JP6968580B2 - Amino-modified silicone composition - Google Patents

Description

The present invention relates to an amino-modified silicone composition. In particular, the present invention relates to a composition in which yellowing of amino-modified silicone is suppressed.

Since amino-modified silicone has high adsorptivity, it is generally used in detergents, textile treatment agents, hair care products, cosmetics and the like.
However, since the amino-modified silicone turns yellow over time, the appearance of the product itself may be affected by the yellowing of the amino-modified silicone in products containing the amino-modified silicone (textile product treatment agents, etc.).
As a means for suppressing yellowing of amino-modified silicone, a technique for blending a specific type of alcohol compound (Patent Document 1), a technique for blending urea (Patent Document 2), and a technique for blending hydrogen peroxide (Patent Document 3). , A technique of blending an oil-soluble antioxidant (Patent Document 4) and a technique of blending a divalent saturated aliphatic carboxylic acid (Patent Document 5) are known.
Further, the benzisothiazolin-based compound is blended in textile product treatment agents and hair care products as a preservative and a bactericide (Patent Documents 6 to 8).

Japanese Unexamined Patent Publication No. 9-59285 Japanese Unexamined Patent Publication No. 2013-57011 JP-A-2007-284843 Japanese Unexamined Patent Publication No. 2006-249605 Japanese Unexamined Patent Publication No. 2006-144190 Japanese Unexamined Patent Publication No. 2002-327375 Special Table 2016-534178A Japanese Unexamined Patent Publication No. 2000-178358

However, there has been no means for suppressing yellowing of a composition containing a high concentration of amino-modified silicone before blending into a final product such as a textile treatment agent.

As a result of diligent studies on the above problems, the present inventor has found that the use of a compound having a specific structure having a 1,2-benzisothiazolin skeleton can suppress yellowing of a composition containing a high concentration of amino-modified silicone. .. The present invention has been made based on this finding.

（式中、
Ｒ¹¹は、水素原子、炭素数１〜２０のアルキル基、炭素数１〜１２のアリール基、炭素数１〜４のアルコキシ基、炭素数１〜１２のアラルキル基、又は、炭素数３〜２０のシクロアルキル基であり、
Ｘは、ハロゲン、ニトロ、シアノ又は炭素数１〜８のアルコキシ基であり、
ｎは、０〜４の整数である。）
を含有し、
（Ａ）成分の含量が、該アミノ変性シリコーン組成物の総質量に対して１５〜７０質量％である、アミノ変性シリコーン組成物。

〔２〕アミノ変性シリコーンを含む最終製品の製造に用いるための、前記〔１〕に記載のアミノ変性シリコーン組成物。

〔３〕アミノ変性シリコーンを含む最終製品が、洗剤又は繊維製品処理剤である、前記〔２〕に記載のアミノ変性シリコーン組成物。

〔４〕（Ａ）成分が、アミノ変性シリコーンオイルである、前記〔１〕〜〔３〕のいずれか１項に記載のアミノ変性シリコーン組成物。

〔５〕アミノ変性シリコーンオイルの２５℃における動粘度が１００〜２００００ｍｍ²／ｓである、前記〔４〕に記載のアミノ変性シリコーン組成物。

〔６〕アミノ変性シリコーンオイルのアミノ当量が１００〜１００００ｇ／ｍｏｌである、前記〔４〕又は〔５〕に記載のアミノ変性シリコーン組成物。

〔７〕（Ｂ）成分が、１，２−ベンズイソチアゾリン−３−オンである、前記〔１〕〜〔６〕のいずれか１項に記載のアミノ変性シリコーン組成物。

〔８〕（Ａ）成分の（Ｂ）成分に対する質量比（（Ａ）／（Ｂ））が３００〜３０００である、前記〔１〕〜〔７〕のいずれか１項に記載のアミノ変性シリコーン組成物。

〔９〕更に（Ｃ）界面活性剤を含む、前記〔１〕〜〔８〕のいずれか１項に記載のアミノ変性シリコーン組成物。

〔１０〕（Ｃ）成分が、非イオン性界面活性剤である、前記〔９〕に記載のアミノ変性シリコーン組成物。

〔１１〕更に（Ｄ）水酸基及び／又はエーテル基を有する水溶性有機溶剤を含む、前記〔１〕〜〔１０〕のいずれか１項に記載のアミノ変性シリコーン組成物。

〔１２〕（Ｄ）成分が芳香族エーテルである、前記〔１１〕に記載のアミノ変性シリコーン組成物。

〔１３〕アミノ変性シリコーン又は前記アミノ変性シリコーンを含む組成物の黄変抑制方法であって、
（Ａ）アミノ変性シリコーン又は前記アミノ変性シリコーンを含む組成物と、
（Ｂ）下記式（ＩＩ）で表される化合物

（式中、
Ｒ¹¹は、水素原子、炭素数１〜２０のアルキル基、炭素数１〜１２のアリール基、炭素数１〜４のアルコキシ基、炭素数１〜１２のアラルキル基、又は、炭素数３〜２０のシクロアルキル基であり、
Ｘは、ハロゲン、ニトロ、シアノ又は炭素数１〜８のアルコキシ基であり、
ｎは、０〜４の整数である。）
とを混合する工程を含む、方法。 That is, the present invention relates to the following [1] to [13].

[1] An amino-modified silicone composition.
The following components (A) to (B):
(A) Amino-modified silicone and
(B) A compound represented by the following formula (II)

(During the ceremony,
R ¹¹ has a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aralkyl group having 1 to 12 carbon atoms, or an aralkyl group having 3 to 20 carbon atoms. It is a cycloalkyl group of
X is a halogen, nitro, cyano or an alkoxy group having 1 to 8 carbon atoms.
n is an integer from 0 to 4. )
Contains,
(A) An amino-modified silicone composition in which the content of the component is 15 to 70% by mass with respect to the total mass of the amino-modified silicone composition.

[2] The amino-modified silicone composition according to the above [1], which is used in the production of a final product containing an amino-modified silicone.

[3] The amino-modified silicone composition according to the above [2], wherein the final product containing the amino-modified silicone is a detergent or a textile product treating agent.

[4] The amino-modified silicone composition according to any one of [1] to [3] above, wherein the component (A) is an amino-modified silicone oil.

[5] The amino-modified silicone composition according to the above [4], wherein the amino-modified silicone oil has a kinematic viscosity of 100 to 20000 mm ^{2 / s at 25 ° C.}

[6] The amino-modified silicone composition according to the above [4] or [5], wherein the amino equivalent of the amino-modified silicone oil is 100 to 10,000 g / mol.

[7] The amino-modified silicone composition according to any one of [1] to [6] above, wherein the component (B) is 1,2-benzisothiazolin-3-one.

[8] The amino-modified silicone according to any one of [1] to [7] above, wherein the mass ratio ((A) / (B)) of the component (A) to the component (B) is 300 to 3000. Composition.

[9] The amino-modified silicone composition according to any one of [1] to [8] above, further comprising (C) a surfactant.

[10] The amino-modified silicone composition according to [9] above, wherein the component (C) is a nonionic surfactant.

[11] The amino-modified silicone composition according to any one of [1] to [10] above, further comprising (D) a water-soluble organic solvent having a hydroxyl group and / or an ether group.

[12] The amino-modified silicone composition according to the above [11], wherein the component (D) is an aromatic ether.

[13] A method for suppressing yellowing of an amino-modified silicone or a composition containing the amino-modified silicone.
(A) Amino-modified silicone or a composition containing the amino-modified silicone,
(B) A compound represented by the following formula (II)

(During the ceremony,
R ¹¹ has a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aralkyl group having 1 to 12 carbon atoms, or an aralkyl group having 3 to 20 carbon atoms. It is a cycloalkyl group of
X is a halogen, nitro, cyano or an alkoxy group having 1 to 8 carbon atoms.
n is an integer from 0 to 4. )
A method comprising the step of mixing with.

As shown in Examples described later, the amino-modified silicone composition of the present invention suppresses yellowing over time.
Therefore, the present invention is excellent as a raw material for final products (textile product treatment agents, etc.) containing amino-modified silicone. Further, some of the compounds having a 1,2-benzisothiazolin skeleton adopted in the present invention have an antibacterial effect, and the amino-modified silicone composition of the present invention containing such a compound is antibacterial to the final product. It can impart sex and antiseptic properties.

[(A) component]
The component (A) is amino-modified silicone.
Amino-modified silicone is a compound obtained by introducing amino groups into both ends and / or side chains of a dimethyl silicone skeleton.

Preferred amino-modified silicones have the following general formula (I):

(In the formula, R is independently _{selected from the group consisting of —H, —OH, −CH 3} and −Si (CH ₃ ) ₃ , and X is − (CH ₂ ) _a −NH ₂ or ,-(CH ₂ ) _a- NH (CH ₂ ) _b NH ₂ (a is an integer from 0 to 3, b is an integer from 1 to 3), n is 1 to 1500, and m is 1 to 20), which is a compound obtained by introducing an amino group into the side chain X.

The amino-modified silicone is preferably a kinematic viscosity at 25 ° C. in a state of the silicone oil is 100~20000mm ² / s, and more preferably 500~10000mm ² / s. When the kinematic viscosity is in this range, the manufacturability and handleability of the amino-modified silicone composition become easy. The kinematic viscosity can be measured with an Ostwald type viscometer.
The amino equivalent of the silicone oil is preferably 100 to 10000 g / mol, more preferably 1200 to 4000 g / mol. When the amino equivalent is in this range, the texture modifying property is good, which is preferable. The amino equivalent can be determined by dividing the weight average molecular weight of the amino-modified silicone by the number of nitrogen atoms contained in the amino-modified silicone. The number of nitrogen atoms can be determined by elemental analysis.

The amino-modified silicone is preferably water-insoluble. Water insoluble means that the amount dissolved in 1 L of water is 10 g or less at 25 ° C.

The amino-modified silicones described above are readily available on the market or are available for synthesis. Specific examples of amino-modified silicone oils available on the market are shown below.

Products of GE Toshiba Silicone Co., Ltd .:
TSF4703 (kinematic viscosity 1000 mm ² / s (25 ° C), amino equivalent 1600 g / mol)
TSF4708 (kinematic viscosity 1000 mm ² / s (25 ° C), amino equivalent 2800 g / mol)

Products of Toray Dow Corning Silicone Co., Ltd .:
SS-3551 (kinematic viscosity 1000 mm ² / s (25 ° C), amino equivalent 1600 g / mol)
FZ-3705 (kinematic viscosity 250 mm ² / s (25 ° C), amino equivalent 4000 g / mol)
FZ-319 (kinematic viscosity 2000 mm ² / s (25 ° C), amino equivalent 4000 g / mol)
SF8451C (kinematic viscosity 600 mm ² / s (25 ° C), amino equivalent 1700 g / mol)
SF8452C (kinematic viscosity 700 mm ² / s (25 ° C), amino equivalent 6400 g / mol)
SF8457C (kinematic viscosity 1200 mm ² / s (25 ° C), amino equivalent 1800 g / mol)
SF8417 (kinematic viscosity 1200 mm ² / s (25 ° C), amino equivalent 1800 g / mol)
BY16-849 (kinematic viscosity 1300 mm ² / s (25 ° C), amino equivalent 600 g / mol)
BY16-850 (kinematic viscosity 1100 mm ² / s (25 ° C), amino equivalent 1100 g / mol)
BY16-892 (kinematic viscosity 1100 mm ² / s (25 ° C), amino equivalent 2000 g / mol)
BY16-897 (kinematic viscosity 900 mm ² / s (25 ° C), amino equivalent 2900 g / mol)
BY16-898 (kinematic viscosity 1300 mm ² / s (25 ° C), amino equivalent 2900 g / mol)

Products of Shin-Etsu Chemical Co., Ltd .:
KF857, KF858, KF859, KF862, KF8001, KF880, and KF-864 (kinematic viscosity 1700 mm ² / s (25 ° C), amino equivalent 3800 g / mol)

Asahi Kasei Wacker Silicone Co., Ltd. products:
WR301 (kinematic viscosity 1000 mm ² / s (25 ° C), amino equivalent 3700 g / mol)
WR1250 (kinematic viscosity 200 mm ² / s (25 ° C), amino equivalent 4000 g / mol)
WT1650 (kinematic viscosity 1000 mm ² / s (25 ° C), amino equivalent 1700 g / mol)

Particularly preferable component (A) is in the general formula (I).
X is − (CH ₂ ) _a −NH ₂ and
Kinematic viscosity (25 ° C.) is 100~20000mm ² / s, preferably 500~10000mm ² / s, particularly preferably from 1000~5000mm ² / s, and,
Amino equivalents are 400 to 8,000 g / mol, preferably 800 to 6,000 g / mol, particularly preferably 1,000 to 4,000 g / mol.
Amino-modified silicone is preferable. Specific examples include KF-864 (kinematic viscosity: 1700 mm ² / s (25 ° C.), amino equivalent: 3800 g / mol) and the like.

The component (A) may be used alone or as a mixture of two or more.

The content of the component (A) is 15 to 70% by mass, preferably 15 to 60% by mass, and more preferably 15 to 50% by mass with respect to the total mass of the amino-modified silicone composition. When the content of the component (A) is 15 to 70% by mass, remarkable suppression of yellowing can be confirmed by the combined use with the component (B) described later.

（式中、Ｒ¹¹は、水素原子、炭素数１〜２０（好ましくは炭素数１〜４）のアルキル基、炭素数１〜１２のアリール基、炭素数１〜４のアルコキシ基、炭素数１〜１２のアラルキル基、又は、炭素数３〜２０のシクロアルキル基であり、Ｘは、ハロゲン、ニトロ、シアノ、又は、炭素数１〜８（好ましくは炭素数１〜４）のアルキル基であり、ｎは、０〜４の整数（好ましくは０〜２の整数）である。 [(B) component]
The component (B) is a compound having a 1,2-benzisothiazolin skeleton represented by the following formula (II).

(In the formula, R ¹¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (preferably 1 to 4 carbon atoms), an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and 1 carbon atom. It is an aralkyl group of ~ 12 or a cycloalkyl group having 3 to 20 carbon atoms, and X is a halogen, nitro, cyano, or an alkyl group having 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms). , N is an integer of 0 to 4 (preferably an integer of 0 to 2).

Specific examples of the compound represented by the formula (II) include 1,2-benzisothiazolin-3-one (BIT) (general formula (II) (in the formula, R ¹¹ is hydrogen and n is 0). ), N-Methyl-1,2-benzisothiazolin-3-one (general formula (II) (in the formula, R ¹¹ is a methyl group and n is 0)). Compound), N-ethyl-1,2-benzisothiazolin-3-one (compound represented by the general formula (II) (in the formula, R ¹¹ is an ethyl group and n is 0)) and the like. Listed,
1,2-Benzisothiazolin-3-one (BIT) is more preferable.

In addition, 1,2-benzisothiazolin-3-one (BIT) is generally used as an isothiazolin-based preservative and antibacterial agent.

The component (B) is blended mainly for the purpose of suppressing yellowing of the amino-modified silicone over time, but when it is a compound having antibacterial and antiseptic properties such as the above-mentioned BIT, it is also added. , The amino-modified silicone composition (and by extension, the final product such as a textile product treatment agent) can be imparted with antiseptic and antibacterial properties.

The component (B) is readily available on the market or can be synthesized by known methods.
Specific examples of the component (B) available on the market include LONZA's Proxel series (for example, BDN ((B) component content: 33% by mass), XL-2 ((B) component content: 10% by mass)). ), GXL ((B) component content: 20% by mass), LV ((B) component content: 20% by mass)), Clariant Nipacide BIT 20 and the like.

As the component (B), one type may be used alone, or two or more types may be used in combination as appropriate.

The content of the component (B) is not particularly limited as long as it can suppress yellowing of the amino-modified silicone, but is preferably 0.001 to 0.1% by mass with respect to the total mass of the amino-modified silicone composition. It is more preferably 0.001 to 0.07% by mass, still more preferably 0.001 to 0.05% by mass.
When the content of the component (B) is 0.001 to 0.1% by mass, a sufficient yellowing suppressing effect (as well as an antiseptic property and antibacterial property imparting effect) can be economically obtained.

In the amino-modified silicone composition which is a preferred embodiment of the present invention, the mass ratio ((A) / (B)) of the component (A) to the component (B) is 300 to 3000, preferably 500 to 2000. More preferably, it is 500 to 1500. When (A) / (B) is 300 to 3000, yellowing suppression and antiseptic power can be ensured at the same time.

[Arbitrary component]
The amino-modified silicone composition may contain any components other than the essential components (A) to (B) above, if necessary, as long as the effects of the present invention are not impaired.
Optional components include surfactant ((C) component), water-soluble organic solvent ((D) component), water, antibacterial agent, preservative, pH adjuster, colorant, silica, antioxidant, deodorant. Examples thereof include agents, cross-linking agents, various catalysts, emulsion stabilizers, chelating agents and the like.
Hereinafter, some optional components will be described in detail.

[(C) component]
The component (C) is a surfactant. The component (C) can be blended when improving the handleability of the component (A) or when preparing an amino-modified silicone composition as an emulsion.
As the component (C), those applicable to amino-modified silicone can be used without particular limitation. As a specific example,
(I) Anionic surfactants such as alkylbenzene sulfonic acid or its salt, alkyl sulfate ester salt, polyoxyalkylene alkyl ether sulfate, olefin sulfonate, alkane sulfonate, fatty acid salt, etc.
(Ii) Nonionic surfactants such as polyoxyalkylene alkyl ether or polyoxyalkylene alkenyl ether, polyoxyalkylene alkyl phenyl ether, fatty acid alkanolamide or alkylene oxide adduct thereof, sucrose fatty acid ester, alkyl glucoside, etc.
(Iii) Amphoteric surfactants such as amine oxides, sulfobetaines, and carbobetaines, and
(Iv) Cationic surfactants such as tri-long chain alkyl quaternary ammonium salts can be mentioned. Of these, nonionic surfactants are preferred.
As the component (C), one kind may be used alone, or two or more kinds may be used in combination as appropriate.
The component (C) is readily available on the market or can be synthesized by known methods.
The content of the component (C) is not particularly limited as long as the blending purpose can be achieved, but is preferably 1 to 50% by mass, more preferably 3 to 30% by mass, based on the total mass of the amino-modified silicone composition. Is.

[(D) component]
The component (D) is a water-soluble organic solvent having a hydroxyl group and / or an ether group. The component (D) can be blended to improve the storage stability and appearance of the amino-modified silicone composition.
As the component (D), those applicable to amino-modified silicone can be used without particular limitation. As a specific example,
(I) Alkanols such as ethanol, propanol, isopropanol, 1-butanol, etc.
(Ii) Polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, and glycerin, and
(Iii) Polyglycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having an average molecular weight of about 200, polyethylene glycol having an average molecular weight of about 400, dipropylene glycol, tripropylene glycol, and polypropylene glycol having an average molecular weight of about 1000. ,
(Iv) Diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, 1-methoxy-2- Propanol, 1-ethoxy-2-propanol, 1-methyl glyceryl ether, 2-methyl glyceryl ether, 1,3-dimethyl glyceryl ether, 1-ethyl glyceryl ether, 1,3-diethyl glyceryl ether, triethyl glyceryl ether, 1- Alkyl ethers such as pentyl glyceryl ether, 2-pentyl glyceryl ether, 1-octyl glyceryl ether, 2-ethylhexyl glyceryl ether, diethylene glycol monobutyl ether, etc.
(V) Aromatic ethers such as 2-phenoxyethanol, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, polyethylene glycol monophenyl ether having an average molecular weight of about 480, 2-benzyloxyethanol, diethylene glycol monobenzyl ether, and the like.
(Vi) 2-aminoethanol, N-methylethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, diethanolamine, N-methyldiethanolamine, N-butyldiethanolamine, triethanolamine, triisopropanolamine, Examples thereof include alkanolamines such as an isopropanolamine mixture (mixture of mono, di, and bird).

As the component (D), one kind may be used alone, or two or more kinds may be used in combination as appropriate.
The component (D) is readily available on the market or can be synthesized by known methods.
The content of the component (D) is not particularly limited as long as the blending purpose can be achieved, but is preferably 0.1 to 40% by mass, more preferably 0.1, based on the total mass of the amino-modified silicone composition. ~ 30% by mass, more preferably 0.1 to 20% by mass. When the content of the component (D) is 0.1 to 40% by mass, a high compounding effect can be obtained without causing problems of ignition and odor.

〔water〕
The amino-modified silicone composition is preferably an aqueous composition (emulsion) containing water.
As the water, tap water, purified water, pure water, distilled water, ion-exchanged water and the like can be used. Of these, ion-exchanged water is preferable.
The blending amount of water is not particularly limited and can be appropriately blended in order to achieve a desired composition, but for example, it is preferably 10 to 85% by mass, based on the total mass of the amino-modified silicone composition. It is preferably 20 to 80% by mass, and particularly preferably 30 to 75% by mass.

[PH of amino-modified silicone composition]
The pH of the amino-modified silicone composition is not particularly limited, but the pH at 25 ° C. is preferably 4 to 10 and more preferably 5 to 8. When the pH is 4 or more, it is possible to suppress an increase in the viscosity of the composition and improve the handleability. When the pH is 10 or less, the application destination (range of applicable final products) of the composition can be broadened.
For pH adjustment, inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as citric acid, acetic acid, malic acid, succinic acid and benzoic acid can be used.

[Manufacturing method of amino-modified silicone composition]
The amino-modified silicone composition can be produced by the same method as a known production method of the amino-modified silicone composition.
For example, the amino-modified silicone composition as an emulsion can be produced by the following steps.
First, the amino-modified silicone (component (A)) is dispersed in the surfactant (component (C)) to prepare a dispersed oil phase. The obtained dispersed oil phase is added to the aqueous phase for emulsification and dispersion, and then if necessary, a water-soluble organic solvent (component (D)) is further added to obtain an emulsion. The component (B) and, if necessary, water are added to the obtained emulsion to obtain an amino-modified silicone composition.

[Method for suppressing yellowing of amino-modified silicone]
The method for producing the amino-modified silicone composition can also be grasped as a method for suppressing yellowing of the amino-modified silicone or a composition containing the amino-modified silicone.
The method for suppressing yellowing includes a step of mixing the component (A) (or a composition containing the component (A)) and the component (B).

[How to use amino-modified silicone composition]
The amino-modified silicone composition of the present invention can be used as a raw material for final products containing amino-modified silicone (for example, detergents, textile treatment agents (softeners), hair care products, cosmetics, etc.).
For example, when the amino-modified silicone composition is used in the production of a textile product treatment agent, the component (A) can exhibit a function of imparting flexibility to the object to be washed. Further, when the component (B) has an antibacterial effect, the component (B) can impart antibacterial and antiseptic properties to the textile product processing agent.
When the amino-modified silicone composition is used for producing a textile product treatment agent, it can be blended with the following composition, for example.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.
In addition, in an Example and a comparative example, the compounding amount of each component shows the mass% (unless specified, the pure content conversion).

The components and production methods used in the production of the liquid softener compositions of Examples and Comparative Examples are shown below.

[(A) component]
The following A-1 was used.

(A-1)
Water-insoluble oil of side chain-modified type amino-modified silicone obtained from Shin-Etsu Chemical Co., Ltd. under the trade name: KF-864 (in general formula (I), X is- _{(CH 2} ) _{3- NH 2} Compound. Dynamic viscosity at 25 ° C.: 1700 mm ² / s, amino equivalent: 3800 g / mol).

[(B) component]
The following B-1 to B-4 were used.

B-1: 1,2-benzisothiazolin-3-one (Clariant Japan Co., Ltd., trade name: Nipacide BIT 20). B-1 is a compound represented by the general formula (II) (in the formula, R ¹¹ is hydrogen and n is 0).

B-2: Isothiazolone solution (ROHM & Haas, trade name: Caisson CG-ICP). B-2 is a mixture of 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one.

B-3: Neoron M-10 (ROHM & Haas). B-3 is 2-methyl-4-isothiazolin-3-one.

B-4: Urea (Kanto Chemical)

B-1 corresponded to the component (B) of the present invention, but B-2 to B-4 did not correspond to the component (B).

[(C) component]
The following C-1 was used.

C-1: Nonionic surfactant (polyoxyalkylene alkyl ether): 60 mol of polyoxyethylene isotridecyl ether EO (60 mol of ethylene oxide (EO) added to BASF's lutenzole TO3)

[(D) component]
The following D-1 was used.

D-1: 2-Phenoxyethanol (Kanto Chemical Co., Inc.)

[Method for preparing amino-modified silicone composition]
(1) Preparation of Emulsion of Component (A) 150 g of component (A) was dispersed in 40 g of component (C) to form a dispersed oil phase. Next, the dispersed oil phase was emulsified and dispersed in 300 g of the aqueous phase charged in the emulsifier vessel to obtain 0.5 L of the modified silicone emulsion. Then, 2.5 g of the component (D) was added and stirred.
The emulsifying machine used for emulsification and dispersion was a Robomix (manufactured by Tokushu Kagaku Kogyo) homomixer. The rotor diameter was φ25 mm, the clearance with the stator was 0.5 mm, and the capacity of the vessel was 0.5 L.

(2) Preparation of amino-modified silicone composition
98.5 g of the emulsion of the component (A) is placed in a 200 ml beaker, then the component (B) is added, ion-exchanged water is further added so that the total mass becomes 100 g, and the mixture is stirred to form an amino having the composition shown in Table 1. Modified silicone compositions (Examples 1 to 5 and Comparative Examples 1 to 4) were obtained.
In Table 1, the numerical values of the components (A), (B), (C) and (D) are the blending amount (% by mass) with respect to the total mass of the amino-modified silicone composition.
In Table 1, "(A) / (B)" indicates the mass ratio of the component (A) to the component (B).
In Table 1, pH is a value at 25 ° C.

[Evaluation method of amino-modified silicone composition]
The yellowing of the amino-modified silicone composition was evaluated by the following procedure.

The amino-modified silicone composition was stored in a glass container having an internal volume of 100 mL and sealed, and used as a “pre-storage sample”.
The amino-modified silicone composition was placed in a glass container having an internal volume of 100 mL, sealed, and then stored under the condition of 40 ° C. for 4 months, which was referred to as a “sample after storage”.
The color change of the "post-storing sample" based on the color of the "pre-storing sample" was evaluated according to the following three-step evaluation criteria. Based on the average value of the evaluation results of 10 people, the judgment was made according to the following criteria. The determination results are shown in Table 1 as "evaluation of yellowing after storage". In terms of product value, ○ is acceptable.

[Evaluation criteria]
◯: It is recognized as equivalent to the sample before storage.
Δ: Yellowing has occurred as compared with the sample before storage.
X: Yellowing occurs significantly compared to the sample before storage.

The present invention can be used in the field of products containing amino-modified silicone (textile product treatment agent, etc.).

Claims (11)

Amino-modified silicone composition
The following components (A), (B) and (D):
(A) Amino-modified silicone ,
(B) A compound represented by the following formula (II)

(During the ceremony,
R ¹¹ has a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aralkyl group having 1 to 12 carbon atoms, or an aralkyl group having 3 to 20 carbon atoms. It is a cycloalkyl group of
X is a halogen, nitro, cyano or an alkoxy group having 1 to 8 carbon atoms.
n is an integer from 0 to 4. ) And ,
(D) Contains a water-soluble organic solvent having a hydroxyl group and / or an ether group ,
(A) content of the component, Ri 15-70% by mass relative to the total weight of the amino-modified silicone composition,
Component (D) Ru der aromatic ethers, amino-modified silicone composition. The amino-modified silicone composition according to claim 1, which is used for producing a final product containing amino-modified silicone. The amino-modified silicone composition according to claim 2, wherein the final product containing the amino-modified silicone is a detergent or a textile treatment agent. The amino-modified silicone composition according to any one of claims 1 to 3, wherein the component (A) is an amino-modified silicone oil. The amino-modified silicone composition according to claim 4, wherein the amino-modified silicone oil has a kinematic viscosity of 100 to 20000 mm ^{2 / s at 25 ° C.} The amino-modified silicone composition according to claim 4 or 5, wherein the amino equivalent of the amino-modified silicone oil is 100 to 10,000 g / mol. The amino-modified silicone composition according to any one of claims 1 to 6, wherein the component (B) is 1,2-benzisothiazolin-3-one. The amino-modified silicone composition according to any one of claims 1 to 7, wherein the mass ratio ((A) / (B)) of the component (A) to the component (B) is 300 to 3000. The amino-modified silicone composition according to any one of claims 1 to 8, further comprising (C) a surfactant. The amino-modified silicone composition according to claim 9, wherein the component (C) is a nonionic surfactant. A method for suppressing yellowing of an amino-modified silicone or a composition containing the amino-modified silicone.
(A) Amino-modified silicone or a composition containing the amino-modified silicone,
(B) A compound represented by the following formula (II)

(During the ceremony,
R ¹¹ has a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aralkyl group having 1 to 12 carbon atoms, or an aralkyl group having 3 to 20 carbon atoms. It is a cycloalkyl group of
X is a halogen, nitro, cyano or an alkoxy group having 1 to 8 carbon atoms.
n is an integer from 0 to 4. )
A method comprising the step of mixing with.