CN102807819B - Parting agent for coating antisticking paper for production of artificial leather and preparation method thereof - Google Patents
Parting agent for coating antisticking paper for production of artificial leather and preparation method thereof Download PDFInfo
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- CN102807819B CN102807819B CN201210301577.7A CN201210301577A CN102807819B CN 102807819 B CN102807819 B CN 102807819B CN 201210301577 A CN201210301577 A CN 201210301577A CN 102807819 B CN102807819 B CN 102807819B
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- parting agent
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Abstract
The invention discloses parting agent for coating antisticking paper for the production of artificial leather, and the parting agent comprises following raw materials by weight percent: 30 to 60 percent of amino silicone oil, 10 to 50 percent of epoxy acrylate, 0.5 to 5 percent of polymerization inhibitor and 10 to 50 percent of solvent. The invention also discloses a preparation method of the parting agent for coating the antisticking paper for the production of the artificial leather. The method comprises following steps of uniformly blending the amino silicone oil, the epoxy acrylate, the polymerization inhibitor and solvent, heating the mixture to 50 to 80 DEG C to be reacted for 1 to 6 hours, decompressing the mixture, evaporating the solvent, cooling the mixture, and preparing the parting agent for coating the antisticking paper for the production of the artificial leather. The parting agent and the preparation method thereof are simple in production process, low in production cost, fast in reaction speed, controllable in molecular weight, good in parting effect and suitable for large-scale industrialized production.
Description
Technical field
The present invention relates to leatheroid processing and manufacturing field, be specifically related to a kind of coating separate paper parting agent for leatheroid production and preparation method thereof.
Background technology
The coating separate paper produced for leatheroid belongs to a kind of special separate-type paper, is the carrier and the temporary formwork that manufacture polyurethane(s) leatheroid (PU leather) and artificial polyvinyl chloride leather (PVC leather).The coating separate paper produced for leatheroid has bilayer structure usually: the first layer is the body paper as base material, and the second layer is release coating.General manufacture method on body paper, first applies one deck undercoat to prevent the infiltration of parting agent, then coating is containing the coating of parting agent, embossing solidifying, and undercoat is formed release coating.
At present, the release coating of the coating separate paper for leatheroid production on market is mainly divided into three major types by processing mode: the release coating of (1) thermofixation; (2) the release coating of thermoplastics film; (3) the release coating of radiation curing.Wherein, the separate-type paper that thermofixation mode is produced adopts off-line embossing, and embossing embossability is poor, and decorative pattern is generally comparatively coarse, is mainly used in the production of low-grade leatheroid; Separate-type paper decorative pattern embossability prepared by thermoplastics film mode is better, and decorative pattern is clear true to nature, but is not suitable for doing the decorative pattern of very meticulous laser effect; The separate-type paper decorative pattern that radiation curing mode is produced is meticulous, fidelity is high, and the production line of the fabricate-leather that almost makes children with the ownership system is mutually compatible, is especially applicable to the production of high-end leatheroid.
Parting agent for the release coating of radiation curing generally contains organosilicon or fluorine-type resin.Pure organosilicon or fluorine-type resin are due to poor with all the other component compatibilities in parting agent, after parting agent forms release coating, pure organosilicon or fluorine-type resin easily penetrate into release coatingsurface, and then formation oil mark causes the leatheroid of production defective, therefore seldom uses.
The parting agent overwhelming majority for using in the release coating of coating separate paper radiation curing that leatheroid is produced is modified organic silicon or fluorine-type resin.The preparation of the modified organic silicon class used in the published release coating of coating separate paper radiation curing for leatheroid production at present mainly contains following methods, with reference to " coating resin synthesis and application ", (Yan Fuan etc. write, Chemical Industry Press, 2008):
(1) dichlorodimethylsilane and Hydroxyethyl acrylate hydrolytic condensation under base catalysis;
(2) diethyldiethoxysilane and Hydroxyethyl acrylate carry out transesterification reaction;
(3) terminal hydroxy group silane and vinylformic acid carry out esterification;
(4) terminal hydroxy group silane and di-isocyanate reaction, then react with Hydroxyethyl acrylate.
Above four kinds of methods, though in theory all have feasibility, still have the following disadvantages in actual applications:
In method (1), dichlorodimethylsilane is except reacting with Hydroxyethyl acrylate, also hydrolytic condensation can be there is in himself, cause the poor controllability of reacting, be difficult to the molecular weight controlling product, and the water molecules of alkali residual in final product and trace can affect the performance of release coating, be not suitable for the coating separate paper radiation curing parting agent that leatheroid is produced; Method (2) though in improve speed of response by adding catalyzer, be difficult to the product obtaining higher molecular weight, be also not suitable for being directly used in the coating separate paper radiation curing parting agent that leatheroid is produced; The terminal hydroxy group silane price used in method (3), (4) is high, and reactive behavior is low, is not suitable for large-scale industrial production.
Application number a kind of fluorine-containing parting agent that has been the disclosure of the invention of 200910096513.6 and the separate-type paper of release coating formed based on this parting agent.Utilize the synthesis such as fluorinated acrylate monomer, fluorine-containing epoxy resin, linking agent, initiator to have the fluorine-containing parting agent of release effect in this invention, and be applied to the preparation of separate-type paper.Employ fluorinated acrylate and fluorine-containing epoxy resin in this invention, production cost is high, and complicated process of preparation is not suitable for large-scale industrial production.
Summary of the invention
The invention provides a kind of coating separate paper parting agent for leatheroid production and preparation method thereof, production technique is simple, and production cost is low, and speed of response is fast, and molecular weight is controlled, release effective, is suitable for large-scale industrial production.
For the coating separate paper parting agent that leatheroid is produced, each raw material weight per-cent consists of:
Amido silicon oil 30% ~ 60%;
Epoxy acrylate 10% ~ 50%;
Stopper 0.5% ~ 5%;
Solvent 10% ~ 50%.
Described amido silicon oil consumption is too much, and when epoxy acrylate consumption is very few, excess of ammonia base silicone oil does not react with epoxy acrylate, and after system leaves standstill, this part excess of ammonia base silicone oil is separated out; Amido silicon oil consumption is very few, when epoxy acrylate consumption is too much, excessive epoxy acrylate does not react with amido silicon oil, after system leaves standstill, the epoxy acrylate precipitation that this part is excessive, meanwhile, because the silicone ingredients content in product with release effect is too low, cause the release effect of the modified organic silicon product obtained poor.
When described stopper consumption is too much, stopper residual in product can affect the radiation curing of release coating, causes radiation curing incomplete; When stopper consumption is very few, can there is thermopolymerization in the carbon-carbon double bond of the part propylene acyloxy in product, the viscosity of the system that induces reaction significantly rises.
When described solvent load is too much, the speed of response of reaction system reduces, and greatly extends the reaction times, causes the reduction of production efficiency; When described solvent is very few, reaction system is nonhomogeneous system, and amido silicon oil and epoxy acrylate are in two-phase, is unfavorable for the carrying out reacted, and speed of response reduces, thus causes the reduction of production efficiency.
As preferably, described amido silicon oil is the polydimethylsiloxane containing at least one amino.
Amino can be that primary amino, secondary amino group or uncle are amino, and the polydimethylsiloxane containing at least one amino is commercial product, and easily obtain, amino can be positioned on the main chain of polydimethylsiloxane, also can be positioned on side chain.
As preferably, described epoxy acrylate is the epoxy resin containing at least one acryloxy.
Epoxy resin containing at least one acryloxy is commercial product, and easily obtain, acryloxy can be positioned on the main chain of epoxy resin, also can be positioned on side chain.
As preferably, described stopper is at least one in Resorcinol, para benzoquinone, toluhydroquinone, MEHQ, 2-Tert. Butyl Hydroquinone, 2,5 di tert butyl hydroquinone.
The selection of stopper not only will consider to have higher inhibition efficiency, need to consider its solubleness in polymerization single polymerization monomer simultaneously, inhibition is played under being typically chosen in room temperature, the stopper that can decompose rapidly when temperature of reaction, if there do not have to be suitable, then should select the stopper that easy distillation or chemical process remove from monomer, preferably, described stopper is MEHQ.
As preferably, described solvent is at least one in benzene, toluene, acetone, butanone, pimelinketone.
Described solvent should be able to dissolve amido silicon oil and epoxy acrylate, and form homogeneous system, preferably, described solvent is at least one in benzene, toluene or butanone, and when multi-solvents uses simultaneously, proportioning does not strictly limit.
As preferably, each raw material weight per-cent of the coating separate paper parting agent produced for leatheroid consists of:
Amido silicon oil 35% ~ 55%;
Epoxy acrylate 20% ~ 40%;
Stopper 0.8% ~ 3.5%;
Solvent 15% ~ 44%.
Each raw material weight per-cent composition is in described scope, and can control reaction system is homogeneous phase, and the proportioning of amido silicon oil and epoxy acrylate is suitable, and reacting balance carries out, and prepared parting agent has good release effect.
Further preferably, each raw material weight per-cent for the coating separate paper parting agent of leatheroid production consists of:
Amido silicon oil 40% ~ 50%;
Epoxy acrylate 25% ~ 35%;
Stopper 1.0% ~ 3.0%;
Solvent 15% ~ 30%.
Each raw material weight per-cent composition is in described scope, and can control reaction system is homogeneous phase, and the proportioning of amido silicon oil and epoxy acrylate is suitable, and reacting balance carries out smoothly, and prepared parting agent has good release effect.
Present invention also offers a kind of preparation method of the described coating separate paper parting agent for leatheroid production, comprise the steps: amido silicon oil, epoxy acrylate, stopper, solvent even, be heated to 50 DEG C ~ 80 DEG C, reaction 1h ~ 6h, decompression steams solvent, be cooled to room temperature, obtain the coating separate paper parting agent produced for leatheroid.
When temperature of reaction is too low, in system amido silicon oil and epoxy acrylate speed of response excessively slow, the reaction times is long, is unfavorable for the lifting of production efficiency; Temperature of reaction is too high, in system amido silicon oil and epoxy acrylate speed of response too fast, react wayward, easily occur excessively crosslinked, cause the viscosity of system too high, what be unfavorable for producing normally carries out.
After reaction terminates, the solvent in system can be easy to reclaim at a lower temperature by underpressure distillation, and recovered solvent can reuse, and to environment, can not save production cost simultaneously.
Compared with prior art, the invention has the beneficial effects as follows:
(1) amido silicon oil used in the present invention and epoxy acrylate can select suitable molecular weight as required, by controlling amido silicon oil and epoxy acrylate proportioning between the two, prepare the product that molecular weight is suitable;
(2) reactive behavior of the amino in the present invention on amido silicon oil far away higher than the reactive behavior of the hydroxyl on terminal hydroxy group silane, thus substantially increases production efficiency, is conducive to suitability for industrialized production;
(3) solvent used in the present invention can make amido silicon oil and epoxy acrylate mix, and fast reaction speed, enhances productivity, and solvent can be recycled simultaneously, reduces production cost;
(4) preparation method of the present invention is simple to operate and without the need to specific installation, production cost is low, is suitable for suitability for industrialized production.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, but the present invention is not limited to this.
Embodiment 1
350g amido silicon oil (is purchased from Shandong Dayi Chemical Industry Co., Ltd, model DY-N322, be not specifically noted in following examples is then same model amido silicon oil), 450g epoxy acrylate (is purchased from Zhongshan City, Guangdong Province Ke Tian Electron Material Co., Ltd, model 4210, be not specifically noted in following examples is then same model epoxy acrylate), 10g MEHQ, 190g benzene joins in 1000mL four-hole boiling flask and is uniformly mixed, be heated to 60 DEG C ~ 65 DEG C, insulation 4h, then reduce pressure and solvent benzol steamed, be cooled to room temperature discharging again, obtain the coating separate paper parting agent produced for leatheroid.
Embodiment 2
400g amido silicon oil, 450g epoxy acrylate, 15g MEHQ, 135g benzene are joined in 1000mL four-hole boiling flask and is uniformly mixed, be heated to 60 DEG C ~ 65 DEG C, insulation 6h, then reduce pressure and solvent benzol steamed, be cooled to room temperature discharging again, obtain the coating separate paper parting agent produced for leatheroid.
Embodiment 3
450g amido silicon oil, 350g epoxy acrylate, 20g MEHQ, 180g benzene are joined in 1000mL four-hole boiling flask and is uniformly mixed, be heated to 60 DEG C ~ 65 DEG C, insulation 6h, then reduce pressure and solvent benzol steamed, be cooled to room temperature discharging again, obtain the coating separate paper parting agent produced for leatheroid.
Embodiment 4
500g amido silicon oil, 300g epoxy acrylate, 25g MEHQ, 175g benzene are joined in 1000mL four-hole boiling flask and is uniformly mixed, be heated to 60 DEG C ~ 65 DEG C, insulation 6h, then reduce pressure and solvent benzol steamed, be cooled to room temperature discharging again, obtain the coating separate paper parting agent produced for leatheroid.
Embodiment 5
500g amido silicon oil, 250g epoxy acrylate, 12.5g MEHQ, 12.5g Resorcinol, 175g benzene, 50 grams of butanone are joined in 1000mL four-hole boiling flask and are uniformly mixed, be heated to 60 DEG C ~ 65 DEG C, insulation 6h, then reduce pressure and solvent benzol and butanone steamed, be cooled to room temperature discharging again, obtain the coating separate paper parting agent produced for leatheroid.
Embodiment 6
500g amido silicon oil, 200g epoxy acrylate, 12.5g MEHQ, 12.5g Resorcinol, 200g toluene, 75 grams of butanone are joined in 1000mL four-hole boiling flask and are uniformly mixed, be heated to 70 DEG C ~ 75 DEG C, insulation 5h, then reduce pressure and solvent toluene and butanone steamed, be cooled to room temperature discharging again, obtain the coating separate paper parting agent produced for leatheroid.
Embodiment 7
500g amido silicon oil, 150g epoxy acrylate, 15g MEHQ, 200g toluene, 135 grams of pimelinketone are joined in 1000mL four-hole boiling flask and are uniformly mixed, be heated to 70 DEG C ~ 75 DEG C, insulation 4h, then reduce pressure and solvent toluene and pimelinketone steamed, be cooled to room temperature discharging again, obtain the coating separate paper parting agent produced for leatheroid.
Comparative example (being the Chinese invention embodiment 1 of 200910096513.6 see application number)
In the reactor through anhydrous and oxygen-free process, add 100g oxirane value is that the Commercial epoxy resins (E-32) of 0.32 is (in the present invention, manufacturer is Shengli Oil Field circumference impregnating material company limited), after the tetrahydrofuran (THF) of 100ml or ether dissolution, the Propylene oxide hexafluoride oligopolymer (polymerization degree is 2) adding 0.17mol more at room temperature reacts 3 ~ 6 hours, distillation, recycling design, obtain fluoro epoxies.With weight parts, get 30 parts of isodecyl acrylates, 5 parts of Perfluoroalkylethyl methacrylates (Zonyl TM), 20 parts of methoxy poly (ethylene glycol) 350 monomethacrylates, 20 parts of tri (propylene glycol) diacrylates, 10 parts of Viscoat 295s, 5 parts of above-mentioned obtained fluoro epoxies, 5 parts of Irgacure, 184,5 parts of diethylenetriamines, at room temperature above-mentioned each component put into successively container mixing, stir, solid constituent is impelled to dissolve, obtain evenly, connect diaphanous coating, be fluorine-containing parting agent.
Performance test
The performance of parting agent prepared by the present invention is characterized by the stripping strength detecting the separate-type paper utilizing this parting agent to prepare, and the preparation method of separate-type paper and the detection method of stripping strength are the Chinese invention of 200910096513.6 see application number.
The stripping strength of the separate-type paper utilizing the parting agent of each embodiment and comparative example synthesis to prepare is listed in table 1.
Table 1
| Embodiment sequence number | Stripping strength (N/M) |
| Embodiment 1 | 15 |
| Embodiment 2 | 20 |
| Embodiment 3 | 10 |
| Embodiment 4 | 20 |
| Embodiment 5 | 15 |
| Embodiment 6 | 20 |
| Embodiment 7 | 15 |
| Comparative example | 20 |
From table 1 data: the stripping strength of the separate-type paper utilizing method provided by the invention to prepare is mostly 10 ~ 20 Newton/meter, and release performance is good, can reach the level of comparative example.
Claims (5)
1., for the coating separate paper parting agent that leatheroid is produced, it is characterized in that, each raw material weight per-cent consists of:
Amido silicon oil 35% ~ 55%;
Epoxy acrylate 20% ~ 40%;
Stopper 0.8% ~ 3.5%;
Solvent 15% ~ 44%;
Described amido silicon oil is the polydimethylsiloxane containing at least one amino;
Described epoxy acrylate is the epoxy resin containing at least one acryloxy.
2. as claimed in claim 1 for the coating separate paper parting agent of leatheroid production, it is characterized in that, described stopper is at least one in Resorcinol, para benzoquinone, toluhydroquinone, MEHQ, 2-Tert. Butyl Hydroquinone, 2,5 di tert butyl hydroquinone.
3., as claimed in claim 1 for the coating separate paper parting agent that leatheroid is produced, it is characterized in that, described solvent is at least one in benzene, toluene, acetone, butanone, pimelinketone.
4., as claimed in claim 1 for the coating separate paper parting agent that leatheroid is produced, it is characterized in that, each raw material weight per-cent consists of:
Amido silicon oil 40% ~ 50%;
Epoxy acrylate 25% ~ 35%;
Stopper 1.0% ~ 3.0%;
Solvent 15% ~ 30%.
5. one kind as arbitrary in Claims 1 to 4 as described in the preparation method of coating separate paper parting agent produced for leatheroid, it is characterized in that, comprise the steps: amido silicon oil, epoxy acrylate, stopper, solvent even, be heated to 50 DEG C ~ 80 DEG C, reaction 1h ~ 6h, decompression steams solvent, is cooled to room temperature, obtains the coating separate paper parting agent produced for leatheroid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210301577.7A CN102807819B (en) | 2012-08-23 | 2012-08-23 | Parting agent for coating antisticking paper for production of artificial leather and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210301577.7A CN102807819B (en) | 2012-08-23 | 2012-08-23 | Parting agent for coating antisticking paper for production of artificial leather and preparation method thereof |
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|---|---|
| CN102807819A CN102807819A (en) | 2012-12-05 |
| CN102807819B true CN102807819B (en) | 2014-12-31 |
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| CN201210301577.7A Expired - Fee Related CN102807819B (en) | 2012-08-23 | 2012-08-23 | Parting agent for coating antisticking paper for production of artificial leather and preparation method thereof |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103397563B (en) * | 2013-07-17 | 2016-02-10 | 浙江池河科技有限公司 | A kind of release liners being coated with separate paper mould release and preparation method thereof and preparing with this mould release |
| CN103740262B (en) * | 2014-01-16 | 2016-01-06 | 浙江凯伦特种材料有限公司 | A kind of artificial synthetic leather separate-type paper high temperature resistant release coated material and its preparation method and application |
| CN105111934A (en) * | 2015-09-06 | 2015-12-02 | 上海应用技术学院 | Antifouling organosilicon paint and preparation method thereof |
| CN111334219B (en) * | 2020-04-26 | 2022-05-20 | 东莞市鼎力薄膜科技有限公司 | Release film for electronic optical adhesive and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102330381A (en) * | 2011-07-12 | 2012-01-25 | 苏州斯迪克电子胶粘材料有限公司 | Method for making fog face release paper |
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- 2012-08-23 CN CN201210301577.7A patent/CN102807819B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102330381A (en) * | 2011-07-12 | 2012-01-25 | 苏州斯迪克电子胶粘材料有限公司 | Method for making fog face release paper |
Non-Patent Citations (2)
| Title |
|---|
| 氨基硅烷改性环氧丙烯酸玻璃漆的结构及性能研究;周新华等;《仲恺农业工程学院学报》;20100930;第23卷(第3期);第7-9和18页,第7页第1节至第9页第4节 * |
| 离型纸用涂层材料的紫外光固化研究;杨海冬;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20120315(第3期);第19-22，29-32和43页 * |
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