KR970000404B1 - Method for manufacturing aminosilicone emulsion - Google Patents

Abstract

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Description

[Name of invention]

Process for preparing amino silicone particulate emulsion

Detailed description of the invention

The present invention relates to a process for preparing amino silicone fine emulsion, which is excellent in storage stability, dilution stability, mechanical stability, has a transparent appearance, and can be most suitably used as a fiber treatment agent, a release agent, a brightening agent, and the like.

As a conventional method for producing an amino silicone emulsion, liquid amino silicone is emulsified and dispersed in water using an emulsifier, for example, a device capable of applying high shear force such as a homer mixer colloid mill or a stirring device such as a propeller blade. Methods of making are known.

However, the amino silicone emulsion prepared in this way has a large average particle diameter of 0.5 or more, poor storage stability and dilution stability, in particular due to mechanical occupancy, and, for example, when processing a fiber, etc. There was a drawback that the emulsion was broken by the rotating roller, the treatment was uneven, and problems such as contamination of the roller were likely to occur.

In addition, as a method for producing an amino silicone emulsion, a method of production by a so-called emulsion polymerization method, which is polymerized and polymerized with a strong alkali catalyst in an emulsion dispersion system using low molecular cyclic siloxanes and aminosilanes as starting materials (JP-A-56-38609) Is also known. In this method, the emulsion particle diameter could be obtained relatively small (0.1-0.2 µm), and the storage stability and the dilution stability were improved, but the stability to the strong mechanical shear was still insufficient. In addition, the emulsion polymerization method has an inherent problem that about 10% of the low molecular cyclic siloxane, which is a starting material, remains in the manufacturing process, and the residual low molecular siloxane is volatilized using the obtained emulsion, and white powder is produced by thermal oxidation in a drying process. There is a problem in that various inconveniences occur, such as the rejection of the paint that is attached to the surrounding surface occurs, such as a bad contact of the electrical equipment existing around.

Therefore, improvement of the manufacturing method of amino silicone fine particle emulsion with high stability and good usability has been desired.

Disclosure of Invention It is an object of the present invention to provide an improved method for preparing an amino silicone particulate emulsion having excellent storage stability, dilution stability and mechanical stability and good usability in view of the above problems.

3, 0

y3, 0x+y

3임]로 표시되는 아미노 실리콘 및(또는) 상기 일반식(1)로 나타낸 아미노 실리콘과

또는

(여기서, R⁷은 1가의 유기기임)로 나타낸 모노에톡시 화합물과의 반응물인 에폭시 변성 아미노 실리콘을 출발 물질로 사용하고, 계면 활성제를 상기 출발 원료(즉, 일반식(1)의 아미노 실리콘, 에폭시 변성 아미노 실리콘)을 합계량 100중량부에 대해 10중량부 이상으로 첨가하고, 아미노 실리콘 및(또는) 에폭시 변성 아미노 실리콘을 수중에 유화 분산시킨 다음, 이 유화 분산 수용액 산성 물질을 상기 출발 원료(즉, 일반식(1)의 아미노 실리콘 및 에폭시 변성 아미노 실리콘) 분자 중의 원자에 대해 0.1몰당량 이상이 되도록 첨가시킨 후, 가열 숙성을 (바람직하게는 50 내지 90℃에서 1시간 이상)시킴으로써, 평균 입경이 0.1 이하이고, 저장 안정성, 희석 안정성 및 기계 안정성이 우수하고, 또한 외관이 투명한 아미노 실리콘 미립자 에멀젼을 얻을 수 있음을 발견했다.[In the formula R ¹ is C 1 hydrocarbon group of 1 to 20, a hydroxyl group or -OR ¹ (wherein R ¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms), and, A is the formula R ² (NR ³ R ⁴⁾ zNR ⁵ R ⁶ , wherein R ² and R ⁴ are each a divalent hydrocarbon group having 1 to 6 carbon atoms, R ³ , R ⁵ and R ⁶ are each hydrogen or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and z is An amino alkyl group represented by 0 to 5), 0x

3, 0

y3, 0x + y

3] and the amino silicone represented by the general formula (1)

or

Epoxy-modified amino silicone, which is a reactant with a monoethoxy compound represented by (wherein R ⁷ is a monovalent organic group), is used as a starting material, and a surfactant is used as the starting material (ie, amino silicone of general formula (1)). And 10 parts by weight or more of epoxy-modified amino silicone) in total with respect to 100 parts by weight in total, and emulsifying and dispersing amino silicone and / or epoxy-modified amino silicone in water. That is, after adding so that it may become 0.1 mol equivalent or more with respect to the atom in the molecule | numerator of amino silicone and epoxy modified amino silicone of General formula (1), and heat-aging (preferably 1 hour or more at 50-90 degreeC), the average The particle size of 0.1 or less, excellent in storage stability, dilution stability and mechanical stability, and the transparent appearance of amino silicone particulate emulsion can be obtained It was found.

In other words, the amino silicone fine particle emulsion obtained by the above method has an average particle diameter of 0.1 μm or less as described above, and the emulsion particles are very fine, so that various stability is significantly improved as compared with the emulsion produced by the conventional method. For example, storage stability does not occur in emulsion separation or the like even in a period of one year or more at room temperature, and the long-term stability of about two times or more is improved compared with the conventional one. In addition, dilution stability and oil spots are not generated. In particular, mechanical stability does not cause any problems such as emulsion breakage or uneven treatment and contamination of the rollers in the high-speed rotating roller as in the prior art. Moreover, the amino silicone particulate emulsions that can be prepared according to the present invention are made into fine particles and the appearance becomes transparent to translucent in conventional suspensions, so that when the other combination components are transparent, no appearance damage occurs. It is a useful particulate emulsion having properties suitable for applications such as brighteners.

Hereinafter, the present invention will be described in more detail.

As described above, the method for producing the amino silicone particulate emulsion according to the present invention adds 10 parts by weight or more of surfactant to 100 parts by weight of the total amount of amino silicone and epoxy modified amino silicone to amino silicone and / or epoxy modified amino silicone. Emulsifying and dispersing amino silicone and / or epoxy modified amino silicone in water, and then adding 0.1 molar equivalents or more to the atoms in the amino silicone and epoxy modified amino silicone and epoxy modified amino silicone molecules in the emulsion dispersion aqueous solution. Subsequently, heat aging is carried out.

In this case, the amino silicone used as the starting material in the present invention can be represented by the following general formula (1).

Wherein R ¹ is an alkyl group such as methyl group, ethyl group, propyl group, octyl group and lauryl group, aryl group such as alkenyl group such as vinyl group and aryl group, phenyl group, tolyl group and naphthyl group, cyclopentyl group and cyclo A cycloalkyl group such as a hexyl group, or a C1-C20 monovalent hydrocarbon group, a hydroxyl group or -OR ¹ in which some or all of the above hydrogen is substituted with halogen, wherein R ¹ is a C1-C20 monovalent hydrocarbon group Qi.

) 등이 있으며, 상기에 한정되는 것은 아니다.In addition, A is an amino alkyl group represented by the general formula -R ² (NR ³ R ⁴ ) zNR ⁵ R ⁶ , and R ² and R ⁴ each have 1 to 6 carbon atoms such as methylene group, ethylene group, propylene group and phenylene group. Is a divalent hydrocarbon group, R ³ , R ⁵ and R ⁶ are each hydrogen or a monovalent hydrocarbon having 1 to 20 carbon atoms such as R ^1, and z is an integer of 0 to 5. Examples of such amino group _{-C 3 H 6 NH 2, -C} 3 H 6 NHC 2 H4NH 2, -C 6 H 12 NHC 2 H 4 NH 2, -C 3 H 6 (NHC 2 H 4) 2 NH 2, -C ₃ H ₆ (NHC ₂ H ₄ ) ₃ NH ₂ , -C ₂ H ₄ NHC ₂ H ₄ NH ₂ , -CH ₂ NHC ₂ H ₄ N (C ₄ H ₉ ) ₂ , -C ₃ H ₆ NH ( CH ₂

) And the like, but are not limited to the above.

3, 0

y3, 0x+y

3이다.And x, y is 0x

3, 0

y3, 0x + y

3

The amino silicone of the general formula (1) is generally blocked at the end of the silicone chain with a trimethylsilyl group, but if the terminal is blocked with a receiver or an alkoxy group, etc. may be used.

In the present invention, the amino silicone of the general formula (1) and the following formula as starting materials

Epoxy modified amino silicones produced by reacting a monoethoxy compound and the like can also be used.

Herein, the substituent R ⁷ in the mono epoxy compound is a monovalent organic group containing no epoxy group, preferably a linear or branched hydrocarbon group or a polyepoxyalkylene group, and examples of the mono epoxy compound include And compound of formula.

When obtaining the said epoxy modified amino silicone, the ratio of the amino silicone of General formula (1) and the said epoxy compound is 0.01-20 mol amount of epoxy in a mono epoxy compound with respect to one nitrogen atom contained in amino silicone, especially 0.1- A 10 molar amount range is preferred.

And the amino silicone of General formula (1) and the said mono epoxy compound are mixed, and it heats at 40-80 degreeC, and following reaction formula is shown

The reaction proceeds to obtain an epoxy modified amino silicone in which the active hydrogen group of the amino group in the amino silicone molecule is block-modified with an epoxy compound as a reaction product.

In the present invention, as the starting material, only one kind or a mixture of the amino silicones of the general formula (1) and the epoxy modified amino silicones can be used, or amino silicones and epoxy modified amino silicones can be used in combination (hereinafter, referred to as starting materials). Are collectively called amino silicones).

In the manufacturing method of the amino silicone microparticles | fine-particles emulsion of this invention, surfactant is added to the said starting raw material first, and amino silicones are disperse | distributed in water.

The surfactant used herein is not particularly limited, and conventionally known ones such as various nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric ionic surfactants can be used. Specific examples of the surfactant include nonionic surfactants such as polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, sorbitan fatty acid ester, sucrose fatty acid ester, alkyl sulfate, alkyl phenyl sulfonate and polyoxy Anionic surfactants such as ethylene alkylphenyl sulfate, amphoteric surfactants such as alkyltrimethyl ammonium chloride, dialkyldimethyl ammonium chloride and benzyltrimethyl ammonium chloride, and amphoteric ionic surfactants such as alkyl betaine and alkyl amino acids. And one or two or more thereof can be used, and among them, it is preferable to use a nonionic surfactant in view of its compatibility with other ionic components. Particularly, One or two or more of the total values 12 to 15 Most preferably used to

In addition, the surfactant is added in an amount of 10 parts by weight or more, preferably 10 to 100 parts by weight with respect to 100 parts by weight of amino silicones, and when the amount is 10 parts by weight or less, it is difficult to obtain a fine particle emulsion having an average particle diameter of 0.1 µm or less. If it is more than the weight part, there is no problem in preparing the fine particle emulsion, but it remains as a non-volatile component when treating fibers and the like, which hinders the properties of amino silicones.

In the present invention, the method of emulsifying and dispersing amino silicones in water is not particularly limited, but in general, amino silicones and surfactants are homogenized by a stirring device such as a propeller blade or a homer mixer, and water is gradually added to the solution while stirring. Most preferred is the method of adding to form an O / W emulsion. The water capacity may be adjusted based on the concentration of the preferred amino silicones, but is usually used in an amount of 100 to 1000 parts by weight based on 100 parts by weight of the amino silicones.

Next, in the present invention, the pH is adjusted by adding an acidic substance to the amino silicones emulsified and dispersed in water, and when the acidic substance is added, the amino group in the amino silicones reacts with the acidic substance to form an amine salt. The hydrophilicity of silicones is increased, and a particulate emulsion can be produced by the following heat aging process.

In this case, examples of acidic materials include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as formic acid, acetic acid, propionic acid, lauric acid and stearic acid, and the like. Lower fatty acids are preferred.

In addition, the acidic substance capacity is used in the range of 0.1 molar equivalents or more, preferably 0.11 to 1 molar equivalents, relative to the nitrogen atom in the amino silicon molecules. If the amount is less than 0.1 molar equivalents, the hydrophilicity of the amino silicon is insufficient and the average particle size is 0.1. A particulate emulsion of less than or equal to micrometers cannot be obtained. If the capacity of the acidic substance is 0.1 molar equivalent or more, there is no particular limitation, but 0.1 to 1 mole in that the acidic substance is generated as a dilute or non-dilute component during the treatment of fibers and the like and may cause deterioration of the properties of amino silicones. The equivalent is more preferable.

In the present invention, the acidic substance is added to the aqueous emulsion dispersion of amino silicones as described above, followed by heat aging. By carrying out this heat aging step, the reaction between the amino group and the acidic substance in the amino silicones described above, that is, the hydrophilicity of the amino silicones is promoted. Due to the hydrophilicity and thermal energy of heating of these amino silicones, the emulsion particles are finely cut by water, and the emulsion particles are subdivided to form fine particles.

Here, the heat aging is preferably performed at 50 to 90 ° C, particularly at 60 to 80 ° C, for at least 1 hour, particularly at 3 to 20 hours. If the temperature is 50 ° C. or less or the aging time is 1 hour or less, the desired particulate emulsion may not be obtained, and the emulsion may be destroyed at a high temperature of 90 ° C. or more.

And it is most preferable to carry out heating aging, stirring the emulsion dispersion liquid of amino silicones with stirring apparatuses, such as a propeller blade.

As described above, the amino silicone fine particle emulsion obtainable by the method of the present invention can be used by itself in various applications such as a fiber treating agent, a releasing agent and a brightening agent, and, if necessary, other aqueous treating agents such as water repellents, absorbents, and the like. , Antistatic agent and flame retardant may be added and used.

As described above, according to the production method of the present invention, an amino silicone fine particle emulsion having an average particle diameter of 0.1 µm or less and excellent in storage stability, dilution stability and mechanical stability can be obtained. In addition, since the emulsion obtained by the method of the present invention is transparent or translucent in appearance, no damage is caused even when used in combination with other ingredients. It can provide amino silicone characteristics, such as a streamability, etc. sufficiently, and can be usefully used as a fiber processing agent, a mold release agent, a gloss agent, etc.

[Example, Comparative Example]

The following examples and comparative examples specifically illustrate the present invention, but the present invention is not limited to the following examples.

Example 1

Formula

150 g of amino silicone and 50 g of polyoxyethylene nonylphenyl ether (HLB = 13.3) represented by the above were placed in a 2-liter beaker and uniformly mixed at 50000 rpm for 5 minutes with a Homer mixer (manufactured by Tokushu Chemical Co., Ltd.), followed by stirring 800 g of water was slowly added thereto to uniformly emulsify and disperse (emulsion A).

Also under the same agitation as above, 4.6 g of acetic acid (1.0 molar equivalent per atom in amino silicon) was added, followed by stirring for 10 minutes (emulsion B).

The emulsion B was transferred to a 2-liter flask and heated and aged at 80 ° C. for 4 hours while stirring at 100 rpm of a propeller blade to obtain an amino silicone fine particle emulsion (emulsion C).

Comparative Example 1

As an example of the emulsion polymerization method, a beaker for 2 liters of octamethylcyclotetrasiloxane 140.6g N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane 7.8g, hexamethyldisiloxane 1.5g, and lauryltrimethyl ammonium chloride 50g After mixing uniformly at 5000 rpm for 5 minutes with a Homer mixer, 781 g of water was gradually added under the same stirring, and then emulsified and dispersed uniformly, transferred to a 2-liter flask and 19 g of potassium hydroxide was stirred at 100 rpm with propeller blades. The thing melt | dissolved in was added. Subsequently, the mixture was heated at 80 ° C. for 40 hours for polymerization, held at 30 ° C. for 10 hours, and then neutralized with 2 g of acetic acid (emulsion D).

Comparative Example 2

An emulsion was prepared using the same method as in Example 1, except that 0.3 g of acetic acid (0.065 molar equivalents relative to the atoms in the amino silicones) was used (emulsion E).

Comparative Example 3

An emulsion was prepared using the same method as Example 1 except that 10 g of the surfactant was used (emulsion F).

The evaluation results of the emulsions obtained in Example 1 and Comparative Examples 1 to 3 are shown in Table 1 below.

Appearance: The emulsion just after manufacture was observed visually.

Average particle size: measured by a subclone particle analyzer (Nikka Kasha).

Storage stability: 100 g of the emulsion was left in a glass bottle at room temperature and visually observed.

Dilution Stability: The emulsion was diluted to 2% with water and after 24 hours the surface condition was visually observed.

Mechanical stability: Dilute the emulsion to 2% with water and stir for 10 minutes at 8000 rpm of Homer mixer, then visually observe the surface condition.

As a result of Table 1, when manufactured by the conventional emulsion polymerization method (comparative example 1), and when the addition amount of an acidic substance and the addition amount of surfactant are outside the range of this invention (comparative examples 2 and 3), the average particle diameter is 0.1 micrometer or less The fine particle emulsion cannot be obtained, and the emulsion stability obtained by the method of the present invention (Example 1, Emulsion C) is low in the appearance of milky white, and the mechanical stability is low. It was confirmed that it is stable for a long time of about 2 times or more, is excellent in storage stability, and the dilution stability is very good without the occurrence of oil spots, and the mechanical stability is also good.

Example 2

Formula

An emulsion was prepared in the same manner as in Example 1, except that 150 g of amino silicone represented by was used, and 1.3 g of formic acid (0.5 molar equivalent to atoms in amino silicon) was used as an acidic substance.

Example 3

Formula

Example 1, except that 150 g of amino silicone and 15.0 g of polyoxyethylene lauryl ether (HLB = 14.0) were used, and 1.1 g of formic acid (0.1 molar equivalent to atoms in amino silicon) was used as an acidic substance. An emulsion was prepared in the same manner as in the following.

Example 4

의 모노에폭시 화합물 11.4g(아미노 실리콘 중의 원자에 대하여 1.0몰당량)을 넣고, 질소가스 통기하의 60℃에서 5시간 동안 반응시켜, 불휘발분(150℃/3시간) 97.6%, 점도 15400cs의 아미노 실리콘을 얻었다. 이 아미노 실리콘을 사용하여 실시예 1과 같은 방법으로 에멀젼을 제조하였다.300 g of amino silicone used in Example 1 in a 1 liter glass reactor equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet and formula

11.4 g of monoepoxy compound (1.0 molar equivalent to atoms in amino silicon) was added and reacted at 60 ° C. for 5 hours under aeration of nitrogen gas to yield 97.6% of nonvolatile matter (150 ° C./3 hours) and an amino silicon having a viscosity of 15400cs. Got. Using this amino silicone, an emulsion was prepared in the same manner as in Example 1.

Table 2 shows the results of the evaluation of the emulsions obtained in Examples 2 to 4.

Claims (1)

General formula (1)

[In the formula, R ¹ is C 1 is a hydrocarbon group of 1 to 20, a hydroxyl group or -OR '(wherein R' is a monovalent hydrocarbon group having 1 to 20 carbon atoms), and, A is the formula -R ² (NR ³ R ⁴ ) zNR ⁵ R ⁶ , wherein R ² and R ⁴ are each a divalent hydrocarbon group of 1 to 6 carbon atoms, R ³ , R ⁵ and R ⁶ are each hydrogen or a monovalent hydrocarbon group of 1 to 20 carbon atoms, z Is an amino alkyl group represented by

Amino silicone represented by the formula [I] and / or amino silicone represented by the formula (1)

or

10 parts by weight or more of the surfactant is added to 100 parts by weight of the total amount of the amino silicone and the epoxy modified amino silicone to the epoxy modified amino silicone, which is a reactant with the monoethoxy compound represented by R ⁷ is a monovalent organic group. And emulsifying and dispersing amino silicone and / or epoxy-modified amino silicone in water, and then adding an acidic substance to the emulsion dispersion aqueous solution at least 0.1 molar equivalents to N atoms in the amino silicone and epoxy-modified amino silicone molecules, followed by heating. A method for producing an amino silicone fine particle emulsion, characterized by aging.