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CN111421729A - Preparation method of butyronitrile microporous breathable foamed gloves - Google Patents

Preparation method of butyronitrile microporous breathable foamed gloves Download PDF

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Publication number
CN111421729A
CN111421729A CN202010249821.4A CN202010249821A CN111421729A CN 111421729 A CN111421729 A CN 111421729A CN 202010249821 A CN202010249821 A CN 202010249821A CN 111421729 A CN111421729 A CN 111421729A
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China
Prior art keywords
foaming
butyronitrile
mass
parts
agent
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Granted
Application number
CN202010249821.4A
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Chinese (zh)
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CN111421729B (en
Inventor
周海涛
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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    • 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
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/14—Dipping a core
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0028—Use of organic additives containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/30—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/48—Wearing apparel
    • B29L2031/4842—Outerwear
    • B29L2031/4864—Gloves
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2309/02—Copolymers with acrylonitrile
    • C08J2309/04—Latex
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2401/08—Cellulose derivatives
    • C08J2401/26—Cellulose ethers
    • C08J2401/28—Alkyl ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2489/00—Characterised by the use of proteins; Derivatives thereof
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • 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
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide
    • 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
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • 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
    • C08K3/02—Elements
    • C08K3/06—Sulfur
    • 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
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C08K5/31—Guanidine; Derivatives thereof
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3437—Six-membered rings condensed with carbocyclic rings
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The invention relates to a preparation method of butyronitrile microporous breathable foamed gloves, which comprises the following steps: s1, infiltrating the glove embryo with coagulant; s2, dip-coating butyronitrile pre-vulcanized foam rubber slurry on the glove blank, homogenizing the glove blank, and hanging a layer of butyronitrile pre-vulcanized foam rubber on the surface of the glove blank; s3 immersing in a foaming surface treating agent prepared as follows: adding 0.5-3 parts by mass of thickening agent and 0.5-5 parts by mass of surfactant into 100 parts by mass of water, foaming, wherein the foaming ratio is 1.5-8 times, and adjusting the viscosity to 800-2500 mpa.s; and S4, vulcanizing and drying to obtain the butyronitrile microporous breathable foamed glove. According to the preparation method, the butyronitrile foaming gloves with a plurality of micro air holes on the surfaces can be obtained by designing the special foaming surface treating agent and the process flow, so that the damp and hot feeling of wearing the gloves is reduced; compared with the prior art, the invention is simpler, saves more water and reduces the waste of rubber materials.

Description

Preparation method of butyronitrile microporous breathable foamed gloves
Technical Field
The invention relates to the technical field of coating gloves, in particular to a preparation method of butyronitrile microporous breathable foamed gloves.
Background
The nitrile rubber gloves have excellent water resistance, chemical corrosion resistance and oil resistance, and are more and more widely applied to the aspects of glove preparation and the like. But the nitrile rubber texture is relatively harder, and the gas permeability is relatively poor, and the wearing property (flexibility and comfort) of the nitrile rubber gloves is poor and the use experience is poor due to the superposition of the two reasons. In addition, nitrile rubber gloves are hard and smooth on their surface, which also results in less than ideal slip resistance when gripping articles. Therefore, it is necessary to treat nitrile rubber gloves to improve their wearability and anti-slip properties. At present, in the prior art, a plurality of fine water beams are sprayed on the surface of a non-solidified foaming butyronitrile rubber cement coating, part of rubber cement is washed off by the water beams, and then a plurality of breathable micropores are formed on a rubber layer after vulcanization and drying. Although such an approach is feasible, there are some problems, mainly including: 1) the water consumption is high, and the used water contains butyronitrile latex and some auxiliaries, so that the water quality is polluted. 2) Much of the glue is flushed away and wasted. 3) The pores formed are often large, the pore size is difficult to control, and the uniformity is poor.
Disclosure of Invention
Technical problem to be solved
In view of the defects and shortcomings of the prior art, the invention provides the preparation method of the butyronitrile microporous breathable foamed gloves, which does not use water spraying, can save water resources, reduce water pollution and waste of rubber materials, and can obtain the butyronitrile foamed gloves with soft texture and fine breathable holes.
(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 butyronitrile microporous breathable foamed gloves, which comprises the following steps:
s1, infiltrating coagulant: heating the glove blank to 40-55 ℃, and infiltrating a pre-prepared coagulant;
s2, dip-coating butyronitrile pre-vulcanized foam rubber slurry on the glove blank, homogenizing the glove blank, and hanging a layer of butyronitrile pre-vulcanized foam rubber on the surface of the glove blank;
s3, soaking the fabric into a foaming type surface treating agent, wherein the foaming type surface treating agent is prepared by the following method: taking 100 parts by mass of water, adding 0.5-3 parts by mass of thickening agent and 0.5-5 parts by mass of surfactant, foaming, wherein the foaming multiple is 1.5-8 times, and adjusting the viscosity to 800-2500 mpa.s;
because the foaming surface treating agent is internally filled with foam holes, after the foaming surface treating agent is soaked, part of the butyronitrile pre-vulcanized foaming adhesive on the surface of the glove blank is washed away by the foaming surface treating agent, and the washed away part is distributed in a star-point dispersed manner;
and S4, vulcanizing and drying to obtain the butyronitrile microporous breathable foamed glove.
In step S3, the foaming surface treatment agent is foamed to a proper foaming ratio, the foaming surface treatment agent is filled with bubbles/holes, when the glove blank with the butyronitrile pre-vulcanized foam rubber is immersed in the foaming surface treatment agent, the butyronitrile pre-vulcanized foam rubber on the surface of the glove blank is washed away, and the washed away portions are distributed in star points and form air holes after vulcanization and drying.
The viscosity and the expansion ratio of the foaming surface treatment agent determine the density of pore formation. Generally, the larger the expansion ratio, the more sparse the pores, and conversely, the denser the pores. Therefore, the foaming ratio of the foaming surface treatment agent needs to be properly controlled to control the formation of reasonable pores. In addition, the water phase with excessive viscosity and no foaming can cause the nitrile butadiene pre-vulcanized foam rubber which is not completely solidified on the surface of the glove blank to be eluted in a large spot shape, and the rubber layer strength is possibly low, so that the protective effect is lost. Therefore, the foaming surface treatment agent must be foamed and the viscosity should be controlled.
In summary, the distribution density and air permeability of the air holes on the finished butyronitrile foaming glove can be adjusted by adjusting the foaming ratio and the viscosity of the foaming surface treating agent, and the pore size of the air holes is mainly related to the viscosity of the butyronitrile pre-vulcanized foaming adhesive cement in the step S2, the viscosity of the foaming surface treating agent in the step S3 and other factors. Generally, the larger the viscosity of the nitrile pre-vulcanized foam cement of S2, the smaller the pores formed, whereas the larger the pores formed, and the more excessive the viscosity, the less the pores formed.
According to a preferred embodiment of the present invention, wherein: in step S1, the coagulant is a water/alcohol solution of calcium chloride, a water/alcohol solution of calcium nitrate, or a water/alcohol solution of zinc chloride, and the alcohol is liquid alcohol at room temperature such as methanol, ethanol, propanol, or the like.
Preferably, the coagulant comprises 100 parts of methanol, ethanol or water, and 2-10 parts of calcium nitrate, calcium chloride or zinc chloride. According to the invention, the glove blank is soaked with the coagulant in advance, so that a part of the rubber cement can be fixed when the butyronitrile pre-vulcanized foaming rubber cement in the step S2 is soaked.
According to a preferred embodiment of the present invention, wherein: in the step S2, the butyronitrile pre-vulcanized foam cement is prepared as follows:
uniformly mixing 90-120 parts by mass of butyronitrile latex, 0.5-5 parts by mass of a vulcanizing agent, 0.3-4 parts by mass of an active agent, 0.3-3 parts by mass of a vulcanization accelerator and 0.5-2 parts by mass of an anti-aging agent to obtain a butyronitrile pre-vulcanized rubber cement mother solution;
taking 90-120 parts by mass of the butyronitrile pre-vulcanized rubber cement mother liquor and 0.5-5 parts by mass of a foaming agent, uniformly stirring and foaming to ensure that the foaming multiple is 1.1-2.5 times; adding 0.5-4 parts by mass of thickening agent, and adjusting the viscosity to 1000-5500mpa.s to prepare the butyronitrile pre-vulcanized foam rubber slurry required by the step S2.
Preferably, the foaming agent is one or a combination of more of potassium oleate, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, potassium laurate, AC and OBSH.
Preferably, the thickening agent can be one or more of CMC, sodium polyacrylate, casein, PVA, hydroxymethyl ethyl cellulose and hydroxyethyl propyl cellulose.
According to a preferred embodiment of the present invention, wherein: in step S2, the vulcanization accelerator is one or a combination of two or more of dithiocarbamates, thiurams, thiazoles, guanidines, thioureas, and the like;
the vulcanizing agent is one or more of sulfur, zinc oxide, magnesium oxide and other metal oxide vulcanizing agents;
the active agent is one or any combination of the zinc oxide, the magnesium oxide, the zinc carbonate and the zinc stearate;
the anti-aging agent is one or a combination of monophenol, polyphenol anti-aging agent, anti-aging agent RD and anti-aging agent 264.
According to a preferred embodiment of the present invention, wherein: the viscosity of the butyronitrile pre-vulcanized foaming adhesive cement in the step S2 is 1500-2500 mpa.s. The viscosity determines the hanging amount, the viscosity of the butyronitrile pre-vulcanized foaming adhesive cement cannot be too small, otherwise, the hanging amount on the surface of a glove blank is too small, and the leakage of an adhesive layer is easily caused; and the glue is difficult to be homogenized when the viscosity is too high, glove products with uniform glue layer thickness are not easy to be prepared, the gloves are harder when the glue layer thickness is larger, the wearing performance is not very good, and air holes are not easy to form when the viscosity is too high. If the non-foamed nitrile rubber cement is used in step S2, and there are no air holes in the uncured nitrile rubber layer, it is difficult to form fine air holes in the glove rubber layer by using the same process, and the non-foamed nitrile rubber glove has a relatively hard texture and poor wearing comfort. Therefore, in step S2 of the present invention, the foamed butyronitrile pre-vulcanized rubber cement is used to replace the non-foamed butyronitrile pre-vulcanized rubber cement.
According to a preferred embodiment of the present invention, wherein: the thickener used in step S3 is one or a combination of several of CMC, sodium polyacrylate, casein, PVA, hydroxymethylethylcellulose and hydroxyethylpropylcellulose.
According to a preferred embodiment of the present invention, wherein: the surfactant used in step S3 is one or a combination of several of an anionic surface foaming agent, a cationic surfactant and an amphoteric surfactant. The anionic surfactant is one or a combination of more of dioctyl sodium sulfosuccinate, sodium alkenyl sulfonate, sodium hexadecyl sulfate, sodium octadecyl sulfate, sodium dodecyl benzene sulfonate, peregal and the like.
According to a preferred embodiment of the present invention, wherein: in step S3, the foaming ratio of the foaming surface treatment agent is 2.5-5 times, and the viscosity is 800-1500 mpa.s.
According to a preferred embodiment of the present invention, wherein: in step S4, low-temperature pre-vulcanization drying is performed first, and then high-temperature vulcanization is performed. Preferably, the low-temperature vulcanization temperature is 70-100 ℃, and the time is 10-40 min; the high-temperature vulcanization temperature is 100 ℃ and 140 ℃, and the time is 1-4 h.
The vulcanizing and drying are divided into two stages: because the latex film forming process is slow and needs to be carried out through a close packing process, if high-temperature vulcanization is used at the beginning, the surface of a product can be quickly formed into a film and is compact, the surface of the product can be easily bulged and exploded, and serious product defects are caused, so that the low-temperature vulcanization (less than or equal to 95 ℃) needs to be carried out for about 20-30 minutes, the product is easier to process, and the defects are avoided; then high-temperature vulcanization (not less than 100 ℃) is carried out for more than 60 minutes, and the use performance and the production standard of the product are achieved.
(III) advantageous effects
The invention soaks the coagulant in the glove blank in advance, then soaks the butyronitrile prevulcanization mucilage which is frothed in advance, can fix a part of sizing material quickly after the glue is homogenized, then soaks the glove blank into the special designed foaming type surface treating agent which is different from the treating fluid of the continuous medium, the inside of the foaming type surface treating agent is full of big and small holes, when the glove blank whose surface is coated with glue is soaked into the foaming type surface treating agent, the butyronitrile glue on the surface of the glove blank is washed off a part in a star point shape, then the 'spot' which is washed off by the glue forms the air hole of the butyronitrile foaming glove after the vulcanization and drying treatment.
According to the preparation method of the butyronitrile microporous breathable foamed gloves, the butyronitrile foamed gloves with the micro air holes on the surfaces can be obtained by designing the special foaming type surface treating agent and the process flow, so that the wearing suffocation and the moist heat feeling are reduced. Compared with the existing preparation process adopting water jet, the method has the advantages of simpler process, more water saving and less waste of sizing material. And more importantly, the process can control the distribution density of the air holes on the butyronitrile microporous breathable foamed gloves. In addition, the butyronitrile microporous breathable gloves prepared by the invention have better wearability, softness and skid resistance.
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.
The invention provides a preparation method of butyronitrile microporous breathable foamed gloves, which comprises the following steps:
s1: pretreating a glove embryo infiltration coagulant:
firstly, the glove blank is soaked with a coagulant so as to quickly fix a part of rubber material in the next gum dipping. The coagulant is water/alcohol solution of calcium chloride, calcium nitrate or zinc chloride, the alcohol is liquid alcohol at normal temperature such as methanol, ethanol, propanol, etc., and the glove blank temperature is 40-55 ℃ when the coagulant is soaked. Preferably, the coagulant comprises 100 parts of methanol, ethanol or water, and 2-10 parts of calcium nitrate, calcium chloride or zinc chloride.
S2, dip-coating butyronitrile pre-vulcanized foam rubber slurry on the glove blank, homogenizing the rubber, and hanging a layer of butyronitrile pre-vulcanized foam rubber on the surface of the glove blank.
The butyronitrile pre-vulcanized foaming adhesive cement is prepared in the following way:
step 1: uniformly mixing 90-120 parts by mass of butyronitrile latex, 0.5-5 parts by mass of a vulcanizing agent, 0.3-4 parts by mass of an active agent, 0.3-3 parts by mass of a vulcanization accelerator and 0.5-2 parts by mass of an anti-aging agent to obtain the butyronitrile pre-vulcanized rubber cement mother liquor.
Step 2: taking 90-120 parts by mass of the butyronitrile pre-vulcanized rubber cement mother liquor and 0.5-5 parts by mass of a foaming agent, uniformly stirring and foaming to ensure that the foaming multiple is 1.1-2.5 times; adding 0.5-4 parts by mass of a thickening agent, and adjusting the viscosity to 1000-5500mpa.s to prepare the butyronitrile pre-vulcanized foam cement.
Wherein the foaming agent is one or more of potassium oleate, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, potassium laurate, AC and OBSH. Wherein the thickener can be one or more of CMC, sodium polyacrylate, casein, PVA, hydroxymethyl ethyl cellulose, and hydroxyethyl propyl cellulose.
S3, soaking the raw materials into a foaming type surface treating agent, wherein the foaming type surface treating agent is prepared by the following method:
taking 100 parts by mass of water, adding 0.5-3 parts by mass of thickening agent and 0.5-5 parts by mass of surfactant, foaming, wherein the foaming ratio is 1.5-8 times, and adjusting the viscosity to 800-2500 mpa.s.
After the foaming type surface treating agent is impregnated, thickening agents containing water and air bubbles are stained on the butyronitrile pre-vulcanized foaming glue on the surface of the glove blank.
The thickener can be one or more of CMC, sodium polyacrylate, casein, PVA, hydroxymethyl ethyl cellulose, and hydroxyethyl propyl cellulose. Wherein the surfactant is one or more of anionic surface foaming agent, cationic surfactant and amphoteric surfactant. The surfactant has a foaming function and can be foamed by physical mechanical stirring. The anionic surfactant is one or a combination of more of dioctyl sodium sulfosuccinate, sodium alkenyl sulfonate, sodium hexadecyl sulfate, sodium octadecyl sulfate, sodium dodecyl benzene sulfonate, peregal and the like.
Wherein, the foaming times of the foaming surface treating agent prepared in the step are 2.5-5 times, and the viscosity is 800-1500 mpa.s. The amount of the foaming agent, the foaming temperature and the foaming time can be controlled, so that the foaming multiple meets the requirement.
And S4, vulcanizing and drying to obtain the butyronitrile microporous breathable foamed glove.
Preferably, the low-temperature prevulcanization drying temperature is 70-100 ℃ for 10-40 min; the high-temperature curing temperature is 100-140 ℃ and the time is 60-240 min.
Wherein, the auxiliary agents in the precured rubber cement mother liquor in the S1 have the following characteristics:
the vulcanization accelerator is one or a combination of more than two of dithiocarbamates, thiurams, thiazoles, guanidines, thioureas and the like. Specifically, the vulcanization accelerator is an accelerator D (diphenylguanidine C)13H13N3) DM (dibenzothiazyl disulfide C)14H8N2S4) DETU (diethyl thiourea C)5H12N2S), DPG (1, 3-diphenylguanidine), M (2-mercaptobenzothiazole C7H5NS2) TMTD (thiuram C)6H12N2S4) BZ (zinc dibutyldithiocarbamate C)18H36N2S4Zn), PZ (Zinc dimethyldithiocarbamate C)6H12N2S4Zn), TP (sodium dibutyldithiocarbamate C18H36N2S4Na2) zDC (zinc diethyldithiocarbamate C)10H20N2S4Zn), and CZ (N-cyclohexyl-2-benzothiazolesulfenamide C)13H16N2S2) One or any combination of the foregoing.
The vulcanizing agent is one or more of sulfur, zinc oxide, magnesium oxide and other metal oxide vulcanizing agents. The metal oxide vulcanizing agent has the advantages of quick vulcanization starting, good flat vulcanization curve, good heat resistance and aging resistance of vulcanized rubber and the like.
The active agent is one or more of zinc oxide, zinc carbonate and zinc stearate. The active agents can be used alone or in combination. Activating agent such as zinc oxide, zinc stearate, and zinc carbonate for promoting growthThe formation of covalent bonds or ionic bonds of polymer molecular chains helps to play a role of bridging among linear molecules, so that a plurality of linear molecules are mutually bonded and crosslinked into a network structure. Therefore, the rubber of the product has better performances of abrasion resistance, chemical resistance and the like through the auxiliary effect of the active agent. The function of the active agent in the mucilage mainly comprises (1) activating a vulcanization system; (2) the crosslinking density of the vulcanized rubber is improved; (3) the aging resistance of the vulcanized rubber is improved. In addition, the activator can fully exert the function of an organic accelerator, and the dosage is reduced/the vulcanization time is shortened. Wherein the activator ZnO2The effect is, besides the vulcanization activity, also a vulcanizing agent/reinforcing/compatibilizing effect.
The anti-aging agent is one or a combination of monophenol, polyphenol anti-aging agent, anti-aging agent RD and anti-aging agent 264. The anti-aging agent is used for delaying the aging speed of rubber. When the concentration of the anti-aging agent added into the rubber is too low, the anti-aging performance of the rubber is not affected. With the increase of the concentration of the anti-aging agent, the performance of the anti-aging agent can be improved. In order to make the anti-aging agent exert anti-aging performance, the concentration of the anti-aging agent is within a certain boundary, but the anti-aging performance is not improved when the concentration reaches the highest limit.
In accordance with the teachings of the present invention, the following description is provided in connection with the preferred embodiment.
Example 1
The embodiment provides a preparation method of butyronitrile microporous breathable foamed gloves, which comprises the following steps:
(1) 100 parts by mass of butyronitrile latex, 1 part by mass of vulcanization accelerator BZ, 1.5 parts by mass of zinc oxide (active agent), 1.5 parts by mass of sulfur and 2641 parts by mass of anti-aging agent are uniformly mixed to obtain the butyronitrile pre-vulcanized rubber cement mother liquor.
(2) And taking 100 parts by mass of the pre-vulcanized rubber cement mother liquor, adding 1.5 parts by mass of foaming agent sodium dodecyl sulfate and 2 parts by mass of 2% CMC, adjusting the foaming times to 1.5 and the viscosity to 4000mpa.s to obtain the butyronitrile pre-vulcanized foamed rubber cement.
(3) Preparing a foaming surface treating agent: 100 parts of water, 4 parts of surfactant sodium alkenyl sulfonate and 0.5 part of 2% CMC, wherein the foaming ratio is 5.5, and the viscosity is 1200 mpa.s.
(4) Sleeving a 13 knitted glove blank on a glove mold, preheating to 40-55 ℃, and infiltrating the glove blank with a pre-prepared coagulant, wherein the coagulant is a methanol solution of 2 wt% of calcium nitrate.
(5) And (3) after taking out the coagulant, dipping the butyronitrile pre-vulcanized foam rubber cement in the step (2), and after the gum dipping is finished, homogenizing for 20 seconds, wherein at the moment, a part of the butyronitrile pre-vulcanized foam rubber cement is fixed.
(6) Soaking the mixture into the foaming surface treating agent prepared in the step (3), and taking out; at this time, the foaming surface treating agent has a certain viscosity and the interior of the foaming surface treating agent is filled with air holes, so that a part of the butyronitrile foaming rubber cement on the surface of the glove blank is washed off in a star point shape.
(7) And (3) vulcanization and drying: and (3) drying for 30 minutes at 90 ℃, raising the temperature to 120 ℃, and drying for 2 hours to obtain the butyronitrile microporous breathable foamed gloves.
The butyronitrile micropore air-permeable foaming glove prepared by the embodiment has the advantages that superfine air holes are formed on the surface, the suffocating feeling and the damp-heat feeling of wearing the butyronitrile glove can be improved, and the air-permeable function is increased. In addition, the antiskid performance and the wearability of the butyronitrile rubber layer are also improved.
Example 2
The embodiment provides a preparation method of butyronitrile microporous breathable foamed gloves, which comprises the following steps:
(1) uniformly mixing 110 parts by mass of butyronitrile latex, 2 parts by mass of vulcanization accelerator D, 1.5 parts by mass of zinc oxide (active agent), 1.5 parts by mass of magnesium oxide and 1 part by mass of anti-aging agent RD to obtain the butyronitrile pre-vulcanized rubber cement mother liquor.
(2) And (3) taking 100 parts by mass of the pre-vulcanized rubber cement mother liquor, adding 1.5 parts by mass of foaming agent sodium dodecyl sulfate and 1 part by mass of casein, adjusting the foaming ratio to 1.5 and the viscosity to 2000mpa.s to obtain the butyronitrile pre-vulcanized foaming rubber cement.
(3) Preparing a foaming surface treating agent: 100 parts of water, 3 parts of surfactant sodium dodecyl benzene sulfonate, 1 part of 2% CMC, 4 of foaming times and 1400mpa.s of viscosity.
(4) Sleeving a 13 knitted glove blank on a glove mold, preheating to 45-50 ℃, and infiltrating the glove blank with a pre-prepared coagulant, wherein the coagulant is a methanol solution of 2 wt% of calcium chloride.
(5) And (3) after taking out the butyronitrile pre-vulcanized foam rubber slurry from the coagulant, dipping the butyronitrile pre-vulcanized foam rubber slurry in the step (2), and after the gum dipping is finished, homogenizing for 20 seconds, wherein a part of the butyronitrile pre-vulcanized foam rubber slurry is fixed.
(6) Then soaking the mixture into the foaming surface treating agent prepared in the step (3), and taking out; at this time, the foaming surface treating agent has a certain viscosity and the interior of the foaming surface treating agent is filled with air holes, so that a part of the butyronitrile foaming rubber cement on the surface of the glove blank is washed off in a star point shape.
(7) And (3) vulcanization and drying: drying at 80 ℃ for 40 minutes, raising the temperature to 110 ℃, and drying for 2.5 hours to obtain the butyronitrile microporous breathable foamed gloves.
Example 3
The embodiment provides a preparation method of butyronitrile microporous breathable foamed gloves, which comprises the following steps:
(1) uniformly mixing 110 parts by mass of butyronitrile latex, 3 parts by mass of vulcanization accelerator MD, 1 part by mass of zinc carbonate, 3 parts by mass of sulfur and 2642 parts by mass of anti-aging agent to obtain the butyronitrile pre-vulcanized rubber cement mother liquor.
(2) And taking 100 parts by mass of the pre-vulcanized rubber cement mother solution, adding 2.5 parts by mass of foaming agent sodium dodecyl sulfate and 2 parts by mass of PVA, adjusting the foaming ratio to 2, and adjusting the viscosity to 3000mpa.s to obtain the butyronitrile pre-vulcanized foamed rubber cement.
(3) Preparing a foaming surface treating agent: 100 parts of water, 5 parts of surfactant sodium dodecyl benzene sulfonate, 1.5 parts of 2% CMC, 6 of foaming times and 1500mpa.s of viscosity.
(4) Sleeving a 13 knitted glove blank on a glove mold, preheating to 45-50 ℃, and infiltrating the glove blank with a pre-prepared coagulant, wherein the coagulant is a methanol solution of 3 wt% of calcium chloride.
(5) And (3) after taking out the butyronitrile pre-vulcanized foam rubber slurry from the coagulant, dipping the butyronitrile pre-vulcanized foam rubber slurry in the step (2), and after the gum dipping is finished, homogenizing for 20 seconds, wherein a part of the butyronitrile pre-vulcanized foam rubber slurry is fixed.
(6) And (4) soaking the glove blank into the foaming type surface treating agent prepared in the step (3), and taking out, wherein the foaming type surface treating agent has certain viscosity and is filled with air holes, so that a part of the butyronitrile foaming adhesive cement on the surface of the glove blank is washed off in a star point shape.
(7) And (3) vulcanization and drying: drying at 90 ℃ for 25 minutes, raising the temperature to 130 ℃, and drying for 1.5 hours to obtain the butyronitrile microporous breathable foamed gloves.
Comparative example 1
The comparative example provides a preparation method of butyronitrile foaming gloves, which comprises the following steps:
(1) 100 parts by mass of butyronitrile latex, 1 part by mass of vulcanization accelerator BZ, 1.5 parts by mass of zinc oxide (active agent), 1.5 parts by mass of sulfur and 2641 parts by mass of anti-aging agent are uniformly mixed to obtain the butyronitrile pre-vulcanized rubber cement mother liquor.
(2) And taking 100 parts by mass of the pre-vulcanized rubber cement mother liquor, adding 1.5 parts by mass of foaming agent sodium dodecyl sulfate and 1.5 parts by mass of 2% CMC, adjusting the foaming times to 1.5, and adjusting the viscosity to 2500mpa.s to obtain the butyronitrile pre-vulcanized foaming rubber cement.
(3) Preparing a foaming surface treating agent: 100 parts by mass of water.
(4) Sleeving a 13 knitted glove blank on a glove mold, preheating to 40-55 ℃, and infiltrating the glove blank with a pre-prepared coagulant, wherein the coagulant is a methanol solution of 2 wt% of calcium nitrate.
(5) And (3) after taking out the coagulant, dipping the butyronitrile pre-vulcanized foam rubber cement in the step (2), after the gum dipping is finished, homogenizing for 20 seconds, dipping the mixture into the water prepared in the step (3), and taking out the mixture.
(6) And (3) vulcanization and drying: and (3) drying for 30 minutes at the temperature of 90 ℃, raising the temperature to 120 ℃, and drying for 2 hours to obtain the butyronitrile foaming gloves.
At the moment, the butyronitrile pre-vulcanized foaming rubber cement is just soaked and then is soaked in water, so that a large piece of butyronitrile rubber cement is eluted, and the prepared butyronitrile foaming glove is unqualified in quality and is a defective product because a large piece of butyronitrile rubber layer is lacked on the surface to form a rubber through hole (a knitted glove blank is exposed).
Comparative example 2
This comparative example was made by removing step (3) from comparative example 1. The method comprises the following steps:
the comparative example provides a preparation method of butyronitrile foaming gloves, which comprises the following steps:
(1) 100 parts by mass of butyronitrile latex, 1 part by mass of vulcanization accelerator BZ, 1.5 parts by mass of zinc oxide (active agent), 1.5 parts by mass of sulfur and 2641 parts by mass of anti-aging agent are uniformly mixed to obtain the butyronitrile pre-vulcanized rubber cement mother liquor.
(2) And taking 100 parts by mass of the pre-vulcanized rubber cement mother liquor, adding 1.5 parts by mass of foaming agent sodium dodecyl sulfate and 1.5 parts by mass of 2% CMC, adjusting the foaming times to 1.5, and adjusting the viscosity to 2500mpa.s to obtain the butyronitrile pre-vulcanized foaming rubber cement.
(3) Sleeving a 13 knitted glove blank on a glove mold, preheating to 40-55 ℃, and infiltrating the glove blank with a pre-prepared coagulant, wherein the coagulant is a methanol solution of 2 wt% of calcium nitrate.
(4) And (3) after taking out the coagulant, dipping the butyronitrile pre-vulcanized foam rubber cement in the step (2), and after the gum dipping is finished, homogenizing for 20 seconds.
(5) And (3) placing the gloves in an oven at 80-85 ℃ for drying for 30min, and then taking out the gloves and putting the gloves into clean water for soaking and washing.
(6) And (3) vulcanization and drying: and (3) drying for 30 minutes at the temperature of 90 ℃, raising the temperature to 120 ℃, and drying for 2 hours to obtain the butyronitrile foaming gloves.
The butyronitrile foaming gloves prepared by the method have no air permeability through tests.
Air permeability test of coated gloves
According to the test method for the artificial leather synthetic leather of QB/T5156 and 2017, the method comprises the following steps: the determination method comprises the following steps: the sample was fixed so that a pressure difference was formed between both sides of the sample, and the air permeability was measured by observing the presence or absence of bubbles in the liquid or the amount of bubbles in the liquid.
The air permeability of example 1 was tested to be approximately 0.038 at 10MPa, the air permeability of example 2 was tested to be approximately 0.041 at 10MPa, the air permeability of example 3 was tested to be 0.035 at 10MPa, and the air permeability of comparative example 1 was tested to be approximately 0.13 at 10MPa (with through holes in the bondline), whereas comparative example 2 was nearly air impermeable.
In terms of wearability, examples 1 to 3 and comparative example 1 are all more flexible than comparative example 2, without significant feeling of oppression and moist feeling.
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 (8)

1. A preparation method of butyronitrile microporous breathable foamed gloves is characterized by comprising the following steps:
s1, infiltrating coagulant: heating the glove blank to 40-55 ℃, and infiltrating a pre-prepared coagulant;
s2, dip-coating butyronitrile pre-vulcanized foam rubber slurry on the glove blank, homogenizing the glove blank, and hanging a layer of butyronitrile pre-vulcanized foam rubber on the surface of the glove blank;
s3, soaking the fabric into a foaming type surface treating agent, wherein the foaming type surface treating agent is prepared by the following method: taking 100 parts by mass of water, adding 0.5-3 parts by mass of thickening agent and 0.5-5 parts by mass of surfactant, foaming, wherein the foaming multiple is 1.5-8 times, and adjusting the viscosity to 800-2500 mpa.s;
because the foaming surface treating agent is internally filled with foam holes, after the foaming surface treating agent is soaked, part of the butyronitrile pre-vulcanized foaming adhesive on the surface of the glove blank is washed away by the foaming surface treating agent, and the washed away part is distributed in a star-point dispersed manner;
and S4, vulcanizing and drying to obtain the butyronitrile microporous breathable foamed glove.
2. The method according to claim 1, wherein in step S1, the coagulant is a water/alcohol solution of calcium chloride, calcium nitrate or zinc chloride, and the alcohol is a liquid alcohol at room temperature such as methanol, ethanol or propanol.
3. The method according to claim 1, wherein in step S2, the butyronitrile pre-vulcanized foam cement is prepared as follows:
uniformly mixing 90-120 parts by mass of butyronitrile latex, 0.5-5 parts by mass of a vulcanizing agent, 0.3-4 parts by mass of an active agent, 0.3-3 parts by mass of a vulcanization accelerator and 0.5-2 parts by mass of an anti-aging agent to obtain a butyronitrile pre-vulcanized rubber cement mother solution;
taking 90-120 parts by mass of the butyronitrile pre-vulcanized rubber cement mother liquor and 0.5-5 parts by mass of a foaming agent, uniformly stirring and foaming to ensure that the foaming multiple is 1.1-2.5 times; adding 0.5-4 parts by mass of a thickening agent, and adjusting the viscosity to 1000-5500mpa.s to prepare the butyronitrile pre-vulcanized foam cement.
4. The method according to claim 3, wherein in step S2, the vulcanization accelerator is one or a combination of two or more selected from the group consisting of dithiocarbamates, thiurams, thiazoles, guanidines, and thioureas;
the vulcanizing agent is one or more of sulfur, zinc oxide, magnesium oxide and other metal oxide vulcanizing agents;
the active agent is one or any combination of the zinc oxide, the magnesium oxide, the zinc carbonate and the zinc stearate;
the anti-aging agent is one or a combination of monophenol, polyphenol anti-aging agent, anti-aging agent RD and anti-aging agent 264;
the foaming agent is one or a combination of more of potassium oleate, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, potassium laurate, AC and OBSH;
the thickening agent is one or a combination of more of CMC, sodium polyacrylate, casein, PVA, hydroxymethyl ethyl cellulose and hydroxyethyl propyl cellulose.
5. The method as claimed in claim 1 or 3, wherein in step S2, the viscosity of the butyronitrile pre-vulcanized foam cement is 1500-2500 mpa.s.
6. The method according to claim 1, wherein the thickener used in step S3 is one or more selected from CMC, sodium polyacrylate, casein, PVA, hydroxymethylethylcellulose and hydroxyethylpropylcellulose; the surfactant is one or a combination of more of an anionic surface foaming agent, a cationic surfactant and an amphoteric surfactant.
7. The method as claimed in claim 1 or 6, wherein the foaming ratio of the foaming surface treatment agent in step S3 is 2.5-5 times, and the viscosity is 800-.
8. The method of claim 1, wherein: step S4, low-temperature prevulcanization drying is carried out, and then high-temperature vulcanization is carried out; the low-temperature vulcanization temperature is 70-100 ℃, and the time is 10-40 min; the high-temperature vulcanization temperature is 100 ℃ and 140 ℃, and the time is 1-4 h.
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Denomination of invention: A preparation method for nitrile microporous breathable foam gloves

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