JPS5871977A - Low temperature curing water and oil repellent - Google Patents

Abstract

PURPOSE:The titled water and oil repellent, consisting of a polymerizable compound having a polyfluoroalkyl group and a specific copolymer containing a polymerizable compound containing a polyfluoroalkyl group and a crosslinkable monomer, and capable of exhibiting a high water and oil repellency by curing at low temperatures due to the improved film-forming properties. CONSTITUTION:A water and oil repellent containing a copolymer having <=30,000 molecular weight and <=0.1 intrinsic viscosity (eta), and containing (A) preferably 50-80wt% polymerizable compound containing a polyfluoroalkyl group, preferably a compound of formulaI[Rf is perfluoroalkyl of CnF2n+1; R<1> is H or methyl; R<2> is alkylene of -CmH2m-; (n) is a positive integer 5-16; (m) is a positive integer 1-10], (B) preferably 2-5wt% crosslinkable monomer, preferably N-methylolacrylamide of formula II (R<1> is H or methyl), and (C) preferably 10-30wt% another copolymerizable monomer, e.g. ethylene or vinyl acetate. USE:Fibrous cloths, glass, paper, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel water and oil repellent that exhibits high water and oil repellency when cured at low temperatures and is made of a specific copolymer containing a polyfluoroalkyl group.

Conventionally, water and oil repellent agent C is made from a copolymer of plum blossoms containing a polyfluoroalkyl group (hereinafter sometimes abbreviated as a PFA group): it is well known. Various other monomers have been proposed to be copolymerized with the compound.

According to the inventor's study, conventional water and oil repellents generally show high performance under curing conditions of 150°C and above, which is the usual temperature for textile processing, but the performance is similar at low curing temperatures of 100°C or less. It is recognized that the problem is that it is difficult to fully demonstrate the performance of the system.

Based on the recognition of the above problems, the present inventor has conducted various studies,
As a result of extensive research, P copolymerized with various monomers
It has been found that by controlling the molecular weight of the FA group-containing copolymer, it can be easily formed into a film during the process of forming a film on the surface of fibers, etc. We have also discovered that by improving film-forming properties, it is possible to exhibit extremely high performance in low-temperature curing.

Specifically, the present invention provides a polymerizable compound containing a polyfluoroargyl base, a copolymer containing various other monomers and a crosslinkable monomer (as a whole constituent unit), The molecular weight of the polymer is 30.000 or less,
The present invention provides a new water-repellent 4Sv oil agent which is characterized by a bloody viscosity [η] (1,11BJ or less).

The water and oil repellent of the present invention 0: has very excellent water and oil repellency, for example, Textile Shop J'! In lj,
Even at low concentrations, it is possible to impart a full oiliness.

Furthermore, the water-repellent oil agent of the present invention can exhibit all the above-mentioned properties well even in a low-temperature curing cylinder of 100° C. or lower.

In the present invention, a conventionally known or well-known compound is used as a compound (hereinafter abbreviated as PF'A compound) that can combine with 11i of PIj'A fund A. Of course, there are no particular limitations, and all examples are unique.

For example, C'3(CF2)7C12CH20COCH=CH2
.

C1j'3(CF2)4C120COC(CH,):
CH2゜CF3(CF2),'(CH2)20COC
(CH3)-CH2゜CF3(CF2)7802N(C
3H7) (CH2)2ocOcH2cH2゜CF3(C
F2)7(CH2)40COCH:, CH2.

CF, (CF,)7So2N(C13)(CH2)2
0COC(CH3): C12゜CF3(CF,,)
, C00CI (=CH2°), and acrylates containing a perfluoroalkyl group having 4 to 20 carbon atoms, or undiminished esters represented by methacrylate-1.

In addition, the PFA compound in the invention includes H(CF2)
, oCH20COCH: CH,.

CF2C1 (CF2), oCH20COC (C horse):
:”: C1,-1,.

PFA compounds such as -hyx2CH2 are also suitable, but those containing a terminal perfluoroalkyl group as mentioned above are usually more desirable. = CR'C0OR" R4
・(7, nl in the formula) is perfluoroalkylno represented by CnF'2n4+, (, R1 dihydrogen atom or methyl group, Indication 7, n tri: 5~
A compound represented by a positive integer of 1 [ ], m is a positive integer of 1 to 10) can be exemplified as a preferred specific example in the present invention. In addition, n is ()~] 3, rn is 2
A positive integer of ~4 is particularly desirable.
This is compound A.

The water and oil repellent copolymer of the present invention preferably contains the PFA compound, other monomers to be copolymerized, and various crosslinkable monomers as all constituent units. The cross-linking monomer is a monomer containing a functional group that forms a covalent bond with the object to be treated through an addition or condensation reaction, or a copolymer that can be completely three-dimensionally cured by the action of a curing catalyst. A wide variety of monomers having functional groups may be exemplified. For example, N-methylol acrylamide, N-methylol methacrylamide, glycidyl acrylate-1-.

Glycidyl methacrylate, aziridinyl axolate, aziridinyl methacrylate-1, diacetone acrylamide, diacetone methacrylamide, methylolated diacetone acrylamide, methylolated diacetone methacrylamide.

Ethylene diacrylate, ethylene dimethacrylate,
Examples include hydroxy7 alkyl acrylate, hydroxyalkyl methacrylate, and 3-chloro-2-hydroxypropyl methacrylate. Suitable crosslinkability +1'
As a fan body, the general formula 〇) T2= cR' C0
Examples include N-methylacrylamide and N-methylolmethacrylamide of NHCH20H (in the formula, R1 is a hydrogen atom or a methyl group).

For the copolymer according to the invention, the copolymerization proportion of the PFA compound is at least 40 ht%, especially 5
Approximately 0 to 80 weight coefficient is appropriate. In addition, the copolymerization ratio of various other copolymerizable monomers is suitably 5 to 40% by weight, particularly 10 to 1% by weight. The proportion of copolymerization may be small, usually 1 to 10 weight percent, especially 2 to 5 weight percent.If the crosslinking monomer is too large, the water and oil repellency will be low. If too much, problems such as decreased durability will occur.Of course, if the PFA group-containing monomer is too small,
Water and oil repellency cannot be fully exhibited.

In addition to 1, a PFA compound, and a crosslinking monomer, the copolymer in the present invention further contains ethylene and vinyl acetate.

Vinyl fluoride, vinyl chloride, acrylamide, methacrylamide, styrene, α-methylstyrene, p-methylstyrene, lower or higher alkyl esters of acrylic acid or methacrylic acid, benzyl acrylate or methacrylate, vinyl alkyl ethers, halogenated alkyl vinyl ethers, It can be obtained by copolymerizing one or more of various polymerizable compounds such as vinyl alkyl ketone, cyclohexyl acrylate or methacrylate, maleic anhydride, phthalene, isoprene, chloroprene as a constituent unit of a copolymer. It will be done. By appropriately selecting and copolymerizing all of these polymerizable compounds, in addition to water and oil repellency and durability, various properties such as dry soil resistance, abrasion resistance, solubility, flexibility, and texture can be achieved. This can be improved appropriately.

In the present invention, the molecular weight of the water and oil repellent copolymer is 30
．． It is important to set the value to OOO or less (intrinsic viscosity [η] of 01 or less), preferably 20.000 or less (intrinsic viscosity [η] of 0.08 or less). If the molecular weight is too high, film-forming properties will be poor during low-temperature heat treatment (below 100° C.), and it will be difficult to maintain water and oil repellency during low-temperature curing. And, T'/K V1 molecular weight is 3,000 or more, preferably 5
．． (More than 100 is adopted. Although it can be controlled by controlling the molecular weight C11, a chain transfer agent such as mercaptans, a solvent, and a polymerization temperature, generally mercaptans, such as n-hexyl mercaptan, are used. , n-octyl mercaptan, n-dodecyl mercaptan.

It is easy and desirable to use t-dodecyl mercaptan, suderyl mercaptan, or the like.

In order to obtain the copolymer of the present invention, the method and conditions of the polymerization reaction of iqr can be arbitrarily selected, and bulk polymerization, solution polymerization,
Any of various polymerization methods such as suspension polymerization, emulsion polymerization, radiation polymerization, and photopolymerization can be employed.For example, a mixture of compounds to be copolymerized is added to water in the presence of a surfactant, etc. A method of emulsification and copolymerization with stirring may be adopted.As a polymerization initiation source, various Tli polymerization initiators (9) such as organic peroxides, azo compounds, and persulfates may be used. - Ionizing radiation such as radiation may be employed.'
11. It is also an anionic surfactant.

Almost all of the various emulsifiers, cationic or nonionic, can be used. So, is it a compound that can be polymerized as a raw material?
It is also possible to carry out solution polymerization by dissolving it in a suitable organic solvent and by the action of a polymerization initiation source (peroxide, azo compound, ionizing radiation, etc. soluble in the organic solvent used). Suitable solvents for solution polymerization include trichlorotrifluoroethane, tetrachlorodifluoroethane, methylchloroform, and the like. Aerosol type, organic solvent type, or latex type water and oil repellents can be directly produced by solution polymerization or emulsion polymerization.

The thus obtained water and oil repellent made of the copolymer of the present invention can be prepared as an emulsion or a solution in a solvent according to a conventional method.

It can be prepared in any form such as an aerosol. For example, as mentioned above, aqueous emulsions can be prepared directly by emulsion polymerization, or dilute bath solutions can be prepared directly by solution polymerization. In addition, those in the solvent range include acetone, methyl ethyl ketone, and copolymers obtained by other polymerization methods such as bulk polymerization and emulsion polymerization.

diethyl ether, dioxane, methyl chloroform,
l-! J dichloroethylene, tetrachloroethylene, and dichlorodifluoroethane.

[such as trichlorotrifluoroethane]'Aλ fluorinated saturated hydrocarbons and suitable organic δ: n'l in one set or in a mixture of two or more;
i can be made. For the reed and aerosol type, prepare a solution type solvent solution as described above, add a propellant such as dichlorodifluoromethane, monofluorotrichloromethane, or dichlorotetrafluoroethane to the liquid, and pour into a suitable container. It's okay if you fill it up.

The water and oil repellent of the invention can be applied to the article to be treated in any manner depending on the knowledge of the article to be treated and the preparation form (solvent-filled liquid range, aerosol type, etc.). For example, if it is an aqueous emulsion or solvent solution type, dip coating 41i
It is possible to adopt a method in which the surface of the object to be treated is coated and dried using known coating methods such as the above. Also, the necessary (
11) Guaring may be performed by applying it together with a suitable crosslinking agent. In the case of an aerosol type water and oil repellent, simply spraying the agent onto the object to be treated dries immediately and provides sufficient water and oil repellency. Furthermore, the water and oil repellent of the present invention may be mixed with other water repellents, oil repellents, insect repellents, flame retardants,
It is of course possible to add appropriate additives such as antistatic agents, dye stabilizers, and anti-wax agents for use in combination.

There are various examples of articles that can be treated with the water and oil repellent of the present invention without particular limitation.

Examples include textile fabrics, glass, paper, wood, leather, 9 fur, 1 asbestos, bricks, cement, metals and oxides, ceramic products, plastic snacks, painted surfaces, and plaster. Then,
Cotton is a textile fabric.

Animal and plant natural fibers such as linen, wool, and silk, polyamide,
Polyester, polyvinyl alcohol.

Various synthetic fibers such as polyacrylonitrile, polyvinyl chloride, polypropylene, and rayon.

(12) Semi-synthetic fibers such as acetate, glass fibers, inorganic fibers such as asbestos fibers, or woven fabrics of mixed fibers thereof may be mentioned.

Next, embodiments of the present invention will be explained in detail, but it goes without saying that this explanation does not completely cover the present invention. The water repellency and oil repellency shown in the following examples are shown on the following scale. That is, water repellency is expressed by the water repellency obtained by spraying Tl1JL-] (l II 5 (see Table 1 below), and oil repellency is expressed by spraying the test solution shown in the following No. Place a few drops (diameter approx. 21an) in the same place, and after 30 seconds see the penetration state V (
1: Judgment (AAT'CC-TM 118-19
66).

Table 1 (13) In Table 2, the water repellency and oil repellency are marked with a 41 mark: This indicates that the tear resistance is slightly better.

Reference Example 1 A typical method of emulsification M@ for producing an uninvented copolymer using this i++, PFA compound.

This will be explained using a specific example of a terpolymer of vinylidene chloride and N-methylolacrylamide.

CM,,=C(CB,)COOCH in a glass autoclave (14) (inner volume 11) equipped with a full stirrer
,, CH2CnF2H+1 (n = 6 to I2 + average 9)] 4 o g, vinylidene chloride 56
! i', N-methylolacrylamide 4g, t-todenlumercabutane 257. Deoxygenated pure water 400f, acetate 7]00f/, CnH2n+%H(CH
3) 26CHCo total (n = 8-16, average 1:(
)6t/.

C, 8H17”f! IH8, CH3C0J” 6 i/
, T Sohisui 7 Fluoramidine-dihydrochloride J
, '2N 3/Nen-jinzai 1, Sufficiently emulsify and disperse by stirring under a nitrogen stream.

Next, the temperature of the reaction vessel was gradually increased by 1, and the temperature was increased to 4.1"L.
Copolymerization was continued at 60° C. for 15 hours. The obtained latex had a solid content of 26.5%. When this latex was mixed in a tube of one poly-7 (L, bathed in pencitrifluoride), [η] n was 0.070 at 30°C.

Examples 1 to 5 and Comparative Examples 1 to 3 A polynisdel cloth was used as a test cloth.A water and oil repellent 1-site copolymer according to the present invention and a water and oil repellent other than the product of the present invention were used. After diluting with water to prepare a concentrated H1, 140, 12-fold emulsion, each test cloth was immersed in the emulsion (15) for 2 seconds, and the cloth was placed between two rubber rollers. I narrowed it down and set the wet pickup to 90.

Subsequently, water and oil repellent treatment was performed by drying at 100° C. for 3 minutes. The water and oil repellency of the treated fabric thus obtained was measured. The results are shown in Table 3. In addition, in Table 3, FMA is CH2=C(CH3)C00CH,, CH2(CF,,
) nCF3 (n = 5-11.

average 8), VclCl, [hynyritene chloride, EHMA
is 2-ethylhexyl methacrylate, GMAU glycidyl methacrylate, VC is vinyl chloride, N-MAMi
dN-methylolacrylamide, t-DoSHU
Each represents t-dotesyl mercaptan.

[η] was measured in bencitrifluoride at 30°C.

(16) Table 3 (17)

Claims (1)

[Scope of Claims] 1. Consisting of a copolymer containing a polymerizable compound containing a polyfluoroalkyl group and a crosslinkable monomer as structural units, the copolymer has a molecular weight of 30.000 or less and an intrinsic viscosity [ η] is 01 or less. 2 A polymerizable compound containing a polyfluoroalkyl group is a general 2CH2-=CR' C00R2Rf (in the formula Rf
is a perfluoroalkyl group coated with CnF2n-1-r, R1 is a hydrogen atom or a methyl group, R2 is -CmH
All alkylene groups represented by 2m-, n is 5 to 16
2. The water and oil repellent according to claim 1, which is a compound represented by the following formula: m is a positive integer of 1 to 10.