JP2002241604A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which has excellent impact resistance and excellent blister resistance and does not blister the surface of a resin-based part, when used as a resin material for the resin-based part to be supplied to a surface-mounting method and after allowed to pass through a reflow oven. SOLUTION: This thermoplastic resin composition comprises (A) a component comprising a polyamide resin and (B) a component comprising a compound represented by the general formula (I) [R1 to R4 are each identically or differently H or a 1 to 8C alkyl, provided that at least one of R1 to R4 is the 1 to 8C alkyl; R5 is H or a 1 to 3C alkyl; X is a 1 to 8C alkylene; Y1 and Y2 are each H or OH, provided that at least of Y1 and Y2 is OH] in a component (A): component (B) weight ratio of 99.99:0.01 to 95:5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a high impact resistance
The present invention relates to a thermoplastic resin having good blister resistance when soldering in a reflow furnace.

[0002]

2. Description of the Related Art Polyamide 4,6 resins (nylon 4,
6) and a polyimide resin obtained from a monomer having an aromatic group such as terephthalic acid has excellent mechanical properties, physical properties and moldability, and also has excellent thermal properties due to its high melting point. It is a resin material, and for such a reason, it is used in a wide range of fields such as electric / electronic parts, vehicle parts, various devices, and miscellaneous goods. However, such a polyamide resin has a high melting point, and thus has high heat resistance, but generally has a high processing temperature, and thus has a reduced impact resistance due to thermal deterioration during processing. There's a problem.

[0003] In recent years, in the field of electric and electronic industries,
With the miniaturization of products and improvement in productivity, resin-based electronic components such as connectors, switches, relays, and coil bobbins have been mounted on surface-mount technology (Surface-Mount Techn.
In this case, a method of soldering on a printed circuit board has been adopted by the "logic method". here,
"Surface mounting method" means that after placing electronic components on a printed wiring board via creamy solder,
This is a mounting method in which electronic components are fixed on a wiring board by melting and solidifying the solder by passing the wiring board through a heating furnace (reflow furnace). In this surface mounting method, the lead wire of the electronic component is passed through the through hole of the wiring board, and soldering (free soldering or wave soldering) is performed directly on the surface opposite to the surface on which the electronic component is mounted It is different from the mounting method (lead-through method). This surface mounting method has the advantages that the mounting density can be increased, mounting on both sides of the board is possible, and manufacturing cost can be reduced by improving efficiency. It has become mainstream.

However, when an electronic component made of a conventionally known resin material such as a polyamide resin is fixed (soldered) to a wiring substrate by applying a surface mounting method, the wiring substrate on which the electronic component is mounted is mounted. When passing through the inside of the reflow furnace, blisters may be generated on the surface of the electronic component, and the use of lead-free solder, which is advantageous from the viewpoint of environmental protection, increases the furnace temperature (set temperature) due to the use of lead-free solder. Therefore, the frequency of blisters tends to increase. The cause of this blister is not fully understood. And there is a problem that the product value of the product in which the blister is generated is significantly reduced. For this reason, the resin material constituting the resin-based electronic component used in the surface mounting method has excellent blister resistance (hereinafter, also simply referred to as “blister resistance”) when soldering in a reflow furnace. Development of a thermoplastic resin material is desired.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made based on the above circumstances, and its object is to provide:
Blister-resistant, which has excellent impact resistance and does not generate blisters on the surface of the resin-based component after passing through a reflow furnace when used as a resin material for a resin-based component subjected to a surface mounting method. An object of the present invention is to provide a thermoplastic resin composition having excellent properties.

[0006]

Means for Solving the Problems In order to achieve the above object, the present inventors have made intensive studies and found that a phenolic compound having a specific structure is contained in a polyamide resin in a specific ratio. It has been found that a thermoplastic resin composition having excellent impact resistance and blister resistance can be obtained, and the present invention has been completed based on such findings.

That is, the thermoplastic resin composition of the present invention comprises a component (A) composed of a polyamide resin and a component (B) composed of a compound represented by the following general formula (I). The ratio of the component (A) to the component (B) is from 99.99: 0.01 to 95: 5 by weight.

[0008]

Embedded image

Wherein R ¹ , R ² , R ³ and R ⁴ are
A hydrogen atom or an alkyl group having 1 to 8 carbon atoms;
¹ , R ² , R ³ and R ⁴ may be the same or different. However, at least one of R ^{1 to} R ⁴ is an alkyl group having 1 to 8 carbon atoms. R ⁵ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. X represents an alkylene group having 1 to 8 carbon atoms. Y ¹ and Y ^{2 each} represent a hydrogen atom or a hydroxyl group,
At least one of Y ¹ and Y ² is a hydroxyl group. ]

[0010] In the thermoplastic resin composition of the present invention,
For a total of 100 parts by weight of the components (A) and (B), 5 to 70 parts by weight of the component (C) composed of a flame retardant and 0 to 50 parts by weight of the component (D) composed of a flame retardant aid. And may be contained. In the thermoplastic resin composition of the present invention, (E) comprising an inorganic filler with respect to a total of 100 parts by weight of the component (A) and the component (B).
5-300 parts by weight of the component may be contained.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the thermoplastic resin composition of the present invention will be described in detail. <Component (A)> In the thermoplastic resin composition of the present invention,
The polyamide resin used as the component (A) is a polymer having an amide bond (—NHCO—). Examples of such a polyamide resin include a polymer obtained by polycondensing a diamine and a dicarboxylic acid; Polymers obtained by polycondensation of carboxylic acids, polymers obtained by ring-opening polymerization of lactams, and the like can be used. The polyamide resin may be used alone or in combination of two or more (A)
It can be used as a component.

As the diamine for obtaining the polyamide resin, aliphatic diamines, aromatic diamines and alicyclic diamines can be used.

The aliphatic diamines have 3 carbon atoms.
It is preferable to use a diamine having a linear or side chain of from 18 to 18, and specific examples thereof include 1,3-trimethylenediamine, 1,4-tetramethylenediamine,
1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,
8-octamethylenediamine, 2-methyl-1,8-octanediamine, 1,9-nonamethylenediamine, 1,
10-decamethylenediamine, 1,11-undecanemethylenediamine, 1,12-dodecamethylenediamine,
1,13-tridecamethylenediamine, 1,14-tetradecamethylenediamine, 1,15-pentadecamethylenediamine, 1,16-hexadecamethylenediamine,
1,17-heptadecamethylene diamine, 1,18-octadecamethylene diamine, 2,2,4-trimethylhexamethylene diamine, 2,4,4-trimethylhexamethylene diamine, and the like. They can be used alone or in combination of two or more.

The aromatic diamines have at least one phenylene group in the molecule and have 6 to 27 carbon atoms.
It is preferable to use a diamine of, for example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 3,4-diaminodiphenyl ether, 4, 4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-
Diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 4,4'-di (m-aminophenoxy) diphenylsulfone, 4,4'-di (p-aminophenoxy) diphenyl Sulfone, benzidine, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 2,2-bis (4-aminophenyl) propane,
1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 4-bis (4-
Aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 4,4′-diamino -3,3'-diethyl-5,5'-dimethyldiphenylmethane, 4,4 '
-Diamino-3,3 ', 5,5'-tetramethyldiphenylmethane, 2,4-diaminotoluene, 2,2'-dimethylbenzidine and the like, and these may be used alone or in combination of two or more. be able to.

The alicyclic diamines are those having at least one cyclohexylene group in the molecule and having 4 carbon atoms.
It is preferable to use diamines of from 15 to 15, and specific examples thereof include 4,4'-diamino-dicyclohexylenemethane, 4,4'-diamino-dicyclohexylenepropane, and 4,4'-diamino-3. 3'-Dimethyl-dicyclohexylenemethane, 1,4-diaminocyclohexane, piperazine and the like can be mentioned, and these can be used alone or in combination of two or more.

As the dicarboxylic acid for obtaining the polyamide resin, aliphatic dicarboxylic acids, aromatic dicarboxylic acids and alicyclic dicarboxylic acids can be used.

As the aliphatic dicarboxylic acids, it is preferable to use saturated or unsaturated dicarboxylic acids having 2 to 18 carbon atoms, and specific examples thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, and adipine. Acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, prasillic acid, tetradecandioic acid, pentadecandioic acid, octadecandioic acid, maleic acid, fumaric acid, and the like. One type may be used alone, or two or more types may be used in combination.

As the aromatic dicarboxylic acids, those having at least one phenylene group in the molecule having 8 to 8 carbon atoms are preferred.
It is preferable to use 15 dicarboxylic acids. Specific examples thereof include isophthalic acid, terephthalic acid, methyl terephthalic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, and diphenylmethane-
4,4'-dicarboxylic acid, diphenyl ether-4,
4'-dicarboxylic acid, diphenylsulfone-4,4 '
-Dicarboxylic acid, 2,6-naphthalenedicarboxylic acid,
Examples thereof include 2,7-naphthalenedicarboxylic acid and 1,4-naphthalenedicarboxylic acid, and these can be used alone or in combination of two or more.

As the aminocarboxylic acid for obtaining the polyamide resin, an aminocarboxylic acid having 4 to 18 carbon atoms is preferably used. Specific examples thereof include 4-aminobutyric acid, 6-aminohexanoic acid, and 7-aminohexanoic acid. Aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 10
-Aminodecanoic acid, 11-aminoundecanoic acid, 12-
Aminododecanoic acid, 14-aminotetradecanoic acid, 16
-Aminohexadecanoic acid, 18-aminooctadecanoic acid, and the like, and these can be used alone or in combination of two or more.

Specific examples of the lactams for obtaining the polyamide resin include ε-caprolactam, ω-laurolactam, ζ-enantholactam, η-caprylactam and the like. These may be used alone or in combination of two or more. Can be used in combination.

The polyamide resin used as the component (A) preferably has a melting point of 270 ° C. or higher, more preferably 280 ° C. or higher. Here, the “melting point” of the polyamide resin refers to a temperature at a peak top of an endotherm detected by crystal melting, which is measured by differential thermal analysis (DSC). When a mixture of two or more polyamide resins is used, the melting point of any of them alone is less than 270 ° C (or 280 ° C).
℃ or less) as long as the melting point of the mixture is 270 ° C or more (or 280 ° C or more). When two or more melting points are detected as a mixture and one of them is less than 270 ° C. (or less than 280 ° C.), the melting point alone is 270 ° C. or more (or 2
(80 ° C. or higher) as long as the mixture contains 50% by weight of the polyimide resin.

Specific examples of the polyamide resin preferable as the component (A) include a polyamide resin (nylon 4,6) obtained from 1,4-tetramethylenediamine and adipic acid, 1,6-hexamethylenediamine and terephthalic acid. A polyamide resin obtained from 1,6-hexamethylenediamine, terephthalic acid and ε-caprolactam, a polyamide resin obtained from 1,6-hexamethylenediamine, terephthalic acid and adipic acid, 1, Polyamide resin obtained from 9-nonamethylenediamine and terephthalic acid, polyamide resin obtained from 1,9-nonamethylenediamine, terephthalic acid and ε-caprolactam, 1,9-nonamethylenediamine and 1,6-hexamethylene From diamine, terephthalic acid and adipic acid Polyamide resin obtained from 2-methyl-1,8-octanediamine, 1,9-nonamethylenediamine and terephthalic acid, polyamide resin obtained from m-xylylenediamine and adipic acid, and the like. Can be Among these,
Polyamide resin obtained from 1,4-tetramethylenediamine and adipic acid, polyamide resin obtained from 1,6-hexamethylenediamine and terephthalic acid, 1,
Polyamide resin obtained from 9-nonamethylenediamine and terephthalic acid, polyamide resin obtained from 2-methyl-1,8-octanediamine, 1,9-nonamethylenediamine and terephthalic acid are more preferable, and 1,4-
A polyamide resin obtained from tetramethylenediamine and adipic acid is particularly preferred. Further, a polyamide resin obtained from ε-caprolactam, a polyamide resin obtained from 1,6-hexamethylenediamine and adipic acid, or a polyamide resin obtained from 1,6-hexamethylenediamine and terephthalic acid, or 1,6 A mixture of a polyamide resin obtained from hexamethylenediamine, adipic acid and ε-caprolactam can also be preferably used.

In the polyamide resin used as the component (A), at least a part of the terminal groups may be blocked by a terminal blocking agent. The terminal capping agent is not particularly limited as long as it is a monofunctional compound having reactivity with the amino group or carboxyl group at the polyamide terminus. Acids or monoamines are preferred, and monocarboxylic acids are more preferred from the viewpoint of easy handling. In addition, acid anhydrides such as phthalic anhydride, monoisocyanates, monoacid halides, monoesters, and monoalcohols can also be used.

The monocarboxylic acid used as the terminal blocking agent is not particularly limited as long as it has reactivity with an amino group. For example, acetic acid, propionic acid, butyric acid,
Valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid,
Aliphatic monocarboxylic acids such as pivalic acid and isobutylic acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, phenylacetic acid And the like, and these can be used alone or in combination of two or more. Among them, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid are considered from the viewpoints of reactivity, sealed terminal stability, and price. And benzoic acid are particularly preferred. When the terminal group of the polyamide is capped with a monocarboxylic acid, the number of moles of the diamine component with respect to the dicarboxylic acid component is slightly increased in the production of the polyamide so that both ends of the polyamide are amino groups, A carboxylic acid may be added as a terminal blocking agent.

The monoamine used as the terminal blocking agent is not particularly limited as long as it has reactivity with a carboxyl group. Examples thereof include methylamine, ethylamine, propylamine, butylamine, hexylamine, and the like.
Aliphatic monoamines such as octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine. Can be mentioned,
These can be used alone or in combination of two or more. Of these, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline are particularly preferred from the viewpoints of reactivity, boiling point, stability of the sealed terminal, and price. When the end group of the polyamide is sealed with a monoamine, the number of moles of the diamine component relative to the dicarboxylic acid component is slightly reduced in the production of the polyamide,
So that both ends of the polyamide are carboxyl groups,
A monoamine may be added as a terminal blocking agent.

The polyamide resin used as the component (A) is polymerized by adding a polyvalent carboxylic acid having three or more functional groups to a reaction system for obtaining the polyamide resin. A structural unit derived from a polycarboxylic acid may be introduced. Here, as the polyvalent carboxylic acid having three or more functional groups, trimellitic acid, trimesic acid, pyromellitic acid and the like can be used, and the use ratio thereof is determined based on the finally obtained thermoplastic resin composition. What is necessary is just a range which does not impair the formability by melt molding.

Although the degree of polymerization of the polyamide resin used as the component (A) is not particularly limited, 1 g of 96% concentrated sulfuric acid is used.
/ Dl (25 ° C.) is 1.5
It is preferable that the polymerization degree be in the range of 6.0 to 6.0.

As a method for producing the polyamide resin used as the component (A), a polymerization method conventionally known as a method for producing a polyamide resin, that is, a melt polymerization method,
A solid phase polymerization method, a solution polymerization method, a polymerization method using a reaction type extruder, a polymerization method combining these, and the like can be used.

Examples of the catalyst which can be used in producing the polyamide resin as the component (A) include conventionally known catalysts such as phosphoric acid, phosphorous acid, hypophosphorous acid; ammonium salts thereof; Salts (potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium,
Metal salts such as titanium and antimony); their esters (ethyl ester, isopropyl ester, butyl ester, hexyl ester, isodecyl ester, octadecyl ester, decyl ester, stearyl ester, phenyl ester) and the like.

<Component (B)> The thermoplastic resin composition of the present invention
The component (B) used in the product is represented by the above general formula (I).
Compounds (hereinafter also referred to as “specific phenolic compounds”)
Say. ). Shows the structure of a specific phenolic compound
In the general formula (I), the group R¹, Group R^Two, Group R^Threeand
Group R^FourIs a hydrogen atom or an atom having 1 to 8 carbon atoms, respectively.
Alkyl group, and these groups R¹~ Group R^FourRespectively
The groups may be the same or different. However,
R¹~ Group R^FourAt least one of which is 1-8 alkyl
Group. Also, the group R^FiveIs a hydrogen atom or one carbon atom
To 3 alkyl groups. Further, the group X has 1 to 1 carbon atoms.
And 8 alkylene groups. Also, the group Y¹And group Y ^TwoIs
A hydrogen atom or a hydroxyl group, and a group Y¹And group Y^TwoHorse
At least one is a hydroxyl group.

In the general formula (I), the groups Y ¹ and Y ² are preferably bonded to a carbon atom near the carbon atom to which the group X is bonded. Further, it is preferable that Y ¹ is a hydroxyl group and Y ² is a hydrogen atom. Also, the group R
It is preferred that at least two of R ¹ to R ⁴ are alkyl groups having 1 to 8 carbon atoms, and more preferably at least three of R ¹ to R ⁴ are alkyl groups having ¹ to 8 carbon atoms. All ^four groups, particularly preferably the groups R ¹ to R ⁴ , have 1 to 1 carbon atoms.
8 alkyl groups. Further, the group R ⁵ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. Among the specific phenolic compounds, preferred compounds are those represented by the following general formula (II).

[0032]

Embedded image

Wherein R ¹ , R ² , R ³ and R ⁴ are
A hydrogen atom or an alkyl group having 1 to 8 carbon atoms;
¹ , R ² , R ³ and R ⁴ may be the same or different. However, at least one of R ^{1 to} R ⁴ is an alkyl group having 1 to 8 carbon atoms, preferably 2 or more, more preferably 3 or more, and particularly preferably all 4 have 1 to 7 carbon atoms. To 8 alkyl groups. X represents an alkylene group having 1 to 8 carbon atoms. ]

In a preferred specific phenol compound, the groups R ¹ and R ² are groups represented by the following formula (1) or groups represented by the following formula (2),
Is a compound represented by the following formula (3) or a group represented by the following formula (4).

[0035]

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In the thermoplastic resin composition of the present invention,
The ratio of the component (A) to the component (B) is 99.9 by weight.
9: 0.01 to 95: 5, preferably 99.9.
5: 0.05 to 97: 3, particularly preferably 99.3.
95: 0.05 to 99: 1. If the proportion of the component (B) is too small (the proportion of the component (A) is too large), it may be difficult to obtain a thermoplastic resin composition having excellent impact resistance and blister resistance. On the other hand, when the proportion of the component (B) is too large (the proportion of the component (A) is too small), it becomes difficult to obtain a thermoplastic resin composition having excellent impact resistance and blister resistance. is there.

<Component (C)> In the thermoplastic resin composition of the present invention, a flame retardant may be contained as the component (C). As such a flame retardant, a halogen-based flame retardant such as a brominated flame retardant or a chlorine-based flame retardant, a phosphorus-based flame retardant, or the like can be used, and these can be used alone or in combination of two or more. Of these, halogen-based flame retardants are preferred, and brominated flame retardants are particularly preferred. Preferred brominated flame retardants include brominated polystyrene, brominated polyphenylene ether, and brominated epoxy oligomer, with brominated polystyrene being particularly preferred.

The brominated polystyrene used as the component (C) is preferably a compound having a structure represented by the following general formula (III).

[0039]

Embedded image

The brominated polystyrene used as the component (C) is produced by polymerizing brominated styrene or by brominating polystyrene. Hereinafter, the brominated polystyrene obtained by the former is also referred to as “polybrominated styrene”, and the brominated polystyrene obtained by the latter is also referred to as “post-brominated polystyrene”. The bromine content in the brominated polystyrene is preferably from 40 to 75% by weight, and more preferably from 50 to 75% by weight.

The brominated polystyrene used as the component (C) may contain a structural unit derived from brominated styrene or a monomer copolymerizable with styrene, if necessary. Such copolymerizable monomers include ethylene,
Examples thereof include propylene, butadiene, butene, hexene, pentene, methylbutene, methylpentene, styrene, acrylonitrile, vinyl chloride, and vinyl acetate. Of these, ethylene, propylene, butadiene, styrene and acrylonitrile are preferred.

In producing brominated polystyrene,
Functional group-containing vinyl monomers can also be used. Such a functional group-containing vinyl monomer may be used for copolymerization with brominated styrene, or may be used for modifying a terminal or the like of brominated polystyrene. As the functional group of the functional group-containing vinyl monomer, a carboxyl group,
Examples thereof include an acid anhydride group, an oxazoline group, and an epoxy group. As specific examples of the functional group-containing vinyl monomer,
Examples include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic anhydride, vinyl oxazoline, glycidyl methacrylate, and allyl glycidyl ether.

The weight average molecular weight (Mw) of the brominated polystyrene used as the component (C) is not particularly limited, but is preferably 5,000 to 500,000, more preferably 10,000 to 300. , 000. The weight average molecular weight (Mw) was determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, dissolving the brominated polystyrene to a concentration of 1 mg / ml,
It can be obtained as a weight average molecular weight in terms of polystyrene by measuring under the conditions of ml / min and a temperature of 36 to 40 ° C.

Specific examples of the brominated polystyrene constituting the component (C) are shown in Table 1 below.

[0045]

[Table 1]

Of the brominated polystyrenes shown in Table 1 above, C-1, C-2 and C-3 which are polybrominated styrenes obtained by polymerizing brominated styrene are preferred. (C)
By using polybrominated styrene as a component,
More excellent effects of the present invention can be obtained.

The content of the component (C) in the thermoplastic resin composition of the present invention is usually 5 to 7 based on 100 parts by weight of the total of the components (A) and (B).
0 parts by weight, preferably 10 to 60 parts by weight. If the content of the component (C) is less than 5 parts by weight, the resin composition cannot be sufficiently imparted with flame resistance as an effect of adding a flame retardant. On the other hand, when the content of the component (C) is 7
If the amount exceeds 0 parts by weight, the impact resistance and the blister resistance of the obtained resin composition decrease.

<Component (D)> The thermoplastic resin composition of the present invention may contain a flame retardant auxiliary as the component (D) in addition to the component (C). Examples of such a flame retardant aid include a metal compound of Group Va of the periodic table and other metal compounds. Here, examples of the metal compound of Group Va of the periodic table include antimony compounds such as antimony trioxide, antimony pentoxide, and sodium antimonate. Examples of other metal compounds include boron oxide, zirconium oxide, iron oxide, zinc oxide, and the like. These metal compounds can be used alone or in combination of two or more. Of these, antimony compounds that are Group Va metal compounds are preferable, and antimony trioxide is particularly preferable.

The content of the component (D) in the thermoplastic resin composition of the present invention is generally from 0 to 5 based on 100 parts by weight of the total of the components (A) and (B).
0 parts by weight, preferably 1 to 30 parts by weight.
When the content of the component (D) exceeds 50 parts by weight, the resulting resin composition has reduced impact resistance and blister resistance.

<Component (E)> In the thermoplastic resin composition of the present invention, an inorganic filler may be contained as the component (E). Examples of the inorganic filler include conventionally known inorganic fillers, for example, various fillers such as fibrous, powdery, granular, plate-like, needle-like, cloth-like, and mat-like fillers. Specific examples of the component (E) include glass fiber, asbestos fiber, carbon fiber, graphite fiber, calcium carbonate, talc, catalbo, walasteinite, silica, alumina, silica alumina, diatomaceous earth, clay, calcined clay, kaolin, and mica. (Fine mica), granular glass, glass flakes, glass balloons (hollow glass), synthetic and natural mineral whiskers such as gypsum, red iron oxide, metal fibers, titanium dioxide, potassium titanate whiskers, aluminum borate whiskers, magnesium oxide, silica Calcium oxide, asbestos, sodium aluminate, calcium aluminate, aluminum, aluminum oxide, aluminum hydroxide, copper, stainless steel, zinc oxide,
Metal whiskers and the like. Among them, glass fiber, carbon fiber, kaolin, mica, talc, and various whiskers are preferable because of their excellent effect of improving mechanical strength, and glass fiber, kaolin, and talc are particularly preferable in terms of economy.

The inorganic filler used as the component (E) is
As long as the moldability and physical properties of the thermoplastic resin composition of the present invention are not impaired, the thermoplastic resin composition may be subjected to a surface treatment. Among them, amino silane, acrylic silane, vinyl,
An inorganic filler subjected to a surface treatment with a compound (such as a sizing agent) represented by urethane, acrylic urethane, or the like can be preferably used.

The content of the component (E) in the thermoplastic resin composition of the present invention may be adjusted to a specific polyamide resin component 100 comprising the component (A) and the component (B).
The amount is usually 5 to 300 parts by weight, preferably 5 to 200 parts by weight, more preferably 5 to 150 parts by weight with respect to parts by weight. When the content of the component (E) is less than 5 parts by weight,
The effect of improving the rigidity and dimensional stability, which is the effect of adding a filler, cannot be sufficiently imparted to the resin composition. On the other hand, when the content of the component (E) exceeds 300 parts by weight, the impact resistance and the blister resistance of the obtained resin composition decrease.

<Other Components> The thermoplastic resin composition of the present invention may be used in accordance with the required properties and the like, as long as the moldability and physical properties are not impaired.
Optional components other than component (E), for example, pigments, dyes, ultraviolet absorbers, weathering agents, lubricants, crystal nucleating agents, release agents, plasticizers,
An antistatic agent, a hydrophilic zeolite, a hydrophobic zeolite, or the like may be contained.

Further, in order to improve the heat resistance of the thermoplastic resin composition of the present invention, copper compounds such as copper iodide, aromatic amine compounds, hindered phenol compounds, organic phosphorus compounds, sulfur compounds and the like are used. An antioxidant or a heat stabilizer can be added and contained. As the antioxidant, hindered phenol compounds, organic phosphorus compounds, and sulfur compounds are preferable, and the use ratio is the same as the ratio of the component (B) described above. It is preferred that it is about.

Further, in the thermoplastic resin composition of the present invention, as a thermoplastic resin other than the polyamide resin, polyphenylene sulfide (PPS) resin, polyetheretherketone (PEEK) resin, polysulfone resin, liquid crystal polymer (LCP), ABS resin, polystyrene (P
S, HIPS) resin, acrylonitrile-styrene copolymer (AS) resin, polyester resin, zindiotactic polystyrene, polytetrafluoroethylene (PTF)
E) resin, polyvinylidene fluoride resin, aramid fiber,
A thermoplastic resin such as a polyethylene resin and a polypropylene resin can be contained. These thermoplastic resins may be modified with a functional group such as a carboxyl group, an acid anhydride group, an epoxy group, a hydroxyl group, an oxazoline group, an amino group, and an amide group.

<Production Method of Thermoplastic Resin Composition> The thermoplastic resin composition of the present invention comprises the components (A) and (B), and if necessary, the components (C) to (E).
The components and other components can be produced by melt-kneading using a kneader. Examples of the kneading machine used for producing the thermoplastic resin composition of the present invention include an extruder, a kneader, a roll, a Brabender, a Banbury mixer, and a continuous kneader, and these can be used in combination. It is. Of these, extruders are preferred, and twin-screw extruders are particularly preferred.

The components of the thermoplastic resin composition of the present invention may be charged into a kneader and kneaded by (i) a method in which all the components are charged at once and a kneading process is performed.
i) a method in which some components are added once or plurally and kneaded, and then the remaining components are added once or multiple times and kneaded, (iii) a part of all components , And kneading the mixture once or a plurality of times, and then kneading the remaining components of all components once or a plurality of times.

<Molding Method of Thermoplastic Resin Composition> The thermoplastic resin composition of the present invention can be molded by any molding method, for example, injection molding, compression molding, vacuum molding, sheet molding, film molding, injection press molding, and blow molding. It can be formed by molding, irregular extrusion molding, two-color molding, thermoejection molding, insert molding, outsert molding, or the like.

<Uses of Thermoplastic Resin Composition> The thermoplastic resin composition of the present invention has excellent performance, and is therefore suitable for use in electric appliances, electronics, vehicles, home appliances, architecture, sanitary, sports, and the like.
It can be used in a wide range of fields such as miscellaneous goods. Specifically, connectors, switches, sensors, sockets, capacitors, jacks, fuse holders, relays, coil bobbins, resistors, IC and LED housings, gears,
Examples include bearing retainers, spring holders, chain tensioners, washers, worm wheels, belts, filters, various housings, auto tensioners and weight rollers, breaker parts, clutch parts, and the like. Above all, the thermoplastic resin composition of the present invention is particularly suitable for a connector, a switch, a sensor, a resistor, a relay, a capacitor, a socket, a jack, a fuse holder, a coil bobbin, an IC for a surface mount system.
And is useful for housings of LEDs and the like.

[0060]

EXAMPLES Hereinafter, specific examples of the present invention will be described, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, “%” and “parts” mean “% by weight” and “parts by weight” unless otherwise specified.

[Component (A)] The following polyamide resin (a)
1) to polyamide resin (a6) were prepared. (1) Polyamide resin (a1): Polyamide 4,6 resin obtained by polycondensation of 1,4-tetramethylenediamine and adipic acid, having a melting point of 300 ° C. and 96% concentrated sulfuric acid 1 g / dl ( 25) and a relative viscosity of 3.5. (2) Polyamide resin (a2): a polyamide 6 resin obtained from ε-caprolactam, having a melting point of 223 ° C.
Having a relative viscosity of 3.3 measured with 1 g / dl of 96% concentrated sulfuric acid (25 ° C.). (3) Polyamide resin (a3): Polyamide 6,6 resin obtained by polycondensation of 1,6-hexamethylenediamine and adipic acid, having a melting point of 261 ° C. and 96% concentrated sulfuric acid 1 g / dl ( 25) and a relative viscosity of 3.2. (4) Polyamide resin (a4): a polyamide resin obtained by polycondensation of 1,6-hexamethylenediamine and terephthalic acid, having a melting point of 370 ° C. and 96% concentrated sulfuric acid 1 g / dl (25 ° C.) With a relative viscosity of 2.9 measured by (5) Polyamide resin (a5): a polyamide resin obtained by polycondensation of 1,9-nonamethylenediamine and terephthalic acid with benzoic acid as a terminal blocking agent, having a melting point of 315 ° C. 96% concentrated sulfuric acid 1 g / dl (25
° C) is 3.5. (6) Polyamide resin (a6): Diamine consisting of 85 mol% of 1,9-nonamethylenediamine and 15 mol% of 2-methyl-1,8-octanediamine and terephthalic acid, and benzoic acid as a terminal blocking agent. A polyamide resin obtained by condensation polymerization using a
Relative viscosity of 3.5 measured with 1 g / dl of 6% concentrated sulfuric acid (25 ° C.).

<Preparation Example 1> The above polyamide resin (a1)
Was used as the component (A) as it was. Hereinafter, this is referred to as (A-1)
Ingredients. <Preparation Example 2> 90 parts of the above-mentioned polyamide resin (a1) and 10 parts of the above-mentioned polyamide resin (a2) were mixed, and this mixture was melt-kneaded using a twin-screw extruder. The ingredients. Hereinafter, this is referred to as a component (A-2). The melting point of the component (A-2) was 292 ° C. <Preparation Example 3> 60 parts of the above-mentioned polyamide resin (a3) and 40 parts of the above-mentioned polyamide resin (a4) are mixed, and this mixture is melt-kneaded using a twin-screw extruder. The ingredients. Hereinafter, this is referred to as a component (A-3). The melting point of the component (A-3) was 304 ° C. <Preparation Example 4> The above polyamide resin (a5) was used as the component (A) as it was. Hereinafter, this is referred to as a component (A-4). <Preparation Example 5> The above polyamide resin (a6) was used as the component (A) as it was. Hereinafter, this is referred to as a component (A-4).

[Component (B)] As the component (B), a compound represented by the following formula (5) (“Sumilyzer GS” manufactured by Sumitomo Chemical Co., Ltd.) and a compound represented by the following formula (6) ( "Sumilyzer GM" manufactured by Sumitomo Chemical Co., Ltd.) was prepared. Hereinafter, the compound represented by the following formula (5) is referred to as (B-1)
A compound represented by the following formula (6) as a component: (B-2)
Ingredients.

[0064]

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[0065]

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[Component (C)] As the component (C) (flame retardant), polybrominated styrene “PDBS-80” (manufactured by Great Lakes Chemical Co., Ltd., bromine content 59% by weight, Mn =
21000, Mw / Mn = 1.86). [Component (D)] Antimony trioxide was prepared as the component (D) (flame retardant aid). [(E) Component] As the (E) component, a glass fiber chopped strand (surface treatment agent: aminosilane, sizing agent: urethane) having a surface diameter of 10 μm and a cut length of 3 mm was prepared. [Other components] As an antioxidant, "Irganox 1098" manufactured by Ciba Special Chemicals Co., Ltd.
Was prepared.

<Examples 1 to 10 and Comparative Examples 1 to 4> Components (A), (B), (C) and (D) and an antioxidant were added to a tumbler according to the formulation shown in Table 3 below. To obtain a mixture. Thereafter, using a twin-screw extruder (44 mmφ) having two vent ports and a side feeder attached to one vent port, the above mixture was put into a hopper of the twin-screw extruder, and the other was charged by a vacuum pump. The mixture was melted and kneaded while the gas in the cylinder was sucked from the vent port of the above, and the component (E) at a ratio shown in Table 3 below was supplied into the cylinder by a side feeder, kneaded, and pelletized. After the obtained pellets were sufficiently dried with a dehumidifying dryer, predetermined test pieces (test pieces for performance evaluation) were prepared using an injection molding machine.

<Evaluation of Resin Composition> For each of the resin composition of the present invention obtained in Examples 1 to 10 and the comparative resin composition obtained in Comparative Examples 1 to 4, the impact resistance and The blister resistance was evaluated. Table 3 also shows the results. The measurement or evaluation method is as follows.

(1) Impact resistance: Notched Izod impact strength was measured according to ASTM D256.

(2) Blister resistance: (i) Test piece: A flat plate having a thickness of 0.8 mm was obtained using an injection molding machine, and left standing for 37 hours in an environment of a temperature of 35 ° C. and a relative humidity of 90% to absorb water ( (Moisture absorption) to obtain a test piece. (Ii) Reflow test conditions: As the reflow device, "Air Reflow AIS-26" manufactured by Atec Techtron Co., Ltd.
0 "was used. The set temperature of the reflow device was as shown in Table 2 below. In Table 2, "PH1,""PH2," and "PH3" respectively mean the set temperature of the reheating preheating zone, and "RE" means the set temperature of the reflow zone.

[0071]

[Table 2]

(Iii) Evaluation: The test piece was passed through the reflow device, and the number of blisters generated on the test piece was counted.

[0073]

[Table 3]

The following can be understood from the results shown in Table 3. (1) Examples 1 to 10: Since the resin compositions according to Examples 1 to 10 contain the component (A) made of a polyamide resin and a specific phenolic compound in a specific ratio, It was confirmed that the resin had excellent impact resistance and blister resistance. (2) Comparative Examples 1-4: The resin composition according to Comparative Example 1
(B) Except that the proportion of the component is too small, the composition is the same as in Example 1, but the impact resistance and the blister resistance are inferior to the resin composition according to Example 1. It is. The resin composition according to Comparative Example 2 had the same formulation as in Example 1 except that the proportion of the component (B) was excessive, but when compared with the resin composition according to Example 1, Poor impact resistance and blister resistance. The resin composition according to Comparative Example 3 had the same formulation as in Example 10 except that the proportion of the component (B) was too small. However, when compared with the resin composition according to Example 10, Poor impact resistance and blister resistance. The resin composition according to Comparative Example 3 had the same formulation as in Example 10 except that the proportion of the component (B) was excessive, but when compared with the resin composition according to Example 10, Poor impact resistance and blister resistance.

[0075]

As described above, the thermoplastic resin composition of the present invention has excellent impact resistance and, when used as a resin material for a resin-based component used in a surface mounting method, exhibits a reflow property. The blister does not generate blisters on the surface of the resin component after passing through the furnace, and has excellent blister resistance.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) C08L 63/00 C08L 63/00 A 71/12 71/12 F term (reference) 4J002 BC112 CD122 CH072 CL001 CL011 CL031 CL051 DA018 DE097 DE107 DE117 DE127 DE238 DJ018 DJ028 DJ038 DJ048 DJ058 DK007 DL008 EJ066 FA048 FD018 FD132 FD137 FD206 GM00 GN00 GQ00

Claims (3)

[Claims] 1. A component (A) comprising a polyamide resin,
A component (B) comprising a compound represented by the following general formula (I) is contained, and the ratio of the component (A) to the component (B) is 99.99: 0.01 by weight. ~ 95: 5
A thermoplastic resin composition, characterized in that: Embedded image [Wherein R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ¹ , R ² , R
³ and R ⁴ may be the same or different. However, at least one of R ^{1 to} R ⁴ is an alkyl group having 1 to 8 carbon atoms. R ⁵ is
It represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. X
Represents an alkylene group having 1 to 8 carbon atoms. Y ¹ and Y ^{2 each} represent a hydrogen atom or a hydroxyl group, and Y ¹ and Y ²
At least one is a hydroxyl group. ] 2. A total of 10 components (A) and (B)
Component (C) consisting of a flame retardant is 5 to 70 parts by weight based on 0 parts by weight
2. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition contains 1 part by weight and 0 to 50 parts by weight of the component (D) composed of a flame retardant aid. 3. 3. A total of 10 components (A) and (B)
(E) component 5 comprising an inorganic filler with respect to 0 parts by weight
3. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition contains 300 parts by weight.