JP2001019851A - Additive for thermoplastic resin composition and resin composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide additives for thermoplastic resin composition which excel in heat resistance and can improve temperature properties of resin without adversely affecting the inherent properties of the resins to a great extent, and also thermoplastic resin compositions mixed with the additives. SOLUTION: An additive for a thermoplastic resin is selected from the group consisting of a polyarylate, a plysufone, a polyethersulfone, a polyarylene sulfide, a polyphenylene ether, a polytherketone, a polyamideimide, a polycarbonate, a polyacetal, a polyester, a polyamide and a thermoplastic polyimide, which have an aromatic carboxylic ester represented by the formula: Ar(COOR)n (wherein n of Rs are the same or different and R is an 8-30C aliphatic hydrocarbon group; Ar is an aromatic group; and n is 3 or 4) as a constituting component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an additive for a thermoplastic resin containing an aromatic carboxylic acid ester as an essential component, and a thermoplastic resin composition using the same.

[0002]

2. Description of the Related Art Recently, thermoplastic resins having heat resistance have been used as engineering plastics as mechanical materials,
Used in electronic components. In molding the thermoplastic resin, various resin modifiers, for example, fatty acids such as stearic acid, fatty acids, fatty acids such as stearic acid, for the purpose of increasing productivity, lowering melt viscosity, accelerating crystallization, and improving mold releasability. A method of kneading metal salts, ester derivatives of fatty acids with polyhydric alcohols such as pentaerythritol and polyethylene glycol, and aliphatic amides such as ethylene bisstearamide has been proposed (Japanese Patent Application Laid-Open No. 60-44547, Kaihei 3-250049).

However, thermoplastic resins having heat resistance are excellent in mechanical properties and heat resistance, but are generally inferior in processability such as high melting temperature and low fluidity. In addition, there is a problem in production, such as the necessity of an excessively high temperature in the latter half of the polymerization reaction.

[0004] When the above-mentioned various resin modifiers are blended in order to solve the above-mentioned problems, there have been problems such as thermal decomposition and boiling at the time of melting, contaminating the mold and generating bubbles in the resin. Therefore, development of a resin modifier having heat resistance has been desired.

[0005]

SUMMARY OF THE INVENTION The present invention provides an additive for a thermoplastic resin which has excellent heat resistance and improves the temperature characteristics of the resin without significantly impairing the inherent characteristics of the resin. It is an object of the present invention to provide a modified thermoplastic resin composition.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, a specific aromatic carboxylic acid ester itself has heat resistance and has been added to a thermoplastic resin. In such a case, it has been found that the melt viscosity of the thermoplastic resin is reduced, the heat-sealing property, the adhesive property is improved, and the like, and it is found that the thermoplastic resin functions as a resin additive having desired performance, and the present invention is completed based on such knowledge. Reached.

That is, the present invention relates to a compound represented by the general formula (1): Ar (COOR) _n (1) wherein n Rs are the same or different and have 8 to 30 carbon atoms.
Represents an aliphatic hydrocarbon group. Ar represents an aromatic group. n
Represents 3 or 4. A polyarylate, polysulfone, polyethersulfone, polyarylene sulfide, polyphenylene ether, polyetherketone, polyamideimide, polycarbonate, polyacetal, comprising an aromatic carboxylic acid ester represented by the following formula:
Provided is an additive for a thermoplastic resin selected from the group of polyester, polyamide, and thermoplastic polyimide.

Further, the present invention provides a compound represented by the general formula (1): Ar (COOR) _n (1) wherein n Rs are the same or different and have 8 to 30 carbon atoms.
Represents an aliphatic hydrocarbon group. Ar represents an aromatic group.
n represents 3 or 4. A thermoplastic resin additive comprising one or more aromatic carboxylic acid esters represented by the following formulas, and polyarylate, polysulfone, polyether sulfone, polyarylene sulfide, polyphenylene ether, polyether ketone, Provided is a thermoplastic resin composition containing at least one thermoplastic resin selected from the group consisting of polyamide imide, polycarbonate, polyacetal, polyester, polyamide, and thermoplastic polyimide.

[0009] The present invention provides a method for producing a polyarylene, polysulfone, polyethersulfone, polyarylene sulfide, polyphenylene ether, polyetherketone, polyamideimide, polycarbonate, polyacetal, polyester, polyamide or thermoplastic polyimide. There is also provided a method for lowering the thermal fusion temperature of a thermoplastic resin by 10 ° C. or more, characterized by adding an aromatic carboxylic acid ester represented by the general formula (1) to the thermoplastic resin.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Aromatic resins for thermoplastic resin additives
Rubonic acid ester Ar in the aromatic carboxylic acid ester represented by the general formula (1) used in the present invention is an aromatic group, and more specifically, phenyl, naphthalene, biphenyl, benzophenone, diphenyl Examples thereof include a sulfone group and a diphenyl ether group.

The n Rs are the same or different and each represents an aliphatic hydrocarbon group having 8 to 30 carbon atoms, and specifically, a linear or branched alkyl group having 8 to 30 carbon atoms. And a linear or branched alkenyl group having 8 to 30 carbon atoms, a cycloalkyl group or cycloalkenyl group having 8 to 30 carbon atoms, a bicyclo ring alkyl group or a bicyclo ring alkenyl group having 8 to 30 carbon atoms, and the like. Is done. Among them, a linear or branched alkyl group having 8 to 30 carbon atoms is preferable, and a 3,5,5-trimethylhexyl group is more preferable.

The aromatic carboxylic acid ester represented by the general formula (1) used in the present invention comprises an aromatic carboxylic acid component (hereinafter referred to as "acid component") and an aliphatic monohydric alcohol having 8 to 30 carbon atoms. An ester compound prepared by esterifying a component (hereinafter, referred to as an “alcohol component”). The ester compound does not necessarily need to have all carboxylic acid groups esterified, and may contain unreacted carboxylic acid groups. That is, the aromatic carboxylic acid ester represented by the general formula (1) used in the present invention includes a triester or diester of an aromatic tricarboxylic acid, a tetraester of an aromatic tetracarboxylic acid,
Triesters or diesters are included.

The acid component of the aromatic carboxylic acid ester includes trimellitic acid, trimesic acid, pyromellitic acid,
Aromatic carboxylic acids such as naphthalenetetracarboxylic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, diphenylsulfonetetracarboxylic acid, diphenylethertetracarboxylic acid or anhydrides thereof, or the carboxylic acids and carbon atoms of 1-4 such as methanol and ethanol. Are exemplified.

Examples of the alcohol component of the aromatic carboxylic acid include linear or branched aliphatic monohydric alcohols having 8 to 30 carbon atoms.
-Octanol, isooctanol, 2-ethylhexanol, n-nonanol, isononanol, 3,5,5
-Trimethylhexanol, n-decanol, isodecanol, n-undecanol, isoundecanol, n
-Dodecanol, isododecanol, n-tridecanol, isotridecanol, n-tetradecanol, isotetradecanol, n-pentadecanol, isopentadecanol, n-hexadecanol, isohexadecanol, n -Heptadecanol, isoheptadecanol,
Examples thereof include n-octadecanol, isooctadecanol, n-octadecenol, alkyl-substituted (2 to 20 carbon atoms) cyclohexanol, and alkyl-substituted (2 to 20 carbon atoms) cyclohexenol. 5,
5-Trimethylhexanol is preferred.

Further, at least 50 mol% of the constituent aliphatic monohydric alcohol may be 3,5,5-trimethylhexanol.

In place of the above-mentioned alcohol, a lower alkyl such as an acetic acid ester of the above-mentioned alcohol (having 1 to 1 carbon atoms) is used.
3) It is also possible to use esters.

Specific examples of the aromatic carboxylic acid esters include tri (n-octyl) trimellitate, tri (isooctyl) trimellitate, and tri (2-octyl trimellitate).
Ethylhexyl), trimellitate tri (n-nonyl), trimellitate tri (isononyl), trimellitate tri (3,5,5-trimethylhexyl), trimellitate tri (n-decyl), trimellitate tri (Isodecyl), tri (n-undecyl) trimellitate,
Tri trimellitate (isoundecyl), trimellitate (n-dodecyl), trimellitate (isododecyl), trimellitate (n-tridecyl), trimellitate (isotridecyl), trimellitate (n -Tetradecyl), trimellitate (isotetradecyl), trimellitate (n-pentadecyl), trimellitate (isopentadecyl), trimellitate (n-hexadecyl), trimellitate (iso) Hexadecyl), trimellitic acid tri (n-
Heptadecyl), Tri trimellitate (isoheptadecyl), Tri trimellitate (n-octadecyl), Tri trimellitate (isooctadecyl), Tri trimesate (n-octyl), Tri trimesate (isooctyl), Tri trimesate ( 2-ethylhexyl), tri (n-nonyl) trimesate, tri (isononyl) trimesate, tri (3,5,5-trimethylhexyl) trimesate, tri (n-decyl) trimesate, tri (isodecyl) trimesate Tri (n-undecyl) trimesate, tri (isoundecyl) trimesate, tri (n-dodecyl) trimesate, tri (isododecyl) trimesate, tri (n-tridecyl) trimesate, tri (isotridecyl) trimesate, trimesine Acid tri (n-tetrade ), Tri (isotetradecyl) trimesate, tri (n-pentadecyl) trimesate, tri (isopentadecyl) trimesate, tri (n-hexadecyl) trimesate, tri (isohexadecyl) trimesate, trimesic acid Tri (n-heptadecyl), tri (isoheptadecyl) trimesate, tri (n-octadecyl) trimesate, tri (isooctadecyl) trimesate, tetra (n-pyromellitate)
Octyl), tetra pyromellitic acid (isooctyl),
Tetra (2-ethylhexyl) pyromellitic acid, Tetra (n-nonyl) pyromellitic acid, Tetra (isononyl) pyromellitic acid, Tetra (3,5,5-pyromellitic acid)
Trimethylhexyl), tetra (n-decyl) pyromellitic acid, tetra (isodecyl) pyromellitic acid, tetra (n-undecyl) pyromellitic acid, tetra (isoundecyl) pyromellitic acid, tetra (n-pyromellitic acid)
Dodecyl), tetra pyromellitic acid (isododecyl),
Tetra (n-tridecyl) pyromellitate, Tetra (isotridecyl) pyromellitate, Tetra (n-tetradecyl) pyromellitate, Tetra (isotetradecyl) pyromellitate, Tetra (n-pentadecyl) pyromellitate, Pyromellitate Tetra (isopentadecyl) acid, tetra (n-hexadecyl) pyromellitic acid, tetra (isohexadecyl) pyromellitic acid, tetra (n-heptadecyl) pyromellitic acid, tetra (isoheptadecyl) pyromellitic acid, tetra pyromellitic acid (N-octadecyl), tetra pyromellitic acid (isooctadecyl),
Tetra (n-octyl) biphenyltetracarboxylate,
Tetra (isooctyl) biphenyltetracarboxylate,
Tetra (2-ethylhexyl) biphenyltetracarboxylate, Tetra (n-nonyl) biphenyltetracarboxylate, Tetra (isononyl) biphenyltetracarboxylate, Tetra (3,5,5) biphenyltetracarboxylate
-Trimethylhexyl), tetra (n-decyl) biphenyltetracarboxylate, tetra (isodecyl) biphenyltetracarboxylate, tetra (n-undecyl) biphenyltetracarboxylate, tetra (isoundecyl) biphenyltetracarboxylate, tetrabiphenyltetracarboxylate (N-dodecyl), tetra (isododecyl) biphenyltetracarboxylate, tetra (n-tridecyl) biphenyltetracarboxylate, tetra (isotridecyl) biphenyltetracarboxylate, tetra (n-tetradecyl) biphenyltetracarboxylate, biphenyltetracarboxylic acid Tetra (isotetradecyl), tetra (n-pentadecyl) biphenyltetracarboxylate, tetra (isopentadecyl) biphenyltetracarboxylate, biphenyltetracarbo Tetra (n- hexadecyl), biphenyltetracarboxylic acid tetra (isohexadecyl), biphenyltetracarboxylic acid tetra (n- heptadecyl), biphenyltetracarboxylic acid tetra (isoheptadecyl), biphenyltetracarboxylic acid tetra (n
-Octadecyl), tetra (isooctadecyl) biphenyltetracarboxylate, tetra (n-octyl) benzophenonetetracarboxylate, tetra (isooctyl) benzophenonetetracarboxylate, tetra (2-ethylhexyl) benzophenonetetracarboxylate, tetrabenzophenonetetracarboxylate (N-nonyl), tetra (isononyl) benzophenonetetracarboxylate, tetra (3,5,5-trimethylhexyl) benzophenonetetracarboxylate, tetra (n-decyl) benzobenzonetetracarboxylate, tetra (isodecyl) benzophenonetetracarboxylate Benzophenone tetracarboxylic acid tetra (n-undecyl), benzophenone tetracarboxylic acid tetra (isoundecyl), benzophenone tetracarboxylic acid tet (N-dodecyl), tetra (isododecyl) benzophenone tetracarboxylate, tetra (n-tridecyl) benzophenone tetracarboxylate, tetra (isotridecyl) benzophenone tetracarboxylate, tetra (n-tetradecyl) benzophenone tetracarboxylate, benzophenone tetracarboxylic acid Tetra (isotetradecyl), benzophenonetetracarboxylate tetra (n-pentadecyl), benzophenonetetracarboxylatetetra (isopentadecyl), benzophenonetetracarboxylatetetra (n-hexadecyl), benzophenonetetracarboxylatetetra (isohexadecyl) Benzophenone tetracarboxylic acid tetra (n-heptadecyl), benzophenone tetracarboxylic acid tetra (isoheptadecyl), benzophenone Rakarubon tetra (n- octadecyl), benzophenone tetracarboxylic acid tetra (iso-octadecyl), diphenylsulfone tetracarboxylic acid tetra (n- octyl), diphenyl sulfone tetracarboxylic acid tetra (isooctyl), diphenylsulfone tetracarboxylic acid tetra (2
-Ethylhexyl), tetra (n-nonyl) diphenylsulfonetetracarboxylate, tetra (isononyl) diphenylsulfonetetracarboxylate, tetra (3,5,5-trimethylhexyl) diphenylsulfonetetracarboxylate, tetraphenylsulfonatetetracarboxylate ( n-decyl), tetra (isodecyl) diphenylsulfonetetracarboxylate, tetra (n-undecyl) diphenylsulfonetetracarboxylate, tetra (isoundecyl) diphenylsulfonetetracarboxylate, tetra (n-dodecyl) diphenylsulfonetetracarboxylate,
Tetra (isododecyl) diphenylsulfonetetracarboxylate, tetra (n-tridecyl) diphenylsulfonetetracarboxylate, tetra (isotridecyl) diphenylsulfonetetracarboxylate, tetra (n-tetradecyl) diphenylsulfonetetracarboxylate, tetraphenyldiphenylsulfonetetracarboxylate (Isotetradecyl), diphenylsulfonetetracarboxylic acid tetra (n
-Pentadecyl), tetra (isopentadecyl) diphenylsulfonetetracarboxylate, tetra (n-hexadecyl) diphenylsulfonetetracarboxylate, tetra (isohexadecyl) diphenylsulfonetetracarboxylate, tetra (n) diphenylsulfonetetracarboxylate
-Heptadecyl), tetraphenyldiphenylsulfontetracarboxylate (isoheptadecyl), tetraphenyldiphenylsulfonetetracarboxylate (n-octadecyl), tetraphenyldiphenylsulfonetetracarboxylate (isooctadecyl), tetraphenyldiphenylethertetracarboxylate (n
-Octyl), tetra (isooctyl) diphenylethertetracarboxylate, tetra (2-ethylhexyl) diphenylethertetracarboxylate, tetra (n-nonyl) diphenylethertetracarboxylate, tetra (isononyl) diphenylethertetracarboxylate, tetra (diphenylethertetracarboxylate) 3,5,5
-Trimethylhexyl), tetra (n-decyl) diphenylethertetracarboxylate, tetra (isodecyl) diphenylethertetracarboxylate, tetra (n-undecyl) diphenylethertetracarboxylate, tetra (isoundecyl) diphenylethertetracarboxylate, tetraphenyldiphenylethertetracarboxylate (N
-Dodecyl), tetra (isododecyl) diphenylethertetracarboxylate, tetra (n-tridecyl) diphenylethertetracarboxylate, tetra (isotridecyl) diphenylethertetracarboxylate, tetra (n-tetradecyl) diphenylethertetracarboxylate, tetra (diphenylethertetracarboxylate) Isotetradecyl), tetra (n-pentadecyl) diphenylethertetracarboxylate, tetra (isopentadecyl) diphenylethertetracarboxylate, tetra (n-hexadecyl) diphenylethertetracarboxylate, tetra (isohexadecyl) diphenylethertetracarboxylate, diphenylether Tetracarboxylic acid tetra (n-heptadecyl), diphenylethertetracarboxylic acid tetra Isoheptadecyl), tetra (n-octadecyl) diphenylethertetracarboxylate, tetra (isooctadecyl) diphenylethertetracarboxylate, and the like, more preferably tri (3,5,5-trimethylhexyl) trimellitate, tri (trimesate) 3,5,5-trimethylhexyl),
Tetra pyromellitic acid (3,5,5-trimethylhexyl), naphthalenetetracarboxylic acid tetra (3,5,5
-Trimethylhexyl), tetra (3,5,5-trimethylhexyl) biphenyltetracarboxylate, tetra (3,5,5-trimethylhexyl) benzophenonetetracarboxylate, tetra (3,5,5-diphenylsulfonetetracarboxylate) Trimethylhexyl) and tetra (3,5,5-trimethylhexyl) diphenylethertetracarboxylate are recommended.

Additive for Thermoplastic Resin As the thermoplastic resin additive according to the present invention, an aromatic carboxylic acid ester represented by the general formula (1) can be applied without adding other additives. In particular, in the field where heat resistance is required, among the aromatic carboxylic acid esters represented by the general formula (1), aromatic carboxylic acids (3,5,5)
-Trimethylhexyl) ester is preferred.

In order to improve the performance, one or more antioxidants can be appropriately blended. Examples of the antioxidant include hindered phenol-based compounds, aromatic amine-based compounds, sulfur-based compounds, and phosphite-based compounds.
About 1 to 5% by weight is added. However, there is no particular limitation as long as a predetermined effect is achieved.

The thermoplastic resin composition according to the present invention includes polyarylene sulfide (PAS) such as polyphenylene sulfide (PPS), polysulfone, polyether sulfone (PES), polyphenylene ether (PPE), and polypolyethylene. Fats such as ether ether ketone (PEEK), aromatic polyamide composed of aromatic dicarboxylic acid and aromatic diamine or aliphatic diamine, 6-nylon, 6,6-nylon, 6,10-nylon, 4,6-nylon Group polyamide, polycarbonate (PC) having bisphenol A in the main skeleton, polyacetal, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalenedicarboxylate (PEN), poly-1,4-cyclohexa Polyester composed of glycol and aromatic dicarboxylic acid such as terephthalate, polyarylate (for example, polyarylate of aromatic dicarboxylic acid composed of terephthalic acid and / or isophthalic acid and bisphenol A), liquid crystal polymer (for example, p-hydroxybenzoic acid) , Biphenol and liquid crystal polymer represented by 4,4'-diphenyldicarboxylic acid), polyamideimide (for example, trimellitic acid and aromatic diamine such as diaminodiphenylmethane, diaminodiphenylether, m- or p-phenylenediamine). Polyamideimide), thermoplastic polyimide, polyetherimide, polymethylpentene, and modified products of these resins, polymer alloys, and the like.

The modified product and the polymer alloy include:
For example, PPE / polystyrene, PPE / polyamide,
A mixture of PC / ABS, PC / polyester, nylon / modified polyolefin, nylon / modified ABS, nylon / polyarylate, POM / thermoplastic polyurethane and the like can be exemplified.

Among the above thermoplastic resins, polyarylate, polysulfone, polyether sulfone, polyarylene sulfide, polyphenylene ether, polyether ketone, polyamide imide, polycarbonate, polyacetal, polyester, polyamide, and thermoplastic polyimide are particularly recommended. More preferably, polyarylene sulfide, polyphenylene ether, polyether ketone, polyamide imide, polyimide and the like are exemplified.

In particular, by adding an aromatic carboxylic acid ester to polyarylene sulfide, polyphenylene ether, polyether ketone, polyamide imide or polyimide, the processability and adhesiveness can be improved more effectively without significantly impairing the heat resistance. And other physical properties can be improved.

In the thermoplastic resin composition according to the present invention, the amount of the thermoplastic resin additive added to the thermoplastic resin is 0.1 to 100 parts by weight of the raw material thermoplastic resin.
It is about 1 to 50 parts by weight, preferably about 0.2 to 20 parts by weight. If the amount is less than 0.1 part by weight, the desired properties will not be improved. If the amount is more than 50 parts by weight, the inherent properties of the resin such as heat resistance may be greatly impaired.

The thermoplastic resin additive of the present invention may be polyarylate, polysulfone, polyether sulfone, polyarylene sulfide, polyphenylene ether, polyether ketone, polyamideimide, polycarbonate,
Polyacetal, polyester, polyamide, resin composition blended with thermoplastic polyimide, it is possible to increase the melt flow of the resin, or to reduce the heat fusion temperature, thereby improving the adhesiveness of the resin .

For example, when tri trimellitate (3,5,5-trimethylhexyl trimellitate) is applied as an additive to a polyimide resin, the heat fusion temperature is 10 ° C. or higher as compared with a resin without an additive. It can be reduced.

As a method of adding the thermoplastic resin additive to the thermoplastic resin, an extruder, an injection molding machine,
A method of kneading and mixing by a known method such as various mixers, or a method of mixing a thermoplastic resin and an aromatic carboxylic acid ester with an organic solvent, for example, N-methyl-2-pyrrolidone (NMP),
There is a method of dissolving and mixing in N, N-dimethylacetamide (DMAc) or the like and then removing the solvent. For example, the mixture may be mixed with the raw material resin to be molded and provided for molding, or the thermoplastic resin additive may be added to the molten resin and melt-mixed, followed by molding.

The thermoplastic resin composition according to the present invention may contain a nucleating agent, a reinforcing agent, a filler, an ultraviolet absorber, an antistatic agent, and the like, in a range that does not impair the purpose of the present invention. Various additives such as a flame retardant, a lubricant, a release agent, a pigment, and a dye can be added.

The kind of the aromatic carboxylic acid ester in the additive for the thermoplastic resin is appropriately selected according to the kind of the thermoplastic resin to be applied and the intended effect. These aromatic carboxylic acid esters may be used alone or in a suitable mixture of several ester compounds, depending on desired physical properties.

The thermoplastic resin composition according to the present invention is prepared by a conventional method such as a master batch method, a direct one-stage blending method, or a method of dissolving and mixing in an organic solvent. For example, the above-mentioned thermoplastic resin, the additive for thermoplastic resin according to the present invention, and the necessary amounts of various additive components appropriately used as needed are mixed in a V-blender, a ribbon blender, a Henschel mixer, a tumbler blender, or the like. Then, using a kneader such as a Banbury mixer, a kneader, an oven roll, a single screw extruder, a twin screw extruder, a single screw reciprocating screw or the like, a temperature exceeding the melting temperature of the resin (preferably, the melting temperature of the resin + (About 20
To about 150 ° C.), or by dissolving and mixing the above components in an organic solvent to obtain a desired resin composition.

The thermoplastic resin composition thus obtained is
Various molding materials or useful as a coating material, according to a method commonly used in this field, for example, injection molding, extrusion molding, blow molding, calender molding, molding by a method such as rotational molding, the molded product The form is a molded product,
It covers all kinds of films, sheets, fibers, non-woven fabrics and the like.

For example, in the case of injection molding, the injection conditions are appropriately selected according to the type of thermoplastic resin to be used, but usually, the resin temperature is about 200 to 400 ° C., the mold temperature is about 0 to 250 ° C., A pressure of about 10 to 1300 kg / cm ² is employed.

In the case of blow molding, the molding conditions can be appropriately selected according to the type of the thermoplastic resin to be used, but usually the resin temperature is about 100 to 400 ° C. and the mold temperature is 0 °.
It is preferable to employ conditions of about 250 ° C. and a blowing pressure of about ² to 10 kgf / cm ² .

Further, in the case of extrusion molding, the molding conditions can be appropriately selected according to the type of the thermoplastic resin to be used. However, the resin is extruded and cooled from a slit or nozzle die at a melting temperature of about 200 to 400 ° C. It can be obtained in the form of an undrawn thread or sheet. Next, the fiber or film can be drawn by heating with a heating roller or a tenter. The preferred temperature during stretching is 50 to 200 ° C.
The preferred stretching ratio is 3 to 7 times.

The molded article prepared as described above includes, for example, electric and electronic parts such as coil bobbins, connectors, relays, switches, condenser cases, motor parts, distributors, carburetors, intake manifolds, ignition coils, pipes, and the like. Automotive parts, gears, cams, bearings and other mechanical parts, CDs and DVs
Optical disks such as D, FDD chassis, and O
A, home appliances, clothing made of fibers, fabrics, knitting, etc.,
It is suitable for household fabrics such as curtains, adhesive tape reinforcing materials, tent fabrics, base films for magnetic tapes, and fabrics for industrial materials such as domes and fences as building materials. Also,
The thermoplastic resin composition using an organic solvent is also suitable for heat-resistant paints, coating materials for electronic materials, heat-resistant adhesives, and the like.

The thermoplastic resin composition of the present invention has the following advantages. That is, by blending the present aromatic carboxylic acid ester with the thermoplastic resin, the melt viscosity of the resin can be reduced, and the heat-fusibility and adhesiveness can be improved.

[0037]

The present invention will be described below in detail with reference to examples. The properties of the thermoplastic resin composition were measured by the following methods.

Melt flow property (MFR) was measured at a predetermined temperature and a predetermined pressure using an elevated flow tester under the conditions of a die diameter of 1 mm and a length of 10 mm. still,
MFR is an index indicating the fluidity of a resin, and the larger the value, the better the fluidity.

The sample after measuring the intrinsic viscosity MFR was subjected to a solvent [phenol / tetrachloroethane = 60/40 (weight ratio)] at a concentration of 0.5 g / dl.
And the intrinsic viscosity [η] was measured at a temperature of 25 ° C.
The intrinsic viscosity [η] is an index indicating the molecular weight of the resin. If there is no change in the intrinsic viscosity, it indicates that there is no decrease in the molecular weight of the resin.

The film of the heat-fusible thermoplastic resin composition (thickness 50 [mu] m) 5 ply by hot pressing, and the press temperature when the the thermal fusion of the temperature. The results show that the lower the temperature, the higher the degree of heat fusion.

A film of the adhesive thermoplastic resin composition and a non-thermoplastic polyimide film “UPILEX 50S (manufactured by Ube Industries, Ltd.)” are overlaid and heat-sealed at 310 ° C., and the adhesiveness is checked by a cross-cut tape method (JIS K5400). Was evaluated.

Glass transition temperature (Tg) The Tg of the thermoplastic resin composition was measured by DSC.

Example 1 410 g of trimellitic acid (2 g) was placed in a 5-liter four-necked flask equipped with a stirrer, a thermometer, and a water fraction receiver with a cooling tube.
Mol), 950 g of 3,5,5-trimethylhexanol
(6.6 mol) and a metal catalyst, and 200
The temperature was raised to ° C. The esterification reaction was carried out for about 5 hours while the generated water was taken into a water fractionation receiver with the amount of water theoretically produced as a target. After completion of the reaction, excess alcohol was removed by distillation, neutralized with an aqueous solution of sodium hydroxide, and then washed with water until neutral. Then, activated carbon treatment is performed, and the activated carbon is further filtered to obtain tri (3,5,5-trimethylhexyl).
1129 g of trimellitate (96% yield) was obtained as a colorless and transparent liquid.

[0044]

IR: shown in FIG.

Example 2 Tri (3,5,5-trimethylhexyl) trimellitate was added in an amount of 0.5 part by weight to 100 parts by weight of a polyethylene terephthalate resin.
, And the obtained strand was water-cooled and cut to obtain a sample. Using this sample, 265 ° C, 1
The melt flow property (MFR) was measured under the conditions of 0 kgf / cm ² , a die diameter of 1 mm, and a length of 10 mm. Further, the intrinsic viscosity [η] is calculated by using phenol / tetrachloroethane = 60/4.
It was measured at 25 ° C. in a 0 (weight ratio) solution. Table 1 shows the obtained results.

Examples 3 to 5 A resin composition was prepared in the same manner as in Example 2 except that a predetermined amount of the aromatic carboxylic acid ester described in Table 1 was used.
The MFR and intrinsic viscosity of this product were measured. Table 1 shows the obtained results.

Comparative Example 1 Example 2 was repeated except that no aromatic carboxylic acid ester was used.
A resin composition was prepared in the same manner as described above, and its MFR and intrinsic viscosity were measured. Table 1 shows the obtained results.

Comparative Examples 2-3 A resin composition was prepared in the same manner as in Example 2 except that a predetermined amount of the aromatic carboxylic acid ester shown in Table 1 was used.
The MFR and intrinsic viscosity of this product were measured. Table 1 shows the obtained results.

[0050]

[Table 1]

Example 6 3,3 ', 4,4'-Diphenylsulfonetetracarboxylic dianhydride (1.02 mol) and 2,2-bis [4-
(P-aminophenoxy) phenyl) propane (1.0
0 mol) in NMP, substrate concentration 20 wt%, 170 ° C.
1 part by weight of tetra (3,5,5-trimethylhexyl) pyromellitate is added to 100 parts by weight of the solution of the thermoplastic polyimide resin obtained by dehydration and condensation in step 1 and mixed to obtain a uniform resin composition. Was. Next, this solution was cast on a glass plate, and the solvent was removed under reduced pressure at 300 ° C. for 1 hour to obtain a thermoplastic polyimide film (48 μm in thickness).
Five such films were stacked and heat-sealed with a hot press (contact pressure) to evaluate the heat-sealing property. In addition, one of the obtained films was stacked on a non-thermoplastic polyimide film “UPILEX 50S (manufactured by Ube Industries, Ltd.)”, and was similarly heat-sealed with a hot press machine, and the adhesiveness was evaluated by a cross-cut tape method. did. Table 2 shows the obtained results.

Examples 7 to 9 A resin composition was obtained in the same manner as in Example 6 except that a predetermined amount of an aromatic carboxylic acid ester shown in Table 2 was used, and further formed into a film. The heat sealing property and adhesive property of the obtained film were evaluated in the same manner as in Example 6. Table 2 shows the results.

Comparative Example 4 Example 6 except that no aromatic carboxylic acid ester was added.
A resin composition was obtained in the same manner as described above, and a film was formed. The heat sealing property and adhesive property of the obtained film were measured in Example 6.
Was evaluated in the same way as Table 2 shows the results.

Comparative Example 5 Di (3,5, phthalic acid) was used as an aromatic carboxylic acid ester.
A resin composition was obtained in the same manner as in Example 6 except that 10 parts by weight of (5-trimethylhexyl) was used, and further formed into a film. The heat sealing property and adhesive property of the obtained film were evaluated in the same manner as in Example 6. Table 2 shows the results.

Example 10 3,3 ′, 4,4′-Diphenylsulfonetetracarboxylic dianhydride (1.10 mol) and 2,2-bis [4-
(P-Aminophenoxy) phenyl] sulfone (1.0
0 mol) and a substrate concentration of 20 wt% in NMP, 180 ° C.
100 parts by weight of the thermoplastic polyimide resin solution obtained by dehydration condensation in
5-trimethylhexyl) and tri trimellitate (3,
5,5-trimethylhexyl) (8 by weight)
5:15) 2 parts by weight were added and mixed to obtain a uniform resin composition solution. Next, this solution was cast on a glass plate, and the solvent was removed under reduced pressure at 300 ° C. for 1 hour to obtain a thermoplastic polyimide film (film thickness 52 μm). Five such films were stacked and heat-sealed by a hot press (non-contact) to evaluate the heat-sealing property. In addition, a single sheet of the obtained film is stacked on a non-thermoplastic polyimide film “UPILEX 50S (manufactured by Ube Industries, Ltd.)” and similarly heat-sealed with a hot press machine, and the adhesiveness is evaluated by a cross-cut tape method. did. Table 2 shows the obtained results.

Comparative Example 6 Example 10 except that no aromatic carboxylic acid ester was added.
A resin composition was obtained in the same manner as described above, and a film was formed. The heat-fusing property and adhesiveness of the obtained film were evaluated in the same manner as in Example 10. Table 2 shows the results.

[0057]

[Table 2]

[0058]

According to the present invention, when the aromatic carboxylic acid ester is blended with the thermoplastic resin, the melt viscosity of the resin is reduced, and the heat fusing property and the adhesive property are improved without greatly impairing the inherent properties of the resin such as heat resistance. Can be done.

[Brief description of the drawings]

FIG. 1 is an IR chart of tri (3,5,5-trimethylhexyl) trimellitate.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4F070 AA42 AA47 AA48 AA50 AA52 AA54 AA55 AA58 AC43 AE09 4J002 BB171 BC032 BN152 CB001 CF002 CF051 CF061 CF071 CF081 CF161 CF162 CF181 CG011 CH071 CH091 CK03 CL01 CL01 CN01 CN011 GK01 GN00 GQ00

Claims (10)

[Claims] 1. General formula (1) Ar (COOR) _n (1) wherein n Rs are the same or different and have 8 to 30 carbon atoms
Represents an aliphatic hydrocarbon group. Ar represents an aromatic group. n
Represents 3 or 4. A polyarylate, polysulfone, polyethersulfone, polyarylene sulfide, polyphenylene ether, polyetherketone, polyamideimide, polycarbonate, polyacetal, comprising an aromatic carboxylic acid ester represented by the following formula:
An additive for a thermoplastic resin selected from the group of polyester, polyamide or thermoplastic polyimide. 2. An aromatic carboxylic acid ester represented by the general formula (1) wherein Ar is a phenyl group, a naphthalene group, a biphenyl group, a benzophenone group, a diphenylsulfone group,
At least one selected from the group of diphenyl ether groups
The additive for a thermoplastic resin according to claim 1, which is a seed. 3. The aromatic carboxylic acid ester represented by the general formula (1) is trimellitic acid ester, trimesic acid ester, pyromellitic acid ester, naphthalenetetracarboxylic acid ester, biphenyltetracarboxylic acid ester, benzophenonetetracarboxylic acid. The additive for a thermoplastic resin according to claim 1, wherein the additive is at least one selected from the group consisting of an acid ester, diphenylsulfonetetracarboxylic acid ester, and diphenylethertetracarboxylic acid ester. 4. The additive for a thermoplastic resin according to claim 1, wherein the aliphatic hydrocarbon group of the aromatic carboxylic acid ester represented by the general formula (1) is a 3,5,5-trimethylhexyl group. 5. General formula (1) Ar (COOR) _n (1) wherein n Rs are the same or different and have 8 to 30 carbon atoms
Represents an aliphatic hydrocarbon group. Ar represents an aromatic group.
n represents 3 or 4. A thermoplastic resin additive comprising one or more aromatic carboxylic acid esters represented by the following formulas, and polyarylate, polysulfone, polyether sulfone, polyarylene sulfide, polyphenylene ether, polyether ketone, A thermoplastic resin composition comprising at least one thermoplastic resin selected from the group consisting of polyamide imide, polycarbonate, polyacetal, polyester, polyamide, and thermoplastic polyimide. 6. The aromatic carboxylic acid ester represented by the general formula (1) wherein Ar is at least one selected from the group consisting of a phenyl group, a naphthalene group, a biphenyl group, a benzophenone group, a diphenyl sulfone group and a diphenyl ether group. The thermoplastic resin composition according to claim 5. 7. The aromatic carboxylic acid ester represented by the general formula (1) is trimellitic acid ester, trimesic acid ester, pyromellitic acid ester, naphthalenetetracarboxylic acid ester, biphenyltetracarboxylic acid ester, benzophenonetetracarboxylic acid. The thermoplastic resin composition according to claim 5, wherein the thermoplastic resin composition is at least one selected from the group consisting of an acid ester, diphenylsulfonetetracarboxylic acid ester, and diphenylethertetracarboxylic acid ester. 8. The thermoplastic resin composition according to claim 5, wherein the aliphatic hydrocarbon group of the aromatic carboxylic acid ester represented by the general formula (1) is a 3,5,5-trimethylhexyl group. 9. The thermoplastic resin composition according to claim 5, wherein the amount of the thermoplastic resin additive is 0.1 to 50 parts by weight based on 100 parts by weight of the thermoplastic resin. 10. A thermoplastic resin selected from the group consisting of polyarylate, polysulfone, polyether sulfone, polyarylene sulfide, polyphenylene ether, polyether ketone, polyamide imide, polycarbonate, polyacetal, polyester, polyamide, and thermoplastic polyimide. A method for lowering the thermal fusion temperature of a thermoplastic resin by 10 ° C. or more, comprising adding an aromatic carboxylic acid ester represented by the general formula (1).