阅读说明：本技术 一种光亮鞋底材料及其制备方法 (Bright sole material and preparation method thereof ) 是由 龚晓春 于 2019-11-21 设计创作，主要内容包括：本发明涉及橡胶领域,具体公开了一种光亮鞋底材料及其制备方法。按重量份计,制备原料至少包括：丁腈橡胶20-40份、塑料母料10-25份、补强剂11-26份、增塑剂3-12份、防老剂0.3-1.5份、增粘剂0.2-1份、防雾剂0.1-0.8份、活性剂0.3-4.5份、硅烷偶联剂0.1-0.8份、促进剂0.3-1.5份。本发明制备的鞋底材料具有较高的光亮程度、耐磨性和舒适度,且其制备工艺简单、成本较低。(The invention relates to the field of rubber, and particularly discloses a bright sole material and a preparation method thereof. The preparation raw materials at least comprise the following components in parts by weight: 20-40 parts of nitrile rubber, 10-25 parts of plastic master batch, 11-26 parts of reinforcing agent, 3-12 parts of plasticizer, 0.3-1.5 parts of anti-aging agent, 0.2-1 part of tackifier, 0.1-0.8 part of antifogging agent, 0.3-4.5 parts of activator, 0.1-0.8 part of silane coupling agent and 0.3-1.5 parts of accelerator. The sole material prepared by the invention has higher brightness, wear resistance and comfort, and the preparation process is simple and the cost is lower.)

1. The bright sole material is characterized by at least comprising the following preparation raw materials in parts by weight: 20-40 parts of nitrile rubber, 10-25 parts of plastic master batch, 11-26 parts of reinforcing agent, 3-12 parts of plasticizer, 0.3-1.5 parts of anti-aging agent, 0.2-1 part of tackifier, 0.1-0.8 part of antifogging agent, 0.3-4.5 parts of activator, 0.1-0.8 part of silane coupling agent and 0.3-1.5 parts of accelerator.

2. The bright sole material according to claim 1, wherein the reinforcing agent is selected from one or more of white smoke, china clay, calcium carbonate, silicon carbide and boron nitride.

3. The bright sole material according to claim 1, wherein the plasticizer is selected from one or more of phthalic acid esters, fatty acid esters, and phosphoric acid esters.

4. The bright sole material according to claim 1, wherein the anti-aging agent is selected from one or more of anti-aging agent D, anti-aging agent RD, anti-aging agent MB, anti-aging agent DNP, anti-aging agent NBC, and anti-aging agent SP.

5. The bright sole material according to claim 1, wherein the tackifier is a tackifying resin.

6. The shiny sole material of claim 1, wherein the active agent is selected from one or more of zinc oxide, stearic acid, calcium oxide, calcium chloride, barium chloride, diethylene glycol, polyethylene glycol.

7. The bright sole material according to claim 1, wherein the silane coupling agent is selected from one or more of bis (triethoxypropyl) silane tetrasulfide, bis- (3-triethoxysilylpropyl) -disulfide, 3-aminopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-isocyanatopropyltriethoxysilane.

8. The shiny sole material of claim 1, wherein the accelerator is selected from one or more of a sulfenamide accelerator, a thiazole accelerator, a thiuram accelerator, and a guanidine accelerator.

9. The bright sole material according to claim 1, wherein the preparation raw material further comprises 3 to 12 parts by weight of a mirror surface master batch.

10. The method for preparing a bright sole material according to any one of claims 1 to 9, comprising the steps of:

(1) preparing nitrile rubber, plastic master batch and mirror master batch into rubber compound at the temperature of 160-;

(2) adding a reinforcing agent and a plasticizer into the rubber compound, mixing in an internal mixer, and standing for 12-15 hours after mixing;

(3) and (3) adding an anti-aging agent, a tackifier, an antifogging agent, an active agent, a silane coupling agent and an accelerator into the step (2), banburying at the temperature of 60-80 ℃ for 1-3min, and cooling to obtain the anti-aging agent.

Technical Field

The invention relates to the field of rubber, in particular to a bright sole material and a preparation method thereof.

Background

With the development of economy and social progress, shoes have been gradually developed from necessities of life to fashion products. The pursuit of shoes is gradually developed from comfortable heat preservation to fashion and trendy, the shining characteristic of the rubber shoe product becomes a demand trend, and the higher the brightness of the sole is, the more popular the shoe is to consumers. Under normal conditions, the outer bottom brightness of the rubber shoe of the model product can meet the requirement of high brightness by the pattern surface polishing treatment of the mold, and the rubber shoe product produced by the calendering process has semi-bright or dull appearance of a rubber part, so that people feel rigid and old.

In order to obtain higher brightness, the traditional technology is to coat a layer of liquid brightener on the surface of the rubber part of the semi-finished rubber shoe to achieve the purpose. However, the method for producing the rubber shoes has the advantages that the brightness of the rubber shoes is not natural and uncomfortable, meanwhile, the production mode has complex process, high production cost and low product competitiveness, the brightness of the rubber shoes is greatly influenced by the quality of the liquid brightener, and the aging cracks of the brightener on the surface of the rubber part are often generated due to the quality change of the brightener, so that the image of the rubber part and the production qualification rate of the rubber part are influenced. In the other method, a large amount of brightener is added into the rubber in a raw material form to increase the surface brightness of the vulcanized rubber product.

Therefore, the research and development of a sole material with low production cost, simple preparation process and high brightness degree becomes the key point of the research of the technical personnel in the field.

Disclosure of Invention

In order to solve the technical problems, the invention provides a bright sole material in a first aspect, which at least comprises the following raw materials in parts by weight: 20-40 parts of nitrile rubber, 10-25 parts of plastic master batch, 11-26 parts of reinforcing agent, 3-12 parts of plasticizer, 0.3-1.5 parts of anti-aging agent, 0.2-1 part of tackifier, 0.1-0.8 part of antifogging agent, 0.3-4.5 parts of activator, 0.1-0.8 part of silane coupling agent and 0.3-1.5 parts of accelerator.

In a preferred embodiment of the present invention, the reinforcing agent is one or more selected from white smoke, china clay, calcium carbonate, silicon carbide, and boron nitride.

In a preferred embodiment of the present invention, the plasticizer is one or more selected from the group consisting of phthalate esters, fatty acid esters, and phosphate esters.

In a preferred embodiment of the present invention, the antioxidant is one or more selected from the group consisting of antioxidant D, antioxidant RD, antioxidant MB, antioxidant DNP, antioxidant NBC, and antioxidant SP.

In a preferred embodiment of the present invention, the tackifier is a tackifying resin.

In a preferred embodiment of the present invention, the active agent is selected from one or more of zinc oxide, stearic acid, calcium oxide, calcium chloride, barium chloride, diethylene glycol, and polyethylene glycol.

As a preferred technical scheme of the invention, the silane coupling agent is selected from one or more of bis (triethoxypropyl) tetrasulfide, bis- (3-triethoxysilylpropyl) -disulfide, 3-aminopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane and 3-isocyanatopropyltriethoxysilane.

In a preferred embodiment of the present invention, the accelerator is one or more selected from the group consisting of sulfenamide accelerators, thiazole accelerators, thiuram accelerators and guanidine accelerators.

As a preferable technical scheme, the preparation raw materials further comprise 3-12 parts of mirror surface master batch by weight.

The second aspect of the present invention provides a method for preparing a bright sole material, comprising the steps of:

(1) preparing nitrile rubber, plastic master batch and mirror master batch into rubber compound at the temperature of 160-;

(2) adding a reinforcing agent and a plasticizer into the rubber compound, mixing in an internal mixer, and standing for 12-15 hours after mixing;

(3) and (3) adding an anti-aging agent, a tackifier, an antifogging agent, an active agent, a silane coupling agent and an accelerator into the step (2), banburying at the temperature of 60-80 ℃ for 1-3min, and cooling to obtain the anti-aging agent.

Has the advantages that: the invention provides a bright sole material and a preparation method thereof, which prepares a sole material with skid resistance, wear resistance, chemical resistance, high surface brightness, softness and good elasticity by adopting nitrile rubber, plastic master batch and mirror master batch as base materials and further adding auxiliary agents such as reinforcing agent, plasticizer, anti-aging agent, tackifier, antifogging agent, activator, silane coupling agent, accelerant and the like.

Detailed Description

The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.

When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.

The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.

Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.

In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.

In order to solve the technical problems, the invention provides a bright sole material in a first aspect, which at least comprises the following raw materials in parts by weight: 20-40 parts of nitrile rubber, 10-25 parts of plastic master batch, 11-26 parts of reinforcing agent, 3-12 parts of plasticizer, 0.3-1.5 parts of anti-aging agent, 0.2-1 part of tackifier, 0.1-0.8 part of antifogging agent, 0.3-4.5 parts of activator, 0.1-0.8 part of silane coupling agent and 0.3-1.5 parts of accelerator.

In a preferred embodiment, the bright sole material of the invention is prepared from at least the following raw materials in parts by weight: 25-35 parts of nitrile rubber, 12-20 parts of plastic master batch, 15-20 parts of reinforcing agent, 5-8 parts of plasticizer, 0.5-0.9 part of anti-aging agent, 0.5-0.8 part of tackifier, 0.2-0.5 part of antifogging agent, 2.6-3.5 parts of activator, 0.2-0.5 part of silane coupling agent and 0.5-0.9 part of accelerator.

In a most preferred embodiment, the bright sole material of the invention is prepared from at least the following raw materials in parts by weight: 32 parts of nitrile rubber, 16 parts of plastic master batch, 18 parts of reinforcing agent, 6.5 parts of plasticizer, 0.75 part of anti-aging agent, 0.65 part of tackifier, 0.3 part of antifogging agent, 3.15 parts of activator, 0.3 part of silane coupling agent and 0.71 part of accelerator.

Nitrile rubber

The nitrile rubber is prepared from butadiene and acrylonitrile by an emulsion polymerization method, is mainly produced by a low-temperature emulsion polymerization method, and has the advantages of excellent oil resistance, higher wear resistance, better heat resistance and strong bonding force. The disadvantages are poor low temperature resistance, ozone resistance, poor insulation properties and slightly low elasticity.

In a preferred embodiment, the acrylonitrile-butadiene rubber of the present invention contains 31 to 35% by mass of acrylonitrile.

In a most preferred embodiment, the nitrile rubber of the present invention has an acrylonitrile content of 33 and is commercially available from a manufacturer including, but not limited to, Guangzhou, R.C. Puff.R. NBR 3355.

Plastic masterbatch

The plastic master batch is a concentrated body prepared by loading plastic additives in a resin in an ultra-constant manner; when the plastic product is manufactured, the plastic additive does not need to be added, and the master batch with the excess amount is added in proportion. Therefore, the plastic master batch is a special material for processing a novel high polymer material. The material has various varieties, such as filling master batch, color master batch, flame retardant master batch, antistatic master batch, wear-resistant master batch, multifunctional master batch and the like.

In a preferred embodiment, the plastic masterbatch of the present invention is a PVC masterbatch, which is commercially available from commercial suppliers including, but not limited to, shoyu paraglider waterproofing materials, inc.

Mirror surface master batch

In a preferred embodiment, the preparation raw material of the invention also comprises 3 to 12 parts of mirror surface master batch by weight.

In a more preferred embodiment, the preparation raw material of the invention further comprises 5 to 10 parts by weight of a mirror surface master batch.

In a most preferred embodiment, the preparation raw material of the present invention further comprises 6 parts by weight of a mirror surface master batch.

The preparation raw materials of the mirror surface master batch comprise nitrile rubber and carbon black, wherein the mass ratio of the nitrile rubber to the carbon black is 3: 2.

reinforcing agent

The reinforcing agent is a compounding agent capable of improving the strength of rubber products.

In a preferred embodiment, the reinforcing agent according to the present invention is selected from one or more of white smoke, china clay, calcium carbonate, silicon carbide, and boron nitride.

In a more preferred embodiment, the reinforcing agent of the present invention is white smoke and kaolin, wherein the mass ratio of white smoke to kaolin is (1-4): 1.

in a more preferred embodiment, the reinforcing agent of the present invention is white smoke and kaolin, wherein the mass ratio of white smoke to kaolin is (2-3): 1.

in a most preferred embodiment, the reinforcing agent of the present invention is white smoke and china clay, wherein the mass ratio of white smoke to china clay is 2.6: 1.

plasticizer

The plasticizer is a substance which can increase the plasticity of the polymer when added into the polymer material, and the use of the plasticizer can improve the performance of the high polymer material, reduce the production cost and improve the production benefit. The plasticizer mainly has the effects of weakening the secondary valence bonds among resin molecules, increasing the mobility of the molecular bonds of the resin, reducing the crystallinity of the resin molecules, increasing the plasticity of the resin molecules, enhancing the flexibility of the resin molecules, being easy to process, being legally applicable to industrial application, and being widely existed in food packaging, cosmetics, medical devices and environmental water.

In a preferred embodiment, the plasticizer of the present invention is selected from one or more of phthalate esters, fatty acid esters and phosphate esters.

As examples of the phthalate, there may be mentioned: dioctyl phthalate, diisooctyl phthalate, diisononyl phthalate, dibutyl phthalate, diisobutyl phthalate.

As examples of fatty acid esters, there may be mentioned: dioctyl adipate, diisodecyl adipate, dioctyl azelate, dibutyl sebacate, dioctyl sebacate.

As examples of the phosphoric acid esters, there may be mentioned: tricresyl phosphate, triphenyl phosphate, diphenyl-octyl phosphate, and cresyl diphenyl phosphate.

In a most preferred embodiment, the plasticizer of the present invention is dioctyl phthalate (CAS: 117-84-0).

Anti-aging agent

The anti-aging agent is a substance capable of delaying aging of a high molecular compound. Most of them can inhibit the action of oxygen, and some can inhibit the action of heat or light, so that the service life of the product can be prolonged.

In a preferred embodiment, the antioxidant of the present invention is selected from one or more of antioxidant D, antioxidant RD, antioxidant MB, antioxidant DNP, antioxidant NBC, and antioxidant SP.

In a preferred embodiment, the antioxidant is antioxidant SP and antioxidant RD, wherein the mass ratio of antioxidant SP to antioxidant RD is (1-3): 1.

in a most preferred embodiment, the antioxidant according to the present invention is antioxidant SP and antioxidant RD, wherein the mass ratio of antioxidant SP to antioxidant RD is 1.5: 1.

tackifier

The tackifier is added into a system, and the bonding surface is wetted by surface diffusion or internal diffusion, so that the bonding strength between the system and the bonded material is improved.

In a preferred embodiment, the tackifier of the present invention is a tackifying resin.

In a more preferred embodiment, the tackifier of the present invention is selected from one or more of hydrogenated rosin resin, α -terpene resin, β -terpene resin, C9 petroleum resin, dicyclopentadiene resin, alkyl phenol resin.

In a most preferred embodiment, the tackifying resin of the present invention is a C9 petroleum resin.

Antifogging agent

The antifogging agent is a low-molecular-weight dispersing agent containing hydrophilic groups, consists of molecules with determined molecular weight, can form a coating when coated on the surface of a transparent object, and the hydrophilic groups in the coating can adsorb water molecules in the air and form a water film (instead of water beads) by wetting and diffusing on the surface of the transparent object, so that light rays penetrating through the object cannot be scattered, and the fogging phenomenon is avoided. The main components are surfactants, such as xylitol ester, sorbitol monopalmitate, lauric acid or hard resin acid monoglyceride and the like, the anti-fog agent is an instant anti-fog agent, the anti-fog duration is short, the adhesive force is poor, and the anti-fog effect disappears immediately after being wiped or washed by water generally for only a few days or a dozen days, so the agent cannot be used as a long-acting anti-fog agent.

In a preferred embodiment, the antifogging agent of the present invention is selected from one or more of the group consisting of an anti-emetic cream SK, an antifogging agent 1956.

In a most preferred embodiment, the antifogging agent of the present invention is antifogging agent 1956.

Active agent

The invention relates to a substance which can increase the activity of an organic accelerator and fully exert the effect, thereby reducing the dosage of the accelerator or shortening the vulcanization time.

In a preferred embodiment, the active agent according to the invention is selected from one or more of zinc oxide, stearic acid, calcium oxide, calcium chloride, barium chloride, diethylene glycol, polyethylene glycol.

In a more preferred embodiment, the active agent of the present invention is zinc oxide, stearic acid, diethylene glycol (CAS: 111-46-6) and polyethylene glycol, wherein the mass ratio of zinc oxide, stearic acid, diethylene glycol and polyethylene glycol is (3-5.5): (0.1-1): 1: (0.5-2.5).

In a most preferred embodiment, the active agent of the present invention is zinc oxide, stearic acid, diethylene glycol and polyethylene glycol, wherein the mass ratio of zinc oxide, stearic acid, diethylene glycol and polyethylene glycol is 4.5: 0.875: 1: 1.5.

in a preferred embodiment, the polyethylene glycol has a molecular weight of 4000 and is commercially available from a commercial source including, but not limited to, Nantong Chen Runji chemical Co., Ltd, and has a PEG-4000 specification.

Silane coupling agent

The molecule of the silane coupling agent of the invention has more than two organosilicon monomers with different reactive groups, which can be chemically bonded with organic materials and inorganic materials.

In a preferred embodiment, the silane coupling agent of the present invention is selected from one or more of bis (triethoxypropyl) tetrasulfide, bis- (3-triethoxysilylpropyl) -disulfide, 3-aminopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-isocyanatopropyltriethoxysilane.

In a more preferred embodiment, the silane coupling agent of the present invention is bis (triethoxypropyl) silane tetrasulfide (CAS: 40372-72-3).

Accelerator

The accelerator is a rubber accelerator. The accelerator is added into the rubber material to promote the activation of the vulcanizing agent, so that the crosslinking reaction of the vulcanizing agent and rubber molecules is accelerated, and the effects of shortening the vulcanizing time and reducing the vulcanizing temperature are achieved.

In a preferred embodiment, the accelerator according to the invention is selected from one or more of the group consisting of sulfenamide accelerators, thiazole accelerators, thiuram accelerators and guanidine accelerators.

As examples of the sulfenamide-based accelerator, there can be cited: CBS (N-cyclohexyl-2-benzothiazolesulfenamide), TBBS (N-tert-butyl-2-benzothiazolesulfenamide), NOBS (N-oxydiethylene-2-benzothiazolesulfenamide), DZ (N, N' -dicyclohexyl-2-benzothiazolesulfenamide).

As examples of thiazole accelerators, mention may be made of: m (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide).

As examples of thiuram accelerators, mention may be made of: TMTD (tetramethylthiuram disulfide), TMTM (tetramethylthiuram monosulfide), TETD (tetraethylthiuram disulfide), and DPTT (pentamethylenethiuram hexasulfide).

As an example of the guanidine accelerator, D (diphenylguanidine) can be cited.

In a more preferred embodiment, the accelerator of the invention is DM (dibenzothiazole disulfide) and D (diphenylguanidine), wherein the mass ratio of DM (dibenzothiazole disulfide) to D (diphenylguanidine) is (2-5): 1.

in a most preferred embodiment, the accelerator of the present invention is DM (dibenzothiazole disulfide) and D (diphenylguanidine), wherein the mass ratio of DM (dibenzothiazole disulfide) to D (diphenylguanidine) is 3.5: 1.

the inventor of the application finds in experiments that the rubber sole prepared by the invention has higher brightness, good elasticity, high wear resistance and soft and comfortable wearing, and the possible reasons are that the invention adopts the nitrile rubber, the plastic master batch and the mirror master batch as base materials, so that the antiskid performance and the brightness of the sole material are improved, and meanwhile, the synergistic effect of the base materials effectively increases the chemical resistance of the sole material; the addition of white smoke and pottery clay also greatly improves the physical and mechanical properties and the anti-skid property of the sole; in addition, according to the selection of the base material, the zinc oxide, the stearate, the diethylene glycol and the polyethylene glycol are preferably used as the active agents, wherein the mass ratio of the zinc oxide to the stearic acid to the diethylene glycol to the polyethylene glycol is (3-5.5): (0.1-1): 1: (0.5-2.5), effectively increasing the crosslinking density and the reaction efficiency of the polymer in the reaction system, and further improving the brightness of the rubber sole.

The second aspect of the present invention provides a method for preparing a bright sole material, comprising the steps of:

(1) preparing nitrile rubber, plastic master batch and mirror master batch into rubber compound at the temperature of 160-;

(2) adding a reinforcing agent and a plasticizer into the rubber compound, mixing in an internal mixer, and standing for 12-15 hours after mixing;

(3) and (3) adding an anti-aging agent, a tackifier, an antifogging agent, an active agent, a silane coupling agent and an accelerator into the step (2), banburying at the temperature of 60-80 ℃ for 1-3min, and cooling to obtain the anti-aging agent.

It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.