JPS61203144A - Composite stabilizer - Google Patents

Abstract

PURPOSE:To provide the title stabilizer which prevents polyurethane from being discolored, by blending an ultraviolet absorber, a tert. phosphite and a 1.1- dialkyl-substd. semicarbazide or carbazinic acid. CONSTITUTION:An ultraviolet absorber (A) [e.g. 2-(2'-hydroxy-5'-methylphenyl) benzotriazole], a tert. phosphite (B) having a phosphorus content of 4.0-14.0wt% and formula I [wherein R1-R3 are each (cyclo)alkyl, (akyl)aryl, arylalkyl] (e.g. phenyl diisodecyl phosphite) and a 1,1-dialkyl-substd. semicarbazide or carbazinic acid (C) contg. a group of formula II, III or IV (wherein R4, R5 are each a 1-10C alkyl, substd. alkyl or R4 and R5 may form a ring when combined together, said ring may be a heterocyclic ring) (e.g. phenyl N- morpholinocarbamate) are blended together to obtain the title stabilizer. 0.05-5wt% of each of components A, B and C is added to polyurethane.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a novel composite stabilizer.

[Conventional technology]

Polyurethane is widely used as a polymer with excellent chemical resistance, abrasion resistance, cold resistance, durability, elasticity, etc.

However, on the other hand, polyurethane is more easily affected by external factors such as light, heat, moisture, oxygen, and combustion gas than other polymers, and deteriorates rapidly both outdoors and indoors, causing yellowing and other problems. It is known to turn brown.

For this reason, in order to improve polyurethane's poor weather resistance against these external factors, conventional methods of adding various UV absorbers, anti-aging agents for rubber, stabilizers such as piperidine compounds, and methods such as titanium white etc. A method of adding or coating a white pigment has been attempted.

[Problem that the invention seeks to solve]

However, these conventional stabilizers and conventional methods are insufficiently effective, and depending on the type of stabilizer, the solubility in polyurethane is poor, so the stabilizer bleeds onto the surface of polyurethane, reducing commercial value. There was a problem. For these reasons, there has been a strong desire for a stabilizer for polyurethane that can sufficiently stabilize polyurethane even after long-term use and does not bleed.

[Means for solving problems]

In view of this situation, the inventors of the present invention conducted intensive research on this point and found that these drawbacks could be overcome by using a certain chemical substance together with an ultraviolet absorber, leading to the present invention.

That is, the present invention comprises (a) an ultraviolet absorber and (b) general formula (1) (where R1, R2, and R2 are the same or different alkyl groups, cycloalkyl groups, aryol groups, alkylaryl groups, (c) a tertiary phosphite ester represented by an alkyl group) and having a phosphorus content in the range of 4.0 to 14.0% by weight; and (c) a 1,1-dialkyl-substituted semicarbazide or carbazic acid ester. The present invention provides a composite stabilizer for polyurethane consisting of:

Since the composite stabilizer composition of the present invention can significantly improve the weather resistance of polyurethane, it can significantly improve the browning resistance of molded articles.

Such excellent effects of the present invention are due to the synergistic effect of the combination of the ultraviolet absorber constituting the stabilizer of the present invention and the tertiary phosphite and the 1,1-dialkyl-substituted semicarbazide or carbazic acid ester. This is a remarkable performance that cannot be predicted from the performance when these compounds are used alone.

As the ultraviolet absorber used in the present invention, salicylic acid derivatives, benzophenone derivatives, benzotriazole derivatives, nitrile derivatives, oxalic acid anilide derivatives and generally known compounds can be used, but among the above compounds, benzotriazole derivatives are particularly preferred, Specific examples include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-
-t-butylphenyl)benzotriazole, 2- (
2'-Hydroxy = 3',5''-t-7'tylphenyl)benzotriazole, 2-(2''-Hydroxy-
3'-t-butyl-5''-methylphenyl)-5-chlorobenzotriazole, 2-(2°-hydroxy-3'
, 5°-di-t-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-
Examples include dialkylphenyl)benzotrimazole and the like.

These ultraviolet absorbers are used alone or in a mixture of two or more together with the tertiary phosphite and 1,1-dialkyl-substituted semicarbazide or carbazic acid ester of the present invention.

Next, the tertiary phosphite compound is a compound represented by general formula (1) with a phosphorus content of 4.0 to 14.0% by weight, where R1% and R1 are the same or different alkyl groups, cyclo selected from the group consisting of an alkyl group, an aryl group, an alkylaryl group, and an arylalkyl group.

The most preferable tertiary phosphites have a phosphorus content of 6.0 to 8.0% by weight, and specific examples include triisodecyl phosphite, phenyldiisodecyl phosphite, and diphenylnonylphenyl phosphite. , triisooctylphosphite, and the like.

These tertiary phosphorous esters are used alone or in combination with the ultraviolet absorber of the present invention and 1,1-dialkyl-substituted semicarbazide or carbazic acid ester.

The 1,■-dialkyl group-substituted semicarbazide or carbazic acid ester used in the present invention has the following -jlk formulas (II) to (IV) (wherein R4 and R5 are the same or different and are an alkyl group having 1 to 10 carbon atoms) group or a substituted alkyl group, R4 and R3 may both constitute the same ring, and the ring may be a heterocycle.

) is a 1,1-dialkyl-substituted semicarbazide or carbazic acid ester having a group such as the following.

(A) (CHs)tNNHcONH(CHz)JHC
ONIN (C1h) has a melting point (Fp) of 144-146°C (B) Biuret triisocyanate (DAS 1
, 101.394) OCN(CHri6NCONH(CIri&NC0C0NH
(CL) JCO + 3 mol 1,1-dimethylhydrazine (C) Biulet triisocyanate (same as B)
+ 2 moles 1.1-dimethylhydrazine 1 mole ethyleneimine (D) Biulet triisocyanate (same as B)
+ 1 mol 1.1-dimethylhydrazine 2 mol ethyleneimine (E) Biulet triisocyanate (same as B)
+3 mol N-amino-morpholine (F) Biulet triisocyanate (same as B)
+2 mol N-amino-morpholine 1 mol ethyleneimine (G) 1.1.5.5-tetramethylcarbohydrazide (CHs) ttNNHCONHF4 (CHs>z
Fp151 153℃(H) (CH3) JNHCO
NHNHCONH (CHz) hNHCONHNHCO
NHN(Clls)z Fp 225-227℃Fp
173-175℃ Fp 196-199℃ Fp 78-80℃ (L) C+slhJHCONIN(ill(s)g
pp 74-76℃ Isomer mixture -NICONIN(CH3) zFp
19B-199°C Fp 250°C n, z.

Fp 246-247° C. These 1,1-dialkyl-substituted semicarbazides or carbazic acid esters are used alone or as a mixture of two or more in combination with the ultraviolet absorber and tertiary phosphite according to the present invention.

In the present invention, the phosphorus content of the tertiary phosphite is
It is determined by the following method.

(1) Preparation of test liquid Accurately weigh 0.1 g of sample (containing 4 to 16 mg of phosphorus) into a 100 ml Kjeldahl flask, and add 2 ml of concentrated sulfuric acid.
Before heating and carbonizing, add 30% hydrogen peroxide drop by drop to decompose the solution until it becomes transparent, then ignite until white smoke of sulfuric acid comes out. After cooling, this solution was heated to 100%
Transfer to an m1 volumetric flask and add water up to the marked line to use as the test solution.

(2) Creating a calibration curve 12, 4, 6, and 8 ml of phosphorus standard solution (4.3939 g of monopotassium phosphate dissolved in water to make 11) were placed in 100 ml volumetric flasks, and each was filled with 50 ml of water.
Add l. Molybdovanadate solution 20
Add water to bring the total volume to 100 ml, and leave it for 30 minutes. This solution was transferred to a 10 mm cell and 400 nm
Measure the absorbance at 100°C using the blank test solution as a control solution, and create a calibration curve.

(3) Measurement Take 5 ml of the test solution in a 100+ wl volumetric flask, add about 50 ml of water and 20 ml of molybdovanadate solution, and proceed in the same manner as creating the calibration curve, measure the absorbance, and calculate the phosphorus content percentage from the calibration curve. calculate.

There is no particular restriction on the amount of stabilizer added according to the present invention, and it is arbitrarily determined depending on the conditions in which the polyurethane composition is used, but usually ultraviolet absorber, tertiary phosphite, 1゜1-dialkyl Both the substituted semicarbazide and the carbazic acid ester each range from 0.05 to 5% by weight, preferably from 0.1 to 3% by weight of the polyurethane. If the amount added is less than this range, the stabilizing effect will be low, and if it is more than this range, the physical properties such as strength and elongation of the product will be lowered, which is not preferable.

Regarding the method of adding the stabilizer in the present invention, the stabilizer may be added after being dispersed in a part of the raw material for producing polyurethane in advance, or it may be used after being heated and dissolved in the raw material for producing polyurethane.

The stabilizer in the present invention can be used for all generally known polyurethanes, but the stabilizer according to the present invention includes toluene diisocyanate, 4.4% polyisocyanate, etc.
It is effective for polyurethanes produced from polyisocyanates such as '-diphenylmethane diisocyanate, mixtures or modified products thereof, or prepolymers thereof.

Moreover, the polyol used in the production of polyurethane has an average molecular weight of 1 hydroxyl group having 2 or more hydroxyl groups per molecule.
Polyester polyols or polyether polyols having a molecular weight of 1,500 to 8,000 or mixtures thereof are preferred.

The polyurethane in the present invention may contain various additives such as chain extenders, catalysts, blowing agents, colorants, inorganic fillers, foam stabilizers, antioxidants, and light stabilizers as other compounds. I can't hold back anything.

〔Effect of the invention〕

As described in detail above, the stabilizer of the present invention prevents coloring of polyurethane, and is the first to make it possible to prevent coloring of polyurethane using toluene diisocyanate or 4,4'-diphenylmethane diisocyanate, which are particularly susceptible to coloring. . As a result, the present invention greatly increases the commercial value of polyurethane products that particularly require whiteness, such as sports shoes.

〔Example〕

The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Furthermore, in Examples and Comparative Examples, "parts" are all parts by weight.

Examples 1 to 7, Comparative Examples 1 to 5 Polyester polyol (hydroxyl value 86, average molecular weight 1
300) Add a predetermined amount of stabilizers other than the tertiary plane phosphate shown in Table 1 to 100 parts, and stabilize the mixture at 60 to 80°C for 2 to 6 hours.
The mixture was heated and stirred for an hour to dissolve it. In this polyol component,
Add and mix 12 parts of ethylene glycol, 0.4 part of water, 0.8 part of triethylene diamine, and 1 part of silicone foam stabilizer,
It was made into a polyol component.

Next, a polyurethane prepolymer (NC0%,
18.5) was mixed with a predetermined amount of tertiary phosphate shown in Table 1 to obtain an incyanate component. Next, 83 parts of the polyol component and 100 parts of the isocyanate component were thoroughly mixed and stirred, and then poured into an aluminum mold at 45 to 50°C coated with a silicone mold release agent, and taken out after 5 minutes, with a specific gravity of 0. 65, 5 mm thick white cured material sheet (1
50+++@X 150@A) was obtained. After conducting an irradiation test for 30 hours with a carbon arc sunshine weather meter using the obtained sheet, the degree of yellowing of the test piece was measured with a colorimeter, and the yellow index (Yl value) was 1st in the yellow index (Yl value).
Shown in the table.

The test machine used in the experiment is as follows.

(1) Carbon Acoustic Weather Meter; Suga Test Instruments ■ Dyu Cycle Sunshine Super Long Life Weather Meter WEL-SUN-DC type (2) Embellishing machine; Suga Test Instruments side

Claims (1)

[Claims] 1. (a) Ultraviolet absorber and (b) General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (Here, R_1, R_2, R_3 are the same or different alkyl groups , cycloalkyl group, aryl group, alkylaryl group, arylalkyl group) and having a phosphorus content in the range of 4.0 to 14.0% by weight; II) ~ (IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (R_4 in the formula, R_5 are the same or different and represent an alkyl group having 1 to 10 carbon atoms or a substituted alkyl group, R_4 and R_5 may both constitute the same ring, and the ring may be a heterocycle.) A composite stabilizer comprising a 1,1-dialkyl-substituted semicarbazide or carbazic acid ester having a group of 2. Phosphorus content of tertiary phosphite ester is 6.0 to 8.0
% by weight of the composite stabilizer according to claim 1.