KR101268584B1 - Silicone release composition and carrier film for adhesive coating films using thereof - Google Patents

Abstract

The present invention relates to a silicone release composition and a carrier film for adhesive processing using the same, and more particularly, in an indirect adhesive coating process of forming an adhesive layer on a release film during an adhesive layer processing step and transferring the substrate film to a base film. Orange Peel defects are easily generated due to the poor wetting of the adhesive layer.These silicone defects can be used for semiconductors, electrical and electronics, and displays, which can directly lead to fatal defects in products, and adhesion using them. It relates to a carrier film for processing. To this end, the silicone release composition according to the present invention comprises from 0.01 to 100 parts by weight of an organopolysiloxane including at least two or more alkenyl groups per molecule, and a hydropolypolysiloxane composed of a siloxane and methylhydryl siloxane copolymer containing a dimethyl group per molecule. It is characterized in that it comprises 10 parts by weight and 5 to 10 parts by weight of platinum catalyst and 0.5 to 10,000 parts by weight of the solvent at a concentration of 0.5wt%.

Description

Silicone release composition and carrier film for adhesive processing using same {SILICONE RELEASE COMPOSITION AND CARRIER FILM FOR ADHESIVE COATING FILMS USING THEREOF}

The present invention relates to a silicone release composition and a carrier film for adhesive processing using the same, and more particularly, in an indirect adhesive coating process of forming an adhesive layer on a release film during an adhesive layer processing step and transferring the substrate film to a base film. Orange Peel defects are easily generated due to the poor wetting of the adhesive layer.These silicone defects can be used for semiconductors, electrical and electronics, and displays, which can directly lead to fatal defects in products, and adhesion using them. It relates to a carrier film for processing.

In recent years, the development of industrialization in the semiconductor, electric, electronic and display fields is rapidly increasing, and in general, the amount of use of the above-mentioned application is also rapidly increasing in the release film field whose main purpose is an adhesive layer protection function and a carrier function for adhesive layer processing. This application requires greater protection of the appearance of the base film than the release film removed after use, and indirect adhesion to minimize the passage of the base film during the adhesive coating process to protect the base film from scratches and foreign matter adsorption. Most coating processes are applied. The indirect adhesive coating process refers to a process of an adhesive product produced by coating an adhesive layer on a coating surface of a release coating film, drying and laminating it with a base film, and transferring the adhesive layer from the release coating surface to the substrate film surface. .

This indirect coating process has the advantage of protecting the appearance of the base film, but the adhesive layer due to poor leveling and wetting of the adhesive layer in that the adhesive layer should be coated directly on the silicon release coating surface having low surface tension. There is a problem that the coating uniformity of the deterioration occurs, and when the non-uniform adhesive coating layer is laminated with the substrate, an orange peel defect such as an orange peel form occurs, and the adhesion between the adhesive layer and the substrate becomes weak. Possible problems may arise.

The appearance defects thus generated tend to be maintained in the shape of the defect on the surface of the adhesive layer, and may cause problems such as lamination due to bubble mixing when the adhesive film is attached.

The present invention has been made to solve the above problems, the object of the present invention is to use the carrier film for adhesive processing of semiconductor, electrical and electronics and display applications through inline or offline manufacturing process, Due to the high surface energy value of the silicone coating layer, it is possible to reduce appearance defects such as orange peel defects due to poor wetting of the adhesive layer due to excellent wetting properties of the adhesive when the adhesive layer is processed on the silicone coating layer. It is an object of the present invention to provide a silicone release composition capable of reducing product defects such as bubble mixing and the like, and a carrier film for adhesive processing using the same.

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 is 0.01 to 10 parts by weight of hydropolypolysiloxane consisting of 100 parts by weight of an organopolysiloxane comprising at least two alkenyl groups per molecule, and a siloxane and methylhydryl siloxane copolymer containing a dimethyl group per molecule and 0.5 wt. It is achieved by a silicone release composition characterized in that it comprises 5 to 10 parts by weight of the platinum catalyst in a concentration of% and 1,000 to 10,000 parts by weight of the solvent.

Here, the alkenyl group of the organo polysiloxane is characterized in that the aliphatic unsaturated hydrocarbon consisting of 3 to 6 carbon atoms.

Preferably, the organopolysiloxane has the structure of Formula 1,

(Formula 1)

R is an alkenyl group, and m and n are each a positive integer satisfying 100 ≦ m + n ≦ 5,000 and 0 ≦ n ≦ 100.

Preferably, the hydropolysiloxane has the structure of Formula 2,

And a and b are positive integers satisfying a + b ≦ 100 and b / (a + b) ≦ 0.5, respectively.

Preferably, the silicone release composition is characterized in that the composition ratio of the Si-H group and the Si-R group satisfies 1.0 ≦ Si—H / Si—R ≦ 5.

In addition, the object is achieved by a carrier film for pressure-sensitive adhesive, characterized in that it comprises a coating layer coated with at least one surface of the polyester base film and the silicone release composition on at least one side of the polyester base film.

Here, the surface energy value of the coating layer is characterized in that more than 13.0.

Preferably, the peel force of the coating layer is less than 30gf / in and the residual adhesion rate is characterized in that more than 80%.

According to the present invention, when used as an adhesive carrier film for semiconductor, electrical and electronics and display through in-line or off-line manufacturing process, the adhesive layer is processed on the silicon coating layer by the high surface energy value of the silicon coating layer on the film surface. Excellent wetting properties of the adhesive can reduce appearance defects such as orange peel defects due to poor wetting of the adhesive layer, and can reduce product appearance defects such as bubble mixing caused by the defects. Has the effect of.

Hereinafter, the present invention will be described in detail with reference to examples of the present invention. It will be apparent to those skilled in the art that these embodiments are provided by way of illustration only for the purpose of more particularly illustrating the present invention and that the scope of the present invention is not limited by these embodiments .

The silicone release composition according to the present invention comprises 0.01 to 10 parts by weight of a hydropolypolysiloxane comprising 100 parts by weight of an organopolysiloxane including at least two alkenyl groups per molecule, and a siloxane and methylhydryl siloxane copolymer containing a dimethyl group per molecule. And 5 to 10 parts by weight of a platinum catalyst at a concentration of 0.5 wt% and 1,000 to 10,000 parts by weight of a solvent.

In addition, the carrier film for adhesion processing according to the present invention is characterized in that it comprises a coating layer coated with the silicone release composition at least once on at least one surface of the polyester base film and the polyester base film.

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. The polyester which comprises the said base film points out the polyester obtained by polycondensing aromatic dicarboxylic acid and aliphatic glycol. Examples of the aromatic dicarboxylic acid include terephthalic acid and 2,6-naphthalenedicarboxylic acid. Examples of the aliphatic glycol include ethylene glycol, diethylene glycol, 1,4-cyclohexanedimethanol and the like. 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 copolymer polyester include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, oxycarboxylic acid (such as P-oxybenzoic acid) Include ethylene glycol, diethylene glycol, propylene glycol, butanediol, 1,4-cyclohexanedimethanol, neopentyl glycol and the like. These dicarboxylic acid components and glycol components may be used in combination of two or more.

The polyester base film according to the present invention preferably uses a uniaxial or biaxially oriented film having high transparency and excellent productivity and processability.

In addition, the organopolysiloxane of the silicone release composition according to the present invention can be used in any type, such as addition type, condensation type, UV curing type, the representative molecular structure is represented by the following formula (1).

(Formula 1)

R is an alkenyl group and an aliphatic unsaturated hydrocarbon having 3 to 6 carbon atoms. M and n are positive integers satisfying 100 ≦ m + n ≦ 5,000 and 0 ≦ n ≦ 100, respectively.

The organopolysiloxane contains an alkenyl group in a molecule, and alkenyl groups may be present in any part of the molecule in a range satisfying the general formula (1), and preferably at least two are present. The molecular structure may be linear or branched, or may be a structure in which both linear and branched molecules are present.

If m + n is less than 100, the molecular weight of the organopolysiloxane is too low in the viscosity of the coating solution, the leveling characteristics of the silicone coating layer is bad, and there is a high possibility of staining during adhesive coating. In addition, when m + n is greater than 5000, the coating layer crosslinking density is lowered, so that the surface energy of the surface of the release coating layer is lowered, which may result in a poor wetting problem when the pressure-sensitive adhesive coating is applied. It may rise and peeling defect may arise.

In addition, as a curing agent in the composition of the silicone release composition according to the present invention, any type such as addition type, condensation type, and ultraviolet curing type may be used. Same as 2.

(Formula 2)

Here, a and b are positive integers satisfying a + b ≦ 100 and b / (a + b) ≦ 0.5, respectively.

The hydropolypolysiloxane 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 used is 1.0 ≤ Si in the composition ratio of the Si-H group of the hydropolysiloxane and the Si-R group of the organopolysiloxane. It is preferable to satisfy -H / Si-R? R is an alkenyl group. In addition, the molecular weight of the hydropolysiloxane is a + b is greater than 100, when b is greater than 0.5 of a + b is low reactivity can cause a poor curing.

In addition, when there are less than 1.0 hydrogen atoms bonded to the silicon atom of the hydropolysiloxane with respect to one alkenyl group of the organopolysiloxane, there may be a problem in that good curing properties may not be obtained. There may be a problem that the physical properties are deteriorated, and there is also a problem that the change in the peel force with time increases due to the reaction of the residual hydroelectric and the pressure-sensitive adhesive layer.

Silicone release composition according to the present invention is 100 parts by weight of the organo polysiloxane, 0.01 to 10 parts by weight of hydropolysiloxane consisting of siloxane and methylhydryl siloxane copolymer containing a dimethyl group per molecule, a catalytic amount of platinum catalyst and solvent 1000 to It is preferable to include 10,000 parts by weight.

If the hydropolysiloxane is less than 0.01 part by weight with respect to 100 parts by weight of the organopolysiloxane, a sufficient hardening does not proceed, and defects occur. Growing problem occurs.

In addition, the carrier film for adhesion processing according to the present invention is characterized in that the surface energy value of the coating layer is 13.0 or more, preferably the peel force of the coating layer is 30gf / in or less and the residual adhesion rate is 80% or more.

Hereinafter, the structure and effect of the present invention will be described in more detail with reference to examples and comparative examples. However, this embodiment is intended to explain the present invention more specifically, and the scope of the present invention is not limited to these embodiments.

Example 1

0.1 weight of hydropolysiloxane consisting of dimethylsiloxane: methylhydrylsiloxane = 30: 45 copolymer based on 100 parts by weight of an organopolysiloxane consisting of dimethylsiloxane: methyl vinylsiloxane = 4000: 100 groups on one side of the polyester base film 5 parts by weight of a platinum catalyst at a concentration of 0.5 wt% and 5000 parts by weight of MEK: Toluene = 1: 1 mixed solvent were prepared and applied to a thickness of 15 microns. After coating, heat-treated for 30 seconds in a 130 ℃ hot air dryer to prepare a carrier film for adhesion processing.

[Example 2]

A carrier film for tacking was prepared in the same manner as in Example 1, except that organopolysiloxane consisting of methylsiloxane: methyl vinylsiloxane = 4000: 10 groups was used.

[Example 3]

A carrier film for tacking was prepared in the same manner as in Example 1, except that organopolysiloxane consisting of methylsiloxane: methyl vinylsiloxane = 4000: 0 group was used.

Example 4

A carrier film for tacking was prepared in the same manner as in Example 1, except that organopolysiloxane consisting of methylsiloxane: methyl vinylsiloxane = 100: 0 group was used.

[Example 5]

A carrier film for adhesive processing was prepared in the same manner as in Example 1, except for adding 1 part by weight of polysiloxane.

[Example 6]

Except adding 5 parts by weight of polysiloxane hydro, it was carried out in the same manner as in Example 1 to prepare a carrier film for pressure-sensitive adhesive processing.

[Example 7]

Except for adding 10 parts by weight of polysiloxane hydro, it was carried out in the same manner as in Example 1 to prepare a carrier film for pressure-sensitive adhesive processing.

 [Example 8]

A carrier film for tackifying was prepared in the same manner as in Example 1, except that 1 part by weight of hydropolysiloxane consisting of dimethylsiloxane: methylhydrylsiloxane = 20: 55 copolymer was added.

[Example 9]

A carrier film for tackifying was prepared in the same manner as in Example 1, except that 1 part by weight of hydropolysiloxane consisting of dimethylsiloxane: methylhydrylsiloxane = 30: 35 copolymer was added.

Comparative Example 1

A carrier film for tacking was prepared in the same manner as in Example 1, except that organopolysiloxane consisting of methylsiloxane: methyl vinylsiloxane = 6000: 10 groups was used.

Comparative Example 2

A carrier film for tacking was prepared in the same manner as in Example 1, except that organopolysiloxane consisting of methylsiloxane: methyl vinylsiloxane = 70: 10 group was used.

[Comparative Example 3]

A carrier film for tackifying was prepared in the same manner as in Example 1, except that 1 part by weight of hydropolysiloxane consisting of dimethylsiloxane: methylhydrylsiloxane = 35: 25 copolymer was added.

[Comparative Example 4]

A carrier film for tackiness was prepared in the same manner as in Example 1, except that 1 part by weight of hydropolysiloxane consisting of dimethylsiloxane: methylhydrylsiloxane = 70: 70 copolymer was added.

Physical properties were measured through the following experimental examples using the carrier film for pressure-sensitive adhesive according to Examples 1 to 9 and Comparative Examples 1 to 4 and the results are shown in Table 1 below.

Experimental Example 1 Surface Energy Measurement

Coating 2.8 μl of distilled water (H ₂ O) and 1.8 μl of diiodomethane (CH ₂ I ₂ ) by the Sessile drop method using a contact angle meter (Dropmaster 500 from Kyowa Interface Science). After dropping the surface, the contact angle was measured 10 times, and the average value was calculated. The surface energy value was calculated using FAMAS analysis software (Gyowa Interface Science) based on Owens-Wendt-geometiric mean.

Experimental Example 2: Orange Peel Evaluation

The silicone-coated film prepared in the manner described above was uniformly coated with an acrylic solvent-type pressure-sensitive adhesive (trade name: BPS-5127, Toyo Ink Co.) at 30 g / m ² using an applicator and heated at 70 ° C. for 2 minutes. do. Then, a 50 μm-thick transparent polyester film (PET FILM) was laminated, and a sample of 10 cm × 10 cm area was visually observed under a three-wavelength lamp to visually check whether orange peel was present or not.

Experimental Example 3 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 a standard adhesive tape (TESA7475) to the silicon coated surface, the sample was pressed for 24 hours under a load of 20 g / cm ² at room temperature (25 ° C.) and high temperature (50 ° C.)

- 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 gf / in and the average value is calculated by measuring 5 times

Experimental Example 4: Measurement of Residual Adhesion Rate

- Sample preparation:

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

(2) A standard adhesive tape (Nitto 31B) was applied to the silicon coated surface, and the sample was squeezed at room temperature for 20 hours under a load of 20 g / cm ²

(3) Adhesive tape adhered to the silicon surface was collected without contamination, adhered to a flat and clean PET film surface, and then subjected to round-trip compression once with a 2 kg tape roller (ASTMD-1000-55T).

④ Peel force measurement

Measuring instrument: cheminstrument 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

- data

Experimental Example 5 Appearance Characteristics of the Release Coating Layer

The coated surface of the silicon coated film prepared in the manner described above was visually observed under a three-wavelength lamp to evaluate the properties and the results are shown by the following criteria.

◎: No appearance defect, △: Stain observation, X: Pinhole observation

Item Surface energy
(dyn / cm) Orange peel Peel force
(gf / in) Residual adhesion rate
(%) Release coating layer
Appearance characteristics Example 1 14.8 radish 23.1 93.2 ◎ Example 2 14.4 radish 21.7 96.1 ◎ Example 3 13.5 radish 20.5 98.5 ◎ Example 4 14.6 radish 19.2 95.1 ◎ Example 5 14.5 radish 22.4 95.7 ◎ Example 6 15.0 radish 22.3 93.2 ◎ Example 7 16.5 radish 24.9 92.1 ◎ Example 8 15.2 radish 24.6 90.5 ◎ Example 9 13.9 radish 24.6 92.3 ◎ Comparative Example 1 10.0 U 20.4 92.4 ◎ Comparative Example 2 14.2 radish 32.9 79.6 X Comparative Example 3 11.7 U 45.7 69.7 △ Comparative Example 4 11.2 U 39.5 72.1 △

As can be seen in Table 1, Examples 1 to 9 according to the present invention are surface energy values and stable peeling force, hardening characteristics and excellent appearance characteristics that can express excellent coating aptitude even in an indirect adhesive coating process. You can check that they hold together. On the contrary, in the case of Comparative Example 1 having a silicon base polymer of 5,000 units or more, the crosslinking density was too low, so that an appropriate surface energy value did not come out, and thus the orange peel phenomenon occurred. The fluidity of the polymer is so great that the coating appearance is poor, the Si-H content ratio of the curing agent is low, or the curing agent of Comparative Example 3 and Comparative Example 4 having a length of 100 units or more is poor in curing, resulting in peeling force and residual adhesion rate. It can be confirmed that the curing properties of the poor.

It is to be understood that the present invention is not limited to the above embodiments and various changes and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention.

Claims (8)

In the silicone release composition,
0.01-5 parts by weight of an organopolysiloxane comprising an alkenyl group having 3 to 6 carbon atoms or more per molecule and a hydroxy and methylhydryl siloxane copolymer containing a dimethyl group per molecule And 5 to 10 parts by weight of a platinum catalyst at a concentration of 0.5 wt% and 1,000 to 10,000 parts by weight of a mixed solvent of methyl ethyl ketone and toluene, and Si-H group in the hydropolysiloxane and Si-R in the organopolysiloxane. A silicone release composition, characterized in that the composition ratio of the group satisfies 1.0 ≦ Si—H / Si—R ≦ 5. delete The method of claim 1,
The organopolysiloxane has the structure of Formula 1,
(Formula 1)

R is an alkenyl group having 3 to 6 carbon atoms, and m and n are positive integers satisfying 100 ≦ m + n ≦ 5,000 and 0 ≦ n ≦ 100, respectively. The method of claim 1,
The hydropolysiloxane has the structure of Formula 2,

And a and b are positive integers satisfying a + b ≦ 100 and b / (a + b) ≦ 0.5, respectively. delete In the carrier film for adhesion processing,
Polyester base film
At least one surface of the polyester base film, characterized in that it comprises a coating layer applied at least once with the silicone release composition according to claim 1, the carrier film for adhesion processing. The method according to claim 6,
Surface energy value of the coating layer is characterized in that 13.0 or more, the carrier film for adhesion processing. 8. The method according to claim 6 or 7,
The peeling force of the coating layer is 30gf / in or less and the residual adhesion rate is characterized in that more than 80%, the carrier film for adhesion processing.