JPH02269737A - New chelate polymer and its use - Google Patents

Abstract

PURPOSE:To provide a new chelate polymer which can impart excellent water and oil repellency to a fiber or the like without heat treatment by using a perfluoropolyether polyimidoylamidine and a specified polyvalent metal ion. CONSTITUTION:A chelate polymer is produced from a perfluoropolyether polyimidoylamidine (A) comprising repeating units of formula I (wherein Rf0 is a perfluoropolyether chain of a number-average MW of 500-80000, e.g. of formula II, III or the like; and p+q=4-500) and a polyvalent metal ion (B) of Group Ib, IIb, IIIa, IIIb, IVb, Vb, VIb, VIIb or VIII of the periodic table (e.g. Al ion or Fe ion). Because a water an oil repellent based on this chelate polymer can impart water and oil repellency to a substrate without high- temperature heat treatment, the hand of the substrate is not impaired.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel fluorine-based chelate polymer and a fluorine-based water- and oil-repellent agent containing the polymer as a main component.

The water and oil repellent of the present invention can be applied to textiles, leather, paper products, etc., does not require heat treatment at high temperatures to develop water and oil repellency, does not impair the texture of the material, and has excellent durability. It is a new water and oil repellent.

(Prior Art and Problems) It is known that a fluorine-containing polymer containing the following (A) monomer and/or the following (B) monomer as a constituent unit exhibits excellent water and oil repellency.

I (A): Rr-R''-0COC-CHl (wherein R
f is a perfluoroalkyl group having 5 to 16 carbon atoms, R1
is a hydrogen atom or a methyl group, R2 is an alkylene group having 1 to 10 carbon atoms, and R' is a hydrogen atom or a methyl group having 1 to 18 carbon atoms.
represents an alkyl group. ) However, these polymers require arrangement of perfluoroalkyl groups in order to fully exhibit water and oil repellency, so heat treatment at high temperatures is essential. This heat treatment at high temperatures results in a significant loss of the feel of the fiber fabric material.

In addition, the water and oil repellency obtained from the above-mentioned fluorine-containing polymers is significantly reduced in appearance by washing and dry cleaning. Heat treatment was essential.

For consumers who actually use textiles treated with water-repellent electro-oil, the dry cleaning itself can be outsourced to a professional company; When it comes to things, it is not easy to iron them, and there are some items such as diaper covers that are not normally ironed, so there was a desire for a water- and oil-repellent agent that does not require heat treatment at high temperatures.

(Means for Solving the Problems) In view of the above-mentioned circumstances, the present inventors have made extensive studies and have found the following general formula (I): (wherein, Rf is a number average molecule of 1500 to 80° 0OO1
It preferably represents a perfluoropolyether chain having a number average molecular weight of 800 to 10.000. ), a novel chelate polymer composed of a perfluoropolyether polyimidoylamidine having an intrinsic viscosity of 0.02 to 0.60 a/g and a polyvalent metal ion, which is composed of repeating units, has excellent properties. The present invention was developed based on the discovery that it exhibits water and oil repellency, does not require heat treatment at high temperatures to develop water and oil repellency, does not impair the texture of the textile material, and has excellent durability. It was completed.

The perfluoropolyether polyimidoylamidine used in the present invention can be synthesized by various methods. As stated,
Polymerization of perfluoropolyether dinitrile (C) and perfluoropolyether cyamidine (D), or perfluoropolyether dinitrile as described in U.S. Pat. No. 4,242,498. It is obtained by bringing (C) into contact with ammonia.

The intrinsic viscosity of perfluoropolyether polyimidoylamidine is 0.02 to 0.60 dl/g.

Preferably it is 0.03 to 0.50 a/g. If the intrinsic viscosity is lower than this, the leprosy and oil repellency will be insufficient, and if the intrinsic viscosity is higher than this, the solubility in the coating solvent will be insufficient, so it is not practical.

NC-Rf, -CN... (C) (C)
In the formula and formula (D), Rr represents a perfluoropolyether chain, for example, - formula (E)
Number average molecular weight represented by ~(J) 500~so, ooo
, preferably a number average molecular weight of 600 to 30,000, more preferably a number average molecular weight of 800 to 10,000.

-Ch (OCFtCF Tsuji 7O-A-01hCFzO piece F!-(F)-CF2MCFICF!
O#CFAr (G)CFi -ChO+CFCPtO)i Lid ChOi CFi-(H
)-CFIChO-(-CFiChCFtOi cpz
cpz-(J) (where p and q are O or an integer of 1 or more, and the value of P+Q is between 4 and 500, preferably 4
and 300. Further, A is a perfluoroalkylene group, a divalent group having a perfluoroether structure, or a substituted product thereof. ) Perfluoropolyether dinitrile (C) can be obtained by ring-opening polymerization of a fluorine-based epoxy compound, by decomposing a polymer obtained by copolymerizing fluorine-based olefin and oxygen, or by ring-opening a cyclic ether containing fluorine and hydrogen. It can be obtained by converting an acid fluoride obtained by fluorination after polymerization to a nitrile via an amide.

Further, perfluoropolyether cyamidine (D) can be obtained by contacting perfluoropolyether dinitrile (C) with ammonia.

The metal ions used in the present invention include Ib, II
b, ma, l1lb, IVa, IVb, Vb, Vlb,
Polyvalent metal ions of group ■b, group ■ (here, subgroup a represents a typical element, and subgroup s represents a transition element.) More preferably, aluminum ions, titanium ions, vanadium ions, manganese ions, chromium ions, Examples include iron ions, cobalt ions, nickel ions, copper ions, zinc ions, gallium ions, zirconium ions, molybdenum ions, silver ions, indium ions, tin ions, tungsten ions, and lead ions.

Further, the types of metal compounds used as a metal ion source in the present invention include inorganic acid salts such as sulfates, nitrates, phosphates, and carbonates; halides such as fluorides, chlorides, and bromides; methoxides, Alkoxides such as ethoxide, isopropoxide, n-butoxide; carboxylates such as acetate, propionate, stearate, oleate; metals such as acetylacetonate, ethylacetoacetate, octadecenylacetoacetate Examples include chelate compounds.

Specific examples of metal compounds used in the present invention include chromium nitrate, ferric sulfate, aluminum nitrate, cobalt nitrate, nickel nitrate, zinc nitrate, copper sulfate, copper acetate, zinc chloride, titanium tetrabutoxide, zirconium tetrabutoxide. , aluminum acetylacetonate, titanium i-proboxyoctylene glycolate, octadecenyl acetoacetate aluminum diisopropylate, and the like.

The chelate polymer of the present invention is obtained by contacting perfluoropolyether polyimidoylamidine with metal ions. Any contact method can be applied depending on the application.

For example, a solution of perfluoropolyether polyimidoylamidine in a fluorine-containing solvent such as 1.1.2-trichloro-1゜2.2-)rifluoroethane is brought into contact with a metal water repellent solution to form a chelate polymer at the interface. or 1. of perfluoropolyether polyimidoylamidine. 1. 2 = A method of producing a chelate polymer by bringing a metal salt into direct contact with a solution of a fluorine-containing solvent such as trichloro-1,2,2-trifluoroethane; Immersion in a solution of ether-based polyimidoylamidine 1. Alternatively, a method may be used in which a chelate polymer is produced on the surface of the fibrous fabric material by immersing the fibrous fabric material carrying perfluoropolyether polyimidoylamidine in a solution of a metal salt or alkoxide.

Note that treatment with perfluoropolyether polyimidoylamidine alone does not result in high water repellency and durability, and high water repellency and high durability are only possible with the chelate polymer of the present invention.

Various operations can be used as a treatment method using 1 g of oil containing chelate polymer of the present invention as a main component.
For example, a material to be treated with water and oil repellency is immersed in a solution or suspension containing 0.01 to 20% by weight of a metal salt or alkoxide, and after drying, the material is coated with perfluoropolyether polyimidoylamidine. It is obtained by immersing it in a solution or emulsion containing oi to 20% and drying it. Although the formation of the chelate polymer is possible at room temperature, it can also be completed in a short time by heating.

Therefore, the chelate polymer formation temperature ranges from 0°C to 250°C.
°C5 is preferably 5°C to 180°C, particularly preferably 10°C to 130'C.

Treatment base materials to which the water- and oil-repellent agent of the present invention can be applied include:
It is used for a wide variety of things, including textile materials.
For example, paper, wood, leather, and fur.

Typical textile materials include natural fibers such as cotton, hemp, wool, or silk; polyamide, polyester, polyurethane, polyvinyl alcohol, polyacrylonitrile, and polyvinyl chloride. or semi-synthetic fibers such as rayon or acetate. It can be used for fiber fabric materials made by mixing these materials, and also for products such as carpets, raw yarn, raw cotton, etc.

The water- and oil-repellent agent of the present invention may be mixed with other polymeric blenders, and used in combination with other water-repellent agents, insect repellents, flame retardants, antistatic agents, softeners, and other appropriate additives. It is also possible.

(Examples) The present invention will be described in more detail below with reference to Examples, but the present invention is not limited thereto.

In addition, each data of I-integrity and electro-oil properties shown in Examples was based on the following measurement method and evaluation criteria.

- Leprosy: After dropping water droplets on the test fabric, the surface condition of the test fabric after removing the water droplets after 5 minutes was observed and expressed as the "water repellency level" shown in Table 1.

■Oil repellency: Various solvents with different surface tensions shown in Table 2 were dropped onto the test fabric, and the droplets were held for 3 minutes to reach the maximum "oil repellency" to determine the oil repellency.

Table 1 Table 2 Reference reaction examples Below are examples of the synthesis of various perfluoropolyether polyimidoylamidines used in the present invention. Although a method for synthesizing amidine is illustrated, the method for synthesizing perfluoropolyether polyimidoylamidine used in the present invention is not limited thereto.

Reference reaction example 1 Polymerization method of hexafluoropropylene oxide described in Japanese Patent Publication No. 53-5360, JP-A-57-17518
According to the method for purifying hexafluoropropylene oxide described in Publication No. 5 and the method for converting polymer end groups described in U.S. Pat. No. 3,317,484, hexafluoropropylene oxide was used as a polymerization initiator. is polymerized and via RF-(COOCH3)z,
RF(CN)z having a number average molecular weight of approximately 5,000 was synthesized.

A viscous substance (hereinafter referred to as D
A) 20g, RF(CN)z and RF −
(CN) z / D A+ preparation weight ratio 0.98
So, 250m 1.1.2-) Sacroro 1.2.2-
Dissolved in trifluoroethane. 1 with evaporator
．． 1.2-) Dichloro-1,2,2-1-lifluoroethane was completely removed and the resulting clear homogeneous mixture was
When left standing for 15 hours at 'C, the intrinsic viscosity was 0.1.
3a/g of perfluoropolyether polyimidoylamidine (hereinafter abbreviated as PTA+) was obtained.

Reference reaction example 2 RF, (CN)! /DA, the preparation weight ratio is 0°86
A perfluoropolyether polyimidoylamidine (hereinafter abbreviated as PIA2) having an intrinsic viscosity of 0.22 dl/g was synthesized in exactly the same manner as in Reference Reaction Example 1, except for the following.

Reference Reaction Example 3 In the same manner as Reference Reaction Example 1, RF (CN) having a number average molecular weight of about 1500 was synthesized.

A viscous substance (hereinafter referred to as D
(abbreviated as At), RFo(CN)z and RF-
At a charging weight ratio of (CN)t/DAz of 0.88, 25
0 m of 1.1.2-trichloro-1,2,2-trifluoroethane. 1.1.2 with evaporator
- Trichloro-1,2,2-trifluoroethane was completely removed and the resulting clear homogeneous mixture was heated at 40 °C for 15 min.
When left standing for an hour, perfluoropolyether polyimidoylamidine (with an intrinsic viscosity of 0.12a/g)
Hereinafter, abbreviated as PIAs) were obtained.

Reference reaction example 4 RF, (CN)t 10A+ charge weight ratio of 1°O
A perfluoropolyether polyimidoylamidine (hereinafter abbreviated as PIA4) having an intrinsic viscosity of 0.09 a/g was synthesized in exactly the same manner as in Reference Reaction Example 1 except that O was used.

Reference Reaction Example 5 NC-CF! according to Example 5 in Canadian Patent No. 960,022! Yun OCF, OF out 5 OCF! hCN(p
/q-about 1.5, number average molecular weight about 1500), (CN)t was synthesized.

A viscous substance (hereinafter referred to as D
(abbreviated as A s) 20g, RF(CN)z and RF
- Charge weight ratio of (CN)t/DAi: 1. OO, 2
50I11 was dissolved in 1,1,2-trichloro-1,2,2-trifluoroethane. 1. With the evaporator.
1.2-Trichloro-1,2,2-)lifluoroethane was completely removed, and the resulting transparent homogeneous mixture was allowed to stand at 40°C for 15 hours, resulting in an intrinsic viscosity of 0.05a/
g of perfluoropolyether polyimidoylamidine (hereinafter abbreviated as PIAs) was obtained.

Example I 1,1,2-trichloro-1, containing 2% PIA,
0.02 parts by weight of zinc acetylacetonate complex was added to 100 parts by weight of the 2,2-)rifluoroethane solution, and the mixture was reacted at room temperature for 4 hours to precipitate a chelate polymer.

This chelate polymer has an IR characteristic absorption of 159
It has an absorption at 0.1510C11-', and no change was observed in either the polymer properties or the IR even after heating at 200°C in air for 1 hour.

Examples 2 to 9 A 2% aqueous solution of various metal salts and a 1,1',2-)dichloro-1,2,2-trifluoroethane solution containing 2.0% PIA were brought into contact and left to stand still for 20 minutes. The third result is
Shown in the table.

As can be seen in Table 3, in each example, 1
, 1. A chelate polymer insoluble in 2-1-dichloro-1,2,2-trifluoroethane was produced.

Example 10 Cotton broadcloth was immersed in a 0.5% aqueous solution of copper acetate for 1 minute, and then dried at 100°C for 10 minutes.

Then, 1°1.2 containing PTA at a concentration of 1.0%
-) The cloth was immersed in dichloro-1,2,2-trifluoroethane solution for 1 minute and then air-dried for 30 minutes at room temperature.

The thus treated fabric had a water repellency of 100 and an oil repellency of 5.

In addition, this cloth is 1,1,2-trichloro-1゜2.2-
) Even after washing with refluoroethane, the water repellency was 100.

Example 11 Zirconium tetrabutoxide was added to 0. l containing at 5% concentration, 1. The polyester cloth was immersed in the 1'-1-refuroethane solution for 1 minute, and then dried at 100°C for 10 minutes. The cloth was then immersed in a 1,1,2-trichloro-12,2-trifluoroethane solution containing PIA at a concentration of 1.0% for 1 minute, and then air-dried for 30 minutes at room temperature.

The thus treated fabric had a water repellency of 100 and an oil repellency of 5.

As a simulated method for evaluating the dry cleaning resistance of this fabric, 1,1.1-) The fabric was stirred in reflow ethane for 30 minutes and then air-dried for 30 minutes, which was repeated 20 times. was maintained.

Example 12 A polyester cloth was immersed for 1 minute in a 1,1.1-) rifloethane solution containing octadecenyl acetoacetate aluminum diisopropylate (manufactured by Yoken Fine Chemical ■; Aluminum Chelate M) at a concentration of 0.5%. After that, i
o o ”c for 10 minutes. Then PIAI
1,1,2-trichloro- containing at a concentration of 1.0%
The cloth was immersed in the 1,2,2-trifluoroethane solution for 1 minute, then air-dried for 10 minutes at room temperature, then 100%
Cure for 10 minutes at °C.

The water repellency of the fabric thus treated was 100. In addition, this cloth was washed with detergent (product name: Newbead>2g/l, bath ratio 1:30.40゛C) using a household electric washing machine.
Water repellency of 100 was maintained even after washing for 5 minutes at room temperature, rinsing for 2 minutes at room temperature, dehydrating, rinsing again for 2 minutes, dehydrating, and drying at 70"C for 20 minutes.

Examples 13-29 Fabric materials shown in Table 4, solutions of metal salts - maximum (1)
Water repellency treatment was performed in the same manner as in Example 10 using a solution of perfluoropolyether polyimidoylamidine. Table 4 summarizes the results of evaluating the water repellency of each fabric.

Example 30 1, 1.2-) Lichloro 1.2.2-) containing 0.5% titanium i-proboxyoctylene glycolate (manufactured by Nippon Soda; TOG) and 1.0% PIA. After soaking the polyester cloth in the refluoroethane solution for 1 minute, it was air-dried at room temperature for 10 minutes, and then at 100 °C for 1 minute.
It was cured for 0 minutes. The water repellency of the fabric treated in this way was 100.

Example 31 A polyester cloth was immersed in a 1,1.2-)lichloroethane solution containing 1,0% PIA for 1 minute and then dried at 100'C for 10 minutes. . Next, the cloth was immersed for 1 minute in a 1, l, i-trichloroethane solution containing 0.5% titanium i-propoxyoctylene glycolate (manufactured by Nippon Soda ■; TOG), and then air-dried for 10 minutes at room temperature. Then 100°
C. for 10 minutes.

The water repellency of the fabric treated in this way was 100.

Comparative Example I 1,1,2-)dichloro- containing 2.0% PIAI
The polyester cloth was immersed in the 1,2,2-trifluoroethane solution for 1 minute, air-dried at room temperature for 10 minutes, and then cured at 100°C for 10 minutes.

The water repellency of the cloth treated with this method was 70, and the water repellency after washing this cloth with 1.1.2-1-lichloro-1,2°2-trifluoroethane was 0.

Comparative Example 2 PIA, <7) Instead of RYTOX 143 A
D (DuPont product; number average molecular weight 8250) CF.

Structural formula; ChCFzChO-+CFChOh FIC
The water repellency of the fabric treated the same as in Comparative Example I, except using Fff, was 70, and the water repellency after washing this fabric with 1.1.2-trichloro-1,2,2-trifluoroethane was O.

Comparative Example 3 PIA, (1) instead of FOMBLIN YR(-
1-7 Tes '70s product; number average molecule i15,500 ~
7.50CF.

Structural formula i cp3o-(cp!o斥→CFICFO piece C
F.

The fabric treated in the same manner as in Comparative Example 1 except that 1.1.2-trichloro-
The water repellency after washing with 1,2,2-)rifluoroethane was O.

(Effects of the Invention) The chelate polymer of the present invention can be used as a fluorine-based water-repellent and oil-repellent agent applied to fibers, leather, paper products, and the like.

In particular, it does not require high-temperature heat treatment to develop water-repellent and oil-repellent properties, does not impair the texture of the material, and has excellent durability.

Claims (2)

[Claims] (1) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, Rf_o is a number average molecular weight of 500 to 80,000.
perfluoropolyether chain. ), indicated by
Intrinsic viscosity consisting of repeating units is 0.02-0.60d
Perfluoropolyether polyimidoylamidine within the range of l/g and I b, IIb, IIIa, IIIb, IV
A chelate polymer composed of polyvalent metal ions of groups a, IVb, Vb, VIb, VIIb, and VIII. (Here, subgroup a represents typical elements, and subgroup b represents transition elements.) (2) A water and oil repellent agent containing the above chelate polymer as a main component.