JP3238891B2 - 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 an organic-inorganic hybrid polymer material useful for various plastic materials, resin additives, coating 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.

[0003] However, these inorganic materials are generally poor in moldability and 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] For this reason, there is an urgent need to develop a material that complements the characteristics of an inorganic material and an organic polymer and makes the most of its advantages.

As one of the means, conventionally, in order to improve various physical properties such as surface hardness, gloss, stain resistance, impact 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 Si, Ti, or Zr is introduced into a skeleton.

In general, the method for preparing an organic-inorganic hybrid polymer material includes a method of radically copolymerizing an organic monomer or an organic polymer with an inorganic skeleton-containing compound such as an alkylsiloxane, and a method for preparing an organic polymer. There is known a method in which an inorganic functional group such as an alkoxysilane is bonded as a side chain, and thereafter, this is crosslinked.

For example, Japanese Patent Application Laid-Open No. 63-57642 discloses
JP-A-3-103486 and J.P. Appl. Po
lym. Sci. Vol. 35, pp. 20-39, 1988
It is described that radical polymerization of an organic monomer or an organic polymer is performed 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 introduce an alkylsiloxane moiety at both ends of the molecule, and it is almost impossible to uniformly introduce a siloxane skeleton in the molecule. . Further, the synthesis of the alkylsiloxane-containing compound used as a radical initiator requires complicated operations.

Also, for example, Macromolecul
es, Vol. 24, No. 6, page 1431, 1991, studies on preparing a siloxane-containing polymer by an anionic polymerization method are being conducted.

However, in order to obtain the desired organic-inorganic hybrid 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, since the anionic polymerization method is costly, 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 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 cross-linking them by a sol-gel method is described.

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

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 are unsuitable for use in industrial plastic materials, particularly structural materials and hard coat materials.

Macromolecules, No. 25
Vol. 4309, 1992, describes a method in which an alkoxysilyl group is bonded to the main chain of a polyalkylene oxide polymer, followed by hydrolysis and condensation. Further, Macromol. Chem. Macrom
ol. Symp. Volume 42/43, Page 303, 199
In one year, a polyoxazoline polymer was used as the main chain,
J. Inorg. Organomet. Polym. 5, page 4, 1995, a polyamine polymer is disclosed. Appl. Polym. Sci. Vol. 58, p. 1263, 1995 describes cellulose polymers. However, all of the polymers disclosed as the main chain in these prior arts are hydrophilic. Since hydrophilic polymers are hygroscopic and have poor water resistance, they are unsuitable for use in plastic molded articles, sealing materials, coating materials, structural materials, hard coat materials and the like.

On the other hand, hydrophobic organic polymers, especially engineering plastics, are excellent in heat resistance, mechanical strength, and water resistance, have a wide range of applications as industrial plastics, and are in great demand. Nevertheless, there is no report of an inorganic-organic polymer hybrid material using a hydrophobic organic polymer.

[0017]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned conventional problems. It is an object of the present invention to provide high-heat resistance, high mechanical strength, and high water resistance, and to obtain industrial plastic materials, especially plastic moldings. Products, plastic films, sealing materials, raw materials such as adhesives and paints, structural materials,
Optical materials, polymer silane coupling materials, resin additives,
An object of the present invention is to provide an organic-inorganic hybrid polymer material using a hydrophobic organic polymer, which is suitable for use as a surface modifier and a hard coat material.

[0018]

According to the present invention, a polymer having a polycarbonate and / or polyarylate moiety as a main skeleton and a metal alkoxide group as a functional group is crosslinked by hydrolysis and polycondensation. The present invention provides an obtained organic-inorganic hybrid polymer material, whereby the above object is achieved.

One preferred aspect of the present invention is that at least one
(A) having a number of functional groups in the molecule and having a polycarbonate and / or polyarylate moiety as a main skeleton, and a metal alkoxide (B) having a functional group capable of forming a bond by reacting with the above functional group To obtain a polymer having a metal alkoxide group as a functional group in the molecule, and then the obtained polymer was hydrolyzed and polycondensed by a sol-gel method to crosslink into a three-dimensional structure. The purpose is to obtain an organic-inorganic hybrid polymer material.

The main skeleton is polycarbonate and / or
Polymer (A) Having Polyarylate Portion In the present invention, preferable examples of the polymer (A) include polycarbonate, polyester carbonate, and polyarylate.

The polymer (A) may be a one-component polymer or a multi-component copolymer. Further, a mixture of a plurality of types may be used. The polymer (A) may have any of a branched shape and a linear shape. However, it is preferably soluble in solvents such as hydrocarbons, halogenated hydrocarbons, and ethers. The number average molecular weight is from 500 to 50,000, preferably from 1,000 to 10,000.

These polymers have at least one molecule per molecule.
And preferably two or more functional groups.
The functional group is not particularly limited as long as it can react with the functional group of the metal alkoxide (B).

Specifically, a hydroxyl group, an amino group, a carboxyl group, a thiol group, an alkenyl group, an alkynyl group, an acid halogen group, an acid ester group, a formyl group, a halogen group,
An epoxy group and an isocyanate group can be exemplified. Preferred are functional groups having active hydrogen such as a hydroxyl group, an amino group, and a carboxyl group. The functional group equivalent of the polymer (A) is 1 to 50, preferably 2 to 10.

Metal alkoxide (B) having a functional group In the present invention, a preferable metal alkoxide (B) is a compound represented by the formula

## STR1 ## _{R l A m M (R'X)} n (1) [ wherein, R 1 to 12 carbon atoms, preferably 1 to 5 alkyl groups, A is 1 to 8 carbon atoms, preferably 1 ~ 4 alkoxy groups, M is Si, Ti, Zr, Fe, Cu, Sn,
A metal element selected from the group consisting of B, Al, Ge, Ce, and Ta, preferably a group consisting of Si, Ti, and Zr, R ′ is an alkylene group having 1 to 4, preferably 2 to 4 carbon atoms or An alkylidene group, X is a functional group selected from the group consisting of an isocyanate group, an epoxy group, a carboxyl group, an acid halogen group, and an acid anhydride group;
And m and n are each independently an integer of 1 to 3. ] The compound shown by this.

Specific examples of such a metal alkoxide (B) include 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 2-isocyanatoethyltriethoxysilane, and 2-isocyanatoethyltripropoxyzirconium. Monoisocyanate trialkoxy metals such as, 2-isocyanatoethyltributoxytin;

Monoisocyanate dialkoxy such as 3-isocyanatopropylethyldiethoxysilane, 3-isocyanatopropylmethyldiisopropoxytitanium, 2-isocyanatoethylethyldipropoxyzirconium, 2-isocyanatoethylmethyldibutoxytin and isocyanatomethyldimethoxyaluminum Metals;

Monoisocyanate monoalkoxy metals such as 3-isocyanatopropyldiethylethoxysilane, 3-isocyanatopropyldimethylisopropoxytitanium, 2-isocyanatoethyldiethylpropoxyzirconium, 2-isocyanatoethyldimethylbutoxytin and isocyanatomethylmethylmethoxyaluminum;

Diisocyanate alkoxymetals such as di (3-isocyanatopropyl) diethoxysilane and di (3-isocyanatopropyl) methylisopropoxytitanium;

Triisocyanate alkoxymetals such as ethoxysilane triisocyanate;

Γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane,
γ-glycidoxypropylmethyldimethoxysilane, γ
-Glycidoxypropyldimethylethoxysilane, γ-
Glycidoxypropylmethyldiethoxysilane, β-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3,4-epoxybutyltrimethoxysilane, γ-glycidoxypropyltriisopropoxytitanium, γ-glycidoxypropylmethyldiisopropoxytitanium, γ-glycid Xypropyldimethylisopropoxytitanium, 3,4-epoxybutyltripropoxyzirconium, 3,4-epoxybutylmethyldipropoxyzirconium, 3,4-epoxybutyldimethylpropoxyzirconium, β- (3,4-epoxycyclohexyl) ethyltri Metal alkoxides having an epoxy group as a functional group such as ethoxytin;

Alkoxy such as methyltrimethoxysilane, ethyltriethoxysilane, isopropyltriisopropoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, diisopropyldiisopropoxysilane, trimethylmethoxysilane, triethylethoxysilane and triisopropylisopropoxysilane Alkylalkoxysilanes having a functional group as a functional group;

Metal alkoxide having a functional group of an acid anhydride group such as 3- (triethoxysilyl) -2-methylpropylsuccinic anhydride;

2- (4-chlorosulfonylphenyl)
Metal alkoxides having an acid halide such as ethyltriethoxysilane as a functional group;

In addition, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,
Alkoxysilanes having a functional group of an amino group or a mercapto group, such as mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane, may be used.

Another example of the metal alkoxide (B) is represented by the formula

## STR2 ## A _p M (2) [In the formula, A 1 to 8 carbon atoms, preferably 1 to 4 alkoxy groups, M is Si, Ti, Zr, Fe, Cu, Sn,
A metal element selected from the group consisting of B, Al, Ge, Ce, and Ta, preferably the group consisting of Si, Ti, and Zr. ] The compound shown by this.

Specifically, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane and tetrabutoxysilane;

Metal alkoxides such as tetrapropoxytitanium, tetraisopropoxytitanium, tetraisopropoxyzirconium, tetrapropoxyzirconium, tetrabutoxytin, tetraisopropoxytin, and triisopropoxyaluminum.

The metal alkoxide (B) may be used alone or in combination of two or more. Alternatively, a metal alkoxide in which two or more metal elements are contained in one molecule or an oligomer-type metal alkoxide having two or more repeating units in one molecule may be used.

Having a metal alkoxide group as a functional group
Polymer polymer (A) can be reacted with metal alkoxide (B) in a conventional manner, as a result, a polymer having a metal alkoxide group in the molecule. In the reaction, a catalyst may be used.

As the catalyst, the functional group of the metal alkoxide (B) is an isocyanate group or an acid halide group,
When the functional group of the polymer (A) is a hydroxyl group, an amino group, a carboxyl group, a thiol group or the like, 1,4-diazobicyclo [2,2,2] octane (DABCO),
1,8-diazabicyclo [5,4,0] -7-undecene (DBU), triethylamine, tributylamine,
Organic bases such as piperidine are commonly used.

When the functional group of the metal alkoxide (B) is an epoxy group and the functional group of the polymer (A) is a hydroxyl group, an amino group, a carboxyl group, a thiol group, or the like, hydrochloric acid, sulfuric acid, nitric acid, Acids such as acetic acid are generally used.

The functional group of the metal alkoxide (B) is a carboxyl group, an acid anhydride group or an alkoxy group, and the functional group of the polymer (A) is a hydroxyl group, an amino group, a carboxyl group,
In the case of a thiol group or the like, both a basic catalyst and an acidic catalyst can be used.

When the functional group of the polymer (A) is an alkenyl group, an alkynyl group or the like, an alkoxysilyl group can be introduced by a hydrosilylation reaction with a silicon compound having a Si—H group.

Specific examples of the reaction between the polymer (A) and the metal alkoxide (B) will be described below.

In the first method, a hydroxyl group, an amino group,
A polymer (A) having a functional group having an active hydrogen such as a carboxyl group or a thiol group, and a metal alkoxide (B) having a functional group such as an isocyanate group, an epoxy group, a carboxyl group, an acid halide group, or an acid anhydride group. ) In a solvent, preferably under an inert gas atmosphere. The solvent to be used may be any one that can well dissolve both the polymer and the metal alkoxide.

In general, after a metal alkoxide solution or a metal alkoxide is gradually added to a polymer solution as it is, the reaction is carried out at room temperature or with gentle heating. The amount of the functional group in the metal alkoxide (B) relative to the functional group in the polymer (A) is desirably 1/10 to 10 equivalent.

After the completion of the reaction, the reaction solution may be used as it is, and the process may be shifted to the sol-gel reaction in the next step, or the reaction product may be concentrated or poured into a large amount of a poor solvent to precipitate a reaction product, which may be washed, After processing such as purification and drying, it may be used for a sol-gel reaction.

In the second method, a polymer (A) having a functional group having active hydrogen and a metal alkoxide (B) which is a tetraalkoxy metal or a trialkoxy metal are dissolved in a solvent.
Preferably, the reaction is performed under an inert gas atmosphere. In order to promote the reaction advantageously, the functional group in the polymer (A) is preferably a functional group adjacent to an aliphatic molecular chain, and the alkoxide of the metal alkoxide (B) is preferably as small as possible.

The solvent used must be capable of dissolving the polymer and the metal alkoxide, and the reaction in a water-free system is desirable. Therefore, the reaction is preferably carried out using a non-polar solvent or a dehydrating solvent. It is better to add a catalytic amount of an acidic catalyst such as hydrochloric acid, sulfuric acid or acetic acid, a basic catalyst such as triethylamine, DBU or piperidine, or a metal catalyst such as iron chloride or zinc chloride.

The amount of the functional group in the metal alkoxide (B) relative to the functional group in the polymer (A) is desirably 1/4 to 100 equivalent.

In the same manner as in the first method, the reaction solution may be used as it is to transfer to the sol-gel reaction, or the reaction product may be taken out, washed, purified, dried and the like, and then subjected to the sol-gel reaction. May be performed.

In the third method, a polymer (A) having a functional group such as an alkenyl group or an alkynyl group is subjected to a hydrosilylation reaction with a metal alkoxide (B) which is a silicon compound having a Si—H group.

Also in this case, the reaction in a solution is desirable, and the catalyst is generally chloroplatinic acid, 1,3-divinyl-1,1,3
A transition metal catalyst such as 1,3,3-tetramethyldisiloxane platinum complex or tris (triphenylphosphine) rhodium chloride is used.

Specific examples of solvents used for these reactions include hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and n-hexane; carbon tetrachloride, chloroform, dichloromethane, chloroethane, dichloroethane, chlorobenzene, and the like. Halogenated hydrocarbon solvents such as dichlorobenzene and trichlorobenzene; ether solvents such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, diethyl ether, dibutyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Examples thereof include ketone solvents, but are not limited thereto.

Organic-Inorganic Hybrid Polymer Material Next, a polymer having a metal alkoxide group as a functional group is hydrolyzed and polycondensed by a sol-gel reaction. This polymer may be in a state of being dissolved in a reaction solution immediately after preparation or in an isolated state.

The hydrolysis and polycondensation by the sol-gel method are the reaction of a polymer having a metal alkoxide group in the molecule with water to convert the alkoxy group into a hydroxyl group. Polycondensation causes a polymer having a hydroxy metal group (e.g., -Si (OH) ₃ ) to undergo a dehydration reaction or a dealcoholization reaction with an adjacent molecule, and a three-dimensional crosslinking reaction through an inorganic covalent bond. Say.

The water used in 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 do it. 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 or a basic catalyst such as sodium hydroxide, potassium hydroxide, ammonia, triethylamine, piperidine or DBU may be used.

In order to further promote the condensation reaction and to make the cross-linking stronger, then at 50 to 400 ° C. for 5 minutes to 4 hours.
Heat treatment is performed for about 8 hours.

In all of 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, and T
Metals such as a, metal oxides, metal complexes, inorganic salts or metal alkoxides may coexist.

[0060]

According to the present invention, it is possible to impart properties such as heat resistance, weather resistance, surface hardness, rigidity, water resistance, chemical resistance, stain resistance, mechanical strength and flame retardancy of an inorganic material to an organic polymer. it can. Industrial plastic materials, especially plastic molded products, plastic films, sealing materials, raw materials such as adhesives and paints, structural materials, optical materials, polymer silane coupling materials, resin additives, surface modifiers, and hard coat materials Thus, an organic-inorganic hybrid polymer material using a hydrophobic organic polymer, which is suitable for use in, for example, is provided.

[0061]

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 Alkoxysilylation of Polycarbonate Diol (PC-diol) PC-diol having a number average molecular weight of 3,900 prepared by referring to the method described in JP-B-7-33441.
(70.00 g) was dissolved in 500 mL of chloroform. Thereafter, 13.32 g of 3-isocyanatopropyltriethoxysilane (IPTES) was added to this solution, heated under reflux for 10 hours, and then cooled to room temperature. This reaction solution was dropped into 7 L of methanol to precipitate a reaction product. The precipitate was separated by filtration, washed with methanol, and dried under reduced pressure (yield 97.0%).

FIG. 1 shows the results of ¹ H-NMR measurement of the obtained product. This confirmed that alkoxysilyl groups were introduced at both ends of the product. As a result of GPC measurement, the number average molecular weight of the product was 4,400.
Met.

Example 2 Alkoxysilylation of PC-diol PC-diol having a number average molecular weight of 6,600 prepared by referring to the method described in JP-B-7-33441.
(70.00 g) was dissolved in 500 mL of chloroform. Thereafter, IPTES (7.87 g) was added to this solution, and the mixture was heated under reflux for 15 hours. After that, post-treatment was performed in the same manner as in Example 1 to obtain a reaction product (yield: 99.3%). The product was confirmed by ¹ H-NMR to have alkoxysilyl groups introduced at both ends. As a result of GPC measurement, the number-average molecular weight of the product was 7,500.

Example 3 Alkoxysilylation of PC-diol A PC-diol having a number average molecular weight of 8,600 prepared by referring to the method described in JP-B-7-33441.
(70.00 g) was dissolved in 500 mL of chloroform. Thereafter, IPTES (6.04 g) was added to this solution, and the mixture was heated under reflux for 15 hours, followed by post-treatment in the same manner as in Example 1 to obtain a reaction product (yield: 99.1%). The product was confirmed by ¹ H-NMR to have alkoxysilyl groups introduced at both ends. As a result of GPC measurement, the product had a number average molecular weight of 9,000.

Example 4 Alkoxysilylation of PC-diol PC-diol having a number average molecular weight of 3,400 prepared by referring to the method described in JP-B-7-33441.
(3.00 g) was dissolved in 30 g of toluene. Thereafter, IPTES (0.65 g) was added to the solution, and the mixture was heated under reflux for 8 hours, and then dropped into 500 mL of methanol to precipitate a reaction product. The precipitate was separated by filtration, washed with methanol, and dried under reduced pressure (yield: 88.9%). The product was confirmed by ¹ H-NMR to have alkoxysilyl groups introduced at both ends. As a result of GPC measurement, the product had a number average molecular weight of 4,300.

Example 5 Alkoxysilylation of PC-diol The experiment was carried out in the same manner as in Example 4 except that the reaction solvent was changed from toluene to 1,2,4-trichlorobenzene to obtain a reaction product. Rate 91.9%). The product is ¹ H-N
By MR, it was confirmed that alkoxysilyl groups had been introduced into both terminals, and as a result of GPC measurement, the number average molecular weight of the product was 4,200.

Example 6 Alkoxysilylation of PC-diol PC-diol having a number average molecular weight of 3,400 prepared by referring to the method described in JP-B-7-33441.
(3.00 g) was dissolved in 30 g of chloroform. Thereafter, 0.65 g of β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and a trace amount of acetic acid were added to this solution, and the mixture was heated under reflux for 8 hours, and post-treated in the same manner as in Example 4. The reaction product was obtained (yield 88.8).
%). The product was confirmed by ¹ H-NMR to have an alkoxysilyl group introduced at both ends, and as a result of GPC measurement, the number average molecular weight of the product was 4,200.

Example 7 Alkoxysilylation of PC-diol PC-diol having a number average molecular weight of 3,400 prepared by referring to the method described in JP-B-7-33441.
(3.00 g) was dissolved in 30 g of chloroform. Thereafter, 0.74 g of γ-glycidoxypropyltriethoxysilane and a trace amount of acetic acid were added to this solution, and the mixture was heated under reflux for 8 hours, and post-treated in the same manner as in Synthesis Example 4 to obtain a reaction product. (92.0% yield). The product is ¹ H-NM
It was confirmed by R that alkoxysilyl groups had been introduced at both ends, and as a result of GPC measurement, the number average molecular weight of the product was 4,200.

Example 8 Alkoxysilylation of PC-diol PC-diol having a number average molecular weight of 3,400 prepared by referring to the method described in JP-B-7-33441.
(5.00 g) was dissolved in 100 g of dimethylformamide. Thereafter, 4.6 g of sodium carbonate and 0.53 g of allyl bromide were added to the solution, and 10
Heated for hours. After cooling, the reaction solution was dropped into 1 L of methanol to precipitate a reaction product. The precipitate was separated by filtration, washed with methanol, and dried under reduced pressure to obtain a polycarbonate having allyl groups at both ends (yield: 85%).

Next, after dissolving the obtained polycarbonate (3.00 g) having allyl groups at both ends in 60 g of tetrahydrofuran, trace amounts of chloroplatinic acid and 0.42 g of triethoxysilane were added thereto. Heated for hours.
After cooling, the reaction solution was dropped into 600 ml of methanol to precipitate a reaction product. The precipitate was separated by filtration, washed with methanol, and dried under reduced pressure (yield 82%). The product is ¹ H-NM
It was confirmed by R that alkoxysilyl groups had been introduced into both terminals, and as a result of GPC measurement, the number average molecular weight of the product was 3,900.

Example 9 Preparation of Film by Sol-Gel Method The alkoxysilylated polycarbonate having a number average molecular weight of 4,400 (4.62 g) synthesized in Example 1 was dissolved in 46 g of tetrahydrofuran, and 0.34 g of 1N hydrochloric acid aqueous solution was obtained. Was added and the mixture was vigorously stirred at room temperature for 1 hour to carry out hydrolysis. This solution was coated on a polyamide substrate using a spin coater (film thickness 18.5 μm).

After casting on a vat at room temperature and evaporating the solvent, it was heat-treated at 150 ° C. to obtain a transparent and good film.

Table 1 shows the results of measurement of surface hardness by pencil hardness, dynamic viscoelasticity measurement, and tensile test of these films.

Example 10 Preparation of Film by Sol-Gel Method The alkoxysilylated polycarbonate having a number average molecular weight of 7,500 (4.62 g) synthesized in Example 2 was dissolved in 46 g of tetrahydrofuran, and 0.20 g of 1N hydrochloric acid aqueous solution was dissolved. Was added and the same treatment as in Example 9 was performed to obtain a transparent and good film.

Table 1 shows the results of surface hardness measurement, dynamic viscoelasticity measurement, and tensile test on these films.

Example 11 Preparation of Film by Sol-Gel Method The alkoxysilylated polycarbonate having a number average molecular weight of 9,000 (4.62 g) synthesized in Example 3 was dissolved in 46 g of tetrahydrofuran and then 0.16 g of 1N hydrochloric acid aqueous solution. Was added and the same treatment as in Example 9 was performed to obtain a translucent and favorable film.

Table 1 shows the results of surface hardness measurement, dynamic viscoelasticity measurement, and tensile test of these films.

Example 12 Preparation of Film by Sol-Gel Method An alkoxysilylated polycarbonate having a number average molecular weight of 5,900 (4.62 g) was dissolved in 46 g of tetrahydrofuran, and 0.24 g of 1N hydrochloric acid was added. A transparent and good film was obtained in the same manner as in Example 9 except that the heat treatment was performed.

Table 1 shows the results of surface hardness measurement, dynamic viscoelasticity measurement, and tensile test on these films.

Example 13 Preparation of Film by Sol-Gel Method An alkoxysilylated polycarbonate having a number average molecular weight of 7,200 (4.62 g) was dissolved in 46 g of tetrahydrofuran, and 0.20 g of 1N hydrochloric acid was added. A transparent and good film was obtained in the same manner as in Example 9 except that the heat treatment was performed.

Table 1 shows the results of measurement of surface hardness by pencil hardness, measurement of dynamic viscoelasticity, and tensile test of these films.

Example 14 Preparation of Film by Sol-Gel Method An alkoxysilylated polycarbonate having a number average molecular weight of 9,400 (4.62 g) was dissolved in 46 g of tetrahydrofuran, and 0.16 g of 1N hydrochloric acid was added. A translucent and good film was obtained in the same manner as in Example 9 except that the heat treatment was performed.

Table 1 shows the results of measurement of surface hardness by pencil hardness, measurement of dynamic viscoelasticity, and tensile test on these films. FIG. 2 shows a characteristic diagram of the measurement results of the dynamic viscoelasticity.

Comparative Example 1 Iupilon (Iu) having a number average molecular weight of 36,000
After dissolving the polycarbonate resin (4.62 g) in 100 g of dichloromethane, the solution was coated on a polyamide substrate using a spin coater (film thickness 7.7 μm). Further, the mixture was cast on a vat at room temperature, and the solvent was evaporated to obtain a transparent polycarbonate film.

Then, after the obtained film was heat-treated at 120 ° C., the surface hardness was measured by pencil hardness, dynamic viscoelasticity, and tensile test were performed for comparison with other samples. Table 1 shows the results. FIG. 3 shows a characteristic diagram of the measurement results of the dynamic viscoelasticity.

Here, comparing FIG. 2 with FIG. 3, the elastic modulus of the polycarbonate film of Comparative Example 1 began to drop sharply from around 140 ° C.
It softened and melted at around 70 ° C. On the other hand, although the modulus of elasticity of the silyl group-crosslinked polycarbonate film of Example 14 began to decrease from around 145 ° C., the decrease was more gradual than in the case of Comparative Example 1. Then, it softens and melts at around 230 ° C. through a wide glass transition region. That is, the silyl group crosslinked polycarbonate film of the present invention maintained its shape up to around 230 ° C., and exhibited heat resistance about 60 ° C. higher than that of a commercially available polycarbonate film.

Comparative Example 2 PC-diol having a number average molecular weight of 3,900 (0.39
g) was dissolved in 4 g of tetrahydrofuran, and 0.03 g of 1N hydrochloric acid was added, followed by vigorous stirring at room temperature for 1 hour.

The solution was transferred to a wide-mouthed container and allowed to stand at room temperature for 24 hours to evaporate the solvent. However, the solution became white powder and no film was obtained.

Comparative Example 3 The same treatment as in Comparative Example 2 was carried out except that 1N aqueous hydrochloric acid was not added. After evaporation of the solvent, it became white powder and no film was obtained.

Comparative Example 4 PC-diol having a number average molecular weight of 8,600 (0.39
g) was dissolved in 4 g of tetrahydrofuran, and 0.015 g of 1N aqueous hydrochloric acid was added, and the same treatment as in Comparative Example 1 was performed. After evaporation of the solvent, it became a white powder and no film was obtained.

Comparative Example 5 The same treatment as in Comparative Example 4 was carried out except that 1N aqueous hydrochloric acid was not added. After evaporation of the solvent, it became white powder and no film was obtained.

Comparative Example 6 An alkoxysilylated polycarbonate having a number average molecular weight of 4,400 (0.39 g) was dissolved in 4 g of tetrahydrofuran, transferred to a wide-mouthed container, and allowed to stand at room temperature for 24 hours to evaporate the solvent. It became a white fine solid and a film was not obtained.

Comparative Example 7 An alkoxysilylated polycarbonate having a number average molecular weight of 9,400 (0.39 g) was dissolved in 4 g of tetrahydrofuran, and the same treatment as in Comparative Example 6 was performed. After evaporation of the solvent, a fine white solid was obtained, and no film was obtained.

[0095]

[Table 1] Film properties of silyl group cross-linked polycarbonate polymer material Example Heat treatment Surface glass transition Tensile yield Tensile fracture Tensile temperature (° C) Hardness temperature (° C) Strength * 3) Elongation (%) Elasticity * 3) * 1) * 2) (10 ⁶・ Pa) * 3) (10 ⁶・ Pa) Comparative Example 1 120 HB 156 54 63.1 1730 (commercially available) Example 9 150 5H 155 73 3.7 2750 Example 10 150 6H 161 80 7.0 2690 Example 11 150 4H 191 75 9.2 2650 Example 12 160 6H 156 78 5.4 2720 Example 13 160 6H 157 81 6.9 2690 Example 14 160 4H 165 75 9.3 2650 1) Surface hardness: Pencil scratch test (JIS K 5400) (Soft) 6B-B, HB, F, H-9H (hard) 2) Glass transition temperature: temperature of tan δ peak measured by dynamic viscoelasticity 3) Tensile test: JIS K 7127

From the results shown in Table 1, the film of the organic-inorganic hybrid polymer material of the present invention has a higher glass transition temperature and higher surface hardness, tensile strength and tensile elastic modulus than the commercially available polycarbonate film. It can be seen that each has improved and the tensile elongation has decreased. That is, the polymer material film of the present invention exhibited higher heat resistance and mechanical strength than commercially available polycarbonate films.

[Brief description of the drawings]

FIG. 1 is a spectrum diagram showing the results of ¹ H-NMR measurement of the alkoxysilylated polycarbonate obtained in Example 1.

FIG. 2 is a characteristic diagram showing the results of dynamic viscoelasticity measurement of the silyl group-crosslinked polycarbonate film obtained in Example 14.

FIG. 3 is a characteristic diagram showing the results of dynamic viscoelasticity measurement of the polycarbonate film obtained in Comparative Example 1.

────────────────────────────────────────────────── ─── 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 (12)

(57) [Claims] An organic-inorganic hybrid polymer obtained by crosslinking a polymer having a polycarbonate and / or polyarylate moiety as a main skeleton and having a metal alkoxide group as a functional group by hydrolysis and polycondensation. material. 2. The method according to claim 1, wherein the metal element of the metal alkoxide group is Si,
The organic-inorganic hybrid polymer material according to claim 1, which is at least one selected from the group consisting of Ti and Zr. 3. The organic-inorganic hybrid polymer material according to claim 1, wherein the metal element of the metal alkoxide group is Si. 4. The polymer has a number average molecular weight of 500-5.
The organic-inorganic hybrid 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. An organic-inorganic hybrid polymer comprising a step of crosslinking a polymer having a polycarbonate and / or polyarylate moiety as a main skeleton and having a metal alkoxide group as a functional group by hydrolysis and polycondensation. Material manufacturing method. 7. The method according to claim 7, wherein the metal element of the metal alkoxide group is Si,
The method according to claim 6, wherein the method is at least one selected from the group consisting of Ti and Zr. 8. The method according to claim 6, wherein the metal element of the metal alkoxide group is Si. 9. A polymer having a number average molecular weight of 500 to 5
7. The method of claim 6, wherein the number is 0000. 10. The method according to claim 6, wherein the polymer has a metal alkoxide group equivalent of 1 to 100. 11. Polycarbonate and / or as a main skeleton.
Or, a polymer having a polyarylate moiety and having a metal alkoxide group as a functional group. 12. A polymer having at least one functional group in a molecule and having a polycarbonate and / or polyarylate moiety as a main skeleton, and a metal having a functional group which reacts with the functional group to form a bond. A method for producing a polymer having a polycarbonate and / or polyarylate moiety as a main skeleton and a metal alkoxide group as a functional group, including a step of reacting with an alkoxide.