JPH0536541B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a silicone-based fiber treatment agent, and more specifically, an organopolysiloxane containing at least two primary and/or secondary amino groups in one molecule (hereinafter referred to as amino silicone). A modified amino silicone obtained by reacting a polyether isocyanate which is reactive with the amino group and an organopolysiloxane containing at least one epoxy group in one molecule (hereinafter referred to as epoxy silicone). Contains a silicone-based fiber treatment agent that has excellent water absorption, durability, excellent flexibility and elasticity, no problems of yellowing or discoloration, and excellent stability in treatment baths. be. [Prior Art] Conventionally, in the field of fiber processing, various silicone-based processing agents have been used that take advantage of the properties of silicone, such as flexibility, smoothness, and water repellency. For example, dimethylpolysiloxane (commonly known as dimethyl oil),
Dimethylhydrodienepolysiloxane (commonly known as H
oil), and various other modified silicones (epoxy-modified silicones, polyether-modified silicones, etc.). Over ten years ago, amino silicone has been used in the softening process of textiles due to its unique texture (excellent flexibility and elasticity) and durability (washing resistance and dry cleaning resistance). It is becoming increasingly used. However, when fibers are treated with amino silicone, the alkyl groups in the silicone are oriented on the surface of the fibers, giving them hydrophobicity, resulting in very poor water absorption. In other words, amino silicone has a problem in that it is difficult to use for softening fibers that require water absorption, such as underwear. Furthermore, amino silicones have the problem of yellowing or discoloration due to heat. This is because the amino groups in the molecules are easily changed by heat, causing problems such as yellowing in white products and discoloration in colored products, resulting in a decrease in commercial value.
Additionally, aminosilicone has the disadvantage of lacking stability in the treatment bath. This drawback is that when aminosilicone is processed into fibers in the form of an emulsion, the stability of the processing bath emulsion is disrupted, leading to oil separation or gummy matter. This phenomenon is observed in all silicone-based processing agents, but is particularly common in the case of amino silicones. This seems to be due to the high reactivity of the amino group. The compatibility with other processing chemicals used in the treatment bath or substances that adhere to and contaminate fabrics (e.g., acids, alkalis, inorganic salts, surfactants, polybasic acids, etc.) is better than that of dimethyl oil. Moreover, the oily or gummy substances adhere to and accumulate on the materials or machines being processed, causing trouble. [Problems to be Solved by the Invention] Various methods have been studied to improve the drawbacks related to yellowing, discoloration, and stability of processing baths. Therefore, methods of acylation [Japanese Patent Publication No. 57-54588, Japanese Patent Application Publication No. 1-306682, Japanese Patent Application Publication No. 1-306683] have been proposed. However, although these methods have been able to improve the drawbacks of aminosilicone, they not only tend to impair the unique feel of aminosilicone, but also do not improve the drawbacks regarding water absorption. In addition, as a method for improving the drawbacks of yellowing, discoloration, and stability of processing baths without impairing the unique texture of aminosilicone, a method of reacting aminosilicone with epoxysilane [Patent Publication No. 1-
22390] has been proposed, but the drawbacks regarding water absorption have not been improved even with this method. Furthermore, although water absorption can be improved by using polyether-modified silicones, such polyether-modified silicones have the disadvantage of being inferior in flexibility, durability, and stretchability compared to amino silicones. As a result of intensive research into these drawbacks, the present inventors discovered that by reacting amino silicone, polyether isocyanate, and epoxy silicone, the present inventors achieved water absorption properties that were much superior to those of conventional methods.
In addition, we have found that it is possible to provide a modified amino silicone fiber treatment agent that provides excellent flexibility and stretchability with durability, does not cause yellowing or discoloration, and has excellent stability in a treatment bath. [Means for Solving the Problems] That is, the present invention provides (A) a compound represented by the following general formula (1) containing on average at least two primary and/or secondary amino groups in one molecule; organopolysiloxane [In the formula, R ¹ is a monovalent hydrocarbon group having 1 to 5 carbon atoms, R ² is a hydrogen atom or a monovalent hydrocarbon group, A ¹
is R ¹ or -Q ¹ (NHCH ₂ CH ₂ ) _a NHR ² or hydroxyl group, Q ¹ is a divalent hydrocarbon group, m is a positive integer,
n is 0 or an integer of 1 or more, and a is an integer of 0 to 10. However, m+n is at least 10,
It is assumed that m/(n+2)=5/1 to 500/1. ] and (B) the following general formula (2), which is reactive with the amino group
Polyether isocyanate represented by [In the formula, R ³ is a hydrogen atom, a monovalent hydrocarbon group, or

[Formula] b is an integer, R ⁴ is a divalent hydrocarbon group, and R ⁵ is a hydrogen atom or a methyl group. ] and (C) the following general formula (3), which is reactive with the amino group
or an organopolysiloxane containing at least one epoxy group in one molecule, represented by (4) [In the formula, R ⁶ is a monovalent hydrocarbon group having 1 to 5 carbon atoms, A ² is R ⁶ or

[Formula] A ³ is R ⁶ or

[Formula] Q ² is a divalent hydrocarbon group, p is a positive integer, q is an integer of 0 or 1 or more, and r is an integer of 0 or 1 or more.
X ¹ is and R ⁷ is a hydrogen atom or a monovalent hydrocarbon group,
s is an integer of 0 or 1 or more, and t is an integer of 0 or 1 or more. ] Provided is a silicone-based fiber treatment agent characterized by containing an organopolysiloxane in which some or all of the amino groups have been reacted. The present invention also provides the above-mentioned (A) component, (B) component and (C)
In addition to these components, (D) an organoorganism in which some or all of the amino groups have been reacted, which is obtained by reacting the amino groups with a reactive organic acid or an anhydride or chloride of an organic acid; A silicone fiber treatment agent characterized by containing polysiloxane is provided. The amino silicone of formula (1) used in the present invention has at least two primary and/or secondary amino groups.
It may be a straight chain or a branched chain. Further, the terminals may be blocked with triorganopolysiloxane or other substances. In formula (1)
R ¹ is a monovalent hydrocarbon group having 1 to 5 carbon atoms,
Examples include methyl group, ethyl group, propyl group, and butyl group. All R ^1s in one molecule need not be the same. The most common R ¹ is a methyl group, but combinations of methyl and other groups are also common. R ² is a hydrogen atom or a monovalent hydrocarbon group,
The latter include methyl group, ethyl group, propyl group,
An example is a phenyl group. A ¹ in formula (1) is R ¹ or −Q ¹ (NHCH ₂ CH ₂ ) _a NHR ² or a hydroxyl group, and both A ¹ are −Q ¹ (NHCH ₂ CH ₂ ) _a NHR ²
In this case, n can also be 0. Q ¹ is a divalent hydrocarbon group, −CH ₂ −, −CH ₂ −CH ₂
−, −CH ₂ −CH ₂ −CH ₂ , −CH ₂ −CH(CH ₃ )−
Alkylene groups such as CH ₂ , -(CH ₂ ) ₄ -, -
_An alkylarylene group such as ( _{CH2 ) 2C6H4-} is exemplified. For m+n to be at least 10,
If it is less than 10, the effect of imparting flexibility and stretchability will be poor, and if it exceeds 1000, it will be difficult to emulsify, so it is preferably 100 to 1000. m/(n+
2) = 5/1 to 500/1 because if it is less than 5/1, the effect of imparting flexibility will be poor, and if it exceeds 500/1, the effect of imparting stretchability will be poor. −
The reason why at least two Q ¹ (NHCH ₂ CH ₂ )NHR ² is required in one molecule is that if there is only one, there will be no crosslinking reaction with the epoxy silicone. As shown in general formula (1), this group may be present in the side chain, at the end of the molecular chain, or both. Further, the viscosity of the oil is preferably in the range of 100,000 to 100,000 cs (25°C). The polyether isocyanate of formula (2) used in the present invention is a component that reacts with the amino group of amino silicone and provides excellent water absorption without damaging the feel of amino silicone.
R ³ is a hydrogen atom or a monovalent hydrocarbon group or

[Formula], and monovalent hydrocarbon groups include straight-chain alkyl groups such as butyl, hexyl, octyl, undecyl, lauryl, myristyl, and cetyl, or branched alkyl groups, and oleyl groups. Examples include alkenyl groups, octylphenyl groups, alkaryl groups such as nonylphenyl groups, and aralkyl groups such as phenyl octyl groups. b is a number of 1 or more, preferably 3-15. R ⁴ is a divalent hydrocarbon group, −
CH ₂ −, −CH ₂ −CH ₂ −, −CH ₂ −CH ₂ −CH ₂ −,
Examples include alkylene groups such as -CH( _CH3 ) _-CH2- , -( _CH2 ) _{4- ,} and alkylarylene groups such as - _{(CH2 ) 2C6H4-} . R ⁵ is a hydrogen atom or a methyl group. All R ^5s in one molecule need not be the same. The epoxy silicone of formula (3) or (4) used in the present invention undergoes a crosslinking reaction with the amino group of the amino silicone, without impairing the feel of the amino silicone.
It is a component that provides excellent flexibility, does not cause yellowing or discoloration, and improves the stability of the processing bath.It can be any component that contains at least one epoxy group, and can be linear or branched. It may have. R ⁶ in formula (3) or (4) is a monovalent hydrocarbon group having 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. All R ⁶ in one molecule need not be the same. The most common R ⁶ is a methyl group, but combinations of methyl and other groups are also common. A ² in formula (3) is R ⁶ or

[Formula], and if both A ² are the latter, q can also be 0. formula
A ³ in (4) is R ⁶ or

〔Example〕

The invention will be explained in detail below using examples.
In addition, parts and % in Examples indicate parts by weight and % by weight, respectively, and the viscosity is the value at 25°C. Example 1 Formula: 195 parts of amino silicone having a viscosity of 1700 centistokes and the formula: 9 parts of polyether isocyanate represented by is charged into a reaction vessel at room temperature, heated under a nitrogen gas flow, and reacted at 90 to 100°C for about 1 hour.
At 90℃ Formula: Add 10 parts of epoxy silicone represented by 90
The reaction was carried out at ~100°C for about 1 hour. After the reaction is completed, cool and add 6 parts of Sunmol TL (manufactured by NICCA Chemical Co., Ltd.), which is a nonylphenol nonionic activator, and Sunmol NP.
Conch (manufactured by Nicca Chemical) 14 parts, Sunmoor N-
10 parts of 170B (manufactured by Nicca Chemical Co., Ltd.) and 750 parts of water were added and emulsified to obtain a stable emulsion (referred to as product A). Example 2 Same amino silicone 195 used in Example 1
Part and 9 parts of polyether isocyanate and formula: A reaction emulsion was carried out in the same manner as in Example 1 using 10 parts of epoxy silicone represented by (Product B). Example 3 Same amino silicone 195 used in Example 1
Part and 9 parts of polyether isocyanate and formula: A reaction emulsion was carried out in the same manner as in Example 1 using 10 parts of epoxy silicone represented by (Product C). Example 4 Same amino silicone 195 used in Example 1
Part and 9 parts of polyether isocyanate and formula: A reaction emulsion was carried out in the same manner as in Example 1 using 10 parts of epoxy silicone represented by (referred to as product D). Example 5 Same amino silicone 195 used in Example 1
Part and expression: 9 parts of polyether isocyanate and 10 parts of the same epoxy silicone as used in Example 1.
1, reaction emulsification was carried out in the same manner as in Example 1 (referred to as product E). Example 6 Same amino silicone 195 as in Example 1
Part and expression: 9 parts of polyether isocyanate and 10 parts of the same epoxy silicone as used in Example 2
1, reaction emulsification was carried out in the same manner as in Example 1 (referred to as product F). Example 7 Same amino silicone 195 used in Example 1
Part and expression: 9 parts of polyether isocyanate and 10 parts of the same epoxy silicone as used in Example 3.
1, reaction emulsification was carried out in the same manner as in Example 1 (referred to as product G). Example 8 Same amino silicone 195 used in Example 1
Part and expression: 9 parts of polyether isocyanate and 10 parts of the same epoxy silicone as used in Example 4.
1, reaction emulsification was carried out in the same manner as in Example 1 (referred to as product H). Example 9 Formula: 195 parts of amino silicone having a viscosity of 1000 centistokes, 5 parts of the same polyether isocyanate used in Example 1, and 10 parts of epoxy silicone were reacted and emulsified in the same manner as in Example 1 (product I). Example 10 Formula: As in Example 1, with 195 parts of amino silicone having a viscosity of 12,000 centistokes, 9 parts of the same polyether isocyanate as used in Example 5, and 10 parts of the same epoxy silicone as used in Example 4. The reaction mixture was emulsified (referred to as product J). Example 11 Formula: with 190 parts of amino silicone having a viscosity of 280 centistokes, 18 parts of the same polyether isocyanate used in Example 6, and 20 parts of the same epoxy silicone used in Example 2,
Reaction emulsification was carried out in the same manner as in Example 1 (referred to as product K). Example 12 Same amino silicone 195 used in Example 1
1 part and 9 parts of polyether isocyanate were charged into a reaction vessel at room temperature, and the temperature was raised under a nitrogen gas stream.
After reacting at 90 to 100°C for about 1 hour, 4 parts of acetic anhydride was added at about 100°C, and after reacting at 100 to 110°C for about 1 hour, it was cooled to about 90°C. Add 10 parts of the same epoxy silicone and heat to 90-100℃
The reaction was carried out for about 1 hour. After the reaction was completed, it was cooled and emulsified in the same manner as in Example 1 (referred to as product L). Example 13 Same amino silicone 195 used in Example 1
9 parts of the same polyether isocyanate used in Example 5, 4 parts of succinic anhydride, and 10 parts of the same epoxy silicone used in Example 2 were reacted and emulsified in the same manner as in Example 12 (product M and do). Example 14 Same amino silicone 195 used in Example 1
A reaction emulsion was carried out in the same manner as in Example 12 using 9 parts of the same polyether isocyanate used in Example 6, 4 parts of acetyl chloride, and 10 parts of the same epoxy silicone used in Example 3 (referred to as product N). ). Example 15 Same amino silicone 195 used in Example 1
A reaction emulsion was carried out in the same manner as in Example 12 using 9 parts of the same polyether isocyanate as used in Example 7, 4 parts of stearic acid, and 10 parts of the same epoxy silicone as used in Example 4 (referred to as product O). ). Example 16 Same amino silicone 195 used in Example 9
1 part, 5 parts of the same polyether isocyanate used in Example 5, 2 parts of palmitic acid, and 10 parts of the same epoxy silicone used in Example 1 were reacted and emulsified in the same manner as in Example 12 (referred to as product P). ). Example 17 Same amino silicone 195 used in Example 10
A reaction emulsion was carried out in the same manner as in Example 12 using 9 parts of the same polyether isocyanate used in Example 6, 4 parts of acetyl chloride, and 10 parts of the same epoxy silicone used in Example 3 (referred to as product Q). ). Example 18 Same amino silicone 190 used in Example 11
Example 12 was prepared using 18 parts of the same polyether isocyanate used in Example 8, 10 parts of acetic anhydride, and 20 parts of the same epoxy silicone used in Example 1.
It was reacted and emulsified in the same manner as (referred to as product R). Comparative Example 1 Same amino silicone 205 used in Example 1
1 part and 18 parts of polyether isocyanate were charged into a reaction vessel, and the mixture was heated at 90 to 100°C under a nitrogen gas stream to approx.
After reacting for a period of time, it was emulsified in the same manner as in Example 1 (referred to as Comparative Product X). Comparative Example 2 Same amino silicone 205 used in Example 1
1 part and 20 parts of epoxy silicone were placed in a reaction vessel, and after reacting for about 1 hour at 90 to 100°C under a nitrogen gas stream, the mixture was emulsified in the same manner as in Example 1 (referred to as Comparative Product Y). Comparative Example 3 Same amino silicone 205 used in Example 1
The sample was emulsified in the same manner as in Example 1 without reacting (referred to as Comparative Product Z). Performance Test Example 1 Products (A) to (R) and comparative products (X) to (Z) were tested for water absorption, flexibility, elasticity, and thermal discoloration (yellowing). The results are shown in the table. (1) Test method (a) Test fabric Polyester processed yarn material (PET) #40 cotton broad fluorescent dyed fabric (cotton) Mercerized cotton knitted fabric (cotton knit) Polyester/cotton (65/35) broad
(T/C) (b) Processing conditions silicone emulsion
0.5% soln (PET) 3.0% soln (cotton) 1.0% soln
(Cotton knit, T/C) Padding 1dip-1nip pick-up
90% (PET) 70% (cotton, cotton knit, T/C) Dry 110℃ x 3mm Cure ring
180℃×30sec (PET) 150℃×2mm (cotton, cotton knit, T/C) (c) Evaluation method (i) Water absorption JIS L-1018 method A (dropping method) (ii) Hand Judging by feel did. ◎-Very flexible, 〇-Flexible, △-Slightly hard, ×-Rough (iii) Stretchability A sample measuring 20 cm in the weft direction and 3 cm in the warp direction was fixed vertically, and an initial load of 5 g was applied. The length after mounting and leaving for 1 minute is (l ₁ ), then a load of 200g is applied, and the length after leaving for 1 minute is (l ₂ ),
Remove the load and let the length after 1 minute be (l ₃ ). Stretching rate (%) = l ₂ - _{l 1} / l ₁ × 100 Recovery rate (%) = l ₂ - l ₃ / l ₂ - l ₁ × 100 (iv) Thermochromic property The sample was further heat-treated at 180°C for 2 minutes. The post-reflectance is measured with Macbeth MS-2020 (λ _nax =440 nm). (d) Results As shown in the table, comparative product . In contrast, the product of the present invention showed very good results in terms of water absorption, texture, elasticity, and thermochromic properties. Performance test example 2 A sample solution of a specified concentration was heated at room temperature using a homomixer.
The stability of the treatment bath was checked by stirring at high speed for 10 minutes. The results are shown in the table. (a) Test conditions 1 Silicone emulsion 2% soln 2 Silicone emulsion 2% soln Sumitex Resin NS-19 [Sumitomo Chemical Co., Ltd.]
[Manufactured by Sumitomo Chemical Co., Ltd.] 7% soln Sumitex Accelerator
500 rpm (b) Evaluation method 〇 Stable with no generation of oily or gummy substances × Unstable with generation of oily or gummy substances (c) Results As shown in the table, the processing bath stability of the product of the present invention is good. It is.

【table】

【table】

【table】

Claims (1)

[Scope of Claims] 1 (A) An organopolysiloxane represented by the following general formula (1) and containing an average of at least two primary and/or secondary amino groups in one molecule. [In the formula, R ¹ is a monovalent hydrocarbon group having 1 to 5 carbon atoms, R ² is a hydrogen atom or a monovalent hydrocarbon group, A ¹
is R ¹ or -Q ¹ (NHCH ₂ CH ₂ ) _a NHR ² or hydroxyl group, Q ¹ is a divalent hydrocarbon group, m is a positive integer,
n is 0 or an integer of 1 or more, and a is an integer of 0 to 10. However, m+n is at least 10,
It is assumed that m/(n+2)=5/1 to 500/1. ] and (B) the following general formula having reactivity with the above amino group
Polyether isocyanate represented by (2) [In the formula, R ³ is a hydrogen atom or a monovalent hydrocarbon group, [Formula] b is an integer, R ⁴ is a divalent hydrocarbon group, and R ⁵ is a hydrogen atom or a methyl group. ] and (C) the following general formula having reactivity with the above amino group
At least one of (3) or (4) in one molecule
Organopolysiloxane containing epoxy groups [In the formula, R ⁶ is a monovalent hydrocarbon group having 1 to 5 carbon atoms, A ² is R ⁶ or [Formula] A ³ is R ⁶ or [Formula] Q ² is a divalent hydrocarbon group, p is a positive An integer, q is an integer of 0 or 1 or more, and r is an integer of 0 or 1 or more.
X ¹ is and R ⁷ is a hydrogen atom or a monovalent hydrocarbon group,
s is an integer of 0 or 1 or more, and t is an integer of 0 or 1 or more. ] A silicone-based fiber treatment agent, characterized in that it contains an organopolysiloxane in which some or all of the above amino groups have been reacted, which is obtained by reacting with 2 Component (A), component (B), and component (C) according to claim 1 are further reacted with (D) an organic acid, an organic acid anhydride, or an organic acid chloride that is reactive with the amino group. A silicone-based fiber treatment agent characterized in that it contains an organopolysiloxane obtained by reacting some or all of the amino groups.