JPS6249041B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a shoe sole. (Prior Art) Diene-based vulcanized rubber or polyurethane has conventionally been used as a material for the soles of sports shoes, for example. However, when diene-based vulcanized rubber is used, productivity is low, and foams such as polyurethane are difficult to produce and are therefore heavy. On the other hand, conventional polyurethane has good abrasion resistance at room temperature but poor heat abrasion resistance, and is relatively strong against rough wear but weak against slippery wear. Therefore, when playing tennis shoes, the relatively smooth tennis court surface rubs against the polyurethane sole under the player's weight, generating frictional heat that softens the polyurethane and makes it more likely to wear out.
Furthermore, when diene-based vulcanized rubber is used for the outer sole and polyurethane for the inner sole, it is difficult to bond different materials, and a buffing process or the like is required, which is time-consuming. As mentioned above, the sole material for sports shoes needs to be able to withstand severe wear conditions, but it is also required to have appropriate hardness and bending resistance. When examining the relationship between the softening point of the sole material of sports shoe soles and its abrasion resistance, it is found that the higher the softening point of the material, the better the abrasion resistance. Generally, in order to obtain a polyurethane material with a high softening point, (1) the amount of polyisocyanate and a low molecular weight chain extender is increased, and the amount of so-called hard segments is increased. (2) Increase the allophanate or biuret bond by increasing the NCO Index to 1.0 or higher. (3) It is possible to introduce a primary network into polyurethane using a polyol with two or more functionalities, but (1)
As the amount of hard segments increases, the hardness also increases, and methods (2) and (3) result in a decrease in bending resistance. (Problems to be Solved by the Invention) The purpose of the present invention is to provide a shoe sole that has appropriate hardness, excellent bending resistance, and wear resistance under severe wear conditions such as thermal wear and slip wear. Our goal is to provide the following. (Means for solving the problem) The present invention is based on the general formula ()

[formula] and/or general formula () [A: n-valent polyoxyalkylene polyol residue obtained by removing a hydroxyl group from an n-valent polyoxyalkylene polyol with a molecular weight of 400 to 10,000 n: an integer of 2 to 8 x: an average value of 0 ≦x<(n-1) number y: average value, 0.05≦y<1 number] Poly(urethane) including a polymer obtained from the reaction of a polyether polyol derivative and a polyisocyanate represented by It relates to a shoe sole whose main component is a urea (amide) polymer. The polyether polyol derivative of the general formula () of the present invention can be used, for example, in Japanese Patent Application No. 57-165447
-53533) and has a molecular weight of 400 to 10,000.
It can be obtained by a method of subjecting a polyoxyalkylene polyol and an aminobenzoic acid alkyl ester to a transesterification reaction and dealcoholization. In the above, it is preferable to use 0.125 n to 1.2 n mol of aminobenzoic acid alkyl ester per 1 mol of n-valent polyoxyalkylene polyol. The polyether polyol derivative () obtained by this method may be an esterified product in which all terminal hydroxyl groups are converted to amino groups, or a partially esterified product in which some unreacted hydroxyl groups remain, and the esterification rate is That is, the degree of amine conversion can vary over a wide range, with the preferred amine conversion being about 50-100%. The polyether polyol derivative of the general formula () of the present invention is described in, for example, Japanese Patent Application No. 59-66599, and is obtained by reacting an n-valent polyoxyalkylene polyol with aminobenzoic acid in the presence of an aliphatic alcohol. . In the above, 0.125n to 2n mol of aminobenzoic acid, preferably 0.5n per mol of n-valent polyoxyalkylene polyol.
Preferably, ~2 nmol is reacted in the presence of 0.125n to 30n equivalents of aliphatic alcohol. The polyether polyol derivative () obtained by this method is an esterified product in which all terminal hydroxyl groups are converted to amino groups, or a partially esterified product in which some unreacted hydroxyl groups remain, and is adjacent to the terminal aminophenyl group. and contains an aromatic amide group. The degree of esterification, i.e. amine conversion and amidation, can vary over a wide range;
Preferably, the amine conversion is about 50 to 100%, and the amide group adjacent to the aminophenyl group is preferably 10 to 50% with respect to the terminal amino group. Suitable polyoxyalkylene polyols used in the present invention include polyoxyalkylene oxides such as ethylene oxide, propylene oxide, tetrahydrofuran, etc. in the presence of a suitable initiator such as water, low molecular weight polyols, low molecular weight amines, etc.
2 to 2 polymerized with addition polymerization of one or more species in any order
Octavalent polyether polyols having a molecular weight of 400 to 10,000 can be mentioned, and these can be obtained by known methods. Examples of low molecular weight polyols suitable as the above-mentioned initiators include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6
-Hexanediol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose, hydroquinone, 2,2-bis(4-hydroxyphenyl)propane, etc., and low molecular weight amines include methylamine, butylamine, ethylenediamine, Examples include aniline and tolylene diamine, and alkanolamines such as ethanolamine, diethanolamine, and triethanolamine can also be used. The aminobenzoic acid used in the present invention is ortho,
Either meta- or para-aminobenzoic acid may be used.
In addition, aminobenzoic acid alkyl esters include methyl, ethyl, isopropyl,
Examples include n-propyl, isobutyl, n-butyl, t-butyl, isoamyl ester, and among these, methyl and ethyl esters are particularly preferred. Various types of aliphatic alcohols can be used in the present invention, and preferred examples include methanol, ethanol, propanol,
Chain or cyclic monoalcohols having 1 to 8 carbon atoms such as butanol, hexanol, octanol, cyclobutanol, cyclopentanol, cycloheptanol, ethylene glycol, propanediol, butanediol, hexanediol,
Examples include diols having 2 to 8 carbon atoms such as heptanediol. Also suitable are cellosolves such as 2-butoxyethanol and 2-ethoxyethanol. The polyisocyanate used in the present invention may be any polyisocyanate known in polyurethane chemistry, for example hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,4-tolylene diisocyanate (2, 4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4'-diphenylmethane diisocyanate (MDI), carbodiimide-modified MDI, polymethylene polyphenyl polyisocyanate (PAPI), ortho-toluidine diisocyanate (TODI), naphthylene diisocyanate (NDI), xylylene diisocyanate (XDI), etc., and one type or two or more types can be used. Among them, preferred polyisocyanates are 2,4-TDI, 2,6-TDI,
MDI, carbodiimide modified MDI, PAPI, TODI,
Such as NDI. In the present invention, the target poly(urethane)urea(amide) polymer can be obtained using each of the above components, but at that time, a chain extender and/or a long chain polyol may be added as necessary. can be used. Examples of the chain extender include di- to tetrafunctional polyols with a molecular weight of 400 or less and diamines having a primary or secondary terminal amino group with a molecular weight of 400 or less. Suitable chain extenders include (a) ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, hexanediol,
Polyols such as glycerin, trimethylolpropane, pentaerythritol, sorbitol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, xylylene glycol (b) Hydrazine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 1,
4-Cyclohexanediamine, phenylenediamine, xylylenediamine, 2,4-tolylenediamine, 4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 1,4 -Diamines such as dichloro-3,5-diaminobenzene and 1,3-propanediol di-para-aminobenzoate (c) Alkanolamines such as ethanolamine, diethanolamine and triethanolamine (d) Hydroquinone, pyrogallol, 4,4'- Examples include polyols with a molecular weight of 400 or less obtained by adding propylene oxide and/or ethylene oxide to isopropylidene diphenol, aniline, and the above polyols, diamines, and alkanolamines in any order, among which diamines are This is preferable for enhancing the effects of the present invention. In addition, as a long chain polyol, the average molecular weight is
Polyols having two or more active hydrogen atoms of 500 to 5000 are preferred, and for example, various polyester polyols, polyether polyols, polycarbonate polyols, polymer polyols, etc. can be used. Specific examples of polyester polyols include adipate polyols such as polyethylene adipate polyol, polybutylene adipate polyol, and polyethylene propylene adipate polyol, terephthalic acid polyols (e.g., Toyobo Co., Ltd., product names Vylon RUX, Vylon RV-200L), and polyester polyols. Caprolactone polyol (e.g., Daicel Chemical,
Examples include polyester polyols having neopentyl residues (trade names Plaxel 210 and Plaxel 220), copolymerized polyester polyols thereof, and polyester polyols having two or more functionalities using one part of trimethylolpropane as a glycol component. Specific examples of polyether polyols include polyoxyethylene glycol, polyoxypropylene polyol, polyoxyethylene polyoxypropylene polyol, polyoxytetramethylene polyol, and the like. Moreover, as the polycarbonate polyol, polybutylene carbonate polyol and polyhexamethylene carbonate polyol are preferable. Polymer polyol is obtained by graft polymerizing a vinyl group-containing monomer to a polyether polyol. Typical examples of commercially available products include POP31/28 manufactured by Mitsui Nisso;
Examples include 32/30, 34/45, 36/28, 40/45, etc. The poly(urethane) urea (amide) polymer of the present invention is disclosed in, for example, Japanese Patent Application No. 57-199384 (Japanese Unexamined Patent Publication No. 59-1999).
No. 89322), No. 59-66599 (Japanese Unexamined Patent Publication No. 60-208320)
It can be manufactured by the method described in No. The polymer of the present invention is suitably used as a sole material for various sports shoes such as so-called spiked point shoes for tennis, basketball, badminton, table tennis, volleyball, soccer, American football, baseball, etc. be done. At that time, it is required that the heat abrasion resistance is significantly higher than that of ordinary shoe soles, but there is a correlation between the heat abrasion resistance and the softening point of the elastomer for shoe soles, and the softening point is 100℃. It is particularly preferable to do the above. Polymers obtained by reacting polyether polyol derivatives having amino groups at the terminals represented by the general formulas [] and [] with polyisocyanates have a high softening point. This is thought to be due to the high thermal stability of the aromatic urea group produced by the reaction of the terminal amino group adjacent to the aromatic group with the polyisocyanate. In manufacturing the sole of the present invention, various conventionally known molding methods can be used.
First, regarding the composition of the stock solution, there are methods such as a prepolymer method, a one-shot method, and a pseudo prepolymer method intermediate between the two methods, and there is no particular limitation. For example, in the prepolymer method, long-chain polyol and polyisocyanate are reacted in advance.
Synthesize an NCO-terminated prepolymer and convert it into NCO
As an ingredient. [] or [] polyether polyol derivatives are used as the active hydrogen component. The polyether polyol derivative [] or [] is approximately
It is used in an amount of 10% by weight or more, preferably about 20% by weight or more. In the present invention, the method for molding the sole may be a unit method in which the elastomer of the present invention is used in a portion that particularly requires abrasion resistance, or a direct urethane sole (DUS) method in which the entire shoe is molded using the elastomer of the present invention. In some cases, it is also effective to have a double bottom and use the elastomer of the present invention in the part that contacts the ground (two-color DUS). In the case of a unit method using a non-foamed elastomer, the above elastomer is cast into a unit mold using a casting machine used for molding thermosetting urethane elastomer, cured, demolded, and then released. Wipe off the agent with a solvent. The obtained unit
It is fixed at a predetermined position in a DUS mold, and molded with a previously prepared upper material and a predetermined DUS stock solution for DUS molding. When using the elastomer of the present invention for the entire shoe sole or the part that contacts the ground, it is preferable to use a DUS molding machine from the viewpoint of productivity, but there is no particular limitation. When using a DUS molding machine, it is preferable from the viewpoint of the liquid ratio and viscosity of the elastomer of the present invention to prepare a stock solution for shoe soles in advance using a pseudo prepolymer method. Further, conventionally known foaming techniques can also be used, and both water foaming and Freon foaming can be applied. By foaming, the density can be selected from a wide range, but since abrasion resistance is required, the density is usually 0.5g/
Densities of cm ³ or higher are preferred. (Effects of the Invention) A shoe sole using the elastomer of the present invention exhibits a high softening point. In the conventional technology of polyurethane, it is possible to raise the softening point by increasing the number of hard segments, but at the same time, the hardness also increases, which is not suitable for sports shoes such as tennis shoes because flexibility is required. Furthermore, when using the elastomer of the present invention, for example, the hardness is JIS A 60 and the softening point is
It is possible to manufacture shoe soles that are heated to over 180℃. The reason why a shoe sole having a high softening point can be obtained according to the present invention is due to the effect on the polymer molecular structure due to the reaction between the amino-terminated polyether polyol derivative and the polyisocyanate. As for the level of physical properties required for the sole material for sports shoes, which is the object of the present invention, based on our long experience, in the case of microcellular sponge and non-foamed elastomer, it satisfies the level of laboratory data shown in Table 1. It is preferable to do so. Furthermore, in order to have even better wear resistance, it is necessary that the softening point is 100°C or higher, preferably 150°C or higher, particularly preferably 180°C or higher.

[Table] (Example) Examples and comparative examples are given and explained below.
The following components were used as the polyether polyol derivative and polyisocyanate. Polyether polyol derivative () Polytetramethylene glycol (manufactured by Mitsubishi Kasei Corporation, PTMG1000, MW1035) 502g, ethyl para-aminobenzoate 160g, tetrabutyl titanate
0.13 g was heated in a three-necked flask while passing dry nitrogen gas, and when the temperature reached 180°C, ethyl alcohol began to distill out. Gradually increase the temperature to 200℃
The distillation of ethyl alcohol reaches the theoretical amount of 82
It stopped at %. The temperature was further raised to 215°C and maintained for 2 hours, and then the pressure was reduced to distill off unreacted ethyl para-aminobenzoate. In this way, the amine value
1.427meq/g, total of amino groups and hydroxyl groups
A polyether polyol derivative of 1.594 meq/g was obtained. This means that 89.5% of the terminal hydroxyl groups of the polyol were converted to amino groups. Polyether polyol derivative () Polyoxytetramethylene glycol [manufactured by Mitsubishi Chemical Industries, Ltd., PTMG1500, MW1498] 3000g
(4.01eq), para-aminobenzoic acid (Hani Chemicals,
Reagent GR) 632g (4.61eq), 2-ethyl-1-hexanol (octanol) 520g (3.99eq), and tetrabutyl titanate 0.6g were heated in a four-necked flask while passing dry nitrogen gas, and the temperature was brought to 215.
When the temperature was lowered to 219°C, 2-ethyl-1-hexanol refluxed, and when the temperature was further raised to 219°C, water droplets began to drip into the separation tube attached to the bottom of the cooler. Heating was further continued and maintained at a temperature in the range of 215 to 230°C for 6 hours, resulting in distillation of 73.5 g of water. Next, 2-ethyl-1-hexanol was distilled off at a temperature of 200 to 210°C under a reduced pressure of 17 to 110 mmHg,
Further, the temperature was raised to 220 to 240°C, and 2-ethyl-1-hexanol was distilled off under reduced pressure of 2.5 to 3 mmHg.
A reddish-brown liquid with a viscosity of 9500 cps at 27°C was obtained.
The yield was 2103g. When this liquid was analyzed by gel permeation chromatography, it was found that
Free para-aminobenzoic acid and para-aminobenzoic acid octyl ester were hardly detected. Furthermore, the production of a polyether derivative having a terminal amino group was confirmed using the following analysis method. That is, the amine value was determined to be 1.082 meq/g by titration with perchloric acid in glacial acetic acid (Handbook of Analytical Chemistry, revised 3rd edition, page 261). In addition, the hydroxyl value measurement method (JIS
According to K1557), it was 1.169meq/g. When this product was analyzed by gel permeation chromatography, free para-aminobenzoic acid and octyl para-aminobenzoate were not detected, and the molecular weight distribution of a single peak was similar to that of the raw material PTMG1500.
It was almost the same. Therefore, 92.6% of the terminal hydroxyl groups of PTMG1500 were converted to amino groups. Furthermore, ¹³ C-NMR analysis of this product confirmed the presence of an amide group. The amide group contained was 11.5% based on the terminal amino group. Furthermore, the elemental analysis value of nitrogen was 1.73%. On the other hand, the nitrogen content based on the amino group calculated from the amine value is 1.51
%. Subtracting the amount of nitrogen content (%) determined from the amine value from the elemental analysis value of nitrogen is taken as nitrogen based on amide groups, and the amount of amide groups contained is determined to be 12.4% based on the terminal amino group. .
The amount of amide groups contained as determined by ¹³ C-NMR analysis and the amount of amide groups contained as determined from elemental analysis differed in analytical method, and no consistent values could be obtained. It shows that it exists. Prepolymer () Polycaprolactone polyol (manufactured by Daicel Chemical Industries, Ltd., Plaxel 210, molecular weight approximately 1000,
OHV113.4) 1 equivalent to 3 equivalents of pure MDI was reacted at 90℃ for 2 hours to obtain an NCO content of 9.62
% prepolymer was obtained. Prepolymer () Same as prepolymer (), 4 times equivalent
A prepolymer with an NCO content of 12.54% was obtained using MDI. Prepolymer () Same as Prepolymer () and 2.5 times equivalent
A prepolymer with an NCO content of 7.80% was obtained using MDI. Prepolymer () 2,
A prepolymer with an NCO content of 6.21% was obtained by reacting 4-TDI at a ratio of 2 equivalents at 90°C for 3 hours. Prepolymer () Same as Prepolymer () and 5.5 times equivalent
A prepolymer with an NCO content of 15.90% was obtained using MDI. Example 1 100 parts of prepolymer () are heated to 60°C.
R obtained by measuring and mixing 130 parts of polyether polyol derivative (), 15 parts of polyester polyol (Nippon Polyurethane, Nipporan 4070, OHV56.8), 0.1 part of pure water, and 0.7 part of triethylenediamine.
Adjust the temperature of the liquid to 50°C. The prepolymer heated to 60°C was added to the R liquid, mixed and stirred, and cast into a mold preheated to 60°C to obtain a high-density foam with a density of 0.9 g/cm ³ . Physical properties were measured after curing at room temperature for one week. Comparative Example 1 100 parts of prepolymer () is heated to 60°C.
1,4-butanediol 8.2 parts, polyester polyol (Nitsuporan 4070) 30 parts, polyester polyol (Nitsuporan 4009, OHV112) 30 parts,
An R solution is prepared using 0.3 part of pure water, 0.2 part of triethylenediamine, and 0.02 part of dibutyltin dilaurate, and the temperature is adjusted to 50°C. Thereafter, a high-density foam having a density of 0.8 g/cm ³ was obtained in the same manner as in Example 1. Example 2 100 parts of prepolymer () are heated to 60°C.
60 parts of polyether polyol derivative (), 15 parts of polyester polyol (Nituporan 4009),
An R solution is prepared using 12 parts of 3,3'-dichloro-4,4'-diaminodiphenylmethane, 0.2 parts of pure water, and 0.3 parts of triethylenediamine, and the temperature is adjusted to 60°C. Hereinafter, in the same manner as in Example 1, the density was 0.75 g/cm ³
A high-density foam was obtained. Example 3 100 parts of prepolymer ( ) and 119 parts of polyether polyol derivative ( ) are each heated to 60°C. After mixing and stirring the two components for 30 seconds, defoaming under reduced pressure for 1 minute, pouring into a mold preheated to 90℃,
It was cured in an oven at 100°C, demolded after 30 minutes, and post-cured at 100°C overnight to obtain a non-foamed product. Example 4 100 parts of prepolymer () are heated to 60°C.
An R solution obtained by measuring and mixing 180 parts of polyether polyol derivative (), 0.2 parts of pure water, and 0.7 parts of triethylenediamine is adjusted to 50°C. Below, Example 1
A high-density foam having a density of 1.0 g/cm ³ was obtained in the same manner as above. Example 5 100 parts of prepolymer () are heated to 80°C.
36 parts of polyether polyol derivative () and 3,
3′-dichloro-4,4′diaminodiphenylmethane
14.5 parts were mixed and dissolved, heated to 80℃, added to the above prepolymer, mixed and stirred for 30 seconds, defoamed under reduced pressure for 2 minutes, poured into a mold preheated to 100℃, and placed in an oven at 100℃. After 1 hour, the mixture was cured, demolded after 1 hour, and then post-cured at 120°C for 3 hours to obtain a non-foamed product. Example 6 100 parts of prepolymer () are heated to 45°C.
87.4 parts of polyether polyol derivative (), polycaprolactone polyol (manufactured by Daicel Chemical Industries, Ltd., Plaxel-220, molecular weight approximately 2000, OHV=
56.3) Prepare R solution using 20 parts of 3,3'-dichloro-4,4'-diaminodiphenylmethane, 0.25 parts of pure water, and 0.4 parts of triethylenediamine, and
Adjust the temperature to ℃. The prepolymer heated to 45°C was added to the R liquid, mixed and stirred, and cast into a mold preheated to 45°C to obtain a high-density foam with a density of 1.0 g/cm ³ . Comparative Example 2 100 parts of prepolymer () is heated to 45°C.
1,4-butanediol 11.3 parts, polyester polyol (Nitsuporan 4070) 60 parts, polyester polyol (Nitsuporan 4009) 24.9 parts, pure water 0.15 parts
1 part and 0.4 parts of triethylenediamine to prepare an R solution and adjust the temperature to 45°C. The prepolymer heated to 45°C was added to the R liquid, mixed and stirred, and preheated to 45°C and cast into a mold to obtain a high-density foam with a density of 1.0 g/cm ³ . Physical Property Test After curing the molded products of Examples and Comparative Examples at room temperature for one week, their physical properties were measured in accordance with JIS K6301.
Type B was used for tear strength. In addition, the softening point was determined by penetration measurement using a TMA device manufactured by Rigaku Denki. The sample has a thickness of 3 to 5 mm, a nickel pin with a diameter of 0.5 mm is placed on the sample, and a load of 20 g is applied. The atmospheric temperature was raised at a rate of 5° C. per minute, the amount of pin penetration was recorded, and the softening point was read from a chart. The results are shown in Table 2.

【table】

[Table] Evaluation of abrasion resistance by test shoes Tennis shoes and soccer shoes were actually molded using the formulations of Examples and Comparative Examples. After curing these molded Shoes at room temperature for a week, they are actually worn for tennis or soccer games, and are used for ball games.
After a certain period of time, the wear conditions of each shoe sole were compared. Sole wear was evaluated based on the amount of weight loss of the shoe for tennis shoes, and the amount of reduction in the height of the point section for soccer shoes. The results are shown in Table 3. The abrasion resistance of the sole material of each example was relatively evaluated by setting the abrasion evaluation value of the sole material of the comparative example to 1.0 for both tennis and soccer games. If the sole material has better abrasion resistance than the comparative sole material, the sole material will have a relative abrasion value of less than 1.0. Third
In the table, it was found that all of the Examples were superior to the Comparative Examples and had approximately twice the durability life.

【table】

Claims (1)

[Claims] 1 General formula () [Formula] and/or general formula () [A: n-valent polyoxyalkylene polyol residue obtained by removing a hydroxyl group from an n-valent polyoxyalkylene polyol with a molecular weight of 400 to 10,000 n: an integer of 2 to 8 x: an average value of 0 ≦x<(n-1) number y: average value, 0.05≦y<1 number] Poly(urethane) including a polymer obtained from the reaction of a polyether polyol derivative and a polyisocyanate represented by A shoe sole whose main component is a urea (amide) polymer. 2. The shoe sole according to claim 1, wherein a chain extender and/or a long chain polyol having a molecular weight of 400 or less is used in producing the polymer. 3. The shoe sole according to claim 1, wherein the polymer has a softening point of 100°C or higher.