CN110317379A - A kind of bilayer stamp rubber and its preparation method and application - Google Patents

A kind of bilayer stamp rubber and its preparation method and application Download PDF

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Publication number
CN110317379A
CN110317379A CN201910617004.7A CN201910617004A CN110317379A CN 110317379 A CN110317379 A CN 110317379A CN 201910617004 A CN201910617004 A CN 201910617004A CN 110317379 A CN110317379 A CN 110317379A
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Prior art keywords
parts
rubber
stamp
primer
preparation
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Chinese (zh)
Inventor
江炳强
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Foshan Nanhai Creative Shoes Material Co Ltd
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Foshan Nanhai Creative Shoes Material Co Ltd
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Priority to CN201910617004.7A priority Critical patent/CN110317379A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/16—Layered products comprising a layer of natural or synthetic rubber comprising polydienes homopolymers or poly-halodienes homopolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/08—Interconnection of layers by mechanical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/043—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554—Wear resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/582—Tearability
    • B32B2307/5825—Tear resistant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2437/00—Clothing
    • B32B2437/02—Gloves, shoes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention discloses a kind of double-deck stamp rubber and its preparation method and application, belong to the technical field of rubber material.Above-mentioned bilayer stamp rubber, its key points of the technical solution are that the ink jet printing layer between the transparent adhesive tape of primer, upper layer including lower layer and two layers, under the protection of primer layer and substratum transparent, to achieve the effect that intermediate ink jet printing layer is not easy to be worn.The invention also discloses the preparation methods of the above-mentioned double-deck stamp rubber, include following steps: prepared by primer, prepared by ink jet printing layer, printed ink stamp, transparent adhesive tape preparation and the double-deck stamp rubber compression moulding on primer, the preparation method clear process, method simple practical is convenient for industrial applications.The invention also discloses the above-mentioned double-deck stamp rubber to prepare the application in rubber product；Preferred rubber product is rubber soles.

Description

A kind of bilayer stamp rubber and its preparation method and application
Technical field
The present invention relates to the technical field of rubber material, in particular to a kind of double-deck stamp rubber and preparation method thereof and answer With.
Background technique
Rubber refers to the high elastic polymer material with reversible deformation, at room temperature high resilience, in the external force of very little Effect is lower to generate larger deformation, remove resilient after external force.Rubber is a kind of resource that extremely important and dosage is very big. For shoe rubber, the performances sole rubber product such as good wearability, tear resistance and waterproof should have basic Function, and measure the index of footwear quality.
With the pursuit of a high quality of life, consumer often has the appearance of shoes when shoes are bought in selection Higher requirement, common sole stamp has catered to consumer and has pursued beautiful needs in the market, although sole stamp is beautiful, But wearability is bad, and during when wearing with ground friction, printed layer is easy to be worn, or even is worn away.Therefore, need The sole being worn is not easy in researching and developing a kind of sole printed layer.
Summary of the invention
In view of the shortcomings of the prior art, the purpose of the present invention one is: a kind of double-deck stamp rubber is provided, in primer layer and thoroughly Under the protection of gelatin layer, to achieve the effect that intermediate ink jet printing layer is not easy to be worn.
The first purpose of this invention has the technical scheme that a kind of double-deck stamp rubber, including Ink jet printing layer between the primer of lower layer, the transparent adhesive tape on upper layer and two layers；
The primer includes by weight following raw material: 2-5 parts of polycarbonate, 18-22 parts of solution polymerized butadiene styrene rubber, suitable fourth 8-12 parts of rubber, 28-32 parts of White Carbon black, 2-5 parts of EVA, 1.5-2 parts of activating agent, 0.8-1.2 parts of coupling agent, crosslinking agent 1-1.4 Part, 0.4-0.8 parts of stearic acid and 2-5 parts of precipitated calcium carbonate；
The ink jet printing layer includes by weight following raw material: 25-35 parts of glass cement, 8-12 parts of color and rubber are molten 55-65 parts of agent；
The transparent adhesive tape includes by weight following raw material: 25-30 parts of butadiene rubber, 8-13 parts of solution polymerized butadiene styrene rubber, 5-10 parts of isoprene rubber, 13-18 parts of fumed silica, 3-8 parts of base oil, 1-1.5 parts of coupling agent, activating agent 0.8- 1.5 parts and ultramarine 0.01-0.03 parts.
Polycarbonate is a kind of tough thermoplastic resin, and the amorphous polymer of almost colourless glassy state has very well Optical, heat-resisting, shock resistance, it is BI grades fire-retardant, have good mechanical performance in commonly used temperature.
Solution polymerized butadiene styrene rubber is that butadiene and styrene cause anionic polymerisation using organolithium in hydrocarbon solvent and makes The copolymer obtained, with wear-resisting, cold-resistant, heat is low, resilience is high, shrinkage is low, color is good, ash content is few, with high purity and sulphur Change the advantages that speed is fast.
It is special that butadiene rubber has that elasticity is high, wearability is good, cold resistance is good, heat is low, flexible resistance and dynamic property are good etc. Point.Major defect is that anti-slippery is poor, and tearing strength and tensile strength are low, and cold flow properties are big, and processing performance is slightly worse, it is necessary to and other Glue kind is used in combination.
White Carbon black, that is, fumed silica popular name, due to its partial size very little, large specific surface area, superficial attractive forces By force, surface can be big, and chemical purity is high, dispersion performance is good, thermal resistance, resistance etc. have special performance, is used as reinforcing rubber Agent can be obviously improved the tensile strength of rubber product, tear resistance and wearability.
EVA is the English abbreviation of ethylene-vinyl acetate copolymer, due to introducing vinyl acetate monomer in strand, To reduce high-crystallinity, flexibility, impact resistance, filler intermiscibility and heat sealing performance are improved.
Stearic acid is added during rubber processing as auxiliary material, has the effect of softening and be plasticized, as external lubrication The abundant diffusion of the advantageous White Carbon black of agent；Or main vulcanization accelerator additive, can play the role of the second promotor, add hardening Speed.Precipitated calcium carbonate has certain reinforcing effect in rubber, easily disperses, does not influence curingprocess rate, can improve vulcanizate mechanics Performance.
Polycarbonate, solution polymerized butadiene styrene rubber, butadiene rubber and the EVA that primer is matched by certain content are used cooperatively, and are mixed Enter White Carbon black as reinforcing agent, then adds auxiliary material activating agent, coupling agent, crosslinking agent, stearic acid and lightweight carbonic acid in proportion Calcium gives full play to the effect of each auxiliary material, and primer is made to have many advantages, such as wear-resisting, shock resistance, resilience height and tear resistance.
Isoprene rubber is a kind of preferable general purpose synthetic rubber of comprehensive performance, has excellent elasticity, wearability, resistance to Hot, tear-proof and low temperature flexibility.
Base oil has preferable abrasion resistance, and extremely low coefficient of friction, bearing capacity is strong；Preferable adhesiveness and lubrication Property, it is well compatible with rubber parts and plastics；Excellent water resistant, anti-aging and corrosion resistance, service life are extremely long.
Transparent adhesive tape is used cooperatively by the butadiene rubbers of special ratios, solution polymerized butadiene styrene rubber, isoprene rubber, is mixed Fumed silica is as reinforcing agent, then adds base oil, coupling agent and activating agent in proportion and play the effect of each auxiliary material, then mix Enter pigment ultramarine, makes the advantages that transparent adhesive tape is strong with bearing capacity, and adhesiveness is strong, tear-proof, anti-aging and attractive appearance.
By using above scheme, by being used cooperatively for primer and transparent adhesive tape, primer and transparent adhesive tape all have excellent Mechanical property and chemical property contact the ink jet printing layer for being sandwiched in middle layer with extraneous direct friction, prevent ink jet printing Layer abrasion is faded.
The present invention is further arranged to: the ink jet printing layer, includes following raw material: glass cement 28- by weight 32 parts, 10-12 parts of color and 58-62 parts of rubber solvent.
By using above scheme, the formula of preferred ink jet printing layer is further limited, makes ink jet printing layer and primer more Good bonding, is not readily separated, makes the apparent beauty of the pattern of ink jet printing layer, the retention time is permanent.
The present invention is further arranged to: the primer, further includes 0.4-0.8 parts of antioxidant.
By using above scheme, antioxidant is added in primer, is improved the antioxygen property of primer, is effectively prevent rubber Aging prolongs the service life.
The present invention is further arranged to: the transparent adhesive tape, further includes 0.08-0.12 parts of resistance to yellow agent and antioxidant 0.4- 1.4 part.
By using above scheme, resistance to yellow agent is added in transparent adhesive tape and can prevent primer from turning yellow, improves native color Persistence；Antioxidant is added, the antioxygen property of transparent adhesive tape is improved, effectively prevent ageing of rubber.
The purpose of the present invention two is: the preparation method of the above-mentioned double-deck stamp rubber is provided, the preparation method include with Lower step:
Primer preparation: step S1 is weighed each component raw material of primer by formula ratio, carries out mixing after mixing, turn 5-7 times, out Piece obtains primer lamella；
The preparation of ink jet printing layer: step S2 weighs glass cement, color and rubber solvent, hybrid modulation egative film, compacting by formula ratio Egative film, egative film thickness 1-2mm draw decalcomania on egative film, obtain stamp egative film；
Printed ink stamp on primer: step S3 by the step S2 stamp egative film obtained and primer compression moulding, obtains stamp bottom Film layers；
Transparent adhesive tape preparation: step S4 is weighed each component raw material of transparent adhesive tape by formula ratio, carries out mixing after mixing, turn 5-7 Secondary, slice obtains transparent adhesive tape lamella；
Step S5, after the stamp primer lamella of step S3 and transparent adhesive tape lamella are successively stacked, compression moulding obtains the double-deck stamp Rubber.
The preparation method first prepares primer, then carries out ink jet printing layer preparation, and ink jet printing layer is first printed on primer, The double-deck stamp rubber, preparation process clear process are pressed into together with transparent adhesive tape again, method simple practical is answered convenient for industrialization With.
The present invention is further arranged to: in the step S1, the process conditions of mixing include: mixing time 2-3min, are beaten 120-130 DEG C of material temperature degree, the dnockout time 500-650 seconds.
By using above scheme, the process conditions of primer mixing are limited, the more efficient of primer preparation process is made, shortened Preparation time, the primer performance being prepared is more preferably.
The present invention is further arranged to: in the step S3, the process conditions of compression moulding include: forming temperature 150- 160 DEG C, briquetting pressure 140-160KG.
By using above scheme, the molding technological condition of ink jet printing layer and primer layer is limited, makes ink jet printing layer more It is firmly adhered on primer layer, is not easy to fall.
The present invention is further arranged to: in the step S4, the process conditions of mixing include: mixing time 2-3min, are beaten 110-115 DEG C of material temperature degree, the dnockout time 500-700 seconds.
By using above schemes, the process conditions of transparent adhesive tape mixing are limited, the more efficient of transparent adhesive tape preparation process is made, Shorten preparation time, the transparent adhesive tape performance being prepared is more preferably.
The present invention is further arranged to: in the step S5, the process conditions of compression moulding include: forming temperature 155- 160 DEG C, briquetting pressure 150-160KG.
By using above scheme, the molding technological condition of stamp primer lamella and transparent adhesive tape lamella is limited, makes to be pressed into The double-deck stamp rubber of type is not easy to come unglued, and protects intermediate ink jet printing layer well.
The purpose of the present invention three is: providing the preparation method system of the above-mentioned double-deck stamp rubber or the above-mentioned double-deck stamp rubber The standby obtained double-deck stamp rubber is preparing the application in rubber product；Preferred rubber product is rubber soles.
In conclusion the invention has the following advantages:
1, being used cooperatively by primer and transparent adhesive tape, connects the ink jet printing layer for being sandwiched in middle layer with extraneous direct friction Touching prevents the abrasion of ink jet printing layer from fading；
2, primer and transparent adhesive tape all have many advantages, such as good wearability, tear resistance, tensile strength height and yellowing resistance；
3, the preparation method clear process, method simple practical are convenient for industrial applications.
Specific embodiment
Invention is further described in detail below.
Embodiment 1
A kind of bilayer stamp rubber, the primer including lower layer, the ink jet printing layer in middle layer and the transparent adhesive tape on upper layer；
Primer includes by weight following raw material: 5 parts of IR2200,18 parts of 1250 solution polymerized butadiene styrene rubber, BR-9000 are suitable 12 parts of buna, 28 parts of White Carbon black, 5 parts of EVA7350,1.5 parts of PEG-4000,1.2 parts of A-172 silane coupling agent, PL-4001 Part, 0.8 part of 1076 antioxidant, 0.4 part of ST-1801 stearic acid and 5 parts of precipitated calcium carbonate；
Ink jet printing layer includes by weight following raw material: 25 parts of glass cement, 12 parts of color and 4,4- difluoro cyclohexanone 55 parts；
Transparent adhesive tape includes by weight following raw material: 30 parts of BR1208 glue, 8 parts of Japan's SSBR303 glue, IR-80 isoamyl 10 parts of diene rubber, 13 parts of SG-200 white cigarette, 8 parts of 150N oil, 1 part of A-172 silane coupling agent, resistance to yellow 0.12 part of agent A1, PEG- 4000 0.8 parts, 0.8 part, DL-TDP0.1 parts and 0.03 part of ultramarine of 1076 antioxidant；
The preparation method of above-mentioned bilayer stamp rubber, comprising the following steps:
Primer preparation: S1 is weighed each component raw material of primer by formula ratio, mixing, mixing time 3min, dnockout is carried out after mixing It 120 DEG C of temperature, the dnockout time 500 seconds, turns 7 times, slice obtains primer lamella；
The preparation of ink jet printing layer: S2 weighs glass cement, color and 4,4- difluoro cyclohexanone, hybrid modulation egative film, pressure by formula ratio Egative film processed, egative film thickness 1-2mm draw decalcomania on egative film, obtain stamp egative film；
S3, printed ink stamp on primer: by the step S2 stamp egative film obtained and primer compression moulding, 150 DEG C of forming temperature, Briquetting pressure 160KG obtains stamp primer lamella；
S4, transparent adhesive tape preparation: being weighed each component raw material of transparent adhesive tape by formula ratio, carry out mixing after mixing, mixing time 2min, It 115 DEG C of dnockout temperature, the dnockout time 700 seconds, turns 5 times, slice obtains transparent adhesive tape lamella；
S5, after the stamp primer lamella of step S3 and transparent adhesive tape lamella are successively stacked, compression moulding, 160 DEG C of forming temperature, at Type pressure 150KG obtains the double-deck stamp rubber.
Embodiment 2
A kind of bilayer stamp rubber, the primer including lower layer, the ink jet printing layer in middle layer and the transparent adhesive tape on upper layer；
Primer includes by weight following raw material: 2 parts of IR2200,22 parts of 1250 solution polymerized butadiene styrene rubber, BR-9000 are suitable 8 parts of buna, 32 parts of White Carbon black, 2 parts of EVA7350,2 parts of PEG-4000,0.8 part of A-172 silane coupling agent, PL-4001.4 Part, 0.4 part of 1076 antioxidant, 0.8 part of ST-1801 stearic acid and 2 parts of precipitated calcium carbonate；
Ink jet printing layer, by weight, 35 parts of glass cement, 8 parts of color and 4,65 parts of 4- difluoro cyclohexanone；
Transparent adhesive tape includes by weight following raw material: 25 parts of BR1208 glue, 13 parts of Japan's SSBR303 glue, IR-80 isoamyl 5 parts of diene rubber, 18 parts of SG-200 white cigarette, 3 parts of 150N oil, 1.5 parts of A-172 silane coupling agent, resistance to yellow A10.08 parts of agent, PEG- 4000 1.5 parts, 0.4 part, DL-TDP0.6 parts and 0.01 part of ultramarine of 1076 antioxidant；
The preparation method of above-mentioned bilayer stamp rubber, comprising the following steps:
Primer preparation: S1 is weighed each component raw material of primer by formula ratio, mixing, mixing time 2min, dnockout is carried out after mixing It 130 DEG C of temperature, the dnockout time 650 seconds, turns 5 times, slice obtains primer lamella；
The preparation of ink jet printing layer: S2 weighs glass cement, color and 4,4- difluoro cyclohexanone, hybrid modulation egative film, pressure by formula ratio Egative film processed, egative film thickness 1-2mm draw decalcomania on egative film, obtain stamp egative film；
S3, printed ink stamp on primer: by the step S2 stamp egative film obtained and primer compression moulding, 160 DEG C of forming temperature, Briquetting pressure 140KG obtains stamp primer lamella；
S4, transparent adhesive tape preparation: being weighed each component raw material of transparent adhesive tape by formula ratio, carry out mixing after mixing, mixing time 3min, It 110 DEG C of dnockout temperature, the dnockout time 500 seconds, turns 7 times, slice obtains transparent adhesive tape lamella；
S5, after the stamp primer lamella of step S3 and transparent adhesive tape lamella are successively stacked, compression moulding, 160 DEG C of forming temperature, at Type pressure 150KG obtains the double-deck stamp rubber.
Embodiment 3
A kind of bilayer stamp rubber, the primer including lower layer, the ink jet printing layer in middle layer and the transparent adhesive tape on upper layer；
Primer includes by weight following raw material: 3 parts of IR2200,20 parts of 1250 solution polymerized butadiene styrene rubber, BR-9000 are suitable 10 parts of buna, 30 parts of White Carbon black, 3 parts of EVA7350,1.8 parts of PEG-4000,1 part of A-172 silane coupling agent, PL-4001.2 Part, 0.6 part of 1076 antioxidant, 0.6 part of ST-1801 stearic acid and 3 parts of precipitated calcium carbonate；
Ink jet printing layer includes by weight following raw material: 30 parts of glass cement, 10 parts of color and 4,4- difluoro cyclohexanone 60 parts；
Transparent adhesive tape includes by weight following raw material: 27 parts of BR1208 glue, 11 parts of Japan's SSBR303 glue, IR-80 isoamyl 7 parts of diene rubber, 15 parts of SG-200 white cigarette, 5 parts of 150N oil, 1.2 parts of A-172 silane coupling agent, resistance to yellow A10.1 parts of agent, PEG- 4000 1.2 parts, 0.6 part, DL-TDP0.3 parts and 0.02 part of ultramarine of 1076 antioxidant；
The preparation method of above-mentioned bilayer stamp rubber, comprising the following steps:
Primer preparation: S1 is weighed each component raw material of primer by formula ratio, mixing is carried out after mixing, mixing time 2.5min is beaten It 120 DEG C of material temperature degree, the dnockout time 600 seconds, turns 6 times, slice obtains primer lamella；
The preparation of ink jet printing layer: S2 weighs glass cement, color and 4,4- difluoro cyclohexanone, hybrid modulation egative film, pressure by formula ratio Egative film processed, egative film thickness 1-2mm draw decalcomania on egative film, obtain stamp egative film；
S3, printed ink stamp on primer: by the step S2 stamp egative film obtained and primer compression moulding, 155 DEG C of forming temperature, Briquetting pressure 150KG obtains stamp primer lamella；
Transparent adhesive tape preparation: S4 is weighed each component raw material of transparent adhesive tape by formula ratio, carries out mixing, mixing time after mixing 2.5min, the dnockout time 600 seconds, is turned 6 times, slice obtains transparent adhesive tape lamella by 110 DEG C of dnockout temperature；
S5, after the stamp primer lamella of step S3 and transparent adhesive tape lamella are successively stacked, compression moulding, 160 DEG C of forming temperature, at Type pressure 150KG obtains the double-deck stamp rubber.
Embodiment 4
A kind of bilayer stamp rubber, the difference with embodiment 3 are that primer includes by weight following raw material: 2 parts of IR2200,22 parts of 1250 solution polymerized butadiene styrene rubber, 8 parts of BR-9000 butadiene rubber, 32 parts of White Carbon black, 2 parts of EVA7350, PEG-40002 parts, 0.8 part of A-172 silane coupling agent, 1.4 parts of PL-400,0.4 part of 1076 antioxidant, ST-1801 stearic acid 0.8 part and 2 parts of precipitated calcium carbonate；Preparation method is same as Example 3.
Embodiment 5
A kind of bilayer stamp rubber, the difference with embodiment 3 are that ink jet printing layer includes by weight following original Material: 55 parts of 25 parts of glass cement, 12 parts of color and 4,4- difluoro cyclohexanone；Preparation method is same as Example 3.
Embodiment 6
A kind of bilayer stamp rubber, the difference with embodiment 3 are that transparent adhesive tape includes by weight following raw material: 30 parts of BR1208 glue, 8 parts of Japan's SSBR303 glue, 10 parts of IR-80 isoprene rubber, 13 parts of SG-200 white cigarette, 150N oil 8 parts, 1 part of A-172 silane coupling agent, resistance to yellow 0.12 part of agent A1,0.8 part of PEG-4000,0.8 part of 1076 antioxidant, DL-TDP0.1 Part and 0.03 part of ultramarine；Preparation method is same as Example 3.
Embodiment 7
A kind of bilayer stamp rubber, the difference with embodiment 3 is, in preparation method S1, primer preparation: weighs bottom by formula ratio The each component raw material of glue, carries out mixing after mixing, mixing time 3min, the dnockout time 500 seconds, turns 7 by 120 DEG C of dnockout temperature Secondary, slice obtains primer lamella.
Embodiment 8
A kind of bilayer stamp rubber, the difference with embodiment 3 is, in preparation method S3, stamp egative film that step S2 is obtained With primer compression moulding, 150 DEG C of forming temperature, briquetting pressure 160KG obtains stamp primer lamella；
Embodiment 9
A kind of bilayer stamp rubber, the difference with embodiment 3 is, in preparation method S4, weighs each of transparent adhesive tape by formula ratio Component raw material, carries out mixing after mixing, mixing time 2min, 115 DEG C of dnockout temperature, the dnockout time 700 seconds, turns 5 times, out Piece obtains transparent adhesive tape lamella.
Embodiment 10
A kind of bilayer stamp rubber, the difference with embodiment 3 is, in preparation method S5, by the stamp primer lamella of step S3 After successively stacking with transparent adhesive tape lamella, compression moulding, 160 DEG C of forming temperature, briquetting pressure 150KG obtains the double-deck stamp rubber.
Comparative example 1
A kind of bilayer stamp rubber, the difference with embodiment 3 are that primer includes by weight following raw material: by weight Measure part meter, include following raw material: 7 parts of polycarbonate, 15 parts of solution polymerized butadiene styrene rubber, 15 parts of butadiene rubber, 26 parts of White Carbon black, EVA8 parts, 3 parts of activating agent, 0.5 part of coupling agent, 2 parts of crosslinking agent, 1 part of stearic acid and 1 part of precipitated calcium carbonate；Remaining and embodiment 3 It is all the same.
Comparative example 2
A kind of bilayer stamp rubber, the difference with embodiment 3 are that transparent adhesive tape includes by weight following raw material: suitable 22 parts of buna, 15 parts of solution polymerized butadiene styrene rubber, 3 parts of isoprene rubber, 20 parts of fumed silica, 10 parts of base oil, coupling 0.5 part of agent, 0.5 part of activating agent and 0.05 part of ultramarine；Remaining is all the same with embodiment 3.
Comparative example 3
A kind of bilayer stamp rubber, the difference with embodiment 3 are that ink jet printing layer includes by weight following original Material: 70 parts of 20 parts of glass cement, 15 parts of color and 4,4- difluoro cyclohexanone；
Comparative example 4
A kind of single layer stamp rubber, the difference with embodiment 3 are, are added without transparent adhesive tape and omit corresponding preparation section.
Experimental example
The double-deck stamp rubber that embodiment 1-10 and comparative example 1-4 are provided is tested for the property, referring to ASTM-D412-6 standard Pulling force is tested, tests tearing strength referring to GBT529-2008, elongation percentage is tested referring to ISO2285-2013, is surveyed referring to GB9867 Wearability is tried, according to the resistance to yellow grade of the A method test of HGT-3689.Testing result is shown in Table 1.
Table 1- testing result
Experimental group Pulling force kg/cm2 Tearing strength kg/cm2 Elongation percentage % Wearability mm3 Resistance to Huang grade
Embodiment 1 0.60 0.40 350 111 4
Embodiment 2 0.63 0.44 357 115 4
Embodiment 3 0.78 0.76 387 152 4+
Embodiment 4 0.71 0.69 375 144 4
Embodiment 5 0.74 0.73 381 148 4
Embodiment 6 0.72 0.72 376 145 4
Embodiment 7 0.69 0.68 371 138 4
Embodiment 8 0.66 0.63 365 130 4
Embodiment 9 0.64 0.58 361 125 4
Embodiment 10 0.61 0.52 357 120 4
Comparative example 1 0.53 0.46 326 105 3
Comparative example 2 0.49 0.47 323 103 3
Comparative example 3 0.46 0.46 321 99 3
Comparative example 4 0.42 0.42 317 95 3-
As shown in Table 1, the double-deck stamp rubber that 1-10 of the embodiment of the present invention is provided has stretch-proof, and tear resistance is good, The advantages that wearability and resistance to Huang.It is good that the properties of the double-deck stamp rubber of comparative example 1-4 test are obviously not so good as embodiment 1-10.
Above-mentioned specific embodiment is only explanation of the invention, is not limitation of the present invention, art technology Personnel can according to need the modification that not creative contribution is made to the present embodiment after reading this specification, but as long as All by the protection of Patent Law in scope of the presently claimed invention.

Claims (10)

1. a kind of bilayer stamp rubber, it is characterised in that: the ink between the transparent adhesive tape of primer, upper layer including lower layer and two layers Printed layer；
The primer includes by weight following raw material: 2-5 parts of polycarbonate, 18-22 parts of solution polymerized butadiene styrene rubber, suitable fourth 8-12 parts of rubber, 28-32 parts of White Carbon black, 2-5 parts of EVA, 1.5-2 parts of activating agent, 0.8-1.2 parts of coupling agent, crosslinking agent 1-1.4 Part, 0.4-0.8 parts of stearic acid and 2-5 parts of precipitated calcium carbonate；
The ink jet printing layer includes by weight following raw material: 25-35 parts of glass cement, 8-12 parts of color and rubber are molten 55-65 parts of agent；
The transparent adhesive tape includes by weight following raw material: 25-30 parts of butadiene rubber, 8-13 parts of solution polymerized butadiene styrene rubber, 5-10 parts of isoprene rubber, 13-18 parts of fumed silica, 3-8 parts of base oil, 1-1.5 parts of coupling agent, activating agent 0.8- 1.5 parts and ultramarine 0.01-0.03 parts.
2. bilayer stamp rubber according to claim 1, it is characterised in that: the ink jet printing layer, by weight, packet Following raw material: 28-32 parts of glass cement, 10-12 parts of color and 58-62 parts of rubber solvent is included.
3. bilayer stamp rubber according to claim 1, it is characterised in that: the primer further includes antioxidant 0.4- 0.8 part.
4. bilayer stamp rubber according to claim 1, it is characterised in that: the transparent adhesive tape further includes resistance to yellow agent 0.08- 0.12 part and antioxidant 0.4-1.4 parts.
5. a kind of preparation method of the described in any item double-deck stamp rubber of claim 1-4, it is characterised in that: the preparation side Method the following steps are included:
Primer preparation: step S1 is weighed each component raw material of primer by formula ratio, carries out mixing after mixing, turn 5-7 times, out Piece obtains primer lamella；
The preparation of ink jet printing layer: step S2 weighs glass cement, color and rubber solvent, hybrid modulation egative film, compacting by formula ratio Egative film, egative film thickness 1-2mm draw decalcomania on egative film, obtain stamp egative film；
Printed ink stamp on primer: step S3 by the step S2 stamp egative film obtained and primer compression moulding, obtains stamp bottom Film layers；
Transparent adhesive tape preparation: step S4 is weighed each component raw material of transparent adhesive tape by formula ratio, carries out mixing after mixing, turn 5-7 Secondary, slice obtains transparent adhesive tape lamella；
Step S5, after the stamp primer lamella of step S3 and transparent adhesive tape lamella are successively stacked, compression moulding obtains the double-deck stamp Rubber.
6. the preparation method of bilayer stamp rubber according to claim 5, it is characterised in that: in the step S1, mixing Process conditions include: mixing time 2-3min, 120-130 DEG C of dnockout temperature, the dnockout time 500-650 seconds.
7. the preparation method of bilayer stamp rubber according to claim 5, it is characterised in that: in the step S3, compacting Molding process conditions include: 150-160 DEG C of forming temperature, briquetting pressure 140-160KG.
8. the preparation method of bilayer stamp rubber according to claim 5, it is characterised in that: in the step S4, mixing Process conditions include: mixing time 2-3min, 110-115 DEG C of dnockout temperature, the dnockout time 500-700 seconds.
9. the preparation method of bilayer stamp rubber according to claim 5, it is characterised in that: in the step S5, compacting Molding process conditions include: 155-160 DEG C of forming temperature, briquetting pressure 150-160KG.
10. the described in any item double-deck stamp rubber of claim the 1-4 any double-deck stamp rubber or claim 5-9 The double-deck stamp rubber that is prepared of preparation method preparing the application in rubber product；Preferred rubber product is rubber boots Bottom.
CN201910617004.7A 2019-07-09 2019-07-09 A kind of bilayer stamp rubber and its preparation method and application Pending CN110317379A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2552690Y (en) * 2002-07-31 2003-05-28 张书仁 Rubber product graphic secondary vulcanizing composition structure
CN107312212A (en) * 2017-07-05 2017-11-03 泉州市华阳鞋材科技有限公司晋江分公司 A kind of rubber foaming sole material material
CN207754648U (en) * 2017-12-15 2018-08-24 清远市广硕鞋业有限公司 Antiskid sole and its anti-skidding diaphragm of sole

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2552690Y (en) * 2002-07-31 2003-05-28 张书仁 Rubber product graphic secondary vulcanizing composition structure
CN107312212A (en) * 2017-07-05 2017-11-03 泉州市华阳鞋材科技有限公司晋江分公司 A kind of rubber foaming sole material material
CN207754648U (en) * 2017-12-15 2018-08-24 清远市广硕鞋业有限公司 Antiskid sole and its anti-skidding diaphragm of sole

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
张军: "《橡塑制鞋材料及应用》", 28 February 1999, 中国轻工业出版社 *

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