CN102817284B - Release layer and release paper used for artificial leather - Google Patents
Release layer and release paper used for artificial leather Download PDFInfo
- Publication number
- CN102817284B CN102817284B CN201210302012.0A CN201210302012A CN102817284B CN 102817284 B CN102817284 B CN 102817284B CN 201210302012 A CN201210302012 A CN 201210302012A CN 102817284 B CN102817284 B CN 102817284B
- Authority
- CN
- China
- Prior art keywords
- release layer
- artificial leather
- tert
- release
- silicone oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
The invention discloses a release layer used for artificial leather, which comprises the following raw material components of polyolefin, vinyl silicone oil and initiating agent. The invention also discloses release paper used for the artificial leather, which comprises body paper and the release layer adhered on one side of the surface of the body paper, wherein the thickness of the release layer is 30-150mu m. The release paper used for the artificial leather, which is disclosed by the invention, is unlikely to curl in the humid environment, the artificial leather prepared from the release paper is easy to strip from the release paper, and the surface of the manufactured artificial leather has excellent smooth feeling and oil wax feeling.
Description
Technical field
The present invention relates to artificial leather processing and manufacturing field, be specifically related to a kind of release layer used for artificial leather and release liners.
Background technology
Release liners claims again barrier paper, is that one both can prevent prepreg adhesion, can protect again the not contaminated separate paper of prepreg.
In artificial leather manufacture process, conventionally use release liners.Release liners comprises base material and is coated in the release layer on base material, and base material is generally body paper, and release layer is conventionally coated in body paper surface one side by materials such as polysiloxanes, alkyd resins, polyolefin and forms.
Application number a kind of synthetic leather release liners that has been 200810079831.7 disclosure of the invention, it arranges a Multifunctional layered between base material and release layer, and the component of described Multifunctional layered and parts by weight thereof are: adhesive 40～95; Water 5～60; Surfactant 1～5; The formation material of described release layer comprises alkyd modified silicones, melmac and acid catalyst.
In prior art, on the release layer of release liners, conventionally form the texture of expection by embossing, in the time producing artificial leather, polyurethane solutions is coated on the release layer of release liners, after being heating and curing, being coated with last layer adhesive and being covered with one deck cloth at polyurethane surface, after heat drying, make adhesive solidification, release liners is peeled off from artificial leather, the artificial leather surface obtaining has the texture contrary with release liners concave-convex surface.
There is following problem in the release liners using in polyurethane artificial leather manufacture process at present:
(1), while using polysiloxanes to do release layer, because the compatibility of polyurethane and polysiloxanes is poor, polyurethane is difficult for film forming, and, in polyurethane film-forming process, easily come off, in the process of coating adhesive, polyurethane film also easily departs from from release layer, i.e. " prestripping ";
(2), while using alkyd resins to do release layer, due to the affine better performances of polyurethane and alkyd resins, after adhesive solidification, polyurethane film is not easy to peel off from release layer; Make the release liners of release layer of alkyd resins in the time of embossing, release liners can constantly produce crack and space, these cracks and space can significantly reduce the ability that polyurethane film departs from from release liners on the one hand, also can significantly reduce on the other hand oily wax sense and the silk smooth felling of polyurethane artificial leather surface.
(3) while using polyolefin (as polypropylene or poly(4-methyl-1-pentene)) to make release layer, because the compatibility of polyolefin and polyurethane is better, polyurethane artificial leather after solidifying is not easy to peel off, particularly difficult while particularly having degree of depth embossing on polyolefin release layer, in addition, easily curling in wet environment containing the release liners of polyolefin release layer.
In embossing operation in artificial leather manufacture process, decorative pattern on knurling rolls has determined the surface texture of release liners release layer, due to the defect of existing knurling rolls manufacturing technology itself, the decorative pattern details of knurling rolls can not be completely smooth, under normal circumstances, can have burr and uneven phenomenon, all there is same problem in the decorative pattern forming on release liners surface by this dandy roll and the artificial leather surface that release liners is made thus, turn white in the artificial leather surface preparing, dry and astringent, without glossy.
Summary of the invention
The invention provides a kind of release layer used for artificial leather and release liners, release liners is difficult for curling in wet environment, and the artificial leather that uses this release liners to prepare is easily peeled off from release liners, and the artificial leather surface producing has splendid silk smooth felling and oily wax sense.
A kind of release layer used for artificial leather, its raw material consists of polyolefin, vinyl silicone oil and initator; Described vinyl silicone oil structural formula is as follows:
Wherein, m span is that 0～5000, n span is 0～6;
R
1, R
2, R
3be-CH independently separately
3or
and when different be-CH
3, n is 0 o'clock R
1, R
3when different, be-CH
3, wherein, x span is 0～10.
Two keys in described initator initiation polyolefin and the two key generation cross-linking reactions in vinyl silicone oil, generate fine and close release layer, described release layer has smooth surface, while utilizing the release liners manufacturer's fabricate-leather that contains described release layer, can make artificial leather surface have oily wax sense and silk smooth felling.
As preferably, described polyolefin is at least one in polyethylene, polypropylene and poly(4-methyl-1-pentene).
Described polyolefin should have two keys that can react of sufficient amount, so as with described vinyl silicone oil generation cross-linking reaction.Poly melt index scope is 6～10g/10min; Polyacrylic melt index scope is 20～30g/10min; The melt index scope of poly(4-methyl-1-pentene) is 22～30g/10min.
As preferably, described initator is di-tert-butyl peroxide, two t-amyl peroxy things, 2, 2-bis-(t-butyl peroxy) butane, 2, 5-dimethyl-2, 5-di-t-butyl hexane peroxide, 2, 5-dimethyl-2, 5-di-t-butyl peroxy-3-hexin, cumyl peroxide, 1, 4-pair-(2-tert-butyl hydroperoxide isopropyl) benzene, tert-butyl peroxide isopropylbenzene, tert butyl peroxy benzoate, tert-butyl hydroperoxide-2 ethyl hexanoic acid ester, tert-butyl hydroperoxide-3, 5, 5-tri-methyl hexanoic acid ester, tert-butyl hydroperoxide isopropyl carbonic acid ester, at least one in tert-butyl hydroperoxide carbonic acid-2-Octyl Nitrite.
Described initator can cause the cross-linking reaction of two keys of polyolefinic pair of key and vinyl silicone oil, the selection of described initator will directly affect the speed of cross-linking reaction and carry out degree, in order to ensure that the release layer generating has good character, should select to have the initator of suitable half-life, preferably, described initator is cumyl peroxide.
As preferably, the weight portion of described raw material consists of:
Polyolefin content is 80～97;
The content of vinyl silicone oil is 2～20;
Initiator content is 0.05～1.
Described polyolefin content is too much, because the compatibility of polyolefin and polyurethane is better, polyurethane artificial leather after solidifying is not easy to peel off, particularly difficult in the time having degree of depth embossing on polyolefin release layer, in addition, the release liners making is easily curling in wet environment, because the compatibility of vinyl silicone oil and polyurethane is poor, suitable interpolation, can improve the off-type force (being the peel strength that artificial leather is peeled off from release layer) of release layer, the consumption of described initator is too much unsuitable, avoids cross-linking reaction excessive velocities, the performance of the release layer that impact generates.
In order to avoid warpage as far as possible, make release layer there is better performance, further preferred, the weight portion of described raw material consists of:
Polyolefin content is 85;
The content of vinyl silicone oil is 2～20;
Initiator content is 0.05～1.
As preferably, the molecular weight of described vinyl silicone oil (number all) is 300～300,000.
Under normal circumstances, the molecular weight of vinyl silicone oil is larger, and the content of vinyl (all vinyl quality account for the percentage of vinyl silicone oil gross mass) is less, in order to ensure carrying out smoothly of cross-linking reaction, in vinyl silicone oil, should contain appropriate vinyl, should select suitable molecular weight ranges, further preferred, the molecular weight of described vinyl silicone oil is 3000～200,000, further preferred, the molecular weight of described vinyl silicone oil is 30,000～100,00.
As preferably, R in described vinyl silicone oil
1and R
3for-CH
3, R
2for-CH=CH
2.R in vinyl silicone oil
1and R
3for-CH
3, R
2for-CH=CH
2, be commercial product, raw material is easy to get.
The present invention also provides a kind of release liners used for artificial leather, comprises body paper and is attached to the release layer of body paper surface one side, and described release layer is release layer provided by the present invention.
Basic demand to body paper in the present invention: quantitative 110～150g/m
2, AKD or the applying glue of rosin/aluminum sulfate, CaCO
3filler is lower than 5%; Bulk to body paper and intensity generally can select the fibre furnish of needlebush and leaf wood to regulate and control.Body paper can affect artificial leather release liners quantitatively, the performance such as intensity, heat resistance, coating adhesion, flexibility.
After each described release layer component is taken according to provided proportion, combination drying, remove volatile components, evenly be coated on body paper surface one side by extruder, or outside knurling rolls inner by extruder are suppressed various floral designs again, for example, for the floral designs on artificial leather surface, make described release liners.
Solidifying of the embossed of release layer and release layer can adopt prior art.
As preferably, described release layer thickness is 30～150 μ m.
The thickness of described release layer is blocked up, can cause the waste of raw material, and release layer is excessively thin, in the process of compacting decorative pattern, can may crack by release layer, thereby be unfavorable for peeling off of artificial leather.
A kind of release layer used for artificial leather of the present invention and release liners, can make artificial leather surface have good oily wax sense and silk smooth felling, and have good fissility, and under wet environment, release liners is not easy to occur curling.
Detailed description of the invention
Embodiment 1
In parts by weight, get 95 parts of polypropylene (melt index MFR:28g/10min), 5 parts of branched chain type vinyl silicone oils (purchased from Shandong Dayi Chemical Industry Co., Ltd, number-average molecular weight: 60,000, contents of ethylene is 0.6%) mix and be heated to 90 DEG C, be incubated 2 hours, remove volatile component, then add 0.05 part of cumyl peroxide and mix, under following Extrusion Coating condition, utilizing extruder to be coated on body paper (is quantitatively 128g/m
2, before applying through corona treatment) surface, when coating, suppress decorative pattern by knurling rolls, prepare release layer thickness and be the release liners of 30 microns.
Extrusion Coating condition:
Each section of temperature of extruder: C1/C2/C3/C4/XH/FP/ die head is respectively
240/270/310/330/320/320/310℃；
Mould Breadth: 1800mm;
Extruded velocity: 80～100m/min.
Embodiment 2
In parts by weight, get 90 parts of polypropylene (MFR (being melt index): 28g/10min), 10 parts of branched chain type vinyl silicone oils are (purchased from Shandong Dayi Chemical Industry Co., Ltd, number-average molecular weight: 60,000, contents of ethylene is 0.6%) mix and be heated to 90 DEG C, be incubated 2 hours, remove volatile component, add again 0.1 part of cumyl peroxide and mix, under the Extrusion Coating condition of embodiment 1, utilizing extruder to be coated on body paper (is quantitatively 128g/m
2, before applying through corona treatment) surface, when coating, suppress decorative pattern by knurling rolls, prepare release layer thickness and be the release liners of 35 microns.
Embodiment 3
In parts by weight, get 85 parts of polypropylene (MFR (being melt index): 28g/10min), 15 parts of branched chain type vinyl silicone oils are (purchased from Shandong Dayi Chemical Industry Co., Ltd, number-average molecular weight: 50,000, contents of ethylene is 0.5%) mix and be heated to 90 DEG C, be incubated 2 hours, remove volatile component, add again 0.15 part of cumyl peroxide and mix, under the Extrusion Coating condition of embodiment 1, utilizing extruder to be coated on body paper (is quantitatively 128g/m
2, before applying through corona treatment) surface, when coating, suppress decorative pattern by knurling rolls, prepare release layer thickness and be the release liners of 37 microns.
Embodiment 4
In parts by weight, get 80 parts of polypropylene (MFR (being melt index): 28g/10min), 5 parts of low density polyethylene (LDPE)s (MFR:8g/10min), 15 parts of branched chain type vinyl silicone oils are (purchased from Shandong Dayi Chemical Industry Co., Ltd, number-average molecular weight: 60,000, contents of ethylene is 0.5%) mix and be heated to 90 DEG C, be incubated 2 hours, remove volatile component, add 0.15 part of cumyl peroxide again and mix, under the Extrusion Coating condition of embodiment 1, utilizing extruder to be coated on body paper (is quantitatively 128g/m
2, before applying through corona treatment) surface, when coating, suppress decorative pattern by knurling rolls, prepare release layer thickness and be the release liners of 35 microns.
Comparative example 1
Get polypropylene (MFR (being melt index): 28g/10min), mix and be heated to 90 DEG C, be incubated 2 hours, remove volatile component, under the Extrusion Coating condition of embodiment 1, utilizing extruder to be coated on body paper (is quantitatively 128g/m
2, before applying through corona treatment) surface, when coating, suppress decorative pattern by knurling rolls, prepare release layer thickness and be the release liners of 30 microns.
Performance test
(1) leather surface surface effect: use the artificial leather PU resin components that scraper for coating method (gap is 250 microns) is 30% by solid content to coat on the release layer of release liners, after dry, on PU resin bed, coat PU resin adhesive by scraper for coating method, again dry, then base cloth is sticked to the surface of adhesive, after dry and curing, PU resin bed with base cloth is peeled off from release liners, obtain being with figuratum artificial leather, the pattern on artificial leather leather surface and the pattern in release liners form contrary concavo-convex.The surface oil wax sense of ready visual contrast embodiment and comparative example; Use again have gentle hands light touches, the sliding effect of surface silk of comparative example and comparative example.
(2) mensuration of peel strength (being also release): use the artificial leather PU resin components that scraper for coating method (gap is 250 microns) is 30% by solid content to coat in the release coating of release liners, after dry, be longitudinally cut into the batten that width is 30mm, constant temperature and humidity one hour in the atmosphere of 25 DEG C of 50% humidity, and test with conventional tensile strength tester in same atmosphere.
The condition of the off-type force that mensuration polyurethane film is peeled off from release liners: peel angle is 180 degree; Peeling rate is 1 m/min.Parallel determination 5 times, the off-type force of averaging and peeling off from release liners as polyurethane film, unit: gram/30 millimeters.
(3) release liners warpage properties is measured: release liners to be measured is placed in to 140 DEG C of baking oven constant temperature 2 minutes, takes out and be placed in room temperature cooling 5 minutes, as a thermal cycle.5 times (i.e. 5 thermal cycles) are carried out in same operation repeatedly, all assess the warpage situation of release liners after each thermal cycle, and warpage amplitude is the smaller the better.
Table 1 has been listed the performance of release liners prepared by each embodiment and comparative example.
Table 1
Result from listing in table 1: release liners used for artificial leather provided by the invention has fabulous release, and warpage amplitude is little, the synthetic leather of being made up of it or the surface of artificial leather have splendid oily wax sense and silk smooth felling.
Claims (6)
1. a release layer used for artificial leather, is characterized in that, its raw material consists of polyolefin, vinyl silicone oil and initator, and the weight portion of described raw material consists of:
Polyolefin is 80～97;
Vinyl silicone oil is 2～20;
Initator is 0.05～1;
Described polyolefin is at least one in polypropylene, poly(4-methyl-1-pentene); Polyacrylic melt index scope is 20～30g/10min; The melt index scope of poly(4-methyl-1-pentene) is 22～30g/10min;
Described vinyl silicone oil structural formula is as follows:
Wherein, m span is that 0～5000, n span is 0～6;
R
1, R
2, R
3be-CH independently separately
3or
and when different be-CH
3, n is 0 o'clock R
1, R
3when different, be-CH
3, wherein, x span is 0～10;
The molecular weight of described vinyl silicone oil is 300～300,000;
Described initator is di-tert-butyl peroxide, two t-amyl peroxy things, 2, 2-bis-(t-butyl peroxy) butane, 2, 5-dimethyl-2, 5-di-t-butyl hexane peroxide, 2, 5-dimethyl-2, 5-di-t-butyl peroxy-3-hexin, cumyl peroxide, 1, 4-pair-(2-tert-butyl hydroperoxide isopropyl) benzene, tert-butyl peroxide isopropylbenzene, tert butyl peroxy benzoate, tert-butyl hydroperoxide-2 ethyl hexanoic acid ester, tert-butyl hydroperoxide-3, 5, 5-tri-methyl hexanoic acid ester, tert-butyl hydroperoxide isopropyl carbonic acid ester, at least one in tert-butyl hydroperoxide carbonic acid-2-Octyl Nitrite.
2. release layer used for artificial leather as claimed in claim 1, is characterized in that, described initator is cumyl peroxide.
3. release layer used for artificial leather as claimed in claim 2, is characterized in that, the molecular weight of described vinyl silicone oil is 3000～200,000.
4. release layer used for artificial leather as claimed in claim 3, is characterized in that, R in described vinyl silicone oil
1and R
3for-CH
3, R
2for-CH=CH
2.
5. a release liners used for artificial leather, comprises body paper and is attached to the release layer of body paper surface one side, it is characterized in that, described release layer is the arbitrary described release layer of claim 1～4.
6. release liners used for artificial leather as claimed in claim 5, is characterized in that, described release layer thickness is 30～150 μ m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210302012.0A CN102817284B (en) | 2012-08-23 | 2012-08-23 | Release layer and release paper used for artificial leather |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210302012.0A CN102817284B (en) | 2012-08-23 | 2012-08-23 | Release layer and release paper used for artificial leather |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102817284A CN102817284A (en) | 2012-12-12 |
| CN102817284B true CN102817284B (en) | 2014-12-03 |
Family
ID=47301701
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210302012.0A Expired - Fee Related CN102817284B (en) | 2012-08-23 | 2012-08-23 | Release layer and release paper used for artificial leather |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102817284B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103225232B (en) * | 2013-01-24 | 2015-10-07 | 浙江凯伦特种材料有限公司 | Synthetic Leather release liners release layer thermoplastic resin composition and adopt release liners and the preparation method of this release layer |
| CN103410058B (en) * | 2013-07-17 | 2016-04-06 | 浙江池河科技有限公司 | A kind of synthetic leather release liners |
| 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 |
| CN103350528A (en) * | 2013-07-17 | 2013-10-16 | 浙江池河科技有限公司 | Release paper for high-simulation leather and manufacturing method thereof |
| CN107234856A (en) * | 2017-07-07 | 2017-10-10 | 昆山致信天城电子材料有限公司 | A kind of release coiled material of use for synthetic leather and manufacturing process |
| TWI706853B (en) * | 2018-01-17 | 2020-10-11 | 南亞塑膠工業股份有限公司 | Polyolefin releasing film and method for manufacturing the same, and thermoplastic polyurethane composite structure |
| CN113082783B (en) * | 2020-01-08 | 2022-07-12 | 万华化学集团股份有限公司 | Silicone branched polymer, preparation method thereof and defoaming agent composition comprising same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2413144A1 (en) * | 2000-06-22 | 2001-12-27 | Dow Corning Corporation | Silicone coatings containing silicone mist suppressant compositions |
| CN101045819A (en) * | 2007-04-30 | 2007-10-03 | 东莞市贝特利新材料有限公司 | Organic silicon resin composite |
| CN102391558A (en) * | 2011-08-22 | 2012-03-28 | 湖南福泰数码材料科技有限公司 | Method for preparing release paper with concave-convex grooved texture |
| CN102408723A (en) * | 2011-08-08 | 2012-04-11 | 吴世维 | Silicone rubber, silicone rubber manufacturing method and feeding bottle manufactured from silicone rubber |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7951452B2 (en) * | 2002-09-30 | 2011-05-31 | Kuraray Co., Ltd. | Suede artificial leather and production method thereof |
| JP4674701B2 (en) * | 2005-12-14 | 2011-04-20 | 信越化学工業株式会社 | Non-halogen flame retardant resin composition |
-
2012
- 2012-08-23 CN CN201210302012.0A patent/CN102817284B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2413144A1 (en) * | 2000-06-22 | 2001-12-27 | Dow Corning Corporation | Silicone coatings containing silicone mist suppressant compositions |
| CN101045819A (en) * | 2007-04-30 | 2007-10-03 | 东莞市贝特利新材料有限公司 | Organic silicon resin composite |
| CN102408723A (en) * | 2011-08-08 | 2012-04-11 | 吴世维 | Silicone rubber, silicone rubber manufacturing method and feeding bottle manufactured from silicone rubber |
| CN102391558A (en) * | 2011-08-22 | 2012-03-28 | 湖南福泰数码材料科技有限公司 | Method for preparing release paper with concave-convex grooved texture |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102817284A (en) | 2012-12-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102817284B (en) | Release layer and release paper used for artificial leather | |
| CN103351812B (en) | A kind of water-based parting agent and preparation method thereof and the separate-type paper utilizing this water-based parting agent to prepare | |
| JP3756406B2 (en) | Cosmetic material | |
| JP4255943B2 (en) | Cosmetic material | |
| CN103410058B (en) | A kind of synthetic leather release liners | |
| CN103764404A (en) | Method for producing a decorated wall, ceiling or floor panel | |
| JP6922214B2 (en) | How to make release paper, synthetic leather, and release paper | |
| KR102694079B1 (en) | Casting paper for synthetic leather and manufacturing method of synthetic leather | |
| TW200927494A (en) | Support sheet for process release sheet, process release sheet and method for producing synthetic leather | |
| CN103938460A (en) | Water dyeing method of semi-polyurethane leather | |
| EP2520710A1 (en) | Silk-effect paper material and corresponding manufacturing method | |
| CN108357283B (en) | A kind of integrated wall 3D chromatography decoration film production process | |
| CN109532178A (en) | 3D chromatography casing pressure decorates film production process, application and intermediate products | |
| JP4680043B2 (en) | Cosmetic material | |
| KR101178267B1 (en) | Decoration sheet and its manufacturing method using hot-melt sheet | |
| CN107867100A (en) | Position flower pattern transfer membrane and its manufacture craft | |
| CN107227625A (en) | A kind of thin folding line low resilience superfine fiber chemical leather and preparation method thereof | |
| JP7358741B2 (en) | Diffractive glossy synthetic leather | |
| CN105774164B (en) | A kind of imitative coat of paint surpasses the preparation method of flat mirror face woven fabric | |
| JP2552515B2 (en) | Manufacturing method of lacquer decoration material | |
| JP7308673B2 (en) | Casting paper for synthetic leather and method for producing synthetic leather | |
| KR101379575B1 (en) | Wallpaper and the method of production of the same | |
| CN208515214U (en) | A kind of transparent laser transfer membrane of aqueous medium | |
| KR102329847B1 (en) | Method for Manufacturing Silicon Heating-Transfer Sheet With Excellent Durability and Abrasion Resistance | |
| JP4772385B2 (en) | Method for producing impregnated paper |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141203 Termination date: 20190823 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |