JP4107552B2 - Organopolysiloxane compound having quaternary ammonium salt-containing group and method for producing the same - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to organopolysiloxane compound having a quaternary ammonium salt-containing group, particularly water repellency, water resistance, suitable organopolysiloxane compound to form a lubricity and excellent silicone coating flexibility, and manufacturing of its It is about the method .
[0002]
[Prior art]
Conventionally, an organic silicone resin has been used as a film forming agent for imparting water repellency to the surface of a substrate such as fiber, paper, metal, or plastic or protecting the surface. However, since the film formed of these organosilicone resins is hard, there is a drawback in that cracks are easily generated or peeled off when the substrate surface is coated. Further, when dimethylpolysiloxane having a high degree of polymerization is used as a film forming agent in order to eliminate these drawbacks, there is a drawback that the adsorbability to the substrate is poor and the sustainability of the effect is small.
[0003]
In addition, dimethylpolysiloxane having an amino group is also used as a functional group having excellent adsorptivity to the base material. However, when the number of functional groups is large, yellowing tends to occur, whereas when the number of functional groups is small, the adsorptivity is insufficient. There was a case. In addition, organopolysiloxane compounds modified with quaternary ammonium salt-containing groups that are more adsorbable than amino groups have also been developed and are mainly used for antibacterial applications (Japanese Patent Publication No. 3-22844, Patent No. 2722221, Patents) No. 2722222, Japanese Patent No. 3062283, Japanese Patent No. 3081049, Japanese Patent Laid-Open No. 2000-290109). However, in these cases, there is no specific description of the production method, it takes a long time for the production process, or it is necessary to remove and purify unreacted substances. No quaternary ammonium salt-containing group-modified organopolysiloxane compound has been proposed.
[0004]
[Problems to be solved by the invention]
Therefore, as a result of intensive studies to solve the above-mentioned drawbacks, the present inventors have obtained a quaternary ammonium salt-containing group obtained by reacting an organopolysiloxane compound having an amino-containing group with an epoxy group-containing cationizing agent. The present inventors have found that an organopolysiloxane compound having a water resistance is suitable for a coating composition that forms a silicone film excellent in water repellency, water resistance, lubricity, flexibility and antibacterial properties.
Accordingly purpose of the present invention, water repellency, water resistance, lubricity, suitable for the coating composition for forming an excellent silicone coating flexibility and antimicrobial, organopolysiloxane compound having a quaternary ammonium salt-containing group and It is in providing the manufacturing method .
[0005]
[Means for Solving the Problems]
The above objects of the present invention include an organopolysiloxane compound having a quaternary ammonium salt- containing group represented by the following general formula (5), and an epoxy group-containing cationizing agent represented by the following formula (2): This was achieved by a method for producing an organopolysiloxane compound having a quaternary ammonium salt-containing group comprising a step of reacting an organopolysiloxane compound having an amino-containing group represented by the following general formula (6).
However, monovalent hydrocarbon group R ⁶ may be the same or different carbon atoms 1 to 10 together in the formula, quaternary ammonium salt-containing radical R ⁷ is represented by the following following general formula (3), R ⁸ is represented by the following general The amino-containing group represented by the formula (1), A is a group selected from the same or different R ⁶ , R ⁷ and R ⁸ , a is 0 to 5000, b is 0 to 50, c is 0 to 50 There, at least one of a when b is 0 is ^{R 7.}
However, R ¹ in the formula is a group represented by the following formula (4).
R ² in the formulas (1) and (3) is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, R ³ is a divalent hydrocarbon group having 2 to 10 carbon atoms, R ⁴ is a hydrogen atom or R ¹ is the same group, R ⁵ is a C 1-10 divalent hydrocarbon group, and n is an integer of 0-3.
However, ^R 6, ^{R 8} and a in the formula (6) is the same as ^R 6, ^{R 8} and a in the above formula (5), B is selected from a different ^{R 6} and ^{R 8} the same or mutually group, d is 0 to 100, at least one of B when d is 0 is ^{R 8.}
[0006]
DETAILED DESCRIPTION OF THE INVENTION
To effectively exhibit the performance of the case of the coating composition, the organopolysiloxane compound having a quaternary ammonium salt-containing group of the present invention, as represented by the following general formula (5), 1 molecule It is necessary that the compound has at least one quaternary ammonium salt-containing group represented by the following general formula (3) .


Where R ⁶ is the same or different monovalent hydrocarbon group having 1 to 10 carbon atoms, R ⁷ is a quaternary ammonium salt-containing group represented by the above general formula (3), and R ⁸ is the following general formula (1) is an amino-containing group represented by (1), A is a group selected from the same or different R ⁶ , R ⁷ and R ⁸ , a is 0 to 5,000, b is 0 to 50, c is 0 is 50, at least one of a when b is 0 is ^{R 7.}
However, ^{R 1} is represented by the following formula (4).
In the formula, R ² is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, R ³ is a divalent hydrocarbon group having 2 to 10 carbon atoms, R ⁴ is a hydrogen atom or the same group as R ¹ , R ⁵ Is a divalent hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 0 to 3.
[0008]
The organopolysiloxane compound having an amino-containing group used in the production method of the present invention needs to use a compound represented by the following general formula (6).
However, ^R 6, ^{R 8} and a in the formula (6) is the same as ^R 6, ^{R 8} and a in the formula (5), B is selected from a different ^{R 6} and ^{R 8} the same or mutually group , D is 0 to 100, and when d is 0, at least one of B is R ⁸ .
[0009]
Specific examples of R ^{2 in} the general formula (3) include a hydrogen atom or a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a decyl group, a phenyl group, a cyclohexyl group, etc. Monovalent hydrocarbon groups and the like. Specific examples of R ³ include divalent hydrocarbon groups having 2 to 10 carbon atoms such as ethylene group, propylene group, butylene group, hexamethylene group, and phenylene group, and specific examples of R ⁵ . Examples include a methylene group, an ethylene group, a propylene group, a butylene group, a hexamethylene group, a divalent hydrocarbon group having 1 to 10 carbon atoms such as a phenylene group.
[0010]
Preferable examples of the general formula (3) include the following.
_{^{-C 3 H 6 -NR 1 H,}} -C 3 H 6 -NH-C 2 H 4 -NR 1 H, -C 3 H 6 -NR 1 -C 2 H 4 -NR 1 H, -C 3 H 6 ^{_{- (NH-C 2 H 4}} ) 2 -NR 1 H, -C 3 H 6 - (NH-C 2 H 4) 3 -NR 1 H
Moreover, the following are mentioned as a preferable example of the said General formula (1).
_{-C 3 H 6 -NH 2, -C} 3 H 6 -NH-C 2 H 4 -NH 2, -C 3 H 6 - (NH-C 2 H 4) 2 -NH 2, -C 3 H 6 - _{(NH-C 2 H 4)} 3 -NH 2
[0011]
R ⁶ is the same or different monovalent hydrocarbon group having 1 to 10 carbon atoms, specifically, methyl group, ethyl group, propyl group, butyl group, hexyl group, decyl group, phenyl group, cyclohexyl group, etc. Can be mentioned. From the viewpoint of ease of production of the organopolysiloxane compound having an amino-containing group represented by the general formula (6) as a raw material, a methyl group and a phenyl group are preferred, and water repellency in the case of a coating composition, From the viewpoint of effectively exhibiting water resistance and lubricity, a methyl group is mainly preferred.
[0012]
Epoxy group-containing cationic agent to be reacted with the amino groups of the organopolysiloxane compound having an amino-containing group used in the manufacturing method of the present invention are represented by the following formula (2), readily available in the form of an aqueous solution commercially (SY-GTA80, 80% aqueous solution manufactured by Sakamoto Pharmaceutical Co., Ltd.).
[0013]
The production method of the present invention utilizes a reaction between an amino group of an organopolysiloxane compound having an amino-containing group and an epoxy group of an epoxy group-containing cationizing agent. be introduced.
[0014]
Since the reaction between the amino group and the epoxy group proceeds rapidly and quantitatively at room temperature even without a catalyst, it is not necessary to add an epoxy group-containing cationizing agent excessively to the amino group. Further, since there is no concern that unreacted cationizing agent remains, a purification step after the reaction is unnecessary. Furthermore, when the amount of the epoxy group-containing cationizing agent is insufficient with respect to the amino group, the amino group remains, but the amino group is also an adsorptive functional group. There is no degradation in performance.
[0015]
Since the organopolysiloxane compound having an amino-containing group and the epoxy group-containing cationizing agent supplied in the form of an aqueous solution are incompatible, it is preferable to use a solvent during the reaction. A solvent will not be restrict | limited especially if it is compatible with both and does not react with an amino group and an epoxy group. Among such solvents, alcohols such as ethanol, isopropanol and t-butanol, and ethers such as diethyl ether, tetrahydrofuran and dioxane are particularly preferable.
[0016]
Without requiring particularly a catalyst in the production process of the present invention, also, the reaction temperature may be room temperature, but in order to complete the earlier reaction is preferably set to 40 to 100 ° C.. Under these conditions, it is possible to complete the reaction sufficiently in 1 to 5 hours. After the reaction, the solvent can be removed by distillation, and the target product can be taken out, but it may be used as it is or further diluted with a solvent to form a coating composition.
[0017]
Organopolysiloxane compound having a quaternary ammonium salt-containing group of the present invention obtained by the above reaction, if necessary, this solvent, to a coating composition by appropriately blending and other various additives Is possible. The solvent in this case is used for the purpose of adjusting the viscosity, drying property, adhesion amount, etc., but the type is not particularly limited. Such solvents naturally include the above-mentioned reaction solvents, but also alcohols such as methanol and n-butanol, hydrocarbons such as hexane, toluene, xylene and light liquid isoparaffin, octamethylcyclotetrasiloxane, deca Volatile silicones such as methylcyclopentasiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, and tris (trimethylsiloxy) methylsilane can also be used. These may be used alone or in combination of two or more. Further, it may be used in the form of an emulsion emulsified and dispersed in water. Examples of the various additives include inorganic or organic fillers, antioxidants, anti-aging agents, antistatic agents, and the like.
[0018]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by this. Incidentally, Me represents a methyl group in the examples, phi is a phenyl group, R ¹ represents a quaternary ammonium salt-containing group of the formula (4). “%” Represents “% by weight” unless otherwise specified.
[0019]
Example 1.
In a glass flask equipped with a stirrer, a thermometer, and a cooler, 200 g of methylphenylpolysiloxane having an amino group at both ends represented by the following formula (7) (amine equivalent 2,200 g / mol) and 20 g of isopropyl alcohol were added. After mixing until uniform, epoxy group-containing cationizing agent SY-GTA80 (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., 80% aqueous solution) 17.2 g is added with stirring, and 4% at 60 ° C. under nitrogen aeration. Reacted for hours.
[0020]
Next, isopropyl alcohol and water were distilled off from this reaction solution at 70 ° C. under vacuum to obtain 205 g of methylphenylpolysiloxane having quaternary ammonium salt-containing groups at both ends represented by the following formula (8). . The appearance of this was a colorless and transparent paste, and the refractive index at 25 ° C. was 1.5002. The quaternary ammonium salt concentration determined by the mercury acetate method was 0.42 meq / g.
[0021]
Example 2
200 g of methylphenylpolysiloxane having amino groups at both ends represented by the following formula (9) (amine equivalent 6,420 g / mol), epoxy group-containing cationizing agent SY-GTA80 (manufactured by Sakamoto Pharmaceutical Co., Ltd., 80 % Aqueous solution) Except for using 5.9 g, the same operation as in Example 1 was performed to obtain 197 g of methylphenylpolysiloxane having quaternary ammonium salt-containing groups at both ends represented by the following formula (10). . The appearance of this was a colorless and transparent paste, and the refractive index at 25 ° C. was 1.4992. The quaternary ammonium salt concentration determined by the mercury acetate method was 0.14 meq / g.
[0022]
Example 3
200 g of dimethylpolysiloxane having amino groups at both ends represented by the following formula (11) (amine equivalent 6,040 g / mol), epoxy group-containing cationizing agent SY-GTA80 (manufactured by Sakamoto Pharmaceutical Co., Ltd., 80%) (Aqueous solution) Except that 6.3 g was used, the same operation as in Example 1 was performed to obtain 195 g of dimethylpolysiloxane having quaternary ammonium salt-containing groups at both ends represented by the following formula (12). The appearance of this product was colorless and transparent jelly, and the refractive index at 25 ° C. was 1.4081. The quaternary ammonium salt concentration determined by the mercury acetate method was 0.15 meq / g.
[0023]
Example 4
200 g of dimethylpolysiloxane having an amino group in the side chain represented by the following formula (13) (amine equivalent 20,100 g / mol), epoxy group-containing cationizing agent SY-GTA80 (manufactured by Sakamoto Pharmaceutical Co., Ltd., 80%) (Aqueous solution) Except that 1.13 g was used, the same operation as in Example 1 was performed to obtain 190 g of dimethylpolysiloxane having a quaternary ammonium salt-containing group and an amino group in the side chain represented by the following formula (14). It was. The appearance of this was a colorless and transparent gum, and the refractive index at 25 ° C. was 1.4040. The quaternary ammonium salt concentration determined by the mercury acetate method was 0.027 meq / g.
[0024]
Example 5 FIG.
200 g of dimethylpolysiloxane having an amino group in the side chain represented by the following formula (15) (amine equivalent: 640 g / mol), epoxy group-containing cationizing agent SY-GTA80 (manufactured by Sakamoto Pharmaceutical Co., Ltd., 80% aqueous solution) Except that 14.7 g was used, the same operation as in Example 1 was performed to obtain 202 g of dimethylpolysiloxane having a quaternary ammonium salt-containing group and an amino group in the side chain represented by the following formula (16). The appearance of this product was a colorless and transparent gum, and the refractive index at 25 ° C. was 1.4065. The quaternary ammonium salt concentration determined by the mercury acetate method was 0.35 meq / g.
[0025]
Application example 1 .
2 g of a transparent liquid obtained by dissolving methylphenylpolysiloxane having a quaternary ammonium salt-containing group obtained in Example 1 in ethanol so as to be 5% by weight was uniformly applied to cowhide (4 cm × 10 cm) and left for 1 day. Then, using a DF / PF meter (manufactured by Kyowa Science Co., Ltd.), the horizontal resistance value was measured under conditions of a vertical load of 50 g and a pen tip moving speed of 19 cm / min, and the smoothness was evaluated. Further, the same measurement was performed after washing with water and drying for 60 minutes. The results are shown in Table 1 together with the measured values of untreated cowhide before application.
[0026]
Application examples 2 to 5 .
The same test as in Application Example 1 was conducted on a 5 wt% solution of the polysiloxane compound having a quaternary ammonium salt-containing group obtained in Examples 2 to 5. The results are shown in Table 1.
Comparative application examples 1 and 2.
About 5 wt% solution of the amino siloxane compound materials used in Examples 1 and 4 were subjected to same tests as Application Example 1. The results are shown in Table 1.
[0027]
[Table 1]
From the results shown in Table 1, it was confirmed that the compound of the present invention was excellent in adsorptivity and therefore hardly deteriorated in performance even after washing with water.
[0028]
Application Example 6 .
Using 100 g of methylphenylpolysiloxane having a quaternary ammonium salt-containing group obtained in Example 1, 15 g of polyoxyethylene alkyl ether (EO: 10 mol adduct, HLB: 13.7) as an emulsifier, and using a homomixer The emulsion was prepared by emulsifying and dispersing in 330 g of water, followed by secondary emulsification with a high-pressure homogenizer. The emulsion is diluted with water to a concentration of 0.5% to make a test solution. After immersing the T / C broad cloth for 5 minutes, it is squeezed with a roll under the condition of a squeezing rate of 100%, and 5% at 100 ° C. A treated cloth was prepared by drying for a minute. Table 2 shows the results of evaluating the flexibility of the obtained treated fabric according to the following criteria.
<Flexibility evaluation criteria>
Evaluation by touch by three panelists ◎: Very good, ○: Good, ×: Bad
Application examples 7 to 10 .
The polysiloxane compound having a quaternary ammonium salt-containing group obtained in Examples 2 to 5 was made into an emulsion in the same manner as in Application Example 6, and the same evaluation was performed. The results are shown in Table 2.
Comparative application examples 3 and 4.
The starting material is an amino siloxane compound used in Example 1 and 4, the emulsion in the same manner as in Application Example 6 were carried out similar evaluation. The results are shown in Table 2.
[0030]
[Table 2]
From the results in Table 2, it was confirmed that the compound of the present invention was excellent in adsorptivity and therefore excellent in the fiber softening effect.
[0031]
【The invention's effect】
According to the present invention, it is possible not only to easily produce an organopolysiloxane compound having a quaternary ammonium salt-containing group, but also to obtain an organopolysiloxane compound having a quaternary ammonium salt-containing group as a main component. Since the resulting coating composition has excellent adsorptivity with the base material, it can form a silicone film excellent in water repellency, water resistance, lubricity and flexibility, and is a leather treatment agent, fiber treatment agent, and paper treatment agent. Application to powder processing agents, car wax, and the like is possible.

Claims (4)

An organopolysiloxane compound having a quaternary ammonium salt-containing group represented by the following general formula (5).
Wherein R ⁶ is the same or different monovalent hydrocarbon group having 1 to 10 carbon atoms, R ⁷ is a quaternary ammonium salt-containing group represented by the following general formula (3), and R ⁸ is the following general formula The amino-containing group represented by (1), A is a group selected from the same or different R ⁶ , R ⁷ and R ⁸ , a is 0 to 5000, b is 0 to 50, c is 0 to 50 at least one of a when b is 0 is ^{R 7.}
However, R ¹ in the formula is a group represented by the following formula (4).
R ² in the formulas (1) and (3) is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, R ³ is a divalent hydrocarbon group having 2 to 10 carbon atoms, R ⁴ is a hydrogen atom or R ¹ is the same group, R ⁵ is a C 1-10 divalent hydrocarbon group, and n is an integer of 0-3. Quaternary ammonium salt-containing group represented by the formula (3) _{^{is, -C 3 H 6 -NR 1 H}} , -C 3 H 6 -NH-C 2 H 4 -NR 1 H, -C 3 H 6 _{^{-NR 1 -C 2 H 4 -NR 1}} H, -C 3 H 6 - (N H -C 2 H 4) 2 -NR 1 H and _{-C 3 H 6 - (N H} -C 2 H 4) 3 The organopolysiloxane compound having a quaternary ammonium salt-containing group according to claim 1, which is a group selected from —NR ¹ H.
However, R ¹ in the formula is a group represented by the formula (4). Amino-containing group represented by the formula (1) _{is, -C 3 H 6 -NH 2,} -C 3 H 6 -NH-C 2 H 4 -NH 2, -C 3 H 6 - (NH-C ₂ H _{4) 2} -NH ₂ and _-C 3 _H 6 _- (a group selected from _{NH-C 2 H 4) 3} -NH 2, 4 quaternary ammonium salt-containing radical as set forth in claim 1 or 2 An organopolysiloxane compound having A manufacturing method of the organopolysiloxane compound having a quaternary ammonium salt-containing radical as set forth in any one of claims 1 to 3, and an epoxy group-containing cationizing agent represented by the following formula (2), the following general A production method comprising a step of reacting an organopolysiloxane compound having an amino-containing group represented by formula (6).
However, ^R 6, ^{R 8} and a in the formula (6) is the same as ^R 6, ^{R 8} and a in the above formula (5), B is selected from a different ^{R 6} and ^{R 8} the same or mutually group, d is 0 to 100, at least one of B when d is 0 is ^{R 8.}