JPS5863749A - Polyurethane composition having improved light-resistance - Google Patents

Abstract

PURPOSE:The titled composition useful as a covering agent for cloth, plastic, etc., artificial leather, etc., obtained by blending polyurethane prepared from a specific high polymer diol, an alicyclic organic diisocyanate, hydrazine, and an alicyclic organic diamine with specified dye. CONSTITUTION:Polyurethane comprising (A) a high polymer diol containing 50-80wt% polyoxyethylene chain (CH2CH2O) (n is 12-100, especially 15-80), having an average molecular weight of 300-5,000, preferably 500-4,000, (B) an alicyclic diisocyanate having a molar ratio to the component A of 2.5-5.5, (C) hydrazine as a chain extender, and (D) an alicyclic organic diamine (with the proviso that the molar ratio of the component D to the total moles of the components C and D is 0.05-0.8) is blended with 3-70wt% dye selecteded from metal-containing complex dye, vat dye, acid dye, and sulfur dye (preferably metal-containing complex dye).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyurethane composition that is not susceptible to deterioration by light and has low dye transferability.
The present invention relates to a polycomposition obtained by reacting a polymeric diol containing a polyoxyethylene chain, an alicyclic organic diisocyanate, an alicyclic organic diamine, and a diamine in a specific ratio. This polyurethane composition has outstanding light resistance and low dye migration, and is particularly excellent as a component of artificial leather or as a coating agent for fabrics.

Polyurethane has excellent properties such as chemical resistance, abrasion resistance, toughness, cold resistance, and durability, and thanks to advances in the development of a wide range of processing technologies, it has also developed into a unique material that fills the gap between rubber and plastics. Due to its elastic properties, it is used in an extremely wide range of fields, including foams from cushioning materials to structural materials, various laminated products, elastic fibers, paints, adhesives, and even artificial leather. Although Polycreta/ has many advantages as described above, it has poor light resistance, and more specifically, it has the disadvantage that it decomposes when exposed to light, resulting in a decrease in strength and elongation. In particular, when polyurethane is used as a surface coating agent for fabrics or as a component of artificial leather, light resistance becomes an extremely expensive condition.

Various methods have been proposed in the past to improve the light resistance, which is the biggest problem with polyurethane. Polyurethane is obtained by reacting a polyester-based, polyether-based, or polycarbonate-based polymeric diol with an organic diisocyanate and an active hydrogen compound as a chain extender. It is known that when an aromatic organic diamine is used as an active hydrogen compound, the resulting polyurethane is likely to deteriorate. The p-light resistance can be improved by using an aliphatic or alicyclic organic diisocyanate or an organic diamine instead of an aromatic organic diisocyanate or an aromatic organic diamino. It is also known that polyurethanes using hydrazine as a chain extender generally have improved light resistance.Based on these perceptions, German Patent No. 225228
No. 0 (U, 8.P, No. 3900688, Br1tis
hPatent No. 1418550) uses polycarbonate glycol as the polymer diol,
Polyurethane synthesized using an aliphatic or alicyclic organic diisocyanate as an organic diisocyanate in combination with an alicyclic or aliphatic organic diamine and hydrazine as a chain extender has excellent light resistance. It is stated that. However, the polyurethane described in this patent is also not fully satisfactory with respect to light resistance.

The purpose of the present invention is to provide a polyurethane composition with excellent light resistance, and to prevent the dyes contained in the polyurethane composition from being removed by dry cleaning, by the action of light or heat, by the adhesion of sweat, or simply over time. It is an object of the present invention to provide a polyurethane composition that does not undergo 71 migration, running, and decomposition. In particular, Honjitsu Ij11 aims to provide a Bo4J urethane composition that has further improved dry cleaning resistance and sweat fading resistance. A further object of the present invention is to provide a polyurethane composition that not only satisfies these properties but also sufficiently satisfies properties such as strength and elongation, bending resistance, heat explosion resistance, and water resistance. Yes 0 These purposes are for polymer +- containing polyoxyethylene chains.
This is achieved by a polyurethane composition in which a specific dye is blended with a polyurethane obtained by reacting 2-ol, an alicyclic organic diisocyanate, an alicyclic organic diamine, and a human 2-diamine in a specific ratio.

That is, the present invention provides (a) an average molecular weight of 300 to 5.0;
00, (b) alicyclic organic diisocyanate, (C) hydrazine 2, and (d) alicyclic organic cyano, and under the following conditions (1% (
II) and (to), (1) The 4-molecular diol has an intramolecular 4C (-CHICH
It is either a diol containing IO−)n or a mixed diol of a diol containing +CHsCH*0+n in its molecule and a diol not containing it. The ratio of 0+0 is within the range of 50 to 80% by weight, and the value of n is on average within the range of -e12 to 100 (Ill The ratio of organic diincyanate to polymeric diol is 2% by weight)
, 5 to 5.5 and (i
A polyurethane composition comprising a polyurethane that satisfies the following: -0.8, and at least one dye selected from the group consisting of metal-containing complex dyes, happy dye dyes, sulfur dyes, and hostile dyes. be.

As mentioned above, the polymeric diol made from one component of the raw material used to synthesize the polyurethane constituting the polyurethane/composition of the present invention has +CHsC in the molecule.
It is either a diol containing HiO−)n, or a mixed diol of a diol containing and not containing 4:ChzO+1 in the molecule, and a high molecular weight diol. Inside +Of (Snow CH2
O+. It is a polymeric diol in which the proportion of n is in the range of 50 to 80% by weight, and @k of the above n is in the range of 12 to 100 on average.

In the present invention, as the polymer diol, polyester glycols such as polyethylene adipate glycol, polypropylene adibate glycol, polytetramethane adipate glycol, polyhexamethylene adipate glycol, polyether/globile/adipate glycol, polycaprolactone glycol, etc. polyethers such as polypropylene ether glycol and polytetramethylene ether glycol (excluding polyethylene ether glycol), polycarbonate glycols represented by t, s-hexyl diol polycarbonate glycol, polyacetal glycol, It is easy to obtain raw materials by using at least one diol selected from the group consisting of general polymer diols such as polyptadiene glycol in combination with polyethylene ether glycol having an average degree of polymerization within the range of 12 to 100. In addition to this, a block copolymer diol having a polyoxyethylene chain in the molecule may be used. Such copolymer diols include
Examples include poly(oxypropylene)poly(oxyethylene)glycol, poly(oxyethylene)polycaprolactone block copolymers, etc.These copolymer diols may be used alone, or may be used in combination with the various types mentioned above. It may also be used by heating it with a polymeric diol. In particular, when polyester glycols and polyethylene ether glycol are used together as polymeric diols, or polycarbonate glycol and polyethylene ether glycol are used together, in addition to the ease of obtaining raw materials, the light resistance and light resistance of dyes are It is preferred in the present invention because it results in a polyurethane composition that is excellent in this respect.

In the present invention, the polymer diols mentioned above are used, but the average molecule 1 of the polymer diol must be within the range of 300 to 5,000. Fi is preferably in the range of 500 to 4,000. If the average molecular weight of the polymeric diol is lower than 300, the resulting polyurethane composition will be too hard and will have the elasticity required for polyurethane, with an extremely low elongation at break. On the other hand, if it is higher than s, ooo, it becomes too soft and loses its elasticity, resulting in an extremely low strength.

ti In the present invention, the number of repeating units in the polyoxyethylene chain contained in the polymeric diol, that is, the number of On when the polyoxyethylene chain is inserted into +CH*CHgαh, is extremely important. The number of n is 12 on average
If the amount is less than The dye molecules will migrate out of the polyurethane, making it difficult to obtain a polyurethane composition with long-term light resistance. If the average value of tn exceeds 100, the resulting polyurethane composition will be too flexible, resulting in reduced strength and elongation.
The object of the present invention can be further achieved when the number is within the range of 80 to 80.

Further, in the present invention, the proportion of polyoxyethylene chains in the polymer diol is within the range of 50 to 80% by weight. If the amount is less than 50% by weight, the resulting polyurethane does not necessarily have sufficient affinity with dye molecules, and even if a dye is added to such polyurethane, it may deteriorate over time, during dry cleaning, or due to the adhesion of sweat. This causes the dye molecules to migrate out of the polyurethane. Light-colored dyed polyurethane obtained by shortening the special Ks dyeing time tends to have poor dry cleaning resistance and sweat resistance, and in such cases, increasing the polyoxyethylene chain is effective. . On the other hand, if the proportion of polyoxyethylene chains exceeds 80, the polyurethane molecules in the resulting polyurethane composition will be extremely susceptible to decomposition by light and oxidation by heat, resulting in poor strength and elongation. In addition to this, the resulting polyurethane becomes extremely susceptible to swelling in water, resulting in a significant decrease in wet strength and extremely poor washing fastness.

As mentioned above, the present invention aims to further improve dry cleaning resistance and sweat fading resistance, which is achieved by increasing the content of polyoxyethylene chains. This is what I discovered.

In addition, polycarbonate glycol is +R-OCO-
), a general term for polymeric diols that have internal groups and hydroxyl groups at both terminals -tS
a, Invention TeId RAE -CH*CHsCH*CH
A polycarbonate glycol such as m Ckl*Ck1m -, that is, 1,6-hexanediol polycarbonate is also preferred (where R is a divalent organic group and p represents the degree of polymerization).

In the present invention, an alicyclic organic diisocyanate is used as the diisocyanate compound. As a representative alicyclic organic diisocyanate, 3-isocyanate methyl-
3,&5-)limethylcyclohexyl isocyanate (
Common names: isophorone diisocyanate), dicyclohexylmethane-4,4'-diisocyanate, isopropylidenecyclohexane diisocyanate, and the like.

When an aliphatic or aromatic organic diisocyanate is used in place of the alicyclic organic diisocyanate, the resulting polyurethane is light-resistant.

In addition to this, it was also inferior in terms of mechanical properties, heat resistance, and water resistance, and especially when aromatic organic diisocyanates were used, light resistance was poor. becomes.

In the present invention, an alicyclic organic diisocyanate must be used as the diisocyanate compound eyelid, but the entire amount does not need to be an alicyclic organic diisocyanate. That is, if the amount is small, it can be replaced with an aliphatic or aromatic organic diisocyanate. however,
As the amount of aliphatic or aromatic organic diincyanate increases, the above-mentioned drawbacks become more serious. Therefore, in the present invention, it is preferable not to use any organic diisocyanate other than alicyclic organic diisocyanate, especially aromatic organic diisocyanate.

In the present invention, the molar ratio of organic diisocyanate to polymeric diol must be within the range of 2.5 to 5.5. In general, when synthesizing polyurethane, conditions in which the ratio of organic diisocyanate to polymeric diol is less than #i2.5 are used, and it is important that this ratio is higher than the conditions generally used in the past. This is one of the features of the invention. In the present invention, if the ratio of the alicyclic organic diisocyanate to the polymeric diol is less than 2.5, the resulting polyurethane composition will have decreased light resistance and insufficient heat resistance. Furthermore, in the present invention, in order to suppress the decrease in water resistance that would be caused by containing a large amount of polyoxyethylene chains, it is preferably 2.5 or more. On the other hand, if it is larger than 5.5, the resulting polyurethane composition will become hard and its elongation will decrease. Preferably it is within the range of 2.7 to 5.0.

It refers to the proportion of all organic diisocyanates used, and therefore, if a small amount of alicyclic organic diisocyanate is replaced with aliphatic or aromatic organic diisocyanate, the proportion also includes these organic diisocyanates. It is.

Further, in the present invention, alicyclic organic diamine and hydrazine must be used together as chain extenders. Representative alicyclic organic diamines used in the present invention include 1-amino-3-aminomethyl-35,5-trimethylcyclohexane (commonly known as isophorone diamine), 4,4'-diaminodicyclosilmethane, 4.4'-diamino-
Examples include 3,3'-dimethylcyclohexylmethane and cyclohexylene diamine.

When an aliphatic or aromatic diamine is used in place of the alicyclic organic diamine, the resulting polyurethane has poor mechanical properties, heat resistance, water resistance, and light resistance. In particular, when an aromatic type is used, the light resistance becomes extremely poor.

In the present invention, alicyclic organic shea 47 must be used as the organic diamine compound, but the entire amount does not have to be alicyclic. Can be replaced with hydrogen compounds. However, as the amount of aliphatic or aromatic active hydrogen compounds increases, the above-mentioned drawbacks become more serious. Therefore, in the present invention, it is preferable not to use any organic active hydrogen compounds other than alicyclic organic diamines, especially aromatic organic diamines.

Note that the organic active hydrogen compound refers to a low-molecular organic compound having two hydroxyl groups or amino groups, and is a compound commonly used as a chain extender for polyurethane. In addition, the alicyclic organic diincyanate and alicyclic organic diamine referred to in the present invention are only compounds in which an incyanate' group or an amino group is directly bonded to an aliphatic ring, for example, a cyclohexane ring. First, it refers to compounds including compounds in which an isocyanate group or an amino group is bonded to an aliphatic ring via an alkyl group.

As described above, in the present invention, it is essential to use an alicyclic organic diisocyanate as the organic diincyanate and an alicyclic organic diamine as the organic diamine. However, is it possible to use isophorone diisocyanate as the alicyclic organic diisocyanate?

Alternatively, isophorone diamine is used as the alicyclic organic cyanide, or alternatively, isophorone diisocyanate is used as the alicyclic organic diisocyanate and isophorone cyanide is used as the alicyclic organic diamine. It is preferable to use an isophorone-based material for at least one of the polyurethanes in terms of ease of synthesizing the polyurethane, ease of storing the synthesized polyurethane solution, and ease of use of the obtained polyurethane solution. In other words, in the present invention, it is essential to use hydrazine as a part of the chain extender, but generally when hydrazine is used, it is necessary to store the polyurethane in a soluble form during the synthesis of polyurethane or after synthesis. During this process, the liquid may gel or thicken, but by using isophorone-based diamine or diisocyanate, such gelation and thickening can be significantly suppressed.

In addition, the amount of hydrazine used as a component of the chain extender in the present invention must be within the range of 5 to 80 molti based on the total amount of alicyclic diamine and hydrazine. If the amount of p is less than morchi,
A composition in which a dye is blended with the obtained polyurethane has low light resistance, and conversely, if the amount exceeds 80 molti, a polyurethane composition in which a dye is blended in a part of the polyurethane will have insufficient washing fastness of the dye. Water resistance also deteriorates, making it unsuitable as a component of artificial leather in the surface coating layer of fabrics, and gelation may occur during the synthesis of polyurethane, and the polyurethane solution may thicken after synthesis. It has its drawbacks. Note that hydrazine used in the present invention may be in the form of a hydrate.

The polyurethane constituting the polyurethane composition of the present invention is synthesized from the above-mentioned higher polymer diol, alicyclic organic diisocyanate, alicyclic organic diamine, and hydrazine. Various methods conventionally used in the synthesis of polyurethane can be employed. Next, we will list typical methods.

First, a polymer diol and an alicyclic organic diisocyanate are mixed in a nitrogen atmosphere at a ratio of 50 to 1
The mixture is heated to 30°C and reacted to obtain a polyurethane prepolymer having incyanate groups at the ends. The obtained prepolymer is dissolved in a solvent, and the prepolymer is chain-extended with hydrazine and alicyclic organic diamine at a temperature around room temperature to obtain a polyurethane solution. If necessary, a carboxylic acid or the like may be added to the obtained polyurethane solution to block unreacted amino groups present in the polyurethane solution to stabilize the polyurethane solution.

Examples of reaction solvents used when synthesizing polyurethane include dimethylformamide, diethylformamide, dimethylacetamide, dimethylsulfoxide, acetone, methylethylactone, toluene, isopropanol, cyclohexane, tetrahydrofuran, ethyl acetate, methyl cellosolve, Examples include cellosolve acetate. Some of these solvents cannot be used as a solvent by themselves, but they can be used as a solvent by mixing with other solvents. When storing in solution,
It tends to grow and wither as it gels. In order to suppress such thickening in the gel pores, there is a method of using isophorone-based diisocyanate or diamine as a raw material, as described above, but other methods include using it as part of the reaction solvent or after the reaction. Another method is to add a lower alcohol such as methanol or ethanol, or water to the polyurethane solution.

In addition, in order to give the obtained polyurethane more anal properties with dyes, compounds containing tertiary i1 elements, such as N-methylamine, nobisprobylamine, N-methyldiethanolamine, N-isobutyljet, etc. Tanolamine, 1,4-bisacinoprobylpiperazine, may be used as part of the chain extender. However, as the amount of compounds containing these tertiary elements increases, physical properties such as hydrolysis resistance and light resistance deteriorate, so the amount of compounds containing tertiary elements is It is preferable to keep the total amount of chain extenders within about 15 molar.

We decided to add dye to the polyurethane obtained by the method described above! Although the polyurethane composition of the present invention can be obtained, there are many kinds of dyes, and the dyes that improve the light resistance of the polyurethane of the present invention include metal-containing complex dyes, tint dyes, sulfur dyes, and Limited to acid dyes. Among them, metal-containing complex salt dyes are preferred. In addition, direct dyes, disperse dyes, basic dyes, etc. also improve the light fastness of polyurethane to some extent, but the extent is small, and dye retention, such as wash-warm brittleness and dry cleaning fastness of dyes, can be improved to some extent. Furthermore, the dye transfer prevention property is poor.

A metal-containing complex salt dye is a dye in which a metal and a dye molecule form a complex salt in a ratio of 1=1 or 1:2, and usually have a sulfonamide group or a sulfonate group in the molecule. It has a y group, etc., and has a negative charge as a whole. The metal that forms complex salts is commonly chromium, and other metals such as cobalt and copper are also used. In the present invention, 1:2 type metal-containing complex dyes are particularly preferred. Both dyes and sulfur dyes are reduced in the presence of an alkali and have no mizucho-curable properties, and are then treated with oxidation. A dye that is water-insoluble. Mafc acidic dyes contain oxy(-OH) and carboxy(-C(JL)
) H), sulfonic acid (-8OsH) Nato f) A dye having an 8-functional group and dyeing using an acidic bath, such as an aqueous sulfuric acid bath. The aforementioned 1:1 type metal-containing lI4#I salt dye is included in this dye, but some are not included in the 1:2 type metal-containing complex acid dye.

In the composition of the present invention, the blending amount of the dye is preferably 3 weight or more based on the weight of the polyurethane. If the amount is less than 3% by weight, the effect of incorporating the dye will be low, that is, the light resistance will be low.The amount of dye blended is usually preferably within 70% by weight of the polyurethane. If the amount added exceeds 70% by weight, the mechanical properties such as strength and elongation I of the polyurethane composition will only decrease, and no improvement in light resistance will be observed. The dye to be specifically blended may be selected from among metal-containing 14 complex dyes, happy dyes, acid dyes, and sulfur dyes depending on the required color, blending amount, and purpose. As a method for obtaining the polyurethane composition of the present invention, the polyurethane St obtained as described above is coated with at least one selected from the group consisting of metal-containing complex dyes, vat dyes, acid dyes and sulfur dyes. After adding the dye,
There is a method for removing #l rope from this polyurethane solution and dyeing the same product (usually in the form of a woven film or leather) with the same dye after removing the solvent from the polyurethane solution. There are two methods for introducing dye molecules inside polyurethane. Which method to use may be determined depending on the dye used, the amount blended, and the intended use.

The polyurethane composition of the present invention may further contain additives such as antioxidants, ultraviolet absorbers, pigments, dyes, flame retardants, fillers, and the like.

Note that the solvent solution containing only polyurethane in the polyurethane composition of the present invention can be used as various coating materials.

The polyurethane composition of the present invention is extremely excellent as a component constituting artificial leather or as an inlay coating layer for fabrics. An example of the method is shown below.

After impregnating a fiber sheet, typically a non-woven fabric, woven fabric, knitted fabric, or a laminated product of these, with polyurethane solution, the organic solvent is removed by wet coagulation or dry cooling, followed by drying and impregnation. Get a sheet. This impregnated sheet is impregnated and, if the polyurethane I# armpit contains no dye, is dyed, and then the surface is puffed to obtain cis-need artificial leather. In addition, a delicate sheet impregnated with a polymeric elastic material is coated with a polyurethane solution after the polymeric elastic material is coagulated if necessary, and this is wet-coagulated to provide a surface coating layer, and the polyurethane solution contains a dye. If not, artificial leather with an Ith1 surface layer can be obtained by dyeing it. Furthermore, a film is formed in advance from a polyurethane solution by a dry or wet method, and this film is then applied to a fiber sheet or
c is achieved by laminating the surface of a fiber sheet containing a polymeric elastomer, or by simply applying a polyurethane bath solution onto the fiber sheet and dry or wet coagulation, and then the polyurethane solution is dyed. If it does not contain 1, artificial leather with a silver shield can also be obtained by dyeing it.

The edge line product containing the polyurethane composition of the present invention on the surface or inside has extremely excellent light resistance, and can be used as clothing, shoes, bags, upholstery for sofas, etc. , suitable for many other fields.

The present invention will be specifically explained below using examples.

In addition, in the examples, there is no special mention@shi, hot water treatment refers to the case of immersion in hot water at 90℃ for KIO days), and fade meter treatment refers to the case of immersion in hot water at 63℃ for 50 hours. This is the value when exposed to light (carbon arc l!i). In addition, dye fading (lighting column ff1) of the dyed object is JISLO 8.
42-1971, dry cleaning fastness was determined by the method of JIS Lo860, and washing resistance was determined by the method of JIS L 0844-1973 (Method A). Judgment was made using gray scale for pollution and gray scale for contamination. In addition, sweat fading fastness was measured using an artificial juice shown in JISL-0848, and a polyester-based polyurethane bath liquid (containing titanium oxide).
) The above artificial juice solution was dropped onto an artificial leather sample in which a polyurethane dry film of the present invention or a comparative example was pasted onto a non-woven fabric impregnated with and coagulated.
The sample was treated for 0 hours and the fading of the sample after treatment was planned in gray school. In these robustness tests, those with a 5th grade fastness are the least fast, and the fastness decreases from 4th grade, 3rd grade, and 2nd grade. This is a case where it is worse. In addition, dye migration was determined by preparing a transparent polyester polyurethane sheet of the same size as a 5α x 5DM test piece, placing one layer of this polyurethane sheet on top of the test piece, and placing it on a glass plate (10 pieces of large paper x 10 sheets).
Tan, thickness 3-)? The sample was pressed under a 7 o'clock load for 24 hours in an open environment at 70°C, and the degree of transfer of dye from the test piece to the polyurethane sheet was determined. A gray scale for contamination is used for judgment, and 1 to
We determined which grade of the 5th grade it falls under. In addition, regarding the viscosity stability of the synthesized polyurethane solutions, those with little thickening of #1 showed viscosity of #01, and those with
is attached. Furthermore, all the raw materials for polyurethane used in the examples are indicated using abbreviations, and the relationship between the abbreviations and the compounds is as follows.

Abbreviation Compound PCL Polycaprolactone glycol PC
1,6-hexanediol polycarbonate P W G
Ho IJ Ethelene Ether Glycol E Pυ
■ Inophorone diisocyanate H12DAM
4,4'-diaminodicyclohexylmethane IP
DA Isophoronediamine HH Hydrazine Hitlerde Example 1.2 Comparative Examples 1 and 2 Each of the polyurethane elastomers was produced from the polymeric diol, organic diisocyanate, and chain extender shown in 1&. That is, a polymeric diol and an organic diisocyanate are stirred and reacted under nitrogen at 60 to 120°C for 5 to 10 hours, and the resulting nine polyurethane grebolymer is mixed with dimethylformamide (hereinafter referred to as 1) MF) for 15 times.
It was melted to a temperature of 111 degrees b\. Next, after dissolving a certain amount of chain extender in DMF, the above-mentioned prepolymer solution was added to this bath solution, and the reaction was carried out by stirring for 2 to 5 hours at 30°C and M1c, and the polyurethane elastomer O
DME' common liquid as bath liquid. The concentration of polycrethane in this bath solution is 1
After applying an amount of 2N to 1A, this solution was cast onto a glass plate and dried to obtain a dry film of 60 μm in thickness.

This film was dyed under the following dyeing conditions, nooping conditions and water washing conditions. The dyed film was subjected to various physical properties. Polished rice is shown in Section 2e.
10% owf (1:2m metal-containing gjIhanawa dye) Bath ratio 1:500 dyeing process f
60℃ Dyeing time 1 hour Noping String bonding surfactant Monogen Uni (anionic) Soaping mixed carbon 60G Soaping time l 0 minutes Washing conditions Under running water for 10 minutes 1st Table below margins! j! Examples 3 and 4 Comparative Examples 3 and 4 A volumetric polyurethane elastomer was produced in the same manner as in Example 1 from the polymeric diol, organic diisocyanate and chain extender listed in Table 3, and further in the same manner as in Example 1. The membrane was stained and a stained membrane was produced. This BL film was then subjected to various physical property tests. 4th result
Shown in the table.

Table 3 Examples 5 to 10, Comparative Example 5.6 The polycrethane film obtained in Example 1 was dyed using the dyes listed in Table 5 below, and the dyed products were subjected to physical property tests by woodcutter. The obtained physical property values are shown in Table 6. In all of the dyed membranes, the dye molecules had sufficiently penetrated into the polyurethane. In the dyeing of Example 8, hydrosulfite was used as a reducing agent, sodium hydrogen sulfide (NaSM) was used as an oxidizing agent, and hydrogen peroxide was used as an oxidizing agent. (7) Sulfur I! An acidic bath was used. The dyeing of Comparative Example 5 was N1zd0420%.
owfs dye.The dyeing was carried out for 1 hour in a dyeing bath at 80°C containing 3% owf.
It was dyed by treatment in a dyeing bath containing wf dye at 80° C. for 1 hour.

Chapter 6 Table

Claims (1)

[Scope of Claims] 1. (a) a polymeric diol having an average molecular weight within the range of 300 to 5,000, (b) an alicyclic organic diinocyanate), ((hydrazine) and (d) an alicyclic organic diinocyanate). synthesized from diamine and under the following conditions (1), (II
) and (2), (1) Polymer diol is present in the molecule with CHzCi(2
It is either a diol containing +CHIICH20+□ in its molecule or a mixed diol containing a diol containing +CHIICH20+□ in its molecule, and a diol that does not contain +CHIICH20+□, and the proportion of CHZCHZO+ in the polymer diol is , 50 to 80% by weight, and the average value of n is in the range of 12 to 100; (II) the molar ratio of the organic diisocyanate to the polymeric diol is 2.5 to 5. (m)t:)'rTotal amount of resin alicyclic organic diamine V
The molar ratio of alicyclic organic diamine to this is 0.05.
-0.8, and at least one dye selected from the group consisting of metal-containing complex dyes, vat dyes, hostile dyes, and sulfur dyes. . 2. The polymeric diol is either a mixed diol consisting of polyester glycol and polyethylene ether glycol, or a mixed diol consisting of polycarbonate glycol and polyethylene ether glycol, and the average degree of polymerization of the polyethylene ether glycol is 12 or more. Within the range of 100 and
The polyurethane composition according to claim 1, wherein the proportion of polyoxyethylene chains in the polymeric diol is in the range of 50 to 80% by weight. 3. The polyurethane composition according to claim 1, wherein n is within the range of 15 to 80. 4. Alicyclic organic diisocyanate is isophorone diino 7
The polyurethane composition according to claims 1 to 3, wherein the polyurethane composition is anate and/or the alicyclic organic diamine is inphorone diamine. 5. The polyurethane composition according to claims 1 to 4, wherein the molar ratio of organic diisocyanate to 1 molecule of diol is within the range of 2.7 to 5.0. 6. Claims 1 to 6, wherein the dye is a metal-containing complex salt dye.
The polyurethane composition according to item 5. 7. The ratio of dye to polyurethane is 3 to 70
The polyurethane composition according to any one of claims 1 to 6, which is within the range of - by weight.