JPS62267359A - Solid material-treating agent - Google Patents

Abstract

PURPOSE:To provide the titled agent capable of affording solid materials (e.g. various textile fibers, paper) with persistent hydrophilicity or antistatic ability, consisting chiefly of an organopolysiloxane of specific structure. CONSTITUTION:The objective agent can be obtained by dissolving or emulsifying in water, either singly or using emulsifying agent, an organopolysiloxane of formula I [R is 1-10C-monovalent hydrocarbon; A are of formula II (X is 1-4C alkoxy; R<1> is 2-5C alkyl; a is 2 or 3) and/or formula III (R<2> is H or 1-5C organic group; b and c are each 0-50; where b+c being 2-200), at least one of them being of formula II, l is 5-500; m is 0-100; n is 0-100; where in case all of the A are of formula II, n is 1-100] prepared by addition polymerization of (1) alkoxysilyl group-contg. alkene compound and alkenyl group-contg. polyoxyalkylene compound to (2) a both terminal diorganohydrogensilyl group-hindered diorganosiloxane-organohydrogensiloxane copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a treatment agent for solid materials. For more details,
The present invention relates to a treatment agent that imparts durable hydrophilic or antistatic properties to solid materials.

[Conventional technology]

Conventionally, molded products, sheet-like products, and foam-like products.

Hydrophilic to solid materials such as fibrous and powdered materials.

Cationic to provide antistatic properties.

Treatment methods using various organic surfactants such as anionic or nonionic surfactants have been used.

In addition, as a silicone-based solid material processing agent,
The organopolysiloxane/polioalkylene copolymer as described in Publication No. 4-6069, and the polyoxyalkylene/polyoxyalkylene with organosilyl groups capped at both ends as described in JP-A-57-139123. Alkoxysilylalkyl-modified organopolysiloxanes are known.

[Problem that the invention seeks to solve]

However, organic surfactants and
Organopolysiloxane as described in Publication No. 9
The method of treating with a polyoxyalkylene copolymer has the disadvantage that the effects of imparting hydrophilicity and antistatic properties are temporary, and the effects are easily lost when exposed to water or organic solvents. Ta.

In addition, the silicone surfactant described in JP-A-57-139123 has an alkoxysilylalkyl group in the side chain, and has a small number of 9-molecule terminals (one of which is an alkoxysilylalkyl group, at least 1
A solid material processing agent based on an organopolysiloxane having two polyoxyalkylene groups at the side chain or at the end of the molecular chain has not yet been known.

The present invention aims to eliminate the above-mentioned drawbacks and provides a novel solid material processing agent capable of imparting durable hydrophilic or antistatic properties to solid materials.

[Means for solving problems]

The above purpose is.

General formula [wherein, R is a monovalent hydrocarbon group having 1 to 10 carbon atoms, A
is Q or G. However, at least one of A is Q
It is. Q is a group represented by the formula %, X is an alkoxy group having 1 to 4 carbon atoms, R1 is an alkyl group having 2 to 5 carbon atoms, and a is 2 or 3.

G is a group represented by the formula % formula %) aZ is a hydrogen atom or a carbon atom number of 1 to
The monovalent i group of 5, b and C are integers of 0 to 50, provided that b+c is an integer of 2 to 200. 1 is an integer of 5 to 500, 3m is an integer of 0 to 100, n is an integer of 0 to 100, provided that when all A is Q, n is an integer of 1 to 100. This is achieved by using a solid material processing agent.

To explain this, in the above formula, R has 1 to 1 carbon atoms.
10 monovalent hydrocarbon groups.

These include methyl, ethyl, and propyl groups.

Examples include an alkyl group such as an octyl group, a substituted alkyl group such as a 2-phenylethyl group or a 2-phenylpropyl group, an alkyl group such as a phenyl group, or a substituted aryl group such as a tolyl group, and preferably an alkyl group. It is the basis. The R's in the molecule may be of the same type (or may be of different types).

A is Q or G. Q is a group represented by the formula % and has the effect of firmly bonding the present organopolysiloxane to a solid material and imparting durability. R
1 is an alkylene group having 2 to 5 carbon atoms;

-CLCL-, -CIIzCllzCllz-, -CI
l(CHz)CHz-.

-(CL)t- and -(Cu2)s- are exemplified. R' in the molecule may be of the same type or different types; X is an alkoxy group having 1 to 4 carbon atoms; group, and methoxyethoxy group. a is 2 or 3.

G is formula%formula%)! R2 is a hydrogen atom or a monovalent organic group having 1 to 5 carbon atoms, and examples of -valent organic groups include methyl group and ethyl group. , an alkyl group such as a propyl group, an acetyl group, and an acyl group such as a propyl group. b and C are integers from 0 to 50.

However, b+c is an integer from 2 to 200.

2 is an integer from 5 to 500, and when l is 50 or more, lubricity can be imparted to the solid material. m is 0
．． -100 integer, n is an integer from 0 to 100. However, when all A's are Q, n is an integer from 1 to 100.

The organopolysiloxane used in the present invention is 1
For example, an alkoxysilyl group-containing alkene compound and an alkenyl group-containing polyoxyalkylene compound are added to a diorganosiloxane/organohydrodiene siloxane copolymer endblocked with diorgano-hydrogen silyl groups at both ends in desired proportions, and platinum such as chloroplatinic acid is added to the copolymer. It is synthesized by addition reaction using a catalyst system.

The solid material processing agent of the present invention can be prepared by dissolving or self-emulsifying the above-mentioned organopolysiloxane alone or as is in water, or by using a suitable emulsifier 1, such as a sulfuric ester salt of a higher alcohol or an alkylbenzene sulfonate.

Higher alcohol polyoxyalkylene adduct.

It may be used after being emulsified with an alkylphenol polyoxyalkylene adduct, higher fatty acid sorbitan ester, or the like.

Also, toluene, xylene, benzene, n-hexane,
It may be used by dissolving it in an organic solvent such as heptane, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, mineral turpentine, perchloroethylene, or trichloroethylene.

To treat a solid material using the treatment agent according to the present invention,
Spray, roll coating.

This is done by methods such as smearing or dipping.

The amount of adhesion varies depending on the solid material and is not particularly limited, but it is generally 0.01 to 10% by weight based on the solid material. It will be given in due course.

Note that the treatment agent of the present invention includes metal salts of organic acids such as zinc stearate, zinc oleate, diptyltin diacetate, diptyltin dioleate, dibutyltin dilaurate, zirconium stearate, and/or organic acids such as zinc, tin, and zirconium. The treatment may be performed using a combination of amino group-containing alkoxysilanes, epoxy group-containing alkoxysilanes, organohydrodiene polysiloxanes, silanol group-containing organopolysiloxanes, and the like.

The solid materials to which the treatment agent of the present invention can be applied include various fibers and their materials; 5. Sheet-like materials such as paper, natural or synthetic leather, cellophane, and plastic films; 1. Foam-like materials such as resin foam; 1-containing resin molded product.

Natural or synthetic rubber molded products, metal molded products.

Examples include glass molded articles, powdered materials such as inorganic powder, or synthetic resin powder.

The fiber mentioned above is actually hair.

Natural fibers such as wool, silk, linen, cotton, asbestos, recycled fibers such as rayon and acetate, polyester,
polyamide, vinylon.

Examples include synthetic fibers such as polyacrylonitrile, polyethylene, polypropylene, and spandex, glass fibers, carbon fibers, and silicone carbide fibers. In terms of shape.

Stables, filaments, tows, and threads are exemplified, and examples of traditional woven fabrics include Akebono, nonwoven fabrics, resin-treated fabrics, and sewn products thereof.

〔Example〕

Next, the present invention will be explained by examples. In the reference examples and examples, 1 part and % mean parts by weight and % by weight,
Viscosity is the value at 25°C.

Reference Example 1 148.2 g of vinyltrimethoxysilane was charged into a 500 ml three-bottle flask equipped with a reflux condenser and heated until the internal temperature reached 60°C.

Chloroplatinic acid 2% isopropyl alcohol solution 0,15
Then, 51.8 g of tetramethyldisiloxane was added dropwise. After that, the reaction was carried out at 100°C for 2 hours, and the temperature was increased to 140°C.
Distillation was carried out under reduced pressure at 5 nHg to obtain organosiloxane I expressed as 1 formula %.

Next, in a 500 ml three-bottle flask equipped with a reflux condenser, 161.4 g of organosiloxane, 59.8 g of cyclic methylhydrodiene tetramer, and 368°9 g of 4ff of cyclic dimethylsiloxane were added, and they were thoroughly dried as a polymerization catalyst. 15 g of activated clay was charged and polymerized at 75° C. for 10 hours. Thereafter, it was cooled and filtered with an auxiliary agent.

Next, 149.7 g of the allyl group-containing polyether represented by the formula % formula % of the obtained organopolysiloxane 13 and 90 g of toluene were added to a 500. Three samples of J were placed in a flask, heated until the internal temperature reached 60°C, and chloroplatinic acid 2% isopropyl alcohol was added. Thereafter, the mixture was reacted at 120°C for 2 hours.

After the reaction was completed, volatile components were removed under reduced pressure. What was obtained was determined from infrared absorption spectroscopy and nuclear magnetic resonance analysis to be an organopolysiloxane with a viscosity of 305CS (formula %).
It was confirmed that it was organopolysiloxane A).

Reference Example 2 Siloxane II 8 9. 1 g, 7.5 g of vinyltrimethoxysilane, and 60 g of toluene. Heat until the internal temperature reaches 80℃. Add 0.1 g of 2% isopropyl chloroplatinic acid≠alcohol solution.
The reaction was carried out at 110°C for 30 minutes. Thereafter, it was cooled to 80°C, 4g of allyl group-containing polyether 1103 represented by the formula % was added, and heated to 90°C to dissolve 2% chloroplatinic acid in isopropyl alcohol. 15g was added. Thereafter, the mixture was allowed to react at 120°C for 1 hour. After the reaction is complete, reduce the volatile content to 1
It was removed under reduced pressure at 40°C/5 vaHg. What I got. From infrared absorption spectrum analysis and nuclear magnetic resonance analysis.

It was confirmed that it was an organopolysiloxane (organopolysiloxane B) having a viscosity of 1100CS as shown by the formula (%).

Reference Example 3 Siloxane 6 represented by the formula was placed in a 500 ml three-bottle flask equipped with a reflux condenser.9. 3 g, methylvinyldimethoxysilane 1 ], O g and toluene 6
Pour 0 g of chloroplatinic acid into 2% isopropyl alcohol-Jl/solution by heating until the internal temperature reaches Qo℃. v! L.O.
1 g was added, and the reaction was allowed to proceed at 105°C for 30 minutes. Thereafter, it was cooled to 80°C to obtain 7-lyl group-containing polyether 119 represented by the formula %.

Add 7g of chloroplatinic acid, heat to 90°C, and add 0.7g of 2% isopropyl alcohol solution of chloroplatinic acid. 15 g was added,
Thereafter, the mixture was allowed to react at 120°C for 1 hour. After the reaction is complete. 14
Volatile components were removed under reduced pressure at 0°C and 75n+Hg. What I got. From infrared absorption spectrum analysis and nuclear magnetic resonance analysis.

Organopolysiloxane (formula%) with a viscosity of 500CS (
It was confirmed that it was organopolysiloxane C).

Reference example 4 500mj equipped with a reflux condenser! 89.1 g of siloxane ■ used in Reference Example 2 and 7.5 g of vinyltrimethoxysilane were placed in three flasks.

Allyl group-containing polyether 1103 used in Reference Example 2
．． Prepare 4 g and 60 g of toluene, and the internal temperature is 80℃.
0.25 g of 2% isopropyl alcohol ia solution of chloroplatinic acid was added, and the mixture was reacted at 125° C. for 1 hour.

After the reaction was completed, volatile components were removed under reduced pressure at 140° C. and 15 mHg.

The obtained product was organopolysiloxane D with a viscosity of 500 cs as shown by infrared absorption spectroscopy and nuclear magnetic resonance analysis.
It was confirmed that

Example 1 Formula synthesized in Reference Example 1 %formula%) Organopolysiloxane A1 part represented by:

8 parts of glyoxal resin (manufactured by Sumitomo Chemical Co., Ltd., product name: Sumitex Re5in N5-2),
Amine catalyst (manufactured by Sumitomo Chemical Co., Ltd., product name: Sumi
tex Accelerator X-80) 2 parts, 5
A treatment bath was prepared by uniformly mixing 0.5 parts of 1t1 catalyst (50% dibutyltin dilaurate emulsion) and 88.9 parts of water.

B? After adjusting the squeezing rate to 100% using a mangle, the sample was left to dry at room temperature for 10 hours. Thereafter, heat treatment was performed in an oven at 150° C. for 5 minutes. Each of the organopolysiloxane-treated fabrics thus obtained was cut in half to give a total of 4 pieces.
After washing three of the treated fabrics once, five times, and ten times under the following conditions.

Washed fabrics were prepared by rinsing with water (without detergent under washing conditions) twice.

Bath ratio: 1; 50 Temperature: 40°C Time: 10 minutes As a water absorption test, the organopolysiloxane-treated fabrics before and after washing were laid out flat on a sheet of paper, and a drop of water was dropped using a dropper. The time until it was diffused was measured.

In addition, as a test to measure the residual rate of organopolysiloxane, a fluorescence Comparative Example 1 of Residual Rate of Siloxane In Example 1, 85 parts of organopolysiloxane with a viscosity of 1200CS represented by 2 formula % was used in place of organopolysiloxane A (treated in the same way and tested in the same manner). The results are shown in Table 1.

Example 2 2 formulas synthesized in Reference Example 2 %formula% 85 parts of organopolysiloxane.

N-β-(aminoethyl)-γ-7minopropyltrimethoxysilane 0.5 part, dibutyltin diacetate 0.2
1 part and 99.5 parts of toluene were uniformly mixed to prepare a treatment bath. This treatment bath was made of 65% polyester to which 3% of the glyoxal resin used in Example 1 was attached.

A broad cloth (40 am x 20 holes) made of 35% cotton was soaked for 30 seconds and squeezed with a mangle to a squeezing rate of 100.
% and then left to dry at room temperature for 10 hours. This was heat-treated in an oven at 150°C for 5 minutes. The organopolysiloxane treated fabric thus obtained was cut in half,
One piece was treated once under the laundering conditions of Example 1 and rinsed with water twice to produce a laundered cloth.

The organopolysiloxane-treated fabric before and after washing was subjected to the water absorption test and organopolysiloxane residual rate measurement test of Example 1. The results are shown in Table 2.

Comparative Example 2 In Example 2, the organopolysiloxane B used in Comparative Example 1 was replaced with the organopolysiloxane B.

Example 3 In Example 2, instead of organopolysiloxane B, organopolysiloxane C (viscosity 500 cs
t) Treatments and tests were carried out in exactly the same manner except that 5 parts were used, and the results are shown in Table 2.

Comparative Example 2 In place of organopolysiloxane B in Example 2, 2
Organopolysiloxane E (viscosity 1000c)
st) Treatments and tests were carried out in exactly the same manner except that 5 parts were used, and the results are shown in Table 2.

Example 4 The organopolysiloxane treated cloth used in Example 1 was uniformly dissolved in 995 parts of toluene.

Broad fabric (40X) made of 65% polyester and 35% cotton with 3% glyoxal resin attached
20 cm in size) was immersed for 30 seconds, and after making #A with a mangle to a squeezing rate of 100%, it was left to dry at room temperature for 10 hours. The organopolysiloxane-treated fabric thus obtained was divided into two parts, one of the organopolysiloxane-treated fabrics was washed once under the washing conditions of Example 1, and then rinsed with water twice to wash the organopolysiloxane-treated fabric. Test fabrics were obtained before and after treatment.

As an antistatic property test, the treated fabric was washed at 20°C before and after washing.
After being left at a relative humidity of 65% for one week, the friction was measured after 60 seconds at a rotation rate of 800 times/min using a rotary static tester at 5Kyo University Kaken2 using cotton cloth (Kanakin No. 3) as the cloth to be rubbed. The charging voltage was measured.

As an antifouling test, 300 g of ASTM-ml oil,
5 ml of an artificially contaminated liquid prepared by sufficiently grinding and mixing 3 g of coal tar, 5 g of dry viscous powder, 5 g of Boatland cement, and 5 g of sodium dodecylbenzenesulfonate in a mortar.
゜5% Marcel soap aqueous solution 100mj! and 10 steel poles were placed in a 450 ml glass bottle, and the organopolysiloxane-treated fabric and untreated fabric before and after washing were placed in the glass bottle, and treated at 60°C for 30 minutes.After lightly washing with water and drying, 0.5% Using Marcel's aqueous soap solution, the clothes were washed for 10 minutes on high strength in an automatic reversing electric washing machine. After washing and drying the test cloth, use a reflectance meter to
The reflectance at a wavelength of 550 mμ was measured. The results of these tests are shown in Table 3.

Comparative Example 4 Example 4 was treated in exactly the same manner as in Example 4, except that 785 parts of the organopolysiloxane used in Comparative Example 3 was used instead of organopolysiloxane A, and the test was conducted in the same manner. The results are shown in Table 3.

Example 5 10 parts of organopolysiloxane A synthesized in Reference Example 1 and 1 part of zinc stearate were dissolved in 89 parts of water to prepare a treatment solution and applied to one side of a plasma-processed polyethylene terephthalate film at 0.2 g per 1 m2. It was applied by spraying so that the amount of organopolysiloxane deposited was as follows. After attachment, dry overnight at room temperature.

Heat treatment was performed for 10 minutes in an oven heated to 130°C.

As a comparative example, 10% aqueous solutions of each of the organopolysiloxane E used in Comparative Example 3 and a nonionic surfactant (manufactured by NOF Corporation, trade name: NS-210) were prepared.

Similarly, one side of a polyethylene terephthalate film that had been plasma processed was sprayed with a coating amount of 0.2 g per 1 m'', and after drying, it was heat-treated.

These three treated films were immersed in running water for 6 hours, each with the treated side facing down, and the top surface of a thermostatic water bath kept at 60°C ± 2°C was covered with the film and sealed, and the condition of the films was observed after 3 hours. did. As a result, the film treated with organopolysiloxane A, which is the processing agent of the present invention, retained its hydrophilicity, and the inner surface of the film was uniformly twisted and transparent, but the inner surface of the other two films was It does not have hydrophilic properties.

It was cloudy with water droplets on it.

Example 6 0.5 of organopolysiloxane D synthesized in Reference Example 4
% water volume it OOg! After adding 1 g of carbon black powder and 50 g of carbon black powder, the organopolysiloxane A was left to dry and heated at 100°C for 5 minutes.
% deposited carbon black powder was obtained.

Further, as a comparative example, carbon black powder was treated in the same manner using organopolysiloxane E to obtain carbon black powder to which 1% of organopolysiloxane E was attached.

Separately 12 pieces of 50g of each of these carbon blacks
of water, stirred for 3 hours, passed through the mouth, and dried.

A paint was prepared by uniformly dispersing each of the obtained carbon black powders into 5 parts of an aqueous acrylic emulsion type paint. The paint to which carbon black powder treated with organopolysiloxane A was added was uniformly dispersed.

There was no sedimentation, but organopolysiloxane E
The carbon blank powder treated with the above sedimentation was rapid and the dispersion state was non-uniform, and the solid processing agent of the present invention was able to impart durable water-resistance properties.

〔Effect of the invention〕

According to the present invention, at least one of the terminals of the nine molecules is a flukoxysilylalkyl group.

Since it is a solid material processing agent based on organopolysiloxane having at least one polyoxyalkylene group at the side chain or molecular chain end, it can impart durable hydrophilicity or antistatic properties to solid materials. , it is useful for industrial soil.

Patent Applicant TOμ Silicone Co., Ltd. Procedures
Amendment 1. Display of the case 1985 Patent Application No. 112391 2゜ Name of the invention Solid material processing agent 3, Person making the amendment Relationship to the case Patent applicant Postal code 103 (Contact information Telephone: 0436-21-3101 Patent Department) Specification "Claims" column and "Detailed Description of the Invention" column 7, Contents of amendment in the specification (1) The claims are amended as shown in the attached sheet.

(2) On page 4, line 9 [R3-a R, Si　Xa　　J. 1- R, -a R4-5i-Xa”.

(3) On page 4, line 10, "the number of carbon atoms is 1" is corrected to "the number of carbon atoms is 14."

(4) On page 4, line 11, "carbon-based" should be corrected to "carbon."

(5) On page 4, lines 11-12, the phrase "alkyl group" is corrected to read "alkylene group."

(6) The second line from the bottom of the fourth line says "2-200." Correct it to "2-100."

(7) 12-2 f) OJ in the 5th line from the bottom of page 6 is corrected to "2-100".

(8) In the 5th line from the bottom of page 10, the text "Methylhydrothene" is corrected to "Methylhydrothene siloxane."

(9) On page 15, 2nd line from the bottom to the bottom line, replace [Organopolysiloxane D] with [Organopolysiloxane (
Correct with organopolysiloxane D)J.

(10) In the 8th line from the bottom of the 16th [AcceleratorJ
Correct the statement with [AccelatorJ・(11
) Page 19, line 4 says ■ 5i (OCII, ), 0-(C2H,O), Cl1
Correct as l J.

(12) In the fourth line from the bottom of page 23, "Comparative Example 2" is corrected to "Comparative Example 3."

(13) On page 25, line 5, the phrase "dry viscous powder" is corrected to "dry clay powder."

(14) In the 5th line from the bottom of page 25, it says "Electric Washing Machine" instead of "Electric Washing Machine".

(15) On page 30, line 7, it says “Solid processing agent j.
Corrected to "solid material processing agent."

(Attachment) 2. Claims General formula [wherein R is a monovalent hydrocarbon group having 1 to 10 carbon atoms, A
is Q or G. However, at least one of A is Q
It is. Q is a group represented by the formula % formula %, X is a flukoxy group having L to 4 carbon atoms R
1 is an alkylene group having 2 to 5 carbon atoms, and a is 2 or 3.

G is a group represented by the formula %, R2 is a hydrogen atom or a carbon atom number of 1
~5 monovalent isogroup, b and Vc are integers of 0 to 50, provided that b+c is an integer of 2 to 100. p is 5-50
An integer of 0, m is an integer of () to 100, n is O-100
An integer of , where A is Q in total, n is 1 to 100
A solid material processing agent whose main ingredient is Olga/polysiloxane, which is an integer of .

Claims (1)

[Claims] General formula▲ Numerical formulas, chemical formulas, tables, etc.▼ [In the formula, R is a monovalent hydrocarbon group with 1 to 10 carbon atoms, A
is Q or G. However, at least one of A is Q
It is. Q is a group represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼, X is an alkoxy group having 1 to 4 carbon atoms, R^1 is an alkyl group having 2 to 5 carbon atoms, a is 2 or It is 3. G is the formula -R^1-O-(C_2H_4O)_b-(C_3H_
6O)_c-R^2 group, R^2 is a hydrogen atom or a monovalent organic group having 1 to 5 carbon atoms, b and c are 0
An integer from 2 to 50, where b+c is an integer from 2 to 200. l is an integer of 5 to 500, m is an integer of 0 to 100, n is an integer of 0 to 100, provided that when all A is Q, n is an integer of 1 to 100]. Solid material processing agent as main ingredient.