JPS61122801A - Shoe sole - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a shoe sole made of a stabilized polyurethane resin. More specifically, the present invention relates to a shoe sole made of polyurethane resin that is extremely stable against external factors such as light, heat, moisture, and oxygen.

[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, 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 cause deterioration of the surface condition of polyurethane molded products. Phenomena unfavorable to the quality of polyurethane products occur, such as surface peeling, cracking, and changes in hue.

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.

A variety of molded products are manufactured using polyurethane containing these stabilizers, and recently, the design freedom and corrosion resistance of polyurethane resins have been utilized for various automobile parts, garden chairs, and other products. products are manufactured.

[Problem that the invention seeks to solve]

However, polyurethane resins produced using stabilizers that have been developed so far are not always satisfactory in terms of the sustainability of their whiteness, in the case of uncolored white polyurethane. It wasn't. That is, although the stabilizer disclosed in JP-A-56400848 serves the purpose of preventing the colored polyurethane from shrinking and cracking, it contains a phenylenediamine compound as an essential component. If this is used in white polyurethane, yellowing will occur, 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.

As mentioned above, various stabilizers for polyurethane are being developed for the purpose of producing polyurethane resins with excellent stabilizers that can withstand long-term use, but it is still not enough. There is a strong desire for the emergence of polyurethane products with excellent weather resistance that can withstand long-term use.

In particular, when a polyurethane resin is used for the sole of a shoe, if the polyurethane has a property of yellowing or fading, the commercial value of the shoe itself will be significantly reduced, which is disadvantageous. Therefore, there is a need for shoe soles made of polyurethane resin that do not discolor or fade.

[Means for solving problems]

The inventors of the present invention have arrived at the present invention as a result of intensive studies, particularly in order to solve the problem that there are no shoe soles on the market that use polyurethane that are resistant to discoloration and matte fading.

That is, the present invention provides (a) an ultraviolet absorber and (b) general formula (I) (R+, Rz, b are the same or different alkyl groups,
cycloalkyl group, aryl group, alkylaryl group,
Represents an aralkyl group. ), and the phosphorus content is 4.
To provide a shoe sole made of a polyurethane resin containing a phosphite ester in a range of 0 to 14.0% by weight and resistant to discoloration and fading.

The polyurethane resin used to manufacture the sole of the present invention is manufactured using an isocyanate compound and an active hydrogen-containing compound, and at that time, an ultraviolet absorber and the above (I) are added. The phosphorous acid ester compound shown above is used as a stabilizer.

Examples of the ultraviolet absorber that can be used in the present invention include generally known ultraviolet absorbers such as salicylic acid derivatives, pencil-like non derivatives, benzotriazole derivatives, nitrile derivatives, and oxalic acid anilide derivatives. Most preferred for use in the present invention are benzotriazole derivatives. 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
Examples include ``-hydroxy-3'', 5''-dialkylphenyl)benzotriazole.

The above ultraviolet absorbers 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 (I) is a compound represented by the general formula (I) in which R+, Rz, and R3 satisfy the above conditions. If so, any one is fine, but the phosphorus content is 4.0~
14.0% by weight, and 6.0-8.0% by weight is particularly preferred. A concrete example of this is
Examples include triisodecylphosphite, phenyldiisodecylphosphite, diphenylnonylphenylphosphite, triisooctylphosphite, and the like. These phosphite esters may be used alone or in combination.
A mixture of more than one species can be used in the present invention.

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.

(I) Preparation of test liquid Precisely weigh 0.1 g of the sample (4-b as phosphorus) into a Kjeldahl flask 100+++1, add concentrated sulfuric acid 21111, heat it, and before carbonizing, add 30% hydrogen peroxide solution one drop at a time. Decompose the solution until it becomes clear, then ignite it until white smoke of sulfuric acid comes out.After cooling, transfer this solution to a 100ml volumetric flask and add water up to the marked line to use it as a test solution.

(2) Creation of calibration curve Phosphorus standard solution, (4.3939 g of monopotassium phosphate dissolved in water to make 11) 0.2.4.6.8 ml
Place each in a 100 liter volumetric flask and add 50 ml of water to each. Add 20n+1 molybdovanadate solution to these, add condensate to make 100ml, and add 30ml of molybdovanadate solution.
Leave for a minute. Transfer this solution to a 10nn+ cell and
The absorbance at 0 nm is measured using a blank test solution as a control solution, and a calibration curve is created.

(3) Pour 5 ml of the measurement test solution into a 100 ml volumetric flask, and add approximately 5 ml of water.
Add 0 ml and 20 ml of molybdovanadate aqueous solution, perform the following operations at the same time as creating a calibration curve, and measure the absorbance.
Calculate the phosphorus content% from the calibration curve.

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 usually both the ultraviolet absorber and the tertiary phosphite are added to the polyurethane. It ranges from 0.05 to 5% by weight, preferably from 0.1 to 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 when manufacturing the sole of the present invention, it is preferable to disperse the stabilizer in advance into a part of the raw material for producing polyurethane or to dissolve it by heating. It is preferable to blend the phosphite represented by I) into the isocyanate compound.

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

In addition, examples of active hydrogen-containing compounds used in producing the polyurethane used in the sole of the present invention include:
Ethylene glycol, propylene glycol, ■, 4-
Low-molecular polyols such as butanediol, neopentyl glycol, 1,6-hexanediol, glycerin, trimethylolpropane, L2,6-hexanediol, pentaerythritol, ethylenediamine, 4.4"
-A polyether polyol obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to an amine compound such as methylenebis-2-chloroaniline or 4,4'-methylenebis-2-ethylaniline, or a low-molecular polyol or amine compound. and polytetramethylene ether glycol, and furthermore, ethylene glycol, propylene glycol,
．． Polyester polyols and polycaprolactones, which are condensation products 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 have hydroxyl groups at the terminals. Examples include polyols, polycarbonate polyols, acrylic polyols, castor oil, and tall oil. In addition, at the end of the molecule, there are hydroxyl groups, amino groups, imino groups,
Liquid rubbers containing active hydrogen groups such as carboxyl groups and mercapto groups and mixtures thereof can also be used.

When producing the polyurethane used in the sole 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, water and low boiling point foaming agents such as organic solvents,
Colorants such as titanium white, calcium carbonate, silica,
Fillers such as clay, organic fibers, and inorganic fibers, softeners such as process oil, foam stabilizers, antistatic agents, antioxidants, and the like may be added as appropriate.

The sole of the present invention can be produced, for example, by mixing and stirring a polyol component containing the ultraviolet absorber and an isocyanate component containing a phosphite represented by (I) above, and then applying a silicone mold release agent. It is manufactured by injecting into a coated aluminum shoe sole mold at 45°C to 50°C.

〔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 6 Polyester polyol (hydroxyl value 86, average molecular weight 1
300) Add a predetermined amount of the ultraviolet absorber shown in Examples 1 to 6 in Table 1 to 100 parts, and add 60 to 80 parts.
The mixture was heated and stirred at ℃ for 2 to 6 hours to dissolve it. To this polyol component, 12 parts of ethylene glycol, 0.4 parts of water, 0.8 parts of triethylene diamine, and 1 part of a silicone foam stabilizer were added and mixed, and this was used as a polyol component.

Next, a polyurethane prepolymer (NC0%,
18.5) was added and mixed with a predetermined amount of phosphorous acid ester shown in Examples 1 to 6 in Table 1, and this was used as an isocyanate component.

83 parts of the above polyol component and 10 parts of the isocyanate component
After thoroughly mixing and stirring 0 parts, the mixture 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 shoe sole of the present invention.

After conducting a 30-hour irradiation test on the six types of shoe soles obtained in this way using a carbon arc sunshine weather meter, the degree of yellowing of the test pieces was measured using a coloring machine.
It was indicated by yellow index (Yl value). The results are shown in Table 1.

The test machine used in the experiment is as follows.

(I) Carbon arc weather meter; Suga Test Equipment side Ducycle Sunshine Super Long Life Weather Meter WEL-5UN-DC type (2) Colorimeter: Suga Test Equipment ■ Needle Color Computer SM-3 Comparative Examples 1~ 7 In Examples 1 to 6, a stabilizer was added during the synthesis of polyurethane, but in Comparative Example 1,
Shoe soles were manufactured using polyurethane to which no stabilizer was added during polyurethane synthesis, and tests similar to those in Examples were conducted.

In Comparative Example 2, during polyurethane synthesis, Example 1
Shoe soles were manufactured using polyurethane synthesized by adding only the ultraviolet absorber used in 2 and 2 to the polyol component as a stabilizer.

In Comparative Example 3, a shoe sole was manufactured using a polyurethane synthesized by adding only the ultraviolet absorber used in Example 3 to the polyol component as a stabilizer during polyurethane synthesis.

In Comparative Example 4, during polyurethane synthesis, Example 1
Shoe soles were manufactured using polyurethane synthesized by adding only the phosphite ester used in 1 to the isocyanate component as a stabilizer.

In Comparative Example 5, a shoe sole was manufactured using a polyurethane synthesized by adding only the phosphite used in Example 2 to the isocyanate component as a stabilizer during polyurethane synthesis.

In Comparative Example 6, trioleyl phosphite with a phosphorus content of 3.8% was added to the isocyanate component as a phosphite during polyurethane synthesis, and was used as an ultraviolet absorber in Example 1. Shoe soles were manufactured using polyurethane synthesized by adding polyurethane to Borriol ingredients.

In Comparative Example 7, N, which is a phenylenediamine compound, was used instead of the phosphite.

A shoe sole was produced in the same manner as in Example 1 except that N''-diphenyl-p-phenylenediamine was used.

The specific means for producing the soles in Comparative Examples 1 to 7 above are all the same as in the Examples except for the operation related to adding the stabilizer.

Table 2 shows the results of tests conducted on the soles manufactured in Comparative Examples 1 to 7 in the same manner as in the Examples.

〔Effect of the invention〕

As specifically shown in the detailed description of the invention and the examples, the sole of the present invention has superior performance in terms of its white color retention, which is not found in previous shoe soles. be.

That is, the sole manufactured according to the present invention contains toluene diisocyanate, which is easily colored, or toluene diisocyanate, which is easily colored, as the polyurethane raw material isocyanate component.
Even shoe soles made of materials such as °-diphenylmethane diisocyanate have the property of being resistant to discoloration and peeling, but this has not been possible with polyurethane using known stabilizers. It was not possible. The sole of the present invention makes it possible to maintain its commercial value at an extremely high level.

Claims (1)

[Claims] 1(a) Ultraviolet absorber and (b) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (R_1, R_2, R_3 are the same or different alkyl groups, cyclo Represents an alkyl group, an aryl group, an alkylaryl group, or an aralkyl group.Shoe sole made of a polyurethane resin blended with a phosphite ester having a phosphorus content in the range of 4.0 to 14.0% by weight. 2. The shoe sole according to claim 1, wherein the phosphorous content of the phosphite ester is 6.0 to 8.0% by weight.