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

Abstract

An object of the present invention is to provide a novel protective film that can easily form and remove a protective film with a simple operation and can effectively provide a pollution prevention effect.

The invention is a glass product 1 with a protective film, which has a protective film 3 of a multilayer structure. The protective film 3 of the multilayer structure has 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 contains a cationic surfactant having a hydrophobic group with a carbon number of 8 or more, or a cationic polymer with an average molecular weight of 5-10 million, and the second film 3b contains An anionic surfactant having a hydrophobic group with a carbon number of 8 or more or a nonionic surfactant having a hydrophobic group with a carbon number of 8 or more.

Description

Glass product with protective film and manufacturing method thereof

The invention relates to a glass product with a protective film and a manufacturing method thereof.

The surface of glass products is easy to be contaminated. If exposed to the external environment, dust or organic substances contained in the environment are attached and immediately contaminated. In particular, glass products used in precision devices such as flat panel displays (FPD, Flat Panel Display) must be cleaned in order to prevent contamination caused by dust or organic matter. Therefore, the manufacturing is performed by a clean room or the like.

However, for example, in the case of a glass substrate for FPD, when the glass substrate is manufactured and processed into a display product, the glass substrate is transported to a display manufacturing factory and stored. At this time, even when the glass substrate is manufactured as a very clean surface, some pollution may occur during its use (when manufacturing a display). As one of the reasons, it is conceivable that a spacer paper is often interposed between the substrates in order to prevent the glass substrates from contacting each other, and may be contaminated by TiO ₂ fine particles or silicone particles derived from the spacer paper.

In addition, such a problem of surface contamination has existed for a long time, and various methods for preventing the surface contamination of glass products have been studied before. For example, a method is known in which the method is incorporated into a glass product manufacturing process to protect the surface of the glass product in order to protect it immediately after the glass product is manufactured. This method is a hot glass product with a temperature higher than 175 ° C. A hydrophobic coating is formed on the surface by at least one surfactant, and the glass product is cut, roughed, and polished. (See Patent Literature 1).

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

[Prior technical literature] [Patent Literature]

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

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

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

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

However, in Patent Document 1, the formation of the protective film is incorporated into the manufacturing process of the glass product, and cannot be applied to the case where the polishing step is performed after the glass product is manufactured. In addition, it is considered that the protective films described in Patent Documents 2 to 4 have weak interactions with silanol groups on the surface of glass products, and it takes time to form the protective films, and the protective films are relatively unstable.

Therefore, an object of the present invention is to provide a novel protective film that can be easily formed and removed with a simple operation, the protective film is relatively stable, and can effectively impart a pollution prevention effect.

The glass product with a protective film of the present invention is characterized in that it has a protective film with a multilayer structure, and the protective film with the multilayer structure has a first film on the surface of the glass product and a surface of the first film The second film above, the first film includes a cationic surfactant having a hydrophobic group with a carbon number of 8 or more, or a cationic polymer having an average molecular weight of 5 to 10 million, and the second film includes a carbon number of 8 or more An anionic surfactant having a hydrophobic group or a nonionic surfactant having a hydrophobic group having a carbon number of 8 or more.

In addition, the method for manufacturing a glass product with a protective film according to the present invention is characterized by There are the following steps: a solution containing a cationic surfactant having a hydrophobic group with a carbon number of 8 or more or a cationic polymer having an average molecular weight of 5-10 million is brought into contact with the surface of a glass product and dried to form the above-mentioned cation A surfactant or the first film of the above-mentioned cationic polymer; and a solution containing an anionic surfactant having a hydrophobic group with a carbon number of 8 or more or a nonionic surfactant having a hydrophobic group with a carbon number of 8 or more The first film is brought into contact with the surface and dried to form a second film containing the anionic surfactant or the nonionic surfactant.

In addition, another method for manufacturing a glass product with a protective film according to the present invention is characterized by having the following steps: 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, anionic surfactants with hydrophobic groups with a carbon number of 8 or more, or nonionic surfactants with hydrophobic groups with a carbon number of 8 or more; and the above mixed solution and glass products The surface of the glass product is contacted and dried to form a first film including the cationic surfactant or the cationic polymer from the surface side of the glass product, and a second film including the anionic surfactant or the nonionic surfactant. Film protective film.

According to the glass product with a protective film of the present invention and a method for manufacturing the same, a protective film is provided on the surface of the glass product to prevent contamination from foreign matter and the like from the time when the glass product is manufactured to before use. Moreover, before using a glass product, this protective film can be easily removed by simple operations, such as water washing and alkali washing.

Furthermore, compared with the case where a surfactant is used as the single-layer protective film, the antifouling effect can be further improved, and the glass product can be effectively prevented from being contaminated.

1‧‧‧ Glass products with protective film

2‧‧‧ glass products

3‧‧‧ protective film

3a‧‧‧The first film

3b‧‧‧Second film

FIG. 1 is a cross-sectional view showing a schematic configuration of a glass product with a protective film according to 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 in Examples and Comparative Examples.

Hereinafter, the glass product with a protective film of this invention is demonstrated, referring drawings. In addition, FIG. 1 is a cross-sectional view showing a schematic configuration of the glass product with a protective film of the present invention. The glass product 1 with a protective film of the present invention includes a glass product 2 and a protective film 3 formed on a surface thereof.

The glass product 2 used here is not specifically limited as long as it is a glass product whose glass is exposed on the surface. Furthermore, it is particularly preferably applied to glass products used in connection with the manufacture of semiconductor products that require the surface of glass products to be kept clean, such as glass substrates for flat panel displays (FPDs), optical multilayer film substrates, and 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 having a carbon number of 8 or more, or a cationic polymer having an average molecular weight of 5 to 10 million.

As the cationic surfactant used herein, any cationic surfactant having a hydrophobic group having a carbon number of 8 or more can be used without particular limitation. When the carbon number of the hydrophobic group is increased, the coverability 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. Examples of such a hydrophobic group include an alkyl group having 8 to 18 carbon atoms, and an alkyl group having 16 to 18 carbon atoms is particularly preferred. The cationic surfactant may be either an amine salt type or a quaternary ammonium salt type, and examples thereof include octyltrimethylammonium chloride, decyltrimethylammonium chloride, and dodecyl chloride. Trimethylammonium salts such as alkyltrimethylammonium, tetradecyltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride; octyl chloride Pyridinium salts such as pyridinium, decylpyridinium chloride, dodecylpyridinium chloride, tetradecylpyridinium chloride, cetylpyridinium chloride, stearylpyridinium chloride; Benzyl ammonium chloride, benzethonium chloride, benzyltrialkylammonium chloride, dialkyldimethylammonium chloride, and the like.

Furthermore, in terms of improving the adsorption density to the surface of glass products, alkyltrimethylammonium salts are preferred, and pyridinium salts can improve the water repellency of glass products, especially cetylpyridine chloride Onium (alias: cetylpyridinium chloride, CPC (cetylpyridinium chloride)) is preferable in terms of mass production and easy availability at low cost.

The cationic polymer used herein may be a polymer having an average molecular weight of 5 to 10 million and a cationic group in the molecule. In addition, in this specification, an average molecular weight means a weight average molecular weight. The cationic group is a group which becomes a cation when dissolved in a solvent such as water, and examples thereof include an amine group and a quaternary ammonium group. At this time, the amine group removes the monovalent functional group of hydrogen from ammonia, primary amine, and secondary amine to form primary amine, secondary amine, and tertiary amine, respectively. The quaternary ammonium group forms a quaternary ammonium cation.

Examples of the cationic polymer used herein include polydiallyl dimethyl ammonium chloride (PDAC or PDADMAC (poly (diallyl dimethyl ammonium chloride))), and poly (dimethylaminoethyl acrylate, methyl chloride, tetrachloromethane). Grade salt), poly (dimethylaminoethyl methacrylate quaternary salt), trimethylammonium alkylpropeneamine polymer salt, dimethylamine epichlorohydrin condensate salt, polyallylamine, Polyethyleneimine and so on.

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

The second film 3b is a film 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.

As the anionic surfactant used herein, any anionic surfactant having a hydrophobic group having a carbon number of 8 or more can be used without particular limitation. Examples of the anionic surfactant include those having a carboxylic acid, a sulfonic acid, a sulfuric acid ester, and a phosphoric acid ester as a hydrophilic group. Examples include dioctyl sodium sulfosuccinate (DOSS). , Sodium stearate, sodium lauryl sulfate, sodium alkylbenzene sulfonate, etc.

Here, the hydrophobic group having a carbon number of 8 or more may be either linear or branched, It is preferably a branched chain group, and octyl (C8) uses 2-ethylhexyl in many cases, and more preferably contains a plurality of such octyl groups. It is generally considered that, as described above, if the hydrophobic group becomes branched, it is likely to be complexed with a cationic surfactant or a cationic polymer to form a more stable film.

The nonionic surfactant used herein can be used without particular limitation as long as it is a nonionic surfactant having a hydrophobic group having a carbon number of 8 or more. Examples of the non-ionic surfactant include those having various structures such as an ester type, an ether type, and an alkyl glycoside. Examples of the non-ionic surfactant include polyoxyethylene alkyl phenyl ether having alkylene oxide repeating units, and alkyl polyethylene glycol. Alcohols, glycerol fatty acid esters, etc.

Here, the hydrophobic group having a carbon number of 8 or more may be any of a linear or branched chain, and a branched chain group is preferred. It is generally considered that if the hydrophobic group becomes branched as described above, it is likely to be complexed 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, compared with the case of a single layer, the stability of the film can be improved, and the effect of preventing pollution can be improved. In addition, the protective film formed here basically contains a surfactant, and there are also cases where a cationic polymer is included. In any case, the surface of the glass product is combined by electrostatic bonding, which can be achieved by using pure water or It is easily removed by washing with alkaline detergent.

Next, the manufacturing method of the glass product with a protective film is demonstrated.

As a method for forming the protective film of the present invention, first, a solution containing a cationic surfactant having a hydrophobic group with a carbon number of 8 or more or a cationic polymer having an average molecular weight of 5 to 10 million and the surface of a glass product are made. It is contacted and dried to form a first film containing a cationic surfactant or a cationic polymer.

At this time, a cationic surfactant or a cationic polymer is dissolved in an aqueous solution of a water-soluble organic solvent such as pure water or ethanol as a solvent to prepare a solution. At this time, the solution concentration of the cationic surfactant is preferably from 0.01 mmol / L to 100 mmol / L. It is appropriate to cover the surface of the glass product without excess, and more preferably from 0.1 to 10 mmol / L. When a cationic polymer is used, the cationic group in the solution is preferably used. The concentration (equivalent) is in the range of 0.01 meq / L to 100 meq / L. In order to properly cover the surface of the glass product without excessive amount, it is more preferably 0.1 meq / L to 10 meq / L. When 1 mol of a cationic group is contained in a 1 L solution, the concentration is expressed as 1 eq / L. In addition, the solution can be used when the pH value is acidic to alkaline (for example, pH value is about 4 to 12), but by promoting the ionization of the silanol groups on the surface of the glass product to make it negatively charged, the electrostatic binding force can be made. In terms of being stronger and increasing the amount of adhesion, the pH of the solution is preferably from 8 to 12, more preferably from 10 to 11.

The solution obtained in the above manner is brought into contact with and coated on the surface of a glass product to be formed into a first film. In this case, examples of the coating method include coating methods used in known film forming methods such as dip coating, spray coating, and coating with a sponge. In addition, in this step, the cationic surfactant or cationic polymer contained in the solution is aligned with the hydrophilic group of the cationic surfactant or the cationic part of the cationic polymer toward the surface side of the glass substrate only by contact. The hydrophobic group of the cationic surfactant or the main chain portion of the polymer of the cationic polymer connected to the cationic portion is aligned in the environment as its opposite side. The reason is that, because the silanol group (-Si-OH) existing on the surface of the glass product is easy to be -charged, only by contacting the hydrophilic group of the cationic surfactant with a charge or the cation of the cationic polymer A part is attracted to the surface side of the glass product by static electricity.

When the cationic surfactant or cationic polymer is arranged in the above-mentioned manner, and the solvent is removed by heating, air blowing, or the like, a homogeneous first film can be easily formed. At this time, it is preferable to heat to 50 to 90 ° C during heating and drying, and to blow air at 15 to 30 ° C during blowing.

Then, a solution containing an anionic surfactant having a hydrophobic group with a carbon number of 8 or more or a nonionic surfactant having a hydrophobic group with a carbon number of 8 or more is brought into contact with the surface of the first film to be formed and applied. Dry to form a second film containing an anionic surfactant or a nonionic surfactant.

At this time, pure water or anionic surfactant or nonionic surfactant is used. An aqueous solution of a water-soluble organic solvent such as ethanol is used as a solvent to dissolve it into a solution. At this time, the solution concentration is preferably from 0.1 mmol / L to 100 mmol / L, in order to properly cover the surface of the glass product without excessive amount, more preferably from 0.5 to 10 mmol / L. In addition, as long as the pH of the solution is not extremely acidic or alkaline, there is no problem. The pH is preferably 5 to 10, and more preferably 6 to 9.

The solution obtained in the above manner is brought into contact with and coated on the first film surface on which a second film is to be formed. In this case, the same coating method as the first film formation can be mentioned as a coating method. In this step, the anionic surfactant or the nonionic surfactant contained in the solution is contacted with the hydrophobic group existing on the surface of the first membrane, so that the anionic surfactant or the nonionic surfactant is allowed to contact the hydrophobic group. The hydrophobic groups are arranged toward the first membrane side, so that the hydrophilic groups of the anionic surfactant or the nonionic surfactant are aligned in the environment as the opposite side.

When the anionic surfactant or the nonionic surfactant is arranged in the above-mentioned manner, and the solvent is removed by heating, blowing, or the like, a homogeneous second film can be easily formed. At this time, it is preferable to heat to 50 to 80 ° C during heating and drying, and it is preferable to blow air at 15 to 30 ° C during blowing.

In addition, as another method for forming the protective film of the present invention, the following methods can be cited: it does not separately prepare a solution of a cationic surfactant or a cationic polymer as described in the above method, and an anionic surfactant or a nonionic surfactant The solution is prepared into a solution, and a protective film is formed by a single coating and drying operation.

This method first prepares 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 5-10 million, and a hydrophobic group having a hydrophobic group having a carbon number of 8 or more. An anionic surfactant or a nonionic surfactant having a hydrophobic group with a carbon number of 8 or more. At this time, the solvent or pH conditions used are the same as those described above for the respective methods of forming a film.

However, at this time, the content of the cationic surfactant or the cationic polymer and the anionic surfactant or the nonionic interface must be aggregated in such a way that the components in the solution will not react and agglutinate. 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 is preferably contained in a range of 1: 0.1 to 1: 1, and more preferably 1: 0.3 to Contained in a ratio of 1: 0.7. In the case of a cationic polymer, the ratio of the content (equivalent) of the cationic group to the content (molar concentration) of the anionic surfactant or nonionic surfactant is preferably 1: 0.1 to 1: It is contained in a range of 1 and is preferably contained at a ratio of 1: 0.3 to 1: 0.7. In this case, if a water-soluble organic solvent such as ethanol is added in an amount of several to several tens percent, it is preferable to have the effect of suppressing aggregation.

The one-liquid type mixed solution obtained in the above manner is brought into contact with and coated on the surface of a glass product to be formed into a protective film. In this case, the same coating method as the first film formation can be mentioned as a coating method. In this step, the cationic surfactant or cationic polymer contained in the solution is relatively contained, and the hydrophilic groups or cationic portions thereof are arranged toward the surface side of the glass product, and the hydrophobic groups of the cationic surfactant are Or, the main chain part of the polymer connected to the cationic part 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 base portion of the anionic surfactant or nonionic surfactant is aligned toward the first film side, and the hydrophilic group of the anionic surfactant or nonionic surfactant is oriented as the opposite side. In the environment.

According to the method for forming the protective film, a solution can be used to manufacture a glass product with a protective film by a simple operation of a film forming operation.

In addition, in the case of forming the first film and the second film separately, or in the case of forming the film at one time by mixing the solution, it can be achieved by a simple operation of applying the solution at room temperature, and further, it can be achieved at When using surfactants, the surface protection of glass products will not violate the drainage restrictions and will not increase the environmental load.

[Example]

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

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

As a cationic surfactant, cetylpyridinium chloride (CPC) was dissolved in a concentration of 1 mmol / L and ammonia was 10 mmol / L, and each component was dissolved in pure water to prepare a solution for forming a first film. . The pH of this solution is about 10.5.

<Solution 2 for first film formation>

As a cationic polymer, polydiallyldimethylammonium chloride (PDAC or PDADMAC; a standard solution for colloidal titration manufactured by Wako Pure Chemical Industries, Inc., molecular weight 60,000 to 110,000) becomes 1 meq / L and ammonia becomes 10 mmol / L concentration method, each component was dissolved in pure water to prepare a solution for the first film formation. The pH of this solution is about 10.5.

<Second film-forming solution 1>

A solution for forming a second film was prepared by dissolving dioctyl sulfosuccinate sodium salt (DOSS) as an anionic surfactant in a concentration of 1 mmol / L in pure water. The pH of this solution is about 7.

<Solution 2 for second film formation>

Sodium hexadecylsulfonic acid sodium salt (HDS, HDS) as an anionic surfactant was dissolved in pure water to prepare a second film-forming solution. The pH of this solution is about 7.

<Mixed solution for protective film formation>

The concentration of cetylpyridinium chloride (CPC) as a cationic surfactant was 1 mmol / L, ammonia was 10 mmol / L, and sodium dioctyl sulfosuccinate (DOSS) was 0.5 mmol / L. Method, each component is dissolved in pure water to prepare a mixed solution. The pH of this solution is about 10.5.

(Example 1)

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

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

(Example 2)

After the surface-polished glass plate made of alkali-free borosilicate glass having a length of 50 mm × width 50 mm × thickness 0.7 mm was immersed in the above-mentioned first film-forming solution 2 for 10 seconds and taken out, the surface was dried by air blowing The solution was formed 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 above-mentioned second film-forming solution 1 for 10 seconds and taken out, and then the solution on the surface was dried by blasting. A second film was formed on the surface to make a glass product with a protective film.

(Example 3)

After the surface-polished glass plate made of alkali-free borosilicate glass having a length of 50 mm × width 50 mm × thickness 0.7 mm was immersed in the above mixed solution for forming a protective film for 10 seconds, and then taken out, the surface solution was dried by air blowing By the above dip coating method, a protective film including a first film and a second film is formed on the surface of the glass plate, and a glass product with a protective film is produced.

(Example 4)

After the surface-polished glass plate made of alkali-free borosilicate glass having a length of 50 mm × width 50 mm × thickness 0.7 mm was immersed in the above-mentioned first film-forming solution 2 for 10 seconds and taken out, the surface was dried by air blowing The solution was formed 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 above-mentioned second film-forming solution 2 for 10 seconds and taken out, and then the solution on the surface was dried by blasting. A second film was formed on the surface to make a glass product with a protective film.

(Comparative example 1)

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

(Comparative example 2)

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

(Test example 1)

The spacer paper coated with the TiO ₂ fine particle pigment for papermaking was pressed against the surface of the glass products of the examples and comparative examples, and the TiO ₂ fine particles were transferred. The glass product was blown with air at about 25 ° C. for 30 seconds, and then ultrasonically cleaned at 100 kHz for 30 seconds in pure water at 25 ° C. Then, a commercially available alkaline lotion stock solution ( Parker Corporation (trade name: PK-LCG211) was diluted 100-fold in an alkaline washing solution and subjected to ultrasonic cleaning at 28 kHz for 30 seconds. Fluorescence X-ray method was used to monitor the residual state of TiO ₂ fine particles on the surface of each processed glass product after blowing, pure water cleaning, and alkaline detergent cleaning, and the results are shown in FIG. 2. Regarding the removal rate of TiO ₂ fine particles after alkali washing compared with that after blowing, Example 1 was 82%, Example 2 was 61%, Example 3 was 76%, Example 4 was 80%, and Comparative Example 1 It was 35% and Comparative Example 2 was 34%.

From this result, the pollution prevention effect of Example 1 was the highest, and Example 4 was the next. In Comparative Examples 1 and 2, the residual amount of TiO ₂ fine particles was large, and the effect of preventing pollution was low. In the case of using an anionic surfactant in Comparative Example 2, it is presumed that during the drying step using a blast, the anionic surfactant does not interact with the surface of the glass product. Therefore, while removing water, the Most of them were removed, and the result was equivalent to that of Comparative Example 1 without a protective film.

(Test Example 2)

Polysilicone oil (polydimethylsiloxane: molecular weight about 4200) was dissolved in acetone so as to be 100 μg / mL, and the solution was impregnated with a spacer paper and dried to give an adhesion amount of 4 μg / cm ² . The spacer paper impregnated with the silicone oil was alternately separated from the glass products of Examples and Comparative Examples, and the whole was clamped with a spring clip to form a sample bundle. Keep it at 50 ° C and 80% humidity for 20 hours to transfer the silicone oil to the surface of the glass product. Ultrasonic cleaning was performed at 28 kHz for 30 seconds in an alkaline lotion obtained by diluting a commercially available alkaline lotion stock solution (manufactured by Parker Corporation, trade name: PK-LCG211) 100 times, and then using a polyvinyl alcohol sponge Use the same alkaline lotion to scrub by hand for 3 minutes, about 200 times. The contact angle was measured immediately after transfer, after ultrasonic cleaning, and after manual scrubbing, and the results are shown in FIG. 3. Although the contact angle does not quantitatively indicate the adhesion amount of silicone oil, the magnitude relationship can qualitatively evaluate the adhesion amount. Regarding the change rate of the contact angle after manual scrubbing compared with immediately after the transfer, Example 1 was 14%, Example 2 was 85%, Example 3 was 20%, Example 4 was 22%, and 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 based on data obtained by photographing water droplets on the surface of the substrate from the side of the substrate, the measurement results at five points were averaged to calculate the contact angle between each substrate and the pure water.

From this result, the pollution prevention effect of Example 1 was the highest, and Example 3 was the next. In Comparative Examples 1 and 2, the residual amount of the silicone oil was large, and the effect of preventing pollution was low. In the case of using an anionic surfactant in Comparative Example 2, it is considered that, in the drying step by blast, there is no interaction between the anionic surfactant and the surface of the glass product. Therefore, while removing water, the Most were also removed. Therefore, it is estimated that it is a result equivalent to the comparative example 1 in which a protective film was not provided.

[Industrial availability]

The glass product with a protective film and the manufacturing method thereof of the present invention can be widely used in glass products, and can effectively prevent the surface of the glass product from being contaminated, especially for flat panel displays. Glass substrates such as the manufacture of liquid crystal displays (FPD) are preferred.

1‧‧‧ Glass products with protective film

2‧‧‧ glass products

3‧‧‧ protective film

3a‧‧‧The first film

3b‧‧‧Second film

Claims (10)

A glass product with a protective film is characterized in that it has a protective film with a multi-layer structure, and the protective film with the multi-layer structure has a first film on the surface of the glass product and a first film on the surface of the first film. A second film 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 5 to 10 million, and the second film containing a hydrophobic group having a carbon number of 8 or more Anionic surfactant. For example, the glass product with a protective film of claim 1, wherein the carbon number of the hydrophobic group of the cationic surfactant is 12 or more. For example, the glass product with a protective film according to 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. For example, the glass product with a protective film of claim 1, wherein the cationic polymer has 4 to 25 cationic groups per 1000 molecular weight. For example, the glass product with a protective film according to claim 4, wherein the cationic group is an amine group or a quaternary ammonium group. For example, the glass product with a protective film of claim 1, 2, 4 or 5, wherein the hydrophobic group of the above anionic surfactant is linear or branched. A method for manufacturing a glass product with a protective film, which comprises the following steps: a solution containing a cationic surfactant having a hydrophobic group with a carbon number of 8 or more or a cationic polymer having an average molecular weight of 5-10 million Contacting and drying the surface of a glass product to form a first film containing the above-mentioned cationic surfactant or the above-mentioned cationic polymer; and a solution containing an anionic surfactant having a hydrophobic group having a carbon number of 8 or more and the The surface of the first film is contacted and dried to form the anion boundary including the above. The second film of surfactant. A method for manufacturing a glass product with a protective film, which is characterized by the following steps: preparing a mixed solution containing a cationic surfactant having a hydrophobic group with a carbon number of 8 or more or a cation having an average molecular weight of 5-10 million A polymer, and an anionic surfactant having a hydrophobic group with a carbon number of 8 or more; and contacting the above-mentioned mixed solution with the surface of a glass product and drying it to form a surface including the above-mentioned cationic interface A first film of an active agent or a cationic polymer, and a protective film of the second film including the above-mentioned anionic surfactant. For example, the method for manufacturing a glass product with a protective film according to claim 7 or 8, wherein the solution used when forming the first film and the second film is an aqueous solution having a pH value of 8-12. For example, the method for manufacturing a glass product with a protective film according to claim 8, wherein the content ratio of the cationic surfactant to the anionic surfactant in the above mixed solution is 1: 0.1 to 1: 1 in molar ratio, or cationic The ratio of the content (equivalent) of the cationic group of the polymer to the content (molar concentration) of the anionic surfactant is 1: 0.1 to 1: 1.