WO2021039661A1 - Method for producing composite molded body - Google Patents

Abstract

A method for producing a composite molded body by welding two or more molded bodies, wherein: the molded bodies are polyamide resin molded bodies; at least one of the polyamide resin molded bodies is a molded body of a polyamide resin composition that is obtained using at least (A) a polyamide, (B) an elastomer and (C) a chain extender; and the two or more molded bodies are welded with each other by means of vibration.

Description

Manufacturing method of composite molded product

The present invention relates to a method for producing a composite molded product in which a polyamide resin molded product is welded using a welding technique.

In recent years, with the tightening of carbon dioxide emission regulations for automobiles, the need for weight reduction of automobile bodies has increased, and metal parts are being made into resins. The merits of using resin include not only weight reduction, but also improved workability, noise reduction, and a high degree of freedom in shape.

In order to further enhance the superiority of shape freedom, a method has been developed in which a plurality of primary molded products are combined and welded to manufacture various hollow molded parts that are difficult to mold by general injection molding. Examples of the method include a vibration welding method, an ultrasonic welding method, a hot plate welding method, a laser welding method, and an injection welding method. The vibration welding method and ultrasonic waves are used because of the reliability of the joint and the wide range of application. A method of welding a molded body by vibration, such as a welding method, is attracting attention.

Since polyamide resin has excellent mechanical strength, toughness, heat resistance, and chemical resistance, composite molded products using the above welding technology are being actively developed even in automobile applications. In particular, since the physical characteristics of the welded portion are generally inferior to those of the primary molded product, a method for improving the physical characteristics of the welded portion has been proposed. For example, Patent Document 1 shows that a composite molded product produced by injection welding has high welding strength by using a polyamide containing a specific amount of triamine units. Patent Document 2 discloses that the weldability and impact resistance of a composite molded product are improved by containing a specific amount of an expensive alcohol compound and a phosphorus-containing compound in a polyamide resin. Patent Document 3 discloses that the tensile elongation of a welded portion is improved by blending an amide wax with a composition containing polyamide and glass fiber.

International release 2015/040863 JP 2018-012760 JP-A-2019-108526

When a composition containing an elastomer was welded in order to improve the toughness and impact resistance of the composite molded product, the toughness of the welded portion was low, and it was difficult to obtain sufficient characteristics as the composite molded product. In Patent Documents 1 to 3, there is no disclosure about the weldability of the composition containing the elastomer, and there is room for improvement in the toughness of the composite molded product.

The present invention provides a manufacturing method capable of obtaining a composite molded product having high toughness in view of these conventional techniques.

As a result of diligent studies to solve the above problems, the present inventors have conceived the following inventions and found that the problems can be solved.
That is, the present invention is as follows.

In the manufacture of a composite molded body in which two or more molded bodies are welded together
The molded product is a polyamide resin molded product.
At least one of the above-mentioned polyamide resin molded articles is a molded article of a polyamide resin composition obtained by using at least a polyamide (A), an elastomer (B), and a chain extender (C).
A method for producing a composite molded body, in which the two or more molded bodies are welded by vibration.

According to the present invention, it is possible to provide a manufacturing method capable of obtaining a composite molded product having high toughness.

It is a schematic diagram of the flat plate produced in Example and Comparative Example. It is a schematic diagram of the composite molded body produced in Example and Comparative Example. It is a schematic diagram of the test piece for a tensile test produced in an Example and a comparative example.

Hereinafter, description will be made based on an example of an embodiment of the present invention. However, the embodiments shown below are examples for embodying the technical idea of the present invention, and the present invention is not limited to the following description.
Further, although the preferred embodiment of the embodiment is shown in the present specification, a combination of two or more individual preferred embodiments is also a preferred embodiment. When there are several numerical ranges for the items shown in the numerical range, the lower limit value and the upper limit value thereof can be selectively combined to form a preferable form.
In this specification, when the numerical range of "XX to YY" is described, it means "XX or more and YY or less".

<Polyamide resin molded product>
In the embodiment of the present invention, the composite molded product is produced by welding two or more polyamide resin molded products by vibration.
At least one of the polyamide resin molded articles is a molded article (hereinafter, may be referred to as "molded article X") of the polyamide resin composition (hereinafter, may be referred to as "composition X") described later. is there.
A molded product made of polyamide is relatively easy to weld, but the molded product tends to be brittle with polyamide alone, so that sufficient mechanical properties may not be obtained. It is conceivable to add an elastomer as a resin material in order to improve the brittleness of the polyamide molded product, but there is a problem that it becomes difficult to weld the molded product by blending the elastomer with the polyamide. According to the present invention, a composite molded product having sufficient mechanical properties and excellent toughness can be obtained by vibration welding the molded product X of the composition X containing a chain extender in addition to the polyamide and elastomer. It is possible.
Further, in the present invention, it is also important to weld the above-mentioned polyamide resin molded product by vibration. By adopting welding accompanied by vibration, deterioration of the welded joint surface is suppressed, and excellent toughness can be exhibited.

The composition for forming the other polyamide resin molded body (that is, the molded body to be welded to the molded body X) may be the same as the composition X forming the other molded body X, but is not the same. It may be a composition included in the technical scope of X.
The above-mentioned "compositions that are not the same but are included in the technical scope of the composition X" include, for example, in the composition X that forms one molded product X and the composition that forms the other polyamide resin molded product. Examples thereof include compositions having the same components but different amounts, or compositions having different optional components.
Further, the composition for forming the other polyamide resin molded product may be a polyamide resin composition different from the composition X. Examples of the polyamide resin composition different from the composition X include a polyamide resin composition using polyamide (A) and elastomer (B) as a matrix resin and not using a chain extender (C).
From the viewpoint of ease of welding, it is preferable to use a polyamide having a melting point close to that of the polyamide (A) used in one molded product X as the composition for forming the other polyamide resin molded product, and the melting points of both polyamides are preferable. The difference between the two is more preferably 5 ° C. or less.

[Polyamide resin composition (composition X)]
Composition X is obtained using at least polyamide (A), elastomer (B) and chain extender (C). Since the polyamide (A), the elastomer (B) and the chain extender (C) can react during melt-kneading, the composition X contains a structure derived from each component, and in addition, each unreacted component is also included. Can be included.

<Polyamide (A)>
The polyamide (A) is preferably a semi-aromatic polyamide from the viewpoint of toughness, heat resistance and chemical resistance.
In the present invention, the semi-aromatic polyamide is mainly a polyamide containing a dicarboxylic acid unit containing an aromatic dicarboxylic acid unit as a main component and a diamine unit containing an aliphatic diamine unit as a main component, or an aliphatic dicarboxylic acid unit. A polyamide containing a dicarboxylic acid unit as a component and a diamine unit containing an aromatic diamine unit as a main component. Here, the term "main component" means that 50 to 100 mol%, preferably 60 to 100 mol%, of all the units are composed.
In the present specification, "-unit" (here, "-" indicates a monomer) means "a structural unit derived from", and for example, "dicarboxylic acid unit" means "dicarboxylic acid". It means "a constituent unit derived from", and "diamine unit" means "a constituent unit derived from diamine".

As the semi-aromatic polyamide used in the present invention, a polyamide containing a dicarboxylic acid unit containing an aromatic dicarboxylic acid unit as a main component and a diamine unit containing an aliphatic diamine unit as a main component is preferable. Among them, a dicarboxylic acid unit containing 50 to 100 mol% of an aromatic dicarboxylic acid unit with respect to the total dicarboxylic acid unit and 60 to 100 mol% of an aliphatic diamine unit having 4 to 13 carbon atoms with respect to the total diamine unit. A semi-aromatic polyamide containing a diamine unit is more preferable.
The total content of the total dicarboxylic acid unit and the total diamine unit in the semi-aromatic polyamide is preferably 60 to 100 mol% with respect to 100 mol% of all the monomer units constituting the semi-aromatic polyamide. , 80 to 100 mol% is more preferable, 90 to 100 mol% is further preferable, and it may be 100 mol%.

(Dicarboxylic acid unit)
The dicarboxylic acid unit constituting the semi-aromatic polyamide preferably contains 50 to 100 mol% of the aromatic dicarboxylic acid unit with respect to the total dicarboxylic acid unit. When a semi-aromatic polyamide containing an aromatic dicarboxylic acid unit in this proportion is used, a polyamide resin composition having good toughness, heat resistance and chemical resistance can be obtained. The content of the aromatic dicarboxylic acid unit in the total dicarboxylic acid unit is more preferably 75 to 100 mol%, further preferably 90 to 100 mol%.

Examples of the aromatic dicarboxylic acid unit include terephthalic acid unit, naphthalenedicarboxylic acid unit (2,6-naphthalenedicarboxylic acid unit, 2,7-naphthalenedicarboxylic acid unit, 1,4-naphthalenedicarboxylic acid unit, etc.), isophthalic acid unit, and the like. 1,4-phenylenedioxydiacetic acid unit, 1,3-phenylenedioxydiacetic acid unit, diphenylic acid unit, diphenylmethane-4,4'-dicarboxylic acid unit, diphenylsulfone-4,4'-dicarboxylic acid unit, 4 , 4'-biphenyldicarboxylic acid unit and the like. The dicarboxylic acid unit may contain one or more of these aromatic dicarboxylic acid units.
Among these, the aromatic dicarboxylic acid unit is preferably a terephthalic acid unit and / or a naphthalene dicarboxylic acid unit. Therefore, the semi-aromatic polyamide preferably contains a dicarboxylic acid unit containing 50 mol% or more of at least one selected from terephthalic acid and naphthalenedicarboxylic acid units with respect to the total dicarboxylic acid units.

The dicarboxylic acid unit constituting the semi-aromatic polyamide may contain a dicarboxylic acid unit other than the aromatic dicarboxylic acid unit in a range of preferably less than 50 mol% with respect to the total dicarboxylic acid unit. Examples of such other dicarboxylic acid units include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelliic acid, suberic acid, azelaic acid, sebacic acid, undecandicarboxylic acid, dodecanedicarboxylic acid, and dimethylmalonic acid. An aliphatic dicarboxylic acid such as 2,2-diethylsuccinic acid, 2,2-dimethylglutaric acid, 2-methyladipic acid, trimethyladipic acid; 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1 , 4-Cyclohexanedicarboxylic acid, cycloheptanedicarboxylic acid, cyclooctanedicarboxylic acid, alicyclic dicarboxylic acid such as cyclodecanedicarboxylic acid; and the like. The dicarboxylic acid unit may contain one or more of these other dicarboxylic acid units. The content of these other dicarboxylic acid units in the dicarboxylic acid unit is preferably 25 mol% or less, and more preferably 10 mol% or less.
The semi-aromatic polyamide used in the present invention may further contain a unit derived from a polyvalent carboxylic acid such as trimellitic acid, trimesic acid, and pyromellitic acid within a range that allows melt molding.

(Diamine unit)
The diamine unit constituting the semi-aromatic polyamide preferably contains 60 to 100 mol% of an aliphatic diamine unit having 4 to 13 carbon atoms with respect to the total diamine unit. When a semi-aromatic polyamide containing an aliphatic diamine unit having 4 to 13 carbon atoms in this ratio is used, a polyamide resin composition having excellent toughness, heat resistance, chemical resistance and light weight can be obtained. The content of the aliphatic diamine unit having 4 to 13 carbon atoms in the total diamine unit is more preferably 75 to 100 mol%, further preferably 90 to 100 mol%.

Examples of the aliphatic diamine unit having 4 to 13 carbon atoms include 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, and 1,8-octane. Linear aliphatic diamines such as diamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine; 2-methyl-1 , 5-Pentane Diamine, 3-Methyl-1,5-Pentane Diamine, 2,2,4-trimethyl-1,6-Hexane Diamine, 2,4,4-trimethyl-1,6-Hexane Diamine, 2-Methyl Units derived from branched chain aliphatic diamines such as -1,8-octanediamine and 5-methyl-1,9-nonandiamine; can be mentioned. The diamine unit may contain one or more of these aliphatic diamine units.

The above-mentioned aliphatic diamine units having 4 to 13 carbon atoms are 1,4-butanediamine, 1,6-hexanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine and 1,10-decane. More preferably, it is at least one selected from units derived from diamine.
Further, since a polyamide resin composition having further excellent heat resistance, low water absorption and chemical resistance can be obtained, the unit is derived from 1,9-nonanediamine and / or 2-methyl-1,8-octanediamine. Is more preferable, and 1,9-nonanediamine unit and 2-methyl-1,8-octanediamine unit are further preferable. When the aliphatic diamine unit contains both units derived from 1,9-nonandiamine and 2-methyl-1,8-octanediamine, the 1,9-nonandiamine unit and 2-methyl-1,8-octanediamine are used. The molar ratio of the units is preferably in the range of 1,9-nonanediamine units / 2-methyl-1,8-octanediamine units = 95/5 to 40/60, preferably in the range of 90/10 to 40/60. It is more preferable to be in the range of 80/20 to 40/60.

The diamine unit constituting the semi-aromatic polyamide may contain other diamine units other than the aliphatic diamine unit having 4 to 13 carbon atoms, preferably in the range of less than 40 mol% with respect to the total diamine unit. Examples of such other diamine units include aliphatic diamines having 3 or less carbon atoms such as ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, and 2-methyl-1,3-propanediamine; Alicyclic diamines such as methylcyclohexanediamine and isophoronediamine; p-phenylenediamine, m-phenylenediamine, xylylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diamino Units derived from aromatic diamines such as diphenyl ether can be mentioned. The diamine unit may contain one or more of these other diamine units. The content of these other diamine units in the diamine unit is preferably 25 mol% or less, and more preferably 10 mol% or less.

(Other units)
The semi-aromatic polyamide may further contain an aminocarboxylic acid unit and / or a lactam unit as long as the effect of the present invention is not impaired.
Examples of the aminocarboxylic acid unit include units derived from 11-aminoundecanoic acid, 12-aminododecanoic acid, and the like, and two or more kinds of aminocarboxylic acid units may be contained. The content of the aminocarboxylic acid unit in the semi-aromatic polyamide is preferably 40 mol% or less, more preferably 20 mol% or less, based on 100 mol% of all the monomer units constituting the semi-aromatic polyamide. It is preferably 10 mol% or less, and more preferably 10 mol% or less.

The semi-aromatic polyamide may further contain lactam units as long as it does not interfere with the effects of the present invention.
Examples of the lactam unit include units derived from ε-caprolactam, enantractum, undecan lactam, lauryl lactam, α-pyrrolidone, α-piperidone, etc., even if two or more lactam units are contained. Good. The content of the lactam unit in the semi-aromatic polyamide is preferably 40 mol% or less, more preferably 20 mol% or less, based on 100 mol% of all the monomer units constituting the semi-aromatic polyamide. It is more preferably 10 mol% or less.

(Semi-aromatic polyamide)
Polytetramethylene terephthalamide is a typical semi-aromatic polyamide containing a dicarboxylic acid unit containing an aromatic dicarboxylic acid unit as a main component and a diamine unit containing an aliphatic diamine unit having 4 to 13 carbon atoms as a main component. (Polyamide 4T), Polypentamethylene terephthalamide (Polyamide 5T), Polyhexamethylene terephthalamide (Polyamide 6T), Polynonamethylene terephthalamide (Polyamide 9T), Poly (2-Methyloctamethylene) terephthalamide (Nylon M8T), Polynonamethylene terephthalamide / poly (2-methyloctamethylene) terephthalamide copolymer (nylon 9T / M8T), polynonamethylenenaphthalenedicarboxamide (polyamide 9N), polynonamethylenenaphthalenedicarboxamide / poly (2-methyloctamethylene) Naphthalenedicarboxamide copolymer (nylon 9N / M8N), polydecamethylene terephthalamide (polyamide 10T), polyhexamethylene isophthalamide (polyamide 6I), copolymer of polyamide 6I and polyamide 6T (polyamide 6I / 6T), polyamide 6T Examples thereof include a copolymer of polyamide canamide (polyamide 11) (polyamide 6T / 11) and a copolymer of polyamide 10T and polyundecan amide (polyamide 11) (polyamide 10T / 11).
Among these, polyamide 10T / 11, polynonamethylene naphthalenedicarboxamide (polyamide 9N), polynonamethylenenaphthalenedicarboxamide / poly (2-methyloctamethylene) naphthalenedicarboxamide copolymer (nylon 9N / M8N), polynonamethylene terephthal. At least one selected from amide (polyamide 9T), polynonamethylene terephthalamide / poly (2-methyloctamethylene) terephthalamide copolymer (nylon 9T / M8T) and polydecamethylene terephthalamide (polyamide 10T) is preferred. Methylenenaphthalenedicarboxamide / poly (2-methyloctamethylene) naphthalenedicarboxamide copolymer (nylon 9N / M8N), polynonamethylene terephthalamide / poly (2-methyloctamethylene) terephthalamide copolymer (nylon 9T / M8T), and polyamide At least one selected from 10T / 11 is more preferable, and polynonamethylene terephthalamide / poly (2-methyloctamethylene) terephthalamide copolymer (nylon 9T / M8T) is further preferable.

On the other hand, among the semi-aromatic polyamides, the semi-aromatic polyamide containing a dicarboxylic acid unit containing an aliphatic dicarboxylic acid unit as a main component and a diamine unit containing an aromatic diamine unit as a main component is an aliphatic dicarboxylic acid unit. Examples of the unit derived from the above-mentioned aliphatic dicarboxylic acid can be mentioned, and one or more of these can be included. In addition, examples of the aromatic diamine unit include units derived from the above-mentioned aromatic diamine, and one or more of these can be included. Further, other units may be included as long as the effects of the present invention are not impaired.
Typical semi-aromatic polyamides containing a dicarboxylic acid unit containing an aliphatic dicarboxylic acid unit as a main component and a diamine unit containing an aromatic diamine unit as a main component include polymethaxylylene adipamide (MXD6) and poly. Examples thereof include paraxylylene sebacamide (PXD10).

It is preferable that 10 mol% or more of the terminal groups of the molecular chain of the semi-aromatic polyamide is sealed with an end sealant. When a semi-aromatic polyamide having a terminal sealing ratio of 10 mol% or more is used, a polyamide resin composition having more excellent physical properties such as melt stability and heat resistance can be obtained.

As the terminal encapsulant, a monofunctional compound having reactivity with a terminal amino group or a terminal carboxyl group can be used. Specific examples thereof include monocarboxylic acids, acid anhydrides, monoisocyanates, monoacid halides, monoesters, monoalcohols and monoamines. From the viewpoint of reactivity and stability of the sealing terminal, a monocarboxylic acid is preferable as the terminal sealing agent for the terminal amino group, and a monoamine is preferable as the terminal sealing agent for the terminal carboxyl group. From the viewpoint of ease of handling, a monocarboxylic acid is more preferable as the terminal encapsulant.

The monocarboxylic acid used as the terminal encapsulant is not particularly limited as long as it has reactivity with an amino group. Examples of monocarboxylic acids include aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, capric acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutylic acid. Acids; alicyclic monocarboxylic acids such as cyclopentanecarboxylic acid and cyclohexanecarboxylic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid and phenylacetic acid. Acid; any mixture thereof and the like can be mentioned. Among these, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, etc., in terms of reactivity, stability of the sealing end, price, etc. , And at least one selected from benzoic acid is preferred.

The monoamine used as the terminal encapsulant is not particularly limited as long as it has reactivity with a carboxyl group. For example, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine and stearyl are not particularly limited. Adipose monoamines such as amines, dimethylamines, diethylamines, dipropylamines and dibutylamines; alicyclic monoamines such as cyclohexylamines and dicyclohexylamines; aromatic monoamines such as aniline, toluidine, diphenylamines and naphthylamines; any mixture thereof and the like. Can be mentioned. Among these, at least one selected from butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline is preferable from the viewpoints of reactivity, high boiling point, stability of the sealing end, and price.

_{The semi-aromatic polyamide preferably has an intrinsic viscosity [η inh} ] of 0.6 dl / g or more, preferably 0.8 dl / g, measured at a concentration of 0.2 g / dl and a temperature of 30 ° C. using concentrated sulfuric acid as a solvent. The above is more preferable, 0.6 dl / g or more is further preferable, and 1.0 dl / g or more is particularly preferable. Further, the intrinsic viscosity [η _inh ] is preferably 2.0 dl / g or less, more preferably 1.8 dl / g or less, and further preferably 1.6 dl / g or less. When the intrinsic viscosity [η _inh ] of the polyamide is within the above range, various physical properties such as moldability are further improved. The intrinsic viscosity [η _inh ] is the flow time of the solvent (concentrated sulfuric acid) t ₀ (sec), the flow time of the sample solution t ₁ (sec), and the sample concentration c (g / dl) in the sample solution (that is, 0.2 g). From / dl), it can be obtained by the relational expression of _{η inh} = [ln (t ₁ / t _{0)] / c.}

The semi-aromatic polyamide preferably has a terminal amino group content ([NH ₂ ]) of 5 to 60 μeq / g, more preferably in the range of 5 to 50 μeq / g, and 5 to 30 μeq / g. It is more preferably within the range. When the terminal amino group content ([NH ₂ ]) is 5 μeq / g or more, the compatibility between the semi-aromatic polyamide and the elastomer described later is good. Further, when the terminal amino group content is 60 μeq / g or less, when an acid-modified elastomer described later is used as the elastomer (B), the terminal amino group reacts too much with the modified portion of the elastomer to cause gelation. Can be avoided.
The terminal amino group content ([NH ₂ ]) referred to in the present specification refers to the amount of terminal amino groups (unit: μeq) contained in 1 g of the semi-aromatic polyamide, and is determined by a neutralization titration method using an indicator. be able to.

A semi-aromatic polyamide containing a dicarboxylic acid unit and a diamine unit and having a terminal amino group content ([NH ₂ ]) in the above range can be produced, for example, as follows.
First, a nylon salt is produced by mixing a dicarboxylic acid, a diamine, and if necessary, an aminocarboxylic acid, a lactam, a catalyst, and an end sealant. At this time, the number of moles (X) of all carboxyl groups and the number of moles (Y) of all amino groups contained in the above reaction raw material are the following formula (1).
-0.5 ≤ [(YX) / Y] x 100 ≤ 2.0 (1)
Is preferable because the semi-aromatic polyamide having a terminal amino group content ([NH ₂ ]) of 5 to 60 μeq / g can be easily produced. Next, the produced nylon salt was heated to a temperature of 200 to 250 ° C. _{to obtain a prepolymer having an intrinsic viscosity [η inh} ] of 0.10 to 0.60 dlL / g at 30 ° C. in concentrated sulfuric acid, and the degree of polymerization was further increased. By doing so, a semi-aromatic polyamide can be obtained. When the intrinsic viscosity [η _inh ] of the prepolymer is in the range of 0.10 to 0.60 dLl / g, the deviation of the molecular balance between the carboxyl group and the amino group and the decrease in the polymerization rate are small at the stage of increasing the degree of polymerization. Further, a semi-aromatic polyamide having a small molecular weight distribution and excellent in various performances and moldability can be obtained. When the step of increasing the degree of polymerization is carried out by the solid phase polymerization method, it is preferably carried out under reduced pressure or under an inert gas flow, and when the polymerization temperature is in the range of 200 to 280 ° C., the polymerization rate is high and the productivity is high. It is excellent in color and can effectively suppress coloring and gelation. Further, when the step of increasing the degree of polymerization is carried out by a melt extruder, the polymerization temperature is preferably 370 ° C. or lower, and when the polymerization is carried out under such conditions, the polyamide is hardly decomposed and the semi-aromatic polyamide with little deterioration is hardly deteriorated. Is obtained.

Examples of the catalyst that can be used in producing the semi-aromatic polyamide include phosphoric acid, phosphorous acid, hypophosphorous acid, and salts or esters thereof. Examples of the above salts or esters include phosphoric acid, phosphite or hypophosphoric acid, potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, antimony and the like. Salt with metal; ammonium salt of phosphoric acid, phosphite or hypophosphoric acid; ethyl ester of phosphoric acid, phosphite or hypophosphoric acid, isopropyl ester, butyl ester, hexyl ester, isodecyl ester, octadecyl ester , Decyl ester, stearyl ester, phenyl ester and the like.
The amount of the catalyst used is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, based on 100% by mass of the total mass of the raw material of the semi-aromatic polyamide. The amount of the catalyst used is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, based on 100% by mass of the total mass of the raw material of the semi-aromatic polyamide. When the amount of the catalyst used is equal to or higher than the above lower limit, the polymerization proceeds satisfactorily. If it is not more than the above upper limit, impurities derived from the catalyst are less likely to occur, and for example, when a polyamide resin composition is molded, problems due to the impurities can be prevented.

<Elastomer (B)>
An elastomer (B) is used for the composition X.
The elastomer (B) is preferably at least one selected from the following (b1) to (b5) from the viewpoint of imparting toughness and impact resistance to the composite molded product.
(B1) α-olefin copolymer (b2) (ethylene and / or propylene) / (α, β-unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) copolymer (b3) ionomer (b4) fragrance Copolymer of Group Vinyl Compound and Conjugated Diene Compound Block (b5) Unsaturated having at least one selected from the above (b1) to (b4) and at least one selected from a carboxyl group and an acid anhydride group. Compound-modified copolymer

(B1) α-olefin-based copolymer The α-olefin-based copolymer includes a copolymer of ethylene and an α-olefin having 3 or more carbon atoms, or a copolymer of propylene and an α-olefin having 4 or more carbon atoms. Examples include copolymers. As the α-olefin copolymer, a copolymer of ethylene and an α-olefin having 3 or more carbon atoms is preferable.
Examples of α-olefins having 3 or more carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, and 1-dodecene. , 1-Tridecene, 1-Tetradecene, 1-Pentadecene, 1-Hexadecene, 1-Hexene, 1-Octadecene, 1-Nonadecene, 1-Eicocene, 3-Methyl-1-butene, 3-Methyl-1-pentene, 3 -Ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene , 3-Ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene. These can be used alone or in combination of two or more. Among the above, as the α-olefin having 3 or more carbon atoms, at least one selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene is preferable, and 1-butene is preferable. Is more preferable.

In addition, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadien, 1,4-octadien, 1,5-octadien, 1,6-octadien, 1,7-octadien, 2-methyl-1, 5-Hexadien, 6-Methyl-1,5-Heptadien, 7-Methyl-1,6-octadien, 4-Etylidene-8-Methyl-1,7-Norbornene, 4,8-Dimethyl-1,4,8- Decatrine (DMDT), dicyclopentadiene, cyclohexadiene, cyclooctadien, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl Non-conjugated diene such as -5-isopropenyl-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,5-norbornene Polyene may be copolymerized. These can be used alone or in combination of two or more.

(B2) (Ethylene and / or propylene) / (α, β-unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) copolymer (ethylene and / or propylene) / (α, β-unsaturated carboxylic acid) The and / or unsaturated carboxylic acid ester) -based copolymer is at least one selected from ethylene and propylene, and at least one selected from α, β-unsaturated carboxylic acid monomer and unsaturated carboxylic acid ester monomer. It is a copolymer obtained by copolymerizing one kind.
Examples of the α, β-unsaturated carboxylic acid monomer include acrylic acid and methacrylic acid. Examples of the α, β-unsaturated carboxylic acid ester monomer include methyl ester, ethyl ester, propyl ester, butyl ester, pentyl ester, hexyl ester, heptyl ester, octyl ester, and nonyl of these α, β-unsaturated carboxylic acids. Examples include esters and decyl esters. One type or two or more types of these monomers can be used.

(B3) Ionomer Ionomer is an ionomer in which at least a part of the carboxyl groups in the copolymer of an olefin and an α, β-unsaturated carboxylic acid is ionized by neutralization of a metal ion. Ethylene is preferably used as the olefin. As the α, β-unsaturated carboxylic acid, acrylic acid and methacrylic acid are preferably used. The above-mentioned copolymer is not limited to those exemplified here, and an unsaturated carboxylic acid ester monomer may be copolymerized. The metal ions include alkali metals such as Li, Na, K, Mg, Ca, Sr, and Ba, alkaline earth metals, Al, Sn, Sb, Ti, Mn, Fe, Ni, Cu, Zn, and Cd. Can be mentioned. One kind or two or more kinds of these metal ions can be used.

(B4) Polymer of aromatic vinyl compound and conjugated diene compound-based block The copolymer of aromatic vinyl compound and conjugated diene compound-based block is an aromatic vinyl compound-based polymer block and conjugated diene-based polymer block. A block polymer comprising at least one aromatic vinyl compound-based polymer block and at least one conjugated diene-based polymer block is used. Further, in the above-mentioned block copolymer, the unsaturated bond in the conjugated diene-based polymer block may be hydrogenated.

The aromatic vinyl compound-based polymer block is a polymer block mainly composed of structural units derived from an aromatic vinyl compound. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, vinylnaphthalene, vinylanthracene, 4-propylstyrene, and 4-. Examples thereof include cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene and the like. These can be used alone or in combination of two or more. Further, the aromatic vinyl compound-based polymer block may have a structural unit composed of a small amount of other unsaturated monomers as the case may be.
The conjugated diene polymer block is conjugated with butadiene, chloroprene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene and the like. A polymer block formed from one or more diene compounds.
In the copolymer of the hydrogenated aromatic vinyl compound and the conjugated diene compound system block, a part or all of the unsaturated bond portion in the conjugated diene polymer block is hydrogenated.

The molecular structure of the aromatic vinyl compound / conjugated diene compound block copolymer and its hydrogenated product may be linear, branched, radial, or any combination thereof. Among these, one aromatic vinyl compound-based polymer block and one conjugated diene-based polymer block are used as a copolymer of an aromatic vinyl compound and a conjugated diene compound-based block and / or a hydrogenated product thereof. Three polymer blocks are linearly bonded in the order of linearly bonded diblock copolymer, aromatic vinyl compound polymer block-conjugated diene polymer block-aromatic vinyl compound polymer block. One or more of the triblock copolymers and their hydrogenated products are preferably used. Specifically, unhydrogenated or hydrogenated styrene / butadiene block copolymer, unhydrogenated or hydrogenated styrene / isoprene block copolymer, unhydrogenated or hydrogenated styrene / isoprene / styrene block copolymer, not yet. Examples thereof include hydrogenated or hydrogenated styrene / butadiene / styrene block copolymer, unhydrogenated or hydrogenated styrene / isoprene / butadiene / styrene block copolymer and the like.

(B5) A polymer obtained by modifying at least one selected from the above (b1) to (b4) with an unsaturated compound having at least one selected from a carboxyl group and an acid anhydride group (b1) to (b4). At least one selected from the above can be modified with an unsaturated compound having at least one selected from a carboxyl group and an acid anhydride group. When modified with such an unsaturated compound, the terminal amino group of the semi-aromatic polyamide reacts with the carboxyl group and / or acid anhydride group of the modified component, which is a component of the elastomer, to form a semi-aromatic polyamide. The affinity between the phase and the elastomeric phase becomes stronger, the impact resistance and elongation characteristics are improved, and flexibility is exhibited. Among the above, a polymer obtained by modifying an α-olefin copolymer with an unsaturated compound having a carboxyl group and / or an acid anhydride group is preferable, and a polymer obtained by modifying an ethylene-butene copolymer with the unsaturated compound. Is more preferable.

Examples of the unsaturated compound having a carboxyl group used in the modified polymer modified with an unsaturated compound having a carboxyl group and / or an acid anhydride group include acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid. Examples thereof include α and β-unsaturated carboxylic acids such as acids. Examples of unsaturated compounds having an acid anhydride group include dicarboxylic acid anhydrides having α, β-unsaturated bonds such as maleic anhydride and itaconic anhydride. As the unsaturated compound having a carboxyl group and / or an acid anhydride group, a dicarboxylic acid anhydride having an α, β-unsaturated bond is preferable, and maleic anhydride is more preferable.

As a modification method using an unsaturated compound having a carboxyl group and / or an acid anhydride group, when the above (b1) to (b4) (hereinafter, also referred to as “base resin”) are produced, the carboxyl group and / or acid anhydride is used. Examples thereof include a method of copolymerizing with an unsaturated compound having a physical group and a method of grafting an unsaturated compound having a carboxyl group and / or an acid anhydride group with the above base resin. Of these, a method of grafting an unsaturated compound having a carboxyl group and / or an acid anhydride group with the above base resin is preferable.
As the elastomer (B), a commercially available product manufactured industrially can be used, and examples thereof include "Toughmer (registered trademark)" manufactured by Mitsui Chemicals, Inc.

<Chain extender (C)>
For the composition X, a chain extender (C) is used from the viewpoint of imparting toughness to the composite molded product. When the chain extender (C) is blended with the polyamide (A) and the elastomer (B), the chain extender (C) is formed on the welded surface between the molded product X and the other polyamide resin molded product due to heat generated by vibration during welding. It is thought that it will react. For example, when two molded bodies X are welded, the polyamide (A) and the chain extender (C) between the molded bodies and the elastomer (B) and the chain extender (C) between the molded bodies are used. It is presumed that a composite molded product having excellent toughness is obtained by reacting with each other. Further, if at least one of the molded bodies to be welded is the molded body X, the chain extender (C) in the molded body X can react with the components (polyamide and the like) in the other molded body. Therefore, at least one of the two molded bodies to be welded may be the molded body X.

The chain extender (C) may contain two or more functional groups reactive with the polyamide (A) in one molecule. Examples of the chain extender (C) include a polyol compound, an oxazoline compound, an isocyanate compound, an epoxy compound, and a carbodiimide compound. Among these, a carbodiimide compound is particularly preferable from the viewpoint of reactivity with the polyamide (A). As the chain extender (C), one kind or two or more kinds can be used.

Examples of the carbodiimide compound include monocarbodiimide and polycarbodiimide, and polycarbodiimide is desirable from the viewpoint of heat resistance. More specifically, the polycarbodiimide is preferably a compound having a repeating unit represented by the following general formula (I).

 

In the above general formula (I), X ₁ represents a divalent hydrocarbon group. Examples of the hydrocarbon group include a chain aliphatic group, an alicyclic structure-containing aliphatic group, and an aromatic ring-containing group. The chain aliphatic group has 1 or more carbon atoms, preferably 1 to 20, and more preferably 6 to 18. The alicyclic structure-containing aliphatic group and aromatic ring-containing group preferably have 5 or more carbon atoms, more preferably 6 to 20, and even more preferably 6 to 18. The hydrocarbon group may have a substituent such as an amino group, a hydroxyl group, or an alkoxy group.

Examples of polycarbodiimides include aliphatic polycarbodiimides, aromatic polycarbodiimides, and mixtures thereof. Of these, an aliphatic polycarbodiimide is more preferable from the viewpoint of chemical resistance and molding processability of the obtained molded product X and reactivity with the polyamide (A).
The aliphatic polycarbodiimide having a repeating unit represented by the general formula (I), X ₁ is polycarbodiimide is preferably a chain aliphatic group or an alicyclic structure-containing aliphatic group. X ₁ is a group selected from the group consisting of an alkylene group having 3 to 18 carbon atoms, a divalent group represented by the following general formula (II), and a divalent group represented by the following general formula (III). It is more preferable that it is a divalent group represented by the following general formula (III).

 

In the general formula (II) and the general formula (III), R ¹ to R ⁵ are independently single bonds or alkylene groups having 1 to 8 carbon atoms. ^{R 1} and R ² in the general formula (II) are preferably single bonds. ^{R 3} and R ⁵ in the general formula (III) are preferably single bonds, and R ⁴ is preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 1 to 3 carbon atoms.

<Mixing amount>
When the total amount of the polyamide (A) and the elastomer (B) is 100 parts by mass, it is preferable to use the polyamide (A) in an amount of 60 to 90 parts by mass.
When the blending amount of the polyamide is within the above numerical range, mechanical strength, toughness, heat resistance and chemical resistance are easily exhibited. When the total amount of the polyamide (A) and the elastomer (B) is 100 parts by mass, the blending amount of the polyamide (A) is more preferably 63 parts by mass or more, further preferably 66 parts by mass or more. The blending amount of the polyamide (A) is more preferably 87 parts by mass or less, and further preferably 84 parts by mass or less.

The blending amount of the elastomer (B) is preferably 3 to 40% by mass with respect to a total of 100% by mass of the polyamide (A), the elastomer (B), and the chain extender (C).
When the blending amount of the elastomer (B) is 3% by mass or more, good toughness is likely to be exhibited, and when it is 40% by mass or less, excellent strength can be exhibited.
From the viewpoint of imparting more excellent toughness and impact resistance, the blending amount of the elastomer (B) is more preferably 4% by mass or more, further preferably 19% by mass or more. Further, from the viewpoint of moldability, the blending amount of the elastomer (B) is more preferably 35% by mass or less, further preferably 31% by mass or less.

The amount of the chain extender (C) to be blended with respect to 100 parts by mass of the total of the polyamide (A) and the elastomer (B) is preferably 0.01 to 5 parts by mass.
When the blending amount of the chain extender (C) is within the above numerical range, excellent toughness and mechanical strength are likely to be exhibited. The blending amount of the chain extender (C) with respect to 100 parts by mass of the total of the polyamide (A) and the elastomer (B) is more preferably 0.05 parts by mass or more, further preferably 0.1 parts by mass or more. The amount of the chain extender (C) to be blended is more preferably 4 parts by mass or less, further preferably 3 parts by mass or less.

The ratio of the total amount of the polyamide (A), the elastomer (B), and the chain extender (C) to 100% by mass of the raw material used in the composition X is preferably 95% by mass or more, preferably 97% by mass or more. More preferred. The ratio of the total amount of the polyamide (A), the elastomer (B), and the chain extender (C) to 100% by mass of the raw material used in the composition X is preferably 99.5% by mass or less, preferably 99% by mass. The following is more preferable.

<Additive>
Composition X contains other types of polymers (other than elastomer (B)), fillers, crystal nucleating agents, colorants, antistatic agents, plasticizers, lubricants, antioxidants, flame retardants and flame retardants, if necessary. Other components such as may be contained as an additive.

Examples of other polymers include polyether resins such as polyacetal and polyphenylene oxide; polysulfone resins such as polysulfone and polyethersulfone; polythioether-based resins such as polyphenylene sulfide and polythioether sulfone; polyether ether ketone and polyallyl ether ketone. Polyketone-based resins such as polyacrylonitrile, polymethacrylonitrile, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, methacrylnitrile-butadiene-styrene copolymer and other polynitrile-based resins; polymethylmethacrylate Polymethacrylate-based resin such as polyethyl methacrylate; polyvinyl ester-based resin such as polyvinyl acetate; polyvinylidene chloride, polyvinyl chloride, vinyl chloride-vinylidene chloride copolymer, vinylidene chloride-methylacrylate copolymer and the like. Vinyl chloride resin; Cellulosic resin such as cellulose acetate, cellulose butyrate; Vinylidene fluoride, polyvinyl fluoride, ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene, ethylene-chlorotrifluoroethylene copolymer, tetra Fluoropolymers such as fluoroethylene-hexafluoropropylene copolymers, tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymers; polycarbonate resins; polyimide resins such as thermoplastic polyimides, polyamideimides and polyetherimides; Thermoplastic polyurethane resin; and the like.

Examples of the filler include fibrous fillers such as glass fiber, and powder fillers such as calcium carbonate, wollastonite, silica, silica alumina, alumina, titanium dioxide, potassium titanate, magnesium hydroxide, and molybdenum disulfide. Examples include flake-like fillers such as hydrotalcite, glass flakes, mica, clay, montmorillonite, and kaolin.

The crystal nucleating agent is not particularly limited as long as it is generally used as a crystal nucleating agent for polyamide. Examples of the crystal nucleating agent include talc, calcium stearate, aluminum stearate, barium stearate, zinc stearate, antimony oxide, magnesium oxide, and any mixture thereof. Of these, talc is preferable because it has a large effect of increasing the crystallization rate of polyamide. The crystal nucleating agent may be treated with a silane coupling agent, a titanium coupling agent, or the like for the purpose of improving compatibility with polyamide.

The colorant is not particularly limited and can be appropriately selected from inorganic or organic pigments and dyes. As the colorant, black inorganic pigments such as carbon black, lamp black, acetylene black, bone black, thermal black, channel black, furnace black, and titanium black are preferable.

The antistatic agent is not particularly limited and may be an organic type or an inorganic type. For example, examples of the organic antistatic agent include ionic compounds such as lithium ion salt, quaternary ammonium salt and ionic liquid; and electron conductive polymer compounds such as polythiophene, polyaniline, polypyrrole and polyacetylene. Examples of the inorganic antistatic agent include metal oxide-based conductive agents such as ATO, ITO, PTO, GZO, antimony pentoxide, and zinc oxide; and carbon-based conductive agents such as carbon nanotubes and fullerenes. From the viewpoint of heat resistance, an inorganic antistatic agent is preferable. In addition, carbon black which is a colorant may also function as an antistatic agent.

The plasticizer is not particularly limited as long as it is generally used as a plasticizer for polyamide, and is, for example, a benzenesulfonic acid alkylamide compound, a toluenesulfonic acid alkylamide compound, or a hydroxybenzoic acid alkylester compound. , Hydroxybenzoic acid alkylamide compounds and the like.

The lubricant is not particularly limited as long as it is generally used as a polyamide lubricant. Examples of the lubricant include higher fatty acid compounds, oxy fatty acid compounds, fatty acid amide compounds, alkylene bis fatty acid amide compounds, fatty acid lower alcohol ester compounds, metal soap compounds, and polyolefin waxes. As the fatty acid amide compound, for example, stearic acid amide, palmitic acid amide, methylene bisstearyl amide, ethylene bisstearyl amide and the like are preferable because they have an excellent external slipping effect.

Examples of the antioxidant include hindered phenol compounds, phosphorus compounds, lactone compounds, hydroxyl compounds and the like.
These other components may be used alone or in combination of two or more.
The blending amount of these other components is preferably 5% by mass or less, more preferably 3% by mass or less, based on 100% by mass of the composition X.

<Method of adjusting composition X>
The preparation of the composition X is not particularly limited, and a known method can be used. For example, the composition X can be prepared by melt-kneading a mixture of a polyamide (A), an elastomer (B), a chain extender (C), and the above other components to be blended if necessary. ..
At this time, the chain extender (C) is added after the polyamide (A) and the elastomer (B) are melt-kneaded, so that the mutual reaction between the polyamide (A) and the elastomer (B) during the melt-kneading is chain-extended. It can be prevented from being inhibited by the agent (C). That is, it is preferable that after the polyamide (A) and the elastomer (B) are melt-kneaded, a chain extender (C) is further added and melt-kneaded.
Specifically, when a twin-screw extruder is used as the melt-kneading device, a mixture of polyamide (A), elastomer (B), and other components to be blended as needed is dry-blended at the base of the twin-screw extruder. It is preferable that the chain extender (C) is charged from the first feed port and the chain extender (C) is charged from the second feed port provided between the first kneading portion and the second kneading portion installed on the screw. At this time, the chain extender (C) may be added after being dry-blended with the polyamide (A), if necessary.

The temperature and time during the melt-kneading can be appropriately adjusted according to the melting point of the polyamide (A) used, etc., but from the viewpoint of suppressing deterioration of the polymerizable property of the elastomer (B), the melt-kneading temperature is 380 ° C. or lower. It is preferably 370 ° C. or lower, more preferably 360 ° C. or lower. The melt-kneading time is preferably about 1 to 5 minutes.
The method of melt-kneading is not particularly limited, and a method capable of uniformly mixing the polyamide (A), the elastomer (B), the chain extender (C) and the above other components can be preferably adopted. For example, a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer and the like are preferable, and a twin-screw extruder is more preferable from the viewpoint of good dispersibility of the elastomer and industrial productivity.

[Molding method]
After adjusting the composition X, for example, pelletized products can be subjected to various molding methods to obtain a molded product X. The molding method of the molded body X may be appropriately selected depending on the intended use, but methods such as injection molding, extrusion molding, hollow molding, compression molding, press molding, and calendar molding can be adopted.

<Welding method>
In the present embodiment, the composite molded body is manufactured by welding the above-mentioned two or more polyamide resin molded bodies by vibration. When a welding method that does not involve vibration is adopted, it becomes difficult to develop excellent toughness. For example, when an infrared welding method or the like is adopted, inconveniences such as excessive deterioration of the elastomer (B) on the welded surface due to oxygen existing in the environment around the molded body during heating occur, and excellent toughness cannot be obtained. .. On the other hand, if welding is performed by vibration, there is almost no possibility that the effect of the present invention will be impaired even by an infrared assisted vibration welding method in which, for example, heat welding and vibration welding are combined. It is considered that this is because the welded surface of the molded product is melted by heating, but the welded surface is welded by the frictional heat of the subsequent vibration, so that the deterioration of the elastomer (B) due to oxygen is suppressed.

As an example of the present embodiment, the surfaces to be pressure-welded between the molded product X and the mating polyamide resin molded product may be welded by a method of welding by frictional heat generated during welding. Examples of the welding method include a vibration welding method, an infrared assisted vibration welding method, an ultrasonic welding method, a spin welding method, and a high frequency welding method. Among these welding methods, the vibration welding method and the infrared assisted vibration welding method are desirable.
The welding conditions may be set according to the form of the molded product and are not particularly limited. For example, the welding pressure of the surface to be pressed is about 0.1 to 25 MPa, the amplitude is about 0.5 to 4.0 mm, and the frequency is. It can be set to about 100 to 300 Hz.

<Use>
The composite molded body obtained by the present invention makes use of its excellent properties, and makes use of its excellent properties, such as automobile parts, aircraft parts, internal combustion engine applications, crude oil drilling / transportation applications, electrical / electronic parts, medical care, food, household / office supplies / building material-related parts. It can be used for such purposes, and is particularly preferably used for automobile parts.

As automobile parts, radiator tank parts, radiator liquid reserve tanks, water pumps, water inlet pipes, water outlet pipes, water pump housings, thermostat housings, etc., which are particularly required to have strength and toughness, can be used as coolant in the automobile engine room. It is suitably used for engine cooling system parts used under the contact of fuel, and fuel system parts such as fuel delivery pipe, fuel pump housing, valve, and fuel tank. It can also be used for interior parts, exterior parts, electrical components and the like.

Applications other than automobile parts include, for example, submarine oil pipes, marine oil pipes, underground oil pipes, pipe liners, submarine cable gears, cams, insulation blocks, valves, power tool parts, agricultural machinery parts, engine covers, and lawnmowers. Examples include small fuel tanks for machines.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

The measurement of each physical property and the welding method in Examples, Comparative Examples, and Production Examples were carried out according to the methods shown below.
《Intrinsic viscosity》
The intrinsic viscosity (dl / g) of the semi-aromatic polyamide (sample) obtained in the production example at a concentration of 0.2 g / dl and a temperature of 30 ° C. was determined from the following relational expression (2) using concentrated sulfuric acid as a solvent. ..
η _inh = [ln (t ₁ / t ₀ )] / c (2)
In the above relational expression, η _inh represents the intrinsic viscosity (dl / g), t ₀ represents the flow time (seconds) of the solvent (concentrated sulfuric acid), t ₁ represents the flow time (seconds) of the sample solution, and c. Represents the concentration of the sample in the sample solution (g / dl) (ie, 0.2 g / dl).

《Melting point》
The melting point of the semi-aromatic polyamide obtained in the production example was measured using a differential scanning calorimetry apparatus "DSC7020" manufactured by Hitachi High-Tech Science Co., Ltd.
The melting point was measured according to ISO11357-3 (2011 2nd edition). Specifically, the sample (semi-aromatic polyamide) is heated from 30 ° C. to 340 ° C. at a rate of 10 ° C./min under a nitrogen atmosphere and held at 340 ° C. for 5 minutes to completely melt the sample. It was cooled to 50 ° C. at a rate of 10 ° C./min and held at 50 ° C. for 5 minutes. The peak temperature of the melting peak that appears when the temperature is raised to 340 ° C at a rate of 10 ° C / min again is defined as the melting point (° C), and when there are multiple melting peaks, the peak temperature of the melting peak on the highest temperature side is defined as the melting point (° C). did.

<< Terminal amino group concentration >>
1 g of the semi-aromatic polyamide obtained in the production example was dissolved in 35 mL of phenol, and 2 mL of methanol was mixed therein to prepare a sample solution. Titration was carried out using thymol blue as an indicator and an aqueous hydrochloric acid solution of 0.01N was carried out, and the terminal amino group content ([NH ₂ ], unit: μeq / g) of the semi-aromatic polyamide was measured.

《Plastic welding test piece》
Using an injection molding machine (mold clamping force: 100 tons, screw diameter: φ32 mm) manufactured by Sumitomo Heavy Industries, Ltd., the pellets of the polyamide resin composition obtained in Examples and Comparative Examples were measured from the melting point of the polyamide. The polyamide resin composition was injection-molded using a fangate mold under the condition that the cylinder temperature was 30 to 40 ° C higher and the mold temperature was 140 ° C, and the flat plate (dimensions: length x width x thickness = 150 mm x). 100 mm × 4 mm) was produced.
Then, the flat plate is cut as shown in FIG. 1, and three rectangular parallelepiped test pieces (dimensions: length x width x thickness = 100 mm x 40 mm x 4 mm) are cut out from one flat plate to form a welding test piece A. did.

《Vibration welding, VW》
Using the welding test piece A produced by the above method, the test piece A is fixed up and down to a vibration welding machine so that the cutting surface becomes a welding surface, and the ends are melted and joined by rubbing with vibration. I let you. Specifically, it was welded under the following conditions using an M-112H type vibration welding device manufactured by Branson.
・ Frequency: 240Hz
・ Welding pressure: 1.5MPa
・ Amplitude: 1.8 mm
・ Welding allowance: 1.2 mm

《Infrared auxiliary vibration welding, IRVW》
In the above vibration welding, an infrared heater (heating part size 130 mm × 4 mm) is inserted between the welding test pieces A before welding the welding test piece A, and the end portion is preheated and then vibration welding is performed. did. The equipment and conditions used for vibration welding are the same as above. The irradiation conditions of the infrared heater are shown below.
-Infrared irradiation output: Upper side 14.3A, lower side 14.4A
・ Infrared irradiation distance: 2.0 mm on the upper side, 2.5 mm on the lower side
・ Infrared irradiation time: 13.0 seconds

《Infrared welding, IRW》
In the above infrared auxiliary vibration welding, after heating the welding test piece A with an infrared heater, the test piece A was crimped and joined without vibrating. The irradiation conditions of the infrared heater are the same as above. The crimping conditions are shown below.
・ Welding pressure: 1.5MPa
・ Crimping time: 5.0 seconds

《Test piece for tensile test》
FIG. 2 shows a schematic view (shape) of the composite molded body obtained by the above welding. In FIG. 2, the cutting surfaces of the two test pieces A are welded to each other via the welding surface 3 to form a composite molded body. A schematic diagram of the test piece B for a tensile test produced by using the composite molded body is shown in FIG. As shown in FIG. 3, the central portion of this composite molded body is cut so that the tensile test test piece B includes the welding surface 3, and the three central portions are each subjected to the tensile test test piece B. And said.
Using the test piece B for a tensile test, the average value of the tensile breaking strength obtained by the following method was used as the welding strength, and the average value of the tensile breaking elongation was calculated as the breaking elongation.

《Tensile test》
Using the test piece B for tensile test prepared by the above method, the tensile strength was 5 mm / min using Instron's Autograph 5969, the distance between chucks was 40 mm, and the tensile fracture at 23 ° C. and 50% RH. The strength (MPa) and the tensile elongation at break (%) were measured. Nominal strain is used for the elongation.

Production Example 1 [Production of semi-aromatic polyamide]
9870.6 g (59.42 mol) of terephthalic acid, a mixture of 1,9-nonandiamine and 2-methyl1,8-octanediamine [50/50 (molar ratio)] 9497.4 g (60.00 mol), benzoic acid 142.9 g (1.17 mol), 19.5 g of sodium hypophosphate monohydrate (0.1 mass% with respect to the total mass of the raw material) and 5 liters of distilled water were placed in an autoclave having an internal volume of 40 liters. , Nitrophobic. The mixture was stirred at 100 ° C. for 30 minutes, and the temperature inside the autoclave was raised to 220 ° C. over 2 hours. At this time, the pressure inside the autoclave was boosted to 2 MPa. After continuing the reaction for 2 hours as it was, the temperature was raised to 230 ° C., and then the temperature was maintained at 230 ° C. for 2 hours, water vapor was gradually removed, and the reaction was carried out while maintaining the pressure at 2 MPa. Next, the pressure was lowered to 1 MPa over 30 minutes and reacted for another 1 hour to obtain a prepolymer having an ultimate viscosity [η] of 0.2 dL / g. This was pulverized to a particle size of 2 mm or less using a flake crusher manufactured by Hosokawa Micron Co., Ltd., dried at 100 ° C. under reduced pressure for 12 hours, and then solid-phase polymerized at 230 ° C. and 13 Pa (0.1 mmHg) for 10 hours. A white polyamide resin (polyamide 1) was obtained.
Polyamide 1 contains terephthalic acid units, 1,9-nonandiamine units and 2-methyl-1,8-octanediamine units (1,9-nonandiamine units / 2-methyl-1,8-octanediamine units = 50/50 ( The molar ratio)), the melting point was 265 ° C., the intrinsic viscosity [η _inh ] was 1.20 dL / g, and the terminal amino group concentration ([NH ₂ ]) was 15 μeq / g.

Production Example 2 [Production of Polyamide Resin Composition A-1, A-2, A-3, B-1, B-2, B-3]
Polyamide (A), elastomer (B), chain extender (C), antioxidant, lubricant, and colorant shown in Table 1 are mixed in advance, and a twin-screw extruder (“TEM-” manufactured by Toshiba Machine Co., Ltd. It was put into the upstream feed port of "26SS"). When the chain extender (C) is used (A-1, A-2, A-3), it is charged from the intermediate feed port between the first kneading part and the second kneading part of the screw, and the cylinder temperature is 300 to 320. A pellet-shaped polyamide resin composition was produced by kneading, extruding, cooling and cutting by melt-kneading at ° C. and a melt-kneading time of about 1 minute.

Each component shown in Table 1 is as follows.
<Polyamide (A)>
Semi-aromatic polyamide (polyamide 1) obtained in Production Example 1
<Elastomer (B)>
Elastomer obtained by modifying an ethylene-butene copolymer with maleic anhydride (Mitsui Chemicals, Inc., Toughmer MH5020)
<Chain extender (C)>
Alicyclic polycarbodiimide (manufactured by Nisshinbo Chemical Co., Ltd., carbodilite HMV-15CA)
<Antioxidant>
Hindered phenolic antioxidant (Sumitomo Chemical Co., Ltd., SUMILIZER GA-80)
<Glidant>
Polyolefin wax (manufactured by Clariant Chemicals, LICOCENE PE MA4221)
<Colorant>
Carbon black (manufactured by Mitsubishi Chemical Corporation, # 980B)

 

[Examples 1 to 3, Comparative Examples 1 to 3]
As shown in Table 2, the pellets of the polyamide resin compositions A-1, A-2, A-3, B-1, B-2, and B-3 obtained in Production Example 2 were used by the above method. The prepared welding test pieces A were welded to each other by the above-mentioned infrared auxiliary vibration welding (IRVW) to prepare a composite molded body. Table 2 shows the evaluation results of the tensile test of the tensile test test piece B obtained by cutting the composite molded body by the above method.

[Examples 4 to 6, Comparative Examples 4 to 6]
As shown in Table 3, a composite molded body and a test piece B for a tensile test were prepared in the same manner as in Examples 1 to 3 and Comparative Examples 1 to 3 except that the above vibration welding (VW) was used as the welding method, and described above. The tensile test was carried out by the method of. The evaluation results are shown in Table 3.

[Comparative Examples 7 to 12]
As shown in Table 4, a composite molded body and a test piece B for a tensile test were prepared in the same manner as in Examples 1 to 3 and Comparative Examples 1 to 3 except that the above infrared welding (IRW) was used as the welding method, and described above. The tensile test was carried out by the method of. The evaluation results are shown in Table 4.

 

 

 

From Examples 1 to 6 and Comparative Examples 1 to 6, by using the chain extender (C) in the polyamide resin composition, the numerical value of tensile elongation at break becomes extremely high while having excellent tensile strength. It can be seen that the composite molded products obtained in Examples 1 to 6 have excellent toughness.
Further, from Comparative Examples 7 to 12 in which the molded product was not welded by vibration, the result was that the tensile elongation at break was inferior regardless of whether or not the chain extender (C) was used in the polyamide resin composition.

According to the manufacturing method of the present invention, a composite molded body having excellent toughness can be manufactured. Therefore, the manufacturing method of the present invention can be used for manufacturing automobile parts, aircraft parts, internal combustion engine applications, crude oil drilling / transportation applications, electrical / electronic parts, medical care, food, household / office supplies / building material-related parts, and the like. It is possible and is particularly preferably used in the manufacture of automotive parts.

1. 1. Flat plate 2. Composite molded body 3. Welded surface A. Welding test piece A
B. Tensile test piece B (3 pieces)

Claims (8)

1. In the manufacture of a composite molded body in which two or more molded bodies are welded together
   The molded product is a polyamide resin molded product.
   At least one of the above-mentioned polyamide resin molded articles is a molded article of a polyamide resin composition obtained by using at least a polyamide (A), an elastomer (B), and a chain extender (C).
   A method for producing a composite molded body, in which the two or more molded bodies are welded by vibration.
2. The method for producing a composite molded product according to claim 1, wherein when the polyamide (A) and the elastomer (B) are 100 parts by mass in total, the polyamide (A) is used in 60 to 90 parts by mass.
3. The first or second claim, wherein the blending amount of the elastomer (B) is 3 to 40% by mass with respect to a total of 100% by mass of the polyamide (A), the elastomer (B), and the chain extender (C). Method for manufacturing a composite molded product.
4. The composite according to any one of claims 1 to 3, wherein the amount of the chain extender (C) blended with respect to a total of 100 parts by mass of the polyamide (A) and the elastomer (B) is 0.01 to 5 parts by mass. A method for manufacturing a molded product.
5. The polyamide (A) contains 60 to 100 mol% of aromatic dicarboxylic acid units with respect to all dicarboxylic acid units and 60 aliphatic diamine units having 4 to 13 carbon atoms with respect to all diamine units. The method for producing a composite molded product according to any one of claims 1 to 4, which is a semi-aromatic polyamide containing a diamine unit containing up to 100 mol%.
6. The aliphatic diamine unit is selected from units derived from 1,4-butanediamine, 1,6-hexanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine and 1,10-decanediamine. The method for producing a composite molded product according to claim 5, which is at least one of the above.
7. The method for producing a composite molded product according to any one of claims 1 to 6, wherein the elastomer (B) is at least one selected from the following (b1) to (b5).
   (B1) α-olefin copolymer (b2) (ethylene and / or propylene) / (α, β-unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) copolymer (b3) ionomer (b4) fragrance Copolymer of Group Vinyl Compound and Conjugated Diene Compound Block (b5) Unsaturated having at least one selected from the above (b1) to (b4) and at least one selected from a carboxyl group and an acid anhydride group. Compound-modified copolymer
8. The method for producing a composite molded product according to any one of claims 1 to 7, wherein the chain extender (C) is a carbodiimide compound.

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