JPS6225155A - Polyamino acid urethane resin molded article - Google Patents

Abstract

PURPOSE:To provide the titled molded article having resistance to fading with gas without lowering excellent light-resistance of the base resin, by compounding a polyamino acid urethane resin with a specific phosphite polycondensate and a semicarbazide compound. CONSTITUTION:(A) A synthetic polymer composed mainly of a polyamino acid urethane resin containing 70-100% polyamino acid urethane resin as a synthetic polymer is compounded with (B) a polycondensed phosphite of formula I (x is 2-10) and (C) a semicarbazide compound of formula II (R is alkylene, methylenediphenylene, etc.). The amounts of the components B and C are >=0.5wt% each and the sum of B and C is 1-3wt% based on the solid component of the polyamino acid urethane resin.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a polyamino acid urethane resin molded product that has good gas fading resistance without reducing its excellent light resistance.

(b) Conventional technology Polyamino acid urethane resins have superior light resistance compared to polyurethane resins, but they are included in combustion gases from petroleum and natural gas and exhaust gases from automobiles, etc., which have recently become a particular problem. It has been found that polyamino acid urethane resins also have the same drawback as polyurethane resins, such as yellowing and deterioration caused by nitrogen oxide gas. In order to solve this drawback, hindered phenol mNA derivatives, henztriazole derivatives, which are conventionally known antioxidants and ultraviolet absorbers used in polyurethane resins as stabilizers,
Even if hindered amine derivatives are included, there is no effect at all; rather, the stabilizer itself becomes colored.

Nitrogen oxide gas fading resistance (hereinafter referred to as NOX resistance) compared to added/added surfaces
(abbreviated as "sexuality") tended to worsen. Also, according to recent patent information, phosphite derivatives (USP, 357
3251), semicarbazide derivatives JP-A-52-1
5548.15549), triazine derivatives (JP-A-53-144957), saturated fatty acid esters (JP-A-49-17449), and the like have been proposed.

When we examined the application of each of these to polyamino acid urethane resins, the actual situation was that none of them had an effect on NOX resistance.

(c) Problems that the invention attempts to solve The present invention was made in view of the above-mentioned current situation.

The purpose of this invention is to improve the NOx resistance of polyamino acid urethane resin without reducing its excellent light resistance.

(d) Means and operation for solving the problems The present invention that achieves the above-mentioned objects has the following configuration. That is, 1. The present invention is characterized in that it is composed of a synthetic polymer mainly composed of polyamino acid urethane resin, and contains a phosphite polycondensate represented by the following formula (1) and a semicarbazide compound represented by the following formula (II). The gist is a polyamino acid urethane resin molded product with excellent gas fading resistance.

(However, X is an integer from 2 to 10.) (However, R
is an alkylene group, methylene diphenylene group, methylene ditolylene group or methylene dixylylene group. ) The following is a detailed explanation of the present invention.

The molded product referred to in the present invention refers to a thread-like product or a sheet-like product.

It means a film-like object, a flat coating object, a three-dimensional three-dimensional object, etc.

The molded article of the present invention is made of a synthetic polymer mainly composed of polyamino acid urethane resin.

Here, the synthetic polymer mainly composed of polyamino acid urethane resin refers to one containing 70 to 100% polyamino acid urethane resin as one synthetic polymer (of course, 100% polyamino acid urethane resin may also be used), and other synthetic polymers. For example, a block copolymer of poly γ-alkyl glutamate and butadiene, a block copolymer of poly γ-alkyl glutamate and leucine, etc. may be contained in a range of less than 30%.

Polyamino acid urethane resin (hereinafter referred to as PAU) used in the present invention
It's called resin. ) is a copolymer consisting of amino acids and polyurethane, and the amino acids include DL-alanine and L-alanine.
-Aspartic acid, L-cystine, L-glutamic acid,
Green, L-lysine.

Examples include L-methionine, L-leucine and their derivatives, and when synthesizing polyamino acids, amino MN-carboxylic acid anhydride (hereinafter referred to as N-
Carboxylic acid anhydride is called NCA. ) is commonly used. As urethane.

A urethane prepolymer with isocyanate groups at the ends, with an equivalent ratio of isocyanate and polyol of NGO10i.
Those obtained by reaction under the conditions of +>1 are used. As the isocyanate component, aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates may be used alone or in mixtures. Examples include 4-cyclohexane diisocyanate. Moreover, polyether polyol and polyester polyol are used as the polyol component. Polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc., and polyester polyols include ethylene glycol.

Examples include reaction products of diols such as propylene glycol and dibasic acids such as adipic acid and cehatic acid, and ring-opening polymers such as caprolactone.

The average molecular weight of these polyethers and polyesters is 2
00 to 300 or more are preferably used. Examples of amines used in copolymerization include 1 such as ethylenediamine.
Alcohol amines such as grade alkyl amines and ethanolamine, tertiary alkyl amines such as triethylamine, and secondary amines such as diethylamine are used. In addition, as a solvent during polymerization, a mixed solvent of dimethylformamide and dioxane (weight ratio 95:5 to 30) is used for mixed PALL resin.
In dry PAU resins, aliphatic chlorinated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane,
1.1.2-) Dichloroethane or a mixture thereof, and aliphatic ketones, aromatic hydrocarbons, aliphatic esters 2 that are good solvents for the urethane component, such as methyl ethyl ketone, diethyl ketone, toluene, xylene,
Methyl acetate.

A mixed solvent with ethyl acetate or a mixture thereof is used.

As described above, PAU resins are obtained by adding amines to the reaction system of various amino acids NCA and urethane prepolymers having isocyanate groups at the terminals. As the amino acid component constituting the PAU resin, optically active T-alkyl glutamate NCAs are particularly preferably used from the viewpoint of film performance, and among the above-mentioned optically active γ-alkyl glutamate NCAs, T-methyl is preferred from the viewpoint of price and film properties. −
L-glutamate NCA or γ-methyl-D-glutamic acid 1.NCA is often advantageously selected as the amino acid component of the PAD resin.

In the present invention, in order to improve NOX resistance (nitrogen oxide gas fading resistance), a phosphite polycondensate represented by the following formula (]) and a semicarbazide compound represented by the following formula (II) are contained in the PAD resin.

(However, it is an integer of 2 to 10 for X.) (However, R
is an alkylene group, methylene diphenylene group, methylene ditolylene group or methylene dixylylene group. ) The phosphite polycondensate represented by formula (I) (hereinafter referred to as compound (A)) is a polycondensate of pentaerythritol, bisphenol A hydrate, and triphenylphosphite, and when X is an integer of 11 or more, , it becomes insoluble in the solvent system of the PAU resin and becomes difficult to handle, so X needs to be an integer of 10 or less.

As the semicarbazide compound represented by formula (II) (hereinafter referred to as compound (B)), either an aliphatic disemicarhamide compound or an aromatic disemicarhamide compound may be used, but in particular, it is preferable to form a PAU resin molded product by wet coagulation. In the case of manufacturing, the compound (B) is eluted into the water of the coagulation bath and the NOX resistance effect is reduced, so it is better to use an aromatic disemicarbazide compound which is relatively difficult to elute.

Both compounds (A) and (B) are contained in an amount of 0.5% by weight or more based on the solid content of PA[I resin. If it is less than 0.5%, the effect on the NOx resistance of the PAU resin will be poor. The total amount of compound (8) and (B) used is preferably 1% or more and 30% or less. If the total amount used exceeds 30%, it is not preferable because it may cause a decrease in strength and elongation in terms of mechanical performance of the PAU resin. In addition, the usage amounts of compounds (8) and (B) are PAU
Since it varies depending on the resin film forming, thread spinning conditions, etc., it should be adjusted within the above range as necessary. For example, P
In the case of dry coagulation of AU resin, most of the compound (A) and compound (B) remain in the PAU resin, so the amount used may be reduced, but r? ! In the case of type A coagulation, a considerable amount of compounds (A) and (B) are extracted together with the solvent during solvent elution in water, so compared to the case of dry coagulation, compounds (8) and Compound (B
) should be kept large.

Preferred compounds (8) and compounds (8) in wet coagulation
The amount of B) used is 5% or more based on the solid content of the PAU resin. In the case of dry coagulation, it is preferably 1% or more and 5% or less.

Compound (8) and compound (B) can be incorporated into the PAU resin using the following method. That is, the compound (A
) and compound (B) are added as solids and mixed.
D Method of dissolving in resin solution or compound (A)
and compound (B) in advance with dimethylformamide and dimethylacetamide.

It is dissolved in a polar amide solvent such as N-methylpyrrolidone or an aliphatic chlorinated hydrocarbon such as methylene chloride, chloroform, or 1,2-dichloroethane.

There are methods such as mixing this with a PAIJ resin solution.

Either method can be used. In addition, mixing the above compound (A) and compound (B) into the PAU resin,
When producing the PA[I resin, the compound (A) and the compound (B) may be directly added to the reaction vessel after the reaction is completed and mixed in the reaction vessel. In this case, compounds (A) and (B) can be easily mixed uniformly into the PAV resin solution, so it can be said that this is a preferable method from the viewpoint of the mechanical performance of the resin. Compound (A) and compound (B) are usually applied to the PAU resin before forming a PAU resin molded product in the form of a thread or sheet by dry coagulation, wet coagulation, etc., as described above, but it is not always necessary to apply the compound (A) and compound (B) to the PAU resin. does not need to be done before the formation of
After obtaining a thread-like or sheet-like molded product using PAU resin alone by dry coagulation or wet coagulation, this is coated with a solution of compound (A) and compound (B) in dimethylformamide or methylene chloride, etc. Law.

It may also be applied by a spray method or the like. However, this post-application method involves applying the surface to the molded product, which has the problem of poor durability against washing, etc. Therefore, if durability is required, compound (A) and It is preferable to adopt a method of incorporating the compound (B) into the PAU resin.

In addition, when applying the compound (A) and the compound (B) to the PAD resin, fillers such as titanium oxide and silica.

Colored pigments, metal powders such as aluminum powder, various surfactants,
It is also possible to add polymeric substances such as polyamide resin and polyester resin in combination.

Regarding the action of compound (A) and compound (B) to improve the NOX resistance of PAU resin, the reason is currently unknown, but the synergistic effect of compound (A) and compound (B) improves the NOX resistance. It is thought that this will be demonstrated.

(e) Examples The present invention will be explained in detail with reference to Examples.

Measurement and evaluation of the performance of the PAII resin molded products in Examples was performed by the following method.

(11 NOX Resistance Fastness to nitrogen oxide gas was measured and evaluated according to J15-L-0855.

(2) Fastness to sunlight) Based on 1s-1, -0842.

Examples 1 to 2 First, two wet-type PAIJ resins (polyamino acid urethane resins) used in these Examples were manufactured by the following method.

Polytetramethylene glycol (08 value 56.9) 19
70g and 1,6-hexamethylene diisocyanate 54
0g was reacted at 90°C for 5 hours to obtain a urethane prepolymer with isocyanate groups at the end (NGO official).
2340) was obtained. This urethane prepolymer 858 and 85 g of T-methyl-L-glutamate NCA were dissolved in 666 g of a mixed solvent of dimethylformamide/dioxane (stratification 7/3), 50 g of 2% triethylamine solution was added while stirring, and the mixture was heated at 30'C. When the reaction was carried out for 5 hours, a wet PAU resin solution having a viscosity of 32.0 OOcps (25° C.) and a yellowish brown emulsion with good fluidity was obtained. This wet PAD resin is used in formulations 1 to 5 described below.

Next, a base fabric for coating the PAU resin was manufactured and prepared in the following manner.

Warp density: 120 wood using 75 denier/36 filament cationic dyeable polyester fiber for warp and weft
inch, weft density 90 threads/inch A plain woven fabric (taffeta) is prepared, and after scouring and dyeing with a fluorescent cationic dye in the usual manner, Asahi Guard 730 (Asahi Glass Co., Ltd.), a fluorine-based water repellent emulsion Product) Pad with 1% aqueous solution (squeezing ratio 35%) and
After heat treatment for 1 minute, using a calendar processing machine with mirror-finished rolls, the temperature was 180°C and the pressure was 30 kg/cm.
Calendering was performed at a speed of 20 m/min to obtain a base fabric for coating.

Here, a coating solution of the following formulation 1 was applied to the base fabric at a coating amount of 80 g/m using a knife over roll coater, and then immersed in a 20°C water bath for 1 minute to wet-coagulate the resin. .

Formulation 1 PAU resin for wet process 100 parts Vernonk BL -501 parts (crosslinking agent for urethane resin, Dainippon Ink Chemical Company product) Pentaerythritol/hydrogenated bisphenol A/triphenyl phosphite polycondensate (molecular weight 2500-30
00) 1.5 part 1.1.1', 1'
-Tetramethyl-4.4' (methylene-di-P-phenylene)disemicarbazide
1.5 parts dimethylformamide 10 parts Thereafter, the PAD resin of the present invention was formed by immersing it in hot water (60°C) for 10 minutes, washing it in hot water, and drying it to form a thin film on the base fabric. I got something.

This was used as the PAU resin molded product of Example 1.

In the production of the PAU resin molded product of Example 1 above.

A PA IJ resin molded article of the present invention formed in the form of a thin film on a base fabric was obtained in exactly the same manner as in Example 1, except that the following formulation 2 was used in place of formulation 1 of the coating liquid. This was used as the PAU resin molded product of Example 2.

Formulation 2 Wet PAU resin 100 parts CRISVON AW-7H 3 parts (polyurethane elastomer Dainippon Ink Chemical Company product) CRISVON ASSISTOR 5D-111 parts (anionic surfactant).

Dainippon Ink Chemical Industry product) Pentaerythritol/hydrogenated bisphenol A/triphenyl phosphite polycondensate (molecular weight 2500-30
00) 1.5 parts, 1.1', 1'
1.5 parts of tetramethyl-4.4'(methylene-di-P-phenylene)disemicalhydride 10 parts of dimethylformamide
For comparison with Examples 1 and 2), the following formulation 3. was used instead of formulation 1 of the coating liquid in Example 1. Prescription 4. Using Prescription 5, the other methods were exactly the same as in Example 1,
Three comparative thin film-like PAD resin moldings were obtained on the base fabric. These are the P of Comparative Example 1 (using Formulation 3), Comparative Example 2 (using Formulation 4), and Comparative Example 3 (using Formulation 5), respectively.
It was made into an AU resin molded product.

Formulation 3 Wet PAU resin 100 parts Harnosoku BL-501 part (crosslinking agent for urethane resin Dainippon Ink Chemical Industry product) Dimethylformamide 10 parts Formulation 4 Wet PAU resin 100 parts Burnock BL-501 part Pentaerythritol/hydrogenated bisphenol A. Triphenylphosphite polycondensate (molecular ffi 2500
~3000) 3-part dimethylformamide
10 parts Prescription 5 Wet PAU resin 100 parts Burnock BL-501 part (crosslinking agent for urethane resins).

1.1.1', 1'Tetramethyl-4.4' (methylene-di-P-phenylene) disemicarbazide 3 parts Dimethylformamide 10 parts Performance of the obtained comparative PAD resin molding P of the present invention
We measured and evaluated the performance of AU resin molded products.

The results are shown in Table 1.

Table 1 As is clear from Table 1, the PAU resin molded proboscis of the present invention has no light resistance and is sufficiently provided with gas fading resistance.

The PAIJ resin molded product in this example is in the form of a thin film, integrally bonded to the base fabric, and has good moisture permeability. Therefore, a fabric having such a laminated structure can be used as a moisture-permeable waterproof fabric as it is.

Example 3 The dry PALI resin used in this example was produced by the following method.

Polytetramethylene glycol (Koh value 56.9) 197
0g and 1,6-hexamethylene diisocyanate 540
g was reacted at 90°C for 5 hours to obtain a urethane prepolymer having an isocyanate group at the end (NGO equivalent weight 2340
) was obtained. 85 g of this urethane prepolymer and 85 g of T-methyl-L-glutamate NCA were mixed in 666 g of a mixed solvent of 1,2-dichloroethane/toluene (weight ratio 515).
When 50 g of 2% triethylamine solution was added to the solution with stirring and the reaction was carried out at 30°C for 3 hours, the viscosity was 20.
,0OOCPS (25℃) Dry type PA with good flowability
A D resin solution was obtained.

This dry PAU resin is used in formulation 6.7 described below.

Here, a cationic dyeable polyester plain fabric (taffeta) of the same standard as in Example 1 was prepared as a base fabric, and after scouring and calendering was performed on it in the same manner as in Example 1, the following formulation 6 was applied. The coating solution shown was applied using a knife over roll coater at a coating rate of 1100 g/m. Thereafter, it was dry-coagulated by dry heat treatment at 120° C. for 2 minutes, thereby obtaining a P A IJ resin molded article of the present invention formed in a membrane shape on the base fabric.

Formulation 6 Dry polyamino acid urethane resin 100 parts Pentaerythritol/hydrogenated bisphenol A/triphenyl phosphite polycondensate (molecular weight 2500-3000)
0.5 parts 1.1.1', 1'-tetramethyl-4.4' (methylene-di-P-phenylene) Disemicarbazide 0.5 parts dichloromethane 5 parts 9 for comparison with the present invention Coating liquid in this example The following recipe 7 was used in place of recipe 6, and otherwise the method was exactly the same as in this example.

A comparative thin film-like PAII resin molded product was obtained on the base fabric.

Formulation 7 Dry PAtl resin 100 parts Dichloromethane 5 parts The performance of the obtained comparative PAU resin molding was compared to the P of the present invention.
The performance of the AU resin molded product was measured and evaluated, and the results are shown in Table 2.

Table 2 As is clear from Table 2, the PAtl resin molded products of the present invention have sufficient gas fading resistance without impairing light resistance.

(e) Effects of the invention The PAU resin (polyamino acid urethane resin) molded product of the present invention has a structure containing a phosphite polycondensate and a semicarbazide compound in the PAU resin, and the present invention having such a structure The PAII resin molded product has excellent gas fading resistance without any loss in light resistance.

Claims (1)

[Claims] (1) It is characterized by being made of a synthetic polymer mainly composed of polyamino acid urethane resin, and containing a phosphite polycondensate represented by the following formula (I) and a semicarbazide compound represented by the following formula (II) Polyamino acid urethane resin molded product with excellent gas fading resistance. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(I) (However, X is an integer from 2 to 10.) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(II) (However, R is an alkylene group, methylene diphenylene group, methylene ditolylene group, or methylene ditolylene group.)