CN115397939A - Release film - Google Patents
Release film Download PDFInfo
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- CN115397939A CN115397939A CN202180002518.7A CN202180002518A CN115397939A CN 115397939 A CN115397939 A CN 115397939A CN 202180002518 A CN202180002518 A CN 202180002518A CN 115397939 A CN115397939 A CN 115397939A
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- release layer
- fluorine
- release film
- release
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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
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
- C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
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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
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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
- 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
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a release film, an optical film comprising the release film and an electronic device comprising the release film. The release film comprises a substrate; and a release layer on at least one side of the substrate, the release layer being a cured layer of a composition for forming the release layer, the composition including a blend of a fluorine-containing organopolysiloxane and a non-fluorine-containing organopolysiloxane, the release layer having a fluorine atom/silicon atom content ratio decreasing from a surface toward a center direction, the release layer having a reduced modulus of elasticity (reduced modulus) of 2GPa to 6GPa as measured by a nano-indentation method, and the release layer having a surface hardness (surface hardness) of 0.3GPa to 0.6GPa as measured by the nano-indentation method.
Description
Technical Field
The invention relates to a release film.
Background
Recently, in the industries of displays, tapes, labels, and the like, in order to improve manufacturability and increase productivity, use of an ultra-light release film having a low peeling force is increasing.
The silicone-based release film used for conventional adhesives such as acrylic and epoxy is softer and the peeling force decreases as the thickness increases because the release layer has a lower hardening density, young's modulus, reduced modulus and hardness (hardness). However, in the silicone-based release film, as the peeling force is reduced, the residual adhesion rate and the adhesion to the substrate are reduced, and the elastic modulus and hardness of the release layer surface are low, so that blocking may occur during the winding process.
In addition, when an organic silicon adhesive is used for the organic silicon release film, the organic silicon release film and the organic silicon adhesive are completely adhered, and no peeling occurs. Thus, a film coated with a release agent including a fluorine-based resin is generally used in the silicone-based adhesive.
However, since the release agent including the fluorine-based resin has a low surface energy and is difficult to be mixed with a general organic solvent, coating defects are easily caused, and thus a fluorine-based solvent should be used. Since the release agent including the fluorine-based resin is more expensive than the general silicone-based release agent by several tens of times, there are problems in terms of productivity and economy.
Therefore, there is a need for a release film that can use both an acrylic adhesive and a silicone adhesive, and has a release layer with a high surface hardness and a high reduced modulus of elasticity (reduced modulus), but a low peel force and a low rate of change in peel force.
Disclosure of Invention
Technical problem
One aspect of the present invention provides a release film in which an acrylic adhesive and a silicone adhesive can be used, and the surface hardness and the reduced modulus of elasticity (reduced modulus) of a release layer are high, but the peel force and the rate of change in peel force are low.
Technical scheme
In one aspect of the present invention, there is provided a release film, wherein,
comprises a substrate; and a release layer on at least one side of the substrate,
the release layer is a cured layer of a composition for forming a release layer, the composition comprising a blend of a fluorine-containing organopolysiloxane and a non-fluorine-containing organopolysiloxane,
the fluorine atom/silicon atom content ratio of the release layer decreases from the surface toward the center,
a reduced modulus of elasticity (reduced modulus) of the release layer measured by a nanoindentation method is 2GPa to 6GPa,
the surface hardness (surface hardness) of the release layer measured by a nanoindentation method is 0.3GPa to 0.6GPa.
The content (atomic%) ratio of fluorine atoms/silicon atoms may be 1.5 to 4.5 in X-ray photoelectron spectroscopy (XPS) analysis of the release layer surface.
The surface energy of the release layer may be 10dyne/cm to 16dyne/cm.
The release film may have a peel force to the acrylic adhesive and the silicone adhesive of 0.5gf/25mm to 10gf/25mm at a peel angle of 180 ° and a peel rate of 0.3 mpm.
The release film may have a peel force variation rate according to the following formula 2 of 50% or less for an acrylic adhesive and a silicone adhesive.
[ formula 2 ]
Peel force change rate (%) = (peel force after seven days-initial peel force)/initial peel force × 100
The residual adhesion rate of the release film can be more than 85%.
The thickness of the release layer may be 0.03 to 2.0 μm.
The fluorine-containing polysiloxane may include an organopolysiloxane represented by the following chemical formula 1.
[ chemical formula 1 ]
[ chemical formula 2 ]
[ chemical formula 3 ]
In the chemical formula 1, the reaction mixture is,
R 1 is a substituted or unsubstituted C1-C10 monovalent hydrocarbon group, or a substituted or unsubstituted C2-C10 alkenyl group;
R 2 is a substituted or unsubstituted C1 to C10 monovalent hydrocarbon group, a substituted or unsubstituted C2 to C10 alkenyl group, or hydrogen;
R 3 and R 4 Each independently is a fluorine-containing alkyl group represented by the chemical formula 2, a fluorine-containing ether group represented by the chemical formula 3, a substituted or unsubstituted C1-C10 monovalent hydrocarbon group, a substituted or unsubstituted C2-C10 alkenyl group, or hydrogen,
the R is 3 And R 4 Is a fluorinated alkyl group represented by the chemical formula 2, a fluorine-containing ether group represented by the chemical formula 3, or a combination thereof;
n is an integer of 1 to 8, m is an integer of 1 to 5;
p is an integer from 1 to 5, q is 0 or 1, r is 0, 1 or 2, v is an integer from 1 to 5;
a is oxygen atom or single bond;
x, y and z are integers of 1 or more;
* Is a binding site to an adjacent atom;
wherein R is 1 And R 2 At least one of (a) may be a substituted or unsubstituted C2 to C10 alkenyl group.
The fluorine-containing organopolysiloxane may be present in an amount of 10 parts by weight to 300 parts by weight, based on 100 parts by weight of the non-fluorine-containing organopolysiloxane.
The release layer may further include organic-inorganic particles.
The release layer may further include at least one of hydrogen polysiloxane (hydrogen polysiloxane) and a catalyst.
Advantageous effects
The release layer according to an aspect of the present invention includes a release layer of a cured layer of a composition for forming a release layer, the composition including a blend of a fluorine-containing organopolysiloxane and a non-fluorine-containing organopolysiloxane. The release film has a low peel force and a low rate of change of peel force for both acrylic adhesives and silicone adhesives, and has a high surface hardness and a reduced modulus of elasticity (reduced modulus), thereby preventing blocking when the film is wound up.
Drawings
Fig. 1 is a cross-sectional view of a release film according to an embodiment of the present invention.
Detailed Description
Hereinafter, a release film will be described in detail with reference to embodiments of the present invention and the accompanying drawings. It will be understood by those of ordinary skill in the art that these examples are given by way of illustration only to more specifically describe the present invention and the scope of the present invention is not limited by these examples.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
All methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, with suitable methods and materials being described herein.
In this specification, unless stated to the contrary, the term "comprising" means that other components may be further included without excluding other components.
In the present specification, the term "combination thereof" means mixing or combination with at least one of the components.
In this specification, the term "and/or" is intended to include any and all combinations of one or more of the items described in connection with the description thereof. In this specification, the term "or" means "and/or". In this specification, the expression "at least one" or "more than one" preceding an element means that a list of all elements can be supplemented but does not mean that each element can supplement the description.
In the present specification, when it is referred to an element being "on" or "over" another element, one element may be directly on the other element or intervening elements may be present. On the other hand, when an element is referred to as being "directly on" or "directly over" another element, there may be no intervening elements present.
In the present specification, the term "resin system", "polymer system" or/and copolymer system "is a broad concept and includes" resin "," polymer "," copolymer "or/and derivatives of resin, polymer or copolymer".
In the present specification, the term "polymer or copolymer crosslinked with a resin thereof" means "polymer or copolymer crosslinked with the above resin".
In this specification, each component is a concept including both singular and plural.
All percentages, parts, ratios, etc., are by weight unless otherwise indicated herein. Further, when an amount, concentration, or other value or parameter is given as either a range, preferred range, or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed.
When a range of numerical values is recited in the specification, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range. It is intended that the scope of the invention not be limited to the specific values recited when defining a range.
The release film according to an embodiment of the present invention includes a substrate; and a release layer on at least one side of the substrate, the release layer being a cured layer of a composition for forming the release layer, the composition including a blend of a fluorine-containing organopolysiloxane and a non-fluorine-containing organopolysiloxane, the release layer having a fluorine atom/silicon atom content ratio decreasing from a surface toward a center direction, the release layer having a reduced modulus of elasticity (reduced modulus) of 2GPa to 6GPa as measured by a nano-indentation method, and the release layer having a surface hardness (surface hardness) of 0.3GPa to 0.6GPa as measured by the nano-indentation method.
The release film according to an embodiment of the present invention has a low peel force and a low rate of change in peel force for both acrylic adhesives and silicone adhesives, and has a high surface hardness and a reduced modulus of elasticity (reduced modulus), so that blocking can be prevented from occurring when the film is wound up.
The substrate constituting the release film, the release layer, the release film, and the optical film and the electronic device including the release film will be described in detail below.
< substrate >
As the substrate used in the present invention, a known substrate film or substrate sheet can be used as a substrate for the release film. For example, a polyester resin film can be used as the substrate. As the polyester-based resin, a known substrate film commonly used in the field of release films can be used. For example, as the polyester-based resin base material film, polyester-based base material films disclosed in korean registered patent No. 10-1268584, korean registered patent No. 2012-45213, korean registered patent No. 2012-99546, and the like can be used. However, in one embodiment of the present invention, in order to describe only the features of the present invention, the description of the polyester-based substrate film is not limited, but should be understood to include technical features related to the known polyester-based substrate film.
The polyester-based substrate film may include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, or the like.
The polyester-based resin used to form the substrate film may be a polyester obtained by polycondensing an aromatic dicarboxylic acid and an aliphatic diol.
Examples of the aromatic dicarboxylic acid include isophthalic acid, phthalic acid, terephthalic acid, 2, 6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, hydroxycarboxylic acid (e.g., p-oxybenzoic acid), and examples of the aliphatic diol include ethylene glycol, diethylene glycol, propylene glycol, butanediol, 1, 4-cyclohexanedimethanol, and neopentyl glycol. As such a polyester resin, two or more of a dicarboxylic acid component and a diol component may be used in combination, or a copolymer including a third component may be used.
In addition, as the polyester-based substrate film, a uniaxially or biaxially oriented film having high transparency and excellent productivity and processability can be used. As the polyester-based substrate film, polyethylene terephthalate (PET), poly (ethylene 2, 6-naphthalate) (PEN), or the like can be used.
In addition, the polyester-based substrate film may include particles to provide excellent inter-roller (Roll) running characteristics, and may be used without limitation as long as the added particles can exhibit excellent sliding characteristics.
Examples of such particles may include particles of silica, calcium carbonate, calcium sulfate, calcium phosphate, magnesium carbonate, magnesium phosphate, barium carbonate, kaolin, alumina, titanium oxide, and the like, and the shape of the particles used is not limited, but any of, for example, spherical, block-shaped, rod-shaped, and plate-shaped particles may be used.
In addition, although there is no limitation in hardness, specific gravity and color of the particles, two or more kinds may be used in parallel according to need, and the average particle diameter of the particles used may be 0.1 to 5 μm, for example, particles in the range of 0.1 to 2 μm may be used. At this time, when the average particle diameter of the particles is less than 0.1 μm, an aggregation phenomenon between the particles may occur, resulting in poor dispersion, and when the average particle diameter of the particles is greater than 5 μm, coating defects may occur during post-processing due to deterioration of surface roughness characteristics of the thin film.
Further, when the polyester-based substrate film includes particles, the content of the particles may be 0.01 to 5 wt%, for example, 0.01 to 3 wt%, based on the total weight of the polyester-based substrate film. When the content of the particles is less than 0.01 wt%, the slip characteristics of the polyester film may be deteriorated, resulting in deterioration of walking characteristics between rolls, and when the content of the particles is more than 5 wt%, the surface smoothness of the film may be deteriorated.
The thickness of the polyester-based base film is not limited, but may be 20 μm to 125 μm.
When the polyester-based substrate is too thin to 20 μm or less, deformation may be caused by heat treatment during processing, and when the polyester-based substrate is too thick to 125 μm or more, problems may occur in curing due to insufficient heat transfer.
< Release layer >
The release layer according to an embodiment of the present invention may be a release layer of a cured layer of a composition for forming a release layer, the composition including a blend of a fluorine-containing organopolysiloxane and a non-fluorine-containing organopolysiloxane.
The release layer may have a fluorine atom/silicon atom content ratio decreasing from the surface toward the center. The higher the content of fluorine atoms in the surface of the release layer is than the content of silicon atoms, the better the releasability when the release layer is bonded to a silicone-based adhesive, so that the release layer can have a low release force and a low rate of change in release force not only with respect to an acrylic-based adhesive but also with respect to a silicone-based adhesive.
The content (atomic%) ratio of fluorine atom/silicon atom may be 1.5 to 4.5 in an X-ray photoelectron spectroscopy (XPS) analysis of the surface of the release layer. In the X-ray photoelectron spectroscopy analysis of the release layer surface, if the content (atomic%) ratio of fluorine atom/silicon atom is less than 1.5, peeling may not occur when the silicone-based adhesive is attached. In the X-ray photoelectron spectroscopy analysis of the release layer surface, if the content (atomic%) ratio of fluorine atom/silicon atom is more than 4.5, since a large amount of heat is required for curing of the fluorine-containing organopolysiloxane, thermal deformation of the substrate may be caused and hardness also increases, so that the peeling force to the acrylic adhesive may increase.
In addition, when the surface of the release layer is etched by plasma treatment and the inside of the release layer is analyzed using an X-ray photoelectron spectroscopy apparatus, the deep portion of the release layer may include less than 80 atomic% of fluorine atoms based on 100 atomic% of silicon atoms. In the present specification, "deep portion" refers to the inside of the release layer etched by plasma on the surface of the release layer, more specifically, refers to a point inside the release layer where the atomic% of C (carbon) on the surface of the release layer is 60 atomic% when analyzed by an X-ray photoelectron spectrometer. Since the more fluorine atoms are present on the surface of the coating layer in the release layer, the better the peeling force is, when the fluorine atoms in the release layer are 80 atomic% or more, the specific gravity of the fluorine atoms on the surface of the release layer decreases and the silicon atom content increases, so that peeling may not occur when the release layer is attached to a silicone adhesive.
The fluorine-containing polysiloxane may include an organopolysiloxane represented by the following chemical formula 1.
[ chemical formula 1 ]
[ chemical formula 2 ]
[ chemical formula 3 ]
In the chemical formula 1, the first and second organic solvents,
R 1 may be a substituted or unsubstituted C1 to C10 monovalent hydrocarbon group, or a substituted or unsubstituted C2 to C10 alkenyl group;
R 2 may be a substituted or unsubstituted C1 to C10 monovalent hydrocarbon group, a substituted or unsubstituted C2 to C10 alkenyl group, or hydrogen;
R 3 and R 4 Each independently is a fluorine-containing alkyl group represented by the chemical formula 2, a fluorine-containing ether group represented by the chemical formula 3, a substituted or unsubstituted C1-C10 monovalent hydrocarbon group, a substituted or unsubstituted C2-C10 alkenyl group, or hydrogen,
the R is 3 And R 4 At least one of a fluorinated alkyl group represented by the chemical formula 2, a fluorine-containing ether group represented by the chemical formula 3, or a combination thereof;
n may be an integer of 1 to 8, m may be an integer of 1 to 5;
p may be an integer from 1 to 5, q may be 0 or 1, r may be 0, 1 or 2, and v may be an integer from 1 to 5;
a can be an oxygen atom or a single bond;
x, y and z may each be an integer of 1 or more;
* May be a binding site to an adjacent atom;
wherein R is 1 And R 2 At least one of them may be a substituted or unsubstituted C2 to C10 alkenyl group.
The non-fluorine-containing organopolysiloxane may be represented by the following chemical formula 4:
[ chemical formula 4 ]
In the chemical formula 4, the first and second organic solvents,
R a may be a substituted or unsubstituted C1 to C10 monovalent hydrocarbon group, or a substituted or unsubstituted C2 to C10 alkenyl group;
R b may be a substituted or unsubstituted C1 to C10 monovalent hydrocarbon group, substitutedOr unsubstituted C2 to C10 alkenyl, or hydrogen;
x 'and y' may be integers of 1 or more, respectively.
According to circumstances, the fluorine-containing polysiloxane may be a blend of the organopolysiloxane represented by chemical formula 1 and the organopolysiloxane represented by chemical formula 5 below, or may be a copolymer in which the organopolysiloxane represented by chemical formula 1 and the organopolysiloxane represented by chemical formula 5 below are linked:
[ chemical formula 5 ]
[ chemical formula 6 ]
In the chemical formula 5, the first and second organic solvents,
R' 1 may be a substituted or unsubstituted C1 to C10 monovalent hydrocarbon group, or a substituted or unsubstituted C2 to C10 alkenyl group;
R' 2 may be a fluorine-containing ether group represented by the chemical formula 5;
n 'may be an integer of 1 to 8, and m' may be an integer of 3 to 17;
* May be a binding site for an adjacent atom.
For example, the weight ratio of the organopolysiloxane represented by chemical formula 1 to the organopolysiloxane represented by chemical formula 5 may be 10:1 to 1:10.
the fluorine-containing organopolysiloxane may be present in an amount of 10 to 300 parts by weight, based on 100 parts by weight of the non-fluorine-containing organopolysiloxane. When the content of the fluorine-containing organopolysiloxane is less than 10 parts by weight based on 100 parts by weight of the non-fluorine-containing organopolysiloxane, since the fluorine group of the surface of the release layer is not sufficiently hardened, the surface energy is increased, and since the hardness is reduced, a large change may occur over time due to blocking and penetration of the adhesive. Thus, when the release layer and the silicone adhesive are bonded, peeling may not occur. When the content of the fluorine-containing organopolysiloxane is greater than 300 parts by weight based on 100 parts by weight of the non-fluorine-containing organopolysiloxane, there is a risk that the substrate may be deformed due to a large amount of energy required during curing of the fluorine-containing organopolysiloxane.
The surface energy of the release layer can be 10dyne/cm to 16dyne/cm. When the surface energy of the release layer is less than 10dyne/cm, the adhesive may not be applied due to the low surface energy. When the surface energy of the release layer is more than 16dyne/cm, the release layer and the silicone-based adhesive may not be peeled off because the fluorine-containing organopolysiloxane on the surface of the release layer is not sufficiently cured.
The reduced modulus of elasticity (reduced modulus) of the release layer measured by the nanoindentation method may be 2GPa to 6GPa.
When the reduced elastic modulus of the release layer is less than 2GPa, the release layer is softened, and therefore, a blocking phenomenon occurs at the time of winding. When the reduced elastic modulus of the release layer is more than 6GPa, the release layer becomes hard to increase the peeling force.
The surface hardness (surface hardness) of the release layer measured by a nano indentation method may be 0.3GPa to 0.6GPa.
When the surface hardness (surface hardness) of the release layer measured by the nanoindentation method is less than 0.3GPa, a large change may occur with time due to adhesive penetration as the surface hardness becomes lower. When the surface hardness (surface hardness) of the release layer measured by the nanoindentation method is greater than 0.6GPa, the peeling force may increase as the surface hardness becomes high.
The release layer may further include organic-inorganic particles.
The organic-inorganic particles may be natural minerals; an oxide, hydroxide, sulfide, nitride or halide of a group 1 to group 4, group 11 to group 12, group 14 and group 16 to group 18 element; carbonates, sulfates, acetates, phosphates, phosphites, carboxylates, silicates, titanates, borates, or hydrates thereof; and inorganic particles selected from complex compounds thereof.
The organic-inorganic particles may be organic particles selected from fluorine-based resins, melamine-based resins, styrene-based resins, acrylic resins, silicone-based resins, styrene-divinylbenzene-based copolymer resins, and polymers or copolymers crosslinked with the resins thereof.
The shape of the organic-inorganic particles used is not particularly limited, and it may be spherical, massive, rod-like, or flat, and the like. In addition, the hardness, specific gravity, color, and the like of the organic-inorganic particles are not limited, and these organic-inorganic particles may be used alone or two or more kinds may be used if necessary.
The organic-inorganic particles may have an average particle diameter (D50) of 1 μm to 5 μm. For example, the organic-inorganic particles may have an average particle diameter (D50) of 3 μm to 5 μm, or 1 μm to 2 μm. In the present specification, "average particle diameter (D50)" means a particle diameter value corresponding to 50% from the smallest particles when the total number of particles is 100% in a distribution curve accumulated in order from the smallest particle diameter to the largest particle diameter. The D50 value can be measured by methods well known to those skilled in the art, for example by a Particle size analyzer (Particle size analyzer), or can be measured from TEM or SEM photographs. As another method, the D50 value can be easily calculated by performing measurement using a dynamic Light-scattering (dynamic Light-scattering) measuring device and performing data analysis, and then counting the number of particles per particle size range.
When the average particle diameter (D50) of the organic-inorganic particles is less than 1 μm, surface roughness cannot be sufficiently obtained, and thus the blocking phenomenon cannot be prevented. When the average particle diameter (D50) of the organic-inorganic particles is greater than 5 μm, it may act as a defect of the thin film.
The release layer may further include at least one of hydrogen polysiloxane (hydrogen polysiloxane) and a catalyst.
The hydrogen polysiloxane may include at least one of an addition reaction type silicone resin, a condensation reaction type silicone resin, and an ultraviolet curing type silicone resin. The hydrogen polysiloxane may be linear, branched or cyclic, or may be a mixture thereof. The hydrogenpolysiloxane is not limited in viscosity and molecular weight, but must be good in compatibility with the above-mentioned organopolysiloxane, and may not include a fluorine group. However, the hydrogenpolysiloxane may also include the same fluoroalkyl and/or fluoroether groups as the above-described organopolysiloxane.
The hydrogen polysiloxane may be contained in an amount of 1.0 to 10.0 wt% based on the total weight of the composition for forming the release layer.
As the catalyst, at least one metal selected from group 4 to group 14 elements or an amphoteric element may be used, and for example, at least one selected from Rh, pt, sn, ti, pd, ir, W, and Co may be used. For example, the catalyst may include a platinum chelate catalyst.
According to circumstances, the release layer may further include an additive for imparting various functions such as a reaction regulator, an antistatic agent, and the like.
The release layer may have a thickness of 0.03 to 2.0 μm. When the thickness of the release layer is less than 0.03um, the release layer has poor coverage, and thus may not be peeled off when being attached with an acrylic adhesive or/and a silicone adhesive. When the thickness of the release layer is greater than 2.0um, a large amount of heat is required during curing, which may cause thermal deformation of the substrate and increase in cost since the releasability is not improved.
The composition for forming a release layer is prepared to include a solvent having a solid content of 0.5 to 10 wt%. The solvent may be used without limitation as long as the solid component can be dispersed and coated on a substrate, and for example, an aromatic hydrocarbon-based solvent such as toluene, xylene, or the like; aliphatic hydrocarbon solvents such as hexane, heptane, n-octane, isooctane, decane, cyclohexane, methylcyclohexane, isoparaffin, and the like; hydrocarbon solvents such as industrial gasoline (rubber gasoline, etc.), petroleum benzene, solvent oil, etc.; ketone solvents such as acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, methyl isobutyl ketone, diisobutyl ketone, acetonyl acetone, cyclohexanone, etc.; ester-based solvents such as ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, and the like; ether solvents such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, 1, 2-dimethoxyethane, 1, 4-dioxane, etc.; solvents having ester and ether moieties such as ethyl 2-methoxyacetate, ethyl 2-ethoxyacetate, propylene glycol monomethyl ether acetate, ethyl 2-butoxyacetate, and the like; siloxane-based solvents such as hexamethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, tris (trimethylsiloxy) methylsilane, tetrakis (trimethylsiloxy) silane, etc.; fluorine-based solvents such as trifluorotoluene, hexafluoroxylene, methyl nonafluorobutyl ether, ethyl nonafluorobutyl ether and the like; or a mixed solvent thereof. For example, heptane may be used as the solvent used in the composition for forming the release layer.
When the solid content of the composition for forming a release layer is less than 0.5 wt%, a sufficient coating thickness may not be formed, and thus release properties may not be exhibited. When the solid content of the composition for forming a release layer is more than 10% by weight, high viscosity of the composition for forming a release layer may cause leveling unevenness, so that thickness uniformity of the release layer is deteriorated, and coating thickness becomes thick to cause non-curing.
As a method of coating the release layer-forming composition on one side of the substrate, an off-line coating method available in the art, such as bar coating, gravure coating, die coating, etc., may be used. The energy source for curing the composition for forming the release layer is not particularly limited, but heat treatment, ultraviolet irradiation or electron beam irradiation, which may be used alone or in combination, and heat treatment may be used alone or a combination of heat treatment and ultraviolet irradiation may be used.
< Release film >
Fig. 1 is a cross-sectional view of a release film 100 according to an embodiment of the present invention.
Referring to fig. 1, a release film 120 according to an embodiment of the present invention has a structure in which a substrate 100 and a release layer 110 are sequentially positioned.
The release film 120 according to an embodiment of the present invention has a low peel force and a rate of change in peel force with respect to both acrylic adhesives and silicone adhesives, and has a high surface hardness and a reduced modulus (reduced modulus) so that blocking can be prevented from occurring when the film is wound up.
The release film 120 may have a peel force from the acrylic adhesive and the silicone adhesive of 0.5gf/25mm to 10gf/25mm at a peel angle of 180 ° and a peel rate of 0.3 mpm.
When the release film 120 has a peeling force to the acrylic adhesive and the silicone adhesive of less than 0.5gf/25mm at a peeling angle of 180 ° and a peeling rate of 0.3mpm, the adhesion between the release layer 110 and the silicone adhesive is deteriorated, so that the attachment interface may float, such as a tunneling phenomenon (tunneling phenomenon). When the release film 120 has a peeling force of more than 10gf/25mm to the acrylic adhesive and the silicone adhesive at a peeling angle of 180 ° and a peeling rate of 0.3mpm, it cannot be properly peeled from the silicone adhesive, which may cause problems in the process.
The release film 120 may have a peel force variation rate according to the following formula 2 of 50% or less for an acrylic adhesive and a silicone adhesive.
[ formula 2 ]
Peel force change rate (%) = (peel force after seven days-initial peel force)/initial peel force × 100
The release film 120 can achieve a stable release force against an acrylic adhesive and a silicone adhesive without time variation.
The residual adhesive ratio of the release film 120 may be 85% or more.
When the residual adhesion of the release film 120 is less than 85%, the release layer is transferred to the adhesive layer due to insufficient curing of the release layer 110, and the adhesiveness of the adhesive may be deteriorated.
In the present specification, "substitution" is induced by replacing at least one hydrogen in an unsubstituted parent group (heat group) with another atom or functional group. Unless otherwise specified, when a functional group is considered to be "substituted", it means that the functional group is substituted with at least one substituent selected from an alkyl group having 1 to 40 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, an alkynyl group having 2 to 40 carbon atoms, a cycloalkyl group having 3 to 40 carbon atoms, a cycloalkenyl group having 3 to 40 carbon atoms, or an aryl group having 7 to 40 carbon atoms. When a functional group is described as "optionally substituted," this means that the functional group may be substituted with the above-described substituent.
In the present specification, the monovalent hydrocarbon group of C1 to C10 means, for example, a linear alkyl group such as methyl, ethyl, n-hexyl, n-octyl or n-decyl; branched alkyl groups such as isopropyl, tert-butyl, neopentyl, isohexyl, etc.; cyclic alkyl groups such as cyclopentyl or cyclohexyl, etc.; aryl groups such as phenyl or tolyl; or aralkyl such as benzyl or phenethyl, and the like. Among them, when considering the availability of raw materials, it may be an alkyl group, and when considering the usefulness of products, it may also be a methyl group or an ethyl group.
In the present specification, the C2-C10 alkenyl group means a branched or unbranched hydrocarbon group having at least one carbon-carbon double bond. Non-limiting examples of alkenyl groups can include vinyl, allyl, butenyl, isopropenyl, isobutenyl, or the like.
The configuration of the present invention and its effects will be described in more detail by examples and comparative examples. However, it is apparent that these examples are for illustrating the present invention in more detail and the scope of the present invention is not limited to these examples.
[ examples ]
Example 1: release film
A50 μm-thick polyester film (Toray advanced material, XD 500P) was prepared.
Separately from this, as a fluorine-containing organopolysiloxane, 100 parts by weight of an organopolysiloxane (produced by Dow Chemical, Q2-7785) represented by the following Chemical formula 1 including a fluoroalkyl group represented by the following Chemical formula 2, 100 parts by weight of a non-fluorine-containing organopolysiloxane (produced by Shin-Etsu, KS 847H) including a vinyl group and a methyl group, 3 parts by weight of a hydrogen polysiloxane (produced by Dow Chemical, Q2-7560), and 0.1 part by weight of a platinum chelate catalyst (produced by Dow Chemical, SYL-OFF 4000) were diluted in a heptane solvent to prepare a composition for forming a release layer having a total solid content of 5% by weight.
The release film was prepared by coating the composition for forming a release layer on one side of the polyester film and heat-treating in a hot air dryer at 150 ℃ for 60 seconds to form a release layer having a thickness of 0.3 μm.
[ chemical formula 1 ]
[ chemical formula 2 ]
In the chemical formula 1, the reaction mixture is,
R 1 is vinyl, R 2 、R 3 Each is methyl, R 4 Is a fluoroalkyl group represented by the chemical formula 2;
n is 4, m is 2, and is a binding site to an adjacent atom.
Example 2: release film
A release film was prepared in the same manner as in example 1, except that 50 parts by weight of the organopolysiloxane (prepared by Dow Chemical, Q2-7785) represented by the Chemical formula 1 including the fluoroalkyl group represented by the Chemical formula 2 was used as the fluorine-containing organopolysiloxane.
Example 3: release film
A release film was produced in the same manner as in example 1, except that 50 parts by weight of the organopolysiloxane (produced by Dow Chemical, Q2-7785) represented by the Chemical formula 1 including the fluoroalkyl group represented by the Chemical formula 2 and 50 parts by weight of the organopolysiloxane (produced by Shin-Etsu Silicone, X-70-201S) represented by the Chemical formula 5 including the fluoroether group represented by the Chemical formula 6 were used as the fluorine-containing organopolysiloxane.
[ chemical formula 5 ]
[ chemical formula 6 ]
In the chemical formula 5, the first and second organic solvents,
R' 1 is vinyl, R' 2 Is a fluoroether group represented by the chemical formula 5;
n ' is 2, m ' is 4, x ' is 1.
Example 4: release film
A release film was produced in the same manner as in example 1, except that 50 parts by weight of the non-fluorine-containing organopolysiloxane (produced by Shin-Etsu, KS 847H) represented by the Chemical formula 4 and 50 parts by weight of the non-fluorine-containing organopolysiloxane (produced by Dow Chemical, LTC 750A) including a hexenyl group were used instead of 100 parts by weight of the non-fluorine-containing organopolysiloxane (produced by Shin-Etsu, KS 847H) represented by the Chemical formula 4.
Example 5: release film
A release film was prepared in the same manner as in example 1, except that the release film was prepared by coating the composition for forming a release layer on one side of the polyester film and heat-treating in a hot air dryer at 150 ℃ for 60 seconds to form a 1 μm-thick release layer.
Example 6: release film
A release film was prepared in the same manner as in example 1, except that a composition for forming a release layer was prepared by further adding 1 wt% of silica particles having a particle diameter of 2 μm based on the total solid content.
Comparative example 1: release film
A release film was produced in the same manner as in example 1, except that 5 parts by weight of the organopolysiloxane (produced by Dow Chemical, Q2-7785) represented by the Chemical formula 1 including the fluoroalkyl group represented by the Chemical formula 2 was used as the fluorine-containing organopolysiloxane.
Comparative example 2: release film
A release film was produced in the same manner as in example 1, except that 500 parts by weight of the organopolysiloxane (produced by Dow Chemical, Q2-7785) represented by the Chemical formula 1 including the fluoroalkyl group represented by the Chemical formula 2 was used as the fluorine-containing organopolysiloxane.
Comparative example 3: release film
A release film was prepared in the same manner as in example 1, except that the release film was prepared by coating the composition for forming a release layer on one side of the polyester film and heat-treating in a hot air dryer at 150 ℃ for 60 seconds to form a release layer of 2.5 μm thickness.
Comparative example 4: release film
A release film was prepared in the same manner as in example 1, except that the release film was prepared by coating the composition for forming a release layer on one side of the polyester film and heat-treating in a hot air dryer at 150 ℃ for 60 seconds to form a 0.01 μm thick release layer.
Comparative example 5: release film
A release film was produced in the same manner as in example 1, except that the fluorine-containing organopolysiloxane was not used.
Comparative example 6: release film
A release film was produced in the same manner as in example 1, except that the non-fluorine-containing organopolysiloxane represented by the chemical formula 4 (manufactured by Shin-Etsu, KS 847H) was not used.
Evaluation example 1: evaluation of physical Properties
The physical properties of the release films prepared in examples 1 to 6 and comparative examples 1 to 6 were evaluated as follows, and the results thereof are shown in table 1.
(1) X-ray photoelectron spectroscopy analysis of release layer surface
The atomic compositions of silicon (Si), fluorine (F), carbon (C) and oxygen (O) were analyzed by X-ray photoelectron spectroscopy on the release layer surface of each release film and expressed in atomic%. As an X-ray photoelectron analyzer, K-ALPHA of ThermoFisher was used, and the analysis area (spot size) was set to 400 μm. In addition, the content (atomic%) ratio of fluorine atom/silicon atom was calculated using the analyzed fluorine atom and silicon atom.
(2) Peeling force (gf/25 mm) and peeling force change rate (%)
Each release film was cut into a size of 500mm × 1500mm to prepare a sample. The samples were stored at 25 ℃, 65% RH for 24 hours (initial peel force sample) and 7 days (peel force sample after 7 days). Then, at 50 ℃ and 20g/cm 2 A silicone-based adhesive tape (symbian, MY 2G) and an acrylic-based adhesive tape (TESA, TESA 7475) were respectively pressed against the release layer of the sample for 24 hours under the load of (d), and then a peel force of 250mm × 1500mm size was measured at 180 ° and 0.3mpm speed using a peel force tester AR-2000 apparatus manufactured by chemistruments. At this time, the peeling force was measured 5 times, and then an average value was calculated, thereby obtaining an initial peeling force and a peeling force after 7 days, and a change rate of the peeling force was obtained by substituting the following formula 2.
[ formula 2 ]
Peel force change rate (%) = (peel force after seven days-initial peel force)/initial peel force × 100
(3) Residual adhesion ratio (%) of release film
Each release film was cut into a size of 500mm × 1500mm to prepare a sample. The samples were stored at 25 deg.C, 65% RH for 24 hours. At room temperature and 20g/cm 2 Was pressed against the release layer of the sample for 24 hours under a load of (3), and was free from contaminationCollecting the adhesive tape adhered on the release layer. The adhesive tape was adhered to a polyethylene terephthalate film surface having a flat and clean surface. The adhesive tape adhered to the polyethylene terephthalate film surface was pressure-bonded once with a 2kg tape roller (astm d-1000-55T) in a reciprocating manner. Then, for the tape sample pressed against the polyethylene terephthalate film surface, the peel force of the 250mm × 1500mm size was measured at 180 ° and 0.3mpm speed using a peel force tester AR-1000 apparatus manufactured by chemistruments, and substituted into the following formula 3 to obtain the residual tackiness rate.
[ formula 3 ]
Residual adhesion (%) = [ peeling force of adhesive tape peeled after adhering to release layer)/(peeling force of adhesive tape not adhering to release layer) ] × 100
(4) Reduced elastic modulus (GPa) and surface hardness (GPa) of the release layer
For the release layer of each release film, a reduced modulus of elasticity (reduced modulus) and a surface hardness were measured using a nanoindenter analyzer (Hysitron, TI950 triboinder).
[ TABLE 1 ]
Referring to table 1, it can be confirmed that the release films prepared in examples 1 to 6 have stable peel force because of their low peel force to the silicone-based adhesive and low change rate of peel force and peel force to the acrylic-based adhesive.
It was confirmed that the release films prepared in comparative example 1 (in the case of using less fluorine-containing organopolysiloxane) and comparative example 5 (in the case of using only non-fluorine-containing organopolysiloxane) did not peel because the release films were completely adhered to the silicone-based adhesive, and the reduced elastic modulus and surface hardness of the release layer were low, and the rate of change in peel force was as high as 50% or more. It was confirmed that the release films prepared in comparative example 2 (in the case of a high content of the fluorine-containing organopolysiloxane) and comparative example 3 (in the case of a thick release layer) were poorly cured, and therefore the residual adhesion rate was reduced and the rate of change in the release force was also high. The release film prepared in comparative example 6 (in the case of using only the fluorine-containing organopolysiloxane alone) exhibited light peeling properties, that is, a peeling force against the silicone-based adhesive was 10gf/25mm or less, but a peeling force against the acrylic-based adhesive was measured to be 10gf/25mm or more. Since the release film prepared in comparative example 4 (the case where the thickness of the release layer is thin) has poor release layer coverage, the measured peel force is large when it is attached to a silicone-based adhesive and an acrylic-based adhesive. From this, it can be seen that the release film of the present invention exhibits light peelability to both acrylic adhesives and silicone adhesives because the release layer has appropriate reduced elastic modulus and surface hardness. In addition, it can be seen that since the release film of the present invention has higher surface hardness than the silicone-based release film, the rate of change of the release force from the acrylic adhesive is lower, and blocking is improved when the release film is wound up.
Claims (11)
1. A release film, comprising:
a substrate; and
a release layer on at least one side of the substrate,
wherein the release layer is a cured layer of a composition for forming a release layer, the composition comprising a blend of a fluorine-containing organopolysiloxane and a non-fluorine-containing organopolysiloxane,
the fluorine atom/silicon atom content ratio of the release layer decreases from the surface toward the center,
a reduced elastic modulus of the release layer measured by a nanoindentation method is 2GPa to 6GPa,
the surface hardness of the release layer measured by a nanoindentation method is 0.3GPa to 0.6GPa.
2. The release film according to claim 1,
in X-ray photoelectron spectroscopy analysis of the surface of the release layer, the content (atomic%) ratio of fluorine atoms/silicon atoms is 1.5 to 4.5.
3. The release film according to claim 1,
the surface energy of the release layer is 10dyne/cm to 16dyne/cm.
4. The release film according to claim 1,
the release film has a peel force to the acrylic adhesive and the silicone adhesive of 0.5gf/25mm to 10gf/25mm at a peel angle of 180 ° and a peel rate of 0.3 mpm.
5. The release film according to claim 1,
the release film has a peel force variation rate according to the following formula 2 of 50% or less for an acrylic adhesive and a silicone adhesive.
[ formula 2 ]
Peel force change rate (%) = (peel force after 7 days-initial peel force)/initial peel force × 100
6. The release film according to claim 1,
the residual adhesion rate of the release film is more than 85%.
7. The release film according to claim 1,
the thickness of the release layer is 0.03-2.0 μm.
8. The release film according to claim 1,
the fluorine-containing polysiloxane includes an organopolysiloxane represented by the following chemical formula 1:
[ chemical formula 1 ]
[ chemical formula 2 ]
[ chemical formula 3 ]
In the chemical formula 1, the first and second organic solvents,
R 1 is a substituted or unsubstituted C1 to C10 monovalent hydrocarbon group, or a substituted or unsubstituted C2 to C10 alkenyl group;
R 2 is a substituted or unsubstituted C1 to C10 monovalent hydrocarbon group, a substituted or unsubstituted C2 to C10 alkenyl group, or hydrogen;
R 3 and R 4 Each independently a fluorine-containing alkyl group represented by the chemical formula 2, a fluorine-containing ether group represented by the chemical formula 3, a substituted or unsubstituted C1-C10 monovalent hydrocarbon group, a substituted or unsubstituted C2-C10 alkenyl group, or hydrogen,
the R is 3 And R 4 Is a fluorinated alkyl group represented by the chemical formula 2, a fluorine-containing ether group represented by the chemical formula 3, or a combination thereof;
n is an integer of 1 to 8, m is an integer of 1 to 5;
p is an integer from 1 to 5, q is 0 or 1, r is 0, 1 or 2, v is an integer from 1 to 5;
a is oxygen atom or single bond;
x, y and z are integers of 1 or more;
* Is a binding site to an adjacent atom;
wherein R is 1 And R 2 At least one of which is a substituted or unsubstituted C2 to C10 alkenyl group.
9. The release film according to claim 1,
the fluorine-containing organopolysiloxane is present in an amount of 10 to 300 parts by weight, based on 100 parts by weight of the non-fluorine-containing organopolysiloxane.
10. The release film according to claim 1,
the release layer further includes organic-inorganic particles.
11. The release film according to claim 1,
the release layer further includes at least one of a hydrogen polysiloxane and a catalyst.
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| KR1020210029591A KR102459382B1 (en) | 2021-03-05 | 2021-03-05 | Release film |
| KR10-2021-0029591 | 2021-03-05 | ||
| PCT/KR2021/008195 WO2022186427A1 (en) | 2021-03-05 | 2021-06-29 | Release film |
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| WO2020137835A1 (en) * | 2018-12-25 | 2020-07-02 | 信越化学工業株式会社 | Silicone release agent composition, release sheet and release film |
| WO2020209450A1 (en) * | 2019-04-11 | 2020-10-15 | 도레이첨단소재 주식회사 | Fluorine group-containing release film |
| WO2021019845A1 (en) * | 2019-07-29 | 2021-02-04 | 三菱ケミカル株式会社 | Mold release film, film laminate, method for producing mold release film, and method for producing film laminate |
| CN113444276A (en) * | 2020-03-27 | 2021-09-28 | 东丽尖端素材株式会社 | Release film and method for producing same |
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| US20050038183A1 (en) * | 2003-08-14 | 2005-02-17 | Dongchan Ahn | Silicones having improved surface properties and curable silicone compositions for preparing the silicones |
| KR101522941B1 (en) * | 2014-02-05 | 2015-05-26 | 도레이첨단소재 주식회사 | Silicone release film and manufacturing method thereof |
| TW201905139A (en) * | 2017-06-23 | 2019-02-01 | 日商道康寧東麗股份有限公司 | 剥离Adhesive stripper composition and release film |
| JP7173045B2 (en) * | 2017-12-11 | 2022-11-16 | 三菱ケミカル株式会社 | Laminate films, release films and laminates |
| EP3895891A4 (en) * | 2018-12-11 | 2022-04-27 | Mitsubishi Chemical Corporation | Release film |
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| WO2020137835A1 (en) * | 2018-12-25 | 2020-07-02 | 信越化学工業株式会社 | Silicone release agent composition, release sheet and release film |
| WO2020209450A1 (en) * | 2019-04-11 | 2020-10-15 | 도레이첨단소재 주식회사 | Fluorine group-containing release film |
| WO2021019845A1 (en) * | 2019-07-29 | 2021-02-04 | 三菱ケミカル株式会社 | Mold release film, film laminate, method for producing mold release film, and method for producing film laminate |
| CN113444276A (en) * | 2020-03-27 | 2021-09-28 | 东丽尖端素材株式会社 | Release film and method for producing same |
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