JP2001316444A - Method for manufacturing antistatic polyurethane resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a polyurethane resin not suffering from a bleeding phenomenon and therefore exhibiting excellent antistatic effects. SOLUTION: The method for manufacturing an antistatic polyurethane resin comprises incorporating a reaction product (A) of a polyisocyanate, containing an isocyanate group-containing prepolymer composed of an alkoxypolyalkylene glycol and an isocyanate compound, with an active hydrogen group-containing compound comprising a trifunctional polyol compound into a polyurethane resin (B) in the mass ratio of (B) to (A) of 100:2 to 100:30.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a polyurethane resin having excellent antistatic properties.

[0002]

2. Description of the Related Art Conventionally, methods for imparting antistatic properties to polyurethane resins include, for example, a method in which an antistatic agent having an ionic bond introduced into a molecule is added to the polyurethane resin, and a method in which a hydrophilic polyol such as polyethylene glycol is added to the polyurethane resin. And the like are known.

[0003]

However, in the conventional method of adding an antistatic agent, the antistatic agent goes out of the polyurethane resin system with time (referred to as bleeding phenomenon), and the antistatic effect gradually decreases. There was a problem. In addition, the method of chemically bonding polyethylene glycol or the like to the polyurethane resin has a problem that the antistatic effect is small and a large amount of polyethylene glycol is required, so that the mechanical strength and chemical resistance of the polyurethane resin are significantly reduced. was there.

An object of the present invention is to provide a polyurethane resin having no bleeding phenomenon and having an excellent antistatic effect.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to solve such conventional problems, and as a result, have found an effective compound to be added to a polyurethane resin, and have completed the present invention. .

That is, the present invention provides a reaction product (A) of a polyisocyanate containing an isocyanate group-containing prepolymer comprising an alkoxypolyalkylene glycol and an isocyanate compound and an active hydrogen group-containing compound containing a trifunctional polyol compound. In a mass ratio to the polyurethane resin (B), (B) :( A) = 100:
A method for producing an antistatic polyurethane resin, characterized by being contained in a ratio of 2 to 100: 30.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The alkoxypolyalkylene glycol used in the present invention is represented by the following formula (1).

[0008]

Embedded image

Formula (1) represents a random copolymer or a block copolymer. R represents a low-molecular alkyl group such as methyl, ethyl or propyl, a low-molecular allyl group, or a low-molecular aryl group. R ₁ represents an ethylene group, and R ₂ represents a propylene group or a butylene group. m is an integer of 5 to 50,
n shows the integer of 0-20.

Preferred examples of the alkoxypolyethylene glycol used in the present invention include a number average molecular weight of 300.
2,000 methoxy polyethylene glycols.

The isocyanate compound used in the present invention includes phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylene diisocyanate, naphthylene diisocyanate, diphenylmethane diisocyanate and the like, and aromatic diisocyanates comprising isomers thereof. 6
-Aliphatic diisocyanates such as hexamethylene diisocyanate, tetramethylhexamethylene diisocyanate, and 1,12-dodecane diisocyanate; alicyclic diisocyanates such as cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate. Further, for example, a carbodiimide modified product, a uretonimine modified product by a carbodiimidization reaction, an isocyanate prepolymer by a reaction with a polyol, an isocyanate dimer or a trimer by an isocyanate self-reaction, and the like can also be mentioned. Also, a polyisocyanate partially or wholly stabilized with a blocking agent having one active hydrogen in the molecule such as methanol, n-butanol, benzyl alcohol, ethyl acetoacetate, ε-caprolactam, methyl ethyl ketone oxime, phenol, cresol, etc. Can also be mentioned.

The polyisocyanate used in the present invention contains an isocyanate group-containing prepolymer produced by the reaction between the above-mentioned alkoxypolyalkylene glycol and an isocyanate compound. In this case, the compounding molar ratio of the NCO group of the isocyanate compound and the OH group of the alkoxypolyalkylene glycol (NCO /
OH) is set to 2.0 or more.

Since it is desirable for the polyisocyanate to have less free isocyanate compound, excess free isocyanate compound may be removed as necessary.
The reaction between the alkoxypolyalkylene glycol and the isocyanate compound can be carried out under the usual urethanization reaction conditions. In this reaction, a solvent can be used if necessary. As the solvent that can be used, all solvents that can be generally used in a urethane reaction can be used.

The active hydrogen group-containing compound used in the present invention contains a trifunctional polyol compound.
Examples of the trifunctional polyol compound include glycerin, trimethylolpropane, diethanolamine, triethanolamine, dipropanolamine, tripropanolamine, and the like, and an average number of functional groups of about 3,
Polyethers having a number average molecular weight of 200 to 10,000,
Polyesters, polyester amides, polycarbonates and the like. Among them, amino group-containing diols are preferable, and diethanolamine, dipropanolamine and the like are particularly preferable.

The reaction product (hydrophilic reaction product) of the polyisocyanate and the compound containing an active hydrogen group in the present invention
Is obtained by mixing and reacting 3 moles of active hydrogen groups of the trifunctional polyol compound with respect to 1 mole of isocyanate groups of the polyisocyanate. Both reactions are carried out under the same conditions as in a normal urethanization reaction. When the polyol compound is dialkanolamine, 60
The reaction can be completed at a reaction temperature of about 3 hours.

The polyurethane resin in the present invention is an ordinary thermoplastic or thermosetting polyurethane resin obtained from a polyol, a chain extender and / or a crosslinking agent, an isocyanate compound and the like. As the polyol, the chain extender and / or the cross-linking agent, and the isocyanate compound used here, all of those usually used can be used.

For example, the polyol is a number average molecular weight of 200 to 1 usually used as a reaction partner of polyisocyanate.
000 polyethers, polyesters, polyesteramides, polycarbonates, and the like.

Examples of the polyethers include polymerization products of tetrahydrofuran, propylene oxide and ethylene oxide, copolymers of these, and graft polymers of vinyl monomers.

Examples of the polyesters and polyesteramides include those obtained by known methods from polyhydric alcohols and polycarboxylic acids, optionally using diamines and amino alcohols in combination. Examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and 1,4-cyclohexanedimethanol. Glycerin, trimethylolpropane and the like. Examples of the polycarboxylic acids include succinic acid, adipic acid, sebacic acid, dimer acid, phthalic acid, alkyl phthalates, trimellitic acid, pyromellitic acid, maleic acid, fumaric acid, and itaconic acid. Further, those obtained by ring-opening polymerization of cyclic esters such as butyrolactone, valerolactone, and caprolactone are also included.

The polyether esters are the same as the above-mentioned polyesters except that polyether polyol is used as a part of the polyhydric alcohols used in the above-mentioned polyesters.

Examples of the polycarbonates include esters of aliphatic diols or alicyclic diols such as 1,6-hexanediol and 1,4-cyclohexanedimethanol with cyclic carbonates such as dialkyl carbonate, diaryl carbonate and ethylene carbonate. A polycarbonate diol obtained by an exchange reaction is exemplified.

It is also possible to use natural polyols such as polyols already containing urethane or urea groups, castor oil, tar oil and carbohydrates. As other polyols, polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, hydrogenated polyisoprene polyol,
Silicon polyol and the like can also be used.

Examples of the chain extender and the crosslinking agent include ethylene glycol, propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-bis (β-hydroxyethoxy) benzene , Glycerin, polyhydric alcohols such as trimethylolpropane, ethylenediamine, hexamethylenediamine, hydrazine, diaminodiphenylmethane, isophoronediamine, diethyltolylenediamine, 3,3 '
-Dichloro-4,4'-diaminodiphenylmethane (M
OCA), polyamines such as various amino alcohols, amino alcohols, and water.

Examples of the isocyanate compound include the above-mentioned isocyanate compounds.

The polyurethane resin having excellent antistatic properties of the present invention can be obtained by adding 2 to 30% by mass of the hydrophilic reaction product of the present invention to an ordinary polyurethane resin. The method of containing, when producing a polyurethane resin, blending a hydrophilic reaction product as a part of the raw material,
This is performed by causing a polyurethane reaction. As the reaction conditions for the polyurethane conversion, those generally used are used.

When the content of the hydrophilic reaction product is 2% by mass
If the amount is less than 30, the antistatic property is low, and if it exceeds 30% by mass, an antistatic effect commensurate with the added amount cannot be obtained.

The mixing ratio of each component such as a polyol other than the hydrophilic reaction product can be selected according to a known method according to the performance of the final molded product.

The method for producing a polyurethane resin of the present invention comprises:
For example, in the case of a thermoplastic polyurethane resin, a polyol,
A method of mixing and stirring a hydrophilic reaction product, a chain extender and an isocyanate compound, transferring the mixture to a vat when the viscosity increases, and ripening the polyol or the like.
There is a method of kneading and reacting in a screw extruder, extruding in a string shape, and solidifying in water. In the case of a thermosetting polyurethane resin, a method of producing an isocyanate-terminated prepolymer from a polyol, a hydrophilic reaction product, and an isocyanate compound, then mixing a crosslinking agent, and injecting the mixture in a liquid state into a mold to cure the mixture. Etc. When producing a polyurethane resin, a solvent may be used, if necessary, to form a coating film.

In the present invention, a catalyst can be used if necessary. Examples of this catalyst include triethylamine, triethylenediamine, zinc octenoate, dibutyltin dilaurate and the like.

For the polyurethane resin obtained by the present invention, all the molding methods and molding conditions of thermoplastic polyurethane resins and thermosetting polyurethane resins which are generally used are applied. For example, electrostatic coating molding, extrusion molding,
It is formed by a molding method such as injection molding, blow molding, spray molding, injection molding, calendar processing, roll processing, press processing, centrifugal molding, and rotational molding.

The polyurethane resin obtained according to the present invention may contain other resins as required. Examples of other resins include ABS polymer, SAN polymer, polyvinyl chloride, polyvinyl alcohol, polystyrene, polyacetal, nylon, polyester, polycarbonate, epoxy resin, amino resin, and phenol resin.

The polyurethane resin obtained according to the present invention may optionally contain other substances such as antioxidants, ultraviolet absorbers, heat resistance improvers, colorants, inorganic and organic fillers,
An antiblocking agent, a plasticizer, a surfactant, a lubricant, an antistatic agent, a conductive agent, a reinforcing material, and a crosslinking agent such as a blocked isocyanate can be added.

[0033]

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 Synthesis Examples, Examples and Comparative Examples, “%” means “% by mass”.

Synthesis Example 1 In a 1,000 ml four-necked flask equipped with a stirrer equipped with an anchor-type stirring bar, a thermometer, a nitrogen gas inlet, etc., 70 methoxypolyethylene glycol having a number average molecular weight of 700 was added.
Then, 0 g was charged, and dehydration was performed at 80 ° C. under a reduced pressure of 2.7 kPa for 2 hours. After returning to normal pressure, 174 g of 2,4-tolylene diisocyanate (2,4-TDI) was charged and reacted at 70 ° C. for 4 hours to obtain an isocyanate group-containing compound A having an NCO content of 4.75%.

Synthesis Example 2 In a flask similar to Synthesis Example 1, a number average molecular weight of 1,000 was added.
Of methoxypolyethylene glycol was charged and dehydrated in the same manner. Isophorone diisocyanate (I
(PDI) 335 g, and reacted at 95 ° C. for 10 hours. In order to remove excess IPDI, IPDI was distilled off at 160 ° C. and 0.7 kPa using a rotary evaporator. An isocyanate group-containing compound B having an NCO content of 3.22% was obtained.

Synthesis Example 3 The same flask as in Synthesis Example 1 was charged with 884 g of the isocyanate group-containing compound A, and 105 g of diethanolamine was charged with water cooling and stirring. After the end of fever, 60
The reaction was carried out at 2 ° C. for 2 hours. NC by infrared absorbance analysis (IR)
Confirming that the O group has disappeared, the hydrophilic reaction product A
(Calculated hydroxyl value 113 mgKOH / g) was obtained.

Synthesis Example 4 In the same flask as in Synthesis Example 1, 1,300 g of the isocyanate group-containing compound B was charged, and 133 g of dipropanolamine was charged while cooling with water and stirring. After the exotherm was completed, the reaction was performed at 60 ° C. for 2 hours. It was confirmed by IR that the NCO group had disappeared, and a hydrophilic reaction product B (calculated hydroxyl value: 78 mgKOH / g) was obtained.

Example 1 A butylene adipate diol having a number average molecular weight of 1,000 and heated to 70 ° C.
0 g, 100 g of the hydrophilic reaction product A, 90 g of 1,4-butanediol, and 530 g of diphenylmethane diisocyanate (MDI) heated at 45 ° C. were mixed and stirred. When the viscosity starts to increase, transfer it to the vat,
Post-curing was performed at 0 ° C. for 30 minutes. After being left at room temperature for 7 days, the mixture was pulverized, and a sheet having a thickness of 3 mm was formed using an injection molding machine. JIS
As a result of obtaining the volume resistivity according to the test method of K6911,
It was 10 ⁹ Ωcm. 5.8% of hydrophilic reaction products in this polyurethane resin (thermoplastic polyurethane resin)
Met.

Comparative Example 1 In the same reactor as in Example 1, butylene adipate diol having a number average molecular weight of 1,000 and heated to 70 ° C.
g, 90 g of 1,4-butanediol and 505 g of MDI heated to 45 ° C., and a sheet was prepared in the same manner as in Example 1. The volume resistivity was determined to be 10 ¹⁴ Ωcm.

Example 2 In a stainless steel beaker, 1,000 g of polytetramethylene glycol (PTG) having a number average molecular weight of 1,000,
150 g of the hydrophilic reaction product A and 2,4-TDI31
3 g isocyanate-terminated prepolymer (NCO
100g (3.6% content) and heated to 85 ° C. 11 g of MOCA heated to 120 ° C. was added and mixed with an agitator. After mixing for 2 minutes, the mixture was poured into a flat mold heated to 120 ° C and cured at 120 ° C for 5 hours. As a result of determining the volume resistivity in the same manner as in Example 1, 1
0 ⁸ Ωcm. The hydrophilic reaction product in this polyurethane resin (thermosetting polyurethane resin) was 10%.

COMPARATIVE EXAMPLE 2 In the same beaker as in Example 2, an isocyanate-terminated prepolymer comprising 1,000 g of PTG having a number average molecular weight of 1,000 and 278 g of 2,4-TDI (NCO content: 3.8)
%) Was weighed and heated to 85 ° C. 120 ° C
Was added MOCA11g heated, create a sheet in the same manner as in Example 2, the results of obtaining the volume resistivity, 10 ¹⁴
Ωcm.

Example 3 In the same reactor as in Example 1, butylene adipate diol 2,000 having a number average molecular weight of 2,000 and heated to 80 ° C., 2,000
g, 150 g of the hydrophilic reaction product B, 270 g of 1,4-butanediol, dibutyltin dilaurate (DBTD
L) 0.09 g and hexamethylene diisocyanate (HDI) 696 g were charged, a sheet was prepared in the same manner as in Example 1, and the volume resistivity was determined. As a result, 10 ¹² Ωcm
Met. The hydrophilic reaction product in this polyurethane resin (thermoplastic polyurethane resin) was 4.8%.

Comparative Example 3 In the same reactor as in Example 1, butylene adipate diol 2,000 having a number average molecular weight of 2,000 heated to 80 ° C. 2,000
g, 1,4-butanediol 270 g, DBTDL0.
They were charged 09g and HDI679g, into a sheet in the same manner as in Example 1, the results of obtaining the volume resistivity, 10 ¹⁵
Ωcm.

[0044]

The polyurethane resin obtained according to the present invention has excellent antistatic properties. Applications of this polyurethane resin cover all fields used for thermoplastic resins and thermosetting resins. In the field of thermoplastic resin, for example, in the case of extrusion molding, oil and pneumatic tubes, fuel tubes, various hoses and tubes such as coating hoses, conveyor belts, air mats, diaphragms, keyboard sheets, synthetic leather, life jackets, Various types of extruded products such as wet suits, hot melt films, various films and spinnings, computer wiring, automobile wiring, various wires and cables such as curl cords, various drive belts, slip stoppers, etc. , Ball joints, dust covers, door lock strikers, spring covers, bearings, anti-vibration parts and other automotive parts, various gears, seals, connectors, rubber screens, printing drums and other mechanical parts, sports shoe soles, air cushions, women Shoe barriers such as shoe top lifts Parts, rollers, casters, also in the field of thermosetting resins, for example, various rolls, various gears, vibration damping component and the like. Further, the present invention can be applied to an adhesive, a paint, a sealing material, and the like using a solvent.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4J034 BA07 BA08 CA04 CA05 CA13 CA15 CB03 CB04 CB08 CE01 DA01 DB01 DB03 DB05 DF01 DF02 DF11 DF12 DF16 DF20 DF21 DF22 DG02 DG03 DG04 DG09 HA12 HC03 HC12 HC13 HC17 HC22 HC46 HC61 HC64 HC67 HC71 HC73 HD03 HD05 HD07 HD12 KA01 KA04 KC17 KD02 KD12 QD01 QD03 QD04 RA03 RA07 RA08 RA11 RA12 RA14

Claims (1)

[Claims] 1. A reaction product of a polyisocyanate containing an isocyanate group-containing prepolymer composed of an alkoxypolyalkylene glycol and an isocyanate compound with an active hydrogen group-containing compound containing a trifunctional polyol compound (A) is a polyurethane resin. A method for producing an antistatic polyurethane resin, characterized in that it is contained in a mass ratio of (B) :( A) = 100: 2 to 100: 30 with respect to (B).