JPH07224225A - Composite polymer - Google Patents

Abstract

PURPOSE:To obtain a composite polymer which has a high refractive index and excellent transparency and can form a transparent coating layer on a plastic substrate with good adhesion thereto by reacting a metal alkoxide with an aromatic polysulfone. CONSTITUTION:10-80wt.% metal alkoxide of formula I (wherein A is Ge, Zx or Ti; R<1> is a 1-4 C hydrocarbon group; R<2> is alkyl, an unsaturated hydrocarbon group, an aromatic hydrocarbon group or a functional substituent; x is 2, 3 or 4; y is 0, 1 or 2; and x+y=4) is reacted with 90-20wt.% aromatic polysulfone comprising repeating units of formula II or comprising repeating units of formula II and repeating units of formula III to obtain a composite polymer having a viscosity-average molecular weight of od 0.4-1.0dl/g (in terms of a reduced viscosity as measured in N,N-dimethylformamide in a concentration of 1g/dl at 30 deg.C). This polymer has a high refractive index and excellent transparency and can form a coating film of good adhesion on a plastic substrate, and therefore it is useful as an optical material for transparent coating layers, optical multilayer films, etc.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a composite polymer having a high refractive index and being useful as an optical material.

[0002]

2. Description of the Related Art Transparent organic polymer materials are widely used as optical materials such as optical fibers, lenses and functional films because they are lightweight and easy to mold.
Since the refractive index, which is one of the important optical characteristics, is smaller than that of the inorganic polymer material, it has a drawback that the range of use is limited.

On the other hand, an inorganic polymer material is superior to an organic polymer material in terms of performance such as heat resistance, mechanical properties, chemical resistance, and high refractive index which is an optical property, but it cannot be easily molded. It has the drawback of

In recent years, active research has been carried out on organic-inorganic hybrid polymers which have improved these drawbacks and have the characteristics of both. As a research example of such a composite polymer, JP-A-2-261827 discloses a technique for a transparent coating layer having excellent surface hardness and a high refractive index. In the method disclosed herein, an epoxy resin is used as an organic material and an organic silicon compound is used as an inorganic material, and it has been shown that a cured product of these can form a film having a high refractive index. However, since the refractive index of this cured film is not so large as 1.556, it has a problem that it is insufficient for use as an antireflection film or the like. In addition, B. Wang, H .; Huang, and G.H. l.
Wilkes, J .; E. Polym. Master. S
ci. Eng. , 63, 892 (1990), aromatic polysulfones having the following repeating units and tetra-i
It has been shown that an organic-inorganic composite material composed of so-propoxide titanium is excellent in transparency and has a high refractive index.

[0005]

[Chemical 3]

In this case, the higher the content of titanium oxide in the organic-inorganic composite material, the higher the refractive index, and when the content is 60% by weight, the refractive index exceeds 1.70. However, as the content of titanium oxide increases, the coefficient of linear expansion of the organic-inorganic composite material decreases, and as a result, there is no problem when the composite material is coated on a glass substrate to form a thin film. In the case of forming a thin film on the above, the linear expansion coefficient of the thin film made of the composite material and that of the plastic base material are largely different from each other, which causes a problem that the adhesion of the thin film to the base material is lowered.

Therefore, the upper limit of the refractive index of the organic-inorganic composite material that can be used for coating a plastic substrate is 1.
It is about 70, and there is no refractive index material exceeding 1.70 necessary for forming an optical multilayer film for antireflection.

[0008]

An object of the present invention is to provide a composite polymer having a high refractive index and excellent transparency, and a transparent coating layer can be formed on a plastic substrate with sufficient adhesion. To provide a composite polymer.

[0009]

That is, the present invention provides a metal alkoxide having a general formula of the following formula (I) of 10 to 80:
% To 90% by weight of an aromatic polysulfone having a repeating unit represented by the following general formula (II) or (II) and (III) is a reaction product having a viscosity average molecular weight of N, Concentration 1 in N-dimethylformamide
g / d1, reduced viscosity measured at a temperature of 30 ° C. is 0.4 to
The present invention provides a composite polymer having a content of 1.0 dl / g.

[0010]

[Chemical 4]

(In the formula, A represents a germanium, zirconium or titanium atom, R ¹ represents a hydrocarbon group having 1 to 4 carbon atoms, R ² represents an alkyl group, an unsaturated hydrocarbon group or an aromatic hydrocarbon group. Or represents a functional substituent, and x is 2, 3
Alternatively, 4, y represents 0, 1 or 2 (however, the sum of x and y is 4). )

[0012]

[Chemical 5]

The metal alkoxide represented by the general formula (I) used in the present invention is titanium alkoxide, zirconium alkoxide or germanium alkoxide,
Titanium, zirconium and germanium atoms exhibit a high refractive index. Alkoxysilane, which is generally used as a metal alkoxide, cannot be used because it has no ability to express a high refractive index in a silicon atom.

R ^{1 in} the formula of the metal alkoxide represented by the above formula (I) is a hydrocarbon group having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, or te
R ² is, for example, an rt-butyl group or the like, and R ² is, for example, an alkyl group such as a methyl group or an ethyl group, an unsaturated hydrocarbon group such as an allyl group or a vinyl group, an aromatic hydrocarbon group such as a phenyl group or a natiful group, or an epoxy group. Groups, functional substituents such as amino groups, and the like.

As specific examples of the metal alkoxide, when A is titanium, for example, tetramethoxy titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetra-iso-propoxy titanium, tetra-n-butoxy titanium, tetra- sec-butoxy titanium, tetra-t
ert-butoxy titanium, etc .; monomethyl trimethoxy titanium, monomethyl triethoxy titanium, monomethyl-n-propoxy titanium, monomethyl-iso-propoxy titanium, monomethyl tri-n-butoxy titanium, monomethyl tri-sec-butoxy titanium, monomethyl trititanium. -Tert-butoxytitanium, ethyltriethoxytitanium, vinyltriethoxytitanium, phenyltriethoxytitanium, epoxytriethoxytitanium, aminotriethoxytitanium, acryloxytriethoxytitanium, etc .; and further dimethyldimethoxytitanium, dimethyldiethoxytitanium, dimethyldi- n-propoxytitanium, dimethyldi-iso-propoxytitanium, dimethyldi-n-
Butoxy titanium, dimethyl di-sec-butoxy titanium, dimethyl di-tert-butoxy titanium, diethyl diethoxy titanium, ethyl vinyl diethoxy titanium, ethyl phenyl diethoxy titanium, methyl epoxy diethoxy titanium, methyl amino diethoxy titanium, methyl acryloxy di Examples include ethoxy titanium.

When A in the formula (1) is germanium or zirconium, a compound in which the titanium is replaced with germanium or zirconium is mentioned.

The aromatic polysulfone used in the composite polymer of the present invention is an aromatic polysulfone having a specific structure and having the repeating unit represented by the general formula (II) or (II) and (III). However, it is used because it has excellent compatibility with the inorganic material composed of the metal alkoxide represented by the above formula (I) and has a high refractive index.

Examples of the monomer capable of forming the repeating unit of the general formula (II) include 4-chloro-4 '(p-hydroxyphenyl) diphenyl sulfone.

Examples of the monomer capable of forming the repeating unit of the general formula (III) include 4,4 "'-dihydroxy-p-quaterphenyl.

Further, the monomer having the repeating unit (II) or (III) may be a copolymerizable monomer, for example, 4,4'-dihydroxybiphenyl, 4,4 "-dihydroxyterphenyl. , Bisphenol A, bisphenol F, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphenyl ketone, 4,4′-dihydroxydiphenyl sulfide, and other dihydroxy compounds, 4,4′-dichlorodiphenyl sulfone, 4, 4'-difluorodiphenyl sulfone, 4,4'-dichlorodiphenyl ketone,
Examples of the dihalogeno compound include 4,4′-difluorodiphenyl ketone, and the amount thereof is preferably 30 mol% or less, and more preferably 25 mol% or less based on all monomers constituting the aromatic polysulfone. When it exceeds 30 mol%, the refractive index of the obtained composite polymer is largely lowered, which is not preferable.

When an aromatic polysulfone having the repeating units of the general formulas (II) and (III) is used, the amount of the monomer capable of forming the repeating unit of the general formula (III) constitutes the aromatic polysulfone. It is preferably 30 mol% or less of all monomers, more preferably 25 mol%.
It is not more than mol%. When it exceeds 30 mol%, the refractive index of the composite polymer increases, but the moldability is lost, which is not preferable.

Further, in the composite polymer of the present invention, in addition to the above-mentioned aromatic polysulfones, among the materials called engineering plastics, polyester, polyarylate, polycarbonate, polysulfone, polyethersulfone, polyetherketone, polyetheretherketone, polyphenylene. Sulfide, polyphenylene sulfide sulfone, polyether nitrile, etc. may be contained within a range that does not impair the effects of the present invention.

The molar fraction of the repeating unit represented by the general formula (II) contained in the aromatic polysulfone having no repeating unit represented by the general formula (III) is usually 70.
% Or more, and in the case of the aromatic polysulfone having the repeating units represented by the general formulas (II) and (III), the molar fraction of the repeating units represented by the general formula (II) is usually 5 to 5. It is 99%, and the molar fraction of the repeating unit represented by the general formula (III) is usually preferably 1 to 25%.

Next, a method for producing the composite polymer of the present invention will be described.

The composite polymer of the present invention can be produced by polymerizing the aromatic polysulfone to a predetermined degree of polymerization, and hydrolyzing and condensing the metal alkoxide in the presence of the aromatic polysulfone.

The aromatic polysulfone can be polymerized by a nucleophilic substitution polycondensation method in which it is polymerized in a polar solvent in the presence of an alkali metal salt. As the alkali metal salt, sodium carbonate,
Potassium carbonate, rubidium carbonate, potassium oxalate, potassium bicarbonate and the like are preferable, but potassium carbonate or sodium carbonate is particularly preferable.

As the polar solvent, sulfone solvents such as sulfolane, diphenyl sulfone and dimethyl sulfoxide, and amide solvents such as N, N-dimethylformamide, dimethylacetamide, dimethylimidazoline and N-methyl-2-pyrrolidone. Are preferably used, but amide solvents are particularly preferable among these.

The polymerization temperature is usually in the range of 80 to 400 ° C, preferably 100 to 350 ° C.

The hydrolysis and condensation reaction of the metal alkoxide proceeds when an alkali metal hydroxide and water are allowed to act in a polar solvent. At this time, the addition amount of the alkali metal hydroxide is preferably equal to or more than the molar amount of the alkoxy group in the metal alkoxide, and particularly preferably 1.0 to 2.0 equivalent. As the alkali metal hydroxide, sodium hydroxide and potassium hydroxide are preferable.

Although the hydrolysis reaction proceeds even if the amount of water added is very small, it is preferably 0.001 to 2.0 equivalents relative to the molar amount of alkoxy groups in the metal alkoxide. As the polar solvent, in addition to solvents such as alcohols, ketones, cellosolves, and carboxylic acids, amide-based and sulfone-based solvents can be used. Among them, N, N-dimethylformamide, N, N-dimethylacetamide, N- Amide solvents such as methyl-2-pyrrolidone are preferred. Since the hydrolysis reaction is an exothermic reaction which proceeds at a relatively low temperature, the temperature is preferably 100 ° C. or lower. The temperature during the condensation reaction after hydrolysis is preferably 100 ° C. or higher and 400 ° C. or lower, more preferably 150 to 30.
It is in the range of 0 ° C.

The reaction between the aromatic polysulfone and the metal alkoxide proceeds due to the presence of the aromatic polysulfone in the polymerization solvent during the condensation reaction of the metal alkoxide.
This reaction is a condensation reaction between the hydroxyl group of the hydrolyzed metal alkoxide and the hydroxyl group or halogen group present at the molecular end of the aromatic polysulfone. Therefore, the aromatic polysulfone is first polymerized, and a metal alkoxide, an alkali metal hydroxide, and water are added to the polymerization solvent to cause the hydrolysis reaction of the metal alkoxide to proceed and the condensation reaction after heating. Although the method is preferable, a method of separately carrying out the polymerization reaction of the aromatic polysulfone and the hydrolysis reaction of the metal alkoxide and mixing the two when the condensation reaction is performed is also possible. At this time, the molecular weight of the aromatic polysulfone before reacting with the metal alkoxide is 0.35 to 0.6 dl / g in N, N-dimethylformamide at a concentration of 1 g / dl and a reduced viscosity measured at a temperature of 30 ° C. It is preferable.

The compounding ratio of the aromatic polysulfone of the present invention and the metal alkoxide can be changed according to the purpose. Generally, when the ratio of the metal alkoxide is increased, the refractive index of the composite polymer is increased, but the adhesion between the coating film formed after coating the plastic base material and the base material is lowered. Furthermore, if the compounding ratio of the metal alkoxide is increased,
The solubility of the obtained composite polymer in a solvent is also lowered, so that it becomes unsuitable as a material for paints and coatings. Therefore, the aromatic polysulfone is limited to 20 to 90% by weight and the metal alkoxide is limited to 10 to 80% by weight,
The aromatic polysulfone is preferably 25 to 85% by weight and the metal alkoxide is 15 to 75% by weight. The molecular weight of the composite polymer of the present invention is 0.4 to 1.0 dl / g in reduced viscosity measured in N, N-dimethylformamide at a concentration of 1 g / dl and a temperature of 30 ° C. Reduced viscosity is 0.4dl
If it is less than / g, the mechanical properties of the reaction product become low, and conversely, 1.
If it exceeds 0, the melt viscosity and the viscosity when formed into a paint become too large, which impairs the moldability.

The composite polymer of the present invention obtained as described above forms a coating film having a high refractive index of more than 1.70 by coating a coating composition containing the composite polymer on various substrates and drying. For example, it can be used for forming an optical multilayer film for antireflection.

Examples of the substrate include inorganic glass and various plastics. Examples of the resin forming the plastic substrate include acrylic resin, polycarbonate, diethylene glycol bisallyl carbonate polymer, di (meth) acrylate polymer of (halogenated) bisphenol A and copolymer thereof, urethane of (halogenated) bisphenol A. Examples include modified di (meth) acrylate polymers and copolymers thereof.

The above-mentioned reaction solvent can be used as a diluent for the composite polymer contained in the above coating composition, and the coating means can be brush coating, dip coating, roll coating, spray coating, spin coating, flow coating, etc. Is mentioned. The film thickness of the coating film is preferably 0.1 to 20 μm from the viewpoints of maintaining adhesive strength and hardness.

[0036]

EXAMPLES Next, the present invention will be described in more detail based on examples.

Evaluation methods of the refractive index, tensile strength, chemical resistance and heat resistance of the films obtained in the following Examples and Comparative Examples, and the evaluation method of the adhesion of the reaction product (composite polymer) to the plastic substrate. Is as follows.

Refractive index: Measured with an Abbe refractometer.

Tensile Strength: ORIENTEC film
Tensileon, manufactured by the company, was used for tensile measurement at a tensile speed of 2 cm / min.

Chemical resistance: The film was immersed in acetone and visually evaluated for the presence or absence of shape change after 24 hours.

Heat resistance: The softening point of the film was measured by the Venelation method of TMA manufactured by Seiko Denshi KK

Adhesion to plastic substrate: The reaction product (composite polymer) was dissolved in N-methyl-2-pyrrolidone to make a 10% solution, and the bar was placed on a 50 micron-thick polyimide film (trade name: Kapton) manufactured by DuPont. A thin film was formed by coating with a coater and drying at 150 ° C. for 5 hours. The adhesion test of this thin film was conducted by a cross-cut peeling test method (MIL-C-675A), and the presence or absence of peeling of the coating film was observed. When there was no peeling, O was marked, and when there was peeling, X was marked.

Example 1 A reaction vessel equipped with a stirrer, a gas inlet tube, a thermometer, and a condenser with a receiver at the tip was placed in a reactor.
112 parts by weight of -chloro-4 '(p-hydroxyphenyl) diphenyl sulfone, 24.7 parts by weight of anhydrous potassium carbonate and 300 parts by weight of N-methyl-2-pyrrolidone were charged, and nitrogen substitution was carried out. Next, in a nitrogen atmosphere, stirring and temperature increase were started, and the reaction was carried out at 200 ° C. for 2 hours. A part of the polymer was taken out from the reaction solution and the reduced viscosity (30 ° C., 1 g / dl in dimethylformamide) was measured.
It was 0.38 dl / g. It has been previously confirmed that the aromatic polysulfone obtained by this polymerization is 100 parts by weight.

100 parts by weight of tetra-n-butoxytitanium, 4.7 parts by weight of sodium hydroxide and 1500 parts by weight of N-methyl-2-pyrrolidone were added to this polymerization system, and the mixture was kept at 100 ° C. for 1 hour. It was stirred. At this time, all the added sodium hydroxide was dissolved in the solution. Further, 100 parts by weight of water was added little by little to the system, and after the addition was completed, 15
The temperature was raised to 0 ° C. At this time, butanol and water were distilled out of the system. After this, the temperature was raised to 200 ° C. and a condensation reaction was carried out for 5 hours. Then, the system was cooled to room temperature, and the reaction solution was poured into water to precipitate the reaction product. The reaction product was filtered, washed with water and methanol, and dried in a vacuum dryer at 150 ° C. for 24 hours. The reaction product (composite polymer) obtained at this time was a white powder. In addition, unreacted tetra-n-butoxytitanium was not included in the filtered filtrate, and the ratio of C: H: O: Ti was found from the results of elemental analysis of titanium and sulfur in the obtained powder. Was 55: 3: 208: 13, and it was found from these results that almost 100% of the tetra-n-butoxytitanium had undergone the condensation reaction.

The reduced viscosity of this powder was 0.42 dl / g when measured in N, N-dimethylformamide under the conditions of 30 ° C. and 1 g / dl.

Further, this powder was dissolved in N-methyl-2-pyrrolidone to form a 5% solution, which was applied onto a glass substrate.
Then 100 ° C for 1 hour, 150 ° C for 1 hour, 200 ° C
And dried for 2 hours to form a film. The obtained film had a thickness of 100 μm and was colorless and transparent.

The refractive index, tensile strength, chemical resistance, and heat resistance of the obtained film were evaluated, and the adhesion to a plastic substrate was measured. The results are shown in Table 2.

(Examples 2 and 3, Comparative Examples 7 and 8) Reactants (composite polymer) similar to Example 1 except that aromatic polysulfone and tetota-n-butoxytitanium were used in the composition ratios shown in Table 1. Was synthesized and evaluated. The results are shown in Table 2.

(Examples 4 to 6) Tetra-n-butoxyzirconium was used instead of tetra-n-butoxytitanium, and the composition ratio of aromatic polysulfone and tetota-n-butoxyzirconium was changed to the composition shown in Table 1. A reaction product (composite polymer) was synthesized and evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Examples 7 to 9) Tetra-n-butoxygermanium was used in place of tetra-n-butoxytitanium, but the composition ratio of aromatic polysulfone and tetota-n-butoxygermanium was as shown in Table 1. A reaction product (composite polymer) was synthesized and evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Examples 10 to 18) 4-chloro-4 '
(P-hydroxyphenyl) diphenyl sulfone 100
Parts by weight 4,4 ′ ″-dihydroxy-p-quaterphenyl 32.8 parts by weight 4,4′-dichlorodiphenyl sulfone 27.9 parts by weight, anhydrous potassium carbonate 33.0
A reaction product similar to that of Example 1 except that an aromatic polysulfone was polymerized with 300 parts by weight of N-methyl-2-pyrrolidone and the obtained aromatic polysulfone and metal alkoxide were blended as shown in Table 1. (Composite polymer) is synthesized,
evaluated. The results are shown in Table 2.

The above-mentioned aromatic polysulfone has a viscosity average molecular weight of reduced viscosity (30 ° C., 1 g / g in dimethylformamide).
dl) was 0.39 dl / g. In addition, as shown in Table 1, the metal alkoxide includes tetra-n-butoxy titanium, tetra-n-butoxy zirconium, and tetra-n.
-Butoxy germanium was used.

Comparative Example 1 The procedure of Example 1 was repeated, except that only aromatic polysulfone was synthesized without reacting with the metal alkoxide and evaluated. The composition and the results are shown in Tables 1 and 2.

(Comparative Example 2) The procedure of Example 1 was repeated except that only the aromatic polysulfone was synthesized without reacting with the metal alkoxide and evaluated. The composition and the results are shown in Tables 1 and 2.

Comparative Example 3 A reaction product was synthesized and evaluated in the same manner as in Example 1 except that polysulfone manufactured by Amoco (the following structural formula) was used as the aromatic polysulfone. The composition and the results are shown in Tables 1 and 2.

[0056]

[Chemical 6]

Comparative Example 4 A reaction product was synthesized and evaluated in the same manner as in Comparative Example 3 except that aromatic polysulfone and tetota-n-butoxytitanium were used in the composition ratios shown in Table 1. The composition and the results are shown in Tables 1 and 2.

(Comparative Example 5) I as an aromatic polysulfone
A reaction product was synthesized in the same manner as in Example 1 except that a polyether sulfone manufactured by CI Co. (the following structural formula) was used,
evaluated. The composition and the results are shown in Tables 1 and 2.

[0059]

[Chemical 7]

(Comparative Example 6) A reaction product was synthesized and evaluated in the same manner as in Comparative Example 5 except that aromatic polysulfone and tetota-n-butoxytitanium were used in the composition ratios shown in Table 1. The results are shown in Tables 1 and 2.

In Table 1, A, B, and C represent the mole fractions of the following repeating units, respectively.

[0062]

[Chemical 8]

Ti, Zr and Ge mean titanium, zirconium and germanium, respectively. D and E represent the compounding ratio (parts by weight) of aromatic polysulfone and metal alkoxide. The molecular weight of Comparative Examples 1 and 2 is the molecular weight of the aromatic polysulfone alone.

In each of Examples 2 to 18 and Comparative Examples 1 to 8, unreacted metal alkoxide was not detected in the solution after polymerization, so that the reaction rate was almost 100%.

[0065]

[Table 1]

[0066]

[Table 2]

[0067]

INDUSTRIAL APPLICABILITY The composite polymer of the present invention has a high refractive index unlike conventional products and can be applied to a plastic substrate to form a film having excellent adhesion. It is useful as a multilayer film.

The composite polymer of the present invention is not only applied to various optical components such as spectacle lenses, various optical lenses and filters and optical multilayer films on the components as a material having a particularly high refractive index, and also has heat resistance. Since it has excellent mechanical properties and chemical resistance and can be molded in various forms such as extrusion and injection, it can be applied to various fields such as the automobile industry, electrical and electronic industry, and aerospace industry.

Front page continuation (72) Inventor Yasushi Nakayama 2-2 Hyakusan, Shimamoto-cho, Mishima-gun, Osaka Prefecture 2-2 (72) Torasuke Saito Saito 5-17-21 Yamatedai, Ibaraki-shi, Osaka (72) Hiroki Kakumachi, Osaka 1-11-3 Minami Kasugaoka, Ibaraki City, Japan

Claims (1)

[Claims] 1. An aroma having 10 to 80% by weight of a metal alkoxide represented by the following general formula (I) and a repeating unit represented by the following general formula (II) or (II) and (III). Group polysulfone is 90
˜20 wt% reaction product, viscosity average molecular weight in N, N-dimethylformamide at a concentration of 1 g / d1, a reduced viscosity measured at a temperature of 30 ° C. of 0.4.
~ 1.0 dl / g composite polymer characterized by: (In the formula, A represents a germanium, zirconium or titanium atom, R ¹ represents a hydrocarbon group having 1 to 4 carbon atoms,
R ² represents an alkyl group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group or a functional substituent, and x is 2, 3 or 4, y
Represents 0, 1 or 2 (however, the sum of x and y is 4). ) [Chemical 2]