JPH03244619A - Production of polyurethane resin and polyurethane resin composition - Google Patents

Abstract

PURPOSE:To produce a polyurethane resin improved in mechanical properties and hydrolysis, light and sweat resistances by reacting a polycarbonate polyol with an alicyclic polyisocyanate and an aromatic polyisocyanate. CONSTITUTION:A polycarbonate polyol (A) with a mol.wt. of 1,000-3,000 (e.g. polyhexamethylene carbonate diol) is made to react with an alicyclic polyisocyanate (B) (e.g. dicyclohexylmethane diisocyanate) in an equivalent ratio of 10/90 to 90/10 and an aromatic polyisocyanate (C) (e.g. diphenylmethane diisocyanate) in an equivalent ratio of the hydroxyl groups of component A to the total isocyanate groups of components B and C of (0.6-1):1 at 20-120 deg.C for 30 min to 24 hr in an organic solvent (e.g. acetone) to obtain a polyurethane resin.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for producing a polyurethane resin that has excellent mechanical properties, hydrolysis resistance, light resistance, and sweat resistance, and a method for producing a polyurethane resin obtained thereby. The present invention relates to a polyurethane resin composition containing as an essential component. In particular, the present invention relates to a method for producing a polyurethane resin useful for applications requiring high physical properties and durability, such as furniture and vehicle seats, and a polyurethane resin composition containing the resulting polyurethane resin as an essential component.

(Prior Art) Polyurethane resins are widely used in molding materials, synthetic leather, adhesives, coatings, etc. due to their excellent properties.

However, in recent years, even more advanced properties have been required, and special performance has been required for new applications.

Particularly in the summer, when people sweat actively, furniture and vehicle seats that are often touched by human hands and feet and are exposed to strong sunlight are subject to significant deterioration.

Therefore, in addition to the mechanical properties, hydrolysis resistance, and light resistance of conventional polyurethane resins, it is desired to develop a polyurethane resin that provides a film that exhibits extremely low deterioration due to sweat and has excellent sweat resistance. ing.

Polyurethane resins with relatively hard sweat resistance include polyether diols such as polyoxytetramethylene diol and 1,4-butanediol, dicyclohexylmethane (alicyclic polyisocyanate), and diphenylmethane diisocyanate (aromatic polyisocyanate). isocyanate)
The polyurethane resin reacted with
It is described in Publication No. 414.

(Problems to be Solved by the Invention) However, the polyurethane resin described in the above publication still had insufficient sweat resistance. Moreover, the mechanical properties
At present, a polyurethane resin that has excellent sweat resistance as well as hydrolysis resistance and light resistance has not yet been obtained.

(Means for Solving the Problems) As a result of intensive research into polyurethane resins that meet these requirements, the present inventors have completed the present invention.

That is, the present invention combines polycarbonate polyol (A) and 1
, a method for producing a polyurethane resin characterized by reacting an aromatic polyisocyanate (B) and an alicyclic polyisocyanate (C), and a polyurethane resin composition containing the polyurethane resin obtained thereby as an essential component. It is something that provides something.

The polycarbonate polyol (A) according to the present invention is
It refers to a polyol having one repeating unit of a carbonate bond, that is, an -OC〇- bond, and includes, for example, polyhexamethylene carbonate diol, polytetramethylene carbonate diol, and the like. Among these, polycarbonate diols having a molecular weight of 1,000 to 3,000 are preferred.

The alicyclic polyisocyanate (B) includes known and commonly used ones, such as dicyclohexylmethane diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate, 2,2-dicyclohexylpropane diisocyanate, di(3-methylcyclohexyl)methane diisocyanate, and 1 mol of trimethylolpropane. and 3 moles of dicyclohexylmethane diisocyanate, adducts of 1 mole of pentaerythritol and 4 moles of dicyclohexylmethane diisocyanate, or mixtures thereof, etc. Polyisocyanates having two or more cyclohexane rings, especially isocyanates, Dicyclohexylmethane diisocyanate is preferred.

Aromatic polyisocyanates (C) include known and commonly used ones, such as tolylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate,
2.2-Diphenylpropane diisocyanate, di(3
-methylphenyl)methane diisocyanate, 2.2-
di(3-methylphenyl)propane diisocyanate,
Examples include an adduct of 1 mol of trimethylolpropane and 3-1-7 L/tolylene diisocyanate, an adduct of 1 mol of pentaerythritol and 3 mol of tolylene diisocyanate, or a mixture thereof, among which aromatic diisocyanates, especially Diphenylmethane diisocyanate is preferred.

Polycarbonate polyol (A), alicyclic polyisocyanate (B), and aromatic polyisocyanate (C)
In the combination, the polycarbonate polyol (A) is polyhexamethylene carbonate diol having a molecular weight i, ooo to 3,000, the alicyclic polyisocyanate (B) is dicyclohexylmethane diisocyanate, and the aromatic polyisocyanate (C ), polyurethane resins made of diphenylmethane diisocyanate are preferred because they provide particularly excellent sweat resistance as well as mechanical properties, hydrolysis resistance, and light resistance.

In the method for producing a polyurethane resin of the present invention, the polycarbonate polyol (A), the alicyclic polyisocyanate (B), and the aromatic polyisocyanate (C)
The order of the reaction is not particularly limited.

As for the reaction order, polycarbonate polyol (A)
and an alicyclic polyisocyanate (B) and then reacted with an aromatic polyisocyanate (C), and a method in which a polycarbonate polyol (A) and an aromatic polyisocyanate (C) are reacted and then an alicyclic polyisocyanate (B) is reacted with the aromatic polyisocyanate (C). A method of reacting isocyanate (B) can be mentioned.

Polycarbonate polyol (A), alicyclic polyisocyanate (B), and aromatic polyisocyanate (C)
The reaction with can be carried out without a solvent, in an organic solvent, or in water, but usually in an organic solvent with 20 to 120
C1 Preferably carried out at 30-100'C for 30 minutes to 24 hours.

The equivalent ratio of the hydroxyl groups of the polycarbonate polyol (A) to the total isocyanate groups of the alicyclic polyisocyanate (B) and aromatic polyisocyanate (C) is not particularly limited, but is usually 0.6:1 to 1. :1.

The equivalent ratio of alicyclic polyisocyanate (B) and aromatic polyisocyanate (C) in the present invention is usually 10/90.
~90/10, especially 50150 ~ 80/20 is preferred because it has excellent mechanical properties and light resistance.

In the method for producing a polyurethane resin of the present invention, a tertiary amine catalyst and/or an organometallic catalyst may be used to accelerate the reaction, if necessary. Examples of organic solvents that can be used in the method for producing polyurethane resins of the present invention include ethyl acetate, butyl acetate, cellosolve, cellosolve acetate, acetone, methyl ethyl ketone, cyclohexanone, toluene, xylene, dimethylformamide, dimethylacetamide, isopropanol, and the like. can be mentioned. Of course, these organic solvents can also be added during the reaction.

In the method for producing a polyurethane resin of the present invention, if necessary, at the beginning of the reaction or during the reaction,
Or, at the end of the reaction, alcohol such as methanol, ethanol, propatool, 1,3-butylene glycol,
And/or amine compounds such as dimethylamine, diethylamine, dipropylamine, dibutylamine, etc. may be added for the purpose of stopping the reaction or adjusting the molecular weight.

In the method for producing a polyurethane resin of the present invention, polyols, polyisocyanates, polyamines, etc. other than the above polycarbonate polyol (A), alicyclic polyisocyanate (B), and aromatic polyisocyanate (C) are used as appropriate. You can also do that.

Examples of polyols other than polycarbonate polyol (A) include low-molecular polyols with a molecular weight of less than 300 and high-molecular polyols with a molecular weight of 300 or more. 3,000 polymeric polyols are preferred. Examples of low-molecular polyols include low-molecular polyols that can be used as raw materials for high-molecular polyols described later.

Examples of the polymer polyol include polyester polyols, polyether polyols, polyether ester polyols, and polyamide polyols.

Examples of polyesters include ethylene glycol, 1
．． 2-propylene glycol, 1.3-propylene glycol, 1.3-butylene glycol, 1.4-butylene glycol, 2.2-dimethyl=1°3-propanediol, 1.6-hexanediol, 3-methyl- 1,
5-bentanediol, 1,8-offranediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4
--One or more types of dimethacrylic acid, succinic acid, maleic acid, adipic acid, glutaric acid, pimelic acid, superic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, hexahydroisophthalic acid, etc. Examples include combinations with one or more of the following. Further, ring-opening polymers such as γ-butyrolactone and ε-caprolactone using the above diol as an initiator can also be mentioned. Examples of polyether polyols include ethylene oxide, propylene oxide, butylene oxide, and styrene oxide, each of which uses the above diol as an initiator, or two of them.
Examples include ring-opening polymers of more than one species. Also included are ring-opening polymers of tetrahydrofuran.

Polyisocyanates other than alicyclic polyisocyanate (B) and aromatic polyisocyanate (C) include hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 1 mol of trimethylolpropane and hexamethylene diisocyanate. Examples include an adduct with 3 moles of pentaerythritol and an adduct with 1 mole of pentaerythritol and 4 moles of hexamethylene diisocyanate.

Examples of the amine include ethylenediamine, propylene diamine, hexamethylene diamine, trimethylhexamethylene diamine, isophorone diamine, diaminocyclohexane, methyldiaminocyclohexane, diaminodiphenylmethane, cyamino diphenyl sulfone, diaminodiphenylpropane, diaminoperhydrobiphenyl, 2° 2-di(aminocyclohexyl)propane,
Diaminodicyclohexylmethane, piperazine, 2-methylpiperazine, diamino(m-chlorophenyl)methane, 2,5-dimethylpiperazine 3,9-bis(aminopropyl 2,4,8,10-tetraoxaspiro[5,
5] undecane, etc.

The polyurethane resin composition of the present invention may further contain antioxidants, ultraviolet absorbers, hydrolysis inhibitors, dyes,
Pigments, fillers, etc. can be added for use.

(Example) Examples will be shown next, but the present invention is not limited to these examples.
All data except retention are based on weight.

The method for producing the polyurethane resin film and the methods for measuring mechanical properties, hydrolysis resistance, light resistance, and sweat resistance are as follows.

After casting each polyurethane resin solution of Bouren onto a release paper and drying it at 80"C for 30 minutes,
The film was left in a 65% atmosphere for 24 hours or more to form a film of about 50 microns.

Toyohashi Sakusei I plate fixed polyurethane resin film 19-21" C1 relative humidity 60
It was pulled at a tensile speed of 300 mm/min in an atmosphere of ~65%, and the drag force at 100% elongation, tensile strength, and elongation at break were measured.

\nS Polyurethane resin film at 69-71°C1 relative humidity 95
19-21' after being left in an atmosphere of 70 days or more.
C. The tensile strength was measured after being left in an atmosphere with a relative humidity of 60 to 65% for 24 hours or more, and the retention rate with respect to the tensile strength before the test was determined.

After irradiating the polyurethane resin film with ultraviolet rays for 400 hours using a light resistance tester with a black panel temperature of 83°C, the yellow index was measured using a color difference meter, and the tensile strength was measured. The retention rate was determined.

Pressure-resistant plate sled (1) Preparation of compounded solution To each polyurethane resin solution, add PPG adduct of glycerin (skeletal weight of about 3,000) as a film-forming agent at 5% based on the solid content of the urethane resin, Solid content concentration 2 in DMF
It was adjusted to 0%.

(2) Preparation of wet film The above-mentioned liquid mixture was applied to a thickness of IM on PET film, and 2
It was coagulated in water at 0'C for 10 minutes, then in hot water at 50°C for 20 minutes, then washed in hot water at 50'C for 40 minutes, dried at 100°C for 20 minutes, and the thickness was 0. A wet coating of .2 mm was obtained on the PET film.

(3) Wet film evaluation Apply oleic acid to the polyurethane resin film, and use a light resistance tester with a black panel temperature of 83°C to expose it to ultraviolet rays for 10 minutes.
After irradiation for 0 hours, oleic acid was applied to the polyurethane resin film again, and ultraviolet rays were irradiated for 100 hours using a light resistance tester with a black panel temperature of 83°C, and changes in appearance were observed.

Example 1 100 parts of polyhexamethylene carbonate diol with a molecular weight of 2,000, 98.3 parts of 4.4'-dicyclohexylmethane diisocyanate, 2 parts of dimethylformamide
After mixing 9 parts of dibutyltin dilaurate and 0.024 parts of dibutyltin dilaurate and reacting at 70°C for 2 hours, 274 parts of dimethylformamide and 31.3 parts of 4.4' diphenylmethane diisocyanate were added and the mixture was heated at 70°C. 0.3 part of methanol was added and reacted for 1 hour at 60°C to give a resin concentration of 30.0% and a viscosity of 1.
A polyurethane resin solution with 000 voids was obtained. This polyurethane resin film showed almost no change in appearance when visually observed, and was excellent in sweat resistance.

Comparative Example 1 The same operation as in Example 1 was performed except that polyoxytetramethylene diol with a molecular weight of 2,000 was used instead of polyhexamethylene carbonate diol with a molecular weight of 12,000, and the resin concentration was 30.0% and the viscosity was A polyurethane resin solution of 1,200 poise was obtained.

The entire surface of this polyurethane resin film melted and turned brown, and had no sweat resistance.

Example 2 100 parts of polyhexamethylene carbonate diol of 12,000 molecules, 16.2 parts of 4,4'-dicyclohexylmethane diisocyanate, 29 parts of dimethylformamide
After mixing 0.024 parts of dibutyltin dilaurate and reacting at 70'C for 2 hours, 274 parts of dimethylformamide, 10.3 parts of 4.4'-diphenylmethane diisocyanate and 3.3 parts of ethylene glycol were added to 70" React for 6 hours at C and further methanol 0
．． 3 parts were added and reacted at 60°C for 1 hour to obtain a polyurethane resin solution with a resin concentration of 30.0% and a viscosity of 1,000 poise.

Table 1 shows the physical properties of the film obtained from this polyurethane resin solution.

Example 3 The same operation as in Example 2 was performed except that 4.8 parts of 1.4-butanediol was used instead of 3.3 parts of ethylene glycol, and the resin concentration was 30.0% and the viscosity was 1.200 voids. A polyurethane resin solution was obtained. Table 1 shows the physical properties of the film obtained from this polyurethane resin solution.

Comparative Example 2 100 parts of polyoxytetramethylene diol with a molecular weight of 2.000 was used instead of 100 parts of polyhexamethylene carbonate diol with a molecular weight of 2.000, and 4.8 parts of 1.4-butanediol was used instead of 3.3 parts of ethylene glycol.
The same operation as in Example 2 was carried out except that the resin concentration was 30.0% and the viscosity was i and oo.

A Boyes polyurethane resin solution was obtained. Table 1 shows the physical properties of the film obtained from this polyurethane resin solution.

/ / (Effects of the Invention) In the present invention, since a polycarbonate polyol is used as the polypolyol, the obtained polyurethane resin has extremely excellent sweat resistance.

The polyurethane resin obtained by the polyurethane resin manufacturing method of the present invention and the polyurethane resin composition containing it as an essential component have excellent mechanical properties, hydrolysis resistance, light resistance, and sweat resistance. It is useful for molding materials, synthetic leather, adhesives, coatings, etc., and is particularly useful for synthetic leather used in furniture and vehicle seats.

Claims (1)

[Claims] 1. Polycarbonate polyol (A), alicyclic polyisocyanate (B), and aromatic polyisocyanate (
A method for producing a polyurethane resin, which comprises reacting with C). 2. The manufacturing method according to claim 1, wherein the alicyclic polyisocyanate (C) is a polyisocyanate having two or more cyclohexane rings. 3. The manufacturing method according to claim 1, wherein the alicyclic polyisocyanate (C) is dicyclohexylmethane diisocyanate. 4. The manufacturing method according to claim 1, wherein the polycarbonate polyol (A) is polyhexamethylene carbonate diol and the alicyclic polyisocyanate (C) is dicyclohexylmethane diisocyanate. 5. The production according to claim 1, wherein the polycarbonate polyol (A) is polyhexamethylene carbonate diol, the aromatic polyisocyanate (B) is diphenylmethane diisocyanate, and the alicyclic polyisocyanate (C) is dicyclohexylmethane diisocyanate. Method. 6. A polyurethane resin composition containing the polyurethane resin obtained by the production method according to any one of claims 1, 2, 3, 4, or 5 as an essential component.