JP6189830B2 - Thermosetting protective liquid for glass mask and glass mask - Google Patents

Description

  The present invention relates to a thermosetting protective liquid for forming a transparent protective film on a thin film pattern surface of a glass mask, and a transparent product comprising a cured product obtained by applying the protective liquid to the thin film pattern surface and thermally curing the liquid. The present invention relates to a glass mask having a protective film.

  For printed wiring boards and resin relief plates, a thin film pattern surface of a photomask (exposure document, hereinafter also referred to as “glass mask”) is adhered to an adhesive photoresist (liquid photoresist, etc.) and then a non-thin film pattern. It is produced by exposing from the surface side. For this reason, unless any treatment is applied to the surface of the photomask that faces the photoresist (hereinafter sometimes referred to as “resist-facing surface”), the photoresist is removed when the photomask is separated from the photoresist after the exposure is completed. A part of the film adheres to the surface of the photomask and remains on the photomask even if it is wiped off, resulting in a problem that the exposure accuracy for the next photoresist is reduced. Therefore, conventionally, a surface protective film having releasability is provided on the resist-facing surface of the photomask to prevent the photoresist from adhering to the photomask after completion of exposure (Patent Document 1).

However, when a surface protective film with a relatively large thickness is attached to a photomask, the exposure accuracy is reduced due to the thickness of the surface protective film, or the exposure accuracy is reduced due to bubbles entering during bonding. There was a problem with inviting.
Therefore, it is conceivable to provide a protective film directly on the resist facing surface of the photomask instead of such a surface protective film.

  On the other hand, in order to protect the surface of an article, a film having a hard coat property is bonded, or a coating film having a hard coat property is provided on the article surface. As a coating film having such hard coat properties, a coating film using a curable resin such as an epoxy resin, an acrylic resin, or a silicone resin is known (Patent Document 2).

WO2007 / 074778 (prior art) Japanese Patent Laying-Open No. 2005-186577 (Claim 2)

  When a protective film is formed using only a silicone resin with excellent hard coat properties, the refractive index of the silicone resin is close to that of glass. Can be prevented. On the other hand, since only a brittle protective film can be obtained, there is a problem that cracks are easily generated and the performance as a protective film cannot be obtained.

  When mixed with an epoxy resin to solve the problem of cracking, the epoxy resin and the silicone resin are not compatible with each other. There was a problem of inhibition.

  Among epoxy resins, when an epoxy resin excellent in hard coat property is provided directly on the resist-facing surface of the photomask as a protective film having hard coat property, hard coat properties can be obtained. There was a problem that adhesion to a glass substrate as a base material of the photomask was poor, and as a result, good adhesion to the photomask could not be obtained. Second, there was a problem that the light resistance was deteriorated, and there was a problem that the hard coat property was lowered when the light resistance was improved.

In one aspect of the present invention, a thermosetting protective liquid for a glass mask capable of forming a protective film having good adhesion to a glass mask, light resistance, excellent hard coat properties, and no cracks, A glass mask having a protective film formed using a protective liquid is provided.
In another aspect of the present invention, a thermosetting protective liquid for glass mask capable of forming a transparent protective film that does not cause whitening due to incompatibility of constituent components, and a protective film formed using the protective liquid And a glass mask.

  The present inventors can increase the compatibility between the silicone resin and the epoxy resin by including a large amount of a hydrogenated aromatic epoxy resin as an epoxy resin with respect to the silicone resin and the silicone oil. It has been found that the adhesion to the glass mask and the light resistance of the coating film can be improved (not yellowed) in the case of film).

  That is, the thermosetting protective liquid for glass mask of the present invention contains a silicone resin, an epoxy resin and a silicone oil, and 50 wt% or more and 100 wt% or less in the epoxy resin is composed of a hydrogenated aromatic epoxy resin. Features.

In addition, a hydrogenated aromatic epoxy resin having at least one of the following properties (1) to (4) is used.
(1) The epoxy equivalent is 200 or more and 280 or less.
(2) The viscosity at 25 ° C. is 0.25 Pa · s to 2.5 Pa · s.
(3) It is obtained by hydrogenating an aromatic ring of an aromatic epoxy resin and has no epoxy group on the carbocyclic ring.
(4) The hydrogenation rate of the aromatic ring is 95 to 100%.

  In addition, the weight ratio of the silicone resin and the epoxy resin is 4: 6 to 8: 2. Moreover, it contains only an amine compound as a curing agent.

  The glass mask of the present invention has a protective film composed of a cured product obtained by thermally curing any one of the protective liquids on the thin film pattern surface of the glass mask having a thin film pattern on a glass substrate. . Further, the glass mask used for forming the protective film is a chromium mask in which a thin film pattern on a glass substrate is formed of a chromium material.

Since the thermosetting protective liquid for glass mask of the present invention contains a specific epoxy resin (hydrogenated aromatic epoxy resin), the coating film is not whitened due to incompatibility between the epoxy resin and the silicone resin, and hard A transparent protective film excellent in coatability and free from cracks can be formed on the glass mask.
The thermosetting protective liquid for glass mask of the present invention also contains a large amount of specific epoxy resin (50 wt% or more and 100 wt% or less in the epoxy resin), and therefore has an adhesive property with a glass mask (especially chromium mask). In addition, a protective film excellent in light resistance can be formed.

  The glass mask of this invention has the specific protective film formed using the thermosetting protective liquid for glass masks of this invention in the thin film pattern surface of the glass mask (glass mask main body) which has a thin film pattern on a glass substrate. Therefore, it is excellent in transparency and the exposure accuracy is improved. Moreover, since a specific protective film is formed using the thermosetting protective liquid for glass masks of this invention, the adhesiveness and light resistance of a protective film are improved. As a result, resistance to repeated use as a photomask increases, which can contribute to improving the productivity of products (printed wiring boards, resin relief plates, etc.).

  In the present specification, the “thermosetting protective liquid” means a mixture of components, and a “protective film” is formed from a cured product obtained by heating and curing the “thermosetting protective liquid”. The “thermosetting protective liquid” may contain other optional components. That is, the “thermosetting protective liquid” in the present specification does not exclude the presence of components other than the constituent components described below. The term “curing type” refers to the property of curing by polymerizing the resin component of the protective liquid.

First, the structural example of the thermosetting protective liquid for glass masks of this invention is demonstrated.
The thermosetting protective liquid for glass mask of this example is configured to include at least a silicone resin, an epoxy resin, and a silicone oil.

  Silicone resin is used to make the refractive index of the protective film close to the refractive index of glass when used as a protective film and to increase the hardness of the protective film. As such a silicone resin, a methyl silicone resin, a methylphenyl silicone resin, a modified silicone resin, or the like can be used. As the modified silicone resin, an ester-modified silicone resin, an epoxy-modified silicone resin, an alkyd-modified silicone resin, or an acrylic-modified silicone resin can be used singly or in combination. In particular, it is preferable to use an ester-modified silicone resin together with a hydrogenated aromatic epoxy resin (described later) because the compatibility between the silicone resin and the epoxy resin can be further improved.

  Specifically, such silicone resins are trade names of Shin-Etsu Chemical Co., Ltd. as KR400, KR500, KR510, KR213, ES1001N, ES1002T, KR5206, KR9706, KR5230, KR5234, KR5235, X-40-2308, X -40-9238, KR5230, KR5234, KR5235, and the like.

  Epoxy resin is mainly used to prevent the generation of cracks when used as a protective film. In this example, at least a hydrogenated aromatic epoxy resin is included as the epoxy resin. In the present specification, the “hydrogenated aromatic epoxy resin” means an epoxy resin obtained by, for example, hydrogenating an aromatic ring of an aromatic epoxy resin and does not have an epoxy group on a carbocyclic ring. And “alicyclic epoxy resin” having an epoxy group on the carbocyclic ring of a cyclic saturated hydrocarbon.

  In this example, the inclusion of a hydrogenated aromatic epoxy resin in the epoxy resin is to prevent the occurrence of cracks when used as a protective film (see above), and to further improve the adhesion to glass, In addition to improving light resistance, the compatibility with the above-described silicone resin is good, and when the protective film is used, whitening of the coating due to incompatibility is not caused. The haze (JIS-K7136: 2000) of such a protective film is preferably less than 1%.

  The aromatic epoxy resin to be used for hydrogenation is not particularly limited, but bisphenol A type epoxy resin, bisphenol F type epoxy resin, and biphenol type epoxy resin are preferable in that a high hydrogenation rate epoxy resin can be obtained. A type epoxy resin is most preferred.

  The hydrogenation rate of an aromatic ring is the ratio at which the aromatic ring has changed to an alicyclic structure, and is determined by nuclear magnetic resonance analysis. In this example, the hydrogenation rate of the aromatic ring of the aromatic epoxy resin is preferably in the range of 90 to 100%, more preferably in the range of 95 to 100%. If the hydrogenation rate is less than 90%, the aromatic ring remaining in the protective film is deteriorated and colored by exposure light, and as a result, the transparency of the protective film may be lowered. This hydrogenation rate is calculated from the hydrogen consumption of the hydrogenation reaction and can be controlled by the reaction conditions.

  The hydrogenated aromatic epoxy resin used in this example has a viscosity at 25 ° C. of usually 0.1 Pa · s or more, preferably 0.2 Pa · s or more, more preferably 0.25 Pa · s or more, and usually 3 0.0 Pa · s or less, preferably 2.7 Pa · s or less, more preferably 2.5 Pa · s or less. When the viscosity at 25 ° C. is too low, there is a risk of poor hardness (hard coat properties cannot be obtained). If the viscosity at 25 ° C. is too high, there is a risk of film formation failure (a uniform coating film cannot be obtained). In addition, the viscosity here is a value determined by the single cylinder rotational viscometer method described in JIS-K7233, the viscosity test method of an epoxy resin and a curing agent (1986) using a B-type viscometer. .

  The hydrogenated aromatic epoxy resin used in this example has an epoxy equivalent (WPE) of usually 150 or more, preferably 180 or more, more preferably 200 or more, and usually 350 or less, preferably 300 or less, more preferably 280. It is as follows. If the epoxy equivalent is too low, the crosslinking density increases, cracking of the coating film cannot be prevented, and the adhesion to glass may be reduced. When the epoxy equivalent is too high, the compatibility with the silicone resin is deteriorated, the coating film is whitened, and the transparency may be lowered.

The “epoxy equivalent” is defined as the molecular weight of the epoxy resin per epoxy group. Here, the “epoxy group” includes oxacyclopropane (oxirane ring) which is a three-membered ether, and in addition to an epoxy group in a narrow sense, a glycidyl group (including a glycidyl ether group and a glycidyl ester group). Is included.
The epoxy equivalent is determined by a method (perchloric acid-tetraethylammonium bromide method) described in JIS-K7236, a method for obtaining an epoxy equivalent of an epoxy resin (2001).

The hydrogenated aromatic epoxy resin used in this example can be produced, for example, by selectively hydrogenating an aromatic ring by a known method in the presence of a catalyst. A more preferable production example includes a method in which an aromatic epoxy resin is dissolved in an organic solvent, and an aromatic ring is selectively hydrogenated in the presence of a catalyst in which rhodium or ruthenium is supported on graphite. For example, graphite having a surface area in the range of 10 to 400 m ² / g is preferably used as the graphite of the catalyst carrier. The reaction is usually carried out within a range of a pressure of 1 to 30 MPa, a temperature of 30 to 150 ° C., and a time of 0.5 to 20 hours. After completion of the reaction, the catalyst and the like are removed by filtration, and the organic solvent is distilled off under reduced pressure until it substantially disappears, whereby the hydrogenated aromatic epoxy resin used in this example can be obtained.
In addition, the compound which hydrogenated the aromatic ring of the compound which has an aromatic ring, and introduce | transduced the epoxy group into the aromatic ring (cyclohexyl ring) after this hydrogenation is also epoxidized as a hydrogenated aromatic epoxy resin of this example. Can be used.

Specifically, the hydrogenated aromatic epoxy resin has a trade name of YX8034 (WPE: 270, viscosity (25 ° C.): 0.28 Pa · s) or YX8000 (WPE: 205, viscosity (25 ° C): 1.85 Pa · s) and the like, and Denasel EX252 (WPE: 213, Viscosity (25 ° C): 2.2 Pa · s) are listed as trade names of Nagase ChemteX Corporation (all hydrogenated bisphenols). A type epoxy resin).
In this example, the hydrogenated aromatic epoxy resin may be used alone or in combination of two or more.

In this example, the content of the hydrogenated aromatic epoxy resin in the total epoxy resin is usually 50% by weight or more, preferably 60% by weight or more, more preferably 75% by weight or more, and further preferably 90% by weight or more. The upper limit is 100% by weight. That is, the total epoxy resin may be composed of a hydrogenated aromatic epoxy resin, and it is preferable that the total epoxy resin be composed of a hydrogenated aromatic epoxy resin to improve the adhesion to the glass mask.
In this example, the reason why the hydrogenated aromatic epoxy resin is included in a large amount in the epoxy resin is to improve the adhesion to a glass mask (particularly, a chromium mask (described later)) when the protective film is used. The higher the content of the hydrogenated aromatic epoxy resin in the epoxy resin, the higher the adhesion to the glass mask is expected.

  In this example, as the epoxy resin, other epoxy resins that can be included in addition to the above-described hydrogenated aromatic epoxy resin have a content in the total epoxy resin of less than 50% by weight, preferably less than 40% by weight, more preferably 25%. Less than 10% by weight, more preferably less than 10% by weight, and the lower limit is 0 (zero).

  The weight ratio of the silicone resin and the epoxy resin contained in the thermosetting protective liquid for glass mask is preferably 4: 6 to 8: 2. When the ratio of the silicone resin further increases from the above ratio, cracks are likely to occur in the coating film, and when the ratio of the epoxy resin further increases from the above ratio, a coating film having sufficient hardness required for the protective film is obtained. I can't.

  Silicone oil is used to impart releasability and antifouling properties to the surface of the protective film when used as a protective film. As such silicone oil, silicone oil such as dimethyl silicone oil, methyl hydrogen silicone oil, methylphenyl silicone oil, and cyclic dimethyl silicone oil, and modified silicone oil in which an organic group is introduced into silicone oil can be used.

  As the modified silicone oil, modified silicone oils such as alkyl modification, polyether modification, fluorine modification, amino modification, mercapto modification, epoxy modification, carboxyl modification, higher fatty acid ester modification, methacryl modification and carbinol modification can be used.

  In particular, in order to maintain releasability and antifouling property, it is preferable to use a reactive silicone oil having a group that reacts with a silicone resin or an epoxy resin in order to maintain releasability and antifouling property. By doing so, deposits such as resist on the surface of the protective film can be easily removed.

  Specific examples of the silicone oil include KF96, KF69, KF99, KF54, KF968 and the like as trade names of Shin-Etsu Chemical Co., Ltd. In particular, as reactive silicone oils, KF410, KF412, KF351, KF354, KF618, KF945, KF859, KF858, KF861, KF864, KF880, X-22-161A, KF1001, KF101, X-22-3701E, X-22-3710 X-22-160AS, KF6001, KF6003, and the like.

  The silicone oil is preferably 0.05 to 1 part by weight with respect to 100 parts by weight of the resin component in the protective liquid. 0.05 parts by weight or more is for obtaining sufficient releasability and antifouling properties, and 1 part by weight or less for reducing the surface tension when the coating liquid is used. This is to prevent the formation of a uniform and difficult to form a uniform coating film.

  The thermosetting protective liquid for glass mask of this example can obtain a hard coat property on the protective film by causing the above-mentioned silicone resin and epoxy resin to undergo a crosslinking reaction with heat. In order to cause such a resin to undergo a crosslinking reaction by heat, a curing agent is required.

  An amine compound can be used as such a curing agent. It is conceivable to use a commonly used metal alkoxide catalyst as a curing catalyst for the silicone resin. However, when a metal alkoxide catalyst is used, it easily reacts with moisture in the atmosphere. There is a problem in terms of stability. On the other hand, by using an amine compound, it can be allowed to act as a curing catalyst for a silicone resin, and can also act as a curing agent for an epoxy resin. Therefore, it is possible to solve the problem of storage stability of the protective liquid, which has been a drawback of the metal alkoxide catalyst.

  As such an amine compound, a cure sol series manufactured by Shikoku Kasei Kogyo Co., Ltd. or a racamide series manufactured by DIC Co. can be used.

  Further, the curing start temperature by the amine compound is preferably 100 ° C. or more in order to obtain storage stability of the liquid.

  The amine compound is preferably 1 to 10 parts by weight with respect to 100 parts by weight of the resin component (solid content) in the protective liquid. The reason why it is 1 part by weight or more is to sufficiently advance the curing reaction of the resin, and the reason that it is 10 parts by weight or less is that the hardness of the coating film is not lowered.

  The thermosetting protective solution for glass mask of this example may contain a fluorine-based silane compound or polydimethylsiloxane having a silanol group. By including one or more of these in the protective liquid, it can be expected that the contact angle of the obtained protective film with respect to the photoresist is improved, and the resist adhesion preventing effect after completion of exposure is improved.

  Specific examples of fluorine-based silane compounds include KBM7103 as a trade name of Shin-Etsu Chemical Co., Ltd., and SIN6597.65, SIN6597.7, SIT8175.0, SIT8176.0 and the like as trade names of Gelest. Can be mentioned. Specific examples of the polydimethylsiloxane having a silanol group include X-21-5841 and KF-9701 as trade names of Shin-Etsu Chemical Co., Ltd., and DMS-S12 and DMS-S14 as trade names of Gelest. , DMS-S15, DMS-S21, and the like.

  The fluorine-based silane compound and the polydimethylsiloxane having a silanol group can be contained in an amount of about 0.5 to 25 parts by weight with respect to 100 parts by weight of the resin component in the protective liquid.

  The thermosetting protective liquid for the glass mask of this example should be prepared by blending the above-described silicone resin, epoxy resin, silicone oil, curing agent and other components as necessary, and dissolving them in a suitable solvent. Can do.

  The protective film obtained with the thermosetting protective liquid for glass mask of this example preferably has a pencil hardness (JIS-K5600-5-4: 1999) of 3H or higher when cured.

Next, a configuration example of the glass mask according to the present invention will be described.
The glass mask of this example is obtained by applying the above-described thermosetting protective liquid for glass mask to a thin film pattern surface of a glass mask (hereinafter abbreviated as “glass mask body”) used for forming a protective film. It has a protective film composed of a cured product that is cured by applying heat.

  In the glass mask main body used in this example, a thin film pattern for forming a fine pattern on a printed wiring board or a resin relief plate is formed on a glass substrate. Examples of such a glass mask body include a thin film pattern formed by applying an emulsion of gelatin and silver halide on a glass substrate (emulsion mask), and a chromium material (such as chromium or chromium oxide) on the glass substrate. (A chrome mask) having a thin film pattern formed of As a constituent material of the thin film pattern, in addition to a chromium material, for example, a silicon material (such as silicon or silicon oxide), an iron material (such as iron oxide), a molybdenum material (such as molybdenum oxide or molybdenum silicide), a nickel material (such as nickel or nickel oxide) Etc.) can also be used (silicon mask, iron mask, molybdenum mask, nickel mask, etc.). In this example, the adhesion of the protective film is particularly high when a chromium mask is used as the glass mask body.

  In the glass mask of this example, after applying the above-described thermosetting protective liquid for glass mask of this example to the entire surface of the thin film pattern surface of the glass mask body, the resin component of the protective liquid is polymerized by applying heat to this ( Heat cured) to obtain a cured product, which is used as a protective film having hard coat properties and releasability.

  By including a silicone resin and an epoxy resin in the protective liquid, a glass mask having a protective film excellent in adhesion to the glass mask body, hard coat properties and light resistance can be obtained. When the adhesiveness and light resistance of the protective film are enhanced, the repeated use resistance as a photomask increases, and as a result, it can contribute to the improvement of the productivity of a product (printed wiring board, resin relief plate, etc.).

  Furthermore, by including a hydrogenated aromatic epoxy resin as the epoxy resin, the compatibility between the epoxy resin and the silicone resin is improved, so that the whitening of the protective film is suppressed and the transparency is improved. Thereby, the exposure accuracy in the case of forming a pattern on a printed wiring board or a resin relief plate is improved, and a fine pattern can be formed.

  As a method for forming the protective film on the thin film pattern of the glass mask main body, a known method such as spin coating, die coating, cap coating, bar coating using a thermosetting protective liquid can be used.

  In addition, the glass mask main body used in this example includes those in which an undercoat layer for improving the adhesion to the protective film is provided on the glass substrate.

  The following examples further illustrate the present invention. “Parts” and “%” are based on weight unless otherwise specified.

[Examples 1-4, Comparative Example 1, Comparative Example 2]
The thermosetting protective liquid for glass mask of each example of the composition shown in Table 1 below is applied onto a patterned chrome mask by spin coating and cured by heating at 150 ° C. for 70 minutes to form a protective film having a thickness of about 2 μm. The glass mask of each example was produced.

  In addition, silicone resin 1 (X-40-2308: Shin-Etsu Chemical Co., Ltd., solid content 100%), silicone resin 2 (ES-1001N: Shin-Etsu Chemical Co., Ltd., solid content 45%), silicone resin 3 (KR5235: Shin-Etsu Chemical) Industrial company, solid content 60%), epoxy resin 1: hydrogenated bisphenol A type epoxy resin (hydrogenated aromatic epoxy resin) (YX8034: Mitsubishi Chemical Corporation, WPE270, viscosity (25 ° C.) 0.28 Pa · s, hydrogenated About 100%, solid content 100%), epoxy resin 2 (Epiclon 860: DIC, solid content 100%), epoxy resin 3 (EPPN 502H: Nippon Kayaku Co., Ltd., solid content 100%), silicone oil (KF6001: Shin-Etsu) Chemical industry, solid content 100%), amine-based catalyst (Cureazole 2PZ-CN: Shikoku Chemicals, solid content 100% , Metal alkoxide catalysts (D-20: Shin-Etsu Chemical Co., Ltd., solid content 100%) was used.

  The following items were evaluated for the glass masks obtained in each example. Table 2 shows the evaluation results of the following items.

[Adhesion to glass mask]
The adhesion between the glass mask and the protective film obtained in each example was evaluated by a cross-cut tape method (JIS-K5600-5-6: 1999). As a result of the peel test by the cross-cut tape method, the case where the cross-cut portion was peeled off was indicated as “X”, and the case where the cross-cut portion was not peeled off was indicated as “◯”.

[Presence of cracks]
It was visually evaluated whether or not cracks occurred in the protective film of the glass mask obtained in each example. The case where a crack that can be visually confirmed was seen was indicated as “X”, and the case where no crack was observed was indicated as “◯”.

[Whitening of protective film]
About the transparent part of the glass mask obtained in each example, haze was measured according to JISK7136: 2000 using the haze meter (NPH2000: Nippon Denshoku). A sample having a haze of less than 1% was indicated by “◯”, a sample having a haze of 1% or more and less than 5% was indicated by “Δ”, and a sample having a haze of 5% or more was indicated by “X”.

[surface hardness]
According to JIS-K5600-5-4: 1999, the pencil hardness of the surface of the protective film formed on the glass mask obtained in each example was measured. As a result, a pencil hardness of 3H or higher was evaluated as “◯”, and a hardness of less than 3H was determined as “X”.

[Liquid storage stability]
The liquid state after 3 days of the thermosetting protective liquid for glass mask used in each example was observed. “X” indicates that the fluidity is lost and it cannot be used as the coating liquid, and “◯” indicates that the fluidity is not problematic as the coating liquid.

[Light resistance]
On the protective film side of the glass mask obtained in each example, UV exposure with an integrated exposure amount of 10,000 J / cm ² was performed using a UV tester (Isuper UV Tester SUV-F1: Iwasaki Electric Co., Ltd.). Before and after the ultraviolet exposure, the light transmittance at a wavelength of 365 nm of the glass mask obtained in each example was measured using a spectrophotometer (UV-3101: Shimadzu Corporation), and the light transmittance before the exposure ( Light resistance was evaluated by the maintenance factor (= (T2 / T1) × 100) of the light transmittance (T2) after exposure to T1). Those with a maintenance rate of 5% or less were evaluated as “◯”, those with a maintenance rate exceeding 5% and 10% or less were “Δ”, and those with a maintenance rate exceeding 10% were “x”.

[Discussion]
Since the glass masks of Examples 1 to 4 used a protective liquid containing a hydrogenated aromatic epoxy resin in an epoxy resin, the formed protective film was not whitened. In addition, since the protective liquid in which the proportion of the hydrogenated aromatic epoxy resin contained in the epoxy resin is 50% by weight or more and 100% by weight or less is used, the formed protective film has good adhesion to the glass mask and light resistance. It was excellent. In addition, since the protective liquid in which the weight ratio of the silicone resin and the epoxy resin is in the range of 4: 6 to 8: 2 is used, the formed protective film does not crack and has a sufficient surface hardness (hardness) Coatability) was obtained.

  In addition, since the thermosetting protective liquid for glass masks of Examples 1, 2, and 4 contained only an amine catalyst as a curing agent, the liquid storage stability was excellent. On the other hand, since the thermosetting protective liquid for glass mask of Example 3 contained a metal alkoxide catalyst in addition to the amine catalyst as a curing agent, a problem occurred in the liquid storage stability.

  The glass mask of Comparative Example 1 contains a hydrogenated aromatic epoxy resin in the epoxy resin, but since the proportion of the protective liquid was 40% by weight in the epoxy resin, whitening was performed on the formed protective film. Although it did not occur, compared with the glass masks of Examples 1 to 4, the adhesion to the glass mask and the light resistance were deteriorated.

  Since the glass mask of Comparative Example 2 used a protective liquid that did not contain a hydrogenated aromatic epoxy resin in the epoxy resin, whitening occurred in the formed protective film, and the adhesion to the glass mask and light resistance were further improved. The deterioration was higher than that of Comparative Example 1. In particular, the reason why the light resistance of the glass mask of Comparative Example 2 was inferior to that of the glass mask of Comparative Example 1 was that all of the epoxy resin was composed of an epoxy resin containing an aromatic ring.

[Example 5]
Instead of epoxy resin 1, epoxy resin 4: hydrogenated bisphenol A type epoxy resin (hydrogenated aromatic epoxy resin) (YX8000: Mitsubishi Chemical Corporation, WPE205, viscosity (25 ° C.) 1.85 Pa · s, solid content 100% ) Was used to prepare a thermosetting protective liquid for glass mask having the same composition as in Example 2. A protective film having a thickness of about 2 μm was formed on the patterned emulsion mask in the same manner as in Example 2 to produce a glass mask. As a result, the same evaluation as in Example 2 was obtained.

[Example 6]
Instead of epoxy resin 1, epoxy resin 5: hydrogenated bisphenol A type epoxy resin (hydrogenated aromatic epoxy resin) (Denacol EX252: Nagase ChemteX Corporation, WPE213, viscosity (25 ° C.) 2.2 Pa · s, solid content A thermosetting protective liquid for glass mask having the same composition as in Example 2 was prepared except that 100%) was used. A protective film having a thickness of about 2 μm was formed on the patterned emulsion mask in the same manner as in Example 2 to produce a glass mask. As a result, the same evaluation as in Example 2 was obtained.

Claims (7)

A protective liquid for forming a protective film on a glass mask with no peeling of the cross-cut portion in the peeling evaluation by the cross-cut tape method (JIS-K5600-5-6: 1999) ,
A silicone resin, an epoxy resin, and a silicone oil are included, the weight ratio of the silicone resin to the epoxy resin is 4: 6 to 8: 2, and 50 wt% to 100 wt% of the epoxy resin is hydrogenated aromatic A thermosetting protective liquid for a glass mask, characterized by comprising an epoxy resin.   2. The thermosetting protective liquid for glass mask according to claim 1, wherein the hydrogenated aromatic epoxy resin has an epoxy equivalent of 200 or more and 280 or less.   3. The thermosetting type for glass mask according to claim 1, wherein the hydrogenated aromatic epoxy resin has a viscosity at 25 ° C. of 0.25 Pa · s to 2.5 Pa · s. Protective liquid.   The protective liquid according to any one of claims 1 to 3, wherein the hydrogenated aromatic epoxy resin is obtained by hydrogenating an aromatic ring of an aromatic epoxy resin and has an epoxy group on a carbocyclic ring. A thermosetting protective liquid for glass masks, characterized in that the hydrogenation rate of the aromatic ring is 95 to 100%. The thermosetting protective solution for a glass mask according to any one of claims 1 to 4 , further comprising a curing catalyst, wherein the curing catalyst is composed only of an amine-based curing catalyst. To the thin film pattern surface of the glass mask having a thin film pattern on a glass substrate, a glass mask characterized by having a protective film composed of any of the protective solution according to claim 1-5 with a cured product obtained by heat-curing . 7. The glass mask according to claim 6, wherein the glass mask used for forming the protective film is a chromium mask in which a thin film pattern on a glass substrate is formed of a chromium material.