KR20140114563A - Silicon Copolymer, its Manufacturing Method and Fabric Softner Using the Same - Google Patents

Abstract

The present invention relates to a quaternary amino-modified silicon copolymer with excellent hygroscopicity and flexibility. The quaternary amino-modified silicon copolymer manufactured in the use of the present invention is assigned with excellent hygroscopicity by quadrupling amine and provides greater tactile sensation, flexibility and hygroscopicity when being treated with high silicon content.

Description

TECHNICAL FIELD [0001] The present invention relates to a modified silicone copolymer having excellent hygroscopicity and flexibility connected to a quaternary amino group and a method for producing the modified silicone copolymer.

The present invention relates to a quaternary ammonium-modified silicone copolymer excellent in hygroscopicity and excellent in flexibility, and more particularly, to a quaternary ammonium-modified silicone copolymer having an epoxy- The quaternary amine of the random block copolymer formed through the epoxy bond ringed by the amine quaternarizes to impart excellent hygroscopicity and the silicone compound having excellent flexibility provides excellent tactile feeling, continuous flexibility and hygroscopicity at the time of fiber treatment .

U.S. Patent No. 4,459,382A discloses a process for preparing a silicone compound that increases the hygroscopicity by introducing a polyalkylene oxide or a carboxy group into the silicone.

World Patent No. 2,009,134, 364 A2 also discloses non-hydrolyzable polyalkylene oxide modified silicone compounds bonded with amine groups to provide excellent fabric softener and cosmetic oil.

Korean Laid-Open Patent Application No. 10-2005-0136021 discloses a process for preparing aminopolysiloxane glycerol carbonate derivatives to have hygroscopicity and low sulfur modification.

However, in the above-described related arts, a method of manufacturing a silicone softener is based on hydrophilicity of a polyalkylene oxide or introducing an amino group or an amido group in order to improve hygroscopicity. The introduction of a non-polar hydrophilic group is helpful in improving flexibility and stability, but it is not sufficient to impart good hygroscopicity.

Accordingly, U.S. Patent No. US2007212326A1 discloses that a quaternary ammonium salt is reacted with an epoxy group-introduced polysiloxane to introduce a quaternized amino group-linked modified polysiloxane.

Korean Laid-open Patent Application No. 10-2003-7014806 discloses a process for producing a non-hydrolyzable block copolymer in an alternating unit by combining a polysiloxane and a terminal epoxy polyalkylene oxide with an amine and quaternizing the amine to impart hygroscopicity Respectively.

However, it is difficult to control a quaternary ammonium group produced by using a linear polysiloxane to impart hygroscopicity to a large amount, and when it is introduced in a large amount, the molecular weight of the polysiloxane becomes small and flexibility is lowered. Further, in order to introduce an epoxy group into the linear polysiloxane, a tetramethyldisiloxane material must be used, and the cost of the material is high, so that the unit cost of the product is high.

Therefore, the present invention relates to a siloxane-polyalkylene oxide copolymer production technology containing quaternary amine having excellent hygroscopicity and flexibility by imparting a large amount of quaternization with an economical side chain polysiloxane and reacting with a linear polyalkylene oxide Has been urgently required.

A silicone softener for imparting excellent hygroscopicity and flexibility is prepared by inducing a combination of a linear silicone compound and a linear polyalkylene oxide. The linear silicone compound is excellent in flexibility and low in risk of gum-up or gellation, and has a high degree of preference. However, it has a disadvantage that it is expensive and difficult to control the functional groups capable of imparting properties.

The object of the present invention is to provide a modified silicone copolymer having good hygroscopicity, flexibility, low risk of inspection and gelation and having continuous flexibility, a method for producing the same, and a fabric softener containing the same.

In order to accomplish the object of the present invention, a side chain epoxy polyalkylene oxide-modified silicone compound represented by the following general formula (1) and a terminal amino group compound represented by the following general formula (3) are formed by copolymerization reaction through an amine ring- The amino-modified silicone copolymer is characterized in that the formula (2) participates in the copolymerization reaction selectively.

In the above formula

R ¹ is an alkyl group containing 1 to 4 carbon atoms, and R ² , R ³ Each independently represents a divalent hydrocarbon group containing 1 to 10 carbon atoms, R ⁴ is an alkyl group, allyl group or alcohol group containing 1 to 10 carbon atoms, and X and Y are independently formed by epoxide ring opening a divalent organic _{group, -CH 2 CH (OH) (} CH 2) v CH (OH) CH 2 -, -CH [CH 2 OH] (CH 2) v CH [CH 2 OH] -, -CH 2 CH (OH) (CH ₂ ) _v CH [CH ₂ OH] -, - (CH ₂ ) _v -OCH ₂ CH (OH) CH ₂ -, wherein v is 2 to 6 and Z A is an integer of 2 to 4, preferably 2 to 3, b is an integer of 0 to 100, and x is an integer of 1 to 3, Y is a positive integer from 1 to 300, and z is a positive integer from 1 to 3

The amine Z of the above formula 3 is a primary or secondary amine group; Formula 1 and 2 in the X, Y will epoxide group, the copolymer in the reaction during the ring-opening epoxide group _{-CH 2 CH (OH) (CH} 2) v CH (OH) CH 2 -, -CH [CH 2 OH] _{(CH 2) v CH [CH} 2 OH] -, -CH 2 CH (OH) (CH 2) v CH [CH 2 OH] -, - (CH 2) v -OCH 2 CH (OH) CH 2 - in Wherein at least one structure selected is formed, wherein v is preferably a positive integer of 2 to 6.

It is preferable that X and Y, which are the epoxy groups of the formulas (1) and (2), are randomly bonded to each other through a ring-opening reaction by Z, which is an amine group of the formula (3).

Wherein the epoxide group X is selected from an allyl glycidyl ether group and an allyl epoxycyclohexyl group, and the epoxide group Y is selected from a glycidyl ether group, an epoxycyclohexylalkylene group, a w- (3,4) -epoxy (3,4-epoxycyclohexyl) -b-methylethylene, or b- (3,4-epoxy-4-methylcyclohexyl) -b-methylethylene Do.

In the formula (2), the polyalkylene oxide compound represented by (C _a H _2a O) is composed of ethylene oxide (a = 2) or propylene oxide (a = 3) in random or block form, or propylene oxide 3) alone.

The amine group connected by the amine group Z is preferably protonated or quaternized.

It is preferable that the amino compound of Formula 3 is selected from a hydrocarbon amine or a hydrocarbon alcohol amine.

It is preferable that the amine is selected from ethylene amine, propylene amine, butylene amine, hexylene amine, methanol amine, ethanol amine, propanol amine, butanol amine.

(A) preparing a side chain epoxy polysiloxane-modified polysiloxane represented by the following formula (1) by reacting a side chain hydrosene polysiloxane having an epoxy group and a polysiloxane group simultaneously in a side chain under a predetermined catalyst; And (B) reacting the side chain epoxy polysiloxane-modified polysiloxane with the amino compound of formula (3) in a predetermined solvent to cause an epoxy ring-opening reaction with an amine of the amino compound of formula (3) to cause a copolymerization reaction; And (C) quaternization of a copolymer containing an amino group. The present invention also provides a method for producing a quaternary amino-modified silicone copolymer.

[Chemical Formula 1]

(3)

[ZR ⁴ ]

In the above formula

R ¹ is an alkyl group containing 1 to 4 carbon atoms,

R ² , R ³ Each independently a divalent hydrocarbon group containing 1 to 10 carbon atoms,

R ⁴ is a divalent hydrocarbon group containing 2 to 10 carbon atoms or a hydrocarbon alcohol which can be represented by [- (CH ₂ ) _n OH]

X 2 is an independently formed by epoxide ring opening and an organic _{group, -CH 2 CH (OH) (} CH 2) v CH (OH) CH 2 -, -CH [CH 2 OH] (CH 2) v CH _{[CH 2 OH] -, -CH} 2 CH (OH) (CH 2) v CH [CH 2 OH] -, - (CH 2) v -OCH 2 CH (OH) CH 2 - will be selected from the group consisting of ,

Wherein v is from 2 to 6,

Z is an amine group, which is any one of primary, secondary and tertiary amines,

a is a positive integer of 2 to 4, preferably 2 to 3, b is an integer of 0 to 100, x is a positive integer of 1 to 100, y is a positive integer of 1 to 100, z is a positive integer from 1 to 50, and m is a positive integer from 1 to 100

(2)

_{[YO (C a H 2a O} ) b Y]

The side chain hydrazone polysiloxane is preferably a partially branched side chain polysiloxane.

The side chain epoxy polysiloxane-modified polysiloxane is preferably one obtained by reacting the partial hydrogen polysiloxane with an epoxide group and then reacting the one-end vinyl polysiloxane to secure a non-linear polysiloxane structure, and the step (B) is preferably carried out after the pre- .

It is preferable that the catalyst is a platinum catalyst, and the solvent is any one of alcohol or a mixed solvent of alcohol and water.

In order to accomplish the object of the present invention, there is provided a fabric softener composition comprising the amino-modified silicone copolymer.

The random amino-modified silicone copolymer of the present invention has the following effects.

First, the amino-modified silicone copolymer of the present invention quaternarizes amines, imparts excellent hygroscopicity, and is free to control the molecular weight of silicon, thereby providing excellent tactile feel, flexibility and hygroscopicity in fiber treatment.

Second, the amino-modified silicone copolymer of the present invention is capable of controlling various functional groups by copolymerizing a pre-reacted silicone-epoxy / polysiloxane-modified copolymer with an amine.

Third, the amino-modified silicone copolymer of the present invention can maximize the self-emulsifying property by quaternizing the amine group sufficiently secured, and can impart excellent hygroscopicity to the fiber treatment.

The present invention also provides use as a softener comprising the copolymer, particularly as a non-contaminated fabric softener.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 illustrates one embodiment of the method of making a composition of the present invention.

Hereinafter, the present invention will be described in detail.

The present invention relates to a resin composition comprising a side-chain epoxy polysiloxane-modified (epoxy and polysiloxane each modified to a branched-chain silicone compound) of the following formula (1), a polysiloxane copolymerized with an amino compound of the formula (3) A random block copolymer using an epoxy ring-opening reaction with an amine is provided.

[Chemical Formula 1]

(2)

_{[YO (C a H 2a O} ) b Y]

(3)

[ZR ⁴ ]

In the above formula

R ¹ is an alkyl group containing 1 to 4 carbon atoms,

R ² , R ³ Are each independently a divalent hydrocarbon group containing 1 to 10 carbon atoms,

R ⁴ is a divalent hydrocarbon group containing 2 to 10 carbon atoms or a hydrocarbon alcohol which can be represented by [- (CH ₂ ) _n OH]

X, Y is a divalent organic group formed by the epoxide ring opening, each _{independently, -CH 2 CH (OH) (} CH 2) v CH (OH) CH 2 -, -CH [CH 2 OH] (CH 2 from the group consisting of _{-) v CH [CH 2 OH} ] -, -CH 2 CH (OH) (CH 2) v CH [CH 2 OH] -, - (CH 2) v -OCH 2 CH (OH) CH 2 ≪ / RTI >

Wherein v is from 2 to 6,

Z is an amine group, which is any one of primary, secondary and tertiary amines,

a is a positive integer of 2 to 4, preferably 2 to 3, b is an integer of 0 to 100, x is a positive integer of 1 to 100, y is a positive integer of 1 to 100, z is a positive integer from 1 to 50, and m is a positive integer from 1 to 100

In the present invention, X in the above formula (1) is introduced by reacting an epoxy compound having an olefin group capable of addition reaction with hydrogen polysiloxane; It has the following example.

Examples of polyalkylene oxide compounds having an epoxy at both ends of the above formula (2) include, but are not limited to, the following compounds.

Examples of the compound having an amine at both terminal ends of the above formula (3) include, but are not limited to, the following compounds.

In the present invention, the following formula (11) can be derived by the combination of the above formula (1) and the above formula (3) or alternatively by the addition reaction of formula (2). In order to obtain flexibility, the linear polyalkylene oxide and the linear polyalkylene oxide represented by the general formula (1) and (2) must have a relative value to silicon. Preferably, the content of the linear polyalkylene oxide in the entire copolymer should be 20 to 50% by weight, and when it is more than 20% by weight, the relative silicone content is low and it is difficult to obtain flexibility. When the content of the linear polyalkylene oxide is 20% by weight or less, it may be difficult to secure the fluidity of the softening agent.

Another important factor controlling the properties of the copolymer may be the difference in degree of polymerization depending on the total amine and epoxy groups. Here, the amine group Z is larger than the sum of X and Y which are epoxy groups, so that a copolymer having an amine group at the terminal can be synthesized.

In Formula 11,

x is a positive integer from 1 to 100, y is a positive integer from 1 to 100, and z is a positive integer from 1 to 50;

R4 is an alkyl group containing from 2 to 10 carbon atoms, or is a hydrocarbon alcohol;

X 'and Y' are ring-opened forms of the epoxide,

Z 'is a secondary or tertiary amine group,

m is a positive integer of 1 to 100,

w is a positive integer from 0 to 50;

The polysiloxane copolymer having a quaternary amino group as in the present invention has stronger ionic properties than the nonionic polysiloxane copolymer having a hydrophilic property, thereby increasing the binding force with water molecules. This strong ionic property allows water molecules to be held on the fiber surface, which can increase the hygroscopicity of the fibers, and the flexibility and softness of silicon can be saved at the same time.

Generally, it is known that the higher quaternary amine groups increase the fiber flexibility. In the present invention, since the side chain hydrazene polysiloxane having many reactors is used, it is possible to control the quaternized amine groups in a wide variety of amounts I have.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 illustrates a method for preparing an exemplary copolymer of the present invention.

(S11) a side chain epoxy polysiloxane-modified polysiloxane of Formula 1 by reacting side-chain hydrogen polysiloxane so as to have both epoxy group and polysiloxane group simultaneously, and reacting the side chain epoxy polysiloxane-modified polysiloxane with the compound of Formula 3 (S12) through an epoxy ring-opening reaction with an amine of the amino compound of the formula (3) in the presence of an amino compound of the formula (3) in the presence of a base, and adding an epoxy polyoxyalkylene composition S13), adding the side chain epoxy polyalkylene oxide modified polysiloxane of Formula 1 further (S14) to react, and performing quaternarization reaction of the amine (S15).

Hereinafter, this will be described in more detail.

An exemplary manufacturing process of the present invention includes a first step of reacting a side chain hydrogen silicone polymer and a cyclosiloxane under an acid catalyst to produce a partial side chain hydrogen silicone polymer; A second step of reacting the partially branched hydrogen silicone polymer with an olefin epoxide and a one-end vinyl polysiloxane in a solvent to prepare an epoxy polysiloxane-modified polysiloxane of Formula 1; And (3) reacting the amino compound of formula (1) with the amino compound of formula (3) in the presence of a solvent to effect addition reaction of the epoxy polyalkylene oxide compound of formula (2) And quaternizing the amine groups of the modified copolymer.

In the first step, in order to synthesize a polysiloxane having a side chain hydrazone functional group at a certain ratio, a side chain hydrosene polysiloxane and a cyclosiloxane are reacted with each other under an acid catalyst to have a hydrosene group of 0.5 to 2.2 mmol / g and a molecular weight of 500 to 10000 .

In the second step, at least two or more olefin epoxides in one molecule are reacted with the partially branched hydrogenpolysiloxane synthesized in the first step, and the remaining hydrosene group and one-end vinyl polysiloxane compound are all adhered to form a silicone copolymer having an epoxy group .

In the third step, the epoxy ring-opening reaction is induced by adding the compound represented by the formula (3) having the amine group in the solvent in the second step to the epoxy ring-opening reaction by adding the polyalkylene oxide compound represented by the formula (2) .

In the fourth step, the amine group is quaternized or protonated to control hygroscopicity.

When the quaternary aminosilicon block copolymer is prepared by the production method according to the present invention, it is possible to control the molecular weight of silicon and has the advantage of securing flexibility. Also, it is easy to control the quaternary ammonium group, which is a hydrophilic group, Respectively.

In addition, the linear polyalkylene oxide compound may be randomly bonded to give insufficient linearity, thereby reducing the risk of inspection or gelation.

The reaction is carried out in an alcohol such as isopropyl alcohol using a solvent in which water, oil and inorganic materials can be suitably mixed, or without a solvent. After termination of the reaction, the solvent may be exchanged with a non-flammable solvent such as water, propylene glycol, and dipropylene glycol. The reaction product may be separated by distilling the solvent under atmospheric or reduced pressure, and the separated reaction product may be a viscous oil or wax depending on the molecular weight and the alkylene oxide content of the copolymer.

The synthesis process of the production process of the present invention and its use are explained in the following examples, but the scope of the present invention is not limited thereto.

Example 1

In the first step, a thermometer, an electric stirrer, a nitrogen bubbler, a condenser and a dropping funnel are prepared in a 1000 mL round bottom flask. To this were added 53 g of a side chain hydrogelpolysiloxane (KF-99, hydrazine = 14 mmol / g, manufactured by Shin-Etsu Co., Ltd.) and 600 g of cyclosiloxane (-OSi (CH ₃ ) _2- ) _n and 7.03 g of acid- , And 50 g of hexamethyldisiloxane were charged, and the temperature was raised to 80 ° C and maintained for 3 hours. After the filter was distilled under reduced pressure to 150 캜, a partial hydrogenated branched polysiloxane having a hydrogen atom number of 1.1 mmol / g and a viscosity of 50 cP was obtained.

In addition, a thermometer, an electric stirrer, a nitrogen bubbler, a condenser and a dropping funnel are prepared in a 1000 mL round bottom flask. To this were added 600 g of cyclosiloxane, 10.8 g of divinyltetramethyldisiloxane and 9 g of hexamethyldisiloxane, and 6.2 g of acid clay as an acid catalyst was added thereto, and the mixture was heated to 80 ° C and maintained for 3 hours. After filtration, the mixture was distilled under reduced pressure to 150 캜 to obtain a side chain vinylpolysiloxane having a vinyl group of 0.18 mmol / g and a viscosity of 50 cP.

In the second step, 300 g of the partially hydrogenated branched polysiloxane synthesized in the first step is put in a 1 L four-necked flask equipped with a stirrer, an addition funnel and a reflux condenser, and 26.37 g of allyl glycidyl ether is added thereto and mixed well. 5 ppm of platinum was added thereto, and the mixture was heated to 80 ° C and maintained for 2 hours. 280 g of the vinylpolysiloxane synthesized in the first step was added thereto. After maintaining the reaction for 3 hours, the hydrosene group was removed by IR, and the reaction was terminated to yield a side chain epoxy polysiloxane To obtain a polysiloxane solution.

In the third step, 5.7 g of monoethanolamine and 82 g of isopropyl alcohol were placed in a 1 L four-necked flask equipped with a stirrer, an addition funnel and a reflux condenser, and the mixture was heated to 80 ° C and stirred. After the side chain epoxy polysiloxane modified 100 g of the polysiloxane solution was added and the reaction was maintained at 80 DEG C for 1 hour. 11.5 g of epoxy polyalkylene oxide (PG-207P, Kukdo Kagaku) at both ends was added and maintained for 1 hour. 100 g of the side chain epoxy polysiloxane- (PG-207P, Kukdo Chemical Co., Ltd.) was added thereto, and the mixture was held for a sufficient time to fully open the epoxy. Check whether the epoxy group is titrated with HBr solution.

In the fourth step, after opening all of the epoxy resin, 2.96 g of 35% hydrochloric acid solution was slowly added to quaternize the remaining amine groups, 37.23 g of dipropylene glycol was added, and then isopropyl alcohol was distilled off under reduced pressure to obtain a pale yellow wax Solution.

Example 2

In the first step, the same hydrogen side chain polysiloxane as in Example 1 was obtained.

In the second step, the same side-chain epoxy polysiloxane-modified polysiloxane solution as in Example 1 was obtained.

In the third step, synthesis was conducted in the same manner as in Example 1 except that 7.85 g of monoethanolamine, 200 g of the total amount of the side-chain epoxy polysiloxane-modified polysiloxane, and 31.6 g of the total amount of epoxy polyalkylene oxide (PG-207P, Otherwise,

In the fourth step, a pale yellow flowable solution was obtained in the same manner as in Example 1 except that 4.08 g of 35% hydrochloric acid solution and 38.98 g of dipropylene glycol were used.

      Example 3

In the first step, the same hydrogen side chain polysiloxane as in Example 1 was obtained.

In the second step, the same side-chain epoxy polysiloxane-modified polysiloxane solution as in Example 1 was obtained.

In the third step, an isopropyl solution was obtained in the same manner as in Example 1.

In the fourth step, 12 g of dimethylsulfate was added to the isopropyl solution synthesized in the third step, and the remaining amine groups were quaternarized by maintaining at 80 ° C for 3 hours, 37.23 g of dipropylene glycol was added Isopropyl alcohol was distilled off under reduced pressure to obtain a brown wax-like solution.

      Example 4

In the first step, the same hydrogen side chain polysiloxane as in Example 1 was obtained.

In the second step, the same side-chain epoxy polysiloxane-modified polysiloxane solution as in Example 1 was obtained.

In the third step, synthesis was conducted in the same manner as in Example 1 except that 7.85 g of monoethanolamine, 200 g of the total amount of the side-chain epoxy polysiloxane-modified polysiloxane, and 31.6 g of the total amount of epoxy polyalkylene oxide (PG-207P, Otherwise,

In the fourth step, 17 g of dimethylsulfate was added to the isopropyl solution synthesized in the third step, and the remaining amine groups were quaternarized by keeping at 80 캜 for 3 hours. Using 38.98 g of dipropylene glycol, Of a flowable solution.

Example 5

Synthesis was carried out in the same manner as in Example 1, and in the third step, a pale yellow flowable solution was obtained by using 9.45 g of amine hexylamine.

Example 6

In the third step, the amine was synthesized in the same manner as in Example 1, and 13 g of hexylamine was used to obtain a pale yellow flowable solution

Example 7

In a fourth step, the amine was quaternized with 12 g of dimethylsulfate to give a brown flowable solution.

Example 8

In a fourth step, the amine was quaternized with 17 g of dimethylsulfate to give a brown flowable solution.

Example 9

In the first step, a thermometer, electric stirrer, nitrogen bubbler, condenser and dropper funnel are prepared in a 1000 mL round bottom flask. To this was added 107 g of side chain hydrosene polysiloxane (KF-99, hydrazine = 14 mmol / g of Shin-Etsu Co., Ltd.) and 600 g of cyclosiloxane ((-OSi (CH ₃ ) _2- ) _n ) and 7.07 g of acid clay acid clay, 30 g of hexamethyldisiloxane was added and the temperature was raised to 80 占 폚 and maintained for 3 hours. After filtration, the mixture was distilled under reduced pressure to 150 캜 to obtain a partial hydrogenated branched polysiloxane having a hydrazine group of 2.2 mmol / g and a viscosity of 45 cP.

In addition, a thermometer, an electric stirrer, a nitrogen bubbler, a condenser and a dropping funnel are prepared in a 1000 mL round bottom flask. To this were added 600 g of cyclosiloxane, 20.8 g of divinyltetramethyldisiloxane and 17 g of hexamethyldisiloxane, and 6.4 g of an acid clay acid catalyst was added. The temperature was raised to 80 ° C and the reaction was maintained for 3 hours. After filtration, the mixture was distilled under reduced pressure to 150 캜 to obtain a one-end vinyl polysiloxane having a vinyl group of 0.35 mmol / g and a viscosity of 30 cP.

In the second step, 300 g of the partially hydrogenated branched polysiloxane synthesized in the first step is put into a 1 L four-necked flask equipped with a stirrer, an addition funnel and a reflux condenser, 36.7 g of allyl glycidyl ether is added and mixed well. 5 ppm of platinum was added thereto, and the mixture was heated to 80 ° C. and maintained for 2 hours. 150 g of the vinylpolysiloxane synthesized in the first step was added thereto. After maintaining the reaction for 3 hours, the hydrosene group was removed by IR, To obtain a modified polysiloxane solution.

In the third step, 8.5 g of monoethanolamine and 82 g of isopropyl alcohol were placed in a 1 L four-necked flask equipped with a stirrer, an addition funnel and a reflux condenser, and the mixture was heated and stirred at 80 캜. After the side chain epoxy polysiloxane modified After the addition of 100 g of the polysiloxane solution, the reaction was maintained at 80 DEG C for 1 hour. 19.7 g of epoxy polyalkylene oxide (PG-207P, Kukdo Kagaku) at both ends was added and maintained for 1 hour. 100 g of side chain epoxy polysiloxane- After the addition, 19.7 g of epoxy polyalkylene oxide (PG-207P, Kukdo Chemical Co., Ltd.) was added to the epoxy resin, and the epoxy resin was fully opened for a sufficient time. Check whether the epoxy group is titrated with HBr solution.

In the fourth step, 4.5 g of a 35% hydrochloric acid solution was slowly added to the solution after quenching the entire epoxy to quaternize the remaining amine groups. 37.23 g of dipropylene glycol was added, and isopropyl alcohol was distilled off under reduced pressure to obtain a pale brown wax Solution.

Example 10

In the first step, the same hydrogen side chain polysiloxane as in Example 9 was obtained.

In the second step, the same side chain epoxy polysiloxane-modified polysiloxane solution as in Example 9 was obtained.

In the third step, 12.5 g of monoethanolamine, 200 g of the total amount of the side-chain epoxy polysiloxane-modified polysiloxane, and 45.8 g of total amount of epoxy polyalkylene oxide (PG-207P, Kukdo Chemical Co., Ltd.) were synthesized in the same manner as in Example 9 and,

In the fourth step, a pale brown waxy solution was obtained by using the same method as in Example 1 except that 8.5 g of 35% hydrochloric acid solution and 38.98 g of dipropylene glycol were used.

Table 1 summarizes the basic physical properties of the copolymers according to the examples.

Viscosity (cPs) Volatile matter (%) Amine Quaternary Example 1 200000 12.5 Ethanolamine Hydrochloric acid Example 2 25000 13 Ethanolamine Hydrochloric acid Example 3 250000 11.8 Ethanolamine Dimethyl sulfate Example 4 18000 12.8 Ethanolamine Dimethyl sulfate Example 5 45000 12.5 Hexylamine Hydrochloric acid Example 6 13000 11.5 Hexylamine Hydrochloric acid Example 7 56000 12.7 Hexylamine Dimethyl sulfate Example 8 16000 13.2 Hexylamine Dimethyl sulfate Example 9 450000 11.5 Ethanolamine Hydrochloric acid Example 10 270000 12.3 Ethanolamine Hydrochloric acid

The test procedure for the fabric softener using the copolymer of the above example is as follows.

Test procedure

1) The emulsifier having the following formulation is prepared and used for the manufacture of the softener. The preparation of the emulsion was as shown in Table 2 below.

Composition 24 Tridecyl alcohol EO 5 mol 10 Tridecyl alcohol EO 10mol 2 Acetic acid 0.5 Sodium acetate 0.4 Water 63.1

2) The concentration of the softening agent in the finishing composition was such that the aqueous solution became 0.5 to 1.0%, and the softening agent water tank was installed to paddle the cotton fabric, and then picked up at a pick-up rate of 70% Respectively. The surface treated with the softener was dried in an oven at 180 ° C for 0.5 minutes, and then measured for flexibility, yellowing and hygroscopicity.

3) Gum-up property was evaluated by increasing the concentration of the softener to 1.0 ~ 10.0% and adding sodium hydroxide aqueous solution.

Absorbency rating Flexibility Rating Yellow grade Gum-up Grade Example 1 2 One 2 3 Example 2 One 2 2 2 Example 3 2 One 3 3 Example 4 One One 3 2 Example 5 3 One 2 3 Example 6 3 2 2 2 Example 7 3 One 3 3 Example 8 3 2 3 2 Example 9 2 One 3 3 Example 10 2 2 3 4

The lower the rating, the better the hygroscopicity and flexibility, and the less yellowing and gumming.

As shown in Table 3, it can be confirmed that the silicone fabric softener prepared by the application example of the present invention has excellent flexibility and yellowing degree, and is superior in hygroscopicity and superiority.

The present invention can be widely applied to the chemical industry, the silicon chemical industry, and the fabric softener manufacturing industry.

Claims (19)

A quaternary amino-modified silicone copolymer characterized in that a side-chain epoxypolysiloxane-modified silicone compound represented by the following formula (1) and an amino compound represented by the following formula (3) are formed by copolymerization reaction through an epoxy ring-opening reaction with an amine.
[Chemical Formula 1]

(3)
[ZR ⁴ ]
In the above formula
R ¹ is an alkyl group containing 1 to 4 carbon atoms,
R ² , R ³ Are each independently a divalent hydrocarbon group containing 1 to 10 carbon atoms,
R ⁴ is a divalent hydrocarbon group containing 2 to 10 carbon atoms or a hydrocarbon alcohol which can be represented by [- (CH ₂ ) _n OH]
X is a 2 is formed by a ring-opening the epoxide is an organic _{group, -CH 2 CH (OH) (} CH 2) v CH (OH) CH 2 -, -CH [CH 2 OH] (CH 2) v CH [CH ₂ OH] -, -CH ₂ CH (OH) (CH ₂ ) _v CH [CH ₂ OH] -, - (CH ₂ ) _v -OCH ₂ CH (OH) CH ₂ -
Wherein v is from 2 to 6,
Z is an amine group, which is any one of primary, secondary and tertiary amines,
a is a positive integer of 2 to 4, b is an integer of 0 to 100, x is a positive integer of 1 to 100, y is a positive integer of 1 to 100, z is an amount of 1 to 50 And m is a positive integer of 1 to 100 The method according to claim 1,
Wherein the amino-modified silicone copolymer is a copolymer obtained by copolymerizing the epoxy compound of the formula (2).
(2)
_{[YO (C a H 2a O} ) b Y]
Y is a 2 are independently formed by epoxide ring opening and an organic _{group, -CH 2 CH (OH) (} CH 2) v CH (OH) CH 2 -, -CH [CH 2 OH] (CH 2) v CH [CH ₂ OH] - it is selected from the group consisting of _{-, -CH 2 CH (OH)} (CH 2) v CH [CH 2 OH] -, - (CH 2) v -OCH 2 CH (OH) CH 2 . 3. The method of claim 2,
The amine Z of the above formula 3 is a primary or secondary amine group;
Formula X and Y in the 1 and 2 is _{-CH 2 CH (OH) (CH} 2) v CH (OH) CH 2 -, -CH [CH 2 OH] (CH 2) v CH [CH 2 OH] -, - _{CH 2 CH (OH) (CH} 2) v CH [CH 2 OH] -, - (CH 2) v -OCH 2 CH (OH) CH 2 - which will not less than one selected from among, v is 2 to 6 Wherein the quaternary amino-modified silicone copolymer is a quaternary amino-modified silicone copolymer. 3. The method of claim 2,
X is selected from an allyl glycidyl ether group and an allyl epoxycyclohexyl group,
Wherein Y represents a glycidyl ether group, an epoxycyclohexylalkylene group, w- (3,4) -epoxycyclohexylalkylene, b- (3,4-epoxycyclohexyl) -b-methylethylene, 3,4-epoxy-4-methylcyclohexyl) -b-methylethylene. ≪ / RTI > 3. The method of claim 2,
In the formula (2)
(C _a H _2a O) is composed of ethylene oxide (a = 2), propylene oxide (a = 3) or propylene oxide (a = 3) Amino-modified silicone copolymer. The method according to claim 1,
Wherein the amine group connected by the amine group Z is protonated or quaternized. The method according to claim 1,
Wherein the amino compound of formula (3) is selected from the group consisting of hydrocarbon amines, hydrocarbon alcohol amines, and polyalkylene oxide imines. 8. The method of claim 7,
Wherein said hydrocarbon amine is selected from the group consisting of ethylene amine, propylene amine, butylene amine, hexylenamine, ethanolamine, propanolamine, butanolamine, heptanolamine and phenolamine amine. (A) reacting a side chain hydrazone polysiloxane having both an epoxy group and a polysiloxane group with a cyclosiloxane under a predetermined catalyst to prepare a side chain epoxy polysiloxane-modified polysiloxane represented by the following formula (1); And
(B) reacting the side chain epoxy polysiloxane-modified polysiloxane with a terminal amino compound of the following formula (III) in a predetermined solvent to cause a copolymerization reaction through an epoxy ring-opening reaction with an amine of a terminal amino compound of the following formula Amino-modified silicone copolymer.
[Chemical Formula 1]

(3)
[ZR ⁴ ]
In the above formula
R ¹ is an alkyl group containing 1 to 4 carbon atoms,
R ² , R ³ Are each independently a divalent hydrocarbon group containing 1 to 10 carbon atoms,
R ⁴ is a divalent hydrocarbon group containing 2 to 10 carbon atoms or a hydrocarbon alcohol which can be represented by [- (CH ₂ ) _n OH]
X is a divalent organic group and is selected from the group consisting of -CH ₂ CH (OH) (CH ₂ ) _v CH (OH) CH ₂ -, -CH [CH ₂ OH] (CH ₂ ) _v CH [CH ₂ OH] ₂ CH (OH) (CH ₂ ) _v CH [CH ₂ OH] -, - (CH ₂ ) _v -OCH ₂ CH (OH) CH ₂ -
Wherein v is from 2 to 6,
Z is an amine group, which is any one of primary, secondary and tertiary amines,
a is a positive integer of 2 to 4, b is an integer of 0 to 100, x is a positive integer of 1 to 100, y is a positive integer of 1 to 100, z is an amount of 1 to 50 And m is a positive integer of 1 to 100 10. The method of claim 9,
(C) further comprising, after the step (B), adding a polyoxyalkylene composition having a terminal end of the following formula (2).
(2)
_{[YO (C a H 2a O} ) b Y] 11. The method of claim 10,
(D) further comprising, after the step (C), further adding a side chain epoxy polysiloxane-modified polysiloxane of the formula (1) to the quaternary amino-modified silicone copolymer. 10. The method of claim 9,
(E) quaternizing the product of step (B). ≪ RTI ID = 0.0 > 11. < / RTI > 10. The method of claim 9,
Wherein the side chain hydrogen polysiloxane is a partial side chain hydrogel polysiloxane. 14. The method of claim 13,
The side chain epoxy polysiloxane-modified polysiloxane is characterized in that the partial hydrogensiloxane is linearly reacted with vinylsiloxane to secure the flexibility of the silicone compound in advance, and the step (B) is carried out after the preliminary reaction A process for producing a quaternary amino modified silicone copolymer. 10. The method of claim 9,
The catalyst is a platinum catalyst,
Wherein the solvent is any one of alcohol or a mixed solvent of alcohol and water. A quaternary amino-modified silicone copolymer produced by the process of any one of claims 1 to 8. A quaternary amino-modified silicone copolymer produced by the process of any one of claims 9 to 15. A fabric softener composition comprising the quaternary amino-modified silicone copolymer of claim 16 A fabric softener composition comprising the quaternary amino-modified silicone copolymer of claim 17

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