JPS5863759A - Polyurethane composition suitable for coating - Google Patents

Abstract

PURPOSE:The titled composition that is made by adding a specific polymeric diol, an alicyclic diisocyanate and an organic carboxylic hydrazide in a specific proportion, thus showing high strength, elongation, resitance to light, coldness and heat, and being suitable for the use in artificial leather, cloths and glass. CONSTITUTION:For example, the objective composition comprises (A) a high polymeric diol of 500-3,000 average molecular weight, (B) 2.0-5.0mol, per mole of component A, of an alicyclic diisocyanate such as isophorone diisocyanate, (C) an organic carboxylic dihydrazide, when necessary, (D) an aliphatic diamine wherein more than 10mol% of total amount of components B, C, and D is isophorone compounds. At this time, 10-60wt% of the solvent is an aprotonic polar solvent and 90-40wt% is a softening solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyurethane composition that can provide a polyurethane composite with excellent performance when used as a coating agent for artificial leather, fabric, plastics, glass, etc. More specifically, the F1 of the present invention has excellent physical properties such as strength and elongation, and has excellent properties such as light deterioration resistance, storage resistance, low temperature flexibility, heat resistance, water resistance, heat deterioration resistance, coating processability, and toxicity. As a coating agent for artificial leather or fabric, or when manufacturing these.
This invention relates to a polyurethane composition comprising a polyurethane and an organic solvent thereof that have a high degree of performance required for IP.

Polyurethane has excellent mechanical strength, abrasion resistance, and flexibility, and is widely used for rounding and conventionally cut artificial leather. In order to obtain polyurethane that is more suitable for these uses, we have improved its properties such as hardness, low-temperature flexibility, heat resistance,
Many attempts have been made to improve heat deterioration resistance, dyeing durability, etc., and various methods have been proposed to improve each required performance. However, in all of the previous attempts, the level of improvement has been only modest, or even if they are satisfactory with respect to the specific required performance for Mamaru's purpose, on the other hand, they have resulted in a steady deterioration of other required performances. The results were not satisfactory.

Polyurethane is obtained by reacting a polymeric diol with an organic diisocyanate and an active hydrogen compound as a chain extender, but for example, when an aromatic organic diisocyanate is used as the organic diisocyanate, the resulting polyurethane has poor light deterioration resistance; Specifically, it is known that light irradiation causes yellowing and a decrease in strength and elongation. Light deterioration resistance is improved by using an aliphatic or alicyclic organic diisocyanate instead of an aromatic organic diisocyanate. However, even in this case, although it is possible to considerably prevent yellowing due to light irradiation in terms of light deterioration resistance, it is often insufficient to prevent a decrease in strength due to light deterioration.

Furthermore, polyurethanes using organic carboxylic acid dihydrazides such as isophthalene dihydrazide are known as polyurethanes with excellent light resistance (Japanese Patent Publications No. 38-11300, No. 52-42840, etc.); It has the disadvantage that elongation residual strain under water tends to be large. Furthermore, the biggest drawback of this polyurethane is its solubility in solvents. In other words, Special Public Interest Publication 52-42
Isophthalic acid dihydrazido di-7-lylohexylmethane-4,4'-diisocyanate-based polyurethane, dimethylformamide (hereinafter referred to as DM
It can only be dissolved in high boiling point, highly toxic aprotic polar solvents such as F (abbreviated as F) or mixed solvents in which a portion of this aprotic polar solvent is replaced with another solvent. When the solvent is a high-boiling, highly toxic, aprotic polar solvent, there are various advantages when drying and solidifying the coated polyurethane solution, such as complete scavenging of solvent vapors. Equipment and drying equipment,
Alternatively, there are disadvantages such as having to adopt a drying time of -& hours. Furthermore, when this polyurethane solution is used as a surface finishing agent for artificial leather, etc., the problem arises that the underlying polyurethane layer is damaged by the solvent.

Polyurethanes using monoaliphatic or alicyclic organic diisocyanates have the disadvantages of low softening temperature, low tensile stress, too much flexibility, and poor surface abrasion fastness. In order to improve this drawback, a method of increasing the ratio of organic diisocyanate and chain extender to polymeric diol may also be considered. However, in this case, regarding the solvent solubility of the obtained polyurethane, a solvent such as DMF having a very high mixing ratio is required.

The present inventors have developed a mixed solvent that satisfies many of the above-mentioned performance requirements, light resistance at #1I level, satisfies other polymer physical properties such as heat resistance, and further contains a large amount of low boiling point and low toxicity soft solvent. As a result of intensive research into obtaining a polyurethane composition that also has a polymer solubility of The effects obtained in accordance with the present invention are not at all predictable from the results obtained when the individual raw materials are used independently.

That is, the present invention provides (1) an average molecular weight of 500 to 3,0
(b) Alicyclic organic diincyanate, (1) organic carboxylic acid dihydrazide.

and if necessary (ψ) In a polyurethane composition consisting of a polyurethane synthesized from alicyclic organic sheavin and a solvent for this polyurethane, (1) one of the solvents is
0 to 60% by weight is the aprotic polar solvent, and 90 to 60% by weight is the aprotic polar solvent.
(11) 10 moles or more of the total amount of organic diisocyanate, organic carboxylic acid dihydrazide, and organic diamine is an isophoro/based compound; and the molar ratio of -2. It is a polyurethane composition suitable for coating agents with a % mold in the range of 0 to 5.0, and this polyurethane has light resistance.

It satisfies heat resistance, high solubility to mixed solvents with a soft solvent ratio, and physical properties such as strong physical properties, water resistance, surface properties such as surface abrasion resistance, and bending resistance. It is also extremely excellent in terms of both tl and tl. In Part 9, each component of the present invention will be specifically explained.

First, the polymeric diols used in the polyurethane composition of the present invention include polytetramethylene glycol,
General polymer diols such as polyglobyl/glycol, polyester glycols, polyacetal glycol, polycarbonate gelcol, and polybutadiene glycol can be mentioned.

The polyurethane obtained by the present invention has sufficient light resistance and oxidation resistance for practical use as a material for artificial leather, etc., but poly-9-urethane with even higher light resistance and oxidation resistance is needed. In this case, it is preferable to use a diol mainly composed of polyester chains or polycarbonate chains as the polymeric diol. .

4.4-diaminodicyclosilmethane, 4.4-diamino-3,3'-dimethyldicyclosilmethane,
Examples of the cyclohexylene diisocyanates used in the present invention include inphorone diisocyanate, dicyclohexylmethane-4,4'-diynone diisocyanate, 4,4'-inopropylidene dicyclohexane diisocyanate, and cyclohexyl diisocyanate. Examples include silane diisocyanate and the like.

If an aliphatic material is used instead of a fatty HA-organic cyanoacetate, the resulting polyurethane will be superior in terms of cold resistance, heat resistance, and mechanical properties. Moreover, when an aromatic type material is used, it becomes significantly inferior in terms of light deterioration resistance.

In the present invention, the molar ratio of the alicyclic 61 diisocyanate to the polymer diol is within the range of 2.0 to 5.0, as well as the average molecular weight of the polymer diol.
It is an academic factor. If the molar ratio is less than 2.0, the heat resistance will be insufficient, that is, the thermal softening temperature will decrease.

Furthermore, the solvent resistance is also seriously poor. If the molar ratio exceeds 5.0, it is preferable from the viewpoint of polymer solution stability (2), and the low elongation stress at room temperature becomes too large, resulting in insufficient flexibility and difficulty in use.

In addition, in the present invention, in order to maintain the polymer solubility in a mixed solvent with a larger soft solvent ratio, it is necessary to use an inphonic compound (i.e. It is essential that the ratio of the total amount of holone diisocyanate and inholo/diamine) be 107 mol. It dissolves only in extremely high mixed solvents, making it impossible to use a mixed solvent with a higher soft solvent ratio, which is the objective of the present invention.As the ratio of inphorone diincyanate and isophorone diamine increases,
The fact that the obtained polyurethane can be dissolved in a mixed solvent with a higher proportion of soft solvent is clearly stated by Reason Company.
Not though.

This is interesting.

In the present invention, a small amount of aliphatic or aromatic organic diisocyanates, organic diamines, and even active hydrogen compounds other than diamines can be substituted.

In the present invention, polyurethane solubility in a mixed solvent with a higher soft solvent ratio is maintained, and in addition to light resistance, physical properties such as heat resistance and general strength and length, II! When better longitudinal strength is required, the alicyclic diisocyanate may be isophorone diisocyanate, a diisocyanate compound represented by the general formula or a lower alkyl group, or a mixture of both. use,
As the alicyclic organic diamine, it is preferable to use a diamine compound represented by isophoro3 (wherein R3 and R4 represent a hydrogen atom or a lower alkyl group) or a mixture of both.

Further, in the present invention, in order to obtain a product with excellent light resistance, it is necessary to use organic carbon dihydrazide as a chain extender. The amount of organic carvone dihydrazide used is
Relative to the total amount of alicyclic organic diamine and organic carbon dihydrazide, 10 moles or more, preferably Ul 5 to
If the amount of organic carboxylic acid dihydrazide used is less than 10 moles, which is more than 80 moles, the light deterioration resistance and oxidative deterioration resistance of the resulting polyurethane will decrease, resulting in a decrease in strength and elongation. When it is necessary to reduce the elongation value of the resulting polyurethane under high-temperature water, or when it is necessary to reduce both elongation and stress, the proportion of organic carboxylic acid dihydrazide used is set to 80 mol or less. It is preferable to use it in combination with cyclic organic cyanogen. Suitable representative examples of organic carboxylic acid dihydrazide include isophthalic acid dihydrazide and adipic acid dihydrazide.

As mentioned above, when a polyurethane solution is used as a coating agent, it is important to increase the I11100 solvent removal efficiency, reduce toxicity, and make it difficult to damage the polyurethane layer on the bottom during application. However, in order to achieve these requirements, it is most preferable not to use an aprotic polar solvent such as DMF, which has traditionally been commonly used as a solvent. In some cases, the polyurethane of the present invention does not dissolve, and thus it is not possible to obtain a liquid solution for coating. Therefore, in the present invention,
A mixed solvent containing an aprotic polar solvent in an amount that dissolves the polyurethane and stabilizes #Q is used.
By using, as a coating agent, a polyurethane composition containing 1% soft solvent at a ratio of 90 to 40%, the coating suitability as mentioned above is greatly improved.

In addition to DMF, specific examples of the aprotic polar solvent constituting the polyurethane composition of the present invention include dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, and hexamenalene phosphoramide. .

tX Soft Bath U+ uses aromatic hydrocarbons such as benzene, toluene, xylene, and enalbenzene, and ester-based compounds such as methyl acetate, ethyl acetate, and butyl acetate.
acetone, methyl enalgtone, menalisuphthylketone, cyclohexanone, etc., chlorinated hydrocarbon baths such as tricrene, dichloroethane, isopropanol, methanol, and other alcohol solvents,
Examples include ether solvents such as tetrahydrofuran and dibutyl ether, cellosolve solvents such as methyl cellosolve, ethyl cellosolve, and acetic acid cellosolve.As mentioned above, the present invention makes it possible to increase the mixing ratio of soft solvents. This is due to the fact that isophorone diisocyanate and inphorone diamine are used to a greater extent. To obtain a composition consisting of this polyurethane solvent,
Normally, polyurethane is polymerized in an aprotic polar bulking agent such as DMF, and after the polymerization is complete, another soft solvent is added, but this method is not fixed. The polyurethane may be polymerized there, or it may be polymerized in DMF and a mixed solvent may be used during the polymerization. The polyurethane concentration of the polyurethane solution is usually 3 to 40% by weight, but the concentration during coating is preferably 5 to 15%. On the other hand, an excess amount of alicyclic diisonanate is heated and stirred at 50 to 130° C. in a nitrogen atmosphere to obtain a prepolymer having an isocyanate group at the end. The resulting prepolymer is dissolved in an amide-based or sulfoxide-based solvent, and chain-extended with an organic carboxylic acid/# dihydrazide and a 71m group 1 organic diamine at a temperature close to the temperature of N1 to obtain a polyurethane solution. Then, a soft solvent is added to this polyurethane bath solution to obtain the composition of the present invention. In addition to the above methods, there are many other methods for obtaining the polyurethane composition of the present invention, and the present invention is not limited to the above method.

In the present invention, in order to improve the dyeability of the resulting polyurethane, a compound containing tertiary nitrogen, such as N-
Methylazunobisbrobylamine, h-methylgetanolamine, N-inbutylgetanolamine, 1.
4-bisaminopropylbiverazine etc. may be used as part of the chain extender; however, these tertiary W
As the amount of the compound containing * increases, the required performance other than dyeing properties will decrease, so it is preferable to keep the compound containing tertiary nitrogen within 15 molar capsules of the total amount of the md-extender.

Furthermore, the polyurethane composition of the present invention includes a Noshiro inhibitor,
The polyurethane composition of the present invention may contain ultraviolet absorbers, pigments, dyes, flame retardants, and other various additives and fillers. It can also be used as a coating agent for glass, etc. By dispersing magnetic powder in the polyurethane composition of the present invention and coating it on the surface of a polyester film, a magnetic tape with excellent durability and surface strength can be obtained. In addition, a coloring agent, typically a pigment, is added to the polyurethane composition of the present invention to produce a polyamide, polyolefin, or polyester.

By printing and coating a film such as a saponified ethylene-vinyl acetate copolymer, a printed film with excellent paper durability, surface strength, etc. can be obtained. For these magnetic tapes or printing films.

When using the polyurethane composition of the present invention, the polyurethane constituting the polyurethane composition preferably uses polycarbonate glycol as a polymeric diol.

The present invention will be specifically explained below with reference to Examples. All raw materials for polyurethane used in Examples are indicated using abbreviations, and the relationship between abbreviations and compounds is as follows. Compound PC1
,6-hexanediol polycarbonate PCL
polycaprolactone diol IF'DI isophorone diisocyanate)hzMDI dicyclohethylmethane-4,4-diincyanate I PDA
Inphorondiamine HI2DAM 4.4'-Diaminodicyclohexylmethane AD)l Adipic dihydrazide ID
)l Isophthalic acid dihydrazide Examples 1 to 4,
Comparative Example 1 A polyurethane extomer was produced using the reagent shown in No. 112. That is, a certain amount of a polymeric diol and an organic diisocyanate are stirred and reacted at 60 to 100° C. for 2 to 6 hours under nitrogen. The nine prepolymers obtained are dissolved in DMF. Next, after dissolving a predetermined amount of chain extender in DMFK, this solution was added to the prepolymer solution mentioned above, and 36
C. Stir and react for 2-5 hours under nitrogen. When this reaction is almost complete, the soft solvent toluene/isopropanol/methanol (15/31.5 by weight) is added to DMF.
/ Soft solvent is added in a weight ratio of 4/6. The resulting polyurethane solution (polyurethane concentration: 8% by weight) is poured onto a glass plate and dried to obtain a dry film with a thickness of about 30μ. This dry film was subjected to various physical property tests. The results are shown in Table Wi2, with the following margins: A polyurethane solution was obtained by the method. The polymerization was carried out in DMF and then diluted with ethyl cellosolve. The solubility of the obtained solution was investigated. The results are shown in Table 4. Table Example 7, Comparative Examples 3 and 4 Table 6 shows the results of polyurethane obtained in the same manner as Example 1 using the reagents listed in Table 5 Table 5 6111 Example 8 The polyurethane of Example 2 was polymerized in DMF (40% concentration), then diluted with various soft solvents, and D
MF was added to obtain a 6.5 superior polyurethane solution, and its solubility and coating properties were investigated. Coating property is the result of impregnating a nonwoven fabric with a solution of polyurethane synthesized from polycaprolactone glycol-diphenylmethane-4°4'-diisocyanate-1,4-butanediol and coating it with a wet coagulation solution.

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Claims (1)

[Scope of Claims] 1 (a) a polymeric diol having an average molecular weight in the range of 500 to 3,00 (1), (b) an alicyclic organic diisocyanate), (e) an organic carboxylic acid dihydrazide, and optionally Accordingly, in a polyurethane composition comprising (d) 9-poly9-urethane synthesized from alicyclic organic diamine and a solvent for this polyurethane, (i) 1 of the solvent
0 to 60% by weight is the aprotic polar solvent, and 90 to 60% by weight is the aprotic polar solvent.
(U) 10 moles or more of the combined amount of organic diiso7anate, organic carboxylic acid dihydrazide, and organic diamine is an isophorone-based compound; A polyurethane composition suitable for a coating agent, characterized in that the molar ratio is in the range of 2.0 to 5.0. 2. The alicyclic diisocyanate is a diisocyanate compound represented by isophorone diamine (provided that R1, Rzij is covered with a hydrogen atom or a lower alkyl group) or a mixture of both, and the alicyclic organic diamine is inphorone diamine or 2. The polyurethane composition according to claim 1, which is a diamine compound represented by (13) (representing an elementary atom or a lower alkyl group) or a mixture thereof. 3. The polymeric diol is a diol having at least one type of chain selected from polyester chains and polycarbonate chains as its living body.Claim 1,
The polyurethane composition according to any one of Item 2.