JPS63101412A - Polyurethane foam for sole - Google Patents

Abstract

PURPOSE:To obtain the title polyurethane of excellent hydrolysis resistance, by using a specified polyol component, a polyisocyanate component, a chain extender and a blowing agent. CONSTITUTION:A polyol component (A) comprising 50-100pts.wt. OH group- terminated polyesterpolyol (a) obtained by condensing 3-methyl-1,5-pentanediol with a dicarboxylic acid (e.g., adipic acid) (e.g., 3-methyl-1,5-pentanediol adipate of an MW of 2,000) and 0-50pts.wt. other polyol components (b) (e.g., ethylene glycol adipate), a polyisocyanate component (B) (e.g., diphenylmethane diisocyanate), a chain extender (C) of an MW<=500 (e.g., ethylene glycol) and a blowing agent (D) (e.g., water) and, optionally, a foam stabilizer (E) and a catalyst, etc. (F) are mixed and reacted together.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to polyurethane foam for shoe soles.

(Prior art) Polyurethane has excellent abrasion resistance and bending resistance, can be made lightweight by foaming, has elasticity suitable for shoe soles, and has a simpler manufacturing process than rubber. It is now being used in footwear instead of rubber.

Conventionally, as a method for producing polyurethane foam suitable for shoe soles, for example, the method described in JP-A-59-27911 is known, but in this method, polyester diols such as 7-nopic acid and ethylene glycol, diethylene glycol, butanediol, etc. are used. Because it uses polyester diol obtained by the condensation reaction of
In order to compensate for this, a compound having three active hydrogens is used in combination.

In addition, as an earlier technology, 3
The gI manufacturing method of polyurethane elastomer using polyester diol obtained from -methylpentanedio-ruic acid is known, but this polyurethane elastomer is a non-foaming elastomer,
Naturally, there is no mention that it can be applied to shoe soles.

(Problems to be Solved by the Invention) An object of the present invention is to provide a polyurethane foam for shoe soles that has excellent hydrolysis resistance without using any trifunctional active hydrogen compound.

(Means for Solving the Problems) The present invention provides a polyol component and a polyisocyanate component containing 50 to 100% by weight of a polyester polyol obtained by condensation of 3-methyl-1,5-pentanediol and dicarboxylic acid. , a foamed polyurethane for shoe soles with excellent hydrolysis resistance obtained using a chain extender and a foaming agent having a molecular weight of 500 or less.

In the present invention, 3-methyl-1 is used as a polyol component.
, 5-pentanediol and dicarboxylic acid and a polyester polyol having a hydroxyl group at the end, the polyol component contains 50 to 100% (weight %, the same applies hereinafter). If it is less than 50%, hydrolysis resistance will be poor and undesirable. Dicarboxylic acids include adipic acid,
Particularly preferred are sebacic acid, succinic acid, and the like. Examples of other polyol components include fullylene glycol and its various isomers such as ethylene glycol, propylene glycol, butylene glycol, pentamethylene glycol, and hexamethylene glycol, and diols such as cyclohexane dimetatool, diethylene glycol, and dipropylene glycol. Polyester polyols obtained by condensation reaction with dicarboxylic acids such as shibic acid, sebacic acid, and succinic acid, or polyether polyols such as polyethylene glyfur, polypropylene glycol, polytetramethylene glycol, polyethylene propylene glycol, and polyethylenetetramethylene glycol; An example is polybutanoene polyol.

As the polyisocyanate component of the present invention, for example, 7
1,000 diisocyanate, 4.4'-diphenylmethane diisocyanate, diphenyl twinocyanate, 2,
4- or 2.6-dolylene noisocyanate, phenylene dicyanate, 7-dyl ether diisocyanate
Aromatic diisocyanates such as ester, inphorone diisocyanate, and aliphatic diisocyanates such as hexamethylene diisocyanate, xylylene diisocyanate, and lysine diisocyanate can be used.

As chain extenders, glycols with a molecule i of less than 500 such as ethylene glycol, propylene glycol, butylene glycol, N-methyljetanolamine, or hydrazine, ethylenecyamine, propylene diamine, tetramethylene diamine, hexamethylene diamine 1. Cyamine having a molecular fi of 500 or less, such as methylenebis(orthochloroaniline), can be used.

As the blowing agent used in the present invention, blowing agents known to those skilled in the art such as water and/or organic blowing agents such as (halodanated) fluorinated hydrocarbons can be used. Further, if necessary, urethanization catalysts known to those skilled in the art, such as amine-based catalysts represented by tertiary amines and metal-based catalysts represented by organotin, can be used.

In producing the foamed polyurethane of the present invention, there is a method in which a polyol component, a polyisocyanate component, a chain extender, a blowing agent, etc. are simultaneously mixed and reacted (Funshot method), or a polyol component and a polyisocyanate component are mixed in advance. react to produce a prepolymer,
This prepolymer is then reacted with a chain extender (
prepolymer method) can be used.

Next, according to the present invention, foamed polyurethane having excellent hydrolysis resistance can be obtained, but from the point of view of the manufacturing process, there is a problem that the cycle time (molding time) is long from α. Therefore, in order to improve this point, it is preferable to use a polyol containing a trifunctional or more functional active hydrogen compound. Such polyols include, for example, Niboran N-200 (average 2.
7-functional polyester, M W 2500. (manufactured by Nippon Polyurethane), P C1, -320 (trifunctional, polycaprolactone ester, M W 2000, manufactured by Daicel),
Trimethylolpropane, triethanolamine, etc. can be mentioned. The amount added is preferably about 0.02 to 20% by weight, particularly about 0.02 to 20% by weight based on the total amount of liquids B and A.
05 to 15% by weight is preferred.

(Example) Reference examples, working examples, and comparative examples will be described below.

Reference example 1 Nophenyl cyane (MDr) 56.1
Chamber tFP MPA-2000 (molecular weight 2000
3-methyl-1,5-pentanediolazibe),
9') was reacted at 70° C. for 2 hours to obtain Prepolymer A with N00% of 17.0%.

Reference example 2 Instead of PMP A-2000, EBA-
2000 (molecule B zooo's ethylene glycol/butanediol adipate, Niboran N-4042
, manufactured by Nippon Polyurethane), and in the same manner as in Reference Example 1, a prepolymer B with N00% of 17.0 was obtained.

Reference example 3 Instead of PMP A-2000, EDA-
2000 (ethylene glycol/diethylene glycol anovate with molecule i 2000, Niboran N-15
4, manufactured by Nippon Polyurethane), and in the same manner as in Reference Example 1, a prepolymer C having an N00% of 17.0% was obtained.

Reference example 4 PMP A-2000 (228S), EBA
Prepolymer D with N00% of 16.9 was obtained in the same manner as in Reference Example 1 except that -2000 (22 parts) was used.

Reference example 5 PMP A-2000 (20.6 parts), E B
Reference example 1 except using A-2000 (26, 3 parts)
Prepolymer E having N00% of 17.0 was obtained in the same manner as above.

Examples 1 to 4 and Comparative Examples 1 to 3 Foamed polyurethane elastomers were obtained according to the blending ratios shown in Table 1. In the table, the foam stabilizer is manufactured by Toray Silicone, 5RX-295, and the catalyst is a 1:2 mixture of triethylenenoamine and ethylene glycol. In addition, Polyurethane Engineering Co., Ltd.'s shoe sole molding 1fl (PECM)
The properties of the sheet obtained using U-20314) were measured, and the results are also shown in Table 1. In the table, Te (tensile strength), Ee (elongation) and Tr (tear strength) are JIS K6
Measured by 301, hydrolysis resistance is 80℃ x 95%RH
After processing for a predetermined number of days under moist heat conditions, 20℃ x 55%R
After aging in a constant temperature room of H for 1 day, a test piece with a notch of 21 spades in width is bent 100,000 times using a Dematchia bending tester, and the life is expressed as the number of days when scratches within 5III are considered acceptable. Ta.

Table 1 Table 1 (continued) Examples 5 to 6 and Comparative Examples 4 to 5 Foamed polyurethane elastomers were obtained using the blending ratios shown in Table 2. In the table, N-200 is Niraporan N.
-200, TMP indicates trimethylolpropane, and the foam stabilizer and catalyst are the same as in Table 1. Also DESNA P
Table 2 also shows the properties of the sheet obtained using the S^90 (525 method) shoe sole forming machine. As shown in the table, the samples of Examples were excellent in both demolding time and hydrolysis resistance, but the samples of Comparative Examples were inferior in either or both.

Table 2 (that's all)

Claims (2)

[Claims] (1) A polyol component containing 50 to 100% by weight of a polyester polyol obtained by condensation of 3-methyl-1,5-pentanediol and dicarboxylic acid, a polyisocyanate component, a chain extender with a molecular weight of 500 or less, and foaming. Foamed polyurethane for shoe soles with excellent hydrolysis resistance obtained using a chemical agent. (2) The foamed polyurethane according to claim 1, further comprising a polyol containing a trifunctional or more functional active hydrogen compound.