CN111925609B - PVC gloves and preparation process thereof - Google Patents
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/02—Direct processing of dispersions, e.g. latex, to articles
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D19/00—Gloves
- A41D19/0055—Plastic or rubber gloves
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- 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
- C08J2327/00—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 a halogen; Derivatives of such polymers
- C08J2327/02—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 a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—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 a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
- C08J2423/30—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by oxidation
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- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/00—Use of organic ingredients
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Abstract
The invention relates to the field of glove PVC glove manufacturing, and discloses a PVC glove and a preparation process thereof, wherein the raw materials of the PVC glove comprise xylene formaldehyde resin and ethylene glycol, the toluene formaldehyde resin as a plasticizer can replace phthalate plasticizer which is widely applied in the market but carcinogenic to human bodies, so that the tolerance of the PVC glove is improved, the ethylene glycol has higher color and luster degree on the PVC glove under the action of the toluene formaldehyde resin, and meanwhile, the ethylene glycol can inhibit the thermal decomposition reaction of the PVC paste resin in a heating environment, inhibit HCl from coming out and reduce the damage to respiratory mucosa of the human bodies; the invention also discloses a preparation process of the PVC gloves, which comprises the processes of mixing, stirring, baking and the like of the raw materials, so that the PVC gloves are safer and more environment-friendly in manufacturing process, and the PVC gloves with better tolerance and color and luster are obtained.
Description
Technical Field
The invention relates to the field of glove manufacturing, in particular to a PVC glove and a preparation process thereof.
Background
The PVC gloves are glove products taking polyvinyl chloride as a main raw material, have antistatic performance and are manufactured by a special process. The gloves are free of allergens, free of powder, low in dust generation amount, low in ion content, free of components such as plasticizers, esters and silicone oil, high in chemical resistance, good in flexibility and touch, convenient and comfortable to wear, and anti-static, and can be used in a dust-free environment. The basic raw materials are as follows; PVC paste resin, plasticizer (DOP \ DINP), viscosity reducer (solvent oil), heat stabilizer, colorant and filler.
The plasticizer can increase the plasticity of the PVC resin, so that the elongation, flexibility and flexibility of the PVC are improved, and the hardness, modulus, softening temperature and brittle temperature are reduced, thereby meeting the requirements of the glove industry.
Most of plasticizers used for producing PVC gloves in the market at present are phthalate esters, but the phthalate ester plasticizer belongs to low molecular weight compounds, has poor durability in materials, is easy to migrate out of polymers, has potential carcinogenicity to human bodies, and has limited the application range of the phthalate plasticizer abroad.
Disclosure of Invention
Aiming at the defects in the prior art, the first purpose of the invention is to provide a PVC glove which has the advantages of strong durability, stable property, excellent strength and no toxicity.
The second purpose of the invention is to provide a preparation process of PVC gloves, and the PVC gloves which have better durability and strength, stable property and no toxicity are obtained.
In order to achieve the first object, the invention provides the following technical scheme: a PVC glove is characterized in that,
the PVC gloves comprise the following raw materials in parts by weight:
450 portions of PVC paste resin and 550 portions of PVC paste resin,
4-8 parts of a stabilizer, namely,
350 portions of the primary plasticizer 230 and 350 portions of,
150 portions of dimethylbenzene formaldehyde resin and 220 portions of dimethylbenzene formaldehyde resin,
100 portions and 150 portions of viscosity reducer,
2-5 parts of polyhydric alcohol.
Through the technical scheme, the inventor discovers that the xylene formaldehyde resin is adopted as the plasticizing auxiliary agent and is a high molecular weight compound, so that the xylene formaldehyde resin has excellent electrical insulation, acid resistance, alkali resistance, strong durability and stability, and the effects of no toxicity and strong durability are obtained, and the cost of the PVC gloves can be greatly reduced; the PVC paste resin is thermally decomposed at the temperature of 120-130 ℃ to generate HCl, the HCl has an irritant effect on respiratory mucosa and causes harm to the health of human bodies, the produced HCl becomes a catalyst to accelerate the reaction of HCl desorption from PVC, so that the PVC decomposition is carried out in a chain manner once being initiated, and meanwhile, the inventor discovers in production research that polyol has an absorption effect on the HCl and can inhibit the reaction of HCl desorption from PVC; meanwhile, the polyalcohol acts on the xylene formaldehyde resin, so that the luster of the xylene formaldehyde resin can be increased, and the PVC gloves are brighter in color.
Further, the primary plasticizer is an alkyl xanthate plasticizer.
By adopting the technical scheme, the inventor thinks that the alkyl xanthate plasticizer has good mechanical property, electrical property and weather resistance, can be used for main plasticization and has good compatibility, and has good plasticization effect when being used with the xylene formaldehyde resin, so that the PVC gloves which are compatible with PVC and have good mechanical property are obtained.
Further, the alkyl sulfonate plasticizer is petroleum phenyl sulfonate.
By adopting the technical scheme, the phenyl petroleum sulfonate enables the tolerance of the PVC gloves to be better.
Further, the stabilizer is a calcium zinc stabilizer.
By adopting the technical scheme, the calcium zinc stabilizer is used for ensuring smooth processing and forming of PVC, meanwhile, the polyalcohol compound and the calcium zinc stabilizer act together to capture HCl separated out from the PVC, the compounding effect is excellent, and the components of the polyalcohol compound and the calcium zinc stabilizer are synergistic, so that on one hand, the PVC can keep good initial color, and on the other hand, the PVC has good capturing reaction capability on HCl, thereby prolonging the thermal stability time.
Furthermore, the raw material also comprises 4-6 parts of beta-diketone compounds.
By adopting the technical scheme, the HCl removal reaction of PVC is controlled from two aspects, the first step is to prolong the induction time of the HCl removal reaction of PVC as far as possible, the second step is to reduce the catalytic action of HCl on the decomposition reaction, in the first step, a small amount of hydrogen chloride is removed from PVC in the induction period to generate a single double-bond structure and an allyl chloride structure, the single double-bond structure is easy to continuously remove HCl under the catalytic action of hydrogen chloride to generate a chromogenic conjugated polyene structure, and the beta-diketone compound can prolong the induction time, prolong the color change time of PVC and further prevent the HCl removal of PVC.
Further, the beta-diketone compound is acetylacetone.
By adopting the technical scheme, the induction time of the acetylacetone on the PVC is prolonged, so that the reaction of HCl removal of the PVC is slow, and the effect is better.
In order to achieve the second object, the invention provides the following technical scheme:
a preparation process of PVC gloves comprises the following steps:
s1: adding raw materials including PVC paste resin, a main plasticizer, xylene formaldehyde resin and a stabilizer into a stirrer, stirring for 1-1.5h under the conditions that the temperature is 50-60 ℃ and the rotating speed is 1000-1500r/min, standing and defoaming to obtain a mixture;
s2: adding the mixture prepared in the step S1 and 130 parts of viscosity reducer into a stirrer, and stirring for 15-20min at the temperature of 50-60 ℃ and the rotation speed of 1000-1500r/min to prepare a steeping fluid;
s3: preheating the hand mold to 60-70 ℃, putting the hand mold into the impregnation liquid prepared in S2, putting the impregnated hand mold into an oven, and baking for 5-10min at the temperature of 170-220 ℃ to obtain the PVC glove.
Further, the process for preparing a PVC glove according to claim 8, wherein the raw material added to the stirring in S1 includes a β -diketone compound, and wherein the stabilizer is a calcium zinc stabilizer, and the β -diketone compound is added prior to the calcium zinc stabilizer.
By adopting the technical scheme, the polyol can be ensured to increase the gloss of the tolualdehyde resin while preventing HCl from being removed from PVC, so that the nontoxic and bright PVC gloves are obtained, and the harm to a human body caused by HCl in the manufacturing process of the PVC gloves is reduced.
In conclusion, the invention has the following beneficial effects:
firstly, because the invention adopts the xylene formaldehyde resin as the plasticizer, and the toluene formaldehyde resin is nontoxic, the effect of the PVC gloves harmless to human bodies is obtained.
Secondly, as the polyhydric alcohol is adopted to absorb HCl which is separated from the PVC paste resin by thermal decomposition, and the gloss of the PVC gloves can be increased by the action of the polyhydric alcohol on the xylene formaldehyde resin, the effects of improving the brightness of the PVC gloves and reducing the damage to human bodies in the manufacturing process are obtained.
Thirdly, the calcium-zinc stabilizer is adopted, and the polyol compound and the calcium-zinc stabilizer act together, so that the PVC can keep good initial color and the thermal stability time can be prolonged.
Detailed Description
The PVC paste resin is a Shandongxin Baihe chemical product,
the calcium zinc stabilizer is a product of blue sky additive company Limited in Taian city,
the alkyl benzene sulfonate is a product of chatting engineering chemical company,
the xylene formaldehyde resin is a product of Hangzhou Zhuo Li chemical industry Co., Ltd,
dipentaerythritol is a product of the Anhui Jinhe industries, Ltd,
the oxidized polyethylene wax is a product of Keyin chemical Co., Ltd,
acetylacetone is a product of the chemical Limited of Waterde, Inc. of Jinan.
In the case of the example 1, the following examples are given,
the PVC gloves comprise the following raw materials in parts by weight: 500 parts of PVC paste resin, 6 parts of calcium zinc stabilizer, 290 parts of alkyl phenyl sulfonate, 130 parts of xylene formaldehyde resin and 100 parts of oxidized polyethylene wax;
which comprises the following steps:
s1: adding 500 parts of PVC paste resin, 290 parts of alkyl phenyl sulfonate, 130 parts of xylene formaldehyde resin, 3 parts of acetylacetone and 6 parts of calcium-zinc stabilizer into a stirrer, stirring for 1.5 hours at the temperature of 55 ℃ and the rotating speed of 1200r/min, and standing and defoaming to obtain a mixture;
s2: adding the mixture prepared in the step S1 and 130 parts of oxidized polyethylene wax into a stirrer, and stirring for 20min at the temperature of 55 ℃ and the rotation speed of 1200r/min to prepare a steeping liquor;
s3: preheating the hand mold to 65 ℃, putting the hand mold into the impregnation liquid prepared in S2, putting the impregnated hand mold into an oven, and baking for 10min at the temperature of 200 ℃ to prepare the PVC glove.
In the case of the example 2, the following examples are given,
based on the PVC gloves and the example 1, the difference is that the raw materials also comprise 3 parts of dipentaerythritol.
In the case of the example 3, the following examples are given,
based on the embodiment 2, the PVC gloves are characterized in that the raw materials comprise the following components: 550 parts of PVC paste resin, 8 parts of calcium zinc stabilizer, 350 parts of alkyl phenyl sulfonate, 220 parts of xylene formaldehyde resin, 150 parts of oxidized polyethylene wax, 3 parts of dipentaerythritol and 3 parts of acetylacetone.
In the case of the example 4, the following examples are given,
based on the embodiment 2, the PVC gloves are characterized in that the raw materials comprise the following components: 450 parts of PVC paste resin, 4 parts of calcium zinc stabilizer, 230 parts of alkyl phenyl sulfonate, 150 parts of xylene formaldehyde resin, 100 parts of oxidized polyethylene wax, 3 parts of dipentaerythritol and 3 parts of acetylacetone.
In the case of the example 5, the following examples were conducted,
PVC gloves based on example 2, with the difference that an equivalent mass of ethylene glycol ester is used instead of phenyl alkylsulphonate.
In the case of the example 6, it is shown,
PVC gloves based on example 2, with the difference that an equivalent mass of ethylene glycol ester is used instead of phenyl alkylsulfonate.
In the case of the example 7, the following examples are given,
PVC gloves based on example 2, with the difference that epoxidized soybean oil of equal mass is used instead of phenyl alkylsulfonate.
In the case of the example 8, the following examples are given,
PVC gloves based on example 2, with the difference that the phenyl alkylsulphonate is replaced by an equal mass of chlorinated phenyl alkylsulphonate.
In the comparative example 1,
PVC gloves based on example 2, with the difference that the amount of the calcium zinc stabilizer is 0.
In a comparative example 2,
PVC gloves based on example 2, with the difference that the amount of acetylacetone is 0.
In the case of the example 9, the following examples are given,
PVC gloves based on example 2, with the difference that tribasic lead sulfate of equal mass is used instead of the calcium-zinc stabilizer.
Example 10, a PVC glove, based on example 2, differs in that zinc stearate of equal mass is used instead of the calcium zinc stabilizer.
In a comparative example 3,
a PVC glove and a preparation process thereof comprise the following steps:
s1: adding 500 parts of PVC paste resin, 290 parts of alkyl phenyl sulfonate, 190 parts of xylene formaldehyde resin, 3 parts of acetylacetone and 3 parts of dipentaerythritol into a stirrer, stirring for 1.5 hours at the temperature of 55 ℃ and the rotating speed of 1200r/min, and standing and defoaming to obtain a mixture;
s2: adding the mixture prepared in the step S1 and 130 parts of oxidized polyethylene wax into a stirrer, and stirring for 20min at the temperature of 55 ℃ and the rotation speed of 1200r/min to prepare a steeping liquor;
s3: preheating the hand mold to 65 ℃, putting the hand mold into the impregnation liquid prepared in S2, putting the impregnated hand mold into an oven, and baking for 10min at the temperature of 200 ℃ to prepare the PVC glove.
In a comparative example 4,
a PVC glove and a preparation process thereof comprise the following steps:
s1: adding 500 parts of PVC paste resin, 290 parts of alkyl phenyl sulfonate, 190 parts of xylene formaldehyde resin, 6 parts of calcium-zinc stabilizer and 3 parts of dipentaerythritol into a stirrer, stirring for 1.5 hours at the temperature of 55 ℃ and the rotating speed of 1200r/min, and standing and defoaming to obtain a mixture;
s2: adding the mixture prepared in the step S1 and 130 parts of oxidized polyethylene wax into a stirrer, and stirring for 20min at the temperature of 55 ℃ and the rotation speed of 1200r/min to prepare a steeping liquor;
s3: preheating the hand mold to 65 ℃, putting the hand mold into the impregnation liquid prepared in S2, putting the impregnated hand mold into an oven, and baking for 10min at the temperature of 200 ℃ to prepare the PVC glove.
In the case of the embodiment 11, the following examples are given,
a PVC glove and a preparation process thereof are based on example 2, and are characterized in that acetylacetone is replaced by ethyl acetoacetate with equal mass.
Example 12, a PVC glove and process for making same, based on example 2, except that acetylacetone is replaced with equal mass of hexafluoroacetylacetone.
Example 13, a PVC glove and process for making same, based on example 2, except that the temperature in S1 is 50 ℃.
Example 14, a PVC glove and process for making same, based on example 2, except that the temperature in S1 is 60 ℃.
Example 15, a PVC glove and process for making the same, based on example 2, except that the temperature in S1 is 40 ℃.
Example 16, a PVC glove and process for making same, based on example 2, except that the temperature in S1 is 70 ℃.
Example 17, a PVC glove and process for making same, based on example 2, except that the calcium zinc stabilizer was added after the addition of acetylacetone and left to stand for 5 min.
Example 18, a PVC glove and process for making same, based on example 2, except that the calcium zinc stabilizer was added and left to stand for 5min and then acetylacetone was added.
Performance test
And (3) detecting the tensile property:
when the test method specified in GB/T528 is used for measurement, a dumbbell-shaped test piece is symmetrically clamped on an upper clamp and a lower clamp of a tensile testing machine, so that tensile force is uniformly distributed on a cross section, an elongation measuring device is assembled according to needs, the testing machine is started, the change of the test length and the force is continuously monitored in the whole process, the precision is within +/-2%, if a sample breaks outside a narrow part, the test result is discarded, and another sample is taken for repeated test. Three sets of experiments were performed to take the median values.
And (3) detecting the elongation property:
the test was carried out according to the test method of GB 7753. The sample is flatly placed in a clamp holder, the clamping distance is 100mm, the clamp holder is properly screwed to prevent the sample from slipping or breaking at the clamp holder when being stretched, and the stress direction of the sample is consistent with the force application direction of the testing machine. The specimen was loaded at a rate of 300mm/min, stretched to break, the elongation of the working portion of the specimen was measured and the maximum tensile force during the break was recorded.
And (3) detecting the breakdown strength test:
the test was carried out according to the test method of GB 7752.
Samples were taken every 300mm, the thickness of each sample was measured, and the samples were mounted on a high voltage breakdown device. The test voltage was continuously and uniformly increased from zero so that the samples were broken down on average between 10 and 20s, and 5 points were measured on each sample. The middle values of the click through voltage of each sample 5 are arranged according to ascending order, and the middle value is taken as the breakdown voltage of the sample.
Withstand voltage test
The assay was performed according to GB/T1410-2006.
The measuring electrodes of the sample are short-circuited by the measuring device, the sensitivity of the current measuring device is gradually increased to meet the requirements, and the change of the short-circuit current is observed at the same time, so that the short-circuit current is continued to reach a quite constant value which is smaller than the stable value of the electrochemical current or smaller than the current of 100min for electrochemical. When the short-circuit current becomes substantially constant, the value and direction of the short-circuit current are noted. The specified dc voltage was then applied to the rack and simultaneously recorded for one measurement per electrochemical time as follows: 1min,2min,5min,10min,50min,100 min. The electrochemical time was recorded when the same measurement was first observed, and if steady state could not be reached within 100min, the volume resistance was recorded as a function of the electrochemical time.
Determination of the amount of HCl liberated:
according to the method determination in HJ 549-one 2009, in the process of manufacturing PVC gloves, a sampler for air tightness inspection and flow calibration is practically carried out, a microporous filter membrane is arranged in a membrane clamp, two large bubble absorption tubes respectively containing 10ml of absorption liquid are connected in series behind the microporous filter membrane, and gas is collected for 60min at the flow rate of 1L/min by using an air sampler. The samples were poured into 50ml cuvettes, diluted with water to the mark and shaken up. And (4) after uniformly mixing all the tubes, injecting the mixture into an ion chromatograph, and measuring a response value and retention time of the instrument.
The test results are as follows
Of these, example 17 is the most preferred and example 1 is the worst.
The performance test of the PVC gloves obtained in the examples and the comparative examples is as follows:
when the primary plasticizer is alkyl xanthate plasticizer, the effect is better than that of other primary plasticizers;
the calcium zinc stabilizer and the polyol can reduce HCl desorption under the combined action, and the color of the PVC gloves produced by the calcium zinc stabilizer is better than that of PVC gloves produced by other stabilizers;
less HCl is precipitated with acetylacetone than without acetylacetone, which prevents HCl from being removed during the manufacturing process.
S1 can be molded at 50-60 deg.C, and PVC gloves beyond 50-60 deg.C can not be made.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (3)
1. The PVC gloves are characterized by comprising the following raw materials in parts by weight:
450 portions of PVC paste resin and 550 portions of PVC paste resin,
4-8 parts of a stabilizer, namely,
350 portions of the primary plasticizer 230 and 350 portions of,
150 portions of dimethylbenzene formaldehyde resin and 220 portions of dimethylbenzene formaldehyde resin,
100 portions and 150 portions of viscosity reducer,
2-5 parts of polyhydric alcohol;
the main plasticizer is alkyl sulfonate plasticizer; the alkyl sulfonate plasticizer is petroleum phenyl sulfonate;
the stabilizer is a calcium zinc stabilizer;
the raw material also comprises 4-6 parts of beta-diketone compounds; the beta-diketone compound is acetylacetone.
2. The PVC gloves according to claim 1, wherein the PVC gloves comprise the following raw materials in parts by weight:
500 parts of PVC paste resin,
6 parts of a calcium-zinc stabilizer, namely,
290 parts of a plasticizer (such as a plasticizer),
180 parts of dimethylbenzene formaldehyde resin,
130 parts of a viscosity reducer, namely 130 parts of,
3 parts of polyol.
3. The process for preparing a PVC glove according to claim 1, comprising the following steps:
s1: adding raw materials including PVC paste resin, a main plasticizer, xylene formaldehyde resin and a stabilizer into a stirrer, stirring for 1-1.5h under the conditions that the temperature is 50-60 ℃ and the rotating speed is 1000-1500r/min, standing and defoaming to obtain a mixture;
s2: adding the mixture prepared in the step S1 and 130 parts of viscosity reducer into a stirrer, and stirring for 15-20min at the temperature of 50-60 ℃ and the rotation speed of 1000-1500r/min to prepare a steeping fluid;
s3: preheating the hand mold to 60-70 ℃, putting the hand mold into the impregnation liquid prepared in S2, putting the impregnated hand mold into an oven, and baking for 5-10min at the temperature of 170-220 ℃ to prepare the PVC glove;
the raw materials added and stirred in the S1 comprise beta-diketone compounds, wherein the stabilizer is a calcium-zinc stabilizer, and the beta-diketone compounds are added in the calcium-zinc stabilizer.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030157150A1 (en) * | 2002-02-19 | 2003-08-21 | Che-Hao Lee | Formulation and process for manufacturing antimicrobial vinyl gloves |
| JP2006233350A (en) * | 2005-02-23 | 2006-09-07 | Seikoh Chem Co Ltd | Method for producing glove made of vinyl chloride resin |
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