JP2001151840A - Method for producing urethane-urea particle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing urethane-urea particles which do not have problems such as friction and static electricity and have excellent heat resistance, chemical resistance, hydrolysis resistance, mechanical strengths, and so on. SOLUTION: This method for producing urethane-urea particles, characterized by reacting (a) an alkoxypolyethylene glycol with (b) an organic polyisocyanate in a (a):(b) weight ratio of 0.1:99.9 to 10.0:90.0, and then emulsifying, dispersing and curing (A) the obtained self-emulsifying type polyisocyanate with (B) water in a (A):(B) weight ratio of 1:99 to 30:70.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing urethane-urea powder.

[0002]

2. Description of the Related Art Polymer powders are used as fillers, matting agents for paints, compounding agents such as suede paints and velvet paints, and additives for cosmetics. JP-A-3-9771
No. 1 discloses a method in which a hydroxyl group-containing surfactant is mixed with a diisocyanate compound or the like, and the mixture is insoluble and emulsified and dispersed in an isocyanate group non-reactive solvent. A method of obtaining without using has been proposed.

[0003]

However, since the method described in Japanese Patent Application Laid-Open No. 3-97711 uses an organic solvent, consideration must be given to accidents due to friction and static electricity.

[0004]

Means for Solving the Problems According to the present invention, as a result of intensive studies to solve the above problems, it was found that urethane-urea powders can be produced in water by using a specific polyisocyanate. The present invention has been completed.

That is, the present invention provides (a) an alkoxypolyethylene glycol and (b) an organic polyisocyanate, wherein the mass ratio of (a) to (b) is (a) :( b) = 0.
(A) a self-emulsifying polyisocyanate obtained by reacting at a ratio of 1: 99.9 to 10.0: 90.0,
(B) Water is added at a mass ratio of (A) :( B) = 1: 99-3.
This is a method for producing a urethane-urea powder, characterized in that it is emulsified, dispersed, and cured at a ratio of 0:70.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The (A) self-emulsifying type polyisocyanate used in the present invention comprises (a) an alkoxypolyethylene glycol and (b) an organic polyisocyanate.
The mass ratio of (a) and (b) is (a) :( b) = 0.1: 9
9.9 to 10.0: 90.0, preferably (a):
(B) = 0.5: 99.5 to 8.0: 92.0.

If the amount of (a) is too large, the resulting urethane-urea powder tends to have insufficient mechanical strength and durability. When (a) is too small, (A) the self-emulsifying polyisocyanate is hardly emulsified and dispersed,
A pulverizing step is required to make the powder.

(A) The alkoxy polyethylene glycol is obtained by ring-opening addition of ethylene oxide by a known method using a monol such as methanol, ethanol or propanol as an initiator. In addition, a monool obtained by ring-opening addition of a mixture of ethylene oxide and propylene oxide can be used, but in this case, the ethylene oxide content of the mixture is required to be 50% by mass or more.
Further, the initiator is preferably one having 5 or less carbon atoms.

The number average molecular weight of the alkoxy polyethylene glycol is preferably from 300 to 2,000, particularly preferably from 35 to 2,000.
0 to 1,000 is most preferred. When the number average molecular weight is too small, (A) a self-emulsifying polyisocyanate
It is difficult to emulsify and disperse in water. When the number average molecular weight is too large, the resulting urethane-urea powder tends to have insufficient mechanical strength and durability.

(B) The organic polyisocyanate includes ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate, 2,4,4-trimethylhexane diisocyanate lysine diisocyanate, 6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, 1,4-cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, ortho-xylylene diisocyanate , Meta-xylylene diisocyanate, para-xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, naphthylene diisocyanate, paraphenylene diisocyanate, polyphenylene polymethylene Examples include polyisocyanate, crude tolylene diisocyanate, and mixtures of two or more thereof.
Modified products of these polyisocyanates (such as carbodiimide group, uretonimine group, uretdione group, isocyanurate group, urea group, biuret group, and allophanate group-containing modified polyisocyanate) can also be used.

The (b) organic polyisocyanate preferred in the present invention is an isocyanurate-modified polyisocyanate of hexamethylene diisocyanate in consideration of weather resistance and the like, and diphenylmethane diisocyanate and polyphenylene polymethylene polyisocyanate in consideration of mechanical strength and the like. Is a mixture of

The (A) self-emulsifying polyisocyanate can be reacted with other active hydrogen group-containing compounds, if necessary, in addition to the above (a) and (b). Examples of the active hydrogen group-containing compound include methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, t-butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, benzyl alcohol, Low molecular weight monools such as cyclohexanol and alkylene glycol monoalkyl ether; low molecular weight primary monoamines such as ethylamine, butylamine and aniline; low molecular weight secondary monoamines such as diethylamine, dibutylamine and methylaniline; active hydrogen group-containing C6 or more carbon atoms such as polyester, active hydrogen group-containing polyether having less than 50 mol% of ethylene oxide units, active hydrogen group-containing polycarbonate, active hydrogen group-containing polyolefin, ricinoleic acid, etc. Include hydroxy higher fatty acid or its esters and the like.

Next, a specific manufacturing process will be described. First, (A) self-emulsifying type polyisocyanate is charged into (B) water, and is emulsified and dispersed by stirring. At this time, an emulsifier can be used if necessary. From the middle of the dispersion, the reaction between the isocyanate group and water gradually progresses.
At this time, it is important that stirring is not stopped. This is because, when the stirring is stopped, the particles are aggregated and do not become powder. The average particle size of the powder is determined by the stirring speed,
It can be controlled by the amount and type of the (a) alkoxypolyethylene glycol (A) introduced into the self-emulsifying polyisocyanate, the emulsifier, and the like. The stirring speed is 2 minutes per minute.
It is preferably at least 00 times. The end of the reaction is where the isocyanate groups no longer remain. Thereafter, the resultant is filtered, dried and sieved to obtain a desired urethane-urea powder.

The urethane-urea powder obtained in this manner is spherical, and has an average particle size of 500 μm or less.

[0015] Additives and auxiliaries can be added to the obtained urethane-urea powder if necessary. As additives and auxiliaries, pigments, dyes, viscosity modifiers, leveling agents, anti-gelling agents, light stabilizers, antioxidants, ultraviolet absorbers, heat resistance improvers, inorganic and organic fillers, plasticizers, Examples include a lubricant, an antistatic agent, a reinforcing material, a catalyst, a thixotropic agent, a surfactant, and an emulsifier.

[0016]

According to the production method of the present invention, since no organic solvent is used, there is no problem of friction and static electricity, and the desired product can be produced safely. Furthermore, at the time of emulsification and dispersion, it is not necessary to use a dispersant such as a surfactant. The urethane-urea powder obtained according to the present invention is excellent in heat resistance, chemical resistance, hydrolysis resistance, mechanical strength and the like. Urethane-urea powder obtained by the present invention is a filler,
It can be used as a matting agent for paint, a compounding agent such as suede-like paint and velvet-like paint, an additive for cosmetics, and the like.

[0017]

EXAMPLES The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. In Examples and Comparative Examples,
“%” Means “% by mass”.

[Production of Self-Emulsifying Polyisocyanate] Synthesis Example 1 Isocyanurate-modified polyisocyanate of hexamethylene diisocyanate was placed in a reactor having a capacity of 1,000 ml equipped with a stirrer, a thermometer, a nitrogen seal tube, and a cooler. 980 g of (Coronate (registered trademark) HX manufactured by Nippon Polyurethane Industry) and 20 g of methoxypolyethylene glycol having a number average molecular weight of 400 were charged, and 70 ° C.
After reacting for hours, the self-emulsifying polyisocyanate P-1
I got

Synthesis Example 2 In a reactor similar to Synthesis Example 1, 970 g of a mixture of diphenylmethane diisocyanate and polyphenylene polymethylene polyisocyanate (Millionate (registered trademark) MR-200, manufactured by Nippon Polyurethane Industry), and methoxypolyethylene having a number average molecular weight of 800 were used. 30 g of glycol was charged and reacted at 70 ° C. for 3 hours to obtain a self-emulsifying polyisocyanate P-2.

Synthesis Example 3 In a reactor similar to Synthesis Example 1, 850 of coronate HX was added.
g, 150 g of methoxypolyethylene glycol having a number average molecular weight of 400 was charged and reacted at 70 ° C. for 3 hours.
A self-emulsifying polyisocyanate P-3 was obtained.

[Production of urethane-urea powder granules] Example 1 A reactor equipped with a stirrer, a thermometer, a nitrogen seal tube, and a cooler and having a capacity of 1,000 ml was charged with 450 g of ion-exchanged water and P- 50 g of 1 was added, and the stirring speed was 50 per minute.
Emulsified and dispersed 0 times. While maintaining the stirring speed, P-
1 and water were reacted. Carbon dioxide was generated as the isocyanate groups reacted with water. The reaction was terminated when the absorption peak of the isocyanate group in the IR of the reaction product disappeared. The emulsification and dispersion and the reaction were all performed at room temperature. After completion of the reaction, the mixture was filtered and dried to obtain urethane-urea powder. The average particle size of the obtained urethane-urea powder was 300 μm.

Example 2 A urethane-urea powder was obtained in the same manner as in Example 1 except that P-1 was changed to P-2. The average particle size of the obtained urethane-urea powder was 150 μm.
Met.

Comparative Example 1 A production was attempted in the same manner as in Example 1 except that P-1 was changed to P-3. As a result, a lump-shaped foamed material was obtained. did not become.

Comparative Example 2 A production was attempted in the same manner as in Example 1, except that coronate HX was used instead of P-1. Did not.

 ──────────────────────────────────────────────────続 き Continued on front page F term (reference) 4F070 AA53 DA40 DC07 DC11 4J034 BA01 BA03 CA01 CA02 CA04 CA11 CA12 CA13 CB03 CC26 CC45 CC52 CC61 CC65 CD04 DA01 DA03 DB04 DE01 DF01 DF02 DG01 DG02 DG03 DG14 DP12 HA01 HA06 HA07 HB06 HC02 HC03 HC09 HC11 HC12 HC13 HC22 HC23 HC24 HC25 HC32 HC34 HC35 HC44 HC46 HC47 HC52 HC61 HC63 HC64 HC65 HC66 HC67 HC71 HC73 JA03 JA25 JA27 LA08 QC04 RA07 RA17

Claims (1)

[Claims] (1) An alkoxypolyethylene glycol and (b) an organic polyisocyanate are combined with (a) and (b)
(A) :( b) = 0.1: 99.9-10.
(A) Self-emulsifying polyisocyanate obtained by reacting at a ratio of 0: 90.0 and water (B) at a mass ratio of (A) :( B) = 1: 99 to 30:70. A method for producing a urethane-urea powder, which is emulsified, dispersed, and cured.