CN102612665A - Thermosetting protective solution for glass mask, and glass mask - Google Patents
Thermosetting protective solution for glass mask, and glass mask Download PDFInfo
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- CN102612665A CN102612665A CN2009801624601A CN200980162460A CN102612665A CN 102612665 A CN102612665 A CN 102612665A CN 2009801624601 A CN2009801624601 A CN 2009801624601A CN 200980162460 A CN200980162460 A CN 200980162460A CN 102612665 A CN102612665 A CN 102612665A
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- glass mask
- epoxy resin
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- silicone resin
- diaphragm
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/38—Masks having auxiliary features, e.g. special coatings or marks for alignment or testing; Preparation thereof
- G03F1/48—Protective coatings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/08—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols from phenol-aldehyde condensates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Preparing Plates And Mask In Photomechanical Process (AREA)
- Paints Or Removers (AREA)
- Respiratory Apparatuses And Protective Means (AREA)
Abstract
Disclosed is a thermosetting protective solution for a glass mask, which exhibits good adhesion to a glass mask. When the thermosetting protective solution for a glass mask is formed into a protective film, the protective film has excellent hardcoat properties, while being free from cracks and capable of preventing the whitening of the coating film due to the incompatibility between an epoxy resin and a silicone resin. In addition, the thermosetting protective solution for a glass mask has improved storage stability since the protective solution only contains an amine compound as a curing agent. Specifically disclosed is a thermosetting protective solution for a glass mask, which contains a silicone resin, an epoxy resin and a silicone oil. A phenolic novolac epoxy resin is contained as the epoxy resin. The thermosetting protective solution for a glass mask additionally contains an amine compound but does not contain any metal alkoxide catalyst, as a curing agent.
Description
Technical field
The present invention relates to glass mask and protect liquid with thermohardening type, the excellent glass mask of the transparency that relates in particular to when processing diaphragm is protected liquid and is possessed the glass mask with transparent diaphragm with thermohardening type.
Background technology
Printed circuit board or resin relief have at aqueous photoresist etc. and adhere to photomask (original copy use in exposure) on the fusible photoresist and make public and make.Therefore; If any processing is not implemented on the surface of photomask, then behind the end exposure with photomask when photoresist is peeled off, the part of photoresist is attached to the photomask surface; Even wiping also can remain on the photomask, can produce the problem that causes exposure accuracy to reduce.From such situation, setting has the surface protective film of release property on the face relative with photoresist on the photomask all the time, thereby prevents that photoresist is attached to (patent documentation 1) on the photomask.
But, paste such surface protective film exist result from surface protective film thickness and the exposure accuracy that produces reduction, cause the problem of the reduction and so on of exposure accuracy because of getting into bubble etc. when pasting.
Therefore, consider on the face relative on the photomask, diaphragm to be set directly with photoresist.
On the other hand, in order to protect the surface of article, stickup has the film of being coated with property firmly, perhaps has filming of being coated with property firmly in the article surface setting.As such filming of being coated with property firmly that have, known film (patent documentation 2) that use epoxy resin or curable resins such as acryl resin, silicone resin are arranged.
The prior art document
Patent documentation
Patent documentation 1:WO2007/074778 communique (prior art)
Patent documentation 2: TOHKEMY 2005-186577 communique (claim 2)
Summary of the invention
Invent problem to be solved
Yet, even if in these curable resins, use being coated with property is excellent firmly epoxy resin when having the diaphragm of being coated with property firmly, glass attachment property is poor, has the problem that can not get with the cementability of glass mask.
In addition, when only using the silicone resin that being coated with property is excellent firmly,,, there is the problem that can not get as the performance of diaphragm so be easy to generate crackle because diaphragm is crisp.
And then, in order to solve problem that crackle takes place the epoxy resin of high rigidity is mixed when using, because epoxy resin is poor with the silicone resin compatibility,, there is the transparent problem that hinders so see the albefaction that causes because of incompatible when processing diaphragm.
Therefore, the objective of the invention is to, provide, the excellence of being coated with property firmly of diaphragm good, the glass mask that can not crack to protect liquid with thermohardening type with the cementability of glass mask.And then, purpose be to provide prevent diaphragm because of the glass mask of the incompatible albefaction that causes with thermohardening type protection liquid and use its glass mask.
The scheme that is used to deal with problems
Further investigate in order to solve above-mentioned problem, the result is, as the 1st viewpoint, finds through comprising linear phenolic resin varnish type epoxy resin as epoxy resin, thereby improves the compatibility of silicone resin and epoxy resin, thereby solve this problem.
As the 2nd viewpoint, find through comprising ester modified silicone resin, thereby improve the compatibility of silicone resin and epoxy resin, and can prevent albefaction, thereby solve this problem as silicone resin.
That is, the described glass mask of the 1st viewpoint of the present invention is protected liquid with thermohardening type, it is characterized in that, comprises silicone resin, epoxy resin and silicone oil, as epoxy resin, comprises linear phenolic resin varnish type epoxy resin.
The described glass mask of the 2nd viewpoint of the present invention is protected liquid with thermohardening type, it is characterized in that, comprises silicone resin, epoxy resin and silicone oil, and 15～35 weight % in the above-mentioned silicone resin are ester modified silicone resin.
In addition, it is characterized in that, comprise the above linear phenolic resin varnish type epoxy resin of 30 weight % in the epoxy resin.
In addition, it is characterized in that the part by weight of silicone resin and epoxy resin is 4: 6～8: 2.
In addition, it is characterized in that, as hardening agent, containing metal alkoxide series catalysts but comprise amine compound not.
In addition, glass mask of the present invention is characterized in that, on glass mask, forms to use above-mentioned glass mask to form with the diaphragm of thermohardening type protection liquid.
The effect of invention
Glass mask of the present invention is good with the cementability of thermohardening type protection liquid and glass mask; When processing diaphragm, the excellence of being coated with property firmly of diaphragm can not crack; Can prevent the incompatible albefaction of filming that causes because of epoxy resin and silicone resin, the transparency is excellent.In addition, owing to as hardening agent not containing metal alkoxide series catalysts comprise amine compound, so can improve the protection liquid storage stability.
Be formed with the glass mask excellent in adhesion that uses glass mask of the present invention can process diaphragm and glass mask with the glass mask of the diaphragm of thermohardening type protection liquid.In addition,, the incompatible albefaction of filming that causes can be prevented,, the glass mask that exposure accuracy is improved can be processed thus so the transparency is excellent because of epoxy resin and silicone resin because the hardness of diaphragm is high.
Embodiment
The embodiment of glass mask of the present invention with thermohardening type protection liquid described.
The described glass mask of the 1st viewpoint comprises silicone resin and epoxy resin, silicone oil with thermohardening type protection liquid, as epoxy resin, comprises linear phenolic resin varnish type epoxy resin.
The described glass mask of the 2nd viewpoint comprises silicone resin, epoxy resin and silicone oil with thermohardening type protection liquid, and 15～35 weight % in the above-mentioned silicone resin are ester modified silicone resin.
When silicone resin is processed diaphragm in order to improve and tack glass and use for the hardness that improves diaphragm.As such silicone resin; Can use methyl is silicone resin, methylbenzene base system silicone resin, modified silicone resin etc.; As the modified silicone resin, can use a kind of in ester modified silicone resin, epoxy radicals modified silicone resin, alkyd modified silicone resin, the acrylic acid modified silicone resin or use mixing more than two kinds.
In the 1st viewpoint, especially through with ester modified silicone resin with after the linear phenolic resin varnish type epoxy resin stated use simultaneously, can further improve the compatibility of silicone resin and epoxy resin, so preferably.
In the 2nd viewpoint, comprise ester modified silicone resin at least.Use ester modified silicone resin be for after the compatibility of the epoxy resin stated good, can not cause albefaction when processing diaphragm because of incompatible, obtain the excellent transparency.The mist degree of such diaphragm (JIS K7105:1981) preferably is lower than 1%.
Such silicone resin particularly; Trade name as Shin-Etsu Chemial Co., Ltd; Can enumerate out KR400, KR500, KR510, KR213, ES1001N, ES1002T, KR5206, KR9706, KR5230, KR5234, KR5235, X-40-2308, X-40-9238 etc.; Especially as ester modified silicone resin, can enumerate out KR5230, KR5234, KR5235 etc.
In the 2nd viewpoint, 15～35 weight % in the silicone resin are ester modified silicone resin, more preferably 20～30 weight %.Being set at more than the 15 weight % is in order to obtain the compatibility with epoxy resin, and being set at below the 35 weight % is the reduction for the hardness that prevents to film.
Epoxy resin is given diaphragm when processing diaphragm with being coated with property firmly and use.As such epoxy resin, can use phenolic resin varnish type epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, biphenyl type epoxy resin, Ppolynuclear aromatic type epoxy resin, hydrogenation alicyclic epoxy resin, mesomorphic framework ring epoxy resins etc.
In the 1st viewpoint, comprise linear phenolic resin varnish type epoxy resin at least.Use linear phenolic resin varnish type epoxy resin, except that in order to obtain processing diaphragm firmly the being coated with property, also for good, can not cause albefaction when processing diaphragm because of incompatible with the compatibility of aforesaid silicone resin.The mist degree of such diaphragm (JIS K7105:1981) preferably is lower than 1%.
In the 2nd viewpoint, especially the being coated with property firmly in order to obtain processing diaphragm is easily preferably used multi-functional epoxy resin such as phenolic resin varnish type epoxy resin, bisphenol A type epoxy resin, Ppolynuclear aromatic type epoxy resin.
Epoxy resin particularly; Trade name as Dainippon Ink. & Chemicals Inc; Can enumerate out EPICLON series, as Japan Epoxy Resins Co., the trade name of Ltd.; Can enumerate out JER series etc.; As linear phenolic resin varnish type epoxy resin, can enumerate out EPICLON N-740, N-770, N-775, N-865, N-740-80M, N-770-70M, N-865-80M of Dainippon Ink. & Chemicals Inc etc., Japan Epoxy Resins Co., the JER152 of Ltd., 154,157S70,1031S, 1032H60,604,630 etc.
Preferably in epoxy resin, comprise the linear phenolic resin varnish type epoxy resin more than the 30 weight %, more preferably more than the 40 weight %, be preferably especially more than the 80 weight %.Being set at more than the 30 weight % is for good with the compatibility of aforesaid silicone resin, can not cause albefaction because of incompatible when processing diaphragm.
Glass mask with the part by weight of silicone resin contained in the thermohardening type protection liquid and epoxy resin be preferably 4: 6～8: 2.If further become many from the ratio of aforementioned proportion silicone resin; Be easy to generate crackle on then filming; If further become many from the ratio of aforementioned proportion epoxy resin, then can not get filming of the required sufficient hardness of diaphragm, can't process excellent glass mask and use diaphragm.
Silicone oil is given the diaphragm surface when processing diaphragm with release property and soil resistance and use.Such silicone oil can use dimethyl silicon oil, Methyl Hydrogen Polysiloxane Fluid, methyl phenyl silicone oil, ring-type dimethyl-silicon wet goods silicone oil or in silicone oil, import the modified silicon oil that organic group forms.
As modified silicon oil, can use alkyl-modified, polyether-modified, fluorine modification, amino modified, sulfhydryl modified, epoxy radicals modification, carboxy-modified, higher fatty acid is ester modified, the modified silicon oil of methacrylic acid modification, carbitol modification etc.
Especially be for release property and soil resistance are continued, so preferred in order release property and soil resistance to be continued, use reactive silicone oil with the group that reacts with silicone resin or epoxy resin.Through such use, can easily remove the attachments such as resist on diaphragm surface.
As silicone oil; Particularly; Trade name as Shin-Etsu Chemial Co., Ltd; KF96, KF69, KF99, KF54, KF968 etc. can be enumerated out,, 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 etc. can be enumerated out especially as reactive silicone oil.
With respect to resinous principle (solid constituent) 100 weight portions in the protection liquid, silicone oil is preferably 0.05～1 weight portion.Being set at more than 0.05 weight portion is to be in order to prevent because the surface tension when processing coating fluid diminishes in order to obtain sufficient release property, soil resistance, to be set at below 1 weight portion, so that coating fluid becomes is granular, is difficult to form and films uniformly.
Cross-linking reaction takes place through making above-mentioned silicone resin and epoxy resin because of heat with thermohardening type protection liquid in glass mask of the present invention, thereby diaphragm can access being coated with property firmly.In order to make such resin cross-linking reaction need hardening agent because of heat causes.
As such hardening agent, preferably under the state of containing metal alkoxide series catalysts not, use amine compound.As the curing catalysts of silicone resin, also consider to use common employed metal alkoxide series catalysts, but when using the metal alkoxide series catalysts since easily with atmosphere in the moisture reaction, so the aspect of the storage stability of protection liquid has problems.On the other hand,, can work as the curing catalysts of silicone resin through using amine compound, and then, also can work as curing agent for epoxy resin.The shortcoming that therefore, can solve the metal alkoxide series catalysts is promptly protected the problem of the storage stability of liquid.
As such amine compound, can use the Curezol series of Shikoku Chem or the Luckamide series of DIC company etc.
In addition, in order to obtain the storage stability of solution, the curing that is caused by amine compound begins temperature and is preferably more than 100 degree.
With respect to resinous principle (solid constituent) 100 weight portions in the protection liquid, preferred 1～10 weight portion of amine compound.Be set at more than 1 weight portion is to be for the hardness of filming is reduced in order fully to carry out the curing reaction of resin, to be set at below 10 weight portions.
Glass mask of the present invention can be through silicone resin, epoxy resin, silicone oil, hardening agent and other components matching as required with above explanation with thermohardening type protection liquid, and is dissolved in the appropriate solvent and prepares.
Be preferably more than the 3H with the pencil hardness (JIS K5600-5-4:1999) of diaphragm when solidifying that thermohardening type protection liquid obtains by glass mask of the present invention.
Then, the embodiment to glass mask of the present invention describes.Glass mask of the present invention is on glass mask, to form to use above-mentioned glass mask to form with the diaphragm of thermohardening type protection liquid.
The glass mask that uses among the present invention is to be used on printed circuit board or resin relief forming fine pattern and to form figuratum glass substrate.Such glass mask has the latex that mixes at coating gelatin and silver halide on the glass substrate and the emulsion mask that obtains, the chrome mask that on glass substrate, is formed with the film that is made up of chromium or chromium oxide etc.
Glass mask of the present invention is with thermohardening type protection liquid and heating through the above-mentioned glass mask that comprises silicone resin, epoxy resin, silicone oil of coating on the figuratum glass mask of this formation; Thereby make the resinous principle generation heat curing of protection liquid, form and to have the glass mask of the diaphragm of being coated with property and release property firmly.
Through making protection comprise silicone resin and epoxy resin in the liquid, thereby can process and the cementability of glass mask, the excellent glass mask of being coated with property firmly.
And then, in the 1st viewpoint,, comprise linear phenolic resin varnish type epoxy resin, thereby the compatibility of epoxy resin and silicone resin is improved as epoxy resin, so the albefaction of diaphragm is inhibited, the transparency improves.Thus, the exposure accuracy when on printed circuit board or resin relief, forming pattern improves, and can form fine pattern.
In the 2nd viewpoint, as silicone resin, comprise ester modified silicone resin, thereby the compatibility of epoxy resin and silicone resin is improved, so the albefaction of diaphragm is inhibited, the transparency improves.Thus, the exposure accuracy when on printed circuit board or resin relief, forming pattern improves, and can form fine pattern.
As the method that on glass mask, forms diaphragm, known method such as can adopt spin coating or mould to be coated with, CAP is coated with, rod is coated with.
The glass mask of the formation pattern that uses among the present invention in addition, comprises and is provided with the glass mask that is used to improve with the undercoat of the cementability of diaphragm.
Embodiment
Below, through embodiment the present invention is further specified.In addition, short of special expression, " part ", " % " they are weight basis.
[embodiment 1～5, comparative example 1～3 and reference example 1]
The glass mask of embodiment 1～5, comparative example 1～3 and the reference example 1 that below table 1 is formed with thermohardening type protection liquid through spin application to the emulsion mask that forms pattern; With 150 ℃, 70 minutes it is heating and curing; Form the diaphragm that thickness is about 2 μ m, made the glass mask of embodiment 1～5, comparative example 1～3 and reference example 1.
In addition; In the above-mentioned example; Use silicone resin 1 (X-40-2308: Shin-Etsu Chemial Co., Ltd, solid constituent 100%), silicone resin 2: epoxy radicals modified silicone resin (ES-1001N: Shin-Etsu Chemial Co., Ltd, solid constituent 45%), silicone resin 3: ester modified silicone resin (KR5235: Shin-Etsu Chemial Co., Ltd, solid constituent 60%), silicone resin 4: acrylic acid modified silicone resin (KR9706: Shin-Etsu Chemial Co., Ltd, solid constituent 100%), epoxy resin 1: linear phenolic resin varnish type epoxy resin (JER157S70:Japan Epoxy ResinsCo., Ltd., solid constituent 100%), epoxy resin 2 (Epiclon 860:DIC company, solid constituent 100%), epoxy resin 3 (Epiclon 840:DIC company, solid constituent 100%), silicone oil (KF6001: Shin-Etsu Chemial Co., Ltd, solid constituent 100%), amine series catalysts (Curezol 2PZ-CN: Shikoku Chem, solid constituent 100%), metal alkoxide series catalysts (D-20: Shin-Etsu Chemial Co., Ltd, solid constituent 100%).
Glass mask for resulting embodiment 1～5 and comparative example 1～3 carries out the evaluation of following project.The result is shown in Table 2.
[with the cementability of glass mask]
Estimate the glass mask that obtains in embodiment 1～5 and the comparative example 1～3 and the cementability of diaphragm through cross-hatching (JIS K5600-5-6:1999).Among the result based on the disbonded test of cross-hatching, grid is not partly peeled off the person and is made as " * ", and the grid part does not have the person of peeling off fully and is made as " zero ".The result is shown in Table 3.
[having or not of crackle]
Visual valuation embodiment 1～5, and comparative example 1～3 in whether crack on the diaphragm of the glass mask that obtains.See the visual crackle person that can confirm and be made as " * ", the person is made as " zero " not see the crackle.Evaluation result is shown in Table 3.
[albefaction of diaphragm]
For the transparent part of the glass mask of embodiment 1～5 and comparative example 1～3, (HGM-2K:Suga Test Instruments Co. Ltd.), measures mist degree according to JIS K7105:1981 to use haze meter.Mist degree is lower than 1% and is made as " zero ", and mist degree is more than 1% and is lower than 5% and is made as " △ " that mist degree is that 5% above person is made as " * ".The result is shown in Table 3.
[skin hardness]
According to JIS K5600-5-4:1999, measure the pencil hardness on the surface of the diaphragm that forms on the glass mask of embodiment 1～5 and comparative example 1～3.Consequently, pencil hardness is that the above person of 3H is made as " zero ", and pencil hardness is lower than 3H person and is made as " * ".The result is shown in Table 3.
[solution storage stability]
Observe the glass mask that uses in embodiment 1～5 and the comparative example 1～3 and protect the solution state of liquid after 3 days with thermohardening type.Flowability disappears and can't be made as " * " as the coating fluid user, and flowability is arranged, and no problem person is made as " zero " as coating fluid.Evaluation result is shown in Table 3.
Table 2
The glass mask of embodiment 1～4 is because the ratio of the linear phenolic resin varnish type epoxy resin in the epoxy resin is more than the 30 weight %, so albefaction does not take place diaphragm.In addition, because the part by weight of silicone resin and epoxy resin is in 4: 6～8: 2 the scope, so do not crack, to obtain as the diaphragm sufficient surface hardness.In addition, the glass mask of embodiment 1～4 is protected liquid owing to only contain the amine series catalysts as hardening agent with thermohardening type, so the solution excellent storage stability.
The glass mask of embodiment 5 is because the ratio of the linear phenolic resin varnish type epoxy resin in the epoxy resin is more than the 30 weight %, so albefaction does not take place diaphragm.In addition, because the part by weight of silicone resin and epoxy resin is in 4: 6～8: 2 the scope, so do not crack, to obtain as the diaphragm sufficient surface hardness.But the glass mask of embodiment 5 comprises amine series catalysts and metal alkoxide series catalysts as hardening agent, so the solution storage stability has problems with thermohardening type protection liquid.
The glass mask of comparative example 1 is not owing to containing linear phenolic resin varnish type epoxy resin, so see the albefaction of diaphragm in epoxy resin.In addition, because the part by weight of silicone resin and epoxy resin is that the ratio of silicone resin is many, so crack outside 4: 6～8: 2 the scope.
The glass mask of comparative example 2 is not owing to containing linear phenolic resin varnish type epoxy resin, so see the albefaction of diaphragm in epoxy resin.In addition, because the ratio of silicone resin and epoxy resin is that the ratio of epoxy resin is many, so can not get as the diaphragm sufficient surface hardness outside 4: 6～8: 2 the scope.
The glass mask of comparative example 3 is not owing to containing the linear phenolic resin varnish type epoxy resin in the epoxy resin, so see the albefaction of diaphragm.
The glass mask of reference example 1 is because the ratio of linear phenolic resin varnish type epoxy resin in the epoxy resin is lower than 30 weight %, so to compare mist degree lower with the glass mask of comparative example 1～3, but sees the albefaction of diaphragm.
[embodiment 6～9 and comparative example 4～8]
The embodiment 6～9 of below table 3 compositions and the glass mask of comparative example 4～8 are passed through spin application to the emulsion mask that forms pattern with thermohardening type protection liquid; With 150 ℃, 70 minutes it is heating and curing; Form the diaphragm that thickness is about 2 μ m, made the glass mask of embodiment 6～9 and comparative example 4～8.
In addition; In the above-mentioned example, use the catalyzer, the silicone resin 5 that use in silicone resin 1～4, epoxy resin 1～2, silicone oil, amine series catalysts, metal alkoxide series catalysts: embodiment 1～5 and the comparative example 1～3: methyl is silicone resin (KR400: Shin-Etsu Chemial Co., Ltd, solid constituent 100%).
For resulting embodiment 6～9, and the glass mask of comparative example 4～8, carry out evaluation with the above embodiments 1～5 and comparative example 1～3 identical items.The result is shown in Table 4.
Table 4
The glass mask of embodiment 6～8 is because the ratio of the ester modified silicone resin in the silicone resin is in the scope of 15～35 weight %, so albefaction does not take place diaphragm.In addition; Because it is in 4: 6～8: 2 the scope that glass mask uses the part by weight of silicone resin and the epoxy resin of thermohardening type protection liquid; So obtain not cracking on the diaphragm as the diaphragm sufficient surface hardness, excellent as glass mask with diaphragm.In addition, the glass mask of embodiment 6～8 is protected liquid owing to only contain the amine series catalysts as hardening agent with thermohardening type, so the solution excellent storage stability.
The glass mask of embodiment 9 is because the ratio of the ester modified silicone resin in the silicone resin is in the scope of 15～35 weight %, so albefaction does not take place diaphragm.In addition; Because it is in 4: 6～8: 2 the scope that glass mask uses the part by weight of silicone resin and the epoxy resin of thermohardening type protection liquid; So obtain not cracking on the diaphragm as the diaphragm sufficient surface hardness, excellent as glass mask with diaphragm.But the glass mask of embodiment 9 protects liquid owing to comprising amine series catalysts and metal alkoxide series catalysts as hardening agent, so solution storage stability existing problems with thermohardening type.
The glass mask of comparative example 4 so can not get raising effect that bring by ester modified silicone resin and compatibility epoxy resin, is seen albefaction because the ratio of the ester modified silicone resin in the silicone resin is below the 15 weight %.
The glass mask of comparative example 5 is because the ratio of the ester modified silicone resin in the silicone resin is more than the 35 weight %, so can not get as the diaphragm sufficient surface hardness.
The glass mask of comparative example 6,8 is not owing to containing ester modified silicone resin, so see the albefaction of diaphragm in silicone resin.In addition, because glass mask uses the part by weight of silicone resin and the epoxy resin of thermohardening type protection liquid is that the ratio of silicone resin is many, so crack on the diaphragm outside 4: 6～8: 2 the scope.
The glass mask of comparative example 7 is not owing to containing ester modified silicone resin, so see the albefaction of diaphragm in silicone resin.In addition, because glass mask uses the part by weight of silicone resin and the epoxy resin of thermohardening type protection liquid is outside 4: 6～8: 2 the scope, so can not get as the diaphragm sufficient surface hardness.
Claims (6)
1. a glass mask is protected liquid with thermohardening type, it is characterized in that, comprises silicone resin, epoxy resin and silicone oil, as epoxy resin, comprises linear phenolic resin varnish type epoxy resin.
2. glass mask according to claim 1 is protected liquid with thermohardening type, it is characterized in that, in epoxy resin, comprises the said linear phenolic resin varnish type epoxy resin more than the 30 weight %.
3. a glass mask is protected liquid with thermohardening type, it is characterized in that, comprises silicone resin, epoxy resin and silicone oil, and 15～35 weight % in the said silicone resin are ester modified silicone resin.
4. protect liquid according to each described glass mask in the claim 1～3 with thermohardening type, it is characterized in that, the part by weight of said silicone resin and said epoxy resin is 4: 6～8: 2.
5. protect liquid according to each described glass mask in the claim 1～4 with thermohardening type, it is characterized in that, as hardening agent, containing metal alkoxide series catalysts but comprise amine compound not.
6. a glass mask is characterized in that, on glass mask, forms to have used each described glass mask in the claim 1～5 to form with the diaphragm of thermohardening type protection liquid.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2009/069935 WO2011064859A1 (en) | 2009-11-26 | 2009-11-26 | Thermosetting protective solution for glass mask, and glass mask |
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| CN102612665A true CN102612665A (en) | 2012-07-25 |
| CN102612665B CN102612665B (en) | 2014-07-30 |
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| Country | Link |
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| KR (1) | KR20120109469A (en) |
| CN (1) | CN102612665B (en) |
| WO (1) | WO2011064859A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105121588A (en) * | 2013-04-19 | 2015-12-02 | 木本股份有限公司 | Mold release performance-restoring solution, mold release performance restoration method, and photomask |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103827989A (en) * | 2011-10-03 | 2014-05-28 | 松下电器产业株式会社 | Powder magnetic core and production method for same |
| WO2013157382A1 (en) * | 2012-04-19 | 2013-10-24 | 株式会社きもと | Heat-curable protective liquid for glass mask and glass mask |
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| US6344495B1 (en) * | 1998-07-31 | 2002-02-05 | Dai Nippon Printing Co., Ltd. | Photo-curable resin composition and method for forming concave-convex pattern |
| CN1392971A (en) * | 2000-09-11 | 2003-01-22 | 昭和电工株式会社 | Photosensitive composition, cured article thereof, and printed circuit board using same |
| CN1817966A (en) * | 2004-12-16 | 2006-08-16 | Jsr株式会社 | Composition for forming protection film and protection film |
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| JP5170510B2 (en) * | 2007-03-30 | 2013-03-27 | 株式会社伏見製薬所 | Reactive group-containing cyclic phosphazene compound and process for producing the same |
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2009
- 2009-11-26 WO PCT/JP2009/069935 patent/WO2011064859A1/en active Application Filing
- 2009-11-26 KR KR1020127005943A patent/KR20120109469A/en active Search and Examination
- 2009-11-26 CN CN200980162460.1A patent/CN102612665B/en active Active
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| JPH06130658A (en) * | 1992-10-20 | 1994-05-13 | Konica Corp | Image forming material and its production |
| JP2000103826A (en) * | 1998-07-31 | 2000-04-11 | Dainippon Printing Co Ltd | Photocurable resin composition and method for forming irregular pattern |
| US6344495B1 (en) * | 1998-07-31 | 2002-02-05 | Dai Nippon Printing Co., Ltd. | Photo-curable resin composition and method for forming concave-convex pattern |
| CN1392971A (en) * | 2000-09-11 | 2003-01-22 | 昭和电工株式会社 | Photosensitive composition, cured article thereof, and printed circuit board using same |
| CN1989161A (en) * | 2004-07-29 | 2007-06-27 | 大日本油墨化学工业株式会社 | Actinic radiation-curable resin composition for shaping, shaping sheet, and shaped product |
| CN1817966A (en) * | 2004-12-16 | 2006-08-16 | Jsr株式会社 | Composition for forming protection film and protection film |
| WO2007074778A1 (en) * | 2005-12-26 | 2007-07-05 | Kimoto Co., Ltd. | Surface-protective film |
| JP2008137848A (en) * | 2006-12-01 | 2008-06-19 | Sumitomo Osaka Cement Co Ltd | Transparent fluid dispersion of inorganic oxide and transparent composite, composition for sealing light-emitting element and light-emitting element, and method for producing the transparent composite |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105121588A (en) * | 2013-04-19 | 2015-12-02 | 木本股份有限公司 | Mold release performance-restoring solution, mold release performance restoration method, and photomask |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20120109469A (en) | 2012-10-08 |
| CN102612665B (en) | 2014-07-30 |
| WO2011064859A1 (en) | 2011-06-03 |
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