CN105155292B - A kind of preparation method of environment-friendly type real leather intimating synthetic leather - Google Patents
A kind of preparation method of environment-friendly type real leather intimating synthetic leather Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of environment-friendly type real leather intimating synthetic leather, it is therefore intended that overcomes in existing synthetic leather product and remains poisonous and harmful substance, the problem of being unfavorable for environmental protection and health.The environment-friendly type real leather intimating synthetic leather preparation method that the present invention is provided includes the preparation of wet method bass, dry mixing, four steps of dry method veneer and post processing, the present invention uses benzyltrimethylammonium chloride modified alta-mud, and it regard modified bentonite as the filler for preparing wet method bass, modified bentonite can effectively adsorb the harmful substance in synthetic leather product, the safer environmental protection of synthetic leather prepared using the present invention.The present invention also uses delustering agent simultaneously, and the synthetic leather of preparation is post-processed, the outward appearance and feel of synthetic leather is improved, the feel of the soft gloss of synthetic leather and similar natural leather is imparted.
Description
Technical field
The present invention relates to synthetic leather field, more particularly to a kind of preparation method of environment-friendly type real leather intimating synthetic leather.
Background technology
Synthetic leather be simulate natural leather the Nomenclature Composition and Structure of Complexes and can as its substitute material plastic products.Generally with through leaching
The non-woven fabrics of stain is lamina reticularis, and microvoid polyurethane layer is made as grain layer.Its positive and negative is all quite similar with leather, and has
Certain gas permeability, than common artificial leather closer to natural leather.Synthetic leather is in the daily life of the mankind in occupation of particularly significant
Status, be widely used in terms of production case and bag, clothes, footwear and in-car ornaments.
In the manufacture of existing synthetic leather, polyurethane resin is by dilution plus wood powder or other packing materials, by oozing
Thoroughly, the technical process such as levelling, froth breaking, solidification, according to the performance of polyurethane resin, can be given birth to using two methods of wet method and dry method
Produce synthetic leather.Dry technology for production is the industrial process that Synthetic Leather is developed earliest, and the synthetic leather produced is strongly
It is excellent, it is firmly bonded, but permeability is relatively poor；Wet process technique is the brand-new synthesis grown up after dry method
Method, the synthetic leather produced has good moisture-inhibiting, permeability, soft, plentiful, is more imbued with the style of natural leather
And outward appearance.No matter which kind of production technology, it is substantial amounts of due to having used in the production process of synthetic leather and during Final finishing
Chemical assistant, cause in synthetic leather product carry a certain amount of poisonous and harmful substance, such as formaldehyde, benzene, pentachlorophenol, heavy metal from
Son etc., these harmful substances remained in synthetic leather product are long-term that health is damaged using meeting.With society
Progressive and growth in the living standard, people, also with raising, there has also been more to material requirement to health, environmentally friendly synthesis leather product
High requirement.
Chinese patent notification number CN102899915A discloses a kind of environmental synthetic leather preparation method, including dry mixed is matched somebody with somebody
Material and two steps of dry method veneer, the polyurethane cover without dimethylformamide, butanone are used in dry mixed dispensing, is helped
Agent and toner high-speed stirred are uniform, the dry method binder without dimethylformamide are made, then by obtained dry method binder
It is coated in release liners, environmentally friendly synthesis, which is made, by steps such as drying, bondings removes from office product.During the method production synthetic leather
Do not use dimethylformamide, it is to avoid dimethylformamide is to the pollution of environment and the injury of workman, but the method exists
A large amount of chemical assistants have been used in production process, have caused to contain a certain amount of poisonous and harmful substance in synthetic leather product, these are residual
The harmful substance stayed in synthetic leather product, it is long-term that health is damaged using meeting.
The content of the invention
It is an object of the invention to overcome in existing synthetic leather product to remain poisonous and harmful substance, it is unfavorable for environmental protection and human body
Healthy the problem of, there is provided a kind of not only environmental protection but also the outward appearance with similar natural leather and the synthetic leather preparation side of sense of touch
Method.
The present invention concrete technical scheme be：A kind of preparation method of environment-friendly type real leather intimating synthetic leather, comprises the following steps：
(1) prepared by wet method bass
A. 10~15 parts by weight dimethylformamides and 2~5 parts by weight mill bases are mixed into 30~40min, then mistake
Filter；
B. by 40~50 parts by weight dimethylformamides, 5~20 part by weight modified bentonites and 20~30 parts by weight are wooden
Cellulose mixes 30~40min, is then fully swelled 20~30min；
C. the mixture filtered in step a is added in the mixture after step b is swelled, stirred, add 50~
60 parts by weight of polyurethane resins, stir 30~40min, 20~30min of deaeration；
D. the mixture of deaeration in step c is applied and scraped in base fabric, then immerse the diformazan that mass fraction is 15~17%
Solidified in base formamide solution, then by washing, drying, obtain wet method bass；
(2) dry mixing
By 30~40 parts by weight of polyurethane resins, 15~20 parts by weight dimethylformamides, 10~14 parts by weight butanone, 5
~10 parts by weight toners, 0.2~0.5 parts by weight levelling agent mixing is stirred evenly, and stirs 20~25min；
(3) dry method veneer
The dry method slurry prepared in step (2) is applied and scraped in release liners, in 100~120 DEG C of drying, cooling, is formed
Dry method veneer, is then adhered to dry method veneer by adhesive by the wet method bass in step (1), after drying cooling, will be from
Type paper is peeled off, and obtains synthetic leather base material；
(4) post-process
Delustering agent is uniformly coated with synthetic leather base material with coating roller, in 100~130 DEG C of drying, environmental protection is produced after cooling
Type real leather intimating synthetic leather.
Bentonite is a kind of clay rock using montmorillonite as essential mineral, and montmorillonite has higher cation exchange capacity
And good adsorption capacity, at normal temperatures and pressures, ion, salt and organic matter can come in and go out montmorillonite mineral interlayer and by
Absorption.Because natural montmorillonite surface silica structure has the water of extremely strong hydrophily and a large amount of exchangeable cations of interlayer
Solution, makes its surface generally there is one layer of thin moisture film, and can not effectively adsorb hydrophobic organic compound.Inhaled to improve bentonite
Ability with organic pollutants, the present invention uses benzyltrimethylammonium chloride modified natural bentonite, and by modified swelling
Soil is as the filler for preparing wet method bass, and modified bentonite can effectively adsorb formaldehyde, benzene etc. in synthetic leather product and be harmful to
Material, the safer environmental protection of synthetic leather prepared using the present invention.Meanwhile, the present invention is also entered using delustering agent to the synthetic leather of preparation
Row post processing, improves the outward appearance and feel of synthetic leather, imparts the feel of the soft gloss of synthetic leather and similar natural leather.
Preferably, the method for preparing modified bentonite is as follows：
A. by after the crushing of bentonite original soil, drying, grinding, 200~300 mesh sieves are crossed；
B. the bentonite after sieving is mixed with mass fraction for 30~40% benzyltrimethylammonium chloride solution, be placed in
Heated in microwave applicator, bentonite is 1 with benzyltrimethylammonium chloride solution quality ratio：1.5~2, control benzyl trimethyl
Ammonium chloride solution pH is 8~9；
C. heating is finished, and product suction filtration is washed 1~2 time with pH for 8~9 sodium hydroxide solution, with distillation water washing
2~3 times, filter cake is freeze-dried, then 1~1.5h is activated at 200~250 DEG C, ground 200~300 mesh sieve produces modification
Bentonite.
The present invention uses benzyltrimethylammonium chloride modified alta-mud, and use microwave reaction mixed liquor, and microwave is strong
Fuel factor makes bentonite and the mixture of benzyltrimethylammonium chloride solution be rapidly increased to higher temperature, thus accelerate to react into
OK, the time of ion-exchange equilibrium is shortened, with reduction energy consumption, time-saving advantage.
Preferably, the microwave applicator power is 700~1000W, the heat time is 3~5min.Microwave power and
Heat time influences bentonite and benzyltrimethylammonium chloride ion-exchange speed and exchange capacity, and microwave power is big, ion exchange
Speed is fast, and the heat time is long, ion exchange capacity increase.
Preferably, the step d setting temperatures are 30~45 DEG C, setting time is 8~10min.Too high temperature meeting
Decline coating failure intensity, surface uniformity coefficient is deteriorated.
Preferably, upper doses of the mixture of the step d deaerations in base fabric is 110~140g/m2。
To be scraped preferably, the step (3) is applied dry method slurry using scraper in release liners, scraper gap is 13~
18mm.Scraper gap is controlled to control the thickness of dry method veneer.
Preferably, step (4) delustering agent is made up of the raw material of following parts by weight：30~40 parts of aqueous polyurethanes,
10~14 parts of aerosils, 0.5~1 part of paraffin, 12~18 parts of ethyl acetate, 10~20 parts of toluene, 0.3~0.8 part of silicon
Alkane coupling agent.Synthetic leather surface is shinny, there is very strong modeling sense, in order that the outward appearance and feel of synthetic leather are more nearly natural skin
Leather, the present invention carries out delustring processing using delustering agent to the synthetic leather of preparation, so as to assign the soft gloss of synthetic leather and similar
The feel of natural leather.
The beneficial effects of the invention are as follows：The present invention uses benzyltrimethylammonium chloride modified natural bentonite, and will be modified
Bentonite afterwards is as the filler for preparing wet method bass, and modified bentonite can effectively adsorb harmful in synthetic leather product
Material, the safer environmental protection of synthetic leather prepared using the present invention.The present invention also uses delustering agent simultaneously, and the synthetic leather of preparation is entered
Row post processing, improves the outward appearance and feel of synthetic leather, imparts the feel of the soft gloss of synthetic leather and similar natural leather.
Embodiment
Below by specific embodiment, technical scheme is described further.
The levelling agent that the present invention is used is DOW CORNING DC-3 levelling agents, and by Dow corning, company produces；Polyurethane resin
It is commercially available prod for solvent type polyurethane resin；Benzyltrimethylammonium chloride is purchased from Beijing Xing Fu fine chemistries research institute；Silane
Coupling agent is silane coupler kh560, is produced by Zhejiang Hua Jin Science and Technology Co., Ltd..
If not other raw materials of the present invention and equipment are refered in particular to, it is commercially available or commonly used in the art,
Method in embodiment, unless otherwise instructed, is the conventional method of this area.
Embodiment 1
A kind of preparation method of environment-friendly type real leather intimating synthetic leather, comprises the following steps：
(1) prepared by wet method bass
A. by 10 parts by weight dimethylformamides and (commercially available) the mixing 30min of 2 parts by weight mill bases, then filter；
B. by 40 parts by weight dimethylformamides, 5 part by weight modified bentonites and the mixing of 20 parts by weight lignocellulosics are stirred
30min is mixed, 20min is then fully swelled；
C. the mixture filtered in step a is added in the mixture after step b is swelled, stirs, add 50 weights
Part polyurethane resin is measured, 30min, deaeration 20min is stirred；
D. by the mixture of deaeration in step c with 110g/m2Upper doses apply and scrape in base fabric, then immerse mass fraction
To solidify 8min in 15% dimethyl formamide solution, setting temperature is 30 DEG C, then by washing, drying, obtains wet method
Bass；
(2) dry mixing
By 30 parts by weight of polyurethane resins, 15 parts by weight dimethylformamides, 10 parts by weight butanone, 5 parts by weight toners,
The mixing of 0.2 parts by weight levelling agent is stirred evenly, and stirs 20min；
(3) dry method veneer
The dry method slurry prepared in step (2) is scraped in release liners with cutter painting is scraped, scraper gap is 13mm, 100
DEG C drying, cooling, formed dry method veneer, then the wet method bass in step (1) is adhered on dry method veneer by adhesive,
After drying cooling, release liners are peeled off, synthetic leather base material is obtained；
(4) post-process
Delustering agent is uniformly coated with synthetic leather base material with coating roller, the upper doses of delustering agent is 30g/m2, in 100 DEG C of bakings
It is dry, environment-friendly type real leather intimating synthetic leather is produced after cooling.Delustering agent is made up of the raw material of following parts by weight：30 parts of aqueous polyurethanes
(production of Zhong Fang auxiliary reagent factories of Taixing City), 10 parts of aerosils, 0.5 part of paraffin, 12 parts of ethyl acetate, 10 parts of toluene, 0.3 part
Silane coupler.
Wherein, method for preparing modified bentonite is as follows：
A. by after the crushing of bentonite original soil, drying, grinding, 200 mesh sieves are crossed；
B. the bentonite after sieving is mixed with mass fraction for 30% benzyltrimethylammonium chloride solution, is placed in microwave
3min is heated in heater, microwave power is 700W, and bentonite is 1 with benzyltrimethylammonium chloride solution quality ratio：1.5, control
Benzyltrimethylammonium chloride pH value of solution processed is 8；
C. heating is finished, and product suction filtration is washed 1 time with pH for 8 sodium hydroxide solution, will with water washing is distilled 2 times
Filter cake is freeze-dried, then activates at 200 DEG C 1h, and ground 200 mesh sieve produces modified alta-mud.
Embodiment 2
A kind of preparation method of environment-friendly type real leather intimating synthetic leather, comprises the following steps：
(1) prepared by wet method bass
A. 12 parts by weight dimethylformamides and 4 parts by weight mill bases are mixed into 35min, then filtered；
B. by 45 parts by weight dimethylformamides, 10 part by weight modified bentonites and the mixing of 25 parts by weight lignocellulosics are stirred
35min is mixed, 25min is then fully swelled；
C. the mixture filtered in step a is added in the mixture after step b is swelled, stirs, add 55 weights
Part polyurethane resin is measured, 35min, deaeration 25min is stirred；
D. by the mixture of deaeration in step c with 125g/m2Upper doses apply and scrape in base fabric, then immerse mass fraction
To solidify 9min in 16% dimethyl formamide solution, setting temperature is 35 DEG C, then by washing, drying, obtains wet method
Bass；
(2) dry mixing
By 35 parts by weight of polyurethane resins, 17 parts by weight dimethylformamides, 12 parts by weight butanone, 8 parts by weight toners,
The mixing of 0.3 parts by weight levelling agent is stirred evenly, and stirs 22min；
(3) dry method veneer
The dry method slurry prepared in step (2) is scraped in release liners with cutter painting is scraped, scraper gap is 15mm, 110
DEG C drying, cooling, formed dry method veneer, the wet method bass in step (1) is then adhered to by dry method veneer by adhesive, pass through
After Drying and cooling, release liners are peeled off, synthetic leather base material is obtained；
(4) post-process
Delustering agent is uniformly coated with synthetic leather base material with coating roller, the upper doses of delustering agent is 35g/m2, in 110 DEG C of bakings
It is dry, environment-friendly type real leather intimating synthetic leather is produced after cooling.Delustering agent is made up of the raw material of following parts by weight：35 parts of aqueous polyurethanes,
12 parts of aerosils, 0.7 part of paraffin, 15 parts of ethyl acetate, 15 parts of toluene, 0.6 part of silane coupler.
Wherein, method for preparing modified bentonite is as follows：
A. by after the crushing of bentonite original soil, drying, grinding, 250 mesh sieves are crossed；
B. the bentonite after sieving is mixed with mass fraction for 35% benzyltrimethylammonium chloride solution, is placed in microwave
4min is heated in heater, microwave power is 800W, and bentonite is 1 with benzyltrimethylammonium chloride solution quality ratio：1.8, control
Benzyltrimethylammonium chloride pH value of solution processed is 8.5；
C. heating is finished, by product suction filtration, wash 2 times for 8.5 sodium hydroxide solution with pH, with distilling water washing 2 times,
Filter cake is freeze-dried, then activates at 250 DEG C 1.5h, ground 250 mesh sieve produces modified alta-mud.
Embodiment 3
A kind of preparation method of environment-friendly type real leather intimating synthetic leather, comprises the following steps：
(1) prepared by wet method bass
A. 15 parts by weight dimethylformamides and 5 parts by weight mill bases are mixed into 40min, then filtered；
B. by 50 parts by weight dimethylformamides, 20 part by weight modified bentonites and the mixing of 30 parts by weight lignocellulosics are stirred
40min is mixed, 30min is then fully swelled；
C. the mixture filtered in step a is added in the mixture after step b is swelled, stirs, add 60 weights
Part polyurethane resin is measured, 40min, 20~30min of deaeration is stirred；
D. by the mixture of deaeration in step c with 125g/m2Upper doses apply and scrape in base fabric, then immerse mass fraction
To solidify 10min in 17% dimethyl formamide solution, setting temperature is 45 DEG C, then by washing, drying, obtains wet method
Bass；
(2) dry mixing
By 40 parts by weight of polyurethane resins, 20 parts by weight dimethylformamides, 14 parts by weight butanone, 10 parts by weight toners,
The mixing of 0.5 parts by weight levelling agent is stirred evenly, and stirs 25min；
(3) dry method veneer
The dry method slurry prepared in step (2) is scraped in release liners with cutter painting is scraped, scraper gap is 18mm, 120
DEG C drying, cooling, formed dry method veneer, the wet method bass in step (1) is then adhered to by dry method veneer by adhesive, pass through
After Drying and cooling, release liners are peeled off, synthetic leather base material is obtained；
(4) post-process
Delustering agent is uniformly coated with synthetic leather base material with coating roller, the upper doses of delustering agent is 40g/m2, 130 DEG C of bakings
It is dry, environment-friendly type real leather intimating synthetic leather is produced after cooling.Delustering agent is made up of the raw material of following parts by weight：40 parts of aqueous polyurethanes,
14 parts of aerosils, 1 part of paraffin, 18 parts of ethyl acetate, 20 parts of toluene, 0.8 part of silane coupler.
Wherein, method for preparing modified bentonite is as follows：
A. by after the crushing of bentonite original soil, drying, grinding, 300 mesh sieves are crossed；
B. the bentonite after sieving is mixed with mass fraction for 40% benzyltrimethylammonium chloride solution, is placed in microwave
5min is heated in heater, microwave power is 1000W, and bentonite is 1 with benzyltrimethylammonium chloride solution quality ratio：2, control
Benzyltrimethylammonium chloride pH value of solution is 9；
C. heating is finished, and product suction filtration is washed 2 times with pH for 9 sodium hydroxide solution, will with water washing is distilled 3 times
Filter cake is freeze-dried, then activates at 250 DEG C 1.5h, and ground 300 mesh sieve produces modified alta-mud.
According to GB/T 19941-2005《The measure of leather and fur chemical experiment content of formaldehyde》, using AAS
Measure in environment-friendly type real leather intimating synthetic leather prepared by the present invention, the content of free formaldehyde is less than 100mg/kg.
Claims (1)
1. a kind of preparation method of environment-friendly type real leather intimating synthetic leather, it is characterised in that comprise the following steps：
（1）It is prepared by wet method bass
A. 10 ~ 15 parts by weight dimethylformamides and 2 ~ 5 parts by weight mill bases are mixed into 30 ~ 40min, then filtered；
B. by 40 ~ 50 parts by weight dimethylformamides, 5 ~ 20 part by weight modified bentonites and 20 ~ 30 parts by weight wood fibres
Element mixes 30 ~ 40min, is then fully swelled 20 ~ 30min；
C. the mixture filtered in step a is added in the mixture after step b is swelled, stirs, add 50 ~ 60
Parts by weight of polyurethane resin, stirs 30 ~ 40min, 20 ~ 30min of deaeration；
D. the mixture of deaeration in step c is applied and scraped in base fabric, then immerse the dimethyl methyl that mass fraction is 15 ~ 17%
Solidified in amide solution, then by washing, drying, obtain wet method bass；
（2）Dry mixing
By 30 ~ 40 parts by weight of polyurethane resins, 15 ~ 20 parts by weight dimethylformamides, 10 ~ 14 parts by weight butanone, 5 ~ 10 weights
Part toner is measured, the mixing of 0.2 ~ 0.5 parts by weight levelling agent is stirred evenly, and stirs 20 ~ 25min；
（3）Dry method veneer
By step（2）In the dry method slurry for preparing apply and scrape in release liners, in 100 ~ 120 DEG C of drying, cooling, form dry method patch
Face, then by adhesive by step（1）In wet method bass be adhered to dry method veneer, after drying cooling, release liners are shelled
From obtaining synthetic leather base material；
（4）Post processing
Delustering agent is uniformly coated with synthetic leather base material with coating roller, in 100 ~ 130 DEG C of drying, environment-friendly type emulation is produced after cooling
Leather synthetic leather；
The method for preparing modified bentonite is as follows：
A. by after the crushing of bentonite original soil, drying, grinding, 200 ~ 300 mesh sieves are crossed；
B. the bentonite after sieving is mixed with mass fraction for 30 ~ 40% benzyltrimethylammonium chloride solution, is placed in microwave
Heated in heater, bentonite is 1 with benzyltrimethylammonium chloride solution quality ratio：1.5 ~ 2, control benzyltrimethylammonium chloride
PH value of solution is 8 ~ 9；
C. heating is finished, by product suction filtration, wash 1 ~ 2 time for 8 ~ 9 sodium hydroxide solution with pH, with distill water washing 2 ~
3 times, filter cake is freeze-dried, then 1 ~ 1.5h is activated at 200 ~ 250 DEG C, ground 200 ~ 300 mesh sieve produces bentone
Soil；
The delustering agent is made up of the raw material of following parts by weight：30 ~ 40 parts of aqueous polyurethanes, 10 ~ 14 parts of aerosils,
0.5 ~ 1 part of paraffin, 12 ~ 18 parts of ethyl acetate, 10 ~ 20 parts of toluene, 0.3 ~ 0.8 part of silane coupler；
The microwave applicator power is 700 ~ 1000W, and the heat time is 3 ~ 5min；
The step d setting temperatures are 30 ~ 45 DEG C, and setting time is 8 ~ 10min；The mixture of the step d deaerations is in base fabric
On upper doses be 110 ~ 140g/m2；The step（3）Dry method slurry is applied using scraper and scraped in release liners, scraper gap
For 13 ~ 18mm.
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| CN106192439A (en) * | 2016-08-17 | 2016-12-07 | 华伦皮塑（苏州）有限公司 | A kind of preparation method of environmental protection easy decontamination synthetic leather |
| CN107385944A (en) * | 2017-09-11 | 2017-11-24 | 苏州瑞高新材料有限公司 | A kind of automobile gear sheath removes from office manufacture method |
| CN107761404B (en) * | 2017-12-06 | 2020-02-11 | 扬州市德运塑业科技股份有限公司 | Preparation method of high-wear-resistance PU synthetic leather fabric |
| CN111543753B (en) * | 2020-06-05 | 2022-07-12 | 杭州天龙手袋股份有限公司 | Handbag with cowhide finishing layer |
| CN112482039A (en) * | 2020-11-24 | 2021-03-12 | 桐乡市汇中纺织有限公司 | Environment-friendly imitated leather fabric and preparation process thereof |
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| JPS56382A (en) * | 1979-06-13 | 1981-01-06 | Kunimine Kogyo Kk | Production of artificial leather |
| CN100522342C (en) * | 2007-07-27 | 2009-08-05 | 浙江大学 | A preparation method of organobentonite for removing water-solubility organic pollutant |
| CN102899921B (en) * | 2011-07-29 | 2015-01-07 | 昆山协孚人造皮有限公司 | Manufacturing method of powder-wax synthetic leather |
| CN102995445B (en) * | 2012-10-23 | 2014-12-10 | 合肥市安山涂层织物有限公司 | Diatomite modified polyvinyl chloride synthetic leather and manufacturing method thereof |
| CN104652137B (en) * | 2015-03-13 | 2017-03-01 | 厦门信得利投资发展有限公司 | A kind of preparation method of environment friendly silicon gluing finished leather |
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Denomination of invention: A preparation method of environmental protection imitation leather Effective date of registration: 20210602 Granted publication date: 20170718 Pledgee: Bank of Huzhou Limited by Share Ltd. Changxin branch Pledgor: ZHEJIANG JINSHANG SYNTHETIC LEATHER Co.,Ltd. Registration number: Y2021330000502 |
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Date of cancellation: 20220406 Granted publication date: 20170718 Pledgee: Bank of Huzhou Limited by Share Ltd. Changxin branch Pledgor: ZHEJIANG JINSHANG SYNTHETIC LEATHER Co.,Ltd. Registration number: Y2021330000502 |
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| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
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Denomination of invention: A preparation method of environmental friendly simulated leather synthetic leather Effective date of registration: 20220414 Granted publication date: 20170718 Pledgee: Changxin Zhejiang rural commercial bank Limited by Share Ltd. Pledgor: ZHEJIANG JINSHANG SYNTHETIC LEATHER Co.,Ltd. Registration number: Y2022330000522 |