CN116005463A

CN116005463A - Antibacterial double-layer PU glove and production process thereof

Info

Publication number: CN116005463A
Application number: CN202310029763.8A
Authority: CN
Inventors: 徐涛; 黄文旭; 张家宁; 刘正杰; 张高超; 周海涛; 周星余
Original assignee: SHANDONG XINGYU GLOVES CO Ltd
Current assignee: SHANDONG XINGYU GLOVES CO Ltd
Priority date: 2023-01-09
Filing date: 2023-01-09
Publication date: 2023-04-25

Abstract

The invention relates to a production process of an antibacterial double-layer PU glove, which comprises the following steps: s1, sleeving a glove core on a hand mould for pre-drying and heating; s2, dipping the glove cores into oily polyurethane adhesive cement; s3, firstly soaking a coagulant, and then soaking the coagulant in warm water; s4, baking to solidify the oily polyurethane cement on the surface of the glove core into a cement surface; s5, pre-baking and heating; s6, dipping the oily PU glove lining into aqueous polyurethane adhesive cement; the aqueous polyurethane mucilage is dispersed with an antibacterial agent, and polyurethane molecules in the aqueous polyurethane mucilage are linear molecular polyurethane; s7, surface treatment: treating with a surface treating agent having a coagulation promoting effect; s8, baking to solidify the aqueous polyurethane adhesive cement on the glove surface into an adhesive surface, and demolding to obtain a finished product. The antibacterial double-layer PU glove has the advantages of good waterproofness, air permeability, comfortable wearing, antibacterial property, light weight, flexibility, wear resistance, sensitive operability and the like.

Description

Antibacterial double-layer PU glove and production process thereof

Technical Field

The invention relates to the technical field of labor protection glove production, in particular to an antibacterial double-layer PU glove and a production process thereof.

Background

With the continuous development of the economy in China, the glove is not only used for hand warming or decoration, but also used for protecting tools for labor operation of people. Various infectious diseases are now found to be transmitted by air or contact, and in order to avoid the transmission of germs by contact, gloves are used for blocking the transmission of viruses in medical treatment, sanitary protection and the like.

At present, most of the fungus-resistant gloves in the market are disposable butyronitrile or disposable natural latex gloves without linings, and although the fit is good after the gloves are worn, the wearing process is very inconvenient, the gloves are airtight and can be used for covering hands, the gloves have strong wet feeling, and the experience of a wearer is poor. The existing disposable gloves are generally poor in wear resistance and wear resistance, perforation or damage occurs after the gloves are worn for 1-2 times, the service life is short, the gloves cannot be used for multiple times, a large amount of garbage can be generated by the discarded gloves, and the environment is damaged; however, the conventional lined glove has better wear resistance but has no germ resistance, the wet feeling problem cannot be solved, and the flexibility of the hand after wearing is poor, so that some fine operations cannot be finished.

Disclosure of Invention

First, the technical problem to be solved

In view of the defects and shortcomings of the prior art, the invention provides an antibacterial double-layer PU glove and a production process thereof, which solve the problems that common disposable gloves are not wear-resistant, poor in wear resistance, poor in wearing experience, not provided with antibacterial performance and the like.

(II) technical scheme

In order to achieve the above purpose, the main technical scheme adopted by the invention comprises the following steps:

in a first aspect, the invention provides a process for producing an antibacterial double-layer PU glove, which comprises the steps of,

s1, primary pre-baking: sleeving the glove core on a hand mould for pre-drying and heating;

s2, soaking oily PU: dipping the glove cores in the oily polyurethane adhesive cement, taking out the glove cores, homogenizing the adhesive, and dripping the adhesive;

s3, solidifying and soaking in warm water: soaking the glove cores into a coagulating agent to promote coagulation, and then adopting warm water for soaking treatment;

s4, baking: solidifying the oily polyurethane cement on the surface of the glove core into a cement surface by baking to obtain an oily PU glove lining;

s5, secondary pre-baking: pre-baking and heating to heat the oily PU glove lining;

s6, dipping the water-based PU: dipping the oily PU glove lining into aqueous polyurethane mucilage; the aqueous polyurethane mucilage is dispersed with an antibacterial agent, and polyurethane molecules in the aqueous polyurethane mucilage are linear molecular polyurethane;

s7, surface treatment: treating the glove prepared in the step S6 by using a surface treating agent, wherein the surface treating agent is a calcium salt, magnesium salt, zinc salt, aqueous solution of formic acid or acetic acid or an alcohol solution of the calcium salt, the magnesium salt, the zinc salt, the formic acid or the acetic acid;

s8, baking: and (3) solidifying the aqueous polyurethane adhesive cement on the surface of the glove into an adhesive surface through baking, and demolding to obtain a finished product.

According to the preferred embodiment of the present invention, in S1, the glove core is a knitted glove core of 18 needles or more than 18 needles; such as 18 or 21 needles. The more the needle number is, the thinner the glove core is, the softer the hand feeling is, and the more the finished product is fit after being worn, thereby being beneficial to improving the operation sensitivity of the antibacterial glove. In S1, pre-baking and heating to the mould temperature of 40-60 ℃.

According to the preferred embodiment of the invention, in S2, the time for dipping the glove core in the oily polyurethane adhesive cement is 1.5-10S, and the adhesive dripping time is 2-5min.

According to the preferred embodiment of the invention, in S2, the oily polyurethane cement comprises 90-120 parts by mass of oily PU resin emulsion, 100-500 parts by mass of DMF, 0.2-1.5 parts by mass of defoamer and 0.05-1.5 parts by mass of flatting agent;

preferably, the viscosity of the oily polyurethane cement is between 200mpa.s and 2500mpa.s.

According to the preferred embodiment of the invention, in S3, the coagulating agent is DMF water solution with the mass concentration of 5-20%.

According to the preferred embodiment of the invention, in S3, the glove core is soaked in the coagulant for 2-5min, and then is soaked in warm water at 40-80 ℃ for 30-60min.

According to a preferred embodiment of the invention, in S4, the baking temperature is 80-120℃and the baking time is 50-100min, preferably 60min.

According to a preferred embodiment of the present invention, in S5, the pre-bake is heated to a mold temperature of 40-60 ℃.

According to the preferred embodiment of the invention, in S6, the aqueous polyurethane cement contains 90-120 parts by mass of aqueous polyurethane linear molecular emulsion, 0-20 parts by mass of neoprene latex or styrene-butadiene latex or natural latex, 0-5 parts by mass of cross-linking agent, 1-10 parts by mass of antibacterial agent, 0-6 parts by mass of thickening agent and 0-60 parts by mass of water; the viscosity of the aqueous polyurethane cement is 300 to 2000mPa.s; when the addition amount of the neoprene latex or the styrene-butadiene latex or the natural latex is 0, the addition amount of the crosslinking agent is 0.

According to a preferred embodiment of the present invention, in S6, the antibacterial agent is one or a combination of several of zinc pyrithione, nano silver, nano copper, nano zinc, hydroxymethyl imidazolidinone, 2-n-octyl-4-isothiazolin-3-one, 10' -oxydiphenoxyarsine or 2-iodo-2-propynyl-carbamic acid n-butanone, isothiazolinone, nonionic antiviral compound (such as ant itm COV-20).

According to the preferred embodiment of the invention, in S6, the oily PU glove lining is immersed in the aqueous polyurethane adhesive cement for 8-20S and then taken out.

Preferably, in S7, the glove is treated with a surface treatment agent by an impregnation method;

according to a preferred embodiment of the present invention, in S8, the baking temperature is 80-120℃and the baking time is 50-100min, preferably 60min.

According to a preferred embodiment of the present invention, in S7, the surface treating agent further comprises at least one of isopropyl alcohol, sodium dodecyl benzene sulfonate, ethylene glycol, aluminum chloride and sodium hypochlorite.

In a second aspect, the invention also provides an antibacterial double-layer PU glove which is prepared by adopting the production process of any embodiment.

(III) beneficial effects

The beneficial effects of the invention are as follows:

(1) The antibacterial double-layer PU glove comprises a glove core, an oily PU adhesive layer and an antibacterial agent-containing aqueous PU adhesive layer, wherein both the oily PU adhesive layer and the aqueous PU adhesive layer have the advantages of good softness, good fitting property and the like, and the oily/aqueous PU adhesive layer does not contain protein and does not introduce allergen, so that the manufactured glove finished product has high softness, wearing comfort and operation sensitivity, and is very suitable for manufacturing medical gloves. The surface of the oily PU has a plurality of sweat pore-shaped pores, the sweat pore-shaped pores have the characteristics of ventilation, moisture removal and the like, the aqueous PU is a linear polyurethane molecule (non-crosslinking molecule), and the adhesive surface of the aqueous PU after solidification has the characteristics of ventilation and water impermeability. According to the invention, the advantages of the oily PU and the aqueous (linear molecule) PU are combined to manufacture the double-layer PU glove with the lining, compared with the traditional anti-fungus glove, the wear resistance and the wear resistance of the glove are improved, the performance reaches EN388 class 4121, the glove can be repeatedly used, and the pollution and the damage to the environment caused by the small use times of the disposable glove are avoided; meanwhile, the characteristics that sweat pores are fully distributed on the surface of the oily PU and the aqueous PU is waterproof and breathable are utilized, so that the glove finished product has good effects of moisture absorption, sweat release, water resistance, bacteria resistance and the like, and the wearing experience is improved; with the help of the good softness and the fit of PU, the operation sensitivity of wearing is improved.

(2) According to the invention, the antibacterial agent is added into the aqueous polyurethane adhesive cement, so that the antibacterial performance of the glove is endowed, and the antiviral activity rate of the glove on H1N1 influenza A virus and H3N2 influenza virus is up to 99%; the antibacterial rate to staphylococcus aureus, klebsiella pneumoniae, escherichia coli and candida albicans can be up to 99%; the average killing rate of the coronavirus HCoV-229E is still more than 97% by adopting the international standard ISO18184:2014 (E) for the determination of antiviral textiles, and contacting with the coronavirus HCoV-229E suspension for 2.0 hours after 20 times of standard washing. The antibacterial agent is preferably a polar compound antibacterial agent such as zinc pyrithione, nano silver, hydroxymethyl imidazolone and nonionic antiviral compound, which can be uniformly dispersed in the aqueous mucilage, are not easy to agglomerate, and effectively ensure the antibacterial performance of the finished glove.

(3) According to the invention, after oily polyurethane is immersed, coagulator treatment and warm water immersion are carried out, DMF in the oily PU adhesive is separated out to form sweat pore-shaped porous adhesive surface, so that the glove has sweat absorption and moisture removal performances, and then the water-based linear molecule PU adhesive cover containing the antibacterial agent is used for endowing the glove with antibacterial property, waterproof property and air permeability. The surface treatment agent is adopted for treatment after the aqueous PU adhesive cement is immersed, so that on one hand, the compactness of the aqueous PU adhesive cement surface is enhanced, water molecules cannot penetrate to improve the water resistance, pathogenic bacteria are prevented from penetrating from the outside to improve the antibacterial property, and the antibacterial agent in the aqueous PU adhesive cement is kept to prevent the antibacterial agent from migrating and losing, so that the antibacterial property and the durability are improved; on the other hand, the bonding degree between the oily PU adhesive and the aqueous PU adhesive is enhanced.

(4) The glove manufactured by the invention has the advantages of good waterproofness and air permeability, comfortable wearing, antibiosis, light and flexible performance, wear resistance, sensitive operability and the like, is convenient for working in a fine type, such as medical gloves, can be repeatedly used for many times, and avoids the problems of a great deal of resource waste and environmental pollution caused by common disposable gloves.

Drawings

FIG. 1 is a schematic flow chart of a production process of the antibacterial double-layer PU glove.

Detailed Description

The invention will be better explained by the following detailed description of the embodiments with reference to the drawings.

Referring to fig. 1, the invention provides a production process of an antibacterial double-layer PU glove, comprising the following steps:

s1, primary pre-baking: and sleeving the glove core on the hand mould for pre-drying and heating.

Preferably, the glove core is a knitted glove core of 18 needles or more than 18 needles; such as 18 or 21 needles. The more the needle number is, the thinner the glove core is, the softer the hand feeling is, and the more the finished product is fit after being worn, thereby being beneficial to improving the operation sensitivity of the antibacterial glove. The pre-baking is carried out to heat the mold to 40-60 ℃, which is beneficial to quick glue hanging.

S2, soaking oily PU: dipping the glove core into the oily polyurethane adhesive, taking out the glove core, homogenizing the adhesive, and dripping the adhesive.

Immersing the glove core into the oily polyurethane adhesive cement for 1.5-10s (preferably 3 s) under the condition of keeping the mold temperature at 40-60 ℃, taking out the hand mold, and dripping adhesive above the adhesive dripping plate for 2-5min (preferably 3 min). Excess mucilage is removed through glue dripping, so that the uniformity of the thickness of a glue surface is ensured, glue dripping can not occur, but the glue dripping time is not suitable to be too long, otherwise, uniform sweat pore-shaped pores are not formed.

Wherein the oily polyurethane adhesive cement comprises 90-120 parts by mass of oily PU resin emulsion (the solid content of a commercial product is about 35-45%), 100-500 parts by mass of DMF, 0.2-1.5 parts by mass of defoamer and 0.05-1.5 parts by mass of flatting agent, and the viscosity is controlled within 200mPa.s-2500mPa.s.

The composition of the oily polyurethane cement is not limited to the above-described components, but the viscosity is preferably kept between 1000mpa.s and 2500mpa.s.

S3, solidifying and soaking in warm water: the glove cores are soaked in a coagulating agent to promote coagulation, and then soaked in warm water.

The coagulating agent is DMF water solution with mass concentration of 5-20%, and the coagulating agent is immersed for 2-5min to accelerate the coagulation of the oily polyurethane gel. Then soaking in water of 40-80deg.C for 30-60min, wherein the hot water is favorable for organic solvent diffusion in the oily polyurethane gel slurry to form sweat pore-like micropores, thereby making the oily PU gel have sweat absorbing and dampness removing effects and increasing softness of the oily polyurethane gel. In addition, the fine hair pore-shaped micropores also provide a combined rough surface for secondary impregnation.

S4, baking: and (3) solidifying the oily polyurethane cement on the surface of the glove core into a cement surface by baking to obtain the oily PU glove lining.

The baking is carried out in an oven at 80-120 ℃ for 50-100min, preferably 60min, and the oily polyurethane cement is completely solidified and molded after the baking.

S5, secondary pre-baking: the oily PU glove lining is heated by pre-baking and heating.

The oily PU glove lining is heated to 40-60 ℃ by pre-baking, which is favorable for glue hanging.

S6, dipping the water-based PU: dipping the oily PU glove lining into aqueous polyurethane mucilage; the aqueous polyurethane mucilage is dispersed with an antibacterial agent, and polyurethane molecules in the aqueous polyurethane mucilage are linear molecular polyurethane.

Wherein the aqueous polyurethane mucilage comprises 90-120 parts by mass of aqueous polyurethane linear molecular emulsion (the solid content of a commercial product is about 20-40%), 0-20 parts by mass of neoprene latex or styrene-butadiene latex or natural latex, 0-5 parts by mass of cross-linking agent, 1-10 parts by mass of antibacterial agent, 0-6 parts by mass of thickening agent and 0-60 parts by mass of water; the viscosity of the aqueous polyurethane cement is controlled to be 300 to 2000mPa.s. Wherein, when the addition amount of the neoprene latex or the styrene-butadiene latex or the natural latex is 0, the addition amount of the crosslinking agent is 0.

The composition of the aqueous polyurethane cement is not limited to the above-mentioned components, and a small amount of a dispersant, an antioxidant, or the like may be added, but the viscosity is preferably maintained at 1500mpa.s to 3000mpa.s. When the aqueous polyurethane cement is not added with neoprene latex (or styrene-butadiene latex or natural latex), the addition of a crosslinking agent is not required. The thickener is added as needed for viscosity adjustment. Optionally, a small amount of neoprene latex or styrene-butadiene latex or natural latex is added for crosslinking, and further the wear resistance, the water resistance and the tearing strength of the water-based PU glue are further enhanced.

Wherein the antibacterial agent is one or more of zinc pyrithione, nano silver, nano copper, nano zinc, hydroxymethyl imidazolinone, 2-n-octyl-4-isothiazolin-3-one, 10' -oxydiphenoxyarsine or 2-iodo-2-propynyl-carbamic acid n-butanone, isothiazolinone, and nonionic antiviral compound (such as ANTITM COV-20). ANTITM COV-20 is a special antibacterial and antiviral material, and achieves long-term non-leachable antiviral and antibacterial effects through contact antibacterial and antiviral. ANTITM COV-20 has antiviral activity, good antibacterial effect, and durable washing resistance.

The time for impregnating the aqueous polyurethane cement is 8-20s, preferably 10s. These antimicrobial agents all have good water dispersibility and thus can be uniformly dispersed in aqueous polyurethane cement. The aqueous polyurethane adhesive cement does not contain engine oil, and can not corrode or swell the inner lining of the oily PU glove.

S7, surface treatment: the glove prepared in the step S6 is soaked by using a surface treating agent, wherein the surface treating agent is calcium salt, magnesium salt, zinc salt, aqueous solution of formic acid or acetic acid or alcohol solution of calcium salt, magnesium salt, zinc salt, formic acid or acetic acid.

Wherein, the water solution of calcium salt, magnesium salt, zinc salt, formic acid or acetic acid or the methanol solution of calcium salt, magnesium salt, zinc salt, formic acid or acetic acid has the functions of demulsification and accelerating the rapid solidification of the aqueous polyurethane gel. The alcohol is mainly methanol or ethanol.

Preferably, the surface treating agent can be further added with any one or more of isopropanol, sodium dodecyl benzene sulfonate, ethylene glycol, aluminum chloride and sodium hypochlorite. The isopropanol, sodium dodecyl benzene sulfonate, ethylene glycol and the like have the effect of stabilizing the components of the surface treatment agent, and the aluminum chloride is trivalent metal ion, has stronger coagulation promoting effect, and is beneficial to further improving the compactness of the rubber surface; sodium hypochlorite helps to improve the flatness and smoothness of the adhesive surface.

Effect of surface treatment: on one hand, the combination degree of the oily PU adhesive and the water-based PU adhesive is enhanced, and the moisture absorption and sweat release characteristics of the oily PU adhesive and the air-permeability and water resistance of the water-based PU adhesive are combined. The macropores on the surface of the aqueous polyurethane adhesive are sealed by surface treatment, so that the adhesive surface of the aqueous PU adhesive is more compact, the inward permeation of water molecules, pathogenic bacteria and other microorganisms is prevented, and the waterproof permeation performance of the glove product is improved. And because the aqueous PU adhesive is linear polyurethane molecules, a cross-linked network is not generated, the solidified aqueous PU adhesive still has air permeability, sweat in the glove is outwards transmitted in a water vapor form, no hot and damp feeling is generated, and the wearing comfort of the glove is improved. The antibacterial agent and the like are further firmly wrapped and sealed in the aqueous PU adhesive surface through the treatment of the surface treating agent, so that the antibacterial performance of the glove is prevented from being influenced due to migration and precipitation of the antibacterial agent and the like.

On the contrary, although the simple oily PU adhesive surface has good flexibility, the surface of the simple oily PU adhesive surface has a large number of fine air holes, the simple oily PU adhesive surface has no water-proof function, and external bacteria easily enter the air holes to cause bacterial growth. After the external aqueous polyurethane adhesive cement is immersed, if surface treatment is not performed, the combination property of the aqueous PU and the oily PU is poor, and the aqueous PU layer of the glove is easy to fall off in the use process, so that the overall waterproof performance and antibacterial performance of the glove are poor.

S8, baking: and (3) solidifying the aqueous polyurethane adhesive cement on the surface of the glove into an adhesive surface through baking, and demolding to obtain a finished product. Wherein the baking temperature is 80-120deg.C, and the baking time is 50-100min, preferably 60min.

Further description will be provided below in connection with specific embodiments of the present invention.

Example 1

The embodiment provides a production process of an antibacterial double-layer PU glove, which comprises the following steps:

(1) The 18-needle knitted glove core is sleeved on a hand mould and is pre-baked to the mould temperature of 50 ℃.

(2) An oily polyurethane cement is prepared, which comprises 100 parts of oily PU resin emulsion (solid content 38+/-2%), 0.5 part of defoamer and 0.8 part of flatting agent, and DMF is added for stirring and dissolving, and the viscosity is controlled to be 1700mPa.s. The glove cores were all immersed in the oily polyurethane cement for 3 seconds.

(3) And (3) dripping glue above the glue dripping plate for 3 minutes.

(4) Soaking in 10% DMF water solution for 3min, and soaking in 60deg.C water for 50min.

(5) Baking in a baking oven at 110 ℃ for 60min to obtain the oily PU glove lining.

(6) Pre-baking to 45 deg.c.

(7) An antibacterial aqueous polyurethane cement was prepared, which contained 100 parts of aqueous polyurethane (linear molecule) emulsion (solid content about 36%), 3.5 parts of zinc pyrithione, stirred well, added with water and thickener, and controlled to have a viscosity of 1500mpa.s. The oily PU glove lining is immersed into the antibacterial aqueous polyurethane mucilage for 10s and then taken out.

(8) Preparing 10% concentration acetic acid methanol solution to obtain the surface treating agent. The glove was immersed in the surface treatment agent for 10 seconds and then taken out.

(9) Baking the glove in a baking oven at 110 ℃ for 60min, and demolding to obtain a finished product.

Example 2

(1) The 18-needle knitted glove core is sleeved on a hand mould and is pre-baked to the mould temperature of 40 ℃.

(2) An oily polyurethane cement is prepared, which comprises 100 parts of oily PU resin emulsion (solid content 38+/-2%), 0.5 part of defoamer and 0.8 part of flatting agent, and DMF is added for stirring and dissolving, and the viscosity is controlled to be 180mpa.s. The glove cores were all immersed in the oily polyurethane cement for 3 seconds.

(3) And (3) dripping glue above the glue dripping plate for 3 minutes.

(4) Soaking in 15% DMF water solution for 3min, and soaking in 70deg.C water for 50min.

(5) Baking in a baking oven at 100 ℃ for 60min to obtain the oily PU glove lining.

(6) Pre-baking to the mould temperature of 50 ℃.

(7) An antimicrobial aqueous polyurethane cement was prepared, which contained 100 parts of aqueous polyurethane (linear molecule) emulsion (solid content about 36%), 3 parts of zinc pyrithione, 0.5 part of nano silver, stirred well, added with water and thickener, and controlled to a viscosity of 190 mpa.s. The oily PU glove lining is immersed into the antibacterial aqueous polyurethane mucilage for 10s and then taken out.

(8) Preparing 5% calcium chloride aqueous solution to obtain the surface treating agent. The glove was immersed in the surface treatment agent for 15 seconds and then taken out.

(9) Baking the glove in a baking oven at 100 ℃ for 60min, and demolding to obtain a finished product.

Example 3

(1) The 21-needle knitted glove core is sleeved on a hand mould and is pre-baked to the mould temperature of 60 ℃.

(2) An oily polyurethane cement is prepared, which comprises 100 parts of oily PU resin emulsion (solid content 38+/-2%), 0.8 part of defoamer and 1 part of flatting agent, and DMF is added for stirring and dissolving, and the viscosity is controlled to be 1000mPa.s. The glove cores were all immersed in the oily polyurethane cement for 3 seconds.

(3) And (3) dripping glue above the glue dripping plate for 3 minutes.

(4) Soaking in 20% DMF water solution for 3min, and soaking in 80deg.C water for 50min.

(5) Baking in a baking oven at 120 ℃ for 60min to obtain the oily PU glove lining.

(6) Pre-baking to 40 deg.c.

(7) An antibacterial aqueous polyurethane cement was prepared, which contained 100 parts of aqueous polyurethane (linear molecule) emulsion (solid content about 36%), 3.5 parts of hydroxymethyl imidazolidinone, 0.1 part of nano silver, and was stirred uniformly, water and thickener were added, and the viscosity was controlled to 2000mpa.s. The oily PU glove lining is immersed into the antibacterial aqueous polyurethane mucilage for 10s and then taken out.

(8) Preparing 5% magnesium chloride aqueous solution to obtain the surface treating agent. The glove was immersed in the surface treatment agent for 8 seconds and then taken out.

(9) Baking the glove in a baking oven at 120 ℃ for 60min, and demolding to obtain a finished product.

Example 4

(2) An oily polyurethane cement is prepared, which comprises 100 parts of oily PU resin emulsion (solid content 38+/-2%), 0.6 part of defoamer and 0.8 part of flatting agent, and DMF is added for stirring and dissolving, and the viscosity is controlled to be 2000mPa.s. The glove cores were all immersed in the oily polyurethane cement for 3 seconds.

(3) And (3) dripping glue above the glue dripping plate for 3 minutes.

(6) Pre-baking to 40 deg.c.

(7) An antibacterial aqueous polyurethane cement was prepared, which contained 100 parts of an aqueous polyurethane (linear molecule) emulsion (solid content about 36%), 3.5 parts of 2-n-octyl-4-isothiazolin-3-one, 0.1 part of nano zinc, stirred uniformly, added with water and thickener, and controlled to a viscosity of 1780mpa.s. The oily PU glove lining is immersed into the antibacterial aqueous polyurethane mucilage for 10s and then taken out.

(8) Preparing 5% calcium nitrate methanol solution to obtain the surface treating agent. The glove was immersed in the surface treatment agent for 10 seconds and then taken out.

Example 5

(2) An oily polyurethane cement is prepared, which comprises 100 parts of oily PU resin emulsion (solid content 38+/-2%), 0.6 part of defoamer and 0.8 part of flatting agent, and DMF is added for stirring and dissolving, and the viscosity is controlled to 1000mPa.s. The glove cores were all immersed in the oily polyurethane cement for 8 seconds.

(3) And (3) dripping glue above the glue dripping plate for 3 minutes.

(4) Soaking in 15% DMF water solution for 3min, and soaking in 60deg.C water for 50min.

(6) Pre-baking to 45 deg.c.

(7) An antibacterial aqueous polyurethane cement was prepared, which contained 100 parts of an aqueous polyurethane (linear molecule) emulsion (solid content about 36%), 2.5 parts of isothiazolinone, 0.1 part of nano silver, 0.5 part of hydroxymethyl imidazolidinone, and was stirred uniformly, water and a thickener were added, and the viscosity was controlled to 2000mpa.s. The oily PU glove lining is immersed into the antibacterial aqueous polyurethane mucilage for 8s and then taken out.

(8) Preparing 8% methanoic acid solution to obtain the surface treating agent. The glove was immersed in the surface treatment agent for 10 seconds and then taken out.

Example 6

(2) An oily polyurethane cement was prepared, which comprised 100 parts of an oily PU resin emulsion (solid content 38.+ -. 2%), 0.8 parts of an antifoaming agent and 0.8 parts of a leveling agent, and was dissolved by adding DMF with stirring, and the viscosity was controlled at 1400mPa.s. The glove cores were all immersed in the oily polyurethane cement for 10 seconds.

(3) And (3) dripping glue above the glue dripping plate for 3 minutes.

(4) Soaking in 5% DMF water solution for 5min, and soaking in 70deg.C water for 60min.

(6) Pre-baking to 55 deg.c.

(7) An antimicrobial aqueous polyurethane cement was prepared, which contained 100 parts of aqueous polyurethane (linear molecule) emulsion (solid content about 36%), 2.5 parts of isothiazolinone, 0.5 part of ANTITM COV-20, stirred well, added with water and thickener, and the viscosity was controlled to be 180mpa.s. The oily PU glove lining is immersed into the antibacterial aqueous polyurethane mucilage for 10s and then taken out.

(8) Preparing 5% zinc chloride aqueous solution to obtain the surface treating agent. The glove was immersed in the surface treatment agent for 12 seconds and then taken out.

Example 7

Steps (1) - (6) of this example are the same as example 1, but steps (7) - (9) are modified as follows:

(7) An antibacterial aqueous polyurethane cement was prepared, which contained 100 parts of aqueous polyurethane (linear molecule) emulsion (solid content about 36%), 8 parts of neoprene latex, 2.5 parts of a crosslinking agent, 2.5 parts of zinc pyrithione, and was stirred uniformly, water and a thickener were added, and the viscosity was controlled to 2000mpa.s. The oily PU glove lining is immersed into the antibacterial aqueous polyurethane mucilage for 10s and then taken out.

Example 8

This example differs from example 1 only in that 2% isopropyl alcohol was added to the "surface treating agent" used in step (8).

Example 9

This example differs from example 2 only in that 1.5% of ethylene glycol and 1% of sodium dodecylbenzenesulfonate are added to the "surface treating agent" used in step (8).

Example 10

This example differs from example 3 only in that 1.0% hypochlorous acid was added to the "surface treating agent" used in step (8).

Example 11

This example differs from example 4 only in that 1.5% aluminum chloride was added to the "surface treatment agent" used in step (8), and the glove was removed by dipping for about 4 to 5 seconds.

Comparative example 1

The comparative example differs from example 1 only in that the comparative example has not been subjected to the surface treatment agent impregnation treatment of step (8).

Comparative example 2

The present comparative example differs from example 1 only in that steps (1) to (5) were changed as follows:

(1) Sleeving the glove core on a hand mould, and keeping the mould temperature at 45 ℃ for pre-drying treatment;

(2) Maintaining the mould temperature of the pre-baked glove core at 45 ℃, immersing the pre-baked glove core in a 3% calcium methoxide solution, and maintaining for 30 seconds;

(3) A natural latex was formulated comprising 100 parts natural latex emulsion, 0.5 parts defoamer and 0.8 parts leveling agent, with water added to control the viscosity to 1700mpa.s.

(4) The glove cores were all immersed in natural latex for 3 seconds and dipped for 3 minutes.

(5) Baking in a baking oven at 110 ℃ for 60min to obtain the natural latex glove liner.

Steps (6) - (9) are the same as in example 1.

Comparative example 3

Steps (1) - (5) of this comparative example are the same as in example 1, except that steps (6) - (9) are modified as follows:

(6) Pre-baking to 45 deg.c.

(7) An antibacterial nitrile latex was prepared, which contained 100 parts of nitrile latex (solid content 50%), 3.5 parts of zinc pyrithione, 2.5 parts of a crosslinking agent, 2.5 parts of a thickener, and water added to control the viscosity to 2000mpa.s. The oily PU glove liner is immersed into the antibacterial butyronitrile mucilage for 10s and then taken out.

(8) Preparing 10% acetic acid methanol solution, and adding 1.5% ethylene glycol to obtain the surface treating agent. The glove was immersed in the surface treatment agent for 10 seconds and then taken out.

Comparative example 4

(6) Pre-baking to 45 deg.c.

(7) An antibacterial nitrile rubber cement was prepared, which contained 100 parts of nitrile latex (solid content 50%), 5 parts of potassium oleate, 3.5 parts of zinc pyrithione, 2 parts of a crosslinking agent, 2.5 parts of a thickener, and a foaming machine for mechanical foaming, the foaming multiple being 1.4 times, and the viscosity was adjusted to 2000mpa.s with water and the thickener. The oily PU glove lining is immersed into the antibacterial butyronitrile foaming adhesive cement for 10s and then taken out.

The examples 1 to 11 and the comparative examples 1 to 4 were subjected to an antiviral property test, an abrasion resistance property test, and a flexibility test; wherein, the test standard refers to a standard test method for measuring the antibacterial activity of the fixed antibacterial agent under the dynamic contact condition of ASTME2149-2020, and the test result is counted in Table 1; test criteria reference ISO18184:2014 (E) antiviral activity (influenza A virus H1N1 (A/PR/8/34) MDCK cells) test was performed and the results are counted in Table 2; the abrasion resistance test method was carried out with reference to EN388:2016, the flexibility test was carried out with reference to EN ISO 21420:2020, the water permeability test was carried out by turning over the glove, filling with water, hanging and observing the glove for 3 days after the upper end was sealed, and the results were counted in Table 3.

TABLE 1

TABLE 2

TABLE 3 Table 3

In addition, water resistance performance tests were conducted on examples 1 to 11 and comparative examples 1 to 4: preparing a liquid detergent water solution with the mass fraction of 0.2%, adjusting the water temperature to 40 ℃, putting the glove into the liquid detergent water solution, stirring for 60 minutes at the speed of 80rpm/min, taking the process as one washing, drying the glove between adjacent washing processes, carrying out 20 times of washing processes, judging the glove after the experiment, wherein the intact glove is marked as excellent, the glove with slightly damaged surface is marked as good, the surface damage is marked as bad, and the test result is counted in Table 4.

TABLE 4 Table 4

Sample name	Water resistance
		Example 1	Excellent (excellent)
Example 2	Excellent (excellent)
		Example 3	Excellent (excellent)
Example 4	Excellent (excellent)
		Example 5	Excellent (excellent)
Example 6	Excellent (excellent)
		Example 7	Excellent (excellent)
Example 8	Excellent (excellent)
		Example 9	Excellent (excellent)
Example 10	Excellent (excellent)
		Example 11	Excellent (excellent)
Comparative example 1	Difference of difference
		Comparative example 2	Excellent (excellent)
Comparative example 3	Excellent (excellent)
		Comparative example 4	Difference of difference

Through the performance tests, the embodiments 1-11 have good germ protection effect, and simultaneously have the advantages of moisture removal, ventilation, wear resistance, washing resistance, high flexibility and water resistance, and the service life of the glove is prolonged; by adding the antibacterial agent and the waterproof permeability of the synthetic glove in the secondary glue, the opportunity of bacteria entering the inner layer of the glove and the breeding probability of the bacteria can be reduced, so that the bacteria can only stay on the surface and can be inhibited by the antibacterial agent. In example 7, the surface of the oily PU glue is immersed with the mixed glue of the aqueous polyurethane and the neoprene latex, and the wear resistance and the washing resistance are better than those of other examples. The comparative example 1 did not carry out surface treatment on the glove, and greatly weakened the performances of antivirus, abrasion resistance, washing resistance and the like of the glove. The inner layer of comparative example 2 was impregnated with natural latex, which had no pores of the oily PU, and thus had poor air permeability, and had a moist and stuffy feel after wearing, and at the same time, the natural latex was liable to cause water-soluble protein allergy. In comparative example 3, the surface of the oily PU adhesive is dipped with the nitrile latex, which is a crosslinked adhesive layer, resulting in poor overall air permeability of the glove. In comparative example 4, the finished product of the polyurethane foam is soft and good in adhesion and has ventilation and perspiration effects, but the waterproof property, the washing resistance and the wear resistance are poor. Examples 8-11 each had one or more of isopropyl alcohol, sodium dodecyl benzene sulfonate, ethylene glycol, aluminum chloride and sodium hypochlorite added to the surface treatment agent, and the product properties were further improved. In the embodiment 10, the low-concentration sodium hypochlorite is added into the surface treating agent to enable the surface of the outer adhesive layer to be smoother, and in the embodiment 11, a small amount of aluminum chloride is added into the surface treating agent, so that the dipping time of the surface treating agent can be shortened, and the combination firmness of the outer layer water-based PU and the oily PU can be enhanced.

Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims

1. A production process of an antibacterial double-layer PU glove is characterized by comprising the following steps of,

2. The process according to claim 1, wherein in S1, the glove core is a knitted glove core of 18 needles or more.

3. The production process according to claim 1, wherein in S2, the time for impregnating the glove core with the oily polyurethane cement is 1.5-10S, and the time for dripping the polyurethane cement is 2-5min.

4. The production process according to claim 1, wherein in S2, the oily polyurethane cement contains 90 to 120 parts by mass of the oily PU resin emulsion, 100 to 500 parts by mass of DMF, 0.2 to 1.5 parts by mass of the antifoaming agent, and 0.05 to 1.5 parts by mass of the leveling agent;

the viscosity of the oily polyurethane cement is 200mPa.s-2500mPa.s.

5. The production process according to claim 1, wherein in S3, the coagulant is DMF aqueous solution with a mass concentration of 5-20%; in step S3, the glove cores are soaked in the coagulant for 2-5min, and then are soaked in warm water at 40-80 ℃ for 30-60min.

6. The production process according to claim 1, wherein in S6, the aqueous polyurethane cement contains 90 to 120 parts by mass of aqueous polyurethane linear molecular emulsion, 0 to 20 parts by mass of neoprene latex or styrene-butadiene latex or natural latex, 0 to 5 parts by mass of a crosslinking agent, 1 to 10 parts by mass of an antibacterial agent, 0 to 6 parts by mass of a thickener, and 0 to 60 parts by mass of water; the viscosity of the aqueous polyurethane cement is 300 to 2000mPa.s; when the addition amount of the neoprene latex or the styrene-butadiene latex or the natural latex is 0, the addition amount of the crosslinking agent is 0.

7. The production process according to claim 6, wherein in S6, the antibacterial agent is one or a combination of several of zinc pyrithione, nano silver, nano copper, nano zinc, hydroxymethyl imidazolidinone, 2-n-octyl-4-isothiazolin-3-one, 10' -oxydiphenoxyarsine or 2-iodo-2-propynyl-carbamic acid n-butanone, isothiazolinone, nonionic antiviral compound.

8. The production process according to claim 1, wherein in S6, the oily PU glove liner is immersed in the aqueous polyurethane cement for 8-20S and then taken out; s7, treating the glove by using a surface treatment agent through an impregnation method; and S8, baking at 80-120 ℃ for 50-100min.

9. The production process according to claim 1, wherein in S7, at least one of isopropyl alcohol, sodium dodecylbenzenesulfonate, ethylene glycol, aluminum chloride and sodium hypochlorite is further added to the surface treatment agent.

10. An antibacterial double-layer PU glove prepared by the manufacturing process of any one of claims 1-9.