CN101965377B - Release film - Google Patents
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- CN101965377B CN101965377B CN2008801275998A CN200880127599A CN101965377B CN 101965377 B CN101965377 B CN 101965377B CN 2008801275998 A CN2008801275998 A CN 2008801275998A CN 200880127599 A CN200880127599 A CN 200880127599A CN 101965377 B CN101965377 B CN 101965377B
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- 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
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/72—Cured, e.g. vulcanised, cross-linked
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/748—Releasability
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
- B32B2309/08—Dimensions, e.g. volume
- B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
- B32B2309/105—Thickness
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a release film, and more specifically, to a release film including a polyester film and a release coating layer that is formed on one side or both sides of the polyester film, wherein the release coating layer is formed by applying an aqueous coating solution including a silicon-based binder resin and an aqueous silicon-based resin having a phenyl group as a crosslinker and crosslinking and curing it, thereby having the improved adhesion to substrate (smear/rub-off ) with the polyester film.
Description
Technical field
The present invention relates to stripping film, relate more specifically between the release coating that uses silicone and polyester film, to improve and the stripping film of bonding (the smearing/wipe (smear/rub-off)) of substrate.
Background technology
Stripping film has stripping performance by the solidified coating that forms silicon composition at substrate surface, to prevent the bonding or adhesion between substrate (such as paper or plastic film etc.) and the cohesive material.When substrate surface is plastic film, usually it is called stripping film.
The tacky adhesion side of stripping film temporary protection binding property article prevents the pollution that causes because of dust, fragment, moisture and other pollutents, until for example prepare to use label.Usually, stripping film separates with adhesive side before the binding property article face use.
Stripping film is with release coating, and release coating can provide bonding (the smearing/wipe) of substrate (substrate) and substrate (base), simultaneously the basad stripping performance that provides.Release coating mainly comprises the silicon stripper.
The performance of stripping film depends primarily on the tackiness agent of the bonding coat that forms the binding property article, or is used for the silicon stripper etc. of release coating.In case stripping film and the combination of tacky adhesion side, it can not separate with it automatically then not have peeling force, but should be easy to separate (stripping performance) and should not cause that tackiness agent reduces the residue of substrate bonding (smearing/wipe) by relatively little peeling force.In addition, when stripping film separated with adhesive side, the release coating itself that stays stripping film was intact, and namely the inside of stripping film is bonding also is important.
In other words, release coating satisfies the obviously condition of opposition: when it and polyester film were combined closely, it was easy to peel off fully at opposition side.
On the other hand, according to the method for release coating being coated on the basilar membrane, stripping film is divided into off-line and films and film online.Usually, off-line coating is a kind of by being coated on basilar membrane on the form of the finished product release coating and with its dry method form of making stripping film.Usually, online coating is a kind of amorphous melt by extruded polymer, they is solidified into sheet, and release coating is coated on the sheet material, then carries out processing and the method form of manufacturing stripping film such as preheating, stretching, thermofixation, cooling etc.
Usually, in stripping film, polyester film is mainly as basilar membrane.Because polyester film has stable chemical structure, so it has high mechanical strength, has good character with regard to physicalies such as thermotolerance, persistence, chemical resistant properties.In these polyester, especially, because polyethylene terephthalate has good stability, good chemical resistant properties, good physical strength, surface properties and thickness evenness and the processing condition of multiple application is had good adaptability with regard to physicals in the wide temperature range from low temperature to high temperature, so it has been widely used in industrial use, medical use, packing purposes etc.In addition, when considering the environmental pollution that proposes in recent years, because the cyclicity of polyethylene terephthalate is high, so the importance of polyethylene terephthalate is in the industrial circle phenomenal growth.
The process of making stripping film by online coating comprises: amorphous melt and the curtain coating in cooling of extruding polyester are roused curtain coating, and they are solidified into sheet, and the release coating solution coat on sheet material, is then heated with stretch processing with the preparation film.In these processes, film toughness, stability and other preferred physical properties are provided.Film stretches in a direction or both direction, then solidifies.
Usually, for productivity and the adaptability of film, answer fast setting by being coated on online the peel-coat compositions that is coated with on the film surface.In addition, peel-coat compositions should be able to stretch under the prerequisite that does not reduce intensity and transparency.
In peel-coat compositions, the silicon stripper can comprise active crosslinkable silicon base compound.Described silicon base compound can comprise hydrogen functional polysiloxanes, alkoxy-functional polysiloxane, hydroxy-functional polysiloxane, vinyl-functional polysiloxane etc.All these compounds are sold with low viscosity and runny liquid resinous form.
Usually, in line painting method, the silicon stripper can be used as water-based emulsion.The known method that forms silicon coating at substrate surface has: (1) uses the platinum based compound to make the further reaction and form the method for stripping coating of vinyl-functional polysiloxane and hydrogen functional polysiloxanes as catalyzer, and (2) carry out method etc. that polycondensation form stripping coating as catalyzer at polysiloxane by use metal salts of organic acids (such as organo-tin compound etc.).
Usually, for as the solution of the aqueous solution for the preparation of the formation release coating, use emulsifying agent.When the water-based coating solution that comprises emulsifying agent and preparation solution phase that solvent and no-solvent type arranged than the time, exist between release coating and the basilar membrane and problem that bonding (the smearing/wipe) of substrate reduced.Therefore, add bonding agent to improve and substrate (smearing/wipe) bonding.As bonding agent, can use usually by U.S. Patent No. 6,020 oxyalkylsiloxane that 412 description is made.
Yet, in most cases, owing to for the manufacture of the emulsifying agent of the water-based coating solution violent stability in storage that reduces coating composition under the state of preparation solution and in the bonding agent reaction, for emulsifying agent is used for actual treatment, must carry out basic improvement to it.Therefore, need exploitation improving between release coating and the basilar membrane under the prerequisite of not using the bonding agent layer and the method for bonding (the smearing/wipe) of substrate.
Summary of the invention
Technical problem
The object of the present invention is to provide the stripping film that comprises release coating, this stripping film uses and forms at line painting method.
In addition, the object of the present invention is to provide the linking agent of bonding (the smearing/wipe) of improving substrate and polyester film, do not use bonding agent at the water-based coating solution that is used for online coating.
Technical scheme
The present invention relates to stripping film, the stripping film of the release coating on the one or both sides that relate more specifically to comprise polyester film and be formed at polyester film, wherein release coating is by being coated with fabric aqueous coating solution and it is crosslinked and be solidified to form, and described water-based coating solution comprises the silicon-based adhesive resin and as the aqueous silicon-base resin with phenyl of linking agent.
The water-based coating solution can comprise silicon-based adhesive resin, linking agent, catalyzer and water as main component, and is used for realizing the additive of various functions.
In other words, the water-based coating solution is coated polyester film with the emulsion in the water or disperse phase.Dispersion can be by mixing and stirring waterborne polymeric (such as polyoxyethylene glycol or polyvinyl alcohol) and tensio-active agent (such as the alkyl phenyl polyglycol ether) is made as additive.
In addition, in order to prepare stripping film, the water-based coating solution is coated on the polyester film as basilar membrane, film preheat with drawing process in its moisture of evaporation, and in curing process crosslinked and curable water-borne coating solution, form thus the coating only deposit final solid.Therefore, the solids component among the present invention represents the solid of the main ingredient except additive that exists in the release coating.
As adhesive resin, can use straight chain or branched alkyl vinyl polysiloxane, concrete use has the dimethione of the one or more functional groups that are selected from hydroxyl, vinyl, ethynyl at its terminal or side chain bonding.
Be cured by the hydrosilylation reactions that uses catalyzer to cause silicon resin adhesive, use one or more metals or the amphoteric element that are selected from the 4th to 14 family, namely be selected from any one of Rh, Pt, Sn, Ti, Pd, Ir, W and Co.
About linking agent, use the linking agent of phenyl being introduced the silicon polymer structure, with bonding (smear/wipe) of improvement between adhesive resin and polyester film with substrate.Particularly, linking agent only uses the silicon resin of wherein having introduced phenyl with following structural 1, or has the silicon resin and the mixture with silicon resin of wherein having introduced phenyl of following structural 2 or structural formula 3 of following structural 1.Thus, if coating comprises the linking agent of phenyl, comprise that with coating the situation of the linking agent of general alkyl is compared, between polyester film and adhesive resin, comparatively improve with bonding (the smearing/wipe) of substrate.Especially, under the situation of polyethylene terephthalate (PET) film, because the chemical attraction between the phenyl of the phenyl of structural formula 1 and PET, and bonding (the smearing/wipe) of substrate can more improve.
[structural formula 1]
In said structure formula 1, m, n and o are selected from 5 to 50 natural number independently of one another.
[structural formula 2]
In said structure formula 2, x is selected from 5 to 50 natural number.
[structural formula 3]
In said structure formula 3, a and b are selected from 5 to 50 natural number independently of one another.
In all solids component content of water-based coating solution, the content of linking agent is 10 to 60 % by weight, more preferably 20 to 50 % by weight.When the content of linking agent during less than 10 % by weight, between polyester film and the release coating and bonding (the smearing/wipe) of substrate reduce; When the content of linking agent surpassed 60 % by weight, unreacted linking agent can remain.Because unreacted and remaining linking agent is in oligomeric state, thereby it can be transferred to the opposition side (when being stored in reeling condition) that has been coated with the water-based coating solution, or be transferred to tackiness agent (when it and tackiness agent are bonding).
Polyester film is by general membrane preparation method preparation, polyethylene terephthalate (PET) resin is comprised of the ethylene glycol terephthalate as main repeating unit in the molecule by using aromatic dicarboxylic acid as the acid constituents of main ingredient and using aklylene glycol as the polycondensation preparation of the diol component of main ingredient.
The detailed example of aromatic dicarboxylic acid can comprise dimethyl terephthalic acid, terephthalic acid, m-phthalic acid, naphthalene dicarboxylic acids, cyclohexane dicarboxylic acid, biphenoxyl ethane dicarboxylic acid, anthracene dicarboxylic acid, α, β-two (2-chlorophenoxy) ethane-4,4 '-dicarboxylic acid etc.Wherein, particularly preferably dimethyl terephthalic acid or terephthalic acid.
The detailed example of aklylene glycol can comprise ethylene glycol, trimethylammonium glycol tetramethylene glycol, pentamethylene glycol hexamethylene glycol etc.Wherein, ethylene glycol particularly preferably.
Can be by any one preparation at line painting method or off-line coating process according to stripping film of the present invention.But preferred by preparing at line painting method.
The water-based coating solution is by known coating process coating.The example of known coating process can comprise print roll coating, gravure roll coating, roller brushing, spraying, airblade coating, seam coating, dip-coating or meniscus coating etc.
When stripping film by in line painting method preparation, be in the situation of monadic stretching membrane at polyester film, preparation monocrystalline sheet material then can be by above-mentioned coating process before drawing process or be coated with before curing process behind the drawing process.
In the situation of biaxial stretch-formed process, preparation amorphous sheet material, then can be before drawing process, before horizontal (TD) drawing process behind vertical (MD) drawing process or before curing process, after the cross directional stretch process, be coated with.
Usually, when before the longitudinal stretching process, being coated with, owing to need independent drying treatment, preferably before cross directional stretch, behind longitudinal stretching, be coated with.
When stripping film by when line painting method prepares, have moisture and in preheating and drawing process, steam
The effect of sending out is solidificated under the heat curing temperature of high temperature and finishes, and silicone is by stretching along the polyester film orientation, thereby can obtain to have filming of excellent physical properties.
In addition, when the surface of polyester film is passed through such as the surface treatment of corona discharge process process before the solution of coating preparation, the hydrophobicity of polyester film reduces, so that the solution of preparation is easy to is wetting, thereby improves release coating to the surface of polyester film with to bonding (the smearing/wipe) of substrate.
In release coating, dry-coated thickness is prepared into 0.01 to 2 μ m.When dry-coated thickness during less than 0.01 μ m, can not obtain sufficient stripping performance; And when dry-coated thickness surpasses 2 μ m, and bonding (the smearing/wipe) of substrate can reduce.
In addition, to the thickness of polyester film without limits, but the thickness of 4 to 500 μ m is suitable for realizing enough stripping performances and to bonding (the smearing/wipe) of substrate.
Beneficial effect
The present invention can provide stripping film, and the preparation solution of this stripping film has good stability in storage, does not use bonding agent because be used to form the water-based coating solution of release coating; Have the linking agent of unique phenyl by use, this stripping film has good bonding (smearing/wipe) to substrate and polyester film.
In addition, owing to be coated with by the online coating that makes the use coating solution, the present invention can form eco-friendly, thin and uniform film.
Embodiment
Describe the present invention in detail below with reference to embodiment.Yet the following example only illustrates the present invention by way of example, and content of the present invention is not limited to the following example.
Measure the physical properties of the film of preparation, measuring result is listed in the table below 2, and main measuring method is as follows.
(1) peel value
Nitto 31B adhesive tape is placed on the release coating, uses the rubber rollers of 2kg to rub mutually twice back and forth, then be cut into the size of 25mm * 20cm with the preparation sample.With 20g/cm
2Load coating preparation sample and be positioned over 70 ℃ after one day, use universal test instrument (model Instron 4304, made by Instron Co.) to carry out the T-shaped assessment of peeling off.Peeling rate is set to 300mm/ minute.
(2) and bonding (the smearing/wipe) of substrate
Assess by following method with bonding (the smearing/wipe) of substrate: by using rub back and forth forcefully release coating five times of thumb.
＜classification 〉
Category-A: do not observe smear phenomenon fully
Category-B: begin to observe and smear phenomenon
C class: begin to observe and wipe phenomenon
D class: be easy to observe and wipe phenomenon
(3) the dorsal part rate of transform (transfer rate)
The PET film of the release coating of the stripping film for preparing in embodiment and the comparing embodiment and separately preparation contacts, and applies 50g/cm
2Power and be positioned over 40 ℃ 3 days.After this, measure the rate of transform of placing polyethylene terephthalate (PET) film front and back.
The peel value before polyethylene terephthalate (PET) film is placed in the dorsal part rate of transform (%)=(peel value behind the peel value before placement polyethylene terephthalate (PET) film-placement polyethylene terephthalate (PET) film) * 100/.
＜classification 〉
The ◎ class: the dorsal part rate of transform be 95% or more than
Zero class: the dorsal part rate of transform is 90 to 95%
The △ class: the dorsal part rate of transform is 80 to 90%
The X class: the dorsal part rate of transform is below 80% or 80%
(4) stability of the solution of preparation
Preparation solution so that the whole solid content of coating solution is 1%, 10%, 25% and 50%, on 30 biaxial stretch-formed μ m PET films, is observed the solution coat of each preparation mist degree along with the variation of time, thereby is measured working life (pot life).Mist degree is measured by ASTM D-1003 method.
At this moment, because the mist degree of the film of process coating increases, the stability that silicon prepares solution reduces; Should measure the time of keeping initial haze value.
Unless description is arranged in addition, in the following example, use divinyl polydimethyl silane (viscosity 14000mPas) as adhesive resin, comprise that the linking agent of phenyl uses following structural 1.
[structural formula 1]
(m＝10，n＝10，o＝10)
The linking agent that does not comprise phenyl uses following structural 3.
[structural formula 3]
(a＝10，b＝10)
Catalyzer uses platinum catalyst (Na
2PtCl
44H
2O), emulsifying agent uses polyvinyl alcohol (Mowiol (4-80), Hoechst Co.), and bonding agent uses γ-acryloxy propyl trimethoxy silicane.
＜embodiment 1 〉
The preparation of coating solution A
Mix, so that adhesive resin is 50 % by weight of whole solid content, the linking agent that comprises phenyl is 10 % by weight of whole solid content, and the linking agent that does not comprise phenyl is 40 % by weight of whole solid content.Add water to mixture, so that the whole solid content in each coating solution is 1%, 10%, 25% and 50%, thus preparation solution.At this moment, as additive, the consumption of catalyzer is the 100ppm with respect to resin content, and emulsifying agent is 5 weight parts with respect to the consumption of the solids content of per 100 weight parts in the coating solution.
Measure the like this stability of the preparation solution of the coating solution of preparation, measuring result is listed in table 2.
The preparation of stripping film
In the sheet material of 95 ℃ of preheatings by melting and extruding polyethylene terephthalate resin and its quick cooling is obtained, (MD) stretches and cools off four times along the longitudinal in the preheating parts.By using the intaglio plate coating machine with the film of coating solution A coating cooling, so that the thickness of coating solution A is 8 μ m, wherein to be prepared into whole solid content be 10% to coating solution A.130 ℃ with its drying and preheating, transversely (TD) stretches four times, and 230 ℃ of thermofixations, thus the preparation stripping film, wherein the dried thickness that picks up is that the coating adequate relief of 0.2 μ m is formed on the basilar membrane that thickness is 30 μ m.
Measure the peel value of the film for preparing like this and bonding (smearing/wipe) and the dorsal part rate of transform of substrate, measuring result is listed in the table below 2.
＜embodiment 2 〉
The preparation of coating solution B
Mix, so that adhesive resin is 50 % by weight of whole solid content, the linking agent that comprises phenyl is 20 % by weight of whole solid content, and the linking agent that does not comprise phenyl is 30 % by weight of whole solid content.Add water to mixture, so that the whole solid content in each coating solution is 1%, 10%, 25% and 50%, thus preparation solution.At this moment, as additive, the consumption of catalyzer is 100ppm, and emulsifying agent is 5 weight parts with respect to the consumption of the solids content of per 100 weight parts in the coating solution.Measure the like this stability of the preparation solution of the coating solution of preparation, measuring result is listed in table 2.
The preparation of stripping film
In the sheet material of 95 ℃ of preheatings by melting and extruding polyethylene terephthalate resin and its quick cooling is obtained, (MD) stretches and cools off four times along the longitudinal in the preheating parts.By using the intaglio plate coating machine with the film of coating solution B coating cooling, so that the thickness of coating solution B is 8 μ m, wherein to be prepared into whole solid content be 10% to coating solution B.130 ℃ with its drying and preheating, transversely (TD) stretches four times, and 230 ℃ of thermofixations, thus the preparation stripping film, wherein the dried thickness that picks up is that the coating adequate relief of 0.2 μ m is formed on the basilar membrane that thickness is 30 μ m.
Measure the peel value of the film for preparing like this and bonding (smearing/wipe) and the dorsal part rate of transform of substrate, measuring result is listed in the table below 2.
＜embodiment 3 〉
The preparation of coating solution C
Mix, so that adhesive resin is 50 % by weight of whole solid content, the linking agent that comprises phenyl is 30 % by weight of whole solid content, and the linking agent that does not comprise phenyl is 20 % by weight of whole solid content.Add water to mixture, so that the whole solid content in each coating solution is 1%, 10%, 25% and 50%, thus preparation solution.At this moment, as additive, the consumption of catalyzer is 100ppm, and emulsifying agent is 5 weight parts with respect to the consumption of the solids content of per 100 weight parts in the coating solution.Measure the like this stability of the preparation solution of the coating solution of preparation, measuring result is listed in table 2.
The preparation of stripping film
In the sheet material of 95 ℃ of preheatings by melting and extruding polyethylene terephthalate resin and its quick cooling is obtained, (MD) stretches and cools off four times along the longitudinal in the preheating parts.By using the intaglio plate coating machine with the film of coating solution C coating cooling, so that the thickness of coating solution C is 8 μ m, wherein to be prepared into whole solid content be 10% to coating solution C.130 ℃ with its drying and preheating, transversely (TD) stretches four times, and 230 ℃ of thermofixations, thus the preparation stripping film, wherein the dried thickness that picks up is that the coating adequate relief of 0.2 μ m is formed on the basilar membrane that thickness is 30 μ m.
Measure the peel value of the film for preparing like this and bonding (smearing/wipe) and the dorsal part rate of transform of substrate, measuring result is listed in the table below 2.
＜embodiment 4 〉
The preparation of coating solution D
Mix, so that adhesive resin is 50 % by weight of whole solid content, the linking agent that comprises phenyl is 40 % by weight of whole solid content, and the linking agent that does not comprise phenyl is 10 % by weight of whole solid content.Add water to mixture, so that the whole solid content in each coating solution is 1%, 10%, 25% and 50%, thus preparation solution.At this moment, as additive, the consumption of catalyzer is 100ppm, and emulsifying agent is 5 weight parts for the consumption of the solids content of per 100 weight parts in the adhesive resin.Measure the like this stability of the preparation solution of the coating solution of preparation, measuring result is listed in table 2.
The preparation of stripping film
In the sheet material of 95 ℃ of preheatings by melting and extruding polyethylene terephthalate resin and its quick cooling is obtained, (MD) stretches and cools off four times along the longitudinal in the preheating parts.By using the intaglio plate coating machine with the film of coating solution D coating cooling, so that the thickness of coating solution D is 8 μ m, wherein to be prepared into whole solid content be 10% to coating solution D.130 ℃ with its drying and preheating, transversely (TD) stretches four times, and 230 ℃ of thermofixations, thus the preparation stripping film, wherein the dried thickness that picks up is that the coating adequate relief of 0.2 μ m is formed on the basilar membrane that thickness is 30 μ m.
Measure the like this peel value of the film of preparation, and bonding (the smearing/wipe) of substrate, and the dorsal part rate of transform, measuring result is listed in the table below 2.
＜embodiment 5 〉
The preparation of coating solution E
Mix, so that adhesive resin is 50 % by weight of whole solid content, the linking agent that comprises phenyl is 50 % by weight of whole solid content.Add water to mixture, so that the whole solid content in each coating solution is 1%, 10%, 25% and 50%, thus preparation solution.At this moment, as additive, the consumption of catalyzer is 100ppm, and emulsifying agent is 5 weight parts with respect to the consumption of the solids content of per 100 weight parts in the coating solution.
Measure the like this stability of the preparation solution of the coating solution of preparation, measuring result is listed in table 2.The preparation of stripping film
In the sheet material of 95 ℃ of preheatings by melting and extruding polyethylene terephthalate resin and its quick cooling is obtained, (MD) stretches and cools off four times along the longitudinal in the preheating parts.By using the intaglio plate coating machine with the film of coating solution E coating cooling, so that the thickness of coating solution E is 8 μ m, wherein to be prepared into whole solid content be 10% to coating solution E.130 ℃ with its drying and preheating, transversely (TD) stretches four times, and 230 ℃ of thermofixations, thus the preparation stripping film, wherein the dried thickness that picks up is that the coating adequate relief of 0.2 μ m is formed on the basilar membrane that thickness is 30 μ m.
Measure the peel value of the film for preparing like this and bonding (smearing/wipe) and the dorsal part rate of transform of substrate, measuring result is listed in the table below 2.
＜embodiment 6 〉
The preparation of stripping film
In the sheet material of 95 ℃ of preheatings by melting and extruding polyethylene terephthalate resin and its quick cooling is obtained, (MD) stretches and cools off four times along the longitudinal in the preheating parts.By using the intaglio plate coating machine with the film of coating solution E coating cooling, so that the thickness of coating solution E is 8 μ m, wherein to be prepared into whole solid content be 5% to coating solution E.130 ℃ with its drying and preheating, transversely (TD) stretches four times, and 230 ℃ of thermofixations, thus the preparation stripping film, wherein the dried thickness that picks up is that the coating adequate relief of 0.1 μ m is formed on the basilar membrane that thickness is 30 μ m.
Measure the peel value of the film for preparing like this and bonding (smearing/wipe) and the dorsal part rate of transform of substrate, measuring result is listed in the table below 2.
＜embodiment 7 〉
The preparation of stripping film
In the sheet material of 95 ℃ of preheatings by melting and extruding polyethylene terephthalate resin and its quick cooling is obtained, (MD) stretches and cools off four times along the longitudinal in the preheating parts.By using the intaglio plate coating machine with the film of coating solution E coating cooling, so that the thickness of coating solution E is 8 μ m, wherein to be prepared into whole solid content be 25% to coating solution E.130 ℃ with its drying and preheating, transversely (TD) stretches four times, and 230 ℃ of thermofixations, thus the preparation stripping film, wherein the dried thickness that picks up is that the coating adequate relief of 0.5 μ m is formed on the basilar membrane that thickness is 30 μ m.
Measure the peel value of the film for preparing like this and bonding (smearing/wipe) and the dorsal part rate of transform of substrate, measuring result is listed in the table below 2.
＜embodiment 8 〉
The preparation of stripping film
In the sheet material of 95 ℃ of preheatings by melting and extruding polyethylene terephthalate resin and its quick cooling is obtained, (MD) stretches and cools off four times along the longitudinal in the preheating parts.By using the intaglio plate coating machine with the film of coating solution E coating cooling, so that the thickness of coating solution E is 8 μ m, wherein to be prepared into whole solid content be 50% to coating solution E.130 ℃ with its drying and preheating, transversely (TD) stretches four times, and 230 ℃ of thermofixations, thus the preparation stripping film, wherein the dried thickness that picks up is that the coating adequate relief of 1.0 μ m is formed on the basilar membrane that thickness is 30 μ m.
Measure the peel value of the film for preparing like this and bonding (smearing/wipe) and the dorsal part rate of transform of substrate, measuring result is listed in the table below 2.
＜embodiment 9 〉
The preparation of stripping film
In the sheet material of 95 ℃ of preheatings by melting and extruding polyethylene terephthalate resin and its quick cooling is obtained, (MD) stretches and cools off four times along the longitudinal in the preheating parts.By using the intaglio plate coating machine with the film of coating solution E coating cooling, so that the thickness of coating solution E is 8 μ m, wherein to be prepared into whole solid content be 10% to coating solution E.130 ℃ with its drying and preheating, transversely (TD) stretches four times, and 230 ℃ of thermofixations, thus the preparation stripping film, wherein the dried thickness that picks up is that the coating adequate relief of 0.2 μ m is formed on the basilar membrane that thickness is 12 μ m.
Measure the peel value of the film for preparing like this and bonding (smearing/wipe) and the dorsal part rate of transform of substrate, measuring result is listed in the table below 2.
＜embodiment 10 〉
The preparation of stripping film
In the sheet material of 95 ℃ of preheatings by melting and extruding polyethylene terephthalate resin and its quick cooling is obtained, (MD) stretches and cools off four times along the longitudinal in the preheating parts.By using the intaglio plate coating machine with the film of coating solution E coating cooling, so that the thickness of coating solution E is 8 μ m, wherein to be prepared into whole solid content be 10% to coating solution E.130 ℃ with its drying and preheating, transversely (TD) stretches four times, and 230 ℃ of thermofixations, thus the preparation stripping film, wherein the dried thickness that picks up is that the coating adequate relief of 0.2 μ m is formed on the basilar membrane that thickness is 100 μ m.
Measure the peel value of the film for preparing like this and bonding (smearing/wipe) and the dorsal part rate of transform of substrate, measuring result is listed in the table below 2.
＜embodiment 11 〉
The preparation of stripping film
In the sheet material of 95 ℃ of preheatings by melting and extruding polyethylene terephthalate resin and its quick cooling is obtained, (MD) stretches and cools off four times along the longitudinal in the preheating parts.By using the intaglio plate coating machine with the film of coating solution E coating cooling, so that the thickness of coating solution E is 8 μ m, wherein to be prepared into whole solid content be 10% to coating solution E.130 ℃ with its drying and preheating, transversely (TD) stretches four times, and 230 ℃ of thermofixations, thus the preparation stripping film, wherein the dried thickness that picks up is that the coating adequate relief of 0.2 μ m is formed on the basilar membrane that thickness is 250 μ m.
Measure the peel value of the film for preparing like this and bonding (smearing/wipe) and the dorsal part rate of transform of substrate, measuring result is listed in the table below 2.
＜comparing embodiment 1 〉
The preparation of coating solution F
Mix, so that adhesive resin is 50 % by weight of whole solid content, the linking agent that does not comprise phenyl is 40 % by weight of whole solid content.Add water to mixture, so that the whole solid content in each coating solution is 1%, 10%, 25% and 50%, thus preparation solution.At this moment, as additive, the consumption of catalyzer is the 100ppm with respect to resin content, and emulsifying agent is 5 weight parts with respect to the consumption of the solids content of per 100 weight parts in the coating solution.Measure the like this stability of the preparation solution of the coating solution of preparation, measuring result is listed in table 2.
The preparation of stripping film
In the sheet material of 95 ℃ of preheatings by melting and extruding polyethylene terephthalate resin and its quick cooling is obtained, (MD) stretches and cools off four times along the longitudinal in the preheating parts.By using the intaglio plate coating machine with the film of coating solution F coating cooling, so that the thickness of coating solution F is 8 μ m, wherein to be prepared into whole solid content be 10% to coating solution F.130 ℃ with its drying and preheating, transversely (TD) stretches four times, and 230 ℃ of thermofixations, thus the preparation stripping film, wherein the dried thickness that picks up is that the coating adequate relief of 0.2 μ m is formed on the basilar membrane that thickness is 30 μ m.
Measure the peel value of the film for preparing like this and bonding (smearing/wipe) and the dorsal part rate of transform of substrate, measuring result is listed in the table below 2.
＜comparing embodiment 2 〉
The preparation of coating solution G
Mix, so that adhesive resin is 50 % by weight of whole solid content, the linking agent that does not comprise phenyl is 49.8 % by weight of whole solid content, and bonding agent is 0.2 % by weight of whole solid content.Add water to mixture, so that the whole solid content in each coating solution is 1%, 10%, 25% and 50%, thus preparation solution.At this moment, as additive, the consumption of catalyzer is the 100ppm with respect to resin content, and emulsifying agent is 5 weight parts with respect to the consumption of the solids content of per 100 weight parts in the coating solution.Measure the like this stability of the preparation solution of the coating solution of preparation, measuring result is listed in table 2.
The preparation of stripping film
In the sheet material of 95 ℃ of preheatings by melting and extruding polyethylene terephthalate resin and its quick cooling is obtained, (MD) stretches and cools off four times along the longitudinal in the preheating parts.By using the intaglio plate coating machine with the film of coating solution G coating cooling, so that the thickness of coating solution G is 8 μ m, wherein to be prepared into whole solid content be 10% to coating solution G.130 ℃ with its drying and preheating, transversely (TD) stretches four times, and 230 ℃ of thermofixations, thus the preparation stripping film, wherein the dried thickness that picks up is that the coating adequate relief of 0.2 μ m is formed on the basilar membrane that thickness is 30 μ m.
Measure the peel value of the film for preparing like this and bonding (smearing/wipe) and the dorsal part rate of transform of substrate, measuring result is listed in the table below 2.
[table 1]
[table 2]
(in upper table 1 and 2,24 ↑ expression stability maintenance 24 hours or more than)
From the above results as can be known,＜comparing embodiment 1〉in, if only be coated with the linking agent that does not comprise phenyl, then poor with bonding (the smearing/wipe) of substrate; And at＜embodiment 1 in, when the linking agent that does not comprise phenyl of coating 40% and be coated with 10% comprise the linking agent of phenyl the time, compare with the situation that the content of the linking agent that comprises phenyl increases, begin to observe and smear phenomenon.In addition, from＜comparing embodiment 2〉be appreciated that when the coat binding auxiliary agent improving and during bonding (the smearing/wipe) of substrate, and bonding (the smearing/wipe) of substrate improve, but the sharply reduction of the stability of the solution of preparation.
Usually, for it is used for factory, the stability of the solution of preparation should guarantee at least 10 hours.Yet when the coat binding auxiliary agent, even because the stability of the solution of preparation when concentration is low is 3 hours or following also, being appreciated that needs separating device maybe to need adjustment situation etc.＜embodiment 2 to 5〉in, in goods, have good preparation stability of solution in order to prepare, in product, have the stripping film of good substrate bonding (smearing/wipe), coating comprises that the linking agent of phenyl is favourable.Be appreciated that effect is good when linking agent is 20% to 50% with respect to the amount of solid.By＜embodiment 6 to 8〉as can be known, no matter coat-thickness is how, equal display effects.From＜embodiment 9 to 11〉as can be known, no matter film thickness how, all shows good effect.
It will be understood by those skilled in the art that previously described principle and specific embodiments can be easily with making an amendment or being designed for the basis of other embodiments of implementing the identical purpose of the present invention.Those skilled in the art also understand, and such equivalent embodiments does not break away from the spirit and scope of claims of the present invention.
Claims (5)
1. stripping film comprises:
Polyester film; With
Be formed at the release coating on the one or both sides of polyester film,
Wherein, described release coating is by being coated with fabric aqueous coating solution and it is crosslinked and be solidified to form, and described water-based coating solution comprises the silicon-based adhesive resin and as the aqueous silicon-base resin with phenyl of linking agent,
Described linking agent only uses the silicone with following structural 1, or has the silicone and the mixture with silicone of following structural 2 or structural formula 3 of following structural 1:
Structural formula 1
In said structure formula 1, m, n and o are selected from 5 to 50 natural number independently of one another,
Structural formula 2
In said structure formula 2, x is selected from 5 to 50 natural number,
Structural formula 3
In said structure formula 3, a and b are selected from 5 to 50 natural number independently of one another.
2. according to claim 1 stripping film, wherein, described adhesive resin is dimethione, its terminal or side chain bonding have the one or more functional groups that are selected from hydroxyl, vinyl and the ethynyl.
3. according to claim 1 stripping film, wherein, described linking agent accounts for 10 to 60% in all solids component content of water-based coating solution.
4. according to claim 1 stripping film, wherein, the thickness of described release coating is 0.01 to 2 μ m.
5. according to claim 4 stripping film, wherein, the thickness of described polyester film is 4 to 500 μ g.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2007-0138124 | 2007-12-27 | ||
| KR1020070138124A KR101348955B1 (en) | 2007-12-27 | 2007-12-27 | Release Film |
| PCT/KR2008/007715 WO2009104865A2 (en) | 2007-12-27 | 2008-12-26 | Release film |
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| Publication Number | Publication Date |
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| CN101965377A CN101965377A (en) | 2011-02-02 |
| CN101965377B true CN101965377B (en) | 2013-03-06 |
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| CN2008801275998A Active CN101965377B (en) | 2007-12-27 | 2008-12-26 | Release film |
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| JP (1) | JP5735278B2 (en) |
| KR (1) | KR101348955B1 (en) |
| CN (1) | CN101965377B (en) |
| WO (1) | WO2009104865A2 (en) |
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| KR102204965B1 (en) * | 2013-09-30 | 2021-01-19 | 코오롱인더스트리 주식회사 | Release film and manufacturing method thereof |
| KR102392098B1 (en) * | 2015-12-31 | 2022-04-28 | 코오롱인더스트리 주식회사 | Release film and manufacturing method thereof |
| DE102018105735A1 (en) * | 2018-03-13 | 2019-09-19 | Mitsubishi Polyester Film Gmbh | Release film for gravure application |
| JP7082890B2 (en) * | 2018-03-23 | 2022-06-09 | リンテック株式会社 | Release film for ceramic green sheet manufacturing process |
| KR102240072B1 (en) * | 2018-09-28 | 2021-04-14 | 주식회사 엘지화학 | Composition for release layer and release film comprising cured product of the same |
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| KR20040036400A (en) * | 2002-10-25 | 2004-04-30 | 도레이새한 주식회사 | Silicone water-soluble emulsion releasing liquid and releasing film using it |
| WO2007066912A1 (en) * | 2005-12-07 | 2007-06-14 | Toray Saehan Inc. | Silicone release compositions with controlled peeling force and silicone release coating films coated with the same |
| WO2007083906A1 (en) * | 2006-01-18 | 2007-07-26 | Lg Chem, Ltd. | Pressure sensitive adhesive for transporting flexible substrate |
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| CA2035964A1 (en) * | 1990-03-06 | 1991-09-07 | Carl R. Kessel | Solventless silicon release coating |
| JP2508898B2 (en) * | 1990-07-16 | 1996-06-19 | 信越化学工業株式会社 | Release paper manufacturing method |
| JP3493023B2 (en) * | 1992-11-30 | 2004-02-03 | 大日本印刷株式会社 | Manufacturing method of thermal transfer image receiving sheet |
| JP3774982B2 (en) * | 1997-04-15 | 2006-05-17 | 三菱化学ポリエステルフィルム株式会社 | Release film |
| DE19734260A1 (en) * | 1997-08-07 | 1999-02-11 | Wacker Chemie Gmbh | Separation force regulation of sticky substances repellent silicone coatings |
| US6020412A (en) * | 1997-12-04 | 2000-02-01 | Mitsubishi Polyester Film, Llc | Controlled release coating comprising blend of silicone polymer and adhesion promoter |
| KR100530518B1 (en) * | 1998-02-17 | 2006-02-13 | 주식회사 새 한 | Manufacturing Method of Silicone Release Film |
| KR20030014587A (en) * | 2001-08-10 | 2003-02-19 | 미쓰비시 가가꾸 폴리에스테르 필름 가부시키가이샤 | Polyester film |
| FR2832414B1 (en) * | 2001-11-20 | 2004-01-30 | Rhodia Chimie Sa | CROSSLINKER FOR LOW TEMPERATURE CROSSLINKABLE SILICONE COMPOSITION BASED ON HYDROGENATED SILICONE OIL COMPRISING SI-H PATTERNS AT THE END OF THE CHAIN AND IN THE CHAIN |
| JP4524549B2 (en) * | 2003-08-14 | 2010-08-18 | 信越化学工業株式会社 | Release agent composition for silicone adhesive and release sheet using the same |
| US20060058486A1 (en) * | 2004-09-16 | 2006-03-16 | Wacker-Chemie Gmbh | Alkenyl-functional organopolysiloxanes |
| JP4646122B2 (en) * | 2005-06-30 | 2011-03-09 | 信越化学工業株式会社 | Silicone composition for release film |
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2007
- 2007-12-27 KR KR1020070138124A patent/KR101348955B1/en active IP Right Grant
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2008
- 2008-12-26 WO PCT/KR2008/007715 patent/WO2009104865A2/en active Application Filing
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| KR20040036400A (en) * | 2002-10-25 | 2004-04-30 | 도레이새한 주식회사 | Silicone water-soluble emulsion releasing liquid and releasing film using it |
| WO2007066912A1 (en) * | 2005-12-07 | 2007-06-14 | Toray Saehan Inc. | Silicone release compositions with controlled peeling force and silicone release coating films coated with the same |
| WO2007083906A1 (en) * | 2006-01-18 | 2007-07-26 | Lg Chem, Ltd. | Pressure sensitive adhesive for transporting flexible substrate |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20090070204A (en) | 2009-07-01 |
| JP5735278B2 (en) | 2015-06-17 |
| JP2011509323A (en) | 2011-03-24 |
| WO2009104865A3 (en) | 2009-10-22 |
| KR101348955B1 (en) | 2014-01-08 |
| CN101965377A (en) | 2011-02-02 |
| WO2009104865A2 (en) | 2009-08-27 |
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