KR20220061777A - Release film and manufacturing method thereof - Google Patents

Abstract

Disclosed are a release film and a method for manufacturing the same. The release film includes a substrate and a release layer disposed sequentially, wherein the release layer has a surface energy of 24 dyne/cm or less and includes organic/inorganic particles, and the organic/inorganic particles have a fluorinated silane compound-containing moiety introduced to the surfaces thereof and can satisfy a range of F/Si elemental content ratio (M_F/M_Si) represented by formula 1 of 0.1 <= M_F/M_Si <= 1.0, wherein M_F represents content of F elements (at%), and M_Si represents content of Si elements (at%).

Description

Release film and manufacturing method thereof

It relates to a release film and a method for manufacturing the same.

In general, silicone-based pressure-sensitive adhesives have heat resistance, weather resistance, flexibility, chemical resistance, and the like, and are recently used in a wide range of applications in IT fields such as mobile phones, semiconductors, and displays as well as general industrial adhesive tapes.

However, since a silicone-based release film using a silicone-based pressure-sensitive adhesive is completely laminated to the pressure-sensitive adhesive and does not peel, a film coated with a release agent containing a fluorine-based resin is commonly used. The release agent containing the fluorine-based resin is highly likely to be cured between layers by the residual curing agent after curing, and peel strength and residual adhesiveness are likely to decrease.

In order to solve these problems, there is still a need for a release film having excellent light peelability, residual adhesion rate, and excellent coating appearance, and a method for manufacturing the same.

One aspect is to provide a release film excellent in light peelability, residual adhesion, and coating appearance.

Another aspect provides a method for manufacturing the release film.

According to one aspect,

The substrate and the release layer are sequentially positioned,

The surface energy of the release layer is 24 dyne / cm or less,

The release layer includes organic and inorganic particles,

In the organic-inorganic particles, a moiety including a fluorine-containing silane compound is introduced on the surface,

The organic-inorganic particles are provided with a release film that satisfies the content ratio (M _F /M _Si ) range of the F/Si element represented by the following formula 1:

[Equation 1]

0.1 ≤ M _F /M _Si ≤ 1.0

during the meal,

M _F may be the content of element F (atomic %), and M _Si may be the content of element Si (atomic %).

The fluorinated silane compound moiety may include a fluorinated silane compound represented by the following Chemical Formula 1:

[Formula 1]

*-OSi(R _a )(R _b )(R _c )

during the meal,

R _a , R _b may be a substituted or unsubstituted C1-C20 alkoxy group;

R _c may be represented by the following formula (2),

* may be a binding site with the surface of the organic/inorganic particle.

[Formula 2]

during the meal,

R _d may be a hydrogen atom or a substituted or unsubstituted C1-C20 alkyl group;

R _e , R _g may be a substituted or unsubstituted C1-C20 alkoxy group;

R _f may be a C4-C20 alkyl group substituted with fluorine;

n ₁ may be an integer from 1 to 10;

* may be a binding site with a Si atom.

The weight ratio of the organic-inorganic particles to the fluorinated silane compound may be 1:1 to 20:1.

In the release layer, a peak in a wavelength range of 1064 to 1066 cm ^-1 in the IR spectrum may be shifted to the right compared to organic/inorganic particles that do not include a fluorinated silane compound moiety on their surface.

The organic-inorganic particles are natural minerals; oxides, hydroxides, sulfides, nitrides, or halides of elements of Groups 1 to 4, 11 to 12, 14 and 16 to 18; carbonate, sulfate, acetate, phosphate, phosphite, carboxylate, silicate, titanate, borate, or hydrates thereof; and inorganic particles selected from these complex compounds.

The release layer may further include a polymer or copolymer including fluorinated polysiloxane.

The fluorinated polysiloxane may include an organo polysiloxane represented by the following Chemical Formula 3:

<Formula 3>

<Formula 4>

<Formula 5>

during the meal,

R ₁ may be a substituted or unsubstituted C1-C10 monovalent hydrocarbon group, or a substituted or unsubstituted C2-C10 alkenyl group;

R ₂ may be a substituted or unsubstituted C1-C10 monovalent hydrocarbon group, a substituted or unsubstituted C2-C10 alkenyl group, or hydrogen;

R ₃ may be a fluorinated alkyl group represented by Formula 4, a fluorine-containing ether group represented by Formula 5, or a combination thereof;

n may be an integer from 1 to 8, m may be an integer from 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, v may be an integer from 1 to 5;

A may be an oxygen atom or a single bond;

x, y, z may each be an integer of 1 or more;

* may be a binding site with a neighboring atom;

However, at least one of R ₁ and R ₂ may be a substituted or unsubstituted C2~C10 alkenyl group.

The release layer may further include at least one of hydrogen polysiloxane and an acid catalyst.

The peeling force of the release film may be 23 gf/25 mm or less.

The residual adhesive rate of the release film may be 90% or more.

According to another aspect,

preparing a substrate;

preparing organic/inorganic particles by adding and stirring inorganic particles, a fluorinated silane compound, and an aminosilane-based co-reactant, followed by heating; and

Preparing the above-mentioned release film by forming a release layer by coating and drying a composition for forming a release layer comprising a polymer or copolymer including a fluorinated polysiloxane, and organic/inorganic particles on at least one surface of the substrate; including; do,

The weight ratio of the inorganic particles to the fluorinated silane compound is 4:1 to 20:1, a method for producing a release film is provided.

The heating may be performed at 60° C. or higher under an air atmosphere.

The weight ratio of the inorganic particles to the fluorinated silane compound may be 1:1 to 20:1.

In the release film according to one aspect, the surface energy of the release layer is 24 dyne/cm or less, the release layer includes organic-inorganic particles, and the organic-inorganic particles include a moiety including a fluorinated silane compound. Introduced to the surface, the organic-inorganic particles may satisfy the content ratio (M _F /M _Si ) range of the F/Si element represented by Equation 1 above. The release film may provide a release film excellent in light peelability, residual adhesion rate, and coating appearance.

1 is a schematic cross-sectional view of a release film according to an embodiment.
2 is an inorganic silica particle as a starting material of the release film prepared in Example 1, an inorganic silica particle having aminosilane introduced thereinto as an intermediate reactant, and an aminosilane and a fluorinated silane compound on the surface as a final product. This is the IR spectrum result of silica inorganic particles.

Hereinafter, the release film and its manufacturing method will be described in detail with reference to the embodiments and drawings of the present invention. It will be apparent to those of ordinary skill in the art that these examples are merely presented by way of example to explain the present invention in more detail, and that 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.

Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described herein.

In the present specification, the term "included" means that other components may be further included, rather than excluding other components, unless otherwise stated.

As used herein, the term “combination of these” means a mixture or combination with one or more of the described components.

As used herein, the term “and/or” is meant to include any and all combinations of one or more of the related listed items. As used herein, the term “or” means “and/or”. In this specification, the expression “at least one type” or “one or more” in front of a component does not mean that it can supplement the entire list of components and can complement individual components of the description.

In the present specification, when it is stated that an element is disposed "on" or "above" another element, one element may be disposed directly on the other element, or the elements interposed between the elements are may exist. On the other hand, when an element is referred to as being disposed "directly on" or "directly on" another element, intervening elements may not be present.

As used herein, "~-based resin", "~-based polymer", or/and "~-based copolymer" means "~ resin", "~ polymer", "~ copolymer", or/and "~ resin, polymer, Or a derivative of a copolymer" is a broad concept including all.

As used herein, the term "polymer or copolymer crosslinked with these resins" means "polymer or copolymer crosslinked with the above-mentioned resins".

In the present specification, "aminosilane-based co-reactant" is a broad concept including both "aminosilane co-reactant" and "co-reactant including aminosilane".

In the release film according to an embodiment, a substrate and a release layer are sequentially positioned, the surface energy of the release layer is 24 dyne/cm or less, the release layer includes organic/inorganic particles, and the organic/inorganic particles are fluorine-containing A moiety including a silane compound may be introduced to the surface thereof, and the organic/inorganic particles may satisfy the F/Si element content ratio (M _F /M _Si ) range represented by the following formula 1:

[Equation 1]

0.1 ≤ M _F /M _Si ≤ 1.0

during the meal,

M _F is the content of element F (atomic %), and M _Si is the content of element Si (atomic %).

The release film according to an embodiment may provide a release film excellent in both light peelability, residual adhesion rate, and coating appearance while having blocking resistance.

The base material constituting the release film, the release layer, the release film, and a manufacturing method thereof will be described in detail as follows.

<Reference>

As the substrate used in the present invention, a known substrate film or sheet may be used as a substrate for a release film. For example, a polyester-based resin film may be used as the substrate. As the polyester-based resin, a known base film commonly used in the field of release film may be used. For example, the polyester-based base film may be a polyester-based base film disclosed in Korean Patent Registration No. 10-1268584, Korean Patent Application Laid-Open No. 2012-45213, and 2012-99546. However, in one embodiment of the present invention, in order to describe only the features of the present invention, the polyester-based base film is described without limitation, but it should be understood as including the technical features of the known polyester-based base film. .

The polyester-based base film may include polyethylene terephthalate, polybutylene terephthalate, or polyethylene naphthalate.

The polyester-based resin forming the base film may be polyester obtained by polycondensation of aromatic dicarboxylic acid and aliphatic glycol, and aromatic dicarboxylic acids include isophthalic acid, phthalic acid, terephthalic acid, and 2,6-naphthalenedica. Leric acid, adipic acid, sebacic acid, oxycarboxylic acid (eg, P-oxybenzoic acid, etc.) can be used, and the aliphatic glycol is ethylene glycol, diethylene glycol, propylene glycol, butanediol, 1,4- Cyclohexanedimethanol, neopentyl glycol, etc. can be used. These polyester-based resins may use two or more of a dicarboxylic acid component and a glycol component in combination, and a copolymer containing a third component is also possible.

In addition, as the polyester-based base film, a uniaxial or biaxially oriented film having high transparency and excellent productivity and processability may be used. As the polyester-based base film, polyethylene terephthalate (PET) or polyethylene-2,6-naphthalene dicarboxylate (PEN) may be used.

In addition, the polyester-based base film may contain particles in order to provide excellent running characteristics between rolls, and as long as the added particles can exhibit excellent sliding properties, they can be used without limitation.

Examples of such particles may include particles such as silica, silicon oxide, calcium carbonate, calcium sulfate, calcium phosphate, magnesium carbonate, magnesium phosphate, barium carbonate, kaolin, aluminum oxide, titanium oxide, and the like, and the shape of the particles used Although not limited to, for example, any of spherical, bulky, rod-shaped, plate-shaped particles may be used.

In addition, the hardness, specific gravity and color of the particles are not limited, but two or more types may be used in parallel as needed, and the average particle diameter of the particles used may be 0.1 to 5 μm, for example, 0.1 to 2 μm that can be used At this time, if the average particle diameter of the particles is less than 0.1 μm, aggregation between particles may occur, resulting in poor dispersion. can occur.

In addition, when particles are included in the polyester-based base film, 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 base film. If the content of the particles is less than 0.01% by weight, the sliding properties of the polyester film may deteriorate and the running characteristics between the rolls may deteriorate, and if the content of the particles exceeds 5% by weight, the surface smoothness of the film may deteriorate.

The thickness of the polyester-based base film is not limited, but may be 30 to 125 μm.

If the polyester-based base film is too thin at 30 μm or less, there is a risk of being deformed by heat treatment during processing, and when it is too thick over 125 μm, heat is not sufficiently transmitted and there may be a problem in curing.

<Release layer>

The release layer of the release film according to an embodiment may have a surface energy of 24 dyne/cm or less. Due to such low surface energy, the release film including the release layer can implement light peelability with low peeling force.

The release layer includes organic-inorganic particles, and a moiety including a fluorinated silane compound is introduced into the organic-inorganic particles on the surface, and the organic-inorganic particles are F/Si elements represented by Formula 1 below. The content ratio (M _F /M _Si ) may satisfy the range:

[Equation 1]

0.1 ≤ M _F /M _Si ≤ 1.0

during the meal,

M _F may be the content of element F (atomic %), and M _Si may be the content of element Si (atomic %).

The organic/inorganic particles may prevent blocking. The organic/inorganic particles include a fluorine-containing silane compound on their surface and satisfy the content ratio (M _F /M _Si ) range of the F/Si element represented by Formula 1, so that light peelability can be improved and residual adhesion rate and coating appearance can both be improved.

The fluorinated silane compound moiety may include a fluorinated silane compound represented by the following Chemical Formula 1:

[Formula 1]

*-OSi(R _a )(R _b )(R _c )

during the meal,

R _a , R _b may be a substituted or unsubstituted C1-C20 alkoxy group;

R _c may be represented by the following formula (2),

* may be a binding site with the surface of the organic/inorganic particle.

[Formula 2]

during the meal,

R _d may be a hydrogen atom or a substituted or unsubstituted C1-C20 alkyl group;

R _e , R _g may be a substituted or unsubstituted C1-C20 alkoxy group;

R _f may be a C4-C20 alkyl group substituted with fluorine;

n ₁ may be an integer from 1 to 10;

* may be a binding site with a Si atom.

For example, in Formulas 1 and 2, R _a , R _b , R _e , and R _g may each independently be a substituted or unsubstituted C1-C20 alkoxy group, or a substituted or unsubstituted C1-C5 alkoxy group. Or, it may be an unsubstituted C1-C5 alkoxy group.

For example, in Formula 2, n ₁ may be an integer of 1 to 10, or an integer of 1 to 5.

For example, in Formula 2, R _f may be a fluorine-substituted C4-C20 alkyl group, a fluorine-substituted C4-C15 alkyl group, or a fluorine-substituted C4-C10 alkyl group. . If R _f in Formula 2 is an alkyl group having the number of carbons substituted with fluorine, excellent light peelability may be realized by lowering the peeling force.

The weight ratio of the organic-inorganic particles to the fluorinated silane compound may be 1:1 to 20:1. If the weight ratio of the organic-inorganic particles to the fluorine-containing silane compound is within the above range, the peeling force may be further lowered to realize better light peelability.

In the release layer, a peak in a wavelength range of 1064 to 1066 cm ^-1 in the IR spectrum may be shifted to the right compared to organic/inorganic particles that do not include a fluorinated silane compound moiety on their surface.

The organic-inorganic particles are natural minerals; oxides, hydroxides, sulfides, nitrides, or halides of elements of Groups 1 to 4, 11 to 12, 14 and 16 to 18; carbonate, sulfate, acetate, phosphate, phosphite, carboxylate, silicate, titanate, borate, or hydrates thereof; and inorganic particles selected from these complex compounds.

If necessary, the organic/inorganic particles include 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 these resins. may include

The shape of the organic/inorganic particles used is not particularly limited, and may be spherical, bulky, rod-shaped, or flat-shaped. In addition, the hardness, specific gravity, color, etc. of the organic-inorganic particles are not limited, and if necessary, these organic-inorganic particles may be used alone or two or more types may be used.

The release layer may further include a polymer or copolymer including fluorinated polysiloxane.

The fluorinated polysiloxane may include an organo polysiloxane represented by the following Chemical Formula 3:

<Formula 3>

<Formula 4>

<Formula 5>

during the meal,

R ₁ may be a substituted or unsubstituted C1-C10 monovalent hydrocarbon group, or a substituted or unsubstituted C2-C10 alkenyl group;

R ₂ may be a substituted or unsubstituted C1-C10 monovalent hydrocarbon group, a substituted or unsubstituted C2-C10 alkenyl group, or hydrogen;

R ₃ may be a fluorinated alkyl group represented by Formula 4, a fluorine-containing ether group represented by Formula 5, or a combination thereof;

n may be an integer from 1 to 8, m may be an integer from 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, v may be an integer from 1 to 5;

A may be an oxygen atom or a single bond;

x, y, z may each be an integer of 1 or more;

* may be a binding site with a neighboring atom;

However, at least one of R ₁ and R ₂ may be a substituted or unsubstituted C2~C10 alkenyl group.

If necessary, the fluorinated polysiloxane may be a blend of the organo polysiloxane represented by the formula (3) and the organo polysiloxane represented by the following formula (6), or the organo polysiloxane represented by the formula (3) and the formula (6) It may be a copolymer in which the organo polysiloxane is linked:

<Formula 6>

<Formula 7>

during the meal,

R′ ₁ may be a substituted or unsubstituted C1-C10 monovalent hydrocarbon group, or a substituted or unsubstituted C2-C10 alkenyl group;

R′ ₂ may be a fluorine-containing ether group represented by Formula 7;

n' may be an integer from 1 to 8, m' may be an integer from 3 to 17;

* may be a binding site with a neighboring atom.

For example, a weight ratio of the organopolysiloxane represented by Formula 3 to the organopolysiloxane represented by Formula 6 may be 10:1 to 1:10.

The release layer may further include at least one of hydrogen polysiloxane and an acid catalyst.

The hydrogen polysiloxane may include at least one of an addition reaction type siloxane resin, a condensation reaction type siloxane resin, and an ultraviolet curing type siloxane resin. The hydrogen polysiloxane may be in one of linear, branched, or cyclic form, and may be in the form of a mixture thereof. Although the viscosity or molecular weight of the hydrogen polysiloxane is not limited, compatibility with the aforementioned organo polysiloxane should be good, and the hydrogen polysiloxane may not include a fluorine group. However, the hydrogen polysiloxane may include the same fluorinated alkyl group and/or fluorine-containing ether group as the aforementioned organo polysiloxane.

The content of the hydrogen polysiloxane may be 1.0 to 10.0 wt% based on the total weight of the composition for forming a release layer.

The acid catalyst may use one or more metals or amphoteric elements selected from Groups 4 to 14 elements, for example, one or more selected from Rh, Pt, Sn, Ti, Pd, Ir, W, and Co. can be used For example, the acid catalyst may include a platinum chelate catalyst.

If necessary, the release layer may further include additives for imparting various functions such as a reaction modifier and an antistatic agent.

The release layer may have a thickness of 0.03 to 3.0 μm. If the thickness of the release layer is less than 0.01 um, the release layer coverage is not good, and if it exceeds 3 um, it may cause thermal deformation of the base film because it requires a large amount of heat during curing.

<Release film>

1 is a schematic cross-sectional view of a release film 100 according to an embodiment.

Referring to FIG. 1 , a release film 120 according to an exemplary embodiment has a structure in which a substrate 100 and a release layer 110 are sequentially positioned.

The release film 120 according to an embodiment may provide a release film excellent in light peelability, residual adhesion, and coating appearance.

The peeling force of the release film may be 23 gf/25 mm or less.

The residual adhesive rate of the release film may be 90% or more.

If the residual adhesive rate of the release film is less than 90%, curing of the release layer is insufficient, so that the release agent is transferred to the pressure-sensitive adhesive layer, and a problem of poor adhesion of the pressure-sensitive adhesive may occur.

<Manufacturing method of release film>

A method of manufacturing a release film according to an embodiment comprises the steps of preparing a substrate; preparing organic/inorganic particles by adding and stirring inorganic particles, a fluorinated silane compound, and an aminosilane-based co-reactant, followed by heating; And preparing the above-described release film by forming a release layer by coating and drying a composition for forming a release layer comprising a polymer or copolymer including a fluorinated polysiloxane, and organic/inorganic particles on at least one surface of the substrate; Including, the weight ratio of the inorganic particles to the fluorinated silane compound may be 4:1 to 20:1.

The release film prepared by the method for manufacturing a release film according to an embodiment can provide a release film excellent in light peelability, residual adhesion, and coating appearance.

In this case, the solvent used in the composition for forming the release layer may be used without limitation as long as it can be applied on the substrate by dispersing the solid content of the composition for forming the release layer. If the total solids content of the composition for forming the release layer is less than 0.5% by weight, a uniform release layer is not formed and problems such as not being properly peeled between the silicone-based adhesive layer and the release film may occur, and 10% by weight If it exceeds, the viscosity of the composition for forming the release layer may be high, and thus leveling unevenness may occur, and thus the thickness uniformity of the release layer may be deteriorated.

Examples of the solvent used in the composition for forming the release layer include aromatic hydrocarbon-based solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane, isooctane, decane, cyclohexane, methyl cyclohexane and isoparaffin; Hydrocarbon solvents, such as industrial gasoline (rubber gasoline etc.), petroleum benzene, and solvent naphtha; Acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, methyl isobutyl ketone, diisobutyl ketone, acetonyl acetone, cyclohexanone, etc. ketone solvents; ester solvents such as ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, and isobutyl acetate; ether solvents such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, 1,2-dimethoxyethane, and 1,4-dioxane; solvents having ester and ether moieties such as 2-methoxyethyl acetate, 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, and 2-butoxyethyl acetate; siloxane solvents such as hexamethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, decanemethylcyclopentasiloxane, tris(trimethylsiloxy)methylsilane, and tetrakis(trimethylsiloxy)silane; fluorine-based solvents such as trifluorotoluene, hexafluoroxylene, methyl nonafluorobutyl ether, and ethyl nonafluorobutyl ether; Alternatively, a mixed solvent thereof may be used. For example, a mixed solvent of heptane and methyl isobutyl ketone may be used as the solvent used in the composition for forming the release layer.

As a method of applying the composition for forming a release layer on a substrate, an offline coating method available in the art, such as bar coating, gravure coating, and die coating, 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 may be used, and these may be used alone or in combination, but heat treatment alone or combination treatment of heat and ultraviolet light may be used. can

The heating may be performed at 60° C. or higher under an air atmosphere. For example, the heating may be performed at 60° C. or higher in an air atmosphere for 24 hours. When the heating is performed at less than 60° C., it is difficult to introduce a moiety including a fluorine-containing silane compound to the particle surface.

The weight ratio of the inorganic particles to the fluorinated silane compound may be 1:1 to 20:1. If the weight ratio of the inorganic particles to the fluorine-containing silane compound is within the above range, the peeling force may be further lowered to implement better light peelability.

As used herein, "substitution" is derived by exchanging one or more hydrogens with another atom or functional group in an unsubstituted mother group. Unless otherwise stated, when a functional group is considered to be “substituted,” it means that the functional group is 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, or a cyclo group having 3 to 40 carbon atoms. It means substituted with one or more substituents selected from an alkyl group, a cycloalkenyl group having 3 to 40 carbon atoms, and an aryl group having 7 to 40 carbon atoms. When a functional group is described as being “optionally substituted”, it is meant that the functional group may be substituted with the aforementioned substituents.

In the present specification, the C1-C10 monovalent hydrocarbon group includes, for example, a linear alkyl group such as a methyl group, an ethyl group, a hexyl group, an octyl group, and a decyl group; branched alkyl groups such as isopropyl group, tert-butyl group, neopentyl group and hexyl group; Cyclic alkyl groups, such as a cyclopentyl group and a cyclohexyl group, Aryl groups, such as a vinyl group, a henyl group, and a tolyl group, Aralkyl groups, such as a benzyl group and a phenethyl group; means etc. Among them, it may be an alkyl group in consideration of the ease of procurement of raw materials, and may be a methyl group or an ethyl group in consideration of the usefulness of the product.

In the present specification, the C1-C20 alkyl group includes, for example, a linear alkyl group such as a methyl group, an ethyl group, a hexyl group, an octyl group, and a decyl group; It may include an isopropyl group, a tert-butyl group, a neopentyl group, a hexyl group, and the like. Among them, it may be an alkyl group in consideration of the ease of procurement of raw materials, and may be a methyl group or an ethyl group in consideration of the usefulness of the product.

In the present specification, the C2-C10 alkenyl group refers to a branched or unbranched hydrocarbon having at least one carbon-carbon double bond. Non-limiting examples of alkenyl groups include vinyl, allyl, butenyl, isopropenyl, or isobutenyl.

In the present specification, the C1-C20 alkoxy group refers to an alkyl group bonded to oxygen. Non-limiting examples of the alkoxy group include a methoxy group, an ethoxy group, and the like.

Hereinafter, the configuration of the present invention and its effects will be described in more detail through Examples and Comparative Examples. However, it will be apparent that these examples are for illustrating the present invention in more detail, and that the scope of the present invention is not limited to these examples.

[Example]

(Manufacturing of organic and inorganic particles)

Preparation Example 1: Organic-inorganic particles

In 100 g of ethanol, inorganic silica particles (manufactured by ABC Nanotech, SILNOS 160) and triethoxy-1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane (Triethoxy-1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane (manufactured by TCI) was added in a weight ratio of 4:1 and stirred for 15 minutes to obtain a mixture. While the mixture was heated to 60° C., aminosilane (KBP-90, manufactured by ShinEtsu, KBP-90) as a co-reactant was slowly added in an amount of 1/4 based on the weight of inorganic silica particles, and then reacted for 24 hours to obtain a reactant. Then, organic-inorganic particles were prepared by removing the solvent from the reactant through a filter.

Preparation Example 2: Organic-inorganic particles

In 100 g of ethanol, inorganic silica particles (manufactured by ABC Nanotech, SILNOS 160) and triethoxy-1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane (Triethoxy-1H, 1H, 2H, Organic-inorganic particles were prepared in the same manner as in Preparation Example 1, except that 2H-tridecafluoro-n-octylsilane (manufactured by TCI) was added in a 1:1 weight ratio.

Preparation Example 3: Organic-inorganic particles

In 100 g of ethanol, inorganic silica particles (manufactured by ABC Nanotech, SILNOS 160) and triethoxy-1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane (Triethoxy-1H, 1H, 2H, Organic-inorganic particles were prepared in the same manner as in Preparation Example 1, except that 2H-tridecafluoro-n-octylsilane (manufactured by TCI) was added in a weight ratio of 20:1.

Preparation Example 4: Organic and Inorganic Particles

In 100 g of ethanol, silica inorganic particles (manufactured by ABC Nanotech, SILNOS 160) and triethoxy-1H, 1H, 2H, 2H-nonafluorohexylsilane (Triethoxy-1H, 1H, 2H, 2H-nonafluorohexylsilane, TCI (manufactured by TCI) was prepared in the same manner as in Preparation Example 1, except that 4:1 weight ratio was added.

Comparative Preparation Example 1: Inorganic Particles

Silica inorganic particles (manufactured by ABC Nanotech, E540+) were prepared.

Comparative Preparation Example 2: Organic and Inorganic Particles

In 100 g of ethanol, inorganic silica particles (manufactured by ABC Nanotech, SILNOS 160) and triethoxy-1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane (Triethoxy-1H, 1H, 2H, Organic-inorganic particles were prepared in the same manner as in Preparation Example 1, except that 2H-tridecafluoro-n-octylsilane (manufactured by TCI) was added in a weight ratio of 40:1.

Comparative Preparation Example 3: Organic Inorganic Particles

In 100 g of ethanol, inorganic silica particles (manufactured by ABC Nanotech, SILNOS 160) and trimethoxy-3, 3, 3-trifluoropropylsilane (manufactured by TCI) were added as a fluorinated silane compound. Organic-inorganic particles were prepared in the same manner as in Preparation Example 1, except that they were added in a 4:1 weight ratio.

Comparative Preparation Example 4: Organic and Inorganic Particles

In 100 g of ethanol, inorganic silica particles (manufactured by ABC Nanotech, SILNOS 160) and trimethoxy-3, 3, 3-trifluoropropylsilane (manufactured by TCI) were added as a fluorinated silane compound. Organic-inorganic particles were prepared in the same manner as in Preparation Example 1, except that they were added in a 1:1 weight ratio.

(Release film)

Example 1: Release film

A 38 μm thick polyester film (Toray Advanced Materials, XD500P) was prepared.

Separately, 100 parts by weight of an organopolysiloxane (Dow Chemical, Q2-7785) represented by the following formula (3) containing a fluorinated alkyl group represented by the following formula (4), hydrogen polysiloxane (Dow Chemical, Q2-7560) 3 parts by weight, 1 part by weight of a platinum chelate catalyst (manufactured by Dow Chemical, SYL-OFF 4000) was diluted in a mixed solvent of heptane and methyl isobutyl ketone (5:1 volume ratio) to prepare a composition having a total solid content of 5% by weight Then, a composition for forming a release layer was prepared by mixing the organic-inorganic particles prepared in Preparation Example 1 here in an amount of 1% by weight based on the total solid content.

A release film was prepared by coating the composition for forming a release layer on one side of the polyester film and heat-treating it for 2 minutes in a hot air dryer at 150° C. to form a release layer with a thickness of 0.3 μm:

<Formula 3>

<Formula 4>

during the meal,

R ₁ is a vinyl group, R ₂ is a methyl group, and R ₃ is a fluorinated alkyl group represented by Formula 4 above;

n=4, m is 2, and * is a binding site with a neighboring atom.

Examples 2-4: release film

A release film was prepared in the same manner as in Example 1, except that the organic/inorganic particles prepared in Preparation Examples 2 to 4 were used instead of the organic/inorganic particles prepared in Preparation Example 1.

Comparative Examples 1-4: release film

Instead of the organic-inorganic particles prepared by Preparation Example 1 A release film was prepared in the same manner as in Example 1, except that the (organic) inorganic particles prepared in Comparative Preparation Examples 1 to 4 were used.

Analysis Example 1: IR spectrum

Inorganic silica particles as a starting material of the release film prepared in Example 1, inorganic silica particles in which aminosilane is introduced on the surface as an intermediate reactant, and inorganic silica particles in which aminosilane and fluorine-containing silane compounds are introduced on the surface as a final product The IR spectrum was analyzed for Here, IR spectrum analysis was performed using FT-IR manufactured by PerkinElmer. The IR spectrum analysis result is shown in FIG. 2 .

Referring to FIG. 2 , as for the final result, the silica inorganic particles introduced with aminosilane and fluorinated silane compounds have a peak in the range of 1064 to 1066 cm ⁻¹ wavelengths in the range of the inorganic silica particles as the starting material and amino on the surface as the intermediate reactant. It can be confirmed that the silane is shifted to the right compared to the silica inorganic particles introduced.

Evaluation Example 1: Physical property evaluation

The physical properties of the (organic) inorganic particles prepared in Preparation Examples 1 to 4 and Comparative Examples 1 to 4 and the release film prepared in Examples 1 to 4 and Comparative Examples 1 to 4 were evaluated in the following way, The results are shown in Table 1.

(1) XPS analysis of (organic) inorganic particles

For each (organic) inorganic particle, the atomic composition of Si, F, C, and O was analyzed using XPS analyzer (ThermoFisher, K-ALPHA) and expressed in atomic%, and the content ratio of F/Si element (M _F /M _Si ) was calculated.

(2) EDAX analysis of (organic) inorganic particles

For each (organic) inorganic particle, the atomic composition of Si, F, C, O was analyzed using an EDAX analyzer (Hitachi, S-4800) and expressed in atomic percent, and the content ratio of F/Si elements (M _F /M _Si ) was calculated.

(3) Measurement of peel force of release film

Each release film was cut into a size of 500 mm x 1500 mm to prepare a sample. The samples were stored at 25° C., 65% RH for 24 hours. After that, the silicone-based adhesive tape (Nitto, 903UL) was pressed on the release layer of the samples for 24 hours at 50° C. under a load of 20 g/cm ² , and then, using a cheminstrument AR-2000 device, 180°, 250 mm at a rate of 0.3 mpm The peel force of the size of x 1500 mm was measured. At this time, the peel force was obtained by calculating the average value after measuring 5 times.

(4) Analysis of residual adhesion rate of release film

Each release film was cut into a size of 500 mm x 1500 mm to prepare a sample. The samples were stored at 25° C., 65% RH for 24 hours. After pressing the adhesive tape (Nitto, 31B) on the release layer of the samples at room temperature and under a load of 20 g/cm ² for 24 hours, the adhesive tape adhered to the release layer was collected without contamination. The adhesive tape was adhered to the surface of the polyethylene terephthalate film with a flat and clean surface. The adhesive tape adhered to the surface of the polyethylene terephthalate film was reciprocally compressed once with a 2 kg tape roller (ASTMD-1000-55T), and using a cheminstrument AR-2000 device at 180°, 0.3 mpm speed 250 mm x 1500 mm After measuring the peel force of the size, the residual adhesion rate was obtained by substituting it in Equation 2 below.

[Equation 2]

Residual adhesion rate (%) = [(Peel force of adhesive tape peeled after adhesion to release layer)/(Peel force of adhesive tape not in contact with release layer) x 100]

(5) Appearance evaluation of the release layer

Each release film was prepared as an A4 size sample, placed on a black bottom evaluation plate, and cratering and appearance defects of the release layer were checked and recorded under a fluorescent lamp.

○: 2 crater rings or less

△: 3 to 5 craters

X: more than 5 craters

F/Si element content ratio (M _F /M _Si ) peel force
(gf/25mm) Residual Adhesion
(%) Appearance evaluation XPS analysis EDAX analysis Example 1 0.58 0.6 22 92 ○ Example 2 0.85 0.8 21 90 ○ Example 3 0.21 0.18 23 94 ○ Example 4 0.4 0.32 23 93 ○ Comparative Example 1 - - 25 93 ○ Comparative Example 2 0.07 0.07 25 94 ○ Comparative Example 3 0.03 0.03 25 94 ○ Comparative Example 4 0.05 0.05 25 92 ○

Referring to Table 1, in the organic/inorganic particles prepared by Preparation Examples 1 to 4 included in the release film prepared in Examples 1 to 4, the content ratio of F/Si element is within the range of 0.1 to 1.0, and Example 1 It can be seen that the peeling force (light-peelability) of the release film prepared by ˜4 is superior to that of the release film prepared by Comparative Examples 1-4. In addition, it can be confirmed that the residual adhesion rate and the coating appearance of the release films prepared in Examples 1 to 4 are excellent. In comparison, it can be seen that the release film prepared in Comparative Examples 1 to 2 has a higher peel strength compared to the release film prepared in Examples 1 to 4. It can be seen that the organic-inorganic particles prepared by Comparative Preparation Examples 3 to 4 included in the release film prepared by Comparative Examples 3 to 4 had a content ratio of F/Si element less than 0.1 and high peel strength.

100: substrate, 110: release layer, 120: release film

Claims (13)

The substrate and the release layer are sequentially positioned,
The surface energy of the release layer is 24 dyne / cm or less,
The release layer includes organic and inorganic particles,
In the organic-inorganic particles, a moiety including a fluorine-containing silane compound is introduced on the surface,
A release film in which the organic-inorganic particles satisfy the content ratio (M _F /M _Si ) range of the F/Si element represented by the following formula 1:
[Equation 1]
0.1 _≤ M _F /M _{Si ≤} 1.0
during the meal,
M _F is the content of element F (atomic %), and M _Si is the content of element Si (atomic %). The method of claim 1,
A release film, wherein the fluorinated silane compound moiety comprises a fluorinated silane compound represented by the following formula (1):
[Formula 1]
*-OSi(R _a )(R _b )(R _c )
during the meal,
R _a , R _b are a substituted or unsubstituted C1-C20 alkoxy group;
R _c is represented by the following formula (2),
* denotes a binding site with the surface of an organic/inorganic particle.
[Formula 2]

during the meal,
R _d is a hydrogen atom or a substituted or unsubstituted C1-C20 alkyl group;
R _e , R _g is a substituted or unsubstituted C1-C20 alkoxy group;
R _f is a C4-C20 alkyl group substituted with fluorine;
n ₁ is an integer from 1 to 10;
* is a bonding site with an Si atom. The method of claim 1,
The weight ratio of the organic-inorganic particles to the fluorinated silane compound is 1:1 to 20:1, a release film. The method of claim 1,
In the release layer, a peak in the range of 1064 to 1066 cm ^-1 wavelengths in the IR spectrum is shifted to the right compared to organic/inorganic particles that do not contain a fluorinated silane compound moiety on the surface thereof, the release film. The method of claim 1,
The organic-inorganic particles are natural minerals; oxides, hydroxides, sulfides, nitrides, or halides of elements of Groups 1 to 4, 11 to 12, 14 and 16 to 18; carbonate, sulfate, acetate, phosphate, phosphite, carboxylate, silicate, titanate, borate, or hydrates thereof; and an inorganic particle selected from these complex compounds, a release film. The method of claim 1,
The release film, wherein the release layer further comprises a polymer or copolymer including a fluorinated polysiloxane. 7. The method of claim 6,
A release film, wherein the fluorinated polysiloxane comprises an organo polysiloxane represented by the following formula (3):
<Formula 3>

<Formula 4>

<Formula 5>

during the meal,
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-C10 monovalent hydrocarbon group, a substituted or unsubstituted C2-C10 alkenyl group, or hydrogen;
R ₃ is a fluorinated alkyl group represented by Formula 4, a fluorinated ether group represented by Formula 5, or a combination thereof;
n is an integer from 1 to 8, m is an integer from 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 an oxygen atom or a single bond;
x, y, and z are each an integer greater than or equal to 1;
* is a binding site with a neighboring atom;
However, at least one of R ₁ and R ₂ is a substituted or unsubstituted C2~C10 alkenyl group. The method of claim 1,
The release layer further comprises at least one of a hydrogen polysiloxane (hydrogen polysiloxane) and an acid catalyst. The method of claim 1,
The peeling force of the release film is 23 gf / 25 mm or less, the release film. The method of claim 1,
A release film having a residual adhesion rate of 90% or more of the release film. preparing a substrate;
preparing organic/inorganic particles by adding and stirring inorganic particles, a fluorinated silane compound, and an aminosilane-based co-reactant, followed by heating; and
Preparing the release film according to claim 1 by coating and drying a composition for forming a release layer comprising a polymer or copolymer including a fluorinated polysiloxane and organic/inorganic particles on at least one surface of the substrate to form a release layer including;
The weight ratio of the inorganic particles to the fluorinated silane compound is 4:1 to 20:1, the method for producing a release film. 12. The method of claim 11,
The heating is carried out at 60 ℃ or higher under an air atmosphere, a method for producing a release film. 12. The method of claim 11,
A method for producing a release film, wherein the weight ratio of the inorganic particles to the fluorinated silane compound is 1:1 to 20:1.

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