JPS62137002A - 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] --No. 1! The present invention is based on the top riffs on sports shoes, soles, leather shoes, chemical shoes, etc., and the book li! To explain in more detail about the soles of shoes such as, by using a specific vulcanized rubber as the main component rubber, it is possible to freely color the soles. II) l! ! Good workability and processability,
Furthermore, the sole of the shoe has excellent wear resistance.

Conventional technology and the invention aim to solve Carbon black compound rubber has excellent processability, high strength, and excellent abrasion resistance, but it is difficult to color it in a color other than black for use as a shoe sole material. This poses a major constraint on shoe design.

For this reason, silica is used instead of carbon black as a rubber for shoe soles that is colored, has high strength, and has excellent abrasion resistance, and to further improve this, silane coupling agents are added. However, in order to obtain the rubber hardness required for shoe soles and increase strength and abrasion resistance, it is necessary to incorporate a large amount of silica, which reduces the fluidity of unvulcanized rubber. This has the disadvantage of causing a significant decrease in workability and processability.

In addition, a method of compounding thermoplastic resins such as high styrene resin is known in order to reduce the rubber hardness required for shoe sole materials by 1q, but in a compound system that requires coloring, the required rubber strength and abrasion resistance are not met. 1, a large amount of silica must be blended in the same way as above, and there is a problem in that workability and processability are inevitably reduced.

The present invention was made in view of the above circumstances, and is a work +! The object of the present invention is to provide a shoe sole with high strength and excellent abrasion resistance, which has improved processability, can be colored, and has a rubber hardness suitable for the intended use.

In other words, in order to achieve the above object, the present inventors have made at least one rubber selected from the group consisting of natural rubber and diene-based synthetic rubber. 100 parts by weight of rubber and 0 to 100 parts by weight of thermoplastic Lt'l resin, a specific silicate filler, i.e., an average particle size measured by an electron microscope of 30 mμ or less, a specific surface area measured by the BET method. is 100I
1 to 100 parts by weight of a silicate filler having an I12/2 or more and a silica (SiO2) content of 80% or more based on a total of 1100 parts by weight of the rubber and resin, and a specific coupling agent. That is, the following general formula (1) % formula % (1) (wherein R1 is an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms, and R2 is a straight alkyl group having 1 to 8 carbon atoms. A chain or branched divalent chain hydrocarbon group or a divalent cyclic hydrocarbon group, m is 1.2 or 3, n is a positive number of 2 to 6, and R3 and R4 each have 1 carbon number. -4 represents a linear or branched hydrocarbon group, R3 and R4 may be the same or different.) The total amount of the rubber and resin is 100%.
'f! When a rubber composition containing 0.1 to 20 parts by weight is vulcanized, conventional silica (silicate filler)
Compared to the case where a silane coupling agent-reinforced rubber composition is used, workability and processability in shoe sole VI construction are improved, and the amount of silicate-based filler added increases strength and wear resistance. The present invention was based on the discovery that it is possible to create a shoe sole that is durable, long-lasting, colorable, and fashionable.

The present invention will be explained in more detail below.

As described above, the sole of the present invention comprises at least one of natural rubber and diene-based synthetic rubber, optionally a thermoplastic resin, a silicate-based filler having the specified properties, and the general formula (1). The main component rubber is a vulcanized rubber obtained by vulcanizing a rubber composition containing the coupling agent shown.

In this case, the rubber component used in the present invention is either natural rubber or diene-based synthetic rubber, as described above.
Diene rubber is understood in a broad sense, such as styrene-butadiene rubber (SBR), polybutadiene rubber (RR), polyisoprene rubber (IR). , acrylonitrile-butadiene rubber, etc., as well as ethylene propylene rubber (F
PDM) and halogenated butyl rubber.

Furthermore, in the present invention, a thermoplastic resin can be blended in order to increase the rubber hardness required for the sole of the shoe, if necessary. As the thermoplastic resin, in addition to styrene resin such as high styrene resin, 1,2-polybutadiene resin can be used. resins, olefin resins, polyurethane resins, polyester resins, polyamide resins, vinyl chloride resins, etc., and one or more of these may be used. Here, the blending amount of the thermoplastic resin is 0 to 1 with respect to 100 parts by weight of the rubber.
00 parts by weight, particularly preferably 5 to 50 parts by weight. This thermoplastic resin may not be added if particular flexibility is required for the shoe sole, but in most cases it is preferable to use it within the above range in order to achieve a hardness that meets the required performance of the shoe sole. .

In this case, if the amount exceeds 100 parts by weight, the excellent properties such as abrasion resistance and slip resistance as a shoe sole will be lost. Not good.

"I" used in the present invention: lli salt-based filler with an average basic particle diameter of 30111μ or less as measured by an electron microscope, B
ETI landing ratio is 100m? /'i) By using this type of filler, the breaking strength and abrasion resistance of the shoe sole can be maintained at a high level.

Note that this filler is composed of Ol-(W on the silica surface and the (
1) In order to increase the bonding of the coupling agent of formula 1 and maintain high strength and wear resistance, the silica (SfO2
) It is necessary to reduce the content to 80% or more.

Here, the blending amount of the silicate filler is that if it is less than the type 1 seedling part, the filler blending will have no effect, and if it exceeds the ioome part, the unvulcanized state will be removed. The amount of phlegm increases and the processability and workability of the rubber composition deteriorates, so the amount should be 1 to 100 parts by weight, more preferably 10 to 60 parts by weight. , Brunauer-1 Met-Tailor (3runaucr-1mmctt-Tell
er ) = 8 = Abbreviation of method, ASTM D-3037-81: Part 17
) The measurement method is specified.

Furthermore, the binder used in the present invention has the general formula (1) as described above. group, R2 is a linear or branched divalent chain hydrocarbon group having 1 to 8 carbon atoms or a 21-valent cyclic hydrocarbon group, m is 1, 2 or 3, and n is a positive number of 2 to 6. and R3 and R4 each represent a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R3 and R4 may be the same or different. It is a ring agent, and this -〇
- has a completely different structure from those used in conventional silica-silane coupling agent systems, and reacts with silica at the end! ! One molecule contains RIO and a vulcanization accelerator residue X at the other end, and during kneading, the group RIO bonds to the silica surface,
During vulcanization, the group X functions as a vulcanization accelerator and has the effect of bonding between polymers by the sulfur in the molecule, such as the following compounds.

If the above-mentioned binder is added in an amount of more than 20 parts by weight per 100 parts by weight of the total rubber and thermoplastic resin components, the fracture strength and abrasion resistance of the rubber after vulcanization will decrease, and if it is added less than 0.1 part by weight, Since no effect can be obtained, the amount is set at 0.1 to 20 parts by weight.

It is usually preferable to further add 0.1 to 5 parts by weight of a vulcanization accelerator per 100 parts by weight of rubber to the rubber composition for shoe soles of the present invention. In this case, if the amount of the vulcanization accelerator exceeds 5 parts by weight, the modulus of the vulcanized rubber (sole) will become too high, causing rubber burning, and if the amount is less than 0.1 part by weight, the effect of adding it will not be obtained. There are cases. Further, a vulcanizing agent such as sulfur does not necessarily need to be blended, but it can be blended in an amount of 4 parts by weight or less while maintaining a balance with the vulcanization accelerator to adjust rubber crosslinking.

In addition, commonly used compounding agents such as process oil, anti-aging agents, antioxidants, etc. can be appropriately added to the rubber composition of the present invention.

Further, in order to color the sole of the shoe, a suitable coloring agent such as a pigment or dye can be added.

-13= The sole of the present invention can be obtained by vulcanizing the above-mentioned rubber composition, and the vulcanization of this rubber composition is usually carried out at a vulcanization humidity of 140 to 180°C and a vulcanization time of 3 to 60°C. Conditions for minutes will be adopted.

The present invention uses vulcanized rubber obtained by vulcanizing the rubber composition as the main component rubber, and is suitable for forming outsoles of sports shoes, leather shoes, top lifts of chemical shoes, etc., and outsoles. used.

As explained above, the sole of the present invention is made by adding a specific silicate filler and a silane coupling agent represented by the general formula (1) to rubber reinforced with thermoplastic resin if necessary. Because it is formulated as a binder, it has excellent workability and moldability when manufacturing shoe soles, and in addition, in conventional silica-silane coupling agents, what is originally used for bonding silica and polymer is used for bonding between polymers. However, in the present invention, the silane coupling agent used contains a reactive moiety with silica as a binder and a vulcanization accelerator. Because the reactive group, which is a residue of , exists stably in one molecule, it is effectively used for bonding between silica and the polymer, resulting in significantly improved fracture properties. Furthermore, since the sole of the present invention does not necessarily have to contain carbon black,
It can be colored in various colors, and when used for shoe soles,
Not only are they excellent in aesthetics, they are also durable from an economic point of view, and are also highly anti-slip, making it possible for office workers to provide highly safe shoes.

EXAMPLES Hereinafter, the present invention will be explained in more detail by showing examples and comparative examples, but the present invention is not limited to the following examples.

[Examples 1 to 6. Comparative Examples 1 to 5] Eleven types of rubber compositions shown in Table 1 were vulcanized to form sheets and shoe soles. I built A. Next, the performance of these sheets and shoe soles was tested, and the results shown in Table 1 were obtained. In addition, the numerical value of a component shows a weight part.

-1, $2. -3: Umbrella manufactured by Japan Synthetic Rubber 4: Manufactured by Nippon Silica Average particle diameter measured with an electron microscope 15 mμ Specific surface area (
BET method) 200 i/gSio2 content 85% *6 in 5 dibenzothiazyl disulfide: Tetramethylthiuram disulfide $7: SI6
9; S4 [CH2CH2CI-I2Si(OC2H.,)3
] 2 (manufactured by Degussa) $8: TMS; $9: BMS; Medium 10: JIS A hardness *1 measured by Pico abrasion test method (based on ASTM D-2228), with the value of Comparative Example 1 as 100 Displayed as an index. The higher the index, the better.

*12 Nijouse was prototyped and evaluated after being worn.

From the results in Table 1, the rubber compositions of the examples all have excellent breaking strength, breaking elongation, tear strength, and abrasion resistance, and when processed into soles, have very good moldability such as rubber flow. The molding time was also appropriate at 3 to 10 minutes, and when actually evaluated as a shub, it was recognized that it exhibited good durability.

Comparative Example 1 is an example in which a conventionally known silane coupling agent was used, but the elongation at break and tear strength were inferior to those of the examples, and the vulcanization time was too long for rubber for shoe soles. There are drawbacks. The same thing can be said about Comparative Example 4. Furthermore, Comparative Examples 2 and 3.5 are examples in which no silane coupling agent is used, but materials with a good balance of physical properties and processability as shown in the Examples were not obtained.

Applicant Brideston Co., Ltd. Agent: Patent Attorney Takashi Kojima

Claims (1)

[Scope of Claims] 1. 100 parts by weight of at least one rubber selected from the group consisting of natural rubber and gene-based synthetic rubber, and 0 to 100 parts by weight of a thermoplastic resin, average measured by an electron microscope. Particle size is 30 mμ or less, specific surface area measured by BET method is 1
00m^2/g or more and a SiO_2 content of 80 parts by weight or more, from 1 to 100 parts by weight based on 100 parts by weight of the total amount of the rubber and resin, and the following general formula (R ^1O)m-Si-R^2-Sn-X (wherein, R^1 is an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms, and R^2 is an alkyl group having 1 to 8 carbon atoms. linear or branched divalent chain hydrocarbon group or divalent cyclic hydrocarbon group, m is 1, 2 or 3, n is a positive number from 2 to 6, X is ▲ mathematical formula, chemical formula, table, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ , and R^3 and R^4 each have 1 to 4 carbon atoms.
represents a straight or branched hydrocarbon group, but R^3 and R
^4 may be the same or different. ) The total amount of the rubber and resin is 100
A shoe sole characterized in that the main component rubber is a vulcanized rubber obtained by vulcanizing a rubber composition containing 0.1 to 20 parts by weight.