JPS61141755A - Composite stabilizer for polyurethane and shoe sole made of polyurethane - Google Patents

Abstract

PURPOSE:To provide a composite stabilizer for polyurethane, which can well retain whiteness of white polyurethane and whose effect persists over a long period of time, consisting of an antioxidant or an ultraviolet absorber and a thiophosphite ester. CONSTITUTION:A composite stabilizer consists of an antioxidant and/or an ultraviolet absorber and a thiophosphite ester of the formula (wherein R1, R2, R3 may be the same or different and each is H, alkyl, cycloalkyl, aryl, alkylaryl, aralkyl). Preferred examples of the antioxidants are hindered phenol compds. wherein at least one branched aliph. lower hydrocarbon group is attached to the benzene ring at ortho position. Benzotriazoles are particularly preferred ultraviolet absorbers. By using the composite stabilizer, polyurethane shoe sole having excellent weather resistance can be easily produced.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel composite stabilizer for polyurethane and a polyurethane shoe sole containing the stabilizer and having excellent weather resistance.

[Prior Art] Polyurethane is a polymer that has excellent impact resistance, chemical resistance, abrasion resistance, cold resistance, etc., so it has traditionally been a material used in various fields and applications. . However, on the other hand, polyurethane also has the property of being easily affected by external factors such as light, heat, moisture, and oxygen, and these external factors can affect the surface condition of polyurethane molded products. Deterioration, that is, phenomena undesirable for the quality of polyurethane products, such as surface peeling, cracking, and change in hue, occur. Therefore, 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, a phenylenediamine compound and a sterically hindered phenol compound, a phenylenediamine compound and a phosphite compound, a phenylenediamine compound and a quinoline compound, a phenylenediamine compound and henctriazole, A phenylenediamine compound and a thiourea compound, a phenylenediamine compound and a hyheridine 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. In addition, white pigments such as titanium white can be added to polyurethane or applied to the polyurethane surface to prevent discoloration of polyurethane.
Prevents fading etc.

[Problems to be Solved by the Invention] 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.

Phosphite esters that have been disclosed as stabilizer components for polyurethane resins are susceptible to hydrolysis by the water used as a blowing agent in the polyol component when added to the polyol component. loses its effectiveness in a short period of time. In addition, when phosphite is added to the isocyanate component, it may react with the isocyanate component and cause the system to gel, or even if gelation does not occur, the isocyanate component may change color. It has the disadvantage of causing

[Means for Solving the 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 no stabilizer has been obtained so far. In order to solve the problem that the stabilizers used in the market are not necessarily satisfactory in terms of the sustainability of their effects, after extensive study, we decided to use a certain compound along with an antioxidant and/or an ultraviolet absorber. The inventors have discovered that the above problems can be solved by the following methods, and have arrived at the present invention. That is, the present invention provides (a) an antioxidant and/or
or an ultraviolet absorber, and (b) general formula (I) (R2
, R1 is hydrogen, an alkyl group, a cycloalkyl group, an aryl group, an alkylaryl group, or an aralkyl group, and R8, R2, and R3 may be the same or different. The present invention provides a composite stabilizer for polyurethane consisting of a periophosphite represented by the following formula, and a polyurethane shoe sole containing the stabilizer and having excellent weather resistance.

As the antioxidant that can be used in the present invention, -a known antioxidants can be used, including hindered phenol compounds having at least one branched lower aliphatic hydrocarbon group bonded to the ortho position. is desirable.

The antioxidant that can be used in the present invention may be any hindered phenol compound having at least one branched lower aliphatic hydrocarbon group bonded to the ortho position; One having 1 to 4 in the molecule is preferred. 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, t-butyl group,
Examples include isopentyl group, [-pentyl group, isohexyl group, etc., and t-butyl group is particularly preferred. 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 antioxidants can be used in the present invention alone or as a mixture of two or more.

Next, examples of ultraviolet absorbers that can be used in the present invention include salicylic acid derivatives, benzophenone derivatives, benzotriazole derivatives, nitrile derivatives,
Although generally known ultraviolet absorbers such as oxalic acid sweetener and lido derivatives can be mentioned, benzotriazole derivatives are most preferable for use in the present invention. Specific examples of henctriazole derivatives include 2-(2
"-Hydroxy-5'-methylphenyl)hencytriazole, 2-(2'-hydroxy-5'-t-butylphenyl)hencytriazole, 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',5'-dialkyl phenyl)benzotriazole, etc. can be mentioned.

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

Next, the thiophosphite compound used in the present invention has the following general formula (R1, R1, R3 are hydrogen, an alkyl group, a cycloalkyl group, an aryl group, an alkylaryl group, or an aralkyl group, R,,Rg
, R1 may be the same or different. ) may be used.

Examples of such thiophosphite include diethylhydrogendithiophosphite, di-n-butylhydrogendithiophosphite, dioctylhydrogendithiophosphite, didecylhydrogendithiophosphite, dilaurylhydrogendithiophosphite, ditridecyl hydrogen dithiophosphite,
Dioleyl hydrogen dithiophosphite, distearyl hydrogen dithiophosphite, phenylisodecyl hydrogen dithiophosphite, phenyl tridecyl hydrogen dithiophosphite, diphenyl hydrogen dithiophosphite, dinonylphenyl hydrogen dithiophosphite, triethyl trithiophosphite, n-butyl trithiophosphite, trioctyl trithiophosphite, tridecyl trithiophosphite, trilauryl trithiophosphite, tridecyl trithiophosphite, trioleyl trithiophosphite, tristearyl trithiophosphite,
Examples include diphenylisodecyltrithiophosphite, diphenyltridecyltrithiophosphite, triphenyltrithiophosphite, trinonylphenyltrithiophosphite, and phenyldiisodecyltrithiophosphite.

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

There is no particular restriction on the amount of the composite stabilizer for polyurethane of the present invention added when blending it into a polyurethane resin, and it is appropriately determined depending on the conditions under which the polyurethane composition is used, but usually each additive is added to the polyurethane resin. against 0
．． The content is preferably 0.5 to 5% by weight, more preferably 0.1 to 3% by weight. If the amount of the composite stabilizer for polyurethane of the present invention added is less than this range, the stabilizing effect will be low, and if it is more than this range, physical properties such as strength and elongation of the product will be adversely affected, which is not preferable.

Regarding the method of adding the composite stabilizer for polyurethane of the present invention when producing polyurethane, a method can be used in which the stabilizer is previously dispersed in a part of the raw material for producing polyurethane or dissolved by heating.

The composite stabilizer for polyurethane of the present invention can be used in the production of any generally known polyurethane, and when the polyisocyanate compound component is, for example, toluene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate,
-phenylene diisocyanate, xylene diisocyanate, 4,4'-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
Used in the production of polyurethane using polyisocyanate compounds such as '-biphenylene diisocyanate, 4゜4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, or mixtures or modified products thereof, or prepolymers thereof. be able to. In particular, toluene diisocyanate, 4,4'-diphenylmethane diisocyanate,
Alternatively, mixtures, modified products, or prepolymers thereof are preferably used in producing polyurethane.

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
．． Low molecular weight polyols such as 2.6-hexanediol and pentaerythritol, ethylenediamine, 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,
．． 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. Furthermore, liquid rubbers having active hydrogen groups such as hydroxyl groups, amino groups, imino groups, carboxyl groups, and mercapto groups at the molecular terminals 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 the reaction catalyst include, for example: List of amine compounds and their salts such as triethylenediamine, tetramethylethylenediamine, and tetramethylhexanediamine, and organometallic compounds such as dibutyltin dilaurate, tin octylate, lead octylate, and manganese octylate, and mixtures thereof. I can do it.

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

The present invention also provides a polyurethane shoe sole containing the above composite stabilizer for polyurethane and having excellent weather resistance. The stabilizer can be added to either the polyol component or the isocyanate component that is prepared prior to manufacturing the polyurethane sole. That is, there is no fear that it will be hydrolyzed when added to the polyol component, unlike the stabilizers known so far, and
When added to the isocyanate component, there is no fear that the system will gel, and by using the stabilizer, polyurethane shoe soles with excellent weather resistance can be easily produced. When manufacturing the sole, the polyol component and isocyanate component are adjusted and auxiliary components are added, etc., according to the above-mentioned manufacturing method for polyurethane resin, and then the polyol component containing the foam stabilizer and the isocyanate component are combined. In addition, the mixture can be sufficiently stirred and mixed and then poured into a heated aluminum shoe sole mold coated with a silicone mold release agent.

〔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.

1. Stability test in polyol component regarding thiophosphite, which is one component in the composite stabilizer for polyurethane of the present invention Polyester polyol (hydroxyl value 86, average molecular weight 1)
300) A polyol component prepared by adding 12 parts of ethylene glycol, 0.4 parts of water, 0.8 parts of triethylene diamine, and 1 part of a silicone foam stabilizer to 100 parts of thiophosphite shown in Table 1. After adding 1 part of each ester (Examples 1 to 5) and allowing the mixture to stand at a temperature of 45 DEG C. for two weeks, the polyol component was subjected to oxidation measurements and foaming tests.

In Comparative Example 1, nothing was added to the same polyol component as in Example, and in Comparative Examples 2 to 6, the phosphorous acid ester shown in Table 1 was added, and evaluation was made in the same manner as in Examples 1 to 5. I did it.

The results are shown in Table 1.

2. Yellowing test on soles manufactured using polyurethane resin containing the composite stabilizer for polyurethane of the present invention (Examples 6 to 11) Polyester polyol (hydroxyl value 86, average molecular weight 1)
300) Add a predetermined amount of the stabilizer shown in Examples 6 to 11 in Table 2 to 100 parts, and add the stabilizer at 60 to 80°.
The mixture was heated and stirred at C for 2 to 6 hours to dissolve the stabilizer. To this polyol component, 12 parts of ethylene glycol and 0.0 parts of water were added.
4 parts of triethylenediamine, 0.8 parts of triethylenediamine, and 1 part of a silicone foam stabilizer were added and mixed, and this was used as a polyol component.

As the isocyanate component, a polyurethane prepolymer (NC0%, 18 .5%) was used.

83 parts of the above polyol component and 10 parts of the isocyanate component
After thoroughly mixing and stirring 0 parts, it was poured into an aluminum shoe sole mold coated with a silicone mold release agent at 45 to 50°C, and taken out after 5 minutes to obtain a white polyurethane resin shoe sole with a specific gravity of 0.65. Ta.

The resulting shoe soles were subjected to a 30-hour irradiation test using a carbon arc sunshine weather meter, and then the degree of yellowing of the soles was measured using a coloring machine and expressed as a yellow index (Yl value). Ta.

The test machine used in the experiment is as follows.

(I) Carbon arc weather meter; Suga Test Instruments ■ Dyu Cycle Sunshine Super Long Life Weather Meter WEL-3UN-DC type (2) Colorimeter; Suga Test Instruments ■ Needle Color Computer S? l-3 (Comparative Examples 7 to 12) In Comparative Example 7, a polyurethane sole was manufactured without adding any stabilizer, and the same tests as in the Examples were conducted.

In Comparative Examples 8 to 12, the ultraviolet absorber used in Example 6, the antioxidant used in Example 7, and Example 7 were used, respectively.
Polyurethane resin shoes were made using only the thiophosphite ester used in Example 1O, the thiophosphite ester used in Example 1O, and the thiophosphite ester used in Example 6 and Example 8 as stabilizers. A sole was manufactured and tested similar to that in the Examples.

The above test results are shown in Table 2.

〔Effect of the invention〕

As specifically shown in the examples, the composite stabilizer for polyurethane of the present invention has the following effects in terms of maintaining the whiteness of white polyurethane and preventing discoloration and fading of colored polyurethane.
It has unprecedented effects. This effect is
The isocyanate component of polyurethane is easily colored, such as toluene diisocyanate or 4.4'
-Diphenylmethane diisocyanate and the like are also effective, and this has not been possible with previously known stabilizers.

Moreover, since the composite stabilizer for polyurethane of the present invention can be used by adding all its components to the polyol component, no complicated operations are involved in producing the polyurethane resin.

As specifically shown in the examples, the polyurethane shoe sole containing the composite stabilizer for polyurethane of the present invention has a Yl value of about 20 after 30 hours of irradiation test using a carbon arc sunshine weather meter. -40, which is an extremely low value, and the polyurethane resin of the present invention and the sole made of the polyurethane resin maintain an extremely high commercial value of urethane products that particularly require whiteness, such as sports shoes. This is what makes it possible.

Claims (1)

[Claims] 1. (a) antioxidant and/or ultraviolet absorber, and (b) general formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼ (I) (R_1, R_2, R_3 are Polyurethane consisting of a thiophosphite represented by hydrogen, an alkyl group, a cycloalkyl group, an aryl group, an alkylaryl group, or an aralkyl group, and R_1, R_2, and R_3 may be the same or different. Composite stabilizer 2 for polyurethane according to claim 1, wherein the antioxidant is a hindered phenol compound having at least one branched lower aliphatic hydrocarbon group bonded to the ortho position, Composite stabilizer 3 for polyurethane according to claim 1, UV rays Composite stabilizer 4 for polyurethane according to claim 1, wherein the absorbent is a benzotriazole ultraviolet absorber, (a) an antioxidant and/or an ultraviolet absorber, and (b) general formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (R_1, R_2, and R_3 are hydrogen, an alkyl group, a cycloalkyl group, an aryl group, an alkylaryl group, or an aralkyl group, and R_1, R_2, and R_3 may be the same or Polyurethane shoe soles containing thiophosphite represented by (may be different) as a stabilizer.