JPS5950167B2 - Urethane prepolymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention comprises 80 to 30% by weight of urethane prepolyfoe,
Compound 1 having 1 mol of organic diisocyanate and 1 hydroxyl group and having no other functional group that reacts with the isocyanate group
The present invention relates to a urethane prepolyfoo composition comprising 20 to 70% by weight of adducts with moles.

Conventionally, various polyurethane paints have been commercially available, but since they all require a large amount of diluting solvent when used, they have caused problems such as air pollution, solvent poisoning, flammability and explosion, and skin damage.

For this reason, there is currently active research into high solids (high solids content) paints, which are not solvent-based paints, but they tend to degrade product performance, change physical properties over time, and are not always satisfactory. There are no kimonos in sight.

In view of the above circumstances, the present inventors have conducted various studies on making polyurethane paints high-solid, and as a result, they have developed an adduct of 1 mole of organic diisocyanate and 1 mole of a compound represented by a monoalcohol into a urethane prepolycarbonate. The present invention was achieved by discovering that a significantly high solidity can be achieved by incorporating a specific amount of .

In the present invention, the adduct of 1 mole of organic diisocyanate and 1 mole of a compound represented by a monoalcohol is liquid at room temperature or slightly warmed, and has one reactive group, so it cannot be used in the form of a paint. It acts as a solvent for urethane prepolyfoam, and during coating film formation, it chemically bonds to the coating resin through isocyanate groups and acts as a reactive diluent.

Therefore, compared to conventional solvent-based urethane prepolyfoo,
The amount of solvent used that evaporates into the atmosphere is significantly reduced. That is, the present invention uses 80 to 30% by weight of urethane prepolymer.
, exists in a urethane prepolymer composition consisting of 20 to 70% by weight of an adduct of 1 mol of an organic diisocyanate and 1 mol of a compound having one hydroxyl group and having no functional group that reacts with the isocyanate group. .

To explain the present invention in detail, in the present invention, an adduct (hereinafter referred to as " When the organic diisocyanate is represented by OCN-Z-)-NCO and the compound represented by the monoalcohol is represented by ROH, it is represented by the following formula.

0CN-Z-NCO+ROH Particularly preferred organic diisocyanates in the present invention include hexamethylene diisocyanate, 2.4- or 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, isocyanate, 4,4'-dicyclohexylmethane diisocyanate, ω,d-diisocyanatodimethylcitalohexane, lysine diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate, etc. Examples include isocyanates, but other diisocyanates can of course also be used.

In the present invention, examples of compounds having one hydroxyl group and no other functional groups that react with isocyanate groups include methyl alcohol, ethyl alcohol, n-propyl alcohol, IsO-propyl alcohol, n-butyl alcohol, IsO-butyl alcohol, Sec-butyl alcohol, tert-butyl alcohol, amyl alcohol, isoamyl alcohol, 3-pentanol,
Cyclohexanol, n-hexanol, methyl amyl alcohol, n-heptyl alcohol, n-octanol, 2-ethylhexanol, n-decyl alcohol,
Lauric alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, furfuryl alcohol, 3-methoxybutanol, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diacetone alcohol and their ethylene oxide, propylene oxide adducts and mixed alcohols ( Alcohols produced from the oxo reaction of α-olefins), but especially alcohols with 3 to 3 carbon atoms.
12 aliphatic alcohols, mixed alcohols having an average carbon number of 6 to 10, or adducts of these with ethylene oxide and propylene oxide are preferred.

The above 1:1 adduct can be easily produced according to conventional methods.

However, during the reaction, the 1:2 adduct RO-C-NH-Z
Since -NH-C-0R is also produced as a by-product, it is desirable to conduct the reaction at a NCO/OH equivalent ratio of 2 to 8, preferably 3 to 6, and a reaction temperature of 0 to 100°C, preferably 0 to 30°C. The reaction time is 5 to 10 hours. In addition, if necessary, ordinary urethanization catalysts such as tertiary amine compounds such as triethylamine and triethylene diamine, organotin compounds such as dibutyltin dilaurate and dibutyltin dioctoate, zinc octenoate, lead octenoate, and manganese acetylacetonate may be used. Alternatively, acetic acid esters such as ethyl acetate and butyl acetate, ketones such as acetone and methyl ethyl ketone, ethers such as dioxane and tetrahydrofuran, and aromatic hydrocarbon solvents such as toluene and xylene may be used as the solvent. It's okay.

By removing excess isocyanate monomer from the product thus obtained by an appropriate method such as distillation extraction,
A 1:1 adduct is obtained.

In this case, some 1:2 adduct is mixed in, but 2
The mixing amount is 0% by weight or less, and it has almost no effect on the viscosity of the adduct, and the urethane prepoly J mixed with the adduct
There is no problem since the properties of the urethane film produced by using this method do not deteriorate at all. Next, the obtained 1:1 adduct is blended into a urethane prepolymer, but the 1:1 adduct is preferably liquid in the range of 10 to 50°C.
The urethane prepolymer is not particularly limited, and for example, hexamethylene diisocyanate (hereinafter abbreviated as HMDI), which is used as a common paint base.
, 2,4 or 2,6-tolylene diisocyanate (hereinafter abbreviated as TDI), xylylene diisocyanate, naphthalene-1,5-disocyanate, diphenylmethane diisocyanate, 3-isocyanatomethyl- 3,
Polyisocyanate such as 5,5-trimethylcyclohexyl isocyanate (hereinafter abbreviated as IPDI) and ethylene glycol, propylene glycol, butylene glycol, diethyllene glycol, inopentyl glycol, trimethylolpropane, polypropylene glycol, polyester polyol (terminated with an isocyanate group) from polyols such as
Examples include urethane prepolymers. The blending amount of the 1:1 adduct to the urethane prepolymer is 20 to 70% of the total amount of the urethane prepolymer and the 1:1 adduct.
Preferably weight %. is 30 to 60% by weight.

If it is less than 20% by weight, the effect of increasing the solidity will be small.
If the amount is 0% by weight or more, the properties such as solvent resistance when formed into a coating film will not be sufficient.

The blending method is not particularly limited, and may be blended according to a conventional method such as: - Adding the adduct to a predetermined amount of urethane prepolymer and stirring until uniform.

As mentioned above, the urethane prepolyfluoride composition of the present invention has been explained by giving an example of a preferable manufacturing method. However, the urethane prepolyfluoride composition of the present invention is not limited to the above method. A compound having a hydroxyl group and no other functional group that reacts with an isocyanate group and a polyol are simultaneously supplied to a reaction vessel, and the raw material supply ratio is adjusted to cause the reaction, thereby producing the urethane of the present invention at once. Prepolymer compositions can also be produced.

For example, if a polyol containing 20 to 70% by weight of a compound having one hydroxyl group and no other functional groups that react with isocyanate groups and an organic diisocyanate are used, one NCO
/0H equivalent ratio 2-8 preferably 3-6, reaction temperature 0-1
The reaction is carried out at 00°C, preferably 0 to 30°C. The reaction is usually completed in 5 to 10 hours. The desired urethane prepolymer composition is obtained by removing excess organic diisocyanate and knobs from the reaction solution thus obtained, for example, by thin film distillation, extraction, or the like. Therefore, the urethane prepolyfoo composition of the present invention is a liquid with low viscosity at room temperature, and can be used as it is, with slight heating, or only by dissolving in a small amount of diluent, and can be used without dilution in a large amount. It is extremely easy to operate as it does not require any agents.

In addition, there are few problems such as air pollution, flammability and explosion, solvent poisoning, skin damage, etc., and it is extremely advantageous industrially. Furthermore, the coating film of the paint using the urethane prepolyfoam composition of the present invention is as follows:
As is clear from the test examples below, it has a housing capacity that is equal to or better than conventional products, and there is no change in housing capacity over time.
Hereinafter, the present invention will be explained in more detail with reference to Reference Examples and Examples.

Note that "parts" and "%" mean "parts by weight" and "% by weight." Reference example 1 80-TDI in a four-loop flask with a thermometer, condenser, stirring bar, and dripping load
(2.4 tolylene diisocyanate 80%) 34
Charge 8θ (4 equivalents) and maintain at 20°C.

To this, n-butanol 741 (1 equivalent) was gradually added dropwise to react with stirring. After the dropwise addition was completed, the reaction was carried out at 20° C. for 5 hours, and the isocyanate group (NCO) content of the reaction solution was measured by a conventional method and found to be 29.8%. (Theoretical value 29
．． 9%). The reaction solution thus obtained was heated to 120°C and 0.0
1m7dIP deprived membrane distillation was carried out. Steam. The distillation residue is the desired reaction diluent, and the NCO content of this is 16.8.
The NCO content of the (1:1) adduct of TDI, .n-butanol is 16.94%) and the viscosity at 25°C was 194 centipoise. In addition, this product is used as gel permeation croftography (hereinafter referred to as G
The content of the (1:1) adduct was 99.3%, and the residual TDI was 0.2.
It was 4%. Reference Example 2 The following formulation was carried out using the same equipment and conditions as in Reference Example 1, and the results shown in Table 1 were obtained.

Reference Examples 3 to 7 Using the same apparatus and conditions as Reference Example 1, 80-TDI and various monoalcohols were reacted at NCO/0H=4, and excess TDI was removed by distillation. The quality was as shown in Table 2.

Reference Examples 8 to 13 Using the same equipment as Reference Example 1, 3
NCO/OH=4 in IPDI containing dibutyltin dilaurate of 0.2-X) (to 1 PDI) at 0°C.
Add monoalcohol in a proportion of .

After the dropwise addition was completed, the mixture was stirred at 30°C for 5 hours to complete the reaction.
The reaction solution thus obtained was subjected to thin film distillation at 160° C. and 0.01° H9, and the desired reaction diluent was obtained as shown in Table 3. Reference Example 14 In the same manner as Reference Example 1, hexamethylene diisocyanate and Sec-butanol were heated to NCO-0H=4 at 30°C.
The mixture was reacted at 60° C. for 6 hours, and further aged at 60° C. for 3 hours.

When excess hexamethylene diisocyanate was removed from the reaction product by thin film distillation, the NCO content of the distillation residue was 14.3% [(1:1), and the NCO content of the adduct was 1
7.3%], and the viscosity at 25°C is 150
CPS″c was also obtained. When this product was analyzed by CPS, the content of the (1:1) adduct was 81.5%, and the residual hexamethylene diisocyanate was 0.7% or less.Example A portion of ethyl acetate from 1 L of 1D Esmodeur (Bayer Corporation trademark, ethyl acetate solution, non-volatile content 75%, isocyanate group content 13.0%, viscosity (25°C) 2000 centipoise) was removed under reduced pressure under heating. , 100 parts of a product with a non-volatile content of 85% were manufactured.

When 72 parts of the TDI-n-butanol adduct of Reference Example 1 was added to this, a product with a nonvolatile content of 92% and a viscosity of 2000 centiboise (25°C) was obtained (composition I). Composition Maki 0] was added to 100 parts, DeSmorphen-1100 and DeSmorphen-1800 (Bayer Corporation trademark, polyester polyol, OH content 6.5%, 8.8% respectively)
%. ) are mixed in an amount of 40.4 parts each. Furthermore, the food cup Af). 4, add thinner (equal mixture of butyl acetate, ethyl acetate, toluene, and ethylene glycol monoethyl ether acetate) for 20 to 30 seconds.
When the solution was diluted with water to form a paint solution that could be spray coated, the non-volatile content was 73%. This paint liquid is 150 x 70
The physical properties of the coating film sprayed on a polished steel plate and baked at 80° C. for 40 minutes were measured and were as shown in Table 4. It conformed to the JIS-K54OO coating film property test method.

As mentioned above, when using the urethane monopolymer composition of the present invention, spray coating can be achieved with a small amount of diluent, and excellent film control properties can be obtained.

Example 2 Takenate D-140N (trademark of Takeda Pharmaceutical Co., Ltd., ethyl acetate solution, non-volatile content 75%, viscosity 2100 centipoise (25°C), isocyanate group content 10.2%) 1
By adding 80 parts of the IPDI-n-octanol adduct of Reference Example 8 to 00 parts, a composition with a nonvolatile content of 86% and a viscosity of 400 centipoise (25°C) was obtained (Composition 1).

Composition 1 to 100 parts Desmorphen 110065
1 part and 0.2 part of dibutyl tin jilau l note were mixed, and further diluted with the thinner of Example 1 for 20 to 30 seconds using a food cup ▲4 to make a paint solution that could be sprayed and was non-volatile. The percentage was 69%. Spread this paint solution onto a 150 x 70 mm polished steel plate, and
When the physical properties of the coating films baked at 00°C for 40 minutes were measured, the coating film ratios were as shown in Table 5. As mentioned above, when using the polyurethane composition of the present invention, it can be coated with a small amount of diluent, and the quality of the coating film is also good.

Example 3 80-TDI279fl (3.
2) was charged and kept at 20°C.

A uniform mixture of 13.41 (0.3 equivalents) of trimethylolpropane, 1,3-butanediol (0.1 equivalents) and 29.61 (0.4 equivalents) of n-butanol was gradually added dropwise to this. Make it react.

After completion of the dropwise addition, the reaction was carried out at 20°C for 6 hours, and the isocyanate group (NCO) content was measured by a conventional method and was found to be 31.0%.
(theoretical value 30.7%). The reaction solution thus obtained was heated to 150°C and 0.02mmHf! thin film distillation was carried out. The NCO content of the obtained urethane prepolymer (1 composition) was 17.8%, and the viscosity at 25°C was 7680 centipoise. Further, when this product was analyzed by GPC, it was found that the TDI (the content of the (1:1) adduct of 5n-butanol was 54.301), and the residual TDI was 0.
It was 31%.

The above Urinotanp lnopolymer composition [] (NCO content 17.8%, viscosity (25°C) 7680 centipoise)
47.5 parts of DeSmorphen-1100 and 47.5 parts of DeSmorphen-800 are mixed with 100 parts.

Claims (1)

[Scope of Claims] 1. An adduct of 80 to 30% by weight of urethane prepolymer, 1 mole of organic diisocyanate, and 1 mole of a compound having one hydroxyl group and no other functional group that reacts with the isocyanate group. A urethane prepolymer composition comprising 20 to 70% by weight. 2 From 70 to 40% by weight of a urethane prepolymer, 30 to 60% by weight of an adduct of 1 mol of an organic diisocyanate and 1 mol of a compound having one hydroxyl group and no other functional group that reacts with the isocyanate group The urethane prepolymer composition according to claim 1.