KR101978033B1 - Released film - Google Patents

Abstract

상기 화학식 4에서 R₁ 및 R₂는 독립적으로 탄소 원자 1~33개의 알킬기나 알케닐기이고, R₃는 H, CH₃ 또는 CH₃CH₂이고, R₄는 N, O, F, P, S 또는 Cl을 포함하는 기능기이며, m 과 n은 각각 1~4의 정수이다.According to an embodiment of the present invention, a base layer comprising a polyester, and a release layer located on at least one surface of the base layer, the release layer is an alkenyl polysiloxane, hydropolysiloxane, platinum catalyst and the following formula It provides a release film formed of a release composition comprising a surfactant represented by 4.
[Formula 4]

In Formula 4, R ₁ and R ₂ are independently an alkyl or alkenyl group having 1 to 33 carbon atoms, R ₃ is H, CH ₃ or CH ₃ CH ₂ , and R ₄ is N, O, F, P, S Or a functional group containing Cl, m and n are each an integer of 1-4.

Description

Release film {RELEASED FILM}

The present invention relates to a release film, and more particularly, to a release film having improved wettability, peeling force, and residual adhesion rate.

A release film means the film which has a mold release property which does not adhere well to an adhesive component, and adheres with protective films, such as an adhesive film and a tape. The release film is mainly used to prevent the adhesive from adhering to unintended adherends or to prevent contamination by foreign matters, and to prevent molds and moldings from sticking in the heating and pressure forming processes, or thin ceramic sheets such as dielectrics for laminated ceramic capacity. It is also used as a carrier film for shape | molding etc.

The release film is generally formed of a silicone release composition comprising a silicone backbone, a silicone curing agent, a silane coupling agent, a surfactant, a catalyst, and the like.

When the release film is coated on a substrate, which is a silicone release composition, due to a compatibility problem between a solvent such as silicone and water, the liquid spreading and wetting may be poor, resulting in poor coating properties such as poor appearance and adhesion after coating.

Accordingly, when the release film is manufactured using the silicone release composition, there is an increasing need for development of a release film technology having excellent peeling force and residual adhesiveness, which are basic characteristics of the release film, and excellent coating appearance and adhesion.

The technical problem to be solved by the present invention is to provide a release film excellent in peel strength and residual adhesion, but also excellent coating appearance and adhesion.

In order to solve this problem, according to an embodiment of the present invention, a base layer comprising a polyester, and a release layer located on at least one surface of the base layer, the release layer is alkenyl polysiloxane, hydropolypolysiloxane It provides a release film formed of a release composition comprising a platinum catalyst and a surfactant represented by the following formula (4).

[Formula 4]

In Formula 4, R ₁ and R ₂ are independently an alkyl or alkenyl group having 1 to 33 carbon atoms, R ₃ is H, CH ₃ or CH ₃ CH ₂ , and R ₄ is N, O, F, P, S Or a functional group containing Cl, m and n are each an integer of 1-4.

The surfactant may include less than 5 parts by weight of 0.01 parts by weight or more based on 100 parts by weight of the alkenyl polysiloxane.

The alkenyl polysiloxane may include a compound represented by the following Formula 1.

[Formula 1]

In Formula 1, R ₁ , R _2, and R ₃ are independently —CH ₃ , —CH═CH ₂ , —CH ₂ CH═CH _2, and — (CH ₂ ) ₄ CH = CH ₂ . It is a nil group, m and n are the integers of 10-500, respectively.

The hydropolysiloxane may include a compound represented by the following Formula 2.

[Formula 2]

In Formulas 2 and 3, a and b are each an integer of 1 to 100.

The hydropolysiloxane may include 2 to 10 parts by weight based on 100 parts by weight of the alkenyl polysiloxane.

The platinum catalyst may include 1 ~ 500ppm relative to the entire release layer.

The release layer further includes a peel force adjusting agent, and the peel force adjusting agent may include at least one of compounds represented by the following Chemical Formulas 3-1 to 3-4.

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

In Formulas 3-1 to 3-3, R ₄ is at least one of methyl, ethyl, hexyl, vinyl, hexenyl, phenyl, hydroxyl, methoxy, and ethoxy.

The release composition may include 0.5 to 15% by weight of solids and the remaining amount of water relative to the total weight of the release composition.

The thickness of the base layer is 15 ~ 300㎛, the thickness of the release layer may be 0.01 ~ 10㎛.

According to the release film according to an embodiment of the present invention as described above, while excellent in the peel force and the residual adhesion rate, it is excellent in coating appearance and adhesion.

1 is a cross-sectional view of a release film according to an embodiment of the present invention.

DETAILED DESCRIPTION Embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.

In the drawings, the thickness of layers, films, panels, regions, etc., are exaggerated for clarity. Like parts are designated by like reference numerals throughout the specification. When a part of a layer, film, region, plate, etc. is said to be "on" another part, this includes not only the other part being "right over" but also another part in the middle. On the contrary, when a part is "just above" another part, there is no other part in the middle.

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. Also, 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.

Hereinafter, a release film according to an embodiment of the present invention will be described in detail with reference to FIG. 1.

1 is a cross-sectional view of a release film according to an embodiment of the present invention.

Referring to FIG. 1, a release film according to an embodiment of the present invention includes a base layer 20 and a release layer 10 positioned on at least one surface of the base layer 20.

That is, the release layer 10 may be located only on one surface of the base layer 20, or may be located on both sides of the base layer 20.

The base layer 20 may be formed of a transparent material to sufficiently transmit visible light, and may be a biaxially stretched polyester film including polyester.

The polyester included in the base layer 20 may be formed by polymerizing dicarboxylic acid and glycol.

Here, dicarboxylic acid is a terephthalic acid, naphthalenedicarboxylic acid, isophthalic acid, diphenyl carboxylic acid, diphenyl sulfone dicarboxylic acid, diphenoxy ethane dicarboxylic acid, 5-sodium sulfone dicarboxylic acid, phthalic acid, etc. Such as aromatic dicarboxylic acids, alicyclic dicarboxylic acids such as aliphatic dicarboxylic acids such as hydroxyl, succinic acid, adipic acid, sebacic acid, dima acid, maleic acid, and fumaric acid, and cyclohexane dicarboxylic acid, and paraoxybenzoic acid; Oxycarboxylic acid and the like.

In addition, glycols are aliphatic glycols such as ethylene glycol, propanediol, butanediol, pentanediol, hexanediol and neopentin glycol, polyoxyalkylene glycols such as diethylene glycol, polyethylene glycol, and polypropylene glycol, cyclohexane dimethanol, and the like. Cycloaliphatic glycols, aromatic glycols such as bisphenol A, bisphenol S, and the like can be used.

The base layer 20 may preferably include a polyester formed by using terephthalic acid or naphthalenedicarboxylic acid as dicarboxylic acid and polymerizing ethylene glycol as glycol, but is not limited thereto. Polyesters.

In addition, the substrate layer 20 may further include particles as necessary for improving the properties of the polyester film.

The thickness of the base layer 20 may be 15 ~ 300㎛, when the thickness of the base layer 20 is less than 15㎛ may be a deformation degree by the external force may be unsuitable as a carrier film, more than 300㎛ This is because the economy can be reduced.

The release layer 10 may be located on at least one surface of the base layer 20.

The release layer 10 according to the embodiment of the present invention may be formed of a release composition including alkenyl polysiloxane, hydropolysiloxane, platinum catalyst and a surfactant.

Alkenyl polysiloxane may be a compound represented by the following formula (1).

R ₁ , R ₂ and R ₃ in Formula 1 are each independently an alkyl or alkenyl group of any one of -CH ₃ , -CH = CH ₂ , -CH ₂ CH = CH ₂ and-(CH ₂ ) ₄ CH = CH ₂ . M and n are each an integer of 10-500.

Here, m and n does not mean a block bond, but means that the sum of the units is m and n, and each unit in Formula 1 may be a random bond or a block bond. In addition, two or more alkenyl groups may be present.

Hydrogen polysiloxane may be a compound represented by the following formula (2).

In Formula 2, a and b are each an integer of 1 to 100.

Here, a and b does not mean a block bond, but means that the sum of the units is a and b, and each unit in Formula 2 may be a random bond or a block bond.

Hydrogen polysiloxane may include 2 to 10 parts by weight, and preferably 4 to 6 parts by weight based on 100 parts by weight of alkenyl polysiloxane.

This may cause process contamination when the unreacted alkenyl polysiloxane is transferred to another layer such as the back side or the adhesive layer of the release film when the hydropolysiloxane is less than 2 parts by weight, and when it is more than 10 parts by weight, the unreacted hydropolypolysiloxane This is because it may remain in the release layer 10 and the peeling force may not only increase, but the peeling force may increase with time, and thus it is difficult to have stable release properties.

Here, the alkenyl polysiloxane represented by the general formula (1), the hydroelectric polysiloxane represented by the general formula (2) may be in the form of at least one of linear, branched, radial and cyclic.

The peel force control agent included in the release layer 10 according to the embodiment of the present invention is an organopolysiloxane resin containing a hydroxyl group, and at least one of the compounds represented by the following Chemical Formulas 3-1 to 3-4 It may include. The compounds represented by the formulas 3-1 to 3-4 may have a repeating structure in a linear, branched, radial and cyclic manner.

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

In Formulas 3-1 to 3-3, R ₄ may be at least one of methyl, ethyl, hexyl, vinyl, hexenyl, phenyl, hydroxyl, methoxy and ethoxy.

The platinum catalyst included in the release layer 10 serves to help the addition reaction of alkenyl polysiloxane and hydropolysiloxane, and may include 1 to 500 ppm relative to the entire release layer 10, and preferably 5 to 500 ppm. It may include.

This is because when the platinum catalyst content is less than 1 ppm, the reaction between the alkenyl polysiloxane and the hydropolypolysiloxane may not proceed sufficiently, and when the platinum catalyst content is higher than 500 ppm, the peeling force may be increased by the platinum catalyst remaining in the release layer 10. to be.

Next, the surfactant included in the release layer 10 may be a compound represented by the following formula (4).

R ₁ and R ₂ in Formula 4 are independently an alkyl or alkenyl group having 1 to 33 carbon atoms, R ₃ is H, CH ₃ or CH ₃ CH ₂ , and R ₄ is N, O, F, P, S or It is a functional group containing Cl, and m and n are the integers of 1-4, respectively.

Here, m and n does not mean a block bond, but means that the sum of the units is m and n, and each unit in Formula 1 may be a random bond or a block bond.

Preferably, R1 and R2 are independently a branched alkyl group of 6 to 16 carbon atoms, R3 is a hydrogen group, R ₄ is an alkyl or alkenyl group of 1 to 11 carbon atoms including N, O, P or S M and n may each be 1;

The surfactant may be included in an amount of 0.01 parts by weight or more and less than 5 parts by weight with respect to 100 parts by weight of alkenyl polysiloxane, and preferably, 0.05 to 1 part by weight.

This is because when the surfactant is less than 0.01 parts by weight, the content is not sufficient to serve as a surfactant, so that the coating appearance improvement effect of the release film is less likely to appear, and when the amount exceeds 5 parts by weight, the peeling force may increase.

The release layer 10 of the release film according to an embodiment of the present invention is applied to the base material layer at least once through a known method such as a bar coating method, a reverse roll coating method, a gravure roll coating method, etc. Can be formed.

The release composition may include 0.5 to 15% by weight of solids and the balance of water relative to the total weight of the release composition.

When the solid content is less than 0.5% by weight, it may be difficult to obtain a uniform coating, and at the same time, the peeling force may increase, and when the content of the solid content is more than 15% by weight, the coating appearance is poor and the release layer 10 and the base layer 20 This is because the adhesion between the liver may be reduced.

In addition, the release composition according to an embodiment of the present invention may further include an organic solvent of 10% by weight or less, preferably 5% by weight or less relative to the total weight of the release composition for improving applicability or transparency.

This is because when the release composition contains more than 10% by weight of the organic solvent, there is a risk of explosion in the drying, stretching and heat treatment process when using the in-line coating method or the like.

The organic solvent may include isopropyl alcohol, butyl cellosolve, ethyl cellosolve, acetan, methanol, ethanol and the like.

The surface tension of the base layer layer 20 may be 1.0 to 1.5 times that of the release composition, which may be difficult to obtain a uniform release layer 10 when the surface tension of the base layer 20 is less than 1.0, resulting in poor wetting. If it is exceeded, aggregation of the release composition may occur, which may result in appearance defects.

Release layer 10 according to an embodiment of the present invention may be formed to a thickness of 0.01 ~ 10㎛.

If the thickness of the release layer 10 is less than 0.01 μm, the uniform release layer 10 may not be formed. If the release layer 10 is larger than 10 μm, the release layer 10 may be formed between one surface and a back surface of the base layer 20 on which the release layer 10 is formed. This is because blocking may occur.

Hereinafter, the configuration and effects of the present invention will be described in more detail with reference to Examples and Comparative Examples. However, this embodiment is intended to illustrate the present invention in more detail, and the scope of the present invention is not limited to these examples.

Example 1

5 parts by weight of hydropolysiloxane represented by Formula 2 to 100 parts by weight of alkenyl polysiloxane (Dow Corning, Shin-Etsu) represented by Formula 1 on one surface of a corona-treated polyester film (Toray Advanced Materials, Excell-50㎛) Corning, Shin-Etsu), 25 ppm of a platinum catalyst (Dow Corning, Shin-Etsu) and 0.2 weight part of surfactant (sodium dioctyl sulfosuccinate) represented by General formula (4) were made into the aqueous emulsion state, and apply | coated.

Then, it dried for 50 second at 180 degreeC, and manufactured the release film.

Example 2

A release film was prepared in the same manner as in Example 1, except that sodium dioctyl 2- (sulfoethyl) succinate was used as the surfactant.

Example 3

A release film was prepared in the same manner as in Example 1, except that sodium dioctyl 2- (phosphoethyl) succinate was used as the surfactant.

Example 4

A release film was prepared in the same manner as in Example 1 except that dioctyl 2- (hydroxyethyl) succinate was used as the surfactant.

Example 5

A release film was prepared in the same manner as in Example 1, except that 0.02 parts by weight of the surfactant was used.

Example 6

A release film was prepared in the same manner as in Example 1, except that 2 parts by weight of the surfactant was used.

Example 7

A release film was prepared in the same manner as in Example 1, except that 8 parts by weight of polysiloxane was used.

Example 8

A release film was prepared in the same manner as in Example 1, except that the release composition further included 25 parts by weight of a peel force adjusting agent including the compound represented by Formula 3-4.

Comparative Example 1

A release film was prepared in the same manner as in Example 1, except that 0.002 parts by weight of sodium dioctyl 2- (sulfo) succinate was used as the surfactant.

Comparative Example 2

A release film was prepared in the same manner as in Example 1, except that 5 parts by weight of sodium dioctyl 2- (sulfo) succinate was used as the surfactant.

Comparative Example 3

A release film was prepared in the same manner as in Example 1, except that 0.02 parts by weight of a silicone-based surfactant (Dow Corning, Shin-Etsu) was used as the surfactant.

Comparative Example 4

A release film was manufactured in the same manner as in Example 1, except that 2 parts by weight of a silicone-based surfactant (Dow Corning, Shin-Etsu) was used as the surfactant.

Comparative Example 5

A release film was prepared in the same manner as in Example 1, except that sodium dimethyl 2- (sulfoethyl) succinate was used as the surfactant.

Comparative Example 6

A release film was prepared in the same manner as in Example 1, except that sodium dipetyl 2- (sulfoethyl) succinate was used as the surfactant.

Comparative Example 7

A release film was prepared in the same manner as in Example 1, except that 1 part by weight of polyhydrogen polysiloxane was used.

Comparative Example 8

A release film was prepared through the same process as in Example 1, except that 12 parts by weight of polysiloxane was used.

Experimental Example

(1) Peel force measurement

After attaching the release film to the cold rolled stainless steel plate with the double-sided adhesive tape up, the adhesive tape (TESA 7475) was put on the release layer and pressed with a 2kg compression roller, left at room temperature for 1 to 7 days, then peeled off. Force was measured.

Peel force was measured using AR-1000 (Chem-Instrument) at a peel angle of 180 ° and a peel rate of 0.3 mpm, and the average value (g / inch) was measured five times, rounded off to one decimal place.

(2) measuring residual adhesion rate

An adhesive tape (Nitto 31B) was placed on the release layer, pressed with a 2 kg pressing roller, and allowed to stand at room temperature for 30 minutes. After peeling the adhesive tape from the release layer, the adhesive tape was attached to a cold rolled stainless plate and the peel force was measured.

In addition, the adhesive tape (Nitto 31B), which has never been used for comparison, was attached to a cold rolled stainless steel plate, and the peel force was measured.

Peel force was measured using AR-1000 (Chem-Instrument) at a peel angle of 180 ° and a peel rate of 0.3 mpm, and was measured five times to calculate an average value.

The residual adhesion rate was calculated according to the following equation.

[Equation 1]

Residual adhesion rate = Peel force of the adhesive tape peeled from the release layer / Peel force of the adhesive tape never used Ⅹ 100 (%)

(3) coating appearance measurement

The area of the bubble defects relative to the area of the release film sample of 5 cm × 5 cm was measured.

The longest length of the bubble defects in the release film sample of 5 cm × 5 cm was measured, and the area was calculated from a circle, and the total was summed to obtain the area (cm ² ) of the bubble defects.

The degree of foaming defect was calculated according to the following equation.

[Equation 2]

Foaming defect (%) = area of foaming defect / 25cm ² X 100

When the degree of foaming defect is 0% or more and less than 1%, it is indicated by ◎, 1% or more and less than 2%, ○, 2% or more and less than 5%, △, and 5% or more and less than 100%, respectively.

The results according to the experimental example are shown in Table 1 below.

division Peel force
(g / in) Residual adhesion
(%) Bubble defect
(%) Stain level Example 1 15 93 ◎ Great Example 2 15 92 ◎ Great Example 3 15 93 ◎ Great Example 4 15 92 ◎ Great Example 5 15 94 ◎ Great Example 6 13 87 ◎ Great Example 7 18 97 ◎ Great Example 8 27 93 ◎ Great Comparative Example 1 15 90 Ｘ Bad Comparative Example 2 10 70 △ Inadequate Comparative Example 3 18 89 Ｘ Bad Comparative Example 4 9 62 Ｘ Bad Comparative Example 5 17 88 Ｘ Bad Comparative Example 6 30 75 Ｘ Bad Comparative Example 7 10 61 ◎ Great Comparative Example 8 68 96 ◎ Great

As shown in Table 1, it was confirmed that the release films of Examples 1 to 8 had almost no foaming defects and had excellent coating appearance, but had a good peel strength, and also had excellent residual adhesion.

In addition, in the case of Example 8 it was confirmed that the peeling force control is also possible when adding the peeling force regulator.

On the contrary, in the release films of Comparative Examples 1 and 2, the content of the surfactant was too small or too much to cause a lot of bubble defects, so that the coating appearance was not improved, and the release films of Comparative Examples 3 and 4 were examples of the present invention. Unlike the conventional silicone-based surfactant was applied to the bubble defects were confirmed that the appearance of the coating was poor.

In addition, the release films of Comparative Examples 5 and 6 showed poor foam appearance due to the poor solubility of the surfactant in the release composition, resulting in poor coating appearance, and the release films of Comparative Examples 7 and 8 contained the content of hydropolysiloxane. Too little or too much, it was confirmed that the release properties such as the peeling force is excessively increased, the residual adhesion rate is excessively lowered.

According to the release film according to the embodiment of the present invention as described above, while excellent in the peel force and residual adhesion rate, the coating appearance and adhesion is excellent.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to the scope of rights.

10: release layer 20: substrate layer

Claims (9)

A base layer comprising polyester, and
It includes a release layer located on at least one side of the base layer,
The release layer is formed of a release composition comprising an alkenyl polysiloxane, hydropolysiloxane, platinum catalyst and a surfactant represented by the following formula (4),
The surfactant includes 0.01 part by weight or more and less than 5 parts by weight with respect to 100 parts by weight of the alkenyl polysiloxane,
The release film has a thickness of 15 to 300 μm, and the release layer has a thickness of 0.01 to 10 μm.
[Formula 4]

In Formula 4, R ₁ and R ₂ are independently an alkyl or alkenyl group having 1 to 33 carbon atoms, R ₃ is H, CH ₃ or CH ₃ CH ₂ , and R ₄ is N, O, F, P, S Or a functional group containing Cl, m and n are each an integer of 1-4. delete In claim 1,
The alkenyl polysiloxane is a release film containing a compound represented by the following formula (1).
[Formula 1]

In Formula 1, R ₁ , R _2, and R ₃ are independently —CH ₃ , —CH═CH ₂ , —CH ₂ CH═CH _2, and — (CH ₂ ) ₄ CH = CH ₂ . It is a nil group, m and n are the integers of 10-500, respectively. In claim 3,
The release polysiloxane is a release film containing a compound represented by the following formula (2).
[Formula 2]

In Formula 2, a and b are each an integer of 1 to 100. In claim 1,
The release polysiloxane is a release film containing 2 to 10 parts by weight based on 100 parts by weight of the alkenyl polysiloxane. In claim 1,
The platinum catalyst is a release film containing 1 ~ 500ppm relative to the entire release layer. In claim 1,
The release layer further includes a peel force control agent,
The release force control agent is a release film containing at least one of the compounds represented by the following formulas 3-1 to 3-4.
[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

In Formulas 3-1 to 3-3, R ₄ is at least one of methyl, ethyl, hexyl, vinyl, hexenyl, phenyl, hydroxyl, methoxy, and ethoxy. In claim 1,
The release composition is a release film containing 0.5 to 15% by weight of solids and the residual amount of water relative to the total weight of the release composition. delete

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