JPS59102950A - Polyurethane composition - Google Patents

Abstract

PURPOSE:To provide a polyurethane composition capable of keeping excellent properties such as whiteness-keeping property to sunlight, NOX gas, exhuast gas, etc., and retainability of strength and elongation after weathering, stably for a long period, by compounding a specific polyurethane elastomer with a solvent of said elastomer and an acidic substance. CONSTITUTION:The objective composition is obtained by compounding (A) a polyurethane elastomer composed of a high polymer diol having a molecular weight of >=500, an organic polyisocyanate, a chain extender and a terminator, wherein a compound of formula [R<1> is H, O, -(R<3>O)n-H, -(COR<4>COOR<5>O)m-H, etc.; R<2> is H, lower aliphatic group, etc.; R<3> is lower alkylene; R<4> is organic dicarboxylic acid residue; R<5> is organic diol residue; R<6> is H, etc.; R<7> and R<8> are lower aliphatic group, etc.; X is OH, etc.; n is 1-50; m is 1-15] having a hindered amino group is used as a part of the above chain extender and the terminator, with (B) 0.8-100mol equivalent, based on the hindered amino group, of an inorganic acid or organic carboxylic acid, etc., and (C) a solvent of the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polyurethane compositions. More specifically, the present invention provides a composition that has excellent oral stability of a polyurethane solution that has excellent white color retention against sunlight, NOx gas, automobile exhaust gas, etc., and also has excellent weather resistance strength retention and one-plane elongation retention. relating to things.

Polyurethane elastic bodies are rich in elasticity and wear resistance, and are widely used as coatings on knitted fabrics, non-woven fabrics, etc., as coatings for artificial leather after being impregnated and solidified, or as materials for elastic threads. However, despite this useful material, its use is severely limited because it has the disadvantages of being affected by sunlight, NOx gas, automobile exhaust gas, etc., discoloration, and a decrease in strength and elongation. It has been known to add various additives to prevent the deterioration of polyurethane elastomers, but they can cause problems such as shedding due to blooming and deterioration of the polymer, especially when applied to clothing materials due to cleaning. It has the disadvantage of falling off.

In order to overcome such drawbacks, the present inventors developed a polyurethane having a weather-resistant function in its molecular chain under Japanese Patent Publication No. 5 < S-424.
28, % Application No. 56-90369, etc.

In particular, the latter polyurethane having a specific hindered amine is disclosed in Japanese Patent Application No. 1130-1983. ．． 2-? % Gansho 54-1
As proposed in No. 03424, etc., the composition exhibits excellent functions as a solidified sheet material by impregnating it into a fiber sheet. For example, the physical properties may be significantly lower than that of general polyurethane solutions, or the terminal amine content may increase.
Although it has an earthquake-resistant fading function in its molecule, it still has the drawback that this function cannot be effectively expressed.

The object of the present invention is to provide a polyurethane composition that overcomes these drawbacks.

In order to achieve such an object, the present invention is as follows.

(A) Consisting of a polymeric diol with a molecular weight of 500 or more, an organic polyisocyanate, and a chain extender, and if necessary, a terminal stopper, and as at least a part of the chain extender and/or end stopper. , a polyurethane elastomer using a compound having a hindered amino group represented by the formula CI), (B) 0.8 to 100 with respect to the hindered amino group
molar equivalents of inorganic acids, organic carboxylic acids, organic sulfonic acids, and their anhydrides/% at least one compound selected from halides, alkali salts, or ammonium salts; and (C) of the polyurethane elastomer. A polyurethane composition comprising a solvent.

First, the polyurethane elastomer (5) constituting the composition of the present invention will be explained.

(5) The polymeric diol that constitutes the polyurethane elastomer has hydroxyl groups at both ends and has a molecular weight of 5.
00 or more, preferably 800 to 4000', and preferably has a melting point of 70°C or less, such as polyester glycol, polyether glycol, polyether ester glycol, polyacetal glycol, polybutadiene glycol, etc., and representative thereof Examples include polyethylene adipate, polypropylene adipate, polytetramethylene adipate, polyhexamethylene adipate, polycaprolactone glycol, poly(ethylene oxide) glycol, poly(propylene oxide)
Glycol, poly(tetramethylene oxide) glycol, etc. or mixtures thereof can be used.

Examples of organic polyisocyanates constituting the polyurethane elastomer of the present invention include phenylene diisocyanate, toluylene diisocyanate, and diphenylmethane-4,4'
-diincyanate, diphenyldimethylmethane-4,
4'-diisocyanate, naphthylene diisocyanate, diphenyl diisocyanate, ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, inphorone diisocyanate, dicyclohexylmethane-4,
Organic diisocyanates such as 4'-diisocyanate, dicyclohexyldimethylmethane-4,4'-diisocyanate, xylylene diisocyanate, etc. and mixtures thereof, as well as reaction products of these organic diisocyanates with polyhydroxy compounds. , polyisocyanates containing incyanate groups, such as those obtained by trimerization of organic diisocyanates, and polyinsyanates containing biuret groups, such as those obtained by the method of German Patent Specification No. 1,101,694. Preferred are organic diisocyanates, and more preferred are aromatic organic diisocyanates and alicyclic organic diisocyanates.

When a sheet is formed, toluylene diisocyanate, diphenylmethane-7-4,4'-diisocyanate, diphenyldimethylmethane-4,4'-diisocyanate, and naphthi are particularly preferred because they improve strength, impact resilience, and heat resistance. Diisocyanate polymers are mixtures thereof.

Strength above a certain level, appropriate rebound elasticity, and sufficient heat resistance on one side.
Aspect 1: In order to obtain a sheet with chemical properties, the organic diisocyanate is used in an amount of 1.7 to 6 molar equivalents, more preferably 1.8 to 5 molar equivalents, relative to the polymeric diol.

The chain extender used in the present invention is preferably a low-molecular compound having two or more functional groups that react with commonly used organic polyisocyanates, such as glycols, diamines, amino alcohols, dihydrogen and/or Or its 94 bodies, water, etc. are used.

Glycol chain extenders used in the present invention include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-bentanediol, neopen 5-L:I-L , hexanediol, cyclohexanediol, 1,4-bis(β-hydroxyethoxy)benzene, N,N'-bis(β-hydroxyethyl)aniline, diethylene glycol, triethylene glycol, etc., or a mixture thereof. Preferably ethylene glycol, propylene glycol, 1.4-butanediol, 1.4-bis(β
-hydroxyethoxy)benzene, etc.

Specific examples of the organic diamine chain extender used in the present invention include P-phenylene diamine, m-phenylene diamine, tolylene cyanone, and naphthylene diamine 44
/-diaminodiphenylmethane, 4.4'-diaminodiphenyl ether, 4.4'-diaminodiphenylthioether, 4.4'-diaminodiphenyl sulfone, 4
．． Aromatic organic diamines such as 4'-diamino-6,3'-dimethyldiphenylmethane, 4,4'-diamino-fila, 6'-dichlorodiphenylmethane, 4,4'-diaminodiphenyldimethylmethane, ethylene diamine, fluoropylene diamine , menzandiamine, inphorondiamine, cyclohexylene diamine, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-ro, 5'-
Aliphatic organic diamines such as dimethyldicyclohexylmethane and xylylene diamine, or mixtures thereof. Aromatic organic diamines or alicyclic organic cyano/are preferred, among which 4,4'-diaminodiphenylmethane, tolylene diamine, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-6,3'- Dimethyldicyclohexylmethane.

More specifically, R1 is a hydrogen atom,
Oxygen atom, methyl group, ethyl group, propyl group, butyl group, octyl group, aryol group, propenyl group, butenyl group, imprenyl group, linalyl group, neryl group, geranyl group, zundzyl group, alkyl and/or Halogen-substituted hensyl group, acetyl group, propargyl group, butynyl group, β-
Substituents selected from hydroxyethyl and Uβ-hydroxyglopyl groups. R2 is preferably a hydrogen atom, a methyl group, an ethyl group, a furoyl group, a phenyl group, a benzyl group, a xylyl group, a phenylethyl group, a vinyl group, a flobenyl group, a butenyl group, an ethynyl group, a propargyl group, and a cyano group. Selected substituents. R6 is preferably a substituent selected from a hydrogen atom, a methyl group, an ethyl group, a propyl group, and a butyl group.

R.7 and R8 are the same or different, methyl group, ethyl group1. Substituents selected from propyl groups and butyl groups, or those that combine to form a 5-, 6-, or 12-membered ring.

In addition to the above-mentioned substituents, the oxygen atom of the amine group, hydroxyl group, and monoalkylamino group of the substituent represented by formula [l] and/or the substituent represented by X may still be bonded to the nitrogen atom. The hydrogen that is -(R”0) n
-14 or -(COR'COOC00R50) may be substituted.

In the former case, R3 represents a lower alkylene group, and n represents an integer of 1 to 50. A lower alkylene group has 2 to 14 carbon atoms.
means. Specific examples of R,30 (alkylene oxide) include ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide, epichlorohydrin, and mixtures thereof.

In the latter case, R4 represents an organic dicarboxylic acid residue, R5 represents an organic diol residue, and m represents an integer from 1 to 15. The organic dicarboxylic acid preferably has 2 to 12 carbon atoms, and specific examples include succinic acid, adipic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, anhydrides thereof, and mixtures thereof. . The organic diol preferably has 2 to 8 carbon atoms, and specific examples include:
Ethylene glycol, propylene glycol, butylene glycol, hexane glycol, octane glycol, diethylene glycol, triethylene glycol, etc.
and mixtures thereof.

Preferably, the compound of formula CI) is 2
．． 2.6.6-tetramethyl-4-hydroxypiperidine, 2.2.6.6-tetramethyl-4-aminopiperidine, 1,2,2,6.6-bentamethyl-4-hydroxypiperidine, 1,2, 2,6,6-bentamethyl-4-aminopiperidine, 1-benzyl-2,2,6,6
-Titramethyl-4-hydroxypiperidine, 1-benzyl-2,2,6,6-tetramethyl-4-aminopiperidine, 1(27-hydroxyethyl) -2,2,6
, 6-tetramethyl-4-hydroxypiperidine. Of the above compounds, those in which R6 is a methyl group, those in which R6 is a methyl group, those in which R7 and I(, 8 are substituted with a methyl group, an ethyl group, a cyclohexyl group, or a cyclododecyl group, respectively) are also preferred compounds. .

When producing the polyurethane elastomer of the present invention, in addition to the monovalent hindered amine compound mentioned above, in order to adjust the degree of polymerization to a desired degree, a commonly used amine group or a hydroxyl group is added.
Uniquely monofunctional compounds can be used.

The polyurethane elastomer of the present invention can be obtained by adding and reacting a polymeric diol, an organic polyinsyanate, a chain extender, and, if necessary, a terminal capping agent all at once, as is generally practiced. It is also possible to use a so-called prepolymer method in which a polymeric diol and an organic polyisocyanate 1 are reacted in advance to synthesize a so-called prepolymer, and then extended with a chain extender.

The hindered amine compound, which is a feature of the present invention, may be added at any stage of the above reaction process. When using a hindered amine compound having a hydroxyl group that has low reactivity with incyanate groups, it is desirable to add it at an early stage of the reaction to ensure intramolecular introduction.

When synthesizing the polyurethane of the present invention, in order to accelerate the reaction rate, for example, S, L, Reegen and K, C
, Fr1scb, ``Advancea in Ure
thane 5science and technology
gy,” 1, (1971) Technomi
c.

It is of course possible to add a 6th class amine such as triethylenediamine as described in Pub. Co., Inc., or an organometallic compound such as dilauryldibutyltin. The amount used is such that the nitrogen content derived from hindered amino groups is o, based on the polyurethane solid content.
o o o i~1% by weight, preferably 0.001~
0.1% by weight, more preferably 0.002-0.01% by weight.

If the nitrogen content is less than this, the weather resistance function will not be sufficiently effective, and if it is too much, side reactions will occur during the polymerization reaction, or the polymer chain will not be sufficiently elongated, resulting in a polymer with the required molecular weight. This is because if it is not obtained or if the hindered amino group-containing compound is still difunctional, the physical properties such as the strong softening point of the desired polymer will be impaired.

Specific examples of the acidic substance as the component (B) of the composition of the present invention include inorganic acids, organic carboxylic acids, organic sulfonic acids, etc.
and/or their acid anhydrides and acid halides. In the case of polybasic acids, they are partially substituted with alkali metals, ammonia and/or amines. More specifically, hydrochloric acid, tt, nitric acid, sulfuric acid, sulfurous acid, bisulfuric acid,
These include phosphoric acid, phosphorous acid, pyrophosphoric acid, oxalic acid, formic acid, acetic acid, chlorobenzoic acid, toluenesulfonic acid, etc., and their chlorides, bromides, acetic anhydride, phosphoric acid, monosodium salts, etc.

Among these, monobasic acids are preferably used in order to improve the rate of wet coagulation.

This is because, by using a -basic acid, a hydrophilic ammonium group that is not largely shielded by the polymer molecular chain is introduced into the polymer, thereby accelerating the infiltration of water molecules and promoting coagulation.

These acidic substances are 0 for hindered amine compounds.
．． It is added in an amount of 8 to 100 molar equivalents, preferably 0.8 to 10 molar equivalents, more preferably 0.9 to 5 molar equivalents.

In addition, if the acid is used in large excess, the hydrolysis of the polymer will be accelerated by trace amounts of moisture in the solution and in the acid, which is undesirable.
If an insufficient amount of less than 0.8 mol is used relative to the hindered amino group, especially when a large amount of the amine group is used, the basicity of the solution will be too high and the effect of the present invention cannot be obtained. .

The acidic substance of component 4 (B) of the present invention forms a salt with an amine group, and is preferably an acidic substance having a PKa of 6.0 or less, more preferably a PKa of 5.0 or less.

This is because when using materials with a PKa of 6.0 or higher, the neutralization of hindered amino groups is often insufficient.
It is difficult to effectively achieve the purpose of the present invention.

The solvent for the polyurethane elastomer of the present invention is not particularly limited as long as it dissolves it, but examples include dimethylformamide, diethylformamide, dimethylacetamide, hexamethylphosphoramide, dimethylsulfoxide, dioxane, tetrahydrofuran, ortho Chlorphenol and mixtures thereof are also used. Among them, dimethyl sulfoxide, dimethylacetamide, and dimethylformamide are preferred.

As already known, the solution of the polyurethane elastomer of the present invention contains various antioxidants, abrading agents such as ultraviolet absorbers, organic and inorganic pigments, carbon black, titanium oxide,
Additives such as coagulation regulators may also be added.

Although the polyurethane composition of the present invention is composed of a polyurethane elastomer having extremely unstable hindered amino groups, it has good physical properties because certain acidic substances form salts with the amine groups. Initial physical properties and their physical properties can be maintained for a long period of time.

Therefore, the polyurethane composition of the present invention can be used for various purposes, but is preferably used as an impregnating agent for elastic fibers, films, artificial leather, and coating materials thereof. Particularly preferably, it is used as a wet coagulation composition (particularly for artificial leather).

If the polyurethane composition of the present invention exhibits good physical properties as a film when molded, it can also be used as artificial leather with good physical properties.

EXAMPLES The present invention will be specifically explained below with reference to Examples, but of course the present invention is not limited to the following Examples.

The following abbreviations are used in the examples: 0 Abbreviation Chemical name PTMG Poly(tetramethylene oxide) glycol P CL Polycaprolactone glycol PEA
Polyethylene adipate glycol MDI Diphenylmethane-4,4'-diisocyanate EG Ethylene glycol MBA 4,4'-diaminodiphenylmethane DMF N,N-dimethylformamide PU
The following methods were used to evaluate polyurethane in the polyurethane examples.

Viscosity Measured using a 13-type viscometer (B-8H, manufactured by Higashi Tokyo Keiki Seisaku Membrane Co., Ltd.) at room temperature using a N [L 60-meter].

Dry membrane A polyurethane solution was applied onto a glass plate (20 cm x 20 cm) using a coating rod with a thickness of 1.5 mm, and then the I) Ml'' was removed under reduced pressure to form a dry membrane.

Wet-type membrane Similar to the dry-type membrane, a polyurethane solution coated on a glass plate was immersed together with the glass plate in water at 20°C to solidify the polyurethane, and then washed with water and dried.

Cutting strength The dry membrane or wet membrane was cut with a No. 6 dumbbell and the cutting strength was measured using a tensile tester (Tensilon UTM-111-100 manufactured by Toyo Baldwin ■).

The film was fixed on cardboard and irradiated using a Weather O meter (WEL-8UN-HMC manufactured by Suga Test Instruments) in an environment with an internal temperature of 60 to 66°C and humidity of 70%. (Hereinafter abbreviated as WM) Example-1a Two times the mole of MDI in PTM () with a molecular weight of 2040
,l! :0 for MD I. 1.2.2 of O55 moles
．． 6. After reacting with 6-pentamethyl-4-hydroxypiperidine to obtain a prepolymer, I) 50% t/
A solution containing MBA and diptylamine in a molar ratio of 96:7 was added in an amount of 0.98 molar equivalent to the remaining incyanate groups, and the mixture was reacted at room temperature for 5 hours. Then DM
F was added to make the solid content concentration 25%.

When 1.8 equivalents of acetic acid was added to the resulting solution based on the nitrogen derived from 1.2.2.6.6-bentamethyl-4-hydroxypiperidine in the solution, the viscosity was 260 p.
It was oise. A dry membrane was prepared from this solution and its tensile strength was measured to be 640 Ky/ct11.

After irradiating the film for 100 hours, the tensile strength was measured and found to be 55 D Kg/cat. (Strength retention rate: 86%) The obtained solution was diluted to 16% with DMF, a wet film was prepared, and the tensile strength was measured.
．． It was 9 Kg/crA.

After leaving the obtained 25% solution i' at room temperature for 45 days, a dry film was prepared in the same way and the tensile strength was measured.
'2 Kg/crd' (Strength retention rate 94%) The film was extracted with perchlorethylene, dried and further washed with W.
544Kg/cni after MiQO time irradiation (85% of same)
Met. The tensile strength of the wet membrane is still 27.3 F4 (
94%).

Examples 1b and c Polyurethane solutions of these Examples 1a, 1b, ic and Comparative Example 1 were obtained and evaluated in the same manner as in Example 1a using the compounds shown in the table as acids. and the results of all evaluations of the film are shown in the table.

As shown by the results in the table, the compositions of Examples 1a, 1b, and 1C, in which hindered amines were introduced into the polyurethane molecule and a specific acid was added to the solution, showed that the stability of the solution and the initial strength of the polyurethane resin were improved. A dramatic improvement in maintenance and weather resistance was achieved.

Example 2a, parts by weight of PTMG5'O with molecular weight 2040, molecular weight 19
80 parts by weight of PCL5D and 6 times the mole of MDI for these diols and 045 moles of 1- for MDI.
Benzyl-2,2,6,6-tet71 thyl-4-hydroxypiperidine, further calculated DM F consisting of 0.96 mol of EG based on the remaining incyanate groups
The solution had a solid content of #+f6o%. While reacting at 50°C, the mixture was gradually diluted with D M J,', and after 60 hours, the total concentration was finally adjusted to 25%, and methanol was added in an amount equivalent to the calculated remaining incyanate group. In the resulting solution, 1-
0.9 mol of acetic anhydride was added to the nitrogen derived from benzyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and stirred. A dry membrane and a wet membrane were prepared from the solution in the same manner as in Example 1a and evaluated. As shown in Table 1, both the dry membrane and the wet membrane had a remarkable strength retention rate of 100% and 98%. Example 21) In place of acetic anhydride, 0 mol of ammonium sulfate was used with respect to the hindered amino group.

As shown in Table 1, both the dry and wet membranes had extremely high strength retention rates of 102% and 95%, and also had extremely high weather resistance.

Comparative Example 2 The same procedure as in Example 2a was carried out except that no acid was added. However, as shown in Table 1, both the top-down type membrane and the wet type membrane, which had poor solution stability, had poor strength retention.

Example 3a PTM () filter with molecular weight 2040 0 parts by weight, molecular weight 195
7 PEA to 2 times molar MDI, MDI to 0.
025 moles of 1-(2-hydroxyethyl)-2,2
, 6,6-tetramethyl-4-hydroxypiperidine to obtain a prepolymer, diluted to 50% with DMF, and added a solution containing MBA and DBA=i92:8 to the remaining incyanate groups. 0.99 molar equivalent was added, the solid content concentration was set to 25%, and the mixture was stirred at room temperature for 5 hours.

2.0 mol of acetyl chloride relative to the hindered amino group was added to the obtained solution, and dry membranes and wet membranes were evaluated in the same manner as in Example 1a. As shown in Table 1, the composition had excellent viscosity stability, strong retention of dry and wet films, and weather resistance.

Example 3b Instead of acetyl chloride, 1.
The same procedure as in Example a was carried out except that 1 molar equivalent of hydrochloric acid was used. As shown in Table 1, the viscosity stability of the composition, the strong retention of dry and wet films, and the weather resistance were excellent.

Comparative Example The same procedure as Example 6a was carried out except that filtrate was not added.
As shown in Table 1, the viscosity stability of the composition was poor, the strength retention of the dry film and the wet film was poor, and the weather resistance of the wet film was also significantly poor.

Comparative Example 4 The same procedure as in Example 1a was carried out except that neither hindered amines nor acids were used. The dry film and wet film were extremely poor in dustability.

Example 4 Consisting of 50 parts of polyethylene terephthalate as the island component and 50 parts of polystyrene as the sea component.2. The number of filaments drawn was 16 per filament. Using a polymer array fiber with a fineness of 6.4 denier, a length of 51 mm, and a number of crimps of 15 fins, the apparent density is o, 1 zo! ? -/i nonwoven fabric was obtained. The nonwoven fabric was impregnated with a 20% aqueous solution of polyvinyl alcohol, dried, and then immersed in carbon tetrachloride to dissolve the polystyrene to obtain a nonwoven fabric in which bundles of ultrafine fibers were entangled.

After the 25-Y polyurethane composition solution obtained in Example 1a was left in a closed container at room temperature for 90 days, DMI;'
It was diluted to 16%. The solution was impregnated and applied to the nonwoven fabric, excess solution was removed with a roll, wet coagulation was performed in water for 1 hour, polyvinyl alcohol was further eluted and removed in warm water, and dried to form a sheet with a thickness of 2°2. I got something. The obtained sheet material is cut in half in the thickness direction, and the surface is further ground with sandpaper to create a sheet with a nap of 0.85 cm thick. The sheet is coated with Resolin Blue 1” B
L (disperse dye) (5o, 2% Pwf was used to process the sheet at 120℃ for 1 hour using a circular dyeing machine, and the sheet was colored pale blue.After dyeing, brush finish was applied and the apparent density was 0.255]/d was obtained. The artificial leather was dry-cleaned using Perclean and then irradiated with WM for 1100 hours. After irradiation, the sheetra irradiated surface was subjected to a load of 8 pounds using a Seafa set abrasion tester. When the weight loss was measured below, it was 8.4, indicating that the notebook had excellent weather resistance.
The weight loss before irradiation was 6.2 g.

Comparison f115 In addition to using a polyurethane solution having the composition of Comparative Example 1, a suede-like sheet material was prepared and evaluated in exactly the same manner as in Example 4, and the weight loss of the %W'M unirradiated product was 5.8 g. However, after WM irradiation, it was broken and could not be measured.

Comparative Example 6 A 7-tate-shaped product was obtained and evaluated in exactly the same manner as in Example 4, except that a polyurethane solution having a composition completely devoid of each acid component gold from Examples 1a to 1c was used. As a result, the weight loss of the WM unirradiated product was also 12
．． 1 ml, lower than the previous two cases, and the weight loss after WM irradiation was 16.879, hindered amine? Comparison column 5 that does not include
Although it was higher, a significant decrease was observed compared to Example 4 in which acid was added. The reason for this is that no acid was added, which accelerated the hydrolysis of the molecular chains around the hindered amino groups of the polymer, causing them to break off and fall off, resulting in a lower molecular weight and lower initial strength of the sheet. These low-molecular compounds, including
Unfortunately, much of the weathering function in the polymer is lost.
This is due to the deterioration of physical properties after WM irradiation. The same can be said of Film Comparative Example 1.6.

Procedures Amendment 1 Display of the case Patent Application No. 211218 of 1972 Name of the invention Polyurethane composition 6 Relationship with the case Patent applicant Address 2-2 Muromachi, Nihonbashi, Chuo-ku, Tokyo
No. 5 The number of inventions will increase due to the amendment. No. 1 in the description. The scope of claims will be amended as shown in the attached sheet.

2 Page 5, line 5 Change “chronological” to “chronological”.

, page 11, line 4, "P-phenylenediamine J is Tp-phenylenediamine."

4 Page 11, lines 11-12 "Dichlor" is changed to "dichloro."

5, page 12, lines 9-10 "Aryl group" is referred to as "allyl group."

6, page 13, lines 14-20, "In the former case, . . . epichlorohydrin, etc." is corrected as follows.

"In the former case, l(,3 means a lower alkylene group having 2 to 14 carbon atoms, and n represents an integer of 1 to 50.
30) Specific examples of n include ethylene oquinide, propylene oquinide, butylene oquinide, tetrahydrofuran, styrene oquinide, epichlorohydrin, etc. 1 to 50
7, page 16, line 17, "The amount to be used is" is changed to "The amount to be used of the hindered amino compound in the present invention is."

8 Page 17, line 1 Let ``is.'' be changed to ``is an amount such that it becomes.''

9 Page 17, lines 18-19 “Phosphoric acid, monosodium salt” is converted to “monostrium phosphate”
shall be.

10, page 18, lines 17, 18 and 20 “PJ<a
” is 1 pKaJ.

11 19th line 19 "Stability" is defined as "solution stability."

12 Page 26 lines 10 and 20 ``Let 100J be ``50''.

1ro Page 26, line 11 1-1) '4G30 parts by weight' to 'I' to 'PTMG70
Part by weight.

14 Page 26, line 12 "PEA J is [30 parts by weight of PEA and these diols"].

15, page 28, line 6 The fineness is 1.

16 Page 28, line 11 "Impregnated potatoes" is changed to "impregnated".

17 Page 30 lines 16-17 Let "eluted" be "eluted".

18, page 31 Table 1 “Physical properties and weather resistance of film” column Let ``After WM 10 screams'' be ``After 1 WM 50 h''.

19, page 31 (Note 4), the line "Film formed. Untreated" is changed to "Film formed, untreated."

(Attachment) Claims (]) CA) Consisting of a polymeric diol with a molecular weight of 500 or more, an organic polyisocyanate, a chain extender, and if necessary, a terminal stopper, and furthermore, a chain extender and 7
A polyurethane elastomer using a compound having a hindered amine group represented by the formula [1] as at least a part of the terminal capping agent, (+3) 0.8 to 1o relative to the hydrogen/dart amino group
.

at least one compound selected from molar equivalents of inorganic acids, organic carboxylic acids, organic sulfonic acids, their anhydrides, halides, alkali salts or ammonium salts, and (q) a solvent for the polyurethane elastomer; Boliureta/#1 product.

(2. In the composition according to claim 1, (13)
), the compound has a pKa (6).

(3) In the composition according to claim 1, formula C
The compound represented by u1l has a nitrogen weight derived from hindered amino groups of 0.00 based on the polyurethane solid content.
A polyurethane composition containing 0.01 to 1% by weight.

(4) The impregnation composition for artificial leather according to claim 1.

Procedure 7 Municipal Correction "B: (Method 0 April 28, 1980 1, Display of the case 1982 Patent Application No. 21121, Title of invention Polyurethane composition 3, Relationship with the amended person case Patent application Personal address: 2-2 Nihonbashi Muromachi, Chuo-ku, Tokyo March 29, 1982 (shipped) 5. Subject of the amendment, scope of claims in the specification and detailed explanation of the invention 6. Details of the amendment ■The scope of the claims is amended as shown in the attached document.

2, page m6, line 13 to page 7, line 10 are corrected as follows.

3 ffTable 1 on page 131 is corrected as follows.

(Attachment) Claims (1,) (A) A polymeric diol having a molecular weight of 500 or more.

It consists of an organic polyisocyanate, a chain extender, and if necessary, a terminal stopper.

Moreover, the polyurethane elastomer uses a compound having a hindered amino group represented by Formula 1 (1) as at least a part of the chain extender and/or terminal stopper.

(B) An inorganic acid or an organic carboxylic acid in an amount of 0.8 to 100 molar equivalents based on the hindered amino group.

Organic sulfonic acids and their anhydrides, halides,
At least one compound selected from alkali salts and ammonium salts.

and (C) Solvent for the polyurethane elastomer A polyurethane composition consisting of.

(2. In the composition according to claim 1) (B)
A polyurethane composition in which the compound has a PKa<6.

(3) In the composition according to claim 1, the formula (
The compound represented by 1) is based on the polyurethane solid content,
The weight of nitrogen in hindered amino Kiyamaki is 0.0001
~1% by weight of a polyurethane composition.

(4) The impregnating composition for artificial leather according to claim 1.

Claims (1)

[Scope of Claims] (1) (5) Consisting of a polymeric diol with a molecular weight of 500 or more, an organic polyisocyanate, a chain extender, and optionally a terminal stopper, and the chain extender and /'!
, or a polyurethane elastomer using a compound having a hindered amine group represented by formula (1) as at least a part of the terminal capping agent, (B) 0.8 to 100 with respect to the hindered amino group.
At least one compound selected from molar equivalents of inorganic acids, organic carboxylic acids, organic sulfonic acids, and their anhydrides, rogens, alkali salts, or ammonium salts,
and (Q) a polyurethane composition comprising a solvent for the polyurethane elastomer. (2. In the composition according to claim 1, (I3)
) is a polyurethane composition of formula (I).
) is the compound represented by polyurethane solid content,
o, o o in terms of nitrogen weight derived from hindered amino group
A polyurethane composition comprising oi~1 weight. (4) The impregnation composition for artificial leather according to claim 1.