JPS58198302A - 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 The present invention provides a thermoplastic block copolymer comprising a block copolymer of a conjugated diene compound and an aromatic vinyl compound;
This shoe sole KpA has excellent oil resistance and fluidity (processability), and is made of an elastic material mainly composed of a copolymer of an aromatic vinyl compound and an acrylic monomer.

Conventionally, thermoplastic block elastic bodies (hereinafter referred to as block elastic bodies) made of block copolymers of conjugated diene compounds and aromatic vinyl compounds have shown good rubber elasticity at room temperature and melt at high temperatures. Because it is fluid, it can be molded and molded in the same way as general thermoplastic resins, and is used for shoe soles and T4 industrial rubber products.

Materials for shoe soles include block elastic, K, soft@
PVI:! There are SBR molds and polyurethane molds, but those using block elastic materials are soft PVOK.
In contrast, it is inferior in oil resistance and abrasion resistance, and it also has the disadvantage that it is inferior to 8BR vulcanized rubber in oil resistance, abrasion resistance, and heat resistance. For this reason, for example, when using littermates for school children on waxed floors, the soles of the shoes will deteriorate and wear more quickly, and due to lack of heat resistance, the soles will be exposed to sudden friction heat. However, there is the problem of flow-a-marking dust, which is thought to be caused by the melting of some polymers.

In order to eliminate this drawback, the following proposal has been made:
It's here.

0) Crosslink the block elastic body using peroxide, (2) Mix the olefin thermoplastic resin.

(3) Mixing oil-resistant rubber (NBR, chlorinated polyethylene, etc.) However, in all of these methods, practical problems such as heat resistance, oil resistance, abrasion resistance, and fluidity (for processing materials) The present invention essentially improves the above-mentioned drawbacks of the block elastic body and provides a shoe sole with excellent oil resistance and fluidity (processability).

a) The present invention provides a thermoplastic block elastic body 1 consisting of a block combination of a conjugated diene compound and an aromatic vinyl compound.
20 parts by weight, (B)) A combination of a vinyl compound and an acrylic extender 1
Combined (hereinafter simply referred to as acrylic tea type 1 combined) 20 to 8
0 heavy lid part, io+ naphthenic Zoroshinasu oil combined with the above block elastic body and acrylic tea type 1 total amount 100゛□
Thermal aJ plastic elastic material contains 10 to 80 parts by weight and 10 to 60 parts by weight per 100 parts of the total amount of the above-mentioned block elastic body and acrylic yarn co-extrusion material. and a shoe sole characterized by thermally crosslinking a J-1P01 plastic elastomer composition with an organic peroxide.

- Block elastic body used in the present invention 1-A -f-
B-A→-, (A-B) Also 6-1 (A-B
) xn-] n
It has a structure of n. In the formula, A is an aromatic vinyl compound block, B is a conjugated diene block, and X
represents a polyfunctional compound in which n offshore bodies e are bonded, and n is an integer of 2 to 4.

The conjugated dienes in the block conjugate are 1,6-putazoene, 1. , 'll-Pentagene 1.3- to now Sacien,
Isoprene, etc., and aromatic vinyl compounds include styrene,
α-methylstyrene, vinyltoluene, t-butylstyrene.

It is sufficient that the block elastic body exhibits rubber elasticity, but it is preferable that the block elastic body contains 25 to 50% by weight of the 4R group vinyl compound block, if it is less than 25% by weight. If it is more than 50% by weight, the elasticity of the aromatic vinyl compound, which is a preferable IA6 used in the present invention, will be reduced. The aromatic vinyl compounds constituting the acrylic tea-based compound are styrene, α-methylstyrene, vinyltoluene, chlorostyrene, and t-butylstyrene, and the acrylic monomer to be combined is acrylonitrile. , methacrylonitrile, methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, etc.

In the acrylic copolymer, the ratio of the acrylic unipupil to the aromatic vinyl compound is from 40:60 to 10:9.
0 is preferable, and if the acrylic yarn monomer in the IIL ratio of the two components of the single bond body exceeds 40''I! If it is less than 7Q, the oil-resistant white clay will be insufficient.

The composition of the block'jllll polymer and the acrylic copolymer is 8n:20 to 20:80, preferably 75:2.
5 to 25 nia 5 parts by weight. Pro 214 outside this range
The ones that often coalesce are the sole's oil resistance, blood heat resistance, and J!
! The improvement of cartilage was insufficient.

Furthermore, if the acrylic copolymer is present in a large amount, the bim elasticity is poor and it cannot be used as a shoe sole for ψ.

The 7-ten based process oil used in the present invention is -
Any one of the commercially available products available in A is fine, but 1 is preferred.
．． < means that the composition is 6 to 101M aromatic and 20 to 42% naphthenic and 62 to 651M aliphatic.

The amount of naphthene thread process oil is 1 for 100 parts by weight VC of the total amount of block elastic body and acrylic Itoi 1.
0 to 80) part, preferably 20 to 6011t-11t
It is part. If it is less than 1011-Okibe, the fluidity is insufficient,
If the amount exceeds 8011 parts, the oil resistance will decrease.The naphthenic process oil will lead to improved flowability and cost reduction of the composition. A Shore hardness A of 50 to 85 is required, and the addition of 10 to 80 parts by weight satisfies this hardness requirement.

Inorganic fillers used in the present invention include solid or heavy calcium carbonate, magnesium carbonate, barium carbonate, silica, aluminum hydroxide, kaolin clay, carbon plaque, and the like.

The amount of the inorganic filler is 10 to 601 parts by weight based on 100 parts by weight of the block elastic body and the acrylic copolymer,
Preferably, it is 10 to 50 parts by weight. If the amount added is less than 10 parts by weight, it will not really help improve oil absorption or rigidity, and the thermoplastic elastomer composition containing more than 60 parts by weight will not be used as a material.'%:! % Hui. This composition has excellent oil resistance and good flowability (processability),
Suitable for shoe soles. .

This composition can be crosslinked with a 4!1 unilateral oxide.
From ll! ! The performance can improve oil resistance by %. Examples of organic peroxides include benzoyl peroxide, zocumyl peroxide, t-butyl peroxide, t-butylperoxybenzoate,
Examples include t-butyl peroxyacetate J and t-butyl peroxyoctoate. The amount of Ichikanka oxide used is 50 to 2000 ppm, preferably 20 ppm, based on the total amount of the block elastic body and acrylic copolymer.
It is 0 to 2000 ppm. If the amount is less than 50 ppm, the crosslinking effect will not be as high as 1J.
If the λ exceeds 00 ppm, the crosslinking becomes a furnace coat, the fluidity decreases, and the strength becomes poor. This peroxide is preferably heated to 180°C to 250°C at F4 during the molding stage.

1TII above] Plastic t% body gauze is +Al, (Bl
, (C) and (I'J) as the d/-copper component, and in addition to the copper component, an anti-aging agent, an ultraviolet rice absorber, an antistatic agent, an IA cooking agent, etc. are added as necessary. It is possible to add additives, light fillers, reinforcing agents, foaming agents, colorants, hj nu or fragrances, etc.

Ship port] 8%! Each sporadic material of the elastic elastic material is mixed with a Henschel Migicer 5 mixing roll, a Banbury mixer 1 linax, or a twin-screw extrusion M&轡, and the shoe sole can be obtained by injection molding into a mold. .

The block elastic bodies used (Al and acrylic copolymer TBI were manufactured as follows; ★ Examples and Comparative Examples are shown below. Part 2 and Part 1 are based on weight.

Manufacture of block elastic body) 50 g of dehydrated cyclohexipne and 1.5 l & Y of styrene monomer were added to autoclay 1001 at noon.
After adding 1 mmol of n-butyllithium 'kI DO at 0°C, 79% of butadiene was added and polymerization was carried out at 60°C for 1 hour. Next, styrene monomer Y1.5V
The mixture was incubated at 40°C for 1 hour. After terminating the polymerization by adding 10F methanol, 4-methyl-2,6-ditertiarybutylphenol and trinonylphenylphosphite were added as anti-aging agents.
150F one swimming method [L5, block elastic body (Al) yr-precipitated by steam stripping method. Melt flow index of the first demic elastic body obtained (200 ° C × 5 applied load) was 0.01.

Pure water 251 &, 3rd in the autoclave of 1507
Add 150 pv of calcium phosphate, stir at 150 rpm, then add 11 Vf of styrene and 61 Vf of acrylonitrile.
, t-butyl peroxy 3.5.5 trimethylhexanoate 25P1 t-butyl peroxy acetate) 15F.

Add Tashi, Yali dodecyl mercaptan 75F,
After that, the mixture was stirred by bubbling with 9 elemental gas for 15 minutes and then sealed.

Styrene monomer was added continuously at a rate of 1.6 drops/hour for 5 hours from the point when the temperature reached 100°C. Maintained at 100°C for 5 hours, then heated to 125°C.
After removing the 8CK and holding it for 2 hours, it was cooled, neutralized, dehydrated, and dried according to a conventional method to obtain a bead-shaped polymer [acrylic copolymer 1B)) v obtained e the obtained acrylic thread copolymer 1 melt flow The index (200°C v5KP load N) was 28.2.

EXAMPLE Table 1 shows the composition of the elastic material composition of the shoe sole used for performance evaluation. However, Sample-5 and Positive-6 are comparative examples.

＼ Mix the compositions listed in Table 1 using a Henschel mixer.
Thereafter, it was pelletized using an extruder 401R/m at an extrusion temperature of 200'CK. The melt flow index of the pellets was measured. The obtained pellets were transferred to Toshiba RS-J20
Using a mold injection 1ft type machine, 191 soles for school children were molded under conditions of a lagoon of 1 degree and 200 degrees Celsius, a mold temperature of 40'O, and a cooling time of 1 minute.

The center part of the heel of the sole was cut out and subjected to an oil resistance test by immersion in J-Ko S-3 Kamiike, and the writing resistance and hardness l were measured using a taper abrasion tester.

Further, a part of the upper was connected and assembled into a shoe, and the resulting shoe was put through a practical wear test, and the service life until the toe wears out by 5X was measured.

My father drove under waxed wax in his practical shoes, and then stopped to observe the degree to which the flow-a-marking phenomenon occurred.

Table 2 shows the results of the first offshore test.

4. According to the results in Table 2. For example, in comparison with the conventional shoe sole 11 Jl+V product (臥・ charge? 5, lkl 6.) K, which has a block elastic body as the main component as a polymer component, the second example has a hardness of γ6, but Significantly improved oil resistance [7
, a shoe sole composition with excellent fluidity (processability) can be obtained.

Patent applicant: Denki Kagaku Kogyo Co., Ltd. 9

Claims (1)

[Claims] +lllAl A thermally plastic block % consisting of a block copolymer of a conjugated diene compound and an aromatic vinyl compound.
fBl % of the copolymer of a metal group vinyl compound and an acrylic non-drying substance, 20 to 8011 parts by weight! Quantity, to+ Naphthenic process oil is combined with the above block elastic body and acrylic yarn σ) Combined tititit 100mm
10 to 801 for the holes and (1)) apply an inorganic optical filler to the above Bootsque elastic body and Acrylic I.
The total amount of J thread combined in 1 is 10011! 10 to parts
601i1 IP plastic elastomer (sole characterized by being made of drink). 1 part to 1 part, fBl 1 part by weight of 20 to 80 parts of co-1 combination of aromatic vinyl compound and acrylic monomer, (total amount of C1 naphthenic process oil of the above block elastic body and 1 part of acrylic tea-based combination to 100 parts) 10 parts by weight
~801, Okibe and (Di) inorganic filler were added to 100 parts by weight of the total amount of Doi block elastic body and acrylic tea type 1 combination.