JP2012148416A - Laminate and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film which is made of polysilazane, is excellent in scratch resistance, transparency and adhesion to a base material, and further has a high refractive index, and to provide a method for producing the film.SOLUTION: A laminate includes: a base material 12; and a silicon-containing film 16 formed on the base material 12. The silicon-containing film 16 includes a nitrogen high concentration region 18 composed of silicon atoms and nitrogen atoms, or silicon atoms, nitrogen atoms and oxygen atoms. The nitrogen high concentration region is formed by irradiating a film 14, mixed with a transition metal compound and formed on the base material 12, with energy rays in an atmosphere substantially not including oxygen or water vapor and by denaturing at least a part of the film.

Description

  The present invention relates to a laminate and a method for producing the same.

  In recent years, transparent gas barrier materials that block gases such as oxygen and water vapor have been used not only for packaging materials such as food and pharmaceuticals, which are the main applications of the past, but also for flat panel displays (FPD) such as liquid crystal displays and solar cells. It has come to be used for such members (substrates, back sheets, etc.), flexible substrates for electronic paper and organic electroluminescent (organic EL) elements, sealing films, and the like. In these applications, a very high gas barrier property is required.

  Currently, transparent gas barrier materials employed in some applications are manufactured by a dry method such as a plasma CVD method, a sputtering method, or an ion plating method, and a wet method typified by a sol-gel method. Both methods are methods in which a silicon oxide (silica) exhibiting gas barrier properties is deposited on a plastic substrate. Unlike the dry method, the wet method does not require large-scale equipment, is not affected by the surface roughness of the base material, and cannot be pinholed. Therefore, it has attracted attention as a method for obtaining a uniform gas barrier film with good reproducibility. Yes.

  As one method for producing such a gas barrier film by a wet method, a method of converting a polysilazane film coated on a base material to silica as in Non-Patent Document 1 is known. It is widely known that polysilazane is converted into silicon oxide (silica) through oxidation or hydrolysis and dehydration polycondensation by heat treatment (150 to 450 ° C.) in the presence of oxygen or water vapor. However, this method has a problem that it takes a long time to form silica and a problem that the base material is exposed to a high temperature and cannot be deteriorated.

  On the other hand, in Patent Document 1 and Patent Document 2, a polysilazane film is formed by applying a coating liquid containing polysilazane to a substrate, and then air or oxygen gas is used as a suitable plasma gas species. A method of performing an oxidation treatment with plasma called a plasma oxidation method on a polysilazane film is disclosed. It is described that the polysilazane film can be converted to silica at a low temperature and in a relatively short time by this method.

Subsequently, optical materials will be described.
High refractive index resins such as diethylene glycol bisallyl carbonate resin and polythiourethane resin are used for one of optical materials such as plastic eyeglass lenses. This high refractive index resin has the disadvantages of low scratch resistance and easy scratching on the surface. Therefore, a method of providing a film having a hard coat and a high refractive index on the surface has been performed. For the same reason, various displays such as word processors, computers and televisions, the surfaces of polarizing plates used in liquid crystal display devices, optical lenses such as camera finder lenses, covers for various instruments, window glass for automobiles, trains, etc. A film having a hard coat and a high refractive index is also required on the surface. In order to impart a high refractive index to such a hard coat film, a coating solution using silica sol and an organosilicon compound to which ultrafine particles are added is mainly used.

  However, in such a coating liquid, it is necessary to match the refractive indexes of the substrate and the coating film in order to suppress the generation of interference fringes. In that case, it was necessary to select an optimal one from a large number of additive fine particles according to the type of substrate. Further, there is room for improvement in scratch resistance, and a film thickness of several μm or more is necessary to impart scratch resistance.

  On the other hand, Patent Document 3 describes a method for forming a silicon nitride thin film in which perhydropolysilazane or a modified product thereof is applied to a substrate and then baked at a temperature of 600 ° C. or higher under vacuum. It is described that the silicon nitride thin film thus formed is excellent in wear resistance, heat resistance, corrosion resistance and chemical resistance and has a high refractive index.

JP-A-8-269690 JP 2007-237588 A JP-A-10-194873

"Painting and paint", Vol. 569, No. 11, pp. 27-33 (1997) “Thin Solid Films”, 515, 3480-3487, author: F.M. Rebib et al. (2007)

  However, the inorganic polymer layer of the gas barrier film of Patent Document 1 is a layer for imparting adhesion of the metal vapor deposition layer and chemical stability of the substrate as an intermediate layer between the substrate and the metal vapor deposition layer. Further, the invention is not an invention that imparts gas barrier properties solely by the polysilazane layer. In addition, in the case of a technique generally referred to as corona treatment using air as a plasma species as described in Examples of Patent Document 1, the obtained inorganic polymer layer did not exhibit sufficient gas barrier properties. Further, there is a problem that the scratch resistance is not good.

The invention of Patent Document 2 is a method for producing a gas barrier film by subjecting a polysilazane film to plasma treatment. However, the invention of Patent Document 2 also relates to a technique for producing a silicon oxide (silica) film by the oxygen plasma treatment as described above. The gas barrier performance required in applications such as FPD, solar cell members, flexible substrates and sealing films for organic EL elements has been difficult to achieve with a silicon oxide (silica) film alone. Therefore, there has been room for improvement in gas barrier properties, particularly for use in these applications.
As described above, the gas barrier films described in Patent Documents 1 and 2 still have problems to be solved in terms of gas barrier properties and scratch resistance against oxygen and water vapor.

  The method described in Patent Document 3 for optical materials requires that the polysilazane film be baked at a high temperature of 600 ° C. or higher. For this reason, when the silicon nitride film is provided on the surface of the optical member, the optical member itself is exposed to a high temperature. Therefore, the method described in this document cannot be applied to optical applications that require precision. On the other hand, when the polysilazane film is heated at a temperature of less than 600 ° C., it is converted into silica having a low refractive index, and a high refractive index film cannot be obtained.

  According to the present invention, a laminate comprising a base material and a silicon-containing film formed on the base material, the silicon-containing film comprising silicon atoms and nitrogen atoms, or silicon atoms and nitrogen atoms and oxygen A high concentration region of nitrogen composed of atoms, and the high concentration region of nitrogen is irradiated with energy rays in an atmosphere substantially free of oxygen or water vapor on a polysilazane film containing a transition metal compound formed on a substrate. To provide a laminate formed by modifying at least a part of the film.

According to one embodiment of the present invention, in the laminate, the high nitrogen concentration region has a composition ratio of nitrogen atoms to all atoms represented by the following formula measured by X-ray photoelectron spectroscopy of 0.1 or more. A range of 1 or less;
Formula: Composition ratio of nitrogen atom / (composition ratio of oxygen atom + composition ratio of nitrogen atom).

According to one embodiment of the present invention, in the laminate, the high nitrogen concentration region has a composition ratio of nitrogen atoms to all atoms represented by the following formula measured by X-ray photoelectron spectroscopy of 0.1 or more. A range of 0.5 or less;
Formula: Composition ratio of nitrogen atom / (composition ratio of silicon atom + composition ratio of oxygen atom + composition ratio of nitrogen atom).

  According to an embodiment of the present invention, in the stacked body, the high nitrogen concentration region is formed over the entire surface of the silicon-containing film.

  According to one embodiment of the present invention, in the laminate, the high nitrogen concentration region has a thickness of 0.001 μm to 0.2 μm.

  According to one embodiment of the present invention, in the laminate, the composition ratio of nitrogen atoms relative to all atoms measured by X-ray photoelectron spectroscopy in the silicon-containing film is such that the upper surface side of the silicon-containing film is from the other surface side. Is also expensive.

According to one embodiment of the present invention, the energy beam is light of 230 nm or less.

  According to one embodiment of the present invention, in the laminate, the energy beam irradiation is performed by plasma irradiation or ultraviolet irradiation.

  According to an embodiment of the present invention, in the laminate, the plasma irradiation or the ultraviolet irradiation uses an inert gas, a rare gas, or a reducing gas as a gas species.

  According to an embodiment of the present invention, in the laminate, nitrogen gas, argon gas, helium gas, hydrogen gas, or a mixed gas thereof is used as the gas species.

  According to one embodiment of the present invention, in the laminate, the plasma irradiation or ultraviolet irradiation is performed under vacuum.

  According to one embodiment of the present invention, in the laminate, the plasma irradiation or ultraviolet irradiation is performed under normal pressure.

According to one embodiment of the present invention, in the laminate, the polysilazane film is at least one selected from the group consisting of perhydropolysilazane, organopolysilazane, and derivatives thereof.
According to one embodiment of the present invention, the transition metal compound is platinum, ruthenium, rhodium, iridium, iron, osmium, cobalt, palladium, nickel, titanium, vanadium, chromium, manganese, molybdenum, tungsten, niobium, tantalum, zirconium. , Hafnium, scandium, yttria, lanthanum, rhenium-containing compounds, or a mixture thereof.

According to an embodiment of the present invention, the transition metal compound is a transition metal halide or complex, a transition metal salt, or a transition metal oxide.

According to an embodiment of the present invention, the halogen of the halide is chlorine, bromine, iodine, or fluorine.

According to one embodiment of the present invention, the complex is an olefin complex, a cyclic olefin complex, a vinyl siloxane complex, a phosphine complex, a phosphite complex, or a carbon monoxide complex.

According to one embodiment of the present invention, the transition metal salt comprises tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, tetrakis (perfluorophenyl) borate, perchlorate and trifluoro. Methyl sulfonate.

According to an embodiment of the present invention, in the stacked body, the high nitrogen concentration region includes silicon nitride and / or silicon oxynitride.
According to one embodiment of the present invention, the laminate has a thickness of 0.02 μm to 2 μm.

  According to one embodiment of the present invention, the laminate is an optical member.

  According to one embodiment of the present invention, the laminate is a gas barrier film.

  In addition, according to the present invention, a step of applying a polysilazane-containing liquid to which a transition metal compound is added on a substrate to form a coating film, and a step of drying the coating film in a low moisture concentration atmosphere to form a polysilazane film The polysilazane film is irradiated with energy rays in an atmosphere substantially free of oxygen or water vapor to modify at least a part of the film, and from silicon atoms and nitrogen atoms, or silicon atoms, nitrogen atoms and oxygen atoms. And a step of forming a silicon-containing film including the nitrogen high-concentration region.

According to one embodiment of the present invention, in the above method, the high nitrogen concentration region has a composition ratio of nitrogen atoms to all atoms represented by the following formula measured by X-ray photoelectron spectroscopy of 0.1 or more, A range of 1 or less;
Formula: Composition ratio of nitrogen atom / (composition ratio of oxygen atom + composition ratio of nitrogen atom).

According to one embodiment of the present invention, in the above method, the high nitrogen concentration region has a composition ratio of nitrogen atoms with respect to the sum of silicon atoms, oxygen atoms, and nitrogen atoms measured by X-ray photoelectron spectroscopy of 0.1. The range is 0.5 or less;
Formula: Composition ratio of nitrogen atom / (composition ratio of silicon atom + composition ratio of oxygen atom + composition ratio of nitrogen atom).

  According to one embodiment of the present invention, in the method, the energy beam irradiation in the step of forming the silicon-containing film is plasma irradiation or ultraviolet irradiation.

  According to an embodiment of the present invention, in the method, the plasma irradiation or the ultraviolet irradiation uses an inert gas, a rare gas, or a reducing gas as a gas species.

  According to an embodiment of the present invention, in the method, nitrogen gas, argon gas, helium gas, hydrogen gas, or a mixed gas thereof is used as the gas species.

  According to an embodiment of the present invention, in the method, the plasma irradiation or ultraviolet irradiation is performed under vacuum.

  According to an embodiment of the present invention, in the method, the plasma irradiation or ultraviolet irradiation is performed under normal pressure.

  According to an embodiment of the present invention, in the method, the polysilazane film is at least one selected from the group consisting of perhydropolysilazane, organopolysilazane, and derivatives thereof.

According to the present invention, there is provided a gas barrier laminate comprising a base material and a silicon-containing film formed on the base material, the silicon-containing film having a high nitrogen concentration region, The concentration region consists of at least silicon atom and nitrogen atom, or silicon atom, nitrogen atom and oxygen atom, and the composition ratio of nitrogen atom to all atoms measured by X-ray photoelectron spectroscopy is 0.1 or more in the following formula, A gas barrier laminate is provided, characterized in that it is in the range of 1 or less;
Formula: Composition ratio of nitrogen atom / (composition ratio of oxygen atom + composition ratio of nitrogen atom).

  According to the present invention, the polysilazane film added with the transition metal compound formed on the substrate is irradiated with energy rays, and the refractive index of the high nitrogen concentration region formed by modifying at least a part of the film is 1. A high-refractive-index film having a region of .55 or more is provided.

  In the laminate of the present invention, a polysilazane film to which a transition metal compound is added is irradiated with energy rays, and at least part of the film is modified to form silicon atoms and nitrogen atoms, or silicon atoms, nitrogen atoms, and oxygen. Since it has a nitrogen high concentration region composed of atoms, it has a high refractive index and is excellent in scratch resistance, transparency, and adhesion to a substrate. Furthermore, the laminate of the present invention can be used as a high refractive index film having excellent productivity and excellent stability of the above characteristics.

  In addition, the laminate of the present invention is superior in gas barrier properties such as water vapor barrier properties and oxygen barrier properties and scratch resistance as compared with gas barrier films as in the prior art.

Moreover, according to the manufacturing method of the laminated body of this invention, since there is little influence with respect to the precision of an optical member, the laminated body suitable for an optical use can be manufactured. Furthermore, the manufacturing method of the laminated body of this invention is a simple method, and is excellent in productivity, and is excellent also in the controllability of a refractive index.
Moreover, the laminated body of this invention can react in a short time compared with the non-added thing by adding a transition metal compound to polysilazane.

FIG. 1 is a process cross-sectional view illustrating a method for manufacturing a laminate according to the present invention. FIG. 2 is a cross-sectional view showing another aspect of the laminate according to the present invention. FIG. 3 is a cross-sectional view showing another aspect of the laminate according to the present invention.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same reference numerals are given to the same components, and the description will be omitted as appropriate.

  The laminated body 10 of this embodiment is provided with the base material 12 and the silicon-containing film | membrane 16 formed on the base material 12, as shown in FIG.1 (b). The silicon-containing film 16 has a high nitrogen concentration region 18 composed of silicon atoms and nitrogen atoms, or silicon atoms, nitrogen atoms, and oxygen atoms. The high nitrogen concentration region 18 is formed by irradiating the polysilazane film 14 formed on the substrate 12 with energy rays (FIG. 1A) and modifying at least a part of the polysilazane film 14.

Hereinafter, each component of the laminated body 10 of this invention is demonstrated.
(Base material)
Examples of materials that can be used as the substrate 12 include metal substrates such as silicon, glass substrates, ceramic substrates, and resin films. In the present embodiment, a resin film is used as the substrate 12.

Examples of the resin film include polyolefins such as polyethylene, polypropylene, and polybutene; cyclic olefin polymers such as Apel (registered trademark); polyvinyl alcohol; ethylene-vinyl alcohol copolymer; polystyrene; polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and the like. Polyesters; polyamides such as nylon-6 and nylon-11; polycarbonates; polyvinyl chloride; polyvinylidene chloride; polyimides; polyether sulfone; polyacrylic; polyarylate; Two or more types can be used in combination.
Moreover, the thickness of the base material 12 can be suitably selected according to the use.

(Silicon-containing film)
The silicon-containing film 16 irradiates energy in an atmosphere substantially free of oxygen or water vapor to the polysilazane film 14 added with the transition metal compound formed on the substrate 12, and at least a part of the polysilazane film 14 is formed. It is obtained by denaturing to form a nitrogen high concentration region 18. Accordingly, the silicon-containing film 16 has a high nitrogen concentration region 18 in the vicinity of the upper surface 16a (FIG. 1B). In this embodiment, “in the vicinity of the upper surface 16a” means a region having a depth of 50 nm downward from the upper surface 16a of the silicon-containing film 16, preferably a region having a depth of 30 nm downward from the upper surface 16a.

Here, the nitrogen high concentration region in the present specification refers to a region where the composition ratio of nitrogen atoms represented by the following formula is 0.1 or more and 0.5 or less;
Composition ratio of nitrogen atom / (composition ratio of silicon atom + composition ratio of oxygen atom + composition ratio of nitrogen atom).
The high nitrogen concentration region 18 preferably has a thickness of 0.001 μm to 0.2 μm, more preferably 0.01 μm to 0.1 μm.

  The silicon-containing film 16 having the high nitrogen concentration region 18 preferably has a thickness of 0.002 μm to 2.0 μm, more preferably 0.05 μm to 1.0 μm.

The silicon-containing film 16 of the present invention has a high nitrogen concentration region 18 formed by irradiating the polysilazane film 14 to which a transition metal compound is added with an energy beam in an atmosphere substantially free of oxygen or water vapor. Portions other than the high nitrogen concentration region 18 in the silicon-containing film 16 can react with water vapor that has permeated from the resin base material side after irradiation with energy rays, and can change to silicon oxide.
That is, the silicon-containing film 16 is composed of a high nitrogen concentration region 18 and a silicon oxide region. Due to the configuration of this high nitrogen concentration region / silicon oxide / resin base material, the silicon-containing film 16 has mechanical properties such as gas barrier properties such as oxygen barrier properties and water vapor barrier properties and hard coat properties such as SiO ₂ and Si ₃ N _4. It is superior to single layer films such as.

The silicon-containing film 16 is preferably made of SiO ₂ , SiNH ₃ , SiO _x N _y or the like.
In the present embodiment, the silicon-containing film 16 has a film thickness of 0.3 μm, and the high nitrogen concentration region 18 is formed over the entire upper surface 16 a of the silicon-containing film 16. The high concentration region 18 may be formed in a part near the upper surface of the silicon-containing film 16.

  Also, the nitrogen high concentration region 18 may be formed over the entire silicon-containing film 16. In this case, the composition of the silicon-containing film 16 is the same as that of the high nitrogen concentration region 18.

The high nitrogen concentration region 18 includes at least silicon atoms and nitrogen atoms, or includes at least silicon atoms, nitrogen atoms, and oxygen atoms. In the present embodiment, the high nitrogen concentration region 18 is composed of Si ₃ N ₄ , SiO _x N _y, or the like.

Further, the composition ratio of nitrogen atoms to all atoms measured by X-ray photoelectron spectroscopy in the high nitrogen concentration region 18 is in the range of 0.1 or more and 1 or less, preferably 0.14 or more and 1 or less in the following formula. is there.
Formula: Composition ratio of nitrogen atom / (composition ratio of oxygen atom + composition ratio of nitrogen atom).

Alternatively, in the high nitrogen concentration region 18, the composition ratio of the nitrogen atom to the total of silicon atoms, oxygen atoms and nitrogen atoms, measured by X-ray photoelectron spectroscopy, is 0.1 or more and 0.5 or less, preferably in the following formula: Is 0.1 or more and 0.4 or less.
Formula: Composition ratio of nitrogen atom / (composition ratio of silicon atom + composition ratio of oxygen atom + composition ratio of nitrogen atom)
The laminate 10 having the nitrogen high concentration region 18 having such a composition is particularly excellent in mechanical properties such as gas barrier properties such as oxygen barrier properties and water vapor barrier properties, and scratch resistance. That is, by having the nitrogen high-concentration region 18 having such a composition, the laminate 10 is excellent in a balance between improving barrier properties and improving mechanical properties.

Further, from the viewpoint of improving gas barrier properties, the composition ratio of nitrogen atoms to all atoms measured by X-ray photoelectron spectroscopy in the silicon-containing film 16 is higher on the upper surface 16a side of the silicon-containing film than on the other surface side. Is preferred.
Note that the atomic composition gradually changes between the silicon-containing film 16 and the high nitrogen concentration region 18. Since the composition continuously changes in this way, the barrier properties are improved and the mechanical properties are also improved.

<Method for producing laminate>
The manufacturing method of the laminated body 10 of this embodiment includes the following processes. Hereinafter, it demonstrates using drawing.
(A) The process of apply | coating the polysilazane containing liquid which added the transition metal compound on the base material 12, and forming a coating film.
(B) A step of drying the coating film in a low oxygen / low moisture concentration atmosphere to form a polysilazane film 14.
(C) The polysilazane film 14 is irradiated with energy rays in an atmosphere substantially free of oxygen or water vapor to modify at least a part of the polysilazane film 14 to form the silicon-containing film 16 including the high nitrogen concentration region 18. Step (FIGS. 1A and 1B).

[Step (a)]
In the step (a), a coating film containing polysilazane added with a transition metal compound is formed on the substrate 12.
Although it does not specifically limit as a method of forming a coating film, It is preferable to form by a wet method, and the method of apply | coating a polysilazane containing liquid is specifically mentioned.

  As the polysilazane, one or a combination of two or more selected from perhydropolysilazane, organopolysilazane, and derivatives thereof can be used. Examples of the derivative include perhydropolysilazane or organopolysilazane in which part or all of hydrogen is substituted with an organic group such as an alkyl group or an oxygen atom.

In this embodiment, it is preferable to use perhydropolysilazane represented by H ₃ Si (NHSiH ₂ ) _n NHSiH ₃ , but organopolysilazane in which part or all of hydrogen is substituted with an organic group such as an alkyl group may be used. . Moreover, you may use by a single composition and may mix and use two or more components.
A transition metal compound acts on the Si—H bond of polysilazane and activates the bonded state, thereby facilitating the reaction of polysilazane by energy beam irradiation. As a result, by adding the transition metal compound, a high effect can be expected with a short irradiation.

As the transition metal species of the above transition metal compounds, platinum (Pt), ruthenium (Ru), rhodium (Rh), iridium (Ir), iron (Fe), osmium (Os), cobalt (Co), palladium (Pd ), Nickel (Ni), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), molybdenum (Mo), tungsten (W), niobium (Nb), tantalum (Ta), zirconium (Zr) ), Hafnium (Hf), scandium (Sc), yttria (Y), lanthanum (La), rhenium (Re), or a mixture thereof.
As the transition metal compound, a transition metal halide, a complex, a transition metal salt, or a transition metal oxide is used as the transition metal compound.

The halide is a compound in which the transition metal is combined with chlorine (Cl), bromine (Br), iodine (I), or fluorine (F).
All of the above transition metal halides can be used effectively, but more preferably, chloroplatinic acid (H ₂ PtCl ₆ .nH ₂ O), PtCl ₂ , PtCl ₄ , PtCl ₂ (NH ₃ ) ₂ , Na ₂ (PtCl ₄ ). nH ₂ O, [PtCl (cyclohexane) ₂ ] (μ-Cl) ₂ , RhCl ₃ , Tris (dibutylsulfide) RhCl ₃ , (NH ₄ ) ₃ [RhCl ₆ ], RhI ₃ , (NH ₃ ) ₆ RhCl _{3 3} , [Ru (p-cymeme) Cl ₂ ] ₂ , [Ru (benzone) _{Cl 2] 2, (NH 4} ) 2 RuCl 6, (NH 3) 4 [RuCl 4 (H 2 O)] 2 (μ-N), Ni (triphenylphosphine) 3 Br 2, Mn (CO) 5 Br, IrCl ₃ , (NH ₄ ) ₂ IrCl ₆ , FeCl ₃ , PdCl ₂ .2H ₂ O, NiCl ₂ , TiCl ₄ , OsCl ₃ , (NH ₄ ) ₂ OsCl ₆ , W (cyclopentadiene) ₂ Cl ₂ , and mixtures thereof It is done.

Examples of the complex include an olefin complex, a cyclic olefin complex, a vinyl siloxane complex, a phosphine complex, a phosphite complex, a carbon monoxide complex (CO), an amine complex, and a nitrile complex. Conventionally, it is used mainly as a catalyst for the reaction between SiH groups and organic substances having a vinyl group and the like, and is known to facilitate the dissociation of Si—H bonds. In the technique of the present invention, the addition can facilitate the reaction of polysilazane by irradiation with energy rays. Any transition metal complex similar to the above can be used, but more preferably, Pt-1,3-divinyl-1,1,3,3-tetramethyldisiloxane (Pt [CH ₂ ═CH (methyl) Si] ₂ O ), Pt (CO) (CH ₂ ═CH (methyl) SiO) ₄ , Pt [CH ₂ ═CH (methyl) SiO] ₄ , Pt (triphenylphosphine) ₂ Cl ₂ , Rh (cycloclotadiene) Cl ₂ , [Rh (cycle) _{)] 2 (μ-Cl)} 2, Rh (acethylacetonato) (CO) 2, Rh (triphenylphosphine) 3 Cl, Rh (triphenylphosphine) 2 Cl 2, [(bicyclo [2.2.1] he _{ta-2,5-diene) RhCl]} 2, Rh (acethylacetonato) (CO) (triphenylphosphine), Rh (acethylacetonato) (cyclooctadiene), Rh (CO) (triphenylphosphine) 2 Cl, RhH (CO) (triphenylphosphine) 3, _{[RhCl (pentametylcyclopentadienyl)] 2 (} μ-Cl) 2, Rh 6 (CO) 16, Ru (triphenylphosphine) 3 Cl 2, [RuCl 2 (CO) 3] 2, [Benzylidene-bis (tricyclophosophine)] RuCl 2, _{ru 3 (CO) 12, [} (2-Methylallyl) PdCl] 2 NaHRu _{3 (CO) 11}
(Triphenylphosphine) ₃ RuH ₂ (CO), Ru (cyclooctadiene) Cl ₂ ] n, (Acenaphthylene) Ru ₃ (CO) ₇ , [RuCl (p-cymeme)] ₂ (μ-Cl) ₂ , (Pentamethydivalent) _{cyclooctadiene) Cl, Cr (CO)} 6, Zr (cyclopentadiene) Cl 3, Zr (cyclopentadiene) 2 Cl 2, Zr (cyclopentadiene) 2 HCl, (Pentametylcyclopentadiene) 2 ZrCl 2, Mo (CO) 6, Mo (cyclopentadiene) 2 Cl _{2
Mo (cyclopentadiene) Cl 4, [} (Pentametylcyclopentadiene) Mo (CO) 3] 2, Nb (cyclopentadiene) Cl 4, Nb (cyclopentadiene) 2 Cl 2, Nb (triphenylphosphine) 4, Pd (triphenylphosphine) 2 Cl 2, Pd ( _{triphenylphosphine) 4, (Pentametylcyclopentadiene) 2} HfCl 2, Hf (cyclopentadiene) Cl 3, (Pentametylcyclopentadiene) HfCl 3, Ir (CO) (triphenylphosphine) 2 Cl, Ir 4 (CO) 12, IrH (triphenylphosph _{ne) 3 Cl, [IrCl (} pentametylcyclopentadiene)] 2 (μ-Cl) 2, [Ir (cyclooctadiene)] 2 (μ-Cl) 2, (Pentametylcyclopentadiene) TaCl 4, (Pentametylcyclopentadiene) 2 Co, [(Pentametylcyclopentadiene) Co _{(CO) 2] 2, La} (cyclooctadiene) 3, Ni (triphenylphosphine) 3 Cl 2, Ni (triphenylphosphine) 3 (CO) 2, Ni (cyclopentadien) 2, Mn 2 (CO) 10, Mn (cyclopentadien) (CO ) _3, Mn (cyclopentadie _{) 2, Mn (pentametylcyclopentadiene) 2} , Ti (benzene) 2 Cl 2, Fe (CO) 5, Fe 2 (CO) 9, [Fe (cyclopentadien) (CO) 2] 2, Os 3 (CO) 12, Re ₂ (CO) ₁₀ , Re (CO) ₅ Cl, Re (CO) ₅ Br, Re (cyclopentadiene) (CO) ₃ , W (CO) ₆ , W (cyclopentadiene) (CO) ₃ , Sc (cyclopentadiene) ₃ , V (CO) ₆ , V (cyclopentadiene) (CO) ₄ , Y [N, N-bis (trimethylsilyl) amide] ₃ , Y (cyclopentadiene) ₃ , a mixture thereof, and the like can be given.

The transition metal salts include tetrafluoroboric acid (BF ₄ ) salt, hexafluorophosphoric acid (PF ₆ ) salt, hexafluoroantimonate, tetrakis (perfluorophenyl) borate, perchlorate and trifluoro It is a methyl sulfonic acid (CF ₃ SO ₃ ) salt. Can be used as long as a transition metal salt like above, more _{preferably, Rh (cyclooctadiene) 2 BF 4} , Pentametylcyclopentadienyltris (acetonitrile) RuPF 6, (Pentametylcyclopentadiene) 2 CoPF 6, La (CF 3 SO 3) 3, Sc (CF ₃ SO ₃ ) ₃
And a mixture thereof.

The transition metal oxide is a compound in which one or more oxygen atoms are bonded to the transition metal.

The transition metal compound / polysilazane weight ratio is preferably 0.0001 to 1.0, more preferably 0.001 to 0.5, and even more preferably 0.01 to 0.2.

  Examples of the solvent include aromatic compounds such as benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, and triethylbenzene; n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, and i-heptane. , N-octane, i-octane, n-nonane, i-nonane, n-decane, i-decane and other saturated hydrocarbon compounds; ethylcyclohexane, methylcyclohexane, cyclohexane, cyclohexene, p-menthane, decahydronaphthalene, dipentene Ethers such as dipropyl ether, dibutyl ether, MTBE (methyl tertiary butyl ether) and tetrahydroxyfuran; ketones such as MIBK (methyl isobutyl ketone), methylene chloride, carbon tetrachloride and the like. May be mixed it may be used in.

  As a method for applying the polysilazane-containing liquid to the substrate, a known application method can be applied, and is not particularly limited. For example, a bar coating method, a roll coating method, a gravure coating method, a spray coating method, an air knife Examples thereof include a coating method, a spin coating method, and a dip coating method.

  According to the method of the present embodiment, unlike the method described in Patent Document 3, it is not necessary to fire the polysilazane film at a high temperature, so that the base material itself is not exposed to a high temperature. Therefore, the silicon-containing film 16 of this embodiment can be directly provided on the surface of an optical member that requires precision. Note that the silicon-containing film 16 may be formed on the surface of the substrate 12 and then peeled off from the substrate 12 for use.

  When a resin film is used as the substrate 12, the surface of the resin film can be subjected to surface treatment such as ultraviolet ozone treatment, corona treatment, arc treatment, or plasma treatment before applying the polysilazane-containing liquid. For example, when a film made of polyolefin or a cyclic olefin polymer is used as the resin film, the adhesion with the polysilazane film is improved by these surface treatments.

[Step (b)]
In step (b), the coating film containing polysilazane formed in step (a) is dried in a low oxygen / low moisture concentration atmosphere to form polysilazane film 14.

  In the drying treatment in the step (b), the oxygen concentration is 20% (200,000 ppm) or less, preferably 2% (20,000 ppm), more preferably 0.5% (5,000 ppm) or less. It is preferable to carry out in a low oxygen / low moisture concentration atmosphere where the humidity is in the range of 70% or less, preferably 50% or less, and more preferably 40% or less. Note that the numerical range of the oxygen concentration and the numerical range of the relative humidity can be appropriately combined.

  By performing the drying process in such a low water vapor concentration atmosphere, it is possible to more effectively suppress the polysilazane film 14 from changing to silicon oxide (silica), and the gas barrier property and refraction of the silicon-containing film 16 can be suppressed. The rate can be controlled effectively.

  The drying process in the step (b) can be performed in an oven filled with an inert gas such as nitrogen or argon gas or dry air, and the drying condition varies depending on the thickness of the polysilazane film 14. In an embodiment, it is 1 to 10 minutes at 50 to 120 ° C.

  When the above-described drying treatment is performed in a low oxygen / water vapor concentration atmosphere, it is necessary to form a high nitrogen concentration region composed of silicon atoms, nitrogen atoms, and oxygen atoms in the silicon-containing film due to dissolved oxygen and moisture in the solvent. An oxygen atom is introduced. According to elemental composition ratio analysis of X-ray photoelectron spectroscopy, the ratio of oxygen atoms to all atoms in the silicon-containing film is 60 atom% or less, preferably 0 to 40 atom%, more preferably 0 to 30 atom%. If the silicon-containing film 16 and the high nitrogen concentration region 18 do not contain oxygen atoms, it is necessary to remove dissolved oxygen and moisture in the solvent.

[Step (c)]
In the step (c), the polysilazane film 14 is irradiated with energy rays in an atmosphere substantially free of oxygen or water vapor to modify at least part of the polysilazane film 14 and contain silicon containing the high nitrogen concentration region 18. A film 16 is formed. Examples of energy beam irradiation include plasma treatment and ultraviolet treatment, and a combination of these treatments can also be used.
The energy ray irradiation preferably has a light wavelength of 230 nm or less, which is the absorption wavelength region of polysilazane. More preferably, the energy ray has a light wavelength of 30 to 230 nm.

  In this specification, the “atmosphere substantially free of oxygen or water vapor” means that oxygen and / or water vapor is not present at all, or the oxygen concentration is 10% (100,000 ppm) or less, preferably 5% (50000 ppm). ), More preferably, oxygen concentration is 1% (10000 ppm) or less, more preferably, oxygen concentration is 0.1% (1000 ppm) or less, more preferably 0.01% (100 ppm) or less, or relative humidity is 10 % Or less, preferably 5% or less relative humidity, more preferably 1% or less relative humidity, and still more preferably 0.1% or less relative humidity. In addition, the water vapor concentration (water vapor partial pressure / atmospheric pressure at a room temperature of 23 ° C.) is 2800 ppm or less, more preferably 1400 ppm, further preferably 280 ppm, and further preferably 28 ppm or less.

Energy irradiation can be performed in a pressure range of vacuum to atmospheric pressure.
In the step (c), the polysilazane film 14 formed on the substrate 12 is irradiated with energy rays, so that the influence on the characteristics of the substrate 12 is small. Even when an optical member is used as the base material 12, the silicon-containing film 16 that can be used as a high-refractive index film suitable for optical applications can be manufactured because the influence on the precision is small. Furthermore, the manufacturing method including such steps is a simple method and excellent in productivity.

(Plasma treatment)
Examples of the plasma treatment include atmospheric pressure plasma treatment and vacuum plasma treatment.
The plasma treatment is performed by introducing the following gas species into the apparatus after making the atmosphere substantially free of oxygen or water vapor by reducing the pressure as described above. The gas species excited by the plasma emits energy and deactivates. At this time, ultraviolet rays having various wavelengths are emitted depending on the kind of the gas species and the gas pressure. As the gas species of the plasma emitting ultraviolet rays having a wavelength of 230 nm or less used in the present invention, one or more gases selected from N2, He, Ne, and Ar are mainly used. The main VUV wavelengths emitted by these gas atoms are 120 nm for N2, 58.4 nm for He, 73.6 nm and 74.4 nm for Ne, 104.8 nm and 106.7 nm for Ar. It is known that

  The plasma treatment can be performed under vacuum that is substantially free of oxygen or water vapor. In this specification, “vacuum” refers to a pressure of 100 Pa or less, preferably a pressure of 10 Pa or less. In the vacuum state in the apparatus, the pressure in the apparatus is reduced from atmospheric pressure (101325 Pa) to a pressure of 100 Pa or less, preferably 10 Pa or less using a vacuum pump, and then the gas described below is introduced to a pressure of 100 Pa or less. Can be obtained.

The oxygen concentration and water vapor concentration under vacuum are generally evaluated by the oxygen partial pressure and the water vapor partial pressure.
The vacuum plasma treatment is performed under the above-described vacuum under an oxygen partial pressure of 10 Pa or less (oxygen concentration 0.001% (10 ppm)) or less, preferably an oxygen partial pressure of 2 Pa or less (oxygen concentration 0.0002% (2 ppm)) or less. The concentration is 10 ppm or less, preferably 1 ppm or less.

Alternatively, the plasma treatment is preferably performed at normal pressure in the absence of oxygen and / or water vapor. Alternatively, the atmospheric pressure plasma treatment is performed with an oxygen concentration of 10% (100,000 ppm) or less, preferably an oxygen concentration of 5% (50000 ppm) or less, more preferably an oxygen concentration of 1% (10000 ppm) or less, more preferably an oxygen concentration of 0.1 % (1000 ppm) or less, more preferably 0.01% (100 ppm) or less, or a relative humidity of 10% or less, preferably a relative humidity of 5% or less, more preferably a relative humidity of 1% or less, more preferably, An atmosphere having a relative humidity of 0.1% or less. In addition, the water vapor concentration (water vapor partial pressure / atmospheric pressure at room temperature 23 ° C.) can be carried out in a low oxygen / low water vapor concentration atmosphere of 2800 ppm or less, more preferably 1400 ppm, more preferably 280 ppm, and even more preferably 28 ppm or less. .
The plasma treatment is also preferably performed in an inert gas or noble gas or reducing gas atmosphere (normal pressure).

  When the plasma treatment is performed in an atmosphere that does not satisfy the above conditions, the nitrogen high concentration region 18 of this embodiment is not formed, and silicon oxide (silica) or silanol groups are generated, so that a sufficient water vapor barrier property cannot be obtained. There is a case.

  Further, when plasma treatment is performed in an atmosphere that does not satisfy the above conditions, silicon oxide (silica) having a low refractive index of about 1.45 is generated in a large amount, so that a silicon-containing film 16 having a desired refractive index is obtained. There may not be.

  As the gas used for the plasma treatment, from the viewpoint of forming the nitrogen high concentration region 18 of the silicon-containing film 16, nitrogen gas that is an inert gas, argon gas that is a rare gas, helium gas, neon gas, krypton gas, xenon gas, and the like And hydrogen gas which is a reducing gas, ammonia gas and the like. More preferable gas includes argon gas, helium gas, nitrogen gas, hydrogen gas, or a mixed gas thereof.

  As the atmospheric pressure plasma treatment, a gas is passed between two electrodes, and the gas is converted into plasma and then irradiated onto the substrate, or a substrate 12 with a polysilazane film 14 irradiated between the two electrodes is disposed. For example, a method of generating plasma through the gas. In order to lower the oxygen / water vapor gas concentration in the processing atmosphere, the gas flow rate in the atmospheric pressure plasma treatment is preferably as high as possible, preferably 0.01 to 1000 L / min, more preferably 0.1 to 500 L / min. is there.

In the atmospheric pressure plasma treatment, the applied power (W), the unit area of the electrode (cm ²⁾ per preferably ^{0.0001W / cm 2 ~100W / cm 2} , more preferably 0.001W ^/ cm 2 ~50W ^/ cm ² . The moving speed of the base material 12 with the polysilazane film 14 in the atmospheric pressure plasma treatment is preferably 0.001 to 1000 m / min, and more preferably 0.001 to 500 m / min. The treatment temperature is room temperature to 200 ° C.

For vacuum plasma, a known electrode or waveguide is placed in a vacuum sealed system, and power such as direct current, alternating current, radio wave, or microwave is applied through the electrode or waveguide. Plasma can be generated. Power applied to the plasma treatment (W), the unit area of the electrode (cm ²⁾ per preferably ^{0.0001W / cm 2 ~100W / cm 2} , more preferably 0.001W ^/ cm ² ~50W ^/ cm 2 is there.
The degree of vacuum in the vacuum plasma treatment is preferably 1 Pa to 1000 Pa, more preferably 1 Pa to 500 Pa. The temperature of the vacuum plasma treatment is preferably room temperature to 500 ° C, and more preferably room temperature to 200 ° C in view of the influence on the substrate. The time for the vacuum plasma treatment is preferably 1 second to 60 minutes, more preferably 60 seconds to 20 minutes.

(UV treatment)
The ultraviolet treatment can be performed under atmospheric pressure or under vacuum. The lamp for generating light below a wavelength 200 nm, is obtained by utilizing argon and xenon, Ar + F2 mixed _gas, the excimer emission by F 2, Kr + Cl mixed gas. Argon excimer emission is 126 nm, xenon excimer emission is 172 nm, Ar + F ₂ mixed gas is 193 nm, F ₂ is 157 nm, and Kr + Cl mixed gas is 222 nm. These lamps or lasers can be used in an atmosphere substantially free of oxygen and water vapor, under atmospheric pressure, or under vacuum. Alternatively, the ultraviolet treatment is performed with an oxygen concentration of 10% (100,000 ppm) or less, preferably an oxygen concentration of 5% (50000 ppm) or less, more preferably an oxygen concentration of 1% (10000 ppm) or less, more preferably an oxygen concentration of 0.1%. (1000 ppm) or less, more preferably 0.01% (100 ppm) or less, or relative humidity 10% or less, preferably relative humidity 5% or less, more preferably relative humidity 1% or less, more preferably relative An atmosphere with a humidity of 0.1% or less. In addition, the water vapor concentration (water vapor partial pressure / atmospheric pressure at room temperature 23 ° C.) can be carried out in a low oxygen / low water vapor concentration atmosphere of 2800 ppm or less, more preferably 1400 ppm, more preferably 280 ppm, and even more preferably 28 ppm or less. .

When ultraviolet treatment is performed in an atmosphere that does not satisfy the above conditions, the high nitrogen concentration region 18 is not formed, and silicon oxide (silica) or silanol groups are generated, so that sufficient water vapor barrier properties may not be obtained. .
When an ultraviolet treatment is performed in an atmosphere that does not satisfy the above conditions, a silicon-containing film having a desired refractive index may not be obtained because a large amount of silicon oxide (silica) having a low refractive index of about 1.45 is generated. is there.

  The refractive index of the silicon-containing film 16 of this embodiment can be arbitrarily controlled in the range of 1.55 to 2.1 by changing the exposure amount, oxygen and water vapor concentration, and processing time in ultraviolet irradiation. is there.

  By performing the above process, the laminated body 10 of this embodiment can be manufactured. In the present embodiment, the following processing may be further performed on the silicon-containing film 16.

  By subjecting the silicon-containing film 16 modified by plasma treatment or ultraviolet treatment to further irradiation with active energy rays or heat treatment, the high nitrogen concentration region 18 in the silicon-containing film 16 can be increased.

  Examples of the active energy rays include microwaves, infrared rays, ultraviolet rays, and electron beams, and infrared rays, ultraviolet rays, and electron beams are preferable.

  Examples of the method for generating ultraviolet rays include methods using a low-pressure mercury lamp, excimer lamp, UV light laser, etc., as described above.

  Examples of the method for generating infrared rays include a method using an infrared radiator or an infrared ceramic heater. Also, when using an infrared radiator, depending on the wavelength used for infrared rays, a near-infrared radiator having an intensity peak at a wavelength of 1.3 μm, a mid-infrared radiator having an intensity peak at a wavelength of 2.5 μm, and a wavelength of 4.5 μm A far-infrared radiator having an intensity peak can be used.

For irradiation with active energy rays, it is preferable to use an infrared laser having a single spectrum. Specific examples of infrared lasers include gas chemical lasers such as HF, DF, HCl, DCl, HBr, and DBr, CO ₂ gas lasers, N ₂ O gas lasers, CO ₂ gas laser excited far infrared lasers (NH ₃ , CF ₄ , etc.), Pb (Cd) S, PbS (Se), Pb (Sn) Te, Pb (Sn) Se, and other compound semiconductor lasers (irradiation wavelength: 2.5 to 20 μm).

As mentioned above, although embodiment of this invention was described with reference to drawings, these are the illustrations of this invention, Various structures other than the above are also employable.
For example, the high nitrogen concentration region 18 may be provided in a part near the upper surface 16 a of the silicon containing film 16, and the entire silicon containing film 16 may be the high nitrogen concentration region 18.

Moreover, the vapor deposition film | membrane 20 may be provided on the upper surface 16a of the silicon-containing film | membrane 16 like the laminated body 10a of FIG. As yet another aspect, a vapor deposition film 20 may be provided between the substrate 12 and the silicon-containing film 16 as in the laminated body 10b shown in FIG.
The vapor deposition film 20 is obtained by at least one vapor deposition method of physical vapor deposition (PVD method) and chemical vapor deposition (CVD method).

  Since the surface of the silicon-containing film 16 having the high nitrogen concentration region 18 of the present embodiment is excellent in thermal stability and smoothness, the influence of the unevenness of the substrate surface and thermal expansion and contraction, which are problematic when the vapor deposition film 20 is produced, is small. A dense vapor deposition film 20 can be formed.

  In addition, when the vapor deposition film 20 is formed between the resin film (base material 12) and the silicon-containing film 16 having the high nitrogen concentration region 18, the silicon-containing film 16 has a defect site such as a pinhole in the vapor deposition film 20. Since it can be compensated, a higher gas barrier property can be exhibited than the silicon-containing film 16 or the vapor deposition film 20 of this embodiment.

  The vapor deposition film 20 used in the present embodiment is made of an inorganic compound. Specifically, selected from Si, Ta, Nb, Al, In, W, Sn, Zn, Ti, Cu, Ce, Ca, Na, B, Pb, Mg, P, Ba, Ge, Li, K, Zr One or more metal oxides or nitrides or oxynitrides as a main component.

  The formation method of a vapor deposition film layer is implement | achieved by means, such as a physical vapor deposition method (PVD method), a low temperature plasma vapor phase growth method (CVD method), ion plating, sputtering. The preferable film thickness of the vapor deposition film 20 is preferably in the range of 1 to 1000 nm, particularly in the range of 10 to 100 nm.

The silicon-containing film 16 formed by the method of this embodiment described above has a high nitrogen concentration region 18. The nitrogen high concentration region 18 has a high refractive index, and the refractive index is 1.55 or more, preferably 1.55 to 2.1, more preferably 1.58 to 2.1. Since the silicon-containing film of the present embodiment is entirely composed of the nitrogen high concentration region 18, the refractive index of the silicon-containing film 16 is in the above range.
The silicon-containing film 16 of the present embodiment has a high refractive index and exhibits sufficient scratch resistance even with a relatively thin coat film thickness. Furthermore, it is excellent in transparency and adhesion to the substrate.

  Therefore, the silicon-containing film 16 of the present embodiment includes, for example, various displays such as word processors, computers, and televisions, polarizing plates used in liquid crystal display devices, sunglasses lenses made of transparent plastics, lenses for glasses with degrees, contact lenses, It is also suitable for use as an optical lens such as a photochromic lens, a camera finder lens, a cover for various instruments, an optical member such as a window glass for automobiles, trains, etc., and a coating material for antireflection. it can.

  As mentioned above, although embodiment of this invention was described with reference to drawings, these are the illustrations of this invention, Various structures other than the above are also employable.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
In the following Examples 1-20 and Comparative Examples 1-16, the laminated body of this invention in the case of using as a gas-barrier laminated body is demonstrated.

  In Examples 1, 2, 11, 14, 17, and 18 and Comparative Examples 9, 11, and 13, the IR spectrum of the nitrogen high-concentration region having a thickness of 0.005 to 0.2 μm or less in the laminate was accurately obtained. In order to measure, a silicon substrate is used instead of a resin substrate as a substrate for IR spectrum measurement.

<Example 1>
In a polysilazane / xylene solution (NN110A-20, manufactured by AZ Electronic Materials Co., Ltd.), tris (dibutylsulfide) rhodium chloride [Tris (dibutylsulfide) RhCl ₃ , manufactured by Gelest, Inc.] was added to the polysilazane. 1 wt% was added, and dehydrated xylene was further added to prepare a 2 wt% xylene (dehydrated) solution.

This was spin-coated (10 s, 3000 rpm) on a silicon substrate (thickness: 530 μm, manufactured by Shin-Etsu Chemical Co., Ltd.) and dried at 80 ° C. for 10 minutes in a nitrogen atmosphere to produce a polysilazane film having a thickness of 0.025 μm. .
This polysilazane film was subjected to vacuum plasma treatment under the following conditions.

Vacuum plasma processing equipment: Utec Co., Ltd. Gas: Ar
Light wavelength: 104.8, 106.7 nm
Gas flow rate: 50 mL / min
Pressure: 19Pa
Temperature: Room temperature Applied power per electrode unit area: 1.3 W / cm 2
Frequency: 13.56MHz
Processing time: 30 seconds

<Example 2>
As in Example 1, 2 wt% polysilazane / xylene (dehydrated) solution added with a rhodium compound was bar-coated on a polyethylene terephthalate (PET) film (thickness 50 μm, “A4100”, manufactured by Toyobo Co., Ltd.). 1 to obtain a polysilazane film having a thickness of 0.3 μm.
Subsequently, vacuum plasma treatment was performed under the same conditions as in Example 1.

<Example 3>
As in Example 1, a 2 wt% polysilazane / xylene (dehydrated) solution added with a rhodium compound was spin-coated (10 s, 3000 rpm) on a silicon substrate (thickness: 530 μm, manufactured by Shin-Etsu Chemical Co., Ltd.). A polysilazane film having a thickness of 0.025 μm was produced by drying under conditions.
Further, the film was irradiated with ultraviolet rays (light wavelength: 172 nm) for 2 minutes using an excimer lamp (“UEP20B”, “UER-172B”, manufactured by USHIO INC.) Under a nitrogen atmosphere.

<Example 4>
As in Example 1, 2 wt% polysilazane / xylene (dehydrated) solution added with a rhodium compound was bar-coated on a polyethylene terephthalate (PET) film (thickness 50 μm, “A4100”, manufactured by Toyobo Co., Ltd.). 1 to obtain a polysilazane film having a thickness of 0.3 μm. Subsequently, ultraviolet rays (light wavelength: 172 nm) were irradiated for 2 minutes under the same conditions as in Example 3.

<Comparative Example 1>
A polyethylene terephthalate (PET) film (thickness 50 μm, “A4100”, manufactured by Toyobo Co., Ltd.) was bar-coated with a 2 wt% polysilazane / xylene (dehydrated) solution to which no transition metal compound was added. The polysilazane film having a thickness of 0.3 μm was produced by drying under the above conditions.
Subsequently, vacuum plasma treatment was performed under the same conditions as in Example 1.

<Comparative example 2>
A polyethylene terephthalate (PET) film (thickness 50 μm, “A4100”, manufactured by Toyobo Co., Ltd.) was bar-coated with a 2 wt% polysilazane / xylene (dehydrated) solution to which no transition metal compound was added. The polysilazane film having a thickness of 0.3 μm was produced by drying under the above conditions.
Subsequently, ultraviolet rays (light wavelength: 172 nm) were irradiated for 2 minutes under the same conditions as in Example 3.

<Film structure analysis / element composition ratio measurement 1>
The composition ratio of the film constituent elements in the film depth direction was measured using an X-ray photoelectron spectroscopy (XPS) apparatus (“ESCALAB220iXL”, manufactured by VG). (X-ray source Al-Kα, argon sputter, SiO ₂ conversion 0.05 nm / sputter second)

<Measurement of water vapor transmission rate>
It measured using the water vapor transmission rate measuring apparatus ("PERMATRAN3 / 31" by MOCON) using the isobaric method-infrared sensor method in 40 degreeC90% RH atmosphere. The lower limit of detection of this device is 0.01 g / m ² · day.

<Oxygen permeability measurement>
It measured using the oxygen permeability measuring apparatus ("OX-TRAN2 / 21" by MOCON) using the isobaric method-electrolytic electrode method in 23 degreeC90% RH atmosphere. The lower limit of detection of this device is 0.01 cc / m ² · day, atm.

<Oxygen concentration measurement>
The oxygen concentration of the outlet gas of the used apparatus was measured using an oxygen sensor (JKO-O2LJDII, manufactured by Zico Corporation). The results are shown in Table 2 as oxygen concentration (%).

<Water vapor concentration measurement>
The water vapor concentration (relative humidity) of the outlet gas of the apparatus used was measured using a thermohygrometer (TESTO625, manufactured by Testo Co., Ltd.). The results are shown in Table 2 as water vapor concentration (% RH).

   The ratio of oxygen atom to nitrogen atom [N / (O + N) ratio], the ratio of silicon atom to oxygen atom and nitrogen atom [N / (Si + O + N) ratio] is shown in Table 1. As shown in Table 1, in Examples 2 and 4, it was 0.5 or more, and the N / (Si + O + N) ratio was 0.1 or more.

  When transition metal compounds were added as in Examples 2 and 4, it was found that high oxygen / water vapor barrier properties were developed as shown in Table 2 by short-time plasma and ultraviolet irradiation. On the other hand, when the transition metal compounds of Comparative Examples 1 and 2 were not added, it was found that sufficient barrier properties could not be obtained by the treatment at the same time.

 The refractive index (at 590 nm) of Example 1 was 1.72, and Example 3 was 1.68, indicating a high refractive index.

Claims (35)

A laminate comprising a substrate and a silicon-containing film formed on the substrate,
The silicon-containing film has a high concentration region of nitrogen composed of silicon atoms and nitrogen atoms, or silicon atoms, nitrogen atoms and oxygen atoms,
In the high nitrogen concentration region, the polysilazane film containing a transition metal compound formed on the base material is irradiated with energy rays in an atmosphere substantially free of oxygen or water vapor to denature at least a part of the film. Formed by
Laminated body. 2. The nitrogen high concentration region according to claim 1, wherein the composition ratio of nitrogen atoms to all atoms represented by the following formula measured by X-ray photoelectron spectroscopy is in the range of 0.1 or more and 1 or less. Laminates;
Formula: Composition ratio of nitrogen atom / (composition ratio of oxygen atom + composition ratio of nitrogen atom). The nitrogen high-concentration region has a composition ratio of nitrogen atoms to a total of silicon atoms, oxygen atoms and nitrogen atoms represented by the following formula measured by X-ray photoelectron spectroscopy of 0.1 or more and 0.5 or less. The laminate according to claim 1, which is a range;
Formula: Composition ratio of nitrogen atom / (composition ratio of silicon atom + composition ratio of oxygen atom + composition ratio of nitrogen atom).   The laminate according to any one of claims 1 to 3, wherein the high nitrogen concentration region is formed over the entire surface of the silicon-containing film.   The laminate according to any one of claims 1 to 4, wherein the high nitrogen concentration region has a thickness of 0.001 µm to 0.2 µm.   The laminate according to claim 1, wherein a composition ratio of nitrogen atoms to all atoms measured by X-ray photoelectron spectroscopy in the silicon-containing film is higher on the upper surface side of the silicon-containing film than on the other surface side.   The laminate according to any one of claims 1 to 6, wherein the energy ray is light having a wavelength of 230 nm or less.   The laminated body according to claim 1, wherein the energy beam irradiation is performed by plasma irradiation or ultraviolet irradiation.   The laminated body according to claim 1, wherein the plasma irradiation or the ultraviolet irradiation uses an inert gas, a rare gas, or a reducing gas as an irradiation gas.   The laminate according to any one of claims 1 to 9, wherein nitrogen gas, argon gas, helium gas, hydrogen gas, or a mixed gas thereof is used as the gas species.   The laminate according to any one of claims 1 to 10, wherein the plasma irradiation or ultraviolet irradiation is performed under vacuum.   The laminate according to any one of claims 1 to 11, wherein the plasma irradiation or ultraviolet irradiation is performed under normal pressure.   The laminate according to any one of claims 1 to 12, wherein the polysilazane film is at least one selected from the group consisting of perhydropolysilazane, organopolysilazane, and derivatives thereof. The transition metal compound is platinum, ruthenium, rhodium, iridium, iron, osmium, cobalt, palladium, nickel, titanium, vanadium, chromium, manganese, molybdenum, tungsten, niobium, tantalum, zirconium, hafnium, scandium, yttria, lanthanum, The laminate according to any one of claims 1 to 13, which is a compound containing rhenium or a mixture thereof. The laminate according to any one of claims 1 to 14, wherein the transition metal compound is a halide or complex of a transition metal, a transition metal salt, or a transition metal oxide. The laminate according to claim 15, wherein the halogen of the halide is chlorine, bromine, iodine, or fluorine. The laminate according to claim 15, wherein the complex is an olefin complex, a cyclic olefin complex, a vinyl siloxane complex, a phosphine complex, a phosphite complex, a carbon monoxide complex, an amine complex, or a nitrile complex. The transition metal salt is tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, tetrakis (perfluorophenyl) borate, perchlorate and trifluoromethylsulfonate. 15. A laminate according to item 15. An optical member comprising the laminate according to claim 1. A gas barrier film comprising the laminate according to claim 1. Applying a polysilazane-containing liquid to which a transition metal compound is added on a substrate to form a coating film;
Drying the coating film in a low moisture concentration atmosphere to form a polysilazane film;
Nitrogen composed of silicon atoms and nitrogen atoms, or silicon atoms, nitrogen atoms, and oxygen atoms is modified by irradiating the polysilazane film with energy rays in an atmosphere substantially free of oxygen or water vapor to modify at least a part of the film. Forming a silicon-containing film including a high concentration region,
A manufacturing method of a layered product. The nitrogen high concentration region has a composition ratio of nitrogen atoms with respect to all atoms represented by the following formula measured by X-ray photoelectron spectroscopy in a range of 0.1 or more and 1 or less. Method;
Formula: Composition ratio of nitrogen atom / (composition ratio of oxygen atom + composition ratio of nitrogen atom). The nitrogen high-concentration region has a composition ratio of nitrogen atoms to a total of silicon atoms, oxygen atoms and nitrogen atoms represented by the following formula measured by X-ray photoelectron spectroscopy of 0.1 or more and 0.5 or less. 23. A method according to claim 21 to 22, wherein the method is a range;
Formula: Composition ratio of nitrogen atom / (composition ratio of silicon atom + composition ratio of oxygen atom + composition ratio of nitrogen atom). The laminate according to any one of claims 21 to 23, wherein the energy ray is light of 230 nm or less. The method according to any one of claims 21 to 24, wherein the energy ray irradiation in the step of forming the silicon-containing film is plasma irradiation or ultraviolet irradiation. The method according to claim 25, wherein the plasma irradiation or ultraviolet irradiation is performed in the presence of an inert gas, a rare gas, or a reducing gas as a gas species. 27. The method according to claim 26, wherein nitrogen gas, argon gas, helium gas, hydrogen gas, or a mixed gas thereof is used as the gas species. The method according to any one of claims 21 to 25, wherein the plasma irradiation or ultraviolet irradiation is performed under vacuum. The method according to any one of claims 21 to 25, wherein the plasma irradiation or ultraviolet irradiation is performed under normal pressure. 30. The method according to any one of claims 21 to 29, wherein the polysilazane film is at least one selected from the group consisting of perhydropolysilazane, organopolysilazane, and derivatives thereof. The transition metal compound is platinum, ruthenium, rhodium, iridium, iron, osmium, cobalt, palladium, nickel, titanium, vanadium, chromium, manganese, molybdenum, tungsten, niobium, tantalum, zirconium, hafnium, scandium, yttria, lanthanum, The method according to any one of claims 21 to 30, which is a compound containing rhenium or a mixture thereof. The method according to any one of claims 21 to 31, wherein the transition metal compound is a halide, a complex, a transition metal salt, or a transition metal oxide. The method according to claim 32, wherein the halogen of the halide is chlorine, bromine, iodine, or fluorine. The method according to claim 32, wherein the complex is an olefin complex, a cyclic olefin complex, a vinyl siloxane complex, a phosphine complex, a phosphite complex, a carbon monoxide complex, an amine complex, or a nitrile complex. The transition metal salt is tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, tetrakis (perfluorophenyl) borate, perchlorate and trifluoromethylsulfonate. 33. The method according to 32.