JP7188439B2 - Laminate manufacturing method - Google Patents

Description

The present invention relates to a laminate manufacturing method.

For example, when a glass substrate is used as the cover member, the glass substrate may be provided with an antifouling film that suppresses adhesion of contamination. A compound having a fluorine group is known as an antifouling film material (see Patent Document 1). On the other hand, when a glass substrate is used as the cover member, the glass substrate may be provided with an anti-glare film. As an example of an anti-glare film, a silica film formed from a silica precursor is known (see Patent Document 2).

Japanese Patent Publication No. 2015-511174 JP-A-2005-038288

A laminate in which an antifouling film is further provided in addition to the antiglare film provided on a substrate such as a glass substrate can further exhibit antifouling performance in addition to antiglare performance. It is preferable that the antifouling film provided in this manner has durability so that the antifouling performance can be easily maintained even under relatively severe conditions. The present invention has been made by finding a configuration that facilitates maintenance of the durability of the antifouling film.

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for manufacturing a laminate that makes it possible to enhance the durability of the antifouling film.

A substrate with an anti-glare film according to one aspect for solving the above-mentioned problems is a substrate with an anti-glare film comprising a substrate and an anti-glare film provided on the substrate, wherein the anti-glare film has a hydroxyl group and is a time-of-flight anti-glare film. The surface has a hydroxide ion count of 127,000 or more when normalized to 1,000,000 total negative ion counts detected by secondary ion mass spectrometry (TOF-SIMS).

Another aspect of a substrate with an anti-glare film for solving the above problem is a substrate with an anti-glare film comprising a substrate and an anti-glare film provided on the substrate, wherein the anti-glare film has a hydroxyl group and the anti-glare film The contact angle of water on the surface of is 10° or less.

In the anti-glare film-coated substrate, the anti-glare film preferably contains SiO ₂ .
In the anti-glare film-attached substrate, the substrate is preferably a glass substrate.

A laminate that solves the above problems includes the substrate with the antiglare film, and an antifouling film that is chemically bonded to the hydroxyl groups of the antiglare film.
A method of manufacturing a laminate according to one aspect for solving the above-described problems is a laminate including a substrate with an anti-glare film, which includes a substrate and an anti-glare film provided on the substrate, and an antifouling film provided on the anti-glare film. A method for manufacturing a laminate comprising: a cleaning step of cleaning the surface of the anti-glare film on the substrate with the anti-glare film; and forming the antifouling film on the surface of the anti-glare film cleaned in the cleaning step. and a film forming step, wherein the anti-glare film has hydroxyl groups, and in the cleaning step, the surface of the anti-glare film is detected by time-of-flight secondary ion mass spectrometry (TOF-SIMS). It is a step of performing washing until the count number of hydroxide ions reaches 127,000 or more when the count number of total anions is normalized to 1,000,000, and the film-forming step chemically bonds with the hydroxyl groups of the anti-glare film. An antifouling film is formed.

Another aspect of a laminate manufacturing method for solving the above problems is a laminate including a substrate with an anti-glare film, which includes a substrate and an anti-glare film provided on the substrate, and an antifouling film provided on the anti-glare film. A method for manufacturing a laminate for manufacturing a body, comprising: a cleaning step of cleaning the surface of the anti-glare film on the substrate with the anti-glare film; a film forming step of forming a film, wherein the anti-glare film has a hydroxyl group, and the cleaning step is a step of performing cleaning until the contact angle of water on the surface of the anti-glare film becomes 10° or less. The film forming step forms an antifouling film that is chemically bonded to the hydroxyl groups of the antiglare film.

In the method for manufacturing a laminate described above, it is preferable that a cleaning liquid containing water is used in the cleaning step.

ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to improve the durability of an antifouling film.

1 is a schematic cross-sectional view showing a substrate with an antiglare film according to an embodiment; FIG. It is a schematic sectional drawing which shows a laminated body. It is a flowchart which shows the manufacturing method of a laminated body.

(First embodiment)
A first embodiment of a substrate with an antiglare film, a laminate, and a method for producing the laminate will be described below with reference to the drawings. In the drawings, for convenience of explanation, the dimensional ratio of each part of the configuration may differ from the actual one.

As shown in FIG. 1, a substrate 11 with an antiglare film has a substrate 12 and an antiglare film 13 provided on the substrate 12 .
The substrate 12 is made of glass or resin material. As the glass, for example, known glass such as alkali-free glass, aluminosilicate glass, soda lime glass, etc. can be used. Further, tempered glass such as chemically strengthened glass and crystallized glass such as LAS-based crystallized glass can also be used.

Examples of resin materials include acrylic resins such as polymethyl methacrylate, polycarbonate resins, and epoxy resins.
The thickness of the substrate 12 may be set in consideration of mechanical properties and the like, and is preferably in the range of 0.05 mm or more and 10 mm or less, for example.

As the substrate 12, it is preferable to use a glass substrate from the viewpoint of heat resistance and strength.
The antiglare film 13 in the substrate 11 with the antiglare film is a film that scatters light with its uneven surface. The anti-glare film 13 has hydroxyl groups, and the number of counts of hydroxide ions when the number of counts of total anions detected by time-of-flight secondary ion mass spectrometry (TOF-SIMS) is standardized as 1 million. has a surface of 127,000 or more, preferably 130,000 or more.

The antiglare film 13 is preferably composed of at least one oxide selected from, for example, _SiO2 , _{Al2O3 ,} ZrO2, and _TiO2 , and _more preferably contains _SiO2 . The surface of oxides such as SiO ₂ has hydroxyl groups, which can be detected as hydroxide ions by TOF-SIMS analysis.

The thickness of the antiglare film 13 is, for example, in the range of 40 nm or more and 500 nm or less.
As shown in FIG. 2, the laminate 14 has a substrate 11 with an antiglare film and an antifouling film 15 chemically bonded to the hydroxyl groups of the antiglare film 13 . The anti-fouling film 15 is formed on the anti-glare film 13 and imparts functionality such as water repellency, oil repellency, anti-fouling property and slipperiness to the substrate 11 with the anti-glare film. The antifouling film 15 can be chemically bonded to the hydroxyl groups of the anti-glare film 13 by silanol groups that undergo a dehydration reaction (dehydration condensation) with the hydroxyl groups of the anti-glare film 13 .

The antifouling film 15 preferably has a fluorine group, and more preferably has a perfluoropolyether group. The thickness of the antifouling film 15 is, for example, in the range of 1 nm or more and 30 nm or less.

Next, a method for manufacturing the laminate 14 will be described.
As shown in FIG. 3, the method for manufacturing the laminated body 14 comprises a cleaning step S11 for cleaning the surface of the anti-glare film 13 on the substrate 11 with the anti-glare film, and an antifouling layer on the surface of the anti-glare film 13 cleaned in the cleaning step S11. and a film forming step S12 for forming the film 15 .

The substrate 11 with the anti-glare film to be subjected to the cleaning step S11 is obtained by applying a coating agent for forming the anti-glare film onto the substrate 12 and then drying (heating) it. This coating agent contains a precursor of the antiglare film 13 . The method of applying the coating agent is preferably a spray coating method. A nozzle such as a well-known two-fluid nozzle or one-fluid nozzle can be used for the spray application of the coating agent. The surface properties (such as surface roughness) of the anti-glare film 13 can be controlled by, for example, the particle size of droplets of the coating agent sprayed from the nozzle.

The particle size of droplets of the coating agent ejected from the nozzle is preferably, for example, 0.1 to 100 μm, more preferably 1 to 50 μm. When the droplet diameter is 0.1 μm or more, the coating film can be formed in a shorter time. When the droplet diameter is 100 μm or less, the performance of the antiglare film 13 can be easily improved. The particle size of droplets can be adjusted by the type of nozzle, spray pressure, liquid volume, and the like. For example, when using a two-fluid nozzle, the higher the spray pressure, the smaller the droplets, and the larger the liquid volume, the larger the droplets. In addition, the particle size of the droplet is the Sauter mean particle size measured by a laser measuring device.

After drying the coating layer on the substrate 12, the anti-glare film 13 is formed by firing at a temperature range of 100° C. or higher and 400° C. or lower, for example.
Examples of the precursor contained in the antiglare film-forming coating agent include inorganic precursors such as silica precursors, alumina precursors, zirconia precursors, and titania precursors. The precursor of the antiglare film 13 preferably contains a silica precursor because the refractive index of the antiglare film 13 is low and reactivity can be easily controlled. Silica precursors include, for example, silane compounds having a hydrocarbon group and a hydrolyzable group bonded to a silicon atom, hydrolytic condensates of silane compounds, and silazane compounds. From the viewpoint of suppressing the occurrence of cracks in the antiglare film 13, the silica precursor preferably contains at least one of a silane compound and a hydrolytic condensate of the silane compound.

The silane compound has a hydrocarbon group bonded to the silicon atom and a hydrolyzable group. The hydrocarbon group is one or two selected from -O-, -S-, -CO-, and -NR'- (R' is a hydrogen atom or a monovalent hydrocarbon group) between carbon atoms. You may have groups in which two or more are combined.

The hydrocarbon group may be a monovalent hydrocarbon group bonded to one silicon atom or a divalent hydrocarbon group bonded to two silicon atoms. Examples of monovalent hydrocarbon groups include alkyl groups, alkenyl groups, and aryl groups. Examples of divalent hydrocarbon groups include alkylene groups, alkenylene groups, and arylene groups.

Examples of hydrolyzable groups include alkoxy groups, acyloxy groups, ketoxime groups, alkenyloxy groups, amino groups, aminoxy groups, amide groups, isocyanate groups, halogen atoms and the like. An alkoxy group, an isocyanate group, and a halogen atom (especially a chlorine atom) are preferable from the point of balance with. As the alkoxy group, an alkoxy group having 1 to 3 carbon atoms is preferable, and a methoxy group or an ethoxy group is more preferable.

Silane compounds include alkoxysilanes (tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, etc.), alkoxysilanes having an alkyl group (methyltrimethoxysilane, ethyltriethoxysilane, etc.), and alkoxysilanes having a vinyl group (vinyl trimethoxysilane, vinyltriethoxysilane, etc.), alkoxysilanes having an epoxy group (2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyl diethoxysilane, 3-glycidoxypropyltriethoxysilane, etc.), alkoxysilanes having an acryloyloxy group (3-acryloyloxypropyltrimethoxysilane, etc.), and the like. Among these silane compounds, it is preferable to use one or both of the alkoxysilane and the hydrolytic condensate of alkoxysilane, and it is more preferable to use the hydrolytic condensate of alkoxysilane.

A silazane compound is a compound having a silicon-nitrogen bond (--SiN--) in its structure. The silazane compound may be a low-molecular-weight compound or a high-molecular-weight compound (a polymer having a predetermined repeating unit). Examples of low-molecular-weight silazane compounds include hexamethyldisilazane, hexaphenyldisilazane, dimethylaminotrimethylsilane, trisilazane, cyclotrisilazane, and 1,1,3,3,5,5-hexamethylcyclotrisilazane. be done.

Examples of alumina precursors include aluminum alkoxides, hydrolytic condensates of aluminum alkoxides, water-soluble aluminum salts, and aluminum chelates. Zirconia precursors include zirconium alkoxides, hydrolytic condensates of zirconium alkoxides, and the like. Examples of titania precursors include titanium alkoxides and hydrolytic condensates of titanium alkoxides.

The coating agent further contains a liquid medium that dissolves the precursor. Examples of liquid media include water, alcohols, ketones, ethers, cellosolves, esters, glycol ethers, nitrogen-containing compounds, and sulfur-containing compounds.

Alcohols include methanol, ethanol, isopropanol, butanol, diacetone alcohol and the like. Ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone and the like. Ethers include tetrahydrofuran, 1,4-dioxane and the like. Cellosolves include methyl cellosolve, ethyl cellosolve, and the like. Examples of esters include methyl acetate and ethyl acetate. Glycol ethers include ethylene glycol monoalkyl ether and the like. Nitrogen-containing compounds include N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone and the like. Dimethyl sulfoxide etc. are mentioned as a sulfur-containing compound. The liquid medium may be used alone or in combination of two or more.

The liquid medium is preferably a liquid medium containing water, that is, water or a mixture of water and another liquid medium. Alcohols are preferred as other liquid media, and methanol, ethanol, isopropyl alcohol and butanol are particularly preferred.

Also, the coating agent for forming an anti-glare film may contain an acid catalyst that promotes hydrolysis and condensation of the precursor. Acid catalysts include inorganic acids (nitric acid, sulfuric acid, hydrochloric acid, etc.) and organic acids (formic acid, oxalic acid, acetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, etc.).

The cleaning step S11 in the method for manufacturing the laminate 14 is performed when the surface of the antiglare film 13 is standardized with the count number of total anions detected by time-of-flight secondary ion mass spectrometry (TOF-SIMS) being 1,000,000. In this step, washing is performed until the count number of hydroxide ions of 127,000 or more, preferably 130,000 or more.

The conditions of the cleaning step S11 can be set according to the surface condition of the antiglare film 13. FIG. Specifically, it can be determined by analyzing the TOF-SIMS after washing a sample of the substrate 11 with the anti-glare film under predetermined conditions. For example, by setting the cleaning conditions in the cleaning step S11 so as to further improve the cleanness of the surface of the antiglare film 13, the count number of hydroxide ions detected by TOF-SIMS on the surface of the antiglare film 13 increases. tend to Specifically, for example, by lengthening the cleaning time in the cleaning step S11 or raising the temperature of the cleaning liquid, the hydroxide ion count tends to increase. The temperature of the cleaning liquid is preferably 35° C. or higher, more preferably 40° C. or higher. It is preferable that the surface of the antiglare film 13 is kept in contact with the cleaning liquid for 1 second or longer.

As the cleaning liquid used in the cleaning step S11, for example, a hydrophilic solvent such as alcohol, water, or the like can be used. The cleaning liquid may contain a cleaning component such as an alkaline component or a surfactant. In the case where the cleaning liquid contains the cleaning components remaining on the surface of the anti-glare film 13, the cleaning components remaining on the surface of the anti-glare film 13 can be removed by washing the surface of the anti-glare film 13 only with water or alcohol. can be removed.

In the film forming step S12 in the method for manufacturing the laminate 14, the antifouling film 15 chemically bonded to the hydroxyl groups of the antiglare film 13 is formed. The antifouling film 15 is obtained by applying a coating agent for forming an antifouling film on the antiglare film 13 and then drying (heating) it. In the film forming step S12, the method of applying the coating agent is preferably a spray coating method. In addition, in the film forming step S12, for example, dip coating, spin coating, flow coating, roll coating, or gravure coating can be used other than spray coating.

A silane compound having a fluorine group can be used as a precursor contained in a coating agent for forming an antifouling film. A silane compound having a fluorine group further has a hydrocarbon group and a hydrolyzable group bonded to the silicon atom. The precursor preferably contains a perfluoropolyether group-containing silane compound. By hydrolyzing the hydrolyzable group of the perfluoropolyether group-containing silane compound, a silanol group that undergoes a dehydration reaction (dehydration condensation) with the hydroxyl group of the antiglare film 13 is formed.

Examples of perfluoropolyether group-containing silane compounds include compounds represented by the following general formula (1a) and compounds represented by the following general formula (1b).

上記式中、Ｒｆ^１は、１個又は２個以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基を表す。ａ、ｂ、ｃ及びｓは、それぞれ独立して０以上２００以下の整数であって、ａ、ｂ、ｃ及びｓの和は、少なくとも１である。ａ、ｂ、ｃ又はｓを付した括弧内の各繰り返し単位の存在順序は式中において任意であり、ｄ及びｆは、０又は１であり、ｅ及びｇは、０以上２以下の整数であり、ｍ及びｌは、１以上１０以下の整数である。Ｘは、水素原子又はハロゲン原子を表し、Ｙは、水素原子又は低級アルキル基を表し、Ｚは、フッ素原子又は低級フルオロアルキル基を表し、Ｔは、加水分解性基を表す。Ｒ^１は、水素原子又は炭素数１～２２のアルキル基を表し、ｎは、１以上３以下の整数である。

In the above formula, Rf ¹ represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms. a, b, c and s are each independently integers of 0 or more and 200 or less, and the sum of a, b, c and s is at least 1; The order of existence of each repeating unit in parentheses with a, b, c or s is arbitrary in the formula, d and f are 0 or 1, e and g are integers of 0 or more and 2 or less and m and l are integers of 1 or more and 10 or less. X represents a hydrogen atom or a halogen atom, Y represents a hydrogen atom or a lower alkyl group, Z represents a fluorine atom or a lower fluoroalkyl group, and T represents a hydrolyzable group. R ¹ represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, and n is an integer of 1 or more and 3 or less.

Specifically, Rf ¹ is preferably an alkyl group having 1 to 3 carbon atoms which may be substituted with one or more fluorine atoms, more preferably a perfluoroalkyl group.

The sum of a, b, c and s is preferably 1-100. Of the repeating units in parentheses with a, b, c and s, the repeating unit —(OC ₄ F ₈ )— may be linear or branched, and —(OCF ₂ CF ₂ CF ₂ CF ₂ )- is preferred. The repeating unit --(OC ₃ F ₆ )-- may be linear or branched, and is preferably --(OCF ₂ CF ₂ CF ₂ )--. The repeating unit --(OC ₂ F ₄ )-- may be linear or branched, and is preferably --(OCF ₂ CF ₂ )--.

When X is a halogen atom, it is preferably an iodine atom, a chlorine atom or a fluorine atom.
When Y is a lower alkyl group, it is preferably an alkyl group having 1 to 20 carbon atoms.

When Z is a lower fluoroalkyl group, the lower fluoroalkyl group includes, for example, a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably trifluoro It is a methyl group or a pentafluoroethyl group, more preferably a trifluoromethyl group. Preferably, d and f are 1 and Z is a fluorine atom.

Examples of hydrolyzable groups represented by T include -OA, -OCOA, -ON=C(A) ₂ , -N(A) ₂ , -NHA and halogen. Here, A represents a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms.

R ¹ is preferably an alkyl group having 1 to 22 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.
Examples of perfluoropolyether group-containing silane compounds include compounds represented by the following general formula (2a) and compounds represented by the following general formula (2b).

上記式中、Ｒｆ^２は、１個又は２個以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基を表す。ａ、ｂ、ｃ及びｓは、それぞれ独立して０以上２００以下の整数であって、ａ、ｂ及びｃの和は少なくとも１である。ａ、ｂ、ｃ又はｓを付した括弧内の各繰り返し単位の存在順序は式中において任意であり、ｄ及びｆは、０又は１であり、ｈ及びｊは、１又は２であり、ｉ及びｋは、２以上２０以下の整数である。Ｚは、フッ素原子又は低級フルオロアルキル基を表し、Ｔは、加水分解性基を表す。Ｒ^２は、水素原子又は炭素数１～２２のアルキル基を表し、ｎは、１以上３以下の整数である。

In the above formula, Rf ² represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms. a, b, c and s are each independently integers of 0 or more and 200 or less, and the sum of a, b and c is at least 1; The order of existence of each repeating unit in parentheses with a, b, c or s is arbitrary in the formula, d and f are 0 or 1, h and j are 1 or 2, i and k is an integer of 2 or more and 20 or less. Z represents a fluorine atom or a lower fluoroalkyl group, and T represents a hydrolyzable group. R ² represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, and n is an integer of 1 or more and 3 or less.

More specifically, Rf ² is preferably an alkyl group having 1 to 3 carbon atoms which may be substituted with one or more fluorine atoms, more preferably a perfluoroalkyl group.

The sum of a, b, c and s is preferably 1-100. Among the repeating units in parentheses with a, b, c and s, -(OC ₄ F ₈ )- may be linear or branched, and -(OCF ₂ CF ₂ CF ₂ CF ₂ )- is preferred. The repeating unit —(OC ₃ F ₆ )— may be linear or branched, and is preferably —(OCF ₂ CF ₂ CF ₂ )—. The repeating unit --(OC ₂ F ₄ )-- may be linear or branched, and is preferably --(OCF ₂ CF ₂ )--.

When Z is a lower fluoroalkyl group, the lower fluoroalkyl group includes, for example, a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably trifluoro It is a methyl group or a pentafluoroethyl group, more preferably a trifluoromethyl group. Preferably, d and f are 1 and Z is a fluorine atom.

Examples of hydrolyzable groups represented by T include -OA, -OCOA, -ON=C(A) ₂ , -N(A) ₂ , -NHA and halogen. Here, A represents a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms.

R ² is preferably an alkyl group having 1 to 22 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.
Examples of perfluoropolyether group-containing silane compounds include compounds represented by the following general formula (3).

Rf ³ [-L ³ pX-R ³¹ -Si(OR ³² ) ₃ ] _q (3)
In the formula, Rf ³ represents a perfluoropolyether group, preferably a perfluoropolyether group having 1 to 300 carbon atoms. However, at least part of the fluorine atoms bonded to the terminal carbon atoms in Rf ³ may be hydrogen atoms. p represents 0 or 1; q represents 1 or 2; R ³¹ represents an alkylene group, preferably an alkylene group having 1 to 3 carbon atoms. R ³² represents an alkyl group, preferably an alkyl group having 1 to 3 carbon atoms. L ³ represents -CO-. X represents a group selected from -O-, -NR ³³ -, -S-, -SO ₂ -, -SO ₂ NR ³³ - and -NR ³³ CO-, and is preferably -O-. ^R33 represents a hydrogen atom or an alkyl group having 3 or less carbon atoms.

The perfluoropolyether group-containing silane compound may be used alone or in combination of multiple types. Further, as the perfluoropolyether group-containing silane compound, the one disclosed in Patent Document 1 may be used.

A coating agent for forming an antifouling film contains a solvent capable of dissolving a perfluoropolyether group-containing silane compound or the like. Hydrofluoroether (HFE), for example, can be used as the solvent. Examples of hydrofluoroethers include perfluoropropyl methyl ether (C ₃ F ₇ OCH ₃ ), perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ), perfluorobutyl ethyl ether (C ₄ F ₉ OC ₂ H ₅ ), and perfluorohexyl methyl ether _{( C2F5CF ( OCH3} ) _C3F7 ). A solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

In addition to the perfluoropolyether group-containing silane compound, the coating agent for forming the antifouling film may contain, for example, the catalyst disclosed in Patent Document 1, fluorine-containing oil, silicone oil, and the like. In addition, the coating agent may further contain a functionality-imparting agent such as a hard coating agent.

Applications of the laminate 14 include, for example, display applications, touch panel applications, and electronic device applications. Further, examples of application locations of the laminate 14 include electrical equipment, vehicles, and the like.

Next, the operation and effects of the first embodiment will be described.
(1-1) The anti-glare film 13 in the substrate 11 with the anti-glare film has a hydroxyl group, and the number of counts of hydroxide ions when the total number of anions detected by TOF-SIMS is normalized to 1,000,000. has over 127,000 surfaces.

When the antifouling film 15 is further provided on the surface of the antiglare film 13, it is thought that the chemical bonding of the antifouling film 15 to the hydroxyl groups on the surface of the antiglare film 13 can be increased.

According to the above configuration, the antifouling film 15 provided on the antiglare film 13 is less likely to peel off. This makes it possible to increase the durability of the antifouling film 15 .
(1-2) Antiglare film 13 in substrate 11 with antiglare film preferably contains SiO ₂ . In this case, for example, the occurrence of cracks in the antiglare film 13 can be suppressed.

(1-3) The substrate 12 in the substrate 11 with anti-glare film is preferably a glass substrate. In this case, for example, the heat resistance and strength of the substrate 11 with the antiglare film can be enhanced.

(1-4) Laminate 14 includes substrate 11 with an antiglare film and antifouling film 15 chemically bonded to the hydroxyl groups of antiglare film 13 .
According to this configuration, as described above, the antifouling film 15 provided on the antiglare film 13 is less likely to peel off, so the durability of the antifouling film 15 can be enhanced.

(1-5) The method for manufacturing the laminate 14 includes a cleaning step S11 for cleaning the surface of the antiglare film 13 on the substrate 11 with the antiglare film, and an antifouling film 15 on the surface of the antiglare film 13 cleaned in the cleaning step S11. and a film forming step S12 for forming a film of. The anti-glare film 13 has hydroxyl groups, and the cleaning step S11 is a step of cleaning the surface of the anti-glare film 13 until the hydroxide ion count number detected by TOF-SIMS becomes 127000 or more. be. The film formation step S<b>12 is a step of forming the antifouling film 15 chemically bonded to the hydroxyl groups of the antiglare film 13 .

According to this method, it is possible to easily obtain the laminate 14 in which the antifouling film 15 is difficult to peel off.
(1-6) In the method for manufacturing the laminate 14, it is preferable to use a cleaning liquid containing water in the cleaning step S11. In this case, the cleaning equipment can be simplified because the handling of the cleaning liquid is improved.

(Second embodiment)
A second embodiment of a substrate 11 with an antiglare film, a layered body 14, and a method for manufacturing the layered body 14 will be described, centering on points different from the first embodiment.

The antiglare film 13 in the substrate 11 with the antiglare film of the second embodiment has hydroxyl groups, and the contact angle of water on the surface of the antiglare film 13 is 10° or less. The contact angle of water can be measured according to JIS R3257 (1999). The cleaning step S11 in the method for manufacturing the laminate 14 is a step of cleaning until the contact angle of water on the surface of the antiglare film 13 becomes 10° or less.

Next, the action and effect of the second embodiment will be described.
(2-1) Antiglare film 13 in substrate 11 with antiglare film has hydroxyl groups, and the contact angle of water on the surface of antiglare film 13 is 10° or less.

When the antifouling film 15 is further provided on the surface of the antiglare film 13, the hydroxyl groups on the surface of the antiglare film 13 are likely to come into contact with the components for forming the antifouling film 15 that bond with the hydroxyl groups, thereby causing antiglare. It is thought that the chemical bonding of the antifouling film 15 to the hydroxyl groups on the surface of the film 13 can be increased.

According to the above configuration, the antifouling film 15 provided on the antiglare film 13 is less likely to peel off. This makes it possible to increase the durability of the antifouling film 15 .
(2-2) The substrate 11 with the anti-glare film of the second embodiment also provides the same effects as those described in sections (1-2) to (1-4) of the first embodiment.

(2-3) The method for manufacturing the laminate 14 includes a cleaning step S11 for cleaning the surface of the antiglare film 13 on the substrate 11 with the antiglare film, and an antifouling film 15 on the surface of the antiglare film 13 cleaned in the cleaning step S11. and a film forming step S12 for forming a film of. The anti-glare film 13 has hydroxyl groups, and the cleaning step S11 is a step of cleaning until the contact angle of water on the surface of the anti-glare film 13 becomes 10° or less. The film formation step S<b>12 is a step of forming the antifouling film 15 chemically bonded to the hydroxyl groups of the antiglare film 13 .

According to this method, it is possible to easily obtain the laminate 14 in which the antifouling film 15 is difficult to peel off.
(2-4) In the method of manufacturing the laminate 14 of the second embodiment, the same effects as those described in section (1-6) of the first embodiment can be obtained.

Next, test examples will be described.
(Test Example 1-1)
A coating agent for forming an antiglare film was spray-coated on one main surface of a glass substrate (soda lime glass, thickness 2.5 mm) and dried to form a coating layer on the substrate. As a coating agent for forming an antiglare film, a solution (precursor concentration: 3% by mass) of an antiglare film precursor (tetraethyl orthosilicate) dissolved in a liquid medium containing water was used. By baking the coating layer on the glass substrate at 180° C. for 30 minutes, sample 11A of the glass substrate with an antiglare film was obtained.

Next, sample 11B was obtained by washing the surface of the antiglare film of sample 11A. In this cleaning, as shown in Table 1, while conveying the sample 11A at a speed of 400 mm/min, an aqueous alkaline cleaning solution adjusted to a concentration of 6.5% and a temperature of 45°C was applied to the surface of the antiglare film using a shower nozzle. After spraying, it was washed with water and dried.

The surface of the anti-glare film of sample 11B was analyzed using time-of-flight secondary ion mass spectrometry (TOF-SIMS) under the following conditions.
Analyzer name: TOF-SIMS IV manufactured by IONTOF
Primary beam conditions: Ga, +2.5 keV, 0.1 pA
Secondary mass spectrometry; time-of-flight mass spectrometer As a result of analyzing the surface of the anti-glare film of sample 11B by TOF-SIMS, the number of hydroxide ions counted when the total number of anions detected was normalized to 1 million was was 141,000.

A coating agent for forming an antifouling film was spray-coated on the anti-glare film of sample 11B and dried to form a coating layer on the anti-glare film. A coating agent for forming an antifouling film is prepared by mixing 0.1 parts by mass of a commercially available product containing a perfluoropolyether group-containing silane compound and 99.9 parts by mass of a solvent (perfluorobutyl ethyl ether). did. By heating the coating layer on the antiglare film at 180° C. for 30 minutes, a laminate sample 11C having an antifouling film was obtained.

(Test Example 1-2)
In Test Example 1-2, Sample 12A was obtained in the same manner as Sample 11A of Test Example 1-1.

Next, sample 12B was obtained by washing the surface of the antiglare film of sample 12A. In this cleaning, as shown in Table 1, while conveying the sample 12B at a speed of 500 mm/min, an aqueous alkaline cleaning solution adjusted to a concentration of 6.5% and a temperature of 45°C was applied to the surface of the antiglare film using a shower nozzle. After spraying, it was washed with water and dried.

The surface of the anti-glare film of sample 12B was analyzed using TOF-SIMS in the same manner as in Test Example 1-1. was 132,000.

Further, a sample 12C of a laminate having an antifouling film was obtained by providing an antifouling film on the antiglare film of the sample 12B in the same manner as in Test Example 1-1.
(Test Example 1-3)
In Test Example 1-3, Sample 13A was obtained in the same manner as Sample 11A of Test Example 1-1.

Next, sample 13B was obtained by washing the surface of the antiglare film of sample 13A. In this cleaning, as shown in Table 1, while conveying the sample 13B at a speed of 1000 mm/min, an aqueous alkaline cleaning solution adjusted to a concentration of 6.5% and a temperature of 45°C was applied to the surface of the antiglare film using a shower nozzle. After spraying, it was washed with water and dried.

The surface of the anti-glare film of sample 13B was analyzed using TOF-SIMS in the same manner as in Test Example 1-1. was 125,000.

Further, a sample 13C of a laminate having an antifouling film was obtained by providing an antifouling film on the antiglare film of the sample 13B in the same manner as in Test Example 1-1.
(Test Example 1-4)
In Test Example 1-4, Sample 14A was obtained in the same manner as Sample 11A of Test Example 1-1.

Next, sample 14B was obtained by washing the surface of the antiglare film of sample 14A. In this cleaning, as shown in Table 1, while conveying sample 14B at a speed of 1000 mm/min, an aqueous alkaline cleaning solution adjusted to a concentration of 5.0% and a temperature of 37° C. was applied to the surface of the anti-glare film using a shower nozzle. After spraying, it was washed with water and dried.

The surface of the anti-glare film of sample 14B was analyzed using TOF-SIMS in the same manner as in Test Example 1-1. was 123,000.

Further, a sample 14C of a laminate having an antifouling film was obtained by providing an antifouling film on the antiglare film of the sample 14B in the same manner as in Test Example 1-1.
(Test Example 1-5)
In Test Example 1-5, Sample 15A was obtained in the same manner as Sample 11A of Test Example 1-1.

Next, sample 15B was obtained by washing the surface of the antiglare film of sample 15A. In this cleaning, as shown in Table 1, while conveying the sample 15B at a speed of 1000 mm/min, an aqueous alkaline cleaning solution adjusted to a concentration of 3.0% and a temperature of 37°C was applied to the surface of the antiglare film using a shower nozzle. After spraying, it was washed with water and dried.

The surface of the anti-glare film of sample 15B was analyzed using TOF-SIMS in the same manner as in Test Example 1-1. was 90,000.

Further, a sample 15C of a laminate having an antifouling film was obtained by providing an antifouling film on the antiglare film of the sample 15B in the same manner as in Test Example 1-1.

（試験例２－１）
試験例２－１では、まず試験例１－１のサンプル１１Ａと同様にしてサンプル２１Ａを得た後、表２に示すように、サンプル１１Ａと同様にしてサンプル２１Ａを洗浄することで、サンプル２１Ｂを得た。

(Test Example 2-1)
In Test Example 2-1, first, Sample 21A was obtained in the same manner as Sample 11A of Test Example 1-1, and then, as shown in Table 2, Sample 21A was washed in the same manner as Sample 11A to obtain Sample 21B. got

As a result of measuring the contact angle of pure water on the surface of the antiglare film of sample 21B, it was 3.3°.
Next, sample 21C of a laminate having an antifouling film was obtained by providing an antifouling film on sample 21B in the same manner as sample 11B of Test Example 1-1.

(Test example 2-2)
In Test Example 2-2, first, Sample 22A was obtained in the same manner as Sample 12A of Test Example 1-2, and then, as shown in Table 2, Sample 22A was washed in the same manner as Sample 12A to obtain Sample 22B. got

As a result of measuring the contact angle of pure water on the surface of the antiglare film of sample 22B, it was 7.8°.
Next, a sample 22C of a laminate having an antifouling film was obtained by forming an antifouling film on the sample 22B in the same manner as the sample 12B of Test Example 1-2.

(Test example 2-3)
In Test Example 2-3, Sample 23A was first obtained in the same manner as Sample 13A of Test Example 1-3, and then, as shown in Table 2, Sample 23A was washed in the same manner as Sample 13A, resulting in Sample 23B. got

As a result of measuring the contact angle of pure water on the surface of the antiglare film of Sample 23B, it was 11.9°.
Next, sample 23C of a laminate having an antifouling film was obtained by providing an antifouling film on sample 23B in the same manner as sample 13B of Test Example 1-3.

(Test Example 2-4)
In Test Example 2-4, Sample 24A was first obtained in the same manner as Sample 14 in Test Example 1-4, and then, as shown in Table 2, Sample 24A was washed in the same manner as Sample 14A to obtain Sample 24B. got

As a result of measuring the contact angle of pure water on the surface of the antiglare film of sample 24B, it was 22.7°.
Next, sample 24C of a laminate having an antifouling film was obtained by providing an antifouling film on sample 24B in the same manner as sample 14B of Test Example 1-4.

(Test Example 2-5)
In Test Example 2-5, Sample 25A was first obtained in the same manner as Sample 15A of Test Example 1-5, and then, as shown in Table 2, Sample 25A was washed in the same manner as Sample 15A to obtain Sample 25B. got

As a result of measuring the contact angle of pure water on the surface of the antiglare film of sample 25B, it was 22.7°.
Next, sample 25C of a laminate having an antifouling film was obtained by providing an antifouling film on sample 25B in the same manner as sample 15B of Test Example 1-5.

＜防汚膜の耐久性の評価＞
上記試験例１－１～１－５のサンプル１１Ｃ～１５Ｃの耐久性について、スチールウール擦り試験によって評価した。スチールウール擦り試験は、防汚膜の表面に対するスチールウール（縦１０ｍｍ×横１０ｍｍ、日本スチールウール社製、ボンスター業務用等級＃００００）の荷重５００ｇ、揺動ストローク６０ｍｍ、揺動速度６０往復／分の条件で行った。スチールウール擦り試験において、往復回数１００回後の水の接触角を測定した。その結果を表１に示す。この結果から、試験例１－１，１－２のサンプル１１Ｃ，１２Ｃの防汚膜の耐久性は、試験例１－３～１－５のサンプル１３Ｃ～１５Ｃよりも優れることが分かる。

<Evaluation of durability of antifouling film>
The durability of samples 11C to 15C of Test Examples 1-1 to 1-5 was evaluated by a steel wool rubbing test. In the steel wool rubbing test, steel wool (10 mm long x 10 mm wide, manufactured by Japan Steel Wool Co., Ltd., Bonstar commercial grade #0000) is applied to the surface of the antifouling film with a load of 500 g, a swing stroke of 60 mm, and a swing speed of 60 reciprocations/minute. was performed under the conditions of In the steel wool rubbing test, the water contact angle was measured after 100 reciprocations. Table 1 shows the results. From these results, it can be seen that the durability of the antifouling films of Samples 11C and 12C of Test Examples 1-1 and 1-2 is superior to that of Samples 13C to 15C of Test Examples 1-3 to 1-5.

Further, as shown in Table 2, the durability of the antifouling films of Samples 21C and 22C of Test Examples 2-1 and 2-2 is also superior to that of Samples 23C to 25C of Test Examples 2-3 to 2-5. This was confirmed by the steel wool rubbing test described above.

DESCRIPTION OF SYMBOLS 11... Substrate with anti-glare film, 12... Substrate, 13... Anti-glare film, 14... Laminated body, 15... Antifouling film.

Claims (2)

a substrate with an antiglare film comprising a substrate and an antiglare film provided on the substrate;
An antifouling film provided on the antiglare film, and a method for manufacturing a laminate comprising:
a cleaning step of cleaning the surface of the anti-glare film on the substrate with the anti-glare film using a cleaning liquid containing water ;
a film forming step of forming the antifouling film on the surface of the anti-glare film cleaned in the cleaning step;
The antiglare film has a hydroxyl group,
In the cleaning step, the surface of the anti-glare film counts hydroxide ions when the count of total anions detected by time-of-flight secondary ion mass spectrometry (TOF-SIMS) is standardized as 1 million. A step of washing until the number reaches 127,000 or more,
The method of manufacturing a laminate, wherein the film forming step forms an antifouling film that is chemically bonded to the hydroxyl groups of the antiglare film. a substrate with an antiglare film comprising a substrate and an antiglare film provided on the substrate;
An antifouling film provided on the antiglare film, and a method for manufacturing a laminate comprising:
a cleaning step of cleaning the surface of the anti-glare film on the substrate with the anti-glare film using a cleaning liquid containing water ;
a film forming step of forming the antifouling film on the surface of the anti-glare film cleaned in the cleaning step;
The antiglare film has a hydroxyl group,
The washing step is a step of washing until the contact angle of water on the surface of the antiglare film becomes 10° or less,
The method of manufacturing a laminate, wherein the film forming step forms an antifouling film that is chemically bonded to the hydroxyl groups of the antiglare film.

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