10.2 mass%.

[0109] Reference Example 6: Preparation of an Amide Polyether Group-Containing Silicone Composition by a Previously Published Method (See Paragraph 0011) 32.3 parts by mass of the polyether-modified silicone composition of Reference Example 5, 40.84 parts by mass of D4, 4.74 parts by mass of a hydrolysis condensate of 3-aminopropylmethyldiethoxysilane, and 300 ppm by mass of an 11N KOH aqueous solution were charged into a reactor, and heating was initiated with stirring under a nitrogen gas flow. After a reaction at 147-152°C for 1 hour, 200 ppm by mass of acetic acid was added to neutralize the alkali catalyst. Further stripping was carried out for 2.5 hours under conditions of 142-150°C and 30 Torr, followed by cooling to below 75°C and restoring the pressure, yielding an intermediate amino / polyether-modified silicone composition. To this was added 22.36 parts by weight of POE(4.5) lauryl ether acetic acid solution (92% by weight of active ingredient, 7.5% by weight of water, 0.5% by weight of NaCl), and the mixture was subjected to a normal pressure amidation reaction at 123-127°C for 3 hours. After cooling to below 75°C and filtering, 91 parts of an amide polyether group-containing silicone composition produced by a previously reported method was obtained as a light brown, almost transparent liquid {1320 mPa s (25°C)}. The COOH / NH molar ratio at the time of the amidation reaction was 1.26, and the excess polyether content in the composition was calculated to be 3.4% by weight.

[0110] Reference Example 7: Preparation of High-Purity Amino / Amide / Single-Polyether-Modified Silicone Composition. 154.25 g of the single-polyether-modified silicone composition of Reference Example 3, 130.78 g of D4, 18.24 g of a hydrolysis condensate of 3-aminopropylmethyldiethoxysilane, and 0.12 g of a 43% aqueous KOH solution were charged into a 500 mL reactor, and heating was initiated with stirring under a nitrogen gas flow. After 3 hours of equilibration reaction at 140-156°C, with intermittent sampling to check viscosity, the mixture was cooled to 75°C and 0.34 g of acetic acid was added to neutralize the alkali catalyst. Stripping was then carried out for 2 hours at 146-163°C and 40-45 Torr. After pressure recovery and sampling, 265.8 g {1838 mPa s (25°C)} of an intermediate amino / polyether-modified silicone composition was obtained as a translucent liquid. To this was added 35.8 g of POE(4.5) lauryl ether acetic acid solution (92 wt% active ingredient, 7.5 wt% water, 0.5 wt% NaCl), and the system was depressurized. After amidation reaction for 4 hours at 122-128°C and 30 Torr, the mixture was cooled to below 90°C, the pressure was restored, and the mixture was filtered through a depth filter to obtain 244 g of a high-purity amino / amide / single polyether-modified silicone composition as a transparent yellow liquid {2012 mPa·s (25°C)}. The COOH / NH2 molar ratio during the amidation reaction was calculated to be 0.54, and the excess polyether content in the final composition was calculated to be 3.9 wt%.

[0111] Reference Example 8: Preparation of High-Purity Amino / Amide / Single-Polyether-Modified Silicone Composition. 154.24 g of the single-polyether-modified silicone composition of Reference Example 4, 127.54 g of D4, 18.25 g of a hydrolysis condensate of 3-aminopropylmethyldiethoxysilane, and 0.13 g of a 43% aqueous KOH solution were charged into a 500 mL reactor, and heating was initiated with stirring under a nitrogen gas flow. After 6 hours of equilibration reaction at 146-158°C, with intermittent sampling for viscosity confirmation, the mixture was cooled to 64°C and 0.30 g of acetic acid was added to neutralize the alkali catalyst. Stripping was then carried out for 1 hour and 40 minutes at 142-150°C and 7-8 Torr. After pressure recovery and sampling, 234 g {1363 mPa s (25°C)} of the intermediate amino / polyether-modified silicone composition was obtained as a pale yellow, almost transparent liquid. To this was added 31.57 g of POE(4.5) lauryl ether acetic acid solution (92 wt% active ingredient, 7.5 wt% water, 0.5 wt% NaCl), and the system was depressurized. After amidation reaction for 4 hours at 118-125°C and 8-9 Torr, the mixture was cooled to below 90°C, the pressure was restored, and the mixture was filtered through a depth filter to obtain 233.8 g of a high-purity amino / amide / single polyether-modified silicone composition as a transparent orange liquid {1767 mPa·s (25°C)}. The COOH / NH2 molar ratio during the amidation reaction was calculated to be 0.54, and the excess polyether content in the final composition was calculated to be 3.9 wt%.

[0112] Reference Example 9: Preparation of amino / two-type polyether-modified silicone composition (intermediate) An amino / two-type polyether-modified silicone composition {723 mPa s (25C)} sampled during the preparation of Example 1 (composition of the present invention) described below was used as Reference Example 9.

[0113] Example 1 Preparation of Amino / Amide / Two-Type Polyether-Modified Silicone Composition 142.95 g of the two-type polyether-modified silicone composition of Reference Example 1, 92.02 g of D4, 15.09 g of a hydrolysis condensate of 3-aminopropylmethyldiethoxysilane, and 0.11 g of a 43% aqueous KOH solution were charged into a 500 mL reactor, and heating was initiated with stirring under a nitrogen gas flow. After allowing time for equilibration reaction at 146-155°C for 6 hours, with intermittent sampling for viscosity confirmation, the mixture was cooled to 78°C and 0.32 g of acetic acid was added to neutralize the alkali catalyst. Stripping was then carried out for 1 hour at 151-153°C and 27 Torr. After cooling, pressure recovery, and sampling, 200.6 g {723 mPa·s (25°C)} of the intermediate amino / two-type polyether-modified silicone composition was obtained as a pale yellow, translucent liquid. To this mixture was added 26.45 g of POE(4.5) lauryl ether acetate solution (92% active ingredient, 7.5% water, 0.5% NaCl), and the system was depressurized. After amidation for 6 hours at 116-122°C and 21-25 Torr, the mixture was cooled to below 95°C, the pressure was restored, and the mixture was filtered through a depth filter to yield 200.2 g of the amino / amide / two-polyether composite-modified silicone composition of the present invention as a pale Cannella-colored, transparent liquid (913 mPa·s (25°C)). The COOH / NH molar ratio during the amidation reaction was 0.54, and the excess polyether content in the final composition was calculated to be 3.1% by mass.

[0114] Example 2: Preparation of Amino / Amide / Two-Polyether-Modified Silicone Composition. 71.05 g and 70.09 g of the two-polyether-modified silicone compositions of Reference Example 1 and Reference Example 2, respectively, were charged into a 500 mL reactor, and heating was initiated with stirring under a nitrogen gas flow. After 5 hours of equilibration at 141-155°C, the mixture was cooled to 74°C and 0.37 g of acetic acid was added to neutralize the alkali catalyst. The pressure was then reduced to 30 Torr, and stripping was initiated. The low-boiling point removal step was terminated when the temperature reached 154°C. After cooling, pressure recovery, and sampling, 222 g {688 mPa·s (25°C)} of an intermediate amino / two-polyether-modified silicone composition was obtained. To this mixture was added 29.43 g of POE(4.5) lauryl ether acetate solution (92% active ingredient by weight, 7.5% water by weight, 0.5% NaCl by weight), and the system was depressurized. After a 5-hour amidation reaction at 117-120°C and 5-10 Torr, the mixture was cooled to below 70°C, the pressure was restored, and the mixture was filtered through a depth filter to obtain 219 g of the amino / amide / two-polyether composite-modified silicone composition of the present invention as a dark orange, transparent liquid (920 mPa·s (25°C)). The COOH / NH molar ratio during the amidation reaction was calculated to be 0.54, and the excess polyether content in the final composition was calculated to be 3.9% by weight.

[0115] Comparative Example 1: Changes over time in the amide polyether group-containing silicone composition of Reference Example 6 The amide polyether group-containing silicone composition obtained in Reference Example 6 was placed in a lidded container (equivalent to 40% of the container's volume), filled with nitrogen gas, and stored at room temperature for 40 days. After opening the container and inspecting the contents, it was found to have changed into a highly turbid, heterogeneous liquid, with floating gel particles also observed. 1 kg of the liquid was then sampled and filtered through a depth filter, yielding 976 g of a pale yellow-brown, translucent liquid amide polyether group-containing silicone composition {2060 mPa s (25°C)}.

[0116] Comparative Example 2: Preparation of an Amide Polyether Group-Containing Silicone Composition by a Previously Published Method (see Paragraph 0011) 154.23 g of the polyether-modified silicone composition of Reference Example 4, 127.53 g of D4, 18.24 g of a hydrolysis condensate of 3-aminopropylmethyldiethoxysilane, and 0.12 g of a 43% aqueous KOH solution were charged into a 500 mL reactor, and heating was initiated with stirring under a nitrogen gas flow. After allowing time for 6 hours of equilibration reaction at 146-163°C, with intermittent sampling for viscosity confirmation, the mixture was cooled to 65°C and 0.33 g of acetic acid was added to neutralize the alkali catalyst. Stripping was then carried out for 1 hour and 40 minutes at 131-159°C and 28-31 Torr. After pressure recovery and sampling, 242 g {1657 mPa·s (25°C)} of the intermediate amino / polyether-modified silicone composition was obtained as a pale yellow-white cloudy liquid. To this was added 67.66 g of POE(4.5) lauryl ether acetic acid solution (92% by weight of active ingredient, 7.5% by weight of water, 0.5% by weight of NaCl), and the mixture was subjected to a normal pressure amidation reaction at 122-127°C for 3 hours. After cooling to room temperature, 296 g of an amide polyether group-containing silicone composition was obtained as a transparent yellow liquid (3970 mPa·s (25°C)) by a previously reported method. The COOH / NH2 molar ratio during the amidation reaction was 1.26, and the excess polyether content in the composition was calculated to be 3.5% by weight.

[0117] Table 1 below summarizes the relationship between the average chemical structure and viscosity of the Examples and some Reference and Comparative Examples based on NMR analysis and reaction rate tests during synthesis experiments. OR’ The content of each structural unit is shown as the number of moles, assuming a total of 2.00 moles of units. Table 1. Average chemical structure of the samples *Reference Examples 7 and 8 are not known co-modified silicones, but unlike the examples of the present application, they do not have a second polyether modifying group. Therefore, for comparison of viscosity and the like and to clarify the technical significance of the present invention, the following tables show these. * is added in the tables below.

[0118] Although Comparative Example 1 (or Reference Example 6) and Comparative Example 2 were very close to the target average chemical structure, the viscosity and M OR’A large variation in content was observed. Therefore, it became clear that amino / amide polyether / polyether-modified silicones with a structure in which both ends of the polysiloxane main chain are blocked with trimethylsilyl groups cannot be produced under the conditions of the previously reported atmospheric amidation reaction. Furthermore, Reference Examples 7 and 8, which were designed to reduce excess carboxyl groups, provided a more stable final product viscosity than the Comparative Examples. In contrast, Examples 1 and 2, which reduced excess carboxyl groups and introduced a low-molecular-weight second polyether, were found to have the additional advantage of extremely little batch-to-batch variation in product viscosity. In addition, their viscosity was lower than that of the Reference Example samples, making them easier to handle.

[0119] That is, the present inventors have found that the average polysiloxane chain length is short and M OR’ It was discovered that only when the four conditions of low content, small total molar number of carboxylate groups and acyloxy groups, and having a low-molecular-weight second polyether group together with the first polyether group in the molecule are satisfied can the co-modified silicone and composition thereof be maintained at a low viscosity, and further the viscosity reproducibility between batches is excellent, making it possible to simultaneously achieve high purity, good handleability, and production stability.

[0120] Table 2 below summarizes the percentage deviations from the average initial viscosity (assumed to be the target value) for two batches each of the Examples, Reference Examples, and Comparative Examples. Table 2. Viscosity Variation from Target Value

[0121] The two batches of Example 1 were confirmed to have the advantage of having even less batch-to-batch viscosity variation than the two batches of Reference Example 2, due to the effect of introducing a low-molecular-weight second polyether. Furthermore, the two batches of Reference Example 1 were able to suppress batch-to-batch viscosity variation more significantly than the two batches of Comparative Example 1, due to the effect of reducing excess carboxyl groups.

[0122] Table 3 below summarizes the general physical properties of the examples and several reference and comparative examples. Data on appearance (transparency) and viscosity after long-term storage at room temperature are also shown. In the table, ND means not detected or below the detectable level, the D4 / D5 / D6 content is the analysis result obtained by gas chromatography (for the examples, headspace gas chromatography was used, which improved detection sensitivity by stabilizing the baseline), and NH2% is the analysis result (unit: mass%) obtained by neutralization titration using dilute hydrochloric acid. Table 3. General physical properties of each sample and their changes

[0123] Examples 1 and 2 maintained low viscosity and good handling properties during storage for 1 to 3 months. There was also little change in appearance transparency. In other words, the Examples surpassed the instability of the quality of the Comparative Example. Furthermore, while the Comparative Example failed to achieve the goal of limiting the cyclic dimethylsiloxane tetramer, pentamer, and hexamer to 0.10% or less, both Examples 1 and 2 achieved this goal.

[0124] To a light-duty transparent liquid detergent composition represented by the formulation in Table 4 below, 0.67% by mass of each of the samples of Examples 1 and 2 and Comparative Example 2 was added, and the mixture was dissolved by heating at 40°C for 1 hour while shaking 2-3 times during the heating period to prepare comparative and inventive transparent liquid detergent compositions. Table 4. Examples of light-duty transparent liquid detergent compositions

[0125] The stability test results for the various clear liquid detergent compositions are summarized in Table 5 below. Table 5. Changes in appearance of clear liquid detergent compositions (40°C, 1 month)

[0126] It was confirmed that the additives of Examples 1 and 2 were stably dissolved in the light-duty, transparent liquid detergent composition and did not impair the transparency of the appearance at all even after storage at 40°C for one month.

[0127] Table 6 below summarizes the calculation results of the molar ratio of oxyethylene groups to Si-CH3 groups from the NMR analysis of Example 1. Table 6. EO / SiMe ratio for Example 1

[0128] Table 7 below summarizes the relationship between the calculated values ​​of the average chemical structure of Reference Example 9 and the viscosity based on NMR analysis and reaction rate tests during synthesis experiments. OR’ The content of each structural unit is shown as the number of moles, assuming that the total number of units is 2.00 moles. Table 7. Average chemical structure of Reference Example 9

[0129] [Summary] As shown in the examples, the average polysiloxane chain length is within a short predetermined range, and M OR’ Low content M:M OR” Co-modified silicones and compositions thereof having amino / amide / two types of polyether-modified groups possess four structural features: a molar ratio within a specified range, a small total number of moles of carboxylate groups and acyloxy groups, and a low-molecular-weight second polyether group in addition to a first main polyether group. These silicones and compositions have low viscosity and are able to suppress viscosity increases, allowing for maintenance and control, including ease of handling. Furthermore, they also have excellent batch-to-batch viscosity reproducibility, thereby simultaneously achieving high purity, good handleability, and stable production. When incorporated into clear liquid detergents, these co-modified silicones and compositions thereof do not impair transparency or only slightly so, allowing them to be used as fabric softeners, textile lubricants, texture enhancers, or textile surface coating components. Their low viscosity also makes them easy to handle when producing clear liquid detergents. Their low impurity content allows for increased incorporation into clear liquid detergents, thereby enhancing the commercial appeal of clear liquid detergents.

Claims

1. The following average structural formula: MD p D (AM) q D (AMD) r D (PE1) s D (PE2) w M OR’ Tx (1) [In the formula, M is an R3SiO 1 / 2 unit, D is an R2SiO unit, D (AM) is an RR 1 SiO unit, D (AMD) is an RR 2 SiO unit, D (PE1) is an RR 3 SiO unit, D (PE2) is an RR 8 SiO unit, M OR’ is an R2(OR’)SiO 1 / 2 unit, T is an R3SiO 3 / 2 represented by a siloxy unit, each p, q, r, s, w is a positive number, satisfying the relationship 50 ≦ p + q + r + s + w ≦ 160, x is a number in the range of 0 to 1, and the molar ratio M:M OR’ is in the range of 1.7:0.3 to 1.2:0.8, R is an alkyl group having 1 to 12 carbon atoms, R 1 is an aminoalkyl (1 to 6 carbon atoms) group, R 2 is -R 4 -NHCO-(CH2) b -O(C2H4O) c -R 5 (wherein R 4 is an alkylene group having 1 to 6 carbon atoms, R 5 is a monovalent hydrocarbon group having 1 to 18 carbon atoms, b is a number in the range of 1 to 6, c is a number in the range of 2 to 20), and R 3 is -R 6 -O-(C2H4O) d (C3H6O) e -R 7 group (wherein R 6 is an alkylene group having 2 to 8 carbon atoms, R ７ is an alkyl group having 1 to 12 carbon atoms, d is a number in the range of 3 to 25, e is a number in the range of 0 to 10, and when e is not 0, d and e satisfy the molar ratio d / e ≧ 7 / 3), and R 8 is -R 6 -O-(C2H4O) f (C3H6O) g -R 7 (wherein R 6 , R ７ is the same group as described above, f and g are each a number from 0 to 4, and satisfy the relationship 1 ≦ f + g ≦ 4), OR’ is a group selected from a hydroxyl group, an alkoxy group-containing group, and an acyloxy group-containing group, and further when the total number of moles of M and M OR’ is 2.0, the total number of moles of the carboxylate group and the acyloxy group in the molecule is 1.0 or less), which is represented by a copolymerized silicone.

2. The covariant silicone according to claim 1, wherein in the average structural formula (1), the number x of the siloxy units represented by T is in the range of 0.01 to 0.

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3. Further, the following average structural formula: Z-O-(C2H4O) d (C3H6O) e -R 7 (2) [In the formula, Z is a group selected from alkenyl groups having 2 to 8 carbon atoms or a hydrogen atom, and R 7 , d, and e have the same definitions as described above], when the sum of the polyether compound represented by the formula and the above-mentioned copolymerized silicone compound is 100 parts by mass, it is contained in the range of 5 parts by mass or less. The copolymerized silicone composition containing the copolymerized silicone according to claim 1.

4. The covariant silicone composition according to claim 3, wherein in the composition, the molar ratio of the oxyethylene (C2H4O) group to 1 mol of the Si-R group is in the range of 0.2 to 0.

6.

5. The covariant silicone composition according to claim 3, wherein in the composition, the content of the aminoalkyl group is in the range of 0.1 to 0.6% by mass.

6. The covariant silicone composition according to claim 3, wherein the content of the cyclic dimethylsiloxane which is a tetramer to hexamer is 0.1% by mass or less of the whole composition, respectively.

7. A liquid detergent comprising the covariant silicone according to any one of claims 1 to 2 or the covariant silicone composition according to any one of claims 3 to 6.

8. A transparent concentrated liquid detergent or a transparent liquid detergent for washing, wherein the covariant silicone according to any one of claims 1 to 2 or the covariant silicone composition according to any one of claims 3 to 6 is formulated as any one or more of a softening agent component, a fiber lubricant component, a texture improving component, and a fiber surface coating component. The liquid detergent according to claim 7.

9. (I) A cleaning organic nonionic surfactant having a polyoxyethylene group (the average number of repeating units of oxyethylene is within the range of 3 to 16): within the range of 10 to 60% by mass of the total liquid detergent. (II) At least one freezing inhibitor selected from the following (II-1) to (II-3): within the range of 2 to 20% by mass of the total liquid detergent. (II-1) Saturated monohydric alcohols having 2 to 4 carbon atoms. (II-2) Glycol ethers monosubstituted with an alkyl group having 1 to 6 carbon atoms (provided that the glycol ether contains an oxyethylene group and / or an oxypropylene group, and the number of its repeating units is within the range of 1 to 3). (II-3) Di- or triol compounds selected from propylene glycol, dipropylene glycol, tripropylene glycol, triethylene glycol, tetraethylene glycol, trimethylene glycol, and glycerin. (III) Water: within the range of 20 to 85% by mass of the total liquid detergent. (IV) The copolymerized silicone according to any one of claims 1 to 2 or the copolymerized silicone composition according to any one of claims 3 to 6: within the range of 0.3 to 3% by mass of the total liquid detergent. The liquid detergent according to claim 7, containing the above components.

10. Further, the liquid detergent according to claim 9, containing 0.1 to 15% by mass of a stabilizer selected from an antibacterial agent (preservative), hydrotrope, antioxidant, and water softener (chelating agent) {provided that the total amount of the above components (I) to (V) is 100% by mass}.

11. Further, the liquid detergent according to claim 10, containing 0.1 to 5% by mass of at least one anti-redeposition agent (anti-redeposition agent or dispersant) (VI), 0.1 to 6% by mass of a pH adjuster (VII), 0.1 to 2% by mass of a preparation of at least one enzyme selected from protease, lipase, amylase, cellulase, esterase, pectinase, and mannanase (VIII), 1 to 150 ppm of a colorant (IX), and 10 to 6000 ppm of at least one aesthetic quality improver selected from 5 to 6000 ppm of a fragrance (X) {provided that the total amount of (I) to (VIII) is 100% by mass}.

12. A method for producing the liquid detergent according to claims 9 to 11, comprising the components (I) to (IV) and optionally the components (V) to (X), wherein the components (I) to (VII) are dissolved by heating and mixing at 40 to 80 ° C, and then cooled to 30 ° C or lower, and then one or more components selected from the components (VIII), (IX) and (X) are added and mixed uniformly.

13. The following average structural formula: MD ｔ D (AM) ｕ D (PE1) ｖ D (PE2) ｚ M OR’ Tx (3) [wherein, M is R3SiO 1 / 2 , D is R2SiO, D (AM) is RR 1 SiO, D (PE1) is RR 3 SiO unit, D (PE2) is RR 8 SiO unit, M OR’ is R2(OR’)SiO 1 / 2 , T is R3SiO 3 / 2 represented by a siloxy unit, t, u, v, z are positive numbers, and satisfy the relationship of 50 ≦ t + u + v + z ≦ 160, x is a number in the range of 0 to 1, and the molar ratio M:M OR’ is in the range of 1.7:0.3 to 1.2:0.8, R is an alkyl group having 1 to 12 carbon atoms, R 1 is an aminoalkyl group having 1 to 12 carbon atoms, R 3 is -R 6 -O-(C2H4O) d (C3H6O) e -R 7 (wherein, R 6 is an alkylene group having 2 to 8 carbon atoms, R ７ is an alkyl group having 1 to 12 carbon atoms, d is a number in the range of 3 to 25, e is a number in the range of 0 to 10, and when e is not 0, d and e satisfy the relationship of d / e ≧ 7 / 3) represented by a group, R 8 is -R 6 -O-(C2H4O) f (C3H6O) g -R 7 (wherein, R 6 , R ７ is the same group as described above, f and g are each a number from 0 to 4, and satisfy the relationship 1 ≦ f + g ≦ 4), and OR’ is a group selected from a hydroxyl group, an alkoxy group-containing group, and an acyloxy group-containing group), an amino / 2-kinds polyether-modified silicone represented by, and the following average structural formula: HOOC-(CH2) b -O(C2H4O) c -R 5 (4) [wherein, R 5 is a monovalent hydrocarbon group having 1 to 18 carbon atoms, b is a number in the range of 1 to 6, and c is a number in the range of 2 to 20], and a polyether group-containing carboxylic acid represented by are heated and mixed at 80 to 180 °C under reduced pressure and in the flow of an inert gas to react, and the molar ratio (reaction ratio) of the aminoalkyl group in the amino / 2-kinds polyether-modified silicone represented by the formula (3) to the carboxyl group in the polyether group-containing carboxylic acid represented by the formula (4) is made to react so as to be in the range of 0.1 ≦ carboxyl group / aminoalkyl group ≦ 1.

0. A method for producing the modified silicone according to any one of claims 1 to 2 or the modified silicone composition according to any one of claims 3 to 6.

14. The production method according to claim 13, wherein in the average structural formula (3), the number x of the siloxy units represented by T is in the range of 0.01 to 0.

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15. The production method according to claim 13, wherein the polyether group-containing carboxylic acid represented by the average structural formula (4) is reacted in the coexistence of an aqueous solution or water.

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