JP4148348B2 - Thermoplastic material - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel thermoplastic material that can be molded by injection molding, extrusion molding, hot press molding, or the like, and a method for producing the same.
[0002]
[Prior art]
In order to improve the properties of various plastic materials, compounding with inorganic compounds has been performed. As one method, an inorganic filler is added. For example, in order to improve the mechanical properties of plastic materials, FRP using inorganic fibers as plastic reinforcing agents is widely used industrially. In order to impart conductivity, carbon black, various metal powders, and tin oxide particles are added. In addition, various inorganic fillers are added to impart or improve electrical and magnetic characteristics.
[0003]
On the other hand, attempts have been made to improve the properties of plastic materials by homogenizing organic polymers and inorganic components at the nano level. In the present specification, such a material is referred to as an organic-inorganic hybrid material.
[0004]
J. Macromol. Sci. Chem. , A27, 1603 (1990), use poly (2-methyl-2-oxazoline), poly (N-vinylpyrrolidone), poly (N, N-dimethylacrylamide) as an organic polymer, and silica as an inorganic component. It is reported that a colorless and transparent homogeneous glassy material can be obtained. It has been reported that such materials have improved thermal characteristics and mechanical characteristics as compared with the organic polymer as a base.
[0005]
JP-A-9-7600 discloses that a silica-carbon hybrid material excellent in acid resistance and oxidation resistance can be obtained by polymerizing a phenol resin and an alkoxysilane, followed by heat treatment. ing.
[0006]
On the other hand, it is possible to produce a photo-curing hybrid material by combining polysiloxane having a UV functional group such as an acrylic group combined with a UV-curing organic matrix, as described in Processes of Red. Tech. Asia '97, 522 (1007).
[0007]
[Problems to be solved by the invention]
However, the above-described method by adding an inorganic filler requires a filler surface treatment, and the combination of an organic polymer and an inorganic filler is limited. Moreover, since there is an upper limit to the amount of filler added, it is unsuitable for applications intended to develop new functions.
[0008]
On the other hand, organic-inorganic hybrid materials are effective even when added in small amounts, and are an effective method for developing new functional materials. However, the molding method is limited to coating, casting, and the like, and has a problem that it cannot be applied by extrusion molding or injection molding, which are the most common molding methods for plastic materials. As a result, there is a serious problem that the applicable range of the obtained organic-inorganic hybrid material is limited.
[0009]
This invention is made | formed in view of the above situations, The objective is to provide the thermoplastic material applicable to extrusion molding and injection molding, and to provide the manufacturing method.
[0010]
[Means for Solving the Problems]
As a result of intensive investigations to achieve the above object, the present inventors have found a completely new thermoplastic material and have completed the present invention.
[0011]
The thermoplastic material according to claim 1, wherein the thermoplastic organic polymer has a general formula R1kR2lR3mM3 (OR) 4-k-lm, wherein R1, R2, and R3 are hydrogen or an alkyl group having 1 to 12 carbon atoms. Or a phenyl group, SH or OH or an alkyl group having a carboxylate terminal, R is an alkyl group having 1 to 8 carbon atoms, M3 is a compound represented by Si, Ti, Ge, 1 ≦ k + 1 + m ≦ 3, and the compound A hybrid material in which an inorganic component consisting of at least one of the hydrolyzed polycondensates is blended at a ratio of 1 to 80% by weight, and all or part of the inorganic component is a polymetalloxane derivative. Or a polysilsesquioxane derivative, which is produced by mixing the thermoplastic organic polymer and the inorganic component in a solvent and then removing the solvent. Kaichijimi polymer, compared terminal groups of hydrolysis products, an alkoxyl group, an acetoxyl group, acetylacetonato cyclohexyl group, or R3M group (wherein, R is hydrogen or an alkyl group or a phenyl group having 1 to 12 carbon atoms, M is a thermoplastic material that has been subjected to blocking treatment with Si, Ti, Ge), and the ratio of the thermoplastic organic polymer to the inorganic component is selected in the range of 99/1 to 20/80% by weight. It is a feature.
[0012]
[0013]
[0014]
The method for producing a thermoplastic material according to claim 2 includes a step of mixing the thermoplastic organic polymer and the inorganic component in a solvent and then removing the solvent.
[0015]
The method for producing a thermoplastic material according to claim 3 includes a step of kneading the thermoplastic organic polymer and the inorganic component under heating.
[0016]
According to said structure, it is possible to shape | mold by the extrusion molding which was impossible until now, injection molding, or hot press molding using the thermoplasticity of a novel thermoplastic material.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
The ratio of the thermoplastic organic polymer to the inorganic component is selected in the range of 99/1 to 20/80% by weight. When the ratio of the inorganic component is less than 1% by weight, the effect of adding the inorganic component cannot be exhibited. On the other hand, when the amount exceeds 80% by weight, thermoplasticity cannot be imparted, which is not preferable. The ratio of the thermoplastic organic polymer to the inorganic component is more preferably in the range of 95/5 to 30/70% by weight, and still more preferably in the range of 90/10 to 45/55% by weight.
[0018]
Any thermoplastic organic polymer that is generally known can be used without particular limitation. For example, polyethylene, polypropylene, vinyl chloride resin, polystyrene, methyl methacrylate resin, polyamide, polyacetal, polycarbonate, polyester, polyphenylene ether, polymethylpentene, polysulfone, polyethersulfone, polyphthalamide, polyphenylene sulfide, polyarylate, polyimide , Polyetherimide, polyetheretherketone and the like are used. These copolymers can also be used. Only one kind of the above exemplified polymers may be used, or two or more kinds thereof may be mixed and used as necessary.
[0019]
As the thermoplastic resin, a single type or a combination type is selected at any time according to desired properties. Moreover, the molecular weight of the thermoplastic resin used is also selected at any time according to the target characteristics.
[0020]
The inorganic component used in the present invention is preferably a compound of at least one of a metal or non-metal alkoxide, a related compound thereof, and a hydrolysis-condensation polymer thereof.
[0021]
The kind of the metal in the inorganic component is selected at any time according to the intended characteristics, and is used alone or in combination, and is not particularly limited. For example, when improving mechanical properties, Si, Al, Ge, Ti, etc., which are likely to be glass forming components, are used. In order to improve the optical characteristics, IVb group elements such as Si, Sn, and Ge, colorless transition metal elements such as Ti, Zr, Nb, and Ta, and colorless rare earth elements such as La and Ce are used.
[0022]
The metal or non-metal alkoxide is represented by the general formula M1 (OR) n or M2O (OR) n [wherein R is an alkyl group having 1 to 4 carbon atoms, preferably 2 to 4 carbon atoms, and M1 is an element forming a metal alkoxide. If it exists, it will not specifically limit, M2 is represented by V, P, etc., n = 3 or 4]. The metal alkoxide-related compound is R1kR2lR3mM3 (OR) 4-k-lm, wherein R1, R2, and R3 are hydrogen or an alkyl or phenyl group having 1 to 12 carbon atoms, preferably 1 to 5, preferably SH or OH. Alternatively, an alkyl group having a carboxylate terminal, R is an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, M3 is represented by Si, Ti, Ge, 1 ≦ k + 1 + m ≦ 3].
[0023]
For the hydrolytic polycondensation product of the metal alkoxide or a related compound, an oligomer type having two or more repeating units in one molecule, such as a tetramethoxysilane oligomer or a tetraethoxysilane oligomer, is used when Si is taken as an example. Further, part or all of the alkoxy group may be an acetoxyl group, an acetylacetoxyl group, or the like.
[0024]
The same applies to other metal elements. The end group of the hydrolysis product may be an OH group, but in order to suppress reactivity at the end and improve compatibility with the thermoplastic organic polymer, an alkoxyl group, an acetoxyl group, an acetylacetoxyl group, or an R3M group [Wherein R is preferably hydrogen or an alkyl group or phenyl group having 1 to 12 carbon atoms, preferably 1 to 5 carbon atoms, and M is Si, Ti, Ge] or the like.
[0025]
It is also preferable that the whole or part of the hydrolyzed polycondensation product of the metal alkoxide or a related compound thereof is a polymetalloxane derivative or a polysilsesquioxane derivative.
[0026]
The thermoplastic material is produced by mixing or reacting a thermoplastic organic polymer with at least one compound of a metal alkoxide, a related compound thereof, and a hydrolysis-condensation polymer thereof.
[0027]
As its production method, it can be produced by mixing a thermoplastic organic polymer and a metal alkoxide or a related compound thereof, or a hydrolysis-condensation polymer thereof in a solvent, and then removing the solvent.
[0028]
The solvent is not particularly limited as long as the thermoplastic polymer and the metal alkoxide or a related compound thereof, or a hydrolysis-condensation polymer thereof is soluble. Hydrocarbon solvents such as benzene, toluene, n-hexane, halogenated hydrocarbon solvents such as chloroform, dichloromethane, dichloroethane, chlorobenzene, tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, diethyl ether, dibutyl ether, etc. Preferably used are ether solvents such as acetone solvents, ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone, ester solvents such as ethyl acetate and butyl acetate, and alcohol solvents such as methanol, ethanol, n-propanol and isopropanol.
[0029]
The metal alkoxide or a related compound thereof may be hydrolyzed in advance and used as a polycondensate. The hydrolysis-condensation polymer can be generally produced by a known sol-gel method or a similar technique. For example, an amount necessary for hydrolysis may be added, moisture in the reaction system may be used, or moisture in the atmosphere may be absorbed. The reaction conditions are preferably about 0.5-50 hours at room temperature-100 ° C. 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, pyridine may be used.
[0030]
The blocking treatment for suppressing the reactivity at the terminal of the inorganic component and improving the compatibility with the thermoplastic organic polymer is carried out by applying an alkoxyl group, an acetoxyl group, an acetylacetoxyl group, or an R3M group [in the formula , R is hydrogen or an alkyl group or phenyl group having 1 to 12 carbon atoms, preferably 1 to 5 carbon atoms, and M is Si, Ti, Ge] or the like.
[0031]
An organic-inorganic hybrid material obtained by mixing and reacting a thermoplastic organic polymer and an inorganic component in an organic solvent is isolated by removing the solvent from the reaction system. The solvent is removed under reduced pressure or under heating. By molding the isolated thermoplastic material by extrusion molding, injection molding or hot press molding, a target molded product is manufactured.
[0032]
It can also be produced by kneading and reacting a thermoplastic organic polymer and a metal alkoxide or a related compound thereof, or a hydrolytic condensation polymer thereof under heating.
[0033]
The heating temperature varies depending on the type of thermoplastic organic polymer used, but is preferably equal to or lower than the molding temperature of the thermoplastic organic polymer. If the temperature is higher than this, decomposition and deterioration of the thermoplastic organic polymer are promoted, so that there is a possibility that the properties of the obtained thermoplastic material may be lowered.
[0034]
Kneading can be performed using a mixer used in extrusion molding or injection molding. The obtained thermoplastic material is directly molded from a mixer to produce a desired molded product.
[0035]
【Example】
Next, specific examples of the present invention will be described, but the present invention is not limited to these examples.
[0036]
<Synthesis of inorganic composition>
(Inorganic component 1) After dissolving 13.6 g of methyltrimethoxysilane in 60 g of methyl isobutyl ketone, 9 g of 0.01M hydrochloric acid was added and stirred at room temperature. Furthermore, a solution in which 0.53 g of sodium carbonate was dissolved in 20 g of distilled water was added and stirred at room temperature. After 1 hour, 22 g of 1M hydrochloric acid was added, and then only the organic layer was taken out. The precipitate in the organic layer was collected by centrifugation and dried to obtain a reaction product.
[0037]
(Inorganic component 2)
After dissolving 24.0 g of phenyltrimethoxysilane in 60 g of methyl isobutyl ketone, 9 g of 0.01M hydrochloric acid was added and stirred at room temperature. Furthermore, a solution in which 0.53 g of sodium carbonate was dissolved in 20 g of distilled water was added and stirred at room temperature. After 48 hours, 1 g hydrochloric acid (22 g) was added, and only the organic layer was taken out. The precipitate in the organic layer was collected by centrifugation and dried to obtain a reaction product.
[0038]
(Inorganic component 3)
After dissolving 9.5 g of methyltrimethoxysilane and 5.9 g of mercaptopropylmethyltrimethoxysilane in 60 g of methyl isobutyl ketone, 9 g of 0.01M hydrochloric acid was added and stirred at room temperature. Furthermore, a solution in which 0.53 g of sodium carbonate was dissolved in 20 g of distilled water was added and stirred at room temperature. One hour later, 22 g of 1M hydrochloric acid was added, and only the organic layer was taken out. The precipitate in the organic layer was collected by centrifugation and dried to obtain a reaction product.
[0039]
(Inorganic component 4)
After dissolving 8.0 g of tetraisopropoxytitanium in 46.7 g of 1-propanol, 14.0 g of 1M hydrochloric acid was added for hydrolysis. After stirring at room temperature for 1 hour, 1.5 g of trimethylsilane was added, and the mixture was further stirred at room temperature for 1 hour. The solvent was removed under reduced pressure to obtain a reaction product.
[0040]
(Inorganic component 5)
After dissolving 8.0 g of tri-t-butoxy yttrium in 70.0 g of 1-propanol, 13.0 g of 1M hydrochloric acid was added for hydrolysis. After stirring at room temperature for 1 hour, 1.5 g of trimethylsilane was added, and the mixture was further stirred at room temperature for 1 hour. The solvent was removed under reduced pressure to obtain a reaction product.
[0041]
<Synthesis of thermoplastic materials>
[Experimental Example 1]
The cycloolefin polymer and the inorganic component 1 were dissolved in tetrahydroxyfuran at a weight ratio of 85/15 and stirred at room temperature for 1 hour to obtain a homogeneous solution. The solvent was removed under reduced pressure to obtain a thermoplastic material.
[0042]
The obtained thermoplastic material had thermoplasticity and was pelletized and then injection molded at 180 ° C. to obtain a molded body having a diameter of 10 mm and a height of 10 mm. The obtained molded body was transparent and had a visible light transmittance of the same level as that of the sample to which no inorganic component was added. Further, the coefficient of thermal expansion from 25 to 100 ° C. was 5% smaller than that of the sample to which no inorganic component was added.
[0043]
A thermoplastic material was prepared in a weight ratio of cycloolefin polymer to inorganic component 1 in the range of 95/5 to 40/60, and in all cases, a thermoplastic hybrid material could be prepared. Further, no significant decrease in visible light transmittance was observed. The coefficient of thermal expansion decreased with an increase in the amount of inorganic component 1 added, and was 24% smaller than the sample with no inorganic component added at a 40/60 composition.
[0044]
Further, it was confirmed that the same effect was obtained even when inorganic components 2 and 3 were used.
[0045]
[Experimental example 2]
The alicyclic acrylic polymer and the inorganic component 4 were dissolved in tetrahydroxyfuran at a weight ratio of 60/40 and stirred at room temperature for 1 hour to obtain a homogeneous solution. The solvent was removed under reduced pressure to obtain a thermoplastic material.
[0046]
The obtained thermoplastic material had thermoplasticity and was pelletized and then injection molded at 180 ° C. to obtain a molded body having a diameter of 30 mm and a thickness of 10 mm. The obtained molded body was transparent and had a visible light transmittance of the same level as that of the sample to which no inorganic component was added. The refractive index at 487 nm is 1.60, which is higher than that of 1.50 of the sample with no inorganic component added. Further, the three-point bending strength was 102 MPa, which was significantly improved as compared with 68 MPa of the sample having no inorganic component added.
[0047]
[Experimental Example 3]
The alicyclic acrylic polymer and the inorganic component 4 were dissolved in tetrahydroxyfuran at a weight ratio of 80/20 and stirred at room temperature for 1 hour to obtain a homogeneous solution. The solvent was removed under reduced pressure to obtain a thermoplastic material.
[0048]
The obtained thermoplastic material had thermoplasticity and was pelletized and then injection molded at 180 ° C. to obtain a molded body having a diameter of 30 mm and a thickness of 10 mm. The obtained molded body was transparent and had a visible light transmittance of the same level as that of the sample to which no inorganic component was added. The refractive index at 487 nm is 1.59, which is higher than that of 1.50 of the sample with no inorganic component added. Further, the three-point bending strength was 98 MPa, which was significantly improved as compared with 68 MPa of the sample having no inorganic component added.
[0049]
[Experimental Example 4]
The alicyclic acrylic polymer and the inorganic component 4 were dry mixed at a weight ratio of 80/20. The obtained mixed powder was heat-kneaded at 180 ° C. for 10 minutes and then directly injection molded without isolation to obtain a molded body having a diameter of 30 mm and a thickness of 10 mm. The obtained molded body was transparent and had the same visible light transmittance as that of Experimental Example 3. The refractive index at 487 nm was 1.59, and the three-point bending strength was 982 MPa.
[0050]
As can be seen from the above experimental examples, according to the present invention, a material in which a thermoplastic polymer and an inorganic component are hybridized can be supplied. In addition, the obtained hybrid material can improve the target properties of the base polymer that cannot be improved only by blending organic polymers. In particular, a composite material in which a conventional filler is dispersed is effective in improving difficult optical characteristics.
[0051]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the thermoplastic material which can be shape | molded by the extrusion molding which was impossible conventionally, injection molding, hot press molding, etc. can be provided, The application range is expanded greatly.

Claims (3)

The thermoplastic organic polymer has the general formula R1kR2lR3mM3 (OR) 4-kl-m [wherein R1, R2, R3 are hydrogen , an alkyl group having 1 to 12 carbon atoms, a phenyl group, SH or OH, or a carboxylate terminal. R3 is an alkyl group having 1 to 8 carbon atoms, M3 is Si, Ti, Ge, a compound represented by 1 ≦ k + 1 + m ≦ 3, or a hydrolytic polycondensation product of the compound Or a hybrid material in which an inorganic component consisting of one kind is blended at a ratio of 1 to 80% by weight, wherein the total amount or a part of the inorganic component is a polymetalloxane derivative or a polysilsesquioxane derivative, The thermoplastic organic polymer and the inorganic component are mixed in a solvent, and then the solvent is removed. The hydrolysis-condensation product is a hydrolysis product. To Tanmoto, alkoxyl group, acetoxyl group, acetylacetonato cyclohexyl group, or R3M group (wherein, R is hydrogen or an alkyl group or a phenyl group having 1 to 12 carbon atoms, M is Si, Ti, Ge) in blocking treatment A thermoplastic material in which the ratio of the thermoplastic organic polymer to the inorganic component is selected in the range of 99/1 to 20/80% by weight. The method for producing a thermoplastic material according to claim 1, further comprising a step of removing the solvent after mixing the thermoplastic organic polymer and the inorganic component in the solvent. The method for producing a thermoplastic material according to claim 2, comprising a step of kneading the thermoplastic organic polymer and the inorganic component under heating.