JPH0571709B2 - - 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 flexible silicone containing a modified amino silicone obtained by reacting an organopolysiloxane containing at least one epoxy group in one molecule (hereinafter referred to as epoxy silicone) which is reactive with the amino group. The present invention relates to a silicone-based fiber treatment agent that has excellent elasticity and elasticity, is free from problems of yellowing and discoloration, and has excellent stability in a treatment bath. [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. Examples include dimethyl polysiloxane (commonly known as dimethyl oil), dimethylhydrodiene polysiloxane (commonly known as H oil), and various other modified silicones (epoxy modified silicone, polyether modified silicone, 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, amino silicone has 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
When processing aminosilicone into fibers in the form of an emulsion, the stability of the processing bath 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. Other processing chemicals used in the processing bath or substances that adhere to and contaminate fabrics (e.g. acids, alkalis, inorganic salts,
The compatibility with surfactants, polybasic acids, etc.) is inferior to dimethyl oil, etc., and 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 these drawbacks, including a method of acylating an amino group with an organic acid, an organic acid anhydride, or an organic acid chloride [Japanese Patent Publication No. 57
-54588, JP-A-1-306682, JP-A-1-306683]
etc. have been proposed. However, these methods
Although the drawbacks of aminosilicone could be improved, the unique feel of aminosilicone tends to be lost. Already, as a method to improve these defects without impairing the unique texture of amino silicone,
A method of reacting amino silicone and epoxy silane [Japanese Patent Publication No. 1-22390] has been proposed, but
Further, as a result of intensive research, the present inventors found that a method of reacting amino silicone and epoxy silicone provides superior flexibility and stretchability compared to conventional methods, does not cause yellowing or discoloration, and is easy to use in processing baths. It has been discovered that it is possible to provide a modified amino silicone fiber treatment agent with excellent stability. [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 ) _a NHR ² or hydroxyl group, Q ¹ is a divalent hydrocarbon group, m is a positive integer, n
is an integer of 0 or 1 or more, and a is an integer of 0 to 10. However, m+n is at least 10, and m/
It is assumed that (n+2)=5/1 to 500/1. ] and (B) the following general formula (2), which is reactive with the amino group
or an organopolysiloxane containing at least one epoxy group in one molecule, represented by (3)

[ka]

[In the formula, R ³ is a monovalent hydrocarbon group having 1 to 5 carbon atoms, A ² is R ³ or

[Formula] A ³ is R ³ 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. ^X1
teeth

[Formula], R ⁴ is a hydrogen atom or a monovalent hydrocarbon group, s is 0
or an integer of 1 or more; t is 0 or an integer of 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 a product obtained by reacting component (A) and component (B) with (C) an organic acid or an anhydride or chloride of an organic acid that is reactive with the amino group. The present invention provides a silicone-based fiber treatment agent characterized by containing an organopolysiloxane in which some or all of the amino groups have been reacted. 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 triorganosiloxane or other substances. R ¹ in formula (1) is
It 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 ^1s in one molecule need not be the same. Methyl group is the most common R ¹ , but
Combinations of methyl groups and other groups are also common. ^R2
is a hydrogen atom or a monovalent hydrocarbon group, and examples of the latter include a methyl group, an ethyl group, a propyl group, and a phenyl group. A ¹ in formula (1) is R ¹ or −Q ¹
(NHCH ₂ CH ₂ ) _a NHR ² or hydroxyl group, A ¹
When both are -Q ¹ (NHCH ₂ CH ₂ ) _a NHR ² , 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 )−CH ₂ −, −
Alkylene _groups such as ( _CH2 ) _{4- ,} -( _CH2 ) _2C6H4
Examples include alkylarylene groups such as -.
The reason why m+n is at least 10 is because 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
The reason for setting the ratio to 500/1 is that 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. −Q ¹ (NHCH ₂
The reason why at least two (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 epoxy silicone of formula (2) or (3) 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 only needs to contain at least one epoxy group, and can be linear or branched. It may have. R ³ in formula (2) or (3) 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 ^R3s in one molecule need not be the same. Methyl group is the most common ^R3 , but
Combinations of methyl groups and other groups are also common. Formula (2)
A ² inside is R ³ or

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

[Formula], and if both A ³ are the latter, q can also be 0. Q ² is a divalent hydrocarbon group, −CH ₂ −, −CH ₂ −CH ₂ −,
−CH ₂ −CH ₂ −CH ₂ −, −CH ₂ −CH(CH ₃ )−CH ₂
Alkylene groups such as −, −(CH ₂ ) ₄ −, −(CH ₂ ) ₂
Examples include alkylarylene groups such _{as C6H4-} . X ¹ is

〔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:

10 parts of epoxy silicone represented by the formula is charged into a reaction vessel at room temperature, heated under a nitrogen gas stream,
The reaction was carried out at 90-100°C for about 1 hour. After the reaction is completed, cool and add 6 parts of Sunmol TL (manufactured by NICCA Chemical Co., Ltd.), a nonylphenol-based 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 formula:

A reaction emulsion was carried out in the same manner as in Example 1 using 10 parts of an epoxy silicone represented by the formula (Product B). Example 3 Same amino silicone 195 used in Example 1
Part and formula:

10 parts of epoxy silicone represented by the formula was reacted and emulsified in the same manner as in Example 1 (referred to as product C). Example 4 Same amino silicone 195 used in Example 1
Part and formula:

A reaction emulsion was carried out in the same manner as in Example 1 using 10 parts of an epoxy silicone represented by the formula (Product D). Example 5 Formula:

[Formula] 195 parts of amino silicone having a viscosity of 1000 centistokes and 10 parts of the same epoxy silicone used in Example 1 were reacted and emulsified in the same manner as in Example 1 (referred to as product E). ). Example 6 Formula:

195 parts of an amino silicone represented by ). Example 7 Formula:

190 parts of an amino silicone represented by ). Example 8 Same amino silicone 195 used in Example 1
1 part and 4 parts of acetic anhydride were placed in a reaction vessel at room temperature, heated under a stream of nitrogen gas, reacted at 100 to 110°C for about 1 hour, and then cooled to about 90°C. Add 10 parts of the same epoxy silicone, 90
The reaction was carried out at ~100°C 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 H). Example 9 Same amino silicone 195 used in Example 1
1 part, 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 8 (referred to as Product I). Example 10 Same amino silicone 195 used in Example 1
1 part, 4 parts of acetyl chloride, and 10 parts of the same epoxy silicone used in Example 3 were used to react and emulsify in the same manner as in Example 8 (referred to as product J). Example 11 Same amino silicone 195 used in Example 1
1 part of stearic acid and 10 parts of the same epoxy silicone used in Example 4 were reacted and emulsified in the same manner as in Example 8 (referred to as product K). Example 12 Same amino silicone 195 used in Example 1
1 part 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 8 (referred to as product L). Example 14 Same amino silicone 195 used in Example 5
1 part of acetic anhydride and 10 parts of the same epoxy silicone as used in Example 2 were reacted and emulsified in the same manner as in Example 8 (referred to as product M). Example 15 Same amino silicone 195 used in Example 6
1 part, 4 parts of succinic anhydride, and 10 parts of the same epoxy silicone as used in Example 3 were reacted and emulsified in the same manner as in Example 8 (referred to as product N). Example 16 Same amino silicone 190 used in Example 7
10 parts of acetyl chloride and 20 parts of the same epoxy silicone used in Example 4 were reacted and emulsified in the same manner as in Example 8 (referred to as product O). Comparative Example 1 Same amino-modified silicone used in Example 1
195 parts were emulsified without reacting in the same manner as in Example 1 (referred to as comparative product X-1). Comparative Example 2 Same amino-modified silicone used in Example 5
195 parts were emulsified without reacting in the same manner as in Example 1 (referred to as comparative product X-2). Comparative Example 3 Same amino-modified silicone used in Example 6
195 parts were emulsified without reacting in the same manner as in Example 1 (referred to as comparative product X-3). Comparative Example 4 Same amino-modified silicone used in Example 7
190 parts were emulsified without reacting in the same manner as in Example 1 (referred to as comparative product X-4). Comparative Example 5 100 parts of the same epoxy-modified silicone used in Example 1 was added to 5 parts of Sunmol TL (manufactured by NICCA Chemical Co., Ltd.), which is a nonylphenol nonionic surfactant, and 5 parts of Sunmol NP Conc (manufactured by NICCA Chemical Co., Ltd.) without reacting. 10 copies (manufactured by Hana Kagaku), Sunmoor N-170B (manufactured by NICCA Kagaku)
8 parts and 900 parts of water were added to emulsify (referred to as comparative product Y-1). Comparative Example 6 100 parts of the same epoxy-modified silicone used in Example 2 was emulsified without reacting in the same manner as in Comparative Example 5 (referred to as Comparative Product Y-2). Comparative Example 7 100 parts of the same epoxy-modified silicone used in Example 3 was emulsified without reacting in the same manner as in Comparative Example 5 (referred to as Comparative Product Y-3). Comparative Example 8 100 parts of the same epoxy-modified silicone used in Example 4 was emulsified without reacting in the same manner as in Comparative Example 5 (referred to as Comparative Product Y-4). Comparative Examples 9-15 Comparative products (X-1) obtained in Comparative Examples 1-8
Immediately before use, (X-4) and (Y-1) to (Y-4) were blended as shown in Table 1, and a performance test was conducted.

[Table] Comparative Example 16 Same amino-modified silicone used in Example 1
195 parts and formula:

10 parts of epoxysilane represented by the following formula was charged into a reaction vessel and reacted at 90 to 100°C for about 1 hour under a nitrogen gas flow. After the reaction is completed, cool and add 13 parts of Sunmol TL (manufactured by NICCA Chemical), which is a nonylphenol-based nonionic activator, and Sunmol NP Conc (manufactured by NICCA Chemical).
27 parts of Sunmol N-170B (manufactured by Nicca Chemical Co., Ltd.) and 750 parts of water were added and emulsified to obtain a stable emulsion (referred to as comparative product Z-1). Comparative Example 17 Same amino-modified silicone used in Example 1
195 parts and 4 parts of acetic anhydride were placed in a reaction vessel and reacted at 100 to 110°C for about 1 hour under a nitrogen gas stream, then cooled to 90°C, and 5 parts of the same epoxysilane used in Comparative Example 16 were added. After reacting at 90 to 100°C for about 1 hour, it was emulsified in the same manner as in Comparative Example 16 (referred to as Comparative Product Z-2). Comparative Example 18 Same amino-modified silicone used in Example 1
Charge 195 parts and 4 parts of succinic anhydride into a reaction vessel,
After reacting at 100 to 110°C for about 1 hour under a nitrogen gas flow, cooling to 90°C, the formula:

Add 5 parts of epoxysilane represented by [Formula] to 90~
After reacting at 100°C for about 1 hour, it was emulsified in the same manner as in Comparative Example 16 (referred to as Comparative Product Z-3). Comparative Example 19 Same amino-modified silicone used in Example 1
205 parts of acetic anhydride and 8 parts of acetic anhydride were charged into a reaction vessel, and the mixture was reacted at 100 to 110°C for about 1 hour under a nitrogen gas flow, and then emulsified in the same manner as in Example 1 (referred to as comparative product Z-4). . Comparative Example 20 Same amino-modified silicone used in Example 1
Charge 195 parts and 4 parts of acetyl chloride into a reaction vessel,
After reacting at 100 to 110° C. for about 1 hour under a nitrogen gas stream, the mixture was emulsified in the same manner as in Example 1 (referred to as comparative product Z-5). Comparative Example 21 Same amino-modified silicone used in Example 1
205 parts were emulsified in the same manner as in Example 1 without reacting (referred to as comparative product Z-6). Performance test example 1 Products (A) to (o), comparative products (X-1) to (X-4),
(Y-1) to (Y-4) and (Z-1) to (Z-
6) was used to test for flexibility, elasticity, and thermal discoloration (yellowing). The results are shown in Table 2. (1) Test method (a) Test fabric Polyester processed yarn fabric (PET) #40 cotton broad fluorescent dyed fabric (cotton) Mercerized cotton knit 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) Drying 110℃ x 3min Curing 180℃ x 30sec (PET) 150℃ x 2min (cotton, cotton knit, T/C) (c) Evaluation method (a) Texture Judged by touch . ◎-Very flexible, ○-Flexible, △-Slightly rough and hard,
×- Rough hardness (A) Stretch back property (elasticity) A sample of 20 cm in the weft direction and 3 cm in the warp direction is fixed vertically, an initial load (5 g) is applied, and the length after being left for 1 minute is (l ₁ ) Then, apply a load of 200g,
After leaving it for 1 minute, take the length (l ₂ ), remove the load,
Let the length after standing for 1 minute be (l ₃ ). Elongation rate (%) = l ₂ - _{l 1} / l ₁ × 100 Recovery rate (%) = l ₂ - l ₃ / l ₂ - l ₁ × 100 (C) Thermochromic property The sample was further heat-treated at 180°C for 2 minutes. Measure the back reflectance with Macbeth MS-2020. (λmax=440nm) (2) Results As shown in Table 2, all comparative products had poor thermochromic properties. In contrast, the products of the present invention showed very good results in terms of hand, stretchability, and thermochromic properties.

[Table] Performance test example 2 A sample solution of a predetermined concentration was stirred at high speed at room temperature in a homomixer to check the stability of the treatment bath. Table 3 shows the results.
Shown below. (1) Test conditions (a) Measurement concentration 1: Silicone emulsion 2% soln 2: Silicone emulsion 2% soln Sumitex Resin NS-19 (manufactured by Sumitomo Chemical Co., Ltd.) 7% soln Sumitex Accele Rater X-80 (manufactured by Sumitomo Chemical Co., Ltd.) 2% soln (b) Measuring equipment Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) (c) Measurement conditions A: Number of revolutions 500 rpm Time 10 minutes B: Number of revolutions 5000 rpm Time 10 minutes (2) Results As shown in Table 3, all comparative products had poor processing bath stability. In contrast, the products of the present invention have good processing bath stability.

【table】

【table】

Claims (1)

[Claims] 1 (A) An organopolysiloxane containing an average of at least two primary and/or secondary amino groups in one molecule, represented by the following general formula (1) [Formula Among them, 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
At least one of (2) or (3) in one molecule
^{Organopolysiloxane containing epoxy groups :} [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. ^X1
is [Formula], R ⁴ is a hydrogen atom or a monovalent hydrocarbon group, and s is 0
or an integer of 1 or more; t is 0 or an integer of 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. The above-mentioned compound obtained by reacting component (A) and component (B) according to claim 1 with (C) an organic acid, an organic acid anhydride, or an organic acid chloride that is reactive with the amino group. A silicone fiber treatment agent characterized by containing an organopolysiloxane in which some or all of the amino groups have been reacted.