Fluorine-containing polymer and surfactant

Abstract

To provide a novel fluorine-containing polymer or fluorine-based surfactant that retains the functions of the conventional fluorine-based surfactants, while having reduced environmental load.SOLUTION: Examples of the invention can include a fluorine-containing polymer that is formed by the copolymerization of a methacryl monomer including a perfluoropolyether chain with its repeat unit consisting of only 'CF2O', and at least one methacryl monomer free of fluorine, and a surfactant comprising the same.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention belongs to the technical field of fluorine-containing polymers or surfactants containing the same. The present invention relates to a polymer and a surfactant containing a perfluoropolyether chain containing only "CF2O" as a repeating unit in the molecule.

Background Art

[0002] Fluorine-based surfactants have hitherto been regarded as indispensable in the manufacturing industry including the semiconductor and electronics fields by taking advantage of their high functionality, particularly the ability to lower the surface tension.

[0003] However, due to the bioaccumulation in the body and the recalcitrance in the environment caused by the chemical stability of fluorine-containing compounds in recent years, regulations have been initiated in various countries. PFOA (perfluorooctanoic acid) - related compounds have already been targeted, and perfluorohexyl group - containing compounds used as alternative compounds are also becoming the subject of regulatory discussions, and further alternative compounds are desired.

[0004] Patent Document 1 discloses a surface treatment agent containing a perfluoropolyether chain having only "CF2O" as a repeating unit. However, the perfluoropolyether chain is a single chain in which the number of repeating units of "CF2O" is 2 to 7, and it is difficult to obtain sufficient surface tension - lowering ability with this.

[0005] Patent Document 2 discloses a fluorine - containing thermally decomposable polymer that decomposes by heat treatment. However, the decomposition site is the linking part of the fluorine chain and does not decompose the fluorine chain itself, so it is difficult to say that it sufficiently addresses environmental concerns about fluorine compounds.

[0006] Non - Patent Document 1 describes that the thermal decomposition starting temperature of a perfluoroalkyl group regarded as an environmental concern substance is at least 200°C or higher.

[0007] The perfluoropolyether group-containing compound is a high heat-resistant substance used in lubricants for hard disks and the like, and Non-Patent Document 2 describes that thermal decomposition starts at about 160°C only in the presence of metal fluorides and metal oxides.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Non-Patent Documents

[0009]

Non-Patent Document 1

Non-Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0010] As described above, there are concerns about the impact of conventional fluorosurfactants on the environment and the human body. The main object of the present invention is to provide a new fluorine-containing polymer or fluorosurfactant with low environmental impact while maintaining the functions of conventional fluorosurfactants.

Means for Solving the Problems

[0011] The inventor of the present invention conducted intensive studies and found that a perfluoropolyether chain having only "CF2O" as a repeating unit decomposes at a much lower temperature compared to a perfluoroalkyl chain or other perfluoropolyether chains. Due to this specific property, it is easily decomposed in the environment and has a low environmental impact. As a result of repeated efforts, the present invention has been completed. Examples of the present invention include the following aspects. [1] A fluorine-containing polymer obtained by copolymerizing a (meth)acrylic monomer containing a perfluoropolyether chain having only "CF2O" as a repeating unit and one or more fluorine-free (meth)acrylic monomers. [2] The fluorine-containing polymer according to [1] above, wherein at least one of the fluorine-free (meth)acrylic monomers contains a repeating unit of C p H 2p O (wherein p is an integer from 2 to 4). [3] The fluorine-containing polymer according to [1] above, wherein the perfluoropolyether chain has a structure represented by the following general formula (1).

[0012] [Chemical formula]

[0013] [4] The fluorine-containing polymer according to [3] above, wherein at least one of the fluorine-free (meth)acrylic monomers contains a repeating unit of C p H 2p O (wherein p is an integer from 2 to 4). [5] A method for producing a fluorine-containing polymer according to any one of [1] to [4] above, comprising a step of copolymerizing a (meth)acrylic monomer containing a perfluoropolyether chain having only "CF2O" as a repeating unit and one or more fluorine-free (meth)acrylic monomers. [6] A surfactant containing the fluorine-containing polymer according to any one of [1] to [4] above. [7] A composition comprising the fluorine-containing polymer according to any one of [1] to [4] above and a solvent. [8] A composition comprising the surfactant and the solvent described in [6] above. [9] The composition according to [7] above, wherein the solvent is water and / or an organic solvent.

[10] The composition according to [8] above, wherein the solvent is water and / or an organic solvent. [Effect of the Invention]

[0014] The perfluoropolyether chain according to the present invention is decomposed at a much lower temperature than the conventional perfluoropolyether chain. Therefore, the fluorine-containing polymer or fluorosurfactant of the present invention has less environmental impact while maintaining the functions of the conventional fluorosurfactant. [Brief Description of the Drawings]

[0015]

Figure 1

[0016] Hereinafter, the present invention will be described in detail. 1 Fluorine-containing polymer of the present invention The fluorine-containing polymer of the present invention (hereinafter referred to as "the polymer of the present invention") is characterized in that it is formed by copolymerizing a (meth)acrylic monomer containing a perfluoropolyether chain consisting only of repeating units of "CF2O" and one or more (meth)acrylic monomers not containing fluorine. As the number of repeating units of "CF2O" in the perfluoropolyether chain according to the present invention, for example, a range of 2 to 10 is appropriate, a range of 3 to 8 is preferable, and a range of 3 to 7 is more preferable. When the (meth)acrylic monomer containing the perfluoropolyether chain is a mixture, these numerical values may be average values (number average, weight or mass average, or z average, etc.). Here, the expression "(meth)acrylic monomer" means a methacrylic monomer or an acrylic monomer. In addition, the same applies to "(meth)acrylate" and the like.

[0017] The polymer of the present invention is difficult to exhibit the function as a surfactant alone. A perfluoropolyether chain having only "CF2O" as a repeating unit is converted into a (meth)acrylic monomer by a conventional method, and then such a (meth)acrylic monomer and other non-fluorine-based monomers are copolymerized by a conventional method to produce it. The present inventor has found that by copolymerizing a compound obtained by converting a perfluoropolyether chain having only "CF2O" as a repeating unit into a (meth)acrylic monomer and a non-fluorine-based monomer, the disadvantages of the single-chain perfluoropolyether chain can be compensated for.

[0018] The (meth)acrylic monomer containing a perfluoropolyether chain having only "CF2O" as a repeating unit is not particularly limited, and for example, the following compounds can be mentioned. CF3O(CF2O)3CF2CH2OC(O)CH=CH2 CF3O(CF2O)3CF2CH2OC(O)C(CH3)=CH2 CF3O(CF2O)4CF2CH2OC(O)CH=CH2 CF3O(CF2O)4CF2CH2C(O)C(CH3)=CH2 CF3O(CF2O)5CF2CH2OC(O)CH=CH2 CF3O(CF2O)5CF2CH2OC(O)C(CH3)=CH2 CF3O(CF2O)6CF2CH2OC(O)CH=CH2 CF3O(CF2O)6CF2CH2OC(O)C(CH3)=CH2 CF3O(CF2O)7CF2CH2OC(O)CH=CH2 CF3O(CF2O)7CF2CH2OC(O)C(CH3)=CH2 CF3O(CF2O)3CF2CONHCH2CH2OC(O)CH=CH2 CF3O(CF2O)3CF2CONHCH2CH2OC(O)C(CH3)=CH2 CF3O(CF2O)4CF2CONHCH2CH2OC(O)CH=CH2 CF3O(CF2O)4CF2CONHCH2CH2OC(O)C(CH3)=CH2 CF3O(CF2O)5CF2CONHCH2CH2OC(O)CH=CH2 CF3O(CF2O)5CF2CONHCH2CH2OC(O)C(CH3)=CH2 CF3O(CF2O)6CF2CONHCH2CH2OC(O)CH=CH2 CF3O(CF2O)6CF2CONHCH2CH2OC(O)C(CH3)=CH2 CF3O(CF2O)7CF2CONHCH2CH2OC(O)CH=CH2 CF3O(CF2O)7CF2CONHCH2CH2OC(O)C(CH3)=CH2 C2F5O(CF2O)3CF2CH2OC(O)CH=CH2 C3F7O(CF2O)4CF2CH2OC(O)C(CH3)=CH2 C2F5O(CF2O)5CF2CONHCH2CH2OC(O)CH=CH2 C3F7O(CF2O)6CF2CONHCH2CH2OC(O)C(CH3)=CH2 In the present invention, the above compounds can be used alone or in admixture of two or more thereof.

[0019] In particular, among the polymers of the present invention, a polymer obtained by copolymerizing a (meth)acrylic monomer containing the above perfluoropolyether chain and a nonionic non-fluorinated (meth)acrylic monomer is preferable because it can exhibit excellent surface activity. In the present invention, the "nonionic non-fluorinated (meth)acrylic monomer" means one containing one or more C p H 2p O (wherein p is an integer of 2 to 4) as a repeating unit.

[0020] Examples of the non-fluorine (meth)acrylic monomer include polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polytetramethylene glycol (meth)acrylate, poly(ethylene glycol-propylene glycol) mono(meth)acrylate, polyethylene glycol-polypropylene glycol mono(meth)acrylate, poly(ethylene glycol-tetramethylene glycol) mono(meth)acrylate, polyethylene glycol-poly(tetramethylene glycol) mono(meth)acrylate, poly(propylene glycol-tetramethylene glycol) mono(meth)acrylate, polypropylene glycol-poly(tetramethylene glycol) mono(meth)acrylate, poly(propylene glycol-butylene glycol) mono(meth)acrylate, polypropylene glycol-poly(butylene glycol) mono(meth)acrylate, poly(ethylene glycol-butylene glycol) mono(meth)acrylate, polyethylene glycol-poly(butylene glycol) mono(meth)acrylate, poly(tetraethylene glycol-butylene glycol) mono(meth)acrylate, poly(tetraethylene glycol-poly(butylene glycol) mono(meth)acrylate, poly(butylene glycol) mono(meth)acrylate, poly(ethylene glycol-trimethylene glycol) mono(meth)acrylate, polyethylene glycol-poly(trimethylene glycol) mono(meth)acrylate, poly(propylene glycol-trimethylene glycol) mono(meth)acrylate, polypropylene glycol-poly(trimethylene glycol) mono(meth)acrylate, poly(trimethylene glycol-tetramethylene glycol) mono(meth)acrylate, poly(trimethylene glycol-poly(tetramethylene glycol) mono(meth)acrylate, poly(butylene glycol-trimethylene glycol) mono(meth)acrylate, poly(butylene glycol-poly(trimethylene glycol) mono(meth)acrylate, etc.

[0021] The molecular weight of the non-fluorine (meth)acrylic monomer according to the present invention is suitably in the range of 160 to 2000, preferably in the range of 200 to 1000.

[0022] In addition, the polymer of the present invention may be a polymer obtained by further copolymerizing one or more non-fluorine polymerizable monomers other than the non-fluorine (meth)acrylic monomer containing C p H 2p O (wherein p is an integer of 2 to 4) as a repeating unit.

[0023] The non-fluorine polymerizable monomers other than the non-fluorine (meth)acrylic monomer as described above are not particularly limited, and examples thereof include acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters and the like.

[0024] The polymer of the present invention can be produced by a conventional method and is not particularly limited. Examples of the production method of the polymer of the present invention include a method of polymerizing a (meth)acrylic monomer containing a perfluoropolyether chain having only "CF2O" as a repeating unit and a non-fluorine monomer (a non-fluorine (meth)acrylic monomer, other non-fluorine polymerizable monomers, etc.) in an organic solvent using a radical polymerization initiator.

[0025] Examples of the organic solvent used in the method for producing the polymer of the present invention include esters, ketones, amides, sulfoxides, ethers, and hydrocarbons. Specifically, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene, etc. can be mentioned. Examples of the radical polymerization initiator include azo compounds such as azobisisobutyronitrile and peroxides such as benzoyl peroxide. Furthermore, a chain transfer agent such as lauryl mercaptan, thioglycerol, 2-mercaptoethanol, ethyl thioglycolic acid, octyl thioglycolic acid, etc. can be used as necessary.

[0026] 2 Surfactant, composition, and use of the present invention The polymer of the present invention has a surfactant action. Therefore, the polymer of the present invention can be used as a surfactant, and as one aspect of the present invention, a surfactant containing the polymer of the present invention (hereinafter referred to as "the surfactant of the present invention") can be mentioned. The surfactant of the present invention may consist of the polymer of the present invention, or may contain, for example, other surfactants and other components (e.g., additives).

[0027] In addition, the surfactant of the present invention may be a composition with a solvent. Such a solvent varies depending on the polymer of the present invention and its use, etc., but examples include water; or organic solvents such as butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene, etc. Among these, water, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate are preferred.

[0028] The content of the polymer of the present invention in the composition varies depending on the type of the polymer of the present invention, the solvent, etc., and is appropriately selected according to the polymer of the present invention, the solvent, the use, etc., but it is suitable within the range of 0.01 to 20% by weight, preferably within the range of 0.1 to 10% by weight, and more preferably within the range of 0.2 to 5% by weight.

[0029] The polymer or surfactant of the present invention can be used in the same manner as conventional fluorine-based surfactants. Specific uses of the composition of the polymer or surfactant of the present invention, or a solvent, include, for example, water repellents, oil repellents, antifouling agents for paper, cloth, etc., foam extinguishers, plating solutions, aircraft hydraulic fluids, greases, floor waxes, detergents, water glass, lens antifogging agents, leveling agents for paints, production of etching agents, production of semiconductor resists, production of business-use photographic films such as photographic emulsions.

Examples

[0030] The present invention will be described more specifically with reference to the following examples and the like, but the present invention is not limited to the following examples at all.

[0031] [Synthesis Example 1] Synthesis of Monomer A Containing a Perfluoropolyether Chain with "CF2O" as a Repeating Unit Using CF3O(CF2O)4CF2CO2CH3 (manufactured by Anles) as a raw material, CF3O(CF2O)4CF2CONHCH2CH2OH (Compound 1) was prepared according to the method described in Patent Document 1.

[0032] Next, 100 g of Compound 1, 21 g of triethylamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 200 mL of tetrahydrofuran (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were placed in a 500 mL four-necked flask equipped with a condenser, thermometer, and dropping funnel, and 18 g of acryloyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise at room temperature with stirring. After the addition, the mixture was stirred at room temperature for 1 hour, then the triethylamine hydrochloride was filtered off, and the tetrahydrofuran was distilled off to obtain 97 g of CF3O(CF2O)4CF2CONHCH2CH2OC(O)CH=CH2 (Compound 2).

[0033] [Synthesis Example 2] Synthesis of Monomer B Containing a Perfluoropolyether Chain with “CF2O” as a Repeating Unit Into a 1 L four-necked flask equipped with a cooling tube and a thermometer, 100 g of CF3O(CF2O) m CF2CO2CH3 (manufactured by Anles, where m is an integer from 3 to 10), 400 mL of tetrahydrofuran (manufactured by Fujifilm Wako Pure Chemical Corporation) were placed, and while stirring, 10 g of sodium borohydride (manufactured by Fujifilm Wako Pure Chemical Corporation) was added little by little at a temperature of 25°C to 35°C. After the addition, it was stirred at 50°C for 5 hours, and then acetone was added to consume the excess sodium borohydride. Tetrahydrofuran was distilled off, diethyl ether (manufactured by Fujifilm Wako Pure Chemical Corporation) and water were added to the residue, stirred, and the diethyl ether fraction was separated by liquid separation, dried over anhydrous sodium sulfate (manufactured by Fujifilm Wako Pure Chemical Corporation), and diethyl ether was distilled off to obtain 85 g of CF3O(CF2O) m CF2CH2OH (Compound 3, where m is an integer from 3 to 10) was prepared.

[0034] Next, into a 300 mL four-necked flask equipped with a cooling tube, a thermometer, and a dropping funnel, 50 g of Compound 2 and 10 g of triethylamine (manufactured by Fujifilm Wako Pure Chemical Corporation) were placed, and while stirring, 9 g of methacrylic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise at room temperature. After the addition, it was stirred at room temperature for 1 hour, the triethylamine hydrochloride was filtered off, and tetrahydrofuran was distilled off to obtain 97 g of CF3O(CF2O) m CF2CH2OC(O)C(CH3)=CH2 (Compound 4, where m is an integer from 3 to 10) was obtained.

[0035] [Example 1] Into a 500 mL four-necked flask equipped with a cooling tube, thermometer, and dropping funnel, 30 g of Compound 2 obtained in the synthesis example, 70 g of Brenmer AME400 (manufactured by NOF Corporation), 4 g of α-thioglycerol (manufactured by Fujifilm Wako Pure Chemical Corporation), and 100 g of ethyl acetate (manufactured by Fujifilm Wako Pure Chemical Corporation) were added. While heating and stirring at 45°C, 4 g of azoisobutyronitrile (manufactured by Fujifilm Wako Pure Chemical Corporation) was added. After stirring at 70°C for 4 hours, ethyl acetate was distilled off to obtain Polymer 1 of the present invention. The structure of Brenmer AME400 is as follows.

[0036] [Chemical formula]

[0037] [Example 2] Polymer 2 of the present invention was obtained in the same manner as in Example 1, except that 20 g of Compound 2 and 80 g of Brenmer AME400 were used.

[0038] [Example 3] Polymer 3 of the present invention was obtained in the same manner as in Example 1, except that Brenmer AE200 (manufactured by NOF Corporation) was used instead of Brenmer AME400. The structure of Brenmer AE200 is as follows.

[0039] [Chemical formula]

[0040] [Example 4] Polymer 4 of the present invention was obtained in the same manner as in Example 3, except that 20 g of Compound 2 and 80 g of Brenmer AE200 were used.

[0041] [Example 5] Polymer 5 of the present invention was obtained in the same manner as in Example 1, except that Compound 4 was used instead of Compound 2 and Brenmer PE350 (manufactured by NOF Corporation) was used instead of Brenmer AME400. The structure of Brenmer PE350 is as follows.

[0042] [Chemical formula]

[0043] [Example 6] The present invention polymer 6 was obtained in the same manner as in Example 5, except that Brenmer PP1000 (manufactured by NOF Corporation) was used instead of Brenmer PE350. The structure of Brenmer PP1000 is as follows.

[0044] [Chemical formula]

[0045] [Examples 7 - 12] The present invention polymer 1 of Example 1, the present invention polymer 2 of Example 2, the present invention polymer 3 of Example 3, the present invention polymer 4 of Example 4, the present invention polymer 5 of Example 5, or the present invention polymer 6 of Example 6 was diluted in water to 0.1% by weight, respectively, and surfactants according to the present invention were prepared as Examples 7 - 12. Then, the surface tension of the diluted solution (surfactant according to the present invention) was measured using a surface tensiometer CBVP - A3 manufactured by Kyowa Interface Science Co., Ltd.

[0046] [Test Example 1] FC4430 (manufactured by 3M Japan Limited), a commercially available nonionic polymer - type fluorosurfactant containing a perfluorobutyl group, was used to prepare a diluted solution in the same manner as in Examples 3 and 4, and the surface tension was measured as a comparative example.

[0047] The results of Examples 7 - 12 and the comparative example are shown in Table 1.

[0048] [Table 1]

[0049] From Table 1, it is clear that the surfactant according to the present invention exhibits a better ability to lower the surface tension than the existing fluorosurfactants.

[0050] [Test Example 2] CF3O(CF2O) m In order to examine the thermal decomposition temperature of CF2CO2CH3 (where m is an integer from 3 to 10), thermogravimetry and differential thermal analysis (TG-DTA analysis) were performed. The measurement was carried out using a thermogravimetric analyzer TG / DTA7200 manufactured by Seiko Instruments Inc., from 25°C to 250°C under a heating rate condition of 4°C / min. The measurement results when using a mixed sample with an average value (number average) of m being 5.5 are shown in Figure 1.

[0051] From the DTG curve in Figure 1, it can be seen that the decomposition reaction shows the maximum acceleration at 94°C of the peak (T p ), and the decomposition is generally completed at around 115°C (T f ). This indicates that the perfluoropolyether chain consisting only of "CF2O" decomposes at a much lower temperature than the conventional perfluoroalkyl group or perfluoropolyether chain. The polymer of the present invention contains a monomer having such a low-temperature decomposable perfluoropolyether chain as a copolymerization component.

[0052] From the above results, it is clear that the polymer of the present invention is a fluorosurfactant with a low environmental impact.

Industrial Applicability

[0053] The polymer or surfactant of the present invention is useful, for example, as a water repellent, an oil repellent, a raw material for antifouling agents for paper and cloth, and a foam fire extinguishing agent component, because it greatly reduces the surface tension and has a smaller environmental impact compared to conventional fluorine-containing polymers of the same kind.

Claims

1. A repeating unit is "CF" ２ A surfactant comprising a fluoropolymer formed by copolymerizing a (meth)acrylic monomer containing a perfluoropolyether chain consisting only of "O" (excluding CF3O(CF2O)3CF2CONHCH2CH2OC(O)CH=CH2) and one or more fluorine-free (meth)acrylic monomers (excluding monoacrylates of block copolymers of polyethylene glycol and polypropylene glycol and octadecyl acrylate).

2. At least one fluorine-free (meth)acrylic monomer contains one or more repeating units of C ｐ H ２ｐ O (wherein p is an integer of 2 to 4). The surfactant according to claim 1.

3. The surfactant according to claim 1, wherein the perfluoropolyether chain has a structure represented by the following general formula (1). 【Chemical Formula 1】

4. At least one fluorine-free (meth)acrylic monomer has one or more C ｐ H ２ｐ O (wherein p is an integer from 2 to 4). The surfactant according to claim 3, which contains a repeating unit of

5. The repeating unit is "CF ２ O", and the method for producing a surfactant according to any one of claims 1 to 4, comprising a step of copolymerizing a (meth)acrylic monomer containing a perfluoropolyether chain consisting only of "CF ２ O" and one or more (meth)acrylic monomers not containing fluorine.

6. A composition comprising the surfactant according to any one of claims 1 to 4 and a solvent.

7. The composition according to claim 6, wherein the solvent is water and / or an organic solvent.

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