JPH02271803A - Shoe sole - Google Patents

Abstract

PURPOSE:To impart water-repellent performance to the shoe sole and to prevent the degradation in flexing resistance in a cold district by constituting the shoe sole of a specific polyester-base foamy polyurethane elastomer. CONSTITUTION:The shoe sole is formed by using the foamy polyurethane elastomer consisting of a polyester-base hydroxy compd., crosslinking agent, foaming agent, foam stabilizer, catalyst and fluorine compd. and/or fluorinated urethane of 0.1 to 10wt.% amt. of addition, and org. diisocyanate. The fluorine compd. is exemplified by the esterified matter of perfluoroalkyl group-contg. alcohol and (meth)acrylic acid. The fluorinated urethane is the urethane compd. consisting of the reaction product of the perfluoroalkyl group-contg. alcohol, polyester polyol and org. diisocyanate and also includes a mixture composed of this compd. and the above-mentioned fluorine compd. The polyester polyol is produced by adding 2 to 4C alkylene oxide or/and tetrahydrofuran to >=2C polyhydric alcohol so as to attain a desired mol.wt..

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a shoe sole with improved various physical properties after immersion in water, humidity, etc., or after water absorption.

(Prior art) Cellular polyurethane elastomer is used for women's Santal,
It is used for various shoe soles such as men's shoes, caller shoes, Soyo E7 shoes, various sports shoes, safety shoes, and school shoes. This cellular polyurethane elastomer has traditionally been based on polyester as a polyhydroxy compound, and its mechanical strength (strength elongation, abrasion resistance, bending resistance), heat resistance, and practicality (comfort ), and has excellent moldability, etc., so it is the mainstream. but,
Because they are inferior in terms of hydrolysis resistance and mold resistance, they may suffer rapid deterioration depending on the storage method and usage conditions of the shoes.

In order to improve this point, in recent years, cellular polyurethane elastomers made of polyether-based polyhydroxy compounds have come into use.

For example, JP-A No. 61-303 discloses poly(urethane) urea(amide) containing a polymer obtained by the reaction of a polyether polyol derivative and a polyinsyanate.
Shoe soles made of cellular and non-cellular polyurethane elastomers whose main components are polyether polyols, polyincyanates, polyureas, and/or polyhydrazodicargen elastomers are disclosed in JP-A-60-40119. Examples include cellular urethane elastomer shoe soles containing a dispersion of C.I.

However, the soles of polyether-based cellular polyurethane elastomers have higher moisture absorption and water absorption rate because the ether bonds in the main chain are more hydrophilic than conventional artificial chill bonds, and their physical properties deteriorate after immersion in water. is a problem.

(Problem to be Solved by the Invention) The present inventors have discovered that the soles of polyether-based cellular polyurethane elastomers swell after being immersed in water, resulting in decreased hardness, decreased strength and elongation, decreased abrasion resistance, and decreased load-bearing properties. In order to solve the problem that the hardness increases and the bending resistance deteriorates extremely, especially in cold regions, the moisture absorption and water absorption properties increase and the bending resistance deteriorates extremely. We have discovered that the deterioration of physical properties can be improved by imparting water/humidity impermeability or water repellency that reduces water absorption to soles made of high-quality polyurethane elastomer, which led us to complete the present invention. be.

(Means for Solving the Problems) That is, the present invention provides (A) a polyether paste human 90oxy compound, (B) a crosslinking agent, (C) a foaming agent, (D) a foam stabilizer,
The present invention provides a shoe sole featuring a cell/X polyurethane disstomer made of (E) a catalyst, (a sophisticated fluorine compound and/or fluorinated urethane, and (G) an organic diincyanate).

(Constitution) Fluorine compounds conveniently used in the present invention (preferably perfluoroalkyl group-containing alcohol and (meth)
Examples include esterified products with acrylic acid.

The fluorinated urethane is a urethane compound made of a reaction product of a 9-fluoroalkyl group-containing alcohol, a polyester polyol, and an organic diincyanate, and also includes a mixture of this and the above-mentioned fluorine compound.

In order to give the fluorine compound a water-repellent effect and a compatibility effect, hydrophobic compounds such as higher fatty acid esters, higher fatty acid metal salts, petroleum-based crude oils, and esters of higher alcohol and acrylic acid are added to the fluorine compound at a concentration of 5 to 60%. ! It may be mixed, preferably 10 to 50% by weight.

The mixing ratio of fluorine compound/fluorinated urethane is preferably 30-90/10-70, particularly preferably 50-90.
/10 to 50 (weight ratio), and in this case, the above-mentioned hydrophobic compound is also contained in the fluorine compound.

The polyester polyol used in the fluorinated urethane is preferably an aliphatic polyester polyol,
Common aliphatic dibasic acids, such as succinic acid, geltaric acid, azobic acid, pimelic acid, superric acid, azelaic acid, cepatic acid, dodecane dicargenic acid, etc. and aliphatic polyols, such as ethylene glycol, diethylene glycol, demipyrene. It can be obtained by a condensation reaction of glycol, butylene glycol, pentyl glycol, hexane glycol, trimethylolpropane, pentaerythritol, etc., but from the economic point of view, asophinic acid ester is preferable. Additionally, 4-liester polyols obtained by ring-opening polymerization of lactones can also be used. Further, higher fatty acid-based ester polyols such as castor oil can also be used.

These polyester polyols can be obtained by mixing two or more types of glycols and performing a condensation reaction, or by mixing two or more types of polyesters having different degrees and/or different molecular weights. The molecular weight of the polyester polyol of the present invention is 600 to 3500, preferably 1000.
~3000.

/4'-fluoroalkyl group-containing alcohol,
A linear or branched perfluoro group having 4 to 16 carbon atoms? -Compounds having a fluoroalkyl group are preferred, and typical examples include (F3((F'2),
go2N(CH,)CH2CH20H(F, ((F2
), 5o2N(CH5)CH(CH,)CH20H(
F3((F2)5S02N(CH2CH3)CH2CH
20H(F, ((F2), 5o2N(CH,)CH
2CH(CM, )OH(F3((F2)7S02N(
CH2CH3)CH20H2CH(F, ((F2), 5
o2N(CH20H2CH,)CH2CH20H(F3
((F2)7SO2N(CH2CH2CH3)CH2C
H20H(F5((F2), 5o2N(CH2CH3)
(CH2)60H(F, ((F'2), So□N(CH
2CH,)(CH2), ,0H(F,((F2),5
O2N(C4H7)(CH2)20H(F, ((F2)
,5O2N(CH,)(CH2)40H(F3((F2
)78'02N(C42H25)(CH2)20H(F
, ((F2),5O2N(C,8H,,)(CH2)2
oH(F, ((F2) ,5o2N(C,H,)CH
20CI(2CI(2CH20H(F, ((F2)
5CON(C2H5)CH2CH20HC4°F2.
C) I2CH20H C12F25CH2CH20H, etc. Preferably, the per-fluoroalkyl group has 8 or more carbon atoms.

Examples of the hydroxyalkyl acrylic ester include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate, and N-methylolacrylamide.

Preferred examples of the organic diisocyanate include inphorone diincyanate, hexamethylene diincyanate, xylylene diincyanate, tolylene diincyanate, diphenylmethane diincyanate, and car-diimide-modified diphenylmethane diincyanate.

Both fluorine compounds and urethanized fluorine compounds are viscous or solid, and include chlorine-based compounds such as trichloroethane, dichloroethane, monochloroethane, and dichloromethane, ketone-based compounds such as hexanone, methyl ethyl ketone, methyl imbutyl ketone, and acetone (or It can be used by dissolving it in (adding other solvents). The amount of the fluorine compound and/or urethanized fluorine compound for the polyether haze cellular polyurethane elastomer for shoe soles is preferably 0.1 to IO! The quantity is particularly preferably 0.
Use 2-5% by weight.

Examples of higher fatty acid esters that can be used as hydrophobic compounds in addition to the fluorine compound Km include lauric acid,
Oleic acid, stearic acid, dimer acid, etc., glycerin, trimethylol chloride, pentaerythritol,
Examples include esters with polyhydric alcohols such as bisphenol-A1-lubitol.

Higher fatty acid metal salts refer to the above-mentioned higher fatty acids A4Zr, Z
Examples include metal salts such as n, F, and the like.

Examples of esters of higher alcohol and acrylic acid include lauryl methacrylate, oleyl methacrylate,
Examples include stearyl methacrylate, lauryl acrylate, oleyl acrylate, and stearyl acrylate.

Polyether polyols are produced by adding alkylene oxide having 2 to 4 carbon atoms or/and tetrahydrofuran to a polyhydric alcohol having 2 or more carbon atoms such as those shown below to obtain a desired molecular weight. Ashi, yle 17 oxyderobylene glycol,
Examples include holioxypropylene/oxyethylene glycol, polyethylene glycol, glycerin paste, polyoxynolopylene triol, polyoxyethylene triol, and polyoxytetramethylene glycol.

Examples of the polyhydric alcohol having 2 or more carbon atoms include propylene glycol, trimethylol glycol, etc.
or,
Examples include bisphenol-A, which has 2 or more carbon atoms.
Examples of the four alkylene oxides include ethylene oxide, zolopylene oxide, and butylene oxide.

In the polyether polyol of the present invention, preferably polyoxypropylene glycol, polyoxypropylene-
Mention may be made of oxyethylene-glycol, tritetramethylene ether glycol and glycerin base I oxyderobylene-oxyethylene-triol. The preferred molecular weight is 300 to 10,000, particularly preferably 1000 to 6000. When the molecular weight is less than 300, the flexibility of the sole becomes poor and the bending resistance decreases. When the molecular weight exceeds 10,000, the strength and elongation of the sole decreases, but this can be solved by increasing the amount of crosslinking agent.

Examples of the crosslinking agent (B) used in the present invention include ethylene glycol, propylene glycol, butylene glycol, pentyl glycol, hexylene glycol,
Diethylene glycol, triethylene glycol, zoderopyrene glycol, triteropylene glycol, trimethylol deronogne, pentaerythritol, l, 3
Examples include butylene glycol and neopentyl glycol, particularly preferably ethylene glycol, diethylene glycol, butylene glycol, diethylene glycol, etc., which can be used alone or in combination.

The blowing agent (C) used in the present invention includes, for example, water,
Freon-11 and Freon-113 are listed, and the preferred foaming agent is water, and the density of the shoe molded product is 0.6017 cm.
When set to , the freeform density is between 0.25 and 0.
The amount of water to be added is determined so that it becomes 3511/cm.

Examples of the foam stabilizer (D) used in the present invention include anionic surfactants such as fatty acid sulfate ester salts and sulfonate salts, and silicone foam stabilizers. Examples of sulfuric acid ester salts include lithium, potassium, sodium, and ammonium salts of sulfated castor oil, alkyl sulfates, alkyl ether sulfates, alkyl allyl ether sulfates, and alkyl acid sulfates. Examples of the sulfonic acid salts include lithium, potassium, sodium, and ammonium salts of alkylsulfonic acids, alkylbenzene and alkylnaphthalenesulfonic acids, sulfosuccinic acids, olefinsulfonic acids, and N-acylsulfonic acids.

As the silicone foam stabilizer, a dimethylpolysiloxane foam stabilizer is usually used. Preferred examples include polyether-modified dimethylpolysiloxane represented by the following structural formula, and commercially available products include Toray Silicone 8RX-274C.
(product of Toshi Silicon Co., Ltd.).

CHCHR' C13 A Foam stabilizer (The foam stabilizer may be either a sulfate ester salt or a sulfonate surfactant alone, or a silicone foam stabilizer alone or in combination. Particularly The mixing ratio is not limited.

The amount of foam stabilizer used is not particularly limited, but is generally 0.1 to 3% by weight based on the total weight of the polyurethane elastomer.
However, if the amount is extremely small, the foam regulating effect and foaming effect will be lost, and if the amount is too large, the water absorption will increase.

Catalyst (Odor: As a foam stabilizer, especially when speeding up the reaction or when adding a silicone foam stabilizer, examples include triethylenediamine, dimethylethanolamine, N-
It is preferable to add an appropriate amount of an amine catalyst such as methylmorpholine and a metal catalyst such as cobalt naphthenate, diptyltin zolaurate, lead octylate, or ferric chloride. A commercially available product includes Toral 8M-2 (manufactured by Dainippon Ink Chemical Industries). Furthermore, various acids such as hydrochloric acid, citric acid, and formic acid may be used to delay the reaction.

In addition, these catalysts (odors) may be used in combination with the crosslinking agent (a).In addition, pigments for coloring and weathering stabilizers (antioxidants, ultraviolet absorbers) are usually added to the polyol compound described below. It is used by adding it to the mother ingredient.

The organic diincyanate (G) used in the present invention is 1
．． 5-naphthylene diincyanate), 4,4'-diphenylmethane diincyanate, tridene diincyanate, hexamethylene diincyanate, inphorone diincyanate, 4,4'-dicyclohexylmethane diincyanate, phenylene diincyanate Examples include cyanate, xylylene diincyanate, tolylene diincyanate, cyclohegysandiincyanate, carbodiimide-modified zophenylmethane diincyanate (liquefied MDI), and 70% of the combination of 4,4'-diphenylmethane diincyanate and liquefied MDI Particularly preferred is a mixture of 96/30 to 41.

It is also convenient to appropriately mix a polyfunctional polyinsyanate such as polyether polyinsyanate.

In addition, as the organic diincyanate used in the fi4t urethane compound, inphorone diincyanate,
Tolylene diin cyanate and hexamethylene di inocyanate are preferred.

The sole of the present invention uses a polyurethane elastomer manufactured by a prepolymer method in which a polyether pace hydroxy compound (A) and/or a crosslinking agent (B) and an organic diincyanate (G) are reacted in advance.

The fluorine compound used in the present invention is added to the urethane prepolymer, and in some cases, (A) / ether paste hydroxy compound, (B) crosslinking agent, (C)
A similar effect can be obtained even if it is added to a polyol compound component consisting of a blowing agent, foam stabilizer, or scent catalyst.

The method for producing a shoe sole of the present invention includes (A) a je IJ ether paste hydroxy compound and/or (B) a crosslinking agent and an organic diincyanate in an air stream at 60 to 130°C.
A urethane prepolymer obtained by reacting for 5 to 180 minutes and a component whose temperature is controlled to 35 to 50°C, and (A) / 9
Terubase human axy compound, (B) crosslinking agent, (C
) foaming agent, (D) foam stabilizer, (barrel catalyst) 20-45
The polyol compound components whose temperature is controlled at ℃ are mixed in a commonly used two-component mixer, two-component automatic mixer, low-pressure foaming machine, injection type high-pressure foaming machine, etc., and a silicone-based or wax-based mold release agent is added to the inner surface. After pouring an appropriate amount of the mixture (the amount that will give the target molded product density) into a mold coated with the mixture and temperature controlled at 40 to 55 degrees Celsius, the mixture was aged for 3 to 6 minutes at room temperature to 55 degrees Celsius, and then the shoe sole was molded. Obtain a molded product.

The reactivity of the polyurethane elastomer composition of the present invention is
Cream time is 4-15 seconds, rise time is 20-6
0 seconds, tack free time is 30 to 90 seconds, catalyst amount,
Adjusted by mixing temperature. In addition, the reactivity is adjusted depending on the foaming machine used; when using the normal low-pressure foaming machine injection method, the reactivity is adjusted to be long and slow, and when using the injection type high-pressure foaming machine injection method, the reactivity is adjusted to be short and fast. be done.

The urethane prepolymer used in the present invention has a rating of ≧1.
It can be obtained by reacting at an equivalent ratio of 6 or 1.8 b, but if the equivalent ratio is less than 1.6 or 1.8, the prepolymer will have a high molecular weight and become highly viscous, so it cannot be used for practical purposes. .

Polyether paste foam for shoe soles used in the present invention [urethane elastomer has 0. B5>-"L-a + b
+ c, the molecular end of the cellular polyurethane elastomer is
Since it theoretically becomes an OH group, crosslinking reactions peculiar to urethane such as allophanate bonding and beeret bonding proceed.
Furthermore, the molecular weight of polyurethane is relatively small, and the sole does not have sufficient strength.

In addition, in 1.2 (, +, +), the molecular terminal of the cellular urethane elastomer theoretically becomes an NCO group, so the crosslinking reaction peculiar to urethane such as allophanate bonding and beeret bonding sieves tends to proceed, but the NCO excess rate is In this range, the linear polyurethane molecular weight does not increase, and the strength and elongation balance of the sole becomes poor.

Therefore, the composition of the elastomer of the present invention has a preferred equivalent ratio of t
L<h'≧t,s,',! 1.8,a
b − 0,85≦−a + b + a−≦1.2 (however, a,
b, a and g are the number of equivalents of a: polyether pace hydroxy compound, b: crosslinking agent, C: blowing agent and g: organic diincyanate, respectively. ), and the density is 0.
30-1.1017 It is good.

(Effects) The sole of the present invention is manufactured by using a two-component mixer, a two-component automatic mixing/low-pressure foaming machine, an injection-type high-pressure foaming machine, or the like.

The sole of the present invention has low moisture/water permeability or water absorption, and swelling is appropriately suppressed, resulting in a decrease in hardness, strength and elongation, decrease in abrasion resistance, and decrease in load bearing capacity. It is an improved version of the polyether-based cellular polyurethane elastomer, and its inherent superior properties in terms of hydrolysis resistance are also amplified, resulting in initial and long-term moisture resistance, water resistance, and hydrolysis resistance. This provides a shoe sole that is highly degradable.

Hereinafter, the present invention will be described in detail with reference to Examples, where "part" and "chi" are based on weight, unless otherwise specified.

Example-1 Polyochinglobylene glycol (molecule t200Q.

OH value 56.1) 39.2 parts under vacuum degree SmHg,
After degassing and dehydrating at 105°C for 30 minutes, the temperature was lowered to 40°C.
．． 4'-diphenylmethane diincyanate (commercial product)
54.0 parts of Millionate distillate flakes (hereinafter abbreviated as MT) manufactured by Nippon Polyurethane Industries and 54.0 parts of liquefied MDI (commercial product MD Kasei Innate 143-L,
143-L) was added and reacted for 15 to 180 minutes at 80 to 130°C in a nitrogen stream to produce a urethane prepolymer (NCO 1t227), then the temperature was lowered to 80°C. 3. Add a fluorine compound (a 15% trichloroethane solution of the esterified product of 08 fluoroalkyl group-containing alcohol and methacrylic acid) to 3.
0 parts were added and stirred uniformly to obtain 1 of a fluorinated prepolymer (NCO equivalent: 234) with Exp No. TO-3-1.

Next, 45 parts of polyoxyethylene propylene glycol (molecular weight 2500, OH value 22.44, ethylene oxide addition rate 20-30%) and polyoxyethylene propylene glycol
Propylene triol (molecule t6000, OH value 28.
05, ethylene oxide addition rate 20-30911+)
45 parts, 9 parts of ethylene glycol, silicone 5RX-
274-CO, 595 parts and 0.405 parts of water were evenly mixed at 40°C to obtain a polyol compound with ExpNo.
To-3-100 was obtained.

Using these two-component components and the catalyst Toral 8M-2 under the following conditions, polyether-based cellular polyurethane elastomer for shoe soles, dense [0.65N, -3 6#11 thick sheet and 0.651ycn? A men's shoe sole molded product was prepared using a hand foaming method.

■Molding compounding ratio <X amount ratio) Mixing temperature (C) Stirring speed (rpm) Demolding time (minutes) Mold release agent mold temperature (C) Aging condition Men's shoe sole mold 6X Mold ■/■ 100/100 ■/■ 35/40 2.800 4~6 Silicone 40~50℃ room temperature, 25.0cm per week! #=320α♂ 0.6x12x29=-(208,8m') Accumulation rate (
Swelling rate) and weight change rate (water absorption rate) under normal conditions, 2
Immediately after being immersed in water for 4 hours, and after being immersed in water for 24 hours and then electrostatically charged at room temperature for 3 days, the results are shown in Tables 3 to 5, and the amounts of fluorine compounds are shown in Tables 1 to 2. .

Example 2-5 and Comparative Example 2 Shoe sole molded products were prepared in the same manner as in Example 1, except that the through molding compounding ratio shown in Tables 1 and 2 was changed, and the same physical properties were obtained. The results were summarized in Tables 3 to 5.

Comparative Example 1 Except for not adding the fluorine compound l shown in Example-1,
Urethane prepoly produced with a similar formulation? -(NCO
Exp No. of 227), To-3-0, Polyol Con Grand To-3-10 shown in Example-1
0 and Toral 5M-2 were molded into shoe soles using the same method as in Example 1, except that the blending ratio and molding blending ratio were changed as shown in Tables 1 and 2. 4 were prepared and the same physical property items were measured, and the results are summarized in Tables 3 to 5.

Using the above molded shoe sole, hardness, strength and elongation properties, body Example 6
~10 and Comparative Example 3 gl, As shown in Table 2, fluorinated urethane ((s))
#-fluoroalkyl group-containing alcohol and 11# = 2
000 I-lyester I-lyol and tolylene diincyanate. ) A molded shoe sole was prepared in the same manner as in Example 1, except that the blending ratio of the 40% methyl in butyl ketone solution and the molding blending ratio were changed, and the same physical property items were measured. We have summarized the results.

Various test methods are as shown below.

I Physical property test method Physical property items Test piece Test method [Normal state - hardness and strength/elongation physical properties] Tensile strength Same as above (No. 3 Dan scratch) Same as above Elongation at break Same as above (Same as above) Same as above lOO~300
Same as above (same as above) Same as above Peel strength Same as above (B type Dan-e/I/) Same as above [Underwater immersion test method] Density 0.6511/an, 6X thick rethane sheet was placed under the water surface of an aquarium. The battery was floated on water and discharged for 24 hours.

[Hardness, strength and elongation properties after immersion in water and immediately after sampling]

A 6X thick sheet is taken out and adjusted to a No. 3 dumbbell or B-shaped dumbbell specimen, and the above items are measured using the same test method. The measurement is completed within 10 minutes.

[Hardness, strength and elongation properties after immersion in water and 3 days after sampling] A 6X thick 7-t was taken out and heated under standard conditions (20 to 23℃
After standing for 3 days in a test room adjusted to 65% RH,
The same items will be measured using the same test method.

■Volume change rate, weight change rate, test method A men's shoe sole (one foot) is used. (However, the volume is a drain circle) [Underwater immersion test method] A men's shoe sole with a density of 0.65110 n3 was floated under the water surface of a water tank and discharged for 24 hours.

[Volume/weight change rate after immersion in water for 24 hours/immediately after sampling] Remove the sole of a men's shoe, immediately measure the volume using the drainage method, then wipe off the moisture on the surface using absorbent paper, etc. and measure the weight within at least 1 minute. and find the rate of change.

Numerical Volume Volume (13) Weight (I) [Change rate of volume and weight after immersion in water and 3 days after sampling] Take out the men's shoes and return them to the standard condition v! After being kept quiet for 3 days in a well-equipped test room, the weight and volume are measured to determine the rate of change.

the law of nature 〆

Claims (1)

[Claims] 1. (A) polyether-based hydroxy compound, (B
) crosslinking agent, (C) foaming agent, (D) foam stabilizer, (E) catalyst,
(F) Fluorine compound and/or fluorinated urethane, (G
) A shoe sole featuring a cellular polyurethane elastomer made of organic diisocyanate. 2. The fluorine compound and/or fluorinated urethane (F) is an esterified product of a perfluoroalkyl group-containing alcohol and (meth)acrylic acid and/or the fluorinated alcohol and a hydroxyalkyl (meth)acrylic ester and 2. The shoe sole according to claim 1, which is a urethane made of a reaction product of/or a polyester polyol and an organic diisocyanate. 3. The shoe sole according to claim 1, wherein the amount of the fluorine compound and/or fluorinated urethane (F) added is 0.1 to 10% by weight.