JPH05105723A - Water-repellent and oil-repellent resin - Google Patents

Abstract

PURPOSE:To obtain the subject resin useful as a water-repellent and oil-repellent treating agent for the surface of glass, metal, plastics, etc., having excellent chemical stability, weather resistance, heat resistance, etc., containing a specific amount of a fumaric diester as a structural unit. CONSTITUTION:The objective resin comprising >=50wt.% fumaric diester of the formula (X is >=3C branched alkyl, >=4C cycloalkyl, etc.; Y is fluoroalkyl containing >=3F and 2-10C or fluorocycloalkyl containing >=4F and >=4C) as a structural unit and a monomer such as preferably vinyl acetate or styrene, having 1,000-300,000 average molecular weight. The polymer is obtained by radical polymerization such as solution polymerization or bulk polymerization in the presence of a polymerization initiator such as azobisisobutyronitrile preferably at 10-100 deg.C for 1-100hours.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention is a water repellent having chemical stability, weather resistance, heat resistance, high light transmittance, soluble in an organic solvent and having excellent water / oil repellency. -Relating to oil repellent resin.

[0002]

2. Description of the Related Art Fluorocarbons are chemically stable due to the strong electron-withdrawing property of fluorine atoms, and fluorine atoms do not have a weak interaction force (van der Waals force) like hydrogen atoms. Interactions between molecules of the class are small, low viscosity, high volatility, and other properties different from hydrocarbon-based substances. These properties due to the fluorine atom are exhibited not only in the low molecular weight substance but also in the polymer substance, that is, in the resin having a large number of fluorine atoms (fluorine resin), similarly to the fluorocarbons. In particular, the fluororesin is used as a water / oil repellent due to its low surface energy (water / oil repellency), chemical stability, heat resistance and the like.

[0003]

However, polymers in which a fluorine atom is introduced into the polymer main chain such as trifluoroethylene, vinylidene fluoride, and perfluoroethylene polymers are heat-resistant and chemically stable. However, when it is used for treating a material such as a thermoplastic resin that requires heat processing, it has a problem in processability and poor solubility in an organic solvent. Furthermore, when the surface of a material such as metal, plastic, glass, or wood is coated with the fluororesin for surface treatment, it is necessary to heat and melt the fluororesin once and then mechanically press-bond it. For substrates with complicated shapes,
There is a problem that the substrates that can be coated are limited, such as being unsuitable for substrates that cannot be coated and are mechanically brittle such as glass.

Therefore, for the purpose of improving these drawbacks, attempts have been made to improve the heat processability and the solubility in organic solvents by copolymerizing the perfluoroethylene monomer with other monomers. However, since it has a methylene group in the polymer main chain, it has poor heat resistance, and its solubility in organic solvents is insufficient.

Further, a polymerizable monomer having a perfluoroalkyl group in its side chain, for example, a polymer containing a fluorine-containing alkyl ester of acrylic acid or a fluorine-containing alkyl ester of methacrylic acid or a polymer containing a fluorine-containing alkylstyrene is proposed. ing.

However, the polymers containing the above-mentioned fluorine-containing alkyl ester or fluorine-containing alkylstyrene have improved solubility in organic solvents,
Unlike the polymer consisting of perfluoroethylene monomer, the heat resistance is low because of the presence of methylene group in the main chain of the polymer, especially in the polymer where the side chain perfluoroalkyl group is introduced through the ester bond. , Is susceptible to a hydrolysis reaction even in the absence of an acid or alkali catalyst, and in the case of a polymer containing a fluorine-containing alkylstyrene, long-term stability ( However, there is a problem in that the glass transition temperature of the polymer is remarkably lowered and the heat resistance is also lowered by introducing a perfluoroalkyl group.

[0007]

An object of the present invention is a resin soluble in an organic solvent, which has excellent weather resistance and heat resistance,
Water repellent with good coating properties and light transmission
It is to provide an oil-repellent resin.

[0008]

According to the present invention, the following general formula 2 (wherein X is a branched alkyl group having 3 or more carbon atoms,
Represents a branched alkyl group having 3 or more carbon atoms or a cycloalkyl group having 4 or more carbon atoms, which contains a cycloalkyl group having 4 or more carbon atoms or a fluoroalkyl group having at least 3 fluorine atoms as a substituent, and Y represents A fumaric acid diester represented by a fluoroalkyl group having at least 3 fluorine atoms and having 2 to 10 carbon atoms or a fluorocycloalkyl group having at least 4 fluorine atoms and having 4 or more carbon atoms (hereinafter, fumaric acid diester 1) The water-repellent / oil-repellent resin comprising a polymer containing 50% by weight or more as a structural unit is provided.

[0009]

[Chemical 2]

The details will be described below.

The water / oil repellent resin of the present invention is characterized by containing a specific amount of a specific fumaric acid diester.

The specific fumaric acid diester used in the water-repellent / oil-repellent resin of the present invention is fumaric acid diester 1 represented by the general formula 2. In the fumaric acid diester 1, when X is a branched alkyl group having 4 or more carbon atoms or a cycloalkyl group having 5 or more carbon atoms, or Y is a fluoroalkyl group having 5 or more carbon atoms or 5 carbon atoms.
In the case of the above fluorocycloalkyl group, the production is difficult.

The above-mentioned fumaric acid diester 1 does not have a methylene group in the main chain structure at the time of polymerization and has a substituent bonded to all carbon atoms in the main chain, so that the glass transition temperature is high and A polymer having excellent heat resistance and weather resistance can be obtained because it is not easily attacked by chain bonds. Of the fumaric acid diesters, fumaric acid diesters in which all carboxylic acid residues have been substituted with fluoroalkyl groups generally have high melting points, and have extremely poor solubility and low polymerizability. However, since the fumaric acid diester 1 used in the present invention has a bulky substituent such as an iso-propyl group or a tert-butyl group in one alcohol residue, it has high polymerizability and good solubility in a solvent.

Specific examples of the fumaric acid diester 1 include iso-propyl-2,2,2 fumarate.
-Trifluoroethyl, iso-propyl fumarate-
2,2,3,3,3-pentafluoropropyl, fumarate iso-propyl-2,2,3,3,4,4,4-heptafluorobutyl, fumarate iso-propyl-2,
2,3,3,4,4,5,5,5-nonafluoropentyl, iso-propyl fumarate-2,2,3,3,4
4,5,5,6,6,6-undecafluorohexyl,
Iso-propyl fumarate-2,2,3,3,4,4
5,5,6,6,7,7,7-tridecafluoroheptyl, iso-propyl fumarate-2,2,3,3,4
4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyl, iso-propyl-3 fumarate,
3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl, iso-propyl fumarate
2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 6, 7, 7,
8,8,9,9,10,10,10-nonadecafluorodecyl, iso-propyl fumarate-3,3,4,4,4
5,5,6,6,7,7,8,8,9,9,10,1
0,10-heptadecafluorodecyl, fumarate iso
-Propyl-2-trifluoromethyl-3,3,3-trifluoropropyl, iso-propyl-3-fumarate
Trifluoromethyl-4,4,4-trifluorobutyl, iso-propyl-1-methyl fumarate-2,2
3,3,3-pentafluoropropyl, fumaric acid iso
-Propyl-1-methyl-2,2,3,3,4,4,4
-Heptafluorobutyl, tert-butyl fumarate-
2,2,2-trifluoroethyl, fumaric acid tert-
Butyl-2,2,3,3,3-pentafluoropropyl, tert-butyl fumarate-2,2,3,3,4
4,4-heptafluorobutyl, tert-butyl fumarate-2,2,3,3,4,4,5,5,5-nonafluoropentyl, tert-butyl fumarate-2,2
3,3,4,4,5,5,6,6,6-undecafluorohexyl, tert-butyl fumarate-2,2,3,3
3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl, tert-butyl fumarate-2,2
3,3,4,4,5,5,6,6,7,7,8,8,8
-Pentadecafluorooctyl, tert-butyl fumarate-3,3,4,4,5,5,6,6,7,7,8,
8,8-Tridecafluorooctyl, tert-fumaric acid
-Butyl-2,2,3,3,4,4,5,5,6,6,6
7,7,8,8,9,9,10,10,10-nonadecafluorodecyl, tert-butyl fumarate-3,3,3
4,4,5,5,6,6,7,7,8,8,9,9,1
0,10,10-Heptadecafluorodecyl, tert-butyl-2-trifluoromethyl fumarate-3,3,3
3-trifluoropropyl, tert-butyl fumarate-3-trifluoromethyl-4,4,4-trifluorobutyl, tert-butyl-1-methyl fumarate,
2,3,3,3-pentafluoropropyl, fumaric acid t
ert-butyl-1-methyl-2,2,3,3,4
4,4-heptafluorobutyl, cyclohexyl fumarate-2,2,2-trifluoroethyl, cyclohexyl fumarate-2,2,3,3,3-pentafluoropropyl, cyclohexyl fumarate-2,2,3,2 3, 4,
4,4-heptafluorobutyl, cyclohexyl fumarate-2,2,3,3,4,4,5,5,5-nonafluoropentyl, cyclohexyl fumarate-2,2,3
3,4,4,5,5,6,6,6-undecafluorohexyl, cyclohexyl fumarate-2,2,3,3,3
4,4,5,5,6,6,7,7,7-tridecafluoroheptyl, cyclohexyl fumarate-2,2,3
3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyl, cyclohexyl fumarate-
3,3,4,4,5,5,6,6,7,7,8,8,8
-Tridecafluorooctyl, cyclohexyl fumarate-2,2,3,3,4,4,5,5,6,6,7,7,
8,8,9,9,10,10,10-nonadecafluorodecyl, cyclohexyl fumarate-3,3,4,4,4
5,5,6,6,7,7,8,8,9,9,10,1
0,10-heptadecafluorodecyl, cyclohexyl-2-trifluoromethyl-3,3,3-trifluoropropyl fumarate, cyclohexyl-3-trifluoromethyl fumarate-4,4,4-trifluorobutyl, fumarate Acid cyclohexyl-1-methyl-2,2,3,3,3
Preferable examples include 3-pentafluoropropyl, cyclohexyl-1-methyl-2,2,3,3,4,4-heptafluorobutyl fumarate, and the like, and they may be used alone or as a mixture when used. ..

The above-mentioned fumaric acid diester 1 is prepared by a conventional esterification reaction of maleic acid or fumaric acid with a corresponding alcohol or a reaction of tert-butyl ester by reaction of a carboxyl group with isobutene and cis-trans. It can be easily obtained by combining with an isomerization reaction.

The average molecular weight of the polymer used as the water / oil repellent resin of the present invention is preferably in the range of 1,000 to 300,000.

The polymer used as the water- and oil-repellent resin of the present invention contains 50 parts of the fumaric acid diester 1 as a constitutional unit.
If the content of the fumaric acid diester is not less than 1% by weight,
The homopolymer of 1 or a copolymer with another monomer may be used. When the content of the fumaric acid diester 1 is less than 50% by weight, desired water / oil repellency cannot be obtained.

Other monomers copolymerizable with the fumaric acid diester 1 include olefins, acrylic acid or methacrylic acid and their alkyl esters, vinyl esters of fatty acids, styrenes, vinyl halides, vinylidene halides, Preferable examples thereof include vinyl alkyl ethers, vinyl alkyl ketones and butadienes. Specifically, for example, ethylene, propylene, methyl acrylate, butyl acrylate, methyl methacrylate,
Butyl methacrylate, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, vinyl stearate, vinyl pivalate, styrene, α-methylstyrene, vinyl chloride, vinylidene chloride, aryl acetate,
Preferable examples include vinyl butyl ether, vinyl methyl ketone, vinyl ethyl ketone, vinyl carbazole, 1,3-butadiene, and isobrene, among which vinyl acetate, vinyl propionate, vinyl pivalate,
Styrene, vinyl butyl ether, vinyl methyl ketone, butadiene and the like are particularly preferable from the viewpoint of copolymerizability.

The polymer used in the present invention can be easily synthesized by a generally used radical polymerization method. Specifically, a radical polymerization initiator such as azobisisobutyronitrile or azobiscyclohexane is used. Azo radical polymerization initiators such as carbonitrile and azobisvaleronitrile; initiation of organic peroxide radical polymerizations such as benzoyl peroxide, tert-butylhiddle peroxide, cumene peroxide and diacyl peroxide; ammonium persulfate , Various radical polymerization initiator systems such as inorganic radical polymerization initiators such as potassium persulfate or redox initiators such as hydrogen peroxide-sodium hydroxide system, solution polymerization, bulk polymerization, emulsion polymerization, Preferred by general-purpose radical polymerization methods of vinyl monomers such as suspension polymerization and radiation polymerization. At the 10~100 ℃, 1~1
It can be synthesized by carrying out a reaction for 00 hours.

The water-repellent / oil-repellent resin of the present invention can be used in any form such as emulsion, solvent solution, and aerosol. Specifically, for example, it is mixed with an emulsifier in water or another medium. , Dispersed emulsion,
Further, the polymer is one of suitable solvents such as acetone, toluene, methyl ethyl ketone, diethyl ether, dioxane, tetrahydrofuran, methylene chloride, chloroform, butane, methyl chloroform, trichloroethylene, tetrachloroethylene, tetrachlorodifluoroethylene, trichlorotrifluoroethylene. Or 2
A solution dissolved in a mixture of at least one kind, and further as a aerosol filled in a suitable container by adding a propellant such as dichlorodifluoromethane, monofluorotrichloromethane, dichlorotrifluoroethane, carbon dioxide gas to the solvent solution described above. Can be used.

The water-repellent / oil-repellent resin of the present invention can be applied to an article to be treated by any method depending on the type of the article to be treated and the above-mentioned preparation form. For example, in the case of an emulsion or solvent solution type, it can be attached to the surface of the object to be processed and dried by a known coating method such as dip coating, and if necessary, a crosslinking agent is added. However, curing may be performed. In the case of an aerosol, it is sufficient to simply spray these onto the agent to be treated,
Immediately dry and shows sufficient water and oil repellency.

Further, in the water / oil repellent of the present invention, a polymer blender may be added in addition to the polymer of the fumaric acid diester 1, and other water / oil repellent treatment agent or insect repellent,
Additives such as flame retardants, antistatic agents, stabilizers and anti-wrinkle agents can also be used in combination.

The substance which can be treated with the water / oil repellent of the present invention is not particularly limited, and examples thereof include fiber, woven fabric, glass, paper, wood, leather, fur, asbestos, brick, cement, Preferable examples include metals and oxides, ceramic products, plastics, painted surfaces and plasters.

[0024]

【The invention's effect】

[0025]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.

[0026]

Example 1 Iso-propyl fumarate-3,3,4
4,5,5,6,6,7,7,8,8,9,9,10,
10,10-Heptadecafluorodecyl (iPr / F ₁₇
-Fu) 9.0 parts by weight, vinyl pivalate (VPiv)
a) 1.0 part by weight was put into a glass ampoule, and 0.05 part by weight of azobisisobutyronitrile (AIBN) was added as a radical polymerization initiator, nitrogen substitution was sufficiently performed, and degassing under reduced pressure was repeated. After that, the ampoule was sealed.
Next, the ampoule was placed in a shaking type constant temperature bath at 50 ° C. and radical polymerization was carried out for 30 hours. After completion of the polymerization, put the product name "CG Triflon" (manufactured by Central Glass Co., Ltd.) in an ampoule, dissolve the generated polymer into a solution, and then pour a large amount of methanol to precipitate the polymer, and then use iPr. / F
_{After the 17} · Fu-VPiva copolymer was isolated and reprecipitation was repeated in a Freon-113-methanol system,
After drying under reduced pressure, 8.5 g of the target polymer was obtained. The glass transition point (Tg) of the obtained polymer was measured by the DSC method. The results are shown in Table 1.

Next, about 0.5 g of the obtained polymer was added to a product name "CG Triflon" (manufactured by Central Glass Co., Ltd.) 50 m.
The solution obtained by dissolving the solution in 1
Pour into a flat petri dish of m and slowly evaporate the product name "CG Triflon" (manufactured by Central Glass Co., Ltd.) while preventing dust and dirt from entering to form a transparent uniform film.
Then, the contact angle of pure water and n-octane on the film surface on the flat petri dish was measured. The results are shown in Table 1.

[0028]

Examples 2 to 8 and Comparative Examples 1 and 2 Polymers were synthesized in the same manner as in Example 1 except that the monomers shown in Table 1 were used, and the contact angle was measured. ..

[0029]

[Table 1]

The abbreviations in the table indicate the following compounds.

IPr / F ₁₇ · Fu: iso-propyl fumarate-3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10- Heptadecafluorodecyl tBu / F ₁₇ · Fu: t-butyl fumarate-3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10, 10-heptadeca fluorodecyl cHe / F ₁₇ · Fu: cyclohexyl fumarate-3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10- heptadecafluorodecyl VPiva: vinyl pivalate MSt: alpha-methylstyrene F ₁₇ AA: acrylic acid -3,3,4,4,5,5,6,6,7,7, 8,8,9,9, 10,10,10-Heptadecafluorodecyl F ₁₇ MA: Methacrylic acid-3,3,4,4,5 , 5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl

Claims (1)

[Claims] 1. The following general formula 1 (wherein X is a branched alkyl group having 3 or more carbon atoms, a cycloalkyl group having 4 or more carbon atoms, or a fluoroalkyl group having at least 3 fluorine atoms as a substituent) It shows a branched alkyl group having 3 or more carbon atoms or a cycloalkyl group having 4 or more carbon atoms, and Y is a fluoroalkyl group having 2 to 10 carbon atoms having at least 3 fluorine atoms or at least 4 fluorine atoms. A water-repellent / oil-repellent resin made of a polymer containing 50% by weight or more of a fumaric acid diester represented by the above formula (which represents a fluorocycloalkyl group having 4 or more carbon atoms) as a constituent unit. [Chemical 1]