JP2010126541A - Flame-retardant resin composition and its use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame-retardant resin composition excellent in the flame retardancy of an obtained molding and excellent in both of moldability and adhesive property to a mold, a flame-retardant insulating sheet or film obtained from the flame-retardant resin composition, and to provide an electric or electronic apparatus using the flame-retardant insulating sheet or film. <P>SOLUTION: The flame-retardant resin composition contains a resin containing a polycarbonate resin or a polyolefin resin and a flame retardant, wherein this flame retardant comprises a nitrogen-containing compound. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a flame retardant resin composition containing a resin such as a polycarbonate resin and its use.

  Conventionally, a flame retardant is blended with a thermoplastic resin to impart flame retardancy to a resin molded body. For example, in order to improve the flame retardancy of a polycarbonate resin, a method of blending a large amount of an oligomer or polymer of a carbonate derivative of brominated bisphenol A has been used.

  However, in order to improve the flame retardancy of the polycarbonate resin, it is necessary to blend a large amount of an oligomer or polymer of a carbonate derivative of brominated bisphenol A, which means that the impact resistance of the molded product is lowered and cracking is likely to occur. There's a problem. In addition, since a large amount of a halogen-containing compound containing bromine is blended, there are many problems such as generation of a gas containing halogen during combustion and generation of a halogenated gas harmful to the human body. Therefore, a flame retardant resin composition using a flame retardant that does not generate a gas containing halogen is desired.

  Patent Document 1 describes a thermoplastic resin composition containing ammonium polyphosphate, a phosphorus-containing compound, and a nitrogen-containing cyclic compound as a flame retardant. Melamine cyanurate is mentioned as the nitrogen-containing cyclic compound.

Patent Documents 2 and 3 describe a flame retardant resin composition containing a polycarbonate resin and the like, a phosphate ester compound as a flame retardant, and a fibrous material.
JP 2000-154322 A JP 2002-30209 A JP 2002-226694 A

However, the technique described in the above document has room for improvement in the following points.
In Patent Document 1, although a nitrogen-containing cyclic compound is used in combination with a large amount of ammonium polyphosphate as a flame retardant, there is a point to be improved in heat resistance and flame retardancy.

  In Patent Documents 2 and 3, low molecular weight phosphate esters such as aromatic diphosphates that are used need to be added in large quantities to impart flame retardancy, which may cause deterioration in heat resistance and mechanical properties There was sex.

  The present inventors have conducted intensive research in such a situation and found the following points.

  Usually, a phosphorus-based, silicone-based, or organometallic salt-based flame retardant is used to make a resin molded body flame-retardant. By blending these flame retardants, a carbonized layer can be formed on the surface of the molded body during combustion. The carbonized layer formed on the surface of the molded body can block heat transfer from the flame to the molded body, and further suppress the release of flammable gas from the molded body, thus making the resin molded body flame-retardant. it is conceivable that. However, with only the resin and the flame retardant, the molded body melts and deforms due to heat at the time of combustion, and the carbonized layer (char) cannot maintain its shape, and effective flame retardancy cannot be expressed. was there.

  In addition, when a fibrous fluorine-based resin (for example, PTFE) is used as the anti-drip agent in the flame-retardant resin composition, a carbonized layer that is stable during combustion in a general UL-94 combustion test and a vertical combustion test. Can be formed. However, there is still room for improvement in flame retardancy, and it was necessary to review the flame retardant mechanism itself that forms the carbonized layer.

  The inventors of the present invention have made further studies, and by adding a flame retardant composed of a nitrogen-containing compound to a predetermined resin, unlike the conventional flame retardant mechanism, the resin has a low molecular weight during combustion. It has been found that flame retardancy is manifested.

  Furthermore, the present inventors can improve the flame retardancy of the molded article by adding a flame retardant comprising a nitrogen-containing compound, and this flame retardant resin composition has moldability and mold adhesion. It was found that both were excellent.

The present invention is shown below.
(1) A resin containing a polycarbonate resin or a polyolefin resin, and a flame retardant,
The flame retardant resin composition, wherein the flame retardant comprises a nitrogen-containing compound.
(2) The flame retardant resin composition according to (1), wherein the nitrogen-containing compound has a triazine skeleton.

(3) The flame retardant resin composition according to (1) or (2), wherein the nitrogen-containing compound is a melamine compound.
(4) The nitrogen-containing compound is one or more selected from the group consisting of melamine, melamine cyanurate, melamine isocyanurate, and derivatives thereof, according to any one of (1) to (3) Flame retardant resin composition.

(5) The flame retardant resin composition according to (4), wherein the nitrogen-containing compound is melamine cyanurate.
(6) The flame retardant resin composition according to any one of (1) to (5), wherein 0.1 to 30 parts by weight of the flame retardant is included with respect to 100 parts by weight of the resin.

(7) The flame retardant resin composition according to any one of (1) to (6), wherein the flame retardant has an average particle size of 0.01 to 30 μm.
(8) The flame retardant resin composition according to any one of (1) to (7), wherein the resin includes a polycarbonate resin.

(9) The flame-retardant resin composition according to any one of (1) to (8), wherein the polycarbonate resin has a weight average molecular weight of 1.2 × 10 ^{4 to} 3.5 × 10 ⁴ .
(10) A flame-retardant insulating sheet or film obtained by molding the flame-retardant resin composition according to any one of (1) to (9).
(11) An electric / electronic device using the flame-retardant insulating sheet or film according to (10).

  According to the present invention, a flame retardant resin composition excellent in both heat resistance and flame retardancy of the obtained molded article, further moldability and mold adhesion, and difficulty obtained from this flame retardant resin composition Provided are a flame-retardant insulating sheet or film, and an electric / electronic device using the flame-retardant insulating sheet or film.

<Flame-retardant resin composition>
The flame retardant resin composition of the present invention includes a resin containing a polycarbonate resin or a polyolefin resin and a flame retardant made of a nitrogen-containing compound.

(resin)
Polycarbonate resin The polycarbonate resin used in the present invention is obtained by a phosgene method in which various dihydroxydiaryl compounds and phosgene are reacted, or a transesterification method in which a dihydroxydiaryl compound and a carbonate such as diphenyl carbonate are reacted.

  Examples of the dihydroxydiaryl compound include bisphenol 4-, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2, 2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3) Bis (hydroxyaryl) alkanes such as tert-butylphenyl) propane, bis (hydroxy) such as 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane Aryl) cycloalkanes, 4,4′-dihydroxydiphenyl ether, 4 Dihydroxy diaryl ethers such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, dihydroxy diaryls such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide Sulfides, 4,4′-dihydroxydiphenyl sulfoxide, dihydroxydiaryl sulfoxides such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxy And dihydroxydiaryl sulfones such as −3,3′-dimethyldiphenyl sulfone. These may be used alone or in combination of two or more.

There is no particular limitation on the weight average molecular weight of the polycarbonate resin used in the present invention, flame retardancy, moldability and mold adhesion surface than ^{1.2 × 10 4 ~3.5 × 10 4} , preferably ^{1.5 × 10 4 ~3.0 × 10 4} , more preferably from ^{1.8 × 10 4 ~2.8 × 10 4} . The weight average molecular weight of the polycarbonate resin can be calculated by polystyrene conversion by gel permeation chromatography.

  Moreover, when manufacturing such polycarbonate resin, a molecular weight regulator, a catalyst, etc. may be added as needed.

Polyolefin resin The polyolefin resin used in the present invention includes a high density polyethylene resin, a polypropylene resin, a polybutene resin, an ethylene- (meth) acrylic acid copolymer, an ethylene- (meth) acrylic acid methyl copolymer, an ethylene- Examples include (meth) ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, maleic anhydride-modified polyethylene, carboxylic acid-modified polyethylene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer. These resins can be used alone or in combination of two or more.

  In the present invention, a polycarbonate resin and a polyolefin resin can be used in combination. In the present invention, a polycarbonate resin is preferably included from the viewpoint of heat resistance and bending workability.

  Resins used in the present invention include polyester resin, polyethylene terephthalate resin, polyarylate resin, polybutylene terephthalate resin, polylactic acid, styrene copolymer, polyacetal resin, polyamide resin, polyphenylene ether resin, polyphenylene sulfide Resin, polymethyl methacrylate resin, cellulose ester resin and the like can be used in combination.

(Flame retardants)
The flame retardant used in the present invention comprises a nitrogen-containing compound. Thus, when the flame retardant is substantially composed only of a nitrogen-containing compound, the resulting molded article is excellent in both flame retardancy and heat resistance, as well as molding processability and mold adhesion.

As the nitrogen-containing compound, a compound having a triazine skeleton is preferably used from the viewpoint of the above effect.
Compounds having a triazine skeleton include melamine; melamine derivatives such as butyl melamine, trimethylol melamine, hexamethylol melamine, hexamethoxymethyl melamine, melamine phosphate; cyanuric acid; methyl cyanurate, diethyl cyanurate, trimethyl cyanurate, triethyl Cyanuric acid derivatives such as cyanurate; isocyanuric acid; methyl isocyanurate, N, N′-diethyl isocyanurate, trismethyl isocyanurate, trisethyl isocyanurate, bis (2-carboxyethyl) isocyanurate, 1,3,5- Isocyanuric acid derivatives such as tris (2-carboxyethyl) isocyanurate, tris (2,3-epoxypropyl) isocyanurate; melamine cyanurate; melamine isocyanurate And so on. These compounds can be used alone or in combination of two or more.

  In the present invention, it is more preferable to use one or more melamine compounds selected from the group consisting of melamine, melamine cyanurate, melamine isocyanurate and derivatives thereof as the compound having a triazine ring skeleton. It is particularly preferable to use it. Thereby, it is excellent in balance with respect to both the flame retardance and heat resistance of the obtained molded body, and further the molding processability and mold adhesion of the flame retardant resin composition.

  In this invention, 0.1-30 weight part of a flame retardant with respect to 100 weight part of resin, Preferably it is 1-20 weight part, More preferably, it can contain 2-10 weight part.

When the blending amount is not less than the lower limit, the resulting molded article has excellent flame retardancy, and when it is not more than the upper limit, the moldability and mold adhesion are excellent. That is, by blending in the above range, the obtained molded article is more excellent in flame retardancy and heat resistance, molding processability, and mold adhesion.
Moreover, in this invention, even if it adds a flame retardant which consists of a nitrogen-containing compound in large quantities, a heat resistant fall is suppressed.

  The average particle size of the flame retardant can be 0.01 to 30 μm, preferably 0.5 to 20 μm, and more preferably 1 to 10 μm. By using a flame retardant having an average particle diameter in this range, both molding processability and mold adhesion are excellent. The average particle diameter can be measured by a laser diffraction / scattering method.

  In the flame retardant resin composition of the present invention, additives usually used as desired, for example, stabilizers, lubricants, processing aids, pigments, antistatic agents, antioxidants, neutralizing agents, ultraviolet absorbers, A dispersant and a thickener can also be contained.

In the flame retardant resin composition of the present invention, the following combinations can be exemplified as preferred embodiments.
The flame retardant resin composition of the present invention contains 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight, more preferably 2 to 10 parts by weight of melamine cyanurate with respect to 100 parts by weight of the polycarbonate resin. be able to.

And as a polycarbonate resin and a melamine cyanurate, it is preferable to satisfy | fill all the following physical properties. Note that these numerical ranges can be arbitrarily combined.
-Viscosity average molecular weight of polycarbonate resin: 1.2 × 10 ^{4 to} 3.5 × 10 ⁴ , preferably 1.5 × 10 ^{4 to} 3.0 × 10 ⁴ , more preferably 1.8 × 10 ⁴ to 2. 8 × 10 ⁴ Average particle size of melamine cyanurate: 0.01 to 30 μm, preferably 0.5 to 20 μm, more preferably 1 to 10 μm

<Flame retardant insulation sheet or film>
A method for producing a flame-retardant insulating sheet or film using the flame-retardant resin composition of the present invention is not particularly limited, and a calendering method, an extrusion method, a pressing method, a casting method, and the like can be used.
The flame retardant insulating sheet or film thus obtained can be used in a part where flame retardancy is required in an electric / electronic device.

  Hereinafter, the present invention will be described by way of examples, but this is merely an example, and the present invention is not limited thereto.

  The materials used in the examples are described below. In addition, the addition amount of each material of Table 1 shows a weight part.

・ Polycarbonate resin A
Product name: E-2000, weight average molecular weight: 20000, manufactured by Mitsubishi Engineering Plastics Co., Ltd., polycarbonate resin B
Product name: H-3000, weight average molecular weight: 27000, manufactured by Mitsubishi Engineering Plastics Co., Ltd.

・ Flame retardant A (melamine cyanurate)
Product name: MC-6000, average particle size (laser diffraction / scattering method): 1-5 μm, manufactured by Nissan Chemical Co., Ltd., flame retardant B (phosphate ester)
Product name: PSP-100, manufactured by Otsuka Chemical Co., Ltd. Flame retardant C (aromatic diphosphate)
Product name: PX-200, manufactured by Daihachi Chemical Co., Ltd.

・ Fibrous material (polytetrafluoroethylene)
Product name: Polyflon FA500, manufactured by Daikin Industries, Ltd.

[Example 1]
According to the composition shown in Table 1, the mixture was melt-kneaded by a twin screw extruder to produce pellets. The manufactured pellets were extruded into a sheet shape using the same-direction biaxial extruder and a T-shaped die, and adjusted to a predetermined thickness. The obtained flame-retardant insulating sheet was evaluated by the following methods. The evaluation results are shown in Table 1.

-Flame retardance evaluation The test piece according to UL94 (V-0) was created from the extruded sheet | seat of predetermined thickness 0.40mm, and the vertical combustion test was implemented.
-Evaluation of heat resistance The heat resistance was evaluated in accordance with ASTM D 648 (load: 1.8 MPa).

-Formability evaluation Formability was evaluated by extruding into a sheet form using the same-direction biaxial extruder and a T-shaped die. The case where the molding processability was good was evaluated as ◯, and the case where the molding processability was poor such as foaming and waving of the sheet and stopping of the extruder was evaluated as x.
-Mold adhesion The mold adhesion was evaluated by visually confirming the contamination of molding machines such as rolls and molds during molding. Evaluation was made with a mark indicating that there was no adhesion to the mold and no contamination, and a mark indicating that there was a lot of adhesion to the mold and a large amount of contamination as x.

[Examples 2 to 5, Comparative Examples 1 to 8]
A flame-retardant insulating sheet was produced in the same manner as in Example 1 except that the materials and addition amounts shown in Table 1 were used. The evaluation results are shown in Table 1.

Claims (11)

A resin containing a polycarbonate resin or a polyolefin resin, and a flame retardant,
The flame retardant resin composition, wherein the flame retardant comprises a nitrogen-containing compound.   The flame retardant resin composition according to claim 1, wherein the nitrogen-containing compound has a triazine skeleton.   The flame retardant resin composition according to claim 1 or 2, wherein the nitrogen-containing compound is a melamine compound.   The flame retardant resin according to any one of claims 1 to 3, wherein the nitrogen-containing compound is at least one selected from the group consisting of melamine, melamine cyanurate, melamine isocyanurate, and derivatives thereof. Composition.   The flame retardant resin composition according to claim 4, wherein the nitrogen-containing compound is melamine cyanurate.   The flame retardant resin composition according to claim 1, comprising 0.1 to 30 parts by weight of the flame retardant with respect to 100 parts by weight of the resin.   The flame retardant resin composition according to claim 1, wherein the flame retardant has an average particle size of 0.01 to 30 μm.   The flame retardant resin composition according to claim 1, wherein the resin contains a polycarbonate resin. The flame-retardant resin composition according to claim 1, wherein the polycarbonate resin has a weight average molecular weight of 1.2 × 10 ^{4 to} 3.5 × 10 ⁴ .   A flame-retardant insulating sheet or film formed by molding the flame-retardant resin composition according to claim 1.   An electric / electronic device using the flame-retardant insulating sheet or film according to claim 10.