JPS6356557A - Complex stabilizer for polyurethane resin - Google Patents

Abstract

PURPOSE:To obtain a complex stabilizer for polyurethane resin, capable of sustaining whiteness of white polyurethane for a long period, consisting of an ultraviolet light absorber, a specific metallic oxide or hydroxide and a specific hindered phenolic compound, etc. CONSTITUTION:A complex stabilizer consisting of (A) an ultraviolet light absorber, preferably benzotriazole derivative, etc., (B) an oxide or hydroxide of Mg, Zn, Ca or Al and (C) one or more compounds selected from (i) a hindered phenolic compound containing one or more branched-chain lower aliphatic hydrocarbon groups (preferably 3-7C group) bonded to the ortho-position, (ii) a nitrogen-containing compound which is a 1,1-dialkyl-substituted semicarbazide or carbazinic acid containing a group shown by formula I-formula III (R1 and R2 are 1-10C alkyl, substituted alkyl, etc.) or a phosphorus ester shown by formula IV (R3-R5 are alkyl, cycloalkyl, etc.) having 4-14wt%, preferably 6-8wt% phosphorus content.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a composite stabilizer for polyurethane resins. More specifically, the present invention relates to a composite stabilizer for polyurethane resins that can maintain the whiteness of white polyurethane for a long period of time.

[Conventional technology]

Polyurethane is a polymer with excellent impact resistance, chemical resistance, abrasion resistance, cold resistance, etc., and is therefore a material that has been conventionally used in various fields and applications. However, polyurethane also has the property of being easily affected by external factors such as light, heat, moisture, oxygen, and combustion gas, and these external factors can cause deterioration of the surface condition of polyurethane molded products. That is, phenomena that are undesirable for the quality of polyurethane products, such as fading of the surface, occurrence of cranks, and changes in hue, occur.

For this reason, various stabilizers have been developed for the purpose of improving polyurethane's poor weather resistance against these external factors. For example, in JP-A-56-100848, phenylenediamine compounds and sterically hindered phenol compounds, phenylenediamine compounds and phosphite compounds, phenylenediamine compounds and quinoline compounds, phenylenediamine compounds and benzotriazole A phenylenediamine compound and a thiourea compound, a phenylenediamine compound and a piperidine compound, or a phenylenediamine compound and a metal oxide are used as stabilizers for polyurethane. or,
In JP-A-57-49653, a hindered phenol compound and a phosphorous acid ester are used to improve the weather resistance of polyurethane, and in JP-A-57-34155, a hindered phenol compound and a phosphorous acid ester are used to improve the weather resistance of polyurethane. We are trying to improve the weather resistance of polyurethane using phosphite esters and metal compounds.

[Problem that the invention seeks to solve]

However, the stabilizers for polyurethane that have been developed so far are not necessarily satisfactory in terms of maintaining the whiteness of white polyurethane. That is, the stabilizer disclosed in JP-A-56-100848 serves the purpose of preventing gloss fading and cracking of colored polyurethane, but it does not contain a phenylenediamine compound as an essential component. Therefore, if it is used in white polyurethane, it will cause yellowing, which is undesirable.

Furthermore, the stabilizer disclosed in JP-A No. 57-49653 is inferior in terms of sustainability of effect;
It cannot be said to be sufficient. Also, Japanese Patent Publication No. 57-34155
The stabilizer disclosed in the publication cannot be said to have a sufficient effect of preventing white polyurethane from yellowing due to light.

[Means for solving problems]

The present inventors have solved the above problems, namely, that no stabilizer has been obtained that is excellent in maintaining the whiteness of white polyurethane, and that the stabilizers obtained so far have a long-lasting effect. In order to solve the problem that these points are not necessarily satisfactory, we have arrived at the present invention as a result of intensive studies.

That is, the present invention provides: (a) an ultraviolet absorber fb) an oxide or hydroxide of magnesium, zinc, calcium, or aluminum (hereinafter referred to as a metal compound) (c) at least one branched lower aliphatic hydrocarbon group at the ortho position or a hindered phenol compound having general formulas (1) to (III) (wherein R+ and Rz are the same or different and have 1 to 1 carbon atoms)
10 alkyl group or substituted alkyl group, R
, and R may both constitute the same ring, and the ring may be a heterocycle) A nitrogen-containing compound that is a 1,1-dialkyl-substituted semicarbazide or carbazic acid ester, or general formula (rV) (Rz, R4, Rs are the same or different alkyl groups,
cycloalkyl group, aryl group, alkylaryl group,
represents an aralkyl group), and its phosphorus content is 4
．． The present invention provides a composite stabilizer for polyurethane resins comprising one or more compounds selected from phosphite esters in a range of 0 to 14.0% by weight.

Examples of the ultraviolet absorber that can be used in the present invention include generally known ultraviolet absorbers such as salicylic acid derivatives, benzophenone derivatives, benzotriazole derivatives, nitrile derivatives, and oxalic acid anilide derivatives. Most preferred for use are benzotriazole derivatives and N-(p-ethoxycarbonylphenyl)-N'-ethyl-phenylformamidine. Specific examples of benzotriazole derivatives include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-
Hydroxy-5°-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-t
-butylphenyl)benzotriazole, 2-(2°-
Hydroxy-3'-t-butyl-5''-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5
-chlorobenzotriazole, 2-(2°-hydroxy-3'15°-dialkylphenyl)benzotriazole, and the like.

The above ultraviolet absorbers can be used in the present invention alone or as a mixture of two or more.

Next, as hindered phenol compounds having at least one branched lower aliphatic hydrocarbon group bonded to the ortho position that can be used in the present invention, those having 1 to 4 phenol nuclei in one molecule are preferred. preferable. When two or more phenol nuclei are present in one molecule, there are no particular restrictions on the bonding state. The branched lower aliphatic hydrocarbon group mentioned above is generally preferably one having 3 to 7 carbon atoms, such as isopropyl group, isobutyl group,
Examples include t-butyl group, isopentyl group, t-pentyl group, isohexyl group, etc., and particularly preferred ones include t-butyl group, isopentyl group, t-pentyl group, isohexyl group, etc.
-butyl group. Various other substituents may be bonded to the above-mentioned hindered phenol compound. Specific examples of the above-mentioned hindered phenol compounds include the following compounds.

The above compounds can be used in the present invention alone or as a mixture of two or more.

Next, the nitrogen-containing compound which is a 1,1-dialkyl-substituted semicarbazide or carbazic acid ester used in the present invention has the following general formulas (I) to (III) (wherein R,, l?! are the same or different number of carbons 1
~10 alkyl groups or substituted alkyl groups,
A nitrogen-containing compound that is a 1,1-dialkyl-substituted semicarbazide or carbazic acid ester having a group in which R2 and R2 may both constitute the same ring, and the ring may be a heterocycle, For example, the following can be mentioned:

(A) (CH3)zNNtlcONH(CHz)6N
HcONHN(CH3)z Melting point (Fp) 144-14
6℃ (B) Biuret triisocyanate (DAS 1
, 101, 394) OCN (CHz) JCONH (CHz) JCOC0NH
(cut) 6NCO + 3 mol Ll-dimethylhydrazine (C) Biulet triisocyanate (same as B)
+ 2 moles 1.1-dimethylhydrazine 1 mole ethyleneimine (D) Biuret 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 (c)lz)zNNHcONHN(CHz)z
Fp151-153℃(H) (CH3) JNHCO
NHNHCONH(CHz) bNHCONHNHCO
NHN(CHi)z Fp 225-227℃Fp
173-175℃ Fp 196-199℃ pp 7B-80℃ (L) C+stl+JHCONlIN(CH+)z
Fp 74-76°C Isomer mixture -N! IC0NI(N(CI(3')
) zFp 198-199°C Fp 250°C n, z.

Fp 246-247 ℃ (X) (C)Ii)zNNHCOOCHzCHt
OCONHN(CHa)zPp 133-135° C. These 1,1-dialkyl-substituted semicarbazides or carbazic acid ester nitrogen-containing compounds can be used in the present invention alone or as a mixture of two or more.

Next, the phosphite compound represented by the general formula (IV) is a compound represented by the general formula (II/) in which R5, R4, and R2 satisfy the above conditions. If so, either one is fine, but the phosphorus content is 4.0
-14.0% by weight, and 6.0-8.0% by weight
Particularly preferred are those. Specific examples of these include triisodecyl phosphite, phenyl diisodecyl phosphite, diphenylnonylphenyl phosphite, and triisooctyl phosphite.

These phosphite esters can be used in the present invention alone or as a mixture of two or more.

The phosphorus content of the phosphite used in the present invention is
Although it can be obtained by simple calculation, it can be obtained experimentally as follows.

(1) Preparation of test solution 0.1g of sample (containing 4 to 16mg of phosphorus) was accurately weighed into a 100m7 Kjeldahl flask, and concentrated sulfuric acid 2+N
Add 1 part of 30% hydrogen peroxide solution before heating and carbonizing.
Add drop by drop to decompose the solution until it becomes clear, then ignite until white fumes of sulfuric acid come out. After cooling, this solution was
0rn! Transfer to a volumetric flask and add water up to the marked line to use as the test solution.

(2) Creation of a calibration curve Put 0.2.4.6.8rn1 of phosphorus standard solution (4.3939 g of monopotassium phosphate dissolved in water to make 11) into a 100-volume flask and add 50 ml of water to each.
Add 7. Molybdovanadate solution 20-
After adding , water was added to bring the temperature to 100 mZ, and the mixture was left to stand for 30 minutes. This solution is transferred to a 10 mm cell, the absorbance at 400 nm is measured using a blank test solution as a control solution, and a calibration curve is created.

(3) Measurement test liquid 5rn! 100rn! Transfer it to a volumetric flask, add about 50ml of water and 20ml of an aqueous molybdovanadate solution, and proceed as in the same manner as creating a calibration curve to measure the change in absorbance.
The percentage of phosphorus content is calculated from the test ffi line.

The amount of the stabilizer used in the present invention is not particularly limited and is arbitrarily determined depending on the conditions in which the polyurethane composition is used, but it is usually an ultraviolet absorber, a metal compound, a hindered phenol compound, or a nitrogen-containing compound. and phosphite ester, each of polyurethane from 0.05 to
5% by weight, preferably in the range of 0.1-3% by weight.

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 used in the present invention, it is preferable to disperse the stabilizer in advance in a part of the raw material for producing polyurethane or to heat it and dissolve it. It is preferable to blend the phosphoric acid ester with the isocyanate compound.

The stabilizer used in the present invention can be used in the production of any known polyurethane, and the polyisocyanate compound component is, for example, toluene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, xylene diisocyanate,
゜4"-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymethylene polyphenylisocyanate, 3,3"
-dimethyl-4,4'-diphenylmethane diisocyanate), 3.3'-dimethyl-4,4'-biphenylene diisocyanate), 3,3'-dichloro-4,4'-biphenylene diisocyanate), It can be used in producing polyurethane using polyisocyanate compounds such as 4.4''-biphenylene diisocyanate and 115-naphthalene diisocyanate, or mixtures or modified products thereof, or prepolymers thereof. In particular, it is preferably used when producing polyurethane using toluene diisocyanate, 4,41-diphenylmethane diisocyanate, a mixture thereof, a modified product, or a prepolymer thereof.

In addition, examples of active hydrogen-containing compounds used in producing polyurethane in the present invention include ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, glycerin, and trimethylolpropane. , 1.
2. Low molecular weight polyols such as 6-hexanetriol and pentaerythritol, ethylene cyanide, 4゜4゛-
Amine compounds such as methylenebis-2-chloroaniline, 4,4'-methylenebis-2-ethylaniline, or
Examples include polyether polyols and polytetramethylene ether glycols obtained by adding alkylene oxides such as ethylene oxide and propylene oxide to low-molecular polyols or amine compounds, and furthermore, ethylene glycol, propylene glycol, 1.
Polyester polyols and polycondensates of polyhydric alcohols such as 4-butanediol and polybasic acids such as phthalic acid, maleic acid, malonic acid, succinic acid, adipic acid, and terephthalic acid, and which have hydroxyl groups at the terminals. Examples include caprolactone polyol, polycarbonate polyol, acrylic polyol, castor oil, and tall oil. In addition, at the end of the molecule, there are hydroxyl groups, amino groups, imino groups,
Liquid rubbers having active hydrogen groups such as carboxyl groups and mercapto groups and mixtures thereof can also be used.

When producing polyurethane using the stabilizer of the present invention, a reaction catalyst may be added in order to lower the reaction temperature or shorten the reaction time. Specific examples of reaction catalysts include amine compounds and salts thereof such as triethylenediamine, tetramethylethylenediamine, and tetramethylhexanediamine, and organic metals such as dibutyltin dilaurate, tin octylate, lead octylate, and manganese octylate. Compounds and mixtures thereof can be mentioned.

In addition, as auxiliary ingredients, foaming agents such as water and low-boiling organic solvents,
Add coloring agents such as titanium white and carbon black, fillers such as calcium carbonate, silica, clay, aliphatic fibers, and inorganic fibers, softeners such as process oil, foam stabilizers, antistatic agents, etc. as necessary. You can also.

〔Example〕

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

Examples 1 to 7 Polyester polyol (hydroxyl value 56, average molecular weight 2
000) To 100 parts, a predetermined amount of stabilizers other than phosphites among the stabilizers shown in Examples 1 to 7 in Table 1 was added, and the mixture was heated and stirred at 60 to 80°C for 2 to 6 hours. Dissolved. In this polyol component, 8 parts of ethylene glycol, 0.4 parts of water, 0.8 parts of triethylene diamine,
One part of a silicone-based foam stabilizer and two parts of a titanium white-based white pigment were added and mixed, and this was used as a polyol component.

Next, 4.4'-difhenylmethane diisocyanate)1
Polyurethane prepolymer (NC0% 1
8.5) was used as the isocyanate component in Examples 1 and 4. In addition, in Examples 3 and 5 to 7, Example 3 in Table 1
A predetermined amount of phosphite esters shown in 1 and 5 to 7 were added and mixed to the above polyurethane prepolymer to form an isocyanate component.

120 parts of the above polyol component and 1 part of the isocyanate component
After thoroughly mixing and stirring 00 parts, it was poured into an aluminum mold at 45 to 50°C coated with a silicone-based mold release agent, and taken out after 5 minutes to form a white cured product sheet with a specific gravity of 0.65 and a thickness of 5 mm ( 150s+m x 150mm) was obtained.

The following two types of evaluations were performed on the seven types of polyurethane sheets obtained in Examples 1 to 7.

Evaluation-A- This is an evaluation of stability against light, heat, and oxygen, and after conducting a 30-hour irradiation test with a carbon arc sunshine weather meter, the degree of yellowing of the specimen was measured with a measuring device, and the yellow index was determined. (Yl value).

Evaluation-B- Evaluation of stability against fuel gas (NO□), 70
3 in a desiccator (7E) containing n7 Not.
After being exposed for 0 minutes, the degree of yellowing of the test piece was measured using a measuring device and expressed as a yellow index (Yl value).

These results are shown in Table 1.

Comparative Example 1 In Examples 1 to 7, a stabilizer was added, but in Comparative Example 1, polyurethane was produced without adding any stabilizer, and the A similar test was conducted.

Comparative Example 2 A polyurethane was produced by adding only the ultraviolet absorber used in Example 1.2.7 to the polyol component as a stabilizer.

Comparative Example 3 A polyurethane was produced by adding only the ultraviolet absorber used in Example 5.6 to the polyol component as a stabilizer.

Comparative Example 4 A polyurethane was produced by adding only the hindered phenol compound used in Example 1.5 to the polyol component as a stabilizer.

Comparative Example 5 A polyurethane was produced by adding only the nitrogen-containing compound used in Example 2 to the polyol component as a stabilizer.

Comparative Example 6 A polyurethane was produced by adding only the phosphorous ester used in Example 3.7 to the isocyanate component as a stabilizer.

Comparative Example 7 Polyurethane was produced by adding only the metal compound used in Example 1.7 to the polyol component as a stabilizer.

Comparative Example 8 A polyurethane was produced by adding only the metal compound used in Example 4 to the polyol component as a stabilizer.

Comparative Example 9 A polyurethane was produced by adding the ultraviolet absorber used in Example 3.4 and the hindered phenol compound used in Example 4.7 to a polyol component as a stabilizer.

Comparative Example 10 A polyurethane was produced by adding the ultraviolet absorber used in Example 1.2.7 and the nitrogen-containing compound used in Example 4 to a polyol component as a stabilizer.

Comparative Example 11 The ultraviolet absorber used in Examples 5 and 6 was added to the polyol component, and the phosphorous acid ester used in Example 5 was added to the isocyanate component to produce polyurethane.

Comparative Example 12 The ultraviolet absorber used in Example 1.2.7 and Example 1.
Polyurethane was produced by adding the metal compound used in 7 to the polyol component as a stabilizer.

Comparative Example 13 A polyurethane was produced by adding the hindered phenol used in Example 4.7 and the nitrogen-containing compound used in Example 6 to the polyol component as a stabilizer.

Comparative Example 14 A polyurethane was produced by adding the nitrogen-containing compound used in Example 4 to the polyol component and adding the phosphorous acid ester used in Example 3.7 to the isocyanate component.

Comparative Example 15 A polyurethane was produced by adding the hindered phenol compound used in Example 1.5 to the polyol component and adding the phosphorous acid ester used in Example 3.7 to the isocyanate component.

Comparative Example 16 A polyurethane was produced by adding the hindered phenol compound used in Example 1.5 and the metal compound used in Example 1.7 to a polyol component as a stabilizer.

Comparative Example 17 A polyurethane was produced by adding the nitrogen compound used in Example 2 and the metal compound used in Example 6 to a polyol component as a stabilizer.

Comparative Example 18 A polyurethane was produced by adding the phosphite used in Example 6 to the isocyanate component and adding zinc oxide as a metal compound to the polyol component.

Comparative Example 19 Ultraviolet absorber used in Example 1.2.7, Example 4.7
The hindered phenol compound used in Example 4 and the nitrogen-containing compound used in Example 4 were added to the polyol component as stabilizers to produce polyurethane.

Comparative Example 20 The ultraviolet absorber used in Example 5.6 and the hindered phenol compound used in Example 1.5 were added to the polyol component, and the sulfite ester used in Example 6 was added to the isocyanate component. was added to produce polyurethane.

Comparative Example 21 The ultraviolet absorber used in Example 5.6 and the nitrogen-containing compound used in Example 2 were added to the polyol component, and the phosphite used in Example 5 was added to the isocyanate component. Manufactured polyurethane.

Comparative Example 22 The hindered phenol compound used in Example 1.5 and the nitrogen-containing compound used in Example 2 were added to the polyol component, and the phosphorous ester used in Example 3.7 was added to the isocyanate component. was added to produce polyurethane.

Comparative Example 23 A polyurethane was produced by adding the hindered phenol compound used in Example 4.7, the nitrogen-containing compound used in Example 4, and the metal compound used in Example 2 as stabilizers to a polyol component.

Comparative Example 24 The hindered phenol compound used in Example 4.7 and the metal compound used in Example 4 were added to the polyol component, and the phosphorous ester used in Example 6 was added to the isocyanate component. Manufactured polyurethane.

Comparative Example 25 The nitrogen-containing compound used in Example 2 and the metal compound used in Example 5 were added to the polyol component, and Example 3.7
A polyurethane was produced by adding the phosphite used in the above to the isocyanate component.

Comparative Example 26 The hindered phenol compound used in Example 1.5, the nitrogen-containing compound used in Example 7, and the metal compound used in Example 3 were added to the polyol component, and the phosphorous compound used in Example 5 was added. A polyurethane was prepared by adding an acid ester into the isocyanate component.

Comparative Example 27 A polyurethane was produced by adding the ultraviolet absorber used in Example 3.4 and the phenylenediamine compound N,N'-diphenyl-p-phenylenediamine to the polyol component as a stabilizer.

The specific means for producing polyurethane in Comparative Examples 1 to 27 above are all the same as in the Examples except for the operation related to adding a stabilizer.

Table 2 shows the results of evaluations performed on the polyurethanes produced in Comparative Examples 1 to 27 in the same manner as in the Examples.

〔Effect of the invention〕

As specifically shown in the detailed description of the invention and in the examples, the composite stabilizer for polyurethane of the present invention can maintain the whiteness of white polyurethane, change color and fade color of colored and transparent polyurethane. In terms of prevention effect, it has an unprecedentedly excellent effect. Even if polyurethane uses toluene diisocyanate or 4,4'-diphenylmethane diisocyanate, which are known to be easily colored, as the raw material isocyanate component of polyurethane, the use of the stabilizer of the present invention prevents coloring and discoloration. No undesirable phenomena occur. This could not be achieved by the previously known methods using stabilizers. The effects of the present invention are due to the synergistic effect of the combination of 3 to 5 components of the above-mentioned ultraviolet absorber, metal compound, and hindered phenol or nitrogen-containing compound or phosphite. As shown in Figure 3, these cannot be obtained by using either one of these components alone or a combination of two components.

The stabilizer of the present invention exhibits its effect when used on not only colored and transparent polyurethane but also white polyurethane. This makes it possible to maintain extremely high commercial value of adhesives, sports shoes, and other urethane products that require particularly high whiteness.

Claims (1)

[Claims] 1 (a) Ultraviolet absorber (b) An oxide or hydroxide of magnesium, zinc, calcium, or aluminum (c) At least one branched lower aliphatic hydrocarbon group is bonded to the ortho position Hindered phenol compounds or general formulas (I) to (III) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (I) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼(III) (In the formula, R_1 and R_2 represent the same or different alkyl groups having 1 to 10 carbon atoms or substituted alkyl groups, and R_1 and R_2 may both constitute the same ring, and the ring is A nitrogen-containing compound that is a 1,1-dialkyl-substituted semicarbazide or carbazic acid ester having a group of R_3, R_4, and R_5 are the same or different alkyl groups, cycloalkyl groups, aryl groups, alkylaryl groups, and aralkyl groups), and the phosphorus content is in the range of 4.0 to 14.0% by weight. A composite stabilizer for polyurethane resins comprising one or more compounds selected from phosphorous esters. 2 The phosphite represented by the general formula (IV) is 6.
The composite stabilizer for polyurethane resins according to claim 1, which has a phosphorus content of 0 to 8.0% by weight.