KR101044957B1 - Water-dispersed silicone releasing liquid and polyester releasing film using them - Google Patents

Abstract

The present invention relates to a water-dispersible silicone release liquid and a polyester release film using the same.

The aqueous silicone release liquid of the present invention is composed of a mixed component consisting of polydimethylsiloxane and a hydrogen silane compound, a platinum catalyst-containing compound, an acetylene compound, and water, and is prepared according to an organic solvent using water as a solvent. As the process is environmentally friendly, and the acetylene-based compound of a specific structure is applied to reduce the surface energy of the water-dispersed silicone release liquid, coating properties and surface roughness may be improved when applied to the base film.

In addition, the polyester release film to which the water-dispersible silicone release solution of the present invention is applied is capable of low surface roughness and thin film molding of the release layer, and when the sheets are laminated on the release layer, the moldability is excellent and the peeling between the release layer and the sheet is performed. Its low power makes it particularly useful as a multilayer ceramic capacitor.

Water dispersion, silicone release liquid, release film, ceramic sheet, capacity

Description

Water-dispersible silicone release liquid and polyester release film using same {WATER-DISPERSED SILICONE RELEASING LIQUID AND POLYESTER RELEASING FILM USING THEM}

The present invention relates to a water-dispersible silicone release liquid and a polyester release film using the same, and more particularly, to uniform coating in the form of an aqueous dispersion in which a polydimethylsiloxane, a hydrogen silane compound and an acetylene compound of a specific structure are dispersed in water. It relates to a water-dispersible silicone release liquid having excellent properties and a polyester release film using the same.

In general, a release film having a release layer formed on a polyester base film such as polyethylene terephthalate and polyethylene naphthalate is used as a mount such as an adhesive label or an adhesive tape, and a multilayer ceramic capacitor (hereinafter referred to as multi-layer ceramic capacitor): In the ceramic thin film constituting the 'MLCC') is used as a support for applying a thin and uniform ceramic slurry (Slury).

MLCC is a type of capacitor (battery battery) generally used to accumulate electricity or stabilize current, and is widely used in various portable devices due to its small size and large capacitance.

Recently, as portable electronic devices such as mobile phones, MP3 players, and PMPs are widely used, the demand for multilayer ceramic capacitors is expanding. In particular, the use of mobile phones is about 250 MLCCs per unit.

MLCC is completed by stacking ceramic thin films and internal metal electrodes in alternating tens to hundreds of layers and connecting external electrodes. The size varies from less than 1 mm to several mm and is becoming smaller. The ceramic sheet used in MLCC is formed by uniformly applying a ceramic slurry on a carrier film as a support and then baking. The carrier film for forming a thin ceramic sheet has excellent mechanical strength, dimensional stability, heat resistance, and price competitiveness. Release films in which a polymer silicone resin film is provided on at least one side of a biaxially stretched polyester film are used.

Recently, in accordance with the trend of miniaturization and high capacity of MLCC, it is required to make the thickness of the ceramic sheet thinner and to laminate it in multiple layers. More specifically, the ceramic sheet has a thickness of 2 to 30 µm, and a ceramic sheet having a thickness of 1 µm or less. The situation is also being examined. Accordingly, in order to form a thin ceramic sheet, a surface having a flat surface can be uniformly formed, and a release film having a low peeling force is required so that the ceramic sheet is not damaged in the process of peeling the ceramic sheet. Conventional techniques for molding ceramic sheets include Korean Patent Nos. 0633230, 0662324, and Korean Patent Publication No. 2006-0126437. Due to the recent trend of thinning ceramic sheets, a release film having a lower peeling force is required.

In particular, the conventional release film commercially available has a high peel force under high-speed peeling conditions, there is a problem that the ceramic sheet is not peeled partially or entirely during the process.

In addition, safety requirements in the manufacturing process of the release film is also a requirement. In general, a release solution in which alcohol, toluene, and ketone are used as a solvent for forming a release layer of an MLCC release film is not used, and thus the environment and work safety are not considered. to be. In particular, solvents such as toluene and ketone are known to act as carcinogens or environmental hormones, and in addition to the spread of the social atmosphere requiring regulation on many organic solvents, development of release liquids using non-hazardous solvents is required. It is becoming.

Examples of release films using water as a solvent include Korean Patent Nos. 502862 and 0519952, but since the uniformity of the release layer is poor and the surface roughness is high, the moldability of the ceramic sheet is low, so it is used in the MLCC ceramic sheet manufacturing process. Not suitable for

Thus, the present inventors have made efforts to solve the problems of the prior art, to produce a water-dispersible silicone release liquid containing a specific compound, it was confirmed that the low peel force and moldability of the polyester release film to which the release liquid is applied. By this, the present invention was completed.

An object of the present invention is to provide a water-dispersible silicone release liquid having excellent coating uniformity.

Another object of the present invention is to apply the release liquid, to provide a polyester release film with improved low peel force and moldability of the release layer.

In order to achieve the above object, the present invention is 1 to 40% by weight of a mixed component consisting of a polydimethylsiloxane represented by the following formula (1) and a hydrogen silane compound represented by the following formula (2), 0.01 to 10% by weight of a platinum catalyst-containing compound, It provides a water-dispersed silicone release solution consisting of 0.001 to 1.0% by weight of an acetylene compound and a residual amount of water.

(In the above, m is an integer of 1 to 100, n is an integer of 20 to 5000, and m + n is 30 to 5000.)

(In the above, a is an integer of 3 to 200, b is an integer of 1 to 120, and 5≤a + b≤200.)

An acetyl diol may be used in which the acetylene compound has an ethoxylate functional group represented by Formula 3 below.

(Wherein c and d are integers from 1 to 10)

At this time, it is preferable that the mixing ratio of the polydimethylsiloxane represented by the formula (1) and the hydrogen silane compound represented by the following formula (2) is 1: 1 to 5 mol, and the total solid content of the aqueous dispersion silicone release liquid is 1 to 51. Weight percent.

Furthermore, the present invention provides a polyester release film in which the release layer is coated by coating the water-dispersible silicone release solution on at least one surface of a polyester base film. At this time, when the sheet is laminated on the release layer, the peeling force between the release layer and the sheet is 10 to 50g / in under a condition of 90 ° angle, 3mpm peel rate.

In addition, it is preferable that the average roughness value Ra of the surface of the release layer is 1 to 40 nm, and the thickness of the release layer is 1 to 100 nm.

The aqueous silicone release liquid of the present invention is environmentally friendly by excluding organic solvents and applying water as a solvent, and by reducing the surface energy of the aqueous silicone release liquid by including an acetylene compound having a specific structure. When applied to the base film, it is possible to secure a release layer of the thin film with excellent coating uniformity and low surface roughness and moldability.

In addition, the polyester release film to which the water-dispersible silicone release liquid is applied is capable of forming a thin film of a release layer, and has excellent moldability when forming a sheet on the release layer and a low peel force between the release layer and the sheet for manufacturing a multilayer ceramic capacitor. Application to films is particularly excellent.

Hereinafter, the present invention will be described in more detail.

The present invention is 1 to 40% by weight of a mixed component consisting of a polydimethylsiloxane represented by the following formula (1) and a hydrogen silane compound represented by the following formula (2), 0.01 to 10% by weight of a platinum catalyst-containing compound, 0.001 to 1.0 weight of an acetylene compound % Provides a disperse silicone release liquid dispersed in residual water.

Formula 1

Wherein m is 1 to 100, n is an integer of 20 to 5000, and m + n is in the range of 30 to 5000. In this case, m and n do not mean a block combination, they merely indicate that the sum of each unit is m, n. Thus, in the above formula, each unit is a random combination or a block combination.

Formula 2

In the above formula, a is 3 to 200, b is 1 to 120, and 5 ≦ a + b ≦ 200, and an appropriate crosslinking reaction is performed within the above range, and a silicone release layer having excellent durability can be obtained. . a and b do not mean block joins, they merely indicate that the sum of the units is a and b. Therefore, in the above formula, each unit is randomly coupled or block coupled.

The content of the polydimethylsiloxane represented by Chemical Formula 1 and the hydrogen silane compound represented by Chemical Formula 2 is preferably 1 to 40% by weight, and if the content is less than 1% by weight, the surface tension of the release liquid may be too high to form a base film. Wetability (wettability) is reduced, there is a problem that the release layer is non-uniform, if the content exceeds 40% by weight, the viscosity of the release solution increases, causing the streaks, bends, etc. in the release layer and the thickness of the release layer is too high blocking (Blocking) occurs or the hardening of the release layer is poor due to poor aging stability of the peel force and release of the release layer occurs.

At this time, the mixing ratio of the polydimethylene siloxane and hydrogen silane-based compound is preferably 1 to 5 mol of hydrogen silane based on 1 mol of polydimethylene siloxane, the curing ratio of the release layer is less than 1 mol If the mixing ratio exceeds 5 mol, the peeling force of the release layer is increased, and thus the utilization as a release film is poor, which is not preferable.

In addition, the platinum catalyst-containing compound performs a function of assisting the addition reaction of the formula (1) and formula (2), and may be selected from the group consisting of organic stone chelate catalysts such as platinum, rhodium and tin as a preferred example.

In this case, the platinum catalyst-containing compound is preferably used in an amount of 0.01 to 10% by weight, and if less than 0.01% by weight, the addition polymerization does not proceed at a desired ratio, and when it exceeds 10% by weight, the release liquid used for coating the release layer is used. Gelling progresses during preservation, resulting in short pot life and inefficient production.

As the acetylene-based compound to be applied to the present invention, an acetyl diol having an ethoxylate functional group represented by Formula 3 is applied, wherein c and d are integers between 1 and 10.

Formula 3

As the acetylene-based compound reduces the surface energy of the water-dispersed silicone release liquid, it is possible to improve the moldability by coating uniformity when applied to the base film, it is possible to secure the release layer of the thin film.

At this time, the acetylene-based chemical is preferably 0.001 to 1% by weight, the effect is insufficient if less than 0.001% by weight, the coating uniformity is greatly deteriorated if it exceeds 1% by weight, and hinder the curing of the coating liquid There exists a tendency to worsen adhesive force of a mold release layer and a base film.

The total solid content of the water-dispersible silicone release liquid of the present invention is 1 to 51% by weight, more preferably 1 to 10% by weight, if the content is less than 1% by weight, the function of the release liquid is insufficient, and the release layer The uniformity of is greatly deteriorated. If it exceeds 51% by weight, the uniformity and surface roughness of the release layer are poor, streaks, bends, blocking, etc. occur in the release layer, and the hardness of the release layer deteriorates due to the decrease in the degree of curing. Problems such as poor stability and release of the release layer occur.

Furthermore, the present invention provides a polyester release film having a release layer formed by coating the water-dispersible silicone release solution on a polyester base film.

At this time, the coating method of the water-dispersible silicone release liquid is not particularly limited, gravure coating or bar coating method is preferable in consideration of the mass-production of the polyester release film, 140 ~ 180 ℃ temperature for drying and curing the release solution Hot air drying is preferred, and the drying time depends on the air volume. At this time, if the drying temperature is less than 140 ℃ hardening (cross-linking reaction) of the release layer is not made sufficiently, the release layer is easily released or buried from the base film may cause contamination of the production line and the ceramic sheet, the drying temperature is 180 When the temperature exceeds ℃, the base film is heat-shrinked, the smoothness of the release film may deteriorate or wrinkles may occur in the release film.

In particular, the water-dispersed silicone release liquid applied in the present invention can achieve a coating thickness of a lower range than the conventional as the acetylene-based compound, the surface roughness of the release layer is thin because it increases as the thickness of the release layer increases. It is preferable to form a uniform release layer. Therefore, the thickness of the release layer is 1 nm to 100 nm, more preferably 100 nm or less, and if the thickness of the release layer is less than 1 nm, the function of the release layer is insufficient. Poor formability when the sheet is applied.

In this case, the average roughness value Ra of the polyester release film release layer may secure 1 to 40 nm.

In addition, the polyester release film of the present invention, when the sheet is laminated on the release layer, the peel force between the release layer and the sheet has a low peel force of 10 to 50g / in under a condition of 90 ° angle, 3mpm peel rate It can be secured.

In particular, the polyester release film can apply the ceramic slurry thinly and uniformly on the release layer, has excellent moldability, and at the same time has a low peel force between the release layer and the ceramic slurry (ceramic sheet) layer, and thus is applied as a multilayer ceramic capacitor. This is excellent.

The polyester base film applicable to the present invention is not particularly limited, but the unstretched sheet is melted with an extruder to extrude the sheet from a T-die into a sheet, and is subjected to a cold close contact with a rotating cooling drum while applying static electricity. The biaxially stretched polyester film can be applied by biaxially stretching the unstretched film, performing a heat set treatment, and performing a relaxation treatment as necessary. Biaxial stretching can be obtained by the method of biaxially stretching an unoriented film in a transverse direction or a longitudinal direction in order, or the method of simultaneously biaxially stretching an unoriented film in a longitudinal direction and a transverse direction. According to the conventional method, the polyester film may be stretched in one or two axes, but in the present invention, since a coating process involving a hot air drying process is required, a biaxially stretched film that can prevent quality problems due to asymmetric heat shrinkage is preferable. .

Although the thickness of the polyester film used for this invention is not specifically limited, It is preferable that it is 10-50 micrometers. In addition, in order to ensure uniform coating property and high adhesion between the substrate and the release layer in the coating of the water-dispersible silicone release liquid, a process of corona treatment is required on the surface of the polyester base film, which is a manufacturing process of the polyester film. It may be performed immediately before the coating process of the heavy or release liquid.

Hereinafter, the present invention will be described in detail with reference to examples.

The following examples are merely illustrative of the present invention, but the scope of the present invention is not limited to the following examples.

< Example  1>

4% by weight of a mixture of a polydimethylsiloxane having a vinyl group represented by the formula (1) and a hydrogen silane compound represented by the formula (2) at a ratio of 1: 1 (manufactured by Dow Corning's SYL-OFF @ 7920), a platinum catalyst-containing compound (Dow Corning SYL-OFF @ 7924) 0.5 wt%, an acetylene compound represented by the formula (3) (Airproduct Surfynon 2502) A water-dispersed silicone release solution consisting of 0.05% by weight and the balance of water was prepared.

< Example 2 >

Except for using 0.01% by weight of the acetylene compound, it was carried out in the same manner as in Example 1 to prepare a water-dispersible silicone release liquid.

< Example 3 >

Except that 40% by weight of a mixture of polydimethylsiloxane having a vinyl group represented by Formula 1 and a hydrogen silane compound represented by Formula 2 in a ratio of 1: 1 (Dow Corning, Inc. SYL-OFF @ 7920) was applied. In the same manner as in Example 1, a water dispersion silicone release liquid was prepared.

< Example 4 >

On the corona-treated polyester film, the water-dispersible silicone release liquid prepared in Example 1 was coated with a 180-mesh gravure roll, and dried at 160 ° C. for 20 seconds to prepare a polyester release film in which a release layer was formed.

< Example 5 >

Except for coating the water-dispersible silicone release solution prepared in Example 2, was carried out in the same manner as in Example 4 to prepare a polyester release film with a release layer.

< Example 6 >

Except for coating the dispersion silicone release liquid prepared in Example 3, was carried out in the same manner as in Example 4 to prepare a polyester release film with a release layer.

< Comparative Example 1 >

Except for using 1.2% by weight of an acetylene compound, the same procedure as in Example 1 was carried out to prepare a water-dispersible silicone release solution.

< Comparative Example 2 >

Except not using an acetylene compound, it was carried out in the same manner as in Example 1 to prepare a water dispersion silicone release liquid.

< Comparative Example 3 >

8% by weight of a mixture of a polydimethylsiloxane having a vinyl group represented by the formula (1) and a hydrogen silane compound represented by the formula (2) in a ratio of 1: 1 (manufactured by Dow Corning's SYL-OFF @ 7920), a platinum catalyst-containing compound (Dow Corning Co., Ltd. SYL-OFF @ 7924) A water-dispersed silicone release solution consisting of 1% by weight and the balance of water was prepared.

< Comparative Example 4 >

An organic solvent-type silicone release liquid consisting of 0.99% by weight of a silicone resin (KS-847 from Shin-Etsu), 0.02% by weight of a curing agent (PL-50T, manufactured by Shin-Etsu), 50% by weight of MEK, and the remaining amount of toluene, and 1% by weight of total solids. Was prepared.

< Comparative Example 5 >

A polyester release film was formed in the same manner as in Example 4 except that the dispersion silicone release solution prepared in Comparative Example 1 was coated.

< Comparative Example 6 >

Except for coating the water-dispersible silicone release liquid prepared in Comparative Example 2 was carried out in the same manner as in Example 4 to prepare a polyester release film with a release layer.

< Comparative Example 7 >

Except for coating the dispersion silicone release liquid prepared in Comparative Example 3 was carried out in the same manner as in Example 4 to prepare a polyester release film with a release layer.

< Comparative Example 8 >

Except for coating the dispersion silicone release liquid prepared in Comparative Example 4 was carried out in the same manner as in Example 4 to prepare a polyester release film with a release layer.

< Experimental Example >

The properties of the release film were evaluated by performing the following experiments with respect to the Examples and Comparative Examples, and the results are shown in Table 1.

1. Measurement of Coating Uniformity

In the polyester release film, the area of the portion where the release layer is not formed relative to the base film area is 1% or less, and when it exceeds 1%, it is marked as bad.

2. Coating thickness measurement

After measuring the silicon content of the release layer with a calibrated XRF equipment (Panalytical's minipal4) it was expressed in terms of coating thickness.

3. Surface roughness measurement

The surface of the release layer of the polyester release film was measured by an interferometer microscope (Veeco NT1100 product) in a non-contact manner and expressed as a Ra value.

4. Peelability  Measure

After attaching an acrylic adhesive tape (product of TESA 7475) to the release layer of the polyester release film, it was pressed with a 2 kg pressing roller, aged at 25 ° C. for 24 hours, and then peeled off five times under conditions of 90 ° and 3 mpm peeling speed. The average value was shown.

5. Ceramic sheet formability measurement

 Area of the area where the ceramic sheet is not formed by applying a ceramic slurry containing a barium titanate particle and a polyvinyl butyral binder in a ratio of 10: 1 using a doctor blade to an A4 sized polyester release film. When 1% or less, the moldability of the ceramic sheet was good, and when it exceeds 1%, it was described as bad.

According to the above results, Examples 4 and 5 to which the water-dispersing silicone release liquid was applied can secure a lower peeling force than Comparative Example 8 to which the organic solvent-type silicone is applied.

In addition, Examples 4 and 5 containing an appropriate content of the acetylene-based compound can be confirmed that the uniformity of the release liquid coating and the moldability of the ceramic sheet than Comparative Examples 6 and 7 that do not contain it.

As a result of the above, the water-disperse silicone release liquid of the present invention is environmentally friendly by excluding the organic solvent and applying water as a solvent, and the surface energy of the water-dispersion silicone release liquid by including an acetylene compound of a specific structure As it reduces, it is excellent in coating uniformity when applied to the base film, the surface roughness is low and the moldability is improved to secure a release layer of the thin film.

In addition, the polyester release film to which the water-dispersible silicone release liquid is applied is capable of forming a thin film of a release layer, and has excellent moldability when forming a ceramic sheet on the release layer, and has a low peel force between the release layer and the ceramic sheet. Excellent application to the capacitor manufacturing film, it can be applied to Jewish electronic devices such as mobile phones, MP3 players, PMP.

Although the present invention has been described in detail only with respect to the embodiments described, it will be apparent to those skilled in the art that various modifications and variations are possible within the technical scope of the present invention, and such modifications and modifications belong to the appended claims.

1 is a schematic view of a polyester release film of the present invention,

Figure 2 is a schematic diagram of the ceramic sheet laminated on the polyester release film of the present invention,

3 is a schematic diagram of a ceramic sheet peeled from a polyester release film of the present invention applied to a multilayer ceramic capacitor (MLCC).

<Brief Description of Drawings>

1: polyester base film

2: release layer

3: ceramic sheet

4: metal electrode

Claims (8)

1 to 40% by weight of a mixed component consisting of a polydimethylsiloxane represented by the following Chemical Formula 1 and a hydrogen silane compound represented by the following Chemical Formula 2, 0.01 to 10% by weight of a platinum catalyst-containing compound, 0.001 to 1.0% by weight of an acetylene-based compound Water-based silicone release liquid consisting of water. Formula 1

(In the above, m is an integer of 1 to 100, n is an integer of 20 to 5000, and m + n is 30 to 5000.) Formula 2

(In the above, a is an integer of 3 to 200, b is an integer of 1 to 120, and 5≤a + b≤200.) The aqueous silicone mold release liquid according to claim 1, wherein the acetylene compound is an acetyl diol having an ethoxylate functional group represented by the following formula (3). Formula 3

(Wherein c and d are integers between 1 and 10) According to claim 1, wherein the mixing ratio of the polydimethylsiloxane represented by the formula (1) and the hydrogen silane compound represented by the formula (2) is 1: 1 to 5 mol, characterized in that the aqueous dispersion silicone release liquid. 2. The aqueous silicone release liquid according to claim 1, wherein the total solid content of the aqueous silicone release liquid is 1 to 51% by weight. Polyester release film in which the release layer is laminated by coating the water-dispersible silicone release solution of claim 1 on at least one surface of the polyester base film. The method of claim 5, wherein when the sheet is laminated on the release layer, the release force between the release layer and the sheet is the polyester release film, characterized in that 10 to 50g / in at 90 ° and 3mpm peel rate. 6. The polyester release film of claim 5, wherein an average roughness value Ra of the surface of the release layer is 1 to 40 nm. 6. The polyester release film according to claim 5, wherein the release layer has a thickness of 1 to 100 nm.

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