WO2020184270A1

WO2020184270A1 - Flame-retardant polyamide resin composition

Info

Publication number: WO2020184270A1
Application number: PCT/JP2020/008807
Authority: WO
Inventors: 英人小笠原; 翔平小泉; 功鷲尾
Original assignee: 三井化学株式会社
Priority date: 2019-03-12
Filing date: 2020-03-03
Publication date: 2020-09-17
Also published as: CN113412298A; JPWO2020184270A1; JP7152592B2

Abstract

The present invention addresses the problem of providing a flame-retardant polyamide resin composition that is free from halogens and generates no halogenated hydrogens when burned, has a reduced environmental impact, further has superb mechanical properties such as flexural strength and toughness, and exhibits excellent heat resistance and flame retardancy in a reflow soldering step. The problem is solved by: a flame-retardant polyamide resin composition containing 20-80 mass% of a polyamide resin component (A) including a semi-aromatic polyamide resin (A-1) and a semi-aromatic polyamide resin (A-2) different from the semi-aromatic polyamide resin (A-1), 3-15 mass% of a flame retardant (B) which is a phosphinic acid salt compound and does not have a halogen group in the molecule, and 0-50 mass% of a reinforcing material (C) (the proportions of (A), (B), and (C) are expressed as mass% with respect to the total amount of the flame-retardant polyamide resin composition); a molded article thereof; and electrical and electronic components.

Description

Flame-retardant polyamide resin composition

The present invention relates to a flame-retardant polyamide resin composition, a molded product thereof, and electrical and electronic parts.

Conventionally, as a material for forming electronic parts, a polyamide resin that can be molded into a predetermined shape by heating and melting has been used. Polyamides widely used include aliphatic polyamides such as 6 nylon and 66 nylon. Such aliphatic polyamides have good moldability, but on the other hand, they have sufficient heat resistance as a raw material for surface mount components such as connectors, which are manufactured through a process of being exposed to a high temperature such as a reflow soldering process. Does not have.

Against this background, 46 nylon was developed as a polyamide with high heat resistance. However, 46 nylon has a problem of high water absorption, and therefore, the dimensions of electrical and electronic parts molded using the 46 nylon resin composition may change due to water absorption. When the molded body absorbs water, problems such as blisters, so-called swelling, occur due to heating in the reflow soldering process. In particular, in recent years, from the viewpoint of environmental problems, there is a shift to a surface mounting method using lead-free solder. Lead-free solder has a higher melting point than conventional lead solder. Therefore, the mounting temperature has inevitably risen by 10 to 20 ° C., and the use of 46 nylon has become difficult.

In response to this, aromatic polyamides derived from aromatic dicarboxylic acids such as terephthalic acid and aliphatic alkylenediamines have been developed. Aromatic polyamide is more excellent in heat resistance and low water absorption than aliphatic polyamide such as 46 nylon.

On the other hand, electrical and electronic components such as the above connectors generally need to have high flame retardancy such as UL94 V-0 standard. Conventional polyamide resin compositions use halogen-containing flame retardants such as brominated polyphenylene ether, brominated polystyrene, and polybrominated styrene in order to comply with the above standards.

Halogen-containing flame retardants such as brominated polyphenylene ether, brominated polystyrene, and polybrominated styrene are concerned about the generation of dioxin compounds during combustion. Therefore, there is a demand from the market for the provision of flame-retardant polyamide resin compositions containing halogen-free flame retardants from halogen-containing flame retardants. Among them, the use of phosphinate compounds has attracted attention (see Patent Documents 1 to 5).

International Publication No. 2008/062755 International Publication No. 2008/126381 International Publication No. 2009/037858 International Publication No. 2009/037859 International Publication No. 2010/073595

The conventional polyamide resin composition containing a phosphinate compound has both high flame retardancy and high mechanical properties. However, with the further miniaturization of electrical and electronic components, along with high flame retardancy and reflow heat resistance for use in electrical and electronic components such as fine pitch connectors, which are thin and have a short distance between connector terminals, and small, thin-walled components. A resin composition having even higher mechanical properties is desired.

As a result of diligent research in view of such a situation, the present inventor has a flame-retardant polyamide resin composition containing at least two different semi-aromatic polyamide resins as polyamide resin components and containing a phosphinate compound as a flame retardant. We have found that the product has excellent mechanical properties such as high bending strength and high toughness without causing deterioration of reflow heat resistance and flame retardancy, and have completed the present invention. That is, the first aspect of the present invention relates to the following flame-retardant polyamide resin composition.

[1] Polyamide resin component (A) 20 to 80% by mass,
A flame-retardant polyamide resin composition containing 3 to 30% by mass of a flame retardant (B) having no halogen group in the molecule and 10 to 50% by mass of a reinforcing material (C) (however, (A), The ratio of (B) and (C) is mass% with respect to the total amount of the flame retardant polyamide resin composition),
The polyamide resin component (A) contains a semi-aromatic polyamide resin (A-1) and a semi-aromatic polyamide resin (A-2) different from the semi-aromatic polyamide resin (A-1).
The flame retardant (B) is a flame-retardant polyamide resin composition which is a phosphinate compound.
[2] The flame retardant according to [1], wherein the ratio of the total amount of the aromatic dicarboxylic acid component unit to the total amount of the dicarboxylic acid component unit of the polyamide resin component (A) is 67 mol% or more and 80 mol% or less. Sexual polyamide resin composition.
[3] The semi-aromatic polyamide resin (A-1) and the semi-aromatic polyamide resin (A-2) are both crystalline resins having a melting point of 270 ° C. or higher and 340 ° C. or lower, or one of them is 270. The flame-retardant polyamide resin composition according to [2], which is a crystalline resin having a melting point of ° C. or higher and 340 ° C. or lower, and the other is an amorphous resin.
[4] At least one of the semi-aromatic polyamide resin (A-1) and the semi-aromatic polyamide resin (A-2) has a terephthalic acid component unit of 30 to 100 mol% as a dicarboxylic acid component, other than terephthalic acid. Aromatic polyfunctional carboxylic acid component unit (a-1) consisting of 0 to 70 mol% of aromatic polyfunctional carboxylic acid component unit and / or 0 to 60 mol% of aliphatic polyfunctional carboxylic acid component unit having 4 to 20 carbon atoms. The flame-retardant polyamide resin composition according to [1] to [3], which comprises a polyfunctional amine component unit (a-2) having 4 to 25 carbon atoms.
[5] The flame retardant (B) is a flame retardant containing a phosphinate compound of formula (I) and / or a bisphosphinate compound of formula (II) and / or a polymer thereof. [1] ] To [4]. The flame-retardant polyamide resin composition according to any one of [4].

[During the ceremony,
R ¹ and ^{R 2,} identical or different, a straight-chain or branched _C 1 -C ₆ alkyl and / or aryl,
R ³ is a straight-chain or branched _C 1 _{-C 10} _alkylene, C 6 _{-C 10} _arylene, C 6 _{-C 10} alkylarylene or _C 6 _{-C 10} arylalkylene,
M is one selected from the group consisting of Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K and protonated nitrogen bases. Yes,
m indicates an integer of 1 to 4, n indicates an integer of 1 to 4, and x indicates an integer of 1 to 4. ]
[6] The flame-retardant polyamide resin composition according to any one of [1] to [5], wherein the reinforcing material (C) is a fibrous substance.
[7] Further containing 0.05 to 2% by mass of the metal compound component (D) selected from the metal hydroxide and the metal oxide.
The metal hydroxide and the metal oxide are compounds containing elements existing in Groups 2 to 12 of the Periodic Table of the Elements, and have an average particle size of 0.01 to 20 μm, [1] to The flame-retardant polyamide resin composition according to any one of [6].
[8] The flame-retardant polyamide resin composition according to [7], wherein the metal compound component (D) is a metal oxide.
[9] The flame retardant according to [8], wherein the metal oxide is at least one selected from the group consisting of an iron oxide, a magnesium oxide, a zinc oxide, and a zinc composite oxide. Sexual polyamide resin composition.
[10] The flame-retardant polyamide resin composition according to any one of [1] to [9], further containing 0.1 to 5% by mass of the flame retardant aid (E).
[11] The flame-retardant polyamide resin composition according to [10], wherein the flame retardant aid (E) is zinc borate.

The second aspect of the present invention relates to a molded product obtained by molding the flame-retardant polyamide resin composition.
[12] A molded product obtained by molding the flame-retardant polyamide resin composition according to any one of [1] to [11].

The third aspect of the present invention relates to an electric / electronic component obtained by molding the flame-retardant polyamide resin composition.
[13] An electrical and electronic component obtained by molding the flame-retardant polyamide resin composition according to any one of [1] to [11].

The flame-retardant polyamide resin composition of the present invention is halogen-free, does not generate hydrogen halide during combustion, has a reduced environmental load, and has high mechanical properties such as bending strength and toughness. Excellent heat resistance and flame retardancy in the reflow soldering process. As described above, the industrial value of the flame-retardant polyamide resin composition of the present invention is extremely high.

Therefore, the molded product of the flame-retardant polyamide resin composition of the present invention is particularly preferably used as an electric / electronic component such as a fine pitch connector having a thin wall and a short distance between connector terminals.

It is a figure which shows the relationship between the temperature and time of the reflow process of the reflow heat resistance test carried out in the Example and the comparative example of this application.

Hereinafter, the present invention will be described in detail.
[Polyamide resin component (A)]
The flame-retardant polyamide resin composition of the present invention comprises a semi-aromatic polyamide resin (A-1) and a semi-aromatic polyamide resin (A-2) different from the semi-aromatic polyamide resin (A-1). Including, the polyamide resin component (A) is contained. In the present invention, the semi-aromatic polyamide resin is a polyamide resin containing a structural unit having an aromatic ring and a structural unit having an aliphatic chain. The polyamide resin component (A) is not particularly limited as long as it can withstand the reflow soldering process, but at least one of the semi-aromatic polyamide resins (A-1) and (A-2) is the following polyfunctional carboxylic acid. A structure containing a component unit (a-1) and a polyfunctional amine component unit (a-2) is preferable, and a structure containing both of the following component units is more preferable.

[Polyfunctional carboxylic acid component unit (a-1)]
The polyfunctional carboxylic acid component unit (a-1) constituting the semi-aromatic polyamide resin (A-1) and / or (A-2) is based on the total amount of the polyfunctional carboxylic acid component unit (a-1). The terephthalic acid component unit is 30 to 100 mol%, the aromatic polyfunctional carboxylic acid component unit other than terephthalic acid is 0 to 70 mol%, and / or the aliphatic polyfunctional carboxylic acid component unit 0 to 20 having 4 to 20 carbon atoms. It has 60 mol%.

Among these, aromatic polyfunctional carboxylic acid component units other than terephthalic acid include, for example, isophthalic acid, 2-methylterephthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, trimellitic acid, pyromellitic acid, trimellitic anhydride, and pyrochloride. Merit acid and the like can be mentioned. Of these, units derived from isophthalic acid are particularly preferred. In addition, these may be used alone or in combination of two or more. When a trifunctional or higher functional polyfunctional carboxylic acid compound is contained, it is preferable that the addition amount is such that the resin does not gel, specifically, 10 mol% or less of the total 100 mol% of all carboxylic acid component units.

The aliphatic polyfunctional carboxylic acid component unit is a unit derived from an aliphatic polyfunctional carboxylic acid compound having 4 to 20, preferably 4 to 12, and more preferably 6 to 10 carbon atoms. Examples of such compounds include adipic acid, suberic acid, azelaic acid, sebacic acid, decandicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid and the like. Of these, adipic acid is particularly preferable from the viewpoint of improving mechanical properties. In addition to this, a trifunctional or higher functional polyfunctional carboxylic acid compound can be appropriately used as needed. However, the amount of the trifunctional or higher functional carboxylic acid compound should be limited so that the resin does not gel, and specifically, it is preferably 10 mol% or less based on the total of all carboxylic acid component units. ..

The semi-aromatic polyamide resin (A-1) and / or (A-2) contained 30 to 100 mol% of the terephthalic acid component unit with respect to the total amount of the polyfunctional carboxylic acid component unit (a-1). It is preferably contained in an amount of 50 to 100 mol%, more preferably 60 to 100 mol%, still more preferably 60 to 70 mol%, and the aromatic polyfunctional carboxylic acid component unit other than terephthalic acid is 0 to 70 mol%. It is preferably contained in an amount of 0 to 40 mol%. When the content of the aromatic polyfunctional carboxylic acid component, particularly terephthalic acid, increases, the amount of moisture absorbed tends to decrease and the reflow heat resistance tends to improve. In particular, the polyamide resin component (A) contained in the polyamide resin composition used in the reflow soldering process using lead-free solder is a semi-aromatic component containing 55 mol% or more, preferably 60 mol% or more of terephthalic acid component units. It is preferable to contain a polyamide resin.

Further, the semi-aromatic polyamide resin (A-1) and / or (A-2) contains 0 to 60 mol%, preferably 0 to 50 mol% of the aliphatic polyfunctional carboxylic acid component unit having 4 to 20 carbon atoms. %, More preferably in an amount of 30-40 mol%.

[Polyfunctional amine component unit (a-2)]
The polyfunctional amine component unit (a-2) constituting the semi-aromatic polyamide resin (A-1) and / or (A-2) contained in the flame-retardant polyamide resin composition of the present invention is linear and / or Examples thereof include polyfunctional amine component units having 4 to 25 carbon atoms having side chains, preferably linear and / or 4 to 12 carbon atoms having side chains, and more preferably 4 to 10 linear carbon atoms. .. Further, the polyfunctional amine component unit (a-2) may contain an alicyclic polyfunctional amine component unit.

Specific examples of the linear polyfunctional amine component unit include 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, and 1, , 10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane. Of these, 1,6-diaminohexane is preferable.

Specific examples of the linear aliphatic diamine component unit having a side chain include 2-methyl-1,5-diaminopentane, 2-methyl-1,6-diaminohexane, and 2-methyl-1,7-diamino. Examples thereof include heptane, 2-methyl-1,8-diaminooctane, 2-methyl-1,9-diaminononane, 2-methyl-1,10-diaminodecane and 2-methyl-1,11-diaminoundecane. Of these, 2-methyl-1,5-diaminopentane and 2-methyl-1,8-diaminooctane are preferable.

As the alicyclic polyfunctional amine component unit, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, isophoronediamine, Piperazine, 2,5-dimethylpiperazin, bis (4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) propane, 4,4'-diamino-3,3'-dimethyldicyclohexylpropane, 4,4'-diamino- 3,3'-Dimethyldicyclohexylmethane, 4,4'-diamino-3,3'-dimethyl-5,5'-dimethyldicyclohexylmethane, 4,4'-diamino-3,3'-dimethyl-5,5' -Dimethyldicyclohexylpropane, α, α'-bis (4-aminocyclohexyl) -p-diisopropylbenzene, α, α'-bis (4-aminocyclohexyl) -m-diisopropylbenzene, α, α'-bis (4-aminocyclohexyl) Examples of component units derived from alicyclic diamines such as aminocyclohexyl) -1,4-cyclohexane and α, α'-bis (4-aminocyclohexyl) -1,3-cyclohexane can be mentioned. Among these alicyclic diamine component units, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis (aminomethyl) cyclohexane, bis (4-aminocyclohexyl) methane, 4,4'-diamino-3 , 3'-Dimethyldicyclohexylmethane is preferred; especially 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane, 1,3-bis (aminocyclohexyl) methane, 1,3- Component units derived from alicyclic diamines such as bis (aminomethyl) cyclohexane are preferred. When a trifunctional or higher functional amine compound is used, the amount added so as not to gel the resin, specifically, 10 mol% or less of the total 100 mol% of all amine component units is preferable.

Among these, the polyfunctional amine component unit (a-2) is particularly preferably composed of only the above-mentioned linear polyfunctional amine component unit. Specifically preferred linear polyfunctional amine components are 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10- Diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane can be mentioned. Of these, 1,6-diaminohexane is preferable. It is preferable to use these linear polyfunctional amine components because the reflow heat resistance tends to be improved.

The semi-aromatic polyamide resins (A-1) and (A-2) contained in the flame-retardant polyamide resin composition of the present invention have an extreme viscosity [η] measured in 96.5% sulfuric acid at a temperature of 25 ° C. It is preferably 0.5 to 1.25 dl / g, more preferably 0.6 to 1.15 dl / g, and further preferably 0.6 to 1.05 dl / g. When the ultimate viscosities [η] of the semi-aromatic polyamide resins (A-1) and (A-2) are in this range, a polyamide resin composition having excellent fluidity, reflow heat resistance, and high toughness can be obtained.

The semi-aromatic polyamide resins (A-1) and (A-2) contained in the flame-retardant polyamide resin composition of the present invention may be crystalline or amorphous, but at least one of them must be crystalline. preferable. The crystalline semi-aromatic polyamide resin has a melting point, and in the present invention, the heat absorption peak based on melting when the temperature is raised at 10 ° C./min using a differential scanning calorimeter (DSC) is set to the semi-aromatic polyamide. It can be measured as the melting point (Tm) of the resin. The melting point of the semi-aromatic polyamide resin measured in this way is preferably 270 to 340 ° C, more preferably 290 to 340 ° C, and even more preferably 315 to 330 ° C. Semi-aromatic polyamide resins having melting points in this range have particularly excellent heat resistance. Further, when the melting point is 270 ° C. or higher, further 290 ° C. or higher, particularly 315 to 330 ° C., the flame-retardant polyamide resin composition of the present invention is used in a lead-free reflow soldering process, particularly using a lead-free solder having a high melting point. Sufficient heat resistance is achieved even when used in a soldering process. On the other hand, when the melting point is 340 ° C. or lower, the melting point is lower than 350 ° C., which is the decomposition point of polyamide, so that decomposition gas is not generated during molding and discoloration of the molded product does not occur, and sufficient thermal stability is achieved. Obtainable.

In the present invention, two different types of semi-aromatic polyamide resins are used in combination, but semi-aromatic polyamide resins (A-1) and (A-2) having different melting points (Tm) are blended to obtain the blend. The melting point (Tm) can be measured using a differential scanning calorimetry (DSC) as described above. The melting point of the semi-aromatic polyamide resin blend measured in this way is observed as a single peak. This means that the resin is homogenized, and as a result, it is considered that the glass transition temperature of the resin composition of the present invention rises and the thermal stability is improved.

[Flame Retardant (B)]
The flame retardant (B) used in the present invention, which does not have a halogen group in the molecule, is added for the purpose of reducing the flammability of the resin. The flame retardant (B) is preferably a phosphinate compound, more preferably a phosphinic acid metal salt compound.

Specific examples of the flame retardant (B) are compounds represented by the following formulas (I) and / or formulas (II).

In formulas (I) and (II), ^{R 1} and ^{R 2,} identical or different, a straight-chain or branched _C 1 -C ₆ alkyl and / or aryl,
R ³ is a straight-chain or branched _C 1 _{-C 10} _alkylene, C 6 _{-C 10} _arylene, C 6 _{-C 10} alkylarylene or _C 6 _{-C 10} arylalkylene,
M is one selected from the group consisting of Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K and protonated nitrogen bases. Yes,
m indicates an integer of 1 to 4, n indicates an integer of 1 to 4, and x indicates an integer of 1 to 4.

Specific compounds of the phosphinate compound include calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, aluminum ethylmethylphosphinate, and ethyl. Zinc methylphosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, methyl-n-propylphosphinic acid Aluminum, zinc methyl-n-propylphosphinate, calcium methanedi (methylphosphinic acid), magnesium methanedi (methylphosphinic acid), aluminum methanedi (methylphosphinic acid), zinc methanedi (methylphosphinic acid), benzene-1,4-( Calcium dimethylphosphinic acid, magnesium benzene-1,4- (dimethylphosphinic acid), aluminum benzene-1,4- (dimethylphosphinic acid), zinc benzene-1,4- (dimethylphosphinic acid), calcium methylphenylphosphinate , Magnesium methylphenylphosphinate, aluminum methylphenylphosphinate, zinc methylphenylphosphinate, calcium diphenylphosphinate, magnesium diphenylphosphinate, aluminum diphenylphosphinate, zinc diphenylphosphinate. Preferably, it is calcium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphine. Yes; more preferably aluminum diethylphosphinate.

Typical examples of the flame retardant (B) containing the phosphinate compound used in the present invention include EXOLIT OP1230 and OP930 manufactured by Clariant Japan.

[Reinforcing material (C)]
The flame-retardant polyamide resin composition of the present invention may contain a reinforcing material (C), and has various inorganic shapes such as fibrous, powdery, granular, plate-like, needle-like, cloth-like, and mat-like. Fillers can be used and can be used alone or in combination with a plurality of materials. More specifically, powdery or plate-like inorganic compounds such as silica, silica-alumina, calcium carbonate, titanium dioxide, talc, wallastonite, caustic soil, clay, kaolin, spherical glass, mica, sekkou, and red iron oxide; Needle-shaped inorganic compounds such as potassium; glass fiber (glass fiber), potassium titanate fiber, metal-coated glass fiber, ceramic fiber, wallastnite, carbon fiber, metal carbide fiber, hardened metal fiber, asbestos fiber and boron fiber Inorganic fibers such as; further, organic fibers such as aramid fibers and carbon fibers are mentioned as the reinforcing material (C). As the reinforcing material (C), a fibrous substance is preferable, and glass fiber is more preferable.

When the reinforcing material (C) is a fibrous substance, particularly glass fiber, the moldability of the flame-retardant polyamide resin composition of the present invention is improved, and the tensile strength, bending strength, flexural modulus, etc. of the molded body are improved. Mechanical properties and heat distortion properties such as heat distortion temperature are improved.

Such an effect is often remarkable especially in glass fiber. The average length of the glass fibers is usually in the range of 0.1 to 20 mm, preferably 0.2 to 6 mm. Further, the aspect ratio of the glass fiber (L (average length of the glass fiber) / D (average outer diameter of the glass fiber)) is usually in the range of 10 to 5000, preferably 2000 to 3000. Glass fibers having an average length and aspect ratio within such a range are preferably used.

Further, when the fibrous reinforcing material (C) is used, the different diameter ratio (ratio of major axis to minor axis) of the fiber cross section is larger than 1, preferably the different diameter ratio, for the purpose of preventing warpage of the molded product. It is effective to use a fibrous substance of 1.5 to 6.0.

Further, the above-mentioned filler can be used by treating it with a silane coupling agent, a titanium coupling agent, or the like. For example, the surface may be treated with a silane compound such as vinyltriethoxysilane, 2-aminopropyltriethoxysilane, or 2-glycidoxypropyltriethoxysilane.

Of the reinforcing material (C), the fibrous filler may be coated with a sizing agent. As the focusing agent, acrylic compounds typified by (meth) acrylic acid and (meth) acrylic acid ester, carboxylic acid compounds having a carbon-carbon double bond other than methacrylic acid such as maleic anhydride, and epoxy compounds. , Urethane compounds and amine compounds. Further, these can be combined to form a reinforcing material (C). Preferred combinations include combinations of acrylic compounds / carboxylic acid compounds, urethane compounds / carboxylic acid compounds, and urethane compounds / amine compounds. The above-mentioned surface treatment agent may be used in combination with a sizing agent, and the combined use improves the bondability between the fibrous filler in the composition of the present invention and other components in the composition, resulting in improved appearance and strength characteristics. improves.

The reinforcing material (C) is preferably added in a proportion of 10 to 50% by mass, preferably 10 to 45% by mass, in the flame-retardant polyamide resin composition of the present invention.

[Metal compound component (D)]
The flame-retardant polyamide resin composition of the present invention may contain a metal compound component (D) selected from a metal hydroxide and a metal oxide, and preferably contains a metal oxide. By containing these, the corrosion and wear of the steel material due to the polyamide resin composition can be further suppressed. The metal hydroxide and the metal oxide can be used alone or in combination of a plurality of compounds.

The metal of the metal hydroxide and the metal oxide is preferably a group 1 to 12 metal of the periodic table of elements, and more preferably a metal of groups 2 to 12 of the same periodic table. In particular, the metal oxide is preferably an oxide of a Group 2 to 12 element in the Periodic Table of the Elements, more preferably an oxide of a Group 4 to 12 element, and even more preferably an oxide of a Group 7 to 12 element.

Metal hydroxides and metal oxides, especially metal oxides, are used in extruders used to produce flame-retardant polyamide resin compositions, molding machines used to obtain molded articles using the compositions, and the like. It is effective in suppressing corrosion and wear of steel materials such as screws, cylinders, dies, and nozzles of the equipment used. In particular, it exerts a high suppressing effect under high temperature conditions such that the processing temperature is 270 ° C. or higher.

The metal hydroxide and the metal oxide may be particles having an average particle diameter of 0.01 to 20 μm, preferably an average particle diameter of 0.01 to 10 μm, more preferably 0.01 to 5 μm, and further preferably 0. Particles of 0.01 to 3 μm, particularly preferably 0.01 to 1 μm, particularly preferably 0.01 to 0.3 μm can be used. This is to obtain a higher effect of suppressing corrosion and wear. For the average particle size of metal hydroxide and metal oxide, the particle amount (%) in each particle size section of the primary particle is plotted using an image diffractometer (Luzex IIIU) based on a transmission electron micrograph. The distribution curve can be obtained, and the cumulative distribution curve can be obtained from the obtained distribution curve and used as the value when the cumulative degree of the cumulative distribution curve is 50%.

The BET specific surface area of the metal oxide or metal hydroxide may be 1 to 50 m ² / g, preferably 3 to 40 m ² / g, and more preferably 5 to 40 m ² / g. When the average particle size and the BET specific surface area are within the above ranges, it is often possible to obtain a molded product having excellent flame retardancy and reflow heat resistance while suppressing corrosion wear of the steel material. If the average particle size exceeds 20 μm or the BET specific surface area is less than 1 m ² / g, the effect of suppressing corrosion and wear may not be sufficiently obtained. On the other hand, if the average particle size is less than 0.01 μm or the BET specific surface area exceeds 50 m ² / g, the effect of suppressing corrosion and wear can be obtained, but flame retardancy, reflow heat resistance, and thermal stability during molding are obtained. Tends to decrease.

In the flame-retardant polyamide resin composition of the present invention, it is presumed that the metal compound component (D) selected from the metal hydroxide and the metal oxide traps the decomposition product of the flame retardant (B). Since it is considered that the trap of the decomposition product of the flame retardant (B) occurs mainly on the surface of the metal hydroxide and the metal oxide component, it is advantageous that the component has a small particle size, that is, a high specific surface area. it is conceivable that. Therefore, it is considered that metal hydroxides and metal oxides in a specific particle size range (for example, particles having an average particle size of 0.01 to 20 μm) are advantageous in suppressing corrosion wear, which is a subject of the present application.

Preferred metal elements of the metal hydroxide and the metal oxide used in the present invention include iron, magnesium and zinc, more preferably magnesium and zinc, and particularly preferably zinc.

Examples of preferable specific metal hydroxides or metal oxides include magnesium hydroxide, magnesium oxide, and zinc oxide. Other preferred examples include composite oxides of metals, more preferably zinc composite oxides such as zinc tintate and zinc hydroxytinate. Of these, zinc oxide, zinc nitrate, magnesium oxide, and magnesium hydroxide are preferable. Further, ordinary single metal oxides are preferable to composite oxides, and zinc oxide is a particularly preferable specific example.

However, borate, which is one of the composite oxides, is not regarded as a metal oxide in the present invention. When an element having a Lewis acidic potential such as boron is contained, it is presumed that corrosion resistance is unlikely to be exhibited because the trapping effect of the decomposition product of the flame retardant described later is reduced.

The flame retardant polyamide resin composition of the present invention may contain a flame retardant aid (E). The flame retardant aid (E) is effective for exhibiting a high flame retardant effect even with a small amount of the flame retardant added. Specific examples thereof include metal oxides and metal hydroxides, and these compounds can be used alone or in combination with a plurality of compounds. Specifically, zinc borate, boehmite, zinc tinate, iron oxide, and tin oxide are preferable, and zinc borate is more preferable.

When a metal oxide or a metal hydroxide is used as the flame retardant aid (E), 0.1 to 5% by mass, preferably 0.5 to 5% by mass, in the flame-retardant polyamide resin composition of the present invention. , More preferably 1 to 3% by mass. By adding a flame retardant aid within the above range, stable flame retardancy and thermal stability during molding can be imparted to the flame retardant polyamide resin composition.

In addition to the above, melamine, tris (hydroxyethyl) isocyanurate (THEIC), melamine phosphate (MP), melamine polyphosphate (MPP), melamine as nitrogen-based flame-retardant aids (E) Nitrogen compounds such as cyanurate (MC) and phosphazene compounds such as cyclic phosphazene compounds and / or linear phosphazene compounds can be used in combination.

[Other additives]
In addition to the above components, the flame retardant polyamide resin composition of the present invention is a flame retardant aid, a flame retardant, an antioxidant, a radical trapping agent, and heat-resistant stable, as long as the object of the present invention is not impaired. Agents, weather stabilizers, fluidity improvers, plastics, thickeners, antistatics, mold release agents, pigments, dyes, inorganic or organic fillers, nucleating agents, fiber reinforcements, carbon black, talc, clay, It may contain various known compounding agents such as an inorganic compound such as mica. Further, the flame-retardant polyamide resin composition of the present invention may contain an additive such as a commonly used ion scavenger. As the ion scavenger, for example, hydrotalcite and zeolite are known. In particular, the flame-retardant polyamide resin composition of the present invention further improves heat resistance, flame retardancy, rigidity, tensile strength, bending strength, and impact strength by containing the fiber reinforcing agent among the above. ..

Further, the flame-retardant polyamide resin composition of the present invention may contain other polymers as long as the object of the present invention is not impaired. Examples of such other polymers include polyethylene, polypropylene, poly4-methyl-1-pentene, ethylene / 1-butene copolymer, propylene / ethylene copolymer, propylene / 1-butene copolymer, and polyolefin elastomer. Polyolefins such as, polystyrene, polyamide, polycarbonate, polyacetal, polysulphon, polyphenylene oxide, fluororesin, silicone resin, SEBS, Teflon (registered trademark) and the like. In addition to these, modified polyolefins and the like can be mentioned. The modified polyolefin is, for example, a polyolefin modified with a carboxyl group, an acid anhydride group, an amino group, or the like. Examples of modified polyolefins include modified aromatic vinyl compounds such as modified polyethylene and modified SEBS / conjugated diene copolymers or hydrides thereof, and modified polyolefin elastomers such as modified ethylene / propylene copolymers. It is preferable that these components do not meet the UL94V-0 standard.

When the total of each component contained in the flame-retardant polyamide resin composition of the present invention is 100% by mass, the content of these polymers is preferably 4% by mass or less, more preferably 2% by mass or less, and further. It is preferably 1% by mass or less.

[Flame-retardant polyamide resin composition]
The flame-retardant polyamide resin composition of the present invention contains a polyamide resin component (A) containing a semi-aromatic polyamide resin (A-2) different from the semi-aromatic polyamide resin (A-1). Therefore, the total amount of the semi-aromatic polyamide resin (A-1) and (A-2) is the amount of the polyamide resin component (A). The ratio of the polyamide resin component (A) (which is the total of the semi-aromatic polyamide resins (A-1) and (A-2)) to the total amount of the polyamide resin composition is 20 to 80% by mass, preferably 35 to 35. It is 60% by mass. When the content of the polyamide resin component (A) in the flame-retardant polyamide resin composition is 20% by mass or more, sufficient toughness can be obtained. Further, when the content of the polyamide resin component (A) in the flame-retardant polyamide resin composition is 80% by mass or less, a sufficient flame retardant can be contained and flame retardancy can be obtained.

As described above, in the blends of semi-aromatic polyamide resins (A-1) and (A-2) having different melting points (Tm), the resins are homogenized, so a differential scanning calorimeter (DSC) is used. The measured melting point (Tm) is observed as a single peak, which increases the glass transition temperature and improves thermal stability. Therefore, in the present invention, by using two different types of semi-aromatic polyamide resins in combination, higher thermal stability can be achieved as compared with a composition containing only one type of polyamide resin. Further, since the crystallinity is lowered by using two different types of semi-aromatic polyamide resins in combination, the flame-retardant polyamide resin composition is hard and not brittle when solidified, and the toughness is improved. The polyamide resin component (A) may contain other semi-aromatic polyamide resins other than the semi-aromatic polyamide resins (A-1) and (A-2) as long as the object of the present invention is not impaired. Good. When other semi-aromatic polyamide resins are included, the total amount of the semi-aromatic polyamide resins is taken as the amount of the polyamide resin component (A).

The combination of the semi-aromatic polyamide resin (A-1) and (A-2) is not particularly limited, and can be selected according to the physical properties required for the flame-retardant polyamide resin composition. For example, when the flame-retardant polyamide resin composition is used for fine electrical and electronic parts such as connectors, a semi-aromatic polyamide resin having low fluidity (for example, to prevent the fluidity from becoming too low) is used. , Polyamide 6T / 6I and Polyamide 6T / DT) are preferably combined with a highly fluid semi-aromatic polyamide resin (for example, Polyamide 6T / 66).

The semi-aromatic polyamide resins (A-1) and (A-2) are dicarboxylic acid components of the polyamide resin component (A) (that is, the sum of the semi-aromatic polyamide resins (A-1) and (A-2)). Types and formulations of semi-aromatic polyamide resins (A-1) and (A-2) so that the ratio of the total amount of aromatic dicarboxylic acid component units to the total amount of units is 67 mol% or more and 80 mol% or less. It is preferable to select the amount. When the ratio of the total amount of the aromatic dicarboxylic acid component units is 67 mol% or more, the strength is improved because the aromatic components are sufficiently present. On the other hand, when it is 80 mol% or less, when the flame-retardant polyamide resin composition is molded, it does not become too hard, so that appropriate toughness is maintained. Moreover, since the melting point is not too high, the resin composition can be easily prepared. The ratio of the total amount of the aromatic dicarboxylic acid component unit to the total amount of the dicarboxylic acid component unit is more preferably 67 mol% or more and 75 mol% or less.

It is preferable that at least one of the semi-aromatic polyamide resins (A-1) and (A-2) is a crystalline resin having a melting point of 270 ° C. or higher and 340 ° C. or lower. Further, both the semi-aromatic polyamide resins (A-1) and (A-2) are crystalline resins having a melting point of 270 ° C. or higher and 340 ° C. or lower, or one of them has a melting point of 270 ° C. or higher and 340 ° C. or lower. More preferably, it is a crystalline resin and the other is an amorphous resin.

When both the semi-aromatic polyamide resins (A-1) and (A-2) are crystalline resins having a melting point of 270 ° C. or higher and 340 ° C. or lower, it may be possible to particularly increase the reflow heat resistance temperature. For example, even if the flame-retardant polyamide resin composition of the present invention is used in a lead-free reflow soldering process, particularly in a soldering process using lead-free solder having a high melting point, sufficient heat resistance is obtained, which is preferable. Examples of such a combination of the semi-aromatic polyamide resin include a combination of polyamide 6T / 66 (melting point: 320 ° C.) and polyamide 6T / 6I (melting point: 330 ° C.), and polyamide 6T / 66 (melting point: 320 ° C.). Examples thereof include a combination with polyamide 6T / DT (melting point: 300 ° C.).

When one of the semi-aromatic polyamide resins (A-1) and (A-2) is a crystalline resin having a melting point of 270 ° C. or higher and 340 ° C. or lower and the other is an amorphous resin, a flame-retardant polyamide resin is used. Since the crystallinity of the composition is particularly low, it is preferable from the viewpoint of increasing the toughness of the flame-retardant polyamide resin composition. Examples of such a combination of semi-aromatic polyamide resins include a combination of polyamide 6T / 66 (melting point: 320 ° C.) and polyamide 6I / 6T (amorphous). It is preferable to use PA6T / 66 in combination with another semi-aromatic polyamide resin because it is excellent in mechanical properties such as fluidity during molding of the flame-retardant polyamide resin composition, heat resistance in the reflow soldering process, strength and toughness. ..

As described above, the blending ratio of the semi-aromatic polyamide resins (A-1) and (A-2) is not particularly limited, and can be determined based on desired physical properties and the ratio of the aromatic dicarboxylic acid component unit. it can. For example, a semi-aromatic polyamide resin (A-1) containing an aromatic dicarboxylic acid component unit and an aliphatic dicarboxylic acid component unit as a dicarboxylic acid component unit, and a half containing only an aromatic dicarboxylic acid component unit as a dicarboxylic acid component unit. When used in combination with the aromatic polyamide resin (A-2), the mass ratio of (A-1) / (A-2) can be 5/95 to 95/5, but is limited to this. It is not something that is done. The mass ratio of (A-1) / (A-2) is preferably 50/50 to 95/5, more preferably 50/50 to 90/10, and even more preferably 55/45 to 85/15. When the ratio of the semi-aromatic polyamide resin (A-2) is 5 or more, a sufficient effect is obtained for improving the mechanical properties, while when it is 95 or less, a sufficient effect is obtained for reflow heat resistance and fluidity. Be done.

In the present invention, by using two or more kinds of semi-aromatic polyamide resins in combination in this way, it is possible to improve mechanical properties while maintaining flame retardancy and reflow heat resistance.

The flame-retardant polyamide resin composition preferably contains the flame retardant (B) in an amount of 3 to 30% by mass, preferably 7 to 20% by mass, based on the total amount of the polyamide resin composition. When the content of the flame retardant (B) in the flame-retardant polyamide resin composition is 3% by mass or more, sufficient flame retardancy can be obtained, and when it is 30% by mass or less, the flow during injection molding. It is preferable because the property does not deteriorate.

The flame-retardant polyamide resin composition preferably contains the reinforcing material (C) in an amount of 10 to 50% by mass, preferably 10 to 45% by mass, based on the total amount of the polyamide resin composition. When this ratio is 50% by mass or less, the fluidity at the time of injection molding does not decrease, which is preferable.

The flame-retardant polyamide resin composition contains a metal compound component (D) selected from a metal hydroxide and a metal oxide, preferably a metal oxide, in an amount of 0.05 to 2 mass with respect to the total amount of the polyamide resin composition. %, preferably 0.1 to 1% by mass, more preferably 0.1 to 0.5% by mass. When the content of the metal compound component (D) selected from the metal hydroxide and the metal oxide in the flame-retardant polyamide resin composition is 0.05% by mass or more, a sufficient effect of suppressing corrosion and abrasion of the steel material is sufficient. When it is obtained and is 10% by mass or less, flame retardancy, reflow heat resistance, and thermal stability during molding are not deteriorated, which is preferable.

In the flame-retardant polyamide resin composition, the flame retardant aid (E) is preferably 0.1 to 5% by mass, more preferably 0.5 to 5% by mass, and further, based on the total amount of the polyamide resin composition. It is preferably 1 to 3% by mass. When the content of the flame retardant aid (E) in the flame-retardant polyamide resin composition is 0.1% by mass or more, a sufficient effect of suppressing corrosion and wear of the steel material is obtained, and it is 5% by mass or less. , Flame retardancy, reflow heat resistance, and thermal stability during molding are not deteriorated, which is preferable.

The flame-retardant polyamide resin composition of the present invention has a flammability evaluation of V-0 according to the UL94 standard. More specifically, the flame-retardant polyamide resin composition of the present invention preferably has a flammability evaluation of V-0 according to the UL94 standard at a thickness of 0.8 mm or less.

The reflow heat resistant temperature after absorbing moisture at a temperature of 40 ° C. and a relative humidity of 95% for 96 hours is preferably 245 to 280 ° C., more preferably 250 to 280 ° C., still more preferably 255 to 280 ° C. It is preferably 255 to 270 ° C.

The fracture energy, which is an index of toughness, is preferably 660 to 800 mJ, more preferably 660 to 750 mJ, and even more preferably 665 to 720 mJ. The flow length obtained by injection molding of the resin into the bar flow mold is preferably 30 to 90 mm, more preferably 40 to 70 mm.

As described above, the flame-retardant polyamide resin composition of the present invention has extremely excellent characteristics and is halogen-free (that is, the content of chlorine and bromine is low), so that the risk of dioxin generation is low. It has excellent thermal stability during molding under high temperature conditions, and can exhibit high flame retardancy during combustion. Further, the flame-retardant polyamide resin composition of the present invention can exhibit excellent mechanical properties such as high bending strength and toughness after molding. The flame-retardant polyamide resin composition of the present invention can be suitably used particularly for electrical and electronic component applications.

[Method for preparing flame-retardant polyamide resin composition]
The flame-retardant polyamide resin composition of the present invention can be produced by using a known resin kneading method for each of the above-mentioned components. For example, a method of mixing each of the above-mentioned components with a Henschel mixer, a V blender, a ribbon blender, a tumbler blender, etc., or after mixing, melt-kneading with a uniaxial extruder, a multi-screw extruder, a kneader, a Banbury mixer, etc. A method of graining or grinding can be adopted.

[Molded parts and electronic and electrical component materials]
The flame-retardant polyamide resin composition of the present invention can be molded into various molded bodies by using known molding methods such as a compression molding method, an injection molding method, and an extrusion molding method. In particular, an injection molding method is preferable, and a molding machine is used for molding in an atmosphere of an inert gas typified by nitrogen, argon, or helium, specifically, for example, at a flow rate of 0.1 to 10 ml / min. It is possible to further reduce the corrosion and wear of steel materials such as cylinders and screws.

The flame-retardant polyamide resin composition of the present invention is excellent in terms of mechanical properties (particularly bending strength and toughness), reflow heat resistance, and flame retardancy. Therefore, the flame-retardant polyamide resin composition of the present invention can be used in fields where these properties are required or in the field of precision molding. Specific examples thereof include electrical components for automobiles, current breakers, connectors, switches, jacks, plugs, breakers, electrical and electronic components such as LED reflective materials, and various molded bodies such as coil bobbins and housings.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention will not be construed as being limited to these Examples.

In the examples and comparative examples, the measurement and evaluation of each property were carried out by the following methods.
[Ultimate viscosity [η]]
In accordance with JIS K6810-1977, 0.5 g of polyamide resin was dissolved in 50 ml of 96.5% sulfuric acid solution, and the number of seconds of flow of the sample solution under the condition of 25 ± 0.05 ° C. was measured using an Ubbelohde viscometer. It was measured. From the measurement results, the ultimate viscosity [η] of the polyamide resin was calculated based on the following formula.
[Η] = ηSP / [C (1 + 0.205ηSP)]
ηSP = (t-t0) / t0
[Η]: Extreme viscosity (dl / g)
ηSP: Specific viscosity, C: Sample concentration (g / dl)
t: Number of seconds (seconds) of flow of the sample solution
t0: Number of seconds (seconds) of blank sulfuric acid flowing down

[Melting point (Tm)]
The polyamide resin sample was heated using a DSC7 manufactured by Perkin Elemer, held at 330 ° C. for 5 minutes, then lowered to 23 ° C. at a rate of 10 ° C./min, and then heated at 10 ° C./min. The endothermic peak based on melting at this time was taken as the melting point of the polyamide resin.

[Bending test]
The polyamide resin composition was injection-molded under the following conditions to prepare a test piece having a thickness of 3.2 mm.
Molding machine: SE75EV-A manufactured by Sumitomo Heavy Industries, Ltd.
Molding machine cylinder temperature: 330 ° C
Mold temperature: 120 ° C
The prepared test piece was left at a temperature of 23 ° C. in a nitrogen atmosphere for 24 hours.
Next, a bending test was performed under an atmosphere of a temperature of 23 ° C. and a relative humidity of 50% at a bending tester: AB5 manufactured by NTESCO, a span of 51 mm, and a bending speed of 12.7 mm / min.
The energy (toughness) required to break the test piece was determined from the bending strength, strain amount, and elastic modulus.

[Flow length test (liquidity)]
The polyamide resin compositions produced in Examples and Comparative Examples were injected using a bar flow mold having a width of 10 mm and a thickness of 0.5 mm under the following conditions to determine the flow length (mm) of the resin in the mold. It was measured.
Injection molding machine: Sodick Plastic Co., Ltd., Tupearl TR40S3A
Injection set pressure: 2000 kg / cm ²
Cylinder set temperature: Melting point of each polyamide resin + 10 ° C
Mold temperature: 120 ° C

[Reflow heat resistance test]
The polyamide resin compositions produced in Examples and Comparative Examples were injection-molded under the following conditions to prepare test pieces having a length of 64 mm, a width of 6 mm, and a thickness of 0.8 mm.
Molding machine: Sodick Plus Tech Co., Ltd., Tupearl TR40S3A
Molding machine cylinder temperature: Melting point of each polyamide resin + 10 ° C
Mold temperature: 100 ° C

The prepared test piece was humidity-controlled at a temperature of 40 ° C. and a relative humidity of 95% for 96 hours.
The test piece subjected to the humidity control treatment was placed on a glass epoxy substrate having a thickness of 1 mm. A temperature sensor was installed on this board. The glass epoxy substrate on which the test piece was placed was set in an air reflow soldering apparatus (AIS-20-82-C manufactured by Atec Techtron Co., Ltd.), and the temperature profile reflow step shown in FIG. 1 was performed. As shown in FIG. 1, the temperature is raised to 230 ° C. at a predetermined rate; then, in 20 seconds, a predetermined set temperature (a is 270 ° C., b is 265 ° C., c is 260 ° C., d is 255 ° C., e was heated to 235 ° C.) and then lowered to 230 ° C. At this time, the maximum value of the set temperature at which the test piece did not melt and blister did not occur on the surface was obtained, and the maximum value of this set temperature was defined as the reflow heat resistant temperature.

In general, the reflow heat resistance temperature of a test piece that has absorbed moisture tends to be inferior to that in an absolutely dry state.

[Combustibility test]
The polyamide resin compositions produced in Examples and Comparative Examples were injection-molded under the following conditions to prepare 1/32 inch × 1/2 × 5 inch test pieces. Using the prepared test piece, a vertical combustion test was conducted in accordance with the UL94 standard (UL Test No. UL94 dated June 18, 1991), and the flame retardancy was evaluated.
Molding machine: Sodick Plus Tech Co., Ltd., Tupearl TR40S3A
Molding machine cylinder temperature: Melting point of each polyamide resin + 10 ° C
Mold temperature: 120 ° C

The polyamide resin component (A), flame retardant (B), reinforcing material (C), metal hydroxide (D), and other components used in Examples and Comparative Examples are shown.

[Polyamide resin component (A)]
(Polyamide 6T / 66)
Composition: Dicarboxylic acid component unit (terephthalic acid: 62.5 mol%, adipic acid: 37.5 mol%), diamine component unit (1,6-diaminohexane: 100 mol%)
Extreme viscosity [η]: 0.8 dl / g
Melting point: 320 ° C

(Polyamide 6T / 6I)
Composition: Dicarboxylic acid component unit (terephthalic acid: 70 mol%, isophthalic acid: 30 mol%), diamine component unit (1,6-diaminohexane: 100 mol%) Extreme viscosity [η]: 1.0 dl / g Melting point: 330 ℃

(Polyamide 6T / DT)
Composition: Dicarboxylic acid component unit (terephthalic acid: 100 mol%), diamine component unit (2-methyl 1,5 pentanediamine: 50 mol%, 1,6-diaminohexane: 50 mol%)
Extreme viscosity [η]: 0.9 dl / g
Melting point: 300 ° C

(Polyamide 6I / 6T)
Composition: Dicarboxylic acid component unit (terephthalic acid: 33 mol%, isophthalic acid: 67 mol%), diamine component unit (1,6-diaminohexane: 100 mol%)
Extreme viscosity [η]: 0.65 dl / g
Amorphous

(Polyamide 12)
Polyamide 12 (PA12): UBESTA 3014B, manufactured by Ube Industries, Ltd.

(Polyamide 6T / 6I / 66)
Composition: Dicarboxylic acid component unit (terephthalic acid: 44 mol%, isophthalic acid: 36 mol%, adipic acid: 20 mol%), diamine component unit (1,6-diaminohexane: 100 mol%)
Extreme viscosity [η]: 1.2 dl / g
Melting point: 260 ° C

[Flame Retardant (B)]
EXOLIT OP1230 (phosphinate compound) manufactured by Clariant Japan Co., Ltd.
Phosphorus content: 23.8% by mass

[Reinforcing material (C)]
Glass fiber / Nippon Electric Glass Co., Ltd., ECS03T-262H

[Metal compound component (D)]
Zinc oxide, average particle size 0.02 μm

In addition to the above-mentioned polyamide resin component (A), flame retardant (B), reinforcing material (C), and metal compound component (D), zinc borate (flame retardant, manufactured by US Borax, Firebrake 500), talc. (Matsumura Sangyo Co., Ltd., trade name: High Filler # 100 Hakudo 95), 12-hydroxystearic acid Ba (sliding, Nitto Kasei Kogyo Co., Ltd., BS-6) was used.

The above polyamide resin was manufactured by the following method.

[Manufacturing Example 1]
Production of Polyamide 6T / 66 (PA6T / 66) 1,6-Hexamethylenediamine 2905 g (25.0 mol), Terephthalic Acid 2475 g (14.9 mol), Adipic Acid 1461 g (10.0 mol), Benzoic Acid 73.2 g (0.60 mol), 5.7 g of sodium hypophosphate monohydrate and 545 g of distilled water were placed in an autoclave having a content of 13.6 L and substituted with nitrogen. Stirring was started at 190 ° C. and the internal temperature was raised to 250 ° C. over 3 hours. At this time, the internal pressure of the autoclave was increased to 3.03 MP (A). After continuing the reaction for 1 hour as it was, the low-order condensate was extracted by releasing it into the atmosphere from a spray nozzle installed in the lower part of the autoclave. Then, the low-order condensate was cooled to room temperature, the low-order condensate was pulverized with a pulverizer to a particle size of 1.5 mm or less, and dried at 110 ° C. for 24 hours. The water content of the obtained low-order condensate was 4100 ppm, and the ultimate viscosity [η] was 0.15 dl / g.
Next, this low-order condensate was placed in a shelf-stage solid-phase polymerization apparatus, and after nitrogen substitution, the temperature was raised to 180 ° C. over about 1 hour and 30 minutes. Then, the reaction was carried out for 1 hour and 30 minutes, and the temperature was lowered to room temperature. The ultimate viscosity [η] of the obtained prepolymer was 0.20 dl / g.
Then, the obtained prepolymer was melt-polymerized by a twin-screw extruder having a screw diameter of 30 mm and L / D = 36 at a barrel set temperature of 330 ° C., a screw rotation speed of 200 rpm, and a resin supply rate of 6 kg / h. , PA6T / 66, which is a semi-aromatic polyamide resin, was obtained.

[Manufacturing Example 2]
Production of Polyamide 6T / 6I (PA6T / 6I) Raw materials are 1,6-diaminohexane 2800 g (24.1 mol), terephthalic acid 2774 g (16.7 mol), isophthalic acid 1196 g (7.2 mol), benzoic acid. Semi-aromatic polyamide in the same manner as the preparation of semi-aromatic polyamide resin (A-1), except that it was changed to 36.6 g (0.30 mol) and 5.7 g of sodium hypophosphate-hydrate. The resin PA6T / 6I was prepared.

[Production Example 3]
Production of Polyamide 6T / DT (PA6T / DT) 1,6-Hexamethylenediamine 1312 g (11.3 mol), 2-Methyl-1,5-pentanediamine 1312 g (11.3 mol), Terephthalic acid 3655 g (22.0 mol) mol), sodium hypophosphite 5.5g (5.2 × ^{10 -2} mol), and deionized water 640ml were charged into a 1 liter reactor. after nitrogen substitution, 250 ° C., under the conditions of 35 kg / cm ² It was allowed to react for 1 hour. The molar ratio of 1,6-hexanediamine to 2-methyl-1,5-pentanediamine was 50:50. After 1 hour, the reaction product produced in the reactor was withdrawn into a receiver connected to the reactor and the pressure was set to be about 10 kg / cm ² lower, and the ultimate viscosity [η] was 0.15 dl. A prepolymer of / g was obtained.
Next, the obtained prepolymer was dried and then melt-polymerized at a cylinder set temperature of 330 ° C. using a twin-screw extruder to obtain PA6T / DT, which is a semi-aromatic polyamide resin.

[Manufacturing Example 4]
Production of Polyamide 6I / 6T (PA6I / 6T) 1,6-Hexanediamine 2800 g (24.1 mol), terephthalic acid 1390 g (8.4 mol), isophthalic acid 2581 g (15.5 mol), benzoic acid 109.5 g (0.9 mol), 5.7 g of sodium hypophosphate monohydrate and 545 g of distilled water were placed in an autoclave having a content of 13.6 L and substituted with nitrogen. Stirring was started from 190 ° C. and the internal temperature was raised to 250 ° C. over 3 hours. At this time, the internal pressure of the autoclave was increased to 3.02 MPa. After continuing the reaction for 1 hour as it was, the low-order condensate was extracted by releasing it into the atmosphere from a spray nozzle installed in the lower part of the autoclave. Then, the low-order condensate was cooled to room temperature, pulverized with a pulverizer to a particle size of 1.5 mm or less, and dried at 110 ° C. for 24 hours. The water content of the obtained low-order condensate was 3000 ppm, and the ultimate viscosity [η] was 0.14 dl / g.
Next, this low-order condensate is melt-polymerized by a twin-screw extruder having a screw diameter of 30 mm and L / D = 36 at a barrel set temperature of 330 ° C., a screw rotation speed of 200 rpm, and a resin supply speed of 6 kg / h. , PA6I / 6T, which is a semi-aromatic polyamide resin, was obtained.

[Production Example 5]
Production of Polyamide 6T / 6I / 66 (PA6T / 6I / 66) 1741 g (10.5 mol) of terephthalic acid, 2800 g (24.1 mol) of 1,6-hexanediamine, 1437 g (9.0 mol) of isophthalic acid, adipic acid Contains 699 g (4.8 mol) of acid, 36.5 g (0.3 mol) of benzoic acid, 5.7 g of sodium hypophosphate-hydrate (0.08% by weight based on raw material) and 545 g of distilled water. It was placed in an autoclave in an amount of 13.6 L and replaced with nitrogen. Stirring was started from 190 ° C. and the internal temperature was raised to 250 ° C. over 3 hours. At this time, the internal pressure of the autoclave was increased to 3.03 MPa. After continuing the reaction for 1 hour as it was, the low condensate was extracted by releasing it into the atmosphere from a spray nozzle installed in the lower part of the autoclave. Then, after cooling to room temperature, it was pulverized with a pulverizer to a particle size of 1.5 mm or less, and dried at 110 ° C. for 24 hours. The water content of the obtained low condensate was 4100 ppm, and the ultimate viscosity [η] was 0.15 dl / g. Next, this low condensate was placed in a shelf-stage solid-phase polymerization apparatus, and after nitrogen substitution, the temperature was raised to 180 ° C. over about 1 hour and 30 minutes. Then, the reaction was carried out for 1 hour and 30 minutes, and the temperature was lowered to room temperature. The ultimate viscosity [η] of the obtained polyamide was 0.20 dl / g. Then, it is melt-polymerized with a twin-screw extruder having a screw diameter of 30 mm and L / D = 36 at a barrel set temperature of 330 ° C., a screw rotation speed of 200 rpm, and a resin supply rate of 6 kg / h to obtain a semi-aromatic polyamide resin. PA6T / 6I / 66 was obtained.

[Examples 1 to 8] and [Comparative Examples 1 to 3]
Each of the above components was mixed in an amount ratio as shown in Table 1, mounted on an extruder with a twin-screw vent set at a temperature of 320 ° C., and melt-kneaded to obtain a pellet-shaped flame-retardant polyamide resin composition. .. Next, each property of the obtained flame-retardant polyamide resin composition was evaluated, and the results are shown in Table 1.

As shown in Table 1, two different types of semi-aromatic polyamide resins are compared with Comparative Example 1 in which only one type of semi-aromatic polyamide resin is contained as the polyamide resin component (A) together with the flame retardant (B). It can be seen that in Examples 1 to 8 containing the polyamide resin component (A), mechanical properties (particularly bending strength and toughness) are improved while maintaining high flame retardancy, reflow heat resistant temperature and flow length.

Further, Example 2 in which the ratio of the total amount of the aromatic dicarboxylic acid component unit is 67 mol% or more and 80 mol% or less is the same except that the ratio of the total amount of the aromatic dicarboxylic acid component unit is less than 67 mol%. Compared with Examples 4 and 5 having the composition of, the bending strength and toughness are high. It is considered that this is because the aromatic component is sufficiently present.

A crystalline resin (a combination of PA6T / 66 and PA6T / 6I or PA6T / DT) in which both the semi-aromatic polyamide resins (A-1) and (A-2) have a melting point of 270 ° C. or higher and 340 ° C. or lower. The flame-retardant polyamide resin compositions of Examples 1 and 2 had a very high reflow heat resistance temperature of 255 ° C. Further, one of the semi-aromatic polyamide resins (A-1) and (A-2) is a crystalline resin (PA6T / 66) having a melting point of 270 ° C. or higher and 340 ° C. or lower, and the other is an amorphous resin (PA6I). The flame-retardant polyamide resin composition of Example 3 of / 6T) had a very high toughness exceeding 700 mJ. It is considered that this is because the crystallinity of the flame-retardant polyamide resin composition is particularly low.

On the other hand, in Comparative Example 2 containing the semi-aromatic polyamide resin and the aliphatic polyamide resin as the polyamide resin component (A), the bending strength, elastic modulus and toughness were lower than those in Comparative Example 1, and the reflow heat resistance temperature was also high. It decreased and the flame retardancy was rejected. Further, in Comparative Example 3 in which PA6T / 6I / 66 having the same monomer composition as in Example 1 in which PA6T / 66 and PA6T / 6I were used alone was used alone, the flame retardancy was good, but the bending strength and bending strength were improved. The toughness was very low, and the flow length and reflow heat resistance temperature were also low.

This application claims priority based on Japanese Patent Application No. 2019-044932 filed on March 12, 2019. All the contents described in the application specification are incorporated in the application specification.

The flame-retardant polyamide resin composition of the present invention does not contain a halogen-based flame retardant, has excellent bending strength and toughness, and also has excellent reflow heat resistance and flame retardancy. In particular, it can be suitably used for electrical and electronic applications in which parts are assembled by a surface mount method using high melting point solder such as lead-free solder. Preferably, it can be applied to the field of thin-walled parts for the above-mentioned applications. Alternatively, it can be satisfactorily used for applications in the precision molding field.

Claims

Polyamide resin component (A) 20 to 80% by mass,
A flame-retardant polyamide resin composition containing 3 to 30% by mass of a flame retardant (B) having no halogen group in the molecule and 10 to 50% by mass of a reinforcing material (C) (however, (A), The ratio of (B) and (C) is mass% with respect to the total amount of the flame retardant polyamide resin composition),
The polyamide resin component (A) contains a semi-aromatic polyamide resin (A-1) and a semi-aromatic polyamide resin (A-2) different from the semi-aromatic polyamide resin (A-1).
The flame retardant (B) is a flame-retardant polyamide resin composition which is a phosphinate compound.
The flame-retardant polyamide resin according to claim 1, wherein the ratio of the total amount of the aromatic dicarboxylic acid component unit to the total amount of the dicarboxylic acid component unit of the polyamide resin component (A) is 67 mol% or more and 80 mol% or less. Composition.
The semi-aromatic polyamide resin (A-1) and the semi-aromatic polyamide resin (A-2) are
Claim 1 or claim, wherein both are crystalline resins having a melting point of 270 ° C. or higher and 340 ° C. or lower, or one is a crystalline resin having a melting point of 270 ° C. or higher and 340 ° C. or lower and the other is an amorphous resin. 2. The flame-retardant polyamide resin composition according to 2.
At least one of the semi-aromatic polyamide resin (A-1) and the semi-aromatic polyamide resin (A-2)
As the dicarboxylic acid component, the terephthalic acid component unit is 30 to 100 mol%, the aromatic polyfunctional carboxylic acid component unit other than terephthalic acid is 0 to 70 mol%, and / or the aliphatic polyfunctional carboxylic acid having 4 to 20 carbon atoms. Polyfunctional amine component unit (a-1) consisting of component unit 0 to 60 mol% and
The flame-retardant polyamide resin composition according to any one of claims 1 to 3, which comprises a polyfunctional amine component unit (a-2) having 4 to 25 carbon atoms.
The flame retardant (B) is a flame retardant containing the phosphinate compound of the formula (I) and / or the bisphosphinate compound of the formula (II) and / or a polymer thereof. The flame retardant polyamide resin composition according to any one of the above.

[During the ceremony,
R 1 and R 2, identical or different, a straight-chain or branched C 1 -C 6 alkyl and / or aryl,
R 3 is a straight-chain or branched C 1 -C 10 alkylene, C 6 -C 10 arylene, C 6 -C 10 alkylarylene or C 6 -C 10 arylalkylene,
M is one selected from the group consisting of Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K and protonated nitrogen bases. Yes,
m indicates an integer of 1 to 4, n indicates an integer of 1 to 4, and x indicates an integer of 1 to 4. ]
The flame-retardant polyamide resin composition according to any one of claims 1 to 5, wherein the reinforcing material (C) is a fibrous substance.
Further containing 0.05 to 2% by mass of the metal compound component (D) selected from the metal hydroxide and the metal oxide,
The metal hydroxide and the metal oxide are compounds containing elements existing in groups 2 to 12 of the Periodic Table of the Elements, and the average particle size is 0.01 to 20 μm, claims 1 to 1. The flame-retardant polyamide resin composition according to any one of 6.
The flame-retardant polyamide resin composition according to claim 7, wherein the metal compound component (D) is a metal oxide.
The flame-retardant polyamide resin according to claim 8, wherein the metal oxide is at least one selected from the group consisting of an iron oxide, a magnesium oxide, a zinc oxide, and a zinc composite oxide. Composition.
The flame-retardant polyamide resin composition according to any one of claims 1 to 9, further containing 0.1 to 5% by mass of the flame-retardant aid (E).
The flame retardant polyamide resin composition according to claim 10, wherein the flame retardant aid (E) is zinc borate.
A molded product obtained by molding the flame-retardant polyamide resin composition according to any one of claims 1 to 11.
An electrical and electronic component obtained by molding the flame-retardant polyamide resin composition according to any one of claims 1 to 11.