JPWO2014163034A1 - Glass product with protective film and method for producing the same - Google Patents

Abstract

Provided is a novel glass product with a protective film that can be easily formed and removed by a simple operation, and that can effectively impart a contamination prevention effect. A glass product with a protective film having a protective film 3 made of a cationic surfactant containing a pyridinium salt 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 2 1. Although this protective film 3 has a single layer structure and is easy to manufacture, it can significantly improve the effect of preventing contamination and can be easily removed by washing.

Description

  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, organic substances, etc. contained in the atmosphere are attached and 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.

  In addition, the problem of such surface contamination is old, and various techniques 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 opposite side of the surface of the hydrophilic member (see Patent Document 3), a hydroxyl group Further, a protective film such as a long-chain organic material having a carboxyl group or the like as a hydrophilic group (see Patent Document 4) is also known.

JP 2000-319038 A Japanese Patent Laid-Open No. 2000-211947 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 is not applicable in the case where a polishing step is performed after the glass product is manufactured. Moreover, since the protective film of patent documents 2-4 has weak interaction with the silanol group of the surface of a glass product, an ingenuity is required for the formation, and it thinks that a protective film is comparatively 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 is a protective product comprising a cationic surfactant containing a pyridinium salt 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. It has a film.

  Moreover, the manufacturing method of the glass product with a protective film of this invention is a cationic surfactant containing the pyridinium salt which has a C8 or more hydrophobic group on the surface of a glass product, or an average molecular weight is 500-10 million. It comprises a step of forming a protective film comprising the cationic surfactant or the cationic polymer by contacting and drying a solution containing the cationic polymer.

  According to the glass product with a protective film of the present invention and the method for producing the same, the protective film is provided on the surface of the glass product, and contamination such as adhesion of foreign substances 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.

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 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 whose glass is exposed on the surface thereof. 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 is a film having a single layer structure provided on the surface of the glass product 2. Here, the protective film 3 is a film composed of a cationic surfactant containing a pyridinium salt having a hydrophobic group having 8 or more carbon atoms or a cationic polymer having an average molecular weight of 500 to 10 million.

  The cationic surfactant used here is not particularly limited as long as it is a pyridinium salt 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. Examples thereof include pyridinium salts such as octylpyridinium chloride, decylpyridinium chloride, dodecylpyridinium chloride, tetradecylpyridinium chloride, hexadecylpyridinium chloride, and octadecylpyridinium chloride. This pyridinium salt can improve the water repellency of glass products. In particular, hexadecylpyridinium chloride (also known as cetylpyridinium chloride) is preferable because it is mass-produced and easily available.

  The cationic polymer used here may be a polymer having an average molecular weight of 500 to 10,000,000 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), trimethylammonium. Examples include alkyl acrylamide polymer salts, dimethylamine epichlorohydrin condensate salts, polyallylamine, polyethyleneimine, and the like.

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

  The protective film 3 is a protective film having a single-layer structure, and the effect of preventing contamination can be improved while the manufacturing operation is simple. Further, the protective film formed here is made of a surfactant, and is bonded to the surface of the glass product by electrostatic bonding, and can be easily removed by washing with pure water or an anionic detergent.

Next, the manufacturing method of the glass product with a protective film is demonstrated.
As a method for forming a protective film in the present invention, a cationic surfactant containing a pyridinium salt 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. What is necessary is just to form the protective film which consists of a cationic surfactant or a cationic polymer by making the solution to contain contact and dry.

  At this time, the cationic surfactant or the cationic polymer is dissolved in a 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 become excessive while appropriately covering the glass product surface. When using a cationic polymer, the concentration (equivalent) of the cationic group in the solution is preferably in the range of 0.01 meq / L to 100 meq / L. 0.1 meq / L to 10 meq / L is more preferable so as not to become excessive while covering. By the way, when 1 mol of the cationic group is contained in 1 L of the solution, the concentration is expressed as 1 equivalent and expressed as 1 eq / L. The pH of the solution can be used between acidic and alkaline (for example, about pH 4 to 12), but the electrostatic bond strength is further strengthened by promoting the ionization of the silanol group on the surface of the glass product and making it negatively charged. However, the pH of the solution is preferably 8 to 12 and more preferably 10 to 11 in that the adhesion amount can be increased.

  The solution thus obtained is applied in contact with the surface of the glass product forming the protective 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 or the cationic polymer of the cationic surfactant charged with + charge only by contacting it. This is because the cationic portion is electrostatically attracted to the surface side of the glass product.

  When the solvent is removed by heating, air blowing or the like in the state where the cationic surfactants or the cationic polymers are aligned in this way, a homogeneous first film can be easily formed. At this time, in heat drying, it is preferable to heat to 50-80 degreeC, and in air blow, it is preferable to spray 15-30 degreeC air.

  In addition, when this protective film is formed, it can be achieved by a simple operation of applying the solution at room temperature, and further, the surface protection of the glass product can be achieved without compromising the drainage regulations and without increasing the environmental load. .

Hereinafter, the present invention will be described in more detail based on examples and comparative examples.
[Preparation of various solutions]
<Solution 1 for forming protective film>
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 to prepare a solution for forming a protective film. . The pH of this solution is about 10.5.
<Solution 2 for forming protective film>
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 solution for forming a protective film. The pH of this solution is about 10.5.
<Solution 3 for forming protective film>
Polyethyleneimine (PEI; Nippon Shokubai Epomin SP-006 (molecular weight: about 600)), which is a cationic polymer, was dissolved in pure water to a concentration of 1 meq / L to prepare a solution 3 for forming a protective film. . The pH of this solution is about 10.5.
<Solution 4 for forming protective film>
Polyethyleneimine (PEI; Nippon Shokubai Epomin SP-200 (molecular weight of about 10,000)), which is a cationic polymer, was dissolved in pure water to a concentration of 1 meq / L to prepare a solution for forming a protective film. The pH of this solution is about 10.5.

Example 1
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 protective film forming solution 1 for 10 seconds, and then pulled up. A protective film was formed on the surface of the glass plate by a dip coating method in which the product was dried by air blow to obtain a glass product with a protective film.

(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 protective film forming solution 2 for 10 seconds, and then pulled up. A protective film was formed on the surface of the glass plate by a dip coating method in which the product was dried by air blow to obtain a glass product with a protective film.

(Example 3)
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 protective film-forming solution 3 for 10 seconds, and then pulled up. A protective film was formed on the surface of the glass plate by a dip coating method in which the product was dried by air blow to obtain a glass product with a protective film.

Example 4
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 protective film forming solution 4 for 10 seconds and then pulled up, and then the surface solution A protective film was formed on the surface of the glass plate by a dip coating method in which the product was dried by air blow 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)
Surface-polished glass plate made of alkali-free borosilicate glass of 50 mm long × 50 mm wide × 0.7 mm thick so that dioctyl sulfosuccinate sodium as an anionic surfactant has a concentration of 1 mmol / L In addition, after dipping in an anionic surfactant solution dissolved in pure water for 10 seconds and pulling it up, the surface solution is dried on the surface of the glass plate by an air blow. A film was formed.

(Test Example 1)
The TiO ₂ fine particles were transferred by pressing against the surface of the glass products of Examples and Comparative Examples against the slip sheet coated with the TiO ₂ fine particle pigment for papermaking. 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 59% in Example 1, 48% in Example 2, 55% in Example 3, 50% 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 3 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 to a concentration of 100 μg / ml, and the solution is impregnated into a slip sheet and dried to prepare 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 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 of contact angle after hand scrub compared to immediately after transfer was 39% in Example 1, 68% in Example 2, 35% in Example 3, 31% 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 4 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 and can effectively prevent the surface of the glass product from being contaminated. It is suitable for a glass substrate.

Claims (6)

  A protective film comprising a cationic surfactant containing a pyridinium salt having a hydrophobic group having 8 or more carbon atoms or a cationic film having an average molecular weight of 500 to 10 million on the surface of a glass product Glass product with.   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, wherein the cationic polymer has 4 to 25 cationic groups per 1000 molecular weight.   The glass product with a protective film according to claim 3, wherein the cationic group is an amino group or a quaternary ammonium group.   The surface of the glass product is contacted and dried with a cationic surfactant containing a pyridinium salt 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, and the positive electrode is dried. The manufacturing method of the glass product with a protective film characterized by including the process of forming the protective film which consists of an ionic surfactant or the said cationic polymer.   The method for producing a glass product with a protective film according to claim 5, wherein the solution used for forming the protective film is an aqueous solution having a pH of 8 to 12.

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