JPS61215683A - Solid material treating agent - Google Patents

Abstract

PURPOSE:To provide the titled treating agent having an excellent durability and capable of imparting water repellency, oil repellency and softness simultaneously to solid materials such as textile materials, which comprises a specific copolymer of an organopolysiloxane with an organic fluorine compound as a main component. CONSTITUTION:5-80pts.wt. organopolysiloxane such as a compound of the formula II having 0.5-50mol% organosiloxane unit having at least one amino group-containing monovalent organic group bonded to Si in its molecule, e.g. a group of the formula I (wherein R<1> is a divalent hydrocarbon residue) and 1-70mol% organosiloxane unit having at least one alkenyl group bonded to Si in its molecule and optionally 90mol% or less other organosiloxane unit is copolymerized with 95-20pts.wt. organic fluorine compound having a perfluoroalkyl group of the formula III (wherein R is H or alkyl) in the presence of a radical polymerization initiator in an organic solvent such as acetone or emulsifier and water at 30-100 deg.C for 1-30hr. The titled treating agent is prepared by using the above product as a main component.

Description

[Detailed Description of the Invention] [Industrial Application Field 1] The present invention relates to a solid material processing agent, and more particularly to a processing agent that can impart durable water and oil repellency to various solid materials. It is.

[Conventional technology 1 Conventionally, in order to impart oil repellency, a treatment agent containing a fluorinated hydrocarbon having perfluoroalkyl as a main component was used!
It is known to treat solid materials such as &m products, leather products, etc.

It is also known to treat these solid materials with a treatment agent based on novolisiloxane in order to impart water repellency.

Furthermore, it is known that solid materials can be treated using a combination of an organic compound containing a perfluoroalkyl group and a novolisiloxane containing a reactive group such as a hydroxy group, an epoxy group, an amide group, or a carboxy group. (Refer to Japanese Patent Publication No. 58-1232 and Japanese Patent Publication No. 59-47071).

[Problem to be Solved by the Invention 1] However, when solid materials, such as WL textile products, are treated with only a treatment agent containing fluorinated hydrocarbons as a main component, the unique texture and texture inherent in the textile products may be affected. The disadvantage was that flexibility was lost.

Furthermore, treatment with organopolysiloxane has the disadvantage that oil repellency cannot be imparted to solid materials.

Furthermore, even by using a combination of an organic compound containing a perfluoroalkyl group and an organopolysiloxane having a reactive group, the expected oil repellency is generally not obtained, or the oil repellency is not durable. It has the disadvantage that it cannot simultaneously provide durable water repellency and oil repellency.

The present invention aims to eliminate the drawbacks of the prior art as described above, and aims to provide water repellency with excellent durability to solid materials.
The present invention provides a novel processing agent that can impart oil repellency.

[Means for Solving the Problems] The above objectives are (8) A monovalent organic group containing amine 7 groups that is bonded to at least one silicon atom in one molecule, and a monovalent organic group that is bonded to at least one silicon atom in one molecule. An organopolysiloxane having an alkenyl group and (B) an organofluorine compound having a group represented by the formula % (in the formula, R is a hydrogen atom or a furkyl group) and a perfluoroalkyl group in one molecule are used as a radical polymerization initiator. This can be achieved by solid material processing agents based on copolymerized products.

To explain this, component (8) is an organoorganic compound having in one molecule a monovalent organic group containing amine 7 groups bonded to at least one silicon atom and an alkenyl group bonded to at least one silicon atom. It is polysiloxane.

A representative example of the monovalent organic group containing amide 7 groups bonded to the silicon atom of this component is a group represented by the general formula %. In the above formula, 81 is a divalent hydrocarbon group, which includes -CH2-1-(C)I2)2-
1-(CH2), -1-eH2CH(CI, )C11
, -1-(C)12L-, -(C
)12) Alkylenearylene groups such as 2-c, tt and - are exemplified. R2 is a hydrogen atom or an alkyl group, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a hexyl group. a is an integer from 0 to 10. Groups that bond to the silicon atom include monovalent hydrocarbon groups, alkoxy groups, and hydroxyl groups; examples of monovalent hydrocarbons include furkyl groups such as methyl, ethyl, propyl, butyl, and pentyl groups. , 2-phenylethyl group, 2-phenylpropyl group, aralkyl group, phenyl group, tolyl group, naphthyl group, unsubstituted monovalent hydrocarbon group such as aryl group such as xylyl group, or hydrogen atom of these groups An example is a group in which is partially substituted with a halogen atom such as a chlorine atom or a fluorine atom. Examples of the alkoxy group include methoxy group, ethoxy group, impropoxy group, and methoxyethoxy group.

Examples of the alkenyl group bonded to a silicon atom include a vinyl group, an allyl group, a butenyl group, and a propenyl group, and preferably a vinyl group and an allyl group. The groups bonded to the silicon atom include monovalent hydrocarbon groups, alkoxy groups, and hydroxyl groups, and the monovalent hydrocarbon groups and alkoxy groups are as described above.

In this component, the proportion of organosiloxane units having a monovalent organic group containing amine 7 groups bonded to a silicon atom is
There is no particular restriction as long as at least one group-containing monovalent hydrocarbon group is present in one molecule, and it varies depending on the purpose and use, but from the point of view of imparting durability, the total amount of organomesiloxane units is 0. It is preferably 5 to 50 mol%,
More preferably, it is 1 to 30 mol%.

In addition, the proportion of organosiloxane units having an alkenyl group bonded to a silicon atom is not particularly limited as long as at least one alkenyl group is present in one molecule, and varies depending on the purpose and use. From the viewpoint of efficiently exhibiting the above, it is preferably 1 to 70 mol%, more preferably 2 to 50 mol% of the total ol/siloxane units.

This component may be composed only of these siloxane units, or may contain a single organosiloxane unit. In the single organosiloxane unit, the group bonded to the silicon atom is a monovalent hydrocarbon group. , alkoxy group, and hydroxyl group. The monovalent hydrocarbon group and alkoxy group are as described above. The proportion of the organosiloxane units is preferably 95 mol% or less, more preferably 20 to 90 mol%.

The molecular structure of the ornovolisiloxane component may be linear, branched, cyclic, or network-like, and the viscosity and molecular weight are not particularly limited.

Specific examples of this ingredient include: NH(CH2)tl’lHi is exemplified.

Component (B) used in the present invention is an organic compound containing a group represented by the formula % (wherein R is a hydrogen atom or an alkyl group) and a perfluoroalkyl group in one molecule.

In the above formula, R is a hydrogen atom or an alkyl group, and examples of the alkyl group include a methyl group, an ethyl group, and a propyl group.

As perfluorofurkyl group, -CF,, "-C2F s, -c, F,, -C,F,,
-C,F,, -C,. F2-CI2F25,-C2
An example thereof is ゜F2I, but from the viewpoint of imparting oil repellency, a perfluoroalkyl group having 3 or more carbon atoms is preferred.

Specific examples of this component include CIl, = (1: HC, F,
3, CH2=CI(C,F,,,C1,=CHC00C
H2C4F,,a112=C[1COQ-C,11,-
CaF+t, C02=CHCOO-C,H,-C,F,
,,CH2=C(CH3)C2■4 CaFI2,
C11,=CHC0O-C2)1. -C,F,,C1
12=CIICOO-C,,H2□-C,F,.

C)1. =C11COOC21f4N(C,)I,
>5O2C,F, ,,C11,=CHCH20COC
,,H,,N((:H,)SO2C,F, .

is exemplified.

The processing agent of the present invention is obtained by copolymerizing component (^) and component (B) in the presence of a radical polymerization initiator.

(^) The proportion of copolymerization of 1&min and (B) component is not particularly limited, but as the proportion of (^) component increases,
The copolymer product becomes softer and more viscous, giving more flexibility to the solid material, and as the proportion of CB>Il, increases, the copolymer product becomes harder and more solid. Preferably, the amount of component (8) is 5 to 80 parts by weight and component B) is 95 to 20 parts by weight, since it imparts more oil repellency to the material.

The radical polymerization initiator may be any polymerization catalyst conventionally used for radical polymerization of vinyl resins, such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl. Peroxide, 2,5-(peroxybenzoate)hexyne-3,1,3-bis(1-butylperoxyisopropyl)benzene, lauryl peroxide, t-butyl peracetate, 2,5-dimethyl-2,5 -shi (t, --f
Chilperoxy)hexyne-3,2,5-dimethyl-2
- Examples include organic peroxide catalysts such as 5-di(t-butylperoxy)hexane, 7-compound catalysts such as azobis-isobutyronitrile, diamethylazodiisobutyrate, or redox catalysts. .

The polymerization reaction can be carried out using organic solvents such as acetone, methyl isobutyl ketone, methyl ethyl ketone, trichloroethylene, perchlorethylene, trichloroethane, trichlorotrifluoroethane, toluene, or higher alcohol polyoxyalkylene adducts, higher fatty acid polyoxyalkylene phenol polysaccharides, etc. The polymerization can be carried out by solution polymerization, suspension polymerization, emulsion polymerization, etc. in a homogeneous or heterogeneous system in the presence of an emulsifier such as an oxy-ex-kylene adduct and water. The polymerization temperature is approximately 30 to 100℃
The polymerization time may be approximately 1 to 30 hours.

To treat a solid material using the treatment agent according to the present invention,
This can be done by spraying, roll coating, coating, dipping, or other methods. The amount of adhesion varies depending on the solid material and is not particularly limited, but 0.0
Generally, it is deposited in an amount of 1 to 10.0% by weight. Then, durable water and oil repellency can be imparted to the solid material by leaving it at room temperature, blowing hot air, heat treatment, etc.

The treatment agent of the present invention may further contain water repellents, oil repellents, antistatic agents, dye stabilizers, anti-wrinkle agents, etc., as long as they do not impede the object of the present invention.

Solid materials to which the treatment agent of the present invention can be applied include various fibers and their ammonium products, paper, natural or synthetic leather, cellophane, sheet-like materials such as plastic films, foam-like materials such as synthetic resin 7 ohm, Examples include synthetic resin molded articles, natural or synthetic rubber molded articles, metal molded articles, glass molded articles, inorganic powders, and powdered materials such as synthetic resin powders.

The above-mentioned fibers include natural fibers such as hair, albeca, mohair, angora, wool, silk, linen, cotton, and asbestos, recycled fibers such as rayon and acetate, polyester, polyamide, vinylon, and polyacrylonitrile. , polyethylene, polypropylene, synthetic fibers such as spandex, glass fibers, carbon fibers, and silicone carbide fibers.

Examples of shapes include stable, filament, tow, top, and thread, and examples of 1.11wt materials include knitted fabrics, woven fabrics, nonwoven fabrics, resin-treated fabrics, and sewn products thereof.

[Use 1] In the copolymer, the organopolysiloxane unit derived from component (A) imparts water repellency, flexibility and durability to the solid material, and the organopolysiloxane unit derived from component (B) imparts water repellency, flexibility and durability to the solid material. The unit imparts water and oil repellency to solid materials, (
8) Organopolysiloxane units derived from component (B)
) The organic fluorine compound units derived from the components combine to provide durable water repellency, oil repellency, and flexibility to solid materials at the same time.

[Example 1 Next, the present invention will be explained by examples.

Example 1 Cyclic methylvinylsiloxane 4HHt, 1 g, cyclic dimethylsiloxane tetramer 80.3 g, amine 7 group-containing ornovorisiloxane represented by the formula 5.2
5.4 g of dimethylpolysiloxane endblocked with trimethylsilyl groups at both ends and having a viscosity of 10 centistokes at 25° C. and 08015 g of potassium hydroxide as a catalyst were charged into a 500 cc four-bottle flask equipped with a stirrer, a reflux condenser, and a thermometer. ”(:') for 10 hours.

After the reaction, the catalyst was neutralized with 0.016 g of acetic acid and heated at 130°C.
Low volatile components were distilled off at 20 mIIIHg to synthesize Orga/Polysiloxane 1 shown by the average compositional formula.

Next, 16.0 g of this or-novolisiloxane and 20.0 g of an organic fluorine compound represented by the formula CH2=CHC00(CH2)2(CF2), F. Azoobisisobutylketone and 150g of 1,1,1-trichloroethane were put into a 500cc four-bottle flask equipped with a stirrer, a reflux condenser, and a thermometer, and heated to 75°C. Processing agent A of the present invention was synthesized by adding 0.15 g of lonitrile and copolymerizing it by keeping it at the same temperature for 2 hours. The resulting treatment agent A was a transparent and stable dispersion with a solid content of 10.6% by weight.

After removing the solvent, the obtained treatment agent A was analyzed using an ultraviolet absorption spectrophotometer and an infrared absorption spectrophotometer, and no vinyl groups were detected, confirming that it was a copolymer.

Further, when the treatment agent Aug was placed in an aluminum dish, the solvent was evaporated at room temperature, and then heat treated at 150°C for 3 minutes, a flexible and transparent film-like substance was observed that adhered to the aluminum dish.

Next, a treatment bath was prepared by diluting treatment agent A with methyl ethyl ketone so that the solid content was 0.5% by weight, and 3
0x30cm size polyester fiber A165% cotton 3
Three pieces of 5% blended Burberry fabric were dipped for 10 seconds and adjusted with a roller so that the drawing rate was 100%. After drying these three cloths at room temperature, they were heat-treated at 150''C for 13 minutes.

One of the three treated cloths was washed for 15 minutes using a 0.3% aqueous solution of synthetic detergent manufactured by Lion Corporation (product name 2221 White), washed with water for 10 minutes, dried, and washed with water. It was laundry.

In addition, another piece of treated cloth was stirred in perchlorethylene (bath ratio 1:50) for 15 minutes to dry clean.

A flexibility test, a texture test, a water repellency test, and an oil repellency test were conducted on each of the obtained fabrics as follows.

Main flexibility test: The extrusion length (1111) was measured according to JIS L1096, general textile testing method, and cannalev method.

Main texture test: The texture was evaluated in the following three grades.

○...Extremely flexible, with good waist and rebound elasticity.

△...Flexibility, waist, and rebound elasticity are insufficient.

×: Rough and hard, with poor elasticity and rebound.

Vehicle inspection water resistance: According to JIS L1092 (1977).

*Oil repellency: One drop of liquid paraffin was dropped on a cloth, and the time (seconds) it took for the drop to disappear after being diffused onto the cloth was measured.

In addition, as Comparative Example 1, Or77' synthesized in Example 1
/Polysiloxane 110. Og, 28.5 g of methyl isobutyl ketone, 61.5 g of 1,1,1-trichloroethane
g and 1910 g of methyl ethyl ketone to prepare a treatment bath with a solid content of 0.5% by weight, and the same Burberry fabric as in Example 1 was immersed in the same bath, and heat treatment, washing treatment, and various tests were conducted in the same manner.

In addition, as Comparative Example 2, only an organic fluorine compound was polymerized in the same manner as in Example 1 except that ornovolisiloxane I was added to the treatment solution, and after the reaction, the solid content was diluted to 0.05% by weight with methyl ethyl ketone. A treatment bath was prepared. Burberry fabric was treated in exactly the same manner as in Example 1, and subjected to heat treatment, washing treatment, and various tests.

Further, as Comparative Example 3, a mixture of equal weights of Comparative Examples 1 and 2 was prepared, and treated on a Parberry fabric in exactly the same manner as in Example 1, and subjected to heat treatment and various tests.

Note that the untreated cloth was also subjected to washing treatment and various tests in the same manner.

As the results are shown in the $1 table, the treatment agent of the present invention can impart water repellency, oil repellency, and flexibility at the same time, and its effects remain almost unchanged even after washing with water and dry cleaning, and the durability is superior. Table 1 Example 2 120 g of Orj/polysiloxane synthesized in Example 1,
After uniformly mixing 3.3 g of polyoxyethylene/nylphenol ether (6 moles of ethylene oxide adduct), 0.7 g of polyoxyethylene nonylphenol ether (12 moles of ethylene oxide adduct), and 75 g of water, emulsion was created using an emulsifier. was prepared.

Next, 23.0 g of an organic fluorine compound represented by the formula %) and 30.0 g of acetone. Og was charged into a 500cc four-bottle flask equipped with a stirrer, a reflux condenser, and a thermometer, and was uniformly dissolved. Add to this the emul resin 30. After adding Og and 16.8 g of water, the mixture was heated to 62° C., 0.2 g of ammonium persulfate was added, and the mixture was stirred at the same temperature for 3 hours to carry out emulsion polymerization to prepare a processing agent B of the present invention.

The obtained treatment agent B was diluted with water so that the solid content was 0.5% by weight, and treated on a raincoat fabric so that the squeezing rate was 100%. After air drying at room temperature, heat treatment and washing treatment were performed under the same conditions as in Example 1, and various tests were conducted in the same manner.

As shown in Table 2, the results show that durable water repellency, oil repellency and flexibility can be imparted at the same time.

Table 2 Example 3 30 g of novolisiloxane and 8! 70 g of fluorine compound, 180 g of methyl isobutyl ketone, and 2 portions of cyto1,1-trichloroethane
10 equipped with a stirrer, reflux condenser and thermometer
After putting four 00 cc into a flask and heating at 75° C., 1.3 g of azobisisobutyronitrile was added and kept at the same temperature for 2 hours to copolymerize to synthesize the processing agent C of the present invention.

After removing the solvent, the obtained treatment agent C was analyzed using an ultraviolet absorption spectrophotometer and an infrared absorption spectrophotometer, and no vinyl groups were detected, confirming that it was a copolymer.

Further, when the treatment agent CIFI was placed in an aluminum dish, the solvent was evaporated at room temperature, and then a heat treatment was performed at 150°C for 3 minutes, a flexible and transparent film-like substance that adhered to the aluminum dish was observed.

A treatment bath was prepared by diluting treatment agent C with methyl ethyl ketone so that the solid content was 0.5% by weight, and 10% of wool was added to this treatment bath.
0% cashmere skin men's clothing fabric was processed at a squeezing rate of 100%. This was subjected to heat treatment and washing treatment under the same conditions as in Example 1, and various tests were conducted in the same manner.

As shown in Table 3, durable water repellency, oil repellency and flexibility could be imparted at the same time.

Table 3 [Effects of the Invention 1] According to the treatment agent of the present invention, an oro-novolisiloxane having 7 amino groups and 8!
Since the main ingredient is a copolymer of fluorine compounds, it is possible to simultaneously impart durable water repellency, oil repellency, and flexibility to solid materials.

Therefore, it can be suitably used as a water repellent, oil repellent, antifouling agent, softener, mold release agent, polishing agent, etc. for various solid materials.

Claims (1)

Scope of Claims: (A) an organopolysiloxane having in one molecule an amino group-containing monovalent organic group bonded to at least one silicon atom and an alkenyl group bonded to at least one silicon atom; B) A product obtained by copolymerizing an organic fluorine compound having a group represented by the formula CH_2=CR- (wherein R is a hydrogen atom or an alkyl group) and a perfluoroalkyl group in one molecule in the presence of a radical polymerization initiator. A solid material processing agent whose main ingredient is solid material.