KR20100060985A - Silicone release coating films for green sheet - Google Patents

Abstract

PURPOSE: A silicone release film for a green sheet is provided to prevent pollutions which are caused by dust and foreign materials by improving static generation when the green sheet is manufactured and is peeled. CONSTITUTION: A silicone release film for a green sheet comprises a polyester base film and a coating layer which is obtained by coating one side of the polyester base film with a silicone release composition of the green sheet over one time. The silicone release film satisfies a chemical formula 1 and a chemical formula 2. The chemical formula 1 is X<=10^10 and the formula 2 is Y>=80. In the formulas, X is a surface resistance(Ω/sq) and Y is a content wear rate(%) of the coating layer.

Description

Silicone Release Films for Green Sheets {Silicone Release Coating Films For Green Sheet}

The present invention relates to a silicone release film for a green sheet, and more particularly, to prevent tearing after peeling after manufacturing the green sheet due to excellent solvent resistance and antistatic properties through an in-line or offline manufacturing process. The present invention relates to a silicone release film for a green sheet which may block generation of contamination by dust or foreign substances by improving static electricity during green sheet manufacturing and peeling.

In general, the term “green sheet” refers to a ceramic shaped body in the form of a sheet, and is mainly used as a dielectric, an electrode, a phosphor, a partition, and the like for an optical use of an LCD, a PDP, and an electric and electronic device such as an MLCC.

When laminating and attaching a molded body of ceramic material to a substrate, a method of coating or printing a ceramic slurry directly on a substrate or processing the ceramic in a sheet form and then applying the substrate to a substrate is widely used. In the former case, the initial capital investment cost is low, but since the desired thickness cannot be obtained with a single coating, a process of coating and printing the same position several times is required. Therefore, this method has a disadvantage in that the uniformity of the ceramic molded part is bad. On the other hand, in the latter case, the initial capital investment is somewhat high, but the uniformity of the ceramic molded body is excellent, and thus, it is widely used for optical and electric electronics.

The green sheet, which is a sheet-shaped ceramic molded body, has a predetermined thickness of a ceramic mixture made of ceramic powder, a binder, a plasticizer, a dissociating agent, a solvent, and the like on a carrier film by a doctor blade coating method, a die coating method, or the like. It is manufactured by the process of apply | coating in the oven, drying and solidifying, and then peeling a ceramic sheet from a carrier film.

As the carrier film used in the green sheet manufacturing process, a release film coated with curable silicone is commonly used for a polyester film having excellent mechanical strength, dimensional stability, heat resistance, and the like.

As in the green sheet manufacturing process, a ceramic mixture is applied to the silicon coating layer based on the silicone release film, wherein the ceramic mixture used is toluene, xylene, ethanol, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl Solvents such as ketones, ethyl acetate, hexane and the like are used. Such a solvent may cause damage to the silicon layer of the release film used as the base substrate, and the ceramic sheet in contact with the damaged silicon coating layer is likely to tear when peeled.

Green sheets used in recent years are becoming thinner due to the miniaturization and cost reduction of products. Such thin green sheets are more likely to have appearance defects such as pinholes and squeezable defects even in very fine dust and foreign materials, and have a great problem of causing huge problems such as product defects.

The present invention has been made to solve the above problems, an object of the present invention for the green sheet excellent in the solvent properties through the in-line or offline coating process to remove the tearing phenomenon generated during peeling after manufacturing the green sheet It is to provide a silicone release film.

Still another object of the present invention is to provide a silicone release film for green sheet having excellent antistatic properties, which can improve the crushing defect of the green sheet by blocking product contamination caused by electrostatic phenomena generated during green sheet processing and use process. It is.

These and other objects and advantages of the present invention will become more apparent from the following description of a preferred embodiment thereof.

The object includes a coating layer applied to the polyester base film and at least one surface of the polyester base film with at least one silicone release composition for the green sheet, but satisfying the following formula 1 and 2, It is achieved by a silicone release film for green sheet.

X ≤ ^{10 10} (Equation 1)

Y ≥80 (Equation 2)

Here, 'X' is the surface resistance (Ω / sq) of the coating layer, and 'Y' is the solvent wear rate (%) of the coating layer.

Preferably, the silicone release composition for green sheet is characterized in that it comprises a silane coupling agent, organopolysiloxane, organohydrogen polysiloxane, conductive polymer resin and platinum chelate catalyst.

Preferably, the conductive polymer resin is characterized in that it is prepared by polymerizing polythiophene or derivatives thereof in polyanions.

Preferably, the conductive polymer resin is characterized in that it comprises 0.05 to 0.5 parts by weight based on 100 parts by weight of the organopolysiloxane.

Preferably, the silane coupling agent is characterized in that it comprises 0.05 to 1 parts by weight based on 100 parts by weight of the organopolysiloxane.

Preferably, the silicone release composition for green sheet is characterized in that the composition diluted in a solvent so that the solid content of 1.2 to 5% by weight relative to the total composition weight.

According to the present invention, by the excellent solvent resistance and antistatic properties through the in-line or off-line manufacturing process it can prevent the tearing phenomenon during peeling after manufacturing the green sheet, and also improve the generation of static electricity during green sheet manufacturing and peeling Or it can have the effect of blocking the generation of contamination (depression quality problems) due to foreign matters.

Hereinafter, the present invention will be described in detail with reference to embodiments of the present invention. These examples are only presented by way of example only to more specifically describe the present invention, it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples. .

The silicone release film for green sheet according to the present invention is characterized in that it comprises a polyester base film and a coating layer applied at least once with a silicone release composition for green sheet on at least one surface of the polyester base film, And 2 at the same time.

X ≤ ^{10 10} (Equation 1)

Y ≥80 (Equation 2)

Here, 'X' is the surface resistance (Ω / sq) of the coating layer, and 'Y' is the solvent wear rate (%) of the coating layer.

The polyester base film used in the present invention is not limited in kind, but may be a known one conventionally known as a base film of silicone release coating. In the present invention, the description will focus on polyester-based resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate and the like, but the base film of the silicone release composition of the present invention is not limited to a polyester sheet or a film.

Polyester which comprises the said base film points out the polyester obtained by polycondensing aromatic dicarboxylic acid and aliphatic glycol. As aromatic dicarboxylic acid, terephthalic acid, 2, 6- naphthalene dicarboxylic acid, etc. are mentioned, As aliphatic glycol, ethylene glycol, diethylene glycol, 1, 4- cyclohexane dimethanol, etc. are mentioned.

Typical polyesters include polyethylene terephthalate (PET), polyethylene-2,6-naphthalenedicarboxylate (PEN), and the like. The polyester may also be a copolymer containing a third component. Examples of the dicarboxylic acid component of the copolyester include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, and oxycarboxylic acid (for example, P-oxybenzoic acid). Examples thereof include ethylene glycol, diethylene glycol, propylene glycol, butanediol, 1,4-cyclohexanedimethanol, neopentylglycol and the like.

These dicarboxylic acid components and glycol components may use 2 or more types together. It is preferable that the polyester base film which concerns on this invention uses the uniaxial or biaxial oriented film which has high transparency and is excellent in productivity and workability.

In addition, the silicone release composition for a green sheet according to the present invention is characterized in that it comprises a silane coupling agent, an organopolysiloxane, an organohydrogen polysiloxane, a conductive polymer resin and a platinum chelate catalyst.

The organopolysiloxane may be any type such as addition type, condensation type, ultraviolet curing type, but the representative molecular structure of the present invention is represented by the following formula (1).

[Formula 1]

Here m and n are integers greater than or equal to zero.

The organopolysiloxane contains an alkenyl group in a molecule, alkenyl group may be present in any part of the molecule, and at least two or more are preferable. The molecular structure may be linear or branched, or may be a structure in which both linear and branched molecules are present.

In addition, as a curing agent in the composition of the coating composition according to the present invention, any type such as addition type, condensation type, and ultraviolet curing type may be used, and the representative molecular structure of organo hydrogen polysiloxane, which is a representative curing agent of the present invention, may be used. It is the same as the following formula (2).

[Formula 2]

Here, p and q are integers 0 or more.

The organohydrogen polysiloxane may be linear, branched or cyclic, or a mixture thereof. In addition, the viscosity and molecular weight are not limited, but the compatibility with the organopolysiloxane should be good, and the amount of use is such that the hydrogen atom bonded to the silicon atom for one alkenyl group of the organopolysiloxane is in the range of 0.5 to 1.2. desirable. If there are less than 0.5 hydrogen atoms bonded to a silicon atom with respect to one alkenyl group of the organopolysiloxane, there may be a problem that a good hardenability may not be obtained. If the number exceeds 1.2, elasticity or physical properties after curing may be deteriorated. Can be. On the other hand, in the silicone release composition according to the present invention, when the amount of the organohydrogen polysiloxane is higher than that of the organopolysiloxane, crosslinking proceeds a lot, resulting in reduced flexibility and cracking of the film, thereby reducing smoothness.

The conductive polymer resin contained in the silicone release composition for green sheets of the present invention is preferably used by polymerizing polythiophene or a derivative thereof to polyanion in order to impart antistatic properties. The compound represented by these can be obtained by polymerizing alone or in mixture in the presence of a polyanion.

(3)

In Formula 1, R ₁ and R ₂ each independently represent a hydrogen atom, a C1-12 aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group, and specifically methyl, ethyl, propyl, isopropyl, butyl, A benzene group etc. correspond to this.

[Formula 4]

In Formula 2, n is an integer of 1 to 4.

In addition, the said polyanion is an acidic polymer, and is high molecular carboxylic acid, high molecular sulfonic acid, polyvinyl sulfonic acid, etc. Examples of the polymer carboxylic acid include polyacrylic acid, polymethacrylic acid and polymaleic acid, and examples of the polymer sulfonic acid include polystyrene sulfonic acid.

In the present invention, an aqueous dispersion of a polymer containing 0.5% by weight of poly (3,4-ethylenedioxythiophene) and 0.8% by weight of polystyrenesulfonic acid is used.

The conductive polymer resin is used at 0.05 to 0.5 parts by weight based on 100 parts by weight of the organopolysiloxane in the composition of the silicone release composition for green sheets. If it is less than 0.05 parts by weight, sufficient charging function does not appear, and if it is 0.5 parts by weight or more, the function of the platinum catalyst is lost, causing problems in curing.

In addition, the platinum chelate complex used as a catalyst in the composition of the silicone release composition for green sheets according to the present invention is a component that plays an important role in curing the coating composition. When the polymer material is contained, the platinum chelate complex loses the catalytic function and thus the uncured phenomenon of the silicone release composition occurs, and the adhesion between the base film and the silicon layer is reduced, so that the release function is not expressed or the silicon is transferred. do.

In the composition of the silicone release composition for green sheets according to the present invention, the silane coupling agent plays an important role of expressing solvent characteristics as a material represented as a crosslinking role of the base film and the coating film. It also serves to block functional groups that act as catalyst poisons in the conductive polymer resin. As the component of the coupling agent, any of epoxy silane, amino silane, vinyl silane, methacryloxy silane, and isocyanate silane can be used, and one or two or more kinds thereof can be mixed.

In general, the antistatic coating is usually treated on the opposite side of the release treatment surface for the reason of acting as a catalyst poison as described above, but in the present invention, a silane coupling agent for blocking such catalyst poison is included. It will not work.

The silicone release composition for green sheet is diluted to include 1.2 to 5% by weight of solids based on the total coating composition weight and then coated on the polyester base film. The solvent used in the coating composition is not limited as long as it can be applied to a polyester base film or an antistatic polyester base film by dispersing the solid content of the present invention, but preferably water is used. If the solid content of the silicone release composition for the green sheet is less than 1.2% by weight, the chargeability may not be expressed, or a tearing phenomenon may occur when peeling after manufacturing the green sheet. Development occurs and can cause changes over time in curing the coating composition.

Hereinafter, the present invention will be described in detail by using examples and comparative examples of the present invention.

Example 1

0.05 parts by weight of a conductive polymer resin (Bayer, Baytron P; water dispersion containing poly3,4-ethylenedioxythiophene, polystyrenesulfonic acid) based on 100 parts by weight of organopolysiloxane on the corona discharge-treated surface of the polyester base film 0.05 parts by weight of the silane coupling agent, 5 parts by weight of the organohydrogen polysiloxane, and 50 ppm of the platinum chelate catalyst were diluted in water to prepare a silicone release composition having a total solid content of 2% by weight, and applied to a thickness of 10 microns. After application, heat treatment was performed for 10 seconds in a 180 ° C. hot air dryer to prepare a silicone release film for green sheets.

Example 2

A silicone release film for green sheets was prepared in the same manner as in Example 1, except that the silane coupling agent was added in an amount of 0.1 parts by weight.

Example 3

A silicone release film for a green sheet was manufactured in the same manner as in Example 1, except that 0.2 parts by weight of the conductive polymer resin and 0.5 parts by weight of the silane coupling agent were added.

[Comparative Example 1]

Except not using a silane coupling agent, the antistatic silicone release film was prepared in the same manner as in Example 1.

Comparative Example 2

An antistatic silicone release film was prepared in the same manner as in Example 1, except that 0.03 parts by weight of the conductive polymer resin was added.

Evaluation of physical properties of the films prepared in Examples 1 to 3 and Comparative Examples 1 and 2 was carried out in the same manner as shown in Table 1 below.

Experimental Example 1: Measurement of Surface Resistance

The surface resistance was measured in accordance with JIS K7194 after installing the sample in the environment of temperature of 23 degreeC, humidity 50% RH using an antistatic measuring device (Mitsubishi Corporation: model name MCP-T600).

Experimental Example 2 Measurement of Peel Force

Sample preparation:

① Preservation of silicon-coated measurement samples at 25 ° C and 65% RH for 24 hours

② After attaching the standard adhesive tape (TESA7475) to the silicon coating, measure the properties after compressing the sample under a load of 20g / cm ² at room temperature (25 ℃) and high temperature (50 ℃) for 24 hours.

Measuring instrument: chem-instrument AR-1000

- How to measure:

① 180 ° peeling angle, peeling speed 12 in / min

② Sample size 500mm x 1500mm, Peel force measuring size 250mm x 1500mm

-Measurement data: Peel force unit is g / in and the average value is calculated by measuring 5 times

Experimental Example 3: Solvent Wear Rate Measurement

The wear rate of solvent was measured under the conditions of 500 gf load by using the Hakjin friction fastness tester (Testa Industrial Co., Ltd .: Model name AB-301).

① Attach a wiper (sonpont) of 20 × 20 mm area to the friction

② Wet 5 ml of solvent test solution (toluene: MEK: EA = 1: 1: 1) in the wiper with friction.

③ Reciprocating the coating layer 10 times at a speed of 30cpm with a friction wiper

④ The silicon content of the coating layer in the sample before and after friction was measured by XRF (OXFORD: LAB X-3500) analyzer.

● data

Experimental Example 4: Measurement of love off property

By pushing the silicone release coating layer strongly with a finger, it is possible to determine the degree of dropping of the silicon on the polyester base film layer to check the adhesive property between the cured silicon and the base.

TABLE 1

Item Surface resistance
(Ω / sq) Peel force
(g / in) Solvent wear rate
(%) Love-off Example 1 10 ⁸ 16.2 95.4 ◎ Example 2 10 ⁸ 16.5 98.2 ◎ Example 3 10 ⁶ 17.9 92.8 ○ Comparative Example 1 10 ⁸ 17.5 40.2 X Comparative Example 2 10 ¹³ 16.3 95.7 ◎

(◎: Excellent, ○: Good, △: Normal, X: under)

As can be seen in Table 1, it can be seen that Examples 1 to 3 according to the present invention possess excellent antistatic function and stable solvent properties. However, in Comparative Example 1, in which the specific silane coupling agent was not included, it was confirmed that there was a problem in solvent resistance and love-off characteristics because the adhesion between the substrate and the coating layer was not maintained, and in Comparative Example 2, the content of the conductive polymer resin was insufficient. In case it can be confirmed that the antistatic function is not expressed.

Claims (6)

In the silicone release film for green sheet, Polyester base film, At least one surface of the polyester base film includes a coating layer applied at least once with a silicone release composition for a green sheet, A silicone release film for green sheet, characterized in that to satisfy the following formula 1 and 2 at the same time: X ≤ ^{10 10} (Equation 1) Y ≥80 (Equation 2) Here, 'X' is the surface resistance (Ω / sq) of the coating layer, and 'Y' is the solvent wear rate (%) of the coating layer. The method of claim 1, The silicone release composition for a green sheet is a silicone release film for a green sheet, characterized in that it comprises a silane coupling agent, an organopolysiloxane, an organohydrogen polysiloxane, a conductive polymer resin, and a platinum chelate catalyst. The method of claim 2, The conductive polymer resin is polysilicon, polythiophene or derivatives thereof, characterized in that the polymer is produced, silicone release film for green sheet. The method of claim 2, The conductive polymer resin, characterized in that 0.05 to 0.5 parts by weight based on 100 parts by weight of the organopolysiloxane, silicon release film for green sheets. The method of claim 2, The silane coupling agent comprises 0.05 to 1 parts by weight based on 100 parts by weight of the organopolysiloxane, silicone release film for green sheets. 6. The method according to any one of claims 1 to 5, The green release silicone release composition for a green sheet, the silicone release film for a green sheet, characterized in that the composition diluted in a solvent so that the solid content of 1.2 to 5% by weight based on the total weight of the composition.