JPH0784518B2 - End-modified fluoroalkyl epoxy alkane polymer and use thereof - Google Patents

Description

TECHNICAL FIELD The present invention relates to a terminal-modified fluoroalkylepoxyalkane polymer and its use, and more specifically, a surface modifier such as a water / oil repellent agent, a non-adhesive agent, The present invention relates to a fluoroalkylepoxyalkane polymer having a terminal hydroxyl group or carboxyl group modified, which is useful as an antifouling agent.

(Prior Art) A large number of fluorine-containing epoxy alkane polymers useful as surface modifiers, particularly water and oil repellents, non-adhesives and antifouling agents, have been proposed and actually used (for example, Japanese Patent Publication No. 46- 2536
1, JP-B-57-11324, JP-B-57-11325, JP-A-6
0-215023, JP-A-60-186531).

However, none of the fluorine-containing polymers have sufficient performance as a surface modifier due to the terminal hydrophilic groups such as hydroxyl groups and carboxyl groups. For example, water- and oil-repellent agents, non-adhesive However, it was insufficient in each function such as antifouling property.

(Object of the Invention) An object of the present invention is to provide a novel fluoropolymer useful as a surface modifier.

Another object of the present invention is to provide a surface modifier containing a novel fluoropolymer as an active ingredient.

(Structure of the Invention) The gist of the present invention is represented by the general formula: [In the formula, Rf represents a fluoroalkyl group having 3 to 21 carbon atoms, and p represents an integer of 1 to 10. ] The polymer which has at least 1 sort (s) of the repeating unit shown by these, whose number average molecular weight is 2000-50000,
The terminal hydroxyl or carboxyl group has the general formula: by acylation or alkoxylation: Or RO- or [In the formula, R represents an alkyl group having 1 to 4 carbon atoms. ] A terminal-modified fluoroalkylepoxyalkane polymer characterized by being modified to a group represented by: [In the formula, Rf and p have the same meanings as described above. ] The polymer which consists of at least 1 type of the epoxy compound shown by these, or the copolymer with another monomer which can be copolymerized with 1 type (s) or 2 or more types of this epoxy compound, Comprising: The number average molecular weight is 2000-50000. And its terminal hydroxyl or carboxyl group is a surface-modifying agent composed of an end-modified fluoroalkylepoxyalkane polymer modified by acylation or alkoxylation.

In the terminal-modified fluoroalkylepoxyalkane polymer of the present invention, since the terminal hydrophilic group is hydrophobized by acylation or alkoxylation, the melting point is about 10 ° C. or more as compared with the unmodified fluoroalkylepoxyalkane polymer. It is considered that the amount of the polymer is decreased and the film-forming property of the polymer is improved, whereby the surface modification effect of the polymer is extremely improved.

A fluoroalkylepoxyalkane polymer having a hydroxyl group or a carboxyl group at the terminal and a method for producing the same are described, for example, in JP-B-46-25361 and JP-A-57-11324.
No. 57-11325, No. 60-215023 and No. 60-186531.
It is described in each publication of the issue.

The terminal-unmodified fluoroalkylepoxyalkane polymer may be a homopolymer of the epoxy compound (I) or a copolymer of two or more epoxy compounds (I). Further, it may be a copolymer of at least one epoxy compound (I) and another copolymerizable monomer.

Examples of the other monomers copolymerizable with the epoxy compound (I) are described in the above-mentioned publications, and preferred examples of the monomers are as follows: Epoxide: ethylene oxide, propylene oxide,
Epichlorohydrin, epifluorohydrin, perfluoropropylene oxide, isobutylene oxide, butadiene oxide, styrene oxide, methylglycidyl oxide, methylglycidyl ether, etc., Cyclic acid anhydrides: succinic anhydride, maleic anhydride, phthalic anhydride, pyromellitic anhydride Acid, 1,2-cyclohexanedicarboxylic acid anhydride, tetrahydrophthalic anhydride, 1,2,
3,4-Cyclopentanetetracarboxylic dianhydride, 1,2-
Cyclobutane dicarboxylic acid anhydride, endic acid anhydride, 1,2-naphthalene dicarboxylic acid anhydride, 2,3-naphthalene dicarboxylic acid anhydride, glutaric anhydride and substituted products thereof, cyclic imino ether: 2-oxazoline, 5, 6-dihydro-4H-1,3-oxazoline and substituted products thereof, cyclic ether: oxetane, tetrahydrofuran, tetrahydropyran, 3,3-bis (chloromethyl) oxetane, etc., cyclic formal: 1,3-dioxolane, trioxane, Tetraoxane, 1,3,6-trioxocane, 1,3,5-trioxocane, etc. Cyclic ester: β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, perfluoro-γ-butyrolactone, etc.

The terminal hydroxyl group or carboxyl group can be modified by a conventional method.

Acylation is carried out by reacting an acylating agent such as an acid anhydride or acid chloride (eg, acetic anhydride, acetyl chloride, etc.) with a fluoroalkylepoxyalkane polymer having a terminal hydroxyl group or a carboxyl group. The acylation reaction may be carried out at a temperature of 0 to 100 ° C., by adding a predetermined number of moles of an acylating agent, and stirring the mixture for 10 minutes to 24 hours.

The alkoxylation is carried out by reacting an alcohol (for example, methanol, ethanol, propanol, etc.), acetone or the like with a terminal hydroxyl group or carboxyl group fluoroalkyl epoxy alkane polymer. The alkoxylation reaction may be carried out at a temperature of 0 to 100 ° C., adding a predetermined number of moles of alcohol or acetone, adding a small amount of a catalyst (BF ₃ or p-toluenesulfonic acid, etc.), and stirring for 10 minutes to 24 hours. .

When the terminal-modified fluoroalkylepoxyalkane polymer of the present invention is used as a surface modifier, the polymer is used in an appropriate solvent in an amount of 0.01 to 30% by weight, preferably 0.1 to 2% by weight.
It dissolves at the concentration of.

Examples of the solvent include acetone, methyl ethyl ketone, ethyl acetate, dimethylformamide, methyl chloroform, trichloroethylene, trichlorotrifluoroethane, tetrachlorotrifluoroethane, tetrachlorodifluoroethane, m-xylene hexafluoride, hexane and toluene. .

In practice, it is convenient to prepare a polymer solution obtained by polymerization by diluting it with the above solvent to an appropriate concentration. It is also possible to add a propellant (dichlorodifluoromethane, monofluorotrichloromethane, dimethyl ether, etc.) to the obtained solution and fill it in a suitable container to obtain an aerosol type surface modifier. Further, it can be prepared as an aqueous emulsion by emulsifying and dispersing the polymer of the present invention together with various additives in an aqueous medium using a suitable surfactant. As the surfactant, any of anionic, nonionic and cationic surfactants can be used. Further, the polymer of the present invention may be directly applied to the substrate. In the present invention, the surface modifier includes a water and oil repellent agent, a non-adhesive agent (including a release agent, a back surface modifier, a release paper processing agent and an anti-blocking agent), an antifouling agent and the like. .

When the surface modifier of the present invention is used as a water and oil repellent,
There are no particular restrictions on the material of the substrate that can be treated, and many articles are targeted. Textile fabrics,
In addition to being particularly useful for paper and the like, it is also useful for porous articles such as wood, leather, fur, felt, asbestos and bricks, and articles having smooth surfaces such as metals, tiles, plastics and various painted surfaces. As the fiber woven fabric, natural animal and vegetable fibers such as cotton, hemp, wool and silk, synthetic fibers such as polyamide, polyester, polyvinyl acetal, polyacrylonitrile, polyvinyl chloride and polypropylene, semi-synthetic fibers such as rayon and acetate, or these Woven fabrics of mixed fibers.

When used as a water and oil repellent, the polymer of the present invention is preferably 0.01 to 30% by weight, particularly preferably 0.2 to 2.0% by weight.
Used in a concentration of.

Even when the polymer of the present invention is used as a non-adhesive, there is no limitation on the article to be treated, and in the case of the water / oil repellent, it can be applied to most of the articles to be treated. Examples of substances to which non-adhesiveness is given include synthetic or natural resins such as polyurethane resin, epoxy resin, phenol resin, vinyl chloride resin, acrylic resin, natural rubber, chloroprene rubber, and fluororubber, and synthetic or natural rubber. To be Examples of industrial applications of non-adhesives include so-called mold release agents such as molds, wood molds, plastic molds and paper molds used in the plastic and rubber molding industry, as well as paper, cellophane, cloth and plastic films. Examples include back treatment of adhesive tapes such as metal foils, production of labels, stickers, release papers such as patches that have been coated with an adhesive in advance.

When used as a release agent, the polymer of the present invention may have a concentration of 0.01% by weight or less for the purpose of one-time release. When life is required, it is suitable to use at a concentration of 0.05 to 10% by weight. When it is used as an internal mold release agent, it may be added to the resin or rubber to which mold releasability is to be added in a proportion of 0.01 to 30% by weight. When it is used as a back surface modifier or an anti-blocking agent, it may be used at almost the same concentration.

Even when the polymer of the present invention is used as a non-adhesive, there is no limitation on the article to be treated, and in the case of the water / oil repellent, it can be applied to most of the articles to be treated.

When used as an antifouling agent for textiles such as textiles, the polymer of the present invention is dissolved or dispersed in a suitable solvent to a concentration of 0.05 to 5% by weight, and the textile is immersed in this and then air-dried. Alternatively, heat treatment is performed at 80 to 150 ° C for 30 seconds to 10 minutes. Generally, a sufficiently durable antifouling treatment can be performed only by drying at room temperature. When used for the prevention of soiling of buildings and machinery, the polymer of the present invention is dissolved, emulsified or dispersed in a suitable solvent at a concentration of 0.01 to 5% by weight, preferably 0.1 to 1% by weight. Then, a coating forming composition is obtained, which is applied to an object and dried to form a polymer film on the surface.

Next, the present invention will be specifically described by showing Examples, Comparative Examples, and Application Examples.

Comparative Example 1 Production of polymer described in Example 1 of JP-A-60-215023 (Hereinafter, referred to as Epoxy compound A.) 9.67 g, tetrahydrofuran 0.33 g and trichlorotrifluoroethyne 3
0 g was placed in a 50 ml flask equipped with a reflux condenser and a stirrer under a nitrogen atmosphere and stirred. After keeping the temperature in the flask at 30 ℃, boron trifluoride etherate 0.1m
1 was charged and reacted at 30 ° C. for 24 hours. From the gas chromatography analysis, the conversion rate of the epoxy compound A was
95.5%, the conversion rate of tetrahydrofuran was 100%.

A transparent precipitate formed when the contents were poured into methanol. The obtained precipitate was dissolved in trichlorotrifluoroethane. When this solution was poured into methanol, it was reprecipitated.

Purification in this way gave 8.32 g of a transparent, grease-like product. Yield 83.2%.

Glass transition point (Tg) = 30 ° C. ^When the signal corresponding to the following structural formula was analyzed by ¹ H-NMR spectrum analysis, it was confirmed to be a binary copolymer.

Chemical shift δ (ppm) Signal intensity A 2.37 4.6H B 1.70 2.4H C 3.3 to 4.3 9.3H D 4.7 0.2H Confirmation of terminal OH group When heavy water (D ₂ O) was added and ¹ H-NMR was measured, d ...
= 4.7ppm changed to the position of δ = 4.83ppm. From this change, it was confirmed that δ = 4.7 ppm was the shift position of the OH group. Calculated values of x, y, z from ¹ H-NMR * Calculate the ratio of the signal intensity per * A proton (2.37 ppm) to the signal intensity per * B proton (1.70 ppm). Then, x = 3.84 and y = 1. Further, from the signal intensity per one proton of * D (4.7 ppm) and the signal intensity per one proton of * A (2.37 ppm), it was calculated that z = 6.0 and the molecular weight was 12,400.

In addition, by liquid chromatography analysis, the number average molecular weight M
Was measured, M = 12500, z = about 6.0, ¹ H
-Almost in agreement with the calculated value from NMR.

Elemental analysis value Experimental value: C, 28.87%; H, 1.28%; F, 65.13% Calculated value: C, 28.73%; H, 1.30%; F, 66.26% Example 1 In the same procedure as in Comparative Example 1, the terminal OH group was used. Immediately after preparing the polymer, 0.28 g of acetic anhydride was added to the reaction mixture, and the mixture was stirred at room temperature for 12 hours.

When the contents were thrown into methanol, a clear precipitate formed. The precipitate thus obtained was dissolved in trichlorotrifluoroethane, poured into methanol for reprecipitation, and purified to obtain 8.46 g of a transparent, grease-like product.

Yield 84.6% Glass transition point (Tg) = 20.5 ° C When the signal corresponding to the following structural formula was analyzed by ¹ H-NMR spectrum analysis, the end group was acetylated from the proton * D (δ = 1.99 ppm). It was confirmed.

Chemical shift δ (ppm) Signal intensity A 2.37 4.6H B 1.70 2.5H C 3.3 to 4.3 9.4H D 1.99 0.8H The ratio of the signal intensity per one proton of * A (δ = 2.37) to the signal intensity per one proton of * B (δ = 1.70 ppm) was calculated to be x = 3.70, y
= 1.

Moreover, when the number average molecular weight M was measured by liquid matography analysis, it was M = 12500 and z = about 6.

Comparative Example 2 Production of Polymer Described in JP-B-46-25361) 50 g (hereinafter referred to as epoxy compound B) and 150 g of trichlorotrifluoroethane were placed in a 500 ml flask equipped with a reflux condenser and a stirrer under a nitrogen atmosphere and stirred.

After keeping the temperature in the flask constant at 30 ° C., 0.1 ml of boron trifluoride etherate was charged and reacted at 30 ° C. for 24 hours. From the gas chromatographic analysis, the conversion of the epoxy compound B was 97.0%.

When 40 g of this content was poured into n-hexane, a transparent precipitate was formed. The obtained precipitate was dissolved in trichlorotrifluoroethane. The solution was poured into n-hexane and reprecipitated. Purification in this way gave 7.23 g of a white solid product. Yield 72.3%.

Glass transition point (Tg) = 84 ° C). ^When the signal corresponding to the following structural formula was analyzed by ¹ H-NMR spectrum analysis, it was confirmed to be a homopolymer.

Chemical shift δ (ppm) Signal intensity A 2.37 7.4H B 3.3 to 4.3 9.9H C 4.7 0.4H The ratio of the signal intensity per one proton of * A (2.37 ppm) to the signal intensity per one proton of * C (1.70 ppm) was calculated to be x = 18.5 and the molecular weight was 87.
It was 50.

Example 2 A terminal OH group polymer was prepared by the same procedure as in Comparative Example 2, immediately after which 0.28 g of acetic anhydride was added to 40 g of the polymer, and the mixture was stirred at 48 ° C. for 4 hours. When the contents were thrown into methanol, a white solid precipitate formed. The precipitate thus obtained was dissolved in trichlorotrifluoroethane and poured into methanol for reprecipitation for purification to obtain 7.32 g of a white solid product. Yield 73.2%.

Glass transition point (Tg) = 68.0 ° C. ¹ H-NMR spectrum analysis confirmed that the terminal group was acetylated by the proton of * C (δ = 1.98).

Chemical shift δ (ppm) Signal intensity A 2.36 6.3H B 3.3 to 4.3 9.6H C 1.98 1.1H Example 3 A terminal OH group polymer was prepared by the same procedure as in Comparative Example 2, immediately after which 5 g of methanol was added to 40 g of the polymer and stirred at 48 ° C. for 12 hours. When the contents were poured into methanol, a white solid precipitate formed. The precipitate thus obtained was dissolved in trichlorotrifluoroethane, poured into methanol for reprecipitation, and purified to obtain 7.82 g of a white solid product. Yield 73.2%. Glass transition point (Tg) = 70 ° C. ^{As a result of 1} H-NMR spectrum analysis, the signal intensity of the terminal OH group (δ = 4.7 ppm) was decreased and the signal intensity of the terminal OCH ₃ group (δ = 1.2 ppm) was observed due to the methoxylation of the terminal group.

Examples 4 to 5 Terminal-modified polymers were obtained by repeating the same procedure as in Example 3 except that the terminal OH group was alkoxylated with propyl alcohol (Example 4) or acetone (Example 5).
The end groups of the product were examined by infrared analysis.

The results are shown in Table 1.

Comparative Example 3 Production of polymer described in Example 2 of JP-B-57-11324 (However, m = 3,55 mol%, m = 4,28 mol%,
m = 5,11 mol%, m = 6.4 mol%, m = 7.1 mol%) (hereinafter referred to as epoxy compound C) 40.7 g (70 mmol), epichlorohydrin 3.1 g (33 mmol) Phthalic anhydride (15.2 g, 103 mmol) and N, N-dimethylbenzylamine (50 mg, 0.3 mmol) were placed in a flask equipped with a stirrer and a recooler under a nitrogen atmosphere and heated with stirring. After reacting at 140 ° C. for about 1 hour, the reaction system became a pale yellow homogeneous system, and the reaction was further continued for 7 hours. From the gas chromatographic analysis, the conversion of the epoxy compound C was 95.5%, the conversion of epichlorohydrin was 76%, and the conversion of phthalic anhydride was 86.0%.

This product was dissolved in 150 g of trichlorotrifluoroethane and poured into methanol to give 44.8 g of a tan solid product.
Got Yield 75.9%. Melting point 79 ° C.

The infrared absorption spectrum of this product shows 1730 cm ^-1 (> C = O of ester group), 1150 to 1250 and 980 cm ^-1 (CF bond), 1070 and 740 cm ^-1 (O = substituted phenyl), 720 cm
Characteristic absorptions such as ^-1 (C-Cl bond) and 3400 cm ^-1 (OH bond of terminal group) were observed.

Considering the results of elemental analysis, it was confirmed that this product was a polyester-based copolymer produced by ring-opening copolymerization at the same ratio as the ratio of the raw material compound used multiplied by the conversion rate.

Example 6 A terminal OH group polymer was prepared by the same procedure as in Comparative Example 3, immediately after which 0.28 g of acetic anhydride was added to 40 g of the polymer, and the mixture was heated at 48 ° C. for 4 hours.
Stir for hours. The contents were thrown into methanol to give 30.4 g of a tan solid product. Yield 76.0%.

The infrared spectrum of this product was almost the same as that of the product of Comparative Example 3, and only the absorption of the OH bond of the terminal group was reduced to less than half.

Example 7 A terminal OH group polymer was prepared by the same procedure as in Comparative Example 3, immediately after which 5 g of methanol and 0.1 g of p-toluenesulfonic acid were added to 40 g of the polymer, and the mixture was stirred at 48 ° C. for 4 hours. The contents were thrown into methanol to yield a tan solid product 30.2
got g. Yield 75.5%.

The infrared spectrum of this product was almost the same as that of the product of Comparative Example 3, and only the infrared absorption of the OH bond of the terminal group was reduced to less than half.

Next, an application example of the merging material of the present invention will be shown.

The water and oil repellency shown in the following examples is shown by the following scale. That is, water repellency is represented by the water repellency No. (see Table 2 below) by the spray method of JIS L-1005, and oil repellency is a composition of each mixing ratio of n-heptane and nujol (see Table 3 below). Oil repellency No. depending on whether or not the liquid under test is held for 3 minutes or more.
Express as.

The contact angle is measured using a contact angle measuring microscope “Goniometer” manufactured by Elma Optical Co., Ltd.

1. Water- and oil-repellent agent for fibers The polymers shown in Table 4 below were dissolved in a mixed solvent of 20% by weight of acetone and 80% by weight of trichlorotrifluoroethane so as to have a solid content concentration of 1% by weight. A polyester Amundsen fabric was dipped in this solution, squeezed to a 100% liquid adhesion rate with a mangle, and dried at 100 ° C. for 3 minutes. The water repellency and oil repellency of this treated fabric were measured. The results are shown in Table 4.

2. Water- and oil-repellent agent for non-fibers 1% solution of the above polymer is applied to each substrate and water or n-
The contact angle of hexadecane was measured. The results are shown in Table 5.

3. Release Agent (Mold) An aluminum mold (diameter 6 cm × 3 cm) was coated with the following concentration solution of each polymer and dried at room temperature. The following semi-rigid urethane foam composition liquid A and liquid B were stirred into this mold at 5000 rpm x 10 sec, poured, and allowed to cure for 10 minutes, and then the force required for mold release using a tensile tester (g / cm ² ) was measured. Liquid A parts by weight Sumicen 3900 (Polyol) 90 (Sumitomo Bayer Urethane) Water (foaming agent) 1.6 Triethanolamine (catalyst) 3 Triethylamine (catalyst) 0.5 Kaolizer No.1 (foam stabilizer) 0.5 (Kao) Liquid B Sumidule 44V20 (isocyanate) 41.3 (Sumitomo Bayer Urethane) The results are shown in Table 6.

4. Internal Release Agent Copolymer 0.2 prepared in Example 1 or Example 6
10 parts by weight of triethylenetetramine were further mixed with 100 parts by weight of Epicoat # 828 (epoxy resin of Shell Chemical Co., Ltd.).

This mixture was poured into a 4 cmφ × 2 mm mold (the mold was previously washed and then no release agent was applied).
When left at room temperature for 2 hours, heated at 100 ° C. for 1 hour, cured, and taken out, the molded articles could be separated from the mold very easily.

For reference, the contact angle of the molded product of this example was measured. The contact angle of water was 119 ° and the contact angle of n-hexadecane was 6 °.
It was 9 °. Further, when the copolymer of Example 1 or Example 6 was not blended in the molded product, the mold and the molded product were completely bonded.

5. Release agent (non-adhesive) Using the copolymer prepared in Comparative Example 3, Example 6 or 7, 180 ° peel strength was measured.

2% by weight of the polymer is dissolved in the solvent shown in Table 7. This solution is applied to a polyester film using Hercoater # 8 and dried. Next, a polyester tape (manufactured by Nitto Denki Kogyo Co., Ltd.) was used for a 180 ° tape peeling test. The results are shown in Table 7.

6. Addition to paint (anti-block, non-adhesion (prevention of adhesion), antifouling property) Vinyl chloride paint (Vinylose, manufactured by Dainippon Paint Co., Ltd.)
5 parts by weight of a 10% n-hexane solution of the polymer prepared in Example 1 or Comparative Example 1 was mixed with 100 parts by weight, and this was overcoated with a bar coater # 8 on a veneer laminated with veneer paper and dried. To do.

A cellophane tape having a width of 18 mm (Nichiban Co., Ltd.) was strongly pressure-bonded to the plywood with a ridge, and then the peeling operation was repeated vigorously to obtain 6 when the polymer of Example 1 was used.
There was no change even after repeating the process once, but when the polymer of Comparative Example 1 was used, the surface turned up in one time.

Also, stain this plywood with soot from the muffler of the car,
When wiped off with a cloth, the plywood coated with the polymer-added paint of Example 1 had less stains and could be wiped off with a cloth, but the plywood coated with the polymer-added paint of Comparative Example 1 It was hard to wipe off the dirt.

Claims (5)

[Claims] 1. A general formula: [In the formula, Rf represents a fluoroalkyl group having 3 to 21 carbon atoms, and p represents an integer of 1 to 10. ] The polymer which has at least 1 sort (s) of the repeating unit shown by these, whose number average molecular weight is 2000-50000,
The terminal hydroxyl or carboxyl group has the general formula: by acylation or alkoxylation: Or RO- or [In the formula, R represents an alkyl group having 1 to 4 carbon atoms. ] A terminal-modified fluoroalkylepoxyalkane polymer characterized by being modified to a group represented by: 2. A general formula: [In the formula, Rf represents a fluoroalkyl group having 3 to 21 carbon atoms, and p represents an integer of 1 to 10. ] A polymer comprising at least one epoxy compound represented by: or a copolymer of at least one epoxy compound with another monomer copolymerizable therewith, having a number average molecular weight of 2000 to 50,000, A surface modifier comprising a terminal-modified fluoroalkyl epoxy alkane polymer in which a terminal hydroxyl group or a carboxyl group is modified by acylation or alkoxylation. 3. The surface modifier according to claim 2, which is a water and oil repellent agent. 4. The surface modifier according to claim 2, which is a non-adhesive agent. 5. The surface modifier according to claim 2, which is an antifouling agent.