JP2003171881A - Keratin fiber shrinkproofing agent and shrinkproofing method - Google Patents

Abstract

(57) [Problem] To provide a shrink-proofing agent and a shrink-proofing method for keratin fiber, which can shrink-proof keratin fiber cloth without impairing the texture. SOLUTION: A shrink-proofing agent for keratin fibers containing the following components (A) and (B) as essential components: (A) a urethane prepolymer satisfying the following conditions (a) to (d): Emulsion; (a) urethane prepolymer obtained by reacting polyether polyol starting from polyhydric alcohol with polyisocyanate compound; (b) average number of functional groups of polyether polyol in (a) above Is 2.2 to 3.0 as an average number of functional groups measured by a quantitative ¹³ C-NMR spectrum, and (c) the polyoxypropylene content of the polyether polyol in the above (a) is 50 to 100%. (D) that the terminal isocyanate of the urethane prepolymer in (a) is blocked with bisulfite; (B) an emulsion of a polyorganosiloxane selected from the group consisting of dimethylsiloxane and hydrogenpolysiloxane.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a shrinkproofing agent for keratin fibers and a shrinkproofing method using the same.

[0002]

2. Description of the Related Art Conventionally, as a shrink-proofing agent for keratin fibers (processing agent for preventing shrinkage due to washing), the Australian Federal Institute for Science and Industry (CSIR)
O), a bisulfite adduct of polyisocyanate (BAP) is known (JP-A-52-37900).
JP-A-51-82100, JP-A-53-2387
No. 9, JP-B-58-2972, JP-B-S60-1005
No. 4). The shrinkproofing method using this is to treat the fiber cloth with an aqueous solution of a bisulfite salt of a urethane prepolymer,
After that, a general dry heat curing method is performed. By this method, it becomes possible to perform shrink-proof processing of keratin fiber cloth even in a general dyeing factory.

However, in such BAP processing,
Although sufficient shrink resistance can be obtained, on the other hand, there is a problem that the impact resilience of the finished fabric becomes strong, that is, the texture becomes hard. As a result, the unique excellent texture of keratin fiber was impaired, and the expansion of applications for shrink-proofing was also restricted.

[0004]

The present invention has been made in view of the above circumstances, and an object thereof is a shrinkproofing agent for keratin fibers, which is capable of shrinkproofing a keratin fiber cloth without impairing the texture. And a shrinkproofing method.

[0005]

The shrink-proofing agent for keratin fibers according to claim 1 is a shrink-proofing agent for keratin fibers comprising the following components (A) and (B) as essential components: A) An emulsion of a urethane prepolymer satisfying the following conditions (a) to (d); (a) The urethane prepolymer is obtained by reacting a polyether polyol having a polyhydric alcohol as a starting material with a polyisocyanate compound. (B) The average number of functional groups of the polyether polyol in (a) above is 2.2 to 3.0 in terms of the average number of functional groups measured by quantitative ¹³ C-NMR spectrum, (c) above (a). The polyoxypropylene content of the polyether polyol in is 50 to 100%, (d) the urethane prepolymer in (a) above. The end isocyanate is blocked with bisulfite; (B) dimethyl siloxane and hydrogen polyorganosiloxane emulsion selected from the group consisting of polysiloxanes.

The mixing ratio of the above-mentioned (A) component and (B) component is
The pure compounding ratio of the urethane prepolymer and the polyorganosiloxane is preferably 40:60 to 97: 3 (claim 2).

According to a third aspect of the present invention, there is provided a shrinkproofing method for keratin fibers, wherein the shrinkproofing agent for keratin fibers according to claim 1 or 2 is added to the keratin fibers in an amount of 0.5 to 0.5 in terms of solid content.
It is made to adhere to 6.0% by weight and then heat-treated.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The keratin fiber referred to in the present invention is one in which some or all of its constituent fibers are made of wool (wool), angora, cashmere, alpaca, mohair and the like.

The raw material polyol used for producing the urethane prepolymer used in the present invention is a polyol synthesized from a polyhydric alcohol as a starting material. The polyhydric alcohol is preferably a trifunctional or higher functional alcohol, and a polyol using a bifunctional or lower functional alcohol cannot provide sufficient shrink resistance.

The trifunctional alcohol used in the present invention is not particularly limited, but examples thereof include triols such as glycerin, hexanetriol, trimethylolethane and trimethylolpropane, triethanolamine and triisopropanolamine, Examples thereof include alkanolamines such as tributanolamine.

An alkylene oxide is polyadded to the above trifunctional alcohol to synthesize a polyether polyol. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide and the like.

¹³ C-of the raw material polyether polyol
Average number of functional groups measured by NMR spectrum (J.
App: Polym. Sci. 52, 1015-102
2 (1994)) is required to have a functionality of 2.2 to 3.0. When it is less than 2.2 functional, sufficient shrink-proof property cannot be obtained, and when it exceeds 3.0 functional, the texture tends to be hard. Further, the polyoxypropylene content in the raw material polyether polyol is 50 to 100%. If it is less than 50%, sufficient shrink resistance cannot be obtained.
The molecular weight of the raw material polyether polyol is not particularly limited, but if the molecular weight exceeds 20,000, it becomes difficult to synthesize the prepolymer, so that the molecular weight is preferably 20,000 or less.

A urethane prepolymer is obtained by reacting the polyether polyol obtained above with an isocyanate compound. The isocyanate compound is not particularly limited, and examples thereof include tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MD
I), polymeric MDI, hexamethylene diisocyanate (HMDI), xylylene diisocyanate (X
DI), tetramethylxylylene diisocyanate (T
MXDI), isophorone diisocyanate (IPDI)
Organic polyisocyanate compounds such as
When considering non-yellowing, aliphatic isocyanate such as HMDI, alicyclic isocyanate such as IPDI,
Aliphatic alicyclic isocyanates such as XDI and TMXDI are preferable.

The above polyether polyol and organic polyisocyanate compound are mixed at an arbitrary ratio such that the molar ratio of NCO group / active hydrogen group is 1.0 or more, and the mixture is mixed at a temperature of 30 to 130 ° C. by a known method at 30 ° C. A urethane prepolymer having 0.45 to 4.0% by weight of a free isocyanate group is obtained by reacting for 50 minutes to 50 hours.

Next, the free isocyanate groups in the urethane prepolymer obtained are blocked with bisulfite. For this, a known method in which bisulfite is dissolved in water at an appropriate concentration can be used. Examples of the bisulfite salt that blocks the terminal isocyanate include sodium bisulfite, potassium bisulfite, ammonium bisulfite, and the like. The use of a blocking agent other than bisulfate (for example, organic oxime, phenolic compound, etc.) is not preferable because it causes a problem that sufficient shrinkage resistance cannot be obtained.

Although the urethane prepolymer is synthesized in a non-solvent system, a solvent which is inactive with isocyanate and can dissolve the urethane prepolymer may be used depending on the viscosity of the urethane prepolymer. Such solvents include dioxane, methyl ethyl ketone, dimethylformamide, tetrahydrofuran, N-methyl-2.
-Pyrrolidone, toluene, propylene glycol monomethyl ether acetate and the like.

The urethane prepolymer synthesized as described above becomes a stable water-soluble heat-reactive urethane treating agent.

Next, the polyorganosiloxane emulsion used in the present invention means an emulsion of dimethylsiloxane or hydrogen polysiloxane (H silicone).
Emulsions of the above, which are commercially available. However, the amino-modified silicone emulsion is
When used in a urethane prepolymer emulsion, it cannot be used because aggregates are generated.

Dimethylsiloxane typically has the following structural formula, where R is a methyl group and X is a methyl group or --OH group. Alternatively, a part of R may be modified with alkyl glycidyl ether.

[0020]

[Chemical 1]

The hydrogen polysiloxane typically has the following structural formula, where R and R'are methyl groups.

[0022]

[Chemical 2]

The shrink-proofing agent of the present invention is essential to be a blend of the above urethane prepolymer emulsion and polyorganosiloxane emulsion, and the blending ratio of both is a pure blending ratio of the urethane prepolymer and polyorganosiloxane. It is within the range of 40:60 to 97: 3. If the urethane prepolymer content is less than 40 (%), sufficient shrink resistance of the treated cloth may not be obtained. Further, when the urethane prepolymer exceeds 97 (%), the soft texture of the treated cloth obtained in the present invention cannot be obtained.

The shrink-proofing method of the present invention comprises a step of applying the above-mentioned shrink-proofing agent of the present invention (hereinafter also referred to as "treatment agent") to keratin fibers and then heat-treating it.

Examples of the method of applying the present treatment agent to the keratin fiber cloth include a method of immersing the treatment agent in an aqueous solution, a method of spraying an aqueous solution of the treatment agent, and a method of coating the treatment agent. The amount of the active ingredient of the treatment agent of the present invention attached to the keratin fibers is preferably 0.5 to 6.0% by weight in terms of solid content. If it is less than 0.5% by weight, sufficient shrink-proof property cannot be obtained, and if it exceeds 6.0% by weight, the soft texture obtained by the present invention cannot be obtained.

Further, as a method of resinizing the treating agent (forming a polyurethane resin) after adhesion, there are a dry heat curing method and a wet heat curing method. The treatment temperature and treatment time are not particularly limited, but the temperature is 100 to 160 ° C. and the time is 1 to 5 minutes.

[0027]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

(Synthesis Example 1) 100 parts of propylene oxide polyaddition product starting from glycerin (average number of functional groups 2.7 measured by quantitative 13C-NMR spectrum, average molecular weight 3,000, PO content 100%) 16.8 parts of hexamethylene diisocyanate was added to
The reaction was carried out at 0 ° C. for 2 hours to give a free isocyanate group of 3.6.
A urethane prepolymer having a weight% was obtained. Then 3
40.5 parts of 0% aqueous sodium bisulfite solution was added, and the temperature was 45 ° C.
After stirring for 60 minutes, dilute with 427 parts of water and
A 0% translucent viscous anionic blocked urethane prepolymer aqueous solution A was prepared.

(Synthesis Example 2) 500 parts of propylene oxide polyadduct using glycerin as a starting material (average number of functional groups 2.2 measured by quantitative 13C-NMR spectrum, average molecular weight 20,000, PO content 100%) Add 6.3 parts of hexamethylene diisocyanate to 10
The reaction was carried out at 0 ° C for 2 hours to give a free isocyanate group of 0.6
A urethane prepolymer having 5% by weight was obtained. Then, 40 parts of a 30% sodium bisulfite aqueous solution was added, and the mixture was stirred at 45 ° C. for 60 minutes and then diluted with 2830 parts of water to give a resin component
A 5% translucent viscous anionic blocked urethane prepolymer aqueous solution B was prepared.

(Synthesis Example 3) 400 parts of propylene oxide polyaddition product starting from glycerin (average number of functional groups 2.8, average molecular weight 10,000, PO content 50%, measured by quantitative 13 C-NMR spectrum) 20.2 parts of hexamethylene diisocyanate was added to 10
The reaction was carried out at 0 ° C for 2 hours to obtain 1.2 free isocyanate groups.
A urethane prepolymer having a weight% was obtained. Then 3
42 parts of 0% sodium bisulfite aqueous solution was added, and the mixture was mixed at 45 ° C. for 6 hours.
After stirring for 0 minutes, dilute with 2340 parts of water to obtain a resin content of 15
% Translucent viscous anionic blocked urethane prepolymer aqueous solution C was prepared.

(Synthesis Example 4) Propylene oxide polyadduct using trimethylolpropane as a starting material (quantitative 13
(Average number of functional groups measured by C-NMR spectrum: 2.4, average molecular weight: 8,000, PO content: 100%)
30 parts of hexamethylene diisocyanate was added to 400 parts and reacted at 100 ° C. for 2 hours to obtain a urethane prepolymer having 1.5% by weight of free isocyanate groups. Next, 41 parts of a 30% aqueous sodium bisulfite solution was added, and the mixture was stirred at 45 ° C. for 60 minutes and then diluted with 1770 parts of water to prepare a semitransparent viscous anionic blocked urethane prepolymer aqueous solution D having a resin content of 15%. did.

COMPARATIVE SYNTHESIS EXAMPLE 1 Propylene oxide polyadduct using glycerin as a starting material (quantitative amount: 13C-NM
25 parts of hexamethylene diisocyanate was added to 500 parts of an average number of functional groups of 2.0, an average molecular weight of 8,000, and a PO content of 100%, measured by R spectrum, to obtain 10
The reaction was carried out at 0 ° C for 2 hours to give a free isocyanate group of 1.5
A urethane prepolymer having a weight% was obtained. Then 3
55 parts of 0% sodium bisulfite aqueous solution was added, and the mixture was added at 45 ° C. for 6 hours.
After stirring for 0 minutes, dilute with 2350 parts of water to obtain a resin content of 15
% Translucent viscous anionic blocked urethane prepolymer aqueous solution E was prepared.

(Comparative Synthesis Example 2) Propylene oxide polyadduct using glycerin as a starting material (quantitative amount: 13C-NM
20.2 parts of hexamethylene diisocyanate was added to 400 parts of the average number of functional groups measured by R spectrum, 2.8, average molecular weight 10,000, PO content 40%),
Reaction was carried out at 100 ° C. for 2 hours to obtain a urethane prepolymer having 1.2% by weight of free isocyanate groups. Then, 40 parts of 30% aqueous sodium bisulfite solution was added, and 45
After stirring at 60 ° C. for 60 minutes, the mixture was diluted with 2340 parts of water to prepare a semitransparent viscous anionic blocked urethane prepolymer aqueous solution F having a resin content of 15%.

COMPARATIVE SYNTHESIS EXAMPLE 3 Propylene oxide polyaddition product (quantitative amount 13
(Average number of functional groups measured by C-NMR spectrum: 1.4, average molecular weight: 8,000, PO content: 100%)
38 parts of hexamethylene diisocyanate was added to 450 parts and reacted at 100 ° C. for 2 hours to obtain a urethane prepolymer having a free isocyanate group of 1.0% by weight. Next, 39 parts of a 30% sodium bisulfite aqueous solution was added, and the mixture was stirred at 45 ° C. for 60 minutes and then diluted with 2473 parts of water to prepare a semitransparent viscous anionic blocked urethane prepolymer aqueous solution G having a resin content of 15%. did.

COMPARATIVE SYNTHESIS EXAMPLE 4 Propylene oxide polyaddition product starting from pentaerythritol (quantitative 1
The average number of functional groups measured by 3C-NMR spectrum is 3.2, the average molecular weight is 10,000, and the PO content is 100.
%) 400 parts of 22 parts of hexamethylene diisocyanate was added and reacted at 100 ° C. for 2 hours to obtain a urethane prepolymer having 1.5% by weight of free isocyanate groups. Next, 50 parts of a 30% aqueous sodium bisulfite solution was added, and the mixture was stirred at 45 ° C. for 60 minutes and then diluted with 2340 parts of water to prepare a semitransparent viscous anionic blocked urethane prepolymer aqueous solution H having a resin content of 15%. did.

(Comparative Synthesis Example 5) Propylene oxide polyadduct using glycerin as a starting material (quantitative amount: 13C-NM
20.2 parts of hexamethylene diisocyanate was added to 400 parts of the average number of functional groups measured by R spectrum, 2.8, average molecular weight 10,000, PO content 20%),
Reaction was carried out at 100 ° C. for 2 hours to obtain a urethane prepolymer having 1.2% by weight of free isocyanate groups. Then, 11 parts of methyl ethyl ketoxime was added, and the temperature was 45 ° C.
After stirring for 60 minutes with water, it was diluted with 2369 parts of water to prepare a semi-transparent viscous nonionic blocked urethane prepolymer aqueous solution I having a resin content of 15%.

Examples 1 to 8 and Comparative Examples 1 to 13 The anionic blocked urethane prepolymers A to D obtained in the above synthesis examples and the urethane prepolymers E to I obtained in the comparative synthesis examples were Emulsion "M-1385C (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)" using a nonionic activator of hydrogen polysiloxane (H silicone) or emulsion "S-1536 (Daiichi Kogyo Co., Ltd.)" using a nonionic activator of dimethyl silicone oil, respectively. Manufactured by Kogyo Seiyaku Co., Ltd. ”,
Alternatively, an emulsion polymer “No. 102 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)” of cyclic siloxane with sodium alkylbenzene sulfonate was blended according to each blending ratio, and 5% aqueous sodium hydrogen carbonate solution was added to the total solid content of 4%. The treating agent mixed so that it might become 3 g / l was prepared.

This resin processing liquid was impregnated with 100% wool cloth and squeezed so that 70% by weight of the resin processing liquid adhered to the cloth. After that, hot air drying was performed at 120 ° C. for 3 minutes, and further heat treatment was performed at 130 ° C. for 2 minutes.

Shrinkproof property of the obtained processed cloth (JIS L02
17 Displayed as area shrinkage of home washing machine according to 103 method (20 times) and texture (KES-FB system 2;
A pure bending tester; manufactured by Kato Tech Co., Ltd., and a texture evaluation by a panelist were performed. The texture evaluation by the panelists was performed by 10 panelists.
The evaluation of the texture is [5; soft texture equivalent to that of the untreated cloth, 4; slightly tensioned compared to the untreated cloth, 3; tensioned compared to the untreated cloth, 2; The evaluation was made based on "there is a strong feeling of tension compared to the untreated cloth, 1; the feeling of tension is very strong compared to the untreated cloth", and the average value is shown. The results are shown in the table.

Further, as Comparative Example 13, the same wool 100% cloth used in the above Examples and Comparative Examples was evaluated for shrink resistance and texture by the above method without any shrink shrink treatment. The results are also shown in the table.

[0041]

[Table 1]

[0042]

[Table 2]

[0043]

[Table 3]

[0044]

The keratin fiber processed by the shrink-proofing agent and the shrink-proofing method of the present invention has a high degree of shrink-proof property and has a softer texture than that of the prior art by CSIRO, and is a keratin fiber. The original excellent texture is not lost. This is considered to be because in the present invention, the resilience of the resin formed is relaxed by the silicone resin used in combination, and the silicone imparts the smoothness peculiar to silicone to the texture.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J034 BA07 DA01 DA08 DB03 DB05                       DB07 DG03 DG04 DG05 DG08                       DG09 DG14 DG23 DM01 HA01                       HA06 HA07 HC03 HC12 HC17                       HC22 HC46 HC52 HC61 HC63                       HC64 HC67 HC71 HC73 HD13                       JA02 JA14 JA42 QC05 RA09                 4L033 AA03 AB01 AC01 AC15 CA51                       CA59

Claims (3)

[Claims] 1. A shrinkproofing agent for keratin fibers, which comprises the following components (A) and (B) as essential components. (A) an emulsion of a urethane prepolymer satisfying the following conditions (a) to (d); (a) a urethane prepolymer obtained by reacting a polyether polyol having a polyhydric alcohol as a starting material with a polyisocyanate compound. To be. (B) The average number of functional groups of the polyether polyol in (a) above is 2.2 to 3.0 in terms of the average number of functional groups measured by quantitative ¹³ C-NMR spectrum. (C) The polyoxypropylene content of the polyether polyol in (a) above is 50 to 100%. (D) The terminal isocyanate of the urethane prepolymer in (a) above is blocked with bisulfite. (B) An emulsion of a polyorganosiloxane selected from the group consisting of dimethylsiloxane and hydrogenpolysiloxane. 2. The compounding ratio of the component (A) and the component (B) is 40:60 to 97: 3 in terms of a pure compounding ratio of the urethane prepolymer and the polyorganosiloxane. Item 1. A shrinkproofing agent for keratin fibers according to Item 1. 3. A shrink-proofing agent for keratin fibers according to claim 1 or 2, which is applied to keratin fibers in an amount of 0.5 to 6.0% by weight in terms of solid content, and then heat-treated. A shrinkproofing method for keratin fibers.