JP2011174188A - Scouring agent composition for fiber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a scouring agent composition which has excellent scouring properties, low foamability, and high permeability into fibers under high alkali conditions, and enables the concentration of an active ingredient, when used together with an anionic surfactant. <P>SOLUTION: The scouring agent composition for fibers includes a specific nonionic surfactant which contains a compound having a 8 to 14C primary straight-chain saturated hydrocarbon group at a rate of ≥80 mol% and has a structure obtained by block-binding ethylene oxide and propylene oxide in this order to the hydrocarbon group. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention is a scouring for fibers used in the process of removing various contaminants for improving the effects of bleaching, dyeing, finishing, etc. of natural fibers such as cotton and synthetic fibers such as polyester and mixed fiber products thereof. The agent composition.

  Natural fibers, such as resin, wax for plant fibers, fats, colloidal materials, etc. for animal fibers, and polyester synthetic fabrics, a large amount of paraffin wax or acrylic ester added at the spinning stage In addition, sizing agents such as polyvinyl alcohol are present as impurities, and if they are not completely removed in the scouring process, smoke, bleaching, dyeing, and finishing unevenness in the drying process are caused.

  In this scouring step, conventionally, nonionic surfactants, anionic surfactants, and mixtures thereof are mainly used as scouring agents. For example, as nonionic surfactant-based scouring agents, propylene oxide (hereinafter abbreviated as PO) and ethylene oxide (hereinafter abbreviated as EO) adducts of alkylphenols and higher alcohols are known. Specifically, Patent Documents 1 and 2 each include an EO / PO / EO triblock adduct of a specific aromatic and aliphatic alcohol, and Patent Document 3 includes a PO / EO / PO triblock adduct of a specific alcohol. It is disclosed. These are all intended to have low foaming properties and high permeability to fibers. Patent Document 4 discloses a scouring agent composition in which a specific alcohol is randomly added with EO and PO, and then a nonionic surfactant added with EO and an anionic surfactant are used in a specific ratio. It is disclosed that it has a low viscosity at high concentrations or low temperatures.

Japanese Examined Sho 62-54840 JP 47-9561 A Japanese Patent No. 2575236 JP-A-8-60532

  However, EO and PO adducts of alkylphenols described in Patent Document 1 are not preferable from the viewpoint of naturalization of raw materials because they have alkylphenol groups, and the nonionic surfactants described in Patent Document 2 and Patent Document 3 are Although it is said to have low foaming property, it is inferior in scourability under high alkaline conditions. Further, the scouring agent composition of Patent Document 4 is said to be able to increase the concentration by using an anionic surfactant in combination, but the scourability under high alkaline conditions is still insufficient and further improvement is desired. ing.

  That is, a scouring agent that has excellent refining properties even under high alkaline conditions, low foaming property, high permeability to fibers, and can concentrate active ingredients when used in combination with an anionic surfactant A composition has not yet been obtained.

The present invention is a fiber scouring agent composition containing (A) a nonionic surfactant represented by the following general formula (1) [hereinafter referred to as component (A)], wherein (A) component: The present invention relates to a fiber scouring agent composition in which R in the general formula (1) is a primary linear saturated hydrocarbon group having 8 to 14 carbon atoms and the proportion of the nonionic surfactant is 80 mol% or more.
R—O— (EO) _m — (PO) _n —H (1)
[Wherein R represents a hydrocarbon group having 6 to 24 carbon atoms, EO represents an ethyleneoxy group, and PO represents a propyleneoxy group. m is the average number of moles of ethyleneoxy group added, and is a number from 3 to 30. n is the average number of added moles of propyleneoxy groups, and is a number of 0.5-5. Note that (EO) _m and (PO) _n are block-coupled in this order. ]

  According to the present invention, it has excellent refining property, low foaming property, high fiber permeability even under high alkaline conditions, and can concentrate active ingredients when used in combination with an anionic surfactant. A scouring agent composition is provided.

  The component (A) of the present invention is a polyoxyalkylene type nonionic surfactant represented by the above general formula (1). In the present invention, R in the general formula (1) is included in the component (A). The ratio of the nonionic surfactant that is a primary linear saturated hydrocarbon group having 8 to 14 carbon atoms is 80 mol% or more. In the general formula (1), R represents a hydrocarbon group having 6 to 24 carbon atoms, preferably 8 to 18 carbon atoms. Examples of the hydrocarbon group include a linear or branched alkyl group, a linear or branched alkenyl group, an aromatic hydrocarbon group which may be substituted with an alkyl group or an alkenyl group, and the like. From the viewpoint of refinability under conditions and from the viewpoint of environmental safety, a group selected from a linear or branched alkyl group and a linear or branched alkenyl group is preferred, and a linear alkyl group and a linear chain are preferred. A group selected from alkenyl groups is more preferable, and a linear alkyl group is particularly preferable. From the viewpoint of environmental safety, a group derived from a natural higher alcohol such as octyl alcohol, decyl alcohol, lauryl alcohol, and myristyl alcohol is preferred. (A) It is preferable that a component contains 2 or more types of compounds from which R differs in carbon number.

  In the present invention, in the component (A), the proportion of the nonionic surfactant in which R in the general formula (1) is a primary linear saturated hydrocarbon group having 8 to 14 carbon atoms is 80 mol% or more. However, from the viewpoint of scourability, it is preferably 90 mol% or more, and more preferably 95 mol% or more.

  Further, in the present invention, from the viewpoint of scourability under high alkali conditions, in the component (A), in the general formula (1), R is a primary linear saturated hydrocarbon group having 8 to 10 carbon atoms. The proportion of the surfactant is 5 to 95 mol%, further 10 to 90 mol%, more preferably 20 to 80 mol%, and R is a primary linear saturated hydrocarbon group having 11 to 14 carbon atoms. The proportion of the nonionic surfactant is preferably 5 to 95 mol%, more preferably 10 to 90 mol%, and still more preferably 20 to 80 mol%.

  In the present invention, from the viewpoint of smeltability under high alkaline conditions and high concentration as a scouring agent, in the component (A), R in the general formula (1) is an n-octyl group. It is preferable that the ratio of the activator is 5 to 95 mol%, further 10 to 90 mol%, further 25 to 75 mol%, and further 30 to 70 mol%. From the same viewpoint, the ratio of the nonionic surfactant in which R in the general formula (1) is an n-dodecyl group is 5 to 95 mol%, further 10 to 90 mol%, further 25 to 75 mol%, It is preferable that it is 30-70 mol%. Furthermore, in the present invention, from the viewpoint of smeltability under high alkaline conditions and high concentration as a scouring agent, in the component (A), R in the general formula (1) is an n-octyl group. The total proportion of the activator and the nonionic surfactant in which R is an n-dodecyl group is 10 to 100 mol%, further 20 to 100 mol%, further 50 to 100 mol%, and further 60 to 100 mol%. It is preferable.

  In the present invention, from the viewpoint of smeltability under high alkaline conditions and high concentration as a scouring agent, R in the general formula (1) is a hydrocarbon group having 9 to 10 carbon atoms in the component (A). It is preferable that the ratio of a certain nonionic surfactant is 0-30 mol%, Furthermore, 0-20 mol%, Furthermore, 0-10 mol%, Furthermore, 0-5 mol%. From the same viewpoint, the proportion of the nonionic surfactant in which R in the general formula (1) is a hydrocarbon group having 11 to 14 carbon atoms (excluding n-dodecyl group) is 0 to 30 mol%, It is preferably 0 to 20 mol%, more preferably 0 to 10 mol%, and further preferably 0 to 5 mol%.

(A) The polyoxyalkylene part which comprises a component is 3-30 mol EO by average addition mole number, and 0.5-5 mol PO by average addition mole number from the R side in General formula (1). Blocks are added in order. If the average added mole number m of EO is 3 or more, the scouring property is good, and if it is 25 or less, the foaming property is appropriate. Further, if the average added mole number n of PO is 0.5 or more, the foaming property is appropriate, and if it is 5 or less, the scouring property is good. m is preferably 4 to 20, more preferably 5 to 15, and still more preferably 6 to 12 from the viewpoints of the foamability and refinability. From the same viewpoint as m, n is preferably 0.8 to 4, more preferably 1 to 3. In addition, by making a block structure of (EO) _m and (PO) _n from the R side, a refining agent composition excellent in scourability and fiber permeability can be obtained, and when an anionic surfactant is used in combination. It becomes easy to concentrate the active ingredients. The component (A) is a mixture of alcohols represented by R—OH (R is a hydrocarbon group having 6 to 24 carbon atoms), and R is a linear saturated hydrocarbon having 8 to 14 carbon atoms in the mixture. A nonionic surfactant obtained by adding a predetermined amount of ethylene oxide and propylene oxide in this order to an alcohol mixture in which the proportion of the primary alcohol as a group is 80 mol% or more may be used.

  The nonionic surfactant of the general formula (1) as the component (A) can be obtained, for example, by the following production method. In addition, a nonionic surfactant in which R in the general formula (1) is a specific hydrocarbon group was produced according to the method of mixing the product produced by the following production method and the following production method. Thereafter, a method of mixing with a hydrocarbon group having a different R can also be applied.

  Examples of the method for producing the component (A) include a method in which ethylene oxide and propylene oxide are reacted in this order with a monohydric alcohol having 6 to 24 carbon atoms. Accordingly, the component (A) is preferably obtained by reacting ethylene oxide and propylene oxide in this order with a monohydric alcohol having 6 to 24 carbon atoms, and further to a monohydric alcohol having 6 to 24 carbon atoms. A catalyst obtained by reacting ethylene oxide and propylene oxide in this order at a reaction temperature of 80 to 180 ° C. in the presence of a catalyst such as a basic catalyst selected from potassium hydroxide and sodium hydroxide is preferred. Specifically, heating, cooling operation, decompression, pressurization operation is possible, and a reactor equipped with a raw material charging port, a product outlet, an alkylene oxide and nitrogen introduction tube, a stirring device, a thermometer, and a pressure gauge, A predetermined amount of an alcohol corresponding to R in the general formula (1) of the present invention, for example, an aliphatic alcohol is charged, and then a base catalyst such as solid potassium hydroxide or sodium hydroxide, or an aqueous solution thereof, or publicly known After the acid catalyst was charged, it was purged with nitrogen and dehydrated under reduced pressure in the temperature range from room temperature to 110 ° C. Next, a predetermined amount of ethylene oxide and propylene oxide are sequentially introduced and added at 80 to 180 ° C.

  In the addition reaction operation, it is more preferable to carry out an operation (aging operation) for continuing the reaction until the pressure decreases and becomes constant after introducing a predetermined amount of ethylene oxide and propylene oxide. Furthermore, the target component can be obtained by adding an appropriate amount of a known acid or base to the obtained reaction crude product to neutralize the catalyst. In the neutralization operation, the catalyst can be removed using a base adsorbent or an acid adsorbent.

  The scouring agent composition of the present invention preferably contains an anionic surfactant as the component (B). An anionic surfactant contributes to improvement of scourability under high alkaline conditions. Specific examples of the component (B) include saturated or unsaturated fatty acids, saturated or unsaturated alcohol sulfates, polyoxyalkylene alkyl sulfates, polyoxyalkylene alkyl mono and diphosphates, and salts thereof.

  Among these, phosphoric acid esters of polyoxyalkylene alkyl ethers, sulfuric acid esters of polyoxyalkylene alkyl ethers, specifically polyoxyalkylene alkyl sulfates, polyoxyalkylene alkyl mono- and diphosphates, and alkali metals and alkaline earths thereof. An inorganic salt such as a similar metal or a salt of an organic base is preferable, and a salt partially or completely neutralized with an alkali metal hydroxide or an organic base is more preferable.

  The component (A) can be used as it is as the scouring agent composition of the present invention. Further, the scouring agent composition of the present invention may be a composition containing 10 to 100% by mass, more preferably 20 to 100% by mass and further 30 to 100% by mass of the component (A).

  When the scouring agent composition of the present invention contains the component (A) and the component (B), the content of the component (A) in the composition is preferably 10 to 80% by mass, more preferably 15 to 70% by mass, Moreover, content in the composition of (B) component is 0.5-50 mass%, Furthermore, 3-40 mass%, Furthermore, 5-30 mass% is preferable. In that case, the total content of the component (A) and the component (B) is preferably 25 to 100% by mass, more preferably 50 to 100% by mass, and particularly preferably 55 to 100% by mass in the composition.

  The scouring agent composition of the present invention may contain water. The content is preferably 0 to 75% by mass. Conventional scouring agents are distributed as an aqueous solution having an active ingredient concentration other than water of about 15 to 50% by mass. However, in the present invention, even when the active ingredient concentration is increased, the viscosity is low, so that the operability is improved. It can be made compact without compromising. Therefore, the water content is preferably 50% by mass or less, and particularly preferably 45% by mass or less.

  Since the scouring agent composition of the present invention has a low foaming property, it is also suitable for scouring that requires attention to the generation of bubbles, such as a liquid dyeing machine and a high-temperature high-pressure dyeing machine.

  Further, the scouring agent composition of the present invention may contain other nonionic surfactants such as polyoxyethylene alkyl ether, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), poly (meth), if necessary. Chelating dispersants such as acrylic acid, (meth) acrylic acid / maleic acid copolymer, alkali builders such as soda ash and caustic soda, and antifoaming agents such as polyoxyalkylene ethers, silicone oils, mineral oils, etc. Drugs can be mixed or used together.

  The scouring agent composition of the present invention has an effective component concentration, that is, the concentration of the component (A) or the total concentration of the component (A) and the component (B) is 0.1 to 10 g / L. It is used by diluting with water and / or other solvents usually used in the refining process in accordance with the soil contained in the cloth so that it becomes ˜5 g / L and the chelating agent becomes 0.05˜5 g / L.

  The scouring agent composition of the present invention can be applied to natural fibers such as cotton, hemp, and wool, synthetic woven fibers such as polyester, nylon, rayon, and triacetate, and their mixed spun woven fibers. The scouring method may be either normal batch processing or continuous processing, and the scouring temperature is usually room temperature to 140 ° C., preferably 50 to 130 ° C., depending on the type of fiber.

  The production examples and comparative production examples of nonionic surfactants used in Examples and Comparative Examples are shown below ("Nonionic surfactant (14)" and "Polyoxyethylene (average added mole number 2.0 ) Lauryl ether sulfate / Na salt "is also shown as Comparative Production Example 6 and Production Example 9 for convenience). In the following, “Cp” means a linear primary saturated hydrocarbon group having carbon number p, and “Cp—OH” indicates a primary alcohol having a linear saturated hydrocarbon group having carbon number p.

Production Example 1: Production of Nonionic Surfactant (1) In an autoclave equipped with a stirrer, a temperature controller, and an automatic introduction device, a linear saturated primary alcohol having 8 carbon atoms [trade name: Calcoal 0898, Kao Co., Ltd.] 65.1 g and a linear saturated primary alcohol having 12 carbon atoms [trade name: Calcoal 2098, manufactured by Kao Corporation] 93.2 g of mixed alcohol (C8-OH / C12-OH = 50 / 50 (molar ratio)) and 1.1 g of potassium hydroxide were charged, dehydration was performed at 110 ° C. and 1.3 kPa (absolute pressure) for 30 minutes, and then nitrogen substitution was performed.

  After nitrogen substitution, the temperature was raised to 150 ° C., 308.4 g of ethylene oxide was introduced, and an addition reaction / aging operation was performed. Subsequently, it cooled to 125 degreeC, 145.2g of propylene oxide was introduce | transduced, and addition reaction and ageing | curing | ripening operation were performed. After completion of the reaction, the mixture was cooled to 80 ° C., and then 1.8 g of lactic acid was added to the autoclave, stirred at 80 ° C. for 30 minutes, then extracted, and the nonionic surfactant (1) [general formula ( In 1), R: C8 / C12 = 50/50 (molar ratio), m = 7, n = 2.5] was obtained.

Production Example 2: Production of Nonionic Surfactant (2) In an autoclave equipped with a stirrer, a temperature controller, and an automatic introduction device, a linear saturated primary alcohol having 8 carbon atoms [trade name: Calcoal 0898, Kao Co., Ltd.] 65.1 g and a linear saturated primary alcohol having 12 carbon atoms [trade name: Calcoal 2098, manufactured by Kao Corporation] 93.2 g of mixed alcohol (C8-OH / C12-OH = 50 / 50 (molar ratio)) and 1.1 g of potassium hydroxide were charged, dehydration was performed at 110 ° C. and 1.3 kPa (absolute pressure) for 30 minutes, and then nitrogen substitution was performed.

  After nitrogen substitution, the temperature was raised to 150 ° C., 660.8 g of ethylene oxide was introduced, and an addition reaction / aging operation was performed. Subsequently, it cooled to 125 degreeC, 145.2g of propylene oxide was introduce | transduced, and addition reaction and ageing | curing | ripening operation were performed. After completion of the reaction, the mixture was cooled to 80 ° C., 1.8 g of lactic acid was added to the autoclave, and the mixture was stirred for 30 minutes at 80 ° C., then extracted, and the nonionic surfactant (2) [general formula ( In 1), R: C8 / C12 = 50/50 (molar ratio), m = 15, n = 2.5] was obtained.

Production Example 3: Production of Nonionic Surfactant (3) In an autoclave equipped with a stirrer, a temperature controller, and an automatic introduction device, a linear saturated primary alcohol having 8 carbon atoms [trade name: Calcoal 0898, Kao 32.6 g, and C10 linear saturated primary alcohol [trade name: Calcoal 1098, manufactured by Kao Corporation] 39.6 g, and C12 linear saturated primary alcohol [product] Name: Calcoal 2098, Kao Co., Ltd.] 46.6 g, and C14 linear saturated primary alcohol [trade name: Calcoal 4098, Kao Co., Ltd.] 53.6 g of mixed alcohol (C8-OH / C10-OH / C12-OH / C14-OH = 25/25/25/25 (molar ratio)) and 1.1 g of potassium hydroxide were charged and dehydrated at 110 ° C. and 1.3 kPa (absolute pressure) for 30 minutes. The After performing, nitrogen substitution was performed.

  After nitrogen substitution, the temperature was raised to 150 ° C., 440.5 g of ethylene oxide was introduced, and an addition reaction / aging operation was performed. Subsequently, it cooled to 125 degreeC, 145.2g of propylene oxide was introduce | transduced, and addition reaction and ageing | curing | ripening operation were performed. After completion of the reaction, the mixture was cooled to 80 ° C., 1.8 g of lactic acid was added to the autoclave, and the mixture was stirred for 30 minutes at 80 ° C., then extracted, and the nonionic surfactant (3) [general formula ( In 1), R: C8 / C10 / C12 / C14 = 25/25/25/25 (molar ratio), m = 10, n = 2.5] was obtained.

Production Example 4: Production of Nonionic Surfactant (4) In an autoclave equipped with a stirrer, a temperature controller, and an automatic introduction device, a linear saturated primary alcohol having 8 carbon atoms [trade name: Calcoal 0898, Kao 58.6 g, and C12 linear saturated primary alcohol [trade name: Calcoal 2098, manufactured by Kao Corporation] 83.8 g, and C16 linear saturated primary alcohol [product] Name: Calcoal 6098, manufactured by Kao Corporation] 12.1 g, and linear saturated primary alcohol having 18 carbon atoms [Product name: Calcoal 8098, manufactured by Kao Corporation] 13.5 g of mixed alcohol (C8-OH / C12-OH / C16-OH / C18-OH = 45/45/5/5 (molar ratio)) and 1.1 g of potassium hydroxide were charged and dehydrated at 110 ° C. and 1.3 kPa (absolute pressure) for 30 minutes. Did , And nitrogen substitution was carried out.

  After nitrogen substitution, the temperature was raised to 150 ° C., 308.4 g of ethylene oxide was introduced, and an addition reaction / aging operation was performed. Subsequently, it cooled to 125 degreeC, 145.2g of propylene oxide was introduce | transduced, and addition reaction and ageing | curing | ripening operation were performed. After completion of the reaction, the mixture was cooled to 80 ° C., 1.8 g of lactic acid was added to the autoclave, and the mixture was stirred at 80 ° C. for 30 minutes, then extracted, and the nonionic surfactant (4) [general formula ( In 1), R: C8 / C12 / C16 / C18 = 45/45/5/5 (molar ratio), m = 7, n = 2.5] was obtained.

Production Example 5 Production of Nonionic Surfactant (5) In an autoclave equipped with a stirrer, a temperature controller, and an automatic introduction device, a linear saturated primary alcohol having 8 carbon atoms [trade name: Calcoal 0898, Kao 97.7 g, and C12 linear saturated primary alcohol [trade name: Calcoal 2098, manufactured by Kao Corporation] 23.3 g, and C14 linear saturated primary alcohol [product] Name: Calcoal 4098, manufactured by Kao Corporation] 26.8 g of mixed alcohol (C8-OH / C12-OH / C14-OH = 75 / 12.5 / 12.5 (molar ratio)) and potassium hydroxide 1 .1 g was charged and dehydrated at 110 ° C. and 1.3 kPa (absolute pressure) for 30 minutes, and then purged with nitrogen.

  After nitrogen substitution, the temperature was raised to 150 ° C., 308.4 g of ethylene oxide was introduced, and an addition reaction / aging operation was performed. Subsequently, it cooled to 125 degreeC, 145.2g of propylene oxide was introduce | transduced, and addition reaction and ageing | curing | ripening operation were performed. After completion of the reaction, the mixture was cooled to 80 ° C., 1.8 g of lactic acid was added to the autoclave, and the mixture was stirred for 30 minutes at 80 ° C., then extracted, and the nonionic surfactant (5) [general formula ( In 1), R: C8 / C12 / C14 = 75 / 12.5 / 12.5 (molar ratio), m = 7, n = 2.5] was obtained.

Production Example 6 Production of Nonionic Surfactant (6) In an autoclave equipped with a stirrer, a temperature controller, and an automatic introduction device, a linear saturated primary alcohol having 8 carbon atoms [trade name: Calcoal 0898, Kao Co., Ltd.] 65.1 g and a linear saturated primary alcohol having 12 carbon atoms [trade name: Calcoal 2098, manufactured by Kao Corporation] 93.2 g of mixed alcohol (C8-OH / C12-OH = 50 / 50 (molar ratio)) and 1.1 g of potassium hydroxide were dehydrated at 110 ° C. and 1.3 kPa (absolute pressure) for 30 minutes, and then purged with nitrogen.

  After nitrogen substitution, the temperature was raised to 150 ° C., 308.4 g of ethylene oxide was introduced, and an addition reaction / aging operation was performed. Next, the mixture was cooled to 125 ° C., 203.3 g of propylene oxide was introduced, and an addition reaction / aging operation was performed. After completion of the reaction, the mixture was cooled to 80 ° C., 1.8 g of lactic acid was added to the autoclave, and the mixture was stirred for 30 minutes at 80 ° C., then extracted, and the nonionic surfactant (6) [general formula ( In 1), R: C8 / C12 = 50/50 (molar ratio), m = 7, n = 3.5] was obtained.

Production Example 7 Production of Nonionic Surfactant (7) In an autoclave equipped with a stirrer, a temperature controller, and an automatic introduction device, a linear saturated primary alcohol having 8 carbon atoms [trade name: Calcoal 0898, Kao Co., Ltd.] 65.1 g and a linear saturated primary alcohol having 12 carbon atoms [trade name: Calcoal 2098, manufactured by Kao Corporation] 93.2 g of mixed alcohol (C8-OH / C12-OH = 50 / 50 (molar ratio)) and 1.1 g of potassium hydroxide were charged, dehydration was performed at 110 ° C. and 1.3 kPa (absolute pressure) for 30 minutes, and then nitrogen substitution was performed.

  After nitrogen substitution, the temperature was raised to 150 ° C., 220.3 g of ethylene oxide was introduced, and an addition reaction / aging operation was performed. Subsequently, it cooled to 125 degreeC, 145.2g of propylene oxide was introduce | transduced, and addition reaction and ageing | curing | ripening operation were performed. After completion of the reaction, the mixture was cooled to 80 ° C., 1.8 g of lactic acid was added to the autoclave, and the mixture was stirred for 30 minutes at 80 ° C., then extracted, and the nonionic surfactant (7) [general formula ( In 1), R: C8 / C12 = 50/50 (molar ratio), m = 5, n = 2.5] was obtained.

Production Example 8 Production of Nonionic Surfactant (8) In an autoclave equipped with a stirrer, a temperature controller, and an automatic introduction device, a linear saturated primary alcohol having 10 carbon atoms [trade name: Calcoal 1098, Kao Made by Co., Ltd.] 158.3 g and 1.1 g of potassium hydroxide were charged, dehydrated at 110 ° C. and 1.3 kPa (absolute pressure) for 30 minutes, and then purged with nitrogen.

  After nitrogen substitution, the temperature was raised to 150 ° C., 308.4 g of ethylene oxide was introduced, and an addition reaction / aging operation was performed. Subsequently, it cooled to 125 degreeC, 145.2g of propylene oxide was introduce | transduced, and addition reaction and ageing | curing | ripening operation were performed. After completion of the reaction, the mixture was cooled to 80 ° C., 1.8 g of lactic acid was added to the autoclave, and the mixture was stirred for 30 minutes at 80 ° C., then extracted, and the nonionic surfactant (8) [general formula ( In 1), R: C10, m = 7, n = 2.5] was obtained.

Comparative Production Example 1: Production of Nonionic Surfactant (9) In an autoclave equipped with a stirrer, a temperature controller, and an automatic introduction device, a linear saturated primary alcohol having 8 carbon atoms [trade name: Calcoal 0898, Kao Corp.] 45.6 g, and C12 linear saturated primary alcohol [trade name: Calcol 2098, Kao Corp.] 65.2 g, and C16 linear saturated primary alcohol [ Product name: Calcoal 6098, manufactured by Kao Corporation] 36.4 g, and linear saturated primary alcohol having 18 carbon atoms [Product name: Calcoal 8098, manufactured by Kao Corporation] 40.6 g of mixed alcohol (C8-OH) / C12-OH / C16-OH / C18-OH = 35/35/15/15 (molar ratio)) and 1.1 g of potassium hydroxide are charged at 110 ° C. and 1.3 kPa (absolute pressure) for 30 minutes. Prolapse After performing water, nitrogen substitution was performed.

  After nitrogen substitution, the temperature was raised to 150 ° C., 308.4 g of ethylene oxide was introduced, and an addition reaction / aging operation was performed. Subsequently, it cooled to 125 degreeC, 145.2g of propylene oxide was introduce | transduced, and addition reaction and ageing | curing | ripening operation were performed. After completion of the reaction, the mixture was cooled to 80 ° C., 1.8 g of lactic acid was added to the autoclave, and the mixture was stirred at 80 ° C. for 30 minutes, then extracted, and the nonionic surfactant for comparison (9) [General formula ( In 1), R: C8 / C12 / C16 / C18 = 35/35/15/15 (molar ratio), m = 7, n = 2.5] was obtained.

Comparative Production Example 2: Production of Nonionic Surfactant (10) In an autoclave equipped with a stirrer, a temperature controller, and an automatic introduction device, a linear saturated primary alcohol having 8 carbon atoms [trade name: Calcoal 0898, Kao Corp.] 65.1 g and C12 linear saturated primary alcohol [trade name: Calcoal 2098, Kao Corp.] 93.1 g mixed alcohol (C16-OH / C18-OH = 50 / 50 (molar ratio)) and 1.1 g of potassium hydroxide were charged, dehydration was performed at 110 ° C. and 1.3 kPa (absolute pressure) for 30 minutes, and then nitrogen substitution was performed.

  After nitrogen substitution, the temperature was raised to 150 ° C., 308.4 g of ethylene oxide was introduced, and an addition reaction / aging operation was performed. Subsequently, it cooled to 125 degreeC, 348.5g of propylene oxide was introduce | transduced, and addition reaction and ageing | curing | ripening operation were performed. After completion of the reaction, the mixture was cooled to 80 ° C., 1.8 g of lactic acid was added to the autoclave, stirred for 30 minutes at 80 ° C., then extracted, and the nonionic surfactant (10) for comparison [general formula ( In 1), R: C8 / C12 = 50/50 (molar ratio), m = 7, n = 6] was obtained.

Comparative Production Example 3: Production of Nonionic Surfactant (11) In an autoclave equipped with a stirrer, a temperature controller, and an automatic introduction device, a linear saturated primary alcohol having 8 carbon atoms [trade name: Calcoal 0898, Kao Corp.] 65.1 g and C12 linear saturated primary alcohol [trade name: Calcoal 2098, Kao Corp.] 93.1 g mixed alcohol (C16-OH / C18-OH = 50 / 50 (molar ratio)) and 1.1 g of potassium hydroxide were dehydrated at 110 ° C. and 1.3 kPa (absolute pressure) for 30 minutes, and then purged with nitrogen.

  After nitrogen substitution, the temperature was raised to 150 ° C., 1541.8 g of ethylene oxide was introduced, and an addition reaction / aging operation was performed. Subsequently, it cooled to 125 degreeC, 145.2g of propylene oxide was introduce | transduced, and addition reaction and ageing | curing | ripening operation were performed. After completion of the reaction, the mixture was cooled to 80 ° C., 1.8 g of lactic acid was added to the autoclave, and the mixture was stirred at 80 ° C. for 30 minutes, then extracted, and the nonionic surfactant for comparison (11) [General formula ( In 1), R: C8 / C12 = 50/50 (molar ratio), m = 35, n = 2.5] was obtained.

Comparative Production Example 4: Production of Nonionic Surfactant (12) In an autoclave equipped with a stirrer, a temperature controller, and an automatic introduction device, a linear saturated primary alcohol having 8 carbon atoms [trade name: Calcoal 0898, Kao Corp.] 65.1 g and C12 linear saturated primary alcohol [trade name: Calcoal 2098, Kao Corp.] 93.1 g mixed alcohol (C16-OH / C18-OH = 50 / 50 (molar ratio)) and 1.1 g of potassium hydroxide were charged, dehydration was performed at 110 ° C. and 1.3 kPa (absolute pressure) for 30 minutes, and then nitrogen substitution was performed.

  After nitrogen substitution, the temperature was raised to 150 ° C., 308.4 g of ethylene oxide was introduced, and an addition reaction / aging operation was performed. Subsequently, it cooled to 125 degreeC, 17.4g of propylene oxide was introduce | transduced, and addition reaction and ageing | curing | ripening operation were performed. After completion of the reaction, the mixture was cooled to 80 ° C., 1.8 g of lactic acid was added to the autoclave, and the mixture was stirred at 80 ° C. for 30 minutes, then extracted, and a nonionic surfactant for comparison (12) [General formula ( In 1), R: C8 / C12 = 50/50 (molar ratio), m = 7, n = 0.3] was obtained.

Comparative Production Example 5 Production of Nonionic Surfactant (13) In an autoclave equipped with a stirrer, a temperature controller, and an automatic introduction device, a linear saturated primary alcohol having 8 carbon atoms [trade name: Calcoal 0898, Kao Corp.] 65.1 g and C12 linear saturated primary alcohol [trade name: Calcoal 2098, Kao Corp.] 93.1 g mixed alcohol (C16-OH / C18-OH = 50 / 50 (molar ratio)) and 1.1 g of potassium hydroxide were dehydrated at 110 ° C. and 1.3 kPa (absolute pressure) for 30 minutes, and then purged with nitrogen.

  After nitrogen substitution, the temperature was raised to 150 ° C., 88.1 g of ethylene oxide was introduced, and an addition reaction / aging operation was performed. Subsequently, it cooled to 125 degreeC, 145.2g of propylene oxide was introduce | transduced, and addition reaction and ageing | curing | ripening operation were performed. After completion of the reaction, the mixture was cooled to 80 ° C., 1.8 g of lactic acid was added to the autoclave, and the mixture was stirred at 80 ° C. for 30 minutes, then extracted, and a comparative nonionic surfactant (13) [general formula ( In 1), R: C8 / C12 = 50/50 (molar ratio), m = 2, n = 2.5] was obtained.

Comparative Production Example 6: Nonionic surfactant (14)
Nippon Shokubai Co., Ltd. Softanol 70 (an ethylene oxide adduct of a linear secondary alcohol) was used.

Comparative Production Example 7 Production of Nonionic Surfactant (15) In an autoclave equipped with a stirrer, a temperature controller, and an automatic introduction device, a synthetic alcohol [trade name: SAFOL23 (manufactured by SASOL), carbon number 12, 194 g of 13 branched-chain alkyl groups [saturated alcohol having 12 carbon atoms / 13 carbon atoms = 55/45 (molar ratio), branching rate (mass composition of branched alcohol) 50 mass%]; 1 g was charged and dehydrated at 110 ° C. and 1.3 kPa (absolute pressure) for 30 minutes, and then purged with nitrogen.

  After the nitrogen substitution, the temperature was raised to 150 ° C., and 308.4 g of ethylene oxide was introduced to perform an addition reaction and an aging operation. Subsequently, it cooled to 125 degreeC and addition reaction and ageing | curing | ripening operation were performed. After completion of the reaction, the mixture was cooled to 80 ° C., 1.8 g of lactic acid was added to the autoclave, and the mixture was stirred at 80 ° C. for 30 minutes, then extracted, and a nonionic surfactant for comparison (15) [General formula ( In 1), R contained a branched alkyl group (branch rate 50 mass%), and m = 7, n = 2.5].

Comparative Production Example 8 Production of Nonionic Surfactant (16) In an autoclave equipped with a stirrer, a temperature controller, and an automatic introduction device, a linear saturated primary alcohol having 8 carbon atoms [trade name: Calcoal 0898, Kao Corp.] 65.1 g and C12 linear saturated primary alcohol [trade name: Calcol 2098, Kao Corp.] 93.2 g mixed alcohol (C8-OH / C12-OH = 50) / 50 (molar ratio)) and 1.1 g of potassium hydroxide were added, dehydration was performed at 110 ° C. and 1.3 kPa (absolute pressure) for 30 minutes, and then nitrogen substitution was performed.

  After nitrogen substitution, the temperature was raised to 150 ° C., 145.2 g of propylene oxide and 308.4 g of ethylene oxide were introduced, and a random addition reaction / aging operation was performed. After completion of the reaction, the mixture was cooled to 80 ° C., 1.8 g of lactic acid was added to the autoclave, and the mixture was stirred at 80 ° C. for 30 minutes, then extracted, and the nonionic surfactant for comparison (16) [General formula ( In 1), R: C8 / C12 = 50/50 (molar ratio), m = 7, n = 2.5 (however, random addition)] was obtained.

<Example 1 and Comparative Example 1>
The performance of the refining agent composition comprising the nonionic surfactants (1) to (16) obtained in the production examples and comparative production examples was evaluated by the method described below. The results are summarized in Table 1. In the table, a nonionic surfactant that does not correspond to the component (A) is also shown as the component (A) for convenience.

[Evaluation of scouring properties (residual fat ratio to cotton)]
A cotton raw machine (residual fat ratio of 1.05% by mass) is scoured under the following conditions, and about 3 to 4 g of a test sample is cut out from the scoured dough, and a Soxhlet extractor (Tokai) is used with diethyl ether as an extraction solvent. The extraction operation was performed with a meter). After the extraction operation for 4 hours, the extraction solvent was distilled off under reduced pressure, the residual mass was measured, and the residual fat ratio was determined by the following formula.
Residual fat ratio (%) = (residual mass after extraction solvent is distilled / mass of test sample) × 100
* Refining treatment conditions Refining agent composition (nonionic surfactant) concentration: 1.0 g / L
Caustic soda concentration: 1.0 g / L
Scouring time: 20 minutes Scouring temperature: 110 ° C
Bath ratio: 1/20
Treated water: 3 ° DH

[Evaluation of scourability (height of sucking)]
The cotton fabric machine is scoured under the above conditions, a sample cloth having a width of 3 cm and a length of 15 cm is cut out from the treated cloth, and a slack is formed so that one end of the sample cloth is immersed on a vat filled with an aqueous solution in which a dye is dissolved. It was hung vertically in the absence, and examined by measuring the suction height (mm) of the dye aqueous solution after 15 minutes. The higher the wicking height, the better the wettability and the better the scouring property of the refining agent.

[Evaluation of scourability (Drip method)]
A 5 cm × 5 cm test sample is cut out from the scoured dough, placed horizontally, and 0.1 mL of the aqueous dye solution used in the evaluation of the suction height is dropped from about 1 cm above the sample dough with a dropper. After natural drying, the water absorption is determined by the spreading form of the aqueous dye solution. The evaluation criteria are as follows.
○: The dye spreads into a large circle, and a circle with a diameter of 1 cm fits in the dyed area.
Δ: Dye spreading is insufficient, or the dye spreading shape is distorted, and a circle with a diameter of 7 mm fits within the dyed area, but a circle with 1 cm does not fit.
X: A circle with a diameter of 7 mm does not fit in the dyed area.

[Evaluation of foaming properties]
200 mL of test liquid (nonionic surfactant concentration; 2.00 × 10 ⁻³ mol / L, balance is water) is placed in a 1 L graduated cylinder, and 1.5 L from the bottom of the graduated cylinder by an air pump with a ball filter. / Minute air was aerated, and the height (mm) of foaming after 2 minutes was measured.

[Evaluation of permeability]
A cotton knit raw machine is cut into 2.5 cm × 2.5 cm and used as a sample. This sample is floated on each test liquid (0.05% by mass aqueous solution of nonionic surfactant) at a temperature of 20 ° C. and a humidity of 65%, and the time (seconds) until the surface is completely wet is measured. The smaller the value, the better the permeability.

Production Example 9: Polyoxyethylene (average added mole number 2.0) lauryl ether sulfate / Na salt EMAL 270J manufactured by Kao Corporation was used.

Production Example 10: Production of polyoxyethylene (average addition mole number 3.0) isodecyl sesquiphosphate / Na salt In a 2000 mL reaction vessel, 1 mol of decanol (chemical name: isodecanol) manufactured by Kyowa Hakko Chemical Co., Ltd. 633.2 g (4.00 mol) of an organic hydroxy compound obtained by adding 3 mol (average molecular weight = 158.3) and 93.7 g of 85% orthophosphoric acid (P ₂ O ₅ .nH ₂ O) ₂ O ₅ ; 0.41 mol, H ₂ O; 2.00 mol), and stirred and mixed, while maintaining the temperature at 50 to 70 ° C., 229.6 g of phosphorus pentoxide (effective content 98.5%) 1.59 mol) was gradually added, and the temperature was raised to 80 ° C. and the reaction was carried out for 12 hours. Thereafter, this reaction product was subjected to a deodorization treatment using a steam distillation apparatus (heat transfer area; 0.03 m ³ , glass) using a forced thin film. Steam distillation is performed at a jacket temperature of 150 ° C. and 2.7 kPa (absolute pressure) by continuously supplying the reaction product and steam at rates of 100 g / hr and 75 g / hr, respectively, and the residue is an organic hydroxy compound. A phosphate ester containing 0.8% content and 0.3% moisture was obtained. Thereafter, this phosphate ester was neutralized while being added to and stirred with a predetermined amount of sodium hydroxide aqueous solution to obtain polyoxyethylene (average number of moles added 3.0) isodecyl sesquiphosphate / Na salt.

<Example 2 and Comparative Example 2>
Various scouring agent compositions were prepared according to the formulations shown in Table 2, and the fluidity of each composition was evaluated according to the following method. In the table, a nonionic surfactant that does not correspond to the component (A) is also shown as the component (A) for convenience.

[Fluidity evaluation]
3 mL of the composition was placed in a sample tube (sample vial No. 3 manufactured by Maruem Co., Ltd.) having an inner diameter of 24.3 mm and a height of 46.5 mm, and allowed to stand at 3 ° C. for 30 minutes. Thereafter, the sample tube containing the composition was inverted, and the time (seconds) required for the bubbles to rise was measured. The evaluation criteria are as follows.
○: Less than 1 second △: More than 1 second and less than 20 seconds ×: More than 20 seconds

Claims (8)

(A) A fiber scouring agent composition containing a nonionic surfactant represented by the following general formula (1) [hereinafter referred to as the component (A)], wherein the component (A) has the general formula (1) ) In which R is a primary linear saturated hydrocarbon group having 8 to 14 carbon atoms, and the proportion of the nonionic surfactant is 80 mol% or more.
R—O— (EO) _m — (PO) _n —H (1)
[Wherein R represents a hydrocarbon group having 6 to 24 carbon atoms, EO represents an ethyleneoxy group, and PO represents a propyleneoxy group. m is the average number of moles of ethyleneoxy group added, and is a number from 3 to 30. n is the average number of added moles of propyleneoxy groups, and is a number of 0.5-5. Note that (EO) _m and (PO) _n are block-coupled in this order. ]   The fiber refining agent composition according to claim 1, wherein the component (A) is obtained by reacting a monohydric alcohol having 6 to 24 carbon atoms with ethylene oxide and propylene oxide in this order.   In the component (A), the ratio of the nonionic surfactant in which R is a primary linear saturated hydrocarbon group having 8 to 10 carbon atoms in the general formula (1) is 5 to 95 mol%, and R is carbon. The scouring agent composition for fibers according to claim 1 or 2, wherein the proportion of the nonionic surfactant which is a primary linear saturated hydrocarbon group of formulas 11 to 14 is 5 to 95 mol%.   Furthermore, the fiber scouring agent composition in any one of Claims 1-3 containing (B) anionic surfactant [henceforth (B) component].   The fiber scouring agent composition according to claim 4, wherein the content of the component (A) is 10 to 80% by mass and the content of the component (B) is 0.5 to 50% by mass.   In the component (A), the ratio of the nonionic surfactant in which R is an n-octyl group in the general formula (1) is 5 to 95 mol%, for fibers according to any one of claims 1 to 5. Scouring agent composition.   In the component (A), the ratio of the nonionic surfactant in which R is an n-dodecyl group in the general formula (1) is 5 to 95 mol%, for fibers according to any one of claims 1 to 6. Scouring agent composition.   In the component (A), the proportion of the nonionic surfactant in which R in the general formula (1) is a hydrocarbon group having 11 to 14 carbon atoms (excluding n-dodecyl group) is 0 to 30 mol%. The refining agent composition according to any one of claims 1 to 7.