JPH04366168A - Polyamide resin composition - Google Patents

Abstract

PURPOSE:To provide a polyamide resin composition having a wide mold temperature range and low adsorptivity and excelling in heat distortion temperature (HDT), mechanical strengths, etc. CONSTITUTION:A polyamide resin composition which comprises 100 pts.wt. aromatic polyamide of a melting point of 290 deg.C or above (e.g. an aromatic polyamide comprising dicarboxylic acid component units comprising 30-100mol% terephthalic acid component units and 0-70mol% aromatic dicarboxylic acid component units other than the terephthalic acid component units or comprising 30-100mol% terephthalic acid component units and aliphatic dicarboxylic acid component units and aliphatic alkylenediamine component units and/or alicyclic alkylenediamine component units and having an intrinsic viscosity [<=] as measured in concentrated sulfuric acid at 30 deg.C in the range of 0.5-3.0dl/g) and 0.5-200 pts.wt. glass fiber bundle prepared by treating glass fibers having a mean length in the range of 0.1-20mm with a carboxylic polymer.

Description

[Detailed description of the invention]

0001

TECHNICAL FIELD OF THE INVENTION The present invention relates to a polyamide resin composition, and more particularly, the present invention relates to a polyamide resin composition that has a wide molding temperature range, low water absorption, and excellent heat resistance stiffness (HDT), mechanical strength, etc. Regarding the composition.

0002

TECHNICAL BACKGROUND OF THE INVENTION Various aromatic polyamide compositions have been proposed in the past. For example, the applicant of the present application has already proposed [A]
Aromatic dicarboxylic acid component units (a) consisting of 60 to 100 mol% of terephthalic acid component units and 0 to 40 mol% of aromatic dicarboxylic acid component units other than terephthalic acid component units and carbon atoms of 6 to 18 A polyamide consisting of linear aliphatic alkylene diamine component units (b) and having [η] in the range of 0.5 to 3.0 dl/g measured at 30°C in concentrated sulfuric acid, and [B] the polyamide 100
The technology is disclosed for moldable polyamide compositions comprising from more than 0 to 200 parts by weight of filler. Further, it is disclosed that silica, silica alumina, alumina, graphite, etc. can be used as the filler [B].

[0003] Furthermore, in Japanese Patent Application Laid-Open No. 155426/1989, the following repetitive component:

0004

[Chemical formula 1]

[0005]...[a]

[0006]

[Case 2]

[0007]...[b] and

[0008]

[Chemical formula 3]

[0009] Crystalline polyamide copolymers consisting of [c] in which the molar ratio of a:b:c units is from about 60:20:20 to about 90:5:5 are described.

Furthermore, the same publication states that if about 10 to about 60% of glass fiber, glass beads, mineral fiber, graphite fiber, or a mixture thereof is blended with the polyamide copolymer, the water absorption rate is low, heat-resistant rigidity,
It is stated that a polyamide resin composition having excellent mechanical strength, impact resistance, etc. can be obtained.

[0011] However, in order to meet increasingly complex market needs such as performance and applications, further improvements in resin performance are expected.

0012

Purpose of the Invention The present invention is intended to meet the above market needs, and is intended to improve water absorption by blending a specific amount of specific glass fiber into an aromatic polyamide having a specific melting point. The object of the present invention is to provide a polyamide resin composition that has low heat resistance, excellent mechanical strength, impact resistance, and the like.

[0013]

[Summary of the invention] The polyamide resin composition according to the present invention is
[A] Aromatic polyamide with a melting point of 290°C or higher: 100
parts by weight, and [B] a glass fiber bundle obtained by treating glass fibers with an average length in the range of 0.1 to 20 mm with a carboxyl group-containing polymer: 0.5 to 200 parts by weight. It is a feature.

[0014] Furthermore, in a preferred embodiment of the present invention,
The above aromatic polyamide resin composition is made by combining 100 parts by weight of aromatic polyamide [A] with a melting point of 290°C or higher and glass fibers having an average length in the range of 0.1 to 20 mm using a carboxyl group-containing polymer. The treated glass fiber bundle [B] consists of 0.5 to 200 parts by weight, and the aromatic polyamide [A] consists of dicarboxylic acid component units (a) and diamine component units (b), The above dicarboxylic acid component unit (a) is terephthalic acid component unit: 30 to 100 mol%, aromatic dicarboxylic acid component unit other than terephthalic acid component unit: 0 to 70 mol% (i), or terephthalic acid component unit: 30 to 100 mol% and aliphatic dicarboxylic acid component units, preferably C4 to C12 aliphatic dicarboxylic acid component units: 0 to 70 mol% (ii), or terephthalic acid component units: 30 to 100 mol%, Aliphatic dicarboxylic acid component units, preferably aliphatic dicarboxylic acid component units having 4 to 12 carbon atoms: 0 to 70 mol%, and aromatic dicarboxylic acid component units other than terephthalic acid component units: 0 to 70 mol% (iii) The diamine component unit (b) consists of an aliphatic alkylene diamine component unit and/or an alicyclic alkylene diamine component unit, preferably a straight chain aliphatic alkylene diamine component unit having 6 to 18 carbon atoms, and The aromatic polyamide [A]
has an intrinsic viscosity [η] of 0.5 measured at 30°C in concentrated sulfuric acid.
-3.0 dl/g, and the glass fiber bundle [B] has an average length of 0.1 to 2.
It is characterized by being made by treating glass fibers in the range of 0 mm with a carboxyl group-containing polymer.

Since the polyamide resin composition according to the present invention is composed of the specific components as described above, it has a low water absorption rate and is excellent in heat resistance, mechanical strength, impact resistance, etc.

[0016]

DETAILED DESCRIPTION OF THE INVENTION As described below, the polyamide resin composition according to the present invention is composed of an aromatic polyamide [A] and a glass fiber bundle [B]. This will be explained in detail.

Aromatic polyamide [A] The aromatic polyamide [A] contained in the polyamide resin composition according to the present invention has a melting point of 290°C or higher, preferably 290°C or higher.
It is an aromatic polyamide in the range of 90 to 330°C.

Such an aromatic polyamide is composed of, for example, a dicarboxylic acid component unit (a) and a diamine component unit (b) as shown below. That is, this dicarboxylic acid component unit (a) may consist of (i) a terephthalic acid component unit and an aromatic dicarboxylic acid component unit other than terephthalic acid, or (ii) a terephthalic acid component unit, It may consist of an aliphatic dicarboxylic acid component unit, preferably an aliphatic dicarboxylic acid component unit having 4 to 12 carbon atoms, or (iii) a terephthalic acid component unit and an aliphatic dicarboxylic acid component unit, preferably an aliphatic dicarboxylic acid component unit. is an aliphatic dicarboxylic acid component unit having 4 to 12 carbon atoms,
It may also consist of aromatic dicarboxylic acid component units other than terephthalic acid.

Examples of aromatic dicarboxylic acid component units other than terephthalic acid component units include those derived from isophthalic acid (IA), phthalic acid, 2-methylterephthalic acid, naphthalene dicarboxylic acid, etc. Component units can be mentioned. Among aromatic dicarboxylic acid component units other than these terephthalic acid component units, component units derived from isophthalic acid or naphthalene dicarboxylic acid are preferred, and isophthalic acid component units are particularly preferred.

Furthermore, the aliphatic dicarboxylic acid component unit is
The number of carbon atoms is not particularly limited, but preferably 4 carbon atoms.
-25, more preferably 4-12 aliphatic dicarboxylic acids.

Examples of aliphatic dicarboxylic acids used to derive such aliphatic dicarboxylic acid component units include succinic acid, adipic acid (AA), azelaic acid,
Mention may be made of sebacic acid, decanedicarboxylic acid, undecanedicarboxylic acid and dodecanedicarboxylic acid.

Among these, adipic acid (AA) is particularly
is preferred. In the present invention, dicarboxylic acid component units (
a) is a terephthalic acid component unit, an aromatic dicarboxylic acid component unit other than the terephthalic acid component unit, and/or an aliphatic dicarboxylic acid component unit, preferably having 4 to 12 carbon atoms.
aliphatic dicarboxylic acid component units, the terephthalic acid component units are 30 to 100 mol%, preferably 40 to 100 mol%, in 100 mol% of the dicarboxylic acid component units.
It is desirable that the aromatic dicarboxylic acid component units other than the terephthalic acid component units are contained in an amount of 0 to 70 mol%, preferably 30 to 60 mol%. Further, the aliphatic dicarboxylic acid component unit preferably has 0 to 7 carbon atoms.
It is desirable that the content is 0 mol%, preferably 30 to 60 mol%.

The dicarboxylic acid component unit (a) contains a terephthalic acid component unit, an aromatic dicarboxylic acid component unit other than the terephthalic acid component unit, and/or an aliphatic dicarboxylic acid component unit in the amounts described above. A molded article obtained from a composition containing an aromatic polyamide [A] consisting of such a dicarboxylic acid component unit (a) and a diamine component unit (b) as described below has good heat aging resistance and heat deformation resistance. It has excellent heat resistance properties such as temperature resistance, mechanical properties such as tensile strength and abrasion resistance, and physical and chemical properties such as chemical resistance and water resistance.

In the present invention, as the dicarboxylic acid component unit (a), a small amount, for example, 10 The polyhydric carboxylic acid component unit may be contained in an amount of about mol % or less. Specific examples of such polyhydric carboxylic acid component units include tribasic acids and polybasic acids such as trimellitic acid and pyromellitic acid.

In the present invention, aromatic polyamide [A]
The diamine component unit (b) constituting may be composed only of aliphatic diamine component units, or may be composed of aliphatic diamine component units and alicyclic diamine component units, It may consist only of system diamine component units.

[0026] Such aliphatic diamine component units are
It may be a linear alkylene diamine component unit or a branched chain alkylene diamine component unit. Among such aliphatic diamine component units, linear or branched chain alkylene diamine component units having 4 to 25 carbon atoms are preferred, and linear alkylene diamine component units having 6 to 18 carbon atoms are more preferred. A linear or branched alkylene diamine component unit is preferable.

Specific examples of such aliphatic diamine component units include 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1 , 10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, etc. component units derived from linear alkylene diamines such as 1,4-diamino-1,1-dimethylbutane, 1, 4-diamino-1-ethylbutane,
1,4-diamino-1,2-dimethylbutane, 1,4-
Diamino-1,3-dimethylbutane, 1,4-diamino-1,4-dimethylbutane, 1,4-diamino-2,3
-dimethylbutane, 1,2-diamino-1-butylethane, 1,6-diamino-2,5-dimethylhexane, 1
, 6-diamino-2,4-dimethylhexane, 1,6-
Diamino-3,3-dimethylhexane, 1,6-diamino-2,2-dimethylhexane, 1,6-diamino-2
, 2,4-trimethylhexane, 1,6-diamino-2
, 4,4-trimethylhexane, 1,7-diamino-2
, 3-dimethylheptane, 1,7-diamino-2,4-
Dimethylheptane, 1,7-diamino-2,5-dimethylheptane, 1,7-diamino-2,2-dimethylheptane, 1,8-diamino-1,3-dimethyloctane,
1,8-diamino-1,4-dimethyloctane, 1,8
-Diamino-2,4-dimethyloctane, 1,8-diamino-3,4-dimethyloctane, 1,8-diamino-
4,5-dimethyloctane, 1,8-diamino-2,2
-dimethyloctane, 1,8-diamino-3,3-dimethyloctane, 1,8-diamino-4,4-dimethyloctane, 1,6-diamino-2,4-diethylhexane, 1,9-diamino-5 - Component units derived from branched chain alkylene diamines such as methylnonane can be mentioned.

Among such linear or branched chain alkylene diamine component units, linear alkylene diamine component units are preferred, particularly 1,6-
Diaminohexane, 1,8-diaminooctane, 1,1
Preferably, the component unit is derived from one or more compounds of linear alkylene diamines such as 0-diaminodecane and 1,12-diaminododecane.

The alicyclic diamine component unit is usually a component unit derived from a diamine having about 6 to 25 carbon atoms and containing at least one alicyclic hydrocarbon ring.

Specific examples of such alicyclic diamine component units include 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, and 1,4-diaminocyclohexane. -Bis(aminomethyl)cyclohexane, isophoronediamine, piperazine, 2,5-dimethylpiperazine, bis(4-aminocyclohexyl)methane, bis(4-aminocyclohexyl)propane, 4,4'-diamino-3,3'-
dimethyldicyclohexylpropane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,
4'-diamino-3,3'-dimethyl-5,5'-dimethyldicyclohexylmethane, 4,4'-diamino-3
, 3'-dimethyl-5,5'-dimethyldicyclohexylpropane, α-α'-bis(4-aminocyclohexyl)-p-diisopropylbenzene, α-α'-bis(
4-aminocyclohexyl)-m-diisopropylbenzene, α-α'-bis(4-aminocyclohexyl)-
Examples include component units derived from alicyclic diamines such as 1,4-cyclohexane and α-α'-bis(4-aminocyclohexyl)-1,3-cyclohexane.

Among these alicyclic diamine component units, bis(aminomethyl)cyclohexane, bis(4-
aminocyclohexyl)methane, 4,4'-diamino-
3,3'-dimethyldicyclohexylmethane is preferred, especially bis(4-aminocyclohexyl)methane, 1,
Component units derived from alicyclic diamines such as 3-bis(aminocyclohexyl)methane and 1,3-bis(aminomethyl)cyclohexane are preferred.

In the present invention, the polyamide [A] can have a structure in which a component unit derived from the above-mentioned dicarboxylic acid and a component unit derived from a diamine are appropriately combined as repeating units, and a single structure can be used. does not mean.

For example, a repeating unit in which the dicarboxylic acid component unit is derived from terephthalic acid and the diamine component unit is derived from hexamethylene diamine has the following formula [I
].

[0034]

[C4]

[0035] The aromatic polyamide [A] may be formed only from repeating units represented by the above formula [I], but may also be formed from an aromatic dicarboxylic acid component unit other than terephthalic acid and an aliphatic acid component unit. Alternatively, it may have a repeating unit consisting of an alicyclic diamine component unit.

A repeating unit in which the aromatic dicarboxylic acid component unit other than terephthalic acid is derived from isophthalic acid and the diamine component unit is derived from hexamethylene diamine is represented by the following formula [II].

[0037]

[C5]

Further, a repeating unit in which the dicarboxylic acid component unit is derived from adipic acid of an aliphatic dicarboxylic acid and the diamine component unit is derived from hexamethylene diamine can be represented by the following formula [III]. -(-CO-(CH2)4-CO-NH-(CH2)6
-NH-)-

...[III
] The polyamide [A] constituting the polyamide composition according to the present invention may be, for example, a mixture of polyamides consisting only of any one type of repeating unit among the above [I] to [III], and It may be a polyamide formed by bonding a low molecular weight unit consisting of only one type of repeating unit among the above [I] to [III], or it may be a polyamide formed by a mixture of these repeating units. It may also be a mixture of these various polyamides, and the composition of the polyamide [A] is not particularly limited.

In any case, these repeating units are
Molar ratio (mol%) of each component unit as described above
It is contained in polyamide [A] in such a proportion that The polyamide [A] used in the polyamide resin composition of the present invention has an intrinsic viscosity [η] of 0.5 to 3.0 dl/g, preferably 0 as measured in concentrated sulfuric acid at a temperature of 30°C.
．． Use one within the range of 8 to 1.5 dl/g.

[0040] Furthermore, in the present invention, such a polyamide has a melting point of 290°C or higher, preferably a melting point of 290°C or higher.
A temperature within the range of ~330°C is preferably used. When a polyamide with a melting point of 290° C. or higher is used in this way, the resulting polyamide resin composition tends to have low water absorption and excellent heat-resistant rigidity, mechanical strength, impact resistance, etc.

[0041] Such polyamide [A] is, for example,
It can be manufactured using a conventionally known method. For example, Polymer Reviews, 10, C
on-densation Polymers by
Interfacial and Solution M
methods (by P.W. Morgan), Int.
er-science Publishers (196
5) or Makromol. Chem. ,47,
93-113 (1961),
Polyamide [A] can be obtained by polycondensing a diacid halide of an aromatic dicarboxylic acid from which the constituent units of polyamide [A] described above can be derived and a diamine using a solution method. Polyamide [A] can also be obtained by interfacial polymerization.

Further, an aromatic dicarboxylic acid corresponding to the aromatic dicarboxylic acid component unit and a diamine or a polyamide salt thereof corresponding to the diamine component unit are melted in the presence or absence of a solvent such as water. Polyamide [A] can be obtained by polycondensation according to the method.

[0043] Furthermore, polyamide [A] can also be obtained by producing an oligomer using the above-mentioned solution method or the like, and then further polycondensing it using a solid phase polymerization method or a melt method using a kneading device.

The diamine component units constituting the polyamide [A] may include aromatic diamine component units in addition to the above-mentioned alkylene diamine component. Specific examples of such aromatic diamine component units include component units derived from aromatic diamines such as m-xylylene diamine and p-xylylene diamine. These aromatic diamines can be used alone or in combination of two or more.

Glass fiber bundle [B] The glass fiber bundle [B] used in the present invention uses a carboxyl group-containing polymer as a sizing agent, and has an average length of 0.1 to 20 mm. Preferably 1-10m
It is made by focusing glass fibers in the range of m.

In this glass fiber bundle [B], the carboxyl group-containing polymer contains a total of 10 glass fibers and a sizing agent.
0 parts by weight, 0.1 to 10% by weight, preferably 0.2% by weight
It is contained in an amount of ~0.5% by weight.

This carboxyl group-containing polymer, ie, a modified polymer modified with the following modifier, is as follows:
For example, graft copolymers of polyethylene and maleic anhydride, graft copolymers of polypropylene and maleic anhydride, graft copolymers of polybutadiene and maleic anhydride, graft copolymers of polyethylene and acrylic acid, and graft copolymers of polypropylene and acrylic acid. graft copolymer,
Examples include copolymers of polybutadiene and acrylic acid, graft copolymers of polyethylene and methacrylic acid, graft copolymers of polypropylene and methacrylic acid, and graft copolymers of polybutadiene and methacrylic acid.

The carboxyl group-containing polymer used as a sizing agent can be obtained by graft-modifying various polymers as described below with a carboxyl group-containing compound (modifier) such as an unsaturated carboxylic acid or a derivative thereof. It will be done.

The grafting amount of the unsaturated carboxylic acid or its derivative modifying the above polymer is about 0.1 to 5.0% by weight, preferably 0.5 to 1.0% by weight, based on the weight of the polymer. It is 0% by weight.

If the graft polymerization amount of the carboxyl group-containing compound as the modifier, ie, the unsaturated carboxylic acid or its derivative, is less than 0.1% by weight, the adhesion to glass will be poor. On the other hand, when the amount of graft polymerization is 5.0% by weight or more, the thermal stability of the sizing agent deteriorates, and the sizing agent (resin) tends to be colored when melted.

Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid TM (endocys-bicyclo[2, 2,1]hept-5-ene-2,3-dicarboxylic acid).

Examples of derivatives include acid halide compounds, amide compounds, imide compounds, acid anhydrides, and ester compounds of the above-mentioned unsaturated carboxylic acids.

Specifically, maleyl chloride, maleimide,
Maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate and glycidyl maleate, (meth)acrylate compounds (e.g. acrylic acid, methacrylic acid, alkyl esters of (meth)acrylic acid (
Examples: Methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate), (meth)acrylic acid compounds having hydroxy groups (Example: 2-hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxymethyl acrylate, 2
-hydroxyethyl acrylate), vinyl acetate, and the like.

Among the above-mentioned carboxylic acids and derivatives thereof, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are particularly preferred. Note that there is no particular limitation on the grafting position of the unsaturated carboxylic acid or its derivative to be grafted onto the polymer, as long as it is bonded to any (random) carbon atom of the polymer.

Polymers to be subjected to graft modification include olefin resin compositions [for example, polyolefins such as polyethylene and polypropylene, ethylene/α-olefin (random/graft) copolymers], cyclic olefin polymers, or cyclic olefins. type resin composition (hereinafter, both are also referred to as cyclic olefin resin composition)
In addition to these, examples include polystyrene, acrylonitrile-butadiene-styrene copolymer, polycarbonate, polyalkylene terephthalate, polyvinyl chloride, and the like. These polymers may be used alone or in combination.

Modification method Next, as an example, regarding the modification method of the above polymer,
The graft modification of the olefin random copolymer composition with the unsaturated carboxylic acid or its derivative will be described.

[0057] When producing a modified product by graft polymerizing an unsaturated carboxylic acid or its derivative (graft monomer) onto an olefin random copolymer composition, it can be produced using various known methods. .

[0058] In producing the olefin random polymer composition, for example, the olefin random copolymer composition can be melted and an unsaturated carboxylic acid or the like can be added thereto for graft copolymerization.

In some cases, the olefin random copolymer composition can be dissolved in a solvent and graft copolymerized. In any case, in order to efficiently graft copolymerize the graft monomer, it is preferable to carry out the graft reaction in the presence of a radical initiator.

In this case, the radical initiator is usually used in an amount of 0.005 to 0 with respect to 100 parts by weight of the random copolymer.
．． It is used in an amount within the range of 8 parts by weight. As such a radical initiator, organic peroxides, organic peresters, azo compounds, etc. can be used.

Specific examples of such radical initiators include dicumyl peroxide, di-tert-butyl peroxide, and 2,5-dimethyl-2,5-di(tert).
Dialkyl peroxides such as t-butylperoxy)hexane-3, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and 1,4-bis(tert-butylperoxyisopropyl)benzene are preferably used.

[0062] The reaction temperature of the graft reaction using a radical initiator as described above or the graft reaction carried out without using a radical initiator is usually set within the range of 60 to 350°C.

In order to graft-polymerize an unsaturated carboxylic acid or a derivative thereof to the olefin random copolymer composition, for example, the raw material polymers ethylene random copolymer (P), propylene random copolymer (P), etc. Q
) etc. Furthermore, various methods can be employed in addition to a method in which a composition is prepared by mixing various formulations in advance, and the above-mentioned graft monomer is blended into this composition to perform graft modification.

That is, in addition to the method described above, for example, the ethylene random copolymer (P) and the propylene random copolymer (Q) may be graft-polymerized separately, and then both may be combined in a desired ratio. Blending method, method of blending grafted ethylene random copolymer (P) and ungrafted propylene random copolymer (Q) in a predetermined ratio, grafted propylene random copolymer (P) and Examples include a method of blending a non-grafted ethylene random copolymer (Q) at a predetermined ratio.

[0065] When modifying other polymers, the same procedure as above may be used. To bundle glass fibers with such a carboxylic acid group-containing polymer, a sizing agent is applied in advance to a roller called a sizing agent applicator, and the glass fibers are coated with the sizing agent in this way. A common method is used in which the sizing agent is transferred and applied to the glass fibers by contact with a roller.

Glass fiber bundle [B
] is based on 100 parts by weight of aromatic polyamide [A],
It is contained in the aromatic polyamide resin composition of the present invention in an amount of 0.5 to 200 parts by weight, preferably in an amount of 1 to 150 parts by weight, and more preferably in an amount of 10 to 100 parts by weight.

[0067] If glass fiber [B] is blended in an amount less than 0.1 part by weight with respect to 100 parts by weight of aromatic polyamide [A], the effect on heat distortion temperature, high temperature rigidity, etc. It is hardly recognized, and even if it is blended in an amount exceeding 200 parts by weight, there is almost no change in the heat distortion temperature, etc.

Manufacture of aromatic polyamide resin composition The aromatic polyamide resin composition according to the present invention is produced by, for example, preparing the aromatic polyamide [A] in a molten state, for example, 290-3
This polyamide [A] is heated and maintained at 60°C,
It can be prepared by a method such as blending a glass fiber bundle [B] using a carboxyl group-containing polymer as a sizing agent.

[0069] At this time, an extruder, a kneader, etc. can be used. The polyamide resin composition according to the present invention as described above can be molded by a conventional melt molding method, such as a compression molding method, an injection molding method, or an extrusion molding method.

As described above, the polyamide resin composition of the present invention contains aromatic polyamide [A] and glass fiber bundle [B] using a carboxyl group-containing polymer as a sizing agent as essential components. However, in addition to these essential ingredients, if necessary, powder fillers, antioxidants, ultraviolet absorbers, photoprotectants, heat stabilizers, phosphite stabilizers, and peroxide decomposers may be added in addition to the above. , a basic adjuvant, a nucleating agent, a plasticizer, a lubricant, an antistatic agent, a flame retardant, a pigment, a dye, etc.

Specific examples of the powder filler include silica, silica alumina, alumina, talc, graphite, titanium dioxide, molybdenum disulfide, and polytetrafluoroethylene. The use of such a powdered filler improves mechanical properties such as tensile strength, bending strength, and flexural modulus, heat resistance properties such as heat distortion temperature, and water resistance of molded articles obtained from aromatic polyamide resin compositions. There is a tendency for physical and chemical properties to improve.

These powdery fillers are usually used in an amount of 0.01 to 10 parts by weight per 100 parts by weight of the aromatic polyamide [A].
It is used in an amount of 0.1 to 5 parts by weight, preferably 0.1 to 5 parts by weight. In the case of a powdered filler, the particle size in the molding material is preferably 0.1 μm to 200 μm, preferably 0.1 μm to 50 μm in average particle size.

If the fine particles are larger than the above value, mechanical strength and appearance defects will occur due to the foreign substance effect. Note that the particle diameter can be measured using an image analyzer or the like. The aromatic polyamide resin composition according to the present invention can be used in fields where particularly excellent heat resistance and excellent chemical resistance are required, or in the precision molding field, specifically in the automotive parts, electrical, It is used in a variety of applications, including electrical components such as connectors, coil bobbins, and housings used in the electronic field.

[0074]

Effects of the Invention The aromatic polyamide resin composition according to the present invention has a low water absorption rate since the aromatic polyamide as described above is blended with the glass fiber bundle as described above in the amount as described above. It has low heat resistance and excellent mechanical strength.

[0075]

[Examples] The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

[0076]

[Example 1] [Synthesis of aromatic polyamide] 255.6 g (2.2 M) of 1,6-diaminohexane, 25 g of terephthalic acid (TA)
5.8g (1.54M), isophthalic acid (IA) 109
．． 6g (0.66M), 0.47g (4.4 x 10-3M) of sodium hypophosphite as a catalyst, and 1 ton of ion-exchanged water.
46 ml was charged into a 1.0 liter reactor, and after purging with nitrogen, the reaction was carried out at 250° C. and 35 kg/cm 2 for 1 hour. After the reaction is completed, the reactor is discharged to a receiver whose pressure is set approximately 10 kg/cm2 lower than that of the reactor, and the intrinsic viscosity [η] is 0.1.
0 dl/g (concentrated sulfuric acid 30°C) polyamide oligomer 5
30g was obtained.

Next, after drying this polyamide, it was melt-polymerized using a twin-screw extruder at a cylinder temperature of 345°C, so that the intrinsic viscosity [η] was 1.14 dl/g (concentrated sulfuric acid 30
℃) aromatic polyamide was obtained.

The amount of terephthalic acid component units in this aromatic polyamide was 70 mol %, and the melting point was 325°C. [Manufacture of polyamide resin composition] Twin screw extruder with vent [
Glass fiber [03MA- manufactured by Asahi Fiberglass Co., Ltd., manufactured by Ikegai Tekko Co., Ltd., model number PCM-45] using 60 parts by weight of the above aromatic polyamide and a carboxylic acid group-containing polymer as a sizing agent FT2A, average length: 3mm]
40 parts by weight was supplied from the vent and granulated at 330°C.

The pellets of the polyamide resin composition thus obtained were molded using an injection molding machine [IS-50 manufactured by Toshiba Machine Co., Ltd.].
] A test piece was injection molded under the following conditions. [Injection molding conditions] Cylinder temperature (℃): 320/330/330/
330 Injection pressure (Kg/cm2): Primary/Secondary =
1000/800 Mold temperature (°C): 120 The above test piece was evaluated for bending properties, heat resistance, etc. according to the following method.

The results are shown in Table 1. [Evaluation method] Bending properties: A bending test is conducted using a test piece measuring 3.2 mm x 12.7 mm x 127 mm in accordance with ASTM D 790 to determine bending strength and bending modulus.

Heat resistance: Evaluation of heat resistance is carried out at the heat distortion temperature. The heat distortion temperature is 18 according to ASTM D 648.
．． Size 6.4 with bending stress of 6Kg/cm2
A test piece of mm x 12.7 mm x 127 mm is heated at a rate of 2° C. per minute, and the temperature is set when the amount of deflection reaches 0.254 mm.

Tensile strength and tensile elongation: According to ASTM D 638. Izod impact strength (notched and non-notched):
Compliant with ASTM D 256.

[0083]

[Examples 2 to 6] In Example 1, the molar ratio of dicarboxylic acid component units, that is, the molar ratio of terephthalic acid (TA): isophthalic acid (IA): adipic acid (AA) component units, was as shown in Table 1. Example 1 except that the cylinder temperature of the twin-screw extruder, the amount of glass fiber, and various conditions during polymer production were changed as shown in Table 1.
The same is true.

The results are also shown in Table 1.

[0085]

[Example 7] The dicarboxylic acid component units of Example 1 were combined with terephthalic acid (TA), isophthalic acid (IA), and sebacic acid (
SA), and the molar ratio of each is changed to TA:I
The procedure was the same as in Example 1 except that an aromatic polyamide synthesized with A:SA=70:20:10, having an intrinsic viscosity [η] of 1.18 dl/g and a melting point of 312°C was used.

The results are shown in Table 1.

[0087]

[Comparative Example 1] The same procedure as described in Table 1 was carried out in Example 1, except that glass fiber using an epoxy group-containing polymer as a sizing agent [03MA486A manufactured by Asahi Fiberglass Co., Ltd., average length: 3 mm] was used. did.

The results are shown in Table 1.

[0089]

[Comparative Examples 2 to 9] Glass fibers as shown in Table 1, that is, glass fibers using a urethane-containing polymer as a sizing agent, were added to the aromatic polyamide resin having dicarboxylic acid component units and molar ratios in Examples 2 to 7. [03 MAFT 558 manufactured by Asahi Fiberglass Co., Ltd., average length: 3 mm
The procedure was the same as in Examples 2 to 7 except that ] was used.

The results are also shown in Table 1.

[0091]

[Table 1]

[0092]

[Table 2]

[0093]

[Table 3]

[0094]

[Table 4]

Claims (3)

[Claims] Claim 1: [A] 100 parts by weight of an aromatic polyamide with a melting point of 290°C or higher, and [B] an average length of 0.1 to 2.
Glass fiber bundle made by treating glass fibers in the range of 0 mm with a carboxyl group-containing polymer: 0.5 to 20
A polyamide resin composition consisting of 0 parts by weight. 2. The aromatic polyamide [A] is (a
) Dicarboxylic acid component unit is terephthalic acid component unit: 3
0 to 100 mol% and aromatic dicarboxylic acid component units other than terephthalic acid component units: 0 to 70 mol%, or terephthalic acid component units: 30 to 100 mol% and aliphatic dicarboxylic acid component units: 0 to 70 mol% ,or,
Terephthalic acid component units: 30 to 100 mol%, aliphatic dicarboxylic acid component units: 0 to 70 mol%, and aromatic dicarboxylic acid component units other than terephthalic acid component units 0 to 7
(b) The diamine component unit is composed of an aliphatic alkylene diamine component unit and/or an alicyclic alkylene diamine component unit, and the intrinsic viscosity [η] measured at 30°C in concentrated sulfuric acid is 0. The polyamide resin composition according to claim 1, wherein the polyamide resin composition is an aromatic polyamide having a melting point in the range of .5 to 3.0 dl/g and a melting point of 290°C or higher. 3. The aromatic polyamide [A] comprises (a) dicarboxylic acid component units, terephthalic acid component units: 30 to 30;
100 mol%, aliphatic dicarboxylic acid component units having 4 to 12 carbon atoms: 0 to 70 mol%, and aromatic dicarboxylic acid component units other than terephthalic acid component units: 0 to 70 mol%
(b) The diamine component unit consists of a linear aliphatic alkylene diamine component unit having 6 to 18 carbon atoms, and the intrinsic viscosity [η] measured at 30°C in concentrated sulfuric acid is 0.5 to 3.0.
The polyamide resin composition according to claim 1, wherein the polyamide resin composition is an aromatic polyamide having a melting point of 290° C. or higher.