JP2003034784A - Water repellent agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water repellent agent that can give water repellency on a soft surface such as fiber and paper and a hard surface such as plastics, stainless steel and glass, and can easily be removed with detergent treatment when removal is required after usage. SOLUTION: This water repellent agent is characterized in that it comprises a silicone-containing macromolecule copolymer that contains a silicone macromer (A), a tertiary amino group- or a quaternary ammonium group-containing vinyl monomer (BQ) and a carboxy group-containing vinyl monomer (C) as essential ingredients, wherein the (A) is contained in a range of 5-60 wt.% and the ratio of (B) and (C) is in a range of 1-40 mol% in B/(B+C).

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface treating agent capable of imparting water repellency to a surface of a substrate to be treated. More specifically, water repellency can be imparted to soft surfaces such as fibers and paper and hard surfaces such as plastic and stainless steel and glass without adversely affecting the human body and the environment and without impairing the texture of the surface, The present invention also relates to a surface treatment agent that can be easily removed from a substrate by washing. [0002] A polymer of a polymerizable monomer containing a perfluoro group or a fluoroalkyl group in the molecule, or a copolymer of the monomer with another polymerizable monomer. Certain fluoropolymers are used as surface treatment agents for fibers, leather, building materials, and the like because they exhibit excellent water-repellent effects even in relatively small amounts. However, 1,1,1-trichloroethane and the like, which are known as solvents for the fluoropolymer, have recently been cited as a cause of destruction of the ozone layer in the atmosphere,
Its use is restricted from the viewpoint of global environmental protection. Further, although alternatives for the above-mentioned fluorine-based polymer solvent have been studied, satisfactory results have not yet been obtained. In order to improve the above problems, Japanese Patent Laid-Open No.
JP-97770 discloses alcohol-soluble and
A silicone-based copolymer containing no fluorine atom has been proposed. However, since the copolymer does not contain an anionic group, it is difficult to remove the copolymer by washing with a detergent and an alkaline aqueous solution. There is a problem that whitening and unevenness occur, and a problem that the texture of the fiber is reduced. Japanese Patent Application Laid-Open No. 1-319518 proposes a carboxyl group-containing silicone copolymer having improved solubility under alkaline conditions and improved accumulation on the surface to be treated. However, the copolymer has a low adsorptivity to the surface to be treated and does not have sufficient water repellency. Japanese Patent Application Laid-Open No. Hei 1-239175 proposes a fiber treating agent using an acrylic graft organopolysiloxane. However, since the organopolysiloxane which is copolymerized at the time of production is an emulsion, the processing requires emulsification, dehydration and de-emulsifier steps, resulting in poor productivity and, further, sufficient water repellency. Requires a complicated use method such as addition of a crosslinking agent and heat treatment. Further, Japanese Patent Application Laid-Open No. 2000-186279 proposes a method of adding a metal alkoxide for the purpose of durability against water repellency. However, metal alkoxides are easily treated with water in the air. Is difficult. SUMMARY OF THE INVENTION The present invention has been made in order to meet the above-mentioned problems and needs, and has been made in consideration of the above-mentioned problems. Another object of the present invention is to provide a surface treatment agent which can impart water repellency to a hard surface such as glass and can be easily removed from a substrate by washing. Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above problems, and as a result, by treating the surface of a substrate with a specific silicone-containing polymer copolymer,
The present inventors have found that water repellency can be imparted without impairing the feel of the surface to be treated, and that the surface can be easily removed from the substrate by washing. That is, the present invention comprises, as essential components, a silicone macromer (A) represented by the following formula (2), a tertiary amino group or quaternary ammonium group-containing vinyl monomer (B), and a carboxyl group-containing vinyl monomer (C): (A) is 5 to 60% by weight
And the ratio of (B) and (C) is B / (B
The above object has been achieved by proposing a silicone-containing polymer copolymer in the range of 1 to 40 mol% in (C). [0009] (Wherein R ¹ is a hydrogen atom or a methyl group, R ² is a divalent aliphatic group having 1 to 6 carbon atoms which may contain an ether group, R ³
Represents an aliphatic group, an aromatic group, or a hydroxyl group having 1 to 30 carbon atoms, h represents a number of 0, 1 or 2, and j represents 0
Represents a number of ~ 500. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. The water repellent according to the present invention comprises a silicone macromer (A), a tertiary amino group or quaternary ammonium group-containing vinyl monomer (B), and a carboxyl group-containing vinyl monomer (C) as essential components. Ｂ60% by weight, and the ratio of (B) and (C) is B /
It is composed of a silicone-containing polymer copolymer in the range of (B + C) 1 to 40 mol%. The substrate to be treated using the water repellent of the present invention includes soft surfaces such as wallpaper, clothing, umbrellas, textiles of curtain and sofa fabric furniture, and various plastics, wood products, painted boards, and the like. Hard surfaces such as stainless steel are exemplified. The silicone macromer (A) used in the present invention has a structure represented by the following formula (3). Embedded image In the above formula, R ¹ is a hydrogen atom or a methyl group, and R ² is a group having 1 to 6 carbon atoms which may contain an ether group, preferably 1 to 6 carbon atoms.
Represents a divalent aliphatic group having from 1 to 4, and R ³ has 1 to ³ carbon atoms.
0, preferably an aliphatic group, an aromatic group, or a hydroxyl group of 2 to 18, h represents a number of 0, 1 or 2, and j represents a number of 0 to 500, preferably 10 to 300. is there. The silicone macromer (A) may be used alone or in combination of two or more. The silicone macromer (A) represented by the above formula (3) can be obtained as a commercial product (manufactured by Chisso Corporation), for example, trade name Cylaprene FM-0711 (in the above formula 3, R ¹ = methyl group , R ² = propylene chain,
h = 2, j = 11, R ³ = butyl group. In the examples described below, hereinafter referred to as FM-0711), the trade name Thyraplane FM-0721 (in the above formula 3, R ¹
= Methyl group, R ² = propylene chain, h = 2, j = 13
0, R ³ = butyl group. As the tertiary amino group or quaternary ammonium group-containing vinyl monomer (B), a tertiary amino group represented by the formula (4) or a quaternary ammonium group-containing vinyl monomer represented by the formula (5) is used. preferable. Embedded image Embedded image (In Formulas 4 and 5, R ⁴ represents a hydrogen atom or a methyl group, Y represents an oxygen atom or NH, A represents a divalent hydrocarbon having 1 to 8 carbon atoms, and may contain one or more oxygen atoms. , R ⁵
Is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R ⁶ , R
⁷ , R ⁸ represents a hydrocarbon group having 1 to 12 carbon atoms. Specific examples thereof include dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dipropylaminoethyl (meth) acrylate, and alkyl halides thereof. Dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, and other quaternary compounds; In this case, one or more of the above compounds may be combined. Examples of the alkyl halide include methyl chloride, ethyl chloride, methyl bromide, ethyl bromide, methyl iodide, benzyl chloride and the like. Of these, dialkylaminoalkyl (meth) acrylate is preferred, and dimethylaminoethyl (meth) acrylate is more preferred. The tertiary amine or quaternary ammonium group of the component (B) is
It is possible to enhance the adsorptivity to the surface to be treated and prevent the copolymer from falling off, and as a result, it is possible to impart water repellency with excellent durability. Examples of the carboxyl group-containing vinyl monomer (C) include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, maleic acid half-ester, fumaric acid half-ester and the like. They may be used, or two or more kinds may be used in combination.
Of these, acrylic acid and methacrylic acid are preferred, and methacrylic acid is more preferred. These (C)
Although the component has good adhesion to the coated surface and exhibits excellent water repellency, it can be completely removed from the substrate by treatment with a detergent or alkaline water. Does not impair the appearance or texture of the material. In addition to the above monomers, copolymerizable hydrophobic monomers (D) can be used in a range that does not adversely affect the performance. As the hydrophobic monomer, one having 1 to carbon atoms
24 (meth) acrylic acid esters of linear or branched alcohols, which can be used alone or in combination of two or more. Of these, preferred are (meth) acrylates of linear or branched alcohols having 1 to 18 carbon atoms, and more preferably 1-carbon atoms.
And (meth) acrylic acid esters of linear to branched alcohols of from 12 to 12. The silicone macromer (A), the tertiary amino group or quaternary ammonium group-containing vinyl monomer (B) and the carboxyl group-containing vinyl monomer (C) used in the present invention are essential components. It is desirable for the copolymer to contain 5 to 60% by weight, preferably 10 to 55% by weight, and more preferably 15 to 50% by weight. If the content of the silicone macromer (A) is less than 5% by weight, sufficient water repellency cannot be obtained, and if it exceeds 60% by weight, the solubility of the copolymer in a solvent will be low. When the film-forming property is deteriorated, the water repellency and the durability water repellency are reduced. The ratio of the tertiary amino group or quaternary ammonium group-containing vinyl monomer (B) and the carboxyl group-containing vinyl monomer (C) is 1 to 40 m in B / (B + C).
ol%, preferably 2 to 35 m
ol%, more preferably 3 to 30 mol%. If the above ratio is less than 1 mol%, the adsorptivity to the surface to be treated is weak, and sufficient water repellency cannot be obtained. Also, 4
If it exceeds 0 mol%, the appearance and texture after the treatment are reduced, and good water repellency cannot be obtained. The above hydrophobic monomer (D) can be used within a range that does not adversely affect the performance. It is desirable for the copolymer of the present invention to be contained in the range of 0 to 47% by weight, and if it exceeds 47% by weight, it remains on the surface to be treated even if it is treated with a detergent or alkaline water and is used repeatedly. As a result, it accumulates on the substrate surface and impairs the appearance and texture. The silicone-containing polymer copolymer according to the present invention can be easily produced by the following method. Examples of the copolymer include alcohols such as methanol, ethanol, isopropanol and propylene glycol as solvents, and lower alcohols such as ethanol and isopropanol are particularly preferable. The polymerization initiator is not particularly limited as long as it can be dissolved in a polymerization solvent, and any initiator used for general radical polymerization can be used, such as peroxides such as benzoyl peroxide, azobisisopropane. An azo compound such as butyronitrile can be used. The monomer solution and the initiator solution are desirably separately, dividedly or continuously added to the polymerization solvent in order to stably produce the solution while suppressing the heat of polymerization and suppressing the polymerization during feeding. . In addition, the polymerization initiator may be partially or wholly incorporated in the polymerization solvent in advance. In the polymerization, the solvent is preferably used by adjusting the concentration of the monomer mixture to about 10 to 50% by weight. Although the polymerization temperature cannot be determined unconditionally depending on the type of polymerization initiator used, it is desirable that the half-life of the polymerization initiator is about 5 minutes to 500 minutes in order to obtain a high reaction rate. It is desirable from the viewpoint of temperature control that the temperature is close to the boiling point of the polymerization solvent used. The polymerization time varies depending on the monomer concentration and the polymerization temperature, but is about 1 to 12 hours. Preferably, it is 2 to 10 hours. Further, the average molecular weight of the copolymer is as follows:
It is preferably from 5,000 to 1,000,000,
More preferably, it is 10,000 to 800,000. The water repellent comprising the copolymer is preferably dissolved in an organic solvent. Examples of the organic solvent include alcohols such as ethanol, isopropanol and propylene glycol, and aromatic solvents such as toluene and xylene. Aliphatic hydrocarbons such as n-hexane and n-heptane; ketones such as acetone and methyl ethyl ketone; and esters such as ethyl acetate. These may be used alone or in combination of two or more. You may use together. From the viewpoints of safety and solubility of the copolymer, it is preferable to use an alcohol such as ethanol or isopropanol. When the above copolymer is used as a water repellent,
Solvents such as butylene glycol, polyhydric alcohols having 4 to 12 carbon atoms such as hexylene glycol, polyethylene glycol, polypropylene glycol and other ethylene oxide and propylene oxide adducts, as long as the performance is not adversely affected, if necessary. Viscosity of dimethyl silicone oil, cyclic silicone oil, modified silicone oil, silicone resin, etc. at 25 ° C.
One or more of the 1,000,000 centistoke organopolysiloxane compounds may be blended. The water-repellent treating agent comprising the thus obtained silicone-containing polymer copolymer of the present invention as a main component is
Trigger spray, pump spray, aerosol spray, or other application containers can be provided with water repellency by simply spraying or applying to the substrate surface, or immersion and drying to provide water repellency to the treated surface. In the case of a mold spray, as a component necessary for spraying the copolymer in the form of a mist, a spray gas can be appropriately selected from known ones and used. For example, carbon dioxide gas, nitrogen gas,
Propane, butane, liquefied petroleum gas, dimethyl ether, etc. are appropriately selected and used alone or in consideration of the gas pressure used.
A mixture of more than one species can be used. The silicone-containing polymer copolymer of the present invention is sprayed, coated, or immersed on the surface of a substrate to impart sufficient durability to water repellency without impairing the texture of the treated surface. It is possible to perform an unprecedented water-repellent treatment that can be performed and can be easily removed from the substrate by washing. EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. (Synthesis Example 1) To a 500-ml separable flask equipped with a stirrer and a cooling tube, 117.4 g of ethanol was added.
Heated to 80 ° C. while blowing nitrogen gas. Silicone macromer (Chisso Corporation, Silaplane FM-0)
711) 21.0 g, dimethylaminoethyl methacrylate 10.5 g, methacrylic acid 42.0 g, tert-
31.5 g of butyl methacrylate and ethanol 5
A mixed solution of 2.2 g, a mixed solution of 1.5 g of 2,2′-azobis (2-methylbutyronitrile) and 25.4 g of ethanol was continuously added dropwise over 2 hours, and then a solution of 3 g at 80 ° C.
The mixture was heated for an hour to obtain a polymer having a weight average molecular weight of 93,000. (Synthesis Example 2) Silicone macromonomer (FM-071)
1) For a monomer mixture solution consisting of 42.0 g, dimethylaminoethyl methacrylate 5.3 g, methacrylic acid 36.8 g, tert-butyl methacrylate 21.0 g and ethanol 52.2 g, the weight average molecular weight was obtained in the same manner as in Synthesis Example 1. 123,000 polymers were obtained. (Synthesis Example 3) Silicone macromonomer (FM-071)
1) 42.0 g, dimethylaminoethyl methacrylate 21.0 g, methacrylic acid 31.5 g, tert-butyl methacrylate 10.5 g and ethanol 52.2 g
In the same manner as in Synthesis Example 1, a polymer having a weight average molecular weight of 51,000 was obtained. (Synthesis Example 4) Silicone macromonomer (FM-071)
1) About a monomer mixed solution consisting of 42.0 g, dimethylaminoethyl methacrylate 21.0 g, methacrylic acid 31.5 g, lauryl methacrylate 21.0 g and ethanol 52.2 g, in the same manner as in Synthesis Example 1, a weight average molecular weight of 85, 000 polymers were obtained. (Synthesis Example 5) 5.3 g of silicone macromer (Chisso Corporation, Silaplane FM-0725) and 117.4 g of ethanol were added to a 500-ml separable flask equipped with a stirrer and a cooling tube, and nitrogen gas was blown therein. While heating to 80 ° C. 31.5 g of silicone macromonomer (FM-0711), 10.5 g of dimethylaminoethyl methacrylate, 26.3 g of methacrylic acid,
A polymer having a weight-average molecular weight of 77,000 was obtained in the same manner as in Synthesis Example 1 using a monomer mixture solution containing 31.5 g of tert-butyl methacrylate and 52.2 g of ethanol. (Synthesis Example 6) Silicone macromonomer (FM-071)
1) 52.0 g, dimethylaminoethyl methacrylate 5.3 g, methacrylic acid 47.3 g and ethanol 5
Synthesis Example 1 for a monomer mixed solution consisting of 2.2 g
In the same manner as in the above, a polymer having a weight average molecular weight of 49,000 was obtained. (Synthesis Example 7) Silicone macromonomer (FM-071)
1) 31.5 g, methacrylic acid 21.0 g, tert-
52.5 g of butyl methacrylate and ethanol
About 2 g of the monomer mixed solution, a polymer having a weight average molecular weight of 52,000 was obtained in the same manner as in Synthesis Example 1. (Synthesis Example 8) Silicone macromonomer (FM-071)
1) 21.0 g, dimethylamino methacrylate methacrylate 42.0 g, lauryl methacrylate 42.0 g
And a monomer mixed solution composed of 52.2 g of ethanol and a weight average molecular weight of 85,
000 polymers were obtained. (Synthesis Example 9) Silicone macromonomer (FM-071)
1) About a monomer mixture solution consisting of 21.0 g, 63.0 g of dimethylamino methacrylate methacrylate, 21.0 g of methacrylic acid and 52.2 g of ethanol, a polymer having a weight average molecular weight of 74,000 was produced in the same manner as in Synthesis Example 1. Obtained. (Synthesis Example 10) Silicone macromonomer (FM-07
11) 52.5 g, 15.8 g of methyl methacrylate,
For a monomer mixture solution consisting of 36.8 g of 2-ethylhexyl methacrylate and 52.2 g of ethanol,
In the same manner as in Synthesis Example 1, the weight average molecular weight was 163,000.
Was obtained. (Synthesis example 11) 31.5 g of methacrylic acid, 73.5 g of tert-butyl methacrylate, and ethanol.
About 2 g of the monomer mixed solution, a polymer having a weight average molecular weight of 48,000 was obtained in the same manner as in Synthesis Example 1. % By weight of the monomers (A) to (D) of the copolymers shown in the above Synthesis Examples 1 to 11, and B / (B + C) mol%
Are shown in Table 1. [Table 1] (Example 1) A 10% by weight ethanol solution of the silicone-containing polymer copolymer obtained in Synthesis Example 1 was sprayed on a cotton cloth with a trigger and dried sufficiently at room temperature. 1
0 ml of ion-exchanged water was sprayed on the sample, and the wet state of the sample was observed. (Evaluation of water repellency) ：: Water droplets adhere without any surface wetting. Δ: The surface is wetted by water droplets. ×: The surface is wet, and water droplets penetrate the cloth. (Appearance) Using the treated surface of the sample, the appearance was visually observed, and whether or not a whitening phenomenon occurred was determined according to the following criteria. ：: Same surface state as untreated cloth. Δ: Slight whitening is observed as compared with the untreated cloth. X: Whitening is observed. (Hand feeling test) Using the treated cloth of the sample, the hand was touched by three panelists and the hand feeling was determined according to the following criteria. ：: Same texture as untreated cloth. Δ: Hand feeling slightly harder than untreated cloth. ×: Hard texture compared to untreated cloth. (Evaluation of removability) The removability of the silicone-containing polymer copolymer having the water repellency evaluation of ○ was evaluated. The cotton cloth was immersed in a 10% by weight ethanol solution of the silicone-containing polymer copolymer for 10 seconds, and then sufficiently dried at room temperature. Apply 5 g of sodium alkylbenzenesulfonate and 2 g of sodium carbonate to 1 liter of water
Was washed with an electric washing machine for home use and dried. 10 ml of ion-exchanged water was sprayed on the sample, and the wet state of the sample was observed. When water droplets permeated the sample surface and the polymer was removed by washing,
No water was observed on the surface, and no polymer was removed by washing. (Examples 2 to 6 and Comparative Examples 1 to 5) The silicone-containing polymer copolymers obtained in Synthesis Examples 2 to 11 were evaluated in the same manner as in Example 1. Table 2 shows the evaluation results.
It was shown to. [Table 2] (Examples 7 to 12 and Comparative Examples 6 to 10) One of the silicone-containing polymer copolymers obtained in Synthesis Examples 1 to 11
A glass plate (10 × 10 c
m) and dried at room temperature. The outer appearance of the dried film was observed, and the film which was uniform was evaluated as ○, and the film which was cracked was evaluated as ×. Next, the treated glass plate was fixed at an angle of 30 degrees with respect to the horizontal plane, and 100 ml of ion-exchanged water was sprayed from a height of 20 cm. Lift the edge of the glass plate, observe the wet state after dropping excess water droplets, repel water, ○ if only small water droplets adhere to the surface, ○ if the whole film is wet, △ Was evaluated as x when the glass surface was peeled off and the glass surface was wet with water. [Table 3] As described above, the water repellent according to the present invention comprises a silicone macromer (A) represented by the above formula 1 and a tertiary amino group or quaternary ammonium group-containing vinyl monomer (A). B), a carboxyl group-containing vinyl monomer (C) as an essential component, and the above (A) is 5 to 60% by weight.
And the ratio of (B) and (C) is B / (B
+ C) in the range of 1 to 40 mol% in a range from 1 to 40 mol%, which is sufficiently sprayed, applied, or immersed on the surface without impairing the feeling of the surface, and sufficient for the surface to be treated. Water repellency, and
It can be easily removed from the substrate by washing.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C23C 26/00 C23C 26/00 A 4L033 D06M 15/263 D06M 15/263 15/267 15/267 15/643 15/643 (72) Inventor Isae Nakamura 1-3-7 Honjo, Sumida-ku, Tokyo F-term within Lion Corporation (reference) 4H020 BA34 4J027 AF05 BA04 BA06 BA07 BA14 CD08 4J038 DL121 DL122 FA081 FA082 FA092 FA162 FA191 FA192 FA201 FA202 FA241 FA242 GA12 NA07 PC02 PC03 PC08 PC10 4K026 AA04 BA01 BB10 CA02 4K044 AA03 AB05 BA21 BB01 BC02 CA16 CA53 4L033 AC03 CA18 CA19 CA59

Claims (1)

Claims: 1. A silicone macromer (A) represented by the following formula (1): a tertiary amino group or quaternary ammonium group-containing vinyl monomer (B) and a carboxyl group-containing vinyl monomer (C) Is an essential component, and (A) is 5 to 60
% By weight, and the ratio of (B) and (C) is B
A water-repellent treatment agent comprising a silicone-containing polymer copolymer in the range of 1 to 40 mol% in (B + C). Embedded image (Wherein R ¹ is a hydrogen atom or a methyl group, R ² is a divalent aliphatic group having 1 to 6 carbon atoms which may contain an ether group, R ³
Represents an aliphatic group, an aromatic group, or a hydroxyl group having 1 to 30 carbon atoms, h represents a number of 0, 1 or 2, j
Represents a number from 0 to 500. )