CN109965412B

CN109965412B - Powder-free PVC gloves and preparation method thereof

Info

Publication number: CN109965412B
Application number: CN201910185940.5A
Authority: CN
Inventors: 桑树军; 李民刚; 王振山; 刘喆; 马保军; 汪金鑫
Original assignee: Zhonghong Pulin Beijing Medical Supplies High And New Technology Research Institute Co ltd
Current assignee: Zhonghong Pulin Beijing Medical Supplies High And New Technology Research Institute Co ltd
Priority date: 2019-03-12
Filing date: 2019-03-12
Publication date: 2021-01-19
Anticipated expiration: 2039-03-12
Also published as: CN109965412A

Abstract

The invention relates to a powder-free PVC glove and a preparation method thereof. Firstly, preparing a special coating agent for a graphene oxide modified polyurethane coating special for PVC; secondly, manufacturing PVC gloves; then adding the coating agent to the surface of the PVC glove, drying, curing and molding; the PVC gloves were peeled off from the mold.

Description

Powder-free PVC gloves and preparation method thereof

Technical Field

The invention relates to a powder-free PVC glove and a preparation method thereof, belonging to the field of application of high polymer materials.

Background

The PVC gloves are widely used in daily life, have the advantages of sanitary protection effect, convenient use, good protection performance, safety, no toxicity, low price and high popularity of users. The PVC gloves are divided into powder PVC gloves and powder-free PVC gloves. The powdered gloves use modified corn starch; the powder-free PVC gloves are coated with waterborne Polyurethane (PU). Most people feel that residual powder is stuck on the hands when the powder-containing gloves are used, and the powder-containing gloves are inconvenient and sanitary, so that more people can choose to use the powder-free gloves. Because the hydrophilic group is introduced in the preparation of the waterborne polyurethane, the waterborne polyurethane is easily polluted by bacteria, and has poor antibacterial and bacteriostatic properties, so that the coating has poor water resistance, mechanical properties and the like, and the hand feeling is poor due to high hardness.

Graphene oxide (graphene oxide) is an oxide of graphene. The carbon material is a novel carbon material with excellent performance, and has higher specific surface area and rich functional groups on the surface. Has excellent performances of heat, electricity, force and the like, and also has certain antibacterial and bacteriostatic functions. The graphene oxide modified polyurethane emulsion for the PVC coating can improve the tensile strength and the elongation of the PVC glove; improve the surface water resistance, antistatic property, hand feeling, bacteriostasis and antibacterial property.

The international cooperation team consisting of Huangqing, Fanghaiping and Fan Chunhai researchers, IBM Watson research center and professor Zhou hong of Columbia university at Shanghai applied to physical research institute closely combines computer simulation and experiments, makes important progress in the research aspect of graphene antibacterial mechanism, proposes a molecular mechanism of interaction between graphene and bacterial cell membrane, and related papers are published in the journal of Nature Nanotechnology (DOI: 10.1038/nnano.2013.125). The team led by the researchers in spring, sea, huangqing in 2010 experimentally found the antibacterial effect of graphene for the first time (ACS Nano, 2010, 4,4317), i.e., graphene oxide can destroy the cell membrane of bacteria, thereby causing the outflow of intracellular substances and killing the bacteria.

How to improve the performance of the powder-free PVC gloves becomes an important development direction of the industry.

Disclosure of Invention

The invention aims to overcome the defects of the prior art, and the powder-free PVC gloves are prepared by modifying the waterborne polyurethane by utilizing the characteristics of the graphene oxide, adjusting the waterborne polyurethane by a special process and coating the modified waterborne polyurethane on the surfaces of the gloves. The mechanical property of the glove is increased, the hand feeling is improved, and the glove is endowed with bacteriostatic and antibacterial functions and the like.

In order to solve the problems, the invention provides a preparation method of a graphene oxide modified polyurethane finishing agent PVC glove, the prepared glove and application of the glove.

The waterborne polyurethane coating is prepared by compounding waterborne polyurethane emulsion, sodium hydroxide, graphene oxide, an adhesion promoter, an opacifier, sodium hydroxide, a wetting agent, a defoaming agent, a thickening agent, waterborne wax and deionized water.

The specific method comprises the following steps:

(1) preparation of aqueous polyurethane emulsion

The graphene oxide modified waterborne polyurethane emulsion for the powder-free PVC gloves comprises the following components in parts by weight:

further, the polyhydric alcohol is preferably adipic acid series polyester diol, the molecular weight is 600-2000, the moisture is less than 0.03%, the acid value (mg KOH/g) is 0.1-0.8, and the hydroxyl value (mg KOH/g) is 100-220.

The isocyanate is one or more of Toluene Diisocyanate (TDI), dicyclohexylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), diphenylmethane diisocyanate (MDI) and p-phenylene diisocyanate (PPDI), and dicyclohexylmethane diisocyanate (HMDI) and/or isophorone diisocyanate (IPDI) are preferred.

The hydrophilic chain extender is preferably dimethylolpropionic acid (DMPA) and/or dimethylolbutyric acid (DMBA).

The alcohol chain extender includes 1, 4-butanediol, diethylene glycol, ethylene glycol, 1, 6-hexanediol, 1, 2-propanediol and the like, and preferably 1, 4-butanediol and diethylene glycol.

The other chain extender is preferably Trimethylolpropane (TMP) or ethylenediamine.

The catalyst is preferably stannous octoate or dibutyltin dilaurate.

The neutralizing agent is triethylamine, sodium hydroxide, ammonia water, triethanolamine and the like, and triethylamine is preferred.

The solvent such as acetone, butanone, ethyl acetate, butyl acetate, N-dimethylformamide and the like is preferably acetone or ethyl acetate.

The water is preferably deionized water.

The preparation method of the waterborne polyurethane emulsion comprises the following steps:

mixing diisocyanate and polyol according to the mass fraction, and reacting in a reaction kettle at 75-85 ℃ for 1.5 hours to obtain a prepolymer; reducing the temperature to 65-75 ℃, mixing the three chain extenders, adding the mixture into the prepolymer, adding the catalyst, adding half of the organic solvent by mass, and reacting for 3.5 hours; when the temperature is reduced to 40-50 ℃, adding the other half mass of organic solvent, and continuing to react for 1 hour; reducing the temperature to 25-30 ℃, accelerating the stirring speed, adding deionized water, emulsifying for 0.5 hour, adding a neutralizing agent and neutralizing for 0.5 hour. And taking out of the kettle to obtain the waterborne polyurethane emulsion.

(2) Preparation of waterborne polyurethane finishing agent

The graphene oxide modified waterborne polyurethane finishing agent for the powder-free PVC gloves comprises the following components in percentage by weight:

further, the aqueous polyurethane emulsion is prepared.

The shading cover agent is preferably nano-scale silicon dioxide or titanium dioxide.

The wetting agent is preferably a substrate wetting agent for polyether modified siloxanes, such as BYK-348 and BYK333 from Bick.

The defoaming agent is preferably a silicone defoaming agent.

The thickener is preferably a thickener for aqueous resin systems, for example Borchi Gel LW44 from Borchers, Germany.

The water is preferably deionized water.

Dispersing an opacifier and sodium hydroxide into deionized water according to the weight percentage, adding the prepared aqueous polyurethane emulsion, mixing, and respectively and sequentially adding graphene oxide, an accelerator, a wetting agent, a defoaming agent, a thickening agent and aqueous wax. And after continuously stirring for 5 hours, detecting and discharging to obtain the graphene oxide modified waterborne polyurethane finishing agent for the powder-free PVC gloves.

2. Making PVC gloves

PVC paste resin, plasticizer, calcium-zinc heat stabilizer and diluent are used for preparing a PVC mixture, and the mixture is dipped in a ceramic grinding tool, cured at high temperature and plasticized and formed.

3. Coating the surface of the glove with the finishing agent

Firstly adding 1.5% methanol into the prepared special coating agent for the graphene oxide modified polyurethane coating, diluting the mixture by 8 times with deionized water, immersing a mould with PVC gloves in the diluent for about 6 seconds, taking out the mould, drying the mould for 3 minutes at 80-100 ℃, and drying the mould for 5 minutes at 180 ℃ for high-temperature curing; cooling at room temperature, and stripping the glove from the mold.

The powder-free PVC gloves prepared by the invention have the following advantages:

the product has good slip property, is convenient for a user to wear and is anti-adhesive;

the adhesive force is strong, the stability is strong, and the water resistance is good;

the coating has corrosion resistance and aging resistance;

the heat conductivity and the antistatic property are good;

has good antibacterial and bacteriostatic properties.

Detailed Description

Detailed embodiments of the present invention will be disclosed in this section. The embodiments disclosed herein are examples of the present invention, which may be embodied in various forms. Therefore, specific details disclosed, including specific structural and functional details, are not intended to be limiting, but merely serve as a basis for the claims. The word "may" is used throughout this application in an permissive sense rather than the mandatory sense. Similarly, unless otherwise specified, the words "include", "comprises", and "consisting of" mean "including but not limited to". The words "a" or "an" mean "at least one" and the words "a plurality" mean more than one. When abbreviations or technical terms are used, these terms are meant to have the generally accepted meaning known in the art.

Example 1:

a preparation method of powder-free PVC gloves comprises the following steps:

the method comprises the following steps: preparing a graphene oxide modified PVC glove polyurethane finishing agent;

(1) preparing aqueous polyurethane emulsion, wherein the composition and the weight fraction are as follows:

the polyhydric alcohol is adipic acid series polyester dihydric alcohol, the molecular weight is 600-2000, the water content is less than 0.03 percent, the acid value (mg KOH/g) is 0.1-0.8, and the hydroxyl value (mg KOH/g) is 100-220-one.

Mixing diisocyanate and polyol according to the mass fraction, and reacting in a reaction kettle at 75-85 ℃ for 1.5 hours to obtain a prepolymer; reducing the temperature to 65-75 ℃, mixing the three chain extenders, adding the mixture into the prepolymer, adding a catalyst, adding half of acetone by mass, and reacting for 3.5 hours; when the temperature is reduced to 40-50 ℃, adding the other half mass of acetone, and continuing to react for 1 hour; reducing the temperature to 25-30 ℃, accelerating the stirring speed, adding deionized water, emulsifying for 0.5 hour, adding neutralizing agent triethylamine, and neutralizing for 0.5 hour. And taking out of the kettle to obtain the waterborne polyurethane emulsion.

(2) The graphene oxide modified waterborne polyurethane finishing agent is prepared from the following components in percentage by weight:

Step two: manufacturing PVC gloves;

preparing a PVC mixture by using PVC paste resin, a plasticizer, a calcium-zinc heat stabilizer and a diluent, impregnating a ceramic grinding tool, curing at high temperature, and plasticizing and forming;

step three: coating the surface of the glove with a finishing agent;

firstly adding 1.5 wt% of methanol into the prepared special coating agent for the graphene oxide modified polyurethane coating, diluting the mixture by deionized water for 8 times, immersing a mould with a PVC glove into the diluent for about 6 seconds, taking out the mould, drying the mould at 80-100 ℃ for 3 minutes, and drying the mould at 180 ℃ for 5 minutes for high-temperature curing; cooling at room temperature, and stripping the glove from the mold.

Graphene-latex protective gloves prepared according to this example of implementation were prepared using ISO 10282: 2002, and the specific test results are shown in the following table.

Example 2: the rest of the procedure was the same as in example 1

Example 3: the rest of the procedure was the same as in example 1

Comparative example

The method is a manufacturing method of a conventional powder-free PVC glove, and is different from the embodiment in that a coating agent in the comparative example is a commercially available polyurethane emulsion which is not modified by graphene oxide, methanol is not added in the using process, low-temperature drying is not carried out after coating, high-temperature drying and curing are carried out, and the rest steps are the same as those in the embodiment 1. Latex protective gloves prepared according to this example were prepared using ISO 10282: 2002, and the specific properties are shown in the following table 1

TABLE 1 glove Performance test

It should be understood that the preferred embodiment processes of this example are not intended to limit the invention to the particular forms disclosed, but that the invention is to cover all modifications, equivalents, and alternatives falling within the scope of the description and defined by the appended claims.

Claims

1. A preparation method of antibacterial and bacteriostatic powder-free PVC gloves comprises the following steps:

(1) preparation of aqueous polyurethane emulsion

The graphene oxide modified waterborne polyurethane emulsion for the powder-free PVC gloves comprises the following components in percentage by mass:

the hydrophilic chain extender is dimethylolpropionic acid (DMPA) and/or dimethylolbutyric acid (DMBA); the alcohol chain extender is selected from one or more of 1, 4-butanediol, diethylene glycol, ethylene glycol, 1, 6-hexanediol and 1, 2-propylene glycol; the other chain extender is Trimethylolpropane (TMP) or ethylenediamine;

mixing diisocyanate and polyol according to the mass fraction, and reacting in a reaction kettle at 75-85 ℃ for 1.5 hours to obtain a prepolymer; reducing the temperature to 65-75 ℃, mixing the three chain extenders, adding the mixture into the prepolymer, adding the catalyst, adding half of the organic solvent by mass, and reacting for 3.5 hours; when the temperature is reduced to 40-50 ℃, adding the other half mass of organic solvent, and continuing to react for 1 hour; reducing the temperature to 25-30 ℃, accelerating the stirring speed, adding deionized water, emulsifying for 0.5 hour, adding a neutralizing agent, and neutralizing for 0.5 hour; obtaining aqueous polyurethane emulsion;

(2) preparation of waterborne polyurethane finishing agent

The waterborne polyurethane coating agent comprises the following components in percentage by weight:

dispersing an opacifier and sodium hydroxide into deionized water according to the weight percentage, adding the aqueous polyurethane emulsion prepared in the step (1), mixing, and sequentially adding graphene oxide, an accelerator, a wetting agent, a defoaming agent, a thickening agent and aqueous wax; continuously stirring to obtain the graphene oxide modified waterborne polyurethane finishing agent for the powder-free PVC gloves;

(3) manufacturing PVC gloves;

(4) and (3) coating the coating agent prepared in the step (2) on the surface of the PVC glove manufactured in the step (3).

2. The method of claim 1, wherein: the polyalcohol in the step (1) is adipic acid series polyester dihydric alcohol; the isocyanate is one or more of Toluene Diisocyanate (TDI), dicyclohexylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), diphenylmethane diisocyanate (MDI) and p-phenylene diisocyanate (PPDI); the catalyst is stannous octoate or dibutyltin dilaurate; the neutralizing agent is selected from one or more of triethylamine, sodium hydroxide, ammonia water and triethanolamine; the solvent is one or more of acetone, butanone, ethyl acetate, butyl acetate and N, N-dimethylformamide.

3. The method of claim 1, wherein: the opacifier in the step (2) is nano-scale silicon dioxide or titanium dioxide; the wetting agent is a base material wetting agent of polyether modified siloxane.

4. The method of claim 1, wherein: in the step (2), the defoaming agent is an organic silicon defoaming agent; the thickening agent is a thickening agent of an aqueous resin system.

5. The method of claim 1, wherein: the step (3) of manufacturing the PVC gloves comprises the following steps: PVC paste resin, plasticizer, calcium-zinc heat stabilizer and diluent are used for preparing a PVC mixture, and the mixture is dipped in a ceramic grinding tool, cured at high temperature and plasticized and formed.

6. The method of claim 1, wherein: the step (4) is as follows: adding 1.5% methanol into the prepared waterborne polyurethane coating agent, diluting the waterborne polyurethane coating agent by 8 times with deionized water, immersing the mould with the PVC gloves in the diluent for 6 seconds, taking out the mould, drying the mould for 3 minutes at 80-100 ℃, and drying the mould for 5 minutes at 180 ℃ for high-temperature curing; cooling at room temperature, and stripping the glove from the mold.

7. A PVC glove produced by the production method according to any one of claims 1 to 6.

8. The glove of claim 7, wherein: the gloves are powder-free PVC gloves.

9. Use of a glove according to claim 7 or 8, characterized in that: is used for sanitary protection.