JPH0342286B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is a thermoplastic polyurethane resin (hereinafter referred to as
Regarding the manufacturing method of TPU (also called TPU). More specifically, the present invention relates to a method for producing a thermoplastic polyurethane resin having high mechanical properties and having perfluoroalkyl groups pendant in the molecule and/or at the end of the molecule. Polyurethane resin has excellent adhesive properties, can withstand repeated bending, is strong, and has excellent abrasion resistance and weather resistance, so it is widely used in molded products, paints, adhesives, binders, etc. It had drawbacks such as a high coefficient and poor surface smoothness. The use of various lubricants has been known to improve slipperiness, but their effectiveness has been insufficient. Therefore, the present inventors conducted various studies on thermoplastic polyurethane resins with excellent long-lasting slip properties, and found that it is effective to introduce a perfluoroalkyl group into the molecule. Reached. That is, the present invention is as follows. (1) Polymer diol (A) with an average molecular weight of 500 to 10,000,
Organic diisocyanate (B), the following general formula []
Alkylene oxide adduct of an acid amide compound having a perfluoroalkyl group represented by
(C), (Here, R ₁ is an alkyl group having 1 to 20 carbon atoms,
R ₂ is an alkylene group having 2 to 4 carbon atoms, and X is

[ _Formula ] Alternatively, l is an integer of 1 to 40, m is 0 or 1, and n is an integer of 1 to 20. ), if necessary, a chain extender (D) having two active hydrogen atoms and an average molecular weight of 500 or less, and, if necessary, a crosslinking agent (E) having three or more active hydrogen atoms, to form a thermoplastic polyurethane resin. When producing , the ratio of the total number of active hydrogens in (A), (C), (D) and (E) above to the number of isocyanate groups in (B) is 1:0.85 to 1:1.1. A method for producing a thermoplastic polyurethane resin, characterized by: Alkylene oxide adduct of acid amide compound having perfluoroalkyl group used in the present invention
(C) is represented by the following general formula. (Here, R ₁ is an alkyl group having 1 to 20 carbon atoms,
R ₂ is an alkylene group having 2 to 4 carbon atoms, and X is

[ _Formula ] Alternatively, l is an integer of 1 to 40, m is 0 or 1, and n is an integer of 1 to 20. ) This general formula []
In, the alkyl group represented by R ₁ is methyl,
These include ethyl, propyl, butyl, hexyl, octyl, and dodecyl groups. Further, the alkylene group represented by R ₂ is ethylene, propylene, butylene group, etc. X is a sulfonyl group or a carbonyl group. In addition, fluorine-substituted alkyl groups include perfluorobutane group, perfluorohexane group,
These include perfluorooctane group, perfluorododecane group, perfluoroeicosane group, etc. These compounds specifically include N-methyl-N
-Hydroxypropyl perfluorobutanesulfonic acid amide, N-propyl-N-hydroxyethyl perfluorooctanesulfonic acid amide,
N-propyl-N-hydroxyethyl perfluorododecanecarboxylic acid amide, N-dodecyl-
N-hydroxyethyl perfluorohexane sulfonic acid amide, propylene oxide addition polymer of perfluorooctane sulfonic acid/N-propylamide, ethylene oxide addition polymer of perfluoroeicosane sulfonic acid N-methylamide, perfluorooctane carboxylic acid - Tetrahydrofuran addition polymer of N-octylamide, etc. The polymer diol (A) used in the present invention has an average molecular weight of
500 to 10,000, and include known polyether diols, polyester diols, polycarbonate diols, etc. Polyether diols include, for example, water, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3- or 1,4-butylene glycol, 1,6-hexamethylene glycol, bisphenol A, etc., and an alkylene oxide such as ethylene. One or more types of oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide, etc. (hereinafter simply abbreviated as alkylene oxide).
It is obtained by adding Polyester diols include, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3- or 1,4-butylene glycol, neopentyl glycol, 1,6-hexamethylene glycol, decamethylene glycol, bis Phenol A, bisphenol F, p-
One or more of xylylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, or alkylene oxide adducts thereof, and malonic acid, maleic acid, succinic acid, adipic acid, glutaric acid, Polyester diol from one or more of pimelic acid, sebacic acid, oxalic acid, phthalic acid, isophthalic acid, terephthalic acid, hexahydrophthalic acid, etc. or propiolactone, butyrolactone,
These are diols produced by ring-opening polymerization of cyclic esters such as caprolactone, and polyester diols made from the above-mentioned glycols and cyclic esters, or from the above-mentioned glycols, dibasic acids, and cyclic esters. In addition, polycarbonate diol is a compound represented by the general formula H-(O-R-OCO-) _o ROH, where (n≧1), where R is a residue of glycol or divalent phenol;
Examples of the phenols include trimethylene glycol, diethylene glycol, 1,3- or 1,4-butylene glycol, 1,6-hexamethylene glycol, decamethylene glycol, p
-Xylylene glycol, bisphenol A
[2,2-bis(4'-hydroxyphenyl)propane], bisphenol F (4,4'-dihydroxydiphenylmethane), and the like. As the polymer diol (A) used in the present invention, 1,2-polybutadiene diol, 1,4-polybutadiene diol, polychloroprene diol, butadiene-acrylonitrile copolymer diol, polydimethylsiloxane dicarbinol, and the like can also be used. These various polymer diols may be used alone or in combination of two or more. The chain extender (D) having two active hydrogen groups and having an average molecular weight of 500 or less used in the present invention is a known aliphatic diol, aromatic diol, N-alkyl or N-
These include aryl dialkanolamines, aliphatic diamines, and aromatic diamines. Aliphatic diols include, for example, ethylene glycol, propylene glycol, 1.3- or 1.
4-butylene glycol, 1,5-pentanediol, 1,6-hexamethylene glycol, neopentyl glycol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3
-pentanediol, 2.2.4- or 2.4
-4-trimethyl-1,6-hexanediol,
decamethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2,2-bis(4'-hydroxycyclohexyl)propane, 3-methyl-1,3-butanediol, p-xylylene glycol or These are alkylene oxide adducts. Aromatic diols are, for example, hydroquinone, bisphenol A, bisphenol F, naphthylene diol, or alkylene oxide adducts thereof. N-alkyl or N-aryl dialkanolamines include, for example, methyldiethanolamine,
Methyldiisopropanolamine, ethyldiethanolamine, phenyldiethanolamine, m
- tolyldiethanolamine, or an alkylene oxide adduct thereof. Aliphatic diamines include ethylenediamine,
hexamethylene diamine, isophorone diamine,
1,3-bis(aminomethyl)cyclohexane,
Polyoxypropylene diamine, bis(p-aminocyclohexyl)methane, etc., and aromatic diamines include metaxylene diamine, tolylene diamine, diphenylmethane diamine, 4.
4'-methylenebis(2-chloroaniline), 1.
5-naphthylene diamine and the like. These various chain extenders (D) with an average molecular weight of 500 or less
may be used alone or in combination of two or more. The organic diisocyanate (B) used in the present invention is, for example, tolylene diisocyanate (including those with various isomer ratios) (TDI), diphenylmethane-4,
4'-diisocyanate (MDI), naphthylene-
1,5-diisocyanate (MDI), 3,3'-dimethyl-4,4'-biphenylene diisocyanate (TODI), xylylene diisocyanate (XDI),
These include dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), and hydrogenated xylylene diisocyanate (HXDI). These various organic diisocyanates may be used alone or in combination of two or more. The crosslinking agent (E) used as necessary in the present invention includes known polyols, polyamines, alkanolamines, and the like. Examples of polyols include trimethylolpropane, glycerin, 3-methylpentane-1,3-5-triol, pentaerythritol, sorbitol, sucrose, polyglycerin, tris(β-hydroxyethyl)isocyanurate, or alkylene oxide adducts thereof. or ε-caprolactone adduct,
Polyester polyols, etc. Examples of polyamines include ethylenediamine, diethylenetriamine, tolylenediamine, diphenylmethanediamine, isophoronediamine, 4.
These include 4'-methylenebis(2-chloroaniline), hexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, polyoxypropylenediamine, bis(p-aminocyclohexyl)methane, metaxylenediamine, and the like. Alkanolamines are, for example, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine or alkylene oxide adducts of the above polyamines. These various crosslinking agents (E) may be used alone or in combination.
It is used in combination of more than one species. Furthermore, in the present invention, a reaction terminator containing one or more active hydrogen groups can be used. The reaction terminator used in the present invention includes monoalcohols such as isopropanol, n-butanol, sec-butanol, and t-butanol, glycols such as ethylene glycol and propylene glycol, triols such as glycerin and trimethylolpropane, and dimethyl Amines, amines such as ethylpropylamine and dibutylamine, alkanolamines such as diethanolamine and triethanolamine, oximes such as acetoxime and methyl ethyl ketoxime, lactams such as γ-butyrolactam and ε-caprolactam, N
-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-
These include silane coupling agents such as aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, and γ-mercaptopropyltrimethoxysilane. The amount of these reaction terminators used is 0.01 per mole of organic diisocyanate (B).
~0.2 mol. The polymer diol (A), chain extender (D), organic diisocyanate (B), alkylene oxide adduct of an acid amide compound having a perfluoroalkyl group (C), and crosslinking agent (E) of the present invention are (1) When producing TPU from A, C, and B, the number of isocyanate groups in B is 0.85 to 1.1 relative to the total number of active hydrogen groups in A and C (1); (2) In addition, as necessary. When D and E are used as necessary, they are used in a quantitative relationship such that the number of isocyanate groups in B is 0.85 to 1.1 with respect to the total number of active hydrogen groups of A, C, D, and E (1). It will be done. In the above item 1 or 2, the number of isocyanate groups in (B) is 0.85 per total number of active hydrogen groups 1.
If it is less than 1.1 or more than 1.1, the mechanical properties of TPU will deteriorate. In the present invention, a conventionally known urethanization catalyst is used as necessary at any stage of the reaction. Further, in the present invention, various additives such as antioxidants, ultraviolet absorbers, and carbodiimides are used as necessary. Furthermore, in the present invention, in addition to the above-described thermoplastic polyurethane resin composition (hereinafter referred to as X), TPU ( Hereinafter (Y) is the TPU of the present invention (X)
Can be mixed with. Its mixing ratio (weight)
A suitable range for X:Y is 95:5 to 5:95. The above-mentioned active hydrogen-containing polyol is a polyol that includes the polymer diol (A) mentioned above, as well as known triols used in the production of polyurethane resins, and one type or a mixture of two or more of these polyols is used. be done. In the present invention, the following solvents are used as necessary.
Amides such as dimethylformamide and dimethylacetamide, sulfoxides such as dimethyl sulfoxide, cyclic ethers such as dioxane and tetrahydrofuran, cyclic ketones such as cyclohexanone, acyclic ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, Glycol ether type known as "cellosolve", "butyl cellosolve", "carbitol", "butyl carbitol", trade name "cellosolve acetate", "butyl cellosolve acetate",
Acetic acid glycol ether series known as “carbitol acetate” and “butyl carbitol acetate” as well as product names “DBE” and “DBE”
-9'', one or more dibasic acid ester solvents, and the above solvents and esters such as ethyl acetate and butyl acetate, aromatic hydrocarbons such as benzene, toluene, and xylene, methylene chloride, trichloroethylene,
These include mixed solvents with chlorine-based solvents such as trichloroethane and perchlorethylene, and alcohol-based solvents such as methanol, ethanol, isopropanol, and butanol. Furthermore, 2,2,4-trimethyl 1,3-pentanediol monoisobutyrate (Kyowanol M: Kyowa Hakko) can also be used as a solvent. Furthermore, the polyurethane resin of the present invention can be used with other resins,
For example, it can be used in combination with epoxy resin, alkyd resin, acrylic resin, polyester resin, vinyl chloride/vinyl acetate copolymer resin, etc.
Further, as fillers, for example, diatomaceous earth, calcium carbonate, silica, carbon black, titanium oxide, iron oxide, copper powder, etc. can be added, and plasticizers such as dioctyl phthalate and dibutyl adipate can also be added. To apply the present invention, a polymeric diol and an organic diisocyanate are heated in a nitrogen atmosphere at a temperature of 60°C to 100°C in the presence of a catalyst and/or solvent as necessary.
A prepolymer is produced by heating and reacting for several hours. For example, an ethylene oxide adduct of perfluorooctanesulfonic acid N-alkylamide is added thereto, and the mixture is further heated and reacted at the same temperature for several hours to obtain a thermoplastic polyurethane resin. If necessary, a reaction terminator can be added and the reaction can be carried out by heating. Further, a solvent is appropriately added to reduce the viscosity at each stage of the reaction. The obtained thermoplastic polyurethane resin solution has a solid content of 15 to 60% by weight and a viscosity of 200 to 70,000 cps/25°C. Separately, one or more known polyols used in the production of polyurethane resins are reacted with organic diisocyanate (B) by a generally known method as well as the method described in JP-A-56-127616, for example, to form a thermoplastic polyurethane. A thermoplastic polyurethane resin mixture is obtained by preparing a resin (Y) and mixing it with the thermoplastic polyurethane resin solution (X) described above. These TPUs and their resin mixtures are
Various changes can be made by changing the raw materials such as B, C, D, and E, as well as the proportions of X and Y used. The general physical properties of resins obtained by removing the solvent from these thermoplastic polyurethane resin solutions and mixtures thereof are as follows. From low modulus products with stress at 100% stretching of 10 to 100 Kg/cm ² and elongation at break of 200 to 1000%, to Young's modulus of 10000 to 30000.
It is possible to obtain products with various desired physical properties, including products with a high Young's modulus of Kg/cm ² and yield elongation of 2 to 10%. By using the TPU of the present invention, effects such as a reduction in the coefficient of friction, water repellency, improvement in leveling properties, reduction in surface resistance, antistatic properties, and improvement in pigment dispersibility, as well as the sustainability and durability of these effects, can be achieved. can be expected to improve. The TPU in the present invention is provided in the form of pellets, flakes, etc., and can be made into molded products, films, sheets, etc. by injection molding, extrusion molding, and calendar molding, or can be provided in the form of a solution.
Or in the form of resins, films, various coating materials, impregnating agents, paints, binders (for printing inks, magnetic paints, conductive paints, etc.) after removing the solvent by a conventional method.
For example, it is used for interior and exterior materials and electrical components of automobiles and railway vehicles, audio equipment, VTRs, communication equipment,
It can be used in various fields such as computers, office machines, lighting equipment, leather, textile and textile processing. Next, the present invention will be specifically explained with reference to Examples. Note that parts indicate parts by weight. Example 1 After purging the reactor with a stirrer and a reflux condenser with nitrogen gas, 300 parts of methyl ethyl ketone (MEK) was charged, and further polyester diol (polyester diol from ethylene glycol, 1,4-butanediol and adipic acid, average molecular weight 1600)
60 parts, 158.8 parts of MDI, and 0.03 parts of dibutyltin dilaurate (DBTDL) were added, and the mixture was reacted at 80°C for 2 hours. After adding 57.7 parts of neopentyl glycol (NPG) to the above solution and reacting at 80°C for 1 hour, 15 parts of N-propyl-N-hydroxyethyl perfluorooctane sulfonic acid amide was added and the mixture was heated to 80°C.
The mixture was allowed to react for 30 minutes. In addition, 400 copies of MEK,
8.5 parts of triethanolamine was added and reacted at 80°C for 1 hour. The resulting TPU solution has a solid content of 30.8
weight%, viscosity is 3000 cps (25°C), and the resin obtained from this solution has Ys (stress at yield) of 565 Kg/cm ² ,
Elongation at yield is 4.0%, Young's modulus is 20000Kg/ ^cm2 ,
The surface had excellent slip properties. Example 2 In Example 1, 15 parts of N-propyl-N-hydroxyethyl perfluorododecanecarboxylic acid amide was used instead of N-propyl-N-hydroxyethyl perfluorooctane sulfonic acid amide, and Example 1 Treated in exactly the same manner as
A thermoplastic polyurethane resin solution of 30.1% by weight and a viscosity of 1600 cps (25°C) was obtained. The resin obtained from this solution has a Ys of 580 Kg/cm ² , an elongation at yield of 5%, and a Young's modulus.
20000Kg/cm ² , and the surface slipperiness was excellent. Example 3 In Example 1, perfluorooctanesulfonic acid/N was used instead of N-propyl-N-hydroxyethyl perfluorooctanesulfonic acid amide.
- Using 15 parts of propylene oxide addition polymer of propylamide (average molecular weight 830), Example 1
Processed in exactly the same manner as , solids content 29.8% by weight, viscosity
A thermoplastic polyurethane resin solution of 2100 cps (25°C) was obtained. The resin obtained from this solution had a Ys of 510 Kg/cm ² , an elongation at yield of 4.8%, a Young's modulus of 19000 Kg/cm ² , and excellent surface slipperiness.

Claims (1)

[Claims] 1. Polymer diol (A) with an average molecular weight of 500 to 10,000,
Organic diisocyanate (B), alkylene oxide adduct (C) of an acid amide compound having a perfluoroalkyl group represented by the following general formula [], (Here, R ₁ is an alkyl group having 1 to 20 carbon atoms,
R ₂ is an alkylene group having 2 to 4 carbon atoms, X is C=O
Alternatively, SO ₂ , l is an integer of 1 to 40, m is 0 or 1, and n is an integer of 1 to 20. ), if necessary, a chain extender (D) having two active hydrogen atoms and an average molecular weight of 500 or less, and, if necessary, a crosslinking agent (E) having three or more active hydrogen atoms, to form a thermoplastic polyurethane resin. When producing , the ratio of the total number of active hydrogens in (A), (C), (D) and (E) above to the number of isocyanate groups in (B) is 1:0.85 to 1:1.1. A method for producing a thermoplastic polyurethane resin, characterized by: