JPH0693075A - Fluorine-containing thermoplastic polyurethane resin - Google Patents

Abstract

PURPOSE:To provide the fluorine-containing thermoplastic polyurethane resin suitable for uses requiring surface-slipping properties. CONSTITUTION:The fluorine-containing thermoplastic polyurethane resin is obtained by reacting a fluorine-containing vinyl-modified diol with a polyisocyanate and a chain extender, the fluorine-containing vinyl-modified diol being produced by reacting 100 pts.wt. of a diol having an unsaturated group in the molecule and an average mol.wt. of 500-5000 with 2-200 pts.wt. of a fluorine-containing vinyl monomer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorine-containing thermoplastic polyurethane resin having excellent surface slip properties.

[0002]

2. Description of the Related Art Heretofore, a method of adding a fluororesin has been known as a method of imparting a slip property to a thermoplastic polyurethane resin (hereinafter, abbreviated as TPU). However, the conventional method of adding a fluororesin has a problem that the compatibility between the fluororesin and TPU is poor, and even if they are mixed, they are separated over time. There is also a method of using a fluorine-containing copolymer having a hydroxyl group such as Lumiflon LF series manufactured by Asahi Glass as one of the compositions of TPU, but this fluorine-containing copolymer has three hydroxyl groups in one molecule. In some cases, it is difficult to use as a thermoplastic resin. The present invention is a diol oligomer which is one of the compositions of TPU.
It is an object of the present invention to provide a TPU using a reaction product of a fluorine-containing monomer.

[0003]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made extensive studies to solve such conventional problems, and as a result, have found that a fluorine-containing vinyl monomer is added to a diol having an unsaturated group in the molecule. The inventors have found that if the reacted product is used as one of the compositions of TPU, it is possible to obtain TPU having excellent slipperiness, which does not change with time, and has completed the present invention.

[0004]

That is, according to the present invention, 100 parts by weight of a diol having an unsaturated group in the molecule and having an average molecular weight of 500 to 5000 is added to a fluorine-containing vinyl monomer-2.
The present invention relates to a fluorine-containing thermoplastic polyurethane resin having excellent slipperiness, which is obtained by reacting 200 parts by weight of a fluorine-containing vinyl modified diol, polyisocyanate and a chain extender.

Geo- having an unsaturated group in the molecule of the present invention
As the polyester, for example, in the case of polyester diol, an unsaturated group-containing glycol or an unsaturated group-containing dicarboxylic acid is used as a part of glycols, dibasic acids and the like which are usually used as raw materials. I can give you what I did. Polyols usually used as a raw material include, for example, ethylene glycol, propylene glycol, butylene glycol, hexane glycol and neopentyl glycol.
And cyclohexyl dimethanol. Examples of dibasic acids include succinic acid, adipic acid, azelaic acid, and phthalic acid. Also, the molecular weight is 3
000 or less hydroxyl-terminated polyester, polyether,
Examples thereof include diol obtained by condensation of polycarbonate and the like and unsaturated group-containing dicarboxylic acid. Examples of the unsaturated group-containing glycol described here include 2-butene-1,4-diol and glycerin monoallyl ether. Further, examples of the unsaturated group-containing dicarboxylic acid include maleic acid, fumaric acid, itaconic acid and the like.

The molecular weight of the diol having an unsaturated group in the molecule is preferably 500 to 5000. When it is less than 500, the performance as a soft segment of TPU cannot be exhibited, and when it exceeds 5,000, the viscosity is increased and the workability is deteriorated, which is not preferable. The concentration of unsaturated groups in the diol is preferably 10 or less per one molecule of the diol, and particularly preferably 0.1 to 2 per one molecule of the diol.

The fluorine-containing vinyl monomer of the present invention includes fluorine-containing olefins such as perfluorohexylethylene and perfluorooctylethylene, 2,2,2.
3,3,3-Pentafluoropropyl methacrylate
, 2- (perfluorooctyl) ethyl methacrylate, fluorine-containing methacrylate such as 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,2
3,3,3-pentafluoropropyl acrylate, 2
-(Perfluorohexyl) ethyl acrylate, 1
Examples thereof include fluorinated acrylates such as H, 1H, 5H-octafluoropentyl acrylate.

The reaction method of the fluorine-containing vinyl monomer with the diole having an unsaturated group in the molecule for obtaining the fluorine-containing vinyl modified diol of the present invention is not particularly limited, and the reaction initiator is not particularly limited. A usual method for polymerizing an ethylenic monomer using a radical initiator or the like can be used. In this reaction, a solvent can be used if necessary. Examples of the solvent include butyl acetate, cyclohexane, xylene and the like. After the reaction, these solvents are removed as needed.

The ratio of the diol having an unsaturated group in the molecule to the fluorine-containing vinyl monomer is 100 diol.
Monomer-2 to 200 parts by weight is preferable with respect to parts by weight. When the amount of the monomer is less than 2 parts by weight, the slipperiness of the obtained fluorine-containing TPU is not sufficient, and when the amount of the monomer exceeds 200 parts by weight, the viscosity of the fluorine-containing vinyl modified diol becomes high. Workability is poor and not preferable.

Examples of the polyisocyanate of the present invention include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylene diisocyanate, naphthylene diisocyanate, diphenylmethane diisocyanate and the like, and aromatic diisocyanates consisting of these isomers, 1,6-hexadiene. Aliphatic diisocyanates such as methylene diisocyanate and 1,12-dodecane diisocyanate, alicyclic diisocyanates such as cyclohexane diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate can be mentioned. Moreover, the isocyanate group terminal compound by reaction of these compounds and an active hydrogen group containing compound, or the isocyanate modified body by reaction of these compounds, for example, carbodiimidization reaction, etc. can also be mentioned.

As the chain extender of the present invention, ethylene glycol, propanediol, butanediol, hexanediol, neopentyl glycol, 1,4-bis (β
-Hydroxyethoxy) benzene, cyclohexyl dimethanol and the like. Hexamethylenediamine,
Isophoronediamine, tolylenediamine, monoethano-
Some amines such as ruamine can be used in combination.

In order to obtain the fluorine-containing TPU of the present invention, fluorine-containing vinyl modified diol (A), polyisocyanate
(B) and the chain extender (C) are reacted. As the reaction method, all the methods used in ordinary TPU production can be used. The charging ratios of A, B, and C cannot be limited because they differ depending on the purpose of use of the fluorine-containing TPU.
The molar ratio of C / A is 0.1 to 10, and the molar ratio of the isocyanate group of B and the hydroxyl groups of A and C is 0.8 to 1.2.
Is. A conventionally known urethanization catalyst can be used in the reaction at any stage, if necessary. Further, a solvent can be used if necessary. Examples of the solvent include dimethylformamide, tetrahydrofuran, cyclohexanone, methyl ethyl ketone, butyl acetate and the like.

In the reaction for obtaining the fluorine-containing TPU of the present invention, a part of the diol having an unsaturated group in the molecule is replaced with another polyester polyol, polyether polyol or polycarbonate carbonate polyol. Etc. can be added. As these polyols, all of those having a molecular weight of 500 to 5,000 which are usually used as a reaction partner of polyisocyanate can be used. The amount of addition is Diol / other Polio
Le = 20/80 to 100/0 (parts by weight). The molecular weight of the fluorine-containing TPU obtained according to the present invention is usually in the range of 10,000 to 200,000. These molecular weights can be obtained by changing the charged molar ratio of isocyanate groups and hydroxyl groups.

Fluorine-containing TPU obtained by the present invention
Other resins can be added as required. As other resins, for example, ABS polymer, styrene acrylonitrile (SAN) polymer, polyvinyl chloride, polystyrene, polyacetal, nylon, polyester,
Examples include polycarbonate, epoxy resin, amino resin, and phenol resin. The fluorine-containing TPU obtained according to the present invention contains other substances, if necessary, such as antioxidants, ultraviolet absorbers, heat resistance improvers, colorants, inorganic and organic fillers, plasticizers, lubricants, antistatic agents, A reinforcing material or the like can be added.

[0015]

EFFECTS OF THE INVENTION The fluorine-containing TPU of the present invention can improve surface slipperiness, abrasion resistance, water repellency, stain resistance, surface resistance and the like. The fluorine-containing TPU of the present invention is provided in the form of pellets, flakes, and the like, and molded products, films, injection molding, extrusion molding, calendar molding, etc.
Sheets are produced and used in various fields such as interior and exterior materials for automobiles, various rolls, electric appliances, leather and medical equipment. In the case of a solution, the solution as it is, or in the form of removing the solvent,
Used for paints, impregnants, binders, etc.

[0016]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In Examples and Comparative Examples,
All "parts" mean "parts by weight" and all "%" mean "% by weight".

Example 1 "Synthesis of unsaturated group-containing diol (BA2)" A 3000 ml four-necked flask was equipped with a stirrer, a thermometer, a distillation column and a nitrogen inlet, and 1216 parts of adipic acid, 1,4.
After charging 952 parts of butanediol, 136 parts of fumaric acid and 0.02 part of acetylacetone tin and gradually heating them to react at 220 ° C. for 10 hours, the pressure was gradually reduced.
The reaction was carried out at 25 mmHg for 15 hours. Hydroxyl value 55mgKOH /
g, an acid value of 0.2 mg KOH / g of diol (BA2) was obtained.

"Synthesis of fluorine-containing vinyl modified diol (BA2X)" A 1000 ml four-necked flask was equipped with a stirrer, a thermometer, a reflux tower, nitrogen introduction and a dropping funnel, and the above BA2 was mixed with 3 parts.
It was charged with 00 parts and heated to 95 ° C. while flowing nitrogen.
A mixed solution of 120 parts of 2,2,3,3,3-pentafluoropropylmethacrylate and 1.8 parts of benzoylperoxide was added dropwise from the dropping funnel over 1 hour. Then, the mixture was reacted at 100 ° C. for 1 hour and further at 120 ° C. for 2 hours to obtain 411 parts of a reaction product (BA2X). BA2
The hydroxyl value of X is 40 mg KOH / g.

"Synthesis of Fluorine-containing TPU" In a 700 ml kneader, the above-mentioned BA2X 280 at 100 ° C is used.
And 27 parts of 1,4-butanediol were charged and mixed, and then diphenylmethane diisocyanate (MD) at 50 ° C.
100 parts were abbreviated as I), the temperature was raised to 120 ° C., and after 1 hour, the mixture was cooled. The reaction product was taken out and pulverized by a pulverizer. The powder was re-kneaded at 180 to 200 ° C. using a 20 mm single-screw extruder (manufactured by Toyo Seiki Co., Ltd., Labo Plastomill) to form pellets. A TPU containing 18.6% of a fluorine-containing vinyl component was obtained. This TPU was dissolved in a mixed solvent of tetrahydrofuran / dimethylformamide = 1/1 to prepare a 10% solution. This solution was applied onto a glass plate and dried to obtain a film. In order to evaluate slipperiness and water repellency, the contact angle due to water droplets was measured by a contact angle meter (Kyowa Interface Science, CA.DT.
The measurement result was 103 ° C. and 60% relative humidity.

Example 2 "Synthesis of unsaturated group-containing diol (BA1)" In the same flask as in Example 1, 1149 parts of adipic acid,
1,4-butanediol 1008 parts, maleic anhydride 1
After charging 18 parts and 0.02 part of acetylacetone tin, gradually heating and reacting at 220 ° C. for 10 hours,
The pressure was gradually reduced, and the reaction was carried out at 25 mmHg for 13 hours. Diol with a hydroxyl value of 110 mgKOH / g and an acid value of 0.5 mgKOH / g (BA
1) was obtained.

"Synthesis of fluorine-containing vinyl modified diol (BA1Y)" A 1000 ml four-necked flask was equipped with a stirrer, a thermometer, a reflux tower, nitrogen introduction and a dropping funnel, and the above BA1 was mixed with 3 parts.
It was charged with 00 parts and heated to 95 ° C. while flowing nitrogen. 1
H, 1H, 5H-octafluoropentyl methacrylate
A mixed solution of 300 parts of benzoyl peroxide and 4.5 parts of benzoylperoxide was added dropwise from the dropping funnel over 2 hours. Then, the mixture was reacted at 100 ° C. for 1 hour and further at 120 ° C. for 2 hours to obtain 582 parts of a reaction product (BA1Y). BA1Y
Has a hydroxyl value of 57 mgKOH / g.

[Synthesis of Fluorine-containing TPU] In a 500 ml polypropylene beaker, 102 parts of BA1Y at 100 ° C. and 1,4-butanediol were added.
3 parts were charged and mixed uniformly. MDI 38.8 at 50 ° C
After being charged for 1 minute and stirred, the mixture was poured into a Teflon-coated vat to form a sheet. This sheet was cured at 80 ° C. for 2 days to give TP containing 32.6% of fluorine-containing vinyl.
I got U. In order to evaluate the slipperiness and water repellency, the contact angle due to the water droplet was the same as in Example 1 (20 ° C., 60 ° C.).
% Relative humidity) and the result was 104 °.

Comparative Example 1 "Synthesis of TPU" Poly (butylene adipate) diol (hydroxyl value 56 mg KOH /
g) 102.4 parts and 1,4-butanediol 9.2
Parts were charged and mixed uniformly. MDI 38.4 at 50 ° C
After being charged for 1 minute and stirred, the mixture was poured into a Teflon-coated vat to form a sheet. This sheet was cured at 80 ° C. for 2 days to obtain a fluorine-free TPU. In order to evaluate the slipperiness and the water repellency, the contact angle due to the water droplet was measured in Example 1
It was 76 ° as a result of measurement with the same contact angle meter (20 ° C., 60% relative humidity).

Example 3 "Synthesis of diol containing unsaturated group (PT2)" In the same flask as in Example 1, 2000 parts of poly (tetramethylene) glycol having a molecular weight of 1000, 118 parts of maleic anhydride and acetylacetone tin were used. After charging 0.005 part, gradually heating and reacting at 180 ° C. for 5 hours,
The pressure was gradually reduced, and the reaction was performed at 25 mmHg for 5 hours. Diol (PT2) with a hydroxyl value of 55 mgKOH / g and an acid value of 2.2 mgKOH / g
Got

"Synthesis of fluorine-containing vinyl modified diol (PT2X)" A 1000 ml four-necked flask was equipped with a stirrer, a thermometer, a reflux tower, a nitrogen introduction and a dropping funnel, and PT2 was mixed with 3 parts.
It was charged with 00 parts and heated to 95 ° C. while flowing nitrogen.
A mixed solution of 150 parts of 2,2,3,3,3-pentafluoropropylmethacrylate and 2.3 parts of benzoylperoxide was added dropwise from the dropping funnel over 1 hour. Then, the mixture was reacted at 100 ° C. for 1 hour and further at 120 ° C. for 2 hours to obtain 438 parts of a reaction product (PT2X). PT2
The hydroxyl value of X is 38 mg KOH / g.

"Synthesis of Fluorine-containing TPU" 2000 ml of a kneader was added to the above PT2X 34 at 100 ° C.
2 parts, 456 parts of poly (tetramethylene) glycol having a molecular weight of 2000 at 70 ° C. and 30.8 parts of 1,4-butanediol were charged and mixed, and then 171 parts of MDI at 50 ° C. was charged and the temperature was raised to 120 ° C. And cooled for 1 hour. The reaction product was taken out and pulverized by a pulverizer. 20 mm of this powder
Was re-kneaded at 180 to 200 ° C. using a single-screw extruder (manufactured by Toyo Seiki Co., Ltd., Labo Plastomill) to pelletize. A TPU containing 10.9% of a fluorine-containing vinyl component was obtained. This T
Sheets were prepared using an injection molding machine (3 ounces, Yamashiro Seiki Seisakusho) in which PU was set to 220 ° C. After the release agent on the surface of the sheet was removed with ethyl acetate, in order to evaluate the slipperiness and water repellency, the contact angle due to a water drop was measured with a contact angle meter (same as Example 1, 20 ° C., 60% relative humidity). The measurement result was 94 °.

Example 4 "Synthesis of fluorine-containing TPU" BA2X of Example 1 at 2000C in a 2000 ml kneader at 100 ° C
206 parts, 441 parts of poly (polylolactone) diol having a molecular weight of 2000 at 80 ° C., 1,4-butanediol 1
After charging and mixing 06 parts and 0.08 part of dibutyltin dilaurate, 247 parts of hexamethylene diisocyanate were charged and the temperature was raised to 120 ° C. and the mixture was cooled for 2 hours. The reaction product was taken out and pulverized by a pulverizer. 20 mm of this powder
Was re-kneaded at 180 to 200 ° C. using a single-screw extruder (manufactured by Toyo Seiki Co., Ltd., Labo Plastomill) to pelletize. A TPU containing 5.6% of fluorine-containing vinyl was obtained. This TP
Sheets were prepared using an injection molding machine (3 ounces, Yamashiro Seiki Seisakusho) in which U was set to 220 ° C. After the release agent on the surface of the sheet was removed with ethyl acetate, in order to evaluate the slipperiness and water repellency, the contact angle due to a water drop was measured with a contact angle meter (same as Example 1, 20 ° C., 60% relative humidity). The measurement result,
It was 96 °.

Claims (1)

[Claims] 1. An average molecular weight of 5 having an unsaturated group in the molecule.
A fluorine-containing vinyl modified diol obtained by reacting fluorine-containing vinyl monomer-2 to 200 parts by weight with 100 parts by weight of diol of 0 to 5000, polyisocyanate and a chain extender are reacted. The resulting fluorine-containing thermoplastic polyurethane resin.