JP2003138146A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition in which a titanium oxide nanosheet is uniformly dispersed and which exhibits excellent mechanical strength and heat resistance. SOLUTION: This resin composition comprises 100 parts wt. of a synthetic resin and 0.5-100 parts wt. of a titanium oxide nanosheet. The titanium nanosheet is a titanium oxide nanosheet obtained by treating a laminar titanate represented by general formula Ax My (square)z Ti2-(y+z) O4 [A and M are each a mutually different monovalent to trivalent metal; (square) is a defect part of Ti; x is a positive real number to satisfy 0<x<1.0 and y and z are each 0 or a positive real number to satisfy 0<y+z<1.0] with an acid or warm water, substituting 40-99% of A and/or M ion with hydrogen and/or hydronium ion, then treating the resulting substance with a basic compound having interlayer swelling action, swelling or releasing the interlayer to give a laminar titanate nanosheet and subjecting the nanosheet to heat treatment or hydrothermal treatment.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition. More specifically, the present invention relates to a resin composition comprising a synthetic resin and a specific titanium oxide nanosheet.

[0002]

2. Description of the Related Art Recently, when chemical substances are miniaturized down to the nanometer (nm) level, there is great interest in showing different characteristics from the original chemical substances. Attempts have been made to synthesize substances.

In the field of inorganic compounds, nanosheets having a thickness in the sub-nm to nm range have been synthesized and research has been conducted to use them as fillers for synthetic resins.
Nanosheets provide good gas and liquid barrier properties to synthetic resins and improve the mechanical strength of various synthetic resins with a smaller filling amount than conventional inorganic fillers in the form of particles, fibers or scales. However, it has the drawback that it is difficult to disperse it uniformly in the resin matrix.

In order to solve such a defect, Japanese Patent Laid-Open No. 62-62
In JP-A-74957, JP-A-63-230766 and JP-A-1-11157, a silicate nanosheet such as montmorillonite is treated with a swelling agent such as 12-aminododecanoic acid, and this and a monomer for polyamide. The polyamide resin composition in which the silicate-based nanosheets are dispersed is produced by carrying out a polymerization reaction in the coexistence of and. Similarly, a polyamide resin composition is known in which a monomer for polyamide and a swelling fluoromica-based mineral (silicate nanosheet) are allowed to coexist to carry out a polymerization reaction, and the swelling fluoromica-based mineral is dispersed therein (Japanese Patent Laid-Open No. H11 (1999) -135242). 8-3310 and JP-A-8-12882).

According to the methods described in these patent publications,
When the monomer component is intercalated between the layers of the silicate nanosheet by the action of the swelling agent, the polymerization occurs simultaneously and in parallel, so that the silicate nanosheet can be dispersed in the polyamide to some extent uniformly. However, this method is limited to polyamide resin type only,
There is no versatility. The obtained polyamide resin composition is a plastic composite material having excellent liquid barrier properties, gas barrier properties, mechanical strength, heat resistance, dimensional stability and the like. However, in the internal mechanical parts and casings of electric and electronic devices, which are the main applications of plastic composite materials, automobile interior and exterior parts, etc., further miniaturization and thinning have been promoted with the demand for smaller size and lighter weight. Under the present circumstances, higher mechanical properties, especially higher elastic modulus are required.

Further, according to JP-A-9-67124, a layered titanate such as cesium titanate is acid-treated to form layered titanic acid, and this layered titanic acid is treated with an amine or an ammonium compound in water. The titanium oxide nanosheets are manufactured by heating the obtained titanic acid nanosheets. The publication also describes that the titanium oxide nanosheet can be used as an additive to a resin. However, the titanium oxide nanosheet is a minute sheet having a thickness of 10 to 30 nm and a width (particle diameter) of about 0.5 to 1 μm, and in particular, due to its small particle diameter, it is a conventional inorganic compound nanosheet. Similarly, the dispersibility in the resin is not good. Therefore, even if the titanium oxide nanosheet is used as a resin additive, the reinforcing performance cannot be expected. In addition, since it needs to be manufactured by the freeze-drying method, it is not industrially efficient, and since the product is an aggregate of flaky titanium oxide, the effect as a resin reinforcing material can be expected unless it is pulverized. Instead, it is a factor that reduces the reinforcing performance.

Furthermore, WO 99/11574 describes a titanium oxide nanosheet (flake titanium oxide) obtained by crushing balloon-shaped titanium oxide. The flaky titanium oxide has a thickness of 1 to 10
0 nm, width and length (particle diameter) are described as 0.1 to 500 μm, but there is a problem that a special spray drying device is required, productivity is poor, and energy consumption is large.
In fact, the resin reinforcement of the flaky titanium oxide obtained economically is not sufficiently satisfactory.

[0008]

An object of the present invention is to provide a resin composition in which titanium oxide nanosheets are uniformly dispersed in a resin matrix, which exhibits good mechanical strength and has a particularly high elastic modulus. Another object of the present invention is to provide a resin composition having excellent heat resistance.

[0009]

Means for Solving the Problems As a result of earnest research, the present inventors have found that when using a titanium oxide nanosheet obtained by heat-treating a titanate nanosheet obtained by peeling off a specific layered titanate nanosheet, They have found that they can be solved and have completed the present invention.

That is, the present invention relates to the following resin compositions 1 to 3. 1. A synthetic resin 100 parts by weight, containing titanium oxide nanosheets 0.5-100 parts by weight, the titanium oxide nano-sheet has the general formula _{A x M y □ z Ti 2-} (y + z) O 4 (1) [ In the formula, A and M represent mutually different valent metals. □ indicates a defect site of Ti. x is a positive real number satisfying 0 <x <1.0, and y and z are 0 <y + z, respectively.
It is 0 or a positive real number that satisfies <1.0. ] The layered titanate represented by the following is treated with an acid or warm water, 40 to 99% of A and / or M ions are replaced with hydrogen and / or hydronium ions, and then a basic compound having an interlayer swelling action is added. A resin composition, which is a titanium oxide nanosheet obtained by heat treatment or hydrothermal treatment of a layered titanic acid nanosheet obtained by allowing the layers to swell or peel off.

2. Titanium oxide nanosheet is a sheet-like material having a plate-like or scale-like shape, and has an average major axis of 0.5.
.About.30 .mu.m and average thickness 0.01 to 0.3 .mu.m.

3. The resin composition according to 1 or 2 above, wherein the synthetic resin is one or more thermoplastic resins selected from polyolefin, polyamide, polyester, polyacetal, polystyrene and aromatic polycarbonate.

The titanium oxide nanosheets used in the present invention have the property that they have good dispersibility in various resin matrices as compared with conventional inorganic compound nanosheets and titanium oxide nanosheets. Furthermore, unlike the conventional layered titanic acid nanosheets, the titanium oxide nanosheets of the present invention do not agglomerate due to drying for powderization, and therefore can be used as a powder rather than an aqueous dispersion, so handling is very easy. It's easy.

Therefore, when the titanium oxide nanosheet of the present invention is blended with a resin, a resin composition in which the titanium oxide nanosheet is uniformly dispersed is obtained by a general method such as melt kneading regardless of the resin species. You can The dispersed titanium oxide nanosheets are in a random state in which a distance of 10 nm or more is usually maintained in the resin matrix, although it depends on the blending amount. This can be confirmed by observation with a transmission electron microscope.

The resin composition of the present invention has an improved mechanical strength, particularly a significantly improved elastic modulus, as compared with the case where the resin alone is used and the case where the conventional inorganic compound type nanosheet or layered titanate nanosheet is blended. It also has excellent heat resistance.

A in the general formula (1) has a valence of 1 to
The metal of No. 3 is preferably at least one selected from K, Rb and Cs. M is a metal having a valence of 1 to 3 different from the metal A, and preferably Li or M
It is at least one selected from g, Zn, Cu, Fe, Al, Ga, Mn, and Ni.

Not only the layered titanic acid used in the present invention, but also a plate-shaped (or flaky or scale-shaped) inorganic compound is a very irregular shape having a square or polygonal shape when viewed from directly above. Yes, there are multiple particle sizes depending on the measurement point. In the present invention, the longest one of the plurality of particle sizes is the major axis.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition of the present invention contains a synthetic resin and a titanium oxide nanosheet as essential components.

In the present invention, as the synthetic resin, a thermoplastic resin and a thermosetting resin can be used. The thermoplastic resin is not particularly limited and any known one can be used, for example, polyetherimide, polyethersulfone, polyphenylene ether, polyetherketone resin (polyketone, polyetherketone, polyetheretherketone, Polyetherketone ketone, polyetheretherketone, etc.), polycarbonate, aromatic polycarbonate, polyolefin (polyethylene, polypropylene, etc.), polyester, aromatic polyester, polyacetal, thermoplastic polyurethane, polyamide, polyacrylate, polyvinyl chloride, polystyrene, polyfluoride Vinylidene chloride, polyvinylidene chloride, polyphenyl sulfone, polysulfone, polyether sulfone, liquid crystal polymer, polyamideimide, thermoplastic polyimide, polya Rate, polyether nitrile, polyphenylene sulfide, thermoplastic elastomer (polystyrene thermoplastic elastomer, polyolefin thermoplastic elastomer, polyurethane thermoplastic elastomer, polyamide thermoplastic elastomer, etc.), vulcanized and unvulcanized rubber (natural rubber , Butadiene rubber, chloroprene rubber,
EPDM, isoprene rubber, isobutylene-isoprene rubber, NBR, SBR, etc.) can be mentioned.

Among these thermoplastic resins, polyolefin, polyamide, polyester, polyacetal,
Polystyrene and aromatic polycarbonate can be preferably used.

Examples of the polyolefin include polypropylene such as propylene homopolymer, random polymer of propylene and other olefins (ethylene, butene-1,4-methylpentene-1, hexene-1, etc.) and block polymer. be able to. In addition, a modified polypropylene having polarity is also usable. Considering moldability etc.,
It is preferable that the melt flow be 0.1 to 100 g / 10 minutes.

Examples of polyamides include nylon 6, nylon 11, nylon 12, nylon 66 (polycondensate of hexamethylenediamine and adipic acid), nylon 610 (polycondensate of hexamethylenediamine and sebacic acid), nylon 612. (Polycondensation product of hexamethylenediamine and dodecanedioic acid), Nylon MXD6 (Polycondensation product of metaxylylenediamine and adipic acid), Nylon 4
6 (polycondensation product of 1,4 diaminobutane and adipic acid), semi-aromatic nylon, copolymerized nylon composed of two or more kinds of monomer components constituting the above nylon, and the like can be mentioned. Among these, nylon 6, nylon 66 and the like are preferable.

Examples of polyesters include polyalkylene terephthalates such as polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, and polylactic acid. Commercially available products of polyacetal include "Delrin" and "Dur
Acon ”(both are trade names) and the like.

Polystyrene includes a polymer of styrene and a polymer containing styrene as a main component. Specifically, general-purpose polystyrene, high-impact polystyrene, acrylonitrile-styrene (AS) resin, acrylonitrile-ptadien- Styrene (ABS) resin etc. can be mentioned.

Examples of aromatic polycarbonates include polycarbonates obtained from sodium salt of bisphenol A and phosgene. The thermoplastic resins may be used alone or in the form of an alloy or a blend of two or more kinds.

On the other hand, the thermosetting resin is not particularly limited and any known one can be used. For example, epoxy resin, unsaturated polyester resin, vinyl ester resin, phenol resin, polyurethane, polyimide, etc. are preferably used. it can.

The epoxy resin is bisphenol A.
-Type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, bisphenol B-type epoxy resin, novolac-type epoxy resin, epoxy resin having a fluorene skeleton, and epoxy resin using a copolymer of phenol compound and dicyclopentadiene as a raw material , Glycidyl ether type epoxy resin, glycidyl amine type epoxy resin and the like.

Examples of the unsaturated polyester include a resin having a double bond of an unsaturated group in the molecular chain of the polyester, which is easily copolymerized with a vinyl monomer which is also a solvent and crosslinked to form a cured product. Can be mentioned. That is, maleic acid or fumaric acid, which is an unsaturated dicarboxylic acid, and ethylene glycol, propylene glycol, di- or triethylene glycol, polycondensed dihydric alcohol such as di- or tri-propylene glycol are dissolved in a vinyl-based monomer such as styrene. It was done. For the purpose of modification, for example, a part of the unsaturated dicarboxylic acid may be replaced with phthalic acid or the like.

Examples of vinyl monomers include styrene and other acrylic acid esters. Examples of the vinyl ester resin include resins obtained by reacting methacrylic acid, acrylic acid and the like with polyvinyl acetate, polyvinyl cinnamate, bisphenol type epoxy resin and the like.

Examples of the phenol resin include addition / condensation products of a phenol compound and an aldehyde compound. Examples of the phenol compound include phenol, cresol, xylenol, propylphenol, butylphenol, nonylphenol, catechol, hydroquinone and bisphenol A. Examples of the aldehyde compound include formaldehyde, acetaldehyde benzaldehyde, glyoxal and the like. More specifically, a resol type phenol resin obtained by reacting a phenol compound and an aldehyde compound under a base catalyst, a novolac type phenol resin reacted under an acid catalyst, and the like can be mentioned.

Examples of polyurethanes include reaction products of polyvalent isocyanate compounds with polyols such as polyethers and polyesters. Specific examples of the isocyanate compound include tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, polynuclear polyisocyanate and the like.
Specific examples of the polyol include diethylene glycol having 2 OH groups, dipropylene glycol, etc., glycerin having 3 OH groups, erythritol having 4 OH groups, arabitol having 5 OH groups, 6
Examples thereof include sorbitol having one OH group.

The thermosetting resins may be used alone or in combination of two or more. The titanium oxide nanosheet used in the present invention is a sheet-like material (inorganic compound nanosheet) having a plate-like or scale-like shape, and its average major axis is usually 0.5 to 30 μm, preferably 1 to 20 μm.
m and the average thickness are usually 0.01 to 0.3 μm, preferably 0.01 to 0.1 μm.

The titanium oxide nanosheet of the present invention is usually 5
The titanium oxide is contained in an amount of 0 to 99.5% by weight, preferably 60 to 98% by weight, and the balance is a metal compound (mainly an oxide) represented by A and / or M in the general formula (1). It is an accessory ingredient derived from.

The titanium oxide nanosheet of the present invention is obtained by treating the layered titanate represented by the above general formula (1) (hereinafter referred to as “layered titanate (1)”) with acid or warm water. 40 to 40 of A and / or M ions in (1)
It can be produced by substituting 99% of hydrogen and / or hydronium ions, then allowing a basic compound having an interlayer swelling action to act, and swelling or peeling between the layers to subject the layered titanate nanosheet to a heat treatment or a hydrothermal treatment. .

The layered titanate (1) can be produced, for example, by the method disclosed in Japanese Patent No. 3062497. Specifically, the oxides of the metals A, M, and Ti or the raw material compounds that become the oxides by heating may be pulverized and mixed, if necessary, and then heated and baked in the presence or mixture of flux. Examples of the flux include alkali metal halides and sulfates, alkaline earth metal halides and sulfates, and the like. The flux may be used so that the weight ratio of flux / raw material compound is 0.1 to 2.0. The heating and firing is performed at a temperature of 700 to 1200 ° C. As another production example, according to the method disclosed in Japanese Patent No. 2979132, cesium carbonate and titanium dioxide are mixed at a molar ratio of 1:
The mixture was mixed at 5.3 and calcined at 800 ° C. to give a lepidocrocite-like titanate compound, orthorhombic cesium titanate (Cs _x Ti _{2-x / 4} O ₄ , x = 0.70). And potassium carbonate (K ₂ CO ₃ ), lithium carbonate (Li ₂ CO ₃ ), and titanium dioxide (TiO ₂ ) in accordance with the method disclosed in International Publication WO99 / 11574.
Triturated and mixed with /Li/Ti=3/1/6.5 (molar ratio), by baking at 800 ° C., a lepidocrocite type similar titanate compound K _0.8 Li _{0 .27} Ti
_1.73 O ₄ can be obtained. Specific examples of the layered titanate (1) include, for example, K _0.80 Li _0.266 T
i _1.733 O ₄ , Rb _0.75 Ti _1.75 Li _0.25 O ₄ , Cs _0.70
Ti _1.77 Li _0.23 O ₄ , Ce _0.7 Ti _1.825 □ _0.175 O ₄ ,
Ce _0.7 Ti _1.65 Mg _0.35 O ₄ , K _0.8 Ti _1.6 Mg
_{0.4 O 4, K 0.8 Ti 1.6} Ni 0.4 O 4, K 0.8 Ti 1. 6 Zn
_0.4 O ₄ , K _0.8 Ti _1.6 Cu _0.4 O ₄ , K _0.8 Ti _1.2 Fe
_{0.8 O 4, K 0.8 Ti 1.} 2 Mn 0.8 O 4, K 0.76 Ti 1.73 Li
_0.22 Mg _0.05 O ₄ , K _0.67 Ti _1.73 Al _0.07 Li _0.2 O ₄
Etc. can be mentioned.

The acid treatment or hot water treatment of the layered titanate (1) is carried out by a known method usually adopted for inorganic compounds. In the case of acid treatment, for example, the acid may be added to the aqueous dispersion of the layered titanate (1), preferably under stirring. The amount of the layered titanate (1) in the aqueous dispersion is not particularly limited and may be appropriately selected in consideration of workability and the like. As the acid, for example, an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or boric acid can be preferably used, but an organic acid may be used. The amount of the acid used can be appropriately selected from a wide range depending on the substitution ratio of A and / or M ions to hydrogen and / or hydronium ions in the general formula of the layered titanate (1), but is usually layered titanium. About 0.1 to 20 times the ion exchange capacity of the acid salt (1) may be used. The acid treatment may be carried out in a single operation, or may be carried out repeatedly by lowering the acid concentration or reducing the amount of acid used. By repeating the acid treatment, the substitution rate can be easily changed.
As a result, the substitution rate can be changed even with a small amount of acid, if the number of times is repeated.

The hot water treatment may be carried out, for example, by dispersing the layered titanate (1) in warm water of usually 40 ° C. or higher, preferably 60 ° C. or higher, and stirring. The hot water treatment is usually completed in 1 to 10 hours, preferably 2 to 5 hours. The hot water treatment may be repeated.

By the acid treatment or the hot water treatment, 40 to 99 of A and / or M ions in the layered titanate (1) can be obtained.
%, Preferably 60-95%, can be obtained with layered titanic acid substituted with hydrogen and / or hydronium ions. In addition, in the obtained layered titanic acid, A and M
The substitution ratio of the metal represented by the formula with hydrogen and / or hydronium ion can be measured by a known method. For example, Li can be quantified by flame photometry after dissolving a sample in sulfuric acid containing ammonium sulfate. Similarly, K, Ti,
Mg, Rb, Cs, Zn, Al, Fe, Ni, Cu, N
i, Ga, etc. can be quantified by a fluorescent X-ray analysis method. Therefore, the substitution rate can be calculated by quantifying the amount of metal before and after the acid treatment or the hot water treatment.

Examples of the basic compound having an interlayer swelling action include methylamine, ethylamine, propylamine, diethylamine, triethylamine, butylamine, pentylamine, hexylamine, octylamine, dodecylamine, stearylamine, dipentylamine, dioctylamine, triethylamine. Alkylamines such as octylamine and 2-ethylhexylamine and their salts, ethanolamine, diethanolamine, triethanolamine,
Isopropanolamine, diisopropanolamine,
Alkanolamines such as triisopropanolamine and 2-amino-2-methyl-1-propanol, and quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide. These salts, dodecyl trimethyl ammonium salt, cetyl trimethyl ammonium salt, stearyl trimethyl ammonium salt, benzyl trimethyl ammonium salt, benzyl tributyl ammonium salt, trimethyl phenyl ammonium salt, dimethyl distearyl ammonium salt,
Quaternary ammonium salts such as dimethyldidecylammonium salt, dimethylstearylbenzylammonium salt, dodecylbis (2-hydroxyethyl) methylammonium salt, 12-aminododecanoic acid and its ammonium salt, aminocaproic acid and its ammonium salt, 3-methoxypropyl Examples thereof include amine, 3-ethoxypropylamine, polyethyleneimine, polydiallyldimethylammonium chloride and the like. The basic compounds can be used alone or in combination of two or more.

To act the basic compound, the basic compound or the basic compound is diluted with the aqueous medium with stirring in a suspension prepared by dispersing the layered titanic acid after the acid treatment or the hot water treatment in the aqueous medium. You can add what you did. Considering efficient swelling or peeling, the amount of the basic compounds added is 1 to 200 equivalent%, preferably 5 to 100 equivalent% of the ion exchange capacity of the layered titanate (1). Good. Ion exchange capacity means layered titanate (1)
When the valence of A is m and the valence of M is n, it means a value represented by mx + ny. The aqueous medium means water, a water-soluble solvent or a mixed solvent of water and a water-soluble solvent, and examples of the water-soluble solvent include methyl alcohol, ethyl alcohol and isopropyl alcohol. Alcohols, acetone, tetrahydrofuran, dioxane,
Acetonitrile, propylene carbonate, etc. can be mentioned.

When the layer is peeled off with the basic compound, it is preferable to avoid a state in which a strong shearing force is applied and to carry out with a weak stirring force. As a result, a layered titanate nanosheet having a particle size distribution close to that of the layered titanate (1) can be obtained.

The layered titanic acid nanosheet thus obtained may be subjected to only the acid treatment or the basic compound treatment, or the acid treatment and the basic compound treatment repeatedly. Both the acid treatment and the treatment with the basic compound are basically carried out in the same manner as described above, but not only the reaction can be accelerated by the combined use of heating during the acid treatment but also titanium oxide having a better dispersibility. The effect of obtaining nanosheets can be expected. The amount of the basic compound used is preferably 0.1 to 100 equivalent% of the ion exchange capacity.

By heat-treating or hydrothermally treating the thus obtained layered titanic acid nanosheet, a titanium oxide nanosheet can be obtained. Heat treatment is usually 20
It is carried out at a temperature of 0 to 1200 ° C., preferably 300 to 1000 ° C., and is usually completed in 1 to 24 hours, preferably 2 to 10 hours. The hydrothermal treatment is usually performed under hydrothermal conditions of 120 ° C. or higher, preferably 150 ° C. or higher, and usually 1 to
It is completed in 50 hours, preferably 5 to 25 hours.

The titanium oxide nanosheets thus obtained may be further surface-treated. As the surface treatment agent, known ones can be used, and examples thereof include a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, and fatty acids.
Further, the above basic compound having an interlayer swelling action can also be used as the surface treatment agent.

The compounding amount of the titanium oxide nanosheets in the resin composition of the present invention is not particularly limited, and may be appropriately selected from a wide range depending on various conditions such as the kind of synthetic resin and the intended use of the resin composition. You can use synthetic resin 100
Usually 0.5 to 100 parts by weight, preferably 1
It may be about 50 parts by weight. Below 0.5 parts by weight,
The reinforcing effect cannot be expected, and if it exceeds 100 parts by weight, molding becomes difficult.

The resin composition of the present invention may be blended with one or more of various organic compounds or inorganic compounds conventionally used as resin additives within a range not impairing the preferable properties thereof. Specific examples thereof include, for example, inorganic fillers of various shapes (particulate, fibrous, scale-like), pigments, antioxidants, antistatic agents, release agents, lubricants,
Examples include heat stabilizers, flame retardants, anti-dripping agents, ultraviolet absorbers, light stabilizers, light-shielding agents, metal deactivators, antioxidants, lubricants, plasticizers, impact strength improvers, and compatibilizers. .

The resin composition of the present invention having a thermoplastic resin as a matrix can be produced by mixing or kneading the thermoplastic resin, a predetermined amount of titanium oxide nanosheets and, if necessary, a resin additive according to known means. . For example, powder, beads, flakes or pellets may be mixed with a mixer or tumbler as needed, and then 1
The resin composition of the present invention can be obtained by mixing and kneading using a twin-screw extruder or other extruder, a Banbury mixer, a kneader, a kneader such as a mixing roll, or the like. The resin composition thus obtained is pelletized using a crusher, a pelletizer, or the like, according to known molding means such as injection molding or extrusion molding, and a film,
It can be processed into an arbitrary shape such as a tube, a sheet and various molded products.

Further, at the stage of forming a masterbatch containing a high concentration of titanium oxide nanosheets and performing a molding process by injection molding, extrusion molding, etc., it is used by diluting or mixing with a resin of the same type or a different type from the resin of the masterbatch. can do.

The resin composition of the present invention containing a thermoplastic resin as a matrix can be used in virtually all applications in which a thermoplastic resin has been used in the past. In particular, the mechanism of electronic, electrical, and precision instruments. Parts and housings, interior / exterior parts for transportation equipment such as automobiles (parts for heat resistance in particular), various containers (particularly for gas barriers), sports equipment (especially for lightweight and high elastic modulus applications), heat resistant household products, packaging materials (Especially for gas barrier property or UV shielding), material for machine parts (especially for high elastic modulus heat resistance), optical material for glass substitute, heat resistant film, UV shielding plate or film, construction material,
Examples thereof include agricultural sheets and gas barrier elastomers.

On the other hand, the resin composition of the present invention containing a thermosetting resin as a matrix contains the thermosetting resin, layered titanic acid and, if necessary, other resin additives, in a general stirring mixer.
It can be produced by mixing with a high speed stirrer, a kneader or the like.

The resin composition of the present invention having a thermosetting resin as a matrix can be used for practically all applications in which the thermosetting resin has been conventionally used, and examples thereof include sports goods, leisure goods, and aviation. Examples include space applications and general industrial applications.

The resin composition of the present invention can be made into a foam for the purpose of weight reduction and the like. Even when the resin composition of the present invention is used as a foam, its mechanical strength and heat resistance are not significantly reduced, and it is at a level that can withstand practical use. A known method can be adopted for foaming the resin composition of the present invention, but a foaming method using a decomposable foaming agent is preferred.

As the decomposing type foaming agent, any of known organic decomposing type foaming agents and inorganic decomposing type foaming agents can be used. Examples of the organic decomposition type foaming agent include azo compounds such as azodicarbonamide, azobisisobutyronitrile, diazoaminobenzene, barium azodicarboxylic acid, and hydrazodicarbonamide, p-toluenesulfonylhydrazide, 4,4. Sulfonyl hydrazide compounds such as'-oxybis (benzenesulfonyl hydrazide),
N, N'-dinitrosopentamethylenetetramine, N,
Nitroso compounds such as N'-dinitroso-N, N'-dimethylterephthalamide, 5-phenyltetrazole, 4
Examples thereof include heterocyclic compounds such as aminourazole. Examples of the inorganic decomposing type foaming agent include calcium carbonate, sodium bicarbonate, sodium carbonate, calcium oxide, sodium oxide, magnesium oxide and the like. Among these, organic decomposition type foaming agents can be preferably used, the decomposition temperature adjustment range, safety,
Azodicarbonamide is particularly preferable in view of handleability and economy. The decomposable foaming agents can be used alone or in combination of two or more. The compounding amount of the decomposing type foaming agent is not particularly limited, and it is in a wide range according to various conditions such as the type of resin, the compounding amount of layered titanic acid, the type of decomposing type foaming agent itself, the foaming conditions, the use of the resulting foam and the like. Although it can be appropriately selected from 1 to 30 parts by weight, preferably 2 to 15 parts by weight, relative to 100 parts by weight of the resin composition of the present invention.

In the present invention, the organic decomposition type foaming agent may be surface-treated. As the surface treatment agent, known ones can be used, and examples thereof include silane coupling agents (methyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N-phenylaminomethyltrimethoxysilane, vinylmethyldiethoxysilane, etc.), aluminum-based coupling agents (aluminum isopropylate, aluminum ethylate, aluminum tris (ethylacetoacetate), ethylacetoacetate aluminum diisopropylate, etc.), titanate Coupling agents (isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, bis (dio Cylpyrophosphate) oxyacetate titanate, etc.), liquid or solid oils and fats (soybean oil, coconut oil, linseed oil, cottonseed oil, rapeseed oil, tung oil, pine oil, rosin, castor oil, beef tallow, squalane) , Vegetable- or animal-derived natural fats and oils such as lanolin and hydrogenated oil, and refined products thereof, hydrocarbons (aliphatic hydrocarbons having 20 to 48 carbon atoms and their derivatives, aromatics having 8 to 19 carbon atoms) Hydrocarbons and their derivatives (for example, dialkyl phthalates such as dioctyl phthalate, higher alcohol phthalates such as nonyl alcohol phthalate), paraffin-based, naphthene-based or aromatic-based process oils, liquid paraffin, etc., fatty acids (laurin) Fatty acids such as acids, myristic acid, palmitic acid, stearic acid, oleic acid, behemic acid And it can be exemplified salts thereof or derivatives thereof) oils such as.

In the present invention, a decomposition accelerating agent may be added within the range of not impairing the physical properties of the resulting foam. Known decomposition accelerators can be used, for example, metal oxides such as zinc oxide and lead oxide, metal carbonates such as zinc carbonate, lead carbonate and potassium carbonate, metal chlorides such as zinc chloride and potassium chloride, Examples thereof include metal acetates such as zinc acetate, zinc oleate, zinc stearate, sodium benzenesulfinate, zinc 2-ethylhexoate, and urea. The decomposition accelerators may be used alone or in combination of two or more. When the decomposition accelerator is added, its amount is not particularly limited, but it is usually 5 to 100 parts by weight, preferably 10 to 50 parts by weight, relative to 100 parts by weight of the decomposition type foaming agent.

In the present invention, a foam nucleating agent may be added within the range that does not impair the physical properties of the resulting foam. Known foam nucleating agents can be used, for example,
Examples thereof include talc, silica, calcium carbonate, clay, zeolite, kaolin, bentonite, aluminum oxide and magnesium carbonate. The nucleating agents may be used alone or in combination of two or more. The blending amount of the foam nucleating agent is not particularly limited, and the type of resin, the type and blending amount of titanium oxide nanosheets, the type of foam nucleating agent itself,
The decomposition type foaming agent may be appropriately selected from a wide range according to the type and amount of the decomposable foaming agent, the foaming conditions, the physical properties of the foam to be obtained, the application, etc.
The amount may be 0 part by weight, preferably 0.5 to 1 part by weight.

As a known foaming method using a decomposable foaming agent, more specifically, (1) a resin, a titanium oxide nanosheet and a decomposable foaming agent are kneaded at a temperature at which the decomposable foaming agent does not decompose, After molding the obtained kneaded product into a predetermined shape by extrusion molding, calendar roll molding, press molding, etc.,
A method of obtaining a foam by heating to decompose the decomposable foaming agent to generate a gas, (2) kneading a resin, a titanium oxide nanosheet and a decomposable foaming agent at a temperature at which the decomposable foaming agent does not decompose, The kneaded product obtained is pulp paper, aluminum hydroxide paper,
Using a coating device such as knife coater, roll coater, sprayer or a printing device such as silk screen printing or rotary screen printing on a substrate such as cloth, gypsum board, fibrin board or perlite board, the film thickness after drying is 0.05. ~
It is coated or printed so as to have a thickness of 0.50 mm, and the temperature at which the decomposition type foaming agent does not decompose (usually 80 to 150 ° C.) is obtained by using a drying furnace such as an electric heating type hot air oven, an LPG combustion type hot air oven, an oil combustion type hot air oven. ) For 30 seconds to 5 minutes, and then raising the temperature to the decomposition temperature of the decomposition type foaming agent to decompose the decomposition type foaming agent to obtain a foam, (3) resin, titanium oxide nanosheet and decomposition type Examples thereof include a method in which a foaming agent is mixed and extrusion molding, injection molding, or press molding is performed at a temperature at which the resin is melted and the decomposition type foaming agent is decomposed to obtain a foam having a predetermined shape. In either method, the foaming (= decomposition of the decomposition type foaming agent) is usually performed at a temperature of 180 to 230 ° C., and is usually completed in about 20 seconds to 3 minutes.

The foamed product of the resin composition of the present invention thus obtained can be used for the same applications as the non-foamed molded product of the resin composition of the present invention.

[0059]

INDUSTRIAL APPLICABILITY The resin composition of the present invention has a mechanical strength higher than that in the case where the titanium oxide nanosheets are uniformly dispersed in the resin matrix and the resin is used alone or the conventional inorganic compound-based nanosheets or layered titanate nanosheets are blended. The mechanical strength is improved, the elastic modulus is remarkably improved, and the heat resistance is also particularly excellent.

[0060]

EXAMPLES The present invention will be specifically described with reference to Examples and Comparative Examples below. In the following, "%" and "part"
The term "by" means "on a weight basis" unless otherwise specified.

<Example 1> (Synthesis of layered titanate (1)) 27.64 g of potassium carbonate, 4.91 of lithium carbonate
g, titanium dioxide 69.23 g, and potassium chloride 7
A raw material prepared by dry-milling 4.56 g was fired at 1050 ° C. for 4 hours. The fired sample was immersed in 10 kg of pure water, stirred for 20 hours, separated, washed with water, and dried at 110 ° C. The white powder obtained was layered titanate K _0.80 L
i _0.266 Ti _1.733 O ₄ , the average major axis was 28 μm, and the average thickness was 2.5 μm.

(Synthesis of Layered Titanic Acid) This K _0.80 Li
_0.266 Ti _1.733 O ₄ 65 g was _added to 1.75% hydrochloric acid 1000
The mixture was dispersed and stirred in g to obtain layered titanic acid in which K ions and Li ions were exchanged for hydrogen ions or hydronium ions. It was separated and washed with water to obtain layered titanic acid having a water content of 44%. The residual amount of K ₂ O after drying of this layered titanic acid was 6.0.
%Met. The exchange rate of K ion is 76 equivalent%, and L
The exchange rate of i ions was 99 equivalent% or more. The combined exchange rate of K ions and Li ions was 82 equivalent%.

20 g of the above undried layered titanic acid was added to 60 g.
It was dispersed in 0 g of water, and 285 g (25 equivalent%) of a 0.6% 3-methoxypropylamine aqueous solution was added with stirring. After stirring for about 1 hour, 100 g of 3.5% hydrochloric acid was added subsequently, the mixture was stirred at 70 ° C., and then separated by suction filtration. The water-containing cake was dispersed in water, washed with water, and separated to perform washing three times, followed by thorough washing and filtration to obtain layered titanic acid.

(Synthesis of Titanium Oxide Nanosheet) The layered titanic acid was placed in an alumina crucible, heated to 400 ° C., and kept for 2 hours. It was crushed with a laboratory hammer mill to obtain a titanium oxide nanosheet. The obtained titanium oxide nanosheets have an average thickness of 0.08 μm and an average major axis of 17
was μm. The X-ray diffraction pattern of this product coincided with that of titanium oxide (anatase). N- as a surface treatment agent
The surface treatment was performed by a dry method using (β-aminoethyl) -γ-aminopropyltrimethoxysilane. Specifically, while stirring the titanium oxide nanosheet with a mixer, the surface treatment agent diluted 10 times with methyl alcohol was sprayed. It was dried at 100 ° C. for 1 hour to obtain a surface-treated titanium oxide nanosheet. The treatment concentration was 0.5% with respect to the titanium oxide nanosheets.

(Preparation and Evaluation of Thermoplastic Resin Composition) Nylon 6 (trade name: Amilan CM1017, Toray Industries, Inc.)
(Manufactured by Toyo Seiki Co., Ltd.). The kneading conditions were 240 ° C., 60 rpm, and 5 minutes. The resin composition taken out was crushed, and an injection molding machine (trade name: Minimat M26, manufactured by Sumitomo Heavy Industries Ltd., cylinder temperature 240 ° C, mold temperature 75 ° C) was used to mold a JIS-compliant test piece. . The flexural modulus (JIS K7203) was obtained using this test piece, and the deflection temperature under load (load 1.8 MPa, JIS K71) was used as an evaluation of heat resistance.
91) was measured. The results are shown in Table 1.

<Example 2> (Synthesis of layered titanate (1)) Layered titanate K _0.80 Li _0.266 Ti _1.733 O ₄ was synthesized under the same conditions as in Example 1 except that the firing temperature was 950 ° C. did. The average major axis was 9 μm and the average thickness was 1 μm.

(Synthesis of Layered Titanic Acid) This K _0.80 Li
_0.266 Ti _1.733 O ₄ 26 g was _added to 1.75% hydrochloric acid 400 g
Was dispersed and stirred to obtain layered titanic acid in which K ions and Li ions were exchanged for hydrogen ions or hydronium ions.
It was separated and washed with water to obtain layered titanic acid having a water content of 45%. The residual amount of K ₂ O after drying of this layered titanic acid was 5.9%. The exchange rate of K ions was 77 equivalent%, and the exchange rate of Li ions was 99 equivalent% or more. K ion and Li
The exchange rate of the combined ions was 83 equivalent%.

20 g of the above-mentioned undried layered titanic acid was added to 60 g.
It was dispersed in 0 g of water, and 250 g (28 equivalent%) of a 0.5% aqueous solution of n-propylamine was added with stirring. Two
After stirring for about an hour, 3.5% hydrochloric acid 100
g was added, and the mixture was stirred at 70 ° C. and separated by suction filtration. The water-containing cake was dispersed in water, washed with water, and separated to perform washing three times. It was again dispersed in 600 g of water, and 180 g (0.4 equivalent%) of a 0.1% aqueous solution of distearyldimethylammonium chloride was added while stirring. After stirring for 30 minutes, the layered titanic acid was taken out by filtration.
After washing twice with 500 g of warm water, it was dried in air at 60 ° C.

(Synthesis of Titanium Oxide Nanosheet) The layered titanic acid was placed in an alumina crucible, heated to 650 ° C., and kept for 2 hours to obtain a titanium oxide nanosheet. The obtained titanium oxide nanosheets have an average thickness of 0.03 μm,
The average major axis was 3.9 μm. The X-ray diffraction pattern of this product was in agreement with titanium oxide (anatase) and a trace amount of potassium hexatitanate. Isopropyltri (N-aminoethylaminoethyl) titanate was used as a surface treatment agent, and the surface treatment was performed by a wet method. Specifically, the obtained titanium oxide nanosheet was dispersed in 500 g of water, and 0.1 g of the surface treatment agent was added while stirring. After stirring for 10 minutes, decantation was performed and filtration was performed. Dry 8
It was performed under reduced pressure at 5 ° C. for 4 hours.

(Preparation and Evaluation of Thermoplastic Resin Composition) A resin test piece was prepared in the same manner as in Example 1 and each test was conducted. The results are shown in Table 1.

Comparative Example 1 A comparative resin composition was prepared using a commercially available silicate-based nanocomposite filler (trade name: Cloisite 30B, manufactured by Southern Clay Co., Ltd.). Nylon 6 (trade name: Amilan CM1017, manufactured by Toray Industries, Inc.) was added with Cloisite 30B to a concentration of 5%, and the resin was treated in the same manner as in Example 1 (Preparation and evaluation of thermoplastic resin composition). A test piece was prepared and each test was conducted. The results are shown in Table 1.

Comparative Example 2 A resin test piece of only nylon 6 (trade name: Amilan CM1017, manufactured by Toray Industries, Inc.) was prepared and each test was conducted. The results are shown in Table 1.

[0073]

[Table 1]

As shown in Table 1, Example 1 according to the present invention
As compared with the resin compositions of Comparative Examples 1 and 2, the resin compositions of Nos. 1 and 2 have higher flexural modulus and deflection temperature under load, and are found to be excellent in mechanical strength and heat resistance.

Example 3 A surface-treated titanium oxide nanosheet was obtained in the same manner as in Example 1 except that the surface treatment agent was γ-glycidoxypropyltrimethoxysilane. P
The above titanium oxide nanosheet was added to BT resin (trade name: Duranex 2002, manufactured by Polyplastics Co., Ltd.) so as to be 5%, and kneaded by a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.). Kneading conditions are 250 ℃, 60 rp
m for 5 minutes. The resin composition taken out is crushed and injection molding machine (trade name: Minimat M26, Sumitomo Heavy Industries, Ltd.)
Manufactured, cylinder temperature 245 ℃, mold temperature 80 ℃),
A test piece conforming to JIS was molded. The flexural modulus (JIS K7203) was determined using this test piece, and the deflection temperature under load (load 1.8 MPa, J
IS K7191) was measured. The results are shown in Table 2.

Comparative Example 3 A resin composition for comparison was prepared using a commercially available silicate-based nanocomposite filler (trade name: Cloisite 10A, manufactured by Southern Clay Co., Ltd.). Cloisite 10A was added to PBT resin in an amount of 5% by weight, and kneaded with a Labo Plastomill under the same conditions as in Example 3. The evaluation results are shown in Table 2.

[0077]

[Table 2]

As shown in Table 2, it is understood that the resin composition of Example 3 has a high flexural modulus and a deflection temperature under load, and is excellent in mechanical strength and heat resistance.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Harue Matsunaga             463 Kagasuno, Kawauchi Town, Tokushima City, Tokushima Prefecture             Tokushima Research Institute F-term (reference) 4G047 CA06 CB04 CD04                 4J002 AA011 BB001 BC021 CB001                       CF001 CG001 CL001 DE186                       FA016 FB076 FB086 GA00                       GC00 GG01 GL00 GM00 GN00                       GP00 GQ00

Claims (3)

[Claims] 1. A synthetic resin containing 100 parts by weight of titanium oxide nanosheet and 0.5 to 100 parts by weight of titanium oxide nanosheet, wherein the titanium oxide nanosheet has the general formula A _x M _y □ _z Ti _{2- (y + z)} O. ₄ [In formula, A and M show mutually different 1-valent metal. □ indicates a defect site of Ti. x is a positive real number satisfying 0 <x <1.0, and y and z are 0 <y + z, respectively.
It is 0 or a positive real number that satisfies <1.0. ] The layered titanate represented by the following is treated with an acid or warm water, 40 to 99% of A and / or M ions are replaced with hydrogen and / or hydronium ions, and then a basic compound having an interlayer swelling action is added. A resin composition, which is a titanium oxide nanosheet obtained by heat treatment or hydrothermal treatment of a layered titanic acid nanosheet obtained by allowing the layers to swell or peel off. 2. A titanium oxide nanosheet is a sheet having a plate-like or scale-like shape, and has an average major axis of 0.5 to 0.5.
The resin composition according to claim 1, which has a thickness of 30 μm and an average thickness of 0.01 to 0.3 μm. 3. The resin composition according to claim 1, wherein the synthetic resin is one or more thermoplastic resins selected from polyolefins, polyamides, polyesters, polyacetals, polystyrenes and aromatic polycarbonates.