JP4969047B2 - Photomask and photomask manufacturing method - Google Patents

Description

  The present invention relates to an easy-adhesion treatment liquid for forming a coating film on the surface of an object to be coated, the surface of which is made of chromium, a film-forming material, and a method for forming the film, and particularly excellent in adhesion to the object to be coated. The present invention relates to an easy-adhesion treatment solution, a film-forming material, and a method for forming a coating film.

  Usually, a printed wiring board is formed by laminating a photoresist such as a dry film on the surface of a substrate material, and closely adhering the surface on which the exposure pattern of the photomask is formed on the surface of the photoresist. After the exposure, the photomask is peeled off, the photoresist is developed, and an etching process is performed. The photomask peeled at this time is repeatedly used for the production of the next printed wiring board.

  In recent years, there has been a great demand for higher density of printed wiring boards and the like, and it has become necessary to improve the dimensional accuracy of photomasks used therefor. For this purpose, a photomask using a glass plate on which glass is used as a support and on which a layer made of a photosensitive emulsion is provided is used, and a higher definition is used instead of the layer made of such a photosensitive emulsion. It is used by depositing chromium.

  Chromium usually has a high surface hardness and is hard to be scratched. However, such a chrome-deposited photomask generates pinholes when the chrome layer deposited by electrostatic sparks breaks during repeated exposure. The problem of end up occurred.

  On the other hand, a photomask provided with a layer of a photosensitive emulsion is usually laminated with a transparent protective film on the surface on which an exposure pattern is formed for the purpose of preventing the adhesion of a photoresist for repeated use. Yes (Patent Document 1).

  Therefore, it is conceivable to prevent adhesion of the photoresist and disconnection of the chromium layer by sticking the transparent protective film as described above to the surface of the photomask on which chromium is deposited. Since the photomask deposited with a high-definition photomask itself has a problem in that the exposure accuracy decreases when the transparent protective film as described above is attached.

  In addition, a coating film (protective film) is formed on the surface of the photomask on which chromium has been deposited by applying a coating liquid for forming a coating film to prevent adhesion of the photoresist and disconnection of the chromium layer. Although it is conceivable, since the adhesion between chromium and organic matter is generally low, the adhesion between the chromium layer and the coating film is not sufficient, and the coating film is peeled off from the chromium layer, so that repeated exposure cannot be performed.

  By the way, it is generally known to use a silane coupling agent in order to improve the adhesion between an inorganic substance and an organic substance. Therefore, when a commercially available silane coupling agent was added to the coating solution for forming a coating film and the silane coupling agent was contained in the coating film, no effect was obtained. In addition, when the silane coupling agent was applied onto the chromium layer as an easy-adhesion treatment liquid, curing at a high temperature for a long time (about 150 ° C. for about 90 minutes) was required to complete the easy-adhesion treatment. It was costly and time consuming. Furthermore, when a coating solution for coating film formation similar to the above was applied on the chromium layer subjected to the easy adhesion treatment, the adhesiveness was improved to some extent, but the formed coating film was uneven. A uniform and beautiful coating film could not be obtained.

Noto 2589276 (Claim 1)

  Therefore, the present invention can perform an easy adhesion treatment on the surface of an object to be coated made of chromium like a photomask on which chromium is vapor-deposited by curing at a relatively low temperature in a short time. An object of the present invention is to provide an easy-adhesion treatment liquid, a film-forming material, and a method for forming a coating film, which can form a uniform and beautiful coating film with good adhesion to an object to be coated.

That is, the photomask of the present invention has a coating film on a photomask whose surface is made of chromium via an easy adhesion layer, and the easy adhesion layer is hydrolyzed partial condensation of an organosilane having an epoxy group. The coating film is formed from a coating liquid for forming a coating film containing a silicone resin and an aminoalkyd resin .

  Preferably, the organosilane having an epoxy group is γ-glycidoxypropyltrimethoxysilane.

In addition, the method for producing a photomask of the present invention comprises applying a coating solution for an easy-adhesion layer containing a hydrolyzed partial condensate of an organosilane having an epoxy group onto a photomask whose surface is made of chromium, and drying it easily A layer is formed, and a coating film-forming coating solution containing a silicone resin and an aminoalkyd resin is applied onto the easy-adhesion layer and dried to form a coating film .

  According to the present invention, the surface of an object to be coated made of chromium can be subjected to an easy adhesion treatment by relatively short curing at a relatively low temperature, and the adhesiveness to the object to be coated is good. A uniform and beautiful coating film can be formed.

  Hereinafter, embodiments of each component will be described. First, the easy adhesion treatment liquid of the present invention will be described. The easy-adhesion treatment liquid is used for improving the adhesion between the coated object made of chromium and the coating film which is an organic substance. In the present invention, the hydrolyzed partial condensate of organosilane having an epoxy group Is included.

  An organosilane having an epoxy group has at least one epoxy group, and has at least one epoxy group, for example, a vinyl group, an amino group, a methacryl group, etc. instead of the epoxy group. Compared to the case where organosilane is used, the adhesion between an object to be coated whose surface is made of chromium and a coating film formed from a coating liquid for forming a coating film described later can be improved. Specific examples of the organosilane having an epoxy group include glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyl. Triethoxysilane, γ-glycidoxypropyltri (methoxyethoxy) silane, γ-glycidoxypropyltriacetoxysilane, glycidoxymethyl (methyl) dimethoxysilane, glycidoxymethyl (ethyl) dimethoxysilane, glycidoxy Methyl (phenyl) dimethoxysilane, glycidoxymethyl (vinyl) dimethoxysilane, glycidoxymethyl (dimethyl) methoxysilane, γ-glycidoxypropyl (methyl) dimethoxysilane, γ-glycidoxypropyl (ethyl) dimethoxysilane γ-glycidoxypropyl (dimethyl) methoxysilane, bis- (glycidoxymethyl) dimethoxysilane, bis- (glycidoxymethyl) diethoxysilane, bis- (glycidoxyethyl) dimethoxysilane, bis- (glycid Xylethyl) diethoxysilane, bis- (glycidoxypropyl) dimethoxysilane, bis- (glycidoxypropyl) diethoxysilane, tris- (glycidoxymethyl) methoxysilane, tris- (glycidoxymethyl) ethoxy Silane, tris- (glycidoxyethyl) methoxysilane, tris- (glycidoxyethyl) ethoxysilane, tris- (glycidoxypropyl) methoxysilane, tris- (glycidoxypropyl) ethoxysilane, glycidylmethyltrimethoxy Silane, glycidyl methyl Riethoxysilane, γ-glycidylpropyltriethoxysilane, γ-glycidylpropyltri (methoxyethoxy) silane, γ-glycidylpropyltriacetoxysilane, 3,4-epoxycyclohexylmethyltrimethoxysilane, 3,4-epoxycyclohexylmethyltri Examples include ethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylpropyltrimethoxysilane, and the like. Of these, γ-glycidoxypropyltrimethoxysilane is preferred from the viewpoint that the reactivity of the alkoxyl group is high and the surface can be further improved in adhesion to an object to be coated made of chromium.

  The organosilane having such an epoxy group needs to be a hydrolyzed partial condensate. Here, the hydrolyzed partial condensate of an organosilane having an epoxy group in the present invention is a condensate obtained by hydrolyzing and condensing an organosilane having an epoxy group, and / or a part obtained by condensation. Refers to condensate. Thus, by hydrolyzing and condensing the organosilane having an epoxy group, a silanol group is generated and the reactivity to an object to be coated can be improved. Thereby, compared with what was not hydrolyzed, adhesiveness with a to-be-coated article can be improved by low temperature and short time curing. The temperature and time required for curing are slightly different depending on the type of organosilane having an epoxy group to be selected. In the case of γ-glycidoxypropyltrimethoxysilane, 150 ° C. is used when an unhydrolyzed one is used. Although it is about 90 minutes, it can be made into 80 to 100 degreeC and about 10 to 30 minutes by setting it as a hydrolysis partial condensate. Furthermore, since it can be easily adhered by low-temperature and short-time curing as described above, a uniform layer can be formed, and when a coating film described later is formed on the upper layer, unevenness is hardly generated and uniform. A beautiful coating film can be obtained.

  Such an organosilane having an epoxy group can be hydrolyzed by using an acid such as hydrochloric acid or a base catalyst such as sodium hydroxide. And it can be set as the hydrolysis partial condensate made into the desired degree of condensation with the time to leave after that.

  Such a hydrolyzed partial condensate of organosilane having an epoxy group is preferably 0.1% by weight or more, more preferably 1% by weight or more as the lower limit in the easy-adhesion treatment liquid, and the upper limit is 30% by weight. % Or less, more preferably 10% by weight or less. By setting the content to 0.1% by weight or more, it is possible to improve the adhesion between the coating object whose surface is made of chromium and the coating film described later. By setting the content to 30% by weight or less, unevenness hardly occurs and is uniform. It can be made into a beautiful coating film.

  The easy-adhesion treatment liquid of the present invention as described above is prepared by diluting an organosilane having an epoxy group with an alcohol solvent such as methanol, ethanol, and isopropyl alcohol, and hydrolyzing it by adding an acid or a base. The desired hydrolyzed partial condensate can be obtained by stirring at constant temperature for a period of time, and it can be obtained by further diluting with an alcohol solvent similar to the above.

  Next, the coating film forming material of the present invention will be described. The coating film-forming material of the present invention comprises two types of coating liquids, that is, the above-described easy adhesion treatment liquid and a coating film-forming coating liquid containing a silicone resin.

  The resin component in the coating film forming coating solution is preferably a silicone resin. By using a silicone resin, when it becomes a coating film, adhesiveness with an easily bonding process layer can be improved, and it can be excellent in a weather resistance, damage prevention property, and electrical insulation. Examples of the silicone resin include straight silicone resins and modified silicone resins such as polyester-modified, epoxy-modified, alkyd-modified, and acrylic-modified.

  Furthermore, the coating liquid for forming a coating film preferably contains an aminoalkyd resin. By using amino alkyd resin, it is possible to improve the adhesion with the easy-adhesion treatment layer, and to form a more uniform and beautiful coating film without reducing the weather resistance and scratch resistance. Can do.

  The content ratio of the silicone resin and the amino alkyd resin in the coating liquid for forming a coating film is not particularly limited, but the silicone resin should be 25 to 75 parts by weight with respect to 100 parts by weight of the amino alkyd resin. Is preferred. By making the content ratio of the silicone resin and amino alkyd resin in the coating liquid for coating film formation in such a range, the adhesion to the easy adhesion treatment layer is further improved without lowering the weather resistance and scratch resistance. Can be made.

  Moreover, the polycondensation ratio of the amino resin and the alkyd resin in the amino alkyd resin is not particularly limited, but the alkyd resin is preferably 70% by weight to 95% by weight.

  The coating liquid for forming a coating film as described above can be obtained by diluting the above-described silicone resin or aminoalkyd resin with a diluting solvent such as an organic solvent. In addition, such a coating liquid for forming a coating film has a lubricant, a colorant, a pigment, a dye, a fluorescent whitening agent, a flame retardant, an antibacterial agent, an antibacterial agent, if necessary, as long as the effect of the present invention is not impaired. Add additives such as fungicides, UV absorbers, light stabilizers, heat stabilizers, antioxidants, plasticizers, leveling agents, flow regulators, antifoaming agents, dispersants, storage stabilizers, crosslinking agents, etc. Also good.

  Next, the method for forming a coating film of the present invention will be described. The method for forming a coating film according to the present invention is a method for forming a coating film using the above-described coating film-forming material. The above-described easy adhesion treatment liquid is applied to an object to be coated whose surface is made of chromium, and dried. The coating liquid for forming a coating film described above is applied and dried. The coating method is not particularly limited, and conventionally known coating methods such as spin coater, bar coater, die coater, blade coater, roll coater, gravure coater, flow coater, dip coater, spray, screen printing. And a method of applying with a brush or a brush.

  As described above, according to the present invention, by forming a coating film in this way, a uniform and beautiful coating film having good adhesion can be formed on the surface of an object to be coated made of chromium. .

  Hereinafter, the present invention will be described in more detail based on examples. In this example, “parts” and “%” are based on weight unless otherwise specified.

[Example 1]
<Adjustment of easy adhesion treatment liquid>
To the container, 50 parts of 0.2 mol / l hydrochloric acid, 70 parts of pure water, and 1261 parts of ethanol were added and sufficiently cooled and stirred to prepare a diluted hydrochloric acid solution.

  In a separate container, 1242 parts of ethanol and 138 parts of γ-glycidoxypropyltrimethoxysilane (KBM-403: Shin-Etsu Silicone) as an organosilane having an epoxy group were added, and the temperature was adjusted to 25 ° C. Thereafter, 1381 parts of the diluted hydrochloric acid solution as a catalyst was added and stirred at a constant temperature of 25 ° C. for 24 hours to obtain a desired hydrolyzed partial condensate. Furthermore, 8280 parts of isopropyl alcohol was added and diluted to obtain an easy adhesion treatment liquid of Example 1.

<Easy adhesion treatment>
The above easy-adhesion treatment liquid is applied to the surface of a photomask on which chromium has been deposited as an object to be coated with chromium using a spin coater (rotation speed: 1000 rpm, rotation time: 30 seconds), and dried at 80 ° C. for 30 minutes. An easy adhesion treatment was performed.

<Preparation of coating liquid for forming coating film and formation of coating film>
10 parts of silicone resin, 20 parts of amino alkyd resin, 40 parts of methyl ethyl ketone, 20 parts of ethanol and 10 parts of toluene were placed in a container and stirred to prepare a coating liquid for forming a coating film of Example 1 (solid content 30%).

  Next, the coating liquid for forming a coating film is applied to an object to be coated, the surface of which has been subjected to the above easy adhesion treatment, using a spin coater (rotation speed: 1000 rpm, rotation time: 30 seconds), and dried at 150 ° C. for 30 minutes. Curing was performed to form the coating film of Example 1.

[Example 2]
A diluted hydrochloric acid solution was prepared in a container in the same manner as in Example 1. In a similar manner to Example 1, 1242 parts of ethanol and 138 parts of an organosilane having an epoxy group were added to another container, and the temperature was adjusted to 25 ° C. Thereafter, 1381 parts of the diluted hydrochloric acid solution was added as a catalyst, and the mixture was stirred at a constant temperature of 25 ° C. for 10 minutes to obtain a desired hydrolyzed partial condensate. Furthermore, 8280 parts of isopropyl alcohol was added and diluted to obtain an easy adhesion treatment liquid of Example 2.

  Next, in the same manner as in Example 1, an easy-adhesion treatment was performed on an object to be coated whose surface is made of chromium, and the coating film of Example 2 was formed.

[ Reference Example 1 ]
In the same manner as in Example 1, an easy adhesion treatment solution was prepared, and an easy adhesion treatment was performed on an object to be coated having a chromium surface.

Next, instead of the coating solution for forming a coating film of Example 1, the coating solution for forming a coating film of Reference Example 1 (solid content: 25%) having the following formulation was used in the same manner as in Example 1 for reference. The coating film of Example 1 was formed.

<Prescription of Coating Solution for Coating Film Formation of Reference Example 1 >
・ Epoxy-modified silicone resin (solid content 60%) 50 parts ・ Toluene 50 parts

[ Reference Example 2 ]
In the same manner as in Example 1, an easy adhesion treatment solution was prepared, and an easy adhesion treatment was performed on an object to be coated having a chromium surface.

Next, instead of the coating solution for forming a coating film of Example 1, the coating solution for forming a coating film of Reference Example 2 (with a solid content of 20%) having the following prescription was used in the same manner as in Example 1 for reference. The coating film of Example 2 was formed.

<Prescription of Coating Solution for Coating Film Formation of Reference Example 2 >
・ Acrylic polyol resin (solid content 50%) 10 parts (Acridic A814: Dainippon Ink & Chemicals, Inc.)
・ Isocyanate-based crosslinking agent (solid content 60%) 3.6 parts (Takenate D110N: Mitsui Takeda Chemical Company)
・ Toluene 7.5 parts ・ Methyl ethyl ketone 7.5 parts

[Example 5]
In the easy adhesion treatment solution of Example 1, 3,4-epoxycyclohexylethyltrimethoxysilane (KBM-303: Shin-Etsu Silicone) was used as an organosilane having an epoxy group instead of γ-glycidoxypropyltrimethoxysilane. A coating film of Example 5 was formed in the same manner as Example 1 except that it was used.

[Example 6]
In the easy-adhesion treatment solution of Example 1, γ-glycidoxypropyltriethoxysilane (KBE-403: Shin-Etsu Silicone) was used instead of γ-glycidoxypropyltrimethoxysilane as an organosilane having an epoxy group. A coating film of Example 6 was formed in the same manner as Example 1 except that.

[Comparative Example 1]
Instead of the easy-adhesion treatment liquid of Example 1, an organosilane having an epoxy group that was not adjusted to a hydrolyzed partial condensate (γ-glycidoxypropyltrimethoxysilane: KBM-403: Shin-Etsu Silicone) was used. Except for the above, in the same manner as in Example 1, an easy-adhesion treatment was applied to the coated object whose surface is made of chromium, and the coating film of Comparative Example 1 was formed.

[Comparative Example 2]
Instead of the easy-adhesion treatment liquid of Example 1, in the same manner as in Comparative Example 1, an organosilane having an epoxy group that was not adjusted to a hydrolyzed partial condensate was used and applied with a spin coater. Next, except that the drying and curing time was set at 150 ° C. for 90 minutes, the surface of the coated object made of chromium was subjected to an easy adhesion treatment in the same manner as in Comparative Example 1, and the coating film of Comparative Example 2 was applied. Formed.

[Comparative Examples 3 to 6]
In the easy-adhesion treatment solution of Example 1, instead of an organosilane having an epoxy group, organosilane having a vinyl group (KBM-1003: Shin-Etsu Silicone) as Comparative Example 3, and organosilane having a methacrylic group as Comparative Example 4 (KBM-503: Shin-Etsu Silicone Co., Ltd.), Comparative Example 5 uses aminosilane-containing organosilane (KBM-903: Shin-Etsu Silicone Co., Ltd.), and Comparative Example 6 uses fluorine-containing organosilane (KBM-7803: Shin-Etsu Silicone Co., Ltd.). A coating film of Comparative Examples 3 to 6 was formed in the same manner as in Example 1 except that.

  About the coating film obtained by the Example and the comparative example, the adhesiveness with the to-be-coated object which the surface consists of chromium, and the external appearance of the coating film were evaluated. The evaluation results are shown in Table 1.

(1) Evaluation of adhesiveness The coating films obtained in Examples and Comparative Examples were evaluated for adhesiveness by adhesion (cross-cut method) according to JIS K5600-5-6: 1999. In the evaluation, “◯” indicates that no peeling occurred, and “×” indicates that almost all peeling occurred.

(2) Evaluation of the appearance of the coating film The coating films obtained in the examples and comparative examples were visually observed. "△", those with unevenness and film defects such as pinholes were evaluated as "X", because the coating film was peeled off from the coated object made of chromium in the test of (1) “−” Was used as the target.

Examples 1 , 2, 5, and 6 and Reference Examples 1 and 2 were easy adhesion treatment liquids containing a hydrolyzed partial condensate of an organosilane having an epoxy group. When completed, the resulting coating film was excellent in adhesiveness to the coated object whose surface is made of chromium.

In particular, the coating films of Examples 1 to 2 , 5, 6 and Reference Example 1 consist of two types of coating liquids: the above-mentioned easy adhesion treatment liquid and a coating liquid for coating film formation containing a silicone resin. Since the coating film was formed using, the film was uniform and beautiful without any unevenness.

  On the other hand, since Comparative Example 1 used an organosilane having an epoxy group that was not adjusted to a hydrolyzed partial condensate as an easy-adhesion treatment liquid, the easy-adhesion treatment was not completed by drying at low temperature for a short time, and the surface was chromium. Adhesiveness with the coated object consisting of was low.

  Next, in Comparative Example 2, as in Comparative Example 1, organosilane having an epoxy group that was not adjusted to a hydrolyzed partial condensate was used as an easy-adhesion treatment solution, and the high temperature, long time (150 ° C., 90 minutes) After drying and curing, the easy adhesion treatment was completed, and the obtained coating film was excellent in adhesiveness with the coated object whose surface is made of chromium. However, since it took a high temperature and a long time to perform the easy adhesion treatment, the coating film became uneven and had coating film defects such as pinholes.

  Next, although Comparative Examples 3-6 used what contained the hydrolysis partial condensate of organosilane as an easily bonding process liquid, since it did not have an epoxy group, the surface of the obtained coating film was chromium. Adhesiveness with the coated object consisting of was low.

Claims (3)

A coating liquid for an easy-adhesion layer comprising a coating film on a photomask whose surface is made of chromium via an easy-adhesion layer, wherein the easy-adhesion layer contains a hydrolyzed partial condensate of an organosilane having an epoxy group A photomask, wherein the coating film is formed from a coating film-forming coating solution containing a silicone resin and an aminoalkyd resin. The photomask according to claim 1, wherein the organosilane having an epoxy group is γ-glycidoxypropyltrimethoxysilane. On the photomask whose surface is made of chromium, an easy-adhesion layer coating solution containing a hydrolyzed partial condensate of an organosilane having an epoxy group is applied and dried to form an easy-adhesion layer. A method for producing a photomask, which comprises applying a coating liquid for forming a coating film containing a silicone resin and an aminoalkyd resin and drying the coating liquid to form a coating film.