JPH0618522B2 - Shoe sole - Google Patents

Description

TECHNICAL FIELD The present invention relates to a shoe sole made of a stabilized polyurethane resin. More specifically, it relates to a shoe sole made of a polyurethane resin which is extremely stable against external factors such as light, heat, moisture, oxygen, combustion gas and the like.

[Conventional technology]

Polyurethane is a polymer that is excellent in impact resistance, chemical resistance, abrasion resistance, cold resistance, etc., and thus has been conventionally used in various fields and applications. However, on the other hand, polyurethane has the property that it is easily affected by external factors such as light, heat, moisture, oxygen, and combustion gas. Due to these external factors, the surface condition of the polyurethane molded article Deterioration, that is, a phenomenon that is not desirable for the quality of the polyurethane product, such as surface glossing, cracking, and hue change, occurs.

For this reason, various stabilizers have been developed for the purpose of ameliorating the drawback of poor weather resistance of polyurethane 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 benzotriazole are disclosed. As a stabilizer for polyurethane, a compound, a phenylenediamine compound and a thiourea compound, a phenylenediamine compound and a piperidine compound, or a phenylenediamine compound and a metal oxide are used. Further, in JP-A-57-49653, the weather resistance of polyurethane is improved by using a hindered phenol compound and a phosphite.

Various molded products have been manufactured using polyurethanes containing these stabilizers.Recently, the degree of freedom in design and corrosion resistance of various automobile parts, garden chairs and other polyurethane resins have been improved. Products are manufactured.

[Problems to be solved by the invention]

However, a polyurethane resin produced using a stabilizer that has been developed so far is a polyurethane resin that is not always satisfactory in terms of the persistence of whiteness when the polyurethane resin is a white polyurethane that is not colored. Was not. That is, the stabilizer disclosed in JP-A-56-100848 serves the purpose of preventing the glossiness and cracking of colored polyurethane, but it contains a phenylenediamine compound as an essential component. Therefore, if this is used for white polyurethane, yellowing occurs, which is not preferable.

Further, the stabilizer disclosed in JP-A-57-49653 is inferior in terms of the sustainability of the effect and cannot be said to be sufficient.

As described above, various stabilizers for polyurethane are being developed for the purpose of producing a polyurethane resin having an excellent stabilizer that can withstand long-term use, but it cannot be said to be sufficient yet. However, the emergence of polyurethane products having excellent weather resistance capable of withstanding long-term use is strongly desired.

In particular, when a polyurethane resin is used for a shoe sole, it is inconvenient if the polyurethane has a property of yellowing or glossing, because the commercial value of the shoe itself is significantly reduced. Therefore, there is a demand for shoe soles that use polyurethane resin that does not discolor or gloss.

[Means for solving problems]

The present inventors have arrived at the present invention as a result of earnest studies in order to solve the problem that a shoe sole made of polyurethane that is resistant to discoloration and glossiness does not exist in the market.
That is, the present invention provides (a) an ultraviolet absorber and (b) a general formula (I). (R ₁ , R ₂ and R ₃ represent the same or different alkyl group, cycloalkyl group, aryl group, alkylaryl group and aralkyl group.) And the phosphorus content is 4.0 to 14.
It is intended to provide a shoe sole that is resistant to discoloration and glossiness and is made of a polyurethane resin containing 0% by weight of a phosphite ester and (c) a 1,1-dialkyl-substituted semicarbazide or carbazate ester.

The polyurethane resin used for using the shoe sole of the present invention is produced by using an isocyanate compound and an active hydrogen-containing compound, and in that case, it is represented by the ultraviolet absorber and the above (I). Phosphorous acid ester compound and
It uses a 1,1-dialkyl-substituted semicarbazide or carbazate as a stabilizer.

Examples of the ultraviolet absorber that can be used in the present invention include salicylic acid derivatives, benzophenone derivatives, benzotriazole derivatives, nitrile derivatives, oxalic acid anilide derivatives, and other commonly known ultraviolet absorbers. Most preferred for use in are benzotriazole derivatives. Specific examples of the benzotriazole derivative include, for example, 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 ', 5'-dialkylphenyl) benzotriazole etc. can be mentioned.

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

Next, the phosphite compound represented by the general formula (I) is a compound represented by the general formula (I), wherein R ₁ , R ₂ and R ₃ satisfy the above conditions. Any one may be used, but the phosphorus content is 4.0 to 14.0% by weight, and the one having 6.0 to 8.0% by weight is particularly preferable. Specific examples thereof include triisodecyl phosphite, phenyldiisodecyl phosphite, diphenylnonylphenyl phosphite, triisooctyl phosphite, and the like. These phosphites can be used in the present invention alone or as a mixture of two or more kinds.

The 1,1-dialkyl-substituted semicarbazide or carbazic acid ester used in the present invention has the following general formula: (In the formula, R ₄ and R ₅ are the same or different and have 1 to 10 carbon atoms.
Represents an alkyl group or a substituted alkyl group of R ₄ and R ₅
May form the same ring, and the ring may be a heterocycle. ) Is a 1,1-dialkyl-substituted semicarbazide or carbazic acid ester having a group of), and examples thereof include the following.

(A) (CH ₃ ) ₂ NNHCONH (CH ₂ ) ₆ NHCONHN (CH ₃ ) ₂ Melting point (F _P ) 144-146 ° C (B) Burette triisocyanate (see DAS1,101,394) +3 mol 1,1-Dimethylhydrazine (C) Buret triisocyanate (same as B) +2 mol 1,1-Dimethylhydrazine 1 mol Ethyleneimine (D) Buret triisocyanate (similar to B) +1 mol 1,1-Dimethylhydrazine 2 mol ethyleneimine (E) buret triisocyanate (same as B) +3 mol N-amino-morpholine (F) buret triisocyanate (similar to B) +2 mol N-amino-morpholine 1 mol ethyleneimine (G) 1,1 , 5,5-Tetramethylcarbohydrazide (CH ₃ ) ₂ NNHCONHN (CH ₃ ) ₂ F _P 151-153 ℃ (H) (CH ₃ ) ₂ NNHCONHNHCONH (CH ₂ ) ₆ NHCONHNHCONHN (CH ₃ ) ₂ F _P 225- 227 ℃ (I) (J) (K) (L) C ₁₈ H ₃₇ NHCONHN (CH ₃ ) ₂ F _P 74-76 ℃ (M) (N) (O) (P) (Q) (R) (S) (T) (U) (V) (W) (X) (CH ₃ ) ₂ NNHCOOCH ₂ CH ₂ OCONHN (CH ₃ ) ₂ F _P 133-135 ° C (Y) (Z) These 1,1-dialkyl-substituted semicarbazides or carbazates are used alone or as a mixture of two or more kinds in combination with the ultraviolet absorber and the tertiary phosphite of the present invention.

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

(1) Preparation of test solution 0.1 g of the sample (containing 4 to 16 mg as phosphorus) is precisely weighed in 100 ml of a Kjeldahl flask, added with 2 ml of concentrated sulfuric acid, heated and carbonized with 1 drop of 30% hydrogen peroxide solution. Add each of them and decompose until the solution becomes clear, then ignite until white smoke of sulfuric acid appears. After cooling, transfer this solution to a 100 ml volumetric flask,
Add water up to the marked line to make the test solution.

(2) Preparation of calibration curve Phosphorus standard solution (4.39 g of potassium dibasic phosphate dissolved in water to make 1 liter) 0, 2, 4, 6, 8 ml of 100 m each
l Add 50 ml of water to each volumetric flask. After adding 20 ml of molybdovanadate solution to these, add water
Make 100 ml and leave for 30 minutes. This solution is transferred to a 10 mm cell, and the absorbance at 400 nm is measured using a blank test solution as a control solution to prepare a calibration curve.

(3) Measurement Take 5 ml of the test solution in a 100 ml volumetric flask, add about 50 ml of water and 20 ml of molybdovanadate solution, and operate the following calibration curve at the same time as measuring the absorbance to determine the phosphorus content% from the calibration curve.
To calculate.

There is no particular limitation on the amount of the stabilizer used in the present invention, which is arbitrarily determined depending on the conditions under which the polyurethane composition is used, but usually an ultraviolet absorber, a tertiary phosphite ester, 1,1- The amount of the dialkyl-substituted semicarbazide or carbazate is in the range of 0.05 to 5% by weight, preferably 0.1 to 3% by weight, of the polyurethane. If the addition amount is less than this range, the stabilizing effect is low, and if it is more than this range, the physical properties such as strength and elongation of the product are deteriorated, which is not preferable.

Regarding the method of adding the stabilizer used when manufacturing the shoe sole of the present invention, it is preferable to disperse the stabilizer in advance in a part of the raw material for producing polyurethane or to dissolve it by heating, and in particular, the general formula ( It is preferable to mix the phosphite represented by I) with the isocyanate compound.

The stabilizer used in the production of the shoe sole of the present invention can be used in the production of any generally known polyurethane, and the polyisocyanate compound component is, for example, toluene diisocyanate, m-phenylene diisocyanate or p-phenylene. Diisocyanate, xylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymethylene polyphenyl isocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4, Polyisocyanate compounds such as 4'-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, or Can be used in the production of polyurethane by using these mixtures, modified products, or, the prepolymers according to this or the like. Particularly, it is preferably used when a polyurethane is produced using toluene diisocyanate, 4,4′-diphenylmethane diisocyanate, a mixture or modified product thereof, or a prepolymer thereof.

Further, as the active hydrogen-containing compound used in producing the polyurethane used for the shoe sole of the present invention, for example,
Ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, glycerin, trimethylolpropane, 1,
Low molecular weight polyols such as 2,6-hexanetriol and pentaerythritol, amine compounds such as ethylenediamine, 4,4'-methylenebis-2-chloroaniline and 4,4'-methylenebis-2-ethylaniline, or low molecular weight Examples thereof include polyether polyols and polytetramethylene ether glycols obtained by adding alkylene oxides such as ethylene oxide and propylene oxide to polyols or amine compounds, and further ethylene glycol, propylene glycol, 1,4-butanediol and the like. A polycondensation product of a polyhydric alcohol with a polybasic acid such as phthalic acid, maleic acid, malonic acid, succinic acid, adipic acid, and terephthalic acid, and having a hydroxyl group at the terminal polyester polyol, polycaprolactone polyol, polycarbonate Triol, acrylic polyols, castor oil, may be mentioned tall oil.
Further, a liquid rubber having a hydroxyl group, an amino group, an imino group, a carboxyl group, an active hydrogen group such as a mercapto group or the like at the molecular end, or a mixture thereof can also be used.

During the production of the polyurethane used for the shoe 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 the reaction catalyst include, for example, triethylenediamine, tetramethylethylenediamine, amine compounds such as tetramethylhexanediamine and salts thereof, dibutyltin dilaurate, tin octylate, lead octylate, and organic metals such as manganese octylate. Examples thereof include compounds and mixtures thereof.

Further, as an auxiliary component, a foaming agent such as water or a low boiling point organic solvent,
Colorants such as titanium white, calcium carbonate, silica,
Clay, fillers such as organic fibers and inorganic fibers, softening agents such as process oils, foam stabilizers, antistatic agents, antioxidants, light stabilizers and the like can be appropriately added as necessary.

The shoe sole of the present invention may be prepared, for example, by mixing a polyol component containing the ultraviolet absorber and an isocyanate component containing the phosphite ester represented by (I) and stirring the mixture, and then adding a silicone release agent. It is manufactured by pouring into a coated mold for aluminum soles at 45 ° C to 50 ° C.

〔Example〕

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In the examples and comparative examples, "part" means "part by weight".

Examples 1 to 7 Polyester polyol (hydroxyl value 86, average molecular weight 130
0) To 100 parts, a predetermined amount of the ultraviolet absorber and 1,1-dialkyl-substituted semicarbazide or carbazic acid ester shown in Examples 1 to 7 of Table 1 are added, and 60 to
The mixture was heated and stirred at 80 ° C for 2 to 6 hours to be dissolved. To this polyol component, 12 parts of ethylene glycol, 0.4 part of water, 0.8 part of triethylenediamine, and 1 part of a silicon foam stabilizer were added and mixed to obtain a polyol component.

Next, 4,4'-diphenylmethane diisocyanate 100
Parts and polyester polyol (hydroxyl value 56, average molecular weight
2000) 66.5 parts were reacted at 60 ° C. for 2 hours to obtain a polyurethane prepolymer (NCO%, 18.5), to which a predetermined amount of phosphite ester shown in each of Examples 1 to 7 in Table 1 was added. This was mixed and used as an isocyanate component.

After 83 parts of the above polyol component and 100 parts of the isocyanate component were thoroughly mixed and stirred, a silicone type release agent was applied.
It was poured into an aluminum shoe sole mold at 45 to 50 ° C., and after 5 minutes, it was taken out to obtain a shoe sole of the present invention.

Comparative Examples 1-5 In Examples 1-7, a stabilizer was added during the synthesis of polyurethane, but in Comparative Example 1,
A shoe sole was manufactured using polyurethane to which no stabilizer was added during the polyurethane synthesis, and the same test as in the example was conducted.

In Comparative Example 2, when the polyurethane was synthesized, Example 1 was used.
A sole was 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, the sole was manufactured by using the polyurethane synthesized by adding only the phosphite ester used in Example 2 as a stabilizer to the isocyanate component at the time of synthesizing the polyurethane.

In Comparative Example 4, Example 1 was used during polyurethane synthesis.
Sole was manufactured by using the polyurethane synthesized by adding only the 1,1-dialkyl-substituted semicarbazide used in 3 and 3 to the polyol component as a stabilizer.

In Comparative Example 5, when the polyurethane was synthesized,
A shoe sole was manufactured using a polyurethane synthesized by adding the ultraviolet absorber used in 1 and 2 and the 1,1-dialkyl-substituted semicarbazide used in Examples 1 and 3 as a stabilizer in a polyol component.

The specific means for manufacturing the shoe sole in Comparative Examples 1 to 5 described above is the same as that of the example except for the operation relating to the addition of the stabilizer.

The 12 types of shoe soles thus obtained were subjected to a 30-hour irradiation test with a carbon arc type sunshine weather meter, and then the yellowing degree of the test piece was measured with a colorimeter to obtain a yellow index ( YI value). The results are shown in Table 1.

The test machine used in the experiment is as follows.

(1) Carbon arc weather meter; Suga Testing Machine Co., Ltd. Ducycle Sunshine Super Long Life Weather Meter WEL-SUN-DC type (2) Colorimeter: Suga Testing Machine Co., Ltd. SM Color Computer SM-3 [Effects of the Invention] As specifically shown in the detailed description of the invention and in the examples, the sole of the present invention is excellent in the whiteness lasting, which is not present in conventional soles. It has performance.

That is, the shoe sole manufactured according to the present invention is not discolored or glossy even if the shoe sole uses toluene diisocyanate or 4,4′-diphenylmethane diisocyanate, which is easily colored, as the isocyanate component of the polyurethane raw material. Although it has the desired property, this cannot be realized by the polyurethane using the stabilizer known so far. The shoe sole of the present invention makes it possible to maintain its commercial value extremely high.

Claims (2)

[Claims] 1. An ultraviolet absorbent (a) and a general formula (I) (b). (R ₁ , R ₂ and R ₃ represent the same or different alkyl group, cycloalkyl group, aryl group, alkylaryl group and aralkyl group.) And the phosphorus content is in the range of 4.0 to 14.0% by weight. A certain phosphite and (c) general formulas (II) to (IV) (In the formula, R ₄ and R ₅ are the same or different and have 1 to 10 carbon atoms.
Represents an alkyl group or a substituted alkyl group of R ₄ and R ₅
May form the same ring, and the ring may be a heterocycle. ) Sole made of polyurethane resin blended with 1,1-dialkyl-substituted semicarbazide or carbazate having 2. The shoe sole according to claim 1, wherein the phosphorus content of the phosphite is 6.0 to 8.0% by weight.