TWI617524B - Glass product with protective film and manufacturing method thereof - Google Patents

Glass product with protective film and manufacturing method thereof Download PDF

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Publication number
TWI617524B
TWI617524B TW103112008A TW103112008A TWI617524B TW I617524 B TWI617524 B TW I617524B TW 103112008 A TW103112008 A TW 103112008A TW 103112008 A TW103112008 A TW 103112008A TW I617524 B TWI617524 B TW I617524B
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Taiwan
Prior art keywords
film
protective film
cationic
surfactant
surface
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TW103112008A
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Chinese (zh)
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TW201446690A (en
Inventor
Atsuyoshi Takenaka
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Asahi Glass Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3405Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of organic materials
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00Methods for coating glass
    • C03C2218/30Aspects of methods for coating glass not covered above
    • C03C2218/355Temporary coating

Abstract

An object of the present invention is to provide a novel protective film which can easily form and remove a protective film by a simple operation and can effectively provide an effect of preventing contamination.
The present invention is a glass product 1 with a protective film having a multi-layered protective film 3 having a first film 3a on the surface of the glass product 2 and the first film. The second film 3b on the surface of 3a, the first film 3a includes a cationic surfactant having a hydrophobic group having 8 or more carbon atoms or a cationic polymer having an average molecular weight of 500 to 10,000,000, and the second film 3b includes An anionic surfactant having a hydrophobic group having 8 or more carbon atoms or a nonionic surfactant having a hydrophobic group having 8 or more carbon atoms.

Description

Glass product with protective film and manufacturing method thereof

The present invention relates to a glass article with a protective film and a method of manufacturing the same.

The surface of the glass product is easily contaminated, and if it is exposed to the external environment, dust or organic matter contained in the environment adheres and is immediately contaminated. In particular, glass products used in precision equipment such as flat panel displays (FPD) must be treated in a clean state in order to prevent contamination by dust or organic matter. Therefore, the manufacture is performed by a clean room or the like.

For example, in the case of a glass substrate for FPD, when the glass substrate is manufactured and processed into a product for a display, the glass substrate is transported to a display manufacturing factory and stored. At this time, even when the glass substrate is manufactured to be a very clean surface, some contamination is likely to occur when it is used (when the display is manufactured). As one of the reasons, it is conceivable that the glass substrates are not in contact with each other, and the spacer paper is often interposed between the substrates, and may be contaminated by the TiO 2 fine particles or the fluorene ketone particles derived from the spacer paper.

Moreover, such surface contamination problems have existed for a long time, and various methods for preventing contamination of the surface of glass products have been studied before. For example, a method is known in which the surface of the glass article is protected in order to incorporate it into the manufacturing process of the glass article in order to protect it immediately after the glass article is manufactured. The method is a method for treating a glass cut, coarsely ground or ground glass by forming a hydrophobic coating on the surface of the hot glass article having a temperature higher than 175 ° C by using at least one surfactant (refer to the patent literature) 1).

Further, a water-soluble protective film containing an anionic surfactant is also known (refer to Patent Document 2) a water-soluble coating layer in which one part of a hydrophilic group is aligned on the side opposite to the surface of the hydrophilic member (see Patent Document 3), and a long-chain organic material having a hydrophilic group such as a hydroxyl group or a carboxyl group (see Patent Document 4) and the like.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-319038

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2000-211947

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2002-46225

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2012-116748

However, in Patent Document 1, the formation of the protective film is incorporated into the manufacturing process of the glass article, and it cannot be applied to the case where the polishing step is performed after the glass article is manufactured. Further, it is considered that the protective film described in Patent Documents 2 to 4 has a weak interaction with the stanol group on the surface of the glass product, which requires labor and formation, and the protective film is relatively unstable.

Therefore, an object of the present invention is to provide a novel protective film which can easily form and remove a protective film by a simple operation, and which is relatively stable in a protective film, and can effectively provide an effect of preventing contamination.

The protective glass film of the present invention is characterized in that it has a protective film having a multi-layer structure, and the protective film of the multi-layer structure has a first film on the surface of the glass product and a surface of the first film In the second film, the first film includes a cationic surfactant having a hydrophobic group having 8 or more carbon atoms or a cationic polymer having an average molecular weight of 500 to 10,000,000, and the second film contains a carbon number of 8 or more. A hydrophobic group anionic surfactant or a nonionic surfactant having a hydrophobic group having a carbon number of 8 or more.

Further, the method for producing a glass article with a protective film of the present invention is characterized by There is a step of contacting a solution containing a cationic surfactant having a hydrophobic group having a carbon number of 8 or more or a cationic polymer having an average molecular weight of 500 to 10 million with a surface of a glass article and drying to form a cation comprising the above cation a first film of a surfactant or the above cationic polymer; and a solution containing an anionic surfactant having a hydrophobic group having 8 or more carbon atoms or a nonionic surfactant having a hydrophobic group having 8 or more carbon atoms The surface of the first film is brought into contact with and dried to form a second film containing the anionic surfactant or the nonionic surfactant.

Further, a method for producing a glass article with a protective film according to the present invention is characterized in that it has a step of preparing a mixed solution containing a cationic surfactant having a hydrophobic group having a carbon number of 8 or more or an average molecular weight of 500. ~10 million cationic polymers, and an anionic surfactant having a hydrophobic group having a carbon number of 8 or more or a nonionic surfactant having a hydrophobic group having a carbon number of 8 or more; and the above mixed solution and glass product The surface is contacted and dried to form a first film comprising the above cationic surfactant or cationic polymer from the surface side of the glass product, and a second film comprising the anionic surfactant or the nonionic surfactant Protective film for the film.

According to the glass article with a protective film of the present invention and the method for producing the same, a protective film is provided on the surface of the glass product to prevent contamination of foreign matter during adhesion from the manufacture of the glass product to the use before use. Further, the protective film can be easily removed by a simple operation such as water washing or alkali washing before using the glass product.

Further, as compared with the case where the surfactant is used as the single-layer protective film, the antifouling effect can be further enhanced, and the contamination of the glass product can be effectively prevented.

1‧‧‧Glass products with protective film

2‧‧‧glassware

3‧‧‧Protective film

3a‧‧‧1st film

3b‧‧‧2nd film

Fig. 1 is a cross-sectional view showing a schematic configuration of a glass product with a protective film of the present invention.

Fig. 2 is a graph showing the residual amount of TiO 2 fine particles in Examples and Comparative Examples.

Fig. 3 is a view showing contact angles with pure water of Examples and Comparative Examples.

Hereinafter, a glass product with a protective film of the present invention will be described with reference to the drawings. 1 is a cross-sectional view showing a schematic configuration of a glass product with a protective film of the present invention, and the glass product 1 with a protective film of the present invention comprises a glass product 2 and a protective film 3 formed on the surface thereof.

The glass product 2 used herein is not particularly limited as long as it is a glass product in which glass is exposed on its surface. Further, it is particularly preferably applied to a glass product used in the production of a semiconductor article which is required to keep the surface of the glass product clean, such as a glass substrate for a flat panel display (FPD), an optical multilayer film substrate, or the like.

The protective film 3 used in the present invention is a film having a multi-layer structure, and has a first film 3a provided on the surface of the glass product 2 and a second film 3b provided on the surface of the first film 3a.

Here, the first film 3a is a film containing a cationic surfactant having a hydrophobic group of 8 or more carbon atoms or a cationic polymer having an average molecular weight of 500 to 10,000,000.

The cationic surfactant used herein is not particularly limited as long as it is a cationic surfactant having a hydrophobic group having 8 or more carbon atoms. When the number of carbon atoms of the hydrophobic group is increased, the coating property of the glass surface is increased and the antifouling property is improved. Therefore, the carbon number of the hydrophobic group is preferably 12 or more. Typical examples of such a hydrophobic group include an alkyl group having 8 to 18 carbon atoms, and more preferably an alkyl group having 16 to 18 carbon atoms. The cationic surfactant may be any of an amine salt type or a quaternary ammonium salt type, and examples thereof include octyltrimethylammonium chloride, decyltrimethylammonium chloride, and chlorinated twelve. a trimethylammonium salt such as alkyltrimethylammonium, tetradecyltrimethylammonium chloride, cetyltrimethylammonium chloride or octadecyltrimethylammonium chloride; octyl chloride a pyridinium salt such as pyridinium chloride, decylpyridinium chloride, dodecylpyridinium chloride, tetradecylpyridinium chloride, cetylpyridinium chloride or octadecylpyridinium chloride; Benzylammonium chloride, benzethonium chloride, benzyltrialkylammonium chloride, dialkyldimethylammonium chloride, and the like.

Further, in terms of increasing the adsorption density to the surface of the glass article, an alkyltrimethylammonium salt is preferred, and the pyridinium salt can improve the water repellency of the glass article, especially cetylpyridinium chloride. It is preferable that 鎓 (alias: cetylpyridinium chloride) can be produced in large quantities and is easily and inexpensively obtained.

Further, the cationic polymer used herein may be a polymer having an average molecular weight of 500 to 10,000,000 and having a cationic group in the molecule. Further, in the present specification, the average molecular weight means a weight average molecular weight. When the cationic group is dissolved in a solvent such as water, it becomes a cation group, and examples thereof include an amine group and a quaternary ammonium group. At this time, the amine group removes one of the hydrogen functional groups from the ammonia, the primary amine, and the secondary amine to form a primary amine, a secondary amine, and a tertiary amine, respectively. Further, the quaternary ammonium group forms a quaternary ammonium cation.

Examples of the cationic polymer used herein include polyacrylic acid diallyldimethylammonium (PDAC or PDADMAC (poly(diallyldimethyl ammonium chloride)), and poly(dimethylaminoethyl chloroformate). Grade salt), poly(dimethylaminoethyl methacrylate chloromethane quaternary salt), trimethylammonium alkyl acrylamide polymer salt, dimethylamine epichlorohydrin condensate salt, polyallylamine, Polyethylenimine and the like.

As the cationic polymer, the number of the cationic groups is preferably 4 to 25 per 1,000 molecular weight.

Further, the second film 3b is a film containing an anionic surfactant having a hydrophobic group having 8 or more carbon atoms or a nonionic surfactant having a hydrophobic group having 8 or more carbon atoms.

The anionic surfactant used herein is not particularly limited as long as it is an anionic surfactant having a hydrophobic group having 8 or more carbon atoms. Examples of the anionic surfactant include those having a structure of a carboxylic acid, a sulfonic acid, a sulfate, and a phosphate as a hydrophilic group. For example, dioctyl sodium sulfosuccinate (DOSS) can be mentioned. , sodium stearate, sodium lauryl sulfate, sodium alkylbenzene sulfonate, and the like.

Here, the hydrophobic group having a carbon number of 8 or more may be either a linear chain or a branched chain. Preferably, it is a branched chain group, and an octyl group (C8) is often a 2-ethylhexyl group, and more preferably a plurality of such octyl groups. It is considered that when the hydrophobic group is branched as described above, it is easily complexed with a cationic surfactant or a cationic polymer to form a more stable film.

In addition, the nonionic surfactant used herein is not particularly limited as long as it is a nonionic surfactant having a hydrophobic group having 8 or more carbon atoms. Examples of the nonionic surfactant include those having a structure such as an ester type, an ether type, or an alkyl glycoside. Examples thereof include a polyoxyethylene alkyl phenyl ether having a repeating unit of ethylene oxide, and an alkyl polyethylene group. Alcohol, glycerin fatty acid ester, and the like.

Here, the hydrophobic group having 8 or more carbon atoms may be either linear or branched, and is preferably a branched group. It is considered that when the hydrophobic group is branched as described above, it is easy to complex with a cationic boundary active agent or a cationic polymer to form a more stable film.

As described above, by forming a protective film having a multilayer structure in which the first film 3a and the second film 3b are laminated, the stability of the film can be improved as compared with the case of the single layer, and the effect of preventing contamination can be improved. Moreover, the protective film formed here basically contains a surfactant, and there is also a case where a cationic polymer is contained. In any case, the surface of the glass article is bonded by electrostatic bonding, by using pure water or The alkaline lotion is easily removed by washing.

Next, a method of manufacturing a glass article with a protective film will be described.

As a method of forming the protective film of the present invention, first, a solution containing a cationic surfactant having a hydrophobic group having a carbon number of 8 or more or a cationic polymer having an average molecular weight of 500 to 10,000,000 and a surface of a glass product are used. Contact and drying to form a first film comprising a cationic surfactant or a cationic polymer.

In this case, the cationic surfactant or the cationic polymer is prepared by dissolving an aqueous solution of a water-soluble organic solvent such as pure water or ethanol as a solvent. At this time, the concentration of the solution of the cationic surfactant is preferably from 0.01 mmol/L to 100 mmol/L, and is appropriately covered on the surface of the glass product, and is not excessively more preferably 0.1 to 10 mmol/L. Further, in the case of using a cationic polymer, it is preferred to make a cationic group in the solution The concentration (equivalent) is in the range of 0.01 meq/L to 100 meq/L, and is appropriately covered on the surface of the glass product, and is not excessive, and more preferably 0.1 meq/L to 10 meq/L. Further, in the case where 1 mol of the cationic group was contained in the 1 L solution, the concentration thereof was expressed as 1 eq/L. Moreover, the pH of the solution can be used when it is acidic to alkaline (for example, a pH of about 4 to 12), but it can be electrostatically bonded by promoting the ionization of the stanol group on the surface of the glass article to be negatively charged. The pH of the solution is preferably from 8 to 12, more preferably from 10 to 11, in terms of being more sturdy and increasing the amount of adhesion.

The solution obtained in the above manner is brought into contact with and applied to the surface of the glass article on which the first film is to be formed. In this case, the coating method may be a coating method used in a known film formation method such as dip coating, spray coating, or coating with a sponge. Further, in this step, the cationic surfactant or the cationic polymer contained in the solution is merely brought into contact with the cationic portion of the cationic surfactant or the cationic portion of the cationic polymer toward the surface side of the glass substrate. The hydrophobic group of the cationic surfactant or the main chain portion of the polymer connecting the cationic portion of the cationic polymer is aligned in an environment as the opposite side thereof. The reason for this is that since the stanol group (-Si-OH) present on the surface of the glass article is easily charged-charged, only the hydrophilic group of the cationic surfactant with a charge or the cation of the cationic polymer is contacted by contact. Part of it is attracted to the surface side of the glass article by static electricity.

When the solvent is removed by heating, blowing, or the like in a state where the cationic surfactant or the cationic polymer is aligned as described above, the homogeneous first film can be easily formed. At this time, in the heat drying, it is preferable to heat to 50 to 90 ° C, and to blow air of 15 to 30 ° C in the blast.

Then, a solution containing an anionic surfactant having a hydrophobic group having a carbon number of 8 or more or a nonionic surfactant having a hydrophobic group having a carbon number of 8 or more is brought into contact with the surface of the formed first film and Drying forms a second film comprising an anionic surfactant or a nonionic surfactant.

At this time, the anionic surfactant or the nonionic surfactant is pure water or An aqueous solution of a water-soluble organic solvent such as ethanol is dissolved as a solvent to prepare a solution. In this case, the solution concentration is preferably from 0.1 mmol/L to 100 mmol/L, which is suitable for covering the surface of the glass product and is not excessive, and more preferably 0.5 to 10 mmol/L. Further, the pH of the solution is not particularly problematic as long as it is not extremely acidic and extremely alkaline, and the pH is preferably 5 to 10, more preferably 6 to 9.

The solution obtained in the above manner was brought into contact with and applied to the surface of the first film on which the second film was to be formed. In this case, the coating method is the same as the coating method of the first film formation. Further, in this step, the anionic surfactant or the nonionic surfactant contained in the solution is anionic surfactant or nonionic surfactant only by contacting the hydrophobic group present on the surface of the first film. The hydrophobic group portion is aligned toward the first film side, and the hydrophilic group of the anionic surfactant or the nonionic surfactant is aligned in an environment as the opposite side.

When the solvent is removed by heating, blowing, or the like in a state where the anionic surfactant or the nonionic surfactant is aligned as described above, the homogeneous second film can be easily formed. At this time, in the heat drying, it is preferably heated to 50 to 80 ° C, and in the blast, it is preferred to blow air of 15 to 30 ° C.

Further, as a method for forming another protective film of the present invention, there may be mentioned a method in which a solution of a cationic surfactant or a cationic polymer, an anionic surfactant or a nonionic surfactant is not separately prepared as described in the above method. The solution is prepared into a solution, and a protective film is formed by one coating and drying operation.

In the method, first, a solution containing a cationic surfactant having a hydrophobic group having 8 or more carbon atoms or a cationic polymer having an average molecular weight of 500 to 10,000,000 and a hydrophobic group having a carbon number of 8 or more are prepared. An anionic surfactant or a nonionic surfactant having a hydrophobic group having a carbon number of 8 or more. At this time, the solvent or pH conditions used are the same as those described above for forming a film, respectively.

However, at this time, the content of the cationic surfactant or cationic polymer and the anionic surfactant or nonionic boundary must be obtained in such a manner that the components in the solution do not react and aggregate. The content of the surfactant is adjusted. For example, the content of the cationic surfactant and the content of the anionic surfactant or the nonionic surfactant are preferably in a range of 1:0.1 to 1:1 in a molar ratio, more preferably 1:0.3. The ratio of 1:0.7 is contained. Further, in the case of a cationic polymer, the ratio of the content (equivalent) of the cationic group to the content of the anionic surfactant or the nonionic surfactant (mole concentration) is preferably 1:0.1 to 1: It is contained in the range of 1, and is preferably contained in a ratio of 1:0.3 to 1:0.7. In this case, when a water-soluble organic solvent such as a few to several tens of % of ethanol is added, the effect of suppressing aggregation is preferable.

The mixed solution of the one-liquid type obtained in the above manner was brought into contact with and applied to the surface of the glass article on which the protective film was to be formed. In this case, the coating method is the same as the coating method of the first film formation. Further, in this step, the cationic surfactant or the cationic polymer contained in the solution is relatively contained, and the hydrophilic group or the cationic portion is aligned toward the surface side of the glass article, and the hydrophobic group of the cationic surfactant is arranged. Or the main chain portion of the polymer connecting the cationic portion of the cationic polymer is aligned toward the opposite side to form a first film. Then, on the surface of the first film, the hydrophobic group portion of the anionic surfactant or the nonionic surfactant is aligned toward the first film side, and the hydrophilic group of the anionic surfactant or the nonionic surfactant is oriented as the opposite side Arranged in the environment.

According to the method for forming the protective film, a glass article with a protective film can be produced by a simple operation of a single film forming operation using a solution.

Further, the case where the first film and the second film are formed separately or the case where the solution is formed once by mixing the solution can be achieved by a simple operation of coating the solution at room temperature, and further, it can be achieved. In the case of using a surfactant, the surface protection of the glass product which does not violate the drainage limit and does not increase the environmental load is not violated.

[Examples]

Hereinafter, the present invention will be further described in detail based on examples and comparative examples.

[Preparation of various solutions] <Solution 1 for forming a first film>

The solution for forming the first film was prepared by dissolving each component in pure water so that the cetylpyridinium ruthenium (CPC) as a cationic surfactant was 1 mmol/L and the concentration of ammonia was 10 mmol/L. . The pH of the solution was approximately 10.5.

<Solution 2 for forming a first film>

Polychlorinated diallyldimethylammonium as a cationic polymer (PDAC or PDADMAC; and colloidal titration standard liquid manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 60,000 to 110,000) becomes 1 meq/L and ammonia becomes 10 mmol. The components of the first film formation were prepared by dissolving each component in pure water in a manner of a concentration of /L. The pH of the solution was approximately 10.5.

<Second film forming solution 1>

The solution for forming a second film was prepared by dissolving it in pure water so that the sodium octyl sulfosuccinate (DOSS) as an anionic surfactant became a concentration of 1 mmol/L. The pH of the solution is about 7.

<Second film forming solution 2>

The solution for forming a second film was prepared by dissolving it in pure water so that the hexadecylsulfonic acid sodium salt (HDS) as an anionic surfactant became a concentration of 1 mmol/L. The pH of the solution is about 7.

<Mixed solution for forming a protective film>

The concentration of cetylpyridinium chloride (CPC) as a cationic surfactant was 1 mmol/L, ammonia was 10 mmol/L, and sodium octyl sulfosuccinate (DOSS) was 0.5 mmol/L. In the manner, each component was dissolved in pure water to prepare a mixed solution. The pH of the solution was approximately 10.5.

(Example 1)

The surface-polished glass plate made of alkali-free borosilicate glass having a length of 50 mm, a width of 50 mm, and a thickness of 0.7 mm was immersed in the solution 1 for forming the first film for 10 seconds, and then taken out, and the surface was dried by air blowing. The solution is formed on the surface of the glass plate by the dip coating method as described above Into the first film.

The obtained glass plate having the first film was immersed in the solution 1 for forming the second film for 10 seconds, and then taken out, and then the solution of the surface was dried by blasting, and the first film was applied by the dip coating method as described above. A second film is formed on the surface to form a glass product with a protective film.

(Example 2)

The surface-polished glass plate made of an alkali-free borosilicate glass having a length of 50 mm, a width of 50 mm, and a thickness of 0.7 mm was immersed in the solution 2 for forming the first film for 10 seconds, and then taken out, and then dried by a blast. The solution was formed into a first film on the surface of the glass plate by the dip coating method as described above.

The obtained glass plate having the first film was immersed in the solution 1 for forming the second film for 10 seconds, and then taken out, and then the solution of the surface was dried by blasting, and the first film was applied by the dip coating method as described above. A second film is formed on the surface to form a glass product with a protective film.

(Example 3)

The surface-polished glass plate made of alkali-free borosilicate glass having a length of 50 mm, a width of 50 mm, and a thickness of 0.7 mm was immersed in the mixed solution for forming a protective film for 10 seconds, and then the solution was dried by air. By the dip coating method as described above, a protective film containing the first film and the second film is formed on the surface of the glass plate to form a glass product with a protective film.

(Example 4)

The surface-polished glass plate made of an alkali-free borosilicate glass having a length of 50 mm, a width of 50 mm, and a thickness of 0.7 mm was immersed in the solution 2 for forming the first film for 10 seconds, and then taken out, and then dried by a blast. The solution was formed into a first film on the surface of the glass plate by the dip coating method as described above.

The glass plate having the first film obtained was immersed in the solution 2 for forming the second film for 10 seconds, and then taken out, and then the solution of the surface was dried by blasting, and the first film was applied by the dip coating method as described above. A second film is formed on the surface to form a glass product with a protective film.

(Comparative Example 1)

The surface-grinded glass plate made of alkali-free borosilicate glass having a length of 50 mm, a width of 50 mm, and a thickness of 0.7 mm was washed with pure water. The glass plate is in a state in which the surface is polished, and a protective film or the like is not provided.

(Comparative Example 2)

The surface-polished glass plate made of alkali-free borosilicate glass having a length of 50 mm, a width of 50 mm, and a thickness of 0.7 mm was immersed in the solution 1 for forming a second film for 10 seconds, and then the solution was dried by blasting. A film of an anionic surfactant was formed on the surface of the glass plate by the dip coating method as described above.

(Test Example 1)

The spacer paper coated with the TiO 2 fine particle pigment for papermaking was pressed against the surfaces of the glass articles of the examples and the comparative examples to transfer the TiO 2 fine particles. The glass product was blown with air blast of about 25 ° C for 30 seconds, and then subjected to ultrasonic cleaning at 100 kHz for 30 seconds in pure water at 25 ° C, and further, a commercially available alkaline lotion solution ( Ultrasonic cleaning at 30 kHz at 30 kHz in an alkali washing solution prepared by Parker Corporation, trade name: PK-LCG211). The residual state of the TiO 2 fine particles was monitored by the fluorescent X-ray method on the surface of each of the treated glass products after blasting, pure water washing, and alkaline washing, and the results are shown in Fig. 2 . Regarding the removal rate of the TiO 2 fine particles after the alkali washing compared with the post-blasting, Example 1 was 82%, Example 2 was 61%, Example 3 was 76%, and Example 4 was 80%. Comparative Example 1 It was 35%, and Comparative Example 2 was 34%.

According to the results, the effect of preventing the contamination of Example 1 was the highest, and the fourth example was the same. In Comparative Examples 1 and 2, the residual amount of TiO 2 fine particles was large, and the effect of preventing contamination was low. In the case of using the anionic surfactant in Comparative Example 2, it is presumed that in the drying step by the blast, since the anionic surfactant has no interaction with the surface of the glass product, the water is removed while it is removed. Most of them were removed, and the results were equivalent to those of Comparative Example 1 in which no protective film was provided.

(Test Example 2)

Polyoxyphthalic acid (polydimethyloxane: molecular weight: about 4,200) was dissolved in acetone so as to be 100 μg/mL, and the solution was impregnated on a spacer paper and dried to have an adhesion amount of 4 μg/cm 2 . The spacer paper impregnated with the polyoxygenated oil was alternately separated from the glass products of the examples and the comparative examples, and the whole was sandwiched by a spring clip to prepare a sample bundle. This was kept at 50 ° C and a humidity of 80% for 20 hours to transfer the polyphthalic acid oil to the surface of the glass article. Ultrasonic cleaning at 30 kHz at 30 kHz in an alkali washing solution obtained by diluting a commercially available alkaline lotion stock solution (manufactured by Parker Corporation, trade name: PK-LCG211) by 100 times, and further using a sponge made of polyvinyl alcohol , scrub with the same alkaline lotion for 3 minutes, about 200 times. The contact angle was measured immediately after the transfer, after the ultrasonic cleaning, and after the manual scrubbing, and the results are shown in Fig. 3 . Although the contact angle is not a quantitative one indicating the amount of adhesion of the polyoxygenated oil, the magnitude relationship can qualitatively evaluate the amount of adhesion. Regarding the rate of change of the contact angle after manual scrubbing immediately after the transfer, Example 1 was 14%, Example 2 was 85%, Example 3 was 20%, and Example 4 was 22%. Comparative Example 1 It was 91%, and Comparative Example 2 was 89%.

[Contact angle]

One drop of pure water was dropped on the surface of the glass substrate to be measured, and the measurement results of the five points were averaged based on the data obtained by photographing the water droplets on the surface of the substrate, and the contact angle between each substrate and pure water was calculated.

According to the results, the effect of preventing the contamination of Example 1 was the highest, and the third embodiment was the same. In Comparative Examples 1 and 2, the residual amount of the polyoxygenated oil was large, and the effect of preventing contamination was low. In the case of using the anionic surfactant in Comparative Example 2, it is considered that in the drying step by the blast, since the anionic surfactant has no interaction with the surface of the glass article, the water is removed while it is removed. Most of it was also removed. Therefore, it is estimated that it is equivalent to the comparative example 1 which does not provide a protective film.

[Industrial availability]

The glass product with the protective film of the invention and the manufacturing method thereof can be widely applied to the glass product, and can effectively prevent the pollution of the surface of the glass product, especially for flat panel display. A glass substrate such as a liquid crystal display such as a device (FPD) is preferable.

Claims (10)

  1. A glass article with a protective film, characterized in that it has a protective film of a multi-layer structure, the protective film of the multi-layer structure having a first film on the surface of the glass product and on the surface of the first film In the second film, the first film includes a cationic surfactant having a hydrophobic group having 8 or more carbon atoms or a cationic polymer having an average molecular weight of 500 to 10,000,000, and the second film contains a hydrophobic having a carbon number of 8 or more. A cationic surfactant.
  2. A glass article with a protective film as claimed in claim 1, wherein the hydrophobic group of the above cationic surfactant has a carbon number of 12 or more.
  3. A glass article with a protective film as claimed in claim 1, wherein the cationic surfactant is a trimethylammonium salt having an alkyl group having 8 to 18 carbon atoms or a pyridinium salt having an alkyl group having 8 to 18 carbon atoms.
  4. A glass article with a protective film as claimed in claim 1, wherein the above cationic polymer has 4 to 25 cationic groups per 1000 molecular weight.
  5. A glass article with a protective film as claimed in claim 4, wherein the above cationic group is an amine group or a quaternary ammonium group.
  6. A glass article with a protective film as claimed in claim 1, 2, 4 or 5, wherein the hydrophobic group of the above anionic surfactant is linear or branched.
  7. A method for producing a glass article with a protective film, comprising the steps of: providing a cationic surfactant having a hydrophobic group having a carbon number of 8 or more or a cationic polymer having an average molecular weight of 500 to 10,000,000 Contacting with the surface of the glass product and drying to form a first film comprising the above cationic surfactant or the above cationic polymer; and a solution containing an anionic surfactant having a hydrophobic group having a carbon number of 8 or more and the solution The surface of the first film is contacted and dried to form an anion boundary The second film of the surfactant.
  8. A method for producing a glass article with a protective film, comprising the steps of: preparing a mixed solution containing a cationic surfactant having a hydrophobic group having a carbon number of 8 or more or a cation having an average molecular weight of 500 to 10,000,000 a polymer, and an anionic surfactant having a hydrophobic group having a carbon number of 8 or more; and contacting the dried solution with the surface of the glass article and drying, and forming the cation interface including the cation interface from the surface side of the glass article A first film of an active agent or a cationic polymer, and a protective film of a second film containing the anionic surfactant.
  9. A method for producing a glass product with a protective film according to claim 7 or 8, wherein the solution used for forming the first film and the second film is an aqueous solution having a pH of from 8 to 12.
  10. The method for producing a glass article with a protective film according to claim 8, wherein a ratio of a cationic surfactant to an anionic surfactant in the mixed solution is 1:0.1 to 1:1 in terms of a molar ratio, or a cation The ratio of the content (equivalent) of the cationic group of the polymer to the content of the anionic surfactant (mole concentration) is from 1:0.1 to 1:1.
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JP6260503B2 (en) * 2014-09-18 2018-01-17 旭硝子株式会社 Glass substrate with antistatic film and method for producing glass substrate with antistatic film
JP6256279B2 (en) * 2014-09-25 2018-01-10 旭硝子株式会社 Glass plate with smoothness improving film, method for producing the same, glass plate package, and method for packing glass plate
CN107488374A (en) * 2017-08-11 2017-12-19 航天凯天环保科技股份有限公司 Dustproof modifier used for glass baking varnish material, modified glass baking varnish paint and application thereof

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TW593189B (en) * 1999-02-26 2004-06-21 Corning Inc Method for temporarily protecting glass articles

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JPS5432521A (en) * 1977-08-17 1979-03-09 Asahi Denka Kogyo Kk Method of protecting glass
GB2028165A (en) * 1978-08-17 1980-03-05 Pilkington Brothers Ltd Treatment of flat glass
JPS5567542A (en) * 1978-11-10 1980-05-21 Nippon Oil & Fats Co Ltd Lubrication treating method for glass container
US6379746B1 (en) * 1999-02-02 2002-04-30 Corning Incorporated Method for temporarily protecting glass articles
AU2009207772B2 (en) * 2008-01-24 2014-03-27 Basf Se Superhydrophilic coating compositions and their preparation

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TW593189B (en) * 1999-02-26 2004-06-21 Corning Inc Method for temporarily protecting glass articles

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