CN113529431A - High-performance silica gel gloves and preparation method thereof - Google Patents

High-performance silica gel gloves and preparation method thereof Download PDF

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Publication number
CN113529431A
CN113529431A CN202110796357.5A CN202110796357A CN113529431A CN 113529431 A CN113529431 A CN 113529431A CN 202110796357 A CN202110796357 A CN 202110796357A CN 113529431 A CN113529431 A CN 113529431A
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China
Prior art keywords
viscosity
glove
fluorosilicone rubber
coupling agent
rubber
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Granted
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CN202110796357.5A
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CN113529431B (en
Inventor
徐凤伟
孙永峰
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SHANDONG XINGYU GLOVES CO Ltd
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SHANDONG XINGYU GLOVES CO Ltd
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/128—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with silicon polymers
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D19/00—Gloves
    • A41D19/0055—Plastic or rubber gloves
    • A41D19/0058—Three-dimensional gloves
    • A41D19/0065—Three-dimensional gloves with a textile layer underneath
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D99/00—Subject matter not provided for in other groups of this subclass
    • B29D99/0064—Producing wearing apparel
    • B29D99/0067—Gloves
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2203/00—Macromolecular materials of the coating layers
    • D06N2203/06—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N2203/066—Silicon polymers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/10—Properties of the materials having mechanical properties
    • D06N2209/103—Resistant to mechanical forces, e.g. shock, impact, puncture, flexion, shear, compression, tear
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/14—Properties of the materials having chemical properties
    • D06N2209/143—Inert, i.e. inert to chemical degradation, corrosion resistant
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/10—Clothing
    • D06N2211/103—Gloves
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2213/00—Others characteristics
    • D06N2213/03—Fibrous web coated on one side with at least two layers of the same polymer type, e.g. two coatings of polyolefin

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Gloves (AREA)

Abstract

The invention relates to a high-performance silica gel glove and a preparation method thereof, wherein the preparation method comprises the following steps: s1, processing the glove blank yarns: adopting a silane coupling agent to carry out surface treatment on the yarns, and weaving a glove blank by using the yarns subjected to the surface treatment; or weaving a glove blank by using yarns, and then carrying out surface treatment on the glove blank by using a silane coupling agent; s2, soaking the glue for one time: preparing a low-viscosity fluorosilicone rubber material with the viscosity of 1000-2000cp, dipping a glove blank into the low-viscosity fluorosilicone rubber material, taking out the glove blank, dripping the rubber, drying until the rubber material on the surface does not flow, and performing vulcanization treatment to obtain the glove blank of which the surface is covered with a layer of fluorosilicone rubber film; s3, dipping the glue for two times: preparing a high-viscosity fluorosilicone rubber material with the viscosity of 4000-; s4, vulcanization: and (3) carrying out low-temperature pre-vulcanization and then high-temperature complete vulcanization to obtain the high-performance silica gel gloves.

Description

High-performance silica gel gloves and preparation method thereof
Technical Field
The invention relates to the technical field of labor protection gloves, in particular to a high-performance silica gel glove and a preparation method thereof.
Background
The fluorosilicone rubber (FMVQ) has a main chain consisting of silicon and oxygen atoms, and a silicon-oxygen bond as a main chain structure, wherein the poly (3,3, 3-trifluoropropylmethyl) silicone rubber is the most widely used fluorosilicone rubber. The organic silicon rubber has the excellent performances of high and low temperature resistance, aging resistance, radiation resistance, ultraviolet ray resistance, electric insulation, wet skid resistance, low compression deformation rate and the like, and the fluororubber has the characteristics of good thermal stability, solvent resistance and the like. Therefore, the fluorosilicone rubber has excellent performances of hydrocarbon solvent resistance, oil resistance, acid and alkali resistance, lower surface energy and the like of the organic fluorine material on the basis of excellent performances of heat resistance, cold resistance, high voltage resistance, weather aging resistance and the like of the organic silicon material, and can work for a long time at the temperature of between 55 ℃ below zero and 200 ℃ due to the introduction of fluorine-containing groups. Therefore, fluorosilicone rubbers are widely used in the automobile industry, the petrochemical industry, the medical health, and the military industry. It has a wide operating temperature range and is resistant to fuels, engine oils and many chemical solvents.
At present, the fluorosilicone rubber is not commonly used in the glove industry, and most of the fluorosilicone rubber is a component in a formula. For example, the invention patent CN201711363289 discloses an antibacterial wear-resistant medical rubber glove, which adopts fluorosilicone rubber and nitrile rubber compounded rubber. The invention patent CN201610555119 discloses an antibacterial flame-retardant electrical insulating glove which takes fluorosilicone rubber as an auxiliary material. The main reasons are that the fluorosilicone rubber has poor strength and low surface energy, belongs to a material difficult to bond, and has the defects of difficult processing and the like.
In view of the excellent characteristics of the fluorosilicone rubber, the invention aims to develop a preparation process of labor gloves completely taking the fluorosilicone rubber as an adhesive layer, so as to produce high-performance silicone gloves.
Disclosure of Invention
Technical problem to be solved
In view of the defects and shortcomings of the prior art, the invention provides a preparation method of high-performance silica gel gloves, which solves the technical problems of poor strength, difficult bonding and the like of fluorosilicone rubber and can produce the high-performance silica gel gloves.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
in a first aspect, the invention provides a preparation method of a high-performance silica gel glove, which comprises the following steps:
s1, processing the glove blank yarns: adopting a silane coupling agent to carry out surface treatment on the yarns, and weaving a glove blank by using the yarns subjected to the surface treatment; or weaving a glove blank by using yarns, and then carrying out surface treatment on the glove blank by using a silane coupling agent;
s2, soaking the glue for one time: preparing a low-viscosity fluorosilicone rubber material with the viscosity of 1000-2000cp, dipping a glove blank into the low-viscosity fluorosilicone rubber material, taking out the glove blank, dripping the rubber, drying until the rubber material on the surface does not flow, and performing vulcanization treatment to obtain the glove blank of which the surface is covered with a layer of fluorosilicone rubber film;
s3, dipping the glue for two times: preparing a high-viscosity fluorosilicone rubber material with the viscosity of 4000-;
s4, vulcanization: low-temperature pre-vulcanization is carried out firstly, and then high-temperature complete vulcanization is carried out to obtain the high-performance silica gel gloves.
According to the preferred embodiment of the present invention, in S1, the yarn or glove blank is surface-treated with the silane coupling agent by immersing the yarn or glove blank in an ethanol solution containing the vinyl silane coupling agent and the trifluoropropyl silane coupling agent. The treatment conditions were: soaking and stirring at normal temperature for 2-6h, preferably 4 h. When the yarn is soaked, the yarn can be fully contacted with the silane coupling agent by a larger surface area, so that the effect of soaking the yarn and then weaving the glove blank is better than that of soaking the glove blank.
The vinyl silane coupling agent is a vinyl trimethoxy silane coupling agent, a vinyl triethoxy silane coupling agent or a vinyl triacetoxy silane coupling agent, and is preferably a vinyl triethoxy silane coupling agent. Wherein, the trifluoropropylsilane coupling agent is preferably trifluoropropyltriethoxysilane coupling agent.
Preferably, in the ethanol solution containing the vinyl silane coupling agent and the trifluoropropyl silane coupling agent, the concentration of the vinyl silane coupling agent is 1-3% (mass percent), and preferably 2%; the concentration of the trifluoropropylsilane coupling agent is 1 to 3%, preferably 2%.
According to the preferred embodiment of the invention, in S2, when preparing the low-viscosity fluorine silicone rubber compound, two-component liquid fluorine silicone rubber or high-temperature cured fluorine silicone rubber is adopted, and a diluting solvent is added to adjust the viscosity to 1000-2000 cp; specifically, the viscosity is controlled according to the thickness of the fluorosilicone rubber film in S2, and is preferably 1000 cp. Preferably, when formulating a low viscosity fluorosilicone gum, the diluent solvent used is acetone, ethyl acetate or butyl acetate, most preferably ethyl acetate. The ethyl acetate is a weak polar solvent, has low toxicity, can well disperse the fluorosilicone rubber, has low boiling point, is easy to volatilize, and the rubber material is easy to dry and solidify.
The preparation method of the low-viscosity fluorine silicone rubber compound comprises the following steps: fully stirring the two-component liquid fluorosilicone rubber or high-temperature cured fluorosilicone rubber sizing material and a diluting solvent for 2-6h (preferably 4h) by using a planetary stirrer so as to ensure that the fluorosilicone rubber is uniformly dispersed and the solution is stable, and the viscosity is in an expected range.
According to a preferred embodiment of the present invention, in S2, the two-component liquid fluorosilicone rubber used for preparing the low viscosity fluorosilicone rubber compound is an addition type fluorosilicone rubber; the high-temperature cured fluorosilicone rubber is general fluorosilicone rubber, high-resilience fluorosilicone rubber and high-tear resistance fluorosilicone rubber; wherein the vulcanized rubber hardness of the fluorosilicone rubber used to formulate the low viscosity fluorosilicone rubber compound is from 20 to 40 Shore A hardness, preferably 30 Shore A hardness.
According to the preferred embodiment of the invention, in S2, the glove blank is dipped into the low-viscosity fluorosilicone rubber material and soaked for 1-3min, the glove blank is taken out, after 2.5-3.5min of glue dripping, the glove blank is sent into an oven to be dried for 4-6min and then taken out (the glove blank is dried until the surface rubber material does not flow), the glove blank is sent into an oven with the temperature of 110-. The low-viscosity fluorosilicone rubber compound contains more diluting solvents, and can only achieve incomplete vulcanization to a certain extent through the vulcanization treatment under the conditions, so that the vulcanization connection between the low-viscosity fluorosilicone rubber compound and the high-viscosity fluorosilicone rubber compound soaked in the S3 is favorably formed in the common vulcanization stage of the S4, and the bonding force between the secondary rubber and the primary rubber is improved.
After the first-time gum dipping treatment of S2, the low-viscosity fluorosilicone rubber compound can soak each yarn of the glove blank, so that the glove blank is bonded by the fluorosilicone rubber compound to form an integral structure, and a thin fluorosilicone rubber film is covered on the surface of the glove blank, so that the glove blank can be smoothly dipped in high-viscosity secondary gum, and a substrate tightly bonded with homogeneous high-viscosity fluorosilicone rubber (secondary gum) is provided.
According to the preferred embodiment of the invention, in S3, when preparing the high-viscosity fluorine silicone rubber compound, two-component liquid fluorine silicone rubber or high-temperature cured fluorine silicone rubber is adopted, and a diluting solvent is added to adjust the viscosity to 4000-6000 cp; the viscosity is regulated according to the thickness of the glue layer of the finished glove product, and is preferably 5000 cp. Preferably, when formulating a high viscosity fluorosilicone rubber compound, the diluent solvent used is acetone, ethyl acetate or butyl acetate, preferably ethyl acetate.
The preparation method of the high-viscosity fluorine silicon rubber material comprises the following steps: fully stirring the two-component liquid fluorosilicone rubber or high-temperature cured fluorosilicone rubber sizing material and a diluting solvent for 2-6h (preferably 4h) by using a planetary stirrer so as to ensure that the fluorosilicone rubber is uniformly dispersed and the solution is stable, and the viscosity is in an expected range.
According to the preferred embodiment of the present invention, in S3, the two-component liquid fluorosilicone rubber used for preparing the high viscosity fluorosilicone rubber compound is an addition type fluorosilicone rubber; the high-temperature cured fluorosilicone rubber is general fluorosilicone rubber, high-resilience fluorosilicone rubber and high-tear resistance fluorosilicone rubber; wherein the vulcanized rubber hardness of the fluorosilicone rubber used in formulating the high viscosity fluorosilicone rubber stock is from 30 to 70 Shore A hardness, preferably from 50 to 60 Shore A hardness, and more preferably 50 Shore A hardness. The secondary rubber is used for forming a surface rubber layer of the finished glove, and the harder the vulcanized rubber is, the higher the strength of the glove product is, the more excellent the wear resistance, the cutting resistance, the tear resistance and the puncture resistance are; the primary glue is mainly used for forming a priming glue film on a fiber glove blank, the lower the hardness, the more easily the fluorosilicone rubber is dispersed and dissolved, and the more excellent the infiltration performance and the bonding performance of the glue material are.
According to a preferred embodiment of the present invention, in S3, before gum dipping, the foam discharging method is performed on the high viscosity fluorine silicone rubber compound, and the foam discharging method is as follows: stirring under negative pressure and ultrasonic assistance. The viscosity of the high-viscosity fluorine silicone rubber is 4000-6000cp, the viscosity is high, once gas is mixed in, the high-viscosity fluorine silicone rubber is easy to remain in the rubber to form bubbles (difficult to be discharged automatically), and if the bubbles are not discharged, a large amount of bubbles are contained in the rubber layer of the glove, and the bubbles expand and burst in the high-temperature vulcanization process to cause pits and damage on the rubber surface, so that the strength and the appearance of the glove product are influenced.
According to the preferred embodiment of the invention, in step S3, the glove blank is dipped into the high-viscosity fluorosilicone rubber compound and soaked for 1-3min, the glove blank is taken out, the glue is dripped for 4-10min (the high-viscosity rubber compound needs longer glue dripping time), the glue is naturally spread and distributed in a flowing manner through glue dripping, and the redundant glue is dripped to ensure the gram weight of the product, the uniformity of the thickness of the rubber layer and the smoothness of the rubber surface.
According to the preferred embodiment of the present invention, in S4, the low-temperature prevulcanization conditions are: treating at 60-80 deg.C for 30-90 min; the high-temperature vulcanization conditions are as follows: treating at 100-140 deg.c for 1-2.5 hr.
According to the preferred embodiment of the invention, in S4, after the treatment at 60-80 ℃ for 30-90min, preferably at 60-70 ℃ for 30-60min, the fluorosilicone rubber on the surface of the glove blank is not completely vulcanized, in order to improve the anti-skid performance of the glove product, the glove is put into an embossing mold to be pressed to form anti-skid patterns, and then is completely vulcanized in the treatment at 100-140 ℃ for 1-2 h. The non-slip pattern may be pressed out only at the major gripping portion of the palm of the glove.
This process of extrusion antiskid line need go on after the prevulcanization with before the complete vulcanization, if gloves are by the complete vulcanization then can't extrude antiskid line, if on the contrary if not carry out the prevulcanization before the impressed watermark, then because the gluey face intensity is not enough, lead to gluey face damage, the glue film by problems such as impressed watermark mould adhesion.
In a second aspect, the present invention provides a high performance silicone glove prepared according to the above-described scheme of any of the embodiments.
(III) advantageous effects
(1) According to the preparation method, the surface treatment is firstly carried out on the yarn or the fiber glove blank by adopting the silane coupling agent, so that the fluorosilicone rubber and the fiber glove blank are connected by chemical bonds through the silane coupling agent, the binding force between the fluorosilicone rubber and the fiber glove blank is improved, and the durability of the silicone glove is improved.
The silane coupling agent is an ethanol solution of a vinyl silane coupling agent and a trifluoropropyl silane coupling agent, and the two coupling agents are compounded for use, so that the advantage is that vinyl in the vinyl silane coupling agent is used as a cross-linking point to react with a fluorosilicone rubber layer to generate chemical bond connection; the trifluoropropyl group in the trifluoropropyl silane coupling agent enables the sizing material and the glove blank of the yarn to be more compatible and the sizing material to be more firmly attached.
(2) The preparation method of the invention firstly impregnates the primary glue before formally forming the glue layer, the primary glue is the low-viscosity fluorosilicone rubber sizing material, and the primary glue has the following functions: the first glue and the first glue can completely infiltrate the glove blanks, a layer of glue film is formed on the surface, the yarns of the fiber glove blanks are bonded together to form an integral structure, and the performances of tearing resistance, cutting resistance, puncture resistance and the like of the glove products are improved. The second and first-time glue provides a homogeneous adhesion substrate for dipping the second-time glue (mainly forming the outer glue layer of the glove) with higher viscosity, and the bonding force of the glue layer on the surface of the glove blank is improved. The fiber glove blank is directly dipped with high-viscosity glue for two times, and the problems of difficult glue hanging, uneven glue hanging, less glue hanging and the like caused by overlarge glue material viscosity exist, and the problems directly cause that the glove product is unqualified, easy to remove glue and poor in durability.
(3) According to the preparation method, after the first rubber dipping, the rubber dripping drying and vulcanization treatment is carried out, after the second rubber dipping, the rubber dripping drying and vulcanization treatment (pre-vulcanization and complete vulcanization) is carried out again, the thickness of the total rubber layer on the surface of the glove blank is improved by the second rubber dipping, the strength, tear resistance, cutting resistance, puncture resistance, excellent hydrocarbon solvent resistance, oil resistance, acid and alkali resistance and the like of the glove are improved, and the problems of slow vulcanization, uneven rubber surface and the like of a thick rubber product are solved.
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail below with reference to specific embodiments.
Example 1
The embodiment provides a preparation method of a silica gel heat insulation glove, which comprises the following steps:
(1) yarn surface treatment
Preparing a surface treatment liquid, wherein the surface treatment liquid is an ethanol solution containing 2% (mass parts) of vinyl triethoxysilane coupling agent and 2% of trifluoropropyl triethoxysilane coupling agent. And (3) putting the 150D polyester yarn into the surface treatment liquid, and soaking and stirring for 4 hours at normal temperature.
(2) Woven glove blank
And (3) drying the polyester yarns treated in the step (1) and weaving the glove blanks. The weaving method of the glove blank comprises the following steps: 15-needle glove knitting machine, common knitting method; little finger (ring) 80, ring finger (ring) 110, middle finger (ring) 120, forefinger (ring) 108, little palm (ring) 54, thumb (ring) 86, big palm (ring) 52, wrist (ring) 90, glove embryo gram weight 33.2 g/pair.
(3) Compounding one-pass glue
Weighing 20 parts by mass of addition type liquid fluorosilicone rubber with the vulcanization hardness of 30 Share A, adding the addition type liquid fluorosilicone rubber into a planetary stirrer, adding ethyl acetate, fully stirring for 4 hours, testing the viscosity, and adjusting to a rubber material with the viscosity of about 1000 cp.
(4) Glue for soaking once
Sleeving the glove blanks prepared in the step (2) on a hand mold, enabling the hand mold to advance on a linkage line in parallel to reach a gum dipping area, rapidly rolling the hand mold under the driving of a conveyor belt, immersing the hand mold in the gum for one time, soaking for 2min, lifting the hand mold, and dropping liquid for 3 min; then the mixture enters an oven to be dried; and (3) taking out after 5min, sending into a drying oven with the temperature of 120 ℃ for drying for 40min, and then sending into a drying oven with the temperature of 140 ℃ for drying for 5 min.
(5) Preparing two-pass glue
Weighing 50 parts by mass of addition type liquid fluorosilicone rubber with the vulcanization hardness of 50 Share A, adding the addition type liquid fluorosilicone rubber into a planetary stirrer, adding ethyl acetate, fully stirring for 4 hours, testing the viscosity, and adjusting the viscosity to a rubber material with the viscosity of about 5000 cp.
(6) Dipping the mixture twice
Firstly, carrying out bubble removal treatment on the secondary glue prepared in the step (5), namely, connecting the opening of a glue containing groove of the secondary glue with negative pressure and ultrasonic treatment. The glove blanks continue to advance in parallel on the linkage line, move to the position above the glue groove for the second time of glue application, and adjust the angle of the hand mold relative to the horizontal plane, so that the fingertips of the hand mold are slowly immersed into the glue material for the second time and are slowly extracted, wherein the immersion time is 1 min; adjusting the angle of the hand mold relative to the horizontal plane to enable the hand mold to be vertical to the horizontal plane in the length direction and enable the finger tips to face downwards, and standing for 5min for glue dripping; through glue dripping, redundant liquid silica gel is dripped, and the gram weight of a product, the uniformity and the thickness of a silica gel layer are ensured; drying in a 70 ℃ oven for 60min for prevulcanization.
(7) Embossing
And (3) putting the pre-vulcanized gloves on a mould pressing plate with lines on the surface to press anti-skid lines, transferring the gloves into a drying oven at 120 ℃, and drying for 1.5h for further complete vulcanization.
Example 2
This example provides a method for preparing a silica gel heat-insulating glove, wherein steps (1) - (3) are the same as example 1, and the preparation method and viscosity of the two-pass adhesive of step (5) are the same as example 1. The rest steps are as follows:
(4) glue for soaking once
Sleeving the glove blanks prepared in the step (2) on a hand mold, enabling the hand mold to advance on a linkage line in parallel to reach a gum dipping area, rapidly rolling the hand mold under the driving of a conveyor belt, immersing the hand mold in the gum for one time, soaking for 2min, lifting the hand mold, and dropping liquid for 3 min; then the mixture enters an oven to be dried; and (3) taking out after 5min, sending into an oven with the temperature of 115 ℃ for drying for 40min, and then sending into an oven with the temperature of 145 ℃ for drying for 3 min.
(6) Dipping the mixture twice
Firstly, carrying out bubble removal treatment on the secondary glue prepared in the step (5), namely, connecting the opening of a glue containing groove of the secondary glue with negative pressure and ultrasonic treatment. The glove blanks continue to advance in parallel on the linkage line, move to the position above the glue groove for the second time of glue application, and adjust the angle of the hand mold relative to the horizontal plane, so that the fingertips of the hand mold are slowly immersed into the glue material for the second time and are slowly extracted, wherein the immersion time is 1 min; adjusting the angle of the hand mold relative to the horizontal plane to enable the hand mold to be vertical to the horizontal plane in the length direction and enable the finger tips to face downwards, and standing for 4min for glue dripping; through glue dripping, redundant liquid silica gel is dripped, and the gram weight of a product, the uniformity and the thickness of a silica gel layer are ensured; drying for 90min in an oven at 60 ℃ for prevulcanization.
(7) Embossing
And (3) putting the pre-vulcanized gloves on a mould pressing plate with lines on the surface to press anti-skid lines, transferring the gloves into an oven at 140 ℃, and drying for 1 hour for further complete vulcanization.
Example 3
This example provides a method for preparing a silica gel heat-insulating glove, wherein steps (1) - (3) are the same as example 1, and the preparation method and viscosity of the two-pass adhesive of step (5) are the same as example 1. The rest steps are as follows:
(4) glue for soaking once
Sleeving the glove blanks prepared in the step (2) on a hand mold, enabling the hand mold to advance on a linkage line in parallel to reach a gum dipping area, rapidly rolling the hand mold under the driving of a conveyor belt, immersing the hand mold in the gum for one time, soaking for 2min, lifting the hand mold, and dropping liquid for 3 min; then the mixture enters an oven to be dried; and (3) taking out after 5min, sending into an oven with the temperature of 125 ℃, drying for 35min, and then sending into an oven with the temperature of 130 ℃, and drying for 8 min.
(6) Dipping the mixture twice
Firstly, carrying out bubble removal treatment on the secondary glue prepared in the step (5), namely, connecting the opening of a glue containing groove of the secondary glue with negative pressure and ultrasonic treatment. The glove blanks continue to advance in parallel on the linkage line, move to the position above the glue groove for the second time of glue application, and adjust the angle of the hand mold relative to the horizontal plane, so that the fingertips of the hand mold are slowly immersed into the glue material for the second time and are slowly extracted, wherein the immersion time is 1 min; adjusting the angle of the hand mold relative to the horizontal plane to enable the hand mold to be vertical to the horizontal plane in the length direction and enable the finger tips to face downwards, and standing for 10min for glue dripping; through glue dripping, redundant liquid silica gel is dripped, and the gram weight of a product, the uniformity and the thickness of a silica gel layer are ensured; drying in an oven at 80 deg.C for 30min for prevulcanization.
(7) Embossing
And (3) putting the pre-vulcanized gloves on a mould pressing plate with lines on the surface to press anti-skid lines, transferring the gloves into a drying oven at 100 ℃, and drying for 2.5 hours for further complete vulcanization.
Example 4
In this example, the vinyltriethoxysilane coupling agent in step (1) was changed to vinyltrimethoxysilane coupling agent based on example 1. The remaining steps and conditions were referenced to example 1.
Example 5
In this example, on the basis of example 1, the concentration of the vinyltriethoxysilane coupling agent in step (1) is reduced to 1%, and the concentration of the trifluoropropyltriethoxysilane coupling agent is increased to 3%. The remaining steps and conditions were referenced to example 1.
Example 6
In this embodiment, on the basis of embodiment 1, the "addition type liquid fluorosilicone rubber" prepared in step (3) is changed to a high temperature curing fluorosilicone rubber with equal hardness. The remaining steps and conditions were referenced to example 1.
Example 7
In this example, the solvent for diluting the once-diluted glue prepared in step (3) is changed from ethyl acetate to butyl acetate based on example 1.
Example 8
In this example, the viscosity of the primary rubber compound in step (3) is adjusted to 2000cp based on example 1; and (3) simultaneously adjusting the viscosity of the sizing material of the second time in the step (5) to 6000 cp. The remaining steps and conditions were referenced to example 1.
Example 9
In this example, the viscosity of the primary rubber compound in step (3) is adjusted to 2000cp based on example 1; and (3) simultaneously adjusting the viscosity of the sizing material of the second time in the step (5) to 4000 cp. The remaining steps and conditions were referenced to example 1.
Example 10
In this embodiment, on the basis of embodiment 1, the vulcanization hardness of the liquid fluorosilicone rubber prepared in step (3) is changed from 30 (shore a hardness) to 20, and the amount of the liquid fluorosilicone rubber is not changed; and meanwhile, the vulcanization hardness of the liquid fluorosilicone rubber prepared in the step (5) for the second time is changed from 50 (Shaoer A hardness) to 70, and the dosage is unchanged. The remaining steps and conditions were referenced to example 1.
Example 11
In this embodiment, on the basis of embodiment 1, the vulcanization hardness of the liquid fluorosilicone rubber prepared in step (3) is changed from 40 (shore a hardness) to 20, and the amount of the liquid fluorosilicone rubber is not changed; and meanwhile, the vulcanization hardness of the liquid fluorosilicone rubber prepared in the step (5) for the second time is changed from 50 (Shaoer A hardness) to 30, and the dosage is unchanged. The remaining steps and conditions were referenced to example 1.
Example 12
In this example, on the basis of example 1, a glove blank was first woven in the same manner as in step (2) of example 1, and then the glove blank was soaked in the surface treatment solution containing the silane coupling agent for 4 hours in the same manner as in step (1) of example 1. The remaining steps and conditions were referenced to example 1.
In addition, in order to investigate the influence of the steps and conditions of the present invention on the glove quality, the following comparative examples were obtained by further changing part of the conditions.
Comparative example 1
In the comparative example, step (1) is removed from example 1, and the glove blank is directly woven by using the terylene 150D yarn which is not treated by the surface treatment solution. The remaining steps and conditions were referenced to example 1.
Comparative example 2
This comparative example is based on example 1, where the glove blank is not dipped once but directly into a high viscosity two-pass glue. The remaining steps and conditions were referenced to example 1.
Comparative example 3
In this comparative example, the yarn was not treated with the surface treatment solution of silane coupling agent based on example 1, and the glove blank was not dipped with the adhesive once but directly with the adhesive having high viscosity twice. The remaining steps and conditions were referenced to example 1.
Comparative example 4
This comparative example is based on example 1, the glove blank was not dipped twice with glue. The remaining steps and conditions were referenced to example 1.
Comparative example 5
In the comparative example, the viscosity of the secondary rubber compound prepared in the step (5) is adjusted to be the same as that of the primary rubber compound, and is 1000cp on the basis of the example 1. The remaining steps and conditions were referenced to example 1.
Comparative example 6
This comparative example was conducted by removing the trifluoropropyltriethoxysilane coupling agent from step (1) and adjusting the concentration of the vinyltriethoxysilane coupling agent to 4% based on example 1. The remaining steps and conditions were referenced to example 1.
The performance of the silicone gloves produced in the above examples and comparative examples was tested and the results are shown in tables 1 and 2.
TABLE 1
Figure BDA0003162918180000111
Figure BDA0003162918180000121
According to the test results in the above table, if the yarns are not treated with the silane coupling agent, the abrasion resistance and wearing resistance of the silicone gloves are significantly reduced, and the cutting resistance, puncture resistance and tear resistance of the gloves are also affected.
In example 8, the viscosity values of the primary rubber material and the secondary rubber material are respectively improved, and the abrasion resistance, the cutting resistance and the puncture resistance of the prepared silicone-fluorine rubber gloves are better than those of other examples. Example 9 increased the liquid fluorosilicone rubber hardness value (70 Shore A hardness) for the two pass compound, example 10 decreased the liquid fluorosilicone rubber hardness value (30 Shore A hardness) for the two pass compound, and the gloves from example 9 were superior to example 10 in abrasion resistance, cut resistance, tear resistance, puncture resistance, and the like.
TABLE 2
Figure BDA0003162918180000131
Figure BDA0003162918180000141
From the test results in the above table, it can be seen that example 11 is closer to example 1 in terms of glove performance. In contrast, in the glove production of comparative example 2, the glove blank was directly dipped twice without being dipped once with the size, and compared with other examples, the glove was inferior in abrasion resistance, cutting resistance, tear resistance, puncture resistance and wearing resistance, which is mainly caused by the reason that the fluorosilicone rubber size with high viscosity for twice could not well infiltrate the glove blank and adhere to the glove blank. In comparative example 3, where the yarn was not surface treated and was not impregnated with glue once, the glove produced was further deteriorated in properties as compared to comparative example 2.
Comparative example 4 did not impregnate the high viscosity fluorosilicone rubber stock twice, and comparative example 5 impregnated the stock twice with the same viscosity as the stock once. In comparative example 4, the viscosity of the rubber material for the first time is very low, only a thin layer of rubber can be hung after the glove blank is dipped, and after the glove blank is completely vulcanized in the later period, although the silica gel glove has acid and alkali resistance, the wear resistance, cutting resistance, tear resistance and puncture resistance are obviously poor. In comparative example 5, the viscosity of the first and second adhesive is low (1000cp), the whole glove has less adhesive coating, the adhesive layer is thin, and the wear resistance, cutting resistance, tear resistance and puncture resistance of the glove are slightly better than those of comparative example 4, but are obviously lower than those of other examples of the invention.
In comparative example 6, the yarn is treated by using the silane coupling agent, but the surface treatment solution of the yarn removes the 'trifluoropropyltriethoxysilane coupling agent', the coupling agent has an important effect of promoting connection on the silicon-fluorine rubber material, and after the coupling agent is removed, the bonding performance of the yarn on the liquid silicon-fluorine rubber material is weakened, so that the service performance of the glove product is poor, the durability is weakened, and the glove performance is still better than that of comparative example 1.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. A preparation method of high-performance silica gel gloves is characterized by comprising the following steps:
s1, processing the glove blank yarns: adopting a silane coupling agent to carry out surface treatment on the yarns, and weaving a glove blank by using the yarns subjected to the surface treatment; or weaving a glove blank by using yarns, and then carrying out surface treatment on the glove blank by using a silane coupling agent;
s2, soaking the glue for one time: preparing a low-viscosity fluorosilicone rubber material with the viscosity of 1000-2000cp, dipping a glove blank into the low-viscosity fluorosilicone rubber material, taking out the glove blank, dripping the rubber, drying until the rubber material on the surface does not flow, and performing vulcanization treatment to obtain the glove blank of which the surface is covered with a layer of fluorosilicone rubber film;
s3, dipping the glue for two times: preparing a high-viscosity fluorosilicone rubber material with the viscosity of 4000-;
s4, vulcanization: low-temperature pre-vulcanization is carried out firstly, and then high-temperature complete vulcanization is carried out to obtain the high-performance silica gel gloves.
2. The method of claim 1, wherein in the step of treating the surface of the yarn or glove blank with the silane coupling agent in the step of S1, the yarn or glove blank is immersed in an ethanol solution containing the vinyl silane coupling agent and the trifluoropropyl silane coupling agent.
3. The method according to claim 2, wherein in S1, the vinyl silane coupling agent is a vinyltrimethoxysilane coupling agent, a vinyltriethoxysilane coupling agent, or a vinyltriacetoxysilane coupling agent; the trifluoropropyl silane coupling agent is trifluoropropyl triethoxysilane coupling agent.
4. The method as claimed in claim 1, wherein in S2, when preparing the low viscosity fluorosilicone rubber compound, a two-component liquid fluorosilicone rubber or a high temperature cured fluorosilicone rubber is used, and a diluent solvent is added to adjust the viscosity to 1000-2000 cp; the diluting solvent is acetone, ethyl acetate or butyl acetate.
5. The method of claim 1 or 4, wherein the vulcanized silicone rubber used to formulate the low viscosity fluorosilicone rubber stock at S2 has a Shore A durometer of 20-40.
6. The method as claimed in claim 1, wherein in S2, the glove blank is dipped into the low viscosity fluorosilicone rubber material and soaked for 1-3min, then taken out, dropped for 2.5-3.5min, put into an oven and dried for 4-6min, then taken out, put into an oven at 125 ℃ for 20-40min, and finally put into an oven at 145 ℃ for 3-8 min.
7. The method as claimed in claim 1, wherein in S3, when preparing the high viscosity fluorosilicone rubber compound, the two-component liquid fluorosilicone rubber or high temperature cured fluorosilicone rubber is used, and a diluent solvent is added to adjust the viscosity to 4000-6000 cp; the diluting solvent is acetone, ethyl acetate or butyl acetate; the vulcanized rubber hardness of the fluorosilicone rubber used for preparing the high-viscosity fluorosilicone rubber compound is 30-70 Shore A hardness.
8. The method according to claim 1, wherein in S4, the conditions of low-temperature prevulcanization are as follows: treating at 60-80 deg.C for 30-90 min; the high-temperature vulcanization conditions are as follows: treating at 100-140 deg.c for 1-2.5 hr.
9. The preparation method of claim 1, wherein in S4, after the glove is processed at 60-80 ℃ for 30-90min, the glove at the moment is put into an embossing die to be pressed to form the antiskid lines, and then is processed at 100-140 ℃ for 1-2.5h to be completely vulcanized.
10. A high performance silica gel glove produced by the production method according to any one of claims 1 to 9.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113881073A (en) * 2021-10-28 2022-01-04 世目特种防护用品科技（江苏）有限公司 Silica gel gloves and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106617402A (en) * 2017-01-06 2017-05-10 广州市聚吉科绿色化学共性技术研究院有限公司 Fluoroether/fluorosilicone composite rubber glove and preparing method thereof
CN112048917A (en) * 2020-09-03 2020-12-08 山东星宇手套有限公司 Preparation method of double-layer butyl chemical-resistant gloves with linings

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106617402A (en) * 2017-01-06 2017-05-10 广州市聚吉科绿色化学共性技术研究院有限公司 Fluoroether/fluorosilicone composite rubber glove and preparing method thereof
CN112048917A (en) * 2020-09-03 2020-12-08 山东星宇手套有限公司 Preparation method of double-layer butyl chemical-resistant gloves with linings

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
张峥等: "氟硅橡胶与聚酯织物的粘接研究", 《粘接》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113881073A (en) * 2021-10-28 2022-01-04 世目特种防护用品科技（江苏）有限公司 Silica gel gloves and preparation method thereof

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