JPS60152585A - Water-and oil-repellant - Google Patents

Abstract

PURPOSE:To provide a water-and oil-repellant which contains a copolymer of polyfluoroalkyl group-contg. monomer, benzyl (meth)acrylate and non-fluorine- contg. monomer and exhibits execellent water and oil repellency when used as either emulsion or soln. CONSTITUTION:About 10wt% or higher monomer (A) having 4C or higher polyfluoroalkyl group (e.g. perfluoro-octylethyl acrylate), about 10-80wt% benzyl (meth)acrylate and about 10-80wt% non-fluorine-based monomer having a glass transition point of below 0 deg.C (e.g. butyl acrylate) are emulsion polymerized at about 40-90 deg.C in an aqueous solvent in the presence of a polymerization initiator. A crosslinking group-contg. monomer (e.g. allyl glycidyl ether) may be used together.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water and oil repellent. More specifically, it relates to Water Repellent 1, which exhibits good 41λ water and oil repellency whether prepared in an emulsion type or a solution type.

A water and oil repellent agent containing as a water and oil repellent component a copolymer containing a polyfluoroalkyl group-containing monomer with a charcoal resistance of 4 or more and a benzyl (meth)acrylate gold constituent unit is disclosed in Japanese Patent Publication No. 1986- It is described in Publication No. 3759. “
It is said that vinyl chloride, etc., can be further copolymerized into this copolymerization as a water and oil repellent component, making it possible to prepare a solution-type water and oil repellent with excellent solubility in organic solvents. However, water and oil repellents prepared in emulsion form exhibit low water and oil repellency of only 2.

Additionally, the applicant has previously proposed the use of this type of copolymerized copolymerized vinyl chloride as a third component instead of vinyl chloride as a water and oil repellent component. (Japanese Patent Application No. 57-144,564), this J& devised water and oil repellent also shows good solubility in perchlorethylene etc. Examples of emulsion-type copolymers include copolymers of polyfluoroalkyl foundation KW Tlj polymerizable monomers and chlorine-containing polymerizable monomers such as vinyl chloride, vinylidene chloride, chloroethyl vinyl ether, and 2-chlorobutadiene. was used exclusively. However, the use of these copolymers may lead to destabilization of the emulsion due to ll01 generated due to decomposition of the 'jA jh-containing monomer component in the copolymer due to alkali, heat, light, etc., and mixing FA. In order to prevent this problem, it has been necessary to use a large proportion of expensive polyfluoroalkyl base right-type compounds in the co-4G reaction. ! ,:,ra-
There was no disadvantage.

The present invention provides a high-performance water and oil repellent using a copolymer that can form not only a solution type water and oil repellent but also an emulsion type water and oil repellent without such disadvantages.

Therefore, the present invention relates to a water and oil repellent, which comprises (a) an In compound Iam compound having a polyfluoroalkyl group having 4 or more carbon atoms, (b) benzyl methacrylate 1
(Ha(Nyl acrylate and (C) 1ii German (11 non-Fun whose glass transition temperature of the combination is 0°C or less)
A copolymer containing Hiratsume Go'/l tK ff1 as the 11-ζ-11-0 position is used as the 1a water and oil repellent component,
Alternatively, in addition to the components (a) to (c) of hjJ, the water-repellent 1a oil component is a co-4n intermediary containing a crosslinkable type/synthesizing compound as a constituent unit as the component (a).

Examples of the polyfluoroalkyl group-containing polyfluoroalkyl group-containing component (a) include compounds represented by the following general formula.

OF, -(-OF2ya→OH2尤6aOaR-oII2
(01,+,], Q,'f? -i-0'l' 2
2j= :day 01! 2→36-000OR-0)i
2〃 However, R: hydrogen atom size methyl group R': alkylene group RILHC4-C8 alkyl group n: 3-19 m: 1-4 1:2-18 These (a) components are It is contained in a proportion of about 10ffii% or more, about 2■i% or more, more preferably about 40% or more.Copolymerization 1;;1
If the amount is less than -, water and oil repellency cannot be obtained.

(b) Component (1) benzyl methacrylate or benzyl methacrylate contains at least about 10 to 80% by weight of the co-IR combination, preferably about 1
It is contained in a proportion of 0 to 50%, more preferably about 15 to 35%. If the copolymerization ratio is higher than this, the resin will be too hard and will not exhibit water and oil repellency, while if the copolymerization ratio is lower than this, water and oil repellency will not be exhibited.

(Q) component, the glass transition temperature of the single car combination is 0
Examples of non-fluorinated monomers having a temperature below 0.degree. C. include the following compounds.

Alkyl acrylate or alkyl methacrylate having a C1 to C20 alkyl group with the general formula DO(-OrIH2,O ○OOR'=OH2[
R: O, -o8 alkyl group, R': hydrogen atom or methyl group, n: 2-6.1n; 1-100] polyoxyalgylene glycol acrylate or polyoxyalgylene glycol Methacrylate C4-C
Alkyl vinyl ether having 6 alkyl groups 0, alkyl vinyl ketone having 0 to C6 alkyl groups Diethyl maleate or diethyl fumarate which cures the alkyl group of 1 to C6 These component (c) contains about 1 in the copolymer. ~100]%,
Preferably about 10 to 60% by weight, more preferably about 15%
It is contained in a proportion of ~50% by amount of melon. If the copolymerization ratio is higher than T, water and oil repellency will not be exhibited, while even if the copolymerization ratio is lower than this, the resin will become too hard and will not exhibit water and oil repellency.

A water and oil repellent agent whose water and oil repellent component is a copolymer containing such component (C) as a constitutional unit is disclosed in Japanese Patent Application Laid-Open No. 53-5
This copolymer is described in Japanese Patent No. 0078, in which tertiary-butyl methacrylate or inbutyl methacrylate is copolymerized in place of the benzyl methacrylate component (b) of the present invention. Water and oil repellents using such copolymers can be prepared in both emulsion type and solution type; Not only is it impossible to obtain water repellency of 100 or more, but there are also cases where alkaline yellowing occurs.

Further, as the crosslinkable group-containing merging monomer of component (i), for example, the following compounds are used.

Allyl glycidyl ether, glycidyl acrylate,
Epoxy group-containing monomers such as glycidyl methacrylate N-methylol acrylamide, N-methylol methacrylamide, N-butoxymethylol acrylamide,
N-methylol group-containing monomers such as N-butoxymethylol methacrylamide, hydroxyl-based right-type materials such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyglobyl acrylate, and 2-hydroxyethyl methacrylate. Acrylamide, methacrylamide, N-methylacrylamide,
amide group-containing single ft aH such as diacetone acrylamide and other compounds represented by the following formula;

Aziridine group-containing monomers such as aziridinylethyl acrylate and aziridinylethyl methacrylate, ethylene diacrylate, ethylene dimethacrylate,
Polyoxyethylene diacrylate, e.

Polyacrylate or polymethacrylate monoclaw bodies such as lyoxyethylene dimethacrylate, polyoxypropylene dimethacrylate, and polyoxypropylene dimethacrylate When these crosslinkable group-containing intermediate bodies are further copolymerized, they can be used as water and oil repellent components. The copolymer used has strong adhesion resistance against profiteering, such as fibers, and has the effect of improving durability, washing resistance, dry cleaning resistance, etc. (It also has the secondary effect of improving the polymerization stability of gold. Therefore, component (d) should be present in an amount of about 0.5 to 15 mass%, preferably about 1
It is used in a proportion of ~15% by weight.

In the copolymerization reaction, these (a) to (c) components or (
The polymerization is carried out by emulsion or solution polymerization using components a) to (d) and, if necessary, other polymerizable comonomers. Emulsion preparation is carried out in the presence of a polymerization initiator and an aqueous solvent at a temperature of about 40-90°C. Since this co-M synthesis reaction is carried out in an aqueous medium, from the viewpoint of stability of the polymer emulsion, it is preferable that the crosslinking group-containing polymer is also water-soluble. Solution polymerization also requires a polymerization initiator and an organic solvent, such as 1,1.1-
) Presence of halogenated hydrocarbons such as lychloroethane, perchloroethylene, and trichlorotrifluoroethane, aromatic hydrocarbons such as toluene and xylene, esters with ethyl acetate and butyl acetate, and ketones such as methyl ethyl ketone and methyl isobutyl ketone. Below, about 40-1
It is carried out at a temperature of 20°C. Regardless of which type of reaction is used, the copolymerization reaction proceeds almost quantitatively.

The obtained copolymer is prepared into a water and oil repellent by diluting the emulsion polymerization liquid with water and the monomer solution with an organic solvent to a solid content concentration of about 0.5%. Water and oil repellent treatment is carried out on cotton, cotton, etc. using the water and oil repellent thus prepared.
Coating of various types of fibers such as wool, silk, polyester, polyamide, and regenerated cellulose is performed on materials to be treated such as woven fabrics, pulp products, and leather made of blends of these materials.

As shown in the following examples, the water- and oil-repellent shaver according to the present invention not only exhibits good water and oil repellency when prepared in either an emulsion type or a solution type, but also exhibits good water and oil repellency.
Since there is no yellowing or rust caused by alkali, it can be effectively applied to the objects to be treated as described above.

Next, the present invention will be explained with reference to examples.

Example 1 The above (a) to (d) were placed in a 500-capacity autoclave.
) Predetermined amounts of ingredients, 40 g of acetone, 1509 water, and nonionic surfactant (Kao soap product Emulgen 930)
69 was added, the whole was stirred to emulsify, and then a portion of azobisisobutyramidine hydrochloride was added as a photoinitiator,
The copolymerization reaction was carried out at about 70°C for 8 hours. In all cases, the combination rate calculated from the solid content was 99% or more.

The results regarding the company using each polymerizable monomer, the pH of the copolymerization reaction solution after the reaction, and alkaline yellowing (change in color of the reaction solution emulsion when pJ (9) with ammonia water H17, 1) are as follows: It is shown in Table 1 below.

Note that A14 to A20 are all comparative examples, in which the component (C) is not used, or instead, the homopolymer thereof has a glass transition temperature of 0° or higher.
! The compound is used in I-containing polymerization 11.

In addition, 1bzi to 24 are also comparative examples, in which the above (
b) b9. Tertiary butyl methacrylate or inbutyl methacrylate has been used in place of min.

Table 1 1 FAAc 28. jlzMA 6 BA 6 MA
M2 5~6 None 2 // 24 // Rtt
8n ny3 N 20 // 10 N 10 t
t n u4 〃 a 〃 6 bet 6 〃 〃 〃5
tt tt tt p ■ 〃〃〃〃6 〃 〃 〃
〃 bu 〃〃〃〃 7FA1111AC20// tt BA14 rt
n rt8 FAAo 28 BZA rp J/ 6
u n rp9 p tt I1 row planting 〃 珂'A t
t tt // ttIQ /l 24 p 3 tt
8tt tt tt11〃 Imperial edict 〃6 BA 5 D
A#, I 〃 〃12〃〃〃〃〃 Alliance 〃 〃 13 // 20 // 10 PPA 10 DAA
M 4 1/14 tt u tt 20 MAM 2
//15 #28 // 12 - tt s /
/16 // 20 tt 10 Vl)01 10
n 4 2-3 Yes 17 〃 28 〃 6 〃 6
〃 〃113 // u tt' tt VO 〃 〃 2 319 tt 〃// u O glare W t
t tt n 3～4 〃2Q tt tt IIJI
A 12 - - tt tt 4-5 None 21 /
/ /l t-ERAA 6 VDOI26 tt t
t 2 ant 22 tt tt j, J] 1v4A p
s tr n tt //23//I/ tt
EA p tt tt 5~6 None tr tt
1-BMk // tt tt un // (Explanation of abbreviations) IPAAc: Bar Fluorooctylethyl acrylate FAMAc: Bar Fluorooctylethyl methacrylate BzMA: Pencil methacrylate BzA: Benzyl acrylate EHA: 2-ethylhexyl acrylate-1 BA Nibutyl Acrylate Ml: Methyl vinyl ether IAVK: Methyl vinyl tetone MEA: Metomi diethyl acrylate PPA: Polypropylene glycol monomethacrylate VDOI2
: Vinylidene chloride VOI : Vinyl chloride 0EVE : Chlorethyl vinyl ether MAM : N-
Methylol acrylamide DAAM Nidiacetone acrylamide AMN: 0H7=O(OH,)OONN
(OH,)20H,0H(OH)OH3t-nraA:
Tertiary butyl methacrylate i-BMA: Isobutyl methacrylate The obtained copolymerization reaction solution was diluted with water to prepare a solution with a solid content concentration of 0.5 IT%, and fill cloth and polyamide were added to the solution. The cloth or polyester cloth was thoroughly wiped and dried, heated at 150° C. for 3 minutes, and the water repellency and oil repellency were measured according to the death value j# described below. The results obtained are shown in Table 2 below.

Table 2 2 110 11'0 110 110 1' 120
3 1/ 110- 110 100 4 100 11.0 5 〃 6 1/ // 120 120 1107110-
100 // 100 100 1008110 11
120
No water droplets adhere to the fluff of the cloth at all 110"/1
20- One part of the beam is attached to the fluff of the cloth - 4 110 Up to 3 water droplets are attached to the fluff of the cloth 110- Example of 4 drops of water is attached to the fluff of 477 100 To the fluff of the cloth 90 Large water droplets adhere to the cloth. 80 Water adheres to the cloth. 70 Water adheres to the cloth: It sticks to each other. 50 The second area of the cloth gets wet with water 0 The back side of the cloth Water penetrates [oil repellency test and evaluation] 1! II
A drop of the test solution (mixture of 6 specific proportions as shown in the following table) was dropped on the cloth, and the condition was observed after 5 minutes and 11 J] had passed. If the dropped H'C test solution is kept on the cloth, test with a test solution containing more n-hepukun, and conversely, if the H'C test solution is not kept on the cloth. is further tested using a test solution with many Nujol spots. Then, using a test liquid that is at the limit of being coated on the cloth, the oil repellency is evaluated based on the oil repellency evaluation shown in the table below.

In the oil repellency evaluation, the case where 100% Nujol is retained is 50, and the case where 100% Nujol is not retained is O.

150 0 100 140 10 90 130 20 80 120 30 70 110 4.0 60 100 50 50 90 60 40 80 70 30 70 80 20 60 90 10 50 100 0 0 (does not retain 100% Nushol) or more From the results, You can say things like power.

(Represented in RenoFff14-15), sea urchin, co-IJ that does not copolymerize a low-Class transition point single ω0 body (if used as such, both water repellency and oil repellency are low).

(2) J shown in fl+16 to 19: Uni, if a copolymer made by copolymerizing a chlorine-containing monomer with a glass transition point of 0°C or higher is used instead of a low glass transition point monomer. Although it has good water and oil repellency, the pH of the locking solution is low and it yellows due to alkali, making it unsuitable for use on textiles as a water and oil repellent.

That is, during the processing of the cloth, there is a step in which the cloth comes into contact with an alkali, and if the alkali that accompanies the process causes the cloth to turn yellow, it cannot be put to practical use. Furthermore, if the pH of the vehicle mixture is low, there is a risk that the crosslinking points in the copolymer may be denatured, causing problems such as decreased storage stability.

(3) As shown in A20, when a copolymer polymer in which benzyl (meth)acrylate is not copolymerized is used, both water repellency and oil repellency are low.

(4)/71ii21-24 (as shown in , when tert-butyl methacrylate or isobutyl methacrylate is used instead of benzyl (meth)acrylate,
Although the oil repellency is good, the water repellency only shows an evaluation of 100 or less.

(5) In contrast to these comparative examples, the emulsion type water and oil repellent according to the present invention not only has good water and oil repellency, but also has an appropriate pH of the polymerization solution, and
c Since no alkali yellowing is observed, it can be used suitably.

Example 2 In an autoclave with a capacity of 500 me, the above (a
) to (d) component predetermined ffi, 1,1.1-)lichloroethane 1609 and azobisisobutyronitrile 19
was added, and a copolymerization reaction was carried out at about 70°C for 24 hours. In all cases, the conversion rate calculated from the solid content was 99% or more.

The amount of each polymerizable monomer used and galvanized sheet steel (1°1.1
-) Dilute the reaction solution with dichloroethane to bring the solid concentration to 0.
．． Pour 50 g of a 5% by weight solution into a sample tube, immerse a 20 x 70 x 1 +111M galvanized iron plate in the sample tube, leave it to stand, and observe the presence or absence of rust after -m has elapsed.) is shown in Table 3 below.

Incidentally, &5 to 7 are all comparative examples, in which either the component (Q) is not used in the component (b).

Table 3 1 FAAc 24 BzWk 4 ]nA 12 E
iGDA O, 2 no 2 // p u tt tt
tt Publication Hi,〃〃3 1/ // // I/ //
// Touching evil 〃 〃4 u tt // tt tt
tt GMA O,5,tt5 tt 〃--tt 1
6 Gall 0,2〃6 〃 〃 B Mackerel 15 − − //
tt tt7 u tt --' VDOI216
// // Yes (explanation of abbreviations) EA: Ethyl acrylate EGDA: Polyethylene glyfur dimethacrylate AzEMA: Aziridinyl ethyl methacrylate GM
A The reaction mixture obtained with nigericidyl methacrylate was diluted with 1.1.1-) +3 chloroethane, and the solution with a solid content concentration of 0.5% was made into W.
, and the water repellency and oil repellency were measured in the same manner as in Example 1. The results obtained are shown in Table 4 below.
is shown.

Table 4 1 100” 100 100 120 110 12
02 110 110 3 // 100- 100 4 tt 100 110 5 80 80+80 100 100 906909
0 90 100 7 // 90" 120 110 120 From the above results, the following can be said.

(1) When a copolymer is used that does not contain benzyl (meth)acrylate and a low glass transition point clear carrier, water repellency is low.

(2) If a copolymer prepared by copolymerizing a chlorine-containing monomer is used instead of a low glass transition point monomer, the water and oil repellent will cause metal corrosion. That is, this water and oil repellent cannot be applied to metal, and also causes rust to metal storage containers.

(3) In contrast to these comparative examples, the solution-type water and oil repellent according to the present invention not only has good water and oil repellency, but also does not exhibit Z tactility (toward metals).

Example 3 In genus 10 of Example 1, in order to stabilize the nail metal during emulsion polymerization without using N-methylol acrylamide, which is a monomer containing a crosslinking agent, hydrophilic group-containing was added. A co-polymerization reaction was carried out using terminal methoxylated polyethylene glycol monoacrylate, which is a polymerizable monomer. The pH of the copolymerization reaction solution was 5 to 6, and no alkali yellowing was observed.

B. The copolymerization reaction solution was diluted with water to prepare a solution containing 0.5% solid content, and the water repellency and oil repellency were measured in the same manner as in Example 1. did.

The obtained results are shown in Table 5 below.

Example 4 In I'a 1 to I'a 4 of Example 2, the copolymerization reaction was carried out without using the crosslinkable group-containing polymer casting body. No occurrence of galvanized sheet steel was observed using the same test method.

The obtained copolymerization reaction, 'g, was diluted with tetrachlorethylene to prepare a solution with a solid content concentration of 0.5%, and water repellency and oil repellency were tested in the same manner as in Example 1. It was measured. The results obtained are shown in Table 5 below.

Table 5 3 110- 110- 110 120 120 1
304 110 110 120 110 120 Representative Patent Attorney Yoshi 1) Instigation Husband Proceedings Neho Seisho (Own Ship July 20, 1981 Commissioner of the Patent Office Shiga Gakudono 1 Case Indication Water Repellent Oil Repellent 3 Soup Case for Amendment Relationship with Patent applicant name: Hiki Mektron Co., Ltd. 4 Agent (〒105) Address: 501 Ato Building, 1-2-7 Shiba Daimon, Minato-ku, Tokyo
No. 2-hydroxyethyl acrylate-1-'' is inserted.

Claims (1)

[Scope of Claims] 1. (a) a nail platform monomer having a polyfluoroalkyl group having 4 or more carbon atoms, (b) benzyl methacrylate or benzyl acrylate, and (Q) a homopolymer thereof whose glass transition temperature is A water- and oil-repellent agent comprising a copolymer containing as a constituent unit a non-fluorine pointable single precipitate having a temperature of 0° C. or lower] jl as an oil component. 2. At least about 10% by weight of component (a), about 10-80% by weight of component (b), and about 10-8% by weight of component (C).
In particular, the water and oil repellent component is a copolymer containing 0%
' The water and oil repellent according to claim 1. 3. <&) Polymerizable monomer having a polyfluoroalkyl group of carbon tIi4 or more, (b) benzyl methacrylate or ltu benzyl acrylate, (C) non-fluorine whose homopolymer has a glass transition temperature of 0°C or less A water- and oil-repellent agent comprising a copolymer containing a system polymerizable monomer and (d) a cross-linkable group-containing vehicle chassis monomer as structural units. 4. (a) Ingredients at least about 1o1ii'its, (
About 10 to 80 mm% of component b), about 10 to 80 mm% of component (c)
80% by weight M, and component (d) about 0.5-15% by weight
The water and oil repellent according to claim 3, wherein the copolymer contained is a water and oil repellent component.