JPH07126396A - Organic/inorganic silicon polymer and its production - Google Patents

Abstract

PURPOSE:To obtain a silicon polymer having both the characteristics of an inorganic material and those of an organic material by covalently bonding an organic polymer layer to a crystalline laminate structure composed of a tetrahedral structure having silicon or germanium as the central atoms and an octahedral structure having a metal as the central atom. CONSTITUTION:This silicon polymer comprises (A) a crystalline laminate structure composed of a tetrahedral structure having at least either Si or Ge or a combination thereof with at least one member selected from among Al, Fe and P as the central atom and an octahedral structure having at least one member selected from among Mg, Al, Ni, Co, Cu, Mn, Fe, Li, V and Zr as the central atom and (B) an organic polymer layer formed by convalently bonding organic groups each having a polymerizable reactive group to part of the Si or Ge atoms as the central atoms of the tetrahedral structure, and bonding the reactive groups of the organic groups to an organic compound polymerizable with the reactive group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic-inorganic polymer which can be used as a coating material, a filler for a resin or various functional materials, and a method for producing the same.

[0002]

2. Description of the Related Art Generally, a main component material such as a coating material or a molded product or an inorganic material as a filler has characteristics such as high hardness and heat resistance. However, it is necessary to form a dense solid phase rapidly from a liquid phase or a solution. Requires heating and firing. In addition, these inorganic materials have poor affinity with organic solvents and organic phases. On the other hand, organic materials have characteristics such as flexibility and rapid film formation at room temperature, but have the drawback of being poor in hardness and heat resistance. For this reason, conventionally, an inorganic-organic hybrid material having the above-mentioned characteristics of an inorganic material and an organic material in combination, and further limiting the above-mentioned drawbacks as much as possible, and such a material are provided under an easy condition such as a temperature near room temperature. It is desired to develop an effective manufacturing method that can be rapidly manufactured below.

As a technique for answering such a request,
JP-A-1-108272 discloses an inorganic-organic hybrid coating material. This paint is an abrasion resistant coating material consisting of a partial hydrolyzate of epoxysilane, a carbonyl group-containing compound and a reaction product of a non-silane based aliphatic polyamine. However, in this case, the inorganic structure in the coating film is limited to one portion introduced into the organic polymer, and further, the inorganic structure portion may grow or form a film in the coating film due to an organic reaction at around room temperature. Since it does not exist, the characteristics of the inorganic material cannot be sufficiently expressed, and a dramatic improvement cannot be expected as compared with the organic polymer.

Next, Japanese Patent Application Laid-Open No. 62-
Japanese Patent No. 74957 discloses an organized clay (an intercalation compound in which an organic compound is introduced between layers of a layered clay mineral by an ion exchange reaction), which is an inorganic-organic hybrid material, although the field of application does not correspond to that of the present invention. Has been done. Although such an organoclay is extremely effective in achieving the object of the invention according to the above application, it is not always sufficient for application to the field intended by the present invention.

Since the above-mentioned organized clay introduces the organic matter between the layers of the clay mineral by an ion exchange reaction, organic matter which is difficult to be ionized, for example, those containing an epoxy moiety and those having an amino group at the end cannot be introduced. In addition, organic matter can be introduced only up to the ion exchange capacity specific to clay minerals. Further, since the clay mineral and the organic substance are bound by an ionic bond, the ionic bond may be broken and the organic substance may be liberated by an operation in practical use.

[0006]

DISCLOSURE OF THE INVENTION The present invention is a polymer in which an inorganic part and an organic part are firmly bonded to each other to form a robust and dense solid phase, and the ratio of the inorganic part and the organic part can be controlled. An object is to provide an easy polymer and a method for producing the same.

[0007]

The present inventors have previously filed an application for a novel silicon-based layered polymer having a polymerizable organic side chain on the surface. When the organic side chain of the silicon-based novel layered polymer has the same type of reactive groups such as acryl, epoxy and vinyl groups, a polymer capable of being shaped can be obtained by the polymerization reaction of the reactive groups. This polymer is superior in heat resistance and hardness to a polymer not containing an inorganic component and has flexibility not possessed by an inorganic material, but it may be required to have higher flexibility depending on the application. The present invention has completed the present invention by discovering that the desired physical properties can be imparted by controlling the ratio of the inorganic part and the organic part by binding an organic molecule to the above polymer.

The first organic-inorganic polymer of the present invention comprises at least one atom selected from silicon and Ge or at least one atom selected from Al, Fe and P.
Tetrahedral structure having an atom replaced by a seed atom as a central atom and Mg, Al, Ni, Co, Cu, Mn, Fe, L
A crystalline laminated structure having an octahedral surface structure having at least one metal selected from i, V and Zr as a central atom, and an organic polymer layer covalently bonded to the laminated structure. Which is a central atom of the tetrahedral surface structure forming the laminated structure, at least a part of at least one atom selected from Ge and Ge has a polymerizable reactive group. It is characterized in that it is bound to an organic group it has by a covalent bond, and the reactive group of the organic group is bound to an organic compound which undergoes a polymerization reaction with the reactive group to form an organic polymer layer.

The second method for producing an organic-inorganic polymer of the present invention comprises a mixing step of mixing the following a), b) and c) to form a mixed solution (having a crystalline layered structure to be produced). Silicon, which is the central atom of the tetrahedral structure of the organic polymer, G
When a part of at least one atom selected from e is replaced by P, the following d) is added. Further, at least one selected from silicon and Ge, which are the central atoms of the tetrahedral surface structure of the organic polymer having a crystalline layered structure to be produced.
When some of the seed atoms are not covalently bonded to the organic group having a polymerizable reactive group, the following e) is added. ), An alkali is added to the mixed solution to adjust the pH of the mixed solution to be alkaline, or as it is, or by aging, a) silicon in the compound, at least one atom selected from Ge, or a part of the atom. B) a tetrahedral structure having an atom substituted by at least one atom selected from P in the compound, Al, Fe and d) of the compound, and b) Mg, Al, Ni, C in the compound
Laminated structure forming step of forming a crystalline laminated structure having an octahedral surface structure having at least one metal selected from o, Cu, Mn, Fe, Li, V and Zr as a central atom, and the laminated structure Silicon, which is the central atom of the tetrahedral structure of the body, Ge
An organic group having a reactive group capable of being polymerized by a covalent bond on at least a part of at least one atom selected from the group consisting of an organic compound capable of reacting with the organic group and forming a polymer by itself. A polymer forming step of mixing and copolymerizing an organic group and an organic compound to form a polymer layer of the organic compound in the laminated structure.

According to the first aspect of the present invention, at least one atom selected from silicon and Ge forming a central atom of a tetrahedral surface structure and Mg, A constituting a central atom of an octahedral surface structure.
At least one metal atom selected from 1, Ni, Co, Cu, Mn, Fe, Li, V, and Zr forms a crystalline laminated structure. This laminated structure includes a so-called 2: 1 type structure in which tetrahedral surfaces are formed on both sides of an octahedral surface, and a so-called 1: 1 type structure in which tetrahedral surfaces are formed on one side of the octahedral surface. There is. The 2: 1 type structure is more preferable when it is desired to include a large amount of organic groups or to improve the bonding strength between the organic groups.

The 2: 1 type or 1: 1 type structure can be formed by adjusting the ratio of the atoms forming the tetrahedral surface to the atoms forming the octahedral surface. Four
A part of at least one of silicon and Ge, which are the central atoms of the facet, can be replaced with one or more atoms selected from Al, Fe and P. These A
l, Fe and P can be easily introduced by central atom substitution with silicon or Ge.

Part or all of the atoms forming the tetrahedral surface structure are covalently bonded to an organic group having a polymerizable reactive group. The maximum amount of organic groups that can be introduced is 4
It is possible to introduce as much as 1 to 3 atoms per one central atom of the face piece. This organic group has a reactive group that is bonded to the reactive group of the organic group, and is itself copolymerized with an organic compound capable of polymerizing to form an organic part of the organic-inorganic polymer. . Therefore, the organicity and inorganicity of the organic-inorganic polymer can be changed by adjusting the compounding ratio of the organic compound to the laminated structure.

Therefore, when this organic-inorganic polymer is used as, for example, a coating material, the organic property can be enhanced to secure the characteristics of the organic material such as flexibility and rapid film formation at room temperature, and It is possible to secure the affinity with an organic solvent or an organic phase when it is used as a filler by increasing the inorganicity.
Furthermore, in this organic-inorganic polymer, the organic group is covalently bonded to the atoms forming the tetrahedral surface structure, so that the bond between both the inorganic part and the organic part is robust, and as a coating material or filler. Even if the composition is mixed with other composition components and various operations for practical use are performed, the bond between them is not impaired.

Further, since this organic-inorganic polymer has more surface organic groups than conventional clay hybrid composite materials and the like, the addition of a very small amount of laminated structure makes the organic compound polymer heat resistant. It is possible to improve the physical properties such as. The additive amount of the laminated structure exceeds 0% in principle and 100
Useful polymer moldings can be obtained with additions of less than%, but 0.05 to 85% by weight is desirable.

Among the organic-inorganic polymers of the present invention, the following ones can be easily synthesized from inexpensive organoalkoxysilanes used as silane coupling agents and may have highly reactive organic side chains. desirable.
It has an organic side chain having an amino, epoxy, mercapto, acryl, methacryl or vinyl group, and has a layer with a structure in which oxygen is tetrahedrally coordinated around Si with covalently bonded Si as the center, and Mg as the center. It is an organosilicon polymer having a crystalline laminated structure in which atoms are formed and a layer having a structure in which oxygen is octahedrally coordinated is laminated around the atoms.

The manufacturing method of the second invention of the present application comprises: a mixing step of mixing the respective components; a layered structure forming step of adjusting the pH of the mixture to form a crystalline layered structure of the inorganic part; And a polymer forming step of adding an organic compound and polymerizing. In the mixing step, a compound a) having an atom forming a tetrahedral surface, a compound b) having an atom forming an octahedral surface, and a compound d) having P as necessary, or a silicon alkoxide, a germanium alkoxide, or a germanium. A mixture of the halide e) and the polar solution c). Compound a) having atoms that form a tetrahedral surface
Examples thereof include organosilicon compounds such as organoalkoxysilanes having an alkoxy group and a polymerizable functional group, organogermanium compounds such as organogermanium, and the like. Examples of the compound b) having atoms forming the octahedron surface include Mg, Al, Ni, Co and C.
An inorganic salt, organic salt or alkoxide of at least one metal atom selected from u, Mn, Fe, Li, V and Zr is used. Of these, Al and Fe are atoms that form the octahedron surface, and part of them are atoms that form the tetrahedron surface (atoms that replace some of silicon and Ge. Polar solvent c) is water, A polar solution prepared by mixing one or more of alcohols, acetone, organic acids and inorganic acids can be used. The above compounds a) and b) do not necessarily have to be completely dissolved, and the object can be achieved even in a dispersed state to some extent.

Incidentally, the compound d) having P can be added at the time of mixing. P in the compound d) becomes an atom that replaces a part of the atoms (silicon, Ge) forming the tetrahedral surface. Examples of the compound d) include phosphoric acid or a derivative thereof, an inorganic salt of P, an organic salt of P, and the like. Also when mixing,
Silicon alcosides, germanium alkoxides, or germanium halides e) can be added. This compound e) is also incorporated into the laminated structure in the same manner as the compound a). In this application, alkoxy groups are not specifically defined as organic groups. 4 by addition of this compound e)
A part of silicon or Ge, which is the central atom of the planar structure, is an atom that is not covalently bonded to an organic group having a polymerizable reactive group. By using the compound e) together with the compound a) in a predetermined ratio, the ratio of the inorganic part in the laminated structure can be adjusted.

In the laminated structure forming step, the pH of the prepared mixed solution is made alkaline to promote the growth of the laminated structure. The pH value that makes the mixed solution alkaline cannot be uniformly regulated due to factors such as the selection of the raw material system, but is, for example, about pH 8 to 10. However, crystals of a laminated structure grow and gelation of the mixed solution is desired. The pH is not so strong that the organic group bonded is impaired at a pH that progresses at a speed higher than that. This step of forming a laminated structure proceeds sufficiently even at room temperature, but it can also be carried out under a temperature condition of a constant height that does not damage the organic groups. This laminated structure forming step may be completed immediately depending on the selection of raw materials and reaction conditions. In addition, aging may be required to some extent, for example, about 1 to 2 days. The obtained gel-like laminated structure is preferably isolated once as a dry powder by removing the solvent.

The mechanism by which the laminated structure is formed in the laminated structure forming step of the present invention is not necessarily clear, but the a), b), d) and e) components are dissolved or dispersed in the polar solution c). Then, if the pH of the mixed solution is adjusted to be alkaline, the crystal structure of the octahedral surface having the metal as the central atom grows in advance, and the silicon or Ge of the organoalkalcoxysilane follows the growth of the crystal structure, resulting in the hydrolysis of the alkoxy group. Bonding to the octahedron surface by dehydration condensation after decomposition, this silicon or G
The crystal structure of the tetrahedron plane grows around the
It is presumed that a laminated structure with the face surface will be formed. Therefore, it is considered that the tetrahedral surface of silicon or Ge is formed following the octahedral surface even when the organic group is directly bonded to a part of the tetrahedral surface of silicon or Ge, and eventually an inorganic laminated structure is formed. ing.

In the polymer forming step, an organic compound is mixed with the laminated structure and the organic group of the laminated structure is copolymerized with the organic compound by a usual polymerization method. In this case, the polymerization is promoted by an initiator or heating, if necessary. As the polymerization method, so-called cast polymerization, bulk polymerization, suspension polymerization and the like can be applied. It is also possible to irradiate with light rays to cause photopolymerization.
This organic compound must be liquid at room temperature or heated or soluble in a solvent in order to uniformly mix it with a powdery laminated structure. Any organic compound satisfying these conditions can be used. For example, if the organic group is an acrylic group, an acrylic organic compound or an organic compound having a vinyl group is suitable, and if it is an epoxy group, an organic molecule having an epoxy group. Alternatively, an organic compound that forms a polymer whose polymerization end is an amino group is suitable. The organic compound mentioned here does not necessarily have a low molecular weight and may be a polymer or an oligomer. By adjusting the amount of this organic compound, the ratio of the organic part to the inorganic part can be controlled.

If the organic compound to be added is in a liquid state, it may be added and mixed as it is to the laminated structure. Further, in the case of an organic compound which becomes liquid by heating, addition and mixing in a hot bath are necessary. When mixing both in a solvent, it is necessary to use a common solvent that swells the laminated structure and dissolves the organic compound. Depending on the organic compound or solvent to be added, the laminated structure may not be dispersed immediately and it may take time, but in that case, the organic compound or solvent is dispersed by forcibly stirring with a mixer or applying ultrasonic waves. Can be promoted.

Depending on the organic compound to be added, a catalyst, an initiator or the like necessary for polymerization is required. In addition to the above organic compounds, components such as pigments and plasticizers can be added. In the organic-inorganic polymer of the present invention, the organic part and the inorganic part are covalently bonded, and the surface is formed with the organic part and the internal inorganic part. Therefore, the organic-
The inorganic polymer is different from a conventional composite material such as FPR in which a synthetic resin and an inorganic substance dispersed therein have no chemical bond and are simply mixed. There is also a clay-hybrid composite material in which the surface of clay is bound to a resin containing an organic ion, but this is different from a covalent bond because the bond between the clay and the organic ion is an ionic bond, and thus the bond strength is weak and easy to break. However, in the present invention, the organic part and the inorganic part of the resin layer are covalently bonded to each other to form a stronger bond than other bonds.

[0023]

In the organic-inorganic polymer of the present invention, the crystalline inorganic structure portion is formed by a structure in which tetrahedral surfaces and octahedral surfaces are laminated, and the central atom forming the tetrahedral surface is Has a polymerizable organic group bound by a covalent bond, and the organic group is copolymerized with another polymerizable organic compound to form an organic part. Therefore, the organic part and the inorganic part are laminated, and when the organic part is the main component, the inorganic part can impart high hardness and high heat resistance to the organic part. On the contrary, when the inorganic part is mainly composed of a filler as an inorganic material covered with an organic substance,
It can be used as a coating material.

Therefore, it is possible to provide a flexible filler and coating material having high affinity with other organic substances. Further, in this method for producing an organic-inorganic polymer, the ratio of the organic part and the inorganic part can be easily controlled during the process. That is, the ratio of the organic part and the inorganic part in the organic-inorganic polymer can be controlled by the amount of the organic compound to be copolymerized and the amount of the alkoxysilane added in the mixing step.

In this organic-inorganic polymer, the central atom constituting the tetrahedral surface of the inorganic structure and the organic group are bonded by a covalent bond, and this organic group is combined with the organic compound constituting the organic layer part. Copolymerizes to form a polymer. For this reason, the inorganic part and the organic part are strongly bonded as compared to the case where the organic part is bonded to the inorganic part by a conventional ionic bond, and the bond between the inorganic part and the organic part during operation and use is It is possible to prevent the both from breaking and peeling.

In the production of this organic-inorganic polymer, a laminated structure can be easily formed by dissolving a predetermined raw material in a polar solution and making the pH of the solution weakly alkaline. An organic compound can be added to and mixed with this laminated structure to be manufactured by a usual polymerization method. The ratio of the inorganic part to the organic part can be easily changed only by changing the blending ratio in the mixing step and the polymerization step.

[0027]

EXAMPLES The present invention will be specifically described below with reference to examples. (Example 1) (Mixing step) 200 ml of 1N sodium hydroxide aqueous solution
An aqueous solution of sodium hydroxide (Liquid A) diluted with 4000 ml of water was prepared. Separately, in 1000 ml of methanol, 49.6 g of 3-methacryloxypropyltrimethoxysilane (MPTS) and magnesium chloride hexahydrate 2
0.4 g was added and well stirred to prepare a liquid B. (Layered structure forming step) While stirring Solution B, Solution A is added and mixed to gel the mixed solution to form a tetrahedral surface structure centered on silicon atoms and an octahedral surface structure centered on magnesium atoms. A laminated structure having the above crystalline laminated structure was synthesized. The gelled product was filtered, washed with water, and dried under vacuum to be isolated as a powder. In this laminated structure, methacrylic acid as an organic group forms a covalent bond to silicon as an active group through a propyl group with silicon as a central atom on the tetrahedral surface to form an organic group. (Polymerization step) 2 g of 2-hydroxyethyl methacrylate (HEMA) and 0.03 g of benzoyl isopropyl ether as a photopolymerization initiator were added to 1 g of the above laminated structure product, and mixed with stirring. This mixed solution was applied to an acrylic plate (film thickness 1
It was applied to about 00 μm and about 500 μm (0.5 mm)) and irradiated with ultraviolet rays for 1 hour with a high-pressure ultraviolet lamp to cause photopolymerization. As a result, a coat film of an organic-inorganic polymer having an organic polymer layer in which HEMA and a methacrylic acid residue were copolymerized was formed on the acrylic plate. When the surface hardness of this coat film was measured by the pencil method, both were 6H.
The surface hardness of the EMA homopolymer was higher than that of 6B or less. This shows that the organic-inorganic polymer can improve the surface hardness of the organic polymer. Further, the thickness is 0.5 mm, which enables thicker coating than the conventional VV type hard coat material (50 μm or less). (Example 2) 5 g of methyl methacrylate (MMA) and 0.07 g of benzoin isopropyl ether as a photopolymerization initiator were added to 12 g of the laminated structure produced in Example 1 and mixed with stirring. This mixed solution is applied in the shape of an acrylic plate to a film thickness of 100 μm.
It was applied to about m and was irradiated with ultraviolet rays for 1 hour with a high-pressure ultraviolet lamp to cause photopolymerization. As a result, a coat film of an organic-inorganic polymer having an organic polymer layer in which MMA and a methacrylic acid residue of the laminated structure were copolymerized was formed. When the surface hardness of this coating film was measured by the pencil method, it was 9H, and M
The surface hardness of the MA polymer was significantly improved as compared with 6B.

(Embodiment 3) The laminated structure produced in the embodiment 1 is compared with HEMA in 0.05, 0.5, 1, 3, 6.
Samples were prepared by mixing with HEMA at the ratios of 5, 12.5, 25, 50, 75 and 85% by weight. 1% by weight of benzoyl isopropyl ether as a photopolymerization initiator was added to each sample and mixed with stirring. 20mm x 10m
It was poured into a m × 1 mm mold and irradiated with ultraviolet rays for 1 hour with a high-pressure ultraviolet lamp to carry out photopolymerization to obtain a plate-like material. DMA (dynamic viscoelasticity) was measured for each plate obtained above. D
The glass transition point of each plate polymer was determined from the peak of loss elastic modulus E ″ obtained from the measurement of MA. The results are shown in FIG.

Table 1 shows the relationship between the ratio of the laminated structure compounded in the HEMA polymer and the glass transition temperature. Table 1
As shown in FIG. 5, the silicon-based polymer obtained by adding 0.05% by weight of HEMA to the laminated structure for polymerization has a glass transition temperature higher by about 4 ° C. than that of a polymer containing HEMA alone. Further HEMA
As the amount of laminated structure added to

[0030]

[Table 1] The glass transition temperature of the base polymer also rises, and when the amount of the laminated structure added is 50% by weight, the glass transition temperature is 15 ° C. higher than that of the polymer of HEMA alone. Furthermore, when the addition ratio of the laminated structure is 75% by weight or more, the glass transition temperature of the organic-inorganic polymer is not exhibited. Therefore, the organic-inorganic polymer has a strong inorganic property.

FIG. 1 is a line graph of the data in Table 1 and shows that the glass transition temperature rises sharply with the addition of a small amount of laminated structure. Further, it was found that there is a relationship of y = 96.752 + 5.3755logx between the glass transition temperature y of this organic-inorganic polymer and the content of the laminated structure x. This indicates that the laminated structure and HEMA react with each other and bond during photopolymerization. In addition, the addition of a very small amount of laminated structure, such as 0.05% by weight
It has been found to contribute to increasing the heat resistance of the EMA polymer.

[0032]

The organic-inorganic polymer can impart properties such as color, surface hydrophilicity / hydrophobicity, and relative dielectric constant depending on the type of the copolymerizable organic compound forming the organic portion. In addition, the organic-inorganic polymer can be used for applications such as a filler and a coating material for the organic polymer by changing the ratio of the organic part and the inorganic part.

[Brief description of drawings]

FIG. 1 is a line graph showing how the glass transition temperature of a polymer changes with the content% of the laminated structure.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akane Okada Aichi Prefecture Aichi-gun Nagakute-cho, Nagachote 1 41st side road, Toyota Central Research Institute Co., Ltd. (72) Inventor Katsumi Mizutani Nakamura-ku, Nagoya City 4-7-23 Toyota Tsusho Corporation

Claims (2)

[Claims] 1. A tetrahedral surface structure having at least one atom selected from silicon and Ge or an atom obtained by substituting a part of the atom with at least one atom selected from Al, Fe and P as a central atom. And Mg, Al, Ni, Co, C
A crystalline laminated structure having an octahedral surface structure having at least one metal selected from u, Mn, Fe, Li, V, and Zr as a central atom, and an organic compound bonded to the laminated structure by a covalent bond. An organic polymer composed of a polymer layer, wherein at least a part of at least one atom selected from silicon and Ge, which is a central atom of the tetrahedral surface structure forming the laminated structure, is Characterized by being covalently bonded to an organic group having a polymerizable reactive group, and the reactive group of the organic group is bonded to an organic compound which undergoes a polymerization reaction with the reactive group to form an organic polymer layer. Organic-inorganic polymers. 2. A mixing step of mixing the following a), b) and c) into a mixed solution (wherein silicon, which is the central atom of the tetrahedral surface structure of the organic polymer having a crystalline layered structure to be produced): When a part of at least one atom selected from Ge is replaced by P, the following d) is added. Further, an organic group having a reactive group capable of polymerizing a part of at least one atom selected from silicon and Ge, which are central atoms of the tetrahedral surface structure of the organic polymer having a crystalline layered structure to be produced. When the atom is not covalently bonded with, the following e) is added. ), An alkali is added to the mixed solution to adjust the pH of the mixed solution to be alkaline, or as it is, or by aging, a) silicon in the compound, at least one atom selected from Ge, or a part of the atoms. B) compound Al, F
e, d) a tetrahedral surface structure having as a central atom an atom substituted with at least one atom selected from P in the compound, and b) Mg, Al, Ni, Co, Cu, M in the compound.
Laminated structure forming step of forming a crystalline laminated structure having an octahedral plane structure having at least one metal selected from n, Fe, Li, V and Zr as a central atom, and four sides of the laminated structure Silicon, which is the central atom of the body structure, G
an organic group having a reactive group capable of being polymerized by a covalent bond on at least a part of at least one atom selected from e, and an organic compound capable of reacting with the organic group and forming a polymer by itself. And a polymer forming step of forming a polymer layer of an organic compound in the laminated structure by mixing an organic group and an organic compound to prepare a polymer layer of the organic compound in the laminated structure. a) a compound having at least one alkoxy group and having silicon which is covalently bonded to an organic group having a polymerizable reactive group, an organic compound having at least one alkoxy group or halogen and having a polymerizable reactive group At least one compound selected from compounds having Ge covalently bonded to a group, compounds having Ge covalently bonded to an organic group having at least one alkoxy group or halogen and having a polymerizable reactive group Compound. b) Mg, Al, Ni, Co, Cu, Mn, Fe, L
An inorganic salt, organic salt or alkoxide of at least one metal selected from i, V and Zr. c) A polar solvent in which one or more kinds of inorganic or organic are mixed. d) A compound having P. e) At least one compound selected from silicon alkoxide having at least one alkoxy group, germanium alkoxide having at least one alkoxy group, and germanium halide.