CN109486413B - Composition for reducing pressure-sensitive adhesion of silicone and application thereof - Google Patents
Composition for reducing pressure-sensitive adhesion of silicone and application thereof Download PDFInfo
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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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- 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
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- C08L83/00—Compositions 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; Compositions of derivatives of such polymers
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- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- C08J2383/00—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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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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Abstract
The invention provides a composition for reducing the adhesiveness of organic silicon pressure-sensitive adhesive and application thereof. The composition comprises modified organic silicone oil with a structure shown in a formula I, polysiloxane and a cationic photoinitiator. The composition has lower surface energy and higher curing speed, and can form good spreading adhesion on the organic silicon pressure-sensitive adhesive layer. The modified organic silicon oil is subjected to polymerization reaction under the action of the cationic photoinitiator, and protonic acid can be generated in the reaction process, so that the composition can be used for killing the organic silicon pressure-sensitive adhesive layer, and the adhesiveness between the composition and the base layer is reduced. Meanwhile, the cation curing can solve the problem of oxygen inhibition, so that nitrogen protection is not needed in the preparation process, and meanwhile, the problem of shrinkage of the conventional cured coating can be solved.
Description
Technical Field
The invention relates to the field of organic silicon adhesives, in particular to a composition for reducing the adhesiveness of organic silicon pressure-sensitive adhesives and application thereof.
Background
In the prior art, in order to prevent a display screen or an outer frame of a mobile phone, a computer, a television and other components from being accidentally rubbed or touched to form scratches during transportation, a protective film is generally attached to a part to be protected for protection. The back adhesive of the protective film is generally a silicone pressure-sensitive adhesive, but some parts are required to have no viscosity in special cases or the silicone pressure-sensitive adhesive layer is required to be directly removed due to the process requirement.
The organic silicon pressure-sensitive adhesive is common organic silicon rubber, can be used for adhering a low-energy surface and a high-energy surface, has long service life, can be used in a low-temperature environment and a high-temperature environment, and can be used for adhering various materials. The solvent resistance, weather resistance, moisture resistance, electrical property and the like of the organic silicon pressure-sensitive adhesive are incomparable with other adhesives.
However, the prior art generally adopts the following procedures when the silicone pressure-sensitive adhesive is subjected to glue killing: in order to remove the viscosity of the pressure-sensitive adhesive layer, a protective film structure is attached on the pressure-sensitive adhesive layer. However, this treatment increases the complexity of the process, and also affects the integrity of the protective film and the aesthetics of the film. Moreover, the organic silicon pressure-sensitive adhesive has lower surface tension, and common glue is difficult to spread on the organic silicon pressure-sensitive adhesive, so that the glue killing effect is poor.
Disclosure of Invention
The invention mainly aims to provide a composition for reducing the adhesiveness of organic silicon pressure-sensitive adhesives and application thereof, and aims to solve the problems of complex process, unattractive appearance and poor adhesive killing effect in the prior art when the adhesiveness of the organic silicon pressure-sensitive adhesives is removed.
In order to achieve the above object, according to one aspect of the present invention, there is provided a composition for reducing tackiness in silicone pressure-sensitive adhesive, comprising a modified silicone oil having a structure of formula I, a polysiloxane, and a cationic photoinitiator;
in the formula I, R1、R2、R3、R4、R5、R6And R7Both have an inert functional group or a hydrolyzable functional group, P is a polymerizable functional group, and n is any natural number greater than 0.
Further, the composition comprises, by weight, 70-100 parts of modified organic silicone oil, 5-20 parts of polysiloxane and 0.5-50 parts of cationic photoinitiator, and preferably comprises 75-85 parts of modified organic silicone oil, 10-20 parts of polysiloxane and 10-20 parts of cationic photoinitiator.
Further, n is 100 to 30000.
Further, in formula I, the inert functional group is selected from C1~C12Straight or branched alkyl, phenyl, C1~C12Alkyl-substituted phenyl, or phenyl-substituted C1~C12Preferably the inert functional group is selected from the group consisting ofAlkyl, ethyl, propyl, butyl or phenyl; the hydrolyzable functional group is an alkoxy group, preferably the hydrolyzable functional group is a methoxy, ethoxy or propoxy group.
Further, the modified silicone oil is one or more of UV POLY200, UV POLY201, UV POLY204, UV POLY215, UV POLY220, UV POLY235, UV POLY305, Mylar (R) Silmer EP-100, SCA-E87M, SCA-E87E, SCA-E87F and SCA-E87T of Netsung silicone.
Further, the cationic photoinitiator is a fluorine anion-containing cationic photoinitiator, preferably one or more selected from the group consisting of hexafluoroantimonate of triarylsulfonium salts, hexafluoroarsenate, hexafluorophosphate, phenyldiazonium fluoride, hexafluoroantimonate of diaryliodonium salts, hexafluoroarsenate, hexafluorophosphate, and phenyldiazonium fluoroborate, and preferably hexafluoroantimonate of triarylsulfonium salts and/or hexafluoroantimonate of diaryliodonium salts.
Further, the cationic photoinitiator is selected from one or more of UV CATA211, UV CATA221, UV CATA232, UV CATA 243, UV CATA 283, UV POLY205+, UV POLY206+, and UV POLY230+ of Lanstar silicone.
Further, the polysiloxane is selected from one or more of vinyl siloxane, methacryloxy siloxane and mercapto siloxane, preferably one or more of 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxytriisopropoxysilane, vinyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane.
Further, the composition also comprises a silicon-containing auxiliary agent and powder wax; preferably, the composition comprises 0-20 parts of silicon-containing auxiliary agent and 0-20 parts of powder wax, and more preferably comprises 2-8 parts of silicon-containing auxiliary agent and 5-10 parts of powder wax.
Further, the silicon-containing additive is one or more of digao 2700, BYK3500 and BYK 3505; preferably, the powder wax is fumed silica and/or polytetrafluoroethylene superfine powder with the particle size of less than 1 mu m; preferably the powdered wax is selected from one or more of CERACOL39 and CERACOL609N of Yingcao 358, Juhua JTF-303S, BYK.
According to another aspect of the present invention, there is also provided a method of detackifying a silicone pressure sensitive adhesive, comprising: the composition is coated on the surface of the organic silicon pressure-sensitive adhesive, and the photocuring reaction is carried out under the illumination condition so as to reduce the viscosity of the organic silicon pressure-sensitive adhesive.
The invention provides a composition for reducing the adhesiveness of organic silicon pressure-sensitive adhesive, which comprises modified organic silicone oil with a structure shown in a formula I, polysiloxane and a cationic photoinitiator. The composition provided by the invention has lower surface energy and higher curing speed, and can form good spreading adhesion on the organic silicon pressure-sensitive adhesive layer. The modified organic silicon oil with the structure shown in the formula I is subjected to polymerization reaction under the action of a cationic photoinitiator, and protonic acid can be generated in the reaction process, so that the composition can be used for killing the organic silicon pressure-sensitive adhesive layer, and the adhesiveness between the composition and the base layer is reduced. Meanwhile, the cation curing can solve the problem of oxygen inhibition, so that nitrogen protection is not needed in the preparation process, and meanwhile, the problem of shrinkage of the conventional cured coating can be solved. In conclusion, the composition of the invention not only has the effect of reducing the viscosity of the organic silicon pressure-sensitive adhesive, but also has the advantage that the coating cannot warp. The organic silicon pressure-sensitive adhesive layer can be effectively removed by using the composition provided by the invention, the process is simple, and the final protective film still has an integrated structure and is more attractive.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 shows a schematic view of a paste structure when a silicone pressure-sensitive adhesive layer on a protective film is removed using the composition of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
As described in the background art, the prior art has the problems of complicated process, unattractive appearance and poor adhesive killing effect when the silicone pressure-sensitive adhesive is removed.
In order to solve the problems, the invention provides a composition for removing a silicone pressure-sensitive adhesive layer, which comprises modified silicone oil with a structure shown in formula I, polysiloxane and a cationic photoinitiator;
in the formula I, R1、R2、R3、R4、R5、R6And R7Both have an inert functional group or a hydrolyzable functional group, P is a polymerizable functional group, and n is any natural number greater than 0.
The composition provided by the invention has lower surface energy and higher curing speed, and can form good spreading adhesion on the organic silicon pressure-sensitive adhesive layer. The modified organic silicon oil with the structure shown in the formula I is subjected to polymerization reaction under the action of a cationic photoinitiator, and protonic acid can be generated in the reaction process, so that the composition can be used for killing the organic silicon pressure-sensitive adhesive layer, and the adhesiveness between the composition and the base layer is reduced. Meanwhile, the cation curing can solve the problem of oxygen inhibition, so that nitrogen protection is not needed in the preparation process, and meanwhile, the problem of shrinkage of the conventional cured coating can be solved. In conclusion, the composition of the invention not only has the effect of reducing the viscosity of the organic silicon pressure-sensitive adhesive, but also has the advantage that the coating cannot warp. The organic silicon pressure-sensitive adhesive layer can be effectively removed by using the composition provided by the invention, the process is simple, and the final protective film still has an integrated structure and is more attractive.
In order to further improve the spreading adhesion of the composition on the silicone pressure-sensitive adhesive layer and enable the composition to have more proper curing speed, in a preferred embodiment, the composition comprises 70-100 parts by weight of modified organic silicone oil, 5-20 parts by weight of polysiloxane and 0.5-50 parts by weight of cationic photoinitiator, and preferably comprises 75-85 parts by weight of modified organic silicone oil, 10-20 parts by weight of polysiloxane and 10-20 parts by weight of cationic photoinitiator.
In order to further improve the film forming and processing properties of the composition, in a preferred embodiment, n is 100 to 30000.
In a preferred embodiment, the inert functional group is selected from C1~C12Straight or branched alkyl, phenyl, C1~C12Alkyl-substituted phenyl, or phenyl-substituted C1~C12Preferably the inert functional group is selected from methyl, ethyl or phenyl; the hydrolyzable functional group is an alkoxy group, preferably the hydrolyzable functional group is a methoxy, ethoxy, propyl, butyl or propoxy group. The inert functional group may act as a blocking group and the hydrolysable functional group may be condensed again by hydrolysis to produce a polymerisable group. These modified silicone oils have a lower surface energy and are capable of further improving the spreading properties of the compositions on silicone pressure sensitive adhesive layers. In addition, these modified silicone oils have better compatibility with other components, and can be cured more sufficiently by the action of a cationic photoinitiator.
More preferably, the modified silicone oil includes, but is not limited to, one or more of UV POLY200, UV POLY201, UV POLY204, UV POLY215, UV POLY220, UV POLY235, UV POLY305, Silmer EP-100 from MEI Silicone, SCA-E87M, SCA-E87E, SCA-E87F, and SCA-E87T from Nanjing energy-producing new materials.
In a preferred embodiment, the cationic photoinitiator is a fluoroanion-containing cationic photoinitiator. The cationic photoinitiator containing fluorine anions has better curing performance for the modified organic silicone oil, can generate more super-strong protonic acid in the curing process (the principle is as follows), and has better biting action for the lower organic silicon oxygen adhesive layer, so that the viscosity reducing action of the composition is stronger.
Wherein X represents any photoinitiator containing a fluorine anion, which reacts to produce a super strong protonic acid.
It should be noted that, when the cationic photoinitiator containing the fluorine anions is adopted, because the ultra-strong protonic acid generated in the reaction process has a strong biting action on the pressure-sensitive adhesive layer below, the pressure-sensitive adhesive layer can be completely removed, and the more effective viscosity reduction effect is achieved. The anti-adhesive layer and the pressure-sensitive adhesive layer after the etching form a whole, and can be directly removed or removed in the subsequent process.
Preferably, the cationic photoinitiator includes, but is not limited to, one or more of hexafluoroantimonate, hexafluoroarsenate, hexafluorophosphate, phenyldiazonium villate, hexafluoroantimonate, hexafluoroarsenate, hexafluorophosphate and phenyldiazonium villate of triarylsulfonium salts, more preferably hexafluoroantimonate of triarylsulfonium salts and/or hexafluoroantimonate of diaryliodonium salts.
In a preferred embodiment, the cationic photoinitiator includes, but is not limited to, one or more of UV CATA211, UV CATA221, UV CATA232, UV CATA 243, UV CATA 283, UV POLY205+, UV POLY206+, and UV POLY230+ of cyans silicone.
In a preferred embodiment, the polysiloxane is selected from one or more of vinylsiloxane, methacryloxysiloxane and mercaptosiloxane, preferably one or more of 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxytriisopropoxysilane, vinyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane.
In order to further improve the glue killing performance of the composition, in a preferred embodiment, the composition further comprises a silicon-containing auxiliary agent and powder wax; preferably, the composition comprises 0-20 parts of silicon-containing auxiliary agent and 0-20 parts of powder wax, and more preferably comprises 2-8 parts of silicon-containing auxiliary agent and 5-10 parts of powder wax.
In a preferred embodiment, the silicon-containing additive is one or more of dyha 2700, BYK3500 and BYK 3505. The silicon-containing auxiliaries have better compatibility with other components, and can further improve the film-forming property of the composition. Preferably, the powder wax is fumed silica and/or polytetrafluoroethylene superfine powder with the particle size of less than 1 mu m; preferably the powdered wax is selected from one or more of CERACOL39 and CERACOL609N of Yingcao 358, Juhua JTF-303S, BYK.
According to another aspect of the present invention, there is also provided a method of detackifying a silicone pressure sensitive adhesive, comprising: the composition is coated on the surface of the organic silicon pressure-sensitive adhesive layer, and photocuring reaction is carried out under the condition of illumination so as to reduce the viscosity of the organic silicon pressure-sensitive adhesive.
Specifically, as shown in fig. 1, the protective film includes a functional layer 4, a base material layer 3 (typically PI, PET, TPU, PVC, TAC, COP, etc.), a silicone pressure-sensitive adhesive layer 2, which are sequentially stacked.
When a cationic initiator containing a fluoroanion is used, the composition can be coated on top of the silicone pressure sensitive adhesive layer 2 and spread to form the adhesive layer 1. And then, carrying out photocuring reaction on the adhesive layer 1 under the illumination condition, and after the generated super-strong protonic acid bites the organic silicon pressure-sensitive adhesive layer 2, greatly reducing the adhesive force between the formed integral adhesive layer and the substrate layer 3 and easily stripping the adhesive layer. And then the glue layer can be removed in the subsequent manufacturing process, for example, the glue layer can be rubbed, peeled, cleaned and the like by hands, so that the operation is convenient.
The beneficial effects of the present invention are further illustrated by the following examples:
example 1
65 parts of an organoalkoxysiloxane UV POLY204 (in which R is1、R2、R3、R4、R5、R6And R7All of which are inert functional groups and are respectively selected from methyl, ethyl, propyl, butyl or phenyl, P is epoxy group, 2 parts of UV CATA211 (hexafluoroantimonate of triarylsulfonium salt), 10 parts of 3-methacryloxypropyltrimethoxysilane, 20 parts of powder wax (BYK-CERACOL39) and 2 parts of silicon assistant BYK3500 are uniformly stirred to obtain the coating liquid composition. Coating the coating liquid composition on a pressure-sensitive adhesive layer of a polyorganosiloxane with a wire bar coater, and cationically curing the dried coating layer by irradiation with ultraviolet rays having an irradiation dose of 300mj/cm2And (4) after surface drying, carrying out heat treatment at 80 ℃ for 8 hours, and controlling the thickness of the coating layer to be 3-4 microns to obtain a transparent film finished product.
Example 2
65 parts of an organoalkoxysiloxane UV POLY204, 5 parts of UV CATA211, 10 parts of 3-methacryloxypropyltrimethoxysilane, 20 parts of powder wax (BYK-CERACOL39) and 2 parts of a silicon assistant BYK3500 were stirred uniformly to obtain a coating liquid composition. Coating the coating liquid composition on a pressure-sensitive adhesive layer of a polyorganosiloxane with a wire bar coater, and cationically curing the dried coating layer by irradiation with ultraviolet rays having an irradiation dose of 300mj/cm2And (4) after surface drying, carrying out heat treatment at 80 ℃ for 8 hours, and controlling the thickness of the coating layer to be 3-4 microns to obtain a transparent film finished product.
Example 3
65 parts of an organoalkoxysiloxane UV POLY204, 10 parts of UV CATA211, 10 parts of 3-methacryloxypropyltrimethoxysilane, 20 parts of powder wax (BYK-CERACOL39) and 2 parts of a silicon assistant BYK3500 were stirred uniformly to obtain a coating liquid composition. Coating the coating liquid composition on a pressure-sensitive adhesive layer of a polyorganosiloxane with a wire bar coater, and cationically curing the dried coating layer by irradiation with ultraviolet rays having an irradiation dose of 300mj/cm2And (4) after surface drying, carrying out heat treatment at 80 ℃ for 8 hours, and controlling the thickness of the coating layer to be 3-4 microns to obtain a transparent film finished product.
Example 4
65 parts of an organoalkoxysiloxane UV POLY204, 20 parts of UV CATA211, 10 parts of 3-methacryloxypropyltrimethoxysilane20 parts of powder wax (BYK-CERACOL39) and 2 parts of silicon assistant BYK3500 were uniformly stirred to obtain a coating liquid composition. Coating the coating liquid composition on a pressure-sensitive adhesive layer of a polyorganosiloxane with a wire bar coater, and cationically curing the dried coating layer by irradiation with ultraviolet rays having an irradiation dose of 300mj/cm2And (4) after surface drying, carrying out heat treatment at 80 ℃ for 8 hours, and controlling the thickness of the coating layer to be 3-4 microns to obtain a transparent film finished product.
Example 5
85 parts of an organoalkoxysiloxane UV POLY200 (where R is1、R2、R3、R4、R5、R6And R7Each of which is an inert functional group selected from methyl, ethyl, propyl, butyl or phenyl, and P is an epoxy group), 5 parts of UV POLY205+ (hexafluoroantimonate salt of diphenylsulfonium salt), and 10 parts of 3-methacryloxypropyltrimethoxysilane, to obtain a coating liquid composition. Coating the coating liquid composition on a pressure-sensitive adhesive layer of a polyorganosiloxane with a wire bar coater, and cationically curing the dried coating layer by irradiation with ultraviolet rays having an irradiation dose of 200mj/cm2And (4) after surface drying, carrying out heat treatment at 80 ℃ for 8 hours, and controlling the thickness of the hardened coating layer to be 3-4 microns to obtain a transparent film finished product.
Example 6
65 parts of an organoalkoxysiloxane UV POLY200, 5 parts of UV POLY205+, 10 parts of 3-methacryloxypropyltrimethoxysilane, and 20 parts of a powder wax (BYK-CERACOL39) were stirred uniformly to obtain a coating liquid composition. Coating the coating liquid composition on a pressure-sensitive adhesive layer of a polyorganosiloxane with a wire bar coater, and cationically curing the dried coating layer by irradiation with ultraviolet rays having an irradiation dose of 200mj/cm2And (4) after surface drying, carrying out heat treatment at 80 ℃ for 4 hours, and controlling the thickness of the hardened coating layer to be 3-4 microns to obtain a transparent film finished product.
Example 7
65 parts of an organoalkoxysiloxane UV POLY200, 5 parts of UV POLY205+, 10 parts of 3-methacryloxypropyltrimethoxysilane, and 20 parts of a powder wax (BYK-CERACOL39) were stirred uniformly to obtain a coating liquid composition. Coating the coating liquid composition with a wire bar coaterCuring the dried coating with ultraviolet rays at a dose of 200mj/cm in the pressure-sensitive adhesive layer2And (4) after surface drying, carrying out heat treatment at 80 ℃ for 8 hours, and controlling the thickness of the hardened coating layer to be 3-4 microns to obtain a transparent film finished product.
Example 8
65 parts of an organoalkoxysiloxane UV POLY200, 5 parts of UV POLY205+, 10 parts of 3-methacryloxypropyltrimethoxysilane, and 20 parts of a powder wax (BYK-CERACOL39) were stirred uniformly to obtain a coating liquid composition. Coating the coating liquid composition on a pressure-sensitive adhesive layer of a polyorganosiloxane with a wire bar coater, and cationically curing the dried coating layer by irradiation with ultraviolet rays having an irradiation dose of 200mj/cm2And (4) after surface drying, carrying out heat treatment at 80 ℃ for 12h, and controlling the thickness of the hardened coating layer to be 3-4 microns to obtain a transparent film finished product.
Comparative example 1
70 parts of a polyacrylic organosiloxane (RC1002) (wherein R is1、R2、R3、R4、R5、R6And R7All inert functional groups selected from methyl, ethyl, propyl, butyl or phenyl, P is acryloyloxy), 3 parts of 2-methyl-1- [ -4-methylthio) phenyl]2-morpholinyl-1-propanone (free radical photoinitiator), 10 parts of 3-methacryloxypropyltrimethoxysilane and 17 parts of powder wax (Yingchuang 358) were uniformly stirred to obtain a coating liquid composition. Applying the coating liquid composition to a polyorganosiloxane pressure-sensitive adhesive layer with a wire bar coater, and curing the dried coating layer by ultraviolet irradiation with an irradiation light amount of 200mj/cm2And controlling the thickness of the hardened coating layer to be 3-4 mu m to obtain a finished transparent film.
Comparative example 2
75 parts of a polyacrylic organosiloxane (ACR D2) (wherein R is1、R2、R3、R4、R5、R6And R7All are inert functional groups, P is methacryloxy group), 3 parts of 2-hydroxy-2-methyl-1-phenyl-1-acetone (free radical photoinitiator), 10 parts of vinyl triisopropoxysilane, 12 parts of powder wax (Yingchuang 358) are evenly stirredTo obtain a coating liquid composition. Coating the coating liquid composition on a pressure-sensitive adhesive layer of a polyorganosiloxane with a wire bar coater, curing the dried coating by ultraviolet irradiation, and protecting with nitrogen gas (oxygen content)<50ppm), the amount of ultraviolet light irradiation was 200mj/cm2And controlling the thickness of the hardened coating layer to be 3-4 mu m to obtain a finished transparent film.
Comparative example 3
85 parts of a polyacrylic organosiloxane (PLOY110) (wherein R1、R2、R3、R4、R5、R6And R7All of which are inert functional groups, P is acryloyloxy), 3 parts of benzophenone (free radical photoinitiator), 5 parts of 3-mercaptopropyltrimethoxysilane and 7 parts of powder wax (JTF-303S) are uniformly stirred to obtain the coating liquid composition. Coating the coating liquid composition on a pressure-sensitive adhesive layer of a polyorganosiloxane with a wire bar coater, curing the dried coating by ultraviolet irradiation, and protecting with nitrogen gas (oxygen content)<50ppm), the amount of ultraviolet light irradiation was 200mj/cm2And controlling the thickness of the hardened coating layer to be 3-4 mu m to obtain a finished transparent film.
Comparative example 4
80 parts of polyacrylic organosiloxane (ACR DI-10) (wherein R is1、R2、R3、R4、R5、R6And R7All of which are inert functional groups, P is methacryloxy group), 3 parts of methyl 2-benzoylbenzoate (radical photoinitiator), 8 parts of 3-methacryloxypropyltriethoxysilane, 9 parts of powdered wax (JTF-303S) are uniformly stirred to obtain a coating liquid composition. Coating the coating liquid composition on a pressure-sensitive adhesive layer of a polyorganosiloxane with a wire bar coater, curing the dried coating by ultraviolet irradiation, and protecting with nitrogen gas (oxygen content)<50ppm), the amount of ultraviolet light irradiation was 200mj/cm2And controlling the thickness of the hardened coating layer to be 3-4 mu m to obtain a finished transparent film.
And (3) performance testing:
the peel strength of the treated silicone pressure-sensitive adhesive layer was tested
Cutting the treated protective film into rectangular films of 100mm × 25mm, adhering the films to a steel plate for 30min, and testing the peel strength of the untreated pressure-sensitive adhesive layer from the substrate layer at a 180-degree peel angle and a 20m/min peel speed.
The performance results are shown in table 1:
TABLE 1
Item | Appearance (visual inspection) | Peel strength (gf/cm) | Removability of silicone pressure sensitive adhesive layer |
Example 1 | Leveling | 5 | Removed but left over |
Example 2 | |
3 | Removal, but for a longer time |
Example 3 | |
2 | Removal in short time |
Example 4 | Leveling | 6 | Removal in short time |
Example 5 | Leveling | 6 | Removal, but for a longer time |
Example 6 | Leveling | 5 | Removal in short time |
Example 7 | |
3 | Removal in short time |
Example 8 | |
3 | Removal in short time |
Comparative example 1 | Surface is not solidified | - | - |
Comparative example 2 | |
3 | Can not be adhered to |
Comparative example 3 | |
2 | Can not be adhered to |
Comparative example 4 | |
2 | Can not be adhered to |
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
the data in the examples show that the composition provided by the invention can form good spreading on the surface of the pressure-sensitive adhesive layer by adopting the cation curing composition, and the pressure-sensitive adhesive layer can be quickly removed to achieve the viscosity reduction effect. From the data in the comparative examples, it is clear that the use of a free radical curing system has high process requirements and a large cost investment. Meanwhile, the free radical curing composition has poor spreadability, cannot be attached to the surface of the pressure-sensitive adhesive layer, and accordingly cannot perform overall viscosity reduction on the pressure-sensitive adhesive layer. The composition of comparative example 2, although capable of spreading on the pressure-sensitive adhesive, also failed to exhibit a viscosity-reducing effect because of failure to adhere.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (18)
1. A composition for reducing the adhesiveness of a silicone pressure-sensitive adhesive is characterized by comprising modified silicone oil with a structure shown in formula I, polysiloxane and a cationic photoinitiator;
formula I
In the formula I, R1、R2、R3、R4、R5、R6And R7Both have an inert functional group or a hydrolyzable functional group, P is a polymerizable functional group, and n is any natural number greater than 0;
the cationic photoinitiator is a cationic photoinitiator containing fluorine anions.
2. The composition according to claim 1, wherein the composition comprises 70 to 100 parts by weight of the modified silicone oil, 5 to 20 parts by weight of the polysiloxane, and 0.5 to 50 parts by weight of the cationic photoinitiator.
3. The composition according to claim 1, wherein the composition comprises 75 to 85 parts by weight of the modified silicone oil, 10 to 20 parts by weight of the polysiloxane, and 10 to 20 parts by weight of the cationic photoinitiator.
4. The composition of claim 1, wherein n is 100 to 30000.
5. Composition according to any one of claims 1 to 4, characterized in that, in formula I, the inert functional group is chosen from C1~C12Straight or branched alkyl, phenyl, C1~C12Alkyl-substituted phenyl, or phenyl-substituted C1~C12Alkyl groups of (a); the hydrolyzable functional group is an alkoxy group.
6. The composition according to claim 5, wherein in the formula I, the inert functional group is a methyl group, an ethyl group, a propyl group, a butyl group or a phenyl group; the hydrolyzable functional group is methoxy, ethoxy or propoxy.
7. The composition of any one of claims 1 to 4 wherein the modified silicone oil is one or more of UV POLY200, UV POLY201, UV POLY204, UV POLY215, UV POLY220, UV POLY235, UV POLY305, Melmer EP-100, SCA-E87M, SCA-E87E, SCA-E87F and SCA-E87T of Needen silicone.
8. Composition according to any one of claims 1 to 4, characterized in that the cationic photoinitiator is chosen from one or more of hexafluoroantimonate, hexafluoroarsenate, hexafluorophosphate, phenyldiazoborofluoride of triarylsulfonium salts, hexafluoroantimonate, hexafluoroarsenate, hexafluorophosphate and phenyldiazoborofluoride of diaryliodonium salts.
9. Composition according to claim 8, characterized in that the cationic photoinitiator is a hexafluoroantimonate of triarylsulfonium salts and/or a hexafluoroantimonate of diaryliodonium salts.
10. A composition according to any one of claims 1 to 4, characterized in that the polysiloxane is selected from one or more of vinylsiloxanes, methacryloxysiloxanes and mercaptosiloxanes.
11. The composition of claim 10, wherein the polysiloxane is one or more of 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxytriisopropoxysilane, vinyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-mercaptopropyltriethoxysilane.
12. The composition according to any one of claims 1 to 4, wherein the composition further comprises a silicon-containing adjuvant and a powder wax.
13. The composition of claim 12, wherein the composition comprises 0 to 20 parts by weight of the silicon-containing adjuvant and 0 to 20 parts by weight of the powder wax.
14. The composition of claim 12, wherein the composition comprises 2 to 8 parts by weight of the silicon-containing adjuvant and 5 to 10 parts by weight of the powder wax.
15. The composition of claim 12, wherein the silicon containing adjuvant is one or more of dyha 2700, BYK3500, BYK 3505.
16. The composition as claimed in claim 12, wherein the powder wax is fumed silica and/or polytetrafluoroethylene submicron powder with a particle size of less than 1 μm.
17. The composition of claim 12 wherein the powdered wax is selected from one or more of CERACOL39 and CERACOL609N of wushu 358, jujuhua JTF-303S, BYK.
18. A method for reducing tackiness of a silicone pressure sensitive adhesive, said method comprising: coating the composition of any one of claims 1 to 17 on the surface of the silicone pressure-sensitive adhesive, and carrying out a photocuring reaction under light conditions to reduce the viscosity of the silicone pressure-sensitive adhesive.
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