KR20210115256A - Release film for carrier and manufacturing method thereof - Google Patents

Abstract

Disclosed are a release film for a carrier and a method for manufacturing the same. The release film for a carrier comprises a base material film; and a release layer positioned on at least one side of the base material film. The release layer is a hardened layer comprising an amino resin and a low molecular or oligomer polyethermodified polysiloxane copolymer. Surface energy of the release layer is 20 to 50 dyne/cm and an area of pinholes per unit square meter (m^2) is 6.3 x 10^-3 m^2 or less. According to the present invention, the release film for a carrier has excellent post-curing peelability even after high temperature and long post-processing.

Description

Release film for carrier and manufacturing method thereof

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

The release film is a film used as a protective film to be attached to the pressure-sensitive adhesive film to protect the pressure-sensitive adhesive component from foreign substances or unwanted adherends in the atmosphere. In general, a release film has a structure in which a release layer is disposed on one surface of a base film.

This release film can be used as a release film for a carrier to obtain a film-shaped workpiece by directly applying an adhesive, an adhesive, a resin sheet, a resin film, a ceramic sheet, etc. on the release film and then peeling the release film.

However, when a release film is applied to a release film for a carrier, poor wettability and/or pinholes occur during direct application of other resins on the release layer of the release film, making it difficult to obtain a uniform coating film, or The release layer may be cemented and not fall off.

Therefore, there is a need for a release film that can uniformly apply adhesives, adhesives, and various resins on the release layer without defects such as poor wettability or pinholes, and realize excellent post-curing peelability even after high temperature and long post-processing. still there

In one aspect, a release film for a carrier can be formed by freely applying an adhesive, an adhesive, various resins, etc. on the release layer to form a uniform film and having excellent post-curing peelability even after high temperature and long post-processing.

Another aspect provides a method of manufacturing the release film for the carrier.

According to one aspect,

base film; and

It may include; a release layer located on at least one surface of the base film,

The release layer may be a cured layer comprising an amino resin and a low-molecular or oligomeric polyether-modified polysiloxane copolymer,

The surface energy of the release layer may be 20 to 50 dyne/cm, and the area of the pinhole per ^{unit square meter (m 2 ) is 6.3x10 -3} m ² or less, a release film for a carrier is provided.

The amino resin may include at least one selected from a melamine resin, a melamine urea resin, and a urea resin.

The low molecular or oligomeric polyether-modified polysiloxane copolymer may be a copolymer including a polyether structural unit including at least one of polyethylene glycol and polypropylene glycol, and a polydimethylsiloxane structural unit having an alkenyl functional group.

The low molecular or oligomeric polyether-modified polysiloxane copolymer is a linear triblock copolymer composed of a polyether structural unit-polydimethylsiloxane structural unit-polyether structural unit, a copolymer of a polydimethylsiloxane structural unit grafted with a polyether structural unit, or combinations thereof.

The molar ratio of the polydimethylsiloxane structural unit to the polyether structural unit may be 0.2 or more.

The number average molecular weight (Mn) of the low molecular or oligomeric polyether-modified polysiloxane copolymer may be 10,000 or less.

The content of the low molecular or oligomeric polyether-modified polysiloxane copolymer may be 100 parts by mass or less based on 100 parts by mass of the amino resin.

It may further include an acid catalyst.

The acid catalyst may include at least one selected from dinonylnaphthalene sulfonic acid, dinonylnaphthalene disulfonic acid, alkylbenzene sulfonic acid, ρ-toluenesulfonic acid, and phosphoric acid. .

The content of the acid catalyst may be 0.1 to 10 parts by mass based on 100 parts by mass of the amino resin.

The release film may be used in a pressure-sensitive adhesive, a semi-curable adhesive, a ceramic sheet for a multilayer ceramic capacitor, a semi-cured resin for a printed circuit, or a prepreg.

According to the other aspect,

preparing a composition for forming a release layer by adding and stirring an amino resin and a low molecular weight or oligomeric polyether-modified polysiloxane copolymer to a solvent; and

A method for producing a release film for a carrier is provided, comprising: applying the composition for forming the release layer on at least one surface of the base film and drying the release layer with hot air to form a release layer.

The solid content of the composition for forming the release layer may be 0.1 wt% or more based on 100 wt% of the total.

The release film for a carrier according to one aspect includes a release layer of a cured layer containing an amino resin and a low molecular or oligomeric polyether-modified polysiloxane copolymer, and a pressure-sensitive adhesive, an adhesive, various resins, etc. are freely applied on the release layer to be uniform. It is possible to provide a release film capable of forming a single coating film and having excellent post-curing releasability even after undergoing post-processing at high temperatures and for a long time. In addition, the method of manufacturing the release film for the carrier can provide a method for easily manufacturing the release film for the carrier while reducing the production cost.

1 is a schematic cross-sectional view of a release film for a carrier according to an embodiment.
2 is a graph showing the relationship between the surface energy and the applicability of the release film for carriers prepared in Examples 1 to 13.

Hereinafter, a release film for a carrier and a manufacturing method thereof will be described in detail with reference to embodiments and drawings of the present invention. It will be apparent to those of ordinary skill in the art that these examples are only presented by way of example to explain the present invention in more detail, and that the scope of the present invention is not limited by these examples. .

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

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

As used herein, the term "on (or on)" includes not only the case where another part is located "directly on (or directly on)" but also the case where another part is interposed therebetween. Conversely, the term “directly on (or directly on)” means without intervening other portions.

In the present specification, "~-based resin", "~-based polymer", "~-based polymer", "~-based copolymer" means "~ resin", "~ polymer", "~ polymer", "~ copolymer", or / and a concept in a broad sense including all of these derivatives.

Unless otherwise specified in the specification, the unit "part by weight" means a weight ratio between each component, and the unit "part by mass" means a value obtained by converting the weight ratio between each component into solid content.

In general, the applicability of the release layer of the release film for a carrier and the peeling force after the processing process are related to the surface energy. For example, the higher the surface energy of the release layer of the release film for the carrier, the better the coating property of the resin, and the lower the surface energy, the better the peelability of the release film.

However, for example, even if the surface energy of the release layer is adjusted by mixing a melamine resin, an acrylic resin, and a silicone resin, a uniform coating film cannot be obtained when a resin with a low solid content is applied due to the low surface energy of the silicone resin, and the molecular weight Since this large polymer silicone resin is used, there is a problem that the curing reaction is slow.

The inventors of the present invention intend to propose the following release film for carriers in order to improve the above problems.

A release film for a carrier according to an embodiment includes a base film; and a release layer located on at least one surface of the base film, wherein the release layer may be a cured layer comprising an amino resin and a low molecular or oligomeric polyether-modified polysiloxane copolymer, and the surface energy of the release layer is It may be 20 to 50 dyne/cm, and the area of the pinhole per ^{unit square meter (m 2 ) may be 6.3x10 -3} m ² or less.

A release film for a carrier according to an embodiment includes a base film; It may include a release layer located on at least one surface of the base film.

The base film may be a polyester-based base film. For example, the polyester-based base film may include polyethylene terephthalate, polybutylene terephthalate, or polyethylene naphthalate. For example, the polyester-based base film may be obtained by polycondensing an aromatic dicarboxylic acid and an aliphatic glycol. Examples of the aromatic dicarboxylic acid include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, or oxycarboxylic acid (for example, ρ-oxybenzoic acid, etc.) Can be used. As the aliphatic glycol, ethylene glycol, diethylene glycol, propylene glycol, butanediol, 1,4-cyclohexanedimethanol, or neopentyl glycol may be used. In the polyester-based base film, two or more of the dicarboxylic acid component and the glycol component may be used in combination, and a copolymer containing a third component is also possible. In addition, the polyester-based base film may use a uniaxial or biaxially oriented film having high transparency and excellent productivity and processability. The polyester-based resin may be, for example, polyethylene terephthalate (PET).

The amino resin may be, for example, a thermosetting amino resin. The amino resin may include at least one selected from a melamine resin, a melamine urea resin, and a urea resin. However, the present invention is not limited thereto, and thermosetting amino resins available in the art may be used.

The low molecular or oligomeric polyether-modified polysiloxane copolymer may be a copolymer including a polyether structural unit including at least one of polyethylene glycol and polypropylene glycol, and a polydimethylsiloxane structural unit having an alkenyl functional group.

The low molecular or oligomeric polyether-modified polysiloxane copolymer is a linear triblock copolymer composed of a polyether structural unit-polydimethylsiloxane structural unit-polyether structural unit, a copolymer of a polydimethylsiloxane structural unit grafted with a polyether structural unit, or combinations thereof.

The molar ratio of the polydimethylsiloxane structural unit to the polyether structural unit may be 0.2 or more. If the molar ratio of the polydimethylsiloxane structural unit to the polyether structural unit is less than 0.2, compatibility with the polyether structural unit component is not good, so that the appearance may be deteriorated and release property may not be sufficiently implemented.

The number average molecular weight (Mn) of the low molecular or oligomeric polyether-modified polysiloxane copolymer may be 10,000 or less. For example, the number average molecular weight (Mn) of the low molecular or oligomeric polyether-modified polysiloxane copolymer may be 500 to 10,000 or 1,000 to 7,000. If the number average molecular weight (Mn) of the low-molecular or oligomeric polyether-modified polysiloxane copolymer is less than 500, curls are likely to occur in the film when forming the coating film, and releasability may not be sufficiently implemented, and the molecular weight exceeds 10,000 If so, it may become difficult to form a coating film at a low temperature and in a short time.

The surface energy of the release layer may be 20 to 50 dyne/cm. If the surface energy of the release layer is less than 20 dyne/cm, it may be difficult to obtain a uniform film because wettability is poor and defects such as pinholes occur when a desired resin is applied on the release layer. If the surface energy of the release layer exceeds 50 dyne/cm, the peeling force of the release film for a carrier may be increased.

By controlling the surface energy of the release layer, various resins can be uniformly applied on the release layer without defects such as poor wettability and/or pinholes, and excellent post-curing peel strength can be implemented even after high temperature and long post-processing. .

The area of the pinhole per unit square meter (m ^{2 ) of the release layer may be 6.3x10 -3} m ² or less. When the area of the pinhole per unit square meter (m ^{2 ) of the release layer exceeds 6.3x10 -3} m ² , it may be difficult to obtain a uniform film.

The content of the low molecular or oligomeric polyether-modified polysiloxane copolymer may be 100 parts by mass or less based on 100 parts by mass of the amino resin. For example, the content of the low molecular or oligomeric polyether-modified polysiloxane copolymer may be 50 parts by mass or less based on 100 parts by mass of the amino resin. If the content of the low-molecular or oligomeric polyether-modified polysiloxane copolymer exceeds 100 parts by mass based on 100 parts by mass of the amino resin, the adhesive force between the base film and the release layer is lowered and the release layer is separated when the release film is peeled off after the processing process can do.

The release film for the carrier may further include an acid catalyst.

The acid catalyst may include at least one selected from dinonylnaphthalene lsulfonic acid, dinonylnaphthalene disulfonic acid, alkylbenzene sulfonic acid, ρ-toluenesulfonic acid, and phosphoric acid. . For example, the acid catalyst may be ρ-toluenesulfonic acid.

The content of the acid catalyst may be 0.1 to 10 parts by mass based on 100 parts by mass of the amino resin. If the content of the acid catalyst is less than 1.0 parts by mass, the curing reaction may be delayed, and if it is more than 10 parts by mass, the storage stability of the composition for forming a release layer may be deteriorated.

The release film for the carrier may be used in an adhesive, a semi-curable adhesive, a ceramic sheet for a multilayer ceramic capacitor, a semi-cured resin for a printed circuit, or a prepreg.

A method of manufacturing a release film for a carrier according to another embodiment includes preparing a composition for forming a release layer by adding and stirring an amino resin, and a low molecular or oligomeric polyether-modified polysiloxane copolymer to a solvent; and applying the composition for forming a release layer to at least one surface of the base film and drying with hot air to form a release layer.

Since the types and contents of the amino resin and the low molecular weight or oligomeric polyether-modified polysiloxane copolymer are the same as those described above, the following description will be omitted.

First, an amino resin and a low molecular or oligomeric polyether-modified polysiloxane copolymer are added to a solvent, for example, an organic solvent, and stirred to prepare a composition for forming a release layer.

The organic solvent may be, for example, ketones. However, the present invention is not limited thereto, and organic solvents available in the art may be used.

The solid content of the composition for forming the release layer may be 0.1 wt% or more based on 100 wt% of the total. If the solid content of the composition for forming the release layer is less than 0.1 wt% based on 100 wt% of the total, the composition for forming the release layer is not uniformly applied on the base film, so that the release layer is not partially formed. Addition may occur, resulting in insufficient releasability. In addition, the upper limit of the solid content is not particularly limited, but if it contains a large amount of solid content, it may cause an increase in production cost.

The composition for forming the release layer may further include an acid catalyst. Since the type of the acid catalyst is the same as described above, a description thereof will be omitted. The composition for forming the release layer may further contain an acid catalyst to shorten drying time, for example, hot air drying time.

Next, the composition for forming the release layer is applied to at least one surface of the base film and dried with hot air to form a release layer.

As a method of applying the composition for forming the release layer to at least one surface of the base film, any one of gravure, comma, Mayer bar, lip, die, or spray can be used. However, the present invention is not limited thereto, and all coating methods available in the art can be performed.

The hot air drying may be performed at a temperature of 100 to 200 ℃ for 1 to 10 minutes.

The method of manufacturing the release film for the carrier can easily manufacture the release film for the carrier while reducing the production cost.

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

Referring to FIG. 1 , the release film 10 for a carrier according to an embodiment may have a structure in which a base film 1 and a release layer 2 are sequentially disposed.

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

[Example]

Example 1: Release film for carrier

100 parts by mass of a melamine resin (Cymel 303LF, Allnex Japan Co., Ltd.) as an amino resin, based on 100 parts by mass of the melamine resin, a polyether structural unit (A) grafted polydimethylsiloxane structural unit (B) 100 parts by mass of polyether-modified polysiloxane copolymer (molar ratio of (B)/(A): 0.28, Mn: 3,100, 193C, manufactured by Dow Corning), and ρ-toluenesulfonic acid as an acid catalyst (manufactured by Allnex Japan Co., Ltd.) 4 A composition for forming a release layer having a solid content of 4% by weight was prepared by adding a mass part to methylethylketone and stirring for 30 minutes.

The composition for forming the release layer was applied to one side of the polyethylene terephthalate base film using a Mayer bar, and then dried at 140° C. for 1 minute with a hot air dryer to prepare a release film for a carrier.

Example 2: Release film for carrier

Molar ratio of polyether-modified polysiloxane copolymer ((B)/(A) of polydimethylsiloxane structural unit (B) to which polyether structural unit (A) is grafted based on 100 parts by mass of the melamine resin: 0.28, Mn: 3,100 , 193C, manufactured by Dow Corning) A release film for a carrier was prepared in the same manner as in Example 1, except that 50 parts by mass was added.

Example 3: Release film for carrier

Molar ratio of polyether-modified polysiloxane copolymer ((B)/(A) of polydimethylsiloxane structural unit (B) to which polyether structural unit (A) is grafted based on 100 parts by mass of the melamine resin: 0.28, Mn: 3,100 , 193C, manufactured by Dow Corning) A release film for a carrier was prepared in the same manner as in Example 1, except that 20 parts by mass was added.

Example 4: Release film for carrier

Molar ratio of polyether-modified polysiloxane copolymer ((B)/(A) of polydimethylsiloxane structural unit (B) to which polyether structural unit (A) is grafted based on 100 parts by mass of the melamine resin: 0.28, Mn: 3,100 , 193C, manufactured by Dow Corning) instead of the polyether structural unit (A) grafted polydimethylsiloxane structural unit (B) polyether-modified polysiloxane copolymer ((B) / (A) molar ratio: 0.32, Mn: 600, Q2-5211, manufactured by Dow Corning) A release film for a carrier was prepared in the same manner as in Example 1, except that 100 parts by mass was added.

Example 5: Release film for carrier

Molar ratio of polyether-modified polysiloxane copolymer ((B)/(A) of polydimethylsiloxane structural unit (B) to which polyether structural unit (A) is grafted based on 100 parts by mass of the melamine resin: 0.28, Mn: 3,100 , 193C, manufactured by Dow Corning) instead of the polyether structural unit (A) grafted polydimethylsiloxane structural unit (B) polyether-modified polysiloxane copolymer ((B) / (A) molar ratio: 0.32, Mn: 600, Q2-5211, manufactured by Dow Corning) A release film for a carrier was prepared in the same manner as in Example 1, except that 50 parts by mass was added.

Example 6: Release film for carrier

Molar ratio of polyether-modified polysiloxane copolymer ((B)/(A) of polydimethylsiloxane structural unit (B) to which polyether structural unit (A) is grafted based on 100 parts by mass of the melamine resin: 0.28, Mn: 3,100 , 193C, manufactured by Dow Corning) instead of the polyether structural unit (A) grafted polydimethylsiloxane structural unit (B) polyether-modified polysiloxane copolymer ((B) / (A) molar ratio: 0.32, Mn: 600, Q2-5211, manufactured by Dow Corning) A release film for a carrier was prepared in the same manner as in Example 1, except that 20 parts by mass was added.

Example 7: Release film for carrier

Molar ratio of polyether-modified polysiloxane copolymer ((B)/(A) of polydimethylsiloxane structural unit (B) to which polyether structural unit (A) is grafted based on 100 parts by mass of the melamine resin: 0.28, Mn: 3,100 , 193C, manufactured by Dow Corning) instead of a polyether structural unit (A) - a polydimethylsiloxane structural unit (B) - a linear triblock polyether modified polysiloxane copolymer consisting of a polyether structural unit (A) ((B) / (A) ) molar ratio: 0.45, Mn: 2,200, Q4-3677, manufactured by Dow Corning) A release film for a carrier was prepared in the same manner as in Example 1, except that 50 parts by mass was added.

Example 8: Release film for carrier

Molar ratio of polyether-modified polysiloxane copolymer ((B)/(A) of polydimethylsiloxane structural unit (B) to which polyether structural unit (A) is grafted based on 100 parts by mass of the melamine resin: 0.28, Mn: 3,100 , 193C, manufactured by Dow Corning) instead of a polyether structural unit (A) - a polydimethylsiloxane structural unit (B) - a linear triblock polyether modified polysiloxane copolymer consisting of a polyether structural unit (A) ((B) / (A) ) molar ratio: 0.45, Mn: 2,200, Q4-3677, manufactured by Dow Corning) A release film for a carrier was prepared in the same manner as in Example 1, except that 15 parts by mass was added.

Example 9: Release film for carrier

Molar ratio of polyether-modified polysiloxane copolymer ((B)/(A) of polydimethylsiloxane structural unit (B) to which polyether structural unit (A) is grafted based on 100 parts by mass of the melamine resin: 0.28, Mn: 3,100 , 193C, manufactured by Dow Corning) instead of a polyether structural unit (A) - a polydimethylsiloxane structural unit (B) - a linear triblock polyether modified polysiloxane copolymer consisting of a polyether structural unit (A) ((B) / (A) ) molar ratio: 0.45, Mn: 2,200, Q4-3677, manufactured by Dow Corning) A release film for a carrier was prepared in the same manner as in Example 1, except that 5 parts by mass was added.

Example 10: Release film for carrier

Molar ratio of polyether-modified polysiloxane copolymer ((B)/(A) of polydimethylsiloxane structural unit (B) to which polyether structural unit (A) is grafted based on 100 parts by mass of the melamine resin: 0.28, Mn: 3,100 , 193C, manufactured by Dow Corning) instead of a polyether structural unit (A) - a polydimethylsiloxane structural unit (B) - a linear triblock polyether modified polysiloxane copolymer consisting of a polyether structural unit (A) ((B) / (A) ) molar ratio: 0.59, Mn: 1900, 2-8692, manufactured by Dow Corning) A release film for a carrier was prepared in the same manner as in Example 1, except that 30 parts by mass was added.

Example 11: Release film for carrier

Molar ratio of polyether-modified polysiloxane copolymer ((B)/(A) of polydimethylsiloxane structural unit (B) to which polyether structural unit (A) is grafted based on 100 parts by mass of the melamine resin: 0.28, Mn: 3,100 , 193C, manufactured by Dow Corning) instead of a polyether structural unit (A) - a polydimethylsiloxane structural unit (B) - a linear triblock polyether modified polysiloxane copolymer consisting of a polyether structural unit (A) ((B) / (A) ) molar ratio: 0.59, Mn: 1900, 2-8692, manufactured by Dow Corning) A release film for a carrier was prepared in the same manner as in Example 1, except that 10 parts by mass was added.

Example 12: Release film for carrier

Molar ratio of polyether-modified polysiloxane copolymer ((B)/(A) of polydimethylsiloxane structural unit (B) to which polyether structural unit (A) is grafted based on 100 parts by mass of the melamine resin: 0.28, Mn: 3,100 , 193C, manufactured by Dow Corning) instead of a polyether structural unit (A) grafted with a polyether-modified polysiloxane copolymer ((B)/(A) of a polydimethylsiloxane structural unit (B) Molar ratio of ((B)/(A): 0.87, Mn: 6,100, 1248, manufactured by Dow Corning) A release film for a carrier was prepared in the same manner as in Example 1, except that 10 parts by mass was added.

Example 13: Release film for carrier

Molar ratio of polyether-modified polysiloxane copolymer ((B)/(A) of polydimethylsiloxane structural unit (B) to which polyether structural unit (A) is grafted based on 100 parts by mass of the melamine resin: 0.28, Mn: 3,100 , 193C, manufactured by Dow Corning) instead of a polyether structural unit (A) grafted with a polyether-modified polysiloxane copolymer ((B)/(A) of a polydimethylsiloxane structural unit (B) Molar ratio of ((B)/(A): 0.87, Mn: 6,100, 1248, manufactured by Dow Corning) A release film for a carrier was prepared in the same manner as in Example 1, except that 5 parts by mass was added.

Comparative Example 1: Release film for carrier

A release film for a carrier was prepared in the same manner as in Example 2, except that 0.5 parts by mass of ρ-toluenesulfonic acid (manufactured by Allnex Japan Co., Ltd.) was added as an acid catalyst based on 100 parts by weight of the melamine resin.

Comparative Example 2: Release film for carrier

A release film for a carrier was prepared in the same manner as in Example 8, except that 0.5 parts by mass of ρ-toluenesulfonic acid (manufactured by Allnex Japan Co., Ltd.) was added as an acid catalyst based on 100 parts by weight of the melamine resin.

Comparative Example 3: Release film for carrier

Molar ratio of polyether-modified polysiloxane copolymer ((B)/(A) of polydimethylsiloxane structural unit (B) to which polyether structural unit (A) is grafted based on 100 parts by mass of the melamine resin: 0.28, Mn: 3,100 , 193C, manufactured by Dow Corning) A release film for a carrier was prepared in the same manner as in Example 1, except that 150 parts by mass was added.

Comparative Example 4: Release film for carrier

Molar ratio of polyether-modified polysiloxane copolymer ((B)/(A) of polydimethylsiloxane structural unit (B) to which polyether structural unit (A) is grafted based on 100 parts by mass of the melamine resin: 0.28, Mn: 3,100 , 193C, manufactured by Dow Corning) instead of a polyether structural unit (A) - a polydimethylsiloxane structural unit (B) - a linear triblock polyether modified polysiloxane copolymer consisting of a polyether structural unit (A) ((B) / (A) ) molar ratio: 0.45, Mn: 2,200, Q4-3677, manufactured by Dow Corning) A release film for a carrier was prepared in the same manner as in Example 1, except that 150 parts by mass was added.

The compositions and contents of the release films for carriers prepared in Examples 1 to 13 and Comparative Examples 1 to 4 were summarized as follows. The results are shown in Table 1 below.

amino resin Polyether-modified polysiloxane copolymer acid catalyst Furtherance content
(parts by mass) composition (form) content
(parts by mass) Furtherance content
(parts by mass) Example 1 melamine
profit 100 193C
(graft) 100 ρ-toluenesulfonic acid 4 Example 2 melamine
profit 100 193C (graft) 50 ρ-toluenesulfonic acid 4 Example 3 melamine
profit 100 193C (graft) 20 ρ-toluenesulfonic acid 4 Example 4 melamine
profit 100 Q2-5211 (graft) 100 ρ-toluenesulfonic acid 4 Example 5 melamine
profit 100 Q2-5211 (graft) 50 ρ-toluenesulfonic acid 4 Example 6 melamine
profit 100 Q2-5211 (graft) 20 ρ-toluenesulfonic acid 4 Example 7 melamine
profit 100 Q4-3667 (linear tree block) 50 ρ-toluenesulfonic acid 4 Example 8 melamine
profit 100 Q4-3667 (linear tree block) 15 ρ-toluenesulfonic acid 4 Example 9 melamine
profit 100 Q4-3667 (linear tree block) 5 ρ-toluenesulfonic acid 4 Example 10 melamine
profit 100 2-8692 (linear treeblock) 30 ρ-toluenesulfonic acid 4 Example 11 melamine
profit 100 2-8692 (linear treeblock) 10 ρ-toluenesulfonic acid 4 Example 12 melamine
profit 100 1248 (graft) 10 ρ-toluenesulfonic acid 4 Example 13 melamine
profit 100 1248 (graft) 5 ρ-toluenesulfonic acid 4 Comparative Example 1 melamine
profit 100 193C (graft) 50 ρ-toluenesulfonic acid 0.5 Comparative Example 2 melamine
profit 100 Q4-3667 (linear tree block) 15 ρ-toluenesulfonic acid 0.5 Comparative Example 3 melamine
profit 100 193C (graft) 150 ρ-toluenesulfonic acid 4 Comparative Example 4 melamine
profit 100 Q4-3667 (linear tree block) 150 ρ-toluenesulfonic acid 4

Evaluation Example 1: Evaluation of physical properties of release film for carrier

The physical properties of the release films for carriers prepared in Examples 1 to 13 and Comparative Examples 1 to 4 were evaluated as follows. The results are shown in Table 2, Table 3, and Figure 2 below.

(1) Surface energy measurement

After dropping distilled water and diiodomethane on the surface of the release layer of each carrier release film prepared in Examples 1 to 13 and Comparative Examples 1 to 4, a contact angle measuring instrument (DSA-) 100, manufactured by KRUSS) to measure the contact angle. Then, the surface energy was calculated by substituting the measured contact angle value into the Owens Wendt model.

(2) Measurement of applicability

On the release films for carriers prepared in Examples 1 to 13 and Comparative Examples 1 to 4, the mixture prepared in the following composition was applied to a thickness of 20 μm using an applicator.

· UV-curable epoxy acrylate resin (RV-214-75, manufactured by Aekyung Chemical) 100 parts by weight,

Based on 100 parts by weight of the UV-curable epoxy acrylate resin,

, 1-hydroxy-cyclohexyl-phenyl ketone (Irgacure ^® 184, Ciba Specialty Chemicals, Ltd.) a first photoinitiator, 2 parts by weight, and

And 2, 4, 6-trimethylbenzoyl-diphenyl-phosphine oxide (Irgacure ^® TPO, BASF Co.) 1 part by weight of a second photo-initiator

Then, the size of the pinhole on the surface of the A4 size epoxy acrylate resin coating was visually measured using a ruler, and then the area of the pinhole per ^{unit square meter (m 2 ) was calculated.} At this time, as shown in Table 2 below, the coatability is expressed as 1 to 10 depending on the area of the pinhole, and if the area of the pinhole ^{per unit square meter (m 2} ) is 6.3x10 ^-3 m ² or less, "good" and 6.3x10 ^-3 m ² If it exceeds, it was evaluated as "bad".

pinhole area resin coating < 0.2x10 ^-4 m ² One


Good ≥ 0.2x10 ^-4 m ² , < 0.1x10 ^-3 m ² 2 ≥ 0.1x10 ^-3 m ² , < 0.5x10 ^-3 m ² 3 ≥ 0.5x10 ^-3 m ² , < 2.0x10 ^-3 m ² 4 ≥ 2.0x10 ^-3 m ² , < 4.4x10 ^-3 m ² 5 ^{≥ 4.4x10 -3 m 2, <6.3x10} -3 m 2 6 ≥ 6.3x10 ^-3 m ² , < 1.2x10 ^-2 m ² 7

error ≥ 1.2x10 ^-2 m ² , < 1.8x10 ^-2 m ² 8 ^{≥ 1.8x10 -2 m 2, <2.4x10} -2 m 2 9 ^{≥ 2.4x10 -2 m 2, <3.1x10} -2 m 2 10

(3) Post-curing peel force measurement

In the case of '(2) Measuring applicability', the UV-curable epoxy acrylate resin formed on each carrier release film prepared in Examples 1 to 13 and Comparative Examples 1 to 4 was subjected to a UV irradiator system (MS TECH). manufacturing) was used to irradiate ultraviolet rays with a light quantity of 100 ~ 500 mJ/cm ² , and after maintaining at room temperature for 24 hours, the post-curing peel strength of the release film for carriers was measured using the following measuring device and measuring method. did.

· Measurement device: AR-100 (Adhesion/Release Tester), chem-instrument manufacturing

·Measuring method: 250 release film for carrier mm Х 1500 After cutting to a sample size of mm, the 180° peel angle and 3000 mm/min peel speed were measured three times, and then the average value was obtained.

surface energy
(dyne/cm) resin coating Post-curing peel strength
(gf/25mm) Example 1 23.7 5 2.9 Example 2 36.9 3 4.0 Example 3 48.2 One 9.2 Example 4 23.4 6 3.2 Example 5 35.4 3 5.7 Example 6 46.8 One 8.3 Example 7 20.2 6 2.1 Example 8 31.5 4 4.4 Example 9 44.6 2 7.8 Example 10 24.6 5 3.8 Example 11 38.7 2 6.1 Example 12 22.5 6 2.4 Example 13 31.2 4 4.1 Comparative Example 1 41.5 9 - Comparative Example 2 44.7 7 - Comparative Example 3 22.8 6 50.0 Comparative Example 4 25.7 6 90.0

As shown in Table 3, the release films for carriers prepared in Examples 1 to 13 had a surface energy of 20-50 dyne/cm, good resin applicability, and excellent post-curing peel strength.

In comparison, the release films for carriers prepared in Comparative Examples 1 to 4 exhibited poor resin applicability and post-curing peel strength due to insufficient curing of the release layer.

Also, referring to FIG. 2 , it can be confirmed that there is a linear relationship between the applicability of the resin and the surface energy.

From this, the release films for carriers prepared in Examples 1 to 13 are various adhesives and semi-curable adhesives, ceramic sheets for multilayer ceramic capacitors, semi-cured resins for printed circuits, prepregs (such as glass fiber or carbon fiber), etc. It can be seen that it can be widely used as a carrier film in the field.

1: base film, 2: release layer, 10: release film

Claims (13)

base film; and
a release layer located on at least one surface of the base film;
The release layer is a cured layer comprising an amino resin and a low-molecular or oligomeric polyether-modified polysiloxane copolymer,
The surface energy of the release layer is 20 to 50 dyne/cm, and the area of the pinhole per ^{unit square meter (m 2 ) is 6.3x10 -3} m ² or less, the release film for a carrier. According to claim 1,
A release film for a carrier, wherein the amino resin comprises at least one selected from a melamine resin, a melamine urea resin, and a urea resin. According to claim 1,
The low-molecular or oligomeric polyether-modified polysiloxane copolymer is a copolymer comprising a polyether structural unit including at least one of polyethylene glycol and polypropylene glycol, and a polydimethylsiloxane structural unit having an alkenyl functional group, a release film for a carrier . According to claim 1,
The low molecular or oligomeric polyether-modified polysiloxane copolymer is a linear triblock copolymer composed of a polyether structural unit-polydimethylsiloxane structural unit-polyether structural unit, a copolymer of a polydimethylsiloxane structural unit grafted with a polyether structural unit, Or a release film for a carrier, including a combination thereof. 4. The method of claim 3,
A release film for a carrier, wherein the molar ratio of the polydimethylsiloxane structural unit to the polyether structural unit is 0.2 or more. According to claim 1,
The number average molecular weight (Mn) of the low molecular or oligomeric polyether-modified polysiloxane copolymer is 10,000 or less, a release film for a carrier. According to claim 1,
The content of the low molecular or oligomeric polyether-modified polysiloxane copolymer is 100 parts by mass or less based on 100 parts by mass of the amino resin, a release film for a carrier. According to claim 1,
A release film for a carrier further comprising an acid catalyst. 9. The method of claim 8,
For a carrier in which the acid catalyst includes at least one selected from dinonylnaphthalene lsulfonic acid, dinonylnaphthalene disulfonic acid, alkylbenzene sulfonic acid, ρ-toluenesulfonic acid, and phosphoric acid release film. 9. The method of claim 8,
A release film for a carrier in which the content of the acid catalyst is 1.0 to 10 parts by mass based on 100 parts by mass of the amino resin. According to claim 1,
The release film is an adhesive, a semi-curable adhesive, a ceramic sheet for a multilayer ceramic capacitor, a semi-cured resin for a printed circuit, or a release film for a carrier used in a prepreg. preparing a composition for forming a release layer by adding and stirring an amino resin and a low molecular weight or oligomeric polyether-modified polysiloxane copolymer to a solvent; and
Forming a release layer by applying the composition for forming the release layer on at least one surface of the base film and drying with hot air to form a release layer; a method for producing a release film for a carrier. 13. The method of claim 12,
The method for producing a release film for a carrier, wherein the solid content of the composition for forming the release layer is 0.1% by weight or more based on 100% by weight of the total.

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