JP2015036411A - Aqueous composition and fiber treatment agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous composition capable of obtaining a fiber treatment agent which is more improved in antifouling property imparting effect on a fabric or washing resistance than conventional one and to provide a fiber treatment agent thereof.SOLUTION: There is provided an aqueous composition which comprises a water-soluble resin (A) and a crosslinking agent (B), wherein the water-soluble resin (A) is (i) a mixture of a polyvinyl alcohol and a polyvinyl pyrrolidone, or a mixture of (ii) a copolymer having a polyvinyl alcohol structure and a polyvinyl pyrrolidone structure or (iii) at least one selected from a polyvinyl alcohol and a polyvinyl pyrrolidone and the copolymer and the crosslinking agent (B) is at least one selected from a melamine compound, an urea compound and a melamine-urea copolymer.

Description

  The present invention relates to an aqueous composition and a fiber treatment agent using the same, and specifically to an aqueous composition containing a polyvinyl alcohol-based resin and a fiber treatment agent.

  Conventionally, a polyvinyl alcohol-based resin has been used as a treating agent for fibers such as a laminating paste. For example, Patent Document 1 discloses a fiber treatment agent mainly composed of acetoacetate group-containing polyvinyl alcohol and used for a warp sizing agent for a fiber, a sizing agent for washing, and the like, and a polyester filament yarn using the same. It is described that it can improve the conjugation force and defogging property, the abrasion resistance of the spun yarn, the fuzz prevention property, and the like.

  However, the conventional fiber treatment agent mainly composed of polyvinyl alcohol resin has a problem that the effect of imparting antifouling property to fibers and the washing resistance are not sufficient, and a specific method for solving this problem. Actually, no means has been proposed yet.

JP-A-8-325946

  The present invention has been made in view of the above, and is a fiber treatment agent containing a polyvinyl alcohol-based resin, and as a fiber treatment agent having an antifouling property imparting effect to a fiber and washing resistance improved from conventional ones. The object is to provide an aqueous composition that can be used.

  The aqueous composition of the present invention is an aqueous composition containing a water-soluble resin (A) and a crosslinking agent (B), and in order to solve the above problems, the water-soluble resin (A) is (i) A mixture of polyvinyl alcohol and polyvinyl pyrrolidone, (ii) a copolymer having a polyvinyl alcohol structure and a polyvinyl pyrrolidone structure, or (iii) a mixture of at least one selected from polyvinyl alcohol and polyvinyl pyrrolidone and the copolymer. The crosslinking agent (B) is at least one selected from the group consisting of a melamine compound, a urea compound, and a melamine-urea copolymer.

  The water-soluble composition of the present invention may further contain an amino alcohol (C).

  It is preferable to contain 1-100 mass parts of said crosslinking agents (B) with respect to 100 mass parts of water-soluble resin (A).

  It is preferable to contain 0.5-10 mass parts of said amino alcohol (C) with respect to 100 mass parts of total amounts of water-soluble resin (A) and a crosslinking agent (B).

  The fiber treatment agent of the present invention contains the above-described aqueous composition of the present invention.

  According to the aqueous composition of the present invention, by using a specific water-soluble resin (A) having a polyvinyl alcohol structure and a polyvinyl pyrrolidone structure in combination with a specific cross-linking agent (B), imparting antifouling properties to fibers. A treatment agent for fibers with improved effects and improved washing resistance can be obtained. Moreover, by further containing amino alcohol (C), the stability of the fiber treatment agent can be further improved while maintaining the above performance.

  The water-soluble resin (A) used in the present invention can be selected from a homopolymer having either a polyvinyl alcohol structure or a polyvinylpyrrolidone structure and a copolymer having both. The homopolymer having a polyvinyl alcohol structure is polyvinyl alcohol, and the homopolymer having a polyvinyl pyrrolidone structure is polyvinyl pyrrolidone. Accordingly, the water-soluble resin (A) includes a mixture of polyvinyl alcohol (A1) and polyvinylpyrrolidone (A2), a copolymer (A3) containing polyvinyl alcohol structure and polyvinylpyrrolidone structure, polyvinyl alcohol (A1) or polyvinylpyrrolidone ( Any of a mixture of A2) and copolymer (A3) and a mixture of polyvinyl alcohol (A1), polyvinylpyrrolidone (A2) and copolymer (A3) can be used. From the viewpoint of imparting antifouling properties and improving washing resistance, which are the objects of the present invention, it is preferable that the content ratio of the copolymer (A3) is high.

  From the same point of view, when the water-soluble resin (A) is a mixture of polyvinyl alcohol (A1) and polyvinylpyrrolidone (A2), the mixing ratio of both is (A1) / (A2) = 5. / 95 to 95/5 is preferable, and 25/75 to 75/25 is more preferable. Moreover, when it is a copolymer (A3), it is preferable that the ratio of a polyvinyl alcohol structure and a polyvinylpyrrolidone structure is 5 / 95-95 / 5 by mass ratio, and it is more preferable that it is 25 / 75-75 / 25. preferable.

  Because of the above-described effects of the present invention, the polyvinyl alcohol (A1) preferably has a polymerization degree of 100 to 4000 and a saponification degree of 70 to 100 mol%. The polyvinyl pyrrolidone (A2) preferably has a polymer having a K value of 12 to 150. The copolymer (A3) preferably has a polyvinyl alcohol structure with a saponification degree of 70 to 100 mol%, and the polyvinyl pyrrolidone structure preferably has a K value of 12 to 150.

  Next, the crosslinking agent (B) used by this invention shall contain at least 1 sort (s) selected from a melamine compound (B1), a urea compound (B2), and a melamine-urea copolymer (B3).

  Examples of the melamine compound (B1) include those obtained by alkyl etherifying a part or all of the methylol group of a methylolated melamine resin. Specifically, methylated melamine resin, ethylated melamine resin and butylated melamine are exemplified. Examples thereof include alkylated melamine resins such as resins. Of these, methylated melamine resins are preferred because of their excellent solubility in aqueous resins.

  Examples of the urea compound (B2) include those obtained by alkyl etherifying a part or all of the methylol group of the methylolated urea resin. Specifically, the methylated urea resin, the ethylated urea resin, and the butylated urea are exemplified. Examples thereof include alkylated urea resins such as resins. Of these, methylated urea resins are preferred because of their excellent solubility in aqueous resins.

  The melamine-urea copolymer (B3) is a copolymer obtained by using at least melamine and urea, for example, a copolymer of the above melamine compound (B1) and urea compound (B2), etc. Can be used.

  It is preferable that the compounding quantity of a crosslinking agent (B) is 1-100 mass parts with respect to 100 mass parts of said water-soluble resins (A), and it is more preferable that it is 10-100 mass parts. By setting it within the above range, the antifouling property imparting effect and the washing resistance are further improved.

  The aqueous composition of this invention can improve the stability as a processing agent for fibers by further containing amino alcohol (C).

  Examples of amino alcohols (C) include monoalkanolamines such as monoethanolamine and monoisopanolamine, dialkanolamines such as diethanolamine and diisopropanolamine, trialkanolamines such as triethanolamine and triisopropanolamine, N -Methylethanolamine, N-methyldiethanolamine, N-dimethylethanolamine, N-diethylethanolamine, N-dibutylethanolamine, N-ethylethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N-butylethanolamine, etc. And aminoalkylalkanolamines such as aminoethylethanolamine. These amino alcohols can be used alone or in combination of two or more.

  The content of the amino alcohol (C) is the sum of the water-soluble resin (A) and the crosslinking agent (B) in order to improve stability while maintaining the antifouling property and washing resistance improvement effect. It is preferable that it is 0.5-10 mass parts with respect to 100 mass parts of quantity, and it is more preferable that it is 1-10 mass parts.

  In the present invention, it is also preferable to adjust the pH of the aqueous composition to 9 to 11 using the amino alcohol (C). This makes it easier to improve stability while maintaining the antifouling effect and washing resistance.

  In the aqueous composition of the present invention, an aqueous resin other than the above, a surfactant, a fungicide, an antiseptic, a leveling agent, a rust preventive, etc., as necessary, are within the range not contrary to the object of the present invention. It can also be blended.

  The fiber treatment agent of the present invention contains the above aqueous composition. The fiber product to be treated is not particularly limited, and examples thereof include polyester fiber, acrylic fiber, and polypropylene fiber. Examples of the polyester fiber include polyethylene terephthalate, polyethylene terephthalate / isophthalate, and polyethylene terephthalate / butylene terephthalate. The form of the fiber product is not limited, but examples include yarn, woven fabric, knitted fabric, and non-woven fabric.

  Although the usage method of the fiber processing agent of this invention is not specifically limited, For example, the aqueous composition of this invention is preferably 0.01-5.0 mass in conversion of solid content with respect to 100 mass parts of fiber used as a process target. Parts, more preferably 0.05 to 1.0 parts by mass.

  As a processing method for adhering, a conventionally known method can be used, and examples thereof include an exhaust method, a padding method, and a spray method.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. All blending ratios shown in each table are solid ratios. In the following description, “part” and “%” mean “part by mass” and “% by mass”, respectively, unless otherwise specified. The raw materials used in the following examples (including synthesis examples) and comparative examples are as follows.

(Raw materials used)
・ Polyvinyl alcohol (A1)
(A1-1) Complete saponification (degree of saponification 98-99 mol%), degree of polymerization 1700 (manufactured by Kuraray Co., Ltd., trade name: Kuraray Poval PVA-117)
(A1-2) Complete saponification (degree of saponification 98-99 mol%), degree of polymerization 500 (manufactured by Kuraray Co., Ltd., trade name: Kuraray Poval PVA-105)
(A1-3) Partial saponification (degree of saponification 87-89 mol%), degree of polymerization 1700 (manufactured by Kuraray Co., Ltd., trade name: Kuraray Poval PVA-217)
(A1-4) Partial saponification (degree of saponification: 86.5-89 mol%), degree of polymerization: 500, manufactured by Kuraray Co., Ltd., trade name: Kuraray Poval PVA-205)

・ Polyvinylpyrrolidone (A2)
(A2-1) K value 30 (Daiichi Kogyo Seiyaku Co., Ltd., trade name: Pitzkor K-30)
(A2-2) K value 50 (Daiichi Kogyo Seiyaku Co., Ltd., trade name: Pitzkor K-50)
(A2-3) K value of 90 (Daiichi Kogyo Seiyaku Co., Ltd., trade name: Pitzkor K-90)

-Copolymer containing polyvinyl alcohol structure and polyvinylpyrrolidone structure (A3)
(A3-1) Graft polymer 1 obtained by Synthesis Example 1 below
(A3-2) Graft polymer 2 obtained in Synthesis Example 2 below
(A3-3) Graft polymer 3 obtained in Synthesis Example 3 below

[Synthesis Example 1: Production of graft polymer 1]
In a reaction vessel, 100 g of vinylpyrrolidone was added to an aqueous solution in which 100 g of polyvinyl alcohol (A1-2) was dissolved in 800 g of water, and the air in the vessel was replaced with nitrogen. Subsequently, the temperature was raised to 70 ° C., 0.01 g of a 1% by mass copper sulfate aqueous solution, 1 g of 28% by mass ammonia water and 1.5 g of 30% by mass hydrogen peroxide solution were added to initiate polymerization. During polymerization, the temperature is maintained at 70 to 80 ° C. and pH 5.5 to 6.5 with aqueous ammonia, and 1.5 g of 30% by mass hydrogen peroxide solution is added 6 times every 15 minutes so that the polymerization rate is 90%. That's it. Subsequently, 4 g of 30% by mass hydrogen peroxide solution was added as a residual vinylpyrrolidone treatment step and reacted for a total of 210 minutes while maintaining the pH at 5 or higher with aqueous ammonia to obtain a 20% by mass aqueous solution of graft polymer 1 having a K value of 45. It was.

[Synthesis Example 2: Production of Graft Polymer 2]
A 20% by mass aqueous solution of graft polymer 2 having a K value of 50 is obtained by performing the same operation as in Synthesis Example 1 except that 100 g of polyvinyl alcohol (A1-1) is used instead of 100 g of polyvinyl alcohol (A1-2). Got.

[Synthesis Example 3: Production of Graft Polymer 3]
A 20% by mass aqueous solution of graft polymer 3 having a K value of 40 was obtained by performing the same operation as in Synthesis Example 1 except that 100 g of polyvinyl alcohol (A1-4) was used instead of 100 g of polyvinyl alcohol (A1-2). Got.

・ Alkylated melamine resin (B1)
(B1-1) Methylated melamine resin (manufactured by DIC Corporation, trade name: becamine M-3)
(B1-2) Butylated melamine resin (Mitsui Chemicals, trade name: Uban 2020)
(B1-3) Isobutylated melamine resin (Mitsui Chemicals, trade name: Uban 2061)
・ Alkylated urea resin (B2)
(B2-1) Butylated urea resin (Mitsui Chemicals, trade name: Uban 132)
・ Melamine-urea copolymer (B3)
(B3-1) Methylated melamine-urea copolymer (manufactured by DIC Corporation, trade name: Beccamin MA-S)

・ Amino alcohol (C)
(C-1) Monoethanolamine (C-2) Diethanolamine (C-3) Triethanolamine

・ Surfactant (D)
(D-1) Polyoxyethylene polyoxypropylene block polymer (Daiichi Kogyo Seiyaku Co., Ltd., trade name: Epan 680)

[Examples 1-42 and Comparative Examples 1-6]
A 0.75% by mass aqueous solution was prepared by dissolving the above raw materials in water. An aqueous composition was obtained by mixing the prepared aqueous solutions of the raw materials so that the solid content ratios were the ratios shown in Tables 1 to 4.

  These aqueous compositions were padded with polyester taffeta (length: 75 denier x 36 filaments, width: 75 denier x 36 filaments, density: length 120 / inch, width 90 / inch), and the drawing rate was 50%. I squeezed it with a mangle. This was heated at 120 ° C. for 1 minute and further heat-treated at 170 ° C. for 1 minute to prepare a test cloth. About the obtained test cloth, antifouling property and wash resistance were measured and evaluated by the following methods. Moreover, the stability of each aqueous composition was evaluated. The results are shown in Tables 1-4.

<Anti-fouling>
The test cloth (5 cm × 6 cm) is added to a solution obtained by dissolving 0.25 g of an artificial sebum stain (0.10 g of triolein, 0.05 g of cholesterol, 0.05 g of squalene and 0.05 g of palmitic acid) in 50 g of normal hexane. It was immersed and allowed to air dry.

  Using this test cloth, an aqueous solution containing a detergent (Genbu Co., Ltd., trade name: New One Det Alpha) at a concentration of 1.5 g / L, a household washing machine was used at a bath ratio of 1:30. It was washed for 10 minutes at 40 ° C., and then washed with water for 5 minutes and dehydrated twice.

  Subsequently, an artificial sebum contaminant was extracted from the test cloth after washing using 5 mL of normal hexane, and the peak areas of the four substances were measured using gas chromatography. Also, extract the test cloth before washing in the same manner, measure the peak area using gas chromatography under the following conditions, and obtain the residual rate of artificial sebum pollutant (%) as an antifouling property evaluation. It was.

  The residual rate of the artificial sebum stain was calculated as a ratio of the total peak area in the test cloth after washing, when the total peak area of the four substances in the test cloth before washing was taken as 100%.

<Gas chromatography measurement conditions>
Apparatus Agilent 7890 (manufactured by Agilent)
Detector FID
Column DB-1 (Agilent J & W)
0.53mmΦ × 15m Film thickness 0.15μm
Column temperature 60 ° C (1 minute) → 15 ° C / minute → 300 ° C (10 minutes)
Inlet temperature 250 ℃
Detector temperature 300 ° C
Carrier gas Helium Sample injection volume 1 μL split injection (split ratio 10: 1)

<Washing resistance>
The test cloth (5 cm × 6 cm) treated with the aqueous composition was washed 10 times by the method described in the antifouling property evaluation method, and then subjected to the above antifouling property property. The rate (%) was calculated.

<Stability>
The aqueous composition was allowed to stand in an oven at 40 ° C. for 12 hours and 72 hours, and the state of the aqueous composition was visually confirmed. The case where no white turbidity was observed was indicated by “◯”, and the case where white turbidity was observed was indicated by “×”.

  From the results shown in Tables 1-4, the antifouling property does not change even when polyvinyl alcohol and polyvinylpyrrolidone alone and a crosslinking agent are used in combination, but the water-soluble resin (A) and crosslinking agent (as defined in the present invention). It can be seen that when B) is used in combination, the antifouling property and the washing resistance are improved. Moreover, it turns out that stability of the aqueous composition improved greatly by using amino alcohol (C) together further.

  The water-soluble composition of the present invention can be used for fiber treatment agents such as antifouling agents for polyester fibers.

Claims (5)

An aqueous composition containing a water-soluble resin (A) and a crosslinking agent (B),
The water-soluble resin (A) was selected from (i) a mixture of polyvinyl alcohol and polyvinyl pyrrolidone, (ii) a copolymer having a polyvinyl alcohol structure and a polyvinyl pyrrolidone structure, or (iii) polyvinyl alcohol and polyvinyl pyrrolidone. A mixture of at least one and the copolymer,
The cross-linking agent (B) is at least one selected from melamine compounds, urea compounds, and melamine-urea copolymers.   The water-soluble composition according to claim 1, further comprising an amino alcohol (C).   The water-soluble composition according to claim 1 or 2, comprising 1 to 100 parts by mass of the crosslinking agent (B) with respect to 100 parts by mass of the water-soluble resin (A).   The amino alcohol (C) is contained in an amount of 0.5 to 10 parts by mass with respect to 100 parts by mass of the total amount of the water-soluble resin (A) and the crosslinking agent (B). The water-soluble composition according to any one of the above.   The processing agent for fibers containing the aqueous composition of any one of Claims 1-4.