JPS62280214A - Polyurethane resin composition - Google Patents

Abstract

PURPOSE:To obtain a polyurethane resin composition excellent in mechanical strength, heat resistance, hydrolysis resistance, low-temperature resistance, abrasion resistance, etc. and suitable for use in automobile parts, etc., by reacting a specified linear polyhydroxy compound with an organic diisocyanate. CONSTITUTION:A hydroxyl group-containing aliphatic and/or alicyclic hydrocarbon diol polycarbonates (e.g., 1,6-hexamethylene polycarbonate diol) is addition- polymerized with a lactone (e.g., epsilon-caprolactone) by ring opening so that the lactone component may be 5-60wt% to produce a linear polyhydroxy compound. The obtained compound is reacted with an organic diisocyanate (e.g., 4,4'-diphenylmethane diisocyanate) and, optionally, an isocyanate group-reactive low-MW compound having a plurality of hydrogen atoms (e.g., ethylene glycol) to obtain the title resin composition.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a novel polyurethane resin composition using a specific linear polyhydroxy compound. For more details,
This invention relates to a polyurethane resin composition with excellent mechanical strength, heat resistance, hydrolysis resistance, cold resistance, and abrasion resistance.

[Prior art and its problems]

Polyurethane resin compositions comprising high molecular weight linear dihydroxy compounds, organic diisocyanates, and optionally low molecular weight compounds having at least two hydrogen atoms that react with isocyanate groups are well known. As the high molecular weight linear dihydroxy compound, dicarboxylic acid polyesters having hydroxyl groups, generally adipic acid polyesters, are mainly used. Polyurethane resins obtained from adipic acid polyester generally have excellent mechanical properties, but have the drawback of poor hydrolysis resistance, although this varies to some extent depending on the glycol component present in the adipic acid polyester. A polyurethane resin in which a ring-opened polymer of caprolactone is used in place of the adipic acid polyester is also provided, but although some improvement is seen in hydrolysis resistance, it is not sufficient. Furthermore, in order to improve the hydrolysis resistance of polyurethane resins, polyethers having hydroxyl groups, generally polytetramethylene ether diol prepared by ring-opening polymerization of tetrahydrofuran, are used as polymeric linear dihydroxy compounds. However, this polytetramethylene ether diol-based polyurethane resin has the disadvantage of being inferior in mechanical strength, heat resistance, and abrasion resistance. In order to maintain the mechanical strength and improve the hydrolysis resistance of polyurethane resins, it has been proposed to use, for example, 1,6-hexamethylene diol-polycarbonate having hydroxyl groups as a high molecular weight linear dihydroxy compound. However, this polyurethane resin has the disadvantage of poor cold resistance.

[Means for solving problems]

The present inventors have conducted extensive research with the aim of improving these drawbacks and providing a polyurethane resin composition that has excellent mechanical strength, heat resistance, hydrolysis resistance, cold resistance, and abrasion resistance. As a result of repeated efforts, the present invention was completed.

That is, the present invention provides a polyurethane composition comprising a linear polyhydroxy compound, an organic diisocyanate, and optionally a low molecular weight compound having a small number (both of which have two) of hydrogen atoms that react with isocyanate groups, in which the linear polyhydroxy compound has a hydroxyl group. A polyurethane resin composition characterized in that it is a polyhydroxy compound obtained by ring-opening addition polymerization of lactone to a polycarbonate of an aliphatic and/or alicyclic hydrocarbon diol having the following: This is what we provide.

The polyhydroxy compound used in the present invention is obtained by ring-opening addition polymerization of lactone to a polycarbonate of an aliphatic and/or alicyclic hydrocarbon diol having hydroxyl groups so that the lactone component is 5 to 601%. A polycarbonate of an aliphatic and/or cycloaliphatic hydrocarbon diol having the following properties is obtained by first obtaining a polycarbonate of an aliphatic and/or cycloaliphatic hydrocarbon diol, which is then subjected to ring-opening addition polymerization of a lactone such that the lactone component is 5 to 6 oTL-jl percent.

Polycarbonates of aliphatic and/or alicyclic hydrocarbon diols having hydroxyl groups are produced by known methods. For example, it can be obtained by reacting an aliphatic and/or alicyclic hydrocarbon diol with diallyl carbonate or dialkyl carbonate under reduced pressure, or by reacting an aliphatic and/or alicyclic hydrocarbon diol with a cyclic alkylene carbonate under reduced pressure. It will be done.

Examples of the diallyl carbonate (diallyl carbonate) include diphenyl carbonate, bischlorobuenyl carbonate, dinaphthyl carbonate, and dialkyl carbonate. Examples of the dialkyl carbonate (dialkyl carbonate) include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, and dibutyl carbonate. Historically, the cyclic alkylene carbonate is
For example, ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,6
-butylene carbonate, 2, butylene carbonate, 1,2-pentylene carbonate, 1,5-pentylene carbonate, 1,4-pentylene carbonate,
Examples include 1,5-benthylene carbonate, 2,3-benthylene carbonate, 2,4-benthylene carbonate, and the like.

The aliphatic hydrocarbon diol used in the present invention preferably has 4 to 12 carbon atoms, such as 1,3-butanediol, 1,4-butanediol, 1,5-bentanediol, 1,6-hexanediol. , 1,7-hebutanediol, 1,8-octanediol, 1,10-decanediol, 2,2-dimethyl-1,3-globandiol, 2-ethyl-1,6-hexanediol, 2 ,2
．． Examples of alicyclic hydrocarbon diols include 4-trimethyl-1,6-hexanediol, and examples include 4-trimethyl-1,6-hexanediol.
-12 are preferred, such as 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,3
-dimethylolcyclohexane, 1,4-dimethylolcyclohexane, 1,6-dihydroxyethylcyclohexane, 1,4-dihydroxyethylcyclohexane, etc., and may be a single diol or a mixture of two or more diols.

The molecular weight of the aliphatic and/or alicyclic hydrocarbon diol-polycarbonate having a hydroxyl group is determined by the reaction molar ratio of the reacting aliphatic and/or alicyclic hydrocarbon diol and diallyl carbonate, dialkyl carbonate, or alkylene carbonate. controlled. The molar ratio of diol dicarbonate is preferably 1:9 to 9:1.

Moreover, its molecular weight is preferably 300 to 4,000.

Examples of lactones to be subjected to ring-opening addition polymerization reaction with polycarbonates of aliphatic and/or alicyclic hydrocarbon diols having hydroxyl groups include 1, such as δ-valerolactone, β-
Ethyl-valerolactone, ε-caprolactone, α-methyl-C-caprolactone, β-methyl-ε-caprolactone, γ-methyl-ε-caprolactone, β, δ-dimethyl-ε-caprolactone, 3,3.5-trimethyl-ε -Caprolactone, enantholactone (7-hebutanolide), dodecanolactone (12-dodecanolide), and the like.

The lactone component in the polyhydroxy compound obtained by ring-opening addition polymerization of the lactone of the present invention is 5 to 60 weight percent, preferably 10 to 50 weight percent. If the lactone component is less than 5% by weight, the cold resistance will be poor, while if it exceeds 6% by weight, the hydrolysis resistance will be poor.

The molecular weight of the polyhydroxy compound obtained by ring-opening force polymerization of a lactone to a polycarbonate of an aliphatic and/or alicyclic hydrocarbon diol having a hydroxyl group according to the present invention so that the lactone component becomes 5 to 603i% is particularly determined. Although not limited, it is preferably 500 to 5,000.

The organic diisocyanates used in the present invention include aliphatic, r+h cyclic, and aromatic diisocyanates, such as tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 1,4-cyclohexadiisocyanate, inphorone diisocyanate, 1- Methyl-2,4-cyclohexane diisocyanate, 1-methyl-2,6-cyclohexane diisocyanate, xylylene diisocyanate, 4,4'-diphenyl diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-
Fujini diisocyanate.

Examples include p-phenyl diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate and the like alone or in a mixture of two or more.

Examples of low molecular weight compounds having at least two hydrogen atoms that react with isocyanates that are used as necessary in the present invention include polyols and polyamines such as ethylene glycol, diethylene glycol, 1,3-propylene glycol, and 1,4-butylene. Glycol, 1,5
-Pentanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-dimethylolhexane, 1,4-dihydroxyethylcyclohexane, 1.4
-dihydroxyethylbenzene, 4,4'-methylenebis(hydroxyethylbenzene), chrycerin, trimethylolpropane, pentaerythyl, N-methylethanolamine, N-ethylethanolamine,
One or more of ethylenediamine, 1,3-diaminopropane, hexamethylenediamine, 4,4'-diphenylmethanediamine, methylenebis(0-chloroaniline), hydrazine, piperazine, N,N'-diaminopiperazine, water, etc. A mixture of the following may be mentioned.

The polyurethane pear composition of the present invention is manufactured into a polyurethane resin by a known method. For example, to obtain a bath-free polyurethane resin, a linear polyhydroxy compound and a low molecular weight compound having at least two hydrogen atoms that react with an isocyanate group, which is used as necessary, are mixed, and an organic diisocyanate is added to the mixture. When using a low molecular weight compound that undergoes a mixed reaction or has at least two hydrogen atoms that react with isocyanate groups, a prepolymer having isocyanate groups obtained by reacting a linear polyhydroxy compound and an organic diisocyanate is obtained. Furthermore, it can be obtained by mixing and reacting a low molecular weight compound having two or more hydrogen atoms that react with an isocyanate group. Furthermore, in order to obtain a polyurethane resin for an organic bath solution, the linear polyhydroxy compound may be mixed with an organic solvent inert toward isocyanate groups, such as dimethylformamide, diethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, methylethylketone, Methyl in butyl ketone, methyl acetate, ethyl acetate, butyl acetate, toluene, and xylene, either alone or in a mixture of two or more, are dissolved in a solution containing at least two hydrogen atoms and react with the isocyanate group used as necessary. After mixing the molecular weight compounds, the organic diisocyanate may be mixed and reacted.
Alternatively, when using a low molecular weight compound having at least two hydrogen atoms that react with isocyanate groups, the linear polyhydroxy compound is dissolved in the organic bath agent and reacted with the organic diisocyanate, and then the hydrogen atoms that react with the isocyanate groups are dissolved. It is obtained by reacting a compound with a low molecule having at least two atoms. It can also be produced as an aqueous dispersion of polyurethane resin.

The amount of organic diisocyanate used is not limited by the desired molecular weight of the resulting polyurethane resin, but when used as an elastomer, it is usually necessary to react with a linear polyhydroxy compound and an isocyanate group used as necessary. CL95 stoichiometrically with respect to the sum of low molecular weight compounds having at least two hydrogen atoms
~t2.

By using a low molecular weight compound having at least three hydrogen atoms that reacts with the isocyanate group, or by combining the urethane bond and/or urea bond with the isocyanate group. It may have a partially crosslinked structure due to reaction. In addition, after producing the polyurethane resin of the present invention, a low molecular weight compound having at least two hydrogen atoms that reacts with isocyanate groups or a low molecular weight compound having at least two isocyanate groups, such as 3 moles of tolylene diisocyanate and 1 mole of trimethylolpropane, is added. It is possible to further react with a reaction product with mole or peroxide to make the silkworm molecular weight or reticulate it.

When the polyurethane resin of the present invention is used, various additives such as colorants, fillers, stabilizers (thermal stabilizers, etc.), ultraviolet absorbers, antioxidants, anti-blocking agents, flame retardants, anti-aging agents, etc. are added and mixed. can do.

In addition, the polyurethane resin of the present invention includes various polymers such as polyvinyl chloride, copolymers of vinyl chloride and other vinyl polymerizable monomers, acrylonitrile-styrene copolymers, acrylonitrile-butadiene copolymers, and styrene. - butadiene copolymers, acrylonitrile-butadiene-styrene copolymers, nitrocellulose, cellulose acetate, cellulose butyrate, cellulose acetate butyrate, other polyurethane resins, such as polyurethanes obtained from polycarbonate diols containing no lactone component Words, polyester-based polyurethane resin obtained from polyester diol, polyester resin, epoxy resin, vinyl ester resin, unsaturated polyester resin, olefin thread balance, fluorine resin, polyacetal side d, polycarbonate Examples include polyamide resin.

〔Effect of the invention〕

Since the polyurethane resin of the present invention has excellent mechanical strength, heat resistance, hydrolysis resistance, abrasion resistance, and abrasion resistance,
It is useful as mechanical parts, automobile parts, chains, belts, films, hoses, tubes, wheels, gears, shoe soles, textile coatings, clothing coatings, synthetic leather materials, binders, adhesives, etc.

〔Example〕

The present invention will be further explained below with reference to Examples, but these are not intended to limit the present invention in any way. It should be noted that all the middle parts and percentages in the examples are X-position parts and weight percentages.

Example 1 61% ring-opening of e-caprolactone to 1,6-hexamethylene polycarbonate diol with molecule 1i1360 2
100 parts of a linear polyhydroxy compound of molecule -71980 combined with 1Oi was dissolved in 666 parts of dimethylformamide, 18 parts of 1,4-butanediol were added, further 66 parts of diphenylmethane diisocyanate were added, and then dipyltin dilaurate [101 parts] was added and reacted at 60°C for 12 hours to obtain a polyurethane resin solution with a resin concentration of 65% and a viscosity of 820 voids. This polyurethane resin solution was applied to a support with mold releasability and dried at 120°C for 30 minutes to obtain a film with a thickness of about 150 microns. Table 1 shows the results of measuring various physical properties of this film.

Comparative Example 1 A resin concentration of 35% and a viscosity of 822 poise were prepared in the same manner as in Example 1 except that 1,6-hexamethylene polycarbonate diol with a molecular weight of 1982 was used in place of the linear polyhydroxy compound with a molecular weight of 19so in Example 1. A polyurethane bath liquid was obtained, a film was prepared in the same manner as in Example 1, and various physical properties were measured. The results are shown in Table 1.

Comparative Example 2 In place of the linear polyhydroxy compound with a molecular weight of 1980 in Example 1, a 19800 linear polyhydroxy compound (molecule ji obtained by ring-opening addition polymerization of 71% ε-caprolactone to 1,6-hexamethylene polycarbonate diol with a molecule f580) was used. A polyurethane solution with a resin concentration of 65% and a viscosity of 828 voids was obtained in the same manner as in Example 1, except for using the compound. A film was prepared in the same manner as in Example 1, and the various physical properties were measured. The results are shown in Table 1. Ta.

Table 1 Various physical properties measurement methods Tensile strength and elongation: Width 10m x Length 20? A tensile test was conducted on a specimen of I11 at 25°C at a tensile speed of 300 m1/min.
The tensile strength and elongation were determined from the load when the specimen was cut and the length of the specimen.

Heat resistance: After the film was left in an atmosphere at 120°C for 30 days, a tensile test was conducted to determine the ratio of tensile strength to the value before the heat resistance test.

Hydrolysis resistance: After the film was left in an atmosphere at 70°C and 95% relative humidity for 50 days, a tensile test was conducted to determine the ratio of tensile strength to the value before the hydrolysis resistance test.

Glass transition temperature: The glass transition temperature was determined by measuring the external elasticity in mJ.

Example 2 Molecule 1i A molecule obtained by cycloaddition polymerizing 21% of ε-caprolactone to 1,6-hexamethylene polycarbonate diol of 1196 molecules! Add 22 parts of 1,4-butanediol to 100 parts of linear polyhydroxy compound of 1510,
76 parts of diphenylmethane diisocyanate at 50°C was added, reacted at 180°C for 2 hours, and heated to 200°C.
A polyurethane resin having a bath melt viscosity of 6.3×1c15 voids was obtained. This polyurethane resin was injection molded into a test piece with a thickness of about 2 nm, and various physical properties were measured. The results are shown in Cloth 2.

Comparative Example 3 79 parts of 1,6-hexamethylene polycarbonate diol with molecule 1i1515, 21 parts of polyε-caprolactone diol with molecule t1510 and 22 parts of 1,4-butanediol were mixed, heated to ao'c, and heated to 50°C. Add 73 parts of diphenylmethane diisocyanate, react at 180°C for 2 hours, and the bath melt viscosity at 200°C is 6.7×10
A 5 poise polyurethane resin was obtained. This polyurethane resin was used in the same manner as in Example 2 to obtain a specimen approximately 211 m thick.
Table 2 shows the results of measuring various physical properties in the same manner as in Example 2.

Table 2 Wear resistance: Abrasion loss was determined using a taper abrasion tester (wearing wheel I (~22, load 1k, 19.1000 times).

Example 3 Molecule 1 has 820 1,4-cyclohexanediol with ε
- Molecular weight 10 obtained by ring-opening addition polymerization of 23% caprolactone
100 parts of the linear polyhydroxy compound No. 60 was dissolved in a mixed solvent of 60 parts of methyl ethyl ketone and 60 parts of cyclohexanone, and 1 part of 2,2-dimethyl-1,3-7'ropanediol-1 ([and 01 parts of diptyltin dilaurate In addition, 1,6-hexamethylene diisocyanate 32
After reacting at 80°C for 18 hours, 267 parts of methyl ethyl ketone was added to obtain a polyurethane four-fat solution with a resin concentration of 35% and a viscosity of 220 poise. This polyurethane g-bleed solution was treated in the same manner as in Example 1 to obtain a film with a thickness of about 150 microns, and the various physical properties were measured in the same manner as in Example 1. The results are shown in Table 6. However, the hydrolysis resistance is higher than that at 70℃.
, and left in an atmosphere with relative humidity of 95% for 15 days.

Comparative Example 4 Example 30 Example 3 except that polyε-caprolactone diol (100% lactone) with a molecule of 11060 was used in place of the linear polyhydroxy compound with a 111060 molecule
In the same manner as above, a polyurethane resin solution having a resin concentration of 35% and a viscosity of 224 voids was obtained. A film was prepared using this polyurethane resin solution in the same manner as in Example 6, and various physical properties were measured. Table 3 shows the results.

Table 3 (that's all)

Claims (1)

[Claims] In a polyurethane resin composition comprising a linear polyhydroxy compound, an organic diisocyanate, and optionally a low molecular weight compound having at least two hydrogen atoms that reacts with an isocyanate group, the linear polyhydroxy compound is an aliphatic compound having a hydroxyl group and/or an aliphatic compound having a hydroxyl group. Or, a polyurethane resin composition characterized in that it is a polyhydroxy compound obtained by ring-opening addition polymerization of lactone to a polycarbonate of an alicyclic hydrocarbon diol so that the lactone component becomes 5 to 60% by weight.