JP5386823B2 - Amorphous thermoplastic resin composition and molded article thereof - Google Patents

Description

  The present invention relates to a novel amorphous thermoplastic resin composition and a molded product thereof, a method for producing the molded product, and a melt viscosity reducing agent for an amorphous thermoplastic resin.

  Amorphous thermoplastic resins are used in various fields from commonly used general-purpose resins to engineering plastics having high performance. In particular, the use of amorphous engineering plastics having high heat resistance has been expanding in recent years in the fields of optical materials, electrical / electronic equipment parts, machine parts, building materials, roofing materials, and the like. Among them, there is a demand for a compact or thin molded body having a complicated and dense shape from the viewpoint of weight reduction and resource saving.

  However, amorphous engineering plastics have high strength and high heat resistance, but have a high melting temperature and a high viscosity at the time of melting, which causes a problem in molding processability. As a method for improving the fluidity at the time of melting of a thermoplastic resin, a method of increasing the melting temperature at the time of molding is known. However, raising the melting temperature is also disadvantageous in terms of energy, and heat may cause decomposition of the resin, which may impair the original physical properties of the resin.

Therefore, the following methods for improving the fluidity at the time of melting the resin have been proposed so far.
(1) A method of performing modification such as copolymerizing a monomer having a small polarity in order to reduce the polarity of the polymer.
(2) A method of branching a polymer to promote internal plasticization.
(3) A method for reducing the degree of polymerization of the polymer.
(4) A method of adding a high fluidity polymer or oligomer.
(5) A method of adding a plasticizer or a melt viscosity reducing agent.

  However, for example, in the methods (1) and (2), the inherent properties (eg, heat resistance) of the resin are often impaired by modification such as copolymerization. In the method (3), although fluidity is improved, impact resistance and heat resistance may be impaired due to a decrease in molecular weight. In the method (4), the mechanical strength of the polymer is often decreased, and the heat resistance of the polymer and the physical properties (for example, transparency) inherent to the resin may be impaired. Therefore, it cannot be said that the modification of the resin by the proposed methods (1) to (4) is sufficient.

  Also, the method of adding a low molecular weight plasticizer or lubricant (for example, a certain diamide compound, ester plasticizer, biphenyl compound or terphenyl compound and polycaprolactone, etc.) as in the method of (5) is a comparison. There is an effect of improving the fluidity (see Patent Documents 1 to 4). However, these low molecular weight additives have a low fluidity-modifying effect at low addition amounts, and when the addition amount is increased, bleed out and plate out occur, and the glass transition that is an indicator of the heat resistance of the resin. The temperature (Tg) is lowered, or the transparency is lowered in a transparent resin.

Therefore, development of a method for further reducing the melt viscosity without substantially impairing the heat resistance and mechanical properties of the amorphous thermoplastic resin is strongly desired.
Japanese Patent Publication No. 5-032430 Japanese Patent Publication No. 6-57783 JP-A-5-17599 JP 2000-195099 A

  An object of the present invention is to provide an amorphous thermoplastic resin composition having a reduced melt viscosity, and a molded article in which heat resistance and mechanical properties obtained by molding the resin composition are not substantially impaired, Another object of the present invention is to provide a melt viscosity reducing agent for an amorphous thermoplastic resin.

  As a result of intensive studies to solve the above-mentioned problems, the inventors have made the amorphous thermoplastic resin contain a specific amount of a specific amide compound, thereby substantially improving the heat resistance and mechanical properties of the resin. It was found that the viscosity at the time of melting of the resin can be reduced without loss. The present invention has been completed based on such findings.

  That is, the present invention provides the inventions described in the following sections.

Item 1 (a) Amorphous thermoplastic resin and
(b) General formula (1)
R ^1- (CONHR ² ) _n (1)
[Wherein n represents an integer of 2 to 6.

When n is 2, R ¹ is a residue obtained by removing all carboxyl groups from an alicyclic dicarboxylic acid having 8 to 20 carbon atoms, or all carboxyl groups from an aromatic dicarboxylic acid having 8 to 20 carbon atoms. And the two R ^{2 s} are the same or different and are each a residue obtained by removing an amino group from an alicyclic monoamine having 6 to 30 carbon atoms, or 6 to 6 carbon atoms. This represents a residue obtained by removing an amino group from 30 aromatic monoamines.

When n is 3 to 6, R ¹ is a residue obtained by removing all carboxyl groups from a linear or branched saturated or unsaturated aliphatic tri- or hexacarboxylic acid having 6 to 18 carbon atoms. A residue obtained by removing all carboxyl groups from an alicyclic tri- or hexacarboxylic acid having 9 to 18 carbon atoms, or excluding all carboxyl groups from an aromatic tri- or hexacarboxylic acid having 9 to 18 carbon atoms Represents a residue obtained, and 3 to 6 R ^{2 s} are the same or different, and each excludes an amino group from a linear or branched saturated or unsaturated aliphatic monoamine having 6 to 30 carbon atoms. Or a residue obtained by removing an amino group from an alicyclic monoamine having 6 to 30 carbon atoms, or a residue obtained by removing an amino group from an aromatic monoamine having 6 to 30 carbon atoms. ]
Containing at least one amide compound represented by:
An amorphous thermoplastic resin composition, wherein the at least one amide compound is present in an amount of 0.001 to 10 parts by weight with respect to 100 parts by weight of the amorphous thermoplastic resin.

  Item 2 The item 1 above, wherein the at least one amide compound represented by the general formula (1) is present in an amount of 0.001 to 3 parts by weight with respect to 100 parts by weight of the amorphous thermoplastic resin. Amorphous thermoplastic resin composition.

  Item 3 The amide compound has the general formula (2)

[In the formula, two R ^{3 s} are the same or different and are each derived from a residue obtained by removing an amino group from an alicyclic monoamine having 6 to 30 carbon atoms, or an aromatic monoamine having 6 to 30 carbon atoms. It represents a residue obtained by removing an amino group. ]
Item 3. The amorphous thermoplastic resin composition according to item 1 or 2, which is an amide compound represented by the formula:

  Item 4. The amorphous thermoplastic resin composition according to Item 1 or 2, wherein the amide compound is an amide compound represented by General Formula (1) in which n represents an integer of 3 to 6.

Item 5 The amide compound is a residue obtained by removing all carboxyl groups from a saturated aliphatic polycarboxylic acid having R ¹ of 6 to 15 carbon atoms, all carboxyls from alicyclic polycarboxylic acids having 9 to 15 carbon atoms The amide compound represented by the general formula (1), which is a residue obtained by removing a group or a residue obtained by removing all carboxyl groups from an aromatic polycarboxylic acid having 9 to 15 carbon atoms, Item 5. The amorphous thermoplastic resin composition according to Item 4.

Item 6 An amide compound wherein R ¹ is a residue obtained by removing all carboxyl groups from 1,2,3,4-butanetetracarboxylic acid, and all carboxyl groups are removed from 1,2,3-propanetricarboxylic acid The amorphous thermoplastic resin according to item 4 or 5, which is an amide compound represented by the general formula (1) indicating a residue obtained by removing all carboxyl groups from trimesic acid Resin composition.

7. amide compound, residue R ² is obtained by removing the linear or branched, saturated or amino groups from an unsaturated aliphatic monoamine having 6 to 18 carbon atoms, straight-chain having 1 to 4 carbon atoms Alternatively, a residue obtained by removing an amino group from an alicyclic monoamine having 6 to 18 carbon atoms which may have 1 to 3 (particularly one) branched alkyl groups, or 1 to 4 carbon atoms A general formula showing a residue obtained by removing an amino group from an aromatic monoamine having 6 to 18 carbon atoms which may have 1 to 3 (particularly 1) linear or branched alkyl groups The amorphous thermoplastic resin composition according to any one of Items 4 to 6, which is an amide compound represented by (1).

Item 8 The amide compound is
(i) General formula (3)

[In the formula, three R ^{4 s} are the same or different and each is a residue obtained by removing an amino group from an aliphatic monoamine having 6 to 30 carbon atoms (especially 6 to 18 carbon atoms), and having 6 to 30 carbon atoms. It represents a residue obtained by removing an amino group from an alicyclic monoamine, or a residue obtained by removing an amino group from an aromatic monoamine having 6 to 30 carbon atoms. An amide compound represented by
(ii) General formula (4)

[In the formula, four R ^{5 s} are the same or different and are each a residue obtained by removing an amino group from an aliphatic monoamine having 6 to 30 carbon atoms (particularly 6 to 18 carbon atoms), and having 6 to 30 carbon atoms. It represents a residue obtained by removing an amino group from an alicyclic monoamine, or a residue obtained by removing an amino group from an aromatic monoamine having 6 to 30 carbon atoms. An amide compound represented by the formula:
(iii) General formula (5)

[In the formula, three R ^{6 s} are the same or different and are each a residue obtained by removing an amino group from an aliphatic monoamine having 6 to 30 carbon atoms (especially 6 to 18 carbon atoms), and having 6 to 30 carbon atoms. It represents a residue obtained by removing an amino group from an alicyclic monoamine, or a residue obtained by removing an amino group from an aromatic monoamine having 6 to 30 carbon atoms. An amide compound represented by
Item 3. The amorphous thermoplastic resin composition according to Item 1 or 2, which is at least one amide compound selected from the group consisting of:

  Item 9. The amorphous thermoplastic resin composition according to any one of Items 1 to 8, wherein the amorphous thermoplastic resin is an amorphous engineering plastic.

  Item 10. The amorphous thermoplastic resin composition according to Item 9, wherein the amorphous engineering plastic is a polycarbonate resin.

  Item 11 A molded article obtained by molding the amorphous thermoplastic resin composition according to any one of Items 1 to 10.

  Item 12 The amorphous resin composition according to any one of Items 1 to 10 above, injection molding, blow molding, extrusion molding, calendar molding, injection compression molding, injection blow molding, extrusion blow molding, injection extrusion blow molding, stretch blow molding A method for producing a molded article, comprising molding by any one of multilayer blow molding, extrusion thermoform molding, spinning molding, rotational molding or sheet / film molding.

Item 13 General formula (1)
R ^1- (CONHR ² ) _n (1)
[Wherein n represents an integer of 2 to 6.

When n is 2, R ¹ is a residue obtained by removing all carboxyl groups from an alicyclic dicarboxylic acid having 8 to 20 carbon atoms, or all carboxyl groups from an aromatic dicarboxylic acid having 8 to 20 carbon atoms. And the two R ^{2 s} are the same or different and are each a residue obtained by removing an amino group from an alicyclic monoamine having 6 to 30 carbon atoms, or 6 to 6 carbon atoms. This represents a residue obtained by removing an amino group from 30 aromatic monoamines.

When n is 3 to 6, R ¹ is a residue obtained by removing all carboxyl groups from a linear or branched saturated or unsaturated aliphatic tri- or hexacarboxylic acid having 6 to 18 carbon atoms. A residue obtained by removing all carboxyl groups from an alicyclic tri- or hexacarboxylic acid having 9 to 18 carbon atoms, or excluding all carboxyl groups from an aromatic tri- or hexacarboxylic acid having 9 to 18 carbon atoms Represents a residue obtained, and 3 to 6 R ^{2 s} are the same or different, and each excludes an amino group from a linear or branched saturated or unsaturated aliphatic monoamine having 6 to 30 carbon atoms. Or a residue obtained by removing an amino group from an alicyclic monoamine having 6 to 30 carbon atoms, or a residue obtained by removing an amino group from an aromatic monoamine having 6 to 30 carbon atoms. ]
A melt viscosity reducing agent for an amorphous thermoplastic resin, comprising at least one amide compound represented by the formula:

  Item 14 The melt viscosity reducing agent for an amorphous thermoplastic resin according to Item 13, wherein the 5% weight loss temperature of the amide compound is 280 ° C or higher.

  The present invention is described in detail below.

Amide Compound The amide compound according to the present invention is a compound represented by the general formula (1), in which a residue derived from a specific polycarboxylic acid and a residue derived from a specific monoamine are linked by an amide bond. The residue derived from polycarboxylic acid represents a residue obtained by removing all carboxyl groups from an aliphatic, alicyclic or aromatic polycarboxylic acid represented by the following general formula (1a), and is a monoamine The derived residue represents a residue obtained by removing an amino group from an aliphatic, alicyclic or aromatic monoamine represented by the following general formula (1b).

  The amide compound is not particularly limited, and an amidation reaction using the following polycarboxylic acid (1a) and the following monoamine (1b) as raw materials according to a conventionally known method, for example, the method described in JP-A-7-242610. Can be obtained. Also, acid anhydrides, chlorides, or reactive derivatives of these polycarboxylic acids (1a), for example, esters of the polycarboxylic acids (1a) and lower alcohols having 1 to 4 carbon atoms are subjected to amidation. Can also be obtained. Representative examples of the method for producing the amide compound are described in the production examples described later.

  The amide compound according to the present invention may contain some impurities, and its purity is recommended to be 90% by weight or more, preferably 95% by weight or more, particularly preferably 97% by weight or more.

  The polycarboxylic acid (1a) and monoamine (1b) are described in detail below.

<Polycarboxylic acid>
The polycarboxylic acid has the general formula (1a)
R ^1- (COOH) _n (1a)
Wherein, ^{R 1} and n have the same meanings as ^{R 1} and n in the general formula (1). ]
It is represented by

  The number n of carboxyl groups in the general formula (1a) is 2 to 6, and preferably 2 to 4. That is, the polycarboxylic acid (1a) is a dicarboxylic acid, a tricarboxylic acid, a tetracarboxylic acid, a pentacarboxylic acid, or a hexacarboxylic acid.

  The polycarboxylic acid includes a hydroxyl group, a linear or branched alkyl group (having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms), a linear or branched alkenyl group (having 2 carbon atoms). -10, preferably 3-4), and 1 or 2 (especially 1 or 2) substituents selected from the group consisting of acetoxy groups.

  In the present specification and claims, the carbon number of dicarboxylic acid and tri- or hexacarboxylic acid includes the carbon number of these substituents.

  In the present specification and claims, an alicyclic carboxylic acid represents a carboxylic acid having an alicyclic group, and an aromatic carboxylic acid represents a carboxylic acid having an aromatic group.

  When n is 2 in the general formula (1a), the polycarboxylic acid (1a) is an alicyclic dicarboxylic acid having 8 to 20 carbon atoms, preferably 8 to 12 carbon atoms, or 8 to 20 carbon atoms, preferably It is an aromatic dicarboxylic acid having 8 to 12 carbon atoms.

  Typical examples of the alicyclic dicarboxylic acid include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-norbornene-5,6-dicarboxylic acid, and the like. As the aromatic dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, biphenyl-2,2′-dicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid Examples of the acid include 2,6-naphthalenedicarboxylic acid and anthracene dicarboxylic acid. Among these, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid are preferable, and 2,6-naphthalenedicarboxylic acid is particularly preferable.

  In the general formula (1a), when n is 3 to 6, the polycarboxylic acid (1a) is a linear or branched saturated or unsaturated group having 6 to 18 carbon atoms, preferably 6 to 15 carbon atoms. It is an aliphatic polycarboxylic acid, an alicyclic polycarboxylic acid having 9 to 18 carbon atoms, preferably 9 to 15 carbon atoms, or an aromatic polycarboxylic acid having 9 to 18 carbon atoms, preferably 9 to 15 carbon atoms.

  Specific examples of the aliphatic polycarboxylic acid include tricarboxylic acids such as 1,2,3-propanetricarboxylic acid, 1,2,3-propenetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, and ethanetetra Carboxylic acid, propanetetracarboxylic acid, pentanetetracarboxylic acid, butanetetracarboxylic acid (particularly 1,2,3,4-butanetetracarboxylic acid), tetracarboxylic acid such as dodecanetetracarboxylic acid, pentanepentacarboxylic acid, etc. Hexacarboxylic acids such as pentacarboxylic acid and tetradecane hexacarboxylic acid are exemplified.

  Specific examples of the alicyclic polycarboxylic acid include tricarboxylic acids such as 1,3,5-cyclohexanetricarboxylic acid, 1,2,3-cyclohexanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclohexane Such as pentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, tetrahydrofurantetracarboxylic acid, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid Examples include hexacarboxylic acids such as tetracarboxylic acid and cyclohexanehexacarboxylic acid.

  Specific examples of the aromatic polycarboxylic acid include hemimellitic acid, trimesic acid, trimellitic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid and other tricarboxylic acids, pyro Merit acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, diphenylmethane tetracarboxylic acid, perylene tetracarboxylic acid, 1,2,5,6-naphthalene tetracarboxylic acid, 1,4,5,8- Naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,6,7-anthracenetetracarboxylic acid, benzidine-3,3′-dicarboxyl-N, N′-tetraacetic acid, diphenyl Tetracarbons such as propanetetracarboxylic acid and phthalocyaninetetracarboxylic acid Carboxylic acid, penta carboxylic acids such as benzene penta carboxylic acid, hexa carboxylic acids such as benzene hexacarboxylic acid.

  Among the above polycarboxylic acids, 1,2,3-propanetricarboxylic acid, trimesic acid, 1,2,3,4-butanetetracarboxylic acid because of the ability to reduce the melt viscosity of the amide compound and the availability of raw materials Etc. are preferred.

<Monoamine>
The monoamine has the general formula (1b)
R ² —NH ₂ (1b)
Wherein, ^{R 2} has the same meaning as ^{R 2} in the general formula (1). ]
It is represented by

  When n is 2 in the general formula (1), the monoamine (1b) is an alicyclic monoamine having 6 to 30 carbon atoms, preferably 6 to 18 carbon atoms, or 6 to 30 carbon atoms, preferably 6 carbon atoms. Represents -18 aromatic monoamines.

  When n is 3 to 6, the monoamine (1b) is a linear or branched saturated or unsaturated aliphatic amine having 6 to 30 carbon atoms, preferably 6 to 18 carbon atoms, 6 to 30 carbon atoms, Preferably, it represents an alicyclic monoamine having 6 to 18 carbon atoms, or an aromatic monoamine having 6 to 30 carbon atoms, preferably 6 to 18 carbon atoms.

  In the present specification and claims, an alicyclic monoamine represents an amine having an alicyclic group, and an aromatic monoamine represents an amine having an aromatic group.

  The alicyclic or aromatic monoamine is a hydroxyl group, a linear or branched alkyl group (having 1 to 12 carbon atoms, preferably 1 to 4 carbon atoms), a linear or branched alkoxy group. Selected from the group consisting of a group (having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms), a linear or branched alkenyl group (2 to 10 carbon atoms, preferably 3 to 4 carbon atoms) and an acetoxy group 1 or 2 or more (especially 1 or 2) substituents may be included.

  In the present specification and claims, the carbon number of the aliphatic, alicyclic or aromatic amine includes the carbon number of these substituents.

  Specific examples of the aliphatic monoamine include hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecyl. Examples include amine, octadecylamine, nonadecylamine, icosylamine, henecosylamine, docosylamine and the like.

  Specific examples of the alicyclic monoamine include cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, 2,3-dimethylcyclohexylamine, 2,4-dimethylcyclohexylamine, 2-ethylcyclohexylamine, 3-ethylcyclohexylamine, 4-ethylcyclohexylamine, 2-n-propylcyclohexylamine, 3-n-propylcyclohexylamine, 4-n-propylcyclohexylamine, 2-iso-propylcyclohexylamine, 3-iso-propylcyclohexylamine, 4-iso-propylcyclohexylamine, 2-n-butylcyclohexylamine, 3-n-butylcyclohexylamine, 4-n-butylcyclohexyl Silamine, 2-iso-butylcyclohexylamine, 3-iso-butylcyclohexylamine, 4-iso-butylcyclohexylamine, 2-tert-butylcyclohexylamine, 3-tert-butylcyclohexylamine, 4-tert-butylcyclohexylamine, 2-n-octylcyclohexylamine, 3-n-octylcyclohexylamine, 4-n-octylcyclohexylamine, cyclohexylmethylamine, 2-methylcyclohexylmethylamine, 3-methylcyclohexylmethylamine, 4-methylcyclohexylmethylamine, dimethyl Cyclohexylmethylamine, trimethylcyclohexylmethylamine, methoxycyclohexylmethylamine, ethoxycyclohexylmethylamine, dimethyl Carboxymethyl cyclohexylmethyl amine, methoxy cyclohexylethylamine, dimethoxy cyclohexylethylamine, methylcyclohexylamine propylamine, dodecylamine cyclohexylamine, and the like.

  Specific examples of the aromatic monoamine include aniline, 1-naphthylamine, 2-naphthylamine, 1-aminoanthracene, o-toluidine, p-toluidine, m-toluidine, 2-ethylaniline, 3-ethylaniline, 4 -Ethylaniline, 2-propylaniline, 3-propylaniline, 4-propylaniline, cumidine, 2-n-butylaniline, 3-n-butylaniline, 4-n-butylaniline, 2-isobutylaniline, 3-isobutyl Aniline, 4-isobutylaniline, 2-sec-butylaniline, 3-sec-butylaniline, 4-sec-butylaniline, 2-tert-butylaniline, 3-tert-butylaniline, 4-tert-butylaniline, 2 -N-pentylaniline, 3-n-pentylaniline 4-n-pentylaniline, 2-isopentylaniline, 3-isopentylaniline, 4-isopentylaniline, 2-sec-pentylaniline, 3-sec-pentylaniline, 4-sec-pentylaniline, 2-tert -Pentylaniline, 3-tert-pentylaniline, 4-tert-pentylaniline, 2-hexylaniline, 3-hexylaniline, 4-hexylaniline, 2-heptylaniline, 3-heptylaniline, 4-heptylaniline, 2- Octylaniline, 3-octylaniline, 4-octylaniline, 2-nonylaniline, 3-nonylaniline, 4-nonylaniline, 2-decylaniline, 3-decylaniline, 4-decylaniline, cyclohexylaniline, diphenylamine, dimethylaniline , Diethylaniline, dipropylaniline, diisopropylaniline, di-n-butylaniline, di-sec-butylaniline, di-tert-butylaniline, trimethylaniline, triethylaniline, tripropylaniline, tri-tert-butylaniline, Anisidine, ethoxyaniline, dimethoxyaniline, diethoxyaniline, trimethoxyaniline, tri-n-butoxyaniline, benzylamine, methylbenzylamine, dimethylbenzylamine, trimethylbenzylamine, methoxybenzylamine, ethoxybenzylamine, dimethoxybenzylamine, α-phenylethylamine, β-phenylethylamine, methoxyphenylethylamine, dimethoxyphenylethylamine, α-phenylpropylamine, β Phenylpropylamine, .gamma. phenylpropylamine, methyl phenylpropylamine and the like.

  Among the above monoamines, from the viscosity-reducing performance when the amide compound is melted, the availability of raw materials, and the fuming properties when added to a molten resin, it is an unsubstituted cyclohexylamine or a straight chain having 1 to 4 carbon atoms as a substituent. Cyclohexylamine having 1 to 3 (especially one) linear or branched alkyl groups (particularly methyl groups) is preferred.

  Specific examples of particularly preferred alicyclic monoamine components include cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, 2-ethylcyclohexylamine, 2-n-propylcyclohexylamine, 2- Examples include iso-propylcyclohexylamine, 2-n-butylcyclohexylamine, 2-iso-butylcyclohexylamine, 2-sec-butylcyclohexylamine, and 2-tert-butylcyclohexylamine.

  The monoamine having the substituent may be any of a cis isomer, a trans isomer, and a mixture of these stereoisomers.

  In addition, preferred monoamines include aniline or anilines having 1 to 3 (particularly 1) linear or branched alkyl groups having 1 to 4 carbon atoms.

<Preferred amide compound>
Among the amide compounds in which n in the general formula (1) is 2, an amide compound in which a residue derived from a carboxylic acid, that is, R ¹ is a residue obtained by removing all carboxyl groups from naphthalene dicarboxylic acid, In particular, an amide compound represented by the following general formula (2), particularly an amide compound in which R ¹ is a residue obtained by removing all carboxyl groups from 2,6-naphthalenedicarboxylic acid is preferable.

[In the formula, two R ^{3 s} are the same or different and each is a residue obtained by removing an amino group from an alicyclic monoamine having 6 to 30 carbon atoms (particularly 6 to 18 carbon atoms), or 6 to 6 carbon atoms. It represents a residue obtained by removing an amino group from 30 (especially 6 to 18) aromatic monoamines. ].

Further, the residue obtained by removing the amino group from the monoamine, that is, R ² in the general formula (1) (particularly R ³ in the general formula (2)) is a straight chain having 1 to 4 carbon atoms as a cyclohexyl group or a substituent. An amide compound which is a residue obtained by removing an amino group from a cyclohexylamine having 1 to 2, particularly 1 chain or branched alkyl group is more preferable. Moreover, when it has a substituent, the substituent is preferably a methyl group, and the substitution position is preferably the 2-position.

  Among the preferable amide compounds, 2,6-naphthalenedicarboxylic acid dianilide, 2,6-naphthalenedicarboxylic acid dicyclohexylamide, and 2,6-naphthalenedicarboxylic acid di (2-methylcyclohexylamide) are preferable, and 2,6- Naphthalenedicarboxylic acid dicyclohexylamide is particularly preferred.

Among the amide compounds in which n in the general formula (1) is 3 to 6, R ¹ is a residue obtained by removing all carboxyl groups from a saturated aliphatic polycarboxylic acid having 6 to 15 carbon atoms, the number of carbon atoms Either a residue obtained by removing all carboxyl groups from an alicyclic polycarboxylic acid having 9 to 15 or a residue obtained by removing all carboxyl groups from an aromatic polycarboxylic acid having 9 to 15 carbon atoms An amide compound represented by is preferable, and an amide compound in which n is 3 to 4 is particularly preferable.

Among the amide compounds represented by the general formula (1) where n is 3 or 4, R ¹ in the general formula (1) removes all carboxyl groups from 1,2,3,4-butanetetracarboxylic acid. Or a residue obtained by removing all carboxyl groups from 1,2,3-propanetricarboxylic acid, or a residue obtained by removing all carboxyl groups from trimesic acid. Amide compounds are preferred.

Among the amide compounds represented by the general formula (1) in which n is an integer of 3 to 6, particularly 3 or 4, R ² is a linear or branched saturated or unsaturated group having 6 to 18 carbon atoms. Residue obtained by removing amino group from saturated aliphatic monoamine, carbon number which may have 1 to 3 (particularly 1) linear or branched alkyl group having 1 to 4 carbon atoms It has 1 to 3 (especially 1) of a residue obtained by removing an amino group from a 6-18 alicyclic monoamine, or a linear or branched alkyl group having 1 to 4 carbon atoms. An amide compound represented by the general formula (1) showing a residue obtained by removing an amino group from an aromatic monoamine having 6 to 18 carbon atoms is preferable.

  Among the amide compounds represented by the general formula (1) in which n is 3 or 4, amide compounds represented by the following general formulas (3) to (5) are particularly preferable.

  (i) General formula (3)

[In the formula, three R ^{4 s} are the same or different and each is a residue obtained by removing an amino group from an aliphatic monoamine having 6 to 30 carbon atoms (especially 6 to 18 carbon atoms). Residue obtained by removing an amino group from an alicyclic monoamine of 6 to 18 in particular (1 to 3 linear or branched alkyl groups having 1 to 4 carbon atoms as a cyclohexyl group or a substituent) (Especially a residue obtained by removing an amino group from a cyclohexylamine) or a residue obtained by removing an amino group from an aromatic monoamine having 6 to 30 carbon atoms (especially 6 to 18 carbon atoms). An amide compound represented by
(ii) General formula (4)

[In the formula, four R ^{5 s} are the same or different and are each a residue obtained by removing an amino group from an aliphatic monoamine having 6 to 30 carbon atoms (particularly 6 to 18 carbon atoms), 6 to 30 carbon atoms ( Residue obtained by removing an amino group from an alicyclic monoamine of 6 to 18 in particular (1 to 3 linear or branched alkyl groups having 1 to 4 carbon atoms as a cyclohexyl group or a substituent) (Especially a residue obtained by removing an amino group from a cyclohexylamine) or a residue obtained by removing an amino group from an aromatic monoamine having 6 to 30 carbon atoms (especially 6 to 18 carbon atoms). An amide compound represented by the formula:
(iii) General formula (5)

[In the formula, three R ^{6 s} are the same or different and each is a residue obtained by removing an amino group from an aliphatic monoamine having 6 to 30 carbon atoms (especially 6 to 18 carbon atoms), particularly 6 to 30 carbon atoms (especially 6-18) residues obtained by removing amino groups from alicyclic monoamines (particularly, cyclohexyl groups or 1 to 3 linear or branched alkyl groups having 1 to 4 carbon atoms as substituents ( (Particularly one) a residue obtained by removing an amino group from a cyclohexylamine), or a residue obtained by removing an amino group from an aromatic monoamine having 6 to 30 carbon atoms (particularly 6 to 18) (particularly aniline or It represents a residue obtained by removing an amino group from aniline having 1 to 3 (especially 1) linear or branched alkyl group having 1 to 4 carbon atoms. An amide compound represented by

Further, among these, R ² is R ^{4 in} the general formula (3), R ^{5 in} the general formula (4), R ⁶ in the general formula (5) is cyclohexylamine or a substituent having 1 to 1 carbon atoms. A residue obtained by removing an amino group from cyclohexylamine having 1 to 4 (especially 1) linear or branched alkyl groups of 4 or a linear chain having 1 to 4 carbon atoms as aniline or a substituent An amide compound represented by the general formula (1), which is a residue obtained by removing an amino group from an aniline having 1 to 3 (particularly 1) linear or branched alkyl groups, is more preferable.

  Among the amide compounds represented by the general formula (3), 1,2,3-propanetricarboxylic acid trihexylamide, 1,2,3-propanetricarboxylic acid tridodecylamide, 1,2,3-propanetricarboxylic acid Acid trioctadecylamide, 1,2,3-propanetricarboxylic acid trianilide, 1,2,3-propanetricarboxylic acid tricyclohexylamide, 1,2,3-propanetricarboxylic acid tris (2-methylcyclohexylamide), 1,2 1,3-propanetricarboxylic acid tris (4-butylanilide) is preferred, and among these, 1,2,3-propanetricarboxylic acid tris (2-methylcyclohexylamide) is particularly preferred.

  Among the amide compounds represented by the general formula (4), 1,2,3,4-butanetetracarboxylic acid tetrahexylamide, 1,2,3,4-butanetetracarboxylic acid tetradodecylamide, 2,3,4-butanetetracarboxylic acid tetraoctadecylamide, 1,2,3,4-butanetetracarboxylic acid tetraanilide, 1,2,3,4-butanetetracarboxylic acid tetracyclohexylamide, 1,2,3 , 4-butanetetracarboxylic acid tetrakis (2-methylcyclohexylamide) and 1,2,3,4-butanetetracarboxylic acid tetrakis (4-butylanilide) are preferable, and among these, 1,2,3,4-butane Tetracarboxylic acid tetracyclohexylamide is particularly preferred.

  Among the amide compounds represented by the general formula (5), trimesic acid trihexylamide, trimesic acid tridodecylamide, trimesic acid trioctadecylamide, trimesic acid trianilide, trimesic acid tricyclohexylamide, trimesic acid tris (2- Methylcyclohexylamide) and trimesic acid tris (4-butylanilide) are preferable, and among these, trimesic acid tricyclohexylamide is particularly preferable.

  The amide compounds according to the present invention can be used singly or in appropriate combination of two or more.

  The crystal system of the amide compound according to the present invention is not particularly limited as long as the effects of the present invention can be obtained, and any crystal system such as hexagonal crystal, monoclinic crystal, cubic crystal and the like can be used. These crystals are also known or can be produced according to known methods.

  The particle diameter of these crystals is not particularly limited and can be arbitrarily selected according to the purpose. For example, when it is desired to dissolve or melt the amide compound in the molten resin for a short time, the particle diameter is usually 120 μm or less as an average diameter although it is affected by the treatment temperature during the dissolution or melt mixing. Preferably, 50 μm or less, more preferably 10 μm or less is recommended.

  The amide compound may be in a pre-blend type form using other additives described below as a binder in advance. The particle diameter of the blend is usually 120 μm or less, preferably 50 μm or less, more preferably 10 μm or less in terms of average particle diameter.

  On the other hand, when it is desired to improve powder characteristics such as powder flowability, the average particle diameter is usually 200 μm or more, preferably 500 μm or more, more preferably 1 mm or more.

  The average particle diameter is a value determined by laser light scattering particle size distribution measurement.

  As the amide compound according to the present invention, an amide compound having a 5% weight loss temperature of 280 ° C. or higher, preferably 300 ° C. or higher, particularly preferably 320 ° C. or higher is recommended. The amide compound having excellent thermal stability is preferable because it does not cause thermal decomposition when melt-mixed with an amorphous thermoplastic resin and does not accelerate decomposition of the resin.

Amorphous thermoplastic resin Specific examples of the amorphous thermoplastic resin include: general-purpose thermoplastic resins such as polystyrene, acrylonitrile-butadiene-styrene resin, vinyl chloride resin, acrylonitrile-styrene resin, polycarbonate, modified polyphenylene ether, polysulfone, Examples include amorphous engineering plastics such as polyethersulfone, polyarylate, polyamideimide, polyetherimide, or thermoplastic polyimide.

  The amorphous thermoplastic resins can be used alone or in appropriate combination of two or more. In addition, it is also possible to use a combination of an amorphous thermoplastic resin and a resin other than those described above. In that case, it is preferable to contain the amorphous thermoplastic resin in an amount of 50% by weight or more based on the entire resin.

  The amide compound represented by the general formula (1) used in the present invention exhibits an excellent melt viscosity reducing effect on a resin having high heat resistance called engineering plastic among the above amorphous thermoplastic resins. Among them, regarding engineering plastics having transparency, especially polycarbonate, when the amide compound represented by the general formula (1) used in the present invention is used, in addition to exhibiting the effect of reducing melt viscosity, transparency is lowered. This is preferable because it is difficult to perform. On the other hand, when ethylene bisstearylamide, which is a melt viscosity reducing agent described in JP-A-2006-37031 published before the filing date of the present application but after the priority date of the present application, is used, Transparency tends to decrease slightly.

  Examples of the polycarbonate resin include aromatic polycarbonate, aliphatic polycarbonate, aliphatic-aromatic polycarbonate, and the like. These polycarbonate resins are produced by a known method, and are generally produced by reacting a dihydroxy or polyhydroxy compound with phosgene or a carbonic acid diester.

  The polycarbonate resin is preferably a polycarbonate obtained from a dihydroxydiarylalkane or a polyhydroxy compound, and may optionally be branched.

  Specific examples of the polycarbonate raw material include 4,4′-dihydroxy-2,2′-diphenylpropane (bisphenol A), tetramethylbisphenol A, and bis (4-hydroxyphenyl) -p-diisopropylbenzene. Dihydroxyarylalkane, 1,4-bis (4 ′, 4,2-dihydroxytriphenylmethyl) -benzene, fluorodalcinol, 4′6-dimethyl-2,4,6-tri (4-hydroxyphenyl) -heptene 2,4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) -heptane, 1,3,5-tri (4-hydroxyphenyl) -benzene, 1,1,1-tri (4- Hydroxyphenyl) -ethane and 2,2-bis [4,4 ′-(4,4′-dihydroxyphenyl) cyclohexyl Polyhydroxy compounds such as propane and the like.

As the amorphous thermoplastic resin according to the present invention, those having an arbitrary molecular weight can be used. Usually, polycarbonate having a viscosity average molecular weight of 1.0 × 10 ^{4 to} 5.0 × 10 ⁴ is used. Polystyrene having a weight average molecular weight (Mw) of about 150,000 to 400,000 is usually used.

  If necessary, an impact resistance improver may be added to the resin composition of the present invention in an appropriate amount, particularly in an amount effective to improve impact resistance, in order to improve impact strength. . Generally, such an impact modifier is a resin composition containing (a) an amorphous thermoplastic resin of the present invention and (b) at least one amide compound represented by the general formula (1). It is preferable to use about 0.001 to 20 parts by weight, particularly about 0.001 to 10 parts by weight with respect to 100 parts by weight.

  Impact modifiers include polybutadiene, SBR, EPDM, EVA, polyacrylate, polyisoprene, hydrogenated isoprene, acrylic elastomers, diblock or triblock copolymers consisting of a polystyrene phase and a hydrogenated polyisoprene phase. (For example, Kuraray Co., Ltd., trade name “Septon”), polyester / polyether coelastomer, polyamide elastomer (for example, Toray Industries, trade name “Pebax”), PA elastomer (for example, Dainippon Manufactured by Ink Chemical Co., Ltd., trade name “Glais A”), ethylene / butene 1 copolymer, styrene / butadiene block copolymer, hydrogenated styrene / butadiene block copolymer, ethylene / propylene copolymer, ethylene・ For both propylene and ethylidene norbonene Coalescence, thermoplastic polyester elastomer, hydrogenated SEBS elastomer (for example, manufactured by Shell Chemical Co., Ltd., trade name “Clayton G”), ethylene-α olefin copolymer and propylene-α olefin copolymer (for example, manufactured by Mitsui Petrochemical Co., Ltd.) , Trade name "Tuffmer"), ethylene methacrylic acid special elastomer (for example, trade name "Tafrit T3000" manufactured by Mitsui DuPont Polychemical Co., Ltd.), a core with a rubber layer and a shell layer made of a hard resin Shell-type elastomer (for example, Takeda Pharmaceutical Co., Ltd., trade name “Staffroid”), acrylic (reaction type) elastomer (for example, Kureha Chemical Co., Ltd., trade name “Paraloid EXL”), MBS ( Methyl methacrylate, butadiene, styrene resin) based elastomers Kureha BTA elastomer, core / shell type elastomer (for example, product name “METABREN S” manufactured by Mitsubishi Rayon Co., Ltd.), core / shell type elastomer with core made of silicon rubber and shell made of acrylic rubber or acrylic resin ( For example, grade name “S2001” or “RK120” manufactured by Mitsubishi Rayon Co., Ltd.) is exemplified.

Amorphous thermoplastic resin composition and melt viscosity reducing agent for amorphous thermoplastic resin The amorphous thermoplastic resin composition of the present invention has a general formula based on 100 parts by weight of the amorphous thermoplastic resin. The amide compound represented by (1) is recommended to be about 0.001 to 10 parts by weight, preferably about 0.001 to 3 parts by weight, more preferably about 0.01 to 3 parts by weight. In particular, when the amorphous thermoplastic resin is a transparent engineering plastic, particularly a polycarbonate transparent resin, the amide compound represented by the general formula (1) of the present invention is added to 100 parts by weight of the amorphous thermoplastic resin. On the other hand, it is advantageous to use it in an amount in the range of about 0.03 to 1 part by weight, especially about 0.1 to 0.8 part by weight.

  By blending within the above range, the effect of reducing the melt viscosity of the desired amorphous thermoplastic resin can be obtained. That is, the amide compound of the present invention acts as a melt viscosity reducing agent. Accordingly, the present invention also provides a melt viscosity reducing agent for an amorphous thermoplastic resin containing at least one amide compound represented by the general formula (1).

  The method for preparing the amorphous thermoplastic resin composition according to the present invention is not particularly limited as long as the effects of the present invention are not impaired. The amide compound can be added to the amorphous thermoplastic resin at any time from the production of the amorphous thermoplastic resin to before molding.

For example,
1) A method for producing a resin composition containing the amide compound or the melt viscosity reducing agent by adding the amide compound together with a raw material monomer of an amorphous thermoplastic resin to a reaction vessel to perform a polymerization reaction,
2) A method in which the amide compound is added to an amorphous thermoplastic resin in a molten state immediately after the polymerization reaction and melt mixed.
3) A method of dry blending amorphous thermoplastic resin pellets and the amide compound with a Henschel mixer, ribbon blender, etc.
4) A method of melt-mixing the dry blend with an extruding granulator or the like to form pellets,
5) A method for preparing a master batch pellet containing a high concentration of the amide compound,
6) A method in which an amide compound is directly added to a melted amorphous thermoplastic resin and melt mixed is exemplified.

  Among these, especially in the case of continuous production (for example, an amorphous thermoplastic resin manufacturer), a method of adding to a molten amorphous thermoplastic resin immediately after the polymerization reaction and melt-mixing the existing apparatus, etc. This is preferable in that an increase in manufacturing cost can be suppressed without improvement. In batch production (semi-continuous production), a method of dry blending amorphous thermoplastic resin pellets (or powder) and the amide compound with a Henschel mixer, ribbon blender or the like, or this dry blend product is a Banbury mixer. Using a conventional kneader such as a kneader, oven roll, single or twin screw extruder, single screw reciprocating screw, etc., the mixture is melt mixed at a temperature 10 to 130 ° C. higher than the melting temperature of the amorphous thermoplastic resin. The method of making pellets is preferable because it is simple and can be used for multi-product production.

  In the amorphous thermoplastic resin composition of the present invention, other additives that are usually used for amorphous thermoplastic resins are appropriately added within the range that does not impair the effects of the present invention, depending on the use and purpose. Can be added. For example, conventionally known melt viscosity reducing agents, fluidity modifiers, antioxidants, UV absorbers, light stabilizers, antistatic agents, lubricants, mold release agents, flame retardants, matting agents, pigments, dyes, filling And additives described in “Positive List Additives Guide” (3rd edition, January 2002, edited by Sanitation Council for Polyolefins, etc.).

Amorphous thermoplastic resin molded article and method for producing the same The amorphous thermoplastic resin molded article of the present invention can be obtained by molding the amorphous thermoplastic resin composition of the present invention according to a conventionally known molding method. The method for producing an amorphous thermoplastic resin molding of the present invention (molding method of an amorphous thermoplastic resin composition) simultaneously provides a method for reducing the melt viscosity of the amorphous thermoplastic resin.

  Examples of such molding methods include injection molding, blow molding, extrusion molding, calendar molding, injection compression molding, injection blow molding, extrusion blow molding, injection extrusion blow molding, stretch blow molding, multilayer blow molding, extrusion thermoform molding, Examples of the molding method include rotational molding, spinning molding, and sheet / film molding. As the form of the molded product, it can be obtained as any type of molded product such as an injection molded product, a film, a sheet, and a bottle.

  The molding conditions of the amorphous thermoplastic resin composition of the present invention may be appropriately selected according to the type and degree of polymerization of the amorphous thermoplastic resin, the type and blending amount of the amide compound.

  The injection molding conditions of the amorphous thermoplastic resin composition of the present invention are appropriately selected according to the kind of amorphous thermoplastic resin and the degree of polymerization. For example, a condition range of a resin temperature of 250 to 380 ° C., a mold temperature of 80 to 140 ° C., and an injection pressure of 80 to 300 MPa is exemplified.

  Blow molding conditions are appropriately selected according to the type of amorphous thermoplastic resin and the degree of polymerization. For example, a condition range of a resin temperature of 250 to 380 ° C., a mold temperature of 20 to 140 ° C., and a blowing pressure of 0.05 to 0.5 MPa is exemplified.

  Extrusion molding conditions are appropriately selected according to the type of amorphous thermoplastic resin and the degree of polymerization. For example, a melting temperature of 200 to 350 ° C. is frequently used. A sheet-like molded body obtained by extrusion molding can be heated with a heating roller, a tenter or the like, and uniaxially stretched or biaxially stretched to obtain a stretched film. Usually, the stretching temperature is 50 to 150 ° C., and the stretching ratio is 1.3 to 8 times.

  Amorphous thermoplastic resin molded articles obtained from the amorphous thermoplastic resin composition of the present invention include, for example, antenna insulation parts, connectors, VTR chassis, VTR camera bodies, AC adapter cases, optical fibers, CDs, DVDs, and the like. Electrical and electronic equipment such as optical discs, motor parts, bumpers and exteriors, wheel covers, meters, lamp lenses, instruments, automotive parts such as heater fans, camera bodies and parts, watch case parts, microscope / projector parts, etc. Safety equipment such as precision equipment, helmets, dustproof glasses, fire extinguisher parts, medical items such as eye drops containers, X-ray parts, blood vessel joints, household items such as baby bottles, heat insulation bottles, food bottles, etc. It is not particularly limited.

  According to the present invention, when the amorphous thermoplastic resin contains a specific amount of the specific amide compound represented by the general formula (1), the viscosity at the time of melting the resin can be reduced.

  Further, an amorphous thermoplastic resin containing a non-crystalline thermoplastic resin and a specific amount of the specific amide compound represented by the general formula (1) or a molded product obtained from the resin composition is The heat resistance and mechanical properties are not substantially impaired as compared to the heat resistance and mechanical properties of the amorphous thermoplastic resin itself.

  Further, in the case where the amorphous thermoplastic resin is a transparent resin, in particular, polycarbonate, it is described in JP-A-2006-37031 published before the filing date of the present application but after the priority date of the present application. When ethylene bisstearylamide, which is a melt viscosity reducing agent, is used, the transparency tends to be slightly lowered. However, when the amide compound represented by the general formula (1) used in the present invention is used, the transparency is lowered. This is preferable because it is difficult to perform.

FIG. 1 is a graph showing the temperature dependence of a general storage elastic modulus E ′ (Pa) for a test piece used for measurement of impact resistance. The temperature corresponding to the intersection of two tangents in this graph was determined as Tg (° C.). FIG. 1 shows how to draw a tangent line.

  Hereinafter, the present invention will be described in detail with reference to production examples (synthesis examples of amide compounds used in the present invention), examples and comparative examples, but the present invention is not limited to these examples. In the following, all parts and percentages are by weight unless otherwise specified. Each physical property value was measured by the following method.

1. Evaluation of amide compounds
Melting point of amide compound The amide compound obtained in each production example was measured under the following conditions using a differential scanning calorimeter (trade name “DSC6220” manufactured by SII Nano Technology Co., Ltd.), and the maximum endothermic peak The peak top of was the melting point.
Nitrogen: 30 ml / min, heating rate: 10 ° C./min, sample: 5 mg, standard sample: silica gel 5 mg.

Using a 5% weight reduction temperature differential thermothermal gravimetric simultaneous measurement apparatus (product name “TG / DTA6200”, manufactured by SII Nano Technology Co., Ltd.) of amide compound, amide compound sample under nitrogen atmosphere under the following conditions And the temperature at which the weight of the sample was 95% of the initial weight was measured to obtain a 5% weight reduction temperature.
Nitrogen: 100 ml / min, heating rate: 10 ° C./min, sample: 10 mg
A higher 5% weight loss temperature indicates better thermal stability.

2. Evaluation of resin composition / molded body
Melt viscosity (250 ° C)
A test piece of 2.5 cm × 2.5 cm × thickness 1 mm was cut out from the molded body prepared in each example and comparative example, and the dynamic viscosity (η ′) was measured using a rheometer under the following measurement conditions. This was taken as the melt viscosity.
<Measurement conditions>
Rheometer: Product name “MR-500 solid meter” manufactured by Rheology Co., Ltd.
Measurement method: Dynamic viscoelasticity measurement Measurement mode: Frequency dispersion (under constant temperature)
Measuring jig: Parallel plate (diameter 1.996 cm)
Frequency f: 3.20Hz
ω = 2πf = 20.1 rad / sec
(The ω in the region where the measurement sample exhibits Newtonian properties was selected.)
Strain angle: 0.5 Deg
Measurement temperature: 250 ° C.

The relative viscosity was measured using the Ostwald viscometer (manufactured by Mutual Rika Glass Co., Ltd.) under the following measurement conditions based on ASTM D2857-95.
<Measurement conditions>
A polycarbonate solution was prepared by dissolving polycarbonate in methylene chloride to a concentration of 4.0 mg / ml, and measured with an Ostwald viscometer at 30 ° C.

Capillograph measurement Using a capillary rheometer (product name “CAPIROGRAPH 1B” manufactured by Toyo Seiki Seisakusho Co., Ltd.), the capillograph measurement was performed on the pellets obtained in each of the examples and comparative examples by a method based on JIS K 7199. . The measurement conditions are as follows.
<Measurement conditions>
Measurement temperature: 300 ° C, capillary length: 10mm, capillary diameter: 1mm
Piston speed: 0.5, 5, 10, 20, 50, 100, 200, 500 mm / min
Evaluation was performed using measured values at 20, 50, 100, 200 and 500 mm / min. The obtained value indicates the melt viscosity at each shear rate, and the smaller the value, the lower the viscosity.

Melt index measurement Melt index measurement was performed using a melt index measurement apparatus (D4002 type, manufactured by Dynasco Polymer Test) in accordance with JIS K7210 except that the following measurement conditions were employed. The melt index indicates a flow rate based on mass per certain time.
<Measurement conditions>
Resin melting temperature 250 ° C
Load 5kg.

Izod impact value Molded bodies (90 mm ×) made in each example and comparative example in accordance with JIS K7110 using an Izod impact tester (manufactured by Yasuda Seiki Co., Ltd., product name “No.258-D”) The Izod impact value (10 mm × 4 mm, with notch) was measured under the following conditions.
The larger the obtained Izod impact value, the higher the impact resistance.
<Measurement conditions>
Test temperature: 25 ° C
Load: 2.75J.

Bending of molded bodies (90 mm x 10 mm x 4 mm) created in each example and comparative example in accordance with JIS K7171 using a bending elastic modulus Instron universal testing machine (manufactured by INSTRON Co., Ltd., "5566 type") The elastic modulus was measured under the following conditions.
It can be said that the greater the value obtained for the bending elastic modulus, the higher the resistance to bending stress, that is, the less the deformation is.
<Measurement conditions>
Test temperature: 25 ° C.

Heat resistance: HDT (deflection temperature under load)
Using the HDT measuring device (Toyo Seiki Seisakusho, "3M-2 type"), the deflection temperature under load of the molded bodies (110 mm x 13 mm x 4 mm) prepared in each example and comparative example in accordance with JIS K7191 is shown below. The measurement was performed under the following conditions.
The higher the obtained deflection temperature, the higher the heat resistance.
<Measurement conditions>
Specimen direction: Edgewise fulcrum distance: 100 mm
Bending stress: 0.45 MPa (B method).

Glass transition temperature (Tg) (° C)
A test piece was cut out from a molded body of 5 cm × 5 cm × thickness 1 mm prepared in Examples 1 to 15 and Comparative Examples 1 to 3, and a storage elastic modulus E ′ using a dynamic viscoelasticity measuring device under the following measurement conditions, The loss tangent tan δ was measured under the following conditions.
<Measurement conditions>
Dynamic viscoelasticity measuring apparatus: manufactured by UBM Co., Ltd., trade name “Rheogel-E4000”
Measurement mode: Tensile measurement Waveform: Sine wave Frequency: 10Hz
Strain control: 5 μm
Measurement temperature range: -150 to 300 ° C
Temperature increase rate: 5 ° C / min
The temperature corresponding to the intersection of the two tangents of the temperature dependence graph of the storage elastic modulus E ′ thus obtained was determined as Tg (° C.). FIG. 1 shows how to draw a tangent line. Tg (° C.) is a measure of the heat resistance of the amorphous thermoplastic resin.

Total light transmittance (%) and haze value (%)
The molded body (thickness 3 mm × 5 cm × 5 cm) prepared in each Example and Comparative Example was used as a test piece, and the test piece was subjected to ASTM D1003 using a haze meter (“HAZE-GARDII” manufactured by Toyo Seiki Seisakusho). Measured. As the total light transmittance is larger, the haze value is smaller, and as the obtained value is smaller, the transparency is more excellent.

Production Example 1
9.7 g (0.055 mol) of 1,2,3-propanetricarboxylic acid (hereinafter abbreviated as “PTC”) is added to a 500 ml four-necked flask equipped with a stirrer, a thermometer, a cooling pipe and a gas inlet. And 100 g of N-methyl-2-pyrrolidone were added, and PTC was completely dissolved while stirring at room temperature under a nitrogen atmosphere. Subsequently, 2-methylcyclohexylamine (trans form: cis form = 74.3: 25.7, GLC area ratio) 20.5 g (0.182 mol), triphenyl phosphite 74.7 g (0.182 mol) ), 14.4 g (0.182 mol) of pyridine and 50 g of N-methyl-2-pyrrolidone were added, and the reaction was performed at 100 ° C. for 4 hours with stirring in a nitrogen atmosphere. After cooling, the reaction solution was slowly poured into a mixed solution of 500 ml of isopropyl alcohol and 500 ml of water and stirred at about 40 ° C. for 1 hour, and then the precipitated white precipitate was filtered off. Further, the obtained white solid was washed twice with 500 ml of isopropyl alcohol at about 40 ° C. and then dried at 100 ° C. and 133 Pa for 6 hours.

  The obtained dried product was pulverized in a mortar, passed through a standard sieve having an aperture of 106 μm (JIS Z8801 standard), and 1,2,3-propanetricarboxylic acid tris (2-methylcyclohexylamide) (hereinafter “PTC-2MeCHA”). 18.8 g (yield 74%).

  As a result of FT-IR analysis of the obtained PTC-2MeCHA, characteristic absorption derived from the amide compound (C═O stretching vibration and N—H stretching vibration) was confirmed. Table 1 shows the melting point measurement results and 5% weight loss temperature of the obtained PTC-2MeCHA.

Production Example 2
In a 500 ml four-necked flask equipped with a stirrer, a thermometer, a cooling pipe and a gas inlet, 1,2.9 g (0. 0) of 1,2,3,4-butanetetracarboxylic acid (hereinafter abbreviated as “BTC”). 055 mol) and 100 g of N-methyl-2-pyrrolidone were added, and BTC was completely dissolved under stirring in a nitrogen atmosphere at room temperature. Subsequently, 24.0 g (0.242 mol) of cyclohexylamine, 74.7 g (0.182 mol) of triphenyl phosphite, 14.4 g (0.182 mol) of pyridine and 50 g of N-methyl-2-pyrrolidone. In addition, the reaction was performed at 100 ° C. for 4 hours with stirring in a nitrogen atmosphere. After cooling, the reaction solution was slowly poured into a mixed solution of 500 ml of isopropyl alcohol and 500 ml of water and stirred at about 40 ° C. for 1 hour, and then the precipitated white precipitate was filtered off. Further, the obtained white solid was washed twice with 500 ml of isopropyl alcohol at about 40 ° C. and then dried at 100 ° C. and 133 Pa for 6 hours.

  The obtained dried product was pulverized in a mortar, passed through a standard sieve having an aperture of 106 μm (JIS Z8801 standard), and 1,2,3,4-butanetetracarboxylic acid tetracyclohexylamide (hereinafter referred to as “BTC-CHA”). 20.6 g (yield 66%) was obtained.

  As a result of FT-IR analysis of the obtained BTC-CHA, characteristic absorption (C═O stretching vibration and N—H stretching vibration) derived from the amide compound was confirmed. Table 1 shows the melting point measurement results and 5% weight loss temperature of BTC-CHA obtained.

Production Example 3
In a 500 ml four-necked flask equipped with a stirrer, a thermometer, a cooling pipe and a gas inlet, 11.6 g (0.055 mol) of trimesic acid (hereinafter abbreviated as “TM”) and N-methyl-2- 100 g of pyrrolidone was added, and TM was completely dissolved while stirring at room temperature in a nitrogen atmosphere. Subsequently, 18.0 g (0.182 mol) of cyclohexylamine, 56.3 g (0.182 mol) of triphenyl phosphite, 14.4 g (0.182 mol) of pyridine and 50 g of N-methyl-2-pyrrolidone. In addition, the reaction was performed at 100 ° C. for 4 hours with stirring in a nitrogen atmosphere. After cooling, the reaction solution was slowly poured into a mixed solution of 500 ml of isopropyl alcohol and 500 ml of water and stirred at about 40 ° C. for 1 hour, and then the precipitated white precipitate was filtered off. Further, the obtained white solid was washed twice with 500 ml of isopropyl alcohol at about 40 ° C. and then dried at 100 ° C. and 133 Pa for 6 hours.

  The obtained dried product was pulverized in a mortar, passed through a standard sieve having an aperture of 106 μm (JIS Z8801 standard), and 19.4 g of trimesic acid tricyclohexylamide (hereinafter abbreviated as “TM-CHA”) (yield 78). %).

  The obtained TM-CHA was subjected to FT-IR analysis, and as a result, characteristic absorption derived from the amide compound (C = O stretching vibration and NH stretching vibration) was confirmed. Table 1 shows the melting point measurement results and 5% weight loss temperature of TM-CHA obtained.

Production Example 4
In a 500 ml four-necked flask equipped with a stirrer, thermometer, condenser and gas inlet, 11.9 g (0.055 mol) of 2,6-naphthalenedicarboxylic acid and 100 g of N-methyl-2-pyrrolidone were added, 2,6-Naphthalenedicarboxylic acid was completely dissolved while stirring at room temperature under a nitrogen atmosphere. Subsequently, 18.0 g (0.182 mol) of cyclohexylamine, 56.3 g (0.182 mol) of triphenyl phosphite, 14.4 g (0.182 mol) of pyridine and 50 g of N-methyl-2-pyrrolidone. In addition, the reaction was performed at 100 ° C. for 4 hours with stirring in a nitrogen atmosphere. After cooling, the reaction solution was slowly poured into a mixed solution of 500 ml of isopropyl alcohol and 500 ml of water and stirred at about 40 ° C. for 1 hour, and then the precipitated white precipitate was filtered off. Further, the obtained white solid was washed twice with 500 ml of isopropyl alcohol at about 40 ° C. and then dried at 100 ° C. and 133 Pa for 6 hours.

  The obtained dried product was pulverized in a mortar, passed through a standard sieve having an aperture of 106 μm (JIS Z8801 standard), and 16.4 g of 2,6-naphthalenedicarboxylic acid dicyclohexylamide (hereinafter abbreviated as “N-CHA”). (Yield 79%) was obtained.

  As a result of performing FT-IR analysis on the obtained N-CHA, characteristic absorption derived from the amide compound (C = O stretching vibration and NH stretching vibration) was confirmed. Table 1 shows the melting point measurement results and 5% weight loss temperature of N-CHA obtained.

Production Example 5
In a 500 ml four-necked flask equipped with a stirrer, a thermometer, a cooling pipe and a gas inlet, 11.6 g (0.055 mol) of trimesic acid (hereinafter abbreviated as “TM”) and N-methyl-2- 100 g of pyrrolidone was added, and 2,6-naphthalenedicarboxylic acid was completely dissolved while stirring at room temperature under a nitrogen atmosphere. Subsequently, 16.9 g (0.182 mol) of aniline, 56.3 g (0.182 mol) of triphenyl phosphite, 14.4 g (0.182 mol) of pyridine and 50 g of N-methyl-2-pyrrolidone were added. The reaction was performed at 100 ° C. for 4 hours with stirring in a nitrogen atmosphere. After cooling, the reaction solution was slowly poured into a mixed solution of 500 ml of isopropyl alcohol and 500 ml of water and stirred at about 40 ° C. for 1 hour, and then the precipitated white precipitate was filtered off. Further, the obtained white solid was washed twice with 500 ml of isopropyl alcohol at about 40 ° C. and then dried at 100 ° C. and 133 Pa for 6 hours.

  The obtained dried product was pulverized in a mortar, passed through a standard sieve having an aperture of 106 μm (JIS Z8801 standard), and 20.2 g of trimesic acid trianilide (hereinafter abbreviated as “TM-tri-ANI”) (yield 84). %).

  The obtained TM-CHA was subjected to FT-IR analysis, and as a result, characteristic absorption derived from the amide compound (C = O stretching vibration and NH stretching vibration) was confirmed. Table 1 shows the melting point measurement results and 5% weight loss temperature of TM-tri-ANI obtained.

Examples 1-15
Each amide compound obtained in the above Production Examples 1 to 5 was added to 100 parts by weight of a polycarbonate resin (pellet; manufactured by Mitsubishi Resin Chemical Co., Ltd., “Iupilon S3000R”) dried at 120 ° C. for 5 hours. These ingredients were mixed. The obtained mixture was melt-kneaded with an extruder at a resin temperature of 280 ° C., and the resulting strand was cooled with water and cut to obtain pellets. The obtained pellets were again dried at 120 ° C. for 5 hours and then injection-molded at 300 ° C., 5 cm × 5 cm × 0.5 mm thick test piece, 5 cm × 5 cm × 1 mm thick test piece, 5 cm × 5 cm X A test piece having a thickness of 3.0 mm, a test piece of 90 mm x 10 mm x 4 mm, and a test piece of 110 mm x 13 mm x 4 mm were obtained.

  The Izod impact value and the flexural modulus were measured using the 90 mm × 10 mm × 4 mm test piece, and the load deflection temperature (HDT) was measured using the 110 mm × 13 mm × 4 mm test piece.

  Using a 2.5 cm × 2.5 cm × 1 mm thick test piece, the melt viscosity η ′ obtained by a rheometer was measured. Further, Tg (° C.) was obtained from a graph showing the temperature dependence of the storage elastic modulus E ′ (Pa) obtained with a dynamic viscoelasticity measuring apparatus using a test piece of 5 cm × 5 cm × thickness 1 mm.

  About the relative viscosity, the test piece obtained by each Example and the comparative example was cut | judged finely, it was made to melt | dissolve in a methylene chloride, the solution was obtained, and the relative viscosity was measured using the obtained solution.

  The results are shown in Table 1.

Comparative Example 1
The procedure was the same as in Example 1 except that no amide compound was added, and the flexural modulus, Izod impact resistance value, deflection temperature under load (HDT), melt viscosity η ′, relative viscosity and Tg (° C.) of the test piece were measured. The results are shown in Table 1.

Comparative Examples 2 and 3
The same procedure as in Examples 3 and 4 except that ethylene bisstearylamide (EBS) was used instead of the amide compound of the present invention, and the flexural modulus, Izod impact resistance value, deflection temperature under load (HDT), and melt viscosity of the test piece η ′ and relative viscosity and Tg (° C.) were measured. The results are shown in Table 1.

  In Comparative Example 2 and Comparative Example 3 in which ethylene bisstearylamide (EBS) was used instead of the amide compound of the present invention, a decrease in melt viscosity η ′ was observed compared to the blank molded body (Comparative Example 1). However, a decrease in Izod impact resistance and deflection temperature under load (HDT) was observed.

  On the other hand, in Examples 1-15 of this invention, compared with the blank molded object (comparative example 1), the fall of melt viscosity (eta) 'by the addition of an amide compound was recognized in all, and also heat resistance The Tg (° C.) and the deflection temperature under load (HDT), which are indicators of the above, were not lowered. This indicates that the amide compound of the example does not substantially reduce the heat resistance of the resin as compared with EBS.

  Further, in Examples 1 to 15 of the present invention, the Izod impact resistance value is slightly decreased as compared with the blank molded body (Comparative Example 1), but the degree is similar to that of the molded bodies of Comparative Examples 2 and 3. Smaller than that.

  In Examples 1 to 15 of the present invention, the relative viscosity is not substantially reduced as compared with the blank molded body (Comparative Example 1). This indicates that the decrease in melt viscosity is not due to a decrease in molecular weight.

Examples 16-30 (capillograph measurement)
Each amide compound obtained in the above Production Examples 1 to 5 was added to 100 parts by weight of a polycarbonate resin (Mitsubishi Resin Chemical Co., Ltd., “Iupilon S3000R”) dried at 120 ° C. for 5 hours in the proportions shown in Tables 2 to 4. The two components were mixed. The obtained mixture was melted and mixed at a resin temperature of 280 ° C. with an extruder, and the resulting strand was cooled with water and cut to obtain pellets. The obtained pellets were again dried at 120 ° C. for 5 hours, and then a capillographic measurement was performed.

  The results are shown in Tables 2-4.

Comparative Example 4
Capillographic measurement was performed using pellets prepared by giving the same thermal history as in Example 16 except that no amide compound was used. The results are shown in Table 2.

Comparative Examples 5 and 6
Capillograph measurement was carried out in the same manner as in Example 17 or 18 except that ethylene bisstearylamide (EBS) was used instead of the amide compound in each Example. The results are shown in Table 4.

  The addition of each amide compound confirmed the effect of reducing the viscosity under shear stress.

In Tables 2 to 4, the degree of viscosity reduction at each piston speed is also shown. The degree of viscosity reduction was determined according to the following formula:
Degree of thinning (%) = [(Vo−Va) / Vo] × 100
[In the formula, Vo represents the measured viscosity of a blank pellet (Comparative Example 4) at a given piston speed, and Va represents the measured viscosity of the pellet at the piston speed of the pellet containing the amide compound. ].

Example 31 and Comparative Example 7
Polycarbonate (manufactured by Mitsubishi Plastics, “Iupilon S3000R”) and 0.5 part by weight of 1,2,3-propanetricarboxylic acid tris (2-methylcyclohexylamide) were melt-kneaded at 250 ° C. for 5 minutes using a blast bender mill. . After the kneading, the melt index representing fluidity was measured. The results are shown in Table 5 together with a system (Comparative Example 7) which gave the same thermal history without using an amide compound.

Example 32 and Comparative Example 8
ABS resin (manufactured by Ube Industries, “Psycolac LM1101”) and 0.5 part by weight of 1,2,3-propanetricarboxylic acid tris (2-methylcyclohexylamide) at 260 ° C. at 8 ° C. at 8 ° C. Melted and kneaded for a minute. After the kneading, the melt index representing fluidity was measured. The results are shown in Table 5 together with a system (Comparative Example 8) which gave a similar thermal history without using an amide compound.

Example 33 and Comparative Example 9
Styrene resin (Mitsubishi Monsanto (currently Mitsubishi MKV), "High Impact Polystyrene HT-76") and 0.5 parts by weight of 1,2,3-propanetricarboxylic acid tris (2-methylcyclohexylamide) are blasted Melting and kneading was performed at 250 ° C. for 5 minutes using a bender mill. After the kneading, the melt index representing fluidity was measured. The results are shown in Table 5 together with a system (Comparative Example 9) which gave a similar thermal history without using an amide compound.

  From the results in Table 5, it can be seen that by adding the amide compound according to the present invention, the melt viscosity is lowered as compared with the resin not containing the amide compound.

Examples 34-42
Each amide compound obtained in the above Production Examples 1 to 5 was added in an amount shown in Table 6 to 100 parts by weight of a polycarbonate resin (manufactured by Mitsubishi Plastics, “Iupilon S3000R”) dried at 140 ° C. for 5 hours, These ingredients were mixed. The obtained mixture was melt-kneaded with an extruder at a resin temperature of 280 ° C., and the resulting strand was cooled with water and cut to obtain pellets.

  The obtained pellets were injection molded at 300 ° C. to obtain test pieces of 5 cm × 5 cm × thickness 3 mm. The total light transmittance (%) and haze value (%) of the test piece having a thickness of 3 mm were measured with a haze meter. The results are shown in Table 6.

Comparative Example 10
Except not mix | blending an amide compound, it carried out like Example 34 and measured the total light transmittance (%) and haze value (%). The results are shown in Table 6.

Comparative Examples 11-12
The same operation as in Example 34 was performed except that ethylene bisstearylamide (EBS) was used in the amounts shown in Table 6 in place of the amide compound of each Example, and the total light transmittance (%) and haze value (% ) Was measured. The results are shown in Table 6.

  From Table 6, it can be seen that the molded product containing ethylene bisstearylamide (EBS) (Comparative Examples 11 and 12) is less transparent than the molded product containing no amide compound (Comparative Example 10). Recognize. In contrast, it can be seen that the addition of the amide compound of the present invention has substantially no influence on the total light transmittance (%) and haze value (%).

  The amide compound represented by the general formula (1) of the present invention reduces the melt viscosity while substantially maintaining the mechanical properties and transparency without substantially reducing the heat resistance of the amorphous thermoplastic resin. It is effective. In particular, it is easy to improve the workability in film processing of amorphous thermoplastic resin, which has high viscosity when melted, and to make the molded product thinner and more precise in the molding process, shorten the molding cycle time, etc. Contributes to quality improvement.

Claims (8)

(a) an amorphous thermoplastic resin and
(b) General formula (1)
R ^1- (CONHR ² ) n (1)
[Wherein n represents an integer of 2 to 4 .
When n is 2, R ¹ represents a residue obtained by removing all carboxyl groups from naphthalenedicarboxylic acid , and two R ^{2 s} are the same or different and each has an alicyclic ring having 6 to 30 carbon atoms. It represents a residue obtained by removing an amino group from an aromatic monoamine, or a residue obtained by removing an amino group from an aromatic monoamine having 6 to 30 carbon atoms.
When n is 3 or 4 , R ¹ is a residue obtained by removing all carboxyl groups from 1,2,3,4- butanetetracarboxylic acid, and all carboxyls from 1,2,3-propanetricarboxylic acid. represents the residue obtained by removing all of the carboxyl group residue obtained by removing a group, or trimesic acid, 3 or 4 R ² are the same or different, each fat having a carbon number of 6 to 30 It represents a residue obtained by removing the amino groups from alicyclic monoamines. ]
Amorphous thermoplastic containing at least one amide compound represented by the formula, wherein the at least one amide compound is present in an amount of 0.001 to 10 parts by weight with respect to 100 parts by weight of the amorphous thermoplastic resin. Resin composition. The at least one amide compound represented by the general formula (1) is present in an amount of 0.001 to 3 parts by weight with respect to 100 parts by weight of the amorphous thermoplastic resin. A crystalline thermoplastic resin composition. The amorphous thermoplastic resin composition according to claim 1, wherein the amorphous thermoplastic resin is an amorphous engineering plastic. The amorphous thermoplastic resin composition according to claim 3 , wherein the amorphous engineering plastic is a polycarbonate resin. The molded object obtained by shape | molding the amorphous thermoplastic resin composition of Claim 1. The amorphous resin composition according to claim 1 is formed by injection molding, blow molding, extrusion molding, calendar molding, injection compression molding, injection blow molding, extrusion blow molding, injection extrusion blow molding, stretch blow molding, multilayer blow molding. A method for producing a molded article, comprising molding by any method of extrusion thermoform molding, spinning molding, rotational molding or sheet / film molding. General formula (1)
R ^1- (CONHR ² ) n (1)
[Wherein n represents an integer of 2 to 4 .
When n is 2, R ¹ represents a residue obtained by removing all carboxyl groups from naphthalenedicarboxylic acid , and two R ^{2 s} are the same or different and each has an alicyclic ring having 6 to 30 carbon atoms. It represents a residue obtained by removing an amino group from an aromatic monoamine, or a residue obtained by removing an amino group from an aromatic monoamine having 6 to 30 carbon atoms.
When n is 3 or 4 , R ¹ is a residue obtained by removing all carboxyl groups from 1,2,3,4- butanetetracarboxylic acid, and all carboxyls from 1,2,3-propanetricarboxylic acid. represents the residue obtained by removing all of the carboxyl group residue obtained by removing a group, or trimesic acid, 3 or 4 R ² are the same or different, each fat having a carbon number of 6 to 30 It represents a residue obtained by removing the amino groups from alicyclic monoamines. ]
A melt viscosity reducing agent for an amorphous thermoplastic resin, comprising at least one amide compound represented by the formula: The melt viscosity reducing agent for amorphous thermoplastic resins according to claim 7 , wherein the amide compound has a 5% weight loss temperature of 280 ° C or higher.

Images