JPH10158358A - Production of urea group-containing thermoplastic urethane resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a urea group-containing thermoplastic polyurethane resin excellent in mechanical strength. SOLUTION: This method for producing a urea group-containing thermoplastic polyurethane resin comprises reacting a long-chain diol containing 5-50wt.% of a urea group-containing polyol obtained from a lactam block substance of a diisocyanate compound and a glycol having <=400 molecular weight with a polyisocyanate in an amount to give 0.97 to 1.03mol of isocyanate group of the polyisocyanate based on active hydrogen groups of the long-chain diol and the glycol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a thermoplastic polyurethane resin, and more particularly, to a method for producing a urea group-containing thermoplastic polyurethane resin having excellent mechanical strength.

[0002]

2. Description of the Related Art Heretofore, the most common method for improving the mechanical strength of a thermoplastic polyurethane resin (hereinafter abbreviated as TPU) is a method in which a polyisocyanate is added in a slightly excessive amount during the production of a TPU. Had been. This is because a small amount of isocyanate groups (hereinafter referred to as NCO)
To improve the mechanical strength by causing a cross-linking reaction such as an allophanate bond by heating or by causing a urea or biuret bond by reacting with moisture in the air or the like. I've been.

[0003]

However, the conventional method of excessively blending a polyisocyanate has a problem in that a stable product such as a variation in mechanical strength or a variation in the melt viscosity of TPU occurs. There was a problem that it could not be produced. This is because the reaction between NCO groups and moisture such as in air is greatly affected by various conditions,
It is presumed that the resulting chemical bonds or products are diverse. An object of the present invention is to improve a conventional method for manufacturing a TPU having many variations, and to provide a method for manufacturing a TPU having stable and excellent mechanical strength.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve such a conventional problem, and as a result, have found that TP
It has been found that by introducing a urea group-containing polyol into a part of the composition of U, a TPU having excellent mechanical strength can be obtained, and the present invention has been completed. That is, according to the present invention, a long-chain diol having 5 to 50% by weight of a urea-containing polyol obtained from a lactam block of a diisocyanate compound and diols, and a molecular weight of 400
Polyisocyanate was added to the following glycols such that the NCO group of the polyisocyanate was 0.97 to 1.03 times the mol of the active hydrogen group of the long chain diol and the glycol. And a method for producing a urea group-containing thermoplastic polyurethane resin having excellent mechanical strength obtained by the reaction.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The urea group-containing polyol used in the present invention is obtained by reacting a lactam block of a diisocyanate compound with diols in the presence of a catalyst. Examples of diisocyanate compounds include 2,4-
Toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate,
2,2'-diphenylmethane diisocyanate, 1,5
-Naphthalene diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenyl ether diisocyanate, 1,4-xylene diisocyanate, 1,
Aromatic diisocyanates such as 3-xylene diisocyanate, 1,6-hexamethylene diisocyanate, aliphatic diisocyanates such as lysine diisocyanate,
Examples include alicyclic diisocyanates such as isophorone diisocyanate, 1,4-cyclohexane diisocyanate, and 4,4'-dicyclohexyl diisocyanate, dimer-modified diisocyanate compounds, and urethane prepolymers having isocyanate group terminals. These can be used alone or in a mixture of two or more.

Examples of lactams include β-propiolactam, γ-butyrolactam, γ-valerolactam, δ
Valerolactam, ε-caprolactam, heptactam and the like, and a particularly desirable lactam is ε-caprolactam.

Examples of the diols used in the urea group-containing polyol of the present invention include ethylene glycol,
1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl- 1,5-pentanediol, 1,6-hexanediol, 1,8-
Octanediol, 1,9-nonanediol, 1,10
-Short chain glycols such as decane diol, diethylene glycol, triethylene glycol, dipropylene glycol 1,4-cyclohexane dimethanol, polyester diols having a number average molecular weight of 300 to 6000, polycarbonate diols, polyether diols, polyalkylene diols and the like. Yes, these may be used alone or in any combination.

Examples of polyester diols include known polyester diols, ie, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid Acid, isophthalic acid, terephthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, 1,5
Dicarboxylic acids such as naphthalenedicarboxylic acid or anhydrides and alkyl esters thereof, and ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, , 3-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-
Octanediol, 1,9-nonanediol, 1,10
-Any combination of a dihydroxy compound such as decanediol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, or a polyhydroxy compound with a diol obtained by adding ethylene oxide or propylene oxide to bisphenol A in an amount of 2 moles. A polyester diol obtained by a dehydration or dealcoholation reaction, or a polyester diol obtained by ring-opening polymerization of a cyclic ester (lactone) monomer such as ε-caprolactone, δ-valerolactone, and alkyl-substituted δ-valerolactone.

Examples of polycarbonate diols include:
A known polycarbonate diol, i.e., 1,4-
Butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10- Demethanol reaction of dihydroxy compound such as decanediol, diethylene glycol, triethylene glycol, dipropylene glycol 1,4-cyclohexanedimethanol with dimethyl carbonate, deethanolation reaction with diethyl carbonate, dephenolization reaction with diphenyl carbonate, ethylene carbonate With propylene carbonate or ε-caprolactone, δ-valerolactone, alkyl-substituted δ- A polycarbonate lactone diol obtained by copolymerizing at a ratio such lactones and from 20 to 80% by weight of Rerorakuton.

Examples of polyether diols include known polyether diols, ie, ethylene glycol,
1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 3-methyl-1,5- Pentanediol, neopentyl glycol, 1,6-hexanediol, 1,8-
Octanediol, 1,9-nonanediol, 1,10
Polyether obtained by adding ethylene oxide and / or propylene oxide with a dihydroxy compound such as decanediol, diethylene glycol, triethylene glycol, dipropylene glycol 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A as an initiator Diol and polyoxypolytetramethylenediol. Examples of the polyalkylene polyol include polybutadiene diol, hydrogenated polybutadiene diol, polyisoprene diol, and the like.

Examples of the catalyst used for the urea group-containing polyol include sodium metal, potassium metal, sodium hydride, antimony acetate, zinc acetate, sodium methoxide, sodium ethoxide, sodium propoxide, sodium n-butoxide, Sodium ter
t-butoxide, potassium methoxide, potassium ethoxide, potassium propoxide, potassium n-butoxide, potassium tert-butoxide, methyl magnesium chloride, methyl magnesium bromide, methyl magnesium iodide, ethyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium ioda And phenylmagnesium chloride, phenylmagnesium bromide, phenylmagnesium iodide and the like.

The ratio of each component in producing the urea group-containing polyol used in the present invention will be described below. The molar ratio of the diols to the equivalent addition product of the isocyanate compound and the lactam is 1: 1.01-1: 1:
100, preferably 1: 1.1 to 1:10, more preferably 1: 1.5 to 1: 4, most preferably 1: 1.
2. The ratio of the catalyst is 0.1 to 10 mol%, preferably 1 to 4 mol%, based on the equivalent adduct of the isocyanate compound and the lactam.

As a method for producing the urea group-containing polyol, a method in which the reaction is carried out in a molten state is desirable, but if necessary, an appropriate organic solvent can be used. As the reaction conditions at this time, the reaction temperature is preferably from 100 to 140 ° C, but most preferably from 125 to 135 ° C. The reaction time is desirably 3 to 12 hours. In addition, various additives can be added to the urea group-containing polyol as necessary. Examples thereof include an antioxidant, a hydrolysis inhibitor, a fungicide, an ultraviolet absorber, a light stabilizer, Examples include a reaction retarder, a foaming agent, a surfactant, a coloring agent, an antistatic agent and the like.

The urea group-containing polyol is generally a white solid or a pale yellow viscous liquid at room temperature, depending on the molecular weight or the kind of the diol used. The molecular weight of the polyol is determined by the ratio of the raw material components depending on the purpose, but generally it is preferably about 1,000 to 3,000. The polyol has -NH-CO- in the molecule.
Although it has NH- (urea group), its presence can be confirmed by the absorption band at 1600 cm ^{-1 in} the infrared absorption spectrum.

Examples of the long-chain diol used in the present invention include polyethers, polyesters, polyetheresters having a hydroxyl group at the terminal and having a molecular weight of 400 to 10,000, which are usually used as a reaction partner of polyisocyanate.
Polycarbonates and the like. Examples of the polyethers include a polymerization product of tetrahydrofuran, propylene oxide and ethylene oxide, a copolymerization product thereof, and a graft polymer of a polyether with a vinyl monomer. Examples of the polyesters include those obtained by a condensation reaction between polyhydric alcohols and polyhydric carboxylic acids. Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, butylene glycol, hexamethylene glycol, 2-methylpropanediol, neopentyl glycol, and 3-methylpentanediol. And 2-methyloctanediol, 1,9-nonanediol, cyclohexanedimethanol, glycerin, and trimethylolpropane. Examples of polycarboxylic acids include succinic acid, adipic acid, sebacic acid, dimer acid, hydrogenated dimer acid, phthalic acid, alkyl phthalates, trimet acid, maleic acid, fumaric acid, and itaconic acid. and so on. Further, those obtained by ring-opening polymerization of cyclic esters such as butyrolactone, valerolactone, and caprolactone are also included. Polyetheresters are those obtained in the same manner as polyesters except that polyethers are used for part or all of the polyhydric alcohols used in the condensation reaction for obtaining the above polyesters. No. Examples of the polycarbonates include diols such as 1,6-hexanediol and 1,4-cyclohexanedimethanol, and dialkyl carbonates, diallyl carbonates or ethylene carbonates. Those obtained by a transesterification reaction with a cyclic carbonate such as a net are exemplified.

Glycols having a molecular weight of 400 or less used in the present invention include ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, and 1,1-glycol. Examples include 9-nonanediol, bis-β-hydroxyethoxybenzene, 3-methyl-1,5 pentanediol, and neopentyl glycol. The glycol used in the present invention preferably has a molecular weight of 400 or less. If the molecular weight exceeds 400, the physical properties of the obtained TPU are generally deteriorated, which is not preferred.

The polyisocyanate used in the present invention includes phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, naphthylene diisocyanate. , Diphenylmethane diisocyanate and the like, and aromatic diisocyanates comprising these isomers;
Aliphatic methylene diisocyanate such as hexamethylene diisocyanate, 1,12-dodecane diisocyanate, trimethyl-hexamethylene diisocyanate, cyclohexane diisocyanate, dicyclohexyl methane diisocyanate And alicyclic diisocyanates such as isophorone diisocyanate, hydrogenated xylylene diisocyanate and norbornane diisocyanate methyl. Further, an isocyanate group-terminated compound obtained by the reaction of these compounds with an active hydrogen group-containing compound, or a modified polyisocyanate obtained by a reaction of these compounds, for example, a carbodiimidation reaction or the like is also included. Also, methanol, n-butanol, benzyl alcohol, ethyl acetoacetate, ε-caprolactam,
A polyisocyanate in which one part is stabilized by a blocking agent having one active oxygen in the molecule such as methyl ethyl ketone oxime, phenol and cresol is also included.

The urea group-containing TPU of the present invention comprises a long chain diol containing 5 to 50% by weight of a urea group-containing polyol, a glycol having a molecular weight of 400 or less, a polyisocyanate, and a long chain diol. And the ratio (R value) of the number of moles of NCO groups of the polyisocyanate to the active hydrogen groups of phenol and glycol is 0.97 to 1.03. R
When the value is less than 0.97, the resulting urea group-containing TPU
Is not preferred because the molecular weight of the polymer decreases and the mechanical strength decreases. On the other hand, when the R value exceeds 1.03, the melt viscosity of the obtained urea-containing TPU increases, and the moldability decreases. Here, the active hydrogen groups of the urea group-containing polyol include the active hydrogen groups of the urea groups and the hydroxyl groups.
The urea group-containing polyol of the present invention is contained in a long chain diol in an amount of 5 to 50% by weight. When the urea group-containing polyol is less than 5% by weight, the mechanical strength of the obtained urea group-containing TPU is undesirably reduced. If the amount exceeds 50% by weight, the melt viscosity of the obtained urea group-containing TPU increases, and the moldability decreases. Molecular weight 400
The following glycols and long-chain diols are represented by the ratio (R 'value) of the number of moles of hydroxyl groups of the glycol to the number of moles of hydroxyl groups of the long-chain diol.
Is 0.1-15.0, preferably 0.5-5.0. If R 'is less than 0.1, the resulting T
It is not preferable because the target product cannot be obtained because the hardness of PU is too low. If it exceeds 15.0, the hardness of the resin becomes too high, which is not preferable.

The method for producing the urea group-containing TPU of the present invention is a known method for producing a thermoplastic polyurethane resin, for example, a one-shot method, a prepolymer method, a batch reaction method, or the like.
Methods such as a continuous reaction method, a kneader method, and an extruder method can be employed. For example, in the method using a kneader, a urea group-containing polyol and a long-chain geo-
And a glycol having a molecular weight of 400 or less.
After heating to ℃, the polyisocyanate is charged and
A minute reaction and cooling are performed to produce a powdery or block-like thermoplastic polyurethane resin. These powder or block resins are formed into pellets by an extruder or the like, if necessary. Equipment used for production is a kneader connected with a multi-component weighing and mixing machine,
A single or multiple screw extruder can be used.

In producing the urea group-containing TPU of the present invention, a catalyst can be added if necessary. Catalysts that can be used include, for example, triethylamine, triethylenediamine, N-methylimidazole, N-ethylmorpholine, 1,8-diazabicyclo, 5,4,0 undecene-
7 (DBU); organometals such as potassium acetate, stanna octoate and dibutyltin dilaurate; and phosphorus compounds such as tributylphosphine, phosphorene and phosphorene oxide.

Urea group-containing TP obtained by the present invention
U can add another resin as needed. Resins that can be used include, for example, ABS resin, SAN resin, vinyl chloride resin, polypropylene, polyethylene, polystyrene, polyacetal, polyamide, polyester,
Examples thereof include polyester ether, polycarbonate, epoxy resin, amino resin, phenol resin, silicone resin, and fluorine resin. These resins are urea group-containing TPs.
1 to 50 parts by weight can be added to 100 parts by weight of U. Urea group-containing TPU obtained by the present invention
Can add other substances as needed. Substances that can be added include, for example, antioxidants, ultraviolet absorbers,
Heat resistance improver, plasticizer, lubricant, antistatic agent, conductivity imparting agent,
Coloring agents, inorganic and organic fillers, fibrous reinforcements, matting agents, hydrolysis inhibitors, reaction retarders and the like.

For the urea group-containing TPU of the present invention, generally used molding methods and molding conditions for thermoplastic polyurethane resins are applied. For example, there are molding methods such as extrusion molding, injection molding, blow molding, calendar processing, roll processing, press processing, centrifugal molding, and rotational molding.

[0023]

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 In a reaction vessel equipped with a stirrer, an ether-based polyol (produced by Hodogaya Chemical Industry Co., Ltd., PTG1000;
90 parts of a hydroxyl value of 112 mg KOH / g and a urea group-containing polyol (Nippon Polyurethane Industry, U-PES85)
M, which contains two urea groups in one molecule,
10 parts of a hydroxyl value (56 mg KOH / g) were added and mixed uniformly, and 1,4-butanediol (hereinafter abbreviated as BG) was added to 9 parts.
After adjusting the temperature to 100 ° C., 50 parts (R value: 1.00) of 4,4′-diphenylmethane diisocyanate (MDI) were added to carry out a urethanization reaction. When the reactant reached 90 ° C., it was poured into a vat and solidified on the vat. The obtained solidified product was aged in an electric furnace at 80 ° C. for 24 hours, and then the solidified product was pulverized to obtain a flaky urea group-containing TPU150.
Got a part.

A sheet (1) is prepared from the flaky urea group-containing TPU using an injection molding machine (manufactured by Nissei Plastics Industries, FS-75).
(10 × 55 × 2 mm), and after a heat treatment at 105 ° C. for 72 hours, the tensile strength was measured according to the method of JIS-K-7311. Table 1 shows the measurement results.

Comparative Example 1 In a reaction vessel equipped with a stirrer, 9 parts of BG were added to 100 parts of ether-based polyol (PTG1000, Hodogaya Chemical, hydroxyl value 110 mgKOH / g) as a long-chain diol.
After the temperature was adjusted to 00 ° C., 52.5 parts (R value: 1.05) of MDI was added to carry out a urethanization reaction. The post-treatment, pulverization, sheet making method and tensile test method of the reaction product were carried out in the same manner as in Example 1. Table 1 shows the measurement results.

Example 2 In a reaction vessel equipped with a stirrer, 70 parts of an ether-based polyol (TG1000, manufactured by Hodogaya Chemical Industries, hydroxyl value 112 mgKOH / g) as a long-chain diol and a urea group-containing polyol were used. And 30 parts of U-PES85M (same as in Example 1) were mixed uniformly, and 8 parts of BG was added.
47 parts of DI (R value: 1.00) were added to carry out a urethanization reaction. The post-treatment, pulverization, sheet making method and tensile test method of the reaction product were carried out in the same manner as in Example 1. Table 1 shows the measurement results.

Example 3 In a reaction vessel equipped with a stirrer, an ester-based polyol (ODX-64, manufactured by Dainippon Ink Industries, Ltd.) was used as a long-chain diol.
0, hydroxyl value 56 mgKOH / g) 80 parts and urea group-containing polyol (Nippon Polyurethane Industry, U-PES2)
1M, containing two urea groups in one molecule, adding 20 parts of a hydroxyl value of 56 mgKOH / g), mixing uniformly, adding 5 parts of BG, adjusting to 100 ° C., and adjusting MDI to 28%.
(R value 0.97), and a urethane-forming reaction was performed. The post-treatment, pulverization, sheet making method and tensile test method of the reaction product were carried out in the same manner as in Example 1. Table 1 shows the measurement results.

Example 4 In a reaction vessel equipped with a stirrer, an ester-based polyol (ODX-640, the same as in Example 3) 9 was used as a long-chain diol.
0 parts and 10 parts of a urea group-containing polyol (U-PES21M, the same as in Example 3) are added and mixed uniformly, 5 parts of BG is added, and the mixture is adjusted to 100 ° C., and 28.5 parts of MDI (R value 1. 0
3) An additional urethanation reaction was performed. The post-treatment, pulverization, sheet making method and tensile test method of the reaction product were carried out in the same manner as in Example 1. Table 1 shows the measurement results.

Comparative Example 2 In a reaction vessel equipped with a stirrer, an ester-based polyol (ODX-640, same as in Example 3) 1 was used as a long-chain diol.
After adding 00 parts and 5 parts of BG and adjusting to 100 ° C.,
8.2 parts (R value: 1.07) were added to carry out a urethanization reaction. The post-treatment, pulverization, sheet production method and tensile test method of the reaction product were performed in the same manner as in Example 1. Table 1 shows the measurement results.

[0031]

[Table 1]

[0032]

The urea group-containing TPU obtained by the method of the present invention has excellent mechanical strength. Further, the urea group-containing TPU of the present invention has improved physical properties such as heat resistance, compression set, water resistance, chemical resistance, and abrasion resistance.

The urea group-containing TPU of the present invention includes, for example, extruded articles such as tubes, hoses, various films, electric wires and cables, various ropes, various belts, casters, snow chains, and shoe soles. Various types of injection molded products such as bearings, gears and packings, various types of calender products such as conveyor belts and flexible containers, various types of blow molded products, hot melt adhesives, and also can be used effectively in adhesives by dissolving in solvents. can do.

Claims (1)

[Claims] 1. A long-chain diol containing 5 to 50% by weight of a urea group-containing polyol obtained from a lactam block of a diisocyanate compound and a diol;
A urea obtained by adding a polyisocyanate to a glycol having a molecular weight of 00 or less so that the isocyanate group of the polyisocyanate is 0.97 to 1.03 times the active hydrogen group of the long-chain diol and glycol and reacting A method for producing a group-containing thermoplastic polyurethane resin.