JP3236817B2 - Organic-inorganic hybrid polymer material and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer material useful for various plastic materials, resin additives, paint materials and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Various types of inorganic materials are used for industrial purposes in consideration of their characteristics and required characteristics. For example, silicon-based ceramics such as silicon carbide and silicon nitride are materials having excellent mechanical strength, chemical stability, and thermal stability. Further, materials such as silicon oxide and titanium oxide also have excellent optical characteristics.

However, these inorganic materials generally have poor moldability and are hard and brittle. Further, the adhesiveness to an organic polymer is poor, and its use is restricted.

On the other hand, organic polymers are generally excellent in moldability and flexibility, but are considerably inferior in hardness and thermal stability as compared with inorganic materials.

[0005] Therefore, development of a material that complements the characteristics of an inorganic material and an organic polymer and makes use of its advantages has been desired.

As one means, Si, T has been conventionally used to improve various physical properties such as surface hardness, gloss, stain resistance, strength, heat resistance, weather resistance and chemical resistance of plastics.
Research has been conducted on organic-inorganic hybrid polymer materials in which an inorganic element such as i or Zr is introduced into a skeleton.

In general, an organic-inorganic hybrid polymer material is prepared by a method in which an organic monomer or an organic polymer is radically copolymerized with a compound having an inorganic skeleton such as an alkylsiloxane, and a method in which a side chain is added to an organic polymer. A method is known in which an inorganic functional group such as an alkoxysilane is bonded as a group, and then this is crosslinked.

For example, JP-A-63-57642, JP-A-3-103486 and Appl. P
olym. Sci. Vol. 35, pp. 20-39, 198
In 8 years, it is described that an organic monomer or an organic polymer is radically polymerized using an alkylsiloxane-containing compound as an initiator to obtain an organic-inorganic hybrid polymer material.

However, in the method using an alkylsiloxane-containing compound as an initiator, it is difficult to even introduce an alkylsiloxane moiety to both ends of a molecule, and it is almost impossible to uniformly introduce a siloxane skeleton into the molecule. . Further, a complicated operation is required for synthesizing an alkylsiloxane-containing compound used as a radical initiator.

In addition, for example, Macromolecule
s Vol. 24, No. 6, pp. 1431, 1991
Studies have been made to prepare siloxane-containing polymers by anionic polymerization.

However, in order to obtain the desired polymer material, complicated control of reaction conditions and study of synthesis conditions are required due to differences in reactivity and physical properties of the materials used. In addition, anionic polymerization is costly, so that it is not practical to perform it industrially.

On the other hand, for example, JP-A-5-43679 and JP-A-5-86188 disclose that after a vinyl polymer is subjected to a hydrosilylation reaction with a silicon compound having a silane group (Si-H group), -A method for obtaining an organic-inorganic hybrid polymer material by crosslinking them by a gel method is described.

JP-A-8-104710 and JP-A-8-104711 disclose an alkoxysilyl-terminated vinyl polymer obtained by radical polymerization of a vinyl monomer using an alkoxysilyl-terminated azo initiator. To obtain an organic-inorganic hybrid polymer material by hydrolysis and polycondensation.

Here, polystyrene, polyvinyl chloride, acrylic resin and the like are described as vinyl polymers.

However, these vinyl polymers have low heat resistance and low mechanical strength, and have high performance plastic materials,
In particular, it is unsuitable for use as a structural material or a hard coat material.

Macromolecules Vol. 25,
On page 4309, 1992, a method is described in which an alkoxysilyl group is bonded to the main chain of a polyalkylene oxide polymer, followed by hydrolysis and polycondensation. Further, Macromol. Chem. Macromol.
Symp. 42/43, p. 303, 1991, a polyoxazoline polymer as the main chain is described in J. Am. I
norg. Organomet. Polym. Volume 5,
Page 4, in 1995, a polyamine polymer and Appl. Polym. Sci. Vol. 58, No. 12
On page 63, 1995, a cellulose polymer is described.

However, all of the polymers disclosed as these backbones are hydrophilic. Hydrophilic polymers are hygroscopic and have poor water resistance, so plastic molded products,
It is not suitable for use as a sealing material, a coating material, a structural material, a hard coat agent, and the like.

On the other hand, hydrophobic organic polymers, especially engineering plastics, are excellent in heat resistance, mechanical strength and water resistance. Since there is a great demand for industrial plastics and a wide range of applications, development of organic-inorganic hybrid polymer materials using these is desired. But,
It is difficult to hybridize a hydrophobic organic polymer because it is insoluble or hardly soluble in an alcohol solvent generally used as a solvent in a sol-gel reaction, and has a small number of reactive terminal functional groups. For this reason, although an organic-inorganic hybrid polymer material using a hydrophobic organic polymer has been studied, there are only the following reports.

Japanese Patent Application No. 9-321012 reported an organic-inorganic hybrid polymer material using polycarbonate as a typical engineering plastic and polyarylate as a super engineering plastic. Here, an organic-inorganic hybrid polymer material is obtained by crosslinking a polymer having a polycarbonate or polyarylate portion in the main skeleton and having a metal alkoxide group at a terminal by a sol-gel method. Since this polymer material has excellent surface hardness, heat resistance and mechanical strength, it is expected to be used in various applications.

For example, a heat-resistant material corresponding to polycarbonate or polyarylate used as a skeleton can be used. Taking polycarbonate, which is in great demand, as an example, the glass transition temperature of commercially available general polycarbonate is around 150 ° C., which is relatively high among engineering plastics. However, when the temperature becomes equal to or higher than the glass transition temperature in a state where a load is applied, the elastic modulus tends to rapidly decrease and soften. Therefore, the upper limit of the practical temperature range of polycarbonate is about 120 ° C.

On the other hand, the organic-inorganic hybrid polymer material using polycarbonate described in Japanese Patent Application No. 9-321012 was found to have a dynamic viscoelasticity of 150 to 19 as a result of dynamic viscoelasticity measurement.
It has a glass transition temperature of 0 ° C and retains its shape up to 230 ° C. That is, it shows a higher heat resistance of at least 60 ° C. than polycarbonate. The heat-resistant polycarbonate marketed several years ago has a heat resistance of about 20 to 30 ° C. higher than that of a general polycarbonate, so that the organic-inorganic hybrid polymer material using the polycarbonate is more heat-resistant than the heat-resistant polycarbonate. It can be said that the material has high properties.

Next, application to a coating agent is mentioned. At present, commercially available hard coat agents are typically acrylic, silicone, and urethane, but there is no versatile one, and they are used properly depending on the purpose. Their surface hardness is F to H in pencil hardness (Polycarbonate resin handbook) and 9H of glass
Since the hardness is still lower than that of, improvement is desired. JP-A-8-104710 and JP-A-8-104711 describe an organic-inorganic hybrid polymer material using a vinyl polymer, and have a pencil hardness of 2H to 3H. 4H-6
The organic-inorganic hybrid polymer material described in Japanese Patent Application No. 9-321012 having a pencil hardness of H is useful.

In addition, the organic-inorganic hybrid polymer material is very useful as a structural material utilizing improved mechanical strength, an optical material, and an insulating material.

However, the organic-inorganic hybrid polymer material described in Japanese Patent Application No. 9-32012 is cross-linked by using only metal alkoxide groups at the terminal of the polymer, and its inorganic content is a few. %. From this, even if an organic-inorganic hybrid polymer material is used, the properties of the organic polymer are strong, and the properties of the applied inorganic material are small, so that there is a limit in improving the physical properties.

In the sol-gel method, a raw material such as a metal alkoxide compound is hydrolyzed and polycondensed to produce a porous gel. Recently, this porous gel has been widely used as a catalyst, but is usually used as a glass or ceramics by closing at a high temperature by treating it at a high temperature. Author). As is well known, glass is a material with a very high gas barrier property, and there is much demand as a closed container,
It has the disadvantage of being heavy and easily broken.

Conversely, polycarbonate is a material having relatively poor gas barrier properties among engineering plastics. For this reason, while having excellent impact resistance and transparency, it has been rarely used for gas barrier packaging materials.

If these can be combined and the advantages of each can be utilized as an organic-inorganic hybrid polymer material, it is expected to be a material having excellent properties in place of glass containers and glass.

[0028]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned conventional problems, and aims at heat resistance, surface hardness, gas barrier properties, water resistance, (transparency, mechanical strength). Another object of the present invention is to provide an organic-inorganic hybrid polymer material using a hydrophobic organic polymer and a metal alkoxide compound, which is suitable for use as a high-performance and high-performance plastic material having excellent performance.

[0029]

SUMMARY OF THE INVENTION The present invention comprises co-hydrolyzing and co-polycondensing a polymer having a polycarbonate or polyarylate moiety as a main skeleton and having a metal alkoxide group as a functional group; The present invention provides an organic-inorganic hybrid polymer material obtained as described above, thereby achieving the above object.

One preferred aspect of the present invention is that at least one
In a state where a polymer (A) having two or more metal alkoxide groups in the molecule and having a polycarbonate or polyarylate portion as a main skeleton and a metal alkoxide compound (B) are mixed, co-hydrolysis and co-hydrolysis are performed by a sol-gel method. The purpose is to obtain an organic-inorganic hybrid polymer material in which the polymer (A) and the compound (B) are uniformly and finely dispersed by polycondensation and crosslinked into a three-dimensional structure.

Polymer (A) In the present invention, the polymer (A) having a metal alkoxide group in the molecule and having a polycarbonate or polyarylate moiety as a main skeleton may be synthesized by any method. . For example, a polycarbonate or polyarylate having a functional group such as a hydroxyl group, an amino group, a carboxyl group, or a thiol group and a metal alkoxide compound having a functional group such as an isocyanate group, an epoxy group, a carboxyl group, an acid halide group, or an acid anhydride group. And a method of hydrosilylating a polycarbonate or polyarylate having a functional group such as an alkenyl group or an alkynyl group with a metal alkoxide compound having a silane group. Such a method is disclosed in Japanese Patent Application No. 9-327842 No. 10 filed by the same applicant as the present application.
It is specifically described in the paragraphs 0039 to 0054 of the page.

The polymer (A) may have a main skeleton of one component such as polycarbonate, polyester carbonate, or polyarylate, or may have a multi-component copolymer skeleton. Further, a mixture of a plurality of types may be used, and any of a branched shape and a linear shape may be used. Further, the compound is preferably soluble in solvents such as halogenated hydrocarbons, ethers, and aprotic polar solvents, and has a number average molecular weight of 50.
It is 0-50000, preferably 1000-15000.

The metal alkoxide groups of the polymer (A) include Si, Ti, Zr, Fe, Cu, Sn, B, Al,
Ge, Ce, Ta and W etc., preferably Si, Ti,
Zr is a central metal, and has 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms.
Has 1 to 5 alkoxy groups. A particularly preferred central metal is Si. This is because Si alkoxide is the most versatile and easy to apply and develop.

The metal alkoxide group equivalent of the polymer (A) is from 1 to 100, preferably from 1 to 50, and more preferably from 2 to 10. When the metal alkoxide group equivalent of the polymer (A) is less than 1, the performance of the material may decrease, and when it exceeds 100, the material may become brittle.

The metal alkoxide groups contained in one molecule of the polymer (A) may be all the same or a plurality of types. Further, a metal alkoxide group containing two or more kinds of metal elements or an oligomer type metal alkoxide group having two or more repeating units may be used.

Metal alkoxide compound (B) In the present invention, any type of metal alkoxide compound (B) can be used. Among them, preferred are those represented by the formula (1) _Ap M (1) [A is an alkoxy group having 1 to 8, preferably 1 to 4 carbon atoms, M is Si, Ti, Zr, Fe, Cu, Sn, B, A
A metal element selected from the group consisting of l, Ge, Ce, Ta, W, and the like, preferably the group consisting of Si, Ti, and Zr, and p represents an integer of 2 to 6. ] It is a compound represented by these.

Specifically, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane and tetrabutoxysilane, and tetraalkoxytitanium such as tetra-n-propoxytitanium, tetraisopropoxytitanium and tetrabutoxytitanium , Tetraalkoxyzirconiums such as tetra-n-propoxyzirconium, tetraisopropoxyzirconium and tetrabutoxyzirconium, and dimethoxycopper, diethoxybarium, trimethoxyboron, triethoxygallium, tributoxyaluminum, tetraethoxygermanium, tetrabutoxylead And metal alkoxides such as pentan-propoxytantalum and hexaethoxytungsten.

Particularly preferred as the metal alkoxide compound (B) of the present invention is those wherein M in the formula (1) is Si. This is because Si alkoxide is the most versatile and easy to apply and develop.

Another example of the metal alkoxide compound (B) is represented by the following formula (2): R _{k Al} M (R ′ _mx ) _n (2) [where R is hydrogen or C 1-12, preferably 1-5 A is an alkoxy group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, and M is Si, Ti, Zr, F
e, Cu, Sn, B, Al, Ge, Ce, Ta and W
A metal element selected from the group consisting of Si, Ti, and Zr; R ′ is an alkylene group or alkylidene group having 1 to 4, preferably 2 to 4 carbon atoms;
Isocyanate group, epoxy group, carboxyl group, acid halide group, acid anhydride group, amino group, thiol group,
General functional groups such as a vinyl group, a methacryl group, and a halogen group, k is an integer of 0 to 5, l is an integer of 1 to 5, m is 0 or 1, and n is an integer of 0 to 5]. Compound.

Taking Si as an example, specific examples include trimethoxysilane, triethoxysilane, tri-n-propoxysilane, dimethoxysilane, diethoxysilane,
Diisopropoxysilane, monomethoxysilane, monoethoxysilane, monobutoxysilane, methyldimethoxysilane, ethyldiethoxysilane, dimethylmethoxysilane, diisopropylisopropoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, n
-Propyltri-n-propoxysilane, butyltributoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, diisopropyldiisopropoxysilane, dibutyldibutoxysilane, trimethylmethoxysilane, triethylethoxysilane, tri-n-propyln-
(Alkyl) alkoxysilanes such as propoxysilane, tributylbutoxysilane, phenyltrimethoxysilane, diphenyldiethoxysilane, triphenylmethoxysilane and the like;

3-isocyanatopropyltriethoxysilane, 2-isocyanatoethyltri-n-propoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 2-isocyanatoethylethyldibutoxysilane, 3-isocyanatopropyldimethylisopropoxysilane, 2-isocyanate (Alkyl) alkoxysilanes having an isocyanate group such as ethyldiethylbutoxysilane, di (3-isocyanatopropyl) diethoxysilane, di (3-isocyanatopropyl) methylethoxysilane, ethoxysilanetriisocyanate, and the like;

3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3, (Alkyl) alkoxysilanes having an epoxy group such as 4-epoxybutyltrimethoxysilane and the like;

(Alkyl) alkoxysilanes having a carboxyl group such as carboxymethyltriethoxysilane, carboxymethylethyldiethoxysilane, carboxyethyldimethylmethoxysilane and the like;

Alkoxysilane having an acid anhydride group such as 3- (triethoxysilyl) -2-methylpropylsuccinic anhydride;

2- (4-chlorosulfonylphenyl)
Alkoxysilanes having an acid halide group such as ethyltriethoxysilane and the like;

3-aminopropyltrimethoxysilane,
3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyl (Alkyl) alkoxysilanes having an amino group, such as trimethoxysilane;

(Alkyl) alkoxysilanes having a thiol group such as 3-mercaptopropyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and the like;

(Alkyl) alkoxysilanes having a vinyl group such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane and the like;

(Alkyl) alkoxysilanes having a methacryl group, such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylpyrmethyldimethylsilane, and the like;

(Alkyl) alkoxysilanes having a halogen group such as triethoxyfluorosilane, 3-chloropropyltrimethoxysilane, 3-bromopropyltriethoxysilane, 2-chloroethylmethyldimethoxysilane and the like. it can.

Of course, not only Si but Ti, Zr,
Similar compounds can be exemplified for other metals such as Fe, Cu, Sn, B, Al, Ge, Ce, Ta and W.

These metal alkoxide compounds (B) may be used alone or in combination of two or more. Further, Mg [Al (iso-OC ₃ H ₇ ) ₄ ] ₂ , Ba [Zr
₂ (OC ₂ H ₅ ) ₉ ] ₂ , (C ₃ H ₇ O) ₂ Zr [Al (OC ₃
H _{7) 4]} 2 or more repeating units per molecule, such as a metal alkoxide compound and tetramethoxysilane oligomer and tetraethoxysilane oligomer appears to contain two or more metal elements in one molecule of _2, etc. An oligomer-type metal alkoxide compound having the following formula: Further, the alkoxy group may be an acetoxy group.

Organic-Inorganic Hybrid Polymer Material A polymer (A) having a metal alkoxide group in the molecule and having a polycarbonate or polyarylate moiety as a main skeleton and a metal alkoxide compound (B) are hydrolyzed by a sol-gel reaction. Decompose and polycondensate. At this time, the composition ratio of the polymer (A) and the compound (B) can be freely changed.

The weight ratio of the polymer (A) to the metal alkoxide compound (B) is 1:99 to 99: 1, preferably 1: 1.
0:90 to 90:10.

The hydrolysis and polycondensation by the sol-gel method means that a polymer having a metal alkoxide group in a molecule is reacted with water to convert an alkoxy group into a hydroxyl group, and then the hydroxyl group is simultaneously simultaneously subjected to polycondensation. The condensation causes a polymer having a hydroxy metal group (for example, -Si (OH) ₃ ) to undergo a dehydration reaction or a dealcoholation reaction with an adjacent molecule, thereby causing a three-dimensional crosslinking reaction through an inorganic covalent bond. To tell.

The water used for the hydrolysis reaction may be added in an amount necessary to convert all the alkoxy groups to hydroxyl groups, or may utilize water in the reaction system or absorb moisture in the atmosphere. You may let me go. The reaction conditions are preferably at room temperature to 100 ° C. for about 0.5 to 24 hours. At that time, an acidic catalyst such as hydrochloric acid, sulfuric acid, acetic acid, benzenesulfonic acid, p-toluenesulfonic acid, sodium hydroxide, potassium hydroxide, ammonia, triethylamine, piperidine, 1,8-diazabicyclo [5,4,0] A basic catalyst such as -7-undecene (DBU) may be used.

In order to further promote the condensation reaction and to make the cross-linking stronger, then at 50 to 500 ° C. for 5 minutes to 4 hours.
Heat treatment is performed for about 8 hours.

In the hydrolysis and polycondensation process of the present invention, the polymer (A) and the compound (B) may be mixed and dissolved in a solvent in advance and then subjected to a sol-gel reaction. After the component (1) is hydrolyzed, the other component may be added and the hydrolysis may be subsequently performed. An organic-inorganic hybrid polymer material produced by such a method can be obtained as a material in which two components are uniformly and finely dispersed and bonded, and have improved heat resistance, mechanical strength, and the like.

Specific examples of the solvent used for the sol-gel reaction include hydrocarbon solvents such as benzene, toluene and n-hexane, halogenated hydrocarbon solvents such as chloroform, dichloromethane, dichloroethane and chlorobenzene, and tetrahydrofuran. , 1,4-dioxane, 1,
Ether solvents such as 3-dioxane, diethyl ether, dibutyl ether, acetone, methyl ethyl ketone,
Ketone solvents such as cyclohexanone, ester solvents such as ethyl acetate and butyl acetate, methanol, ethanol,
Examples include, but are not limited to, alcoholic solvents such as n-propanol and isopropanol and mixed solvents of the above-mentioned solvents. Generally, a polar solvent such as an alcohol solvent is often used.

In all the hydrolysis processes in the present invention, the content of the inorganic substance and the content of the polymer are improved in order to improve or newly impart functions such as strength, hardness, weather resistance, chemical resistance, flame retardancy and antistatic property. Si, Ti, Z to adjust the crosslink density of
r, Fe, Cu, Sn, B, Al, Ge, Ce, Ta,
A metal such as W, a metal oxide, a metal complex, an inorganic salt, or the like may coexist. Further, in order to suppress cracking that may occur during gelation, drying, and heat treatment, formamide, dimethylformamide, dioxane, oxalic acid, and the like may be added as a drying inhibitor, or acetylacetone or the like may be added as an additive. May be.

In the organic-inorganic hybrid polymer material of the present invention, the heat resistance, weather resistance, surface hardness,
Properties such as rigidity, water resistance, chemical resistance, stain resistance, mechanical strength, and flame retardancy are favorably imparted to the organic polymer. Conversely, properties such as impact resistance, flexibility, processability, and light weight of the organic polymer are favorably imparted to the inorganic material.

In order to obtain a plastic material having a higher heat resistance than a conventional engineering plastic such as polycarbonate, the content of the metal alkoxide compound (B) may be set to 10% by weight or more. Also,
In order to obtain a plastic material having a surface hardness superior to that of a conventional engineering plastic, the content of the metal alkoxide compound (B) should be 10% by weight or more, preferably 50% by weight or more.

Further, the organic-inorganic hybrid polymer material of the present invention exhibits a very excellent gas barrier property as compared with conventional film materials such as polyethylene, polypropylene and polystyrene. When preparing a gas barrier film using the organic-inorganic hybrid polymer material of the present invention, the weight ratio of the polymer (A) to the metal alkoxide compound (B) is 1: 9 to 9: 1, preferably 1: 9. ~ 5: 5
And

[0064]

According to the present invention, high-performance and high-performance plastic materials, plastic molded products or films, sealing agents, adhesives, paint binders, structural materials, optical materials, polymer silane coupling agents, resin additives, surfaces Provided is an organic-inorganic hybrid polymer material using a hydrophobic organic polymer and a metal alkoxide compound, which is suitable for use as a modifier, a hard coat agent, an electric or electronic material, a medical material, a filler, or the like.

[0065]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Example 1 70.00 g of a polycarbonate diol (PC diol) having a number average molecular weight of 3900 and a hydroxyl equivalent of 1.8 was dissolved in 500 mL of chloroform, and then 3-isocyanatopropyltriethoxysilane (IP
(TES) was added, and the mixture was heated under reflux for 10 hours and then cooled to room temperature. This reaction solution was treated with 7 L of methanol.
The product was precipitated by dropping. The precipitate was separated by filtration, washed with methanol, and dried under reduced pressure (yield 97.0).
%).

Measurement was performed by ¹ H-NMR, and it was confirmed that the obtained product was a triethoxysilylated polycarbonate (PCS) having both ends having an alkoxysilyl group introduced therein. The alkoxysilyl group equivalent of this product was 1.8. As a result of GPC measurement, the product had a number average molecular weight of 4,400.

After dissolving this PCS (1.20 to 1.80 g) and 0.20 to 0.80 g of tetramethoxysilane oligomer MKC silicate MS-56 (TMOS) manufactured by Mitsubishi Chemical Corporation in 20 ml of tetrahydrofuran (THF) at room temperature. 0.12 to 0.66 g of 1N HCl water is added,
Hydrolysis was carried out by vigorous stirring at room temperature for 1 hour.

This solution was coated on a polyamide substrate (thickness: 2 mm) and a polyethylene film (thickness: 30 μm) using a spin coater.
A silica / polycarbonate film having a composition of MOS = 9/1 to 1/9 was obtained. Further, the solution was cast on a vat at room temperature to evaporate the solvent, and the PCS / TM
A transparent and good silica / polycarbonate film having a composition of OS = 9/1 to 1/9 was obtained.

The film formed on a polyamide substrate was subjected to a hardness test below, the film formed on a polyethylene film was subjected to a gas barrier property test below, and the cast film was used below for a scanning electron microscope (SEM).
It was subjected to observation and dynamic viscoelasticity measurement.

Example 2 70.00 g of polycarbonate diol (PC diol) having a number average molecular weight of 6600 and a hydroxyl equivalent of 1.6 was dissolved in 500 mL of chloroform, and then 3-isocyanatopropyltriethoxysilane (IP
TES) was added, and the mixture was heated under reflux for 15 hours and then cooled to room temperature. This reaction solution was dropped into 7 L of methanol to precipitate a product. The precipitate was separated by filtration, washed with methanol, and dried under reduced pressure (yield 97.0).
%).

Measurement was performed by ¹ H-NMR, and it was confirmed that the obtained product was a triethoxysilylated polycarbonate (PCS) having both ends having an alkoxysilyl group introduced therein. The alkoxysilyl group equivalent of this product was 1.6. As a result of GPC measurement, the number-average molecular weight of this product was 7,500.

This PCS (0.20 to 1.80 g) and T
MOS (0.20-0.80 g) in THF (20 ml)
In 1N HCl at 0.10 to 0.6
6 g was added and hydrolysis was carried out by vigorously stirring at room temperature for 1 hour.

This solution was coated on a polyamide substrate (thickness 2 mm) and a polyethylene film (thickness 30 μm) using a spin coater, and the PCS / TMOS =
A silica / polycarbonate film having a composition of 9/1 to 1/9 was obtained. The solution was cast on a vat at room temperature to evaporate the solvent, and PCS / TMOS = 9.
A transparent and good silica / polycarbonate film having a composition of 1/1 to 1/9 was obtained.

Example 3 PCS prepared in Example 1 (0.20 to 1.80 g) and tetraethoxysilane (TEOS) 0.20 to 1.80
g in THF (20 ml) at room temperature.
Hydrolysis was performed by adding 0.12 to 0.63 g of Cl water and strongly stirring at room temperature for 1 hour.

This solution was coated on a polyamide substrate (thickness: 2 mm) and a polyethylene film (thickness: 30 μm) using a spin coater, followed by PCS / TEO
A silica / polycarbonate film having a composition of S = 9/1 to 1/9 was obtained. Also, cast on a vat at room temperature to evaporate the solvent, PCS / TEOS = 9/1 ~
A transparent and good silica / polycarbonate film having a composition of 1/9 was obtained.

Example 4 PCS (0.20 to 1.80 g) prepared in Example 2 and TEOS (0.20 to 1.80 g) were mixed with THF (20 m
1) After dissolving in room temperature at room temperature, 0.3N
Hydrolysis was performed by adding 0.63 g and stirring vigorously at room temperature for 1 hour.

This solution was coated on a polyamide substrate (thickness: 2 mm) and a polyethylene film (thickness: 30 μm) using a spin coater.
A silica / polycarbonate film having a composition of S = 9/1 to 1/9 was obtained. Also, cast on a vat at room temperature to evaporate the solvent, PCS / TEOS = 9/1 ~
A transparent and good silica / polycarbonate film having a composition of 1/9 was obtained.

Comparative Example 1 2.00 g of a polycarbonate resin (Iupilon) (number average molecular weight: 36,000) manufactured by Mitsubishi Engineering-Plastics Corporation was diluted with 50 m of dichloromethane.
l. This solution was coated on a polyamide substrate (thickness 2 mm) and a polyethylene film (thickness 30 μm) using a spin coater to obtain a PC film. Further, a transparent PC film was obtained by casting on a vat at room temperature and evaporating the solvent.

Comparative Example 2 PCS (2.00 g) prepared in Example 1 was replaced with THF (2
0 ml), 1 g of 1N HCl aqueous solution (0.05 g) was added, and the mixture was stirred vigorously at room temperature to carry out hydrolysis.
This solution was applied to a polyamide substrate (2 mm thick) and a polyethylene film (30 μm thick) using a spin coater.
m) to obtain a PCS film. Further, a transparent PCS film was obtained by casting on a vat at room temperature and evaporating the solvent.

Comparative Example 3 PCS (2.00 g) prepared in Example 2 was replaced with THF (2
0 ml), 0.03 g of 1N HCl aqueous solution was added, and the mixture was hydrolyzed by vigorous stirring at room temperature.
This solution was applied to a polyamide substrate (2 mm thick) and a polyethylene film (30 μm thick) using a spin coater.
m) to obtain a PCS film. Further, a transparent PCS film was obtained by casting on a vat at room temperature and evaporating the solvent.

Comparative Example 4 TMOS (2.00 g) was dissolved in THF (20 ml), and 0.72 g of 1N HCl aqueous solution was added, followed by hydrolysis at room temperature for 1 hour with vigorous stirring. This solution was applied to a polyethylene film (thickness 3) using a spin coater.
0 μm) to obtain a transparent silica film. The solvent was evaporated by casting on a vat at room temperature to obtain a transparent silica film.

Comparative Example 5 TEOS (2.00 g) was dissolved in THF (20 ml), and 0.70 g of 1N aqueous HCl was added thereto, followed by hydrolysis at room temperature for 1 hour with vigorous stirring. This solution was applied to a polyethylene film (thickness 3) using a spin coater.
0 μm) to obtain a transparent silica film. Further, a transparent silica film was obtained by casting on a vat at room temperature and evaporating the solvent.

Comparative Example 6 The above "Iupilon" polycarbonate resin 0.60
g and TEOS (1.40 g) were dissolved in THF (50 ml), and then 0.49 g of 1N HCl aqueous solution was added, followed by vigorous stirring at room temperature for 1 hour. This solution was cast on a vat at room temperature and the solvent was evaporated to produce a sol-gel film having a PC / TEOS = 3/7 composition. No good film was obtained.

Comparative Example 7 The above-mentioned "Iupilon" polycarbonate resin 0.60
g and TEOS (1.40 g) were dissolved in 50 ml of THF, and then cast on a vat at room temperature to evaporate the solvent.
An attempt was made to produce a cast film having a composition of PC / TEOS = 3/7, but the film became a large shrinkable white brittle film, and a good film could not be obtained.

Scanning Electron Microscope (SEM) Observation Sections of the films obtained in Examples 1 to 4 and Comparative Examples 1 to 7 were observed by SEM. The device is JSM made by JEOL
-5800LVC type was used.

As a result, a uniform surface was observed in the PC film obtained in Comparative Example 1, the silyl group crosslinked PC films obtained in Comparative Examples 2 and 3, and the silica films obtained in Comparative Examples 4 and 5. Was. However, the P obtained in Comparative Example 6
In the C / TEOS-based sol-gel film and the PC / TEOS-based mixed cast film obtained in Comparative Example 7, countless pores having a size of several μm to 10 μm or more were observed,
The structure was full of gaps.

On the other hand, in all the silica / polycarbonate hybrid polymer materials of the present invention obtained in Examples 1 to 4, no macroscopic phase separation of two components was observed, and the surfaces were uniform.

PC / TEOS = 3/7 in Comparative Example 6
Composition and PCS / TEOS in Example 3 = 3/7
SEM photographs of the composition are shown in FIGS.

Dynamic Viscoelasticity Measurement The dynamic viscoelasticity was measured using the films obtained in Examples 1 to 4 and Comparative Examples 1 to 5, and the dynamic glass transition temperature (Tg) was determined from the temperature of the tan δ peak. Was determined from the E ′ curve. In the measurement, the sample film, the silyl group crosslinked PC film and the silica film were subjected to a heat treatment at 150 ° C. for 6 hours using a hot air drier, and the PC film was similarly treated at 120 ° C. for 6 hours. .

The measurement was carried out using a viscoelastic spectrometer SDM5600 manufactured by Seiko Denshi Kogyo Co., Ltd., and a test piece having a length of 25 × width 10 (mm) was used in a tensile mode. Other measurement conditions include a heating rate of 2 ° C./min and a heating temperature of 25 ° C.
３００300 ° C., frequency 1 Hz.

Table 1 shows the measurement results. FIG. 3 is a characteristic diagram of the composition of PCS / TMOS = 7/3 in Example 2.

Compared with commercially available PC and silyl group-crosslinked PC, the silica / polycarbonate hybrid polymer material of the present invention exhibits a glass transition temperature higher by 10 to 55 ° C.,
The higher the silica component, the higher the tendency. It is considered that, because the PC component is chemically bonded to the silica component, the molecular motion of the PC is suppressed, and the glass transition temperature is increased. Also, the elastic modulus at 280 ° C. tends to increase as the silica component increases, and PCS /
In the case of TMOS and TEOS = 5/5 composition and 3/7 composition, the elasticity was greatly improved by the effect of the hybrid, and large heat resistance was exhibited even at high temperatures. The heat resistance is expected to increase as the silica component increases,
With the 9 composition and the silica film, the sample film was damaged after the start of the measurement, and the measurement could not be performed.

The results will be specifically described.
The elastic modulus began to drop sharply around ℃, and after passing the glass transition temperature, it softened and melted at around 170 ℃. The silyl group-crosslinked PC softened and melted at around 220 ° C. after the elastic modulus gradually decreased. In contrast, the silica / polycarbonate hybrid polymer material has a gradual decrease in elastic modulus of 2%.
It stopped at 20-240 ° C and then kept its shape up to 280-300 ° C. That is, it is 100 ° C.
As described above, high heat resistance was exhibited.

[0095]

[Table 1] Physical heat resistance of silica / polycarbonate hybrid polymer material Example Composition ratio Film thickness Tg ¹⁾ Elastic modulus-1 ²⁾ Elastic modulus-2 ³⁾ (μm) (° C) (× 10 ⁹ Pa) (× 10 ⁷ Pa) Comparative Example 1 (PC) 117 156 1.4 Softening and Melting Comparative Example 2 (PCS) 216 155 3.1 Softening and Melting Comparative Example 3 (PCS) 190 161 2.8 Softening and Melting Example 1 PCS / TMOS = 9/1 205 168 2.5 2.1 7/3 114 176 2.5 7.5 5/5 109 178 1.6 33 3/7 92 192 2.1 50 1/9 85 − − − Example 2 PCS / TMOS = 9/1 145 174 3.4 3.1 7/3 147 192 2.9 12 5/5 88 202 1.7 38 3/7 101 209 2.4 74 1/9 96 − − − Example 3 PCS / TEOS = 9/1 197 171 3.1 2.5 7/3 174 176 2.5 9.3 5/5 131 182 1.9 29 3/7 120 196 2.3 58 1/9 81 − − − Example 4 PCS / TEOS = 9/1 162 172 2.6 2.6 7/3 108 186 1.8 11 5/5 116 191 1.7 34 3/7 100 198 1.7 76 1/9 85 - - - Comparative example 4 (TMOS) 82 - - - Comparative example 5 (TEOS) 77 - - - 1) at 100 ° C. obtained from dynamic glass transition temperature 2) E 'curve obtained from tanδ peak Sex ratio 3) E 'modulus at 280 ° C. obtained from curve

Surface Hardness Measurement Using the coating films on the polyamide substrates obtained in Examples 1 to 4 and Comparative Examples 1 to 3, surface hardness was measured by pencil hardness. In the measurement, the sample coating film and the silyl group-crosslinked PC coating film were subjected to a heat treatment at 150 ° C. for 6 hours using a hot air drier, and the PC coating film was similarly treated at 120 ° C. for 6 hours.
Time processing was performed. Thereafter, these coating films were allowed to stand for 48 hours in a constant temperature chamber at 23 ° C. and 50% humidity, and then used for measurement.

The measurement was performed using a pencil scratch test (JIS K5).
400), and the equipment was Peeling / Slipping / Scratchi manufactured by HEIDON.
ngTester HEIDON-14 type, a pencil used was a Mitsubishi uni pencil manufactured by Mitsubishi Pencil. The measurement conditions were a moving speed of the sample table of 30 mm / min and a load of 1.00 kg. Table 2 shows the measurement results.

Compared to commercially available PCs, the silica /
The pencil hardness of the polycarbonate hybrid polymer material was greatly improved. As compared with the silyl group-crosslinked PC, the surface hardness was equal to or better than that of the PC. Also, as the silica component increases, the hardness increases, and PCS / TMOS and TES
The composition of OS = 1/9 showed the same pencil hardness as glass.

[0099]

[Table 2]

Measurement of Gas Barrier Property Using the polyethylene film coating films obtained in Examples 1 to 4 and Comparative Examples 1 to 5, gas barrier properties against oxygen were measured. For the measurement, all the coating films were heat-treated at 60 ° C. for 48 hours, and then 23 hours in a vacuum dryer at 25 ° C. for 48 hours.
After drying for 48 hours in a desiccator using calcium chloride as a desiccant in a constant temperature chamber at ℃, it was used.

The measurement was carried out with reference to the differential pressure method in the gas permeability test method for plastic films and sheets (JIS K7126), and the apparatus used was a gas permeability measuring device M-C3 manufactured by Toyo Seiki Seisaku-sho. The measurement conditions were a cell adapter of 0 cc, a transmission area of 38.46 cm ² , and a high pressure side pressure of 780 mmHg. Table 3 shows the measurement results.

Compared with commercially available PC, silyl group-crosslinked PC, and silica, the silica / polycarbonate hybrid polymer material of the present invention shows generally good gas barrier properties, and PCS / TMOS and TEOS = 4/6 to The composition of 2/8 showed particularly high gas barrier properties.

This is because the silica material (glass) itself is known as a material having a very high gas barrier property. However, in the silica prepared by the sol-gel method, the internal pores are not completely independent, but are partially separated. This is probably because some of them penetrated the film. However, in the silica / polycarbonate hybrid polymer material, as the PC component increased, the PC component entered the pores of the silica, and the gas barrier property was greatly improved. However, when the PC component exceeded the amount that completely filled the silica pores, the gas barrier of the PC itself having a lower gas barrier property than the silica component was developed, and the value was reduced. From these, the maximum value was shown in the 3/7 composition. That is, it is considered that a phenomenon in which the PC component enters the pores of silica occurs at an appropriate composition ratio, and the gas barrier property is improved by a synergistic effect of the two components.

[0104]

Table 3 Oxygen Permeability Coefficient of Silica / Polycarbonate Polymer Material Example Composition Ratio Film Thickness Oxygen Permeability Coefficient (μm) (× 10 ^-11 cm ³ · cm / cm ² · sec · cmHg) Comparative Example 1 (PC) 12 7.7 Comparative Example 2 (PCS) 11 7.5 Comparative Example 3 (PCS) 12 7.4 Example 1 PCS / TMOS = 9/1 11 6.3 7/3 12 6.6 5/5 10 5 0.8 4/6 9 2.8 3/7 9 2.5 2/8 7 3.8 1/9 7 7.8 Example 2 PCS / TMOS = 9/1 11 6.8 7/3 10 6. 4 5/5 9 5.7 3/7 8 2.5 1/9 6 7.7 Example 3 PCS / TEOS = 9/1 12 7.0 7/3 10 6.3 5/5 10 5.5 4/6 8 2.9 3/7 8 2.3 2/8 7 4.1 1/9 6 7.6 Example 4 PCS / TEOS = 9/1 12 6.3 7/3 11 6.5 5 / 5 12 6.0 3/7 10 2.6 1/9 8 7.2 Comparative Example 4 (TMOS) 6 24 Comparative Example 5 (TEOS) 7 21

[Brief description of the drawings]

FIG. 1 PC / TEOS = 3/7 obtained in Comparative Example 6
SEM photograph of a sol-gel product having a composition.

FIG. 2 PCS / TEOS obtained in Example 3 = 3 /
SE of 7 composition silica / polycarbonate polymer material
M photo.

FIG. 3 shows PCS / TMOS obtained in Example 2 = 7 /
FIG. 4 is a characteristic diagram showing results of dynamic viscoelasticity measurement of silica / polycarbonate polymer materials having three compositions.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Masayuki Shimada, Inventor 3-11-6 Takakuradai, Sakai City, Osaka (72) Inventor Yasuyuki Kamishi 1-53-1, 1-13-1 Higashidaira, Chuo-ku, Osaka-shi, Osaka ( 56) References U.S. Pat. No. 5,175,027 (US, A) WO 93/4094 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB names) C08G 63/00-63/91 C08G 64/00 -64/42

Claims (11)

(57) [Claims] An organic compound obtained by co-hydrolyzing and co-polycondensing a polymer having a polycarbonate or polyarylate moiety as a main skeleton and having a metal alkoxide group as a functional group; and a metal alkoxide compound.
Inorganic hybrid polymer material. 2. The organic-inorganic hybrid polymer material according to claim 1, wherein the metal element of the metal alkoxide group and the metal alkoxide compound is at least one selected from the group consisting of Si, Ti, and Zr. 3. The organic-inorganic hybrid polymer material according to claim 1, wherein the metal element of the metal alkoxide group and the metal alkoxide compound is Si. 4. The polymer has a number average molecular weight of 500-5.
The polymer material according to claim 1, wherein the molecular weight is 0000. 5. The organic-inorganic hybrid polymer material according to claim 1, wherein the polymer has a metal alkoxide group equivalent of 1 to 100. 6. The organic-inorganic hybrid polymer material according to claim 1, wherein the weight ratio of the polymer to the metal alkoxide compound is 1:99 to 99: 1. 7. The organic-inorganic hybrid polymer material according to claim 6, wherein the content of the metal alkoxide compound is 10% by weight or more, which has excellent heat resistance. 8. The organic-inorganic hybrid polymer material according to claim 6, wherein the content of the metal alkoxide compound is 10% by weight or more, the material having excellent surface hardness. 9. The organic compound according to claim 1, wherein the weight ratio of the polymer to the metal alkoxide compound is 1: 9 to 9: 1.
An inorganic hybrid polymer material having excellent gas barrier properties. 10. A plastic molded article or film comprising the organic-inorganic hybrid polymer material according to claim 1, a sealing agent, an adhesive, a binder for paint, a structural material, an optical material, a polymer silane coupling agent, and a resin added. Object, surface modifier, hard coat agent, electric or electronic material, medical material, or filler. 11. An organic-inorganic hybrid compound comprising a step of co-hydrolyzing and co-polycondensing a polymer having a polycarbonate or polyarylate moiety as a main skeleton and having a metal alkoxide group as a functional group with a metal alkoxide compound. Manufacturing method of molecular material.