CN104646352A - Method for quickly cleaning plasmas of release agent on surface of rubber shoe material - Google Patents
Method for quickly cleaning plasmas of release agent on surface of rubber shoe material Download PDFInfo
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- CN104646352A CN104646352A CN201510066362.5A CN201510066362A CN104646352A CN 104646352 A CN104646352 A CN 104646352A CN 201510066362 A CN201510066362 A CN 201510066362A CN 104646352 A CN104646352 A CN 104646352A
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- plasma
- rubber boots
- releasing agent
- material surface
- glow discharge
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
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- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
Abstract
The invention relates to a method for quickly cleaning plasmas of release agent on the surface of rubber shoe material. The method comprises the following steps of (1) heating the rubber shoe material in an atmospheric pressure environment until that the surface temperature of the rubber shoe material is 80-90 DEG C; (2) by using the wet air, within the atmospheric pressure range of 20-60Pa, cleaning the low-temperature plasmas of which mean electron energy is larger than 4eV in a manner of glow discharge cleaning for 5-200s, and then removing the release agent on the surface of the material; (3) pumping the base vacuum until to be lower than 10Pa; after reducing the content of oxygen in the vacuum cavity, by using methylamine, within the atmospheric pressure range of 20-100Pa, cleaning the low-temperature plasmas of which mean electron energy is larger than 4eV in a manner of glow discharge cleaning, and modifying the rubber shoe material for 4-20s. According to the method provided by the invention, pre-treatment by washing with water is saved, rubber processing agent does not need to be used, and the adhering strength of the shoe material achieves the degree of material broken.
Description
Technical field
The invention belongs to shoemaking adhesive technology field, relate to the plasma Rapid Cleaning method of a kind of rubber boots material surface releasing agent.
Background technology
Rubber is widely used material in shoemaking industry, and because the surface energy of rubber is little, the pretreatment must carrying out surface modification just can be carried out bonding.In current shoemaking industry, the brush coating technique for sticking pre-treatment of rubber boots material is that buck (activating agent) cleaning is carried out on first surface, then washes, dries, then brush rubber finishing agent.Serious problem of environmental pollution (the containing the hypertoxic volatile organic contaminants such as stupid class of waste water, rubber finishing agent) is there is in this art production process.The method of rubber surface modification mainly contains two kinds, one be chemical technology modification (surperficial halogenation, fluoridize, chlorination, bromination and iodate, surface oxidation and covalent functionalization modification.Two is that (radiation of face coat, plasma treatment and plasma polymerization modification, g ray, ultraviolet and electron beam causes surface grafting polymerization etc. in physical technique modification.Due to problem of environmental pollution, efficiency problem, the plasma modification technology of rubber surface demonstrates unique advantage.It will bring revolutionary breakthrough for shoe industry.The work that domestic and international academia carries out plasma rubber surface study on the modification is a lot, and has a lot of patent.But these numerous achievements in research all have no formation productivity at home and abroad, the footwear plasma washing machine that the grand allusion quotation industry in Taiwan is developed also to fail accept by market.Its profound cause has three: one studies in China follows international research method and Research Thinking, has no novelty and breaks through.The plasma surface modification technology of its two routine also needs the pretreatment of washing rubber, can not solve the waste water pollution problem of enterprise.Its three processing time is long, cannot grafting to production line.Therefore, no matter domestic or have no the illustration that plasma treatment rubber boots material moves towards to apply abroad.In order to address this problem, based on our CN201220136649.2 and CN103564985A patent, through a large amount of experimental studies, invent the plasma Rapid Cleaning method of a kind of rubber boots material surface releasing agent.
Summary of the invention
The technical problem solved: in order to superseded shoe industry rubber boots material bonding before water-washing pre-treatment and adopt the technique of environmental pollution of rubber finishing agent, the invention provides the plasma Rapid Cleaning method of a kind of rubber boots material surface releasing agent, this technology does not only need the pretreatment of carrying out washing, and do not need rubber finishing agent, Simplified flowsheet, minimizing cost and manpower, non-environmental-pollution.
Technical scheme: the plasma Rapid Cleaning method that the invention discloses a kind of rubber boots material surface releasing agent, described method comprises the following steps:
(1) heat to rubber boots material under atmospheric pressure environment, being heated to rubber boots material surface temperature is 80 ~ 90 DEG C;
(2) utilize humidifying air, under the air pressure range of 20 ~ 60Pa, the electron energy that is averaged is greater than the low temperature plasma Glow Discharge Cleaning 5 ~ 200 seconds of 4eV, removes the releasing agent of material surface;
(3) take out base vacuum lower than 10Pa, after reducing the oxygen element content in vacuum chamber, adopt methylamine, under the air pressure range of 20 ~ 100Pa, the low temperature plasma glow discharge that the electron energy that is averaged is greater than 4eV carries out modification 4-20 second to rubber boots material.
Further, the plasma Rapid Cleaning method of described a kind of rubber boots material surface releasing agent, adopt methylamine in step (3), under the air pressure range of 30 ~ 100Pa, the low temperature plasma glow discharge that the electron energy that is averaged is greater than 4eV carries out modification 4-20 second to rubber boots material.
Further, the plasma Rapid Cleaning method of described a kind of rubber boots material surface releasing agent, described low temperature plasma glow discharge comprises Capacitance Coupled, inductive, microwave excitation, RF excited, direct-current discharge, alternating current discharge.
Further, the plasma Rapid Cleaning method of described a kind of rubber boots material surface releasing agent, plasma Glow Discharge Cleaning 20 ~ 120 seconds in step (2).
Further, the plasma Rapid Cleaning method of described a kind of rubber boots material surface releasing agent, plasma Glow Discharge Cleaning 30 ~ 50 seconds in step (2).
Further, the plasma Rapid Cleaning method of described a kind of rubber boots material surface releasing agent, plasma Glow Discharge Cleaning 40 seconds in step (2).
Rubber boots material is heated in atmospheric pressure environment surface temperature 80 ~ 90 DEG C, the releasing agent on its surface (main component is paraffin) is softened, the object heated in atmospheric pressure environment suppresses to escape to footwear material surface outside the small-molecule substance of rubber inside.
Due to the mixture that paraffin is solid-state higher alkane, the molecular formula of main component is CnH2n+2, wherein n=17 ~ 35.The air with certain humidity produces the oxygen groups with dehydrogenation in plasma atmosphere, what produce under hydroxyl and nitrogen oxygen excitation state is infrared, ultraviolet light, these groups have good decomposition to paraffin, in addition footwear material is preheated, thus there is the remarkable result removing releasing agent fast.
Carry out plasma discharge, methylamine decomposites amino and nitrogen, hydrogen, the hydrophilic radical such as hydrocarbon.These hydrophilic radicals are beneficial to water-base cement scattering and permeating, and the coating being beneficial to glue is even.The amino being grafted to footwear material surface utilizes its covalent bond to be combined with water-base cement, forms very strong bonding force.
Reach the object of cleaning to there be enough energy and make methylamine decomposite the object of ammonia, nitrogen, hydrogen, the group such as hydrocarbon, no matter adopt the electric discharge (Capacitance Coupled, inductive, microwave excitation, RF excited, direct-current discharge, alternating current discharge etc.) of which kind of form, ensure that plasma mean electron energy is greater than 4eV.
Because plasma both can make methylamine produce amino, amino can be decomposed again.In order to the amino prevented is decomposed again, carry out the short time electric discharge of 4-20 second, make amino enough on footwear material surface grafting.
The adhesive strength of this invention technology footwear material is adopted to reach the broken degree of material.
beneficial effect:the plasma Rapid Cleaning method of rubber boots material surface of the present invention releasing agent, does not need water-washing pre-treatment not use rubber finishing agent, and the adhesive strength of footwear material also reaches the broken degree of material.
Accompanying drawing explanation
Fig. 1 is the flow chart of the plasma Rapid Cleaning method of rubber boots material of the present invention surface releasing agent.
Detailed description of the invention
Embodiment 1
In FIG, 1 is that rubber boots material is warmed to surface temperature 80 ~ 90 DEG C, and the releasing agent of rubber surface is softened, and the fast degradation being beneficial to plasma is removed.Escaping to material surface for reducing outside the small-molecule substance in elastomeric material, heating in atmospheric environment.2 is that the footwear material of heating is placed in low vacuum plasma producing apparatus, and open vavuum pump, pump drainage air is to low vacuum in 10Pa.3 is the air passing into humidification, makes air pressure be elevated to 20Pa ~ 60Pa.Carry out plasma electric discharge in 5 ~ 200 seconds, discharge power ensures that plasma mean electron energy is greater than 4eV.Infrared, ultraviolet light that the air of humidification produces produce oxygen groups, hydroxyl and the nitrogen oxygen excitation state with dehydrogenation under the effect of plasma under, these groups have good decomposition to hydrocarbon, thus have the remarkable result removing releasing agent fast.4 stop, into humidifying air, parking electricity, are evacuated to below 10Pa.The methylamine gas of 5 admission makes vacuum to 30 ~ 100Pa, discharges to carry out plasma modification process 4-20 second to rubber boots material surface.6 shut down taking-up material, complete footwear material process of surface treatment.
Utilize the technology of the present invention to Wan Bang and and the footwear material of Cheng Liang large enterprises carry out surface modification treatment.Footwear material is without washing, surface temperature 80-90 DEG C is warmed under atmospheric environment, through the process of the cryogenic vacuum glow plasma of humidifying air, after disposing surperficial releasing agent, then carry out the modification of grafted amino group with methylamine gas plasma, utilize its covalent bond to be combined with water-base cement at the amino on footwear material surface, form very strong bonding force, adhesive strength even can exceed the mechanical strength of footwear material self, during tensile test, occurs broken material phenomenon.Table 1 is the adhesive strength experimental result of rubber boots material at the different scavenging period of humidifying air plasma.Result shows: under identical methylamine plasma grafting conditions, and there is very desirable effect in the processing time of the cryogenic vacuum glow plasma of humidifying air from 20 seconds by 120 seconds, and adhesive strength is far above professional standard (>3.0N/mm).
Form
rubber boots material is in the adhesive strength experimental result of the different scavenging period of humidifying air plasma.
Claims (6)
1. a plasma Rapid Cleaning method for rubber boots material surface releasing agent, is characterized in that: described method comprises the following steps:
(1) heat to rubber boots material under atmospheric pressure environment, being heated to rubber boots material surface temperature is 80 ~ 90 DEG C;
(2) utilize humidifying air, under the air pressure range of 20 ~ 60Pa, the electron energy that is averaged is greater than the low temperature plasma Glow Discharge Cleaning 5 ~ 200 seconds of 4eV, removes the releasing agent of material surface;
(3) take out base vacuum lower than 10Pa, after reducing the oxygen element content in vacuum chamber, adopt methylamine, under the air pressure range of 20 ~ 100Pa, the low temperature plasma glow discharge that the electron energy that is averaged is greater than 4eV carries out modification 4-20 second to rubber boots material.
2. the plasma Rapid Cleaning method of a kind of rubber boots material surface according to claim 1 releasing agent, it is characterized in that: in step (3), adopt methylamine, under the air pressure range of 30 ~ 100Pa, the low temperature plasma glow discharge that the electron energy that is averaged is greater than 4eV carries out modification 4-20 second to rubber boots material.
3. the plasma Rapid Cleaning method of a kind of rubber boots material surface according to claim 1 releasing agent, is characterized in that: described low temperature vacuum plasma body glow discharge comprises Capacitance Coupled, inductive, microwave excitation, RF excited, direct-current discharge, alternating current discharge.
4. the plasma Rapid Cleaning method of a kind of rubber boots material surface according to claim 1 releasing agent, is characterized in that: plasma Glow Discharge Cleaning 20 ~ 120 seconds in step (2).
5. the plasma Rapid Cleaning method of a kind of rubber boots material surface according to claim 1 releasing agent, is characterized in that: plasma Glow Discharge Cleaning 30 ~ 50 seconds in step (2).
6. the plasma Rapid Cleaning method of a kind of rubber boots material surface according to claim 1 releasing agent, is characterized in that: plasma Glow Discharge Cleaning 40 seconds in step (2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510066362.5A CN104646352A (en) | 2015-02-10 | 2015-02-10 | Method for quickly cleaning plasmas of release agent on surface of rubber shoe material |
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| CN201510066362.5A CN104646352A (en) | 2015-02-10 | 2015-02-10 | Method for quickly cleaning plasmas of release agent on surface of rubber shoe material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106827486A (en) * | 2017-01-13 | 2017-06-13 | 中国科学院合肥物质科学研究院 | A kind of air plasma improves pen tongue moistened surface method and application thereof |
| CN108506730A (en) * | 2018-05-09 | 2018-09-07 | 苏州卫鹏机电科技有限公司 | A kind of air supply system and its air supply method |
| CN115999868A (en) * | 2022-12-27 | 2023-04-25 | 泉州市瑞鑫体育用品有限公司 | Sole reprocessing treatment process |
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| KR20010084070A (en) * | 2000-02-23 | 2001-09-06 | 손명호 | Method for bonding sole by plasma surface treatment |
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| KR20090106722A (en) * | 2008-04-07 | 2009-10-12 | (주)유이온 | Shoes bonding and cleaning process by atmospheric pressure plasma |
| CN102296283A (en) * | 2010-06-24 | 2011-12-28 | 苏州卫鹏机电科技有限公司 | Method for treating surfaces of shoe materials |
| CN102783768A (en) * | 2011-05-18 | 2012-11-21 | 苏州卫鹏机电科技有限公司 | Method for treating surfaces of shoes |
| CN104015351A (en) * | 2014-06-03 | 2014-09-03 | 石家庄佑生机械设备有限公司 | Normal-pressure high-density microwave plasma shoe material surface treatment method |
| CN104292489A (en) * | 2014-08-08 | 2015-01-21 | 苏州卫鹏机电科技有限公司 | Surface modification method for improving shoe material bonding strength and application thereof |
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2015
- 2015-02-10 CN CN201510066362.5A patent/CN104646352A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010084070A (en) * | 2000-02-23 | 2001-09-06 | 손명호 | Method for bonding sole by plasma surface treatment |
| KR20010106606A (en) * | 2000-05-22 | 2001-12-07 | 박차철 | Surface treatment of the mid-sole for footwear |
| KR20090106722A (en) * | 2008-04-07 | 2009-10-12 | (주)유이온 | Shoes bonding and cleaning process by atmospheric pressure plasma |
| CN102296283A (en) * | 2010-06-24 | 2011-12-28 | 苏州卫鹏机电科技有限公司 | Method for treating surfaces of shoe materials |
| CN102783768A (en) * | 2011-05-18 | 2012-11-21 | 苏州卫鹏机电科技有限公司 | Method for treating surfaces of shoes |
| CN104015351A (en) * | 2014-06-03 | 2014-09-03 | 石家庄佑生机械设备有限公司 | Normal-pressure high-density microwave plasma shoe material surface treatment method |
| CN104292489A (en) * | 2014-08-08 | 2015-01-21 | 苏州卫鹏机电科技有限公司 | Surface modification method for improving shoe material bonding strength and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106827486A (en) * | 2017-01-13 | 2017-06-13 | 中国科学院合肥物质科学研究院 | A kind of air plasma improves pen tongue moistened surface method and application thereof |
| CN108506730A (en) * | 2018-05-09 | 2018-09-07 | 苏州卫鹏机电科技有限公司 | A kind of air supply system and its air supply method |
| CN115999868A (en) * | 2022-12-27 | 2023-04-25 | 泉州市瑞鑫体育用品有限公司 | Sole reprocessing treatment process |
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Application publication date: 20150527 |
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