JPS6321715B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a water and oil repellent having a high degree of durability, and more specifically, it is made of a polymer in which branch segments having blocked polyfluoroalkyl groups are bonded to specific trunk segments, and is treated with low concentration treatment. However, the present invention relates to a water and oil repellent that can impart high water and oil repellency and has durability such as high friction resistance. A polymer of a polymerizable compound containing a polyfluoroalkyl group such as acrylates containing a perfluoroalkyl group (R _f group) or methacrylates, or this and an alkyl acrylate,
Water and oil repellents comprising copolymers with other polymerizable compounds such as maleic anhydride, chloroprene, butadiene, methyl vinyl ketone, and vinyl chloride are known. Therefore, such conventional water and oil repellents are generally made of random copolymers, and have a high degree of durability, such as resistance to fibers that do not have reactive active sites such as polyester fibers. There are few materials that have abrasion resistance, wash resistance, and dry cleaning resistance. In other words, in the case of a random copolymer, even if a component with excellent adhesion to fibers is used as a comonomer, it will coexist with R _f groups in the polymer chain, and such hydrophilic and lipophilic groups A certain adhesive group and the R _f group, which is a water- and oil-repellent group, mutually inhibit their functions, making it difficult to obtain a polymer that is highly durable and has a high degree of water- and oil-repellency. In order to solve the above-mentioned difficulties, that is, to make contradictory functions compatible, it has been proposed to use a polymer having a block structure of an adhesive group and a water/oil repellent group as a water/oil repellent. For example, if a polymer with adhesive groups is used as a backbone polymer, R _f
These include polymers obtained by graft copolymerization of group-containing monomers, or block copolymers consisting of an R _f segment and an adhesive segment. Treatment of fibers with polymers having such a blocked structure can impart a high degree of water and oil repellency and excellent durability. JP 52-43955, JP 54-132694, JP 37-10090,
See Special Publications No. 18627, No. 10394, etc. As a result of various studies and studies on water and oil repellents having a blocked structure, the present inventors discovered a polymer with a structure in which a branch segment having a blocked R _f group is graft-bonded to a trunk polymer having adhesive properties. It has been found that the above-mentioned purpose is met well, and that the selection of the backbone polymer is very important.
That is, as a backbone polymer capable of imparting high durability even to polyester fibers, it is effective to use a material whose main components are alkyl acrylates and hydroxyalkyl acrylates or methacrylates, and the ratio of both is within a certain range. It was discovered that it is important to have the following. Thus, the present invention was completed based on the above findings, and provides a water and oil repellent agent comprising a polymer in which a branch segment having a blocked polyfluoroalkyl group is bonded to a trunk segment. [A] CH ₂ = CHCOOR (however, R is an alkyl group)
and [B]

[Formula] (where R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom or an alkyl group),
The present invention provides a new water and oil repellent characterized by a weight ratio of [A]/[B] of 10/90 to 90/10. The water and oil repellent of the present invention can impart a high degree of water and oil repellency to fiber surfaces even when treated at low concentrations, and also has very good durability against friction and washing. Conventional water and oil repellents have abrasion resistance,
The water and oil repellent of the present invention can impart a high degree of durability even in the treatment of polyester fibers, etc., which have been difficult to impart durability, such as washing resistance. In the present invention, it is important that a branch segment having a blocked polyfluoroalkyl group is bonded to a specific trunk segment.
And the specific stem segment is [A] CH ₂ = CHCOOR and [B]

It consists of a copolymer whose main component is [Formula]. R is an alkyl group, usually an alkyl group having 1 to 8 carbon atoms, preferably a lower alkyl group having 1 to 3 carbon atoms. It is important that component [A] is an acrylate; if it is a methacrylate, the durability imparting effect will be insufficient. R ¹ may be a hydrogen atom or a methyl group, and R ² is a hydrogen atom or an alkyl group, preferably a hydrogen atom or a lower alkyl group such as a methyl group. Particularly preferred trunk segments include R being an ethyl group;
It is a copolymer mainly composed of ethyl acrylate and 2-hydroxyethyl acrylate in which R ¹ and R ² are hydrogen atoms. The trunk segment in the present invention is [A]/[B]
The weight ratio is 10/90 to 90/10, preferably 20/80 to
80/20, especially 50/50 to 75/25 is adopted. And the trunk segments are [A] and [B]
It may consist only of the main component, or it may contain other crosslinking components, graft active components, etc. [X]. The content of [X] can be selected from a range of 0 to 20 parts by weight, preferably 2 to 10 parts by weight, per 100 parts by weight of the trunk segment. As [X], component [B] can be used as a graft or crosslinking component, but N-methylol acrylamide,
Crosslinking components such as N-butoxymethylacrylamide and glycidyl methacrylate, allyl methacrylate and P-isopropylstyrene may be selected depending on the necessity of the grafting means. In the present invention, [A], [B] of the trunk segment
The reason why the main components are effective in improving the durability of polyester fibers etc. is not necessarily clear, but the interfacial tension with the fiber material is small (especially the [A] component),
This is thought to be because it contains factors that are advantageous for adhesion to fiber materials, such as hydrogen bonding of OH groups (component [B]), low glass transition point, and ease of forming into a film. It goes without saying that such explanations are provided to aid understanding of the present invention, and do not limit the present invention in any way. The branch segment in the present invention has a blocked polyfluoroalkyl group. The polyfluoroalkyl group (hereinafter sometimes abbreviated as PFA group) is usually selected from those having 4 to 20 carbon atoms, and is preferably a perfluoroalkyl group. In particular, perfluoroalkyl groups having 6 to 18 carbon atoms are preferred. A plurality of such PFA groups, preferably three or more, particularly five or more, are contained in the branch segment. Various means for blocking the PFA group may be employed. For example, there is a method of graft polymerizing a PFA group-containing monomer to a backbone polymer. As a branch segment, CH ₂
A homopolymer of =C(R ¹ )COOQR _f or a copolymer of this with alkyl acrylate, alkyl methacrylate, styrene, etc. can be exemplified. R ¹ is a hydrogen atom or a methyl group, Q is 1 carbon number
~10 divalent alkylene groups, R _f has ~6 carbon atoms
18 perfluoroalkyl groups, preferably
R ¹ is a methyl group, and Q is -CH ₂ CH ₂ -. As a component to be copolymerized with CH ₂ =C(R ¹ )COOQR _f as a branch segment, CH ₂ =C(CH ₃ )COOR ³
(R ³ is an alkyl group having 1 to 4 carbon atoms) is preferable. In a preferred embodiment, as a branch segment
_CH2 =C( ^R1 ) _COOQRf / _CH2 =C( _CH3 )
COOR ³ weight ratio is 70/30 to 100/0, especially 80/20
It is desirable to select one with a rating of ~95/5. Methods for synthesizing polymers in which branch segments are grafted onto trunk segments as described above include (1) chain transfer method, (2) polymer radical initiation, for trunk segments synthesized by conventional solution polymerization, emulsion polymerization, etc. (3) Ce() initiation method, (4) polymer reaction method, etc., and these are shown below. In addition, in the following example, CH ₂ =C(CH ₃ )COOQR _f
is shown in FMA. (1) Chain transfer method (2) Polymer radical initiation method (3) Starting method with Ce() (4) Polymer reaction method In addition, in the present invention, blocked
The repellent of the present invention can also be obtained by synthesizing a monomer having a branch segment having a PFA group (hereinafter referred to as a macromer) and copolymerizing the macromer with the main components [A] and [B] of the trunk segment. Water and oil repellents can be produced. (5) Macromer method As a method for copolymerizing such a macromer with other monomers, conventional polymerization methods such as solution polymerization and emulsion polymerization can be used. In solution polymerization, a solvent that dissolves the macromer, such as benzotrifluoride, 1,1,2-trifluorotrichloroethane, acetone, tetrahydrofuran, ethyl acetate, or a mixed solvent thereof, is used,
It is customary to polymerize at 30-120°C. Emulsion polymerization is also preferably carried out in the presence of these solvents. Next, embodiments of the present invention will be described in more detail, but it goes without saying that the present invention is not limited by such explanations. In addition, water repellency is JIS L-1005, oil repellency is AATCC-TM118.
(1966). Abrasion resistance was evaluated by measuring water repellency and oil repellency after processing at 2000 rpm for a predetermined time using a Toyo Seiki Accela rotor. In addition, the washing resistance was determined by washing once for 10 minutes at 40℃ using a household electric washing machine using 55g of detergent (Blue Diamond: product name), bath volume 20, rinsing for 10 minutes, and then drying. The water repellency and oil repellency were measured and evaluated after a predetermined number of times. Example 1 80 ml of tetrahydrofuran (THF) was placed in a 300 ml four-necked flask equipped with a stirrer, cooling tube, thermometer, and nitrogen gas inlet tube, and nitrogen gas was passed through it for about 30 minutes.
Degassed for a minute. Ethyl acrylate (EA) 30gr,
2-Hydroxyethyl acrylate (HEA)
20 gr and allyl methacrylate (AM) 2.5 gr were charged, and degassing was continued to bring the temperature to 30°C.
After adding 0.25 gr of initiator diisopropyl peroxydicarbonate and reacting for 18 hours while maintaining the temperature at 28-30°C, the conversion rate of EA, HEA, and AM was 100% as determined by gas chromatography. After the reaction is complete, increase the temperature until THF refluxes, and CnF _2o+1
CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ (=8.9, FMA)
110gr, methyl methacrylate (MMA) 11gr,
and initiator butyl peroxyisobutyrate
When 0.5 gr was added and the reaction was carried out while maintaining the temperature at 70 to 72°C, the conversion of FMA and MMA reached 100% by gas chromatography in 18 hours, so the reaction was stopped. The reaction solution thus obtained was diluted to a predetermined concentration with a mixed solvent of trichlorotrifluoroethane/methanol (70/30: volume ratio), a polyester cloth was immersed in this diluted solution for 1 minute, and air-dried for 30 minutes.
Next, it was heat treated at 150°C for 3 minutes to make it water and oil repellent. The water repellency and oil repellency of the cloth treated in this manner are shown in Table 1 below, including initially, after rubbing, and after washing. For comparison, the performance of a water and oil repellent (commercially available) made of a random copolymer having an R _f group is also shown in Table 1 below. Indicated by oil repellency/water repellency.

[Table] Examples 2 to 11 Copolymers having trunk segments and branch segments of various compositions were synthesized in the same manner as in Example 1,
Table 2 below shows the performance of polyester cloth treated with a water- and oil-repellent treatment using a 0.05% diluted solution.
The weight ratio of trunk segment/branch segment is 30/
It is 70.

[Table] Example 12 In a four-necked flask similar to Example 1, add 120 gr of ion exchange water, 60 gr of dimethyl sulfoxide, and 20 gr of EA/Hydroxypropyl acrylate (HPA) copolymer (EA/HPA weight ratio 60/40). ,as well as
FA20gr was added and degassed at 40°C. about 30
After minutes, 0.40 gr of (NH ₄ ) ₂ Ce(NO ₃ ) ₆ was added and the temperature was maintained at 25-40° C. with further stirring. After 3 hours, gas chromatography showed that the conversion rate of FA was 100.
%, the reaction was stopped, and the white solid precipitate formed was separated, washed, and dried to obtain 38.6 gr of polymer solid. This solid was dissolved in a mixed solvent of trichlorotrifluoroethane/THF (70/30: volume ratio), and polyester cloth was treated with a water- and oil-repellent treatment using a 0.05% diluted solution in the same manner as in Example 1. The gender was evaluated. As a comparative example, the performance of a random copolymer having the same composition was also evaluated. The evaluation results are shown in Table 3 below.

[Table] Example 13 In a four-necked flask similar to Example 1, 80gr of tetrahydrofuran (THF), 72gr FMA,
MMA8gr and thioglycolic acid (TGA) 0.64gr were added and degassed under nitrogen for about 30 minutes. After degassing, reduce the temperature
The temperature was raised to 60°C, and 0.2g of α,α′-azobisisobutyronitrile (AIBN) was added to carry out a low polymerization reaction. After 18 hours, FMA was detected by gas chromatography.
After confirming that 99% or more of MMA has reacted, the reaction mixture was reprecipitated into 800gr of methanol to obtain the resulting branched segment polymer, which was dried under reduced pressure to produce 73.6gr of pale yellow solid. Obtained. 70gr of this branch segment, 70gr ethyl acrylate/hydroxyethyl acrylate copolymer (weight ratio 80/20), and 500gr benzotrifluoride.
Put it inside, add 7gr of paratoluenesulfonic acid,
The esterification reaction was carried out at 100 to 110°C while removing the produced water. The performance of the obtained polymer was comparable to that of the polymer of Example 10. Example 14 A branch segment was obtained in the same manner as in Example 13 using thioglycol instead of thioglycolic acid. 70gr of this branch segment was mixed with 1,1,2-trifluorotrichloroethane/THF (50/50 weight ratio)
Dissolve in 140gr of mixed solvent and add 3.25gr pyridine.
added. 3.72 gr of acrylic acid chloride was added dropwise while maintaining the reaction solution at 30 to 35°C to carry out the esterification reaction. After 4 hours, the reaction mixture was reprecipitated into 2100 gr of methanol and the resulting precipitate was dried under reduced pressure to obtain 71.2 gr of a pale yellow solid. When the nuclear magnetic resonance spectrum of this product in benzotrifluoride was measured, a vinylic proton (CH ₂ =CH-) was observed at a σ value of 3.4 to 4.4.
It was confirmed that it is a macromer with a double bond. In a four-neck flask similar to Example 1, 35 gr of this macromer, 21 gr of ethyl acrylate (EA),
Hydroxyethyl acrylate (HEA) 14gr,
280gr of benzotrifluoride was added, and after degassing, the temperature was raised to 60°C, and 0.2gr AIBN was added to carry out a polymerization reaction. After 10 hours, complete reaction of EA and HEA was confirmed by gas chromatography. The performance of the produced polymer was comparable to that of Example 11.

Claims (1)

[Scope of Claims] 1. A water and oil repellent made of a polymer in which a branch segment having a blocked polyfluoroalkyl group is bonded to a trunk segment, wherein the trunk segment is [A]CH ₂ =CHCOOR (where R is an alkyl group) and [Formula] (where R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom or an alkyl group),
The weight ratio of [A]/[B] is 10/90 to 90/10,
A water- and oil-repellent agent characterized in that the branch segments have five or more polyfluoroalkyl groups. 2. The water and oil repellent according to claim 1, wherein the polyfluoroalkyl group is a perfluoroalkyl group having 6 to 18 carbon atoms. 3 Weight ratio of trunk segment/branch segment is 20/
The water and oil repellent according to claim 1, which has a ratio of 80 to 70/30. 4 The branch segment is CH ₂ = C (R ¹ ) COOQR _f (where, R ¹ is a hydrogen atom or a methyl group, and Q is a carbon number of 1
~10 divalent alkylene groups, R _f has ~6 carbon atoms
18. The water and oil repellent according to claim 1, which is composed mainly of 18 perfluoroalkyl groups.