CN108577049A - Plastic shoes of cracking resistance and preparation method thereof - Google Patents

Plastic shoes of cracking resistance and preparation method thereof Download PDF

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Publication number
CN108577049A
CN108577049A CN201810447064.4A CN201810447064A CN108577049A CN 108577049 A CN108577049 A CN 108577049A CN 201810447064 A CN201810447064 A CN 201810447064A CN 108577049 A CN108577049 A CN 108577049A
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China
Prior art keywords
parts
dosage
preparation
neoprene
adhesive
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CN201810447064.4A
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Chinese (zh)
Inventor
胡银
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Wuhu Fengxue Rubber Co Ltd
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Wuhu Fengxue Rubber Co Ltd
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Priority to CN201810447064.4A priority Critical patent/CN108577049A/en
Publication of CN108577049A publication Critical patent/CN108577049A/en
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    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43D—MACHINES, TOOLS, EQUIPMENT OR METHODS FOR MANUFACTURING OR REPAIRING FOOTWEAR
    • A43D25/00—Devices for gluing shoe parts
    • A43D25/18—Devices for applying adhesives to shoe parts
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43D—MACHINES, TOOLS, EQUIPMENT OR METHODS FOR MANUFACTURING OR REPAIRING FOOTWEAR
    • A43D25/00—Devices for gluing shoe parts
    • A43D25/20—Arrangements for activating or for accelerating setting of adhesives, e.g. by using heat
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)

Abstract

The present invention relates to rubber adhesives, disclose a kind of plastic shoes of cracking resistance and preparation method thereof, the preparation process of the present invention improves the dispersivity of each raw material in adhesive, and epoxy group is introduced into neoprene and styrene butadiene styrene block copolymer, improve the binding performance of adhesive and the rubber or plastic cement that are binded, on the other hand, in conjunction with composition B, butyl acrylate, crosslinking agent, magnesia and zinc oxide containing nitroso-fluoro-elastomers raw rubber, viscosity and the bonding stronger adhesive of persistence have been obtained.The preparation method of the adhesive is simple, and raw material is easy to get, and has higher application value.Using the viscosity, strong and permanent tack adhesive, not only overcomes not strong also not lasting enough the defect of adhesive viscosity in the prior art, and provides a kind of plastic shoes of cracking resistance, and preparation method is simple.

Description

Plastic shoes of cracking resistance and preparation method thereof
Technical field
The present invention relates to adhesives, and in particular, to a kind of plastic shoes of cracking resistance and preparation method thereof.
Background technology
Plastic shoes because its use environment particularity, it is more demanding to the adhesive of rubber overshoes, not so, easily cause upper of a shoe with It cracks the bonding place of sole.
Rubber adhesive is widely used in the preparation process of rubber product, and neoprene adhesive is as rubber adhesive One kind, using also more universal in plastic cement adhesive, but in the prior art used in neoprene adhesive it is logical Often it is neoprene and the single combination of solvent, thus in sticking rubber product, especially in the different rubber product of bonding In the process, often cause bond it is insecure, easily it is loose phenomena such as so that bond effect is poor, and product quality is also significantly by shadow It rings.
Chinese patent application 201410225215.3 discloses a kind of neoprene adhesive composition, wherein described group It includes neoprene, Styrene-Butadiene-Styrene Block Copolymer, resorcinol formaldehyde resin, magnesia and oxidation to close object Zinc；Relative to the neoprene of 100 parts by weight, the Styrene-Butadiene-Styrene Block Copolymer is 5-35 parts by weight, The resorcinol formaldehyde resin is 30-70 parts by weight, and the magnesia is 2-8 parts by weight, and the zinc oxide is 2-8 weight Part.By adding Styrene-Butadiene-Styrene Block Copolymer and resorcinol formaldehyde in traditional neoprene adhesive Resin, so that the bond properties of adhesive obtained is more preferable, it is viscous to rubber to solve common neoprene adhesive Resultant force is not strong, the problem of leading to rubber product poor product quality.
But the technical solution although overcome in the prior art use single rubber bound loosely the case where, but should Though the viscosity of adhesive is strong, persistence is not strong, easily cracks in use, is more than especially 40 degree in temperature Operating mode in the case of, bonding place is easily cracked, and the service life of the product using the adhesive is substantially reduced.
Therefore, how to provide one kind not only having higher viscosity, but also the persistent adhesive of bonding can be improved, to be resisted The plastic shoes of cracking are current urgent problems to be solved.
Invention content
The object of the present invention is to provide a kind of plastic shoes of cracking resistance and preparation method thereof, present invention application viscosity it is strong and The adhesive of permanent tack not only overcomes not strong also not lasting enough the defect of adhesive viscosity in the prior art, and provides A kind of plastic shoes of cracking resistance, moreover, the preparation method of the adhesive is simple, and raw material is easy to get, and there is higher popularization to answer With value.
To achieve the goals above, the present invention provides a kind of preparation method of the plastic shoes of cracking resistance, the preparation sides Method includes the following steps：(1) neoprene and Styrene-Butadiene-Styrene Block Copolymer are ground dispersion, are added Pentamethylene, which is stirred to neoprene and Styrene-Butadiene-Styrene Block Copolymer, fully to be dissolved, and benzoyl peroxide is then added Formic acid, controlling reaction temperature obtain composition A after reaction；(2) nitroso-fluoro-elastomers raw rubber is dense with the quality of 50-60% Degree, which is dissolved in dimethoxymethane, is configured to solution, obtains composition B；(3) by composition A, composition B, butyl acrylate, friendship Join agent, magnesia and zinc oxide mixing, obtains neoprene adhesive；(4) in upper of a shoe edge and sole with the upper of a shoe edge Correspondence junction one layer of silicone grease is respectively coated, 10-15min is heated in 40-50 DEG C, then with ethyl alcohol by silicone grease wiped clean； (5) corresponding bonding place is compressed after the corresponding bonding place neoprene-coating adhesive of wiped clean, 3-5min.
The present invention also provides a kind of plastic shoes for the cracking resistance being prepared according to previously described preparation method.
Through the above technical solutions, the preparation process of the present invention improves the dispersivity of each raw material in adhesive, and by ring Oxygen groups are introduced into neoprene and Styrene-Butadiene-Styrene Block Copolymer, the rubber for improving adhesive and being binded The binding performance of glue or plastic cement, on the other hand, in conjunction with the composition B containing nitroso-fluoro-elastomers raw rubber, butyl acrylate, crosslinking Agent, magnesia and zinc oxide have obtained viscosity and the bonding stronger adhesive of persistence.Using silicone grease to bonding before bonding The matrix at place is swollen, and keeps the combination effect of adhesive and matrix more preferable, moreover, the preparation method letter of the adhesive Single, raw material is easy to get, and has higher application value.The present invention applies the viscosity strong and the adhesive of permanent tack, not only Not strong also not lasting enough the defect of adhesive viscosity in the prior art is overcome, and provides a kind of plastic shoes of cracking resistance, and Preparation method is simple.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.
To achieve the goals above, the present invention provides a kind of preparation method of the plastic shoes of cracking resistance, the preparation sides Method includes the following steps：(1) neoprene and Styrene-Butadiene-Styrene Block Copolymer are ground dispersion, are added Pentamethylene, which is stirred to neoprene and Styrene-Butadiene-Styrene Block Copolymer, fully to be dissolved, and benzoyl peroxide is then added Formic acid, controlling reaction temperature obtain composition A after reaction；(2) nitroso-fluoro-elastomers raw rubber is dense with the quality of 50-60% Degree, which is dissolved in dimethoxymethane, is configured to solution, obtains composition B；(3) by composition A, composition B, butyl acrylate, friendship Join agent, magnesia and zinc oxide mixing, obtains neoprene adhesive；(4) in upper of a shoe edge and sole with the upper of a shoe edge Correspondence junction one layer of silicone grease is respectively coated, 10-15min is heated in 40-50 DEG C, then with ethyl alcohol by silicone grease wiped clean； (5) corresponding bonding place is compressed after the corresponding bonding place neoprene-coating adhesive of wiped clean, 3-5min.
Through the above technical solutions, the preparation process of the present invention improves the dispersivity of each raw material in adhesive, and by ring Oxygen groups are introduced into neoprene and Styrene-Butadiene-Styrene Block Copolymer, the rubber for improving adhesive and being binded The binding performance of glue or plastic cement, on the other hand, in conjunction with the composition B containing nitroso-fluoro-elastomers raw rubber, butyl acrylate, crosslinking Agent, magnesia and zinc oxide have obtained viscosity and the bonding stronger adhesive of persistence.Using silicone grease to bonding before bonding The matrix at place is swollen, and keeps the combination effect of adhesive and matrix more preferable, moreover, the preparation method letter of the adhesive Single, raw material is easy to get, and has higher application value.The present invention applies the viscosity strong and the adhesive of permanent tack, not only Not strong also not lasting enough the defect of adhesive viscosity in the prior art is overcome, and provides a kind of plastic shoes of cracking resistance, and Preparation method is simple.
In the above-mentioned technical solutions, the synthesis of liquid nitroso-fluoro-elastomers raw rubber is referring to patent application 201310133404.3。
In a kind of more preferred embodiment of the present invention, viscosity and the bonding stronger bonding of persistence in order to obtain Agent, to obtain the plastic shoes of cracking resistance, it is preferable that in parts by weight, relative to 100 parts of neoprene, styrene-fourth two The dosage of alkene-styrene block copolymer is 45-65 parts, and the dosage of perbenzoic acid is 8-12 parts, and the dosage of pentamethylene is 80-150 parts.
In a kind of more preferred embodiment of the present invention, viscosity and the bonding stronger bonding of persistence in order to obtain Agent, to obtain the plastic shoes of cracking resistance, it is preferable that reaction temperature is 80-90 DEG C, reaction time 40-50min.
In a kind of more preferred embodiment of the present invention, viscosity and the bonding stronger bonding of persistence in order to obtain Agent, to obtain the plastic shoes of cracking resistance, it is preferable that in terms of mass parts, relative to 100 parts of composition A, the use of composition B Amount is 50-70 parts, and the dosage of butyl acrylate is 8-10 parts, and the dosage of crosslinking agent is 20-30 parts, and the dosage of magnesia is 2-3 Part, the dosage of zinc oxide is 2-3 parts.
In a kind of more preferred embodiment of the present invention, viscosity and the bonding stronger bonding of persistence in order to obtain Agent, to obtain the plastic shoes of cracking resistance, it is preferable that further include being added with initiator, antiager and antioxidant in step (3).
In a kind of more preferred embodiment of the present invention, viscosity and the bonding stronger bonding of persistence in order to obtain Agent, to obtain the plastic shoes of cracking resistance, it is preferable that in terms of mass parts, relative to 100 parts of composition A, the initiator Dosage is 0.5-1.5 parts by weight, and the dosage of the antiager is 0.5-2 parts by weight, and the dosage of the antioxidant is 0.5-2.5 weights Measure part.
In a kind of more preferred embodiment of the present invention, viscosity and the bonding stronger bonding of persistence in order to obtain Agent, to obtain the plastic shoes of cracking resistance, it is preferable that the initiator is benzoyl peroxide.
In a kind of more preferred embodiment of the present invention, viscosity and the bonding stronger bonding of persistence in order to obtain Agent, to obtain the plastic shoes of cracking resistance, it is preferable that the antioxidant is the double lauryls of thio-2 acid and/or thio dipropyl Sour double octadecyls.
In a kind of more preferred embodiment of the present invention, viscosity and the bonding stronger bonding of persistence in order to obtain Agent, to obtain the plastic shoes of cracking resistance, it is preferable that the neoprene be elongation at break be 850-1000%, rebound degree For the neoprene that 60-80% and hardness are 55-70Shore A.
In a kind of more preferred embodiment of the present invention, viscosity and the bonding stronger bonding of persistence in order to obtain Agent, to obtain the plastic shoes of cracking resistance, it is preferable that the average molecular of the Styrene-Butadiene-Styrene Block Copolymer Quality is 15-25 ten thousand.
In a kind of more preferred embodiment of the present invention, viscosity and the bonding stronger bonding of persistence in order to obtain Agent, to obtain the plastic shoes of cracking resistance, it is preferable that the inherent viscosity of the nitroso-fluoro-elastomers raw rubber is 0.05- 0.06dLg-1, physical aspect is liquid form, has room temperature flowability.
In a kind of more preferred embodiment of the present invention, viscosity and the bonding stronger bonding of persistence in order to obtain Agent, to obtain the plastic shoes of cracking resistance, it is preferable that the crosslinking agent is organic multicomponent amine, low molecular polyether amine, nitrogen third One or any two or more combination in pyridine, polycarbodiimide.
Wherein, the material of the sole of plastic shoes can be one in rubber-sole, shoe with beef tendon sole, layers of cloth firmly stitched together for soles of cloth shoes, foam bottom, composite base Kind is a variety of, and the material of upper of a shoe can be igelite, rubber etc., and the effect of the present invention can be achieved, in this regard, no longer superfluous It states.In embodiment later, the material of upper of a shoe and sole is all made of rubber.
The present invention also provides a kind of plastic shoes for the cracking resistance being prepared according to previously described preparation method.
Through the above technical solutions, the preparation process of the present invention improves the dispersivity of each raw material in adhesive, and by ring Oxygen groups are introduced into neoprene and Styrene-Butadiene-Styrene Block Copolymer, the rubber for improving adhesive and being binded The binding performance of glue or plastic cement, on the other hand, in conjunction with the composition B containing nitroso-fluoro-elastomers raw rubber, butyl acrylate, crosslinking Agent, magnesia and zinc oxide have obtained viscosity and the bonding stronger adhesive of persistence.Using silicone grease to bonding before bonding The matrix at place is swollen, and keeps the combination effect of adhesive and matrix more preferable, moreover, the preparation method letter of the adhesive Single, raw material is easy to get, and has higher application value.The present invention applies the viscosity strong and the adhesive of permanent tack, not only Not strong also not lasting enough the defect of adhesive viscosity in the prior art is overcome, and provides a kind of plastic shoes of cracking resistance, and Preparation method is simple.
The present invention will be described in detail by way of examples below.
Embodiment 1
The preparation method of the plastic shoes of cracking resistance, the preparation method comprises the following steps：
(1) neoprene and Styrene-Butadiene-Styrene Block Copolymer are ground dispersion, pentamethylene is added Stirring is fully dissolved to neoprene and Styrene-Butadiene-Styrene Block Copolymer, and perbenzoic acid is then added, For controlling reaction temperature to 80 DEG C, reaction 50min obtains composition A after reaction；Wherein, the additive amount of each material is：With weight Part meter is measured, relative to 100 parts of neoprene, the dosage of Styrene-Butadiene-Styrene Block Copolymer is 45 parts, peroxide The dosage for changing benzoic acid is 8 parts, and the dosage of pentamethylene is 80 parts；
Wherein, neoprene is the neoprene that elongation at break is 850%, rebound degree is 60% and hardness is 55ShoreA Rubber；The relative molecular mass of Styrene-Butadiene-Styrene Block Copolymer is 150,000；
(2) nitroso-fluoro-elastomers raw rubber is dissolved in 50% mass concentration in dimethoxymethane and is configured to solution, Obtain composition B；Wherein, the inherent viscosity of nitroso-fluoro-elastomers raw rubber is 0.05dLg-1, physical aspect is liquid form, is had Room temperature flowability；
(3) by composition A, composition B, butyl acrylate, aziridine, magnesia and zinc oxide, benzoyl peroxide, right Benzenediol and the double lauryl mixing of thio-2 acid；Wherein, the amount of the addition of each material is：In terms of mass parts, relative to 100 parts Composition A, the dosage of composition B is 50, and the dosage of butyl acrylate is 8 parts, and the dosage of aziridine is 20 parts, magnesia Dosage is 2 parts, and the dosage of zinc oxide is 2 parts, and the dosage of benzoyl peroxide is 0.5 parts by weight, and the dosage of hydroquinone is 0.5 The dosage of parts by weight, the double lauryls of thio-2 acid is 0.5 parts by weight, obtains neoprene adhesive；
(4) one layer of silicone grease is respectively coated with the corresponding junction at the upper of a shoe edge in upper of a shoe edge and sole, in 40 DEG C heating 15min, then with ethyl alcohol by silicone grease wiped clean；
(5) corresponding bonding place is compressed after the corresponding bonding place neoprene-coating adhesive of wiped clean, 3min.
Embodiment 2
The preparation method of the plastic shoes of cracking resistance, the preparation method comprises the following steps：
(1) neoprene and Styrene-Butadiene-Styrene Block Copolymer are ground dispersion, pentamethylene is added Stirring is fully dissolved to neoprene and Styrene-Butadiene-Styrene Block Copolymer, and perbenzoic acid is then added, For controlling reaction temperature to 90 DEG C, reaction 40min obtains composition A after reaction；Wherein, the amount of the addition of each material is：With Parts by weight meter, relative to 100 parts of neoprene, the dosage of Styrene-Butadiene-Styrene Block Copolymer is 65 parts, mistake The dosage for aoxidizing benzoic acid is 12 parts, and the dosage of pentamethylene is 150 parts；
Wherein, neoprene is the chlorine that elongation at break is 1000%, rebound degree is 80% and hardness is 70ShoreA Buna；The relative molecular mass of Styrene-Butadiene-Styrene Block Copolymer is 250,000；
(2) nitroso-fluoro-elastomers raw rubber is dissolved in 60% mass concentration in dimethoxymethane and is configured to solution, Obtain composition B；Wherein, the inherent viscosity of nitroso-fluoro-elastomers raw rubber is 0.06dLg-1, physical aspect is liquid form, is had Room temperature flowability；
(3) by composition A, composition B, butyl acrylate, aziridine, magnesia and zinc oxide, benzoyl peroxide, right Benzenediol and the double lauryl mixing of thio-2 acid；Wherein, the amount of the addition of each material is：In terms of mass parts, relative to 100 parts Composition A, the dosage of composition B is 70 parts, and the dosage of butyl acrylate is 10 parts, and the dosage of aziridine is 30 parts, oxidation The dosage of magnesium is 3 parts, and the dosage of zinc oxide is 3 parts, and the dosage of benzoyl peroxide is 1.5 parts by weight, the dosage of hydroquinone Dosage for 2 parts by weight, the double lauryls of thio-2 acid is 2.5 parts by weight, obtains neoprene adhesive；
(4) one layer of silicone grease is respectively coated with the corresponding junction at the upper of a shoe edge in upper of a shoe edge and sole, in 50 DEG C heating 10min, then with ethyl alcohol by silicone grease wiped clean；
(5) corresponding bonding place is compressed after the corresponding bonding place neoprene-coating adhesive of wiped clean, 5min.
Embodiment 3
The preparation method of the plastic shoes of cracking resistance, the preparation method comprises the following steps：
(1) neoprene and Styrene-Butadiene-Styrene Block Copolymer are ground dispersion, pentamethylene is added Stirring is fully dissolved to neoprene and Styrene-Butadiene-Styrene Block Copolymer, and perbenzoic acid is then added, For controlling reaction temperature to 85 DEG C, reaction 45min obtains composition A after reaction；Wherein, the amount of the addition of each material is：With Parts by weight meter, relative to 100 parts of neoprene, the dosage of Styrene-Butadiene-Styrene Block Copolymer is 55 parts, mistake The dosage for aoxidizing benzoic acid is 10 parts, and the dosage of pentamethylene is 105 parts；
Wherein, neoprene is the neoprene that elongation at break is 920%, rebound degree is 70% and hardness is 63ShoreA Rubber；The relative molecular mass of Styrene-Butadiene-Styrene Block Copolymer is 200,000；
(2) nitroso-fluoro-elastomers raw rubber is dissolved in 55% mass concentration in dimethoxymethane and is configured to solution, Obtain composition B；Wherein, the inherent viscosity of nitroso-fluoro-elastomers raw rubber is 0.055dLg-1, physical aspect is liquid form, tool There is room temperature flowability；
(3) by composition A, composition B, butyl acrylate, aziridine, magnesia and zinc oxide, benzoyl peroxide, right Benzenediol and the double lauryl mixing of thio-2 acid；Wherein, the amount of the addition of each material is：In terms of mass parts, relative to 100 parts Composition A, the dosage of composition B is 60 parts, and the dosage of butyl acrylate is 9 parts, and the dosage of aziridine is 25 parts, magnesia Dosage be 2.5 parts, the dosage of zinc oxide is 2.5 parts, and the dosage of benzoyl peroxide is 1 parts by weight, the dosage of hydroquinone Dosage for 1.5 parts by weight, the double lauryls of thio-2 acid is 1.3 parts by weight, obtains neoprene adhesive；
(4) one layer of silicone grease is respectively coated with the corresponding junction at the upper of a shoe edge in upper of a shoe edge and sole, in 45 DEG C heating 13min, then with ethyl alcohol by silicone grease wiped clean；
(5) corresponding bonding place is compressed after the corresponding bonding place neoprene-coating adhesive of wiped clean, 4min.
Comparative example 1
The preparation method of the plastic shoes of cracking resistance, the preparation method comprises the following steps：
(1) in terms of mass parts, by 50 parts of neoprene, 30 parts of Styrene-Butadiene-Styrene Block Copolymer and 60 Part pentamethylene mixing, obtains composition A；
Wherein, neoprene is the chlorine that elongation at break is 1000%, rebound degree is 80% and hardness is 70ShoreA Buna；The relative molecular mass of Styrene-Butadiene-Styrene Block Copolymer is 250,000；
(2) nitroso-fluoro-elastomers raw rubber is dissolved in 60% mass concentration in dimethoxymethane and is configured to solution, Obtain composition B；Wherein, the inherent viscosity of nitroso-fluoro-elastomers raw rubber is 0.06dLg-1, physical aspect is liquid form, is had Room temperature flowability；
(3) by composition A, composition B, butyl acrylate, aziridine, magnesia and zinc oxide, benzoyl peroxide, right Benzenediol and the double lauryl mixing of thio-2 acid；Wherein, the amount of the addition of each material is：In terms of mass parts, relative to 100 parts Composition A, the dosage of composition B is 70 parts, and the dosage of butyl acrylate is 10 parts, and the dosage of aziridine is 30 parts, oxidation The dosage of magnesium is 3 parts, and the dosage of zinc oxide is 3 parts, and the dosage of benzoyl peroxide is 1.5 parts by weight, the dosage of hydroquinone Dosage for 2 parts by weight, the double lauryls of thio-2 acid is 2.5 parts by weight, obtains neoprene adhesive；
(4) the upper of a shoe edge of plastic shoes and the upper of a shoe edge junction neoprene-coating corresponding with sole are bonded After 4min, the corresponding junction of upper of a shoe edge and sole is compressed, stands 25min for agent.
Comparative example 2
The preparation method of the plastic shoes of cracking resistance, the preparation method comprises the following steps：
(1) neoprene and Styrene-Butadiene-Styrene Block Copolymer are ground dispersion, pentamethylene is added Stirring is fully dissolved to neoprene and Styrene-Butadiene-Styrene Block Copolymer, and perbenzoic acid is then added, For controlling reaction temperature to 90 DEG C, reaction 40min obtains composition A after reaction；Wherein, the amount of the addition of each material is：With Parts by weight meter, relative to 100 parts of neoprene, the dosage of Styrene-Butadiene-Styrene Block Copolymer is 65 parts, mistake The dosage for aoxidizing benzoic acid is 12 parts, and the dosage of pentamethylene is 150 parts；
Wherein, neoprene is the chlorine that elongation at break is 1000%, rebound degree is 80% and hardness is 70ShoreA Buna；The relative molecular mass of Styrene-Butadiene-Styrene Block Copolymer is 250,000；
(2) by composition A, butyl acrylate, aziridine, magnesia and zinc oxide, benzoyl peroxide, hydroquinone and The double lauryl mixing of thio-2 acid；Wherein, the amount of the addition of each material is：In terms of mass parts, relative to 100 parts of composition The dosage of A, butyl acrylate are 10 parts, and the dosage of aziridine is 30 parts, and the dosage of magnesia is 3 parts, and the dosage of zinc oxide is 3 Part, the dosage of benzoyl peroxide is 1.5 parts by weight, and the dosage of hydroquinone is 2 parts by weight, the double lauryls of thio-2 acid Dosage is 2.5 parts by weight, obtains neoprene adhesive；
(4) the upper of a shoe edge of plastic shoes and the upper of a shoe edge junction neoprene-coating corresponding with sole are bonded After 4min, the corresponding junction of upper of a shoe edge and sole is compressed for agent.
Comparative example 3
The preparation method of the plastic shoes of cracking resistance, the preparation method comprises the following steps：
(1) neoprene and Styrene-Butadiene-Styrene Block Copolymer are ground dispersion, pentamethylene is added Stirring is fully dissolved to neoprene and Styrene-Butadiene-Styrene Block Copolymer, and perbenzoic acid is then added, For controlling reaction temperature to 90 DEG C, reaction 40min obtains composition A after reaction；Wherein, the amount of the addition of each material is：With Parts by weight meter, relative to 100 parts of neoprene, the dosage of Styrene-Butadiene-Styrene Block Copolymer is 65 parts, mistake The dosage for aoxidizing benzoic acid is 12 parts, and the dosage of pentamethylene is 150 parts；
Wherein, neoprene is the chlorine that elongation at break is 1000%, rebound degree is 80% and hardness is 70ShoreA Buna；The relative molecular mass of Styrene-Butadiene-Styrene Block Copolymer is 250,000；
(2) nitroso-fluoro-elastomers raw rubber is dissolved in 60% mass concentration in dimethoxymethane and is configured to solution, Obtain composition B；Wherein, the inherent viscosity of nitroso-fluoro-elastomers raw rubber is 0.06dLg-1, physical aspect is liquid form, is had Room temperature flowability；
(3) composition A, composition B, butyl acrylate are mixed；Wherein, the amount of the addition of each material is：With mass parts Meter, relative to 100 parts of composition A, the dosage of composition B is 70 parts, and the dosage of butyl acrylate is 10 parts, obtains neoprene Adhesive；
(4) the upper of a shoe edge of plastic shoes and the upper of a shoe edge junction neoprene-coating corresponding with sole are bonded After 4min, the corresponding junction of upper of a shoe edge and sole is compressed for agent.
Detect example 1
Peel strength is detected according to GB/T2791-1995, after testing, the upper of a shoe in comparative example 1-3 and sole junction Peel strength peel strength after 3.1-3.8kN/m, 48 hours is 3.5-4.4kN/m, is placed 3 months under room temperature, peel strength Decline about 10%, and placed 50 days in the environment of 68 DEG C, the peel strength of sample is remarkably decreased, until 1.6-2.4kN/m.
Peel strength, after testing, the stripping of upper of a shoe and sole junction in embodiment 1-3 are detected according to GB/T2791-1995 From intensity, peel strength is 6.1-6.8kN/m after 4.9-5.4kN/m, 48 hours, is placed 3 months under room temperature, peel strength base This is unchanged, and is placed 50 days in the environment of 68 DEG C, and the peel strength of sample is not remarkably decreased, and range is still in 5.9- 6.4kN/m, the maximum range of decrease are no more than 10%.
Therefore, adhesive of the invention both has preferable adhesive strength, it may have persistence is preferably bonded, meanwhile, Illustrate under 68 DEG C of so high temperature conditions, adhesive of the invention has preferable adhesion stability, is highly suitable as The adhesive of articles for daily use, clothes, footwear etc. uses.
The present invention by force and the adhesive of permanent tack, not only overcomes in the prior art that adhesive viscosity is not using the viscosity Strong also not lasting enough defect, and a kind of plastic shoes of cracking resistance are provided, and preparation method is simple.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims (10)

1. a kind of preparation method of the plastic shoes of cracking resistance, which is characterized in that the preparation method comprises the following steps：
(1) neoprene and Styrene-Butadiene-Styrene Block Copolymer are ground dispersion, pentamethylene stirring is added It is fully dissolved to neoprene and Styrene-Butadiene-Styrene Block Copolymer, perbenzoic acid is then added, controlled Reaction temperature obtains composition A after reaction；
(2) nitroso-fluoro-elastomers raw rubber is dissolved in the mass concentration of 50-60% in dimethoxymethane and is configured to solution, obtained Composition B；
(3) composition A, composition B, butyl acrylate, crosslinking agent, magnesia and zinc oxide are mixed, obtains neoprene bonding Agent；
(4) one layer of silicone grease is respectively coated with the corresponding junction at the upper of a shoe edge in upper of a shoe edge and sole, in 40-50 DEG C 10-15min is heated, then with ethyl alcohol by silicone grease wiped clean；
(5) corresponding bonding place is compressed after the corresponding bonding place neoprene-coating adhesive of wiped clean, 3-5min.
2. preparation method according to claim 1, wherein in parts by weight, relative to 100 parts of neoprene, benzene second The dosage of alkene-butadiene-styrene block copolymer is 45-65 parts, and the dosage of perbenzoic acid is 8-12 parts, pentamethylene Dosage is 80-150 parts.
3. preparation method according to claim 1, wherein reaction temperature is 80-90 DEG C, reaction time 40-50min.
4. preparation method according to claim 1, wherein in terms of mass parts, relative to 100 parts of composition A, composition The dosage of B is 50-70 parts, and the dosage of butyl acrylate is 8-10 parts, and the dosage of crosslinking agent is 20-30 parts, the dosage of magnesia It it is 2-3 parts, the dosage of zinc oxide is 2-3 parts.
5. according to claim 1-4 any one of them preparation methods, wherein further include added with initiator in step (3), resist Old agent and antioxidant.
6. preparation method according to claim 5, wherein described to draw relative to 100 parts of composition A in terms of mass parts The dosage for sending out agent is 0.5-1.5 parts by weight, and the dosage of the antiager is 0.5-2 parts by weight, and the dosage of the antioxidant is 0.5-2.5 parts by weight.
7. preparation method according to claim 5, wherein the initiator is benzoyl peroxide；
And/or the antiager is hydroquinone；
And/or the antioxidant is the double lauryls of thio-2 acid and/or the double octadecyls of thio-2 acid.
8. preparation method according to claim 5, wherein the neoprene be elongation at break be 850-1000%, The neoprene that rebound degree is 60-80% and hardness is 55-70ShoreA；
And/or the relative molecular mass of the Styrene-Butadiene-Styrene Block Copolymer is 15-25 ten thousand.
9. preparation method according to claim 5, wherein the inherent viscosity of the nitroso-fluoro-elastomers raw rubber is 0.05- 0.06dLg-1, physical aspect is liquid form, has room temperature flowability；
And/or the crosslinking agent is one kind in organic multicomponent amine, low molecular polyether amine, aziridine, polycarbodiimide Or arbitrary two or more combination.
10. a kind of plastic shoes for the cracking resistance being prepared according to claim 1-9 any one of them preparation methods.
CN201810447064.4A 2018-05-11 2018-05-11 Plastic shoes of cracking resistance and preparation method thereof Withdrawn CN108577049A (en)

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