JPS63199261A - Polyamino acid urethane resin composition - Google Patents

Abstract

PURPOSE:To provide a polyamino acid urethane resin composition containing a polyamino acid urethane resin and a stabilizer selected from benzotriazole-type ultraviolet absorber, etc., having remarkably improved light resistance and useful especially as a coating material. CONSTITUTION:The objective composition can be produced by compounding (A) a polyamino acid urethane resin produced by reacting an alpha-amino acid-N- carboxylic acid anhydride, a urethane prepolymer having isocyanate group at the terminal (produced by the reaction of excess polyisocyanate with a polyol), water and hydrazine or an organic amine in an organic solvent (e.g. dimethylformamide) with (B) 0.01-20wt.% (based on the solid component of the resin A) one or more stabilizers selected from benzotriazole-type ultraviolet absorber, benzophenone-type ultraviolet absorber, hindered amine-type light stabilizer and hindered phenol-type antioxidant. Preferably, the component B is dissolved in an organic solvent and added to the component A at the final stage of the production of the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to stabilized compositions of polyamino acid urethane resins. More specifically, the present invention relates to a composition that significantly reduces deterioration or yellowing of a polyamino acid urethane resin caused by ultraviolet rays or the like.

[Conventional technology]

Polyamino acid urethane resin is obtained by reacting α-amino acid-N-carboxylic acid anhydride, a urethane prepolymer having an isocyanate group at the end, and water, hydrazine, or an organic amine in an organic solvent, and is used for synthetic leather and moisture-permeable waterproofing. used for cloth. A product with excellent texture can be obtained.

However, there is a problem that the resin deteriorates (reduces strength) or turns yellow due to ultraviolet rays and the like.

[Purpose of the invention]

As a result of the inventors' studies aimed at solving the above problems,
We discovered that adding a specific aromatic compound significantly reduces the deterioration or yellowing of resin when exposed to ultraviolet rays.
We have arrived at the present invention.

That is, the present invention relates to a polyamino acid urethane resin obtained by reacting an α-amino acid-N-carboxylic acid anhydride, a urethane prepolymer having an isocyanate group at the end, and water, hydrazine, or an organic amine in an organic solvent, and a benzo This is a polyamino acid urethane resin composition comprising one or more types selected from the group consisting of triazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, hindered amine-based light stabilizers, and hindered phenol-based antioxidants.

[Structure of the invention]

The present invention will be explained in detail below.

The polyamino acid urethane resin which is the resin component in the present invention is produced by reacting an α-amino acid-N-carboxylic acid anhydride, a urethane prepolymer having an isocyanate group at the end, and water, hydrazine or an organic amine in an organic solvent. can get.

The organic solvent used here is dichloromethane, /
Chlorinated aliphatic hydrocarbons such as kodichloroethane, /, /, 2-) dichloromethane, chloroform, /, /, 2.2-tetra, chloroethane, aromatic hydrocarbons such as benzene, toluene, xylene, chloro Chlorinated aromatic hydrocarbons such as benzene and dichlorobenzene, acetate esters such as ethyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, dimethylformamide, diethylformamide, dimethyl 7damide, Water-soluble organic solvents that do not contain active hydrogen, such as N-methylpyrrolidone, ethylene carbonate, dimethyl sulfoxide, dioxane, tetrahydroctane, and hexamethylphosphoramide;
Examples of these include mixtures of two or more of these.

α-Amino acid-N-carboxylic acid anhydride used in the present invention (hereinafter, N-carboxylic acid anhydride is abbreviated as IOA)
What are glycine, alanine, leucine, inleucine,
Carbon number of valine, α-aminepeptanoitsuccinic acid, etc.
/2 neutral amino acids, β-benzylaspartic acid, γ
- The ω-amino group of monoesterified acidic amino acids such as methyl-L-glutamate, r-methyl-D-glutamate, and r-benzyl-L-glutamate, 8-acylyldine, and δ-acylorutinine is protected with an appropriate masking group. Anhydrides such as α-ω-diaminocarboxylic acid derivatives and α-amino acid derivatives such as 〇-acetylsthreonine are used.

The urethane prepolymer having isocyanate groups at the terminals has a high ratio of polyisocyanate compound and polyol to N.
It is obtained by reacting under the conditions of 0O10H)/. As the polyisocyanate component, aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates are generally used alone or in mixtures thereof. For example, toluene-2,4C-diisocyanate, Hiroshi, ≠'-diphenylmethane diisocyanate, metaphenylene diincanate, J, P-dimethyl-Hiroshi, 44/-biphenyl diisocyanate, metaxylene diisocyanate, paraxylene diisocyanate, /, 4-hexane diisocyanate, /, 10-decamethylene diisocyanate)
, /, 44-cyclohexane diisocyanate, cyclohexylmethane-Hiro, Hiro'-diisocyanate, 3-
Methi isocyanate/l/-3,! ,! -) Limethylcyclohexyl isocyanate (isophorone diisocyanate) and the like.

Examples of the polyol component include polyether polyols and polyester polyols, singly or in mixtures thereof. Examples of polyether polyols include polypropylene ether glycol, polyethylene polypropylene ether glycol, polytetramethylene ether glycol, polypentamethylene ether glycol, polyethylene polytetramethylene ether random copolymer, polyethylene polytetramethylene ether block copolymer alone or A mixture of these, bisphenol A
Examples include glycols having an aromatic ring obtained by adding propylene oxide or ethylene oxide to .

Typical examples of polyether polyols used include polycaprolactone polyols, or those obtained by reacting diols such as ethylene glycol, φ-butanediol, etc. with dibasic acids such as adipic acid and sepacic acid.

Special polyols such as polyols obtained by adding caprolactone to t+ polytetramethylene ether polyols or polypropylene ether polyols, and polysiloxane polyols can also be used.

The number average molecular weight of these polyether polyols, polyester polyols and special polyols is preferably 2OO or more.

The water used in the present invention refers to ordinary water, and may be tap water, non-desalinated water, or desalinated water.

Hydrazine may be either anhydrous hydrazine or hydrated hydrazine, and hydrated hydrazine is industrially more advantageous in terms of safety.

Typical examples of organic amines include tertiary amines such as trimethyl 7one, triethylamine, and triethylamine, secondary cyanocarbons such as piperazine, and 7th class cyanoamines such as ethylenediamine, l,3-propaneditemine, and tributanediamine. Both 7th and -class amines such as kin, l, co-7' a-pancyamine, i, s-butanediamine, and dihydrazides having a hydantoin ring, such as l,! -bis(human 2
Cytocarboethyl)-! −Inglovirhydantoin
° etc. are appropriate.

α-amino acid N when obtaining polyamino acid urethane resin,
What is the weight ratio of OA and urethane prepolymer? onlo
~toHdeO, more preferably ro:2o~2Q
: Range of IO.

This weight ratio is determined depending on the desired physical properties of the product; for example, when providing an artificial leather grain surface with excellent texture and moisture permeability, it is preferable to have a large amount of α-amino acid NOA; When adhesion is important, it is preferable to have a large amount of the urethane prepolymer component.

The amount of hydrazine and organic amine having primary or secondary active hydrogen used is 72 groups per 72 groups per isocyanate group of the urethane prepolymer. It is preferably at least the equivalent, more preferably at least the handle equivalent. The amount of tertiary amine used is preferably at least 000 moles of α-amino acid NCA.

Since water reacts with isocyanate groups to produce amino groups, it can be used as a substitute for amines.

The amount of organic solvent used is usually such that the resin concentration in the polyamino acid urethane resin solution of the final product is 3 to 3 in terms of the resulting resin solution.
! The range is preferably 10 to 30 weight. If the Atb concentration is too high, the viscosity will be extremely high and it will become gel-like.When applying or impregnating an adherend, it may be diluted with a solvent, but it is difficult to handle. Also, if the concentration is too low, the viscosity will be high (IO, 0
00 ape or higher) but lacks versatility.

〉 ・ In addition, in the present invention, the reaction temperature when producing the polyamino acid resin solution is set at a temperature ranging from α-amino acid NO to high molecular weight polyamino acid single poly! The temperature at which - can be synthesized is preferably in the range of 10 to 10°C. If the temperature rises above 50°C, it becomes difficult for the amino acid chain to break out of the α-hesox structure during copolymerization, so the degree of polymerization of the amino acid chain may not increase and a product with a high molecular weight may not be obtained.

Furthermore, if the reaction is carried out at high temperatures, the isocyanate group may undergo a vinylet reaction with the urea bond produced by the reaction between the isocyanate group and the amino group, resulting in gelation.

When the polyamino acid and urethane resin liquid obtained as described above has a small amount of α-amino acid NCA, for example, the weight ratio of α-amino acid IOA to urethane prepolymer is 1. :the law of nature!
Within the range of ~1r:rs, the solution becomes relatively less cloudy, but as the ratio of α-amino acid NO increases, the cloudiness increases, and the viscosity is 10 ape ~ 1 million ape 725
Any viscosity can be obtained within the range of °C.

A preferred method for obtaining a polyamino acid urethane resin is (a) a method in which the urethane prepolymer and α-amino acid NCA are mixed in the organic solvent, and then a tertiary amine is added and reacted.

(b) A method in which α-amino acid NOA and urethane prepolymer are mixed in the organic solvent, and then water, hydrazine, or an organic amine having active hydrogen is added and reacted.

e→ After mixing the urethane prepolymer and the α-amino acid IOA in the organic solvent, water and hydrazine are reacted by adding an organic amine having active hydrogen, and then a tertiary amine is further added to react. .

B) In the organic solvent, a urethane prepolymer, water,
Hydrazine is a method of reacting with an organic amine having active hydrogen and then adding α-amino acid NCA.

(e) A method of mixing the α-amino acid NCA and the urethane prepolymer in the organic solvent, adding water, hydrazine, or an organic amine having active hydrogen to cause a reaction, and then adding the urethane prepolymer.

(f) After reacting the urethane prepolymer with water, hydrazine, or an amine having active hydrogen in the organic solvent, adding α-amino acid-N-carboxylic acid anhydride;
A method in which water, hydrazine, or amines having active hydrogen are further added and reacted after mixing.

etc.

The composition of the present invention comprises boria obtained by K as described above,
Add a benzotriazole ultraviolet absorber, etc. to the amino acid urethane resin.

V''' Ben F) IJ azole-based external radiation absorber is 1
The following general formula (1) (wherein, zl and zl are ■ or lower alkyl group, Y is H
The next one shows halogen. ) The lower alkyl group in general formula (1) used is methyl, t-butyl, t-amyl,
Preferred examples of the t-octyl group and the halogen are chlorine atoms.

Specific examples of this benzotriazole-based ultraviolet absorber include λ-(!-methyl-cohydroxyphenyl)benzotriazole, 2-(cohydroxy-3.!-bis(α,α-dimethylbenzyl)phenyl)- 2m-pen'I triazole, co(3,j-di-t-butyl-cohydroxyphenyl)benzotriazole,! −(
J-t-7'f-j-methyl-2-hydroxyphenyl)-5-chloropenz)! 77 Thor h1. z-(
3,j-di-t-butyl-cohydroxyphenyl)-
j-chlorobenzotriazole, co-(j, j-t
-acyl-cohydroxyphenyl)benzotriazole1.2-(hydroxy-s-t-octylphenyl)benzotriazole, 2-(,2H-benzotriazol-2-yl)-c(/,l,3,3- Tetramethylbutylene, phenol, or the magazine “Polyplastic J vol, Js, A//p4jS-4
Examples include those listed in Part B.

As a benzophenone ultraviolet absorber, the following general formula (
It) (In the formula, R is H, meaning is an alkyl group. X is H, -0H1y
l is Hl-0H, -0CH3, 2 is H, -8O3H, -
Indicates 000H. ), specifically, λ, 2'
-dihydroxy-Hiro-methoxypenzophenone, cohydroxy≠-methoxy-j-sul7obenzophenone trihydrate, cohydroxy≠-n-octoxy-benzophenone or "polyplastic Jvo
1. Jj.

Examples include those described in A//p≦≠~ts.

Examples of the hindered amine light stabilizer include dimethyl succinate-t-(,2-hydroxyethyl)-cyhydroxy-2,w2,6. t-tetramethylpiperidine polycondensate (molecular weight 5ooo or more), poly[[≦-(/, /, J,
J-tetramethylbutyl)innot,! , s-) riazine-2,41-diyl](co,co,otsu,6-titramethyl-derpiperidyl)imino]hexamethylene((2
w2t't'-tetramethyl-Hiro-piperidyl)imino]], 2-(J, s-di-t-butyl-syl-hydroxybenzyl)-2-n-butylmalonic acid bis(/, λ,
2°4, G-pentamethyl-triple-piperidyl) and Cyasorb avxs≠6 (light stabilizer manufactured by American Cyanamid Co., Cyasorb is a trademark).

As a hindered phenolic antioxidant, triethylene glycol-bis(j-(j-t-phthyl!-methyl-sulfate-4x-7enyl)propionate)%/
$4-hexanediolubis(J-(j,,r-di-
t-Butyl-φ-hydroxyphenyl)propionate], Hiro-bis-(n-octylthio)-4-(see-
Hydroxy-j,j-t-butylanilino')-'t'
s! - triazine, pentaerythrityl-tetrakis (
J-(J,r-di-t-butyl-hiro-hydroxyphenyl)propionate L't2-thiodiethylenebis(
j-(j, z-di-t-butyl-hydroxyphenyl) flobionate], octadecyl-J-(J, j-
di-t-butyl-hydroxyphenyl) flobionate, 2,2-thiobis(st-methyl-d-t-butylphenol), N,N'-hexamethylenebis(3,
j-di-t-butyl-ref.-hydroxyethyldrocinnamard), J, s-di-tert-butyl-ref.-hydroxy-benzylphos 7-onate diethyl ester, /! , s-)limethyl-2, #.

6-tris(3,!-di-t-butyl-hydroxybenzyl)benzene, bis(J,z-di-t-butyl-
mixture of tris(ethyl hydroxybenzylphosphonate) calcium and polyethylene wax,
,! -di,-1-butyl-hydroxybenzyl)-
inocyanurate, /, J, f-, tris(ref.-t-butyl-3-hydroxy-2,6-dimethylpendi/I/
) isocyanurids. Addition of these additives: 0
．． 0 j to 10%, more preferably 0. /~j%
is within the range of

If the amount added is too small, the effect on yellowing due to ultraviolet rays or deterioration of film mechanical properties will be small, and if the amount added is too large, it will bring about a large change in the modulus and strength and elongation of the film, which is often undesirable.

Although it may be added at the time of production of the polyamino acid urethane resin, it is preferably added at the end of production. As for the method of addition, it may be added directly, but preferably it is added after being dissolved in an organic solvent used in the synthesis of polyamino acid urethane resin (hereinafter sometimes referred to as PAU).

In the present invention, although it is effective to add the above-mentioned additives alone, it is more effective to add them in combination with other additives. A preferred combination is -1(!-methyl-co and droxyphenyl)benzotria:/-7
+/, J-(J-hydroxy-3,j-bis(α,
-α-dimethylbenzyl)phenylucoH-penztriazole, J-(3,5-t-butyl-2-and-droxyphenyl)benzotriazole, -1(JH-penzotriazole-coyl)-Hiroshi-(t , t, !, !-tetramethylbutyl) phenol, dimethyl succinate-/-(2-hydroxyethyl)-hydroxy-2,2,t,t,-tetramethylpyridine polycondensate,
-1 ('s'-') -t -7'Tyl-Hiro-Hydroxybenzyl)-2-n-butylmalonic acid bis(t, 2
,2. If one or more of
t-Butyl-! -Methyl-hydroxyphenyl)fluorionate, pentaerythrityl-tetrakis [3-
(z,j-di-t-butyl-≠-hydroxyphenyl)
A mixture with at least one type of propionate] is preferred.

One eleven! Preferred combinations of λ-(j-mef-λ-hydroxyphenyl)benzotriazole,
2-(J,j-di-t-butyl-≠-hydroxybenzyl)-co-n-butylmalo/acid bis(/,co,2,6.
t-pentamethyl-Hiro-piperidyl) totriethylene glycol-bis(J-(J-1-butyl-!-methyl-≠-hydroxyphenyl)propionate) or pentaerythrityl-tetrakis[3-(3,5-
di-t-bunaru-t-hydroxyphenyl)propionate], and --(JH-benzotriazol-2-yl)-≠-(/, /, J, J-tetramethylbutyl)phenol, cyasorpe ['7j J$4
and/, J,! - Tris(4cm t-butyl-3-hydroxy-λ, t-dimethylbenzyl)isocyanuric acid.

The film obtained by desolvation from the PAU solution to which the specific additive of the present invention has been added is itself moisture permeable, air permeable film, separation material for liquid or gas mixtures, filter, and permeable to water vapor, oxygen, carbon dioxide, etc. It can be applied to composite films for highly occlusive bandages, etc.

The polyamino acid urethane resin of the present invention is particularly useful as a coating material.

Substrates to be coated include sheet materials such as woven fabrics, nonwoven fabrics, porous films, and the like.

Further, after applying or impregnating the base molded article with the Pjt7 solution, the solvent may be removed by either a dry method or a wet method.

In the case of a dry method, the solvent can be removed by applying or impregnating the TAUffJ solution onto the base material and drying the hole by heating or air drying. In the case of a wet method, the solvent can be removed by coating or impregnating a base material with a PAtr' solution and placing it in water or a non-solvent.

In both the dry and wet methods, surfactants, water repellents, colorants, and other additives may be added to the PATT solution in advance, if necessary.

The amount of PAU solution applied or impregnated onto the base material is determined depending on the use, type, and required performance of the product (sheet-like material).

The nine-coated molded product obtained by this method has moisture permeability,
Excellent waterproofness, gas permeability, separability, mechanical strength, etc. can be obtained, and by appropriately selecting the type of substrate and coating method, it is possible to develop it into various uses.

Typical examples of its uses include synthetic leather, artificial leather such as artificial leather, and waterproof cloth.

In particular, waterproof fabrics with high moisture permeability and waterproof performance can be obtained, and specific applications thereof include tents, waterproof clothing, packaging materials, diapers, and diaper covers.

〔Effect of the invention〕

The PA17 composition of the present invention has significantly improved light resistance, and the homogeneous films and porous films obtained therefrom have excellent moisture permeability and air permeability, so they are useful for various industrial applications such as waterproof fabrics.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.

Example/Polytetramethylene ether glycol (OR value! 6.
7) Riri! ? A urethane prepolymer having an isocyanate group at the terminal was obtained by reacting φ'-di7-dylmethane diisocyanate/7-Hirot at 70°C for 5 hours.

The urethane prepolymer/JJ,/t and r-methyl-L-glutamate NCA/co3.7f were dissolved in t-dimethylformamide and ethylenediamine 3. When J/f dissolved in dimethylformamide/662 is reacted dropwise, the viscosity is 3! ,
A PAU solution with good fluidity at oθOcps/21°C was obtained. PAD solution alone and 100 parts of PAU solution plus 2-(j-methyl-cohydroxyphenyl)penztriazole H-rubis(J-(j-t-butyl-!-methyl-e-
hydroxyphenyl)propio*-))-(J, s-di-t-butyl-hiro-hydroxybenzyl) -, z -
n-butylmalonate bis(/, λ.

-9 Otsu, ≦-pentamethyl-zhen-biveridyl) each 0.
7 parts each were added and cast onto a glass plate and heated at 60°C.
It was further dried with hot air at 10° C. for 30 minutes. This was immersed in room temperature water for about 20 hours and then dried to obtain a film made from the PAD solution alone (sample a) and a film made by adding the above-mentioned specific aromatic compound to the PA17 solution (sample b).

Samples a and b were measured with a 7 edometer (f1 degree, iGJ℃) for 5
When irradiated with ultraviolet rays for 0 hours, the film of sample a is destroyed due to deterioration, but the sample A retains its film shape and has almost no coloring, and its strength retention rate is 5≦chi compared to the one before irradiation with ultraviolet rays, indicating high light resistance. It has been greatly improved.

Example 2 For 100@IIC of PA17 solution obtained in Example 1, 1
-(coH-benzotriazole-coyl)-sanichi(/
, /, J, J-tetramethylbutyl) phenol, hindered amine-based cyasorb vv334c (manufactured by American Cyanamid Company) and /,! ,! -) Lis(≠-1-butyl-3-hydroxy-2.t-dimethylbenzyl)isocyanuric acid at 0% each. The mixture containing I f was cast onto a glass plate and kept at 50°C for 30 minutes. It was dried with hot air at θ'°C for 30 minutes. Add this to room temperature water for about 2
The film obtained by drying after being immersed for Q hours had a strength retention rate of 10% after being irradiated with ultraviolet rays for 50 hours using a fetometer (temperature: 63°C).

Applicant: Mitsubishi Chemical Industries, Ltd. Agent: Patent Attorney: Mr. Hase - and 7 others Procedural amendments (voluntary): March 9, 1985, Commissioner of the Japan Patent Office, 41. Indication of case: 1988 Patent Application No. 3iPttt
No. 2 Name of the invention Polyamino acid urethane resin composition 3 Person making the amendment,
(Other l names) Subject of 5 amendments Contents of 6 amendments in column 6 of “Detailed description of the invention” of the specification (1) In the letter of specification, page 22, page 1/, line 72, “Please, t”
l-diphenylmethane diisocyanate"
Correct to "tolylene diisocyanate."

(2) On the 3rd line from the bottom of page 22, replace "3.3♂?" with [4L, /r? Correct to J.

(3) On the second line from the bottom of page 22, "/44rJ" is corrected to "l"1t9tJ.

Proceedings Amendment/Indication of Case Patent Application No. 3/9/'I of 1939 Title of Invention Polyamino Acid Urethane Resin Composition 3 Applicant (tVX) Mitsubishi Chemical Industries, Ltd. Agent Address: 2-5-2 Marunouchi, Chiyoda-ku, Tokyo 100 Mitsubishi Chemical Industries, Ltd. (and 7 others) Between [b, b-pentamethyl-tt-piperidyl)" and "and", [, bis( Insert '+2+co,6,6-bentamethyl-q-piperidyl)sebacate, bis(2,t,A,A-tetramethylda-piperidyl)sebacate'.

that's all

Claims (2)

[Claims] (1) A polyamino acid urethane resin obtained by reacting an α-amino acid-N-carboxylic acid anhydride, a urethane prepolymer having an isocyanate group at the end, and water, hydrazine, or an organic amine in an organic solvent, and benzotriazole. A polyamino acid urethane resin composition comprising one or more selected from the group consisting of UV absorbers, benzophenone UV absorbers, hindered amine light stabilizers, and hindered phenol antioxidants. (2) The composition according to claim 1, wherein the content of the additive is 0.01 to 20% by weight based on the polyamino acid urethane resin (solid content).