JP2002114972A - Treating agent for water repellency and water- repellent cloth - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a treating agent for water repellency which excels in not only water repellency but also smoothness and flexibility and, in addition, excels in the durability thereof on treating an article to be treated therewith, and a water-repellent cloth. SOLUTION: The treating agent for water repellency comprises (A) a diorganopolysiloxane having a molecular terminal blocked with a hydroxyl group or a 1-3C alkoxy group and at least one functional group selected from the group consisting of an epoxy group, a carboxyl group, and a mercapto group in the side chain and (B) an organopolysiloxane having two or more hydrogen atoms bonded to the silicon atom in the molecule. The treating agent for water repellency comprises the components (A) and (B) and, and additionally (C) a condensation reaction catalyst. The water-repellent cloth is obtained by treating a cloth with the above treating agent for water repellency.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a silicone-based water-repellent agent, and more particularly, it imparts excellent water-repellency to fabrics and leathers.
The present invention relates to a silicone-based water-repellent agent having excellent durability and a water-repellent cloth treated with the water-repellent agent.

[0002]

2. Description of the Related Art Fabric products such as lane coats, umbrellas, mountaineering jackets, tents, jumpers and hats for outdoor sports, snowwear, osme covers, leather products such as shoes, jumpers and gloves for outdoor sports, and synthetic leather. Most of the products are water-repellent because they are exposed to rain, water, snow or urine. For this purpose, perfluoro compound-based water repellents and methylhydrogenpolysiloxane-based water repellents have been widely used so far. For example, Japanese Patent Publication No. 58-1232 and Japanese Patent Application Laid-Open No. 60-75678 propose a water repellent treatment agent based on a perfluoro compound. The water repellency of the cloth or the like treated with the water repellent agent is good, but the texture is not so good. Also, recently, it is necessary to pay attention to products generated when burning waste.

For this reason, recently, a methylhydrogenpolysiloxane-based water-repellent treatment agent, which has almost no such concerns as compared with a perfluoro compound-based compound, has been rapidly reviewed. However, although the fabric treated with the methylhydrogenpolysiloxane-based water-repellent agent has good initial water repellency, it has a drawback that the water repellency is easily reduced by rubbing or washing. A water-repellent treatment agent in which aminoalkylalkoxysilanes are added to methyl hydrogen polysiloxane to improve the adhesion to the object to be treated has been proposed,
Insufficient washing resistance, JIS L-1096: 19
When washing is repeated three times under the conditions of the 8.23.1A method (method using a stirrer type washing machine) of 99 "General Fabric Testing Method", there is a disadvantage that the water repellency is reduced. For example, in a lane-coated ground or an umbrella ground, the water repellency [JIS L-1092: 199]
8 "Determination of the waterproofness of textiles" by 6.2 water repellency test (spray test)] is 75 or more, preferably 80 or more.
~ 100 is required, but the water repellency is 5
There is a disadvantage that it drops to the 0th place.

[0004]

SUMMARY OF THE INVENTION According to the present invention, when an object to be treated such as a cloth or leather is treated, not only water repellency but also smoothness and flexibility are excellent, and furthermore, their durability is excellent. It is an object to provide a water treatment agent and a water-repellent fabric.

[0005]

The object of the present invention is to provide (A) a molecular chain terminal selected from the group consisting of an epoxy group, a carboxyl group and a mercapto group, wherein the terminal of the molecular chain is blocked by a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms. A water-repellent treating agent comprising: a diorganopolysiloxane having at least one functional group and (B) an organopolysiloxane having two or more silicon-bonded hydrogen atoms in the molecule. Or a diorganopolysiloxane blocked with an alkoxy group having 1 to 3 carbon atoms and having at least one functional group selected from an epoxy group, a carboxyl group and a mercapto group in a side chain, (B) two in a molecule A water repellent comprising the organopolysiloxane having a silicon-bonded hydrogen atom and (C) a condensation reaction catalyst, wherein the fabric is treated with the water repellent. Water-repellent fabric. "

[0006]

DETAILED DESCRIPTION OF THE INVENTION (A) A molecular chain terminal is blocked with a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, and at least one selected from the group consisting of an epoxy group, a carboxyl group and a mercapto group in a side chain. Diorganopolysiloxane having the functional group of the above, because these functional groups are present, it is easy to be adsorbed to the object to be treated, the functional group of the object to be treated,
For example, it reacts with hydroxyl group of cotton, hemp and rayon, amino group, carboxy group and mercapto group of wool, silk, leather and fur, amino group and carboxyl group of nylon, hydroxyl group and carboxyl group of polyester, and is durable. Provides water repellency, flexibility and smoothness.

[0007] This component is generally straight-chain,
It may be a branched chain or ring. Straight-chain ones are flat
Equivalent molecular formula: RO [(CH_Three)_TwoSiO]_x[CH_ThreeQSi
O] yR. Where R is a hydrogen atom or a carbon atom
It is an alkyl group of formulas 1 to 3. The alkyl group is a methyl group,
Ethyl or propyl group, methyl group is the most representative
It is a target. x is mol% of (CH3) 2SiO unit
And preferably 99.9 to 95.0 mol%, and y is C
Mol% of H3QSiO units, preferably 0.1 to 0.1%.
5.0 mol%. x + y, ie, the degree of polymerization is 10
The range of ~ 1000 is preferred. -Q is an epoxy group,
Divalent hydrocarbon with a boxyl or mercapto group bonded
Group, preferably an alkyl group. As useful,
3-glycidyloxypropyl group, 2- (3,4-epoxy)
Cyclohexyl) ethyl group, 3-mercaptopropyl
Group, formula -CH_Two CH (CH_Three) COOH, -CH_TwoCH_TwoC
OOH,-(CH_Two)_FiveCOOH,-(CH_Two)_TenCOO
Carboxyl group-bonded alkyl groups represented by H
You.

The diorganopolysiloxane having these functional groups is represented by the general formula: Q (CH ₃ ) Si (OR) ₂ (wherein
R is an alkyl group having 1 to 3 carbon atoms), and is easily produced by a dealcoholization condensation reaction of an organodialkoxysilane represented by the formula (1) and dimethylpolysiloxane having a hydroxyl group at both terminals. For example, methyl (3-glycidyloxypropyl) dimethoxysilane 2 under a nitrogen gas seal
Mol% and wherein HO - [(CH _{3) 2} SiO] ₈₀ a dimethylpolysiloxane 98 mole% represented by -H, 75-80
It is easily manufactured by holding at 5 ° C. for 5 to 8 hours.
By adding 0.1 to 2 parts by weight of a condensation reaction catalyst such as dibutyltin diacetate or barium hydroxide as needed per 100 parts by weight of the raw material, a desired polymer can be obtained in a shorter time. The component (A) can also be produced by emulsion polymerization. An emulsion of a diorganopolysiloxane having a carboxyl-bonded alkyl group in the side chain is disclosed in
The diorganopolysiloxane having an epoxy group-bonded alkyl group on the side chain can be produced by the emulsion polymerization method disclosed in JP-A-63-295768. Each is a manufacturing method proposed by the present inventors.

The hydroxyl group, which is the terminal group of the diorganopolysiloxane having a functional group, is dehydrated and condensed with the silicon-bonded hydrogen atom of the component (B) to form a water-repellent film on the surface of the untreated material. The alkoxy group, which is the terminal group of the diorganopolysiloxane having these functional groups, is hydrolyzed to a hydroxyl group, and is dehydrated and condensed with the silicon-bonded hydrogen atom of the component (B) to form a water-repellent film on the surface of the object to be treated. To form If the carboxy group is too large, hydrophilicity and water repellency are reduced, and if the mercapto group is too large, an odor is given, and if the number of functional groups is too small, the degree of bonding to the object is reduced.
The mole% of the functional group in the molecule is preferably 0.1 to 5.0 mole%, more preferably 0.2 to 2.0 mole% of all the substituents bonded to the silicon atom. The degree of polymerization is preferably 1
It is 0-1000, more preferably 50-500.

The organopolysiloxane (B) having two or more silicon-bonded hydrogen atoms in the molecule reacts with the hydroxyl group in the component (A) because of the presence of the silicon-bonded hydrogen atoms, and To give durable water repellency. The molecular structure is not particularly limited as long as the degree of polymerization is 2 or more. Linear, partially branched chain, branched, and cyclic are exemplified. A typical example is an average molecular formula: R ¹ (CH ₃ ) ₂ SiO [(CH ₃ ) ₂ SiO] x
[CH ₃ (H) SiO] y Si (CH ₃ ) ₂ R ¹ (where R ¹ is a methyl group or a hydrogen atom, x is 0 to 800, and y is 0 to 20)
0, provided that when y is 0, R ¹ is a hydrogen atom and x + y is 1 to 1000). When used as a water-repellent treatment agent for fibers, those having x of 0 and y of 30 to 50 are preferable in terms of water repellency and cost. Dimethylpolysiloxane or methylphenylpolysiloxane having silicon-bonded hydrogen atoms at both ends may be used. Although the mixing ratio of the component (A) and the component (B) is not limited, the weight ratio is preferably from 98/2 to 2/98, and more preferably from 90/10 to 80/20.

The components (A) and (B) may be used as they are, but are preferably used after dilution with an organic solvent. As organic solvents, toluene, xylene, hexane, volatile oil,
Octamethylcyclotetrasiloxane is exemplified. Further, it is preferable to treat with an emulsion obtained by emulsifying the components (A) and (B) in water. In this case, the component (A) and the component (B) are separately emulsified to prepare an emulsion,
When treating the object to be treated, both emulsions may be blended and treated, or both may be emulsified to form a single emulsion. Nonionic surfactants are most preferred as emulsifiers. For example, polyoxyethylene (9
Mol) octyl phenol ether, polyoxyethylene (6 mol) nonyl phenol ether, polyoxyethylene (12 mol) lauryl ether, polyoxyethylene (13 mol) stearyl ether, polyoxyethylene stearic acid ester, polyoxyethylene oleate ester Is exemplified. Not only nonionic surfactants, but also anionic surfactants such as sodium dodecylbenzenesulfonate, potassium higher fatty acid, sodium sulfonate of polyoxyethylene (6 mol) lauryl ether, lauryl trimethyl ammonium chloride, tallow trimethyl ammonium chloride Such cationic surfactants and amphoteric surfactants may be used. In addition to the emulsifier, an emulsifier such as polyvinyl alcohol, carboxymethylcellulose, and methylcellulose may be blended. When water-repellent treatment is performed on fibers, cloth, leather, and synthetic leather, treatment with an aqueous emulsion is preferable.

The terminal hydroxyl group of the component (A) reacts with the silicon-bonded hydrogen atom of the component (B) and easily undergoes dehydrocondensation. When a condensation reaction catalyst is added, the reaction takes place at a lower temperature and in a shorter time. Typical examples thereof are tin compounds and zinc compounds, and examples thereof include dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dioctate, zinc octate, and zinclaurate. When the functional group in the component (A) is an epoxy group, an object to be treated such as a fiber, a cloth or a leather can be obtained by using a catalyst such as zinc borofluoride, ammonium dihydrogen phosphate, ammonium hydrogen phosphate monophosphate together. Reacts with the hydroxyl group, amino group, carboxyl group, mercapto group, etc. of the compound and binds firmly. When the functional group in the component (A) is a carboxyl group, a phosphate catalyst is useful. When the component (A) contains a mercapto group, wool,
It is particularly suitable as a water-repellent agent for animal fibers such as silk, leather, and fur.

If necessary, a silane coupling agent such as aminoalkyl trialkoxylan and glycidyloxyalkyl trialkoxysilane, a preservative, and a dye may be added to the water repellent. When treating the object to be treated, the component (A) and the component (B) are diluted or emulsified with a solvent to obtain 0.1 to 4% by weight, preferably 0.5 to 2% by weight as an organopolysiloxane. A treatment bath is prepared.
If necessary, a condensation reaction catalyst and other additives are added. Next, a sheet-like object to be treated such as cloth or leather is continuously passed through the treatment bath, and the squeezing ratio is adjusted by a squeezing roller to adjust the squeezing rate to 0.2 to 3% by weight, preferably 0% to the object to be treated. .8 ~
1.5% by weight of organopolysiloxane are deposited.
Then, after drying, the mixture is heated to promote the condensation reaction or crosslinking between the organopolysiloxanes and the reaction between the object to be treated and the organopolysiloxane, thereby obtaining a water-repellent treated material having high water repellency and durability. Alternatively, the treatment bath is sprayed or applied to the object, dried, and heated.

Examples of the object to be treated include fibers and textile products, especially cloth, leather, synthetic leather, fur, wood, woodwork, inorganic building materials,
A powder is exemplified. Examples of the fibers include natural fibers such as cotton, hemp, silk, and wool; regenerated fibers such as rayon and Bemberg (registered trademark); semi-synthetic fibers such as acetate; and synthetic fibers such as nylon, polyester, and acrylic. There are woven, knitted and non-woven fabrics. Fabric products include tents, umbrellas, lane courts, blousons, snowwear, golf wear, and the like. Nylon, polyester, acetate, cotton, and blends of these are typical materials.

The water-based fabric of the present invention is obtained by treating the above-described cloth with the water-repellent treating agent of the present invention, and has excellent water repellency and durability. That is, the water repellency (the water repellency of the following example) after washing under the washing conditions of the following example (however, the number of washing times is 3) is 75 or more, preferably 80.
That is all. Therefore, it is useful as a tent place, an umbrella place, a raincoat place, a sportswear place, a diaper place, and the like.

[0016]

Next, the present invention will be described with reference to examples and comparative examples. In the examples, parts and% mean parts by weight and% by weight, and the viscosity is a value at 25 ° C. The evaluation was as follows. Texture: Judgment was made by a touch test by hand. S Very flexible, rich in drape as a lane coat, and very good texture. M The texture is rather hard, and the drape property is slightly poor. H Very hard and poor drape. Water repellency: Measured according to JIS L1092: 1998 "Water resistance test for textile products", 6.2 water repellency test (spray test). Washing condition: According to 8.23.1A method of JIS L1096: 1999 “General fabric test method”, a cycle of washing for 12 minutes, dehydration for 2 minutes, and rinsing for 2 minutes is defined as 3 times for one washing.
Was repeated 5 times.

[0017]

Example 1 Average molecular formula: CH_ThreeO [(CH_Three)_TwoSiO]₉₈[CH_ThreeESiO]_TwoCH_Three (Wherein E is a 3-glycidyloxypropyl group)
Indicated, kinematic viscosity 3050 mm^Two/ S (cSt) epoxy
Group-containing diorganopolysiloxane (numbers in the main chain are moles
%), Average molecular formula: (CH_Three)_ThreeSiO (CH_ThreeHSiO)₄₅Si (CH_Three)_Three
, The kinematic viscosity is 28 mm^Two / S (cSt) methyl high
Polyoxyethylene in 15 parts of drogen polysiloxane
(6 mol) lauryl ether 2 parts, polyoxyethylene
(10 mol) nonylphenol ether 2 parts, polyoxy
2 parts of ethylene (20 mol) nonylphenol ether
Was added and stirred, and 5 parts of water was added and mixed uniformly.
Next, after passing the mixture through a colloid mill-type emulsifier,
An emulsion was prepared by adding 65 parts of water. This emulge
1450 parts of water and 50 parts of dibutyltin dilaurate
Aqueous emulsion (milk in water with nonionic surfactant)
Is an emulsion that has been converted to dibutyltin dilaurate.
4 parts, 20% aqueous solution of zinc borofluoride 5
The treatment liquid (a) was prepared by adding the mixture.

[0018] Five laminar burrs for lane coating of a blend of 65% polyester and 35% cotton cut into 25cm x 25cm were sequentially immersed and 100% squeezed with a mangle roller.
And squeezed one by one. -Hang and dry at night
Heat treatment was performed at 50 ° C. for 3 minutes. Check the texture, no washing,
The water repellency after washing three times and after washing five times was examined. The results are shown in Table 1.

For comparison, the treatment bath (b) was the same as above except that the methyl hydrogen polysiloxane was omitted.
And treating solution (c) was prepared in the same manner as above except that the epoxy group-containing diorganopolysiloxane was removed,
The texture and water repellency were examined. The results are shown in Table 1.

Table 1 Number of washings Example 1 Comparative example 1 Comparative example 2 (Treatment bath a) (Treatment bath b) (Treatment bath c) 0 Texture S SH water repellency 100 80 100 3 Texture S SH water repellency 100 70 70 5 Texture S SH Water repellency 90-100 50-700 Barbary ground treated with the water repellent agent of the present invention has excellent water repellency and texture, and its durability is excellent, so it is used for lane coating. It can be seen that this is very suitable.

[0021]

Example 2 Dodecylbenzenesulfonic acid 2 was added to 60 parts of water.
Part, kinematic viscosity 80mm^Two/ s (cSt) hydroxyl groups at both ends
28.5 parts of blocked dimethylpolysiloxane and CH_ThreeKSi
O (where K is -CH_TwoCH (CH_Three) COOH)
Stir 1.5 parts of the cyclic tetrasiloxane
Was added. After heating this to 60 ° C, homogenizer
To give an emulsion three times. This emulsion
Hold at 85 ° C. for 2 hours with gentle stirring, then add
Hold at 0 ° C for 4 hours and neutralize with dimethylformamide
did. The emulsion obtained by this emulsion polymerization is
98 mol% of tylsiloxane units and CH_ThreeKSiO (wherein
K is -CH_TwoCH (CH_Three2) units) which are COOH)
%, Both ends of which are hydroxyl groups
It contained xane. 10 parts of this emulsion was added to water 2
Diluted in 90 parts. This diluted emulsion 300
4 parts of a 20% aqueous solution of sodium dihydrogen phosphate and
Chill hydrogen polysiloxane emulsion (flat
Uniform molecular formula: (CH_Three)_ThreeSiO (CH_ThreeHSiO)₄₅Si
(CH_Three)_Three, The kinematic viscosity is 28 mm^Two / s (cSt)
Polyoxy to 15 parts of chill hydrogen polysiloxane
2 parts of ethylene (6 mol) lauryl ether, polyoxy
2 parts of ethylene (10 mol) nonylphenol ether,
Polyoxyethylene (20 mol) Nonylphenol A
After adding 2 parts of water and stirring, add 5 parts of water and mix uniformly.
And prepared by passing through a colloid mill type emulsifier) 30
0 parts were added to prepare a treatment bath (d), and the same as in Example 1
The barbary ground for lane coating was subjected to a water-repellent treatment. Comparison
From the treatment bath (d)
A treatment bath (e) was prepared except for the sun alone. Also processing
From the bath (d), 98 mol% of dimethylsiloxane units and CH
3KSiO (where K is -CH2CH (CH3) COO
H) unit consisting of 2 mol%, and both terminals are hydroxyl groups.
Of emulsions containing diorganopolysiloxanes
A treatment bath (f) was prepared except for the above. These treatment baths
To repel barbary ground for lane coat in the same manner as in Example 1.
Water treated. About these water-repellent barbary grounds
The texture and water repellency were examined. The results are shown in Table 2.

Table 2 Number of washings Example 2 Comparative example 3 Comparative example 4 (Treatment bath d) (Treatment bath e) (Treatment bath f) 0 Texture S SH water repellency 100 70 100 3 Texture S SH water repellency 100-90 50-70 70 5 Texture S SH Water repellency 90 50 50 The barbary ground treated with the water repellent treatment agent of the present invention has excellent water repellency and texture, and also has excellent durability. It turns out that it is suitable for lane coating.

[0023]

Example 3 Average molecular formula: CH_ThreeO [(CH_Three)_TwoSiO]
₃₀₀[CH_Three(HSC_ThreeH₆) SiO]₉Si (CH_Three)_TwoO
CH_ThreeIndicated by kinematic viscosity 1250mm^Two/ S (cSt)
5 parts of diorganopolysiloxane containing a rucapto group, average content
Child formula: (CH_Three)_ThreeSiO (CH_ThreeHSiO)₄₅Si (CH_Three)_Three
, The kinematic viscosity is 28 mm^Two / S (cSt) methyl high
2.5 parts of drogen polysiloxane and average molecular formula:
 H [(CH_Three)_TwoSiO]₁₄Si (CH_Three)_TwoIndicated by H
Kinematic viscosity 21mm^Two/ S (cSt) molecule of dimethylpoly
Dissolve 2.5 parts of siloxane in 990 parts of toluene and treat
A liquid was prepared. 75% polyester, wool
25% cashmere skin (25cm x 25c)
m) Immerse the two pieces and use a mangle roller to reduce the drawing rate to 100%.
Prepared and squeezed. 30 while pulling in the draft chamber
Dry for 150 minutes, confirm that there is no toluene odor,
For 3 minutes. The treated fabric has a good texture
And had a high rebound resilience. One of the dough
After washing three times, the degree of water repellency was determined to be 80.

[0024]

EFFECT OF THE INVENTION Fabrics and leathers,
When an object to be treated such as synthetic leather is treated, not only water repellency but also smoothness and flexibility are excellent, and further, their durability is excellent.

Continued on the front page (72) Inventor Tsutomu Naganawa 2-2 Chikusa Beach, Ichihara City, Chiba Prefecture Toray Dow Corning Silicone Co., Ltd. Research and Development Headquarters F-term (reference) 4H020 BA32 BA33 4J002 CP04X CP05W CP10W GK02 4L033 AA02 AA07 AB05 AC03 CA59 DA01

Claims (3)

[Claims] (A) A molecular chain terminal is blocked with a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, and an epoxy group is added to a side chain.
A water-repellent treatment comprising a diorganopolysiloxane having at least one functional group selected from the group consisting of a carboxyl group and a mercapto group, and (B) an organopolysiloxane having two or more silicon-bonded hydrogen atoms in a molecule. Agent. (A) A molecular chain terminal is blocked with a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, and has at least one functional group selected from an epoxy group, a carboxyl group and a mercapto group in a side chain. A water-repellent treatment agent comprising: a diorganopolysiloxane, (B) an organopolysiloxane having two or more silicon-bonded hydrogen atoms in a molecule, and (C) a condensation reaction catalyst. 3. A water-repellent cloth obtained by treating a cloth with the water-repellent treating agent according to claim 1 or 2.