JPH09316232A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition without causing the deterioration in both mechanical properties and moldability even when a large amount of inorganic fine particles are contained therein, excellent in mechanical strength, heat resistance and dimensional stability and useful for automotive parts, etc., by melt kneading a thermoplastic elastomer with the inorganic fine particles in a specific proportion. SOLUTION: This resin composition is obtained by blending (A) 100 pts.wt. thermoplastic elastomer such as a urethane-based thermoplastic elastomer with (B) 260-900 pts.wt. one or more inorganic fine particles selected from the group consisting of silica fumes, incinerated and dehydrated sludge ash and fly ash such as spherical fine particles having 0.1-50μm average particle diameter and melt kneading the resultant blend. Furthermore, the resin composition is prepared by adding and reacting 100-900 pts.wt. inorganic fine particles and 1-100 pts.wt. polyfunctional isocyanate compound with 100 pts.wt. oligomer having two or more functional groups selected from the group consisting of, e.g. carboxyl groups, amino groups and hydroxyl groups and 0.1-0.9d/g intrinsic viscosity.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition which is excellent in mechanical properties and heat resistance in a high temperature range, has a small molding shrinkage, and has good dimensional stability and molding processability.

[0002]

2. Description of the Related Art Resin compositions are used in various fields such as electric / electronic parts, automobile parts and medical supplies.
Such a resin composition exhibits further excellent performance by reducing manufacturing costs, improving strength and mechanical properties against tension and impact, improving dimensional stability, and imparting various functions such as flame retardancy. It is required to improve so that it can be done.

Above all, there is a high demand for improvement in rigidity, dimensional stability and heat resistance. For example, in the fields of electric / electronic parts, automobile parts, medical supplies, etc., dimensional stability of molded products is emphasized.

In electric / electronic parts, automobile parts, etc., heat resistance is important in consideration of the environment during transportation and heat generation during use. For example, when used in electric / electronic devices such as printers, plotters, facsimiles, floppy disk drives, hard disk drives, etc., JIS
The heat distortion temperature measured according to K 7207 is 10
It is desired to be 0 ° C or higher.

In order to improve such physical properties, methods such as modification of the resin composition itself or addition of various stabilizers to the resin composition can be considered. However, these methods increase the manufacturing cost and complicate the manufacturing process. Therefore, various resin compositions have been developed in which various inorganic fine particles are blended as an inorganic filler to attempt to improve the physical properties while reducing the manufacturing cost.

[0006] By the way, slag discharged from iron making processes and casting processes, fuel shell components discharged from incinerators, sewage treatment plants, etc. have been conventionally landfilled as waste. However, these are produced in large quantities, and landfill treatment is limited. Further, even if it is buried in the ground, it does not solidify easily, so it becomes a soft ground, and there is a difficulty in building a building on the landfill. The amount of such wastes has remarkably increased along with the expansion of industrial activities, and development of effective utilization methods is desired. Therefore, it has been studied to prepare a resin composition by mixing it with a thermoplastic resin as an inorganic filler.

Japanese Unexamined Patent Publication (Kokai) No. 61-720529 discloses a resin composition in which fly ash discharged from a thermal power plant or the like is mixed with a thermoplastic resin. JP Hei 3
Japanese Patent Publication No. 146564 discloses a resin composition in which an inorganic filler having a double wall such as a fly ash balloon is mixed with a binder such as an elastomer or a synthetic resin.

Conventionally, the sewage sludge discharged in the sewage treatment step has been treated by landfill, etc., after dehydration and incineration to produce dehydrated sludge incineration ash. However, in recent years,
With the widespread use of sewers, the amount of sewage sludge generated has increased significantly and environmental awareness has increased. Therefore, attempts have been made to effectively use sewage sludge.

Examples of such attempts include utilization in soil for gardening, lightweight aggregates, soil conditioners, secondary concrete products, cement raw materials, and the like. However, these are not high value-added products and cannot be a solution to the waste treatment problem. Therefore, as a solution to the high-value-added waste treatment problem, attempts have been made to obtain a resin composition by melting and mixing dewatered sludge incineration ash and a thermoplastic resin.

Japanese Unexamined Patent Publication No. 6-114365 discloses a resin composition comprising a thermoplastic resin and dehydrated sludge incineration ash. Further, JP-A-6-121440 discloses a cable trough using this resin composition.

However, although such a technique can utilize waste such as slag and sewage sludge as the inorganic filler, in any case, if the amount of addition of the inorganic filler is increased, the mechanical properties will be increased. There is a limit to the amount of the inorganic filler to be added, because deterioration and deterioration of moldability occur.

[0012]

SUMMARY OF THE INVENTION In view of the above, the present invention does not cause deterioration of mechanical properties and deterioration of moldability even when a large amount of inorganic fine particles is contained, and has high mechanical strength and heat resistance in a high temperature range. It is an object of the present invention to provide a resin composition which is excellent in dimensional stability and can obtain a molded product having a small molding shrinkage.

[0013]

The present invention provides a resin composition obtained by melt-kneading a thermoplastic elastomer and inorganic fine particles, wherein the inorganic fine particles are 260 to 900 relative to 100 parts by weight of the thermoplastic elastomer. It is characterized by being a weight part. Hereinafter, the present invention will be described in detail.

The resin composition of the present invention is obtained by melt-kneading a thermoplastic elastomer and inorganic fine particles. The thermoplastic elastomer is not particularly limited, and known ones can be used, and examples thereof include styrene-based thermoplastic elastomer, olefin-based thermoplastic elastomer, urethane-based thermoplastic elastomer, vinyl chloride-based thermoplastic elastomer, and ester-based thermoplastic elastomer. Examples thereof include thermoplastic elastomers, amide-based thermoplastic elastomers and 1,2-polybutadiene.

The inorganic fine particles are not particularly limited,
For example, heavy calcium carbonate; light calcium carbonate; colloidal calcium carbonate; natural silica; synthetic silica; kaolin; clay; titanium oxide; barium sulfate; zinc oxide; aluminum hydroxide; alumina; magnesium hydroxide; talc; mica; glass flakes Synthetic hydrotalcite; Wollastonite; Potassium titanate; Basic magnesium sulfate (Mosheidi); Sepiolite; Zonolite; Aluminum borate; Fly ash, clinker ash and other coal ash; Dewatered sludge; Silica fume; Glass beads; Silica beads Carbon beads; Organic beads such as phenol beads, styrene beads, acrylic beads; Silica balloons; Alumina beads; Aluminum silicate glass beads; Sodium silicate glass beads; Volcanic gas such as shirasu and obsidian Scan balloons carbon black, graphite, carbon fibers, and the like. In the present invention, among these, fly ash, dehydrated sludge, silica fume, spherical calcium carbonate, silica balloon, alumina beads, aluminum silicate glass beads, sodium silicate glass beads, volcanic shirasu and obsidian, etc. Spherical inorganic fine particles such as glass balloons are preferably used. These may be used alone or in combination of two or more.

In the present invention, the inorganic fine particles are preferably spherical fine particles having an average particle diameter of 0.1 to 50 μm in order to improve the moldability and fluidity of the obtained resin composition. If it is less than 0.1 μm, secondary aggregation of the inorganic fine particles occurs, and the dispersibility decreases, and if it exceeds 50 μm, the strength of the obtained molded product becomes insufficient. More preferably,
It is a spherical fine particle of 0.5 to 30 μm.

Generally, the resin material is
Volume change occurs in many cases accompanied by chemical and physical changes. On the other hand, a filler such as inorganic fine particles has a volume change that is significantly smaller than that of a resin material, so that a large residual strain occurs at the interface between the filler and the resin after molding. A fibrous or plate-like anisotropic filler has a non-uniform strain direction. On the other hand, the spherical filler has a uniform strain direction.
Therefore, by using spherical inorganic fine particles, a product having higher dimensional stability can be manufactured more stably. Even if the filling rate of the filler is increased, the moldability and fluidity of the resin composition can be improved.

In the present invention, at least one selected from the group consisting of silica fume, dehydrated sludge incineration ash and fly ash is more preferably used as the above-mentioned inorganic fine particles. The silica fume is a known inorganic fine particle, which is a particle close to a perfect sphere having an amorphous active silica as a main component, and is obtained by collecting silica fume fine particles by gas filtration during the production of ferroalloy. You can The average particle size of the resulting silica fume is about 0.15 μm, and the passing weight percentage of 45 μm is 9
It is 5 to 100%. The silica fume contains iron oxide, aluminum oxide, magnesium oxide and the like in addition to silica.

The dehydrated sludge incineration ash is obtained by liquefying a dehydrated cake generated in a sewage treatment plant under high temperature and high pressure and burning organic matter in an incinerator, the main component of which is SiO ₂ , Al ₂ O ₃ , P ₂ O ₅ , CaO, F
e ₂ O ₃ , MgO and the like.

When the liquefied dewatered cake of the above dehydrated sludge is treated in a fluidized bed incinerator, the dewatered sludge incinerated ash is in a crushed form having an average particle size of 20 to 30 μm. In the case of being processed in a flame incinerator, since the inorganic substance is melted, it becomes spherical with an average particle size of 7 to 8 μm.

The fly ash is obtained by burning finely pulverized coal and then suspending particles of ash in a molten state in high-temperature combustion gas and forming glass-like particles as the temperature decreases. Is the coal ash recovered. The fly ash contains silica and alumina as main components.

The blending amount of the inorganic fine particles is 260 to 900 parts by weight based on 100 parts by weight of the thermoplastic elastomer. If it is less than 260 parts by weight, the effect of improving physical properties such as heat resistance and dimensional stability due to the increase in amount is insufficient,
The cost cannot be reduced, and when it exceeds 900 parts by weight, the fluidity of the obtained resin composition is lowered, resulting in insufficient moldability. Therefore, the content is limited to the above range. Preferably, it is 300 to 700 parts by weight.

When the inorganic fine particles are melt-kneaded with the thermoplastic elastomer, the dispersibility of the inorganic fine particles is improved, the filling is increased, the heat resistance and flame retardancy are improved, and the water resistance is improved.
Silane-based, titanate-based, aluminate-based, zircoaluminum-based, phosphoric acid-based, carboxylic acid-based, fatty acid-based oils and fats, waxes, surfactants, etc. for the purpose of improving moldability, homogenizing physical properties, reducing costs, etc. Coupling agent;
A surface treatment agent may be used. Above all, it is preferable to use a silane coupling agent.

The method of melt-kneading is not particularly limited, and for example, the thermoplastic elastomer is heated and melted, and the inorganic fine particles are added in that state, for example, a kneader, a plastomill or the like kneader; an extruder or the like. And a method of uniformly kneading.

Since the resin composition of the present invention uses a thermoplastic resin as a binder, it can be formed into a molded product by melt molding such as press molding, extrusion molding, injection molding, blow molding, and injection compression molding.

Since the molded product has a small molding shrinkage,
Automotive parts, electrical / electronic parts, where dimensional accuracy is important,
It can be suitably used as a precision molded article for industrial articles, sports articles, medical articles and the like.

The above-mentioned automobile parts are not particularly limited,
For example, boots such as constant velocity joint boots and rack and pinion boots; ball joint seals; safety belt parts; bumper facias; emblems; moldings and the like. The electric and electronic parts are not particularly limited, and examples thereof include housings of various electric products, electric wire coating materials, gears, rubber switches, membrane switches, tact switches, o-rings, and the like. The industrial parts are not particularly limited, and examples thereof include hydraulic hoses, coil tubes, sealing materials, packings, V-belts, rolls,
Anti-vibration / damping materials, shock absorbers, couplings, diaphragms, etc.

The above sports equipment is not particularly limited, and examples thereof include shoe soles, balls for ball games, and the like. The medical supplies are not particularly limited, and examples thereof include medical tubes, infusion packs, catheters and the like. In addition to the above applications, it can be suitably used as an elastic fiber, an elastic sheet, a composite sheet, a hot melt adhesive, a material for alloying with other resins, and the like.

The present invention 2 has at least two functional groups selected from the group consisting of a carboxyl group, an amino group and a hydroxyl group, and has an intrinsic viscosity (in o-chlorophenol, 30%).
10) is 0.1 to 0.9 dL / g
0 to 100 parts by weight of inorganic fine particles, and
1 to 100 parts by weight of a polyfunctional isocyanate compound is added,
It is a resin composition obtained by reaction.

The oligomer used in the present invention 2 has at least two functional groups in the molecule. The functional group is selected from the group consisting of a carboxyl group, an amino group and a hydroxyl group, and may be the same type or different types. The oligomer is not particularly limited, but those capable of chain extension reaction with a polyfunctional isocyanate compound, particularly those having a main chain mainly composed of polyester are preferable.

The intrinsic viscosity of the above oligomer is 0.1 to
It is 0.9 dL / g (in o-chlorophenol, 30 degreeC). If it is less than 0.1 dL / g, the high temperature physical properties of the molded product obtained from the resin composition will be poor, and if it exceeds 0.9 dL / g, it will be difficult to quantitatively proceed the chain extension reaction with the polyfunctional isocyanate compound. Therefore, it is limited to the above range. It is preferably 0.15 to 0.7 dL / g.

The inorganic fine particles used in the present invention 2 are not particularly limited, and examples thereof include those similar to those exemplified in the present invention 1. In the second aspect of the present invention, the blending amount of the above-mentioned inorganic fine particles is the above-mentioned oligomer 10
It is 100 to 900 parts by weight with respect to 0 parts by weight. 100
If it is less than 100 parts by weight, the effect of improving physical properties such as heat resistance and dimensional stability by increasing the amount is insufficient, and the cost cannot be reduced. If it exceeds 900 parts by weight, the resin composition obtained is The flexibility and mechanical properties are lowered, and the fluidity is lowered, so that the moldability is deteriorated, so that the content is limited to the above range. It is preferably 250 to 700 parts by weight.

The polyfunctional isocyanate compound used in the present invention 2 is not particularly limited, but diisocyanate is preferable because the chain extension reaction can be efficiently carried out while avoiding gelation of the polyesteramide copolymer.

The diisocyanate is not particularly limited as long as it is a compound having two isocyanate groups in the molecule, and examples thereof include aromatic compounds such as 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, phenylene diisocyanate and naphthalene diisocyanate. Diisocyanate; 1,2-ethylene diisocyanate, 1,3-propylene diisocyanate, 1,4-butane diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenation And aliphatic diisocyanates such as 4,4'-diphenylmethane diisocyanate.

In the present invention 2, a compound having three or more isocyanate groups such as triphenylmethane triisocyanate and polyisocyanate may be used within the range in which the moldability of the molded product obtained from the resin composition is maintained.

In the present invention 2, the compounding amount of the polyfunctional isocyanate compound is 1 to 100 parts by weight based on 100 parts by weight of the oligomer. If the amount is less than 1 part by weight, it is difficult to increase the molecular weight by chain extension of the oligomer, and a molded product having sufficient strength cannot be obtained.
If it exceeds 100 parts by weight, excess isocyanate groups cause intermolecular cross-linking reaction, resulting in poor fluidity of the molded product. Therefore, the amount is limited to the above range. It is preferably 2 to 30 parts by weight.

The resin composition of the present invention 2 can be obtained by adding the inorganic fine particles to the oligomer and mixing them, and then adding and mixing the polyfunctional isocyanate compound to proceed the reaction.

The inorganic fine particles are added to the oligomer,
At the time of mixing, silane is used for the purpose of improving the dispersibility of the above-mentioned inorganic fine particles, increasing packing, improving heat resistance and flame retardancy, improving water resistance, improving moldability, homogenizing physical properties, reducing costs, etc. A coupling agent such as a system, a titanate system, an aluminate system, a zirco aluminum system, a phosphoric acid system, a carboxylic acid system, a fatty acid system, an oil / fat, a wax or a surfactant; a surface treatment agent may be used. Above all, it is preferable to use a silane coupling agent.

To add and mix the polyfunctional diisocyanate compound to the mixture of the oligomer and the inorganic fine particles to allow the reaction to proceed, for example, a kneader such as a kneader or an extruder can be used. The kneading and reaction temperatures are preferably 60 to 240 ° C. If it is lower than 60 ° C, it is difficult to obtain a molded product having sufficient strength, and if it exceeds 240 ° C, the oligomer and the polyfunctional isocyanate compound are decomposed, and the strength is sufficient. A molded product cannot be obtained. More preferably, it is 100 to 220 ° C.

Polycarbodiimide may be added to the resin composition of the present invention 2 in order to improve water resistance and heat resistance. As the polycarbodiimide, if it has an average of 1 to 20 carbodiimide groups in one molecule,
There is no particular limitation. When the number of carbodiimide groups is less than 1, the improvement in heat deterioration resistance and water deterioration resistance of the molded product obtained from the resin composition becomes insufficient, and when it exceeds 20, the reaction excessively proceeds during compounding and kneading, Since the fluidity is lowered, a good molded product cannot be obtained. More preferably, it is 1 to 10 on average.

The amount of the polycarbodiimide added is appropriately changed depending on the number of carbodiimide groups present in one molecule, but is 0.1 to 2 per 100 parts by weight of the oligomer.
0 parts by weight is preferred. If it is less than 0.1 part by weight, the effect of addition of polycarbodiimide is not observed, and if it exceeds 20 parts by weight, the reaction proceeds during compounding and kneading to lower the fluidity, and the resulting molded article has a machine. Strength becomes insufficient.
More preferably, it is 1 to 10 parts by weight.

Since the resin composition of the present invention 2 uses a thermoplastic resin as a binder, it can be formed into a molded product by melt molding such as press molding, extrusion molding, injection molding, blow molding, injection compression molding and the like. The molded product has a small molding shrinkage because the resin composition of the present invention 2 contains the inorganic fine particles, so that the dimensional accuracy is important for an automobile part,
It can be suitably used as a precision molded product of electric / electronic parts, industrial products, sports products, medical products and the like.

The present invention 3 is a dicarboxylic acid represented by the following general formula (1); HOOC-R ¹ -COOH (1) (wherein R ¹ represents an alkylene group having 2 to 8 carbon atoms). At least one of
Following general formula ^{(2); HO-R 2} -OH (2) (. Wherein, R ² is representative of the alkylene group having 2 to 6 carbon atoms) at least one diol represented by, and, reducing 100 parts by weight of a polyesteramide copolymer obtained by reacting a polyamide having a viscosity (1 g / dL 98% sulfuric acid solution, 20 ° C.) of 0.5 to 7 dL / g, 100 to 900 parts by weight of inorganic fine particles, and It is a resin composition obtained by adding and reacting 1 to 100 parts by weight of a functional isocyanate compound.

The resin composition of the present invention 3 can be obtained by adding inorganic fine particles and a polyfunctional isocyanate compound to a polyesteramide copolymer and reacting them. The polyester amide copolymer comprises a dicarboxylic acid represented by the general formula (1), a diol represented by the general formula (2), and a polyamide.

The dicarboxylic acid represented by the general formula (1) is not particularly limited, and examples thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid,
Suberic acid, azelaic acid, sebacic acid and the like can be mentioned. In the present invention, of these, the reactivity is high,
Adipic acid is preferably used because it is inexpensive. In the present invention, other various dicarboxylic acids may be appropriately used as long as the physical properties of the molded product obtained from the resin composition are not impaired.

The diol represented by the general formula (2) is not particularly limited, and examples thereof include ethylene glycol and
1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3- Propanediol, 1-methyl-2-methyl-1,2-ethanediol, 2,2-
Dimethyl-1,3-propanediol, 1,1-dimethyl-1,2-ethanediol, 1-ethyl-1,2-ethanediol and the like can be mentioned. Of these, those having branching are preferable when flexibility is required. Considering reactivity, a combination of 1,4-butanediol and 2,2-dimethyl-1,3-propanediol, ethylene, Glycol and 2,2-dimethyl-1,3-
Combination with propanediol is preferred.

For the purpose of increasing the molecular weight of the resulting polyesteramide copolymer, increasing the viscosity and shortening the polymerization time, a branching agent such as polyol, polycarboxylic acid or oxyacid is further added to the components constituting the polyester. May be.

The above-mentioned polyol is not particularly limited,
For example, glycerin, trimethylolpropane, pentaerythritol, 1,2,6-hexanetriol, sorbitol, 1,1,4,4-tetrakishydroxymethylcyclohexane, tris (2-hydroxyethyl).
Examples thereof include isocyanurate and dipentaerythritol.

The polycarboxylic acid is not particularly limited, and examples thereof include hemimellitic acid, trimellitic acid, trimesic acid, pyromellitic acid, 1,1,2,2-ethanetetracarboxylic acid and the like. These may be used alone or in combination of two or more.

The oxyacid is not particularly limited, and examples thereof include citric acid, tartaric acid, 3-hydroxyglutaric acid,
4-β-hydroxyethylphthalic acid and the like can be mentioned. These may be used alone or in combination of two or more.

The amount of the branching agent added is 10% of dicarboxylic acid.
0.1-2.5 mol is preferable with respect to 0 mol. 0.1
When it is less than 2.5 mols, the molecular weight of the obtained polyesteramide copolymer does not become sufficiently large, so that a molded product excellent in mechanical strength cannot be obtained, and when it exceeds 2.5 mols, gelation occurs.

The polyamide preferably has an amide bond in the polymer main chain and is soluble in the dicarboxylic acid and the diol, which are the constituents of the polyesteramide copolymer, and can be melted by heating.

The polyamide is not particularly limited,
For example, 4-nylon, 6-nylon, 6,6-nylon, 11-nylon, 12-nylon, 6,10-nylon, 6,12-nylon and other aliphatic nylons; isophthalic acid, terephthalic acid, metaxylylene diene Amine, 2,
2-bis (paraaminocyclohexyl) propane, 4,
4'-diaminodicyclohexylmethane, 2,2,4-
Examples thereof include polyamides obtained by polycondensation of aromatic, alicyclic, and side-chain substituted aliphatic monomers such as trimethylhexamethylenediamine and 2,4,4-trimethylhexamethylenediamine.

The reduced viscosity of the above polyamide is 0.5 to 7
dL / g (1 g / dL 98% sulfuric acid solution, 20 ° C.). If it is less than 0.5 dL / g, the mechanical strength of the molded product obtained from the resin composition at high temperature will be insufficient, resulting in 7 dL / g.
If it exceeds, the solubility in the above dicarboxylic acid and the above diol is lowered and the synthesis becomes difficult. Therefore, it is limited to the above range. Preferably, it is 1.0 to 6.0 dL / g.

The polyamide preferably has a degree of swelling in a toluene / isooctane = 1/1 (weight ratio) mixed solution of 5.0% or less in terms of weight change rate. 5.0%
When it exceeds, the solubility in the above dicarboxylic acid and the above diol decreases, and the reaction becomes difficult to proceed. The polyamide preferably has a molecular weight of 10,000 to 60,000. More preferably, it is 20,000 to 50,000.

The polyamide content in the polyesteramide copolymer is preferably 3 to 90% by weight. If it is less than 3% by weight, the mechanical strength of the molded product obtained from the resin composition will be insufficient, and if it exceeds 90% by weight, the above polyamide will not dissolve during the polymerization reaction and the polymerization reaction will not proceed sufficiently. More preferably, it is 5 to 80% by weight.

The above polyesteramide copolymer can be synthesized by a known method or the like, for example, by polymerizing a dicarboxylic acid and a diol in the presence of polyamide. The above-mentioned polymerization usually comprises a two-step reaction in which the esterification reaction is the first step and the polycondensation reaction is the second step.

The esterification reaction is carried out by dissolving the polyamide in the polyester component and making it a transparent and homogeneous solution. The reaction does not proceed efficiently in a heterogeneous state. The melting temperature is preferably 150 to 230 ° C.
When the temperature is lower than 150 ° C, it is difficult to dissolve the polyamide, and when the temperature is higher than 230 ° C, an ester-amide exchange reaction in which the polyester component cleaves the polyamide chain becomes active, and the resulting polyesteramide copolymer has block properties. Be damaged.

The polycondensation reaction is carried out under reduced pressure, preferably 1
It is preferably performed at 180 to 260 ° C. at 0 mmHg or less. If it is lower than 180 ° C, the reaction rate is low and the polymerization viscosity becomes high, so that efficient polymerization becomes difficult, and if it exceeds 260 ° C, decomposition reaction or coloration occurs, and the obtained polyesteramide copolymer The blockiness of coalescence is impaired.

When the polyesteramide copolymer is synthesized, it is preferable to charge 1.2 to 3 mol of the diol with respect to 1 mol of the dicarboxylic acid. If it is less than 1.2 mol, the esterification reaction will not proceed efficiently,
When it exceeds 3 mol, the cleavage reaction of the polyamide is likely to occur due to the excess diol component, so that the block property is lowered and the heat resistance is lowered.

When synthesizing the above polyesteramide copolymer, a catalyst generally used in the production of polyester may be used. The catalyst is not particularly limited, for example, lithium, sodium, potassium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tungsten, tin, lead, antimony, arsenic, cerium, boron. Metals such as elemental, cadmium, manganese, and zirconium; organometallic compounds, organic acid salts, metal alkoxides, metal oxides, and the like of these. These may be used alone or in combination of two or more. In the present invention, among these, tetrabutoxy titanium, calcium acetate, diacyl stannous, tetraacyl stannic,
Dibutyltin oxide, dibutyltin dilaurate, dimethyltin malate, tin dioctanoate, tin tetraacetate, triisobutylaluminum, tetrabutyl titanate, tetrapropoxy titanate, titanium (oxy) acetylacetate, germanium dioxide, tungstic acid, antimony trioxide, etc. are suitable. Used for.

When synthesizing the above polyesteramide copolymer, a stabilizer may be used, if necessary. The stabilizer is not particularly limited, and examples thereof include 1, 3, 5
-Trimethyl-2,4,6-tris (3,5-di-t-
Butyl-4-hydroxybenzyl) benzene, 3,9-
Bis [2- {3- (3-t-butyl-4-hydroxy-
5-methylphenyl) -propionyloxy} -1,1-
Dimethylethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane and other hindered phenolic antioxidants; tris (2,4-di-t-butylphenyl)
Phosphite, trilauryl phosphite, 2-t-butyl-α- (3-t-butyl-4-hydroxyphenyl) -p-cumenylbis (p-nonylphenyl) phosphite, dimyristyl-3,3′-thiodipro Pionate, distearyl-3,3'-thiodipropionate,
Examples include heat stabilizers such as pentaerythyl tetrakis (3-lauryl thiopropionate) and ditridecyl-3,3'-thiodipropionate.

In the present invention 3, the intrinsic viscosity of the polyesteramide copolymer synthesized as described above is
0.1 to 0.9 dL / g (in o-chlorophenol, 3
0 ° C.) is preferred. If it is less than 0.1 dL / g, the molded product obtained by filling the polyesteramide copolymer with inorganic fine particles to obtain a high molecular weight will have poor high-temperature physical properties, and if it exceeds 0.9 dL / g, it will be high. The chain extension reaction by the functional isocyanate compound does not proceed quantitatively.
More preferably, it is 0.15-0.7 dL / g.

The resin composition of the present invention 3 can be obtained by adding inorganic fine particles to the above polyesteramide copolymer and mixing them, and then adding and mixing a polyfunctional isocyanate compound to proceed the reaction.

The inorganic fine particles used in the present invention 3 are not particularly limited, and examples thereof include those similar to those exemplified in the present invention 1. The blending amount of the above-mentioned inorganic fine particles is the same as that in the case of the present invention 2.

The polyfunctional isocyanate compound used in the present invention 3 is not particularly limited, and examples thereof include those similar to those exemplified in the present invention 2. The compounding amount of the polyfunctional isocyanate compound is the same as in the case of the present invention 2.

When the above-mentioned inorganic fine particles are added to and mixed with the above polyesteramide copolymer, the dispersibility, heat resistance, flame retardancy, water resistance and moldability of the above-mentioned inorganic fine particles are improved, and high filling is achieved. A coupling agent and a surface treatment agent may be used in order to make the physical properties uniform and reduce the cost.
The coupling agent and the surface treatment agent are not particularly limited, and examples thereof include the same as those exemplified in the second aspect of the present invention.

In order to proceed the reaction by adding the above polyfunctional isocyanate compound to the mixture of the above polyesteramide copolymer and the abovementioned inorganic fine particles and allowing the reaction to proceed, for example, a kneader such as a kneader or an extruder is used. The polyfunctional diisocyanate compound may be added to and kneaded with the mixture of the polyesteramide copolymer and the inorganic fine particles. The kneading temperature is 60 to 240.
C is preferred. If the temperature is lower than 60 ° C, it is difficult to obtain a molded product having a sufficient strength because the reactivity is low.
If the temperature exceeds 0 ° C, the polyesteramide copolymer and the polyfunctional isocyanate compound are decomposed, and a molded product having sufficient strength cannot be obtained. More preferably, 10
0-220 ° C.

Polycarbodiimide may be added to the resin composition of the present invention 3 in order to improve water resistance and heat resistance. Examples of the polycarbodiimide include the same as those exemplified in the second aspect of the present invention.
The addition amount of the above polycarbodiimide is the same as in the case of the present invention 2.

Since the resin composition of the present invention 3 uses a thermoplastic resin as a binder, it can be formed into a molded product by melt molding such as press molding, extrusion molding, injection molding, blow molding, and injection compression molding. Since the molded product has a small molding shrinkage ratio, it is important for dimensional accuracy of automobile parts, electric
It can be suitably used as a precision molded product of electronic parts, industrial products, sports products, medical products and the like.

The fourth aspect of the present invention is the above-mentioned polyesteramide copolymer, further comprising an alkoxysilane compound of 0.01 to 10
It is a resin composition containing parts by weight.

The alkoxysilane compound used in the present invention 4 is a silane compound having one or more alkoxy groups in the structure. In the present invention, among these, those having 2-3 alkoxy groups in the structure are reactive,
It is preferable in terms of cost and the like. The alkoxy group is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, and a propoxy group. In the present invention, of these, a methoxy group and an ethoxy group are preferable.

As the above-mentioned alkoxysilane compound, those having a functional group of high polarity in addition to the above-mentioned alkoxy group are preferable. The highly polar functional group is not particularly limited, and examples thereof include an amino group, an epoxy group, a carboxyl group, a vinyl group, a glycidyl group, an allyl group, a chlorine group, a bromine group, an iodine group, an isocyanate group, and an acetoxy group. To be In the present invention, of these, an amino group, an epoxy group, a glycidyl group and an isocyanate group are preferable. Most preferably, an alkoxysilane compound having an isocyanate group is used.

As the above-mentioned alkoxysilane compound, those having an alkylene group are preferable because the adhesive force at the interface between the above polyesteramide copolymer and the above-mentioned inorganic fine particles is improved. More preferably, it has the alkylene group between the alkoxy group and the highly polar functional group. The alkylene group preferably has 1 to 10 carbon atoms. More preferably, it is 1-6.

Specific examples of the alkoxysilane compound are not particularly limited, and include, for example, allyltriethoxysilane, allyltrimethoxysilane, allyltrimethylsilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3
-Aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-
Chloropropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3
-Glycidoxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, methyltrimethoxysilane, 3-triethoxysilylpropyl isocyanate, 3-trimethoxysilylpropyl isocyanate, 3-dimethylethoxysilylpropyl isocyanate, 3-methyldiethoxy Examples thereof include silylpropyl isocyanate, 3-methyldimethoxysilylpropyl isocyanate and 3-dimethylmethoxysilylpropyl isocyanate.

Of the above alkoxysilane compounds, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane and 3 are preferred.
-Triethoxysilylpropyl isocyanate, 3-trimethoxysilylpropyl isocyanate, 3-dimethylethoxysilylpropyl isocyanate, 3-methyldiethoxysilylpropyl isocyanate, 3-methyldimethoxysilylpropyl isocyanate, 3-dimethylmethoxysilylpropyl isocyanate, More preferred are 3-triethoxysilylpropyl isocyanate, 3-trimethoxysilylpropyl isocyanate, 3-methyldiethoxysilylpropyl isocyanate, and 3-methyldimethoxysilylpropyl isocyanate.

When the alkoxysilane compound has an isocyanate group, a compound having a structure represented by the following formula (I) is preferable in terms of reactivity, cost and the like.

[0078]

Embedded image

In the formula, a represents an integer of 1 to 3. b is
It represents an integer of 1 to 3. c represents an integer of 1 to 15.

In the resin composition of the present invention 4, the compounding amount of the above alkoxysilane compound is 0.01 to 10 parts by weight with respect to 100 parts by weight of the polyesteramide copolymer. If the amount is less than 0.01 part by weight, the effect of adding the alkoxysilane compound is not recognized, and if it exceeds 10 parts by weight, the alkoxysilane compound reacts with each other, and a machine for forming a molded product using the resin composition. Since the mechanical strength is insufficient, it is limited to the above range. Preferably, 0.1-5
Parts by weight.

In the resin composition of the present invention 4, a method in which the polyester amide copolymer is added with a mixture of the inorganic fine particles and the alkoxysilane compound in advance, and then the polyfunctional isocyanate compound is added and reacted Or, to the premixed polyester amide copolymer and the alkoxysilane compound, after adding the inorganic fine particles, the polyfunctional isocyanate compound is added,
It can be obtained by a reaction method. Which method is used depends on the type of the alkoxysilane compound, the polyfunctional isocyanate compound, and the inorganic fine particles.

In the method in which the polyester amide copolymer is mixed with the inorganic fine particles and the alkoxysilane compound in advance and then the polyfunctional isocyanate compound is added and reacted, the inorganic fine particles and the alkoxy In order to enhance the reactivity with the silane compound and to cause a uniform reaction, the above-mentioned inorganic fine particles are mixed with a solution obtained by dissolving the above-mentioned alkoxysilane compound in water, an organic solvent or the like, and after drying, the polyesteramide copolymer It is preferable to mix with the coalescence. In this case, as the alkoxysilane compound, those having an alkoxy group and an isocyanate group are preferably used.

In the present invention 4, the temperature at which the above polyfunctional isocyanate compound is added and mixed and the reaction proceeds is preferably 60 to 260 ° C. If the temperature is lower than 60 ° C, it is difficult to obtain a molded product having sufficient strength because the reactivity is low. If the temperature exceeds 260 ° C, the polyesteramide copolymer and the polyfunctional isocyanate compound may decompose. There is. More preferably, 100 to 2
30 ° C.

The present invention 5 is a dicarboxylic acid represented by the following general formula (1); HOOC-R ¹ -COOH (1) (wherein R ¹ represents an alkylene group having 2 to 8 carbon atoms). At least one of
HO-R ² —OH (2) (wherein R ² represents an alkylene group having 2 to 6 carbon atoms) represented by the following general formula (2): reduced viscosity (at least one) 1 g / dL 98% sulfuric acid solution, 20 ° C) is 0.5 to
A resin composition obtained by adding 1 to 100 parts by weight of a polyfunctional isocyanate compound to 100 parts by weight of a polyester amide copolymer obtained by reacting a polyamide of 7 dL / g and inorganic fine particles, and reacting. .

The dicarboxylic acid represented by the general formula (1), the diol represented by the general formula (2) and the polyamide used in the present invention 5 are not particularly limited.
For example, the same ones as exemplified in the third aspect of the invention may be mentioned.

The inorganic fine particles used in the present invention 5 are not particularly limited, and examples thereof include those similar to those exemplified in the present invention 1.

In the fifth aspect of the present invention, the inorganic fine particles are
20 to 90% by weight in the above polyesteramide copolymer
It is preferable that it is blended so that When it is less than 20% by weight, the dimensional stability and heat distortion temperature of the molded product obtained from the resin composition of the present invention are insufficient, and when it exceeds 90% by weight, a uniform molded product cannot be obtained. More preferably, it is 50 to 90% by weight, still more preferably 50 to 90% by weight.
80% by weight.

A branching agent such as a polyol, a polycarboxylic acid or an oxyacid is further added to the components constituting the polyester for the purpose of increasing the molecular weight of the resulting polyesteramide copolymer, increasing the viscosity and shortening the polymerization time. May be. The branching agent is not particularly limited, and examples thereof include the same ones exemplified in the present invention 3.

The polyesteramide copolymer in the present invention 5 can be synthesized by a known method.
It can be carried out by polymerizing a dicarboxylic acid and a diol in the presence of the inorganic fine particles and the polyamide. The above-mentioned polymerization usually consists of a two-step reaction in which the esterification reaction is the first step and the polycondensation reaction is the second step.
Specifically, it is carried out in the same manner as in the present invention 3.

In this case, for the purpose of improving the dispersibility of the above-mentioned inorganic fine particles, increasing the filling, improving the heat resistance / flame retardancy, improving the water resistance, improving the moldability, homogenizing the physical properties, and reducing the cost. , Silane type, titanate type, aluminate type, zirco aluminum type, phosphoric acid type, carboxylic acid type,
Coupling agents such as fatty acids, oils and fats, waxes and surfactants; surface treatment agents may be used.

An alkoxysilane compound can be preferably used as the surface treatment agent. The alkoxysilane compound is not particularly limited, and examples thereof include those exemplified in the present invention 4.

When the above-mentioned surface treatment agent is used, an appropriate method can be adopted for the synthesis of the above polyesteramide copolymer depending on the types of the surface treatment agent, polyfunctional isocyanate compound and inorganic fine particles to be blended. For example, a mixture of the inorganic fine particles and the surface treatment agent previously mixed with the dicarboxylic acid represented by the general formula (1), the diol represented by the general formula (2), and the polyamide. Alternatively, a method of reacting to synthesize a polyesteramide copolymer can be adopted.

At this time, when the above-mentioned alkoxysilane compound is used as the above-mentioned surface treatment agent, in order to increase the reactivity between the above-mentioned inorganic fine particles and the above-mentioned alkoxysilane compound and to make the reaction uniformly, The inorganic fine particles dissolved in an organic solvent or the like are mixed and dried, and then the dicarboxylic acid represented by the general formula (1), the diol represented by the general formula (2), and the above. Mixing with a polyamide is preferred.

The inorganic fine particles are added to a mixture of the dicarboxylic acid represented by the general formula (1), the diol represented by the general formula (2), the polyamide, and the surface treatment agent in advance. A method of synthesizing a polyesteramide copolymer by mixing and reacting can also be adopted.

At this time, when the alkoxysilane compound is used as the surface treatment agent, the dicarboxylic acid represented by the general formula (1), the diol represented by the general formula (2), and the polyamide are used. In order to enhance the reactivity with the above-mentioned alkoxysilane compound, it is preferable to mix them in the range of 60 to 260 ° C. More preferably 100
~ 230 ° C. In this method, the alkoxysilane compound having an alkoxy group and an isocyanate group can be preferably used.

Further, the dicarboxylic acid represented by the general formula (1), the diol represented by the general formula (2), the polyamide, and the inorganic fine particles are mixed and reacted to form a polyesteramide copolymer. A method of adding the above-mentioned surface treatment agent after synthesis can also be adopted.

In the present invention 5, the intrinsic viscosity of the resin (polyester amide) excluding the above-mentioned inorganic fine particles in the polyester amide copolymer synthesized as described above is
0.1 to 0.9 dL / g (in o-chlorophenol, 3
0 ° C.) is preferred. If it is less than 0.1 dL / g, the molded product obtained by filling the polyesteramide copolymer with inorganic fine particles to obtain a high molecular weight will have poor high-temperature physical properties, and if it exceeds 0.9 dL / g, it will be high. The chain extension reaction by the functional isocyanate compound does not proceed quantitatively.
More preferably, it is 0.15-0.7 dL / g.

The resin composition of the present invention 5 can be obtained by adding a polyfunctional isocyanate compound to the above polyesteramide copolymer, mixing them, and proceeding the reaction.

The polyfunctional isocyanate compound used in the present invention 5 is not particularly limited, and examples thereof include those similar to those exemplified in the present invention 2.

In the present invention 5, the compounding amount of the polyfunctional isocyanate compound is 1 to 100 parts by weight based on 100 parts by weight of the polyesteramide copolymer. 1
When the amount is less than parts by weight, the resin (polyester amide) excluding the inorganic fine particles in the polyester amide copolymer
It is difficult to obtain a polymer having a high molecular weight by the chain extension reaction, and if the amount exceeds 100 parts by weight, excess isocyanate groups cause intermolecular crosslinking reaction, resulting in a resin composition. Since the fluidity of the product is poor, it is limited to the above range. It is preferably 1 to 30 parts by weight.

To add the above polyfunctional isocyanate compound to the above polyester amide copolymer and mix it to allow the reaction to proceed, for example, a kneader such as a kneader, an extruder or the like may be used. The above polyfunctional diisocyanate compound may be added and kneaded to the mixture and the mixture of the above-mentioned inorganic fine particles. The kneading temperature is preferably 60 to 260 ° C. If the temperature is lower than 60 ° C, it is difficult to obtain a molded product having sufficient strength because the reactivity is low. If the temperature exceeds 260 ° C, the polyesteramide copolymer and the polyfunctional isocyanate compound may decompose. There is. More preferably, 100 to
It is 230 ° C.

In the resin composition of the present invention 5, since the inorganic fine particles are mixed and dispersed in the monomer components of dicarboxylic acid and diol and then the above monomer components are reacted, the inorganic fine particles are uniformly dispersed in the system. The effect is to improve the physical properties of the obtained molded product, such as mechanical properties and heat resistance.

Since the resin composition of the present invention 5 uses a thermoplastic resin as a binder, it can be formed into a molded product by melt molding such as press molding, extrusion molding, injection molding, blow molding, injection compression molding and the like.

Since the molded product has a small molding shrinkage,
Automotive parts, electrical / electronic parts, where dimensional accuracy is important,
It can be suitably used as a precision molded article for industrial articles, sports articles, medical articles and the like. Also, since it is filled with a large amount of inorganic fine particles, it has excellent flame retardancy,
It can also be suitably used for applications requiring flame retardancy such as housing materials.

The present invention 6 is a dicarboxylic acid represented by the following general formula (1); HOOC-R ¹ -COOH (1) (wherein R ¹ represents an alkylene group having 2 to 8 carbon atoms). At least one of
And at least one of diols represented by the following general formula (2); HO—R ² —OH (2) (wherein R ² represents an alkylene group having 2 to 6 carbon atoms). Reduced viscosity (1 g / dL 98% to 100 parts by weight of the mixture)
Sulfuric acid solution, 20 ° C.) dissolves 3 to 250 parts by weight of polyamide having 0.5 to 7 dL / g and performs an esterification reaction at 150 to 230 ° C., and then under reduced pressure 200 to 260 ° C.
100 parts by weight of the inorganic fine particles to 100 parts by weight of the polyesteramide copolymer obtained by polymerization at
It is a resin composition obtained by mixing 00 parts by weight.

The resin composition of the present invention 6 is obtained by mixing the polyesteramide copolymer with inorganic fine particles. The polyester amide copolymer is prepared by dissolving a polyamide in a mixture of a dicarboxylic acid represented by the general formula (1) and a diol represented by the general formula (2) and performing an esterification reaction, Obtained by polymerizing.

The dicarboxylic acid represented by the above general formula (1) and the diol represented by the above general formula (2) are not particularly limited, and examples thereof include those similar to those exemplified in the present invention 3. Is mentioned.

In the sixth aspect of the present invention, as the diol represented by the above general formula (2), two hydroxyl groups are bonded to an alkylene group having 3 to 5 carbon atoms and having at least one alkyl group as a branched side chain. It is preferable to use the above-mentioned ones because the flexibility of the polyesteramide copolymer containing them as a constituent is improved. Such a diol is not particularly limited, and examples thereof include 1,2-propanediol, 1,3-butanediol, 2-methyl-1,3-
Propanediol, 1-methyl-2-methyl-1,2-
Examples thereof include ethanediol, 1,1-dimethyl-1,2-ethanediol, 1-ethyl-1,2-ethanediol and neopentyl glycol. Among these, neopentyl glycol is preferable, and 1,2-propanediol is more preferable because it is highly effective in improving flexibility.

When only a diol having no branch is used as the diol represented by the general formula (2), the crystallinity of the polyesteramide copolymer produced is high,
As a result, the hardness increases, which may result in poor elastomer properties. On the other hand, the above general formula (2)
When a branched diol is used as the diol represented by, the resulting polyesteramide copolymer is
The crystallization is suppressed by the presence of the branch, and the flexibility is improved. When a branched diol is used, the polymerization rate generally tends to decrease, so it is more preferable to appropriately use a branched diol in combination.

In the sixth aspect of the present invention, as long as the physical properties of the molded product obtained from the resulting resin composition are not impaired,
Aliphatic diols such as glycol and polyalkylene oxide can be appropriately used.

The above glycol is not particularly limited,
For example, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1. , 3
-Diol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol and the like can be mentioned. These may be used alone or in combination of two or more.

The polyalkylene oxide is not particularly limited, and examples thereof include polyethylene oxide, polypropylene oxide, polytetramethylene oxide, polyhexamethylene oxide and the like. These may be used alone or in combination of two or more.

The polyalkylene oxide preferably has a number average molecular weight of 500 to 20,000. When it is less than 500, the flexibility of the polyesteramide copolymer produced is insufficient, and when it exceeds 20,000, the physical properties such as heat stability of the produced polyesteramide copolymer are poor.

In the present invention 6, as the polyester constituent component, an aromatic dicarboxylic acid or aromatic diol can be used as long as the flexibility of the obtained polyesteramide copolymer is not impaired.

The above aromatic carboxylic acid is not particularly limited, and examples thereof include terephthalic acid, isophthalic acid, metal salts of 5-sulfoisophthalic acid, 4,4'-dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether,
4,4'-dicarboxydiphenyl sulfide, 4,
4'-dicarboxydiphenyl sulfone, 3,3'-dicarboxybenzophenone, 4,4'-dicarboxybenzophenone, 1,2-bis (4-carboxyphenoxy) ethane, 1,4-dicarboxynaphthalene, 2,6
-Dicarboxynaphthalene and the like.

The aromatic diol is not particularly limited, and examples thereof include hydroquinone, resorcin, chlorohydroquinone, bromohydroquinone, methylhydroquinone, phenylhydroquinone, methoxyhydroquinone, phenoxyhydroquinone, 4,4'-dihydroxybiphenyl,
4,4'-dihydroxydiphenyl ether, 4,4 '
-Dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylmethane, bisphenol A, 1,1-di (4-hydroxyphenyl) cyclohexane, 1,2- Examples thereof include bis (4-hydroxyphenoxy) ethane and 1,4-dihydroxynaphthalene.

A branching agent such as a polyol, a polycarboxylic acid or an oxyacid is further added to the components constituting the polyester for the purpose of increasing the molecular weight of the resulting polyesteramide copolymer, increasing the viscosity and shortening the polymerization time. May be. The branching agent is not particularly limited, and examples thereof include the same ones exemplified in the present invention 3.

The polyamide is not particularly limited,
For example, the same ones as exemplified in the third aspect of the invention may be mentioned.

In the sixth aspect of the invention, the polyesteramide copolymer is synthesized by the dicarboxylic acid represented by the general formula (1) and the diol represented by the general formula (2) in the presence of the polyamide. Polymerization with. The above-mentioned polymerization comprises a two-step reaction in which the esterification reaction is the first step and the polycondensation reaction is the second step.

The esterification reaction is carried out by dissolving the polyamide in the polyester component and forming a transparent and homogeneous solution. The reaction does not proceed efficiently in a heterogeneous state. The melting temperature is 150 to 230 ° C. Fifteen
When the temperature is lower than 0 ° C, it is difficult to dissolve the polyamide, and when the temperature is higher than 230 ° C, a decomposition reaction may occur, so the content is limited to the above range. Preferably 170-
It is 220 ° C.

The polycondensation reaction is carried out under reduced pressure, preferably 1
It is performed at 180 to 260 ° C. at 0 mmHg or less. 180
When the temperature is lower than 0 ° C, the reaction rate is low and the polymerization viscosity is high, so that efficient polymerization is difficult, and when the temperature is higher than 260 ° C, a decomposition reaction and coloring occur, so the range is limited. The temperature is preferably 190 to 250 ° C.

When synthesizing the polyesteramide copolymer, it is preferable to charge 1.2 to 3 mol of the diol to 1 mol of the dicarboxylic acid. If it is less than 1.2 mol, the esterification reaction will not proceed efficiently,
When it exceeds 3 mol, the cleavage reaction of the polyamide is likely to occur due to the excess diol component, so that the block property is lowered and the heat resistance is lowered.

When synthesizing the above polyesteramide copolymer, the amount of the above polyamide blended is a mixture of a dicarboxylic acid represented by the above general formula (1) and a diol represented by the above general formula (2). It is 3 to 250 parts by weight with respect to 100 parts by weight. If the amount is less than 3 parts by weight, the mechanical strength of the molded product obtained from the resulting polyesteramide copolymer will be insufficient, and if it exceeds 250 parts by weight, it will be difficult to dissolve nylon and an elastomer having good rubber elasticity will be obtained. Cannot be obtained, so the above range is limited. It is preferably 3 to 200 parts by weight, more preferably 3 to 180 parts by weight.

When synthesizing the above polyester amide copolymer, a catalyst generally used for producing polyester can be used. The catalyst is not particularly limited, and examples thereof include those exemplified in the present invention 3. When synthesizing the above polyester amide copolymer, a stabilizer can be used. The stabilizer is not particularly limited, and examples thereof include the same as those exemplified in the present invention 3.

In the present invention 6, the intrinsic viscosity of the polyesteramide copolymer synthesized as described above is
0.6-2.7 dL / g (in o-chlorophenol, 3
0 ° C.) is preferred. If it is less than 0.6 dL / g, the mechanical strength of the obtained molded product will be insufficient, and if it exceeds 2.7 dL / g, the fluidity will decrease due to the high viscosity, and melt molding will be difficult. More preferably, it is 0.8 to 2.0 dL / g.

The resin composition of the present invention 6 is obtained by mixing the polyesteramide copolymer obtained as described above with inorganic fine particles. The inorganic fine particles are not particularly limited, and examples thereof include the same as those exemplified in the first aspect of the invention.

In the present invention 6, the content of the inorganic fine particles is 100 to 900 parts by weight based on 100 parts by weight of the polyesteramide copolymer. If it is less than 100 parts by weight, the effect of improving the physical properties is not recognized, and if it exceeds 900 parts by weight, it is difficult to obtain a molded product, so the content is limited to the above range. It is preferably 200 to 700 parts by weight.

The method of mixing the inorganic fine particles with the polyesteramide copolymer is not particularly limited, and for example, a kneader such as a kneader or an extruder can be used. The temperature at that time is preferably 60 to 260 ° C. If it is lower than 60 ° C, it is difficult to obtain a molded product having sufficient strength, and if it is higher than 260 ° C, the polyesteramide copolymer is decomposed to give a molded product having sufficient strength. Can't get More preferably,
It is 100-230 degreeC.

In this case, for the purpose of improving the dispersibility of the above-mentioned inorganic fine particles, increasing the filling, improving the heat resistance and flame retardancy, improving the water resistance, improving the moldability, homogenizing the physical properties, reducing the cost, etc. , Silane type, titanate type, aluminate type, zirco aluminum type, phosphoric acid type, carboxylic acid type,
Coupling agents such as fatty acids, oils and fats, waxes and surfactants; surface treatment agents may be used. Above all, it is preferable to use a silane coupling agent.

An alkoxysilane compound can be preferably used as the silane coupling agent. The alkoxysilane compound is not particularly limited, and examples thereof include the same ones as exemplified in the fourth aspect of the invention.

In order to improve mechanical strength and heat resistance, a polyfunctional isocyanate compound or polycarbodiimide may be added to the resin composition of the present invention 6 and reacted.

The polyfunctional isocyanate compound is not particularly limited, and examples thereof include those similar to those exemplified in the second aspect of the present invention. The amount of the polyfunctional isocyanate compound added is preferably 0.1 to 30 parts by weight. If it is less than 0.1 part by weight, the effect of increasing the degree of polymerization is not seen, and if it exceeds 30 parts by weight, the mechanical strength of the obtained molded product is insufficient.

The polycarbodiimide is not particularly limited, and examples thereof include the same ones exemplified in the present invention 2. The amount of the polycarbodiimide added is the same as in the case of the second aspect of the present invention.

The above polyfunctional isocyanate compound,
Alternatively, when the chain extension reaction is performed by reacting with the polycarbodiimide, the intrinsic viscosity of the polyesteramide copolymer is preferably 1.0 dL / g (in o-chlorophenol, 30 ° C.) or less. When it exceeds 1.0 dL / g, the chain extension reaction by the polyfunctional isocyanate compound or the polycarbodiimide does not proceed quantitatively.

Further, the resin composition of the present invention 6 can be further improved in mechanical strength and heat resistance by increasing the molecular weight by solid phase polymerization. The solid phase polymerization is
It is preferable to carry out each polymerization sample in a temperature range from a temperature 30 ° C. lower than the melting point to the melting point. If the solid phase polymerization is carried out at a temperature lower than the melting point by 30 ° C., the progress of the polymerization becomes difficult, and if it is carried out at a temperature higher than the melting point, the sample is melted. More preferably, it is carried out in a temperature range from a temperature 15 ° C lower than the melting point to a temperature 5 ° C lower than the melting point. The solid phase polymerization is preferably carried out under reduced pressure of 5 Torr or less. If it exceeds 5 Torr, the progress of polymerization becomes difficult. More preferably, it is 1 Torr or less.

Since the resin composition of the present invention uses a thermoplastic resin as a binder, it can be formed into a molded product by melt molding such as press molding, extrusion molding, injection molding, blow molding, injection compression molding and the like. Since the molded product has a small molding shrinkage ratio, it is important for dimensional accuracy of automobile parts, electric
It can be suitably used as a precision molded product of electronic parts, industrial products, sports products, medical products and the like.

[0137]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 190 parts by weight of adipic acid, 1,4-butanediol 14
0 parts by weight, 162 parts by weight of 2,2-dimethyl-1,3-propanediol (adipic acid component / diol component charge ratio of 1 / 2.4), Toyobo Co., Ltd. 6-nylon (T850, Reduced viscosity at 20 ° C in 98% sulfuric acid 3.5
dL / g) 628 parts by weight, tetrabutoxy titanium 0.1 part by weight as a catalyst, and 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-) as a stabilizer. 0.4 parts by weight of 4-hydroxybenzyl) benzene and 0.4 parts by weight of tris (2,4-di-t-butylphenyl) phosphite were added, and the reaction system was heated to 200 ° C. under nitrogen. After 10 minutes, the nylon dissolved and became a clear solution. The mixture was kept at this temperature for 1 hour to carry out an esterification reaction. The progress of the esterification reaction was confirmed by measuring the amount of distilled water. After the esterification reaction proceeds, 20
The temperature was raised to 240 ° C. over a minute, and a pressure reduction operation was performed. The polymerization system reached a reduced pressure of 1 mmHg or less in 10 minutes. In this state, a polycondensation reaction was performed for 30 minutes to obtain a polyesteramide copolymer. The intrinsic viscosity of the obtained polyesteramide oligomer was 30 ° C in an orthochlorophenol solution.
Thus, [η] = 0.25.

Polyesteramide Copolymer 10 Obtained
10 parts by weight of 0 parts by weight, 220 parts by weight of fly ash (true specific gravity 2.2) (volume ratio 50/50), and 10 parts by weight of 4,4-diphenylmethane diisocyanate at 10 ° C. using a Brabender plastomill. Kneading was carried out for a minute to obtain a resin composition.

Molding shrinkage of the obtained resin composition, and
When the heat distortion temperature was evaluated by the following method, the molding shrinkage was 0.1% and the heat distortion temperature was 120 ° C.

Evaluation method 1. Molding Shrinkage The obtained resin composition was injection molded under the following molding conditions. Injection molding machine: Toshiba Machine Co., Ltd. EPN-IS30 (30t) Injection pressure: 1500 kgf / cm ² Mold temperature: 30 ° C. Cylinder temperature: 160-210 ° C. Molding shrinkage of the obtained molded product is calculated by the following formula. It was (Mold shrinkage rate) = {(mold size at room temperature-molded product size at room temperature) / mold size at room temperature} × 100

[0142] 2. Heat Deformation Temperature According to JIS K 7207, the heat deformation temperature was measured (dimensions of test piece: width 6.4 mm, height 12.7 mm, length 110 mm; bending stress: 4.6 kg / cm ² ). .

Example 2 A resin composition was obtained in the same manner as in Example 1 except that the addition amount of 6-nylon was 269 parts by weight and the addition amount of fly ash was 120 parts by weight. When the molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1, it was found to be 0.
It was 13%. When the heat distortion temperature was measured in the same manner as in Example 1, it was 110 ° C.

Example 3 A resin composition was obtained in the same manner as in Example 1 except that the amount of 6-nylon added was 30 parts by weight and the amount of fly ash added was 800 parts by weight. When the molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1, it was 0.0
It was 9%. When the heat distortion temperature was measured in the same manner as in Example 1, it was 105 ° C.

Example 4 Styrenic thermoplastic elastomer (manufactured by Japan Synthetic Rubber Co., Ltd.,
100 parts by weight of a pellet-shaped resin sample of TR2825) and 220 parts by weight of fly ash (true specific gravity 2.2) (volume ratio = 50/50) were kneaded at 170 ° C. for 10 minutes using a Brabender plast mill. I got a thing. When the molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1, it was 0.1%.

Example 5 Nipporan N-40, a polyester for elastomers
70 parts (manufactured by Nippon Polyurethane Co., Ltd.) and 220 parts by weight of fly ash (true specific gravity 2.2) (volume ratio = 5).
0/50) and 10 parts by weight of 4,4-diphenylmethane diisocyanate were kneaded at 150 ° C. for 10 minutes using a Brabender plastomill to obtain a resin composition. When the molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1, it was 0.1%.

Comparative Example 1 Example 1 except that no fly ash was added.
In the same manner as in the above, a resin composition was obtained. When the molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1,
1.0%. When the heat distortion temperature was measured in the same manner as in Example 1, it was 98 ° C.

Comparative Example 2 A resin composition was obtained in the same manner as in Example 2 except that the amount of fly ash added was 80 parts by weight. The molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1, and it was 1.1%. When the heat distortion temperature was measured in the same manner as in Example 1, it was 97 ° C.

Comparative Example 3 Melt kneading was carried out using a Brapender plastomill in the same manner as in Example 3 except that the amount of fly ash added was 1000 parts by weight, but the composition obtained was injection-moldable. There wasn't.

Comparative Example 4 Example 4 except that no fly ash was added.
In the same manner as in the above, a resin composition was obtained. When the molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1,
1.0%.

Comparative Example 5 Example 5 except that no fly ash was added.
In the same manner as in the above, a resin composition was obtained. When the molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1,
1.1%.

Example 6 Polyesteramide Copolymer 89 in the same manner as in Example 1
7 parts by weight were obtained. The intrinsic viscosity of the obtained polyesteramide oligomer was 30% in an orthochlorophenol solution.
At [deg.] C., [[eta]] = 0.25.

Polyesteramide oligomer 1 obtained
00 parts by weight and 275 parts by weight of calcium carbonate (Whiten SB, true specific gravity 2.75, manufactured by Shiraishi Calcium Co., Ltd.),
10 parts by weight of 4,4-diphenylmethane diisocyanate was kneaded at 200 ° C. for 10 minutes using a Brabender plastomill to obtain a resin composition.

The molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1, and it was 0.12%.
When the heat distortion temperature was measured in the same manner as in Example 1, it was 1
It was 17 ° C. Flexural modulus is measured according to JIS K 7203
It was 65000 kg / cm ² when evaluated in accordance with.

Example 7 538 parts by weight of polyesteramide copolymer were prepared in the same manner as in Example 1 except that the addition amount of 6-nylon was 269 parts by weight and the addition amount of tetrabutoxytitanium was 0.3 parts by weight. Got The intrinsic viscosity of the obtained polyesteramide copolymer was [η] = 0.38.

The polyesteramide copolymer thus obtained was used as 1
00 parts by weight, talc (crown talc HS, true specific gravity 2.
65-2.75, manufactured by Matsumura Sangyo Co., Ltd.) 120 parts by weight, 4,
A resin composition was obtained in the same manner as in Example 6 except that the amount of 4-diphenylmethane diisocyanate was 8 parts by weight.

The molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1, and it was 0.13%.
When the heat distortion temperature was measured in the same manner as in Example 1, it was 1
It was 06 ° C. When the flexural modulus was measured in the same manner as in Example 6, it was 12000 kg / cm ² .

Example 8 300 parts by weight of a polyesteramide copolymer were prepared in the same manner as in Example 1 except that the addition amount of 6-nylon was 30 parts by weight and the addition amount of tetrabutoxytitanium was 0.6 parts by weight. Got The intrinsic viscosity of the obtained polyesteramide copolymer was [η] = 0.8.

The polyesteramide copolymer thus obtained was used as 1
00 parts by weight, blast furnace slag fine powder (ESMENT, true specific gravity 2.89, manufactured by Nippon Steel Chemical Co., Ltd.) 800 parts by weight, 4,4-
A resin composition was obtained in the same manner as in Example 6 except that 5 parts by weight of diphenylmethane diisocyanate was used.

The molding shrinkage percentage of the obtained resin composition was measured in the same manner as in Example 1, and it was 0.11%.
When the heat distortion temperature was measured in the same manner as in Example 1, it was 1
02 ° C. The flexural modulus was measured in the same manner as in Example 6 and found to be 5000 kg / cm ² .

Example 9 97 parts by weight of ethylene glycol and 119 parts by weight of propyl glycol were used as diol components, the addition amount of 6-nylon was 233 parts by weight, the addition amount of tetrabutoxytitanium was 0.1 parts by weight, and polycondensation was performed. 466 parts by weight of a polyesteramide copolymer was obtained in the same manner as in Example 1 except that the time was 10 minutes. The intrinsic viscosity of the obtained polyesteramide copolymer was [η] = 0.15.

The obtained polyesteramide copolymer was used as 1
00 parts by weight, zinc oxide (special No. 1 zinc oxide, true specific gravity 5.5
.About.5.7, manufactured by Hakusui Chemical Co., Ltd.) was 500 parts by weight and 4,4-diphenylmethane diisocyanate was 13 parts by weight to obtain a resin composition in the same manner as in Example 6.

The molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1, and it was 0.09%.
When the heat distortion temperature was measured in the same manner as in Example 1, it was 1
It was 11 ° C. When the flexural modulus was measured in the same manner as in Example 6, it was 51000 kg / cm ² .

Example 10 Except that 97 parts by weight of ethylene glycol and 162 parts by weight of 2,2-dimethyl-1,3-propanediol were used as diol components, and the amount of 6-nylon added was 251 parts by weight. In the same manner as in Example 1, 502 parts by weight of a polyesteramide copolymer was obtained. The intrinsic viscosity of the obtained polyesteramide copolymer was [η] = 0.25.

The polyesteramide copolymer thus obtained was used as 1
00 parts by weight, hollow spherical calcium carbonate (cal balloon,
800 parts by weight of true specific gravity 2.69, made by Calceed Co.,
A resin composition was obtained in the same manner as in Example 6 except that 8 parts by weight of 4,4-diphenylmethane diisocyanate was used.

The molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1, and it was 0.1%. When the heat distortion temperature was measured in the same manner as in Example 1, it was 12
2 ° C. When the flexural modulus was measured in the same manner as in Example 6, it was 84000 kg / cm ² .

Example 11 119 parts by weight of propylene glycol as a diol component and 2,2-dimethyl-1,3-propanediol 162
780 parts by weight of a polyesteramide copolymer was obtained in the same manner as in Example 1 except that 1 part by weight was used. The intrinsic viscosity of the obtained polyesteramide copolymer is [η] =
It was 0.28.

The polyesteramide copolymer thus obtained was used as 1
Example 6 except that 00 parts by weight, Shirasu balloon (Terafine, manufactured by Calceed Co., Ltd.) were 700 parts by weight, and 4,4-diphenylmethane diisocyanate was 9 parts by weight.
In the same manner as in the above, a resin composition was obtained.

The molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1, and it was 0.1%. When the heat distortion temperature was measured in the same manner as in Example 1, it was 12
3 ° C. When the flexural modulus was measured in the same manner as in Example 6, it was 82000 kg / cm ² .

Example 12 The same as Example 6 except that 220 parts by weight of dehydrated sludge (crushed particles, true specific gravity 2.2, average particle size 20 μm (by electron microscope)) was used in place of calcium carbonate. To obtain a resin composition.

The molding shrinkage percentage of the obtained resin composition was measured in the same manner as in Example 1, and it was 0.11%.
When the heat distortion temperature was measured in the same manner as in Example 1, it was 1
It was 23 ° C. When the flexural modulus was measured in the same manner as in Example 6, it was 68000 kg / cm ² .

Example 13 A resin was prepared in the same manner as in Example 9 except that 120 parts by weight of dehydrated sludge (spherical, true specific gravity 2.2, average particle size 7 μm (by electron microscope)) was used in place of zinc oxide. A composition was obtained.

The molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1, and it was 0.08%.
When the heat distortion temperature was measured in the same manner as in Example 1, it was 1
It was 19 ° C. When the flexural modulus was measured in the same manner as in Example 6, it was 54000 kg / cm ² .

Example 14 The same as Example 10 except that 800 parts by weight of dehydrated sludge (spherical, true specific gravity 2.2, average particle size 7 μm (by electron microscope)) was used instead of hollow spherical calcium carbonate. To obtain a resin composition.

The molding shrinkage percentage of the obtained resin composition was measured in the same manner as in Example 1, and it was 0.09%.
When the heat distortion temperature was measured in the same manner as in Example 1, it was 1
It was 23 ° C. When the flexural modulus was measured in the same manner as in Example 6, it was 86000 kg / cm ² .

Example 15 Polyesteramide copolymer 93 was prepared in the same manner as in Example 1.
9 parts by weight were obtained. The intrinsic viscosity of the obtained polyesteramide copolymer was [η] = 0.25.

Polyesteramide Copolymer 10 Obtained
3-triethoxysilylpropyl isocyanate (KBE-900), which is 0 part by weight and an alkoxysilane compound.
(7, manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part by weight was kneaded for 3 minutes at 180 ° C. using a Brabender Plastomill, and then fly ash (true specific gravity 2.2, average particle size 20 μm) 220
Add 4 parts by weight, knead for 5 minutes, and then add 4,4-
10 parts by weight of diphenylmethane diisocyanate was added and kneaded for 7 minutes to obtain a resin composition.

The molding shrinkage percentage of the obtained resin composition was measured in the same manner as in Example 1, and it was 0.1%. When the heat distortion temperature was measured in the same manner as in Example 1, it was 12
5 ° C.

Example 16 A polyesteramide copolymer 1046 parts by weight was obtained in the same manner as in Example 1 except that the amount of 6-nylon added was 269 parts by weight. The intrinsic viscosity of the obtained polyesteramide copolymer was [η] = 0.32.

The polyester amide copolymer thus obtained was used as 1
A resin composition was obtained in the same manner as in Example 15, except that 00 parts by weight, 120 parts by weight of fly ash and 0.05 parts by weight of 3-triethoxysilylpropyl isocyanate were used.

The molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1, and it was 0.12%.
When the heat distortion temperature was measured in the same manner as in Example 1, it was 1
It was 15 ° C.

Example 17 The same as Example 1 except that 280 parts by weight of 1,4-butanediol was used as the diol component, the addition amount of 6-nylon was 30 parts by weight, and the polycondensation time was 45 minutes. Thus, 332 parts by weight of polyesteramide copolymer was obtained. The intrinsic viscosity of the obtained polyesteramide copolymer is
[Η] = 0.45.

Alkoxysilane compound N- (2-
A 1% aqueous solution of (aminoethyl) -3-aminopropyltrimethoxysilane was prepared, and fly ash (true specific gravity: 2.2, average particle size: 3 μm) was immersed in the obtained aqueous solution, and a stirring operation was performed. The precipitated fly ash was washed with methanol and then thoroughly dried.

Polyesteramide Copolymer 10 Obtained
0 parts by weight and 800 parts by weight of the obtained fly ash were added at 5 ° C at 5 ° C using a Brabender Plastomill.
After kneading for 5 minutes, 5 parts by weight of 4,4-diphenylmethane diisocyanate was added and kneading for 7 minutes to obtain a resin composition.

The molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1, and it was 0.19%.
When the heat distortion temperature was measured in the same manner as in Example 1, it was 9
It was 0 ° C.

Comparative Example 6 A resin composition was obtained in the same manner as in Example 6 except that calcium carbonate was not added. When the molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1,
It was 1.2%. When the heat distortion temperature was measured in the same manner as in Example 1, it was 98 ° C.

Comparative Example 7 A resin composition was obtained in the same manner as in Example 7, except that the amount of talc added was 80 parts by weight. When the molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1,
1.1%. When the heat distortion temperature was measured in the same manner as in Example 1, it was 97 ° C. When the flexural modulus was measured in the same manner as in Example 6, it was 3000 kg / cm ^2.
Met.

Comparative Example 8 A resin composition was obtained in the same manner as in Example 8 except that the addition amount of blast furnace slag fine powder was 1000 parts by weight. The obtained resin composition was injection-molded. I couldn't.

Comparative Example 9 A resin composition was obtained in the same manner as in Example 9 except that zinc oxide was not added. The molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1 and found to be 1.5%.
Met.

Comparative Example 10 Except that no hollow spherical calcium carbonate was added,
A resin composition was obtained in the same manner as in Example 10. The molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1, and it was 1.5%.

Comparative Example 11 A resin composition was obtained in the same manner as in Example 11 except that the amount of shirasu balloon added was 1000 parts by weight. The resin composition obtained was injection-moldable. There wasn't.

Comparative Example 12 A resin composition was obtained in the same manner as in Example 13 except that the amount of dehydrated sludge added was 80 parts by weight. The molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1, and it was 0.9%. When the heat distortion temperature was measured in the same manner as in Example 1, it was 97 ° C. When the flexural modulus was measured in the same manner as in Example 6, it was 3200 kg / c.
m ² .

Comparative Example 13 Except that the amount of dehydrated sludge added was 1000 parts by weight,
A resin composition was obtained in the same manner as in Example 14, but the obtained resin composition could not be injection-molded.

Comparative Example 14 Example 1 except that no fly ash was added.
A resin composition was obtained in the same manner as in 5. When the molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1,
It was 1.2%. When the heat distortion temperature was measured in the same manner as in Example 1, it was 98 ° C.

Comparative Example 15 Except that the alkoxysilane compound was not added,
A resin composition was obtained in the same manner as in Example 15. The molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1, and the heat distortion temperature was measured in the same manner as in Example 1. The result was 99 ° C.

Comparative Example 16 A resin composition was obtained in the same manner as in Example 16 except that the amount of fly ash added was 80 parts by weight. The molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1, and it was 1.1%. The heat distortion temperature was determined as in Example 1.
It was 97 ° C. when measured in the same manner as in.

Comparative Example 17 A resin composition was obtained in the same manner as in Example 17 except that the amount of fly ash added was 1000 parts by weight. The resin composition obtained was injection-moldable. There wasn't.

Example 18 Instead of calcium carbonate, silica fume (true specific gravity: 2.
2, a resin composition was obtained in the same manner as in Example 6 except that the average particle size was 0.15 μm). The molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1, and it was 0.10%. When the heat distortion temperature was measured in the same manner as in Example 1, it was 125 ° C.
When the flexural modulus was measured in the same manner as in Example 6, it was 7
It was 1000 kg / cm ² .

Example 19 A resin composition was obtained in the same manner as in Example 9 except that 120 parts by weight of silica fume (true specific gravity: 2.2, average particle size: 0.15 μm) was used instead of zinc oxide. . The molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1, and it was 0.07%. The heat distortion temperature was determined as in Example 1.
It was 121 ° C. when measured in the same manner as in. When the flexural modulus was measured in the same manner as in Example 6, it was 560.
It was 00 kg / cm ² .

Example 20 A resin composition was prepared in the same manner as in Example 10 except that 800 parts by weight of silica fume (true specific gravity: 2.2, average particle size: 0.15 μm) was used instead of hollow spherical calcium carbonate. Obtained. The molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1, and it was 0.08%. When the heat distortion temperature was measured in the same manner as in Example 1, it was 125 ° C.
Met. When the flexural modulus was measured in the same manner as in Example 6, it was 90000 kg / cm ² .

Comparative Example 18 A resin composition was obtained in the same manner as in Example 19 except that the amount of silica fume added was 80 parts by weight. The molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1, and it was 0.9%. The heat distortion temperature was determined as in Example 1.
It was 100 degreeC when measured in the same manner as. When the flexural modulus was measured in the same manner as in Example 6, it was found to be 330.
It was 0 kg / cm ² .

Comparative Example 19 A resin composition was obtained in the same manner as in Example 20 except that the amount of silica fume added was 1000 parts by weight. The obtained resin composition was injection-moldable. There wasn't.

Example 21 190 parts by weight of adipic acid, 1,4-butanediol 14
0 parts by weight, 162 parts by weight of 2,2-dimethyl-1,3-propanediol (mixing ratio of adipic acid component / diol component is 1 / 2.4), Toyobo Co., Ltd. 6-nylon (T850, Reduced viscosity at 20 ° C in 98% sulfuric acid 3.5
dL / g) 628 parts by weight, tetrabutoxy titanium 0.1 part by weight as a catalyst, and 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-) as a stabilizer.
4-hydroxybenzyl) benzene 0.4 part by weight, tris (2,4-di-t-butylphenyl) phosphite 0.4 part by weight, and fly ash (true specific gravity 2.2,
1800 parts by weight of average particle size 20 μm) are added and stirred,
The reaction system was heated to 200 ° C. under nitrogen. After 10 minutes, the nylon dissolved and became a clear solution. The mixture was kept at this temperature for 1 hour to carry out an esterification reaction. The progress of the esterification reaction was confirmed by measuring the amount of distilled water. After the progress of the esterification reaction, the temperature was raised to 240 ° C. in 20 minutes, and the pressure was reduced. Polymerization system is 1mmH for 10 minutes
g or less. In this state, a polycondensation reaction was performed for 30 minutes to obtain 2697 parts by weight of a polyesteramide copolymer (inorganic fine particle content: 66.7% by weight). The obtained polyesteramide copolymer was immersed in toluene at 90 ° C. to extract the polyesteramide, and after drying, the intrinsic viscosity was measured and the result was 30 ° C. in an orthochlorophenol solution.
Thus, [η] = 0.25.

Polyesteramide Copolymer 10 Obtained
3-triethoxysilylpropyl isocyanate (KBE-900), which is an alkoxysilane compound, is added to 0 part by weight.
(7, manufactured by Shin-Etsu Chemical Co., Ltd.) and kneaded for 3 minutes at 180 ° C. using a Brabender Plastomill, and then 10 parts by weight of 4,4-diphenylmethane diisocyanate and kneaded for 7 minutes, A resin composition was obtained.

The molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1, and it was 0.1%. When the heat distortion temperature was measured in the same manner as in Example 1, it was 12
7 ° C.

Example 22 Example 21 except that the amount of 6-nylon added was 30 parts by weight and the amount of fly ash added was 1200 parts by weight.
In the same manner as in (1), 1499 parts by weight of a polyesteramide copolymer (inorganic fine particle content: 80.1% by weight) was obtained. When the intrinsic viscosity of the obtained polyesteramide copolymer was measured in the same manner as in Example 21, it was [η] = 0.32.

Example 21 except that the polyesteramide copolymer thus obtained was used and the amount of 3-triethoxysilylpropyl isocyanate added was 0.05 part by weight.
In the same manner as in the above, a resin composition was obtained. When the molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1,
0.12%. When the heat distortion temperature was measured in the same manner as in Example 1, it was 110 ° C.

Example 23 280 parts by weight of 1,4-butanediol was used as the diol component, and the addition ratio of the adipic acid component / diol component was 1 / 2.4) 6-nylon at a molar ratio of 300 parts by weight. A polyesteramide copolymer 960 parts by weight (inorganic fine particle content: 31.3% by weight) was obtained in the same manner as in Example 21, except that the amount of fly ash added was 300 parts by weight and the polycondensation time was 45 minutes. It was When the intrinsic viscosity of the obtained polyesteramide copolymer was measured in the same manner as in Example 21, it was [η] = 0.45.

Polyesteramide Copolymer 10 Obtained
180 parts by weight using a Brabender Plastomill
After kneading at 5 ° C for 5 minutes, 5 parts by weight of 4,4-diphenylmethane diisocyanate was added and kneading for 7 minutes to obtain a resin composition. The molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1, and it was 0.23%.
When the heat distortion temperature was measured in the same manner as in Example 1, it was 1
00 ° C.

Comparative Example 20 A resin composition was obtained in the same manner as in Example 22 except that the amount of fly ash added was 80 parts by weight. The molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1, and it was 1.1%. The heat distortion temperature was determined as in Example 1.
It was 95 ° C. when measured in the same manner as in.

Comparative Example 21 A resin composition was obtained in the same manner as in Example 23, except that the amount of fly ash added was 7,000 parts by weight. The resin composition obtained was injection-moldable. There wasn't. The obtained polyesteramide copolymer was 7
It was 660 parts by weight (inorganic fine particle content 91% by weight).

Example 24 897 parts by weight of a polyesteramide copolymer was obtained in the same manner as in Example 1 except that the polycondensation time was 60 minutes. The intrinsic viscosity of the obtained polyesteramide copolymer was [η] = 0.95.

Polyesteramide Copolymer 10 Obtained
3-triethoxysilylpropyl isocyanate (KBE-900), which is an alkoxysilane compound, is added to 0 part by weight.
(7, manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part by weight was kneaded for 3 minutes at 180 ° C. using a Brabender Plastomill, and then fly ash (true specific gravity 2.2, average particle size 20 μm) 200
A part by weight was added and further kneaded for 5 minutes to obtain a resin composition.

The molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1, and it was 0.1%.
When the heat distortion temperature was measured in the same manner as in Example 1, it was 1
It was 27 ° C.

Example 25 The amount of 6-nylon added was 30 parts by weight, and the polycondensation time was 90.
299 parts by weight of a polyesteramide copolymer was obtained in the same manner as in Example 1 except that the time was changed. The intrinsic viscosity of the obtained polyesteramide copolymer is [η] = 1.2.
Met.

A resin composition was obtained in the same manner as in Example 24 except that the obtained polyesteramide copolymer was used and the amount of fly ash added was 400 parts by weight. The molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1, and it was 0.12%. When the heat distortion temperature was measured in the same manner as in Example 1, it was 110 ° C.

Example 26 The same as Example 1 except that 280 parts by weight of 1,4-butanediol was used as the diol component, the addition amount of 6-nylon was 300 parts by weight, and the polycondensation time was 90 minutes. Thus, 660 parts by weight of a polyesteramide copolymer was obtained.
The intrinsic viscosity of the obtained polyesteramide copolymer is
[Η] = 1.05.

Polyesteramide Copolymer 10 Obtained
45 parts by weight of fly ash (true specific gravity 2.2, average particle size 20 μm) was added to 0 parts by weight, and kneaded at 180 ° C. for 5 minutes using a Brabender plast mill to obtain a resin composition. The molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1, and it was 0.23%. When the heat distortion temperature was measured in the same manner as in Example 1, it was 100 ° C.
Met.

Comparative Example 22 Example 24 except that no fly ash was added.
A resin composition was obtained in the same manner as in. When the molding shrinkage ratio was measured in the same manner as in Example 1, it was 1.2%. When the heat distortion temperature was measured in the same manner as in Example 1, it was 98
° C.

Comparative Example 23 A resin composition was obtained in the same manner as in Example 25 except that the amount of fly ash added was 10 parts by weight. The molding shrinkage of the obtained resin composition was measured in the same manner as in Example 1, and it was 1.1%. When the heat distortion temperature was measured in the same manner as in Example 1, it was 95 ° C.

Comparative Example 24 A resin composition was obtained in the same manner as in Example 26 except that the amount of fly ash added was 1100 parts by weight. The resin composition obtained was injection-moldable. There wasn't.

[0222]

Since the resin composition of the present invention has the above-mentioned constitution, it does not cause deterioration of mechanical properties and deterioration of moldability even if a large amount of inorganic fine particles is contained, and has high mechanical strength in a high temperature range. It is possible to obtain a molded product having excellent heat resistance and dimensional stability and a small molding shrinkage ratio. In addition, the waste can be effectively used.

Claims (13)

[Claims] 1. A resin composition obtained by melt-kneading a thermoplastic elastomer and inorganic fine particles, wherein 2 parts of the inorganic fine particles are contained in 100 parts by weight of the thermoplastic elastomer.
A resin composition comprising 60 to 900 parts by weight. 2. Having at least two functional groups selected from the group consisting of a carboxyl group, an amino group and a hydroxyl group, and having an intrinsic viscosity (in o-chlorophenol, 30 ° C.),
It is obtained by adding 100 to 900 parts by weight of inorganic fine particles and 1 to 100 parts by weight of a polyfunctional isocyanate compound to 100 parts by weight of an oligomer having a concentration of 0.1 to 0.9 dL / g, and reacting them. Resin composition. 3. A dicarboxylic acid represented by the following general formula (1); HOOC-R ¹ —COOH (1) (wherein R ¹ represents an alkylene group having 2 to 8 carbon atoms). One,
Following general formula ^{(2); HO-R 2} -OH (2) (. Wherein, R ² is representative of the alkylene group having 2 to 6 carbon atoms) at least one diol represented by, and, reducing 100 parts by weight of a polyesteramide copolymer obtained by reacting a polyamide having a viscosity (1 g / dL 98% sulfuric acid solution, 20 ° C.) of 0.5 to 7 dL / g, 100 to 900 parts by weight of inorganic fine particles, and A resin composition obtained by adding 1 to 100 parts by weight of a functional isocyanate compound and reacting them. 4. A polyesteramide copolymer, further comprising:
The resin composition according to claim 3, wherein 0.01 to 10 parts by weight of the alkoxysilane compound is mixed. 5. The resin composition according to claim 4, wherein the alkoxysilane compound has an isocyanate group. 6. The resin according to claim 4, which is obtained by adding a mixture of inorganic fine particles and an alkoxysilane compound in advance to a polyesteramide copolymer, and then adding a polyfunctional isocyanate compound and causing a reaction. Composition. 7. The resin according to claim 4, which is obtained by adding inorganic fine particles to a mixture of a polyesteramide copolymer and an alkoxysilane compound in advance, and then adding a polyfunctional isocyanate compound and reacting the mixture. Composition. 8. A dicarboxylic acid represented by the following general formula (1); HOOC-R ¹ —COOH (1) (wherein R ¹ represents an alkylene group having 2 to 8 carbon atoms). One,
HO-R ² —OH (2) (wherein R ² represents an alkylene group having 2 to 6 carbon atoms) represented by the following general formula (2): reduced viscosity (at least one) 1 g / dL 98% sulfuric acid solution, 20 ° C) is 0.5 to
It is characterized by being obtained by adding 1 to 100 parts by weight of a polyfunctional isocyanate compound to 100 parts by weight of a polyester amide copolymer obtained by reacting a polyamide of 7 dL / g and inorganic fine particles, and reacting. Resin composition. 9. The resin composition according to claim 8, wherein the inorganic fine particles are mixed in the polyesteramide copolymer in an amount of 20 to 90% by weight. 10. A dicarboxylic acid represented by the following general formula (1); HOOC-R ¹ —COOH (1) (wherein R ¹ represents an alkylene group having 2 to 8 carbon atoms). One,
And at least one of diols represented by the following general formula (2); HO—R ² —OH (2) (wherein R ² represents an alkylene group having 2 to 6 carbon atoms). Reduced viscosity (1 g / dL 98% to 100 parts by weight of the mixture)
Sulfuric acid solution, 20 ° C.) dissolves 3 to 250 parts by weight of polyamide having 0.5 to 7 dL / g and performs an esterification reaction at 150 to 230 ° C., and then under reduced pressure 200 to 260 ° C.
100 parts by weight of the inorganic fine particles to 100 parts by weight of the polyesteramide copolymer obtained by polymerization at
A resin composition comprising a mixture of 00 parts by weight. 11. A dicarboxylic acid represented by the following general formula (1); HOOC-R ¹ —COOH (1) (wherein R ¹ represents an alkylene group having 2 to 8 carbon atoms). One,
Following general formula ^{(2); HO-R 2} -OH (2) (. Wherein, R ² is representative of the alkylene group having 2 to 6 carbon atoms) at least one diol represented by, and, reducing A polyesteramide copolymer obtained by reacting a polyamide having a viscosity (1 g / dL 98% sulfuric acid solution, 20 ° C.) of 0.5 to 7 dL / g has an intrinsic viscosity (in o-chlorophenol, 30 ° C.) of 0. .1 to 0.9 dL / g
The resin composition according to claim 3, which is 12. The inorganic fine particles have an average particle diameter of 0.1 to 50.
The resin composition according to claim 1, wherein the resin composition is spherical fine particles of μm. 13. The resin composition according to claim 1, wherein the inorganic fine particles are at least one selected from the group consisting of silica fume, dehydrated sludge incineration ash, and fly ash.