CN107722864A - A kind of middle off-type force and the mould release membrance of high remaining adhesion rate and preparation method thereof - Google Patents
A kind of middle off-type force and the mould release membrance of high remaining adhesion rate and preparation method thereof Download PDFInfo
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- CN107722864A CN107722864A CN201711019239.3A CN201711019239A CN107722864A CN 107722864 A CN107722864 A CN 107722864A CN 201711019239 A CN201711019239 A CN 201711019239A CN 107722864 A CN107722864 A CN 107722864A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2467/00—Presence of polyester
- C09J2467/005—Presence of polyester in the release coating
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2483/00—Presence of polysiloxane
- C09J2483/005—Presence of polysiloxane in the release coating
Abstract
The invention provides a kind of middle off-type force and the mould release membrance of high remaining adhesion rate, the mould release membrance includes film substrate and release layer, release layer includes 45 65 parts of liquid silicone resins, 45 25 parts of vinyl silicone oils, 5 25 parts of containing hydrogen silicone oils, 0.1 0.3 parts of catalyst, 0.005 0.02 parts of inhibitor, 0.05 0.10 parts of tackifier and 300 400 parts of organic solvents, and liquid silicone resin is that methyl vinyl MQ silicon resin and methyl vinyl silicon oil are 0.05 0.15 in mass ratio:1 forms in temperature for 100 150 DEG C of dissolvings；Catalyst is platinum chelate；Inhibitor is alkynol compound；Tackifier are hydroxyl, the silane coupler of methoxy or ethoxy.The mould release membrance of the present invention, the high mechanical strength of release layer, and lower-molecular substance is few, so remaining Stickiness is high, greatly reduces anti-peel off and fuel-displaced phenomenon.
Description
Technical field
The present invention relates to a kind of mould release membrance, more particularly to it is a kind of be used to be die cut and photovoltaic field of deep it is release
Film, specifically relate to it is a kind of be used to be die cut and the middle off-type force of photovoltaic field of deep and high remaining adhesion rate it is release
Film.The invention further relates to the preparation method of a kind of above-mentioned middle off-type force and the mould release membrance of high remaining adhesion rate.
Background technology
After mould release membrance refers to that there is the film of separation property, mould release membrance to be contacted under limited conditions with specific material on surface
Without viscosity, or slight viscosity.Mould release membrance is usually to be formed by film substrate and coated on the mould release on base material, release
Film by the big I of off-type force be divided into light release mould release membrance, in release mould release membrance and the release mould release membrance of weight；Middle off-type force it is release
Film is generally used for cross cutting and photovoltaic field of deep.Mould release currently as mould release membrance is mainly that organic silicon is release
Agent, this mould release can use the mode that is heating and curing, compare for the acrylic system material of photocuring, heat cure is processed into
The silica gel of type can accomplish relatively low off-type force, and cost is lower.But this of current domestic production uses organosilicon as release
The mould release membrance of agent, anti-stripping, crawling and fuel-displaced phenomenon often occurs；Anti- stripping is exactly that the coating on mould release membrance can be tied
Bigger pad pasting is taken away with joint efforts, and the mould release membrance coating area for being difficult to clean out is partially formed in pad pasting, destroys pad pasting entirety
Pure, uniformity；And fuel-displaced phenomenon be exactly in mould release unreacted small molecule infiltrate, cause mould release membrance layer upper surface oil
It is greasy, or even through the partially deep film substrate of shrinkage pool after sided corona treatment, make the back side appearance of base material greasy；All these phenomenons, all
It is relevant with the material system of mould release.The material system of existing mould release, it is using vinyl organosilicon resin to be main former mostly
Material, the material system of some functional auxiliary agents compositions is coordinated further according to the function needed for mould release membrance application field, due to ethene
Base organic siliconresin is that the small resin of this molecular weight, crosslinking degree is not high directly using molecular weight is small, resin in liquid,
So as to cause the mechanical strength of colloid not high enough, and the release layer that mechanical strength is not high, then easily there is anti-peel off and show with fuel-displaced
As；The big vinyl organosilicon resin of molecular weight can increase crosslinking degree, but due to being powdered, direct use is not easy point
Dissipate.
The content of the invention
To solve the problem present on, it is an object of the invention to provide a kind of middle off-type force and high remaining adhesion rate from
Type film, the mould release membrance coating uniform, anti-peel off substantially reduce with fuel-displaced phenomenon.
It is a further object of the present invention to provide the preparation side of a kind of above-mentioned middle off-type force and the mould release membrance of high remaining adhesion rate
Method.
To realize object above, the mould release membrance of middle off-type force of the invention and high remaining adhesion rate, including film substrate and
Release layer, it is characterised in that：The film substrate is one kind in BOPET, BOPP, PP, PE, PC film, and release layer includes as follows
Each component and number：
Liquid silicone resin 45-65 parts
Vinyl silicone oil 45-25 parts
Containing hydrogen silicone oil 5-25 parts
Catalyst 0.1-0.3 parts
Inhibitor 0.005-0.02 parts
Tackifier 0.05-0.10 parts
Organic solvent 300-400 parts
Wherein liquid silicone resin be by relative molecular weight between 15000-20000, the methyl vinyl MQ silicon resin of M/Q=1.2
The methyl vinyl silicon oil that with viscosity be 200-5000 mpa.s, vinyl molar percentage is 0.1-1.0 % is in mass ratio
0.05-0.15:1 stirs what 1-1.5 hours obtained under conditions of temperature is 100-150 DEG C, mixing speed is 500-1000rpm
Viscosity is 2500-3000 mpa.s liquid silicone；Catalyst is platinum chelate；Inhibitor is alkynol compound；Increase
Stick is hydroxyl, the silane coupler of methoxy or ethoxy；The structural formula of methyl vinyl MQ silicon resin is：
。
The end-vinyl silicon that above-mentioned vinyl silicone oil is viscosity 500-5000mpas, vinyl molar percentage is 0.2-1.0%
Oil, its structural formula are：
Above-mentioned containing hydrogen silicone oil be viscosity be 200-500mpas, hydrogeneous molar percentage than the containing hydrogen silicone oil for 0.2-1.4%, it is tied
Structure formula is：
The reaction product of the preferred chloroplatinic acid of above-mentioned catalyst and tetramethyl divinyl disiloxane.
The above-mentioned preferred ethynylcyclohexanol of inhibitor.
One or both of the preferred toluene of above-mentioned solvent or butanone.
Above-mentioned film substrate preferred thickness is 25 μm -100 μm of BOPET films.
The present invention also provides the preparation method of a kind of above-mentioned middle off-type force and the mould release membrance of high remaining adhesion rate, this method bag
Include following steps：
（1）The preparation of film substrate：Film substrate surface is purified and corona or plasma treatment；
（2）The preparation of mould release：Weighed the weight of each component by the formula of mould release, by liquid silicone resin, vinyl silicone oil,
Catalyst, inhibitor, tackifier and organic solvent are added in reactor, are first stirred in the case where rotating speed is 400rpm/60min
It is even, containing hydrogen silicone oil is added, is uniformly mixed under 800rpm/60min；
（3）In film substrate through step（1）Mould release is coated with treated face and is dried, the wet coating amount of mould release is 3g/
m2-15g/m2, drying temperature is 80-150 DEG C；
（4）Winding packaging is carried out to the mould release membrance of drying.
In above-mentioned preparation method, step（1）Film substrate surface cleaning be using Roller for sticking dust remove surface dirt；Corona
Or the film that plasma treatment is crossed, its surface tension >=50 dyne.
In above-mentioned preparation method, step（3）Drying using heat stepwise carry out, dryer speed is 20m/min-80m/
Min, Segmented heating are 80 DEG C, 100 DEG C, 120 DEG C, 150 DEG C, and last cooling area temperature is 130 DEG C.
The mould release membrance of the middle off-type force of the present invention and high remaining adhesion rate, is contained by using particular viscosity, special ethylene base
The methyl vinyl silicon oil of amount dissolves to the methyl vinyl MQ silicon resin of macromolecule at high temperature, can not only make powdery
MQ silicones be easily dispersed, can be directly added into formula in use, and can make MQ silicones the fine spread apart of macromolecular come,
Contribute to the dispersed of macromolecular structure so that cross-linking reaction can be carried out more thoroughly.The mould release membrance of the present invention, using macromolecular
Material based on the methyl vinyl MQ silicon resin that amount and reactive group are-CH=CH2, group crosslinking degree is high, makes coating
Mechanical strength be increased, and a small amount of uncapped-OH in methyl vinyl MQ silicon resin periphery also contributes to improve mould release
With the adhesive force of basement membrane, greatly reduce the anti-phenomenon peeled off, while the three-dimensional Rzeppa shaped structure of methyl vinyl MQ silicon resin
The overall levelability of colloid is favorably improved, additionally aids to twine and ties up some linear low molecular materials, reduce fuel-displaced phenomenon.This hair
Bright mould release membrance, surface dry, smooth, not tacky, remaining Stickiness height.
Embodiment
Technical scheme is further described with reference to specific embodiment, but these embodiments are not used
To limit the scope of the invention, on the premise of theory of the present invention is not departed from, being equal for release layer functional aid, is replaced
Change, protection scope of the present invention all should be belonged to.
First, the preparation of liquid silicone resin
By relative molecular weight between 17000-19000, the methyl vinyl MQ silicon resin of M/Q=1.2 and viscosity be 500
mpa.s（25℃）, vinyl molar percentage be that 0.2 %, the terminal methyl vinyl silicone oil of 200 DEG C of fugitive constituent≤1.5 press matter
Amount is than being 0.1:1 mixes 1 hour under conditions of temperature is 130 DEG C, mixing speed is 1000rpm, and the viscosity of acquisition is
2500-3000mpas（25℃）Liquid silicone resin.
2nd, the preparation of mould release membrance
1st, the formula of release layer
Wherein the viscosity of vinyl-terminated silicone fluid is 800 mpa.s（25℃）, vinyl molar percentage be 0.45%, 200 DEG C
Fugitive constituent≤1.5；The viscosity of containing hydrogen silicone oil is 200mpas, hydrogeneous mol ratio is 0.20%.
2nd, the preparation of mould release
The weight of each component is weighed by above-mentioned formula, by liquid silicone resin, vinyl-terminated silicone fluid, platinum catalyst, acetenyl
Cyclohexanol, dimethyldiethoxysilane and organic solvent are added in reactor, in the case where rotating speed is 400-450rpm/60min first
It is uniformly mixed, adds containing hydrogen silicone oil, be uniformly mixed under 800-850rpm/60min, acquisition viscosity is 50-
105mpas coating fluid.
3rd, the preparation of mould release membrance
（1）It is 25 μm -100 μm of BOPET basement membranes from thickness, the dust of BOPET membrane surfaces is first removed using Roller for sticking dust, then
Corona or corona treatment are carried out to its clean surface, make its surface tension >=50 dyne；
（2）In BOPET basement membranes through step（1）Above-mentioned mould release is coated with treated face, it is 3g/m to control wet coating amount2-
15g/m2, drying temperature is 80-150 DEG C, is carried out using heat stepwise, dryer speed is 20m/min-80m/min, and segmented adds
Heat is 80 DEG C, 100 DEG C, 120 DEG C, 150 DEG C, and last cooling area temperature is 130 DEG C；
（3）Winding packaging is carried out to the mould release membrance of drying.
3rd, properties of product are tested
Embodiment a-d and the comparative example product obtained and commercially available prod are carried out to the test of respective item, it is as a result as follows：
As can be seen from the above table, in Si-H:In Vi indexs identical embodiment c and comparative example, do not added in comparative example formula
The product that MQ silicones obtains, its peel strength and remaining adhesion rate are below the production that embodiment c with the addition of the acquisition of MQ silicones
Product；Commercially available prod of the off-type force between embodiment b and embodiment c, product of its remaining adhesion rate significantly lower than the present invention.
The mould release membrance of the present invention, it is surface dry, smooth, not tacky, simultaneously because the high mechanical strength of release layer, and lower-molecular substance
It is few, so remaining adhesion rate is high, and it is not fuel-displaced.
Claims (10)
1. the mould release membrance of a kind of middle off-type force and high remaining adhesion rate, including film substrate and release layer, it is characterised in that：It is described
Film substrate is one kind in BOPET, BOPP, PP, PE, PC film, and release layer includes following each component and number：
Liquid silicone resin 45-65 parts
Vinyl silicone oil 45-25 parts
Containing hydrogen silicone oil 5-25 parts
Catalyst 0.1-0.3 parts
Inhibitor 0.005-0.02 parts
Tackifier 0.05-0.10 parts
Organic solvent 300-400 parts
Wherein liquid silicone resin be by relative molecular weight between 15000-20000, the methyl vinyl MQ silicon resin of M/Q=1.2
The methyl vinyl silicon oil that with viscosity be 200-5000 mpa.s, vinyl molar percentage is 0.1-1.0 % is in mass ratio
0.05-0.15:1 stirs what 1-1.5 hours obtained under conditions of temperature is 100-150 DEG C, mixing speed is 500-1000rpm
Viscosity is 2500-3000 mpa.s liquid silicone；Catalyst is platinum chelate；Inhibitor is alkynol compound；Increase
Stick is hydroxyl, the silane coupler of methoxy or ethoxy；The structural formula of methyl vinyl MQ silicon resin is：
。
2. the mould release membrance of middle off-type force according to claim 1 and high remaining adhesion rate, it is characterised in that：The vinyl
The vinyl-terminated silicone fluid that silicone oil is viscosity 500-5000mpas, vinyl molar percentage is 0.2-1.0%.
3. the mould release membrance of middle off-type force according to claim 1 or 2 and high remaining adhesion rate, it is characterised in that：It is described to contain
Hydrogen silicone oil be viscosity be 200-500mpas, hydrogeneous molar percentage is than the containing hydrogen silicone oil for 0.2-1.4%.
4. the mould release membrance of middle off-type force according to claim 3 and high remaining adhesion rate, it is characterised in that：Its feature exists
In：The catalyst is the reaction product of chloroplatinic acid and tetramethyl divinyl disiloxane.
5. the mould release membrance of middle off-type force according to claim 4 and high remaining adhesion rate, it is characterised in that：Institute's inhibitor is
Ethynylcyclohexanol.
6. the mould release membrance of middle off-type force according to claim 5 and high remaining adhesion rate, it is characterised in that：The solvent is
One or both of toluene or butanone.
7. the mould release membrance of middle off-type force according to claim 1 or 2 and high remaining adhesion rate, it is characterised in that：It is described thin
Film base material preferred thickness is 25 μm -100 μm of BOPET films.
8. the preparation method of any middle off-type force described in a kind of claim 1-7 and the mould release membrance of high remaining adhesion rate, this method
Comprise the following steps：
（1）The preparation of film substrate：Film substrate surface is purified and corona or plasma treatment；
（2）The preparation of mould release：Weighed the weight of each component by the formula of mould release, by liquid silicone resin, vinyl silicone oil,
Catalyst, inhibitor, tackifier and organic solvent are added in reactor, are first stirred in the case where rotating speed is 400rpm/60min
It is even, containing hydrogen silicone oil is added, is uniformly mixed under 800rpm/60min,
（3）In film substrate through step（1）Mould release is coated with treated face and is dried, the wet coating amount of mould release is 3g/
m2-15g/m2, drying temperature is 80-150 DEG C；
（4）Winding packaging is carried out to the mould release membrance of drying.
9. the preparation method of middle off-type force according to claim 8 and the mould release membrance of high remaining adhesion rate, it is characterised in that：
In the preparation method, step（1）Film substrate surface cleaning be using Roller for sticking dust remove surface dirt；Corona or plasma
Treated film, its dyne of >=50 dynes of value.
10. the preparation method of middle off-type force according to claim 9 and the mould release membrance of high remaining adhesion rate, its feature exist
In：In the preparation method, step（3）Drying using heat stepwise carry out, dryer speed is 20m/min-80m/min, divide
Segmentation is heated to be 80 DEG C, 100 DEG C, 120 DEG C, 150 DEG C, and last cooling area temperature is 130 DEG C.
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| CN109306248A (en) * | 2018-09-27 | 2019-02-05 | 苏州市星辰科技有限公司 | A kind of low difference silicon systems release film and preparation method thereof |
| CN109762192A (en) * | 2018-12-30 | 2019-05-17 | 苏州市奥贝膜业有限公司 | Release release film and preparation method thereof during a kind of peeling force is stable |
| CN109991162A (en) * | 2019-04-15 | 2019-07-09 | 深圳市普利司德高分子材料有限公司 | A kind of FINAT remnants then rate test method |
| CN110527122A (en) * | 2019-07-12 | 2019-12-03 | 四川羽玺新材料股份有限公司 | A kind of ultralight PET release film of two-sided antistatic and preparation method thereof |
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| CN104684730A (en) * | 2012-10-09 | 2015-06-03 | 道康宁东丽株式会社 | Curable organopolysiloxane composition, sheet-like article having a cured layer formed from said composition, and laminate |
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