Novel co-modified silicones, co-modified silicone compositions comprising same, liquid detergents comprising same, and methods of making same

Abstract

This invention provides a co-modified organosilicon compound with intramolecular amino / amide / two polyether groups, which is highly useful as a raw material for liquid detergents. It exhibits stable quality, can be obtained with high purity, and maintains low viscosity. [Solution] A co-modified organosilicon compound and its composition, wherein the co-modified organosilicon compound has the following average chemical structural formula: MD p D (AM) q D (AMD) r D (PE1) s D (PE2) w M OR’ Tx(1) [where M is R3SiO] 1 / 2 Unit, D (AM) For RR 1 SiO unit, D (AMD) For RR 2 SiO unit, D (PE1) For RR 3 SiO unit, D (PE2) For RR 8 SiO unit, M OR’ R2(OR')SiO 1 / 2 Unit, 50 ≤ p + q + r + s + w ≤ 160, x is 0~1, molar ratio M:M OR’ The ratio is 1.7:0.3 to 1.2:0.8, where R is an alkyl group. 1 It is an aminoalkyl group, R 2 For -R 4 -NHCO-(CH2) b -O(C2H4O) c -R 5 The group represented by R 3 R is the first polyether group. 8 It is a second polyether group, and M and M OR’ When the total number of moles is set to 2.0, the total number of moles of carboxylic acid groups and acyloxy groups in the molecule is less than 1.0.

Description

Technical Field

[0001] This invention relates to a novel co-modified organosilicon with excellent viscosity and appearance stability, high purity, and containing amino / amide groups / two different polyether groups, a co-modified organosilicon composition containing the same, a liquid detergent containing the same, and a method for manufacturing the co-modified organosilicon / the composition thereof. This organosilicon, in particular, exhibits minimal obstruction to transparency when formulated into a transparent liquid detergent, and can be used as a softener component, a fiber lubricant component, a hand-feel-enhancing component, or a fiber surface coating component. Furthermore, the composition has low viscosity, resulting in excellent workability when manufacturing transparent liquid detergents. Moreover, because the co-modified organosilicon and its composition involved in this invention have high purity and few impurities derived from raw materials, their dosage in transparent liquid detergents can be increased, thereby enhancing the commercial appeal of transparent liquid detergents. Background Technology

[0002] Several reports have been published to date regarding amide-containing polyether-based silicones, their analogues, and their applications. However, none of these reports address the quality issues of amide-containing polyether-based silicones, and practical, high-quality stable silicones and methods for manufacturing such stable silicones are unknown. Furthermore, methods for manufacturing such silicones with high purity are also unknown.

[0003] Patent Document 1 reports a fiber treatment agent composition consisting of (A) an amino-containing organopolysiloxane (amino-modified organosilicon) and (B) a polyether-containing carboxylic acid in a specific ratio. This composition only requires uniform mixing of (A) and (B), but it is preferable to mix while heating at 40–180°C. Furthermore, it is described that component (B) forms a salt with the amino group of component (A), or forms an amide bond under heating conditions.

[0004] Patent Document 2 reports a detergent composition containing (a) 5-70% by weight of a surfactant and (b) 0.05-5% by weight of an amide-polyether-based organosilicon. In the examples, a detergent composition is disclosed comprising a secondary amino / amide polyether co-modified organosilicon [organosilicon (1)] with a structure incorporating a polysiloxane backbone end-capped with trimethylsilyl groups. However, no method for manufacturing component (b) is described.

[0005] Patent Document 3 reports a specific liquid detergent composition comprising (a) 0.05–5 wt% of a specific amino-modified organosilicon derivative further containing an amide polyether group and another polyether group, and (b) 5–70 wt% of a surfactant {wherein, 95–75 wt% is (i) a specific nonionic surfactant with an HLB value of 12–15, and 5–15% is (ii) a specific nonionic surfactant with an HLB value of 7–10 and a small molar distribution of ethylene oxide addition}, and specifies the (a) / (b) weight ratio. In the examples, a liquid detergent composition of a primary amino / amide polyether / polyether composite modified organosilicon [organosilicon (1)] with a structure incorporating a polysiloxane backbone end-capped with trimethylsilyl groups is disclosed. However, no method for manufacturing this organosilicon is described.

[0006] Patent Document 4 reports that the lightweight detergent containing the amino-modified organosilicon compound described in Patent Document 2 is not sufficiently stable as it may yellow or separate during storage.

[0007] Patent Document 5 reports a composition containing (A) an amide polyether-modified organopolysiloxane (an amino-free amide polyether-modified organosilicon) and (B) a polyoxyethylene alkyl ether fatty acid (a carboxylic acid containing a polyether group) in a predetermined ratio. In the manufacture of this composition, a reaction equivalent or greater of component (B) is used during the amidation reaction. In Reference Example 1, a mixture of an amino-modified organopolysiloxane with trimethylsilyl-terminated ends 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 organosilicon and 5.4% by weight of component (B). However, there are no reports regarding the quality stability, appearance, viscosity, etc., of the composition of Reference Example 1 itself.

[0008] Patent document 6 reports a detergent composition for delicate clothing containing (a) a nonionic surfactant, (b) monoethanolamine, (c) a specific carboxylic acid with a molecular weight of 100-500, and (d) an amino-modified organosilicon, specifying the mass ratio of (a), (b), and (c) and the pH value. In the examples, a detergent composition for delicate clothing is disclosed, which incorporates a primary amino / amide polyether / polyether composite modified organosilicon [amino-modified organosilicon 1] with a polysiloxane backbone end-capped by trimethylsilyl groups at both ends. However, no method for manufacturing this organosilicon is described.

[0009] Patent Document 7 discloses a treatment agent for wiping paper containing an organopolysiloxane with an amide polyether group. This composition may further contain surfactants, polyols, water, etc., but the surfactant is mainly used in small amounts to emulsify the aforementioned organopolysiloxane, resulting in a composition different from a detergent. There is no record or suggestion regarding its application in detergents. In Reference Example 1, a mixture of an amino- and polyether-containing organopolysiloxane with 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 organosilicon [an organopolysiloxane containing an amide polyether group (viscosity 1000 mPa·s)] with both ends of the polysiloxane backbone capped by trimethylsilyl groups. However, there are no reports regarding the quality stability or appearance of the polysiloxane of Reference Example 1.

[0010] Patent documents 8 and 9 report a transparent laundry detergent composition using a quaternary ammonium cationic surfactant as a softener component. Patent document 11 reports a liquid detergent composition with improved transparency containing a specific organic cationic polymer having a quaternary ammonium salt structure as a softener component.

[0011] Patent document 10 reports a liquid detergent composition characterized by comprising (A) a specific nonionic surfactant, (B) an anionic surfactant (excluding higher fatty acid salts) containing linear alkylbenzene sulfonic acid and polyoxyethylene ether sulfate at 1-40% by mass, and (C) an organosilicon having at least one modifying group selected from amino-modified groups, amide-modified groups, and polyether-modified groups within its structure. The liquid detergent compositions obtained in the examples are considered to have a uniform appearance, but their transparency is not clearly defined. Furthermore, details regarding the manufacturing method and chemical structure of component (C) are not yet clear.

[0012] In other words, while there are some descriptions of manufacturing methods for amide-containing polyether-based silicones in Patent Documents 1, 5, and 7, it is only known that amino-containing silicones and polyether-containing carboxylic acids are heated and mixed for a certain period of time; other information is unknown. Furthermore, Patent Documents 1-11 do not mention the quality of the amide-containing polyether-based silicones themselves. Patent Documents 2-4 and Patent Document 6 disclose a detergent composition containing an amide-containing polyether-based silicone with a structure in which both ends of a polysiloxane backbone are capped with trimethylsilyl groups, but the specific method of manufacturing this silicone is not clearly stated.

[0013] The inventors have discovered that amide-containing polyether-based silicones manufactured by the reported methods have several unreported problems: (i) they can only be obtained as low-purity compositions; (ii) they contain a high amount of cyclic dimethylsiloxane; (iii) the composition's properties or appearance are unstable; even if it is a transparent liquid when first manufactured, it becomes opaque during storage; and (iv) the viscosity of the composition increases significantly during storage. Furthermore, the inventors have found that it is difficult to accurately manufacture amide-containing polyether-based silicones with trimethylsilyl end-cappings on both ends of the polysiloxane backbone. That is, the detergent compositions in Patent Documents 2-4 and Patent Document 6 have the following problems: the amide-containing polyether-based silicones used as raw materials cannot be accurately manufactured, or the method for accurately reproducing them by practical means is unknown.

[0014] As stated above, previous literature failed to recognize the quality issues of organosilicon containing amide polyether groups. Therefore, there is no record or suggestion regarding a practical and stable organosilicon, or a method for manufacturing such a stable organosilicon. Furthermore, there is no record or suggestion regarding a method for manufacturing this organosilicon with high purity. Moreover, co-modified organosilicones and their compositions containing two different polyether groups in one molecule besides amino and amide polyether groups are not disclosed in these documents; they are novel substances, and these documents also do not record or suggest any technical effects or advantages derived from their structure, etc.

[0015] Existing technical documents

[0016] Patent documents

[0017] Patent Document 1: Japanese Patent Publication No. 7-122222 (US Patent No. 4973620)

[0018] Patent Document 2: Japanese Patent Application Publication No. 3-207798

[0019] Patent Document 3: Japanese Patent No. 2863137

[0020] Patent Document 4: Japanese Patent No. 3299865

[0021] Patent Document 5: Japanese Patent Application Publication No. 11-5903 (US Patent No. 5965649)

[0022] Patent Document 6: Japanese Patent No. 4166564

[0023] Patent Document 7: Japanese Patent No. 5702926 (US Patent No. 8802239)

[0024] Patent Document 8: U.S. Patent No. 5,622,925 (Japanese Patent No. 2,968,340)

[0025] Patent Document 9: Description of European Patent No. 862609

[0026] Patent Document 10: Japanese Patent No. 6956712

[0027] Patent Document 11: US Patent No. 11,505,766 Summary of the Invention

[0028] The problem that the invention aims to solve

[0029] As mentioned above, amide-containing polyether-based silicones have several unreported problems: (i) they can only be obtained as low-purity compositions; (ii) they contain a high amount of cyclic dimethylsiloxane; (iii) the properties or appearance of the compositions are unstable, becoming opaque even when freshly manufactured; and (iv) the viscosity of the compositions increases significantly during storage. Furthermore, while transparent liquid detergent compositions containing amide-containing polyether-based silicones with trimethylsilyl end-capping structures on both ends of the polysiloxane backbone have been disclosed in past literature as softener components or feel-enhancing components, they cannot be industrially and reproducibly manufactured. Moreover, co-modified silicones with such molecular chain ends cannot adequately solve the above problems, and further improvements are strongly needed.

[0030] This invention addresses the aforementioned problems and aims to provide a novel co-modified organosilicon that is practical, stable in quality, and contains amino / amide groups / two different polyether-modified groups within its molecule. Further, it aims to provide a co-modified organosilicon composition with low impurities, high purity, practicality, and stable quality. Further, it aims to provide a liquid detergent comprising this co-modified organosilicon or its composition, particularly a transparent concentrated liquid detergent or transparent liquid detergent with excellent transparency, and a method for manufacturing this co-modified organosilicon or its composition. Additionally, it is desirable to use this co-modified organosilicon or its composition in transparent concentrated liquid detergents or transparent liquid detergents as a softener component, a fiber lubricant component, a hand-feel-enhancing component, or a fiber surface coating component.

[0031] Solution for solving the problem

[0032] To solve the above problems, the inventors, through in-depth research, discovered that the two ends of the polysiloxane backbone are composed of M[R3SiO] 1 / 2 Unit and M OR’ [R2(OR')SiO] 1 / 2Unit composition [where R represents an alkyl group (1-12 carbon atoms), OR' represents a group selected from hydroxyl, alkoxy-containing groups, and acyloxy-containing groups], molar ratio M:M OR’ Within the range of 1.7:0.3 to 1.2:0.8, further, M and M OR’ When the total molar number is set to 2.0, a specific amino / amide / two-polyether composite modified organosilicon composition with a total molar number of carboxylic acid groups and acyloxy groups of less than 1.0 exhibits improved transparency with minimal degradation over time. Compared to organosilicon containing amide polyether groups obtained by previously reported manufacturing methods, viscosity increase during storage is significantly suppressed. Even after removing cyclic dimethylsiloxanes by heating and depressurization, the viscosity of the composition remains at a low level, and batch-to-batch viscosity reproducibility is excellent. Thus, it can achieve a balance between high purity, good operability, and production stability. Therefore, it is particularly excellent as an additive for transparent liquid detergents, completely solving the aforementioned complex and challenging problems, thereby completing the present invention.

[0033] More specifically, the problems addressed by this invention are solved by the following means:

[0034] "[1] A co-modified organosilicon, which has the following average structural formula:

[0035] MD p D (AM) q D (AMD) r D (PE1) s D (PE2) w M OR’ Tx(1)

[0036] [In the formula, M is R3SiO] 1 / 2 Unit, D is an R2SiO unit, D (AM) For RR 1 SiO unit, D (AMD) For RR 2 SiO unit, D (PE1) For RR 3 SiO unit, D (PE2) For RR 8 SiO unit, M OR’ R2(OR')SiO 1 / 2 Unit, T is composed of R3SiO 3 / 2 The silyloxy group represents a silyloxy group where p, q, r, s, and w are all positive numbers, and satisfy the relationship 50 ≤ p + q + r + s + w ≤ 160, x is a number in the range of 0 to 1, and the molar ratio is M:M OR’Within the range of 1.7:0.3 to 1.2:0.8,

[0037] R is an alkyl group having 1 to 12 carbon atoms.

[0038] R 1 It is an aminoalkyl group (1 to 6 carbon atoms).

[0039] R 2 For -R 4 -NHCO-(CH2) b -O(C2H4O) c -R 5 (where R) 4 R is an alkylene group having 1 to 6 carbon atoms. 5 A group represented by a monovalent hydrocarbon group having 1 to 18 carbon atoms, where b is a number in the range of 1 to 6, and c is a number in the range of 2 to 20.

[0040] R 3 For -R 6 -O-(C2H4O) d (C3H6O) e -R 7 Basis (where R) 6 R is an alkylene group having 2 to 8 carbon atoms. 7 An alkyl group having 1 to 12 carbon atoms, where d is a number ranging from 3 to 25 and e is a number ranging from 0 to 10, and when e is not 0, d and e satisfy the molar ratio d / e ≥ 7 / 3.

[0041] R 8 For -R 6 -O-(C2H4O) f (C3H6O) g -R 7 (where R) 6 R 7 For groups similar to those described above, where f and g are each numbers from 0 to 4, and satisfy the relationship 1 ≤ f + g ≤ 4, the group is represented by...

[0042] OR' is a group selected from hydroxyl, alkoxy-containing groups, and acyloxy-containing groups.

[0043] Furthermore, M and M OR’ When the total molar number is set to 2.0, the total molar number of carboxylic acid groups and acyloxy groups within the molecule is less than 1.0.

[0044] express.

[0045] [2] According to the co-modified organosilicon described in [1], wherein the number x of silanoxy units represented by T in the average structural formula (1) is in the range of 0.01 to 0.70.

[0046] [3] A co-modified organosilicon composition comprising the co-modified organosilicon described in [1], and further comprising the following average structural formula:

[0047] ZO-(C2H4O) d (C3H6O) e -R 7 (2)

[0048] [In the formula, Z is a group selected from alkenyl or hydrogen atoms with 2 to 8 carbon atoms, R] 7 The definitions of d and e are the same as above.

[0049] The polyether compound is defined as follows: when the sum of the co-modified organosilicon compound and the polyether compound is set to 100 parts by mass, the content of the polyether compound is in the range of 5 parts by mass or less.

[0050] [4] According to the co-modified organosilicon composition described in [3], wherein the molar ratio of oxyethylene (C2H4O) groups to 1 mole of Si-R groups in the composition is in the range of 0.2 to 0.6.

[0051] [5] The co-modified organosilicon composition according to [3], wherein the content of aminoalkyl groups in the composition is in the range of 0.1 to 0.6% by mass.

[0052] [6] According to the co-modified organosilicon composition of [3], the content of each of the cyclic dimethylsiloxanes as 4-6 polymers is less than 0.1% by mass of the whole composition.

[0053] [7] A liquid detergent comprising any one of the co-modified organosilicones in [1] to [2] or any one of the co-modified organosilicon compositions in [3] to [6].

[0054] [8] The liquid detergent according to claim [7] is a transparent concentrated liquid detergent or a transparent liquid detergent for laundry, wherein the co-modified organosilicon composition of any one of [1] to [2] or any one of [3] to [6] is formulated as any one or more of the following components: softener component, fiber lubricant component, hand feel improving component, and fiber surface coating component.

[0055] [9] The liquid detergent according to [7] contains: (I) a detergent-active organic nonionic surfactant having polyoxyethylene (the average number of repeating ethylene oxides is in the range of 3 to 16): in the range of 10 to 60% by mass of the liquid detergent as a whole.

[0056] (II) At least one antifreeze selected from (II-1) to (II-3) below: in the range of 2% to 20% by mass of the total liquid detergent.

[0057] (II-1) Saturated monohydric alcohols with 2 to 4 carbon atoms

[0058] (II-2) Diol ethers monosubstituted with alkyl groups having 1 to 6 carbon atoms (wherein the diol ether contains oxyvinyl and / or oxypropylene groups, the number of which is in the range of 1 to 3).

[0059] (II-3) A diol or triol compound selected from propylene glycol, dipropylene glycol, tripropylene glycol, triethylene glycol, tetraethylene glycol, trimethylene glycol, and glycerol.

[0060] (III) Water: 20-85% by mass of the total liquid detergent

[0061] (IV) The co-modified organosilicon as described in any one of [1] to [2] or the co-modified organosilicon composition as described in any one of [3] to [6]: in the range of 0.3% to 3% by mass of the liquid detergent as a whole.

[0062]

[10] The liquid detergent according to [9] further contains (V) a stabilizer selected from antibacterial agents (preservatives), cosolvents, antioxidants, and water softeners (chelating agents) at a mass of 0.1 to 15% of the total mass of the above components (I) to (V).

[0063]

[11] The liquid detergent according to

[10] further comprises: 0.1 to 5% by mass (VI) at least one anti-re-fouling agent (anti-re-adhesion agent or dispersant); 0.1 to 6% by mass (VII) a pH adjuster; 0.1 to 2% by mass (VIII) a preparation of at least one enzyme selected from protease, lipase, amylase, cellulase, esterase, pectinase, mannanase; 10 to 6000 ppm of colorant selected from (IX) 1 to 150 ppm; and (X) fragrance 5 to 6000 ppm of at least one aesthetic quality improver {however, the total amount of (I) to (VIII) is set to 100% by mass}.

[0064]

[12] A method for manufacturing a liquid detergent described in [9] to

[11] comprising the ingredients (I) to (IV) and optionally the ingredients (V) to (X), characterized in that, after heating and mixing at 40 to 80°C to dissolve the ingredients (I) to (VII), the mixture is cooled to below 30°C, and then one or more ingredients selected from the ingredients (VIII), (IX) and (X) are added and mixed evenly.

[0065]

[13] A method for manufacturing a co-modified organosilicon according to any one of [1] to [2] or a co-modified organosilicon composition according to any one of [3] to [6], characterized in that the composition comprises the following average structural formula:

[0066] MD t D (AM) u D (PE1) v D (PE2) z M OR’ Tx(3)

[0067] [In the formula, M is R3SiO] 1 / 2 D is R2SiO, D (AM) For RR 1 SiO, D (PE1) For RR 3 SiO unit, D (PE2) For RR 8 SiO unit, M OR’ R2(OR')SiO 1 / 2 T is composed of R3SiO 3 / 2 The silyloxy group represents a silyloxy unit, where t, u, v, and z are positive numbers and satisfy the relationship 50 ≤ t + u + v + z ≤ 160, and x is a number in the range of 0 to 1.

[0068] Molar ratio M:M OR’ Within the range of 1.7:0.3 to 1.2:0.8,

[0069] R is an alkyl group having 1 to 12 carbon atoms.

[0070] R 1 It is an aminoalkyl group having 1 to 12 carbon atoms.

[0071] R 3 For -R 6 -O-(C2H4O) d (C3H6O) e -R 7 (where R) 6 R is an alkylene group having 2 to 8 carbon atoms. 7An alkyl group having 1 to 12 carbon atoms, where d is a number ranging from 3 to 25 and e is a number ranging from 0 to 10, and when e is not 0, d and e satisfy the molar ratio d / e ≥ 7 / 3.

[0072] R 8 For -R 6 -O-(C2H4O) f (C3H6O) g -R 7 (where R) 6 R 7 For groups similar to those described above, where f and g are each numbers from 0 to 4, and satisfy the relationship 1 ≤ f + g ≤ 4, the group is represented by...

[0073] OR' is a group selected from hydroxyl, alkoxy-containing groups, and acyloxy-containing groups.

[0074] The amino / two polyether co-modified organosilicon and

[0075] The following average structural formula:

[0076] HOOC-(CH2) b -O(C2H4O) c -R 5 (4)

[0077] [In the formula, R] 5 [where b is a monovalent hydrocarbon group with 1 to 18 carbon atoms, and c is a number in the range of 1 to 6, and c is a number in the range of 2 to 20] represents a polyether-containing carboxylic acid.

[0078] Under reduced pressure and inert gas flow, the mixture is heated and mixed at 80–180 °C to react, and the reaction is carried out in such a way that the molar ratio (reaction ratio) of the amino alkyl group in the amino / polyether co-modified organosilicon represented by formula (3) and the carboxyl group in the polyether-containing carboxylic acid represented by formula (4) is in the range of 0.1 ≤ carboxyl group / amino alkyl group ≤ 1.0.

[0079]

[14] According to the manufacturing method described in

[13] , the number x of silanoxy units represented by T in the average structural formula (3) is in the range of 0.01 to 0.70.

[0080]

[15] The manufacturing method according to

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

[0081] Let's solve it.

[0082] The effects of the invention

[0083] The novel co-modified organosilicon and its composition involved in this invention have higher purity than amide polyether-modified organosilicones prepared by previously reported manufacturing methods, and their quality remains stable at low viscosity and with reduced cyclic dimethylsiloxane content, resulting in excellent operability and production stability. Specifically, the transparency is improved while exhibiting minimal degradation over time, with reduced impurities. The composition remains a stable transparent liquid from the moment it is manufactured until storage, with no increase in viscosity during storage, or if it does occur, the increase is minimal.

[0084] Because the co-modified organosilicon and its compositions involved in this invention exhibit excellent quality and production stability, they are suitable for commercial transactions. Furthermore, especially when formulated into transparent liquid detergents, they have minimal impact on transparency or stability, making them ideally suited for use as softener components, fiber lubricant components, hand-feel-enhancing components, or fiber surface coating components. Moreover, since the co-modified organosilicon compositions involved in this invention have low impurity levels, their formulation amount in transparent liquid detergents can be increased, thereby enhancing the commercial appeal of transparent liquid detergents.

[0085] Furthermore, the co-modified organosilicones and their compositions involved in this invention can be stably manufactured industrially, solving multiple and complex problems inherent in existing co-modified organosilicon manufacturing methods, and both exhibit excellent reproducibility in terms of quality. Therefore, by utilizing the manufacturing method involved in this invention, the industrial production and quality of co-modified organosilicones can be improved simultaneously, further enhancing their commercial applicability. That is, even in the invention related to this manufacturing method, particularly in the design of its manufacturing conditions, it is considered to possess a high degree of inventiveness and unpredictable and highly significant technical effects compared to the prior art. Detailed Implementation

[0086] The co-modified organosilicon and compositions comprising the same, as disclosed herein, will now be described. The co-modified organosilicon of the present invention is characterized by having an aminoalkyl group (hereinafter referred to as R) within the molecule. 1 ), amide polyether group (R described later) 2 ) and two different polyether groups (R, described later) 3 and R 8 ), and the end of the polysiloxane backbone is composed of M [R3SiO 1 / 2 Unit and M OR’ [R2(OR')SiO 1 / 2 Unit composition, M:M of the terminal base OR’ The molar ratio is in the range of 1.7:0.3 to 1.2:0.8. Furthermore, M and M... OR’When the total molar number is set to 2.0, the total molar number of carboxylic acid groups and acyl groups is 1.0 or less, and optionally a small amount of T units may also be included. Further, the co-modified organosilicon composition of the present invention preferably contains the co-modified organosilicon in high purity, and preferably is a high-purity composition. When the sum of the above-mentioned co-modified organosilicon compound and the polyether compound with a hydrosilylation reactive end as a raw material is set to 100 parts by mass, the content of the polyether compound with a hydrosilylation reactive end as a raw material is 5 parts by mass or less.

[0087] More specifically, the co-modified organosilicon involved in this invention is made from...

[0088] The following average structural formula:

[0089] MD p D (AM) q D (AMD) r D (PE1) s D (PE2) w M OR’ Tx(1)

[0090] [In the formula, M is R3SiO] 1 / 2 Unit, D is an R2SiO unit, D (AM) For RR 1 SiO unit, D (AMD) For RR 2 SiO unit, D (PE1) For RR 3 SiO unit, D (PE2) For RR 8 SiO unit, M OR’ R2(OR')SiO 1 / 2 Unit, T is composed of R3SiO 3 / 2 The silyloxy group represents a silyloxy group where p, q, r, s, and w are all positive numbers, and satisfy the relationship 50 ≤ p + q + r + s + w ≤ 160, x is a number in the range of 0 to 1, and the molar ratio is M:M OR’ Within the range of 1.7:0.3 to 1.2:0.8,

[0091] R is an alkyl group having 1 to 12 carbon atoms.

[0092] R 1 It is an aminoalkyl group (1 to 6 carbon atoms).

[0093] R 2 For -R 4 -NHCO-(CH2) b -O(C2H4O) c-R 5 (where R) 4 R is an alkylene group having 1 to 6 carbon atoms. 5 A group represented by a monovalent hydrocarbon group having 1 to 18 carbon atoms, where b is a number in the range of 1 to 6, and c is a number in the range of 2 to 20.

[0094] R 3 For -R 6 -O-(C2H4O) d (C3H6O) e -R 7 Basis (where R) 6 R is an alkylene group having 2 to 8 carbon atoms. 7 An alkyl group having 1 to 12 carbon atoms, where d is a number ranging from 3 to 25 and e is a number ranging from 0 to 10, and when e is not 0, d and e satisfy the molar ratio d / e ≥ 7 / 3.

[0095] R 8 For -R 6 -O-(C2H4O) f (C3H6O) g -R 7 (where R) 6 R 7 For groups similar to those described above, where f and g are each numbers from 0 to 4, and satisfy the relationship 1 ≤ f + g ≤ 4, the group is represented by...

[0096] OR' is a group selected from hydroxyl, alkoxy-containing groups, and acyloxy-containing groups.

[0097] Furthermore, M and M OR’ When the total molar number is set to 2.0, the total molar number of carboxylic acid groups and acyloxy groups within the molecule is less than 1.0.

[0098] express.

[0099] In the formula, R is an alkyl group having 1 to 12 carbon atoms, and industrially, methyl is preferred. 1 It is an aminoalkyl group with 1 to 12 carbon atoms, preferably 2 to 6 carbon atoms, and can be a primary aminoalkyl group or a secondary aminoalkyl group, preferably an aminopropyl group.

[0100] R 2 For -R 4 -NHCO-(CH2) b -O(C2H4O) c -R 5 The group indicated contains both amide and polyether structures within its functional group. R in the formula... 4 It is an alkylene group having 1 to 6 carbon atoms, preferably propylene or methylpropylene.5 It 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 in the range of 1 to 6, and c is a number in the range of 2 to 20.

[0101] R 3 For -R 6 -O-(C2H4O) d (C3H6O) e -R 7 The first polyether group represents a functional group in which the number of oxyethylene units (C2H4O) (d) and the number of oxypropylene units (C3H6O) (e) satisfy a specific relationship, or it can be a functional group that does not contain oxypropylene units (e=0). Further, R 3 The oxyethylene unit and oxypropylene unit can be either a random addition structure or a block addition structure. Additionally, R... 3 It can be a single structure, a mixture of multiple different polyether groups, or a functional group represented by the average structural formula of multiple polyether groups.

[0102] In the formula, R 6 It is an alkylene group having 2 to 8 carbon atoms, preferably propylene or methylpropylene. 7 The alkyl group has 1 to 12 carbon atoms, preferably methyl. d and e are numbers where d is in the range of 3 to 25 and e is in the range of 0 to 10. When e is not 0, from the viewpoint of the formulation stability of the co-modified organosilicon composition of the present invention in transparent liquid detergent, d and e satisfy the relationship that their molar ratio d / e ≥ 7 / 3. When the molar ratio (d / e) is less than 7 / 3, the proportion of oxypropylene units (C3H6O) in the polyether structure is excessive. After being formulated into transparent liquid detergent, it may sometimes cause the liquid detergent to become cloudy due to cloud point phenomenon when the storage temperature is high, such as in summer. Furthermore, as mentioned above, e can be 0. In this case, R... 3 It is a functional group containing only oxyethylene units in its polyether structure, which is one of the preferred forms in this invention.

[0103] R 8 For -R 6 -O-(C2H4O) f (C3H6O) g -R 7 The second polyether group represents the sum of the number (f) of ethylene oxide units (C2H4O) and the number (g) of propylene oxide units (C3H6O) in the functional group, and their relationship with the first polyether group (R) mentioned above. 3 The two polyether groups are different. Specifically, f and g are each numbers from 0 to 4, and satisfy the relationship 1 ≤ f + g ≤ 4. The coexistence of these two different polyether groups within the molecule is a structural feature of the co-modified organosilicon involved in this invention.

[0104] In the formula, p, q, r, s, x, and w represent the number of siloxane units, and their sum corresponds to the degree of polymerization of the co-modified organosilicon 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. When p + q + r + s is less than 50, its effects as a softener, fiber lubricant, hand feel enhancer, or fiber surface coating component sometimes become difficult to achieve when formulated into a transparent liquid detergent. On the other hand, when p + q + r + s + w exceeds 160, the formulation stability in the transparent liquid detergent tends to decrease. To improve solubility, improvements such as increasing the amount of component (II) described later or selecting a component with compatibility effects in component (I) are required for formulation improvements, which sometimes lead to difficulties in designing transparent liquid detergent formulations or increased costs.

[0105] x is any structural unit of the co-modified organosilicon compound involved in this invention, i.e., composed of T(R3SiO2). 3 / 2 The number of silanoxy units with a branched structure, represented by T, is in the range of 0 to 1, preferably in the range of 0 to 0.7. In particular, when silanoxy units represented by T are included, x is preferably in the range of 0.01 to 0.70. If the co-modified organosilicon compound of the present invention contains T(R3SiO2) as a structural unit... 3 / 2 If the silanoxy units represented by ) exceed the above-mentioned upper limit, it can sometimes be difficult to adjust the viscosity of the composition containing the co-modified organosilicon compound or its raw materials to the target range in terms of process / quality management, and the risk of thickening / gelling in the process increases when manufacturing the composition involved in this invention, and sometimes it is difficult to achieve stable production in industry.

[0106] The co-modified organosilicon compound of the present invention is characterized in that the terminal portion of its polysiloxane backbone is composed of M[R3SiO] 1 / 2 Unit and M OR’ [R2(OR')SiO] 1 / 2 Unit composition, M:M of the terminal base OR’ The molar ratio is in the range of 1.7:0.3 to 1.2:0.8, preferably between 1.40:0.60 and 1.20:0.80. Structures with a proportion of M units at the ends exceeding the above upper limit are difficult to manufacture using practical methods. On the other hand, M... OR’ Structures with a unit ratio exceeding the aforementioned lower limit are unstable. During storage, the co-modified organosilicon composition involved in this invention may experience a decrease in transparency (=opaqueness) or a significant increase in viscosity, sometimes failing to achieve the intended technical effects of this invention. Additionally, M:M OR’ The molar ratio can be determined by29 The Si NMR analysis yielded the result.

[0107] In the above average structural formula, further, M and M OR’ When the total molar number is set to 2.0, the total molar number of carboxylic acid groups and acyloxy groups within the molecule needs to be below 1.0. This is because when the total molar number of carboxylic acid groups and acyloxy groups exceeds 1.0, co-modified organosilicon compounds or their compositions with amino / amide / two polyether modified groups tend to become unstable, potentially leading to opacity or a significant increase in viscosity during storage. Furthermore, the total molar number of carboxylic acid groups and acyloxy groups can be controlled by... 13 Determined by C NMR analysis.

[0108] The composition comprising the co-modified organosilicon of the present invention preferably comprises the co-modified organosilicon in high purity, and preferably comprises a certain amount or less of a polyether compound having a hydrosilylation reactive end as a raw material. Specifically, regarding the following average structural formula:

[0109] ZO-(C2H4O) d (C3H6O) e -R 7 (2)

[0110] [In the formula, Z is a group selected from alkenyl or hydrogen atoms with 2 to 8 carbon atoms, R] 7 The definitions of d and e are the same as above.

[0111] When the sum of the aforementioned co-modified organosilicon compound and the polyether compound is set to 100 parts by mass, the content of the polyether compound with a hydrosilylation reactive end, which is a raw material, in this 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. When the content of the polyether compound exceeds the above-mentioned upper limit, it is easy to separate from the co-modified organosilicon composition of the present invention, or turbidity may occur as a result, sometimes requiring attention to product management.

[0112] Similarly, compositions comprising the co-modified organosilicon of the present invention preferably contain a certain amount or less of a polyether compound having a hydrosilylation reactive end as a raw material. Specifically, regarding the following average structural formula:

[0113] ZO-(C2H4O) f (C3H6O) g -R 7 (2´)

[0114] [In the formula, Z is a group selected from alkenyl or hydrogen atoms with 2 to 8 carbon atoms, R] 7 The definitions of f and g are the same as above.

[0115] When the sum of the aforementioned co-modified organosilicon and the polyether compound is set to 100 parts by mass, the content of the polyether compound having a hydrosilylation reactive end as a raw material 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.

[0116] Particularly preferably, when the sum of the above-mentioned co-modified organosilicon and the two polyether compounds represented by the above-mentioned average structural formula (2) or (2´) is set to 100 parts by mass, the content of the two polyether compounds having hydrogen silanization reactive ends as raw materials 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.

[0117] When the co-modified organosilicon and compositions comprising it, as disclosed in this invention, are formulated as raw materials for transparent concentrated liquid detergents or transparent liquid detergents, the molar ratio of ethylene oxide (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 molar ratio of ethylene oxide to Si-R groups is less than the lower limit mentioned above, the formulation stability may sometimes decrease. On the other hand, if the ratio exceeds the upper limit mentioned above, although the formulation stability is excellent, the softness, fiber lubrication, and hand feel may sometimes decrease. Furthermore, this ratio can be adjusted by... 13 Determined by C NMR analysis.

[0118] When the co-modified organosilicon and compositions comprising it, as disclosed in this invention, are formulated as raw materials for transparent concentrated liquid detergents or transparent liquid detergents for laundry use, the content of aminoalkyl groups (-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. Furthermore, the mass percentage of aminoalkyl groups can be calculated by neutralization titration.

[0119] When the mass percentage of the amino alkyl group is less than the lower limit mentioned above, the viscosity of the composition tends to increase, which can sometimes be detrimental to workability and solubility in transparent liquid detergents. Therefore, when formulating amino-containing organosilicon compounds into transparent liquid detergents, neutralization with pH adjusters or similar agents is generally considered effective in improving solubility or formulation stability in the system.

[0120] When the mass percentage of aminoalkyl groups exceeds the aforementioned upper limit, the hydrophilic effect resulting from neutralization increases, leading to improved solubility and stability in liquid detergent formulations without anionic surfactants. However, in liquid detergent formulations containing anionic surfactants, the higher the mass percentage of amino groups in the silicone, the lower the formulation stability in the detergent. This not only easily leads to reduced transparency or separation but also raises concerns about adverse effects on cleaning power. Furthermore, when the mass percentage of aminoalkyl groups exceeds the aforementioned upper limit, transparent liquid detergents containing these groups are prone to discoloration under adverse conditions such as high summer temperatures during storage. Repeated washing with detergents containing these groups may result in gradual discoloration of the washed items, leading to quality defects.

[0121] The co-modified organosilicon and compositions comprising thereof of the present invention preferably have their contents as impurities, namely tetramers, pentamers, and hexamers, reduced to 0.1% by mass or less of the total composition, more preferably 0.01% by mass or less, and particularly preferably below the detection limit under conventional methods. Furthermore, the co-modified organosilicon and compositions comprising thereof that reduce the content of cyclic dimethylsiloxanes as tetramers to hexamers can be readily manufactured by the methods described later.

[0122] [Regarding the technical significance of this invention]

[0123] As described above, the co-modified organosilicon and its composition involved in this invention contain technical elements that overlap with the defining portions of the amino-modified organosilicon derivative disclosed as general formula (I) in Patent Document 3 and the amino-modified organosilicon disclosed as general formula (II) in Patent Document 6. However, none of these documents mention co-modified organosilicon having two different polyether groups in one molecule besides the amino and amide polyether groups, nor do they describe or imply any technical benefits thereof. Furthermore, the "amide-containing polyether-based organosilicon with a structure in which the ends of the polysiloxane backbone are capped with trimethylsilyl groups" disclosed in these documents does not specifically disclose its production method, making it difficult to manufacture by practical means. Similarly, Patent Document 7 (Reference Example 1) reported that after reacting a mixture of an amino- and polyether-based organopolysiloxane with polyoxyethylene (4,5) lauryl ether acetic acid at 130°C for 2 hours, the resulting reaction mixture was described as "an amide-containing polyether-based organopolysiloxane with a structure in which the ends of the polysiloxane backbone are capped by trimethylsilyl groups". However, after conducting additional experiments under the same conditions, the inventors found that the specified structure could not be obtained under the above manufacturing conditions. Furthermore, the actual product had many unreported composite problems: (i) it was a low-purity composition, (ii) it contained a large amount of cyclic dimethylsiloxane, (iii) the composition was unstable in terms of properties or appearance, and even though it was a transparent liquid when it was first manufactured, it became opaque during storage, and (iv) the viscosity of the composition increased significantly during storage.

[0124] On the other hand, the co-modified organosilicon and its composition of the present invention, possessing the aforementioned structural characteristics as co-modified organosilicones, exhibit sustained transparency over a long period, unlike similar compounds disclosed in the prior art. Furthermore, compared to amide-containing polyether-based organosilicon compositions obtained by reported manufacturing methods, viscosity increases during storage are significantly suppressed. Moreover, after removing cyclic dimethylsiloxanes through heating and depressurization, the viscosity of the co-modified organosilicon and its composition of the present invention remains at a low level, achieving a balance between high purity and good operability and production stability. Therefore, the co-modified organosilicon and its composition of the present invention, as additives for transparent liquid detergents, possess particularly superior properties from a commercial point of view, achieving a remarkably significant technical effect by effectively solving the multiple and complex problems inherent in the prior art.

[0125] [Preparation of co-modified organosilicon and its compositions]

[0126] The co-modified organosilicon and its compositions involved in this invention, through...

[0127] The following average chemical structural formula will be used: MD t D (AM) u D (PE1)v D (PE2) z M OR’ Tx(3)

[0128] The amino / two polyether co-modified organosilicon and

[0129] Based on the following average chemical structural formula:

[0130] HOOC-(CH2) b -O(C2H4O) c -R 5 (4)

[0131] The indicated polyether-containing carboxylic acid,

[0132] The compounds are prepared by heating and mixing them at 80–180 °C under reduced pressure and with an inert gas flow, in a molar ratio (reaction ratio) of 0.1 ≤ carboxyl group / aminoalkyl group ≤ 1.0 to form an amino / polyether co-modified organosilicon. The compounds are further described below.

[0133] In equation (3), M is R3SiO 1 / 2 D is R2SiO, D (AM) For RR 1 SiO, D (PE1) For RR 3 SiO unit, D (PE2) For RR 8 SiO unit, M OR’ R2(OR')SiO 1 / 2 T is composed of R3SiO 3 / 2 The silyloxy unit represents

[0134] t, u, v, and z are positive numbers, and satisfy the relationship 50 ≤ t + u + v + z ≤ 160.

[0135] x is a number in the range of 0 to 1.

[0136] Molar ratio M:M OR’ Within the range of 1.7:0.3 to 1.2:0.8,

[0137] R is an alkyl group having 1 to 12 carbon atoms.

[0138] R 1 It is an aminoalkyl group having 1 to 12 carbon atoms.

[0139] R 3 For -R 6 -O-(C2H4O)d (C3H6O) e -R 7 (where R) 6 R is an alkylene group having 2 to 8 carbon atoms. 7 An alkyl group having 1 to 12 carbon atoms, where d is a number ranging from 3 to 25 and e is a number ranging from 0 to 10, and when e is not 0, d and e satisfy the molar ratio d / e ≥ 7 / 3.

[0140] R 8 For -R 6 -O-(C2H4O) f (C3H6O) g -R 7 (where R) 6 R 7 For groups similar to those described above, where f and g are each numbers from 0 to 4, and satisfy the relationship 1 ≤ f + g ≤ 4, the group is represented by...

[0141] OR' is a group selected from hydroxyl, alkoxy, and acyloxy groups.

[0142] In formula (3), R is preferably methyl, R 1 Preferably aminopropyl, but it can also be secondary aminoalkyl, R 3 R 8 The oxyethylene and oxypropylene portions can be either random addition structures or block addition structures, R 3 R 8 It can be a structure that mixes multiple different polyether groups. Additionally, R... 6 Preferably propylene or methylpropylene, R 7 Methyl is preferred.

[0143] In equation (3), t, u, and v are all positive numbers. To provide co-modified organosilicon represented by the corresponding average structural formula, it is preferable to satisfy the relationship 50 ≤ t + u + v ≤ 160. Similarly, the molar ratio M:M OR’ The preferred ratio is within the range of 1.7:0.3 to 1.2:0.8. Structures with an M-unit ratio exceeding 1.7 are considered difficult to manufacture using practically advantageous methods. Furthermore, M:M... OR’ The molar ratio can be determined by 29 The Si NMR analysis yielded the result.

[0144] For the amino / two polyether co-modified organosilicon represented by formula (3), M and M OR’ When the total number of moles is set to 2.0, it is preferable to contain T units (made from R3SiO) in the range of 0 to 1 mole. 3 / 2The silanoxy group (represented as a structural unit) is used as the structural unit, and the content (x) of the T unit is preferably 0.7 mol or less (i.e., x is in the range of 0 to 0.7). When the amount of T unit exceeds 0.7 mol, the process / quality management of adjusting the viscosity of the amino / two polyether co-modified organosilicon and its composition as raw materials to the target range becomes difficult, and the risk of abnormal thickening or gelation in the manufacturing process may sometimes increase.

[0145] In equation (4), R 5 It is a monovalent hydrocarbon group with 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, preferably a number in the range of 4 to 10.

[0146] In the manufacture of the co-modified organosilicon and its composition of the present invention, the polyether-containing carboxylic acid represented by formula (4) can be used directly as a raw material, but from the point of view of economy and productivity, it is preferable to use an aqueous solution of the polyether-containing carboxylic acid that is commercially available as a raw material.

[0147] The molar ratio (reaction ratio) of the amino alkyl group in the amino / two polyether co-modified organosilicon represented by formula (3) to the carboxyl group in the polyether-containing carboxylic acid represented by formula (4) can vary according to the correlation of their average chemical structures. In the manufacturing method of the present invention, it is necessary to be in the range of 0.1 ≤ carboxyl group / amino alkyl group ≤ 1.0, preferably in the range of 0.2 ≤ carboxyl group / amino alkyl group ≤ 0.8, and particularly preferably in the range of 0.3 ≤ carboxyl group / amino alkyl group ≤ 0.6.

[0148] The temperature at which the amino alkyl group in the amino / two polyether co-modified organosilicon represented by formula (3) reacts with the polyether-containing carboxylic acid represented by formula (4) under heating is preferably in the range of 90 to 150°C, and more preferably in the range of 100 to 130°C. When the reaction temperature is below 80°C, the amidation reaction is extremely slow and sometimes cannot proceed at practical rates. On the other hand, at high temperatures, especially above 180°C, side reactions tend to become significant, and sometimes it is necessary to be aware of the reduction in the yield of the target compound.

[0149] A key feature of the manufacturing method of the present invention is that the reaction between the amino alkyl group in the amino / polyether co-modified organosilicon represented by formula (3) and the polyether-containing carboxylic acid represented by formula (4) is carried out under reduced pressure and with an inert gas flow within the above-mentioned molar ratio and reaction temperature range. The inventors of the present invention have recently discovered that by selecting such reaction conditions, water from the raw materials or byproducts of the condensation reaction, as well as cyclic dimethylsiloxane 4-6 polymers as impurities, can be efficiently removed. The amidation reaction is carried out more efficiently than under normal pressure, and the chemical structure and quality of the co-modified organosilicon containing amino / amide groups / two different polyether-modified groups, as the target material, are stabilized. Furthermore, operations such as initially carrying out the amidation reaction under normal pressure and then switching to reduced pressure midway to achieve the target reaction rate can be arbitrarily performed.

[0150] Furthermore, patent documents 1, 5, and 7 do not describe or imply any method for reacting amino-containing organosilicon with polyether-containing carboxylic acid under reduced pressure, nor do they suggest any advantages thereof. Based on the manufacturing methods described in these documents, it is difficult to obtain the co-modified organosilicon and its composition of the present invention.

[0151] While the duration of the aforementioned vacuum amidation reaction also depends on the reaction temperature, the amidation rate can be achieved at the target level when carried out for 4 to 6 hours, for example, at 120–130°C. In industrial production, when an atmospheric pressure amidation step is initially included, there is also an option to set the vacuum amidation step to less than 4 hours.

[0152] Regarding the depressurization degree during the aforementioned vacuum amidation reaction, since the reaction mixture will foam in the reaction apparatus during depressurization, it is necessary to gradually reduce the pressure from atmospheric pressure to vacuum while avoiding bumping. Therefore, the pressure is variable. For example, it is preferable to perform a stepwise depressurization operation such as atmospheric pressure => 380 Torr => 250 Torr => 180 Torr => 120 Torr => 80 Torr => 50 Torr => 30 Torr => 15 Torr => 5 Torr => less than 1 Torr.

[0153] While argon and the like can be used as the inert gas in the manufacture of the co-modified organosilicon and its composition of the present invention, nitrogen is the most suitable from an economic perspective. Methods for circulating these inert gases include circulating them in the top space within the reaction vessel, and circulating them in the system while bubbling the feed liquid within the reaction vessel; the latter is more advantageous as it more easily removes impurities or water.

[0154] The above-described manufacturing method can efficiently produce the co-modified organosilicon and its compositions of the present invention, wherein the contents of cyclic dimethylsiloxane tetramer, pentamer, and hexamer are each less than 0.1% by mass.

[0155] [Filtration process]

[0156] When the intermediates (amino / two polyether co-modified organosilicones and their compositions) and the reaction raw materials (polyether carboxylic acid, etc.) used in the manufacture of the co-modified organosilicones and their compositions of the present invention contain neutralizing salts, these neutralizing salts can transfer into the final product and become the cause of turbidity or precipitation. In this case, filtration is required after the above-mentioned amidation reaction. Filtration can be performed using any filter, depending on the turbidity, the type and size of the precipitate, or multiple filtrations can be performed. Thus, even when using low-cost intermediates or raw materials, it is possible to obtain the high-purity co-modified organosilicones and their compositions of the present invention with excellent quality stability.

[0157] [Preparation of intermediate (amino / two polyether co-modified organosilicon composition)]

[0158] There are no particular limitations on the method for manufacturing intermediate compositions comprising amino / two polyether co-modified organosilicones represented by formula (3) above, but industrially advantageous methods are preferred. For example, a method can be described as follows: a hydrolysis condensate of a dimethyl polysiloxane having a polyether group, an aminoalkyl diethoxymethylsilane, and, if necessary, a cyclic dimethylsiloxane or dimethyl polysiloxane, is added in calculated amounts to a reactor, and an equilibrium reaction is carried out in the presence of a base catalyst. The conditions for the equilibrium reaction should preferably follow those used in the manufacture of general amino-modified organosilicones.

[0159] For example, potassium hydroxide or its aqueous solution, an aqueous solution or methanol solution of tetramethylammonium hydroxide, potassium silanolate, tetramethylammonium silanolate, etc., are readily used as alkaline catalysts. When using potassium hydroxide or potassium silanolate, it is preferable to add acetic acid or the like after the equilibration reaction to neutralize the catalyst. When using tetramethylammonium hydroxide or tetramethylammonium silanolate, thermal decomposition treatment is preferred. Subsequently, it is desirable to remove or reduce low-boiling-point components present in the reaction system by stripping. Further, filtration can optionally be performed.

[0160] It should be noted that, in order to manufacture a composition containing an amino / two polyether co-modified organosilicon represented by the above formula (3), and further containing a T unit (composed of R3SiO2), 3 / 2Compositions containing siloxane units (represented by T units) can be produced by using an appropriate amount of a polysiloxane compound or an alkoxysilane compound having T units as one of the starting materials. Alternatively, for example, when an appropriate amount of aminoalkyltrialkoxysilane is intentionally or as an impurity present in the starting material of a hydrolytic condensate of an aminoalkyldialkoxymethylsilane, an equilibration reaction for obtaining an amino / two polyether co-modified organosilicon represented by formula (3) can be carried out intramolecularly to generate a predetermined amount of T units. Another route for the generation of T units is when a dimethyl polysiloxane having two different polyether groups has a small amount of -SiMe(OR'')- structural units [here, OR'' is a group selected from hydroxyl, alkoxy-containing groups, and acyloxy-containing groups]. Dimethyl polysiloxanes having two different polyether groups are typically produced by hydrosilylation of a Si-H-based dimethyl polysiloxane with two different polyethers terminally having vinyl groups in the presence of a platinum catalyst. However, due to the presence of water in the reaction system or the influence of alcohols as solvents for the platinum catalyst, a slight dehydrogenation reaction sometimes occurs, resulting in the formation of the aforementioned -SiMe(OR'')- structural units. When an equilibrium reaction is carried out with such raw materials to obtain the amino / two polyether-modified organosilicon composition of formula (3), a small amount of T units are generated.

[0161] [Manufacturing of raw materials (including polyether carboxylic acid)]

[0162] There are no particular limitations on the manufacturing method of the polyether-containing carboxylic acid represented by the above formula (4). For example, in the manufacture of the polyether-containing carboxylic acid represented by the following average chemical structural formula:

[0163] HOOC-CH2-O(C2H4O) c -C 12 H 25 (5)

[0164] In the case of a polyether-containing carboxylic acid, the following average chemical structural formula can be used: HO(C2H4O) c -C 12 H 25 (6)

[0165] The polyoxyethylene lauryl ether indicated, and

[0166] Based on the average chemical structural formula: HOOC-CH2-Cl(7)

[0167] The method described above involves the etherification of monochloroacetic acid in the presence of alkali metal hydroxides such as sodium hydroxide or potassium hydroxide. During this process, salts such as NaCl or KCl are produced as byproducts. Therefore, the polyether-containing carboxylic acid of formula (5) is obtained in the form of a solution containing water and salt at a main component concentration of 90–96% by mass, and is often commercially available in this form. Such a solution-form raw material can also be used in the manufacturing method of this invention.

[0168] As other impurities included in the polyether-containing carboxylic acid of formula (5) above, for example, the following average chemical structural formula can be considered:

[0169] HOOC-CH2-OC 12 H 25

[0170] The compound is represented by [the compound name]. This is because lauryl alcohol, which may remain in small amounts in formula (6) above, reacts with formula (7) above.

[0171] Furthermore, as other impurities included in the polyether-containing carboxylic acid of formula (5) above, the following average chemical structural formula can be considered:

[0172] HOOC-CH2-O-CH2-COOH

[0173] The compound is diethylene glycol. It is formed by the hydrolysis of monochloroacetic acid of formula (7) in the presence of an alkali metal hydroxide to produce glycolic acid, which then undergoes a further etherification reaction with another monochloroacetic acid molecule.

[0174] By selecting the manufacturing method of the present invention, even when using polyether-containing carboxylic acids containing the above-mentioned impurities as raw materials, it is possible to obtain high-purity co-modified organosilicones and their compositions as described in this invention with excellent quality stability.

[0175] [Preparation of starting material (dimethyl polysiloxane with two polyether groups)]

[0176] Two polyether-modified organosilicones and their compositions, which are one of the starting materials for manufacturing the amino / two polyether co-modified organosilicones represented by formula (3) and compositions comprising therein (intermediates), can be designed to correspond to the target structure of the final product, namely the co-modified organosilicones and their compositions involved in this invention, and are preferably manufactured by industrially advantageous methods. As a general example, for the average chemical structure of the following:

[0177] MD m D (PE1) n D (PE2) j M(10)

[0178] [In the formula, M is (CH3)3SiO] 1 / 2 Unit, D is (CH3)2SiO unit, D (PE1) For RR 3 SiO unit, D (PE2) For RR 8 SiO unit, m is 0 or a positive number, n and j are positive, R 3 By -R 6 -O-(C2H4O) d (C3H6O) e -R 7 Base indicates that R 6 It is an alkylene group (2-8 carbon atoms), R 7 It is an alkyl group (1-12 carbon atoms), R 8 By -R 6 -O-(C2H4O) f (C3H6O) g -R 7 This means that d is a number from 3 to 25, e is a number from 0 to 25, f and g are each a number from 0 to 4, and 1 ≤ f + g ≤ 4. Furthermore, the molar ratio d / e ≥ 7 / 3 is satisfied here. 3 The oxyethylene and oxypropylene portions can be either random addition structures or block addition structures, R 3 and R 8 A brief description is given of the general manufacturing method of polyether-modified organosilicon and its compositions, which may be represented by a structure containing a variety of different polyether groups.

[0179] The polyether-modified organosilicon and its composition represented by formula (10) above, by...

[0180] From the average chemical structural formula: MD m D H (n+j) M(11)

[0181] [In the formula, M, D, m, n, j represent the same meanings as above, D] H [H(CH3)SiO unit] represents a Si-H-based dimethyl polysiloxane, preferably with...

[0182] Based on the average chemical structural formula: H₂C=CH(R) 8 )-(CH2) k -O(C2H4O) d (C3H6O) e -R 7 (12)

[0183] [In the formula, R] 8 For hydrogen or methyl, R 7The first terminal vinyl polyether, represented by alkyl groups (1-12 carbon atoms), k (0-6), d (3-25), and e (0-25), satisfies a molar ratio d / e ≥ 7 / 3. The oxyethylene and oxypropylene groups can be either random addition or block addition structures.

[0184] Preferably, it is derived from the following average chemical structural formula:

[0185] H2C=CH(R 8 )-(CH2) k -O(C2H4O) f (C3H6O) g -R 7 (1k)

[0186] [In the formula, R] 8 R 7 ,k represents the same meaning as above, f and g are each numbers from 0 to 4 and satisfy 1 ≤ f + g ≤ 4, the oxyethylene part and the oxypropylene part can be random addition structures or block addition structures, R 3 The second terminal vinyl polyether, which may be a structure containing a variety of different polyether groups, is manufactured by removing or reducing the second terminal vinyl polyether after a hydrosilylation reaction under known conditions in the presence of a platinum catalyst, and particularly preferably by stripping under heating and reduced pressure.

[0187] It is known that during the hydrosilylation reaction, a portion of formulas (12) and (1k) undergoes terminal vinyl isomerization (becoming inactive to hydrosilylation due to internal transfer of the double bond). To completely consume the Si-H group, the first polyether of formula (12) can be used in excess of the Si-H group at a molar ratio of H2C=CH / Si-H of approximately 1.1 to 1.4, and the second polyether of formula (1k) can be used in excess of the remaining Si-H group at a molar ratio of H2C=CH / Si-H of approximately 1.3 to 2.0. Since the second polyether can be removed by stripping after the reaction, it is acceptable to further increase the amount added. Therefore, the corresponding amount of unreacted polyether, mainly derived from the first polyether, is usually contained in the two polyether-modified organosilicon compositions represented by formula (10).

[0188] In addition, the polyether of formula (12) often contains small amounts of the following average chemical structure as an impurity:

[0189] H2C=CH(R 8 )-(CH2) k -O(C2H4O) d (C3H6O) e -H(13)

[0190] [In the formula, R] 8 [k, d, e represent polyethers containing terminal hydroxyl groups, with the same meaning as above], or those represented by the following average chemical structural formula:

[0191] HO(C2H4O) d (C3H6O) e -R 7 (14)

[0192] [In the formula, R] 7 [d, e represent polyethers with terminal hydroxyl groups as described above.] Therefore, these substances can also be included in the two polyether-modified organosilicon compositions represented by the above formula (10).

[0193] In the manufacturing method of the present invention, the two polyether-modified organosilicones and their compositions represented by formula (10) may optionally be further subjected to hydrolysis treatment in the presence of acidic inorganic salts based on the method described in Japanese Patent No. 5491152, hydrogenation treatment based on the method described in Japanese Patent Application Publication No. 07-330907, removal of low-boiling-point substances, or purification treatment by filtration, etc. Furthermore, in the polyether-modified organosilicones and their compositions represented by formula (10), an antioxidant may be pre-added and dissolved in the range of 10 to 1000 ppm by mass. Examples of antioxidants include vitamin E or BHT (2,6-di-tert-butyl-p-cresol).

[0194] As described above, in the method for manufacturing co-modified organosilicon and its compositions, from the viewpoint of suppressing side reactions, it is preferable to use substances that deteriorate less over time after manufacturing, including intermediates, raw material compounds and starting materials.

[0195] The liquid detergent involved in this invention preferably contains:

[0196] (I) Detergent organic nonionic surfactants containing polyoxyethylene (with an average repeatability of ethylene oxide in the range of 3 to 16): in the range of 10 to 60% by mass of the total transparent liquid detergent.

[0197] (II) At least one antifreeze agent selected from (II-1) to (II-3) below: in the range of 2% to 20% by mass of the total transparent liquid detergent.

[0198] (II-1) Saturated monohydric alcohols with 2 to 4 carbon atoms

[0199] (II-2) Diol ethers monosubstituted with alkyl groups having 1 to 6 carbon atoms (wherein the diol ether contains oxyvinyl and / or oxypropylene groups, the number of which is in the range of 1 to 3).

[0200] (II-3) A diol or triol compound selected from propylene glycol, dipropylene glycol, tripropylene glycol, triethylene glycol, tetraethylene glycol, trimethylene glycol, and glycerol.

[0201] (III) Water: 20-85% by mass of the total liquid detergent

[0202] (IV) The above-mentioned co-modified organosilicon composition: in the range of 0.3 to 3% by mass of the liquid detergent as a whole.

[0203] The liquid detergent may further contain (V) 0.1 to 15% by mass of a stabilizer selected from antibacterial agents (preservatives), solubilizers, antioxidants, and water softeners (chelating agents) {wherein, the total amount of the above components (I) to (V) is set to 100% by mass}. Similarly, the liquid detergent may further contain 0.1 to 5% by mass (VI) at least one anti-re-fouling agent (anti-re-adhesion agent or dispersant), 0.1 to 6% by mass (VII) a pH adjuster, 0.1 to 2% by mass (VIII) a formulation of at least one enzyme selected from protease, lipase, amylase, cellulase, esterase, pectinase, and mannanase, 10 to 6000 ppm of a colorant selected from (IX) 1 to 150 ppm; and (X) at least one aesthetic quality improver selected from (I) to (VIII) 5 to 6000 ppm {however, the total amount of (I) to (VIII) is set to 100% by mass}.

[0204] [(I) Organic nonionic surfactants]

[0205] Component (I) is a detergent-grade organic nonionic surfactant containing polyoxyethylene (with an average repeat number of oxyethylene in the range of 3 to 16). Various surfactants equivalent to (I) can be used in combination. Component (I) is preferably selected from substances with excellent availability, such as alkyl polyethoxylates (AE) and fatty acid polyethoxylate methyl ethers (FEM), but polyoxyethylene / polyoxypropylene alkyl ethers (AEP) are also preferred as AEs with antifoaming properties. Furthermore, HLB, generally considered a good detergency standard, is generally in the range of 12 to 14.

[0206] AEs have the advantages of being less affected by water hardness or electrolytes and being compatible with all other surfactants. Due to differences in the structure and carbon number distribution of the alkyl lipophilic groups and the chain length differences with the hydrophilic groups of polyoxyethylene, AEs exhibit a variety of characteristics in terms of permeability, emulsification / dispersibility, and detergency. Therefore, they also have the advantage of allowing for precise adjustment of these diverse functional balances to suit the design purpose of liquid detergents. Furthermore, alkyl groups that generally impart good detergency are considered to be groups with 10 to 16 carbon atoms, more preferably groups with 11 to 15 carbon atoms. Among these, AEs with straight-chain primary alkyl groups have high crystallinity and a significant tendency to gel or thicken at high concentrations in aqueous media. Therefore, when formulating them into transparent concentrated liquid detergents, in addition to avoiding large quantities, it is necessary to take measures such as adding cosolvents or antifreeze. When formulating AEs with straight-chain primary alkyl groups into the transparent liquid detergent composition of the present invention, the amount is preferably in the range of 0 to 10% by mass, and particularly preferably in the range of 0 to 5% by mass. It is advantageous that branched alkyl AEs and AEs derived from secondary (sec) alcohols have a lower tendency to gel or thicken at high concentrations in aqueous media. However, considering biodegradability, AEs derived from linear secondary (sec) alcohols are considered more preferred, and are among the most preferred components in component (I) constituting the transparent liquid detergent composition of the present invention. In the transparent liquid detergent composition of the present invention, when AEs derived from linear secondary (sec) alcohols are formulated as the main nonionic surfactant, the formulation amount is preferably in the range of 10 to 35% by mass, and particularly preferably in the range of 15 to 30% by mass. When treated as an auxiliary surfactant component, a formulation amount of less than 10% is acceptable. On the other hand, even with linear primary alkyl groups, AEPs can be formulated at higher concentrations than usual AEs due to reduced aggregation. The formulation amount of AEPs in the transparent liquid detergent composition of the present invention is preferably in the range of 0 to 30% by mass, and particularly preferably in the range of 10 to 20% by mass.

[0207] FEM can also control functional characteristics such as permeability, emulsification / dispersion, and detergency through the combination of differences in the carbon number distribution of aliphatic alkyl groups and differences in chain length with the hydrophilic groups of polyoxyethylene. Generally, alkyl groups that impart good detergency are considered to be groups with 10 to 16 carbon atoms, more preferably groups with 11 to 15 carbon atoms. Unlike AE or AEP, FEM does not have hydroxyl groups in its molecule, thus suppressing hydrogen bonding interactions. This results in a characteristic of being extremely difficult to gel or thicken at high concentrations in aqueous media. Therefore, FEM is one of the preferred components in component (I) of the transparent liquid detergent composition of the present invention. In the transparent liquid detergent composition of the present invention, when FEM is formulated as the main nonionic surfactant, its formulation amount is preferably in the range of 10 to 50% by mass, and particularly preferably in the range of 20 to 40% by mass. When FEM is treated as an auxiliary surfactant component, its formulation amount of less than 10% is acceptable. Like AE or AEP, FEM has the advantage of its cleaning power being less affected by water hardness. However, due to the presence of ester groups within its molecule, it may undergo hydrolysis after being formulated into liquid detergents, depending on conditions such as pH or temperature, potentially leading to a gradual decrease in performance or quality. When formulating FEM, the pH of the liquid detergent is preferably in the range of 6.0 to 8.0, and more preferably in the range of 6.5 to 7.5. Furthermore, when formulating FEM into transparent liquid detergents, care should be taken to avoid incorporating esterases or lipases.

[0208] In the household laundry detergent composition of the present invention, the total amount of component (I) is preferably in the range of 10 to 60% by mass of the total transparent liquid detergent. Furthermore, the preferred formulation ranges for AE, FEM, or AEP as component (I) are as described above; however, when a high concentration is desired in the transparent concentrated liquid detergent, the total amount of component (I) can be formulated in the range of 10 to 60% by mass, 20 to 60% by mass, or 30 to 60% by mass.

[0209] [(II) Antifreeze]

[0210] Component (II) is at least one antifreeze selected from (II-1) to (II-3) below, formulated in the range of 2 to 20% by mass of the transparent liquid detergent composition of the present invention. These can be used in various combinations. The preferred formulation amount of (II) is in the range of 4 to 15% by mass, more preferably in the range of 6 to 10% by mass. If the formulation amount of (II) is less than 2%, the fluidity of the transparent liquid detergent will decrease, and therefore, depending on the geographical environment, it will cause the problem of easy freezing in winter. On the other hand, although it can be formulated at more than 20%, the amount of water in component (III) is relatively reduced, thus reducing the cost-effectiveness balance.

[0211] (II-1) is a saturated monohydric alcohol with 2 to 4 carbon atoms, examples of which include ethanol, denatured ethanol, 1-propanol, 2-propanol, 1-butanol, isobutanol, sec-butanol, tert-butanol, and any mixture thereof. From the viewpoint of low odor, ethanol and low-odor denatured ethanol are preferred. In terms of defoaming properties, 1-butanol may be slightly advantageous.

[0212] (II-2) is a glycol ether monosubstituted with an alkyl group having 1 to 6 carbon atoms (wherein the glycol ether contains oxyvinyl and / or oxypropylene groups, the number of repetitions being in the range of 1 to 3). (II-2) is preferably selected from substances with excellent availability. Examples of such substances 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. Generally, substances with a repetition number of 2 offer a good balance between safety and cost and are easy to use. On the other hand, from the viewpoint of compatibility with other components, n-butyl ethers or n-hexyl ethers with a large number of carbon atoms in the alkyl substituent are preferred. Therefore, from a comprehensive viewpoint, diethylene glycol n-butyl ether, diethylene glycol n-hexyl ether, and dipropylene glycol n-butyl ether are particularly preferred.

[0213] (II-3) is a diol or triol compound selected from propylene glycol, dipropylene glycol, tripropylene glycol, triethylene glycol, tetraethylene glycol, trimethylene glycol, and glycerol. Among these, propylene glycol, dipropylene glycol, tripropylene glycol, and trimethylene glycol are more preferred, and propylene glycol or dipropylene glycol is most preferred.

[0214] [(III) Water]

[0215] Component (III) is water, formulated in the range of 20-85% by mass of the transparent liquid detergent composition of the present invention. There are no particular restrictions on (III) as long as it is used for cleaning; preferably, it is ion-exchanged water, sterilized water, distilled water, purified water, pure water, etc., and sometimes tap water or well water may also be used. When the amount of (III) is less than 20% by mass, in addition to the increased cost of the liquid detergent, it is often difficult to stably formulate the enzyme. When the amount of (III) exceeds 85% by mass, the scope for formulating effective amounts of various essential components decreases, making it difficult for consumers to experience the claimed effects, thus making the design of practical transparent liquid detergent products difficult. Furthermore, when the proportion of water in the detergent is too high, the proportion of water transportation costs during detergent transportation increases, leading to waste in logistics costs, etc.

[0216] [(IV) Co-modified organosilicon and its compositions]

[0217] Component (IV) is the co-modified organosilicon and its composition as described in this invention, typically formulated in the range of 0.3 to 3% by mass of the total transparent liquid detergent. Within this range, it offers excellent cost-effectiveness and is readily soluble in existing lightweight transparent liquid detergent formulations that primarily use nonionic surfactants as the washing agent. When the content is less than 0.3% by mass, it is difficult to perceive softening, fiber lubrication, improved hand feel, or fiber surface coating effects. When the content exceeds 3% by mass, the formulation stability in transparent liquid detergents tends to decrease. To improve solubility, improvements such as increasing the amount of component (II) or selecting a compatibility-enhancing component in component (I) are required in the formulation, thus sometimes worsening economics. In particular, the co-modified organosilicon composition of this invention, due to its high purity, allows for quantitative and efficient formulation of the co-modified organosilicon as the main agent, provided the formulation amount is within the above range. Furthermore, it has minimal impact on transparency or stability in transparent concentrated liquid detergents, offering the advantage of enhancing the commercial appeal of transparent liquid detergents.

[0218] [(V) stabilizer]

[0219] Component (V) is a stabilizer selected from antibacterial agents (preservatives), cosolvents, antioxidants, and water softeners (chelating agents), and its formulation amount is 0.1 to 15% by mass of the transparent liquid detergent composition of the present invention {wherein, the total amount of (I) to (V) is set to 100% by mass}.

[0220] Antibacterial agents (preservatives) involving ingredient (V) are not particularly restricted as long as they can be formulated into household laundry detergents. Examples include phenoxyethanol, phenoxypropanol, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, saturated alkyl glycols with 4 to 8 carbon atoms, monoalkyl or alkenyl ethers of glycerol, borates, benzoic acid, p-hydroxybenzoate, sodium benzoate, sodium dehydroacetate, formic acid, glutaraldehyde, benzyl alcohol, isopropyl methylphenol, triclocarban, triclosan, chlorophenol, p-chloro-m-xylenol, chlorothymol, carvacrol, dichlorophenol, hexachlorophenol, chlorocresol, methylisothiazolinone / methylchloroisothiazolinone mixture, isothiazolinone / benzisothiazolinone mixture, 5-chloro-2-methyl-4-isothiazolin-3-one, 1,2-benzothiazolinone, 2-(4-methylaminomethylthio)benzimidazole, etc. Among them, phenoxyethanol, phenoxypropanol, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, saturated alkyl glycols with 4 to 8 carbon atoms, and monoalkyl or alkenyl ethers of glycerol are mostly liquid at room temperature and are relatively inexpensive among preservatives / antibacterial agents, so the formulation amount can be increased to 10% by mass. Other preservatives are also very effective, but most are also expensive, so they are usually preferred to be formulated in the range of 0.1% to 2% by mass.

[0221] Examples of co-solvents involving component (V) include toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, or sodium or potassium salts of these. In this invention, the amount of co-solvent prepared is preferably in the range of 0 to 4% by mass, more preferably 0 to 2% by mass.

[0222] The antioxidants involved in component (V) are generally preferably formulated in the range of 0.01 to 1% by mass, and antioxidants with minimal impact on the design color of liquid detergents are selected. Multiple antioxidants may also be used in combination. Examples include sodium sulfite, sodium bisulfite, and phenolic antioxidants. Examples of phenolic antioxidants include butylated hydroxytoluene, butylated hydroxyanisole, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), stilbenecresol, dl-α-tocopherol, d-δ-tocopherol, and natural vitamin E, with butylated hydroxytoluene being particularly preferred.

[0223] The water softener (chelating agent) involved in component (V) is not particularly restricted as long as it can be formulated into household laundry detergents. It is generally preferred to formulate it in the range of 0.1% to 3% by mass, and multiple formulations can be used together. Furthermore, in geographical environments where the water used for washing has high hardness, the amount of chelating agent added to the clear liquid detergent is sometimes increased to about 5% by mass. Specific examples include polycarboxylic acids or their salts such as malonic acid, succinic acid, malic acid, diethylene glycol, tartaric acid, and citric acid. Other chelating agents that can be used include ethylenediaminetetraacetic acid (salt), diethylenetriaminepentaacetic acid (salt), methylglycine diacetic acid (salt), ethylglycine diacetic acid (salt), aminotriacetic acid (salt), iminodisuccinic acid (salt), iminodiacetic acid (salt), tetrasodium aspartate-N,N-diacetic acid, trisodium serine diacetate, and tetrasodium glutamate diacetate. Alternatively, 1-hydroxyethane-1,1-diphosphonic acid, aminotris(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), 2-phosphono-1,2,4-butanetricarboxylic acid, and their sodium, potassium, ammonium, and alkanolamine salts can also be used. Citric acid, malic acid, trisodium methylglycine diacetate, and 1-hydroxyethane-1,1-diphosphonate are preferred.

[0224] [(VI) Anti-recontamination agent]

[0225] The amount of anti-re-fouling agents (anti-re-adhesion agents or dispersants) involved in component (VI) is generally preferably in the range of 0.1% to 5% by mass. These agents adsorb onto fibers or dirt components to increase their electrostatic repulsion, and stabilize the dirt components in the washing liquid to prevent re-adhesion onto the fibers. Commonly used polymers include polyalkylene glycols, polyacrylic acids, cellulose polymers, polyvinylpyrrolidone polymers, and ethoxylated polyethyleneimine, and multiple polymers can be used in combination. Specific examples include polyacrylic acid, polymaleic acid, acrylic acid / maleic acid copolymers, carboxymethyl cellulose, polyvinylpyrrolidone, polyethylene glycol, polypropylene glycol, propylene oxide adducts of polyols, ethoxylated polyethyleneimine, and propoxylated polyethyleneimine.

[0226] [(VII) pH adjuster]

[0227] Component (VII) is a pH adjuster. The amount of component (VII) varies depending on the target pH value of the transparent liquid detergent, typically ranging from 0.1% to 6% by mass, preferably from 0.5% to 3% by mass. Examples of components (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 can be used together. 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 as it is believed to prevent deformation / deterioration and fading of the washed items.

[0228] [(VIII) enzyme]

[0229] Component (VIII) is a preparation of at least one enzyme selected from protease, lipase, amylase, cellulase, esterase, pectinase, and mannanase, and is generally preferably formulated in the range of 0.1% to 2% by mass. Furthermore, when formulating component (VIII) into a transparent liquid detergent composition, in order to inhibit the decrease in enzyme activity, the techniques described or referenced in Japanese Patent No. 5436199 (Japanese Unexamined Patent Application Publication No. 2011-137074), Japanese Patent No. 6188239 (Japanese Unexamined Patent Application Publication No. 2016-017133), and Japanese Patent No. 6732424 (Japanese Unexamined Patent Application Publication No. 2017-071664) may be utilized.

[0230] [Aesthetic quality improvers: (IX) colorants and (X) fragrances]

[0231] From the viewpoint of user experience and the appearance / fragrance of the formulation, the liquid detergent of the present invention can be further formulated with an aesthetic quality improver. Specifically, component (IX) is a colorant of 1 to 150 ppm, and component (X) is a fragrance of 5 to 6000 ppm, preferably within the range of 10 to 6000 ppm {however, the total amount of (I) to (VIII) is set to 100% by mass}, at least one aesthetic quality improver selected from (IX) and (X). Furthermore, regarding fragrance formulations, representative examples are shown in Japanese Patent Application Publication No. 2002-146399 and Japanese Patent Application Publication No. 2021-134324. In addition, depending on the formulation, appearance, and fragrance of the target liquid detergent, components (IX) and (X) can also be intentionally set to be omitted.

[0232] [Ingredient formulation]

[0233] The liquid detergent (particularly a transparent liquid detergent) of the present invention, comprising the above-mentioned components (I) to (IV) and optionally components (V) to (X), can be manufactured by heating and mixing at 40 to 80°C to dissolve components (I) to (VII), cooling to below 30°C, and then adding one or more components selected from components (VIII), (IX), and (X) and mixing thoroughly. Alternatively, depending on the formulation of the target liquid detergent, components (V) to (X) may be partially or entirely omitted during the above manufacturing process.

[0234] The liquid detergents involved in this invention (particularly including transparent concentrated liquid detergents or transparent liquid detergents for laundry) can optionally be formulated with ingredients, particularly those that can be formulated into transparent liquid detergents for household laundry, within a range that does not impair the technical effects of this invention, and are any other ingredients that are not among the aforementioned ingredients (I) to (X).

[0235] Examples of other optional ingredients include organic surfactants other than ingredient (I), oils, softeners, or hand feel improvers known to be formulated in household liquid detergents other than ingredient (IV) (e.g., organic oils, polyether-modified silicones or amide-containing polyether-based silicones manufactured by reported methods, organic cationic polymers for imparting elasticity or toughness or for reducing wrinkles, etc.), agents for stabilizing enzymes, fluorescent whitening agents, appropriate amounts of inorganic salts, polyethylene glycol phenyl ether detergent enhancers, fatty acids (salts), defoamers, etc. Furthermore, the defoamers that can be used in the liquid detergents involved in this invention explicitly include the ingredients disclosed in Japanese Patent Application No. 2023-47481 and the priority application based thereon.

[0236] Regarding organic surfactants other than component (I), considering the basic formulation framework of lightweight, transparent liquid detergents (balanced products that provide moderate cleaning power while also softening or improving the feel of washed fabrics), it is appropriate to select and formulate them in suitable amounts. Examples of such surfactants include anionic surfactants, amphoteric surfactants, cationic surfactants, and weakly cationic surfactants. Since they are not essential components in this invention, their content in transparent liquid detergents is generally below 5% by mass, and preferably below 10% by mass when these effects are to be emphasized.

[0237] [Formulation of ionic surfactants]

[0238] In order to design a lightweight, transparent liquid detergent containing the co-modified organosilicon and its composition as described in this invention, a formulation that can be used without adversely affecting almost all clothing materials such as wool, silk, cotton, linen, and synthetic fibers, is considered both waste-free and convenient, as reported in Patent Documents 3 and 6, by using a variety of specific organic nonionic surfactants as detergent surfactants and not containing ionic surfactants. On the other hand, it does not preclude the optional use of small amounts of ionic surfactants according to the convenience of the detergent manufacturer. In this case, to avoid damage to wool or silk, it is considered good to design the pH of the liquid detergent to be neutral at around 7.0, and to prepare lipases or esterases as enzymes.

[0239] When a lightweight, transparent liquid detergent containing the co-modified organosilicon and its composition of the present invention is primarily used for clothing made of relatively strong and durable synthetic fibers such as cotton or polyester, the cleaning power can be enhanced by appropriately adjusting the dosage of specific anionic surfactants as described in Patent Documents 8, 10, and 11, in addition to component (I). In this design concept, it is preferable to further adjust the dosage of protease as an enzyme in component (VIII) above, which enhances the cleaning power against protein-based stains. From the viewpoint of maintaining enzyme function, it is preferable to design the pH of the liquid detergent to be neutral, around 7.0.

[0240] When it is desired to add a hand feel or softening effect, antistatic or antibacterial effect, etc., to a transparent liquid detergent containing the co-modified organosilicon and its composition of the present invention using cationic surfactants, specific quaternary ammonium salts described in Patent Documents 8, 9, and International Publication No. 1994 / 06899 can be appropriately formulated. Among these, ester quaternary ammonium salts with excellent biodegradability are preferred, and examples include TEAQ (triethanolamine quaternary salt), DEEDMAC (diethyloxyethyl dimethyl ammonium chloride), HEQ ((Z)-2-hydroxy-3-[(1-oxo-9-octadecenyl)oxy]propyltrimethylammonium chloride), bis[2-(stearoyloxy)ethyl]dimethyl ammonium chloride, bis[2-(hexadecanoyloxy)ethyl]dimethyl ammonium chloride, and dimethyl sulfate quaternary ammonium compounds of the reaction product of octadecenoic acid and triethanolamine. Alternatively, amide-type alkyl ammonium salts such as stearamide propyl dimethyl-β-hydroxyethyl ammonium salt can also be used. When using ester quaternary ammonium salts, it is preferable to design the pH of the liquid detergent to be neutral, around 7.0.

[0241] [Use, advantages and other applications of the co-modified organosilicon and its compositions in transparent liquid detergents]

[0242] As previously described, the co-modified organosilicon and its composition of the present invention can be formulated for use in concentrated transparent liquid detergents or transparent liquid detergents for laundry. When formulated into a transparent liquid detergent, the composition does not impede its transparency or causes minimal impairment, and can be used as a softener component, fiber lubricant component, hand-feel-enhancing component, or fiber surface coating component. Furthermore, the composition has low viscosity and does not cause thickening or appearance changes during storage, or if it does, the degree is very small, thus facilitating quality control, demonstrating excellent practicality, and exhibiting superior operability in the manufacture of liquid detergents. Due to its low impurity content, the amount that can be formulated into a transparent liquid detergent can be increased, thereby improving the traceability effect of the transparent liquid detergent.

[0243] Furthermore, the co-modified organosilicon and its compositions involved in this invention can also be used for purposes other than liquid detergents, such as in the fields of fiber treatment agents listed in Patent Document 1, wipe paper treatment agents listed in Patent Document 7, personal care products such as hair detergents or hair treatment agents, and fabric softeners. Additionally, they can be added to opaque liquid or solid detergents without particular limitation.

[0244] Example

[0245] The present invention will be further described in detail below through examples and comparative examples, but the present invention is not limited thereto. In addition, unless otherwise specified, "%" in the experimental examples refers to mass percentage. For simplicity, M represents (CH3)3SiO in the following reference examples, comparative examples, and embodiments. 1 / 2 Unit, D represents (CH3)2SiO unit, D H This represents the H(CH3)SiO unit, and T represents CH3SiO. 3 / 2 Unit, D (AM) Represents the (CH3)(C3H6NH2)SiO unit, D (AMD) It represents (CH3){C3H6NHCO-CH2O(EO)} 4.5 -C 12 H 25 SiO unit, D (PE1) This represents (CH3){C3H6O(EO)} 11 -CH3}SiO unit, D (PE2) The expression represents the (CH3){C3H6O(EO)3-CH3}SiO unit, EO represents the CH2CH2O unit, PO represents the C3H6O unit {mainly CH2(CH3)CHO unit}, Me represents the CH3 group, IPA represents 2-propanol, CPA represents chloroplatinic acid H2[PtCl6]・(H2O)6, D4 represents octamethylcyclotetrasiloxane, and POE(4.5) represents polyoxyethylene (the molar number of oxyethylene addition is 4.5). Furthermore, the average chemical structural formula of each compound is obtained by using... 29 Si、 13 The NMR analysis of the C-type nuclides was performed. The viscosity (mPa·s) of each composition was measured by rotational viscometer at 25°C.

[0246] [Reference Example 1] Preparation of two polyether-modified organosilicon compositions (raw materials)

[0247] The average chemical structure MD in the design will be determined by 51.3 D H 6.3 M represents 134.1g of Si-H-based dimethyl polysiloxane, with the average chemical structure H2C=CH-CH2-O(EO) designed. 11103.1 g of the first allyl-terminated polyether (represented by -Me) was added to a 500 mL reactor and heated under flowing nitrogen with stirring. 0.33 mL of an IPA solution (Pt concentration 0.75% by mass) of a 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex was added to the mixture, and the mixture was aged at 40–82 °C for 1.5–2.5 hours until the target reaction rate was achieved. Next, 14.8 g of the 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 aforementioned platinum catalyst solution were added, and the mixture was aged at approximately 80 °C for 3–3.5 hours until the reaction was complete. The system was then subjected to reduced pressure and stripping at 130–138 °C and 1–10 Torr for 1.5–5 hours. After cooling to below 55 °C and restoring pressure, the mixture was filtered through a depth filter to obtain the product represented by the average chemical structure MD. 51.3 D (PE1) 5.2 D (PE2) 1.1 M { (PE1) = -C3H6O(EO) 11 -Me, (PE2) = -C3H6O(EO)3-Me} represents 217g of two polyether-modified organosilicon compositions, which are almost colorless and transparent liquids. Since the H2C=CH / Si-H molar ratio during the hydrosilylation reaction is 1.15 with respect to the first polyether, the residual polyether content in the two polyether-modified organosilicon compositions is calculated to be 5.5% by mass.

[0248] [Reference Example 2] Preparation of two polyether-modified organosilicon compositions (raw materials)

[0249] After conducting the same experiment as in Reference Example 1 on the following day, it was found that although the reactivity of the first polyether decreased slightly, it was not a problem, and the polyether obtained was derived from the average chemical structure MD. 51.3 D (PE1) 5.0 D (PE2) 1.3 M { (PE1) = -C3H6O(EO) 11 -Me, (PE2) = -C3H6O(EO)3-Me} represents 216g of two polyether-modified organosilicon compositions, which are light brown transparent liquids. Based on the reaction rate of the first polyether, the H2C=CH / Si-H molar ratio during the first hydrogenation silylation reaction is 1.20 with respect to the first polyether. Therefore, the residual polyether content in the two polyether-modified organosilicon compositions is calculated to be 6.9% by mass.

[0250] [Reference Example 3] Preparation of a single polyether-modified organosilicon composition

[0251] The average chemical structure MD in the design will be determined by 72.8 D H 4.8 M represents 253.53g of Si-H-based dimethyl polysiloxane, with the average chemical structure H2C=CH-CH2-O(EO) designed. 11 146.48 g of the allyl-terminated polyether (represented by -Me) was added to a 500 mL reactor and heated under flowing nitrogen with stirring. 0.48 mL of an IPA solution (Pt concentration 0.75% by mass) of a 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex was added to the mixture, with intermittent sampling for reaction rate confirmation. The mixture was aged at 54–98 °C for a total of 5 hours until the reaction was essentially complete, yielding 385.3 g of a light brown turbid liquid. 220 g of this liquid was filtered through an activated carbon-supported depth filter, resulting in a product with the average chemical structure MD... 72.8 D (PE1) 4.8 M { (PE1) = -C3H6O(EO) 11 The single polyether-modified silicone composition represented by {-Me} is 197g, a colorless and transparent liquid {582mPa・s (25C)}. Since the H2C=CH / Si-H molar ratio during the hydrosilylation reaction is 1.30, the residual polyether content in the polyether-modified silicone composition is calculated to be 8.5% by mass.

[0252] [Reference Example 4] Preparation of a single polyether-modified organosilicon composition

[0253] The same experiment was repeated using 90% of the total amount of main raw materials from Reference Example 3. 0.30 mL of an IPA solution containing 5% CPA was used as the hydrosilylation catalyst. The reaction temperature was 60–102 °C, and the reaction was completed after a total aging period of 4 hours, yielding 344.3 g of a light brown turbid liquid. This was filtered in the same manner as in Reference Example 3, resulting in a liquid with the average chemical structure MD. 72.8 D (PE) 4.8 M { (PE) = -C3H6O(EO) 11 The single polyether modified organosilicon composition represented by -Me} is 317g, which is a colorless and transparent liquid.

[0254] [Reference Example 5] Preparation of a single polyether-modified organosilicon composition

[0255] The average chemical structure MD in the design will be determined by 108.4 DH 8.1 M represents 40.93 parts by mass of Si-H-based dimethyl polysiloxane, with the average chemical structure H2C=CH-CH2-O(EO) designed. 11 59.07 parts by mass of allyl-terminated polyether (represented by -Me) were added to the reactor, and heating was initiated under flowing nitrogen with stirring. 200 ppm by mass of an IPA solution containing 5% CPA was added, and the reaction was allowed to mature at 60–85°C for 2 hours, at which point the reaction was essentially complete. The mixture was then filtered through a 1 μm filter, yielding a product with the average chemical structure MD. 108.4 D (PE) 8.1 M { (PE) = -C3H6O(EO) 11 The single polyether-modified organosilicon composition represented by {-Me} consists of 99 parts by mass, which is a pale yellowish-brown, almost transparent liquid. Since the H₂C=CH / Si-H molar ratio during the hydrosilylation reaction is 1.33, the residual polyether content in the polyether-modified organosilicon composition is calculated to be 10.2% by mass.

[0256] [Reference Example 6] Preparation of amide-containing polyether-based organosilicon compositions based on a reported method (see paragraph 0011)

[0257] 32.3 parts by mass of the polyether-modified organosilicon composition of Reference Example 5, 40.84 parts by mass of D4, 4.74 parts by mass of the hydrolysis condensate of 3-aminopropylmethyldiethoxysilane, and 300 ppm by mass of 11N KOH aqueous solution were added to a reactor, and heating was initiated while stirring under flowing nitrogen. After reacting at 147–152°C for 1 hour, 200 ppm by mass of acetic acid was added to neutralize the alkaline catalyst. Further, stripping was carried out at 142–150°C and 30 Torr for 2.5 hours, followed by cooling to below 75°C and pressure recovery to obtain the intermediate amino / polyether-modified organosilicon composition. 22.36 parts by mass of a POE(4.5) lauryl ether acetic acid solution (containing 92% by mass of active ingredient, 7.5% by mass of water, and 0.5% by mass of NaCl) were added to the mixture. After an amidation reaction at 123–127°C for 3 hours under normal pressure, the mixture was cooled to below 75°C and filtered to obtain 91 parts of an amide-containing polyether-based silicone composition manufactured by a previously reported method. The composition was a light brown, almost transparent liquid {1320 mPa・s (25°C)}. The COOH / NH2 molar ratio during the amidation reaction was 1.26, and the residual polyether content in the composition was calculated to be 3.4% by mass.

[0258] [Reference Example 7] Preparation of high-purity amino / amide / monopolyether modified organosilicon composition

[0259] 154.25 g of the single polyether modified organosilicon composition of Reference Example 3, 130.78 g of D4, 18.24 g of the hydrolysis condensate of 3-aminopropylmethyldiethoxysilane, and 0.12 g of 43% KOH aqueous solution were added to a 500 mL reactor and heated under flowing nitrogen with stirring. During the process, samples were taken for viscosity confirmation. After equilibration at 140–156 °C for 3 hours, the mixture was cooled to 75 °C and 0.34 g of acetic acid was added for neutralization with the alkaline catalyst. Subsequently, stripping was performed at 146–163 °C and 40–45 Torr for 2 hours. After pressure recovery and sampling, 265.8 g of the intermediate amino / polyether modified organosilicon composition was obtained as a semi-transparent liquid {1838 mPa·s (25 °C)}. 35.8 g of a POE (4.5%) lauryl ether acetic acid solution (containing 92% by mass of active ingredient, 7.5% by mass of water, and 0.5% by mass of NaCl) was added, and the system was brought under reduced pressure. After an amidation reaction at 122–128 °C and 30 Torr for 4 hours, the system was cooled to below 90 °C to restore pressure and filtered through a depth filter to obtain 244 g of a high-purity amino / amide / monopolyether modified organosilicon composition, which was a yellow transparent liquid {2012 mPa·s (25 °C)}. The COOH / NH2 molar ratio during the amidation reaction was 0.54, and the residual polyether content in the final composition was calculated to be 3.9% by mass.

[0260] [Reference Example 8] Preparation of high-purity amino / amide / monopolyether modified organosilicon composition

[0261] 154.24 g of the single polyether modified organosilicon composition of Reference Example 4, 127.54 g of D4, 18.25 g of the hydrolysis condensate of 3-aminopropylmethyldiethoxysilane, and 0.13 g of 43% KOH aqueous solution were added to a 500 mL reactor and heated under flowing nitrogen with stirring. During the process, samples were taken for viscosity confirmation. After equilibration at 146–158 °C for 6 hours, the mixture was cooled to 64 °C and 0.30 g of acetic acid was added for neutralization with the alkaline catalyst. Then, stripping was performed at 142–150 °C and 7–8 Torr for 1 hour and 40 minutes. After pressure recovery and sampling, 234 g of the intermediate amino / polyether modified organosilicon composition was obtained, which was a slightly yellow, almost transparent liquid {1363 mPa·s (25 °C)}. 31.57 g of a POE(4.5) lauryl ether acetic acid solution (containing 92% by mass of active ingredient, 7.5% by mass of water, and 0.5% by mass of NaCl) was added, and the system was brought under reduced pressure. After an amidation reaction at 118–125 °C and 8–9 Torr for 4 hours, the system was cooled to below 90 °C to restore pressure, and then filtered through a depth filter to obtain 233.8 g of a high-purity amino / amide / monopolyether modified organosilicon composition, which was an orange transparent liquid {1767 mPa・s (25 °C)}. The COOH / NH2 molar ratio during the amidation reaction was 0.54, and the residual polyether content in the final composition was calculated to be 3.9% by mass.

[0262] [Reference Example 9] Preparation of amino / two polyether modified organosilicon compositions (intermediates)

[0263] The amino / two polyether modified organosilicon composition {723 mPa·s (25°C)} taken during the preparation of Example 1 (the composition of the present invention) described below will be treated as Reference Example 9.

[0264] [Example 1] Preparation of amino / amide / two polyether modified organosilicon compositions

[0265] 142.95 g of the two polyether-modified organosilicon compositions of Reference Example 1, 92.02 g of D4, 15.09 g of the hydrolysis condensate of 3-aminopropylmethyldiethoxysilane, and 0.11 g of 43% KOH aqueous solution were added to a 500 mL reactor and heated while stirring under flowing nitrogen. During the process, samples were taken for viscosity confirmation. After equilibration at 146–155 °C for 6 hours, the mixture was cooled to 78 °C and 0.32 g of acetic acid was added for neutralization with the alkaline catalyst. Then, stripping was performed at 151–153 °C and 27 Torr for 1 hour. After cooling, pressure recovery, and sampling, 200.6 g of the intermediate amino / two polyether-modified organosilicon compositions was obtained as a pale yellow, semi-transparent liquid {723 mPa・s (25 °C)}. 26.45 g of a POE (4.5%) lauryl ether acetic acid solution (containing 92% by mass of active ingredient, 7.5% by mass of water, and 0.5% by mass of NaCl) was added to the system, and the pressure was initially reduced. After an amidation reaction at 116–122 °C and 21–25 Torr for 6 hours, the system was cooled to below 95 °C to restore pressure and filtered through a depth filter to obtain 200.2 g of the amino / amide / two polyether composite modified organosilicon composition of the present invention, which is a light cinnamon-colored transparent liquid {913 mPa・s (25 °C)}. The COOH / NH2 molar ratio during the amidation reaction was 0.54, and the residual polyether content in the final composition was calculated to be 3.1% by mass.

[0266] [Example 2] Preparation of amino / amide / two polyether modified organosilicon compositions

[0267] 71.05 g and 70.09 g of the two polyether-modified organosilicon compositions from Reference Example 1 and Reference Example 2, 1.02 g of D49, 14.88 g of the hydrolysis condensate of 3-aminopropylmethyldiethoxysilane, and 0.12 g of 43% KOH aqueous solution were sequentially added to a 500 mL reactor. Heating was initiated under flowing nitrogen with stirring. After equilibration at 141–155 °C for 5 hours, the reactor was cooled to 74 °C and 0.37 g of acetic acid was added for neutralization with an alkaline catalyst. Subsequently, the pressure was reduced to 30 Torr and the reactor was stripped. The removal of low-boiling-point components was completed at 154 °C. After cooling, pressure recovery, and sampling, 222 g of the intermediate amino / two polyether-modified organosilicon compositions {688 mPa·s (25 °C)} was obtained. 29.43 g of a POE (4.5%) lauryl ether acetic acid solution (containing 92% by mass of active ingredient, 7.5% by mass of water, and 0.5% by mass of NaCl) was added, and the system was brought under reduced pressure. After an amidation reaction at 117–120 °C and 5–10 Torr for 5 hours, the system was cooled to below 70 °C to restore pressure and filtered through a depth filter to obtain 219 g of the amino / amide / two polyether composite modified organosilicon composition of the present invention, which was a dark orange transparent liquid {920 mPa·s (25 °C)}. The COOH / NH2 molar ratio during the amidation reaction was 0.54, and the residual polyether content in the final composition was calculated to be 3.9% by mass.

[0268] [Comparative Example 1] Changes in the amide-containing polyether-based silicone composition of Reference Example 6 over time

[0269] The amide-containing polyether-based silicone composition obtained in Reference Example 6 was placed in a covered container (equivalent to 40% of the container volume), sealed with nitrogen, and stored at room temperature for 40 days. Afterwards, the contents were opened and examined; it was found to have become a cloudy, heterogeneous liquid, and suspended gel particles were observed. Therefore, 1 kg was taken and filtered through a depth filter to obtain 976 g of the pale yellowish-brown, semi-transparent amide-containing polyether-based silicone composition {2060 mPa・s (25°C)}.

[0270] [Comparative Example 2] Preparation of amide-containing polyether-based organosilicon compositions based on the reported method (see paragraph 0011)

[0271] 154.23 g of the polyether-modified organosilicon composition of Reference Example 4, 127.53 g of D4, 18.24 g of the hydrolysis condensate of 3-aminopropylmethyldiethoxysilane, and 0.12 g of 43% KOH aqueous solution were added to a 500 mL reactor and heated under flowing nitrogen with stirring. During the process, samples were taken for viscosity confirmation. After equilibration at 146–163 °C for 6 hours, the mixture was cooled to 65 °C and 0.33 g of acetic acid was added for neutralization with the alkaline catalyst. Then, stripping was performed at 131–159 °C and 28–31 Torr for 1 hour and 40 minutes. After pressure recovery and sampling, 242 g of the intermediate amino / polyether-modified organosilicon composition was obtained as a pale yellow-white turbid liquid {1657 mPa・s (25 °C)}. 67.66 g of a POE(4.5) lauryl ether acetic acid solution (containing 92% by mass of active ingredient, 7.5% by mass of water, and 0.5% by mass of NaCl) was added to the mixture. After an amidation reaction at 122–127 °C for 3 hours under normal pressure, the mixture was cooled to room temperature to obtain 296 g of an amide-containing polyether-based silicone composition prepared by a previously reported method. The composition was a yellow, transparent liquid {3970 mPa・s (25 °C)}. The COOH / NH2 molar ratio during the amidation reaction was 1.26, and the residual polyether content in the composition was calculated to be 3.5% by mass.

[0272] Table 1 below summarizes the correlation between the average chemical structure and viscosity of the examples based on NMR analysis and reaction rate tests during synthesis experiments, and several reference / comparative samples. Here, the correlation between the assumed M unit and M... OR’ The content (in moles) of each structural unit when the total number of units is 2.00 moles.

[0273] Table 1. Average chemical structure of the samples

[0274] [Table 1]

[0275]

[0276] *Examples 7 and 8 are not known co-modified organosilicones, but differ from the embodiments of this application in that they do not have a second polyether modifying group. Therefore, for the purpose of comparing viscosity and other parameters and clarifying the technical significance of the present invention, they are shown in the following tables. * is appended to the tables below.

[0277] Although the target average chemical structure of Comparative Example 1 (or Reference Example 6) is very close to that of Comparative Example 2, it was confirmed that the viscosity and M OR’The content varies considerably. Therefore, it is clear that, based on the reported atmospheric pressure amidation reaction conditions, it is impossible to produce amino / amide polyether / polyether-modified organosilicon with a structure where both ends of the polysiloxane backbone are capped with trimethylsilyl groups. Furthermore, Reference Examples 7 and 8, with the remaining carboxyl groups reduced, yielded more stable final product viscosities than the comparative examples. In contrast, Examples 1 and 2, with the remaining carboxyl groups reduced and a low molecular weight second polyether introduced, were found to have the further advantage of minimal batch-to-batch variation in product viscosity. Combined with their lower viscosity than the samples of the reference examples, this resulted in excellent operability.

[0278] That is, the inventors discovered that only when the average polysiloxane chain length is short and M... OR’ Under the conditions of low content, small total molar number of carboxylic acid groups and acyloxy groups, and low molecular weight second polyether groups together with the first polyether group in the molecule, co-modified organosilicon and its composition can maintain low viscosity and have excellent viscosity reproducibility between batches, thus achieving both high purity and good operability and production stability.

[0279] Table 2 below summarizes the variation of two batches of each of the Examples, Reference Examples, and Comparative Examples, starting from the average initial viscosity (assuming it is the target value).

[0280] Table 2. Viscosity differences relative to target values

[0281] [Table 2]

[0282]

[0283] The effects of introducing a low molecular weight second polyether in the two batches of the examples were confirmed, demonstrating a further advantage of smaller batch-to-batch viscosity variations compared to the two batches of the comparative examples. Furthermore, the two batches of the comparative examples, by reducing the residual carboxyl groups, significantly suppressed batch-to-batch viscosity variations compared to the two batches of the comparative examples.

[0284] Table 3 below summarizes the general physical properties of the examples and several reference / comparative examples. Data on appearance (transparency) and viscosity after long-term storage at room temperature are also shown. Additionally, ND in the table indicates not detected or below the detection limit, D4 / D5 / D6 content is the result of analysis by gas chromatography (for the examples, headspace gas chromatography with improved detection sensitivity through baseline stabilization), and NH2% is the result of analysis using neutralization titration with dilute hydrochloric acid (unit: mass %).

[0285] Table 3. General physical properties and their variations for each sample

[0286] [Table 3]

[0287]

[0288] Examples 1 and 2 maintained low viscosity and good operability during storage for 1 to 3 months. Furthermore, the change in transparency was minimal. In other words, the examples outperformed the comparative examples in terms of quality instability. Further, while the comparative examples failed to achieve the target of setting the cyclic dimethylsiloxane 4, 5, and 6 polymers to below 0.10%, Examples 1 and 2 both achieved this target.

[0289] For the lightweight transparent liquid detergent compositions represented by the formulations in Table 4 below, 0.67% by mass of the samples of Examples 1-2 and Comparative Example 2 were added respectively, and the mixture was shaken 2-3 times during the process while being heated at 40°C for 1 hour to dissolve it, thus preparing the transparent liquid detergent compositions for comparison and the present invention.

[0290] Table 4. An example of a lightweight, transparent liquid detergent composition

[0291] [Table 4]

[0292]

[0293] Table 5 below summarizes the stability test results of the various transparent liquid detergent compositions mentioned above.

[0294] Table 5. Appearance changes of transparent liquid detergent compositions (40°C, 1 month)

[0295] [Table 5]

[0296]

[0297] It was confirmed that the additives of Examples 1 and 2 dissolved stably and transparently in the light, transparent liquid detergent composition, and did not hinder the transparency of the appearance even after being stored at 40°C for 1 month.

[0298] Table 6 below summarizes the calculated molar ratio of the oxyethylene group relative to the Si-CH3 group in Example 1 by NMR analysis.

[0299] Table 6. EO / SiMe ratio in Example 1

[0300] [Table 6]

[0301]

[0302] Table 7 below summarizes the relationship between the calculated values ​​of the average chemical structure and viscosity of Reference Example 9, based on NMR analysis and reaction rate tests during synthesis experiments. Here, the relationship between the calculated values ​​and viscosity is shown under the assumption of M unit and M... OR’ The content (in moles) of each structural unit when the total number of units is 2.00 moles.

[0303] Table 7. Average chemical structure of Reference Example 9

[0304] [Table 7]

[0305]

[0306] [Summarize]

[0307] As shown in the examples, the average polysiloxane chain length is within a specified short range, M OR’ Low content and M:M OR” Co-modified organosilicones and their compositions, possessing four structural characteristics—a low molar ratio within a specified range, a small total molar number of carboxylic acid and acyloxy groups, and a low molecular weight second polyether group along with the first main polyether group—not only exhibit low viscosity but also suppress viscosity rise for maintenance / management, including operability. Furthermore, they demonstrate excellent batch-to-batch viscosity reproducibility, thus achieving a balance between high purity and good operability and production stability. When formulated into transparent liquid detergents, these co-modified organosilicones and their compositions do not impede transparency or impede it minimally, making them suitable as softener components, fiber lubricant components, hand-feel-enhancing components, or fiber surface coating components. Due to their low viscosity, they also offer excellent operability in the manufacture of transparent liquid detergents. The low impurity content allows for increased dosage in transparent liquid detergents, thereby enhancing their commercial appeal.

Claims

1. A co-modified organosilicon, having 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 R3SiO] 1 / 2 Unit, D is an R2SiO unit, D (AM) For RR 1 SiO unit, D (AMD) For RR 2 SiO unit, D (PE1) For RR 3 SiO unit, D (PE2) For RR 8 SiO unit, M OR’ R2(OR')SiO 1 / 2 Unit, T is composed of R3SiO 3 / 2 The silyloxy group represents a silyloxy group where p, q, r, s, and w are all positive numbers, and satisfy the relationship 50 ≤ p + q + r + s + w ≤ 160, x is a number in the range of 0 to 1, and the molar ratio is M:M OR’ Within 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 It is an aminoalkyl group (1 to 6 carbon atoms). R 2 For -R 4 -NHCO-(CH2) b -O(C2H4O) c -R 5 (where R) 4 R is an alkylene group having 1 to 6 carbon atoms. 5 A group represented by a monovalent hydrocarbon group having 1 to 18 carbon atoms, where b is a number in the range of 1 to 6, and c is a number in the range of 2 to 20. R 3 For -R 6 -O-(C2H4O) d (C3H6O) e -R 7 Basis (where R) 6 R is an alkylene group having 2 to 8 carbon atoms. 7 An alkyl group having 1 to 12 carbon atoms, where d is a number ranging from 3 to 25 and e is a number ranging from 0 to 10, and when e is not 0, d and e satisfy the molar ratio d / e ≥ 7 / 3. R 8 For -R 6 -O-(C2H4O) f (C3H6O) g -R 7 (where R) 6 R 7 For groups similar to those described above, where f and g are each numbers from 0 to 4, and satisfy the relationship 1 ≤ f + g ≤ 4, the group is represented by... OR' is a group selected from hydroxyl, alkoxy-containing groups, and acyloxy-containing groups. Furthermore, M and M OR’ When the total molar number is set to 2.0, the total molar number of carboxylic acid groups and acyloxy groups within the molecule is less than 1.

0. express.

2. The co-modified organosilicon according to claim 1, wherein, In the average structural formula (1), the number x of silanoxy units represented by T is in the range of 0.01 to 0.

70.

3. A co-modified organosilicon composition comprising the co-modified organosilicon of claim 1, and further comprising the following average structural formula: Z-O-(C2H4O) d (C3H6O) e -R 7 (2) [In the formula, Z is a group selected from alkenyl or hydrogen atoms with 2 to 8 carbon atoms, R] 7 The definitions of d and e are the same as above. The polyether compound represented, wherein, When the sum of the co-modified organosilicon compound and the polyether compound is set to 100 parts by mass, the content of the polyether compound is in the range of less than 5 parts by mass.

4. The co-modified organosilicon composition according to claim 3, wherein, The molar ratio of ethylene oxide (C2H4O) groups to 1 mole of Si-R groups in the composition is in the range of 0.2 to 0.

6.

5. The co-modified organosilicon composition according to claim 3, wherein, The content of aminoalkyl groups in the composition is in the range of 0.1% to 0.6% by mass.

6. The co-modified organosilicon composition according to claim 3, wherein, The content of each cyclic dimethylsiloxane as a 4-6 polymer is less than 0.1% by mass of the whole composition.

7. A liquid detergent comprising the co-modified organosilicon of any one of claims 1 to 2 or the co-modified organosilicon composition of any one of claims 3 to 6.

8. The liquid detergent according to claim 7, wherein it is a transparent concentrated liquid detergent or a transparent liquid detergent for laundry, wherein, The co-modified organosilicon composition of any one of claims 1 to 2 or any one of claims 3 to 6 is formulated as any one or more of the following components: softener component, fiber lubricant component, hand feel enhancing component, and fiber surface coating component.

9. The liquid detergent according to claim 7, comprising: (I) a detergency organic nonionic surfactant having polyoxyethylene (with an average repeatability of ethylene in the range of 3 to 16): in the range of 10 to 60% by mass of the total liquid detergent. (II) At least one antifreeze selected from (II-1) to (II-3) below: in the range of 2% to 20% by mass of the total liquid detergent. (II-1) Saturated monohydric alcohols with 2 to 4 carbon atoms (II-2) Diol ethers monosubstituted with alkyl groups having 1 to 6 carbon atoms (wherein, The glycol ether contains oxyvinyl and / or oxypropylene groups, with a repeat number in the range of 1 to 3. (II-3) A diol or triol compound selected from propylene glycol, dipropylene glycol, tripropylene glycol, triethylene glycol, tetraethylene glycol, trimethylene glycol, and glycerol. (III) Water: 20-85% by mass of the total liquid detergent (IV) The co-modified organosilicon of any one of claims 1 to 2 or the co-modified organosilicon composition of any one of claims 3 to 6: in the range of 0.3 to 3% by mass of the liquid detergent as a whole.

10. The liquid detergent according to claim 9, further comprising (V) 0.1-15% by mass of a stabilizer selected from antibacterial agents (preservatives), cosolvents, antioxidants, and water softeners (chelating agents). The total amount of the components (I) to (V) is set to 100% by mass.

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

12. A method for manufacturing a liquid detergent according to claims 9-11, comprising said components (I) to (IV) and optionally said components (V) to (X), characterized in that, After heating and mixing at 40–80°C to dissolve components (I)–(VII), cool to below 30°C, then add one or more components selected from components (VIII), (IX), and (X) and mix thoroughly.

13. A method for manufacturing a co-modified organosilicon composition according to any one of claims 1 to 2 or any one of claims 3 to 6, characterized in that, The following average structure will be used: MD t D (AM) u D (PE1) v D (PE2) z M OR’ Tx(3) [In the formula, M is R3SiO] 1 / 2 D is R2SiO, D (AM) For RR 1 SiO, D (PE1) For RR 3 SiO unit, D (PE2) For RR 8 SiO unit, M OR’ R2(OR')SiO 1 / 2 T is composed of R3SiO 3 / 2 The silyloxy group represents a silyl group, where t, u, v, and z are positive numbers and satisfy the relationship 50 ≤ t + u + v + z ≤ 160, and x is a number in the range of 0 to 1. Molar ratio M:M OR’ Within 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 It is an aminoalkyl group having 1 to 12 carbon atoms. R 3 For -R 6 -O-(C2H4O) d (C3H6O) e -R 7 (where R) 6 R is an alkylene group having 2 to 8 carbon atoms. 7 An alkyl group having 1 to 12 carbon atoms, where d is a number ranging from 3 to 25 and e is a number ranging from 0 to 10, and when e is not 0, d and e satisfy the molar ratio d / e ≥ 7 / 3. R 8 For -R 6 -O-(C2H4O) f (C3H6O) g -R 7 (where R) 6 R 7 For groups similar to those described above, where f and g are each numbers from 0 to 4, and satisfy the relationship 1 ≤ f + g ≤ 4, the group is represented by... OR' is a group selected from hydroxyl, alkoxy-containing groups, and acyloxy-containing groups. The amino / two polyether co-modified organosilicon and The following average structural formula: HOOC-(CH2) b -O(C2H4O) c -R 5 (4) In the formula, R 5 [where b is a monovalent hydrocarbon group with 1 to 18 carbon atoms, and c is a number in the range of 1 to 6, and c is a number in the range of 2 to 20] represents a polyether-containing carboxylic acid. Under reduced pressure and inert gas flow, the mixture is heated and mixed at 80–180 °C to react, and the reaction is carried out in such a way that the molar ratio (reaction ratio) of the amino alkyl group in the amino / two polyether co-modified organosilicon represented by formula (3) and the carboxyl group in the polyether-containing carboxylic acid represented by formula (4) is in the range of 0.1 ≤ carboxyl group / amino alkyl group ≤ 1.

0.

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

70.

15. The manufacturing method according to claim 13, characterized in that, The carboxylic acid containing a polyether group, represented by the average structural formula (4), is reacted in an aqueous solution or in the presence of water.

Images