JPS59230083A - Water-repellent and oil-repellent processing - Google Patents

Abstract

PURPOSE:To provide a base material such as fiber products, etc. with durable water-repellent, oil-repellent, and antifouling effects inexpensively, by treating the base material with a fluoroalkyl group-containing compound and a multi-stage copolymer of a specific ethylenic unsaturated monomer and a specified crosslinking agent. CONSTITUTION:A base material is treated with (A) a fluoroalkyl group-containing compound, (B) a multi-stage copolymer consisting of (i) 1-40wt% cationic group-containing alpha,beta-ethylenic unsaturated monomer, (ii) 1-20wt% alpha,beta-ethylenic unsaturated monomer having a group containing an active hydrogen, and (iii) 40-98wt% alpha,beta-ethylenic unsaturated monomer copolymerizable with the components i and ii, and (C) a crosslinkable compound selected from a polyglycidyl compound, a (stabilized) polyisocyanate compound, a polyaziridine compound, and an amino resin in a weight ratio of preferably (100):(400-1):(100-0.1). The components A, B, and C may be used as one, two, or three solutions.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a processing method that can impart durable water-repellent, oil-repellent and antifouling effects to base materials such as textile products.

In recent years, with the development of fluorine chemistry, fluorine-containing compounds such as compounds and polymers having perfluoroalkyl groups (hereinafter referred to as fluorine-containing compounds) have become easily available.
Water-repellent, oil-repellent, and antifouling treatments using these materials have also become widely used. These processing agents are usually provided in the form of organic solvent solutions or aqueous emulsions, but since fluorine-containing compounds are generally expensive, processed products are also expensive, and there is a strong demand for lower prices. However, conventional products generally have the disadvantage of low durability against friction and washing,
The processing effect tends to decrease in a short period of time, causing inconvenience, and as a countermeasure to this problem, it has been necessary to increase the concentration of the fluorine-containing compound used, or to perform reprocessing each time the effect decreases. However, this method is more expensive and requires more complicated work, so there has been a strong demand for the development of an inexpensive and durable processing method.

As a result of intensive research, the present inventors have found that all of the above-mentioned drawbacks have been significantly improved by using a fluorine-containing compound mainly consisting of an ethylenically unsaturated monomer and a special copolymer and a crosslinking agent. The present inventors have discovered that the present invention is possible and have completed the present invention.

The water and oil repellent finishing method of the present invention comprises: A, a fluoroalkyl group-containing compound, B, ((a) 1 to 4% by weight of an α,β-ethylenically unsaturated monomer having a cationic group; 1 to 20% by weight of α, β-ethylenically unsaturated monomer having a group containing active hydrogen, and G/→ (a) above
A multicomponent copolymer obtained from 40 to 98% by weight of α,β-ethylenically unsaturated monomer copolymerizable with the monomer of (C), polyglycidyl compound, polyisocyanate compound, stabilized The method is characterized in that the base material is treated with at least one cross-linking compound selected from the group consisting of a polyisocyanate compound, a phoriasilidine compound, and an amino resin.

The three components A, B, and C may be applied as the same treatment solution, that is, one component, or they may be applied as two or three components in which at least one component of A, B, and C is a separate treatment solution. . A
, the weight of each component B and C used is 100:400-1
: A ratio of 100-0.1 is preferable, and if each component is not within this range, the water repellency, oil repellency and antifouling effects may be insufficient, the durability may be weak, and the texture may be hard. ,
Tendencies such as discoloration are more likely to appear. The ratio of each component A, B, and C used is particularly preferably 100:200 to 5:30 to 1.

The fluorine-containing compound used as component A in the present invention is preferably one in which the fluoroalkyl group is usually a perfluoroalkyl group having 3 to 20 carbon atoms, particularly 5 to 16 carbon atoms. Such a fluorine-containing compound is, for example, a homopolymer of a vinyl monomer having a fluoroalkyl group having 3 to 20 carbon atoms, or a combination of the vinyl monomer and a fluorine-free vinyl monomer. Examples include copolymers, urethane compounds having a fluoroalkyl group having 3 to 20 carbon atoms, glycidyl compounds, esters, and polymers thereof, or reaction products of these with other components that do not contain fluorine.

(6) α having a cationic group constituting component B.

β-ethylenically unsaturated monomers include α-containing onium-type groups such as quaternary ammonium salts or aminobase salts.
, the use of β-ethylenically unsaturated monomers and or ((2)
Included are α,β-ethylenically unsaturated monomers having a group that can be quaternized or converted into an onium type, such as an acid salt, after copolymerization with a tzi monomer. In the latter case, after copolymerization, it is necessary to quaternize all or part of the copolymer or convert it into an acid salt using various quaternizing reagents or organic or inorganic acids. The monomer has
Examples Vinylpyridine collections such as evavinylpyridine, methylvinylpyridine, Dimethylaminoethyl acrylate and methacrylate, Dialkylaminoalkyl acrylates and methacrylates such as diethylaminoethyl acrylate and methacrylate, 2-hydroxy-3-
Acrylic esters and methacrylic acids such as dimethylaminopropyl acrylate and methacrylate, 2-hydroxy-3-dimethylaminopropyl acrylate and methacrylate, glycidyl acrylate and methacrylate, methylglycidyl acrylate and methacrylate, 2-hydroxy-3-chloropropyl acrylate and methacrylate Esters; dialkylaminoalkyl vinyl ethers such as dimethylaminoethyl vinyl ether and diethylaminoethyl vinyl ether; acrylamide and methacrylamide containing alkylamino groups such as dimethylaminoethyl acrylamide and methacrylamide, diethylaminoethyl acrylamide and methacrylamide; vinyl halides; Allyl halide; ant? lglycidyl ether/I/; Contains other monomers having phosphonium, oxonium or sulfonium groups, which can be used as is or after amination with various quaternizing reagents or organic acids or inorganic acids. Either a compound or an acid salt, or a quaternized compound or an onium salt such as an acid salt after copolymerization are applicable.

(b) Copolymerizable α, β having an active hydrogen-containing group
- ethylenically unsaturated monomers such as hydroxyethyl acrylate and methacrylate, hydroxypropyl acrylate and methacrylate, 3-chloro-2
-Hydroxypropyl acrylate and methacrylate, hydroxypolyoxyalkylene acrylate and methacrylate (alkylene refers to ethylene, propylene and butylene alone or as a mixture), hydroxymethylacrylamide and methacrylamide, acrylic acid, methacrylic acid, maleic acid, maleic anhydride Examples include acids, fumaric acid, itaic acid, itaconic anhydride, allyl alcohol, allylamine, etc., and further copolymerization with glycidyl acrylate and methacrylate, glycidyl vinyl ether, glycidyl allyl ether, acrylamide and methacrylamide, vinyl halides, etc. An active hydrogen-containing group such as a hydroxyl group or an amino group may be introduced before or after by a known method.

The monomer (c) is an α,β-ethylenic monomer copolymerizable with the monomers (a) and (b), such as alkyl acrylates and methacrylates, dialkyl maleates, fumarates, Unsaturated carboxylic acid esters such as itaconate, vinyl esters such as vinyl acetate, vinyl propionate, vinyl versatate, vinyl laurate, aromatic vinyls such as styrene, α-methylstyrene, vinyltoluene, ethylene, propylene, etc. α-olefins, dienes such as butadiene, acrylonitrile, methacrylate trile, alkyl vinyl ethers,
Examples include vinyl halides and vinylidenes such as vinyl chloride and vinylidene chloride.

Component B is obtained by combining one or more of these monomers (a), (d), and (c), diradical polymerizing in an organic solvent or water by a conventional method, and quaternizing if necessary. , acid salts, etc. are converted into onium salts to form multi-component copolymers in the form of solutions or emulsions.

(The cationic monomer (a) is preferably contained in the copolymer in an amount of 1 to 40% by weight, and even if it is more or less than this, the water and oil repellent effect will not be adversely affected.

The monomer (b) is used in a proportion of 1 to 20% by weight in the copolymer, but if it is outside this range, the durability of the water and oil repellent effect will deteriorate, and if it is too large, the water and oil repellency will deteriorate. Deteriorate.

The content of the V→ monomer is 40 to 98% by weight, but outside this range, the water and oil repellency and durability deteriorate, and at the same time, emulsification, solubility, etc. are likely to be poor.

Next, the crosslinkable compounds used as component C in the present invention include (1) polyglycidyl compounds such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, chrycerin, trimethylolpropane, pentaerythritol, and sorbitol. and polyglycidylated products of these oxyalkylene compounds, polyepoxybisphenols, diamine polyepoxides, etc. (++1 As polyisocyanate compounds, 2,4- or 2,6-lylene diisocyanate, diphenylmethane diisocyanate, isocyanate,
Examples include xytylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, bis(isocyanatomethyl)cyclohexane, and their trimerization, trimerization into ducts, or prepolymers. (
The polyisocyanate compounds (11) are stabilized with alcohols, phenols, amines, oximes, etc. as stabilized polyisocyanate compounds, and can be activated by heating, catalytic action, contact with functional groups, etc. Examples include things that change. (■Polyaziridine compounds include trisaziridinylphosphine oxide, 2.4
．． 6. -) Lis(2-methyl-1-aziridinyl)-
8-) Rear chain, carbonylbisaziridine, 4.
4'-bis(ethyleneiminocarbonylamino)diphenylmethane, 2,4-diethyleneureidotoluene, hexamethylenebisethyleneurea, etc. (ψamino resins include urea, ethylvinylaminoureas, propyleneureas,
It is obtained by reacting formalin glyoxal with melamine, guanidine, aniline, sulfamide, etc. Urea resin, modified urea resin, melamine resin, aniline resin,
Examples include sulfamide resins.

Components A, B, and C are usually prepared in a liquid or three-liquid form for treatment, and the solvent used for this purpose may be water, various solvents, or a mixture thereof.

The treatment liquid may be applied to the substrate by any method that allows the treatment liquid to adhere to the substrate, such as dipping, padding, or spraying.It is best to dry and heat-treat the treatment liquid after it has been applied to the substrate. .

The treatment liquid may contain waxes, oils/agents, surfactants, various resins such as silicone resins, amino resins, acrylic resins, catalysts, and other additives, if necessary.

The present invention provides extremely durable water and oil repellency. Although the reason for the effects of the present invention has not yet been determined, it is presumed as follows. In general, fluorine-based water and oil repellents have a fluorine-containing part and a fluorine-free part in their molecular structure. When treating base materials such as textile products with water and oil repellency, in order to make the effect even stronger,
It is sufficient to orient more of the fluorine-containing portions on the outer surface.

Therefore, it is sufficient to distribute more of the fluorine-free portion at the interface with the base material, and furthermore, by strengthening these bonds, durability can be increased. The B component of the present invention is largely adsorbed on the substrate surface, thus promoting the above-mentioned orientation, and furthermore, C
It is believed that the unique combination of the present invention exhibits excellent interaction because it has the effect of strengthening the bond between the components A1B and the base material.

Note that the method of the present invention can be applied to various textile products, paper, films,
It can be effectively applied to base materials such as tatami mats. Also includes knitted fabrics and various industrial materials including other fibers.

Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

Parts and % in the examples indicate parts by weight and % by weight, respectively, unless otherwise specified.

The methods for measuring water repellency and oil repellency, washing tests, and dry cleaning tests used in the Examples are as follows. "Water repellency r JIS, L, 1092-77.5.2 Spray test oil repellency, washing test according to AATCC11B i +
+8. L, No. 103 of 0217-1976.

Dry cleaning test i JIS, L, '101B-
77.6° Conforms to 36.2E-2 method.

Example (1) 100 parts of monomer and 0.4 part of Cortamine 24P (emulsifier manufactured by Kao Soap Co., Ltd.) and water were added to a reactor equipped with a thermometer, stirrer, dropping funnel, nitrogen inlet, and reflux condenser. , adjust the monomer concentration to 30%,
The pH was adjusted to 7 using acetic acid. Thereafter, the system was purged with nitrogen, and a polymerization reaction was carried out at 35°C for 4 hours using potassium persulfate and sodium metabisulfite as catalysts at a weight ratio of 2=1 at 1.1% to obtain a polymer emulsion. .

Table 1 shows the monomer composition, catalyst amount, and monomer polymerization rate.

Table 1 *l) MA: Methyl acrylate EH: 2-ethylhexyl acrylate HEMA
: 2-hydroxyethyl methacrylate DE :
Diethylaminoethyl methacrylate DM: Dimethylaminoethyl methacrylate DMC: Ethyl methacrylate 1-limethylammonium chloride Using the five polymer emulsions thus obtained, Table 2
The treatment solution shown in is prepared. After immersing a polyester knitted fabric and a nylon woven fabric in this treatment solution, the fabric was squeezed with a padding mange to a shrinkage rate of 65%, dried at 1000C for 3 minutes, and then heat-treated at 1700C for 1 minute.

Table 2 *1) Water was added to each treatment solution to make 100 parts.

*2) Fluororesin emulsion manufactured by Asahi Glass Co., Ltd.

*5) Polyisocyanate manufactured by Nippon Polyurethane Co., Ltd. Meiselin R13oX (a surfactant manufactured by Meisei Chemical Industry Co., Ltd.) was added and mixed in an amount of 15%, and added to the treatment agent.

The water and oil repellency of the treated fabric was measured after processing and after washing 5, 10, and 20 times. The results are shown in Table 5.

Example (2) Asahi Guard AG'730 (2 parts) and polymer emulsion layer 2 (
The following two treatments were carried out using 4 parts) and HL (0.4 parts).

(A) Asahi Guard AG730 and polymer emulsion layer 2
A polyester knitted fabric and a nylon woven fabric were immersed in the solution made up to 100 parts by adding water, and after drying, water was added to Coronate HL to which Meiselin R130X was added as in Example (1). It was immersed in a solution made up to 100 parts and subjected to dry heat treatment.

CB) Asahi Guard AG730 and Coronet) HL (
A polyester knitted fabric and a nylon woven fabric were immersed in 100 parts of an aqueous solution by adding Macerin R130
It was then immersed in separator solution, dried and heat treated.

Alternatively, (C) Add the same amount of Asahi Guard as the treatment solution/165 in Table 2 to 730. Polymer emulsion/I65 and Coronae) HL
Each was diluted with water to form three baths of 100 parts,
Polyester knitted fabric and nylon woven fabric are sequentially soaked and dried.
Finally, it was heat treated.

(A) (B) (C) In all methods, the dipping, squeezing rate, drying and heat treatment conditions were the same as in Example (1).

Table 4 shows the results of measuring the water and oil repellency of each treated fabric after processing and after washing 5, 10, and 20 times.

Table 4 Example (1) Table 3 Treatment liquid/I61 and Ro 5 show good durability.

Example (3) A treatment solution shown in Table 5 was prepared in the same manner as in Example (1), and a polyester/cotton (65/35) blended fabric was dipped in the treatment solution, and then squeezed with one padding mange to a squeezing rate of 70%. C, 100°
After drying for 1 minute at 17°C, heat treatment was performed for 1 minute at 17°C.

Table 5 *1) Water was added to each treatment solution to make 100 parts.

*2) Fluororesin emulsion manufactured by Asahi Glass Co., Ltd.

*3) Amino resin manufactured by Sumitomo Chemical Co., Ltd.

*4) Catalyst manufactured by Sumitomo Chemical Co., Ltd.

The water and oil repellency of the treated fabric was measured after processing and after dry cleaning 5 times, 10 times, and 20 times.

The results are shown in Table 6.

Table 6 Fabrics treated with the treatment liquid/I67 of the present invention exhibited water and oil repellency with excellent dry cleaning resistance.

Example (4) A treatment solution shown in Table 7 was prepared in the same manner as in Example (1), a cotton fabric was immersed in this treatment solution, and the squeezing rate was 80 using a padding mangle.
%, dried at 100°C for 3 minutes, and then heat-treated at 1500C for 3 minutes.

Table 7 *l) Water was added to each treatment solution to make 100 parts.

*2) Fluororesin emulsion manufactured by Asahi Glass Co., Ltd.

*3) Sumitex Resin M-3: Amino resin manufactured by Sumitomo Chemical Co., Ltd.

Denacol EX832: Polyglycidyl compound manufactured by Nagase Sangyo Co., Ltd. A small amount of Meiselin H'1OOX (a surfactant manufactured by Meisei Chemical Industry Co., Ltd.) was added to make it water dispersible, and n-butylamine was added as a catalyst to Bunacol EXs32.
It was added to the treatment solution at 10%.

5O-125F: Polyaziridine compound dispersion manufactured by Meisei Chemical Industry Co., Ltd.

Elastron E37: Stabilized isocyanate manufactured by Dai-Kogyo Seiyaku Co., Ltd. Elastron Catalyst 3 as a catalyst
2 was used in combination with 03 parts of the treatment solution.

The water and oil repellency of the treated fabric was measured after processing and after washing 5, 10, and 20 times. The results are shown in Table 8.

Table 8 Treatment liquid according to the present invention/1613.15.16.17
All of the treated fabrics showed durable water and oil repellency.

Example (5) A treatment solution shown in Table 9 was prepared in the same manner as in Example (1), and an acrylic knitted fabric was immersed in this treatment solution, then squeezed to a squeezing rate of 65% using a padding mangle, and dried at 1000C for 3 minutes. After, 1
Heat treatment was performed at 300C for 3 minutes.

Table 9 *l) Each treatment solution was made up to 100 parts by adding THF *2
] Table 10 shows the water repellency and contact repellency of the solvent-type fluororesin-treated cloth manufactured by Asahi Glass Co., Ltd. after processing and after dry cleaning 3 times, 5 times, and 10 times.

Table 1O The treated fabric using the treatment liquid A23 of the present invention had water and oil repellency with excellent dry cleaning resistance.

Example (6) Using the polymer emulsion/165 of Example (1), Table 11
Prepare the treatment liquid and spray the treatment liquid on both sides of the tatami surface (coating amount: 30cc/d).After air drying,
Heat treatment was performed at 180°C for 100 seconds.

Table 11 *1) Water was added to each treatment solution to make 100 parts.

Processing finish and friction test of treated tatami surface (2 with wet rag)
Table 12 shows the water repellency, stain resistance 7, and staining effect after 0 strong rubbings.

Table 12 *l) JIS P-sa7 *2) Contaminants; sauce, ketchup, soybean oil, milk,
Salad oil, machine oil, sake, coffee *3) Wiping: Drop staining agent, wipe off with tissue paper after 1 hour.

*4) A: All except ketchup are spherical oil or water droplets.

*5) B: Spreads over the surface without becoming spherical.

*6) C: Easily wiped off and leaves no residue.

*7) D: Contaminant stains.

The treatment liquid/16.28 according to the present invention exhibited durable water repellency and stain resistance.

Patent Applicant: Meisei Chemical Industry Co., Ltd. Agent: Ken Shinjitsu 1 External Procedural Amendment Statement July 13, 1981 1, Case Indication: 1988 Patent M1 No. 104696
No. 2, Title of the invention Water and oil repellent finishing method 3, Relationship with the person making the amendment A'1 Name of patent applicant Meisei Chemical Industry Co., Ltd. 411 Agent Address: 604 6. Inventions increased by amendment Contents of the numerical amendment ill Amend the statement of claim and the scope of claims as shown in the attached sheet.

(2) In the same book, page 11, line 5, the word ``quintylene'' is corrected to ``xylylene.''

(3) In the same book, page 'Jl', line 6, the text ``Formalin, Ririokizar'' has been amended to read ``Formalin, Ririokizar.''

(4) In the same book, on page 15, second line from the bottom, the words "and amount of catalyst" are deleted.

2. Claim 0) A, fluoroalkyl group-containing compound, B, (he) cationic group-containing α,β-ethylenically unsaturated monomer 1
~40% by weight, (b) 1 to 20% by weight of an α,β-ethylenically unsaturated monomer having a group containing active hydrogen, and a multicomponent copolymer obtained from C, a polyglycidyl compound, a polyglycidyl compound, A water- and oil-repellent finishing method comprising treating a base material with a β component of at least one crosslinkable compound selected from the group consisting of an isocyanate compound, a stabilized polyisocyanate compound, a boriasilidine compound, and an amino resin.

(21) The method according to claim 1, characterized in that the substrate is treated with a treatment liquid containing the above three components A% B and C.

(3) The method according to claim 1 or 2, characterized in that the substrate is treated using at least one of the components A, B, and C as a separate treatment liquid.

(4) The convenience needle ratio of A, B and C above is 100 =
400-1: 100-0.1, The method according to any one of claims 1 to 3.

Claims (1)

[Claims] (t) A, a fluoroalkyl group-containing compound, B
, (c) 1 to 40% by weight of an α,β-ethylenically unsaturated monomer having a cationic group, (b) 1 to 40% by weight of an α,β-ethylenically unsaturated monomer having a group containing active hydrogen. 20% by weight, and (/→ the above (10 (b)) copolymerizable monomers α, β
- a multicomponent copolymer obtained from 40 to 98% by weight of an ethylenically unsaturated monomer, selected from the group consisting of C, a polyglycidyl compound, a polyisocyanate compound, a stabilized polyisocyanate compound, a polyacylidine compound and an amino resin. A water- and oil-repellent finishing method characterized by treating a base material with three components of at least one crosslinkable compound. (2) The method according to claim 1, characterized in that the substrate is treated with a treatment liquid containing the three components A, B, and C. (3) The method according to claim 1 or 2, characterized in that the substrate is treated using at least one component of ASB and C as a separate treatment liquid. (4) The weight ratio of the above A, B and C used is l○0:40
The method according to any one of claims 1 to 3, characterized in that the ratio is 0 to 1:100 to 0.1.