JP3055166B2 - Method for producing polyurethane resin and polyurethane resin composition comprising the resin - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel method for producing a urethane resin having the properties of an acrylic resin and a resin composition comprising the resin.

(Prior art) Conventionally, polyurethane resins are used for molding materials, synthetic leather, surface treatment agents, paints, films, etc. because of their excellent mechanical strength and elasticity. There was a defect that the surface was tacky or tacky at high temperatures.

In order to eliminate these disadvantages, it has been proposed to mix an acrylic resin with a polyurethane resin.

However, since the acrylic resin has poor compatibility with the polyurethane resin, the mixture solution becomes opaque, and the film of the mixture becomes opaque, and mechanical properties such as tensile strength and elongation are reduced. Further, this film is inferior in water whitening resistance, and has a defect that when the film is immersed in water, the film is whitened.

(Problems to be Solved by the Invention) It is an object of the present invention to provide a polyurethane resin composition which provides a film having excellent mechanical strength and water whitening resistance together with a method for producing a polyurethane resin having no surface tackiness.

(Means for Solving the Problems) The present inventors have conducted intensive studies on the above-described method for producing a polyurethane resin, and as a result, completed the present invention.

That is, the present invention provides a mercaptan-based chain transfer agent having two hydroxyl groups and one mercapto group at one end obtained by radical polymerization of a monomer having a radically polymerizable unsaturated bond having no hydroxyl group. A macromonomer (A) having two hydroxyl groups, a polyester polyol,
A method for producing a polyurethane resin (D), comprising reacting at least one polyol (B) selected from the group consisting of polyether polyols and polyester ether polyols with a polyisocyanate (C), preferably the method described above. A mercaptan-based chain transfer agent having two hydroxyl groups and one mercapto group,
The polyurethane resin (D) and the organic solvent must be mercapto-1,2-propanediol, preferably the monomer having a radical polymerizable unsaturated bond having no hydroxyl group is methyl methacrylate. A polyurethane resin composition characterized in that it is contained as a component.

The polyurethane resin obtained in the present invention has the characteristics of a polyurethane resin and the characteristics of an acrylic resin, and
It is a novel polyurethane resin having no problems such as a decrease in water whitening resistance in mechanical properties and transparency as in the case where both are blended.

(Constitution) Examples of the mercaptan-based chain transfer agent having two or more hydroxyl groups and one mercapto group used in the present invention include:
For example, 1-mercapto-1,1-methanediol, 1-
Mercapto-1,1-ethanediol, 3-mercapto-
1,2-propanediol (thioglycerin), 2-mercapto-1,3-propanediol, 2-mercapto-2
-Methyl-1,3-propanediol, 2-mercapto-
2-ethyl-1,3-propanediol, 1-mercapto-2,3-propanediol, 2-mercaptoethyl-2
-Methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol, and the like.

As the monomer having a radical polymerizable unsaturated bond used in the present invention, for example, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate,
Butyl methacrylate, alkyl acrylates and / or methacrylates such as octyl methacrylate,
Acrylonitrile, methacrylonitrile, styrene, vinyl acetate and the like can be mentioned.

As the polyester polyol used in the present invention, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 2,2-dimethyl-1,2 Three
-Propanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, diethylene glycol, triethylene glycol,
Dipropylene glycol, tripropylene glycol,
Cyclohexane-1,4-diol, cyclohexane-1,4
-One or more polyhydric alcohols such as dimethanol, glycerin, trimethylolpropane, trimethylolethane, hexanetriol, pentaerythritol, sorbitol, methylglycoside and succinic acid, adipic acid, glutaric acid, pimelic acid, suberin Polybasic acids such as acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, hexahydroisophthalic acid Alternatively, it is a condensate with one or more acid anhydrides. Further, ring-opening polymers such as γ-butyrolactone and ε-caprolactone using the polyol as an initiator are also exemplified. Furthermore, poly (hexamethylene carbonate)
Polycarbonate diols such as diols are also included.

Examples of the polyether polyol include one or more ring-opening polymers of ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran, and the like using one or more of the above polyols and polyamines as initiators. .

Examples of the polyisocyanate of the present invention include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, and phenylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetra Various aliphatic or alicyclic (cycloaliphatic) diisocyanates, such as methylxylylene diisocyanate, triphenylmethane triisocyanate, polyphenyl polymethylene polyisocyanate, polyisocyanates having carbodiimide groups, allophanate groups Polyisocyanates containing isocyanurates Such polyisocyanates containing group.

Furthermore, in the present invention, a low-molecular compound having two or more groups that react with an isocyanate group can also be used. Examples thereof are 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-pentanediol, 1,8
-Octanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, glycerin, trimethylolpropane, trimethylolethane, hexanetriol, pentaerythritol , Sorbitol, polyols such as methyl glycoside, ethylenediamine,
1,3-propylene diamine, 1,2-propylene diamine,
Hexamethylenediamine, hydrazine, piperazine, N,
N'-diaminopiperazine, 2-methylpiperazine, 4,
4 'diaminodicyclohexylmethane, isophoronediamine, diaminobenzene, diphenylmethanediamine,
One or a mixture of two or more polyamines such as methylenebisdichloroaniline can be used.

In the method for producing a polyurethane resin of the present invention, the macromonomer (A), the polyol (B) and the polyisocyanate (C) may be reacted as essential components, and the reaction order is not particularly limited. Absent. The reaction can be carried out without a solvent in an organic solvent or in water, but is usually carried out in an organic solvent at 20 to 120 ° C, preferably 30 to 100 ° C for 30 minutes to 24 hours.

The equivalent ratio of the total hydroxyl groups of the macromonomer (A), the polyol (B) and the low molecular weight compound having two or more groups that react with the isocyanate group to the isocyanate group of the polyisocyanate (C) is particularly limited. However, it is usually performed at a ratio of 2: 1 to 1: 2.

In the method for producing the polyurethane resin of the present invention, the reaction can be promoted by using a tertiary amine catalyst and / or an organometallic catalyst as necessary.

Examples of the organic solvent that can be used in the polyurethane resin production method of the present invention include, for example, ethyl acetate, butyl acetate,
Cellosolve, cellosolve acetate, acetone, methyl ethyl ketone, cyclohexanone, toluene, xylene, dimethylformamide, dimethylacetamide, isopropanol and the like. Of course, these organic solvents can be added during the reaction.

In the method for producing a polyurethane resin of the present invention, an alcohol such as methanol, ethanol, propanol, 1,3-butylene glycol, and the like, if necessary, at the beginning of the reaction, during the reaction, or at the end of the reaction, and An amine compound such as dimethylamine, diethylamine, dipropylamine, dibutylamine and / or the like may be added for the purpose of terminating the reaction or controlling the molecular weight.

In the method for producing a polyurethane resin of the present invention, a polyol, a polyamine, and the like other than the macromonomer (A) and the polyol (B) can be used as needed.

The polyurethane resin composition of the present invention may further contain an antioxidant, an ultraviolet absorber, a hydrolysis inhibitor, a dye, a pigment, a filler, and the like, if necessary.

The urethane resin of the present invention provides a transparent solution and a film, and the film is excellent in mechanical properties, non-adhesive, and excellent in water whitening resistance, so that it is useful for molding materials, synthetic leather, surface treatment agents, paints, films, etc. It is.

(Examples) Next, examples will be described, but the present invention is not limited to these examples. In the text, “parts” are based on weight.

In addition, the preparation method of a polyurethane resin film, a mechanical property, water whitening resistance, and a non-adhesion test method are as follows.

<Preparation method of polyurethane resin film> Each polyurethane resin solution was cast on release paper and kept at 80 ° C for 30 minutes.
After drying for 20 minutes, the film was allowed to stand in an atmosphere at a temperature of 19 to 21 ° C. and a relative humidity of 60 to 65% for 24 hours or more to form a film of about 50 μm.

<Measurement of mechanical properties> Polyurethane resin film at 19 ~ 21 ℃, relative humidity 60 ~ 65%
The sample was pulled at a tensile speed of 300 mm / min in an atmosphere of, and the tensile strength at 100% elongation, tensile strength and elongation at break were measured.

<Water resistance test method> After the film prepared by the above method was immersed in warm water at 80 ° C for 5 hours, the appearance of the film was observed immediately.

<Adhesiveness test> The films were stacked as they were, a load of 100 grams per square centimeter was applied, the film was kept at 70 ° C for 24 hours, cooled to room temperature, and the degree of adhesion of the film surface was observed.

Example 1 Polybutylene adipate diol 100 having a molecular weight of 2,000
Parts, 100 parts of polymethyl methacrylate macromonomer having a molecular weight of 6,000 (methyl methacrylate oligomer having a diol group at one end obtained by polymerizing methyl methacrylate in the presence of thioglycerin), 49 parts of diphenylmethane diisocyanate, 0.05 part of stannous octylate, methyl ethyl ketone After mixing 110 parts and reacting at 70 ° C. for 2 hours, 489 parts of dimethylformamide and 8 parts of ethylene glycol were added and reacted at 70 ° C. for 12 hours. Further, 3 parts of methanol was added and reacted at 60 ° C. for 1 hour. Resin concentration
A polyurethane resin solution having a 30% viscosity of 7,000 centipoise was obtained. The solution of this polyurethane resin was transparent.
Table 1 shows the physical properties of the film obtained from this polyurethane resin solution.

Comparative Example 1 Polybutylene adipate diol 100 having a molecular weight of 2,000
70 parts by mixing 45 parts of diphenylmethane diisocyanate, 0.03 part of stannous octylate, 65 parts of methyl ethyl ketone.
After reacting at 2 ° C. for 2 hours, dimethylformamide 52
Add 5 parts and 8 parts of ethylene glycol and add 12 parts at 70 ° C.
After reacting at 60 ° C. for 1 hour, 100 parts by weight of methyl methacrylate resin having a molecular weight of about 10,000 were blended and mixed at 60 ° C. for 1 hour.
The mixture was stirred for an hour to obtain a polyurethane resin solution having a concentration of 30% and a viscosity of 8,000 centipoise. The solution of this polyurethane resin was opaque. Table 1 shows the physical properties of the film obtained from this polyurethane resin solution.

Comparative Example 2 Polybutylene adipate diol 100 having a molecular weight of 2,000
70 parts by weight, 45 parts of diphetylmethane diisocyanate, 0.03 part of stannous octoate and 65 parts of methyl ethyl ketone.
After reacting at 2 ° C. for 2 hours, dimethylformamide 29
Add 2 parts and 8 parts of ethylene glycol and add 12 parts at 70 ° C.
After reacting for 3 hours, 3 parts of methanol was added and reacted at 60 ° C. for 1 hour to obtain a polyurethane resin solution having a concentration of 30% and a viscosity of 8,000 centipoise. The solution of this polyurethane resin was transparent. Table 1 shows the physical properties of the film obtained from this polyurethane resin solution.

Example 2 Polyhexylene adipate diol 100 having a molecular weight of 2,000
Parts, polymethyl methacrylate macromonomer having a molecular weight of 2,000 (methyl methacrylate oligomer having a diol group at one end obtained by polymerizing methyl methacrylate in the presence of thioglycerin) 50 parts, diphenylmethane diisocyanate 36 parts, stannous octylate 0.04 part methyl ethyl ketone 83 After mixing and reacting at 70 ° C for 2 hours,
Add 370 parts of dimethylformamide and 8 parts of 1,6 hexanediol and react at 70 ° C for 12 hours.
And react for 1 hour at 60 ° C, resin concentration 30%,
A polyurethane resin solution having a viscosity of 6,500 centipoise was obtained. The solution of this polyurethane resin was transparent. Table 2 shows the physical properties of the film obtained from this polyurethane resin solution.

Comparative Example 3 Polyhexylene adipate diol 100 having a molecular weight of 2,000
Parts, 29 parts of diphenylmethane diisocyanate, 0.03 part of stannous octoate, and 57 parts of methyl ethyl ketone
After reacting at 70 ° C. for 2 hours, 379 parts of dimethylformamide and 8 parts of 1,6 hexanediol were added, reacted at 70 ° C. for 12 hours, further added 3 parts of methanol and reacted at 60 ° C. for 1 hour, Approx. 1 molecular weight after reaction
50 parts by weight of a methyl methacrylate resin of 0,000 were blended and stirred at 60 ° C for 1 hour to obtain a polyurethane resin solution having a concentration of 30% and a viscosity of 8,000 centipoise. The solution of this polyurethane resin was opaque. Table 2 shows the physical properties of the film obtained from this polyurethane resin solution.

Comparative Example 4 Polyhexylene adipate diol 100 having a molecular weight of 2,000
70 parts by weight, 30 parts of diphenylmethane diisocyanate, 0.03 part of stannous octylate and 60 parts of methyl ethyl ketone.
After reacting at 2 ° C. for 2 hours, dimethylformamide 26
Add 2 parts and 8 parts of 1,6 hexanediol and add 12 parts at 70 ° C.
After reacting for 3 hours, 3 parts of methanol was added and reacted at 60 ° C. for 1 hour to obtain a polyurethane resin solution having a concentration of 30% and a viscosity of 8,000 centipoise. The solution of this polyurethane resin was transparent. Table 2 shows the physical properties of the film obtained from this polyurethane resin solution.

Example 3 Polyhexamethylene carbonate diol having a molecular weight of 2,000 100 parts, polymethyl methacrylate macromonomer having a molecular weight of 6,200 67 parts 1,4 butylene glycol 5 parts Isophorone diisocyanate 48 parts Stannous octylate 0.047 parts Dimethylformamide 60 parts Toluene 40 parts Mix at 70 ℃
After reacting for 6 hours in dimethylformamide 135
And 17 parts of isophoronediamine, stirred and further added 200 parts of toluene. The mixture was reacted at 70 ° C. for 1 hour.
A 5% polyurethane resin solution having a viscosity of 8,000 centipoise was obtained. The solution of this polyurethane resin was transparent. Table 3 shows the physical properties of the film obtained from this polyurethane resin solution.
It was shown to.

Comparative Example 5 100 parts of polyhexamethylene carbonate diol having a molecular weight of 2,000, 5 parts of 1,4 butylene glycol, 45 parts of isophorone diisocyanate, 0.047 parts of stannous octylate, 42 parts of dimethylformamide and 29 parts of toluene were mixed and reacted at 70 ° C. for 6 hours. Thereafter, 135 parts of dimethylformamide and 17 parts of isophoronediamine were added and stirred. Further, 229 parts of toluene was added and reacted at 70 ° C. for 1 hour.After the reaction was completed, 67 parts by weight of methyl methacrylate resin having a molecular weight of about 10,000 was blended. Stir at 60 ° C for 1 hour, resin concentration 35
%, A polyurethane resin solution having a viscosity of 8,000 centipoise was obtained. The solution of this polyurethane resin was opaque.
Table 3 shows the physical properties of the film obtained from this polyurethane resin solution.

Comparative Example 6 100 parts of polyhexamethylene carbonate diol having a molecular weight of 2,000, 5 parts of 1,4 butylene glycol 45 parts of isophorone diisocyanate 0.047 parts of stannous octylate 42 parts of dimethylformamide 29 parts of toluene were mixed and reacted at 70 ° C. for 6 hours. Thereafter, 135 parts of dimethylformamide and 17 parts of isophoronediamine were added and stirred, and 102 parts of toluene were further added and reacted at 70 ° C. for 1 hour. Resin concentration 35%, viscosity
A 8,000 centipoise polyurethane resin solution was obtained. The solution of this polyurethane resin was transparent. Table 3 shows the physical properties of the film obtained from this polyurethane resin solution.

As a result, the polyurethane resin of the present invention has a transparent solution and the appearance of the film, and has good tensile strength, elongation, water whitening resistance and non-adhesiveness as compared with the case where the methyl methacrylate resin is blended. Met.

(Effect of the Invention) The urethane resin of the present invention gives a transparent solution and a film, and the film has excellent mechanical properties, is non-adhesive, and has excellent water whitening resistance, so that molding materials, synthetic leather, surface treatment agents, Useful for paints, films, etc.

Claims (4)

(57) [Claims] 1. A mercaptan-based chain transfer agent having two hydroxyl groups and one mercapto group is subjected to radical polymerization of a monomer having a radically polymerizable unsaturated bond having no hydroxyl group. A macromonomer having a hydroxyl group (A) is reacted with at least one polyol (B) selected from the group consisting of polyester polyol, polyether polyol and polyester ether polyol, and polyisocyanate (C). And a method for producing a polyurethane resin (D). 2. Production of the polyurethane resin (D) according to claim 1, wherein the mercaptan-based chain transfer agent having two hydroxyl groups and one mercapto group is 3-mercapto-1,2-propanediol. Method. 3. The method for producing a polyurethane resin (D) according to claim 1, wherein the monomer having a radically polymerizable unsaturated bond having no hydroxyl group is methyl methacrylate. 4. A polyurethane resin composition comprising the polyurethane resin (D) according to claim 1 and an organic solvent as essential components.