CN101194862A - Elastic polyurethane cladding non-powder rubber medical glove and method for producing the same - Google Patents
Elastic polyurethane cladding non-powder rubber medical glove and method for producing the same Download PDFInfo
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- CN101194862A CN101194862A CNA2007100482108A CN200710048210A CN101194862A CN 101194862 A CN101194862 A CN 101194862A CN A2007100482108 A CNA2007100482108 A CN A2007100482108A CN 200710048210 A CN200710048210 A CN 200710048210A CN 101194862 A CN101194862 A CN 101194862A
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Abstract
The invention discloses elastic polyurethane coating powder-free rubber medical gloves and a production method. The gloves are characterized in that the coating on the inner surface of the glove body is a coating solution layer which is prepared by the mixing emulsion of elastic polyurethane emulsion (PU133-211) and ultra-fine mineral silicon (PHC-20), and the coating on the outer surface of the glove body is a coating solution layer which is prepared by the mixing emulsion of polyacrylic acid (MAX-30) and composition rubber. The production method comprises coating polyurethane coating solution on the inner surface of the glove under the condition of below 30 DEG C, then drying and taking off mold, coating polyacrylacid ester coating solution on the outer surface of the glove under the condition of below 40 DEG C, and finally plasticizing by heat air to obtain the finished product. The invention has the advantages of strong adhesive force of layer, free dropping, favorable water-solubility, dry touch of wearing and excellent humidity resistance, which keeps the natural color of the rubber, can effectively prevent the evolution of natural latex protein, is friendly to environment in the process of production, and can be industrially produced.
Description
Technical field
The present invention relates to medical supplies, specifically a kind of elastic polyurethane cladding non-powder rubber medical glove and production method.
Background technology
Chlorine gas treatment process is mainly adopted in the production of non-powder rubber medical glove at present, carries out chloridized in glove surface, and chlorine and natural gum film reaction make the glued membrane degeneration, and frictional force greatly reduces, and is easy to dress; But this processing method has been used chlorine, and production process causes environmental pollution, and the jaundice of glove color, loses the Heveatex true qualities, can not effectively intercept proteinic separating out.Shanghai " coating and New Chemical Materials " Ceng Youyong aqueous polyacrylamide acid in 2000 or modified polyurethane emulsion and organosilicon blend are as the report of non-powder rubber glove coating liquid., structurally there are some defectives in aqueous polyacrylamide acid, and one is because film forming matter is a linear molecule, and summer, easy deliquescing became sticky, and winter, easy hardening became fragile; Its two be since film forming matter molecule side group be the polarity ester group, molecule has certain hydrophilic; It is three because the granularity of its emulsion particle is bigger, and the film of formation is fine and close inadequately.More than 3 weatherability, resistance to water, resistance tocrocking and resistances to ag(e)ing that can cause filming relatively poor, the glossiness of film and attachment fastness are also undesirable.In addition, polyacrylate solidifies difficult control, does not have elasticity or elasticity minimum after solidifying on the glove, adds with the affinity of rubber badly, and glove use floating coat very easily comes off, and causes secondary pollution, and no powder rate does not reach requirement.And modified polyurethane emulsion and organosilicon blend are perfect inadequately at material and process aspect as non-powder rubber glove coating liquid, do not see suitability for industrialized production so far.
Summary of the invention:
The objective of the invention is for overcoming the deficiencies in the prior art, and provide a kind of coating strong adhesion, water-fast dissolubility is good, can keep the Heveatex true qualities, dress smoothly, can effectively intercept natural latex proteins matter and separate out, production process is environmentally friendly, coating processes is simple, and coating liquid concentration is low, and the elastic polyurethane cladding non-powder rubber medical glove and the production method of energy suitability for industrialized production.
Elastic polyurethane cladding non-powder rubber medical glove of the present invention, interior outer covering layer by glove body and body is formed, it is characterized in that: the elastic polyurethane cladding of the coating of body inner surface for being formed by elastic polyurethane coating liquid dipping, the coating of glove cover external surface is for being soaked the modified polyacrylate coating that forms by the modified polyacrylate coating liquid.
Above-mentioned elasticity is gathered the propylhomoserin cladding non-powder rubber medical glove, and the weight that forms the polyurethane-coated liquid each component of coating on inner surface consists of:
PU133-211 elastic polyurethane (concentration is 30%) 8-17%
PHC-20 superfine inorganic silicon (concentration is 20%) 0.01～0.15%
The soft water surplus;
The each component weight ratio that forms the modified polyacrylic acid coating liquid of external surface coating is: modified polyacrylate MAX-30: soft water=1: 30～50.
The optimum that above-mentioned weight is formed is: the weight that forms the polyurethane-coated liquid each component of coating on inner surface consists of:
PU133-211 elastic polyurethane (concentration is 30%) 14.3%
PHC-20 superfine inorganic silicon (concentration is 20%) 0.025%
The soft water surplus;
The each component weight ratio that forms the modified polyacrylic acid coating liquid of external surface coating is: modified polyacrylate MAX-30: soft water=1: 40.
The polyurethane-coated liquid solid content that forms coating on inner surface is below 6%, and its optimum is 4.2%.
Elastic polyurethane is the polyurethane of modification, its characteristics are meant after emulsion is coated in the glove surface film forming to have hardness and the percentage elongation extremely close with the glove glued membrane, as the technology controlling and process appropriateness just in elasticity, it can be flexible altogether and do not rupture and peel off with glued membrane, and is firm on the glove glued membrane.And can make glove have good moisture resistance.Though elastic polyurethane cladding has above-mentioned advantage, weak point is that its smooth degree is not good enough, not easy donning.Elastic polyurethane emulsion of the present invention and superfine inorganic silicon and usefulness, inorganic silicon can effectively reduce the coefficient of friction of system, to remedy the deficiency of the smooth degree of elastane, makes glove be easy to dress.The organosilicon material that uses in this superfine inorganic silicon and the prior art report is compared also and had the following advantages: 1. superfine inorganic silicon particle is scattered in the elastic polyurethane emulsion less than 1 micron, presents thermodynamical equilibrium, can not produce the phenomenon of coagulation sedimentation; The coating film forming is even, and it is stable that action effect is soaked in long-time culvert; 2. the silicon particle is little, and less solid use amount just can reach identical overlay masking rate; 3. the particle specific surface area is big, easily by the sticking connection of elastic polyurethane base material, incrust dry linting; 4. also with several near-transparents of elastic polyurethane cladding of superfine inorganic silicon coating, product appearance presents the visual effect of transparent no powder.
Wherein said modified polyacrylate is polyacrylic acid and elastomeric blended liquid.Because its vitrification point of polyacrylic acid macromolecule is lower, higher percentage elongation is arranged, but hot strength is lower, allow itself and nonprotein synthetic rubber blend, remedied this deficiency.Person in addition, modified polyacrylate has high friction coefficient, thereby good grasping performance is arranged.
The preparation technology of non-powder rubber medical glove of the present invention comprises the steps:
1. prepare natural latex rubber glove body;
2. be mixed in proportion to stir with PU133-211 elastic polyurethane (concentration is 30%), PHC-20 superfine inorganic silicon (concentration is 20%) and soft water and make the elastic polyurethane coating liquid;
3. be lower than adversary's body inner surface (wearing face) dipping elastic polyurethane cladding under 30 ℃ of conditions;
4. homogenate, drying, the demoulding;
5. be lower than adversary's condom external surface immersion modified polyacrylate coating under 40 ℃ of conditions, soaking technology carries out in centrifugal vulcanizer, stirs 3～5 minutes;
6. decocting in water sulfuration: during the water curing product, water temperature rises to 65～90 ℃, temperature retention time 15～20 minutes gradually from 45 ℃;
After the plasticizing of 80～90 ℃ of hot-airs finished product.
In the above-mentioned steps, elastic polyurethane coating liquid temperature remains on below 40 ℃, and the body inner surface is immersed in the above-mentioned elastic polyurethane coating liquid for preparing, and soaks time 10s-15s, lifting time 10s-20s down.
Soak hot water time 90s-120s, temperature fall time 15s-20s during body inner surface elastic polyurethane cladding demoulding.
When elastic polyurethane cladding demoulding temperature is reduced to below 50 ℃, with artificial no powder off-type.
The invention has the advantages that: 1., have good adhesive force, coating difficult drop-off, good springiness, intensity height, wear-resisting, oil resistant owing to the special construction of amino-formate bond in the elastic polyurethane strand.Its good biocompatibility the more important thing is that its compactness is good, can intercept proteinic separating out in the natural glued membrane glove preferably, has improved the safety that glove use greatly; 2. the elastic polyurethane emulsion is a kind of emulsion type material, the production process environmentally safe; 3. technology is simple, and dipping once can be finished, and impregnation concentration is below 6%, and, consumption simpler than the technology of repeatedly dipping, the concentration 5～10% of prior art lacks; 4. in elastic polyurethane coating liquid recipe design, added the superfine inorganic silicon, given elastic polyurethane cladding less coefficient of friction, thereby strengthened the smooth effect of glove, dressed easily; 5. the outer surface of glove coating can be prevented not only that glove are sticking and takes, and rough surface, good antiskid effect; 6. mature preparation process of the present invention can be carried out suitability for industrialized production.
Description of drawings:
Fig. 1 is technological process of production figure of the present invention.
The specific embodiment:
The present invention is made up of the elastic polyurethane cladding of natural rubber gloves body, glove body inner surface, the modified polyacrylic acid coating of glove cover external surface, and its preparation technology comprises the steps:
1. prepare the elastic polyurethane coating liquid: mix by following raw material and percentage by weight and stir preparation, mixing time is 10～20 hours, and mixing speed is 60～100 rev/mins:
PU133-211 elastic polyurethane (concentration is 30%) 8.5
PHC-20 superfine inorganic silicon (concentration is 20%) 0.02
The soft water surplus
2. the preparation of modified polyacrylate coating liquid:
Press modified polyacrylate MAX-30: soft water=1: 32 (component weight ratio) dilution proportion, stir and can use after 30 minutes.
3. coating elastic polyurethane cladding:
During with the dipping of the natural rubber gloves body inner surface behind crimping polyurethane cladding liquid, control glued membrane dry tack free degree, require glove glued membrane inner surface exclusion, the glued membrane temperature reaches 40～45 ℃, the glued membrane state that is translucent wherein, soaks coating liquid time 10s～15s, lifting time 10s～20s, coating liquid use being lower than under 40 ℃ of temperature;
4. dry, the demoulding: the upper and lower mould temperature is even when guaranteeing product drying, avoids fingerprint finger tip portion temperature too high, influences off-type; Wherein, product soaks hot water time 90s～120s, and temperature fall time needs 15s～20s, and surperficial moisture content is evaporated completely entirely (use Pneumatic drying device), when the glued membrane temperature is reduced to below 50 ℃, with artificial no powder off-type;
5. apply the modified polyacrylate coating: after washing the coagulant of glove surface with water, put into the centrifugal vulcanizer that fills modified polyacrylate coating liquid and stirred 3～5 minutes.Because the effect glove of centrifuge are extruded the glove internal layer are adjacent to, the emulsion of modified polyacrylate is few attached to the amount of glove inner surface, only at glove wrist oral area, account for inner surface about 5%, thereby do not influence the performance of glove internal layer elastic polyurethane cladding;
6. decocting in water sulfuration: the water curing product is warming up to 65～90 ℃, about 10～15 minutes of heating-up time, temperature retention time 15～20 minutes gradually from 45 ℃;
7. take out with 80-90 ℃ of hot-air and carry out the glove surface plastics processing.
Embodiment 2
The present invention is made up of the elastic polyurethane cladding of natural rubber gloves body, glove body inner surface, the modified polyacrylic acid coating of glove cover external surface, and its preparation technology comprises the steps:
1. prepare the elastic polyurethane coating liquid: mix by following raw material and percentage by weight and stir preparation, mixing time is 10～20 hours, and mixing speed is 60～100 rev/mins:
PU133-211 elastic polyurethane (concentration is 30%) 12
PHC-20 superfine inorganic silicon (concentration is 20%) 0.1
The soft water surplus
2. the preparation of modified polyacrylate coating liquid:
Press modified polyacrylate MAX-30: soft water=1: 40 (component weight ratio) dilution proportion, stir and can use after 30 minutes.
3. coating elastic polyurethane cladding:
During with the dipping of the natural rubber gloves body inner surface behind crimping polyurethane cladding liquid, control glued membrane dry tack free degree, require glove glued membrane inner surface exclusion, the glued membrane temperature reaches 40～45 ℃, the glued membrane state that is translucent wherein, soaks coating liquid time 10s～15s, lifting time 10s～20s, coating liquid use being lower than under 40 ℃ of temperature;
4. dry, the demoulding: the upper and lower mould temperature is even when guaranteeing product drying, avoids fingerprint finger tip portion temperature too high, influences off-type; Wherein, product soaks hot water time 90s～120s, and temperature fall time needs 15s～20s, and surperficial moisture content is evaporated completely entirely (use Pneumatic drying device), when the glued membrane temperature is reduced to below 50 ℃, with artificial no powder off-type;
5. apply the modified polyacrylate coating: after washing the coagulant of glove surface with water, put into the centrifugal vulcanizer that fills modified polyacrylate coating liquid and stirred 3～5 minutes.Because the effect glove of centrifuge are extruded the glove internal layer are adjacent to, the emulsion of modified polyacrylate is few attached to the amount of glove inner surface, only at glove wrist oral area, account for inner surface about 5%, thereby do not influence the performance of glove internal layer elastic polyurethane cladding;
6. decocting in water sulfuration: the water curing product is warming up to 65～90 ℃, about 10～15 minutes of heating-up time, temperature retention time 15～20 minutes gradually from 45 ℃;
7. take out with 80-90 ℃ of hot-air and carry out the glove surface plastics processing.
Embodiment 3
The present invention is made up of the elastic polyurethane cladding of natural rubber gloves body, glove body inner surface, the modified polyacrylic acid coating of glove cover external surface, and its preparation technology comprises the steps:
1. prepare the elastic polyurethane coating liquid: mix by following raw material and percentage by weight and stir preparation, mixing time is 10～20 hours, and mixing speed is 60～100 rev/mins:
PU133-211 elastic polyurethane (concentration is 30%) 16
PHC-20 superfine inorganic silicon (concentration is 20%) 0.14
The soft water surplus
2. the preparation of modified polyacrylate coating liquid:
Press modified polyacrylate MAX-30: soft water=1: 40 (component weight ratio) dilution proportion, stir and can use after 30 minutes.
3. coating elastic polyurethane cladding:
During with the dipping of the natural rubber gloves body inner surface behind crimping polyurethane cladding liquid, control glued membrane dry tack free degree, require glove glued membrane inner surface exclusion, the glued membrane temperature reaches 40～45 ℃, the glued membrane state that is translucent wherein, soaks coating liquid time 10s～15s, lifting time 10s～20s, coating liquid use being lower than under 40 ℃ of temperature;
4. dry, the demoulding: the upper and lower mould temperature is even when guaranteeing product drying, avoids fingerprint finger tip portion temperature too high, influences off-type; Wherein, product soaks hot water time 90s～120s, and temperature fall time needs 15s～20s, and surperficial moisture content is evaporated completely entirely (use Pneumatic drying device), when the glued membrane temperature is reduced to below 50 ℃, with artificial no powder off-type;
5. apply the modified polyacrylate coating: after washing the coagulant of glove surface with water, put into the centrifugal vulcanizer that fills modified polyacrylate coating liquid and stirred 3～5 minutes.Because the effect glove of centrifuge are extruded the glove internal layer are adjacent to, the emulsion of modified polyacrylate is few attached to the amount of glove inner surface, only at glove wrist oral area, account for inner surface about 5%, thereby do not influence the performance of glove internal layer elastic polyurethane cladding;
6. decocting in water sulfuration: the water curing product is warming up to 65～90 ℃, about 10～15 minutes of heating-up time, temperature retention time 15～20 minutes gradually from 45 ℃;
7. take out with 80-90 ℃ of hot-air and carry out the glove surface plastics processing.
Embodiment 4
The present invention is made up of the elastic polyurethane cladding of natural rubber gloves body, glove body inner surface, the modified polyacrylic acid coating of glove cover external surface, and its preparation technology comprises the steps:
1. prepare the elastic polyurethane coating liquid: mix by following raw material and percentage by weight and stir preparation, mixing time is 10～20 hours, and mixing speed is 60～100 rev/mins:
PU133-211 elastic polyurethane (concentration is 30%) 16
PHC-20 superfine inorganic silicon (concentration is 20%) 0.14
The soft water surplus
2. the preparation of modified polyacrylate coating liquid:
Press modified polyacrylate MAX-30: soft water=1: 48 (component weight ratio) dilution proportion, stir and can use after 30 minutes.
3. coating elastic polyurethane cladding:
During with the dipping of the natural rubber gloves body inner surface behind crimping polyurethane cladding liquid, control glued membrane dry tack free degree, require glove glued membrane inner surface exclusion, the glued membrane temperature reaches 40～45 ℃, the glued membrane state that is translucent wherein, soaks coating liquid time 10s～15s, lifting time 10s～20s, coating liquid use being lower than under 40 ℃ of temperature;
4. dry, the demoulding: the upper and lower mould temperature is even when guaranteeing product drying, avoids fingerprint finger tip portion temperature too high, influences off-type; Wherein, product soaks hot water time 90s～120s, and temperature fall time needs 15s～20s, and surperficial moisture content is evaporated completely entirely (use Pneumatic drying device), when the glued membrane temperature is reduced to below 50 ℃, with artificial no powder off-type;
5. apply the modified polyacrylate coating: after washing the coagulant of glove surface with water, put into the centrifugal vulcanizer that fills modified polyacrylate coating liquid and stirred 3～5 minutes.Because the effect glove of centrifuge are extruded the glove internal layer are adjacent to, the emulsion of modified polyacrylate is few attached to the amount of glove inner surface, only at glove wrist oral area, account for inner surface about 5%, thereby do not influence the performance of glove internal layer elastic polyurethane cladding;
6. decocting in water sulfuration: the water curing product is warming up to 65～90 ℃, about 10～15 minutes of heating-up time, temperature retention time 15～20 minutes gradually from 45 ℃;
7. take out with 80-90 ℃ of hot-air and carry out the glove surface plastics processing.
Claims (9)
1. elastic polyurethane cladding non-powder rubber medical glove, form by the interior outer covering layer on glove body and the body, it is characterized in that: the elastic polyurethane cladding of the coating of body inner surface for being formed by elastic polyurethane coating liquid dipping, the coating of glove cover external surface is for being soaked the modified polyacrylate coating that forms by the modified polyacrylate coating liquid.
2. elasticity according to claim 1 is gathered the propylhomoserin cladding non-powder rubber medical glove, it is characterized in that: the weight that forms the polyurethane-coated liquid each component of coating on inner surface consists of:
PU133-211 elastic polyurethane (concentration is 30%) 8-17%
PHC-20 superfine inorganic silicon (concentration is 20%) 0.01～0.15%
The soft water surplus;
The each component weight ratio that forms the modified polyacrylic acid coating liquid of external surface coating is: modified polyacrylate MAX-30: soft water=1: 30～50.
3. elasticity according to claim 1 is gathered the propylhomoserin cladding non-powder rubber medical glove, it is characterized in that: the weight that forms the polyurethane-coated liquid each component of coating on inner surface consists of:
PU133-211 elastic polyurethane (concentration is 30%) 14.3%
PHC-20 superfine inorganic silicon (concentration is 20%) 0.025%
The soft water surplus;
The each component weight ratio that forms the modified polyacrylic acid coating liquid of external surface coating is: modified polyacrylate MAX-30: soft water=1: 40.
4. according to claim 1, the poly-propylhomoserin cladding non-powder rubber medical glove of 2 or 3 described elasticity, it is characterized in that: the polyurethane-coated liquid solid content that forms coating on inner surface is below 6%.
5. according to claim 1, the poly-propylhomoserin cladding non-powder rubber medical glove of 2 or 3 described elasticity, it is characterized in that: the polyurethane-coated liquid solid content that forms coating on inner surface is 4.2%.
6. the preparation method of elastic polyurethane cladding non-powder rubber medical glove comprises the steps:
1). preparation natural latex rubber glove body;
2). be mixed in proportion stirring with PU133-211 elastic polyurethane (concentration is 30%), PHC-20 superfine inorganic silicon (concentration is 20%) and soft water and make the elastic polyurethane coating liquid;
3). be lower than adversary's body inner surface (wearing face) dipping elastic polyurethane cladding under 30 ℃ of conditions;
4). homogenate, drying, the demoulding;
5). be lower than adversary's condom external surface immersion modified polyacrylate coating under 40 ℃ of conditions, soaking technology carries out in centrifugal vulcanizer, stirs 3～5 minutes;
6). the decocting in water sulfuration: during the water curing product, water temperature rises to 65～90 ℃, temperature retention time 15～20 minutes gradually from 45 ℃;
7). after the plasticizing of 80～90 ℃ of hot-airs finished product.
7. preparation method according to claim 6 is characterized in that: elastic polyurethane coating liquid temperature remains on below 40 ℃, and the body inner surface is immersed in the above-mentioned elastic polyurethane coating liquid for preparing, and soaks time 10s-15s, lifting time 10s-20s down.
8. preparation method according to claim 6 is characterized in that: soak hot water time 90s-120s, temperature fall time 15s-20s during body inner surface elastic polyurethane cladding demoulding.
9. preparation method according to claim 6 is characterized in that: when elastic polyurethane cladding demoulding temperature is reduced to below 50 ℃, with artificial no powder off-type.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2007100482108A CN101194862A (en) | 2007-01-01 | 2007-01-01 | Elastic polyurethane cladding non-powder rubber medical glove and method for producing the same |
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| CNA2007100482108A CN101194862A (en) | 2007-01-01 | 2007-01-01 | Elastic polyurethane cladding non-powder rubber medical glove and method for producing the same |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101632496B (en) * | 2008-08-22 | 2011-03-30 | 桂林乳胶厂 | Preparation method of compound floss lining household rubber gloves |
| CN102126271A (en) * | 2011-01-12 | 2011-07-20 | 江苏尤佳手套有限公司 | PVC (Polyvinyl Chloride)/NBR (Nitrile Butadiene Rubber) composite gloves |
| CN102173018A (en) * | 2011-03-01 | 2011-09-07 | 桂林乳胶厂 | Production linkage line for producing covered surgical medical latex gloves |
| CN106313397A (en) * | 2016-09-22 | 2017-01-11 | 桂林紫竹乳胶制品有限公司 | Medical rubber glove containing trace amount of powder and preparation method of medical rubber glove |
| CN109056130A (en) * | 2018-10-24 | 2018-12-21 | 苏州萧然新材料有限公司 | A kind of tow rapid moving mechanism of elasticizer |
| CN110625967A (en) * | 2019-08-13 | 2019-12-31 | 山东星宇手套有限公司 | Surface treatment method for preventing frosting of rubber product |
| CN112956766A (en) * | 2021-03-03 | 2021-06-15 | 苏州市第五人民医院 | Anti-needling glove and preparation process thereof |
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2007
- 2007-01-01 CN CNA2007100482108A patent/CN101194862A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101632496B (en) * | 2008-08-22 | 2011-03-30 | 桂林乳胶厂 | Preparation method of compound floss lining household rubber gloves |
| CN102126271A (en) * | 2011-01-12 | 2011-07-20 | 江苏尤佳手套有限公司 | PVC (Polyvinyl Chloride)/NBR (Nitrile Butadiene Rubber) composite gloves |
| CN102126271B (en) * | 2011-01-12 | 2013-03-20 | 江苏尤佳手套有限公司 | Production process of PVC (Polyvinyl Chloride)/NBR (Nitrile Butadiene Rubber) composite gloves |
| CN102173018A (en) * | 2011-03-01 | 2011-09-07 | 桂林乳胶厂 | Production linkage line for producing covered surgical medical latex gloves |
| CN106313397A (en) * | 2016-09-22 | 2017-01-11 | 桂林紫竹乳胶制品有限公司 | Medical rubber glove containing trace amount of powder and preparation method of medical rubber glove |
| CN109056130A (en) * | 2018-10-24 | 2018-12-21 | 苏州萧然新材料有限公司 | A kind of tow rapid moving mechanism of elasticizer |
| CN109056130B (en) * | 2018-10-24 | 2023-11-03 | 苏州萧然新材料有限公司 | Quick tow moving mechanism of elasticizer |
| CN110625967A (en) * | 2019-08-13 | 2019-12-31 | 山东星宇手套有限公司 | Surface treatment method for preventing frosting of rubber product |
| CN110625967B (en) * | 2019-08-13 | 2021-06-08 | 山东星宇手套有限公司 | Surface treatment method for preventing frosting of rubber product |
| CN112956766A (en) * | 2021-03-03 | 2021-06-15 | 苏州市第五人民医院 | Anti-needling glove and preparation process thereof |
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Open date: 20080611 |