CN102817284A - Release layer and release paper used for artificial leather - Google Patents
Release layer and release paper used for artificial leather Download PDFInfo
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- CN102817284A CN102817284A CN2012103020120A CN201210302012A CN102817284A CN 102817284 A CN102817284 A CN 102817284A CN 2012103020120 A CN2012103020120 A CN 2012103020120A CN 201210302012 A CN201210302012 A CN 201210302012A CN 102817284 A CN102817284 A CN 102817284A
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- artificial leather
- release layer
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- silicone oil
- vinyl silicone
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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 used for artificial leather release layer and release liners.
Background technology
Release liners is claimed barrier paper again, is a kind ofly both can prevent the prepreg adhesion, can protect the not contaminated separate paper of prepreg again.
Usually use release liners in the artificial leather manufacture process.Release liners comprises base material and is coated in the release layer on the base material, and base material is generally body paper, and release layer is coated in body paper surface one side by materials such as polysiloxanes, alkyd resins, polyolefin usually and forms.
Application number is 200810079831.7 disclosure of the Invention, and a kind of synthetic leather is used release liners, and it is provided with a multi-functional layer between base material and release layer, and the component and the parts by weight thereof of said multi-functional layer are: adhesive 40～95; Water 5～60; Surfactant 1～5; The formation material of said release layer comprises alkyd modified silicones, melmac and acid catalyst.
In the prior art, form the texture of expection on the release layer of release liners usually through embossing, when producing artificial leather; Polyurethane solutions is coated on the release layer of release liners, after being heating and curing, is coated with the last layer adhesive and is covered with one deck cloth at polyurethane surface; Behind the heat drying; Make adhesive solidification, release liners is peeled off from artificial leather, the artificial leather surface that obtains has the texture opposite with the release liners concave-convex surface.
At present, there is following problem in the release liners of using in the polyurethane artificial leather manufacture process:
When (1) using polysiloxanes to do release layer, because the compatibility of polyurethane and polysiloxanes is relatively poor, polyurethane is difficult for film forming; And, come off easily in the polyurethane film-forming process, in the process of coating adhesive; Polyurethane film also breaks away from from release layer easily, i.e. " prestripping ";
When (2) using alkyd resins to do release layer, because the affine better performances of polyurethane and alkyd resins, polyurethane film is not easy to peel off from release layer behind the adhesive solidification; The release liners of making release layer of alkyd resins is when embossing; Release liners can constantly produce crack and space; These cracks and space can significantly reduce the ability that polyurethane film breaks away from from release liners on the one hand, also can significantly reduce the oily wax sense and the silk smooth felling of polyurethane artificial leather surface on the other hand.
(3) use polyolefin (like polypropylene or poly(4-methyl-1-pentene)) when making release layer; Because the compatibility of polyolefin and polyurethane is better; Polyurethane artificial leather after the curing is not easy to peel off; Particularly difficult when particularly on the polyolefin release layer, degree of depth embossing being arranged, in addition, the release liners that contains the polyolefin release layer is prone to curl in wet environment.
In the embossing operation in the artificial leather manufacture process, the decorative pattern on the knurling rolls has determined the surface texture of release liners release layer, because the defective of existing knurling rolls manufacturing technology itself; The decorative pattern details of knurling rolls can not be smooth fully, generally, can have burr and uneven phenomenon; The decorative pattern that forms on release liners surface through this dandy roll and thus the release liners artificial leather surface of processing all have same problem; Turn white in the artificial leather surface for preparing, dry and astringent, no glossy.
Summary of the invention
The invention provides a kind of used for artificial leather release layer and release liners, release liners is difficult for curling in wet environment, and the artificial leather that uses this release liners to prepare is peeled off from release liners easily, and the artificial leather surface that produces has splendid silk smooth felling and oily wax sense.
A kind of used for artificial leather release layer, its raw material consists of polyolefin, vinyl silicone oil and initator; Described vinyl silicone oil structural formula is following:
Wherein, the m span is 0～5000, and the n span is 0～6;
R
1, R
2, R
3Independently be-CH separately
3Or
And be not simultaneously-CH
3, n is 0 o'clock R
1, R
3Be not simultaneously-CH
3, wherein, the x span is 0～10.
Two keys in the said initator initiation polyolefin and the two key generation cross-linking reactions in the vinyl silicone oil; Generate fine and close release layer; Described release layer has smooth surface, utilizes when containing release liners manufacturer's fabricate-leather of said release layer, can make the artificial leather surface have oily wax sense and silk smooth felling.
As preferably, said polyolefin is at least a in polyethylene, polypropylene and the poly(4-methyl-1-pentene).
Said 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; Said initator is di-tert-butyl peroxide, two t-amyl peroxy things, 2,2-two (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-is two-(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, at least a in 5-tri-methyl hexanoic acid ester, tert-butyl hydroperoxide isopropyl carbonic acid ester, the tert-butyl hydroperoxide carbonic acid-2-Octyl Nitrite.
The cross-linking reaction that said initator can cause two keys of polyolefinic pair of key and vinyl silicone oil gets final product; The selection of said initator will directly influence the speed of cross-linking reaction and carry out degree; For the release layer that guarantees to generate has good properties; Should select to have the initator of suitable half-life, preferably, said initator is a cumyl peroxide.
As preferably, the weight portion of said 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, the polyurethane artificial leather after the curing is not easy to peel off; Particularly difficult when on the polyolefin release layer degree of depth embossing being arranged, in addition, the release liners that makes is prone to curl in wet environment; Because the compatibility of vinyl silicone oil and polyurethane is relatively 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, and the consumption of said initator is too much unsuitable; Avoid the cross-linking reaction excessive velocities, the performance of the release layer that influence generates.
In order to avoid warpage as far as possible, make release layer have more performance, further preferred, the weight portion of said 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 said vinyl silicone oil (number average) is 300～300,000.
Generally, the molecular weight of vinyl silicone oil is big more, and then the content of vinyl (all vinyl quality account for the percentage of vinyl silicone oil gross mass) is more little, in order to guarantee carrying out smoothly of cross-linking reaction; An amount of vinyl should be contained in the vinyl silicone oil, promptly suitable molecular weight ranges should be selected, further preferred; The molecular weight of said vinyl silicone oil is 3000～200,000, and is further preferred; The molecular weight of said vinyl silicone oil is 30,000～100,00.
As preferably, R in the said vinyl silicone oil
1And R
3For-CH
3, R
2For-CH=CH
2R in the 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 used for artificial leather release liners, comprises that body paper reaches the release layer attached to body paper surface one side, and described release layer is a release layer provided by the present invention.
Among the present invention to the basic demand of body paper: quantitative 110～150g/m
2, AKD or rosin/aluminum sulfate applying glue, CaCO
3Filler is lower than 5%; Bulk and intensity to body paper generally can select for use the fibre furnish of needlebush and leaf wood to regulate and control.Body paper can influence the artificial leather release liners quantitatively, performances such as intensity, heat resistance, coating adhesion, flexibility.
After each component of described release layer taken by weighing according to the proportion that is provided; Combination drying; Remove volatile components, evenly be coated on body paper surface one side, suppress various floral designs through extruder inside or outside knurling rolls again through extruder; For example be used for the floral designs on artificial leather surface, process described release liners.
The embossed of release layer and the curing of release layer can be adopted prior art.
As preferably, said release layer thickness is 30～150 μ m.
The thickness of said release layer is blocked up, can cause the waste of raw material, and release layer is thin excessively, the compacting decorative pattern process in, but release layer possibly crack, thereby be unfavorable for peeling off of artificial leather.
A kind of used for artificial leather release layer of the present invention and release liners can make the 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 take place to curl.
The specific embodiment
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 are (available 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 ℃; Be incubated 2 hours, remove volatile component, add 0.05 part of cumyl peroxide again and mix; Extrude under the coated conditions following, utilize extruder to be coated on body paper and (quantitatively be 128g/m
2, before applying through sided corona treatment) surface, through knurling rolls compacting decorative pattern, prepare release layer thickness and be 30 microns release liners in the time of coating.
Extrude coated conditions:
Each section of extruder temperature: the 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, (MFR (being melt index): 28g/10min), 10 parts of branched chain type vinyl silicone oils are (available from Shandong Dayi Chemical Industry Co., Ltd to get 90 parts of polypropylene; Number-average molecular weight: 60,000, contents of ethylene is 0.6%) mix and be heated to 90 ℃; Be incubated 2 hours, remove volatile component, add 0.1 part of cumyl peroxide again and mix; Extruding under the coated conditions of embodiment 1, utilize extruder to be coated on body paper and (quantitatively be 128g/m
2, before applying through sided corona treatment) surface, through knurling rolls compacting decorative pattern, prepare release layer thickness and be 35 microns release liners in the time of coating.
Embodiment 3
In parts by weight, (MFR (being melt index): 28g/10min), 15 parts of branched chain type vinyl silicone oils are (available from Shandong Dayi Chemical Industry Co., Ltd to get 85 parts of polypropylene; Number-average molecular weight: 50,000, contents of ethylene is 0.5%) mix and be heated to 90 ℃; Be incubated 2 hours, remove volatile component, add 0.15 part of cumyl peroxide again and mix; Extruding under the coated conditions of embodiment 1, utilize extruder to be coated on body paper and (quantitatively be 128g/m
2, before applying through sided corona treatment) surface, through knurling rolls compacting decorative pattern, prepare release layer thickness and be 37 microns release liners in the time of coating.
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 (available 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 ℃; Be incubated 2 hours, remove volatile component, add 0.15 part of cumyl peroxide again and mix; Extruding under the coated conditions of embodiment 1, utilize extruder to be coated on body paper and (quantitatively be 128g/m
2, before applying through sided corona treatment) surface, through knurling rolls compacting decorative pattern, prepare release layer thickness and be 35 microns release liners in the time of coating.
Comparative Examples 1
Get polypropylene (MFR (being melt index): 28g/10min), mix and be heated to 90 ℃, be incubated 2 hours, remove volatile component,, utilize extruder to be coated on body paper and (quantitatively be 128g/m extruding under the coated conditions of embodiment 1
2, before applying through sided corona treatment) surface, through knurling rolls compacting decorative pattern, prepare release layer thickness and be 30 microns release liners in the time of coating.
Performance test
(1) leather surface surface effect: using scraper rubbing method (gap is 250 microns) is that 30% artificial leather PU resin component is coated on the release layer of release liners with solid content; After the drying; On the PU resin bed, coat the PU resin adhesive with the scraper rubbing method, dry once more, then base cloth is sticked to the surface of adhesive; After drying and the curing; The PU resin bed that will have base cloth is peeled off from release liners, promptly obtains having the artificial leather of pattern, and pattern on the artificial leather leather surface and the pattern on the release liners form opposite concavo-convex.The surface oil wax sense of ready visual contrast embodiment and Comparative Examples; Use the have gentle hands light touches again, the sliding effect of surface silk of comparative example and Comparative Examples.
(2) mensuration of peel strength (also being release): using scraper rubbing method (gap is 250 microns) is that 30% artificial leather PU resin component is coated on the release coating of release liners with solid content; Longitudinally be cut into the batten that width is 30mm after the drying; Constant temperature and humidity is one hour in the atmosphere of 25 ℃ of 50% humidity, and in same atmosphere, tests with conventional tensile strength tester.
Measure the condition of the off-type force that polyurethane film peels off from release liners: peel angle is 180 degree; Peeling rate is 1 meter/minute.Parallel determination 5 times, the off-type force of averaging and peeling off from release liners, unit: restrain/30 millimeters as polyurethane film.
(3) the release liners warpage properties is measured: release liners to be measured was placed 140 ℃ of baking oven constant temperature 2 minutes, take out and place 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 the warpage amplitude is more little good more.
Table 1 has been listed the performance of the release liners of each embodiment and Comparative Examples preparation.
Table 1
Can be known by the result who lists in the table 1: used for artificial leather release liners provided by the invention has fabulous release, and the warpage amplitude is little, has splendid oily wax sense and silk smooth felling by the surface of its synthetic leather processed or artificial leather.
Claims (10)
1. a used for artificial leather release layer is characterized in that, its raw material consists of polyolefin, vinyl silicone oil and initator; Described vinyl silicone oil structural formula is following:
Wherein, the m span is 0～5000, and the n span is 0～6;
R
1, R
2, R
3Independently be-CH separately
3Or
And be not simultaneously-CH
3, n is 0 o'clock R
1, R
3Be not simultaneously-CH
3, wherein, the x span is 0～10.
2. used for artificial leather release layer as claimed in claim 1 is characterized in that, said polyolefin is at least a in polyethylene, polypropylene and the poly(4-methyl-1-pentene).
3. used for artificial leather release layer as claimed in claim 2; It is characterized in that; Said initator is di-tert-butyl peroxide, two t-amyl peroxy things, 2,2-two (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-is two-(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, at least a in 5-tri-methyl hexanoic acid ester, tert-butyl hydroperoxide isopropyl carbonic acid ester, the tert-butyl hydroperoxide carbonic acid-2-Octyl Nitrite.
4. used for artificial leather release layer as claimed in claim 3 is characterized in that, described initator is a cumyl peroxide.
5. like claim 2 or 3 described used for artificial leather release layers, it is characterized in that the weight portion of said raw material consists of:
Polyolefin is 80～97;
Vinyl silicone oil is 2～20;
Initator is 0.05～1.
6. used for artificial leather release layer as claimed in claim 5 is characterized in that, the molecular weight of said vinyl silicone oil is 300～300,000.
7. used for artificial leather release layer as claimed in claim 6 is characterized in that, the molecular weight of said vinyl silicone oil is 3000～200,000.
8. used for artificial leather release layer as claimed in claim 7 is characterized in that, R in the said vinyl silicone oil
1And R
3For-CH
3, R
2For-CH=CH
2
9. a used for artificial leather release liners comprises that body paper reaches the release layer attached to body paper surface one side, is characterized in that described release layer is the arbitrary described release layer of claim 1～8.
10. used for artificial leather release liners as claimed in claim 9 is characterized in that, said 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 |
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| 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 |
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| CN102817284B CN102817284B (en) | 2014-12-03 |
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| CN103225232A (en) * | 2013-01-24 | 2013-07-31 | 浙江凯伦特种材料有限公司 | Release layer hot-melt resin composition of release paper for polyurethane synthetic leather, the release paper with the release layer and preparation method of the release paper |
| 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 |
| CN103397563A (en) * | 2013-07-17 | 2013-11-20 | 浙江池河科技有限公司 | Release agent for coating release paper, preparation method of release agent and release paper prepared by utilizing release agent |
| CN103410058A (en) * | 2013-07-17 | 2013-11-27 | 浙江池河科技有限公司 | Release paper for synthetic leather |
| 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 |
| CN113082783A (en) * | 2020-01-08 | 2021-07-09 | 万华化学集团股份有限公司 | Silicone branched polymer, preparation method thereof and defoaming agent composition comprising same |
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| 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 |
| CN113082783A (en) * | 2020-01-08 | 2021-07-09 | 万华化学集团股份有限公司 | Silicone branched polymer, preparation method thereof and defoaming agent composition comprising same |
| 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 |
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Granted publication date: 20141203 Termination date: 20190823 |