KR100529053B1 - Adhesive film for protection of photomask and photomask using the same - Google Patents

Abstract

The present invention; A primer layer formed on the upper surface of the substrate and including a urethane-modified polyester resin or a derivative thereof; A first release layer formed on an upper surface of the primer layer; An adhesive layer formed on the lower surface of the substrate; And to a photomask protective adhesive film comprising a second release layer formed on the lower surface of the adhesive layer and a photomask using the same, by using a primer layer to improve the adhesion and friction resistance between the primer layer and the first release layer By enhancing the durability of the first release layer, it is possible to provide a pressure-sensitive adhesive film for protecting a photomask, which improves workability and prevents quality deterioration due to poor exposure.

Description

Adhesive film for photomask protection, and photomask using the same {Adhesive film for protection of photomask and photomask using the same}

The present invention relates to a photomask protective adhesive film and a photomask using the same, and more particularly, to a photomask protective adhesive film and a photomask using the same, which can be used without damage even after repeated exposure of the resist.

In general, the photomask protective film is used to protect the photomask 10 from the resist film 02 applied to the substrate 01 in a resist photosensitive process as shown in FIG. ), The base material 11, the primer layer 12, and the release layer 13.

Particularly, when a highly viscous resist such as a liquid resist or a solder resist is used to form the resist film 02, a release function is required to enable a smooth separation between the photomask protective film and the resist. .

However, as the extinction of the release layer is accelerated by repeated exposure and separation, the resist is buried on the surface of the protective film as the number of exposures of the resist is increased. As a result, the workability decreases due to frequent exchange of the protective film. As a result, there is a problem of deterioration of quality due to poor exposure, which requires improvement.

The present invention, in order to solve the above problems, by improving the durability of the release layer positioned adjacent to the resist film improves workability and prevents the degradation of the quality due to poor exposure, the adhesive film for photomask and photomask using the same To provide.

In order to achieve the above technical problem,

In the present invention, the substrate; A primer layer formed on the upper surface of the substrate and including a urethane-modified polyester resin or a derivative thereof; A first release layer formed on an upper surface of the primer layer; An adhesive layer formed on the lower surface of the substrate; And a second release layer formed on the lower surface of the adhesive layer.

Another technical problem of the present invention is achieved by a photomask having a resultant in which the second release layer is peeled off and removed from the adhesive film for protecting the photomask.

The urethane-modified polyester derivative included in the primer layer is a urethane-modified polyester resin, at least one reaction product selected from a silane coupling agent and a curing agent.

The urethane-modified polyester resin and derivatives thereof included in the primer layer preferably have a weight average molecular weight of 10,000 to 100,000 and a glass transition temperature (Tg) of -3 ° C to 100 ° C.

The thickness of the primer layer is preferably 0.1 to 1.0 micron.

The first release layer may include a silicone-based resin, the thickness is preferably 0.1 to 0.5 microns.

The adhesive layer may include an acrylic resin, the thickness of which is preferably 1 to 10 microns.

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

As shown in FIG. 2, the present invention provides an adhesive film for protecting a photomask including a first release layer 23, a primer layer 22, a substrate 21, an adhesive layer 24, and a second release layer 25. to provide.

Since the pressure-sensitive adhesive film of the present invention has a thickness of the substrate 21 of 20 microns or less, the thickness of the entire pressure-sensitive adhesive film is thin, and the thickness of the primer layer 22 and the first release layer 23 is each 1 micron or less. Shrinkage hardly occurs. In addition, since the primer layer 22 includes a urethane-modified polyester resin or a derivative thereof, adhesion and friction resistance with the first release layer 23 are improved, so that durability of the first release layer 23 is improved and workability is improved. As a result, quality deterioration due to poor exposure can be prevented.

More specifically, the primer layer 22, which is a component of the protective film of the present invention, includes a urethane-modified polyester resin or a derivative thereof, and thus has a highly viscous resist such as a liquid resist or a solder resist. Even if using the adhesive layer between the primer layer 22 and the first release layer 23 is enhanced to improve the durability of the first release layer 23 to improve the workability, it is possible to prevent the degradation of quality due to poor exposure do.

The weight average molecular weight of the urethane-modified polyester resin or a derivative thereof contained in the primer layer 22 according to the present invention is preferably about 10,000 to 100,000. More preferably between 30,000 and 50,000 are most suitable. The glass transition temperature is suitably -3 ° C to 100 ° C and most preferably about 50 ° C to 90 ° C. If the Tg is too low or the molecular weight is too small, it may not express sufficient durability. If the Tg is too high or the molecular weight is too high, the adhesive force between the primer worm 22 and the first release layer 23 is lowered.

As described above, the urethane-modified polyester resin included in the primer layer 22 of the present invention contains a urethane group in its own structure using an aromatic polyester as a basic skeleton. Therefore, it is possible to increase the adhesive strength with the first release layer 23 by the urethane component contained in the structure excellent in hydrolysis resistance, excellent weather resistance and friction resistance, which is the basic property of the aromatic polyester. In addition, the primer layer 22 of the present invention may include a derivative of a urethane-modified polyester resin. The derivative refers to a urethane modified polyester and at least one reaction product selected from a silane coupling agent and a curing agent.

As the curing agent, an isocyanate compound, a melamine compound, an epoxy compound, or the like may be used, and an isocyanate compound is most preferable. Specifically, as the isocyanate compound, aliphatic diisocyanates such as hexamethylene diisocyanate or trimethylhexamethylene diisocyanate and cyclic aliphatic diisocyanates such as xylene diisocyanate or isophorone diisocyanate, tolylene diisocyanate or 4,4 ' Aromatic diisocyanates, such as diphenylmethane diisocyanate, etc. are mentioned, The hardening | curing agent in the case of using the said epoxy resin is an amine substance, For example, aromatic polyhydric amines, such as phenylenediamine and tolylene diamine, and an aliphatic polyhydric acid are mentioned. Modified amines, such as amine and polyamide amine, are mentioned. In addition, as the melamine curing agent, hexamethylol melamine, pentamethylol melamine, tetramethylol melamine and the like can be used.

The curing agent may be used 1.0 to 15 parts by weight based on 100 parts by weight of the urethane-modified polyester resin, when the content is less than 1 part by weight it is difficult to exert the friction resistance effect, when the content exceeds 15 parts by weight Is high, but the adhesion to the first release layer is inferior, and there is a risk that coating defects occur when the first release layer is coated.

In addition, when the silane coupling agent is used to form the primer layer 22 of the present invention, the adhesion with the first release layer 23 may be increased. The silane coupling agent may be used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the urethane-modified polyester resin. When the content of the silane coupling agent is less than 0.1 part by weight, it is difficult to provide sufficient adhesive strength. When the content of the silane coupling agent exceeds 5 parts by weight, the adhesive force between the primer layer 22 and the first release layer 23 is rather increased. It is not preferable because there is a problem of deterioration.

As described above, the silane coupling agent used in the primer layer 22 of the present invention includes at least one silane coupling compound having a specific reactive functional group, and the silane coupling compound includes an active hydrogen-containing amino group, epoxy, vinyl group, mer As long as it has at least one reactive functional group selected from a capto group and a (meth) acryloxy group, any can be used regardless of the chemical structure. Specific examples of these are as follows.

(1) a compound having an amino group

N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane

N- (aminoethyl) -3-aminopropyltrimethoxysilane

3-aminopropyltriethoxysilane

(2) a compound having an epoxy group

3-glycidoxypropyltrimethoxysilane

3-glycidoxypropylmethyldimethoxysilane

2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane

(3) a compound having a vinyl group

Vinyltriethoxysilane

(4) a compound having a mercapto group

3-mercaptopropyltrimethoxysilane

(5) A compound having a (meth) acryloxy group

3-methacryloxypropyltrimethoxysilane

3-methacryloxypropylmethyldimethoxysilane

Of the silane coupling agents, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, vinyltriethoxysilane and 3-glycidoxypropyltrimethoxysilane are particularly preferred.

A method of forming the primer layer 22 will be described in detail.

The composition forming the primer layer is prepared by mixing a urethane-modified polyester resin and an organic solvent such as toluene, methyl ethyl ketone, ethyl acetate and the like. The content of the organic solvent is 100 to 1,000 parts by weight based on 100 parts by weight of the urethane-modified polyester resin.

A silane coupling agent and a curing agent may be optionally added to the composition.

The primer layer 22 may be formed to a thickness of 1.0 micron or less, more preferably 0.1 to 1.0 micron in thickness. When the thickness exceeds 1.0 micron, shrinkage of the adhesive film may occur, which is not preferable.

As the base material 21 used for the photomask protective adhesive film of this invention, although it can select suitably from well-known materials, It is polyester, such as polyethylene terephthalate, polypropylene, polyethylene, polyvinyl chloride, polystyrene, polycarbonate, As a plastic film which has a triacetate etc. as a main component, an oriented film is suitable and a biaxially stretched film is more preferable. The manufacturing process follows a conventional method well known in the art. Such a substrate 1 can be used with a thickness of 20 microns or less, more preferably from 2 to 16 microns. When the thickness of the base material exceeds 20 microns, the thickness of the pressure-sensitive adhesive film becomes too thick, which is not preferable.

The first release layer 23, which is one component of the photomask protective adhesive film of the present invention, is formed on the upper surface of the primer layer 22, and the first release layer 23 in the technical field to which the present invention pertains. Any component can be used without limitation, but it is preferable to include a silicone-based resin, for example, an addition reaction type silicone release agent can be used.

A method of forming the first release layer 23 will be described.

The composition forming the first release layer is prepared by mixing a catalyst and an organic solvent in addition to the silicone resin. The catalyst may be used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the silicone resin, and there is no particular limitation, for example, a platinum catalyst may be used. The organic solvent that can be used in the first release layer 23 is not particularly limited, but toluene, normal hexane, methyl ethyl ketone, and the like may be used, and the content thereof is 100 to 1,000 parts by weight based on 100 parts by weight of the silicone resin. Can be used.

The thickness of such a 1st release layer 23 is 1 micron or less, and the thickness of 0.1-0.5 micron is more preferable. If the thickness exceeds 1 micron, there is a fear that shrinkage of adhesion occurs.

The adhesive layer 24, which is one of the constituents of the photomask protective adhesive film of the present invention, is formed on the lower surface of the substrate 21 used as the substrate, and may be formed by applying the adhesive component by various coating methods, and the thickness thereof. 10 microns or less are preferable and the thickness of 1-10 microns is more preferable. The adhesive layer 24 may be used without any limitation as long as it has been conventionally used in the art, and mainly includes acrylic resins, for example, crosslinked with polyisocyanate using a composition containing butyl acrylate. Can be.

The second release layer 25, which is one of the constituents of the photomask protective adhesive film of the present invention, may be used without limitation as long as it has been commonly used in the art, for example, having a thickness of 12 to 25 microns. What apply | coated the addition type silicone resin to the base material can be used.

The method of coating each composition according to the present invention, for example, the primer layer 22, the first release layer 23, the adhesive layer 24, and the like on the substrate may be performed by a method known in the art. Representative examples thereof include roll coating, spray coating, gravure coating, reverse gravure coating, maybar coating, die coating, and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1

As shown in FIG. 2, the photomask protective film includes a substrate 21, a primer layer 22 formed on the upper surface of the substrate 21, and a first release layer 23 formed on the upper surface of the primer layer 22. And an adhesive layer 24 formed on the lower surface of the substrate 21, and a second release layer 25 formed on the lower surface of the adhesive layer 24.

The thickness of the substrate (1) was 5.6 micron ultra-thin film, the primer layer (22) was prepared by the composition of the following formulation, and then the composition of 1 micron using the gravure coating method on the upper surface of the substrate (21) The primer layer 22 was formed by applying to a thickness. The first release layer 23 was formed to a thickness of 0.5 micron using the gravure coating method of the composition for forming the first release layer 23 formed on the upper surface of the primer layer 22 by the following formulation.

On the lower surface of the base material 21, a butyl acrylate-based composition crosslinked with polyisocyanate was applied to a thickness of 2 microns to form an adhesive layer 24, and then on the lower surface of the base material having a thickness of 25 microns. The second release layer 25 obtained by applying the additional silicone resin was bonded to prepare a photomask protective adhesive film having a laminated structure as shown in FIG. 2.

Mixing of the composition for forming the primer layer 22

100 parts by weight of urethane-modified polyester resin (TOYOBO, UR-4122)

Silane Coupling Agent (Shinetsu, KBM1003) 3 parts by weight

400 parts by weight of methyl ethyl ketone

Mixing of the composition for forming the first release layer 23

100 parts by weight of addition reaction type silicone release agent (Shinetsu, KS847H)

1 part by weight of platinum catalyst (Shinetsu, PL50T)

Toluene 499 parts by weight

Example 2

A photomask protective pressure-sensitive adhesive film was prepared in the same manner as in Example 1, except that 5 parts by weight of an isocyanate compound was further added to the formulation of the composition for forming the primer layer 22.

Comparative Example 1

Except that the urethane-modified polyester resin was changed to unsaturated polyester resin in the formulation of the composition for forming the primer layer 22 was carried out in the same manner as in Example 1 to prepare a pressure-sensitive adhesive film for the photomask.

Comparative Example 2

Except for changing the urethane-modified polyester resin to the polyurethane resin in the formulation of the composition for forming the primer layer 22 was carried out in the same manner as in Example 1 to prepare a pressure-sensitive adhesive film for a photomask.

Comparative Example 3

Except for adding 5.0 parts by weight based on 100 parts by weight of an unsaturated polyester resin as a curing agent to the formulation of the composition for forming the primer layer 22 was carried out in the same manner as in Comparative Example 1 to protect the photomask A film was prepared.

Comparative Example 4

Except for adding 5.0 parts by weight of the isocyanate compound to 100 parts by weight of the polyurethane resin as a curing agent in the formulation of the composition for forming the primer layer 22 was carried out in the same manner as in Comparative Example 2 to provide a pressure-sensitive adhesive film for protecting the photomask Prepared.

Experimental Example: Performance Evaluation

The photomask protective adhesive films prepared in Examples and Comparative Examples were evaluated for the following items, and the results are shown in Table 1 below.

(1) Durability of the first release layer 23: The surface of the first release layer 23 was repeatedly subjected to reciprocating friction while applying a load of 500 grams with a cotton cloth dipped in resist ink.

(2) Peeling force: The peeling force of the part of the 1st release layer 23 which reciprocated friction with the cotton cloth was measured. As the adhesive tape used when measuring the peel force, 31B of the same major was used.

division Reciprocating Friction Recovery 0 times 100 times 300 times 500 Example 1 2.0g / 10mm 5.2 grams / 10 mm 11.5g / 10mm 15.7g / 10mm Example 2 2.3 grams / 10 mm 4.0 grams / 10mm 6.7g / 10mm 8.3 grams / 10 mm Comparative Example 1 2.0g / 10mm 7.3 g / 10 mm 19.4 g / 10 mm 25.7 grams / 10mm Comparative Example 2 2.0g / 10mm 8.4 grams / 10 mm 23.4g / 10mm 35.8g / 10mm Comparative Example 3 2.5 g / 10 mm 5.4g / 10mm 13.7g / 10mm 19.5g / 10mm Comparative Example 4 2.4 g / 10 mm 5.3 grams / 10 mm 14.4g / 10mm 22.7g / 10mm

As for the peeling force measurement result of the said Table 1, the case of Examples 1-2 containing the urethane modified polyester resin in the composition for forming the primer layer 22 of this invention is a comparative example containing an unsaturated polyester resin or a polyurethane resin. The values smaller than the case of 1 to 4 are shown. This is because the urethane-modified polyester resin or derivative thereof forming the primer layer 22 increases the adhesive force with the first release layer 23 while providing excellent friction resistance, thereby releasing the release force of the first release layer 23. It can be seen that the result is not. In addition, as can be seen from Example 2, when the isocyanate-based curing agent was further added to the primer layer 22, the durability of the first release layer was excellent.

The pressure-sensitive adhesive film for photomask protection according to the present invention improves the adhesion and friction resistance between the primer layer 22 and the first release layer 23 by using a primer layer 22 containing a urethane-modified polyester resin and derivatives thereof. By enhancing the durability of the first release layer 23, it is possible to provide an adhesive film for protecting the photomask, which improves workability and prevents quality deterioration due to poor exposure.

1 is a diagram illustrating a state of use of an adhesive film for protecting a general photomask;

2 shows a cross-sectional view of an adhesive film for protecting a photomask according to the present invention.

<Brief description of symbols used in the drawings>

01: substrate 02: resist film 10: photomask

11: base material 12: primer layer

13: release layer 14: adhesive layer

21 base material 22 primer layer 23 first release layer

24: adhesive layer 25: second release layer

Claims (11)

materials; A primer layer formed on the upper surface of the substrate and including a urethane-modified polyester resin or a derivative thereof; A first release layer formed on an upper surface of the primer layer; An adhesive layer formed on the lower surface of the substrate; And a second release layer formed on the lower surface of the adhesive layer. The pressure-sensitive molecular film of claim 1, wherein the weight-average molecular weight of the urethane-modified polyester resin or a derivative thereof contained in the primer layer is 10,000 to 100,000. The pressure-sensitive adhesive film for photomask protection according to claim 1, wherein a glass transition temperature (Tg) of the urethane-modified polyester resin or derivative thereof included in the primer layer is -3 ° C to 100 ° C. The pressure-sensitive adhesive film of claim 1, wherein the urethane-modified polyester derivative is at least one reaction product selected from a urethane-modified polyester resin, a silane coupling agent, and a curing agent. 5. The pressure-sensitive adhesive film of claim 4, wherein the curing agent is selected from an isocyanate compound, a melamine compound, and an epoxy compound. The pressure-sensitive adhesive film of claim 4, wherein 1 to 15 parts by weight of a curing agent or 0.1 to 5 parts by weight of a silane coupling agent is used based on 100 parts by weight of the urethane-modified polyester resin. The adhesive film for photomask protection of Claim 1 whose thickness of the said primer layer is 1 micron or less. The pressure-sensitive adhesive film for photomask protection according to claim 1, wherein the first release layer contains a silicone-based resin and has a thickness of 1 micron or less. The pressure-sensitive adhesive film of claim 1, wherein the pressure-sensitive adhesive layer contains an acrylic resin and its thickness is 10 microns or less. 2. The pressure-sensitive adhesive film for photomask protection according to claim 1, wherein the base material comprises polyester, and its thickness is 20 microns or less. The resultant which the said 2nd release layer peeled and removed from the adhesive film for photomask protection of any one of Claims 1-9 was affixed. The photomask characterized by the above-mentioned.