GLASS-LIKE FILM

Abstract

The present application relates to a glass-like film. The present application can provide a glass-like film capable of solving the disadvantages of the glass material, while having at least one or more advantages of the glass material. Such a glass-like film of the present application can be easily formed through a simple low temperature process without using expensive equipment.

Claims

1. A glass-like film, comprising: a hard coat layer and a silica layer, wherein the hard coat layer and the silica layer are formed sequentially and wherein the silica layer comprises a silica network formed of one or more units selected from the group consisting of units of the following formulae A and B, and a nitrogen atom:
R.sub.nSiO.sub.(4-n)/2  [Formula A]
SiO.sub.3/2L.sub.1/2  [Formula B] wherein, R is hydrogen, an alkyl group, an alkenyl group, an aryl group, an arylalkyl group, an epoxy group or a (meth)acryloyloxyalkyl group, n is 0 or 1, and L is a divalent linking group comprising any one selected from the group consisting of an alkylene group and an arylene group, or comprising a combination of two or more thereof.

2. The glass-like film according to claim 1, wherein the film has a 500 g steel wool resistance of at least 5,000 times.

3. The glass-like film according to claim 1, wherein the film has a pencil hardness of at least 5H as measured by a method of drawing a pencil lead on a surface of the glass-like film at a load of 500 g and an angle of 45 degrees at a temperature of 25° C. and 50% relative humidity.

4. The glass-like film according to claim 1, wherein the film has a maximum holding curvature radius in a range of 1 to 40 pi as measured by the Mandrel flexure evaluation method according to ASTM D522 standard.

5. The glass-like film according to claim 1, wherein the silica layer does not contain a linkage (Si—N) of a nitrogen atom and a silicon atom.

6. The glass-like film according to claim 5, wherein the nitrogen atom is contained in or derived from an amine compound having a pKa of 8 or less.

7. The glass-like film according to claim 5, wherein the nitrogen atom is contained in or derived from an amine compound having a boiling point in a range of 80° C. to 500° C.

8. The glass-like film according to claim 5, wherein the nitrogen atom is contained in or derived from an amine compound having a room temperature vapor pressure of 10,000 Pa or less.

9. The glass-like film according to claim 5, wherein the nitrogen atom is contained in or derived from a compound represented by the following formula 6; an ionic compound having a cationic compound represented by any one of the following formulae 8 to 10 or a compound of the following formula 13: ##STR00020## wherein, R.sub.9 is hydrogen, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, R.sub.11 and R.sub.12 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, and R.sub.10 is hydrogen, an alkyl group having 1 to 4 carbon atoms, an arylalkyl group having 7 to 16 carbon atoms or a substituent of the following formula 47: ##STR00021## wherein, L.sub.1 is an alkylene group having 1 to 4 carbon atoms: ##STR00022## wherein, R.sub.13 to R.sub.20 are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms: ##STR00023## wherein, R.sub.21 to R.sub.24 are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms: ##STR00024## wherein, R.sub.25 to R.sub.30 are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms: ##STR00025## wherein, R.sub.31 and R.sub.32 are each independently hydrogen, a linear or branched alkyl group having 1 to 4 carbon atoms or a cyclic alkyl group having 4 to 8 carbon atoms, or R.sub.31 and R.sub.32 are linked to each other to form a nitrogen-containing heterocyclic structure together with the nitrogen atom to which R.sub.31 and R.sub.32 are linked, Ar is an aryl group, and L.sub.2 is -L.sub.3-O— or an alkenyl group having 2 to 4 carbon atoms, where L.sub.3 is an alkylene group having 1 to 4 carbon atoms or an alkylidene group having 1 to 4 carbon atoms.

10. The glass-like film according to claim 5, wherein the silica layer comprises the nitrogen atom in an amount of 0.0001 to 6 wt % weight %.

11. The glass-like film according to claim 1, wherein the hard coat layer comprises a cationically cured product of a compound of the following formula F:
(R.sup.1.sub.3SiO.sub.1/2).sub.a(R.sup.2.sub.2SiO.sub.2/2).sub.b(R.sup.3SiO.sub.3/2).sub.c(SiO.sub.4/2).sub.d(RO.sub.1/2).sub.e  [Formula F] wherein, R.sup.1 to R.sub.3 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a cation curable functional group, at least one of R.sup.1 to R.sup.3 is a cation curable functional group, R is a hydrogen atom or an alkyl group, and when the sum of a, b, c and d is converted into 1, c/(a+b+c+d) is a number of 0.7 or more, and e/(a+b+c+d) is a number in a range of 0 to 0.4.

12. The glass-like film according to claim 1, further comprising a base film layer, wherein the hard coat layer and the silica layer are sequentially formed on the base film layer.

13. The glass-like film according to claim 1, further comprising a base film layer, wherein the hard coat layer is formed on both sides of the base film layer.

14. The glass-like film according to claim 13, wherein the silica layer is formed on at least one hard coat layer among the hard coat layers formed on both sides of the base film.

15. The glass-like film according to claim 12, wherein the base film layer comprises one base film or two or more base films.

16. The glass-like film according to claim 13, wherein the base film layer comprises one base film or two or more base films.

Description

BRIEF DESCRIPTIONS OF DRAWINGS

[0189] FIGS. 1 to 6 are diagrams showing exemplary structures of glass-like films.

[0190] Hereinafter, the glass-like film will be described in more detail through Examples and the like according to the present application, but the scope of the present application is not limited to the following.

[0191] 1. 500 g Steel Wool Resistance Evaluation

[0192] Steel wool resistance was evaluated using a steel wool of grade #0000 sold by Briwax of Europe as the steel wool. The steel wool was contacted with a silica layer under a load of 500 g using a measuring instrument (manufacturer: KIPAE ENT, trade name: KM-M4360), and the steel wool resistance was evaluated while moving it left and right. At this time, the contact area was set so that the width and length were approximately 2 cm and 2 cm or so, respectively (contact area: 2 cm.sup.2). The movement was performed at a speed of about 60 times/min and the moving distance was approximately 10 cm. The steel wool test was performed until reflexes were observed by visual observation and indentations, scratches or ruptures, and the like were identified.

[0193] 2. Pencil Hardness Evaluation

[0194] For measurement of pencil hardness, while the silica layer surface was drawn with a cylindrical pencil lead at a load of 500 g and an angle of 45 degrees using a pencil hardness measuring instrument (manufacturer: Chungbuk Tech, trade name: Pencil Hardness Tester), the hardness of the pencil lead was increased in steps until the occurrence of defects such as indentations, scratches or ruptures was confirmed. Here, the speed of the pencil lead was about 1 mm/sec, and the moving distance was about 10 mm. This test was performed at a temperature of about 25° C. and 50% relative humidity.

[0195] 4. Maximum Holding Curvature Radius Evaluation

[0196] The maximum holding curvature radius was evaluated by the Mandrel flexure evaluation method according to ASTM D522 standard.

[0197] 5. Method of Measuring Nitrogen Atom Ratio

[0198] Such a ratio of nitrogen or phosphorus atoms in a silica layer can be measured by X-ray photoelectron spectroscopy (XPS). The method is based on a photoelectric effect and performs the analysis by measuring the kinetic energy of electrons emitted by the photoelectric effect due to the interaction of a surface with high energy light. The binding energy can be measured by emitting core electrons of an element of an analytical sample using X-rays as a light source, and measuring kinetic energy of the emitted electrons. The elements constituting the sample can be identified by analyzing the measured binding energy, and information on the chemical bonding state and the like can be obtained through chemical shift. In the present application, after a silica layer is formed on a silicon wafer to a thickness of about 0.5 μm to 3 μm or so, the ratio of nitrogen or phosphorus atoms can be measured in the manner described in each example or the like. In this case, the specific kind of the applied measuring equipment is not particularly limited as long as it is capable of the measurement of the photoelectron spectroscopy.

[0199] 6. Measurement of Thickness

[0200] After taking an SEM (scanning electron microscope) photograph about a glass-like film, thicknesses of a base film, a hard coat layer, a silica layer, etc. were confirmed based on the photograph.

[0201] 7. Water Vapor Transmission Rate (WVTR) Evaluation

[0202] The water vapor transmission rate was evaluated for a silica layer according to ASTM F1249 standard. It was evaluated after the silica layer was formed on a PET (poly(ethylene terephthalate)) film having a thickness of 50 μm to a thickness of about 1 μm in the same manner as described in each of the following examples. Here, the applied PET film has a water vapor transmission rate of approximately 3.9 to 4.1 g/m.sup.2/day when equally measured according to ASTM F1249 standard.

[0203] 8. Heating Test

[0204] Using an instrument equipped with a touch tip (K-9232, MIK21), the heating test on a glass-like film was performed by heating the glass-like film with the touch tip. At this time, it was performed by setting the pressure on heating as a level of about 250 gf and setting the once heating time as 0.5 seconds.

[0205] 9. Writing Test

[0206] The writing test on a glass-like film was performed using an instrument equipped with a touch tip (K-9700, MIK21). The writing ranges were set such that the X-axis, Y-axis and Z-axis ranges were 700 mm, 550 mm and 100 mm, respectively, and the pressure on writing was set as a level of about 250 gf.

EXAMPLE 1

[0207] 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane and 3-glycidoxypropyl trimethoxysilane were condensed in a molar ratio of 1:1 in a known dehydration/condensation manner to prepare an oligomer (polyorganosiloxane), thereby forming a hard coat layer. The average unit of this oligomer is approximately (R.sup.1SiO.sub.3/2).sub.0.5(R.sup.2SiO.sub.3/2), wherein R.sup.1 is a 2-(3,4-epoxycyclohexyl)ethyl group and R.sup.2 is a 3-glycidoxypropyl group. The oligomer and a cationic photoinitiator (CPI-100P, San-Apro) were further mixed to prepare a composition for a hard coat layer. The cationic photoinitiator was applied at a ratio of approximately 5 to 6 parts by weight relative to 100 parts by weight of the oligomer. After coating the composition for the hard coat layer on one surface of a base film (ZRT, Zero Retardation TAC, FujiFilm) having a thickness of about 40 μm or so as a base film, it was dried at a temperature of 80° C. or so for about 2 minutes and then irradiated with ultraviolet rays at a light quantity of about 1,000 mJ/cm.sup.2 using an ultraviolet irradiation instrument (Fusion, D bulb) and cured, thereby forming a hard coat layer having a thickness of about 30 μm o so. A hard coat layer having a thickness of about 30 μm or so was formed on the other side of the base film in the same manner (double-sided hard coat film having a structure of hard coat layer/base film/hard coat layer).

[0208] Subsequently, a silica layer was formed on any one hard coat layer of the double-sided hard coat film. TEOS (tetraethoxy silane), ethanol (EtOH), water (H.sub.2O) and hydrochloric acid (HCl) were mixed in a weight ratio of 1:4:4:0.2 (TEOS:EtOH:H.sub.2O:HCl) and stirred at room temperature (25° C.) for 3 days or so to form a silica precursor composition. The silica precursor composition was applied on the hard coat layer by a bar coating method and dried at 80° C. for 1 minute or so. After drying, the layer of the silica precursor composition was subjected to atmospheric plasma treatment and then immersed in trioctylamine (TOA) (pKa: 3.5, boiling point: about 366° C., flash point: about 163° C., room temperature vapor pressure: about 0.002 Pa), which was maintained at a temperature of 80° C. or so, for approximately 5 minutes or so to form a silica layer. The formed silica layer was washed with running water at 60° C. or so for 2 minutes or so and dried in an oven at 80° C. or so for 1 minute. In the heating test on the silica layer of the produced glass-like film, no damage was observed until the heating of 1,000,000 times; in the writing test, no damage was observed until the writing of 100,000 times; the 500 g steel wool resistance of the silica layer in the glass-like film was 7,000 times or so; the pencil hardness was 9H or so; the amount of nitrogen atoms contained in the inside of the silica layer was 0.005 weight % or so; the maximum holding curvature radius of the glass-like film was 2 pi or so; and the water vapor transmission rate (WVTR) of the silica layer was 3.9 to 4.0 g/m.sup.2/day or so.

EXAMPLE 2

[0209] A glass-like film was produced in the same manner as in Example 1, except that the formation method of the silica layer was changed as follows. TEOS (tetraethoxy silane), ethanol (EtOH), water (H.sub.2O) and hydrochloric acid (HCl) were mixed in a weight ratio of 1:4:4:0.01 (TEOS:EtOH:H.sub.2O:HCl) and stirred at 65° C. for 1 hour or so to form a silica precursor composition. The silica precursor composition was applied to the hard coat layer by a bar coating method and dried at 80° C. for 1 minute or so. After drying, the layer of the silica precursor composition was subjected to atmospheric plasma treatment and then immersed in trioctylamine (TOA) (pKa: 3.5, boiling point: about 366° C., flash point: about 163° C., room temperature vapor pressure: about 0.002 Pa), which was maintained at a temperature of 80° C. or so, for approximately 5 minutes or so to form a silica layer. The formed silica layer was washed with running water at 60° C. or so for 2 minutes or so and dried in an oven at 80° C. or so for 1 minute. In the heating test on the silica layer of the produced glass-like film, no damage was observed until the heating of 1,000,000 times; in the writing test, no damage was observed until the writing of 100,000 times; the 500 g steel wool resistance of the silica layer in the glass-like film was 7,000 times or so; the pencil hardness was 9H or so; the amount of nitrogen atoms contained in the inside of the silica layer was 0.005 weight % or so; the maximum holding curvature radius of the glass-like film was 2 pi or so; and the water vapor transmission rate (WVTR) of the silica layer was 3.9 to 4.0 g/m.sup.2/day or so.

EXAMPLE 3

[0210] A glass-like film was produced in the same manner as in Example 1, except that the formation method of the silica layer was changed as follows. BTEST (bis(triethoxysilyl) ethane), ethanol (EtOH), water (H.sub.2O) and hydrochloric acid (HCl) were mixed in a weight ratio of 1:6:6:0.01 (BTEST:EtOH:H.sub.2O:HCl) and stirred at 65° C. for 1 hour or so to form a silica precursor composition. The silica precursor composition was applied to the hard coat layer to a thickness of approximately 10 μm or so by a bar coating method and dried at 80° C. for 1 minute or so. After drying, the layer of the silica precursor composition was subjected to atmospheric plasma treatment and then immersed in trioctylamine (TOA) (pKa: 3.5, boiling point: about 366° C., flash point: about 163° C., room temperature vapor pressure: about 0.002 Pa), which was maintained at a temperature of 80° C. or so, for approximately 5 minutes or so to form a silica layer. The formed silica layer was washed with running water at 60° C. or so for 2 minutes or so and dried in an oven at 80° C. or so for 1 minute. In the heating test on the silica layer of the produced glass-like film, no damage was observed until the heating of 1,000,000 times; in the writing test, no damage was observed until the writing of 100,000 times; the 500 g steel wool resistance of the silica layer in the glass-like film was 8,000 times or so; the pencil hardness was 8H or so; the amount of nitrogen atoms contained in the inside of the silica layer was 0.005 weight % or so; the maximum holding curvature radius of the glass-like film was 2 pi or so; and the water vapor transmission rate (WVTR) of the silica layer was 3.9 to 4.0 g/m.sup.2/day or so.

EXAMPLE 4

[0211] A glass-like film was produced in the same manner as in Example 1, except that the formation method of the silica layer was changed as follows. TEOS (tetraethoxy silane), ethanol (EtOH), water (H.sub.2O) and hydrochloric acid (HCl) were mixed in a weight ratio of 1:4:4:0.01 (TEOS:EtOH:H.sub.2O:HCl) and stirred at 65° C. for 1 hour or so to form a silica precursor composition. Approximately 4 parts by weight of a latent base generator (Formula F below, WPBG-018, WAKO) was mixed therewith relative to 100 parts by weight of the solid content of the silica precursor composition.

##STR00013##

[0212] The silica precursor composition mixed with the latent base generator was applied on the hard coat layer by a bar coating method and dried at 80° C. for 1 minute or so. After drying, the silica precursor composition was irradiated with ultraviolet rays at a light quantity of about 660 mJ/cm.sup.2 using an ultraviolet irradiation instrument (Fusion, D bulb) to form a silica layer. In the heating test on the silica layer of the produced glass-like film, no damage was observed until the heating of 1,000,000 times; in the writing test, no damage was observed until the writing of 100,000 times; the 500 g steel wool resistance of the silica layer in the glass-like film was 6,000 times or so; the pencil hardness was 8H or so; the amount of nitrogen atoms contained in the inside of the silica layer was 0.15 to 0.18 weight % or so; the maximum holding curvature radius of the glass-like film was 2 pi or so; and the water vapor transmission rate (WVTR) of the silica layer was 3.9 to 4.0 g/m.sup.2/day or so.

EXAMPLE 5

[0213] A glass-like film was produced in the same manner as in Example 1, except that the formation method of the silica layer was changed as follows.

[0214] BTESE (bis(triethoxysilyl) ethane), ethanol (EtOH), water (H.sub.2O) and hydrochloric acid (HCl) were mixed in a weight ratio of 1:6:6:0.01 (BTESE:EtOH:H.sub.2O:HCl) and stirred at 65° C. for 1 hour or so to form a silica precursor composition. Approximately 4 parts by weight of a latent base generator (Formula F below, WPBG-018, WAKO) was mixed therewith relative to 100 parts by weight of the solid content of the silica precursor composition.

##STR00014##

[0215] The silica precursor composition mixed with the latent base generator was applied on the hard coat layer by a bar coating method and dried at 80° C. for 1 minute or so. After drying, the silica precursor composition was irradiated with ultraviolet rays at a light quantity of about 660 mJ/cm.sup.2 using an ultraviolet irradiation instrument (Fusion, D bulb) to form a silica layer. In the heating test on the silica layer of the produced glass-like film, no damage was observed until the heating of 1,000,000 times; in the writing test, no damage was observed until the writing of 100,000 times; the 500 g steel wool resistance of the silica layer in the glass-like film was 7,000 times or so; the pencil hardness was 8H or so; the amount of nitrogen atoms contained in the inside of the silica layer was 0.15 to 0.18 weight % or so; the maximum holding curvature radius of the glass-like film was 2 pi or so; and the water vapor transmission rate (WVTR) of the silica layer was 3.9 to 4.0 g/m.sup.2/day or so.

EXAMPLE 6

[0216] A glass-like film was produced in the same manner as in Example 1, except that the formation method of the silica layer was changed as follows.

[0217] TEOS (tetraethoxy silane), ethanol (EtOH), water (H.sub.2O) and hydrochloric acid (HCl) were mixed in a weight ratio of 1:4:4:0.01 (TEOS:EtOH:H.sub.2O:HCl) and stirred at 65° C. for 1 hour or so to form a silica precursor composition. Approximately 2 parts by weight of a latent base generator (Formula G below, C11Z, Shikoku chemical) was mixed therewith relative to 100 parts by weight of the solid content of the silica precursor composition.

##STR00015##

[0218] The silica precursor composition mixed with the latent base generator was applied on the hard coat layer by a bar coating method and dried at 80° C. for 1 minute or so. After drying, the silica precursor composition was maintained at approximately 120° C. for 10 minutes to form a silica layer. In the heating test on the silica layer of the produced glass-like film, no damage was observed until the heating of 1,000,000 times; in the writing test, no damage was observed until the writing of 100,000 times; the 500 g steel wool resistance of the silica layer in the glass-like film was 7,000 times or so; the pencil hardness was 9H or so; the amount of nitrogen atoms contained in the inside of the silica layer was 0.22 to 0.24 weight % or so; the maximum holding curvature radius of the glass-like film was 2 pi or so; and the water vapor transmission rate (WVTR) of the silica layer was 3.9 to 4.0 g/m.sup.2/day or so.

EXAMPLE 7

[0219] A glass-like film was produced in the same manner as in Example 1, except that the formation method of the silica layer was changed as follows.

[0220] BTESE (bis(triethoxysilyl) ethane), ethanol (EtOH), water (H.sub.2O) and hydrochloric acid (HCl) were mixed in a weight ratio of 1:6:6:0.01 (BTESE:EtOH:H.sub.2O:HCl) and stirred at 65° C. for 1 hour or so to form a silica precursor composition. Approximately 2 parts by weight of a latent base generator (Formula G below, C11Z, Shikoku chemical) was mixed therewith relative to 100 parts by weight of the solid content of the silica precursor composition.

##STR00016##

[0221] The silica precursor composition mixed with the latent base generator was applied on the hard coat layer by a bar coating method and dried at 80° C. for 1 minute or so. After drying, the silica precursor composition was maintained at approximately 120° C. for 10 minutes to form a silica layer. In the heating test on the silica layer of the produced glass-like film, no damage was observed until the heating of 1,000,000 times; in the writing test, no damage was observed until the writing of 100,000 times; the 500 g steel wool resistance of the silica layer in the glass-like film was 8,000 times or so; the pencil hardness was 8H or so; the amount of nitrogen atoms contained in the inside of the silica layer was 0.22 to 0.24 weight % or so; the maximum holding curvature radius of the glass-like film was 2 pi or so; and the water vapor transmission rate (WVTR) of the silica layer was 3.9 to 4.0 g/m.sup.2/day or so.

EXAMPLE 8

[0222] A glass-like film was produced in the same manner as in Example 1, except that the formation method of the silica layer was changed as follows.

[0223] BTESE (bis(triethoxysilyl) ethane), ethanol (EtOH), water (H.sub.2O) and hydrochloric acid (HCl) were mixed in a weight ratio of 1:6:6:0.01 (BTESE:EtOH:H.sub.2O:HCl) and stirred at 65° C. for 1 hour or so to form a silica precursor composition. Approximately 2 parts by weight of a latent base generator (Formula H below, C17Z, Shikoku chemical) was mixed therewith relative to 100 parts by weight of the solid content of the silica precursor composition.

##STR00017##

[0224] The silica precursor composition mixed with the latent base generator was applied on the hard coat layer by a bar coating method and dried at 80° C. for 1 minute or so. After drying, the silica precursor composition was maintained at approximately 120° C. for 10 minutes to form a silica layer. In the heating test on the silica layer of the produced glass-like film, no damage was observed until the heating of 1,000,000 times; in the writing test, no damage was observed until the writing of 100,000 times; the 500 g steel wool resistance of the silica layer in the glass-like film was 7,000 times or so; the pencil hardness was 7H or so; the amount of nitrogen atoms contained in the inside of the silica layer was 0.14 to 0.17 weight % or so; the maximum holding curvature radius of the glass-like film was 2 pi or so; and the water vapor transmission rate (WVTR) of the silica layer was 3.9 to 4.0 g/m.sup.2/day or so.

EXAMPLE 9

[0225] A glass-like film was produced in the same manner as in Example 1, except that the formation method of the silica layer was changed as follows.

[0226] BTESE (bis(triethoxysilyl) ethane), ethanol (EtOH), water (H.sub.2O) and hydrochloric acid (HCl) were mixed in a weight ratio of 1:6:6:0.01 (BTESE:EtOH:H.sub.2O:HCl) and stirred at 65° C. for 1 hour or so to form a silica precursor composition. Approximately 2 parts by weight of a latent base generator (Formula I below, 2MZ-H, Shikoku chemical) was mixed therewith relative to 100 parts by weight of the solid content of the silica precursor composition.

##STR00018##

[0227] The silica precursor composition mixed with the latent base generator was applied on the hard coat layer by a bar coating method and dried at 80° C. for 1 minute or so. After drying, the silica precursor composition was maintained at approximately 120° C. for 10 minutes to form a silica layer. In the heating test on the silica layer of the produced glass-like film, no damage was observed until the heating of 1,000,000 times; in the writing test, no damage was observed until the writing of 100,000 times; the 500 g steel wool resistance of the silica layer in the glass-like film was 6,000 times or so; the pencil hardness was 7H or so; the amount of nitrogen atoms contained in the inside of the silica layer was 0.64 to 0.67 weight % or so; the maximum holding curvature radius of the glass-like film was 2 pi or so; and the water vapor transmission rate (WVTR) of the silica layer was 3.9 to 4.0 g/m.sup.2/day or so.

EXAMPLE 10

[0228] A glass-like film was produced in the same manner as in Example 1, except that the formation method of the silica layer was changed as follows.

[0229] BTESE (bis(triethoxysilyl) ethane), ethanol (EtOH), water (H.sub.2O) and hydrochloric acid (HCl) were mixed in a weight ratio of 1:6:6:0.01 (BTESE:EtOH:H.sub.2O:HCl) and stirred at 65° C. for 1 hour or so to form a silica precursor composition. Approximately 2 parts by weight of a latent base generator (Formula J below, 1B2MZ, Shikoku chemical) was mixed therewith relative to 100 parts by weight of the solid content of the silica precursor composition.

##STR00019##

[0230] The silica precursor composition mixed with the latent base generator was applied on the hard coat layer by a bar coating method and dried at 80° C. for 1 minute or so. After drying, the silica precursor composition was maintained at approximately 120° C. for 10 minutes to form a silica layer. In the heating test on the silica layer of the produced glass-like film, no damage was observed until the heating of 1,000,000 times; in the writing test, no damage was observed until the writing of 100,000 times; the 500 g steel wool resistance of the silica layer in the glass-like film was 6,000 times or so; the pencil hardness was 6H or so; the amount of nitrogen atoms contained in the inside of the silica layer was 0.29 to 0.32 weight % or so; the maximum holding curvature radius of the glass-like film was 2 pi or so; and the water vapor transmission rate (WVTR) of the silica layer was 3.9 to 4.0 g/m.sup.2/day or so.

COMPARATIVE EXAMPLE 1

[0231] A glass-like film was produced in the same manner as in Example 1, except that the formation method of the silica layer was changed as follows.

[0232] TEOS (tetraethoxy silane), ethanol (EtOH), water (H.sub.2O) and hydrochloric acid (HCl) were mixed in a weight ratio of 1:4:4:0.01 (TEOS:EtOH:H.sub.2O:HCl) and stirred at 65° C. for 1 hour or so to form a silica precursor composition. The silica precursor composition was applied on the hard coat layer by a bar coating method and dried at 80° C. for 1 minute or so. After drying, the layer of the silica precursor composition was subjected to atmospheric plasma treatment and then immersed in acetic acid, which was maintained at a temperature of 120° C. or so, for approximately 10 minutes or so to form a silica layer. The formed silica layer was washed with running water at 60° C. or so for 2 minutes or so and dried in an oven at 80° C. or so for 1 minute. The 500 g steel wool resistance of the silica layer in the produced glass-like film was less than 1,000 times or so, the pencil hardness was 1H or so, the nitrogen atoms were not observed inside the silica layer, the maximum holding curvature radius of the film was 2 pi or so, and the water vapor transmission rate (WVTR) of the silica layer was 3.9 to 4.0 g/m.sup.2/day or so.

COMPARATIVE EXAMPLE 2

[0233] A glass-like film was produced in the same manner as in Example 1, except that the formation method of the silica layer was changed as follows.

[0234] TEOS (tetraethoxy silane), ethanol (EtOH), water (H.sub.2O) and hydrochloric acid (HCl) were mixed in a weight ratio of 1:4:4:0.01 (TEOS:EtOH:H.sub.2O:HCl) and stirred at 65° C. for 1 hour or so to form a silica precursor composition. The silica precursor composition was applied on the hard coat layer by a bar coating method, dried at 80° C. for 1 minute or so, and then maintained at a temperature of 120° C. or so for 10 minutes or so to form a silica layer. The formed silica layer was washed with running water at 60° C. or so for 2 minutes or so and dried in an oven at 80° C. or so for 1 minute. The 500 g steel wool resistance of the produced glass-like film was less than 1,000 times, the pencil hardness was 2H or so, the nitrogen atoms were not observed inside the silica layer, the maximum holding curvature radius of the film was 2 pi or so, and the water vapor transmission rate (WVTR) of the silica layer was 3.9 to 4.0 g/m.sup.2/day or so.