WO2014163033A1 - Protective-film-equipped glass product and method for producing same - Google Patents

Abstract

Provided is a novel protective film which can be easily formed and removed by a simple operation, and which effectively imparts a contamination prevention effect. A protective-film-equipped glass product (1) having a protective film (3) which has a multi-layered structure having: a first film (3a) which is positioned on the surface of a glass product (2) and comprises a cationic surfactant having a hydrophobic group having a carbon number of 8 or higher, or a cationic polymer having an average molecular weight of 5,000,000 to 10,000,000; and a second film (3b) which is positioned on the surface of the first film and comprises an anionic surfactant having a hydrophobic group having a carbon number of 8 or higher, or a nonionic surfactant having a hydrophobic group having a carbon number of 8 or higher.

Description

Glass product with protective film and method for producing the same

The present invention relates to a glass product with a protective film and a method for producing the same.

The surface of glass products is easily contaminated, and when exposed to an external atmosphere, dust or organic matter contained in the atmosphere adheres and is immediately contaminated. In particular, glass products used for precision devices such as flat panel displays (FPD) need to be handled in a clean state so that contamination by dust, organic matter, etc. does not occur. Therefore, the manufacture is performed in a clean room or the like.

By the way, for example, in the case of a glass substrate for FPD, after such a glass substrate is manufactured, to process it into a display product, the glass substrate is transported to a display manufacturing factory, stored, and the like. Become. At this time, even when the glass substrate is manufactured as a very clean surface, some contamination often occurs during its use (display manufacturing). As one of the causes, it is often performed that a slip sheet is sandwiched between the substrates so that the glass substrates do not contact each other, but it is contaminated by TiO ₂ fine particles or silicone balls derived from the slip sheet. The possibility is considered.

Also, the problem of such surface contamination is old, and various methods for preventing contamination of the surface of glass products have been studied so far. For example, a method for protecting the surface of a glass product by incorporating the technique during the glass product manufacturing process is known so that the glass product is protected immediately after the manufacture. This method is a glass treatment method in which a hydrophobic coating is formed on a surface of a hot glass product having a temperature higher than 175 ° C. with at least one surfactant, and the glass product is cut, roughened, and polished ( Patent Document 1).

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

JP 2000-319038 A JP 2000-211947 A JP 2002-46225 A JP 2012-116748 A

However, in Patent Document 1, the formation of a protective film is incorporated in the glass product manufacturing process, and cannot be applied in the case where a polishing step is performed after the glass product is manufactured. Further, since the protective films described in Patent Documents 2 to 4 have weak interaction with silanol groups on the surface of the glass product, it is necessary to devise the formation thereof, and the protective film is considered to be relatively unstable. It is done.

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

The glass product with a protective film of the present invention comprises a first film comprising a cationic surfactant having a hydrophobic group having 8 or more carbon atoms or a cationic polymer having an average molecular weight of 5 to 10 million on the surface of the glass product. A second film made of 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 on the surface of the first film; It has the protective film of the multilayer structure which has these.

Further, the method for producing a glass product with a protective film of the present invention contains a cationic surfactant having a hydrophobic group having 8 or more carbon atoms or a cationic polymer having an average molecular weight of 5 to 10 million on the surface of the glass product. A solution to be contacted and dried to form a first film made of the cationic surfactant or the cationic polymer, and a hydrophobic group having 8 or more carbon atoms on the surface of the first film. A solution containing an anionic surfactant or a nonionic surfactant having a hydrophobic group having a carbon number of 8 or more is contacted and dried to form a first surfactant comprising the anionic surfactant or the nonionic surfactant. Forming a second film.

In addition, another method for producing a glass product with a protective film according to the present invention is a cationic surfactant having a hydrophobic group having 8 or more carbon atoms or a cationic polymer having an average molecular weight of 5 to 10 million and a carbon number of 8 or more. A step of preparing a mixed solution containing an anionic surfactant having a hydrophobic group or a nonionic surfactant having a hydrophobic group having 8 or more carbon atoms, and the mixed solution on the surface of the glass product. The first film made of the cationic surfactant or the cationic polymer, the second film made of the anionic surfactant or the nonionic surfactant, from the surface side of the glass product after being contacted and dried, And a step of forming a protective film.

According to the glass product with a protective film of the present invention and the method for producing the glass product, a protective film is provided on the surface of the glass product, and contamination such as foreign matter adhering between the production and use of the glass product can be prevented. Moreover, this protective film can remove a protective film easily by simple operation, such as water washing | cleaning or alkali washing | cleaning, before using a glass product.

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

It is sectional drawing which shows schematic structure of the glass product with a protective film of this invention. It is a diagram showing a residual amount of TiO ₂ fine particles of Examples and Comparative Examples. It is the figure which showed the contact angle with the pure water of an Example and a comparative example.

The glass product with a protective film of the present invention will be described below with reference to the drawings. In addition, FIG. 1 is sectional drawing which shows schematic structure of the glass product with a protective film of this invention, and the glass product 1 with a protective film of this invention is the glass product 2 and the protective film 3 formed in the surface. Composed.

The glass product 2 used here is not particularly limited as long as it is a glass product with glass exposed on its surface. In particular, 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 (FPD), optical multilayer film substrates, etc. Preferably applied.

The protective film 3 used in the present invention has a multilayer structure having 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. It is a film.

Here, the first film 3a is a film made of a cationic surfactant having a hydrophobic group having 8 or more carbon atoms or a cationic polymer having an average molecular weight of 5 to 10 million.

The cationic surfactant used here 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 carbons of the hydrophobic group is increased, the coverage of the glass surface is increased and the antifouling property is improved. Therefore, the number of carbons of the hydrophobic group is preferably 12 or more. Such a hydrophobic group typically includes an alkyl group having 8 to 18 carbon atoms, and an alkyl group having 16 to 18 carbon atoms is particularly preferable. The cationic surfactant may be either an amine salt type or a quaternary ammonium salt type. For example, octyltrimethylammonium chloride, decyltrimethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, hexadecyl chloride. Trimethylammonium salts such as trimethylammonium and octadecyltrimethylammonium chloride; pyridinium salts such as octylpyridinium chloride, decylpyridinium chloride, dodecylpyridinium chloride, tetradecylpyridinium chloride, hexadecylpyridinium chloride and octadecylpyridinium chloride; benzalkonium chloride and benzethonium chloride Benzyltrialkylammonium chloride, dialkyldimethylammonium chloride and the like.

Alkyltrimethylammonium salts are preferred in that they can increase the adsorption density on the surface of glass products, and pyridinium salts can improve the water repellency of glass products, especially hexadecylpyridinium chloride (also known as chloride). Cetylpyridinium, CPC) is preferred because it is mass-produced and easily available.

The cationic polymer used here may be any polymer having an average molecular weight of 5 to 10 million and having 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 that becomes a cation when dissolved in a solvent such as water, and examples thereof include an amino group and a quaternary ammonium group. At this time, the amino group is a monovalent functional group obtained by removing hydrogen from ammonia, primary amine, or secondary amine, and forms a primary amine, secondary amine, or tertiary amine, respectively. The quaternary ammonium group forms a quaternary ammonium cation.

Examples of the cationic polymer used here include polydiallyldimethylammonium chloride (PDAC or PDADMAC), poly (dimethylaminoethyl acrylate methyl chloride quaternary salt), poly (dimethylaminoethyl methacrylate methyl chloride quaternary salt), and trimethylammonium alkyl. Examples include acrylamide polymer salt, dimethylamine epichlorohydrin condensate salt, polyallylamine, polyethyleneimine and the like.

The cationic polymer preferably has 4 to 25 cationic groups per 1000 molecular weight.

The second film 3b is a film made of 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.

As the anionic surfactant used here, any anionic surfactant having a hydrophobic group having 8 or more carbon atoms can be used without particular limitation. Examples of the anionic surfactant include those having carboxylic acid, sulfonic acid, sulfate ester, and phosphate ester structures as hydrophilic groups, such as dioctyl sulfosuccinate sodium salt (DOSS), sodium stearate. , Sodium lauryl sulfate, sodium alkylbenzene sulfonate and the like.

Here, the hydrophobic group having 8 or more carbon atoms may be either linear or branched, but is preferably a branched group, and the octyl group (C8) is a 2-ethylhexyl group. It is more preferable that it contains a plurality of such octyl groups. Thus, when the hydrophobic group is branched, it is likely to be entangled with the cationic surfactant or the cationic polymer, and a more stable film can be formed.

The nonionic surfactant used here 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 structures such as ester type, ether type, and alkylglycoside. For example, polyoxyethylene alkylphenyl ether, alkyl polyethylene glycol, glycerin fatty acid having ethylene oxide repeating units. Examples include esters.

Here, the hydrophobic group having 8 or more carbon atoms may be either linear or branched, but is preferably a branched group. Thus, when the hydrophobic group is branched, it is likely to be entangled with the cationic surfactant or the cationic polymer, and a more stable film can be formed.

As described above, by forming a protective film having a multilayer structure in which the first film 3a and the second film 3b are stacked, the stability of the film can be improved as compared with the case of a single layer, and the effect of preventing contamination can be obtained. Can also be improved. In addition, the protective film formed here is basically made of a surfactant and may contain a cationic polymer, but in any case, the protective film is bound to the surface of the glass product by electrostatic bonding. And can be easily removed by washing with an alkaline detergent.

Next, a method for producing a glass product with a protective film will be described.

As one method for forming a protective film in the present invention, first, a cationic surfactant having a hydrophobic group having 8 or more carbon atoms or a cationic polymer having an average molecular weight of 5 to 10 million is formed on the surface of a glass product. The contained solution is contacted and dried to form a first film made of a cationic surfactant or a cationic polymer.

At this time, the cationic surfactant or the cationic polymer is dissolved in pure water or an aqueous solution of a water-soluble organic solvent such as ethanol as a solvent to obtain a solution. At this time, the solution concentration of the cationic surfactant is preferably 0.01 mmol / L to 100 mmol / L, and more preferably 0.1 to 10 mmol / L so as not to be excessive while covering the surface of the glass product appropriately. . When a cationic polymer is used, the concentration (equivalent) of the cationic group in the solution is preferably in the range of 0.01 meq / L to 100 meq / L. In order not to become excessive while being covered, 0.1 meq / L to 10 meq / L is more preferable. Incidentally, when 1 mol of a cationic group is contained in 1 L of the solution, the concentration is expressed as 1 eq / L. The pH of the solution can be used from acidic to alkaline (for example, about pH 4 to 12), but the electrostatic bond strength can be further increased by promoting the ionization of silanol groups on the surface of the glass product and making it negatively charged. The pH of the solution is preferably 8 to 12 and more preferably 10 to 11 from the viewpoint that the adhesion amount can be increased while strengthening.

The solution thus obtained is applied in contact with the surface of the glass product forming the first film. At this time, examples of the coating method include coating methods used in known film forming methods such as dip coating, spray coating, and sponge coating. Further, in this step, the cationic surfactant or cationic polymer contained in the solution can be brought into contact with the cationic group so that the hydrophilic group of the cationic surfactant or the cationic portion of the cationic polymer is placed on the surface side of the glass substrate. Alignment is toward an atmosphere in which the main chain portion of the polymer that connects the hydrophobic group of the surfactant or the cationic portion of the cationic polymer is on the opposite side. This is because the silanol group (-Si-OH) present on the surface of the glass product is easily charged to -charge, so that the hydrophilic group of the cationic surfactant or the cationic polymer that is charged only by contact is charged. This is because the cationic portion is electrostatically attracted to the surface side of the glass product.

If the solvent is removed by heating, air blowing or the like in the state where the cationic surfactants or cationic polymers are aligned in this way, a homogeneous first film can be easily formed. At this time, it is preferable to heat to 50 to 90 ° C. in heat drying, and air at 15 to 30 ° C. may be blown in air blow.

Next, the surface of the formed first film contains 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 solution is contacted and dried to form a second film made of an anionic surfactant or a nonionic surfactant.

At this time, the anionic surfactant or nonionic surfactant is dissolved in pure water or an aqueous solution of a water-soluble organic solvent such as ethanol as a solvent to obtain a solution. At this time, the solution concentration is preferably 0.1 mmol / L to 100 mmol / L, and more preferably 0.5 to 10 mmol / L so as not to be excessive while covering the surface of the glass product appropriately. The solution has no problem if it is not extremely strongly acidic or strongly alkaline, and the pH is preferably 5 to 10, more preferably 6 to 9.

The solution thus obtained is applied in contact with the surface of the first film forming the second film. At this time, as the coating method, the same coating method as in the first film formation can be used. Further, in this step, the anionic surfactant or nonionic surfactant contained in the solution is merely brought into contact with the hydrophobic group present on the surface of the first membrane, or the anionic surfactant or The hydrophobic group portion of the nonionic surfactant is aligned on the first membrane side and toward the atmosphere where the hydrophilic group of the anionic surfactant or nonionic surfactant is on the opposite side.

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

In addition, as another method for forming a protective film in the present invention, a solution of a cationic surfactant or a cationic polymer and a solution of an anionic surfactant or a nonionic surfactant are separately used as in the above method. The method of preparing these as one solution and forming a protective film by one application | coating and drying operation is mentioned.

In this method, first, a cationic surfactant having a hydrophobic group having 8 or more carbon atoms or a cationic polymer having an average molecular weight of 5 to 10 million and an anionic surfactant having a hydrophobic group having 8 or more carbon atoms Alternatively, a solution containing a nonionic surfactant having a hydrophobic group having 8 or more carbon atoms is prepared. At this time, the solvent and pH conditions to be used are the same as those in the above-described method for forming a film separately.

However, at this time, the content of the cationic surfactant or cationic polymer and the content of the anionic surfactant or nonionic surfactant must be adjusted so that each component does not react and aggregate in the solution. There is. For example, the content of the cationic surfactant and the content of the anionic surfactant or nonionic surfactant are preferably contained in a molar ratio of 1: 0.1 to 1: 1. It is preferably contained in a ratio of 0.3 to 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 1: 0.1 to 1 : 1 is preferable, and it is preferable that the ratio is 1: 0.3 to 1: 0.7. At this time, it is preferable to add several to several tens of percent of a water-soluble organic solvent such as ethanol because it has an effect of suppressing aggregation.

The one-component mixed solution thus obtained is applied in contact with the surface of the glass product forming the protective film. At this time, as the coating method, the same coating method as in the first film formation can be used. In this step, a relatively large amount of the cationic surfactant or cationic polymer contained in the solution is contained, and these hydrophilic groups or cationic parts are present on the surface side of the glass product. The first chain is formed by aligning the main chain portion of the polymer connecting the hydrophobic groups of the cationic groups or the cationic portion of the cationic polymer on the opposite side. Next, the hydrophobic group portion of the anionic surfactant or nonionic surfactant is present on the first membrane side, and the hydrophilic group of the anionic surfactant or nonionic surfactant is present on the first membrane surface. Align toward the opposite atmosphere.

According to this method for forming a protective film, a glass product with a protective film can be manufactured by using a single solution and by a simple operation of a single film forming operation.

In addition, when forming each of the first film and the second film, or when forming the mixed film at once, it can be achieved by a simple operation of applying the solution at room temperature, and when a surfactant is used. Therefore, it is possible to achieve the surface protection of the glass product without increasing the environmental load without compromising the drainage regulations.

Hereinafter, the present invention will be described in more detail based on examples and comparative examples.
[Preparation of various solutions]
<First Film Formation Solution 1>
Each component was dissolved in pure water so that the concentration of cetylpyridinium chloride (CPC), which is a cationic surfactant, was 1 mmol / L and ammonia was 10 mmol / L. Prepared. The pH of this solution is about 10.5.
<First film forming solution 2>
Polydiallyldimethylammonium chloride that is a cationic polymer (PDAC or PDADMAC; colloid titration standard solution manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 60,000 to 110,000) is 1 meq / L and ammonia is 10 mmol / L. Each component was dissolved in pure water to prepare a first film-forming solution. 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 dioctylsulfosuccinate sodium salt (DOSS), which is an anionic surfactant, in pure water so that the concentration was 1 mmol / L. The pH of this solution is about 7.
<Second film forming solution 2>
A solution for forming a second film was prepared by dissolving hexadecylsulfonic acid sodium salt (HDS), which is an anionic surfactant, in pure water so as to have a concentration of 1 mmol / L. The pH of this solution is about 7.
<Mixed solution for protective film formation>
Each component was adjusted so that the concentration of the cationic surfactant cetylpyridinium chloride (CPC) was 1 mmol / L, ammonia was 10 mmol / L, and dioctylsulfosuccinate sodium salt (DOSS) was 0.5 mmol / L. A mixed solution was prepared by dissolving in pure water. The pH of this solution is about 10.5.

(Example 1)
A 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 dipped in the first film-forming solution 1 for 10 seconds and then pulled up. A first film was formed on the surface of the glass plate by a dip coating method in which the solution was dried by air blow.
The obtained glass plate having the first film is dipped in the second film-forming solution 1 for 10 seconds and then pulled up, and then the surface solution is dried by air blow by the dip coating method. A second film was formed on the surface of the film to obtain a glass product with a protective film.

(Example 2)
A 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 dipped in the first film-forming solution 2 for 10 seconds and then pulled up. A first film was formed on the surface of the glass plate by a dip coating method in which the solution was dried by air blow.
The obtained glass plate having the first film is dipped in the second film-forming solution 1 for 10 seconds and then pulled up, and then the surface solution is dried by air blow by the dip coating method. A second film was formed on the surface of the film to obtain a glass product with a protective film.

(Example 3)
A 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 dipped in the mixed solution for forming the protective film for 10 seconds and then pulled up, and then the surface solution A protective film composed of the first film and the second film was formed on the surface of the glass plate by a dip coating method in which the film was dried by air blow to obtain a glass product with a protective film.
Example 4
A 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 dipped in the first film-forming solution 2 for 10 seconds and then pulled up. A first film was formed on the surface of the glass plate by a dip coating method in which the solution was dried by air blow.
The obtained glass plate having the first film is dipped in the second film-forming solution 2 for 10 seconds and then pulled up, and then the surface solution is dried by air blow by the dip coating method. A second film was formed on the surface of the film to obtain a glass product with a protective film.

(Comparative 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 washed with pure water. This glass plate has a surface after polishing, and is not provided with a protective film or the like.

(Comparative Example 2)
A surface-polished glass plate made of non-alkali borosilicate glass having a length of 50 mm, a width of 50 mm, and a thickness of 0.7 mm was dipped in the second film-forming solution 1 for 10 seconds and then pulled up. A film of an anionic surfactant was formed on the surface of the glass plate by a dip coating method in which the solution was dried by air blow.

(Test Example 1)
The slip sheet coated with the TiO ₂ fine particle pigment for papermaking was pressed against the surface of the glass products of Examples and Comparative Examples to transfer the TiO ₂ fine particles. This glass product is blown with air at about 25 ° C. for 30 seconds, and then ultrasonically cleaned at 100 kHz in pure water at 25 ° C. for 30 seconds. Further, a commercially available alkaline detergent stock solution (manufactured by Parker Corporation) , Trade name: PK-LCG211) was subjected to ultrasonic cleaning at 28 kHz for 30 seconds in an alkali cleaning solution diluted 100 times. The surface of the glass product after each of air blow, pure water cleaning, and alkaline detergent cleaning was monitored for the residual state of TiO ₂ fine particles by the fluorescent X-ray method, and the results are shown in FIG. The removal rate of TiO ₂ fine particles after alkali cleaning compared with after air blowing was 82% in Example 1, 61% in Example 2, 76% in Example 3, 80% in Example 4, and 35 in Comparative Example 1. %, And Comparative Example 2 was 34%.

From this result, Example 1 had the highest anti-contamination effect, and Example 4 was the next highest. 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 where the anionic surfactant of Comparative Example 2 was used, in the drying process by air blow, since the anionic surfactant has no interaction with the surface of the glass product, most of the water is removed at the same time. Is removed, and it is presumed that the same result as in Comparative Example 1 in which no protective film was provided was obtained.

(Test Example 2)
Silicone oil (polydimethylsiloxane: molecular weight of about 4200) is dissolved in acetone so as to have a molecular weight of 100 μg / mL, and the resulting solution is impregnated into a slip sheet and dried to obtain an adhesion amount of 4 μg / cm ² . The silicone oil-impregnated interleaving paper was alternately sandwiched with the glass products of the examples and comparative examples, and the whole was sandwiched between spring clips to form a sample bundle. This is kept for 20 hours under an atmosphere of 50 ° C. and 80% humidity, and the silicone oil is transferred to the surface of the glass product. Ultrasonic cleaning at 28 kHz was performed for 30 seconds in an alkaline cleaning solution obtained by diluting a commercially available alkaline detergent stock solution (manufactured by Parker Corporation, trade name: PK-LCG211) 100 times, and further using a polyvinyl alcohol sponge with the same alkaline cleaning solution. Rubbing was performed about 200 times for 3 minutes with hand scrub. The contact angle was measured immediately after transfer, after ultrasonic cleaning and after hand scrubbing, and the results are shown in FIG. Although the contact angle does not quantitatively represent the amount of silicone oil deposited, the magnitude relationship can qualitatively evaluate the amount deposited. The rate of change in contact angle after hand scrubbing compared to immediately after transfer was 14% in Example 1, 85% in Example 2, 20% in Example 3, 22% in Example 4, and 91% in Comparative Example 1. Comparative Example 2 was 89%.
[Contact angle]
One drop of pure water is dropped on the surface of the glass substrate to be measured, and the contact angle with the pure water on each substrate is averaged by averaging the five measurement results based on data obtained by imaging the water droplets on the surface from the side of the substrate Calculated.

From this result, Example 1 had the highest anti-contamination effect, and Example 3 was the next highest. In Comparative Examples 1 and 2, the residual amount of silicone oil was large, and the effect of preventing contamination was low. When the anionic surfactant of Comparative Example 2 is used, the anionic surfactant does not interact with the surface of the glass product in the drying process by air blow, so that water is removed at the same time. Most of them are thought to have been removed. For this reason, it is presumed that the same result as in Comparative Example 1 in which no protective film was provided was obtained.

INDUSTRIAL APPLICABILITY The glass product with a protective film of the present invention and the manufacturing method thereof can be widely applied to glass products, can effectively prevent contamination of the surface of the glass products, and particularly used for manufacturing liquid crystal displays such as flat panel displays (FPD). It is suitable for a glass substrate.

Claims (10)

On the surface of the glass product, a first film comprising a cationic surfactant having a hydrophobic group having 8 or more carbon atoms or a cationic polymer having an average molecular weight of 5 to 10 million, and a surface of the first film, A protective film having a multilayer structure having an anionic surfactant having a hydrophobic group having 8 or more carbon atoms or a second film made of a nonionic surfactant having a hydrophobic group having 8 or more carbon atoms A glass product with a protective film, comprising: The glass product with a protective film according to claim 1, wherein the hydrophobic group of the cationic surfactant has 12 or more carbon atoms. The glass product with a protective film according to claim 1 or 2, 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. The glass product with a protective film according to claim 1, wherein the cationic polymer has 4 to 25 cationic groups per 1000 molecular weight. The glass product with a protective film according to claim 4, wherein the cationic group is an amino group or a quaternary ammonium group. The glass product with a protective film according to any one of claims 1 to 5, wherein the hydrophobic group of the anionic surfactant or the nonionic surfactant is linear or branched. A cationic surfactant having a hydrophobic group having 8 or more carbon atoms or a solution containing a cationic polymer having an average molecular weight of 5 to 10 million is contacted and dried on the surface of a glass product, and the cationic surfactant is obtained. Or a step of forming a first film made of the cationic polymer;
Contacting and drying 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 on the surface of the first film And forming a second film made of the anionic surfactant or the nonionic surfactant;
The manufacturing method of the glass product with a protective film characterized by having. Cationic surfactant having a hydrophobic group having 8 or more carbon atoms or a cationic polymer having an average molecular weight of 5 to 10 million and an anionic surfactant having a hydrophobic group having 8 or more carbon atoms or having 8 or more carbon atoms Preparing a mixed solution containing a nonionic surfactant having a hydrophobic group of
The mixed solution is contacted and dried on the surface of the glass product, and from the surface side of the glass product, the first film made of the cationic surfactant or the cationic polymer, the anionic surfactant, or the non-ion Forming a protective film as a second film made of a surfactant;
The manufacturing method of the glass product with a protective film characterized by having. The 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 8 to 12. The content ratio of the cationic surfactant to the anionic surfactant or nonionic surfactant in the mixed solution is from 1: 0.1 to 1: 1 in terms of molar ratio, or the content of the cationic group of the cationic polymer. The glass product with a protective film according to claim 8 or 9, wherein the ratio of (equivalent) to the content (molar concentration) of an anionic surfactant or nonionic surfactant is 1: 0.1 to 1: 1. Production method.

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