JPH05247239A - Flame-retardant sheet made from polyester resin composition and thermoformed product thereof - Google Patents

Abstract

PURPOSE:To obtain a thermoformable film or sheet excellent in toughness and flame retardancy by using a resin composition prepared by mixing a specified polyester with a specified polypropylene resin and a flame retardant and a flame retardant aid in a specified ratio. CONSTITUTION:The title sheet is prepared from a resin composition prepared by mixing 100 pts.wt. total of 77-100wt.% polyester consisting mainly of repeating units of ethylene terephthalate and 23-0wt.% polypropylene copolymerized with ethylene and maleic anhydride with 10-30 pts.wt. at least one flame retardant desirably selected from among a brominated phenoxy resin, a brominated epoxy resin, a brominated polystyrene resin and a brominated polycarbonate resin (including oligomers thereof) and 0-15 pts.wt. at least one flame retardant aid desirably selected from among Sb2O3, Sb2O4, Sb2O5, a mixture thereof and sodium salts thereof.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant thermoplastic polyester film or sheet (hereinafter sometimes simply referred to as a sheet) and a thermoformed body thereof. This sheet or a thermoformed body thereof is, for example, an electric / electronic device,
It is used as a constituent material for automobiles, machine tools, etc., and is a useful molding material especially for parts requiring flame retardancy.

[0002]

2. Description of the Related Art Flame-retardant thermoplastic plastic products (parts) in the above-mentioned fields of use such as electric and electronic devices.
Is widely used.

However, these products (parts) are generally molded by an injection molding method, and particularly for polyester, a flame-retardant sheet and a thermoformed product obtained by processing the sheet are almost known. Not not.

[0004]

OBJECT OF THE INVENTION The present inventors arrived at the present invention as a result of diligent efforts to provide a flame-retardant product of a thin sheet or a thermoformed article excellent in toughness which cannot be obtained by an injection molding method.

[0005]

The present inventor selected a polyester having ethylene terephthalate as a main repeating unit, which is generally known as a polyester, and invented a flame-retardant polyester sheet having the polyester as a main constituent and a thermoformed product thereof.

That is, the present invention is configured as follows. (1) Polypropylene (B) in which 100% by weight of polyester (A) containing ethylene terephthalate as a main repeating unit and ethylene and maleic anhydride are copolymerized
0 to 30% by weight (in other words, 77 to 100% by weight of the polyester (A) and 23 to 0% by weight of the copolymerized polypropylene (B)), these resin compositions (A) and (B) Is a film or sheet comprising the resin composition (I) in which 10 to 30 parts by weight of the flame retardant (E) and 0 to 15 parts by weight of the flame retardant aid (F) are mixed with 100 parts by weight of the total amount of ..

Further, the mixing ratio of any one of polyester (A), copolymerized polypropylene (B), crystal nucleating agent (C), additive (D), flame retardant (E) and flame retardant aid (F) is used. A multilayer film or sheet formed by laminating different resin compositions into at least two layers is also one of the embodiments of the present invention.

Further, a thermoformed product obtained by thermoforming a single-layer or multi-layered film or sheet is the second invention.

In the present invention, the flame retardant means at least one selected from the group consisting of brominated polystyrene, brominated epoxy resin, brominated oligocarbonate and brominated phenoxy resin.

The flame retardant aid is at least one selected from the group consisting of antimony trioxide, antimony tetraoxide, antimony pentoxide, and partial or total sodium salts of these antimony oxide compounds.

Further, the crystal nucleating agent includes graphite, carbon black, magnesium oxide, calcium silicate, magnesium silicate, talc, kaolin, calcium carbonate,
At least one selected from the group consisting of magnesium carbonate, sodium carbonate, potassium carbonate, zinc oxide, alumina, barium sulfate and calcium sulfate.

The present invention will be described.

In the present invention, polyester means not only a homopolymer of polyethylene terephthalate but also a part of terephthalic acid component such as isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, diphenyletherdicarboxylic acid, diphenylsulfone. Aromatic dicarboxylic acids such as dicarboxylic acids: alicyclic dicarboxylic acids such as hexahydroterephthalic acid, hexahydroisophthalic acid: aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid: p-β-hydroxyethoxy One or more components of other difunctional carboxylic acids such as oxyacids such as benzoic acid, p-oxybenzoic acid, ε-oxycaproic acid, and /
Alternatively, a part of the ethylene glycol component is, for example, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, neopentyl glycol, diethylene glycol, 1,1-cyclohexanedimethylol, 1,4-cyclohexanedimethylol, 2,2. -Copolyesters substituted with one or more components of other glycols such as bis (4-β-hydroxyethoxyphenyl) propane, bis (4-β-hydroxyethoxyphenyl) sulfone. The total proportion of copolymerization components in this copolyester is preferably 3 mol% or less based on all acid components. Of these, a homopolymer of polyethylene terephthalate is preferable.

In the present invention, 100 parts by weight of an ethylene terephthalate polymer which allows a small amount of modification, and 0 to 30 parts by weight of polypropylene (hereinafter sometimes abbreviated as Co-PP) obtained by copolymerizing ethylene and maleic anhydride. Part melt mix. By adding Co-PP,
The low temperature toughness of the sheet and / or thermoformed body of the present invention is improved. The amount of Co-PP (B) component added is 30
If it exceeds the weight part, the effect of improving the toughness becomes poor, and it becomes difficult to obtain a molded product having a good wall thickness distribution, and further the thermal deformation resistance of the thermoformed product becomes poor. Co-P
P has the effect of improving the toughness of the molded article at low temperatures, and it is preferable to add 5 to 15 parts by weight to 100 parts by weight of the polyester (A).

The Co-PP copolymerization ratio was ethylene of 5 to 30 mol% and maleic anhydride of 0.5 to 5 mol%, and the Vicat softening point of 70 to 8.
Those having a temperature of 5 ° C., a density of 0.88 to 0.92 g / cm ³ , and a melt flow rate (hereinafter sometimes abbreviated as MFR) of 4 to 8 are extremely finely dispersed in the polyester and have a large effect of improving the toughness.

The polyester film or sheet used in the present invention comprises polyethylene terephthalate as a main component and the above Co-PP, a flame retardant and a flame retardant aid, and more preferably a crystal nucleating agent. In the present invention, it is preferable that the polyester component is substantially amorphous and the intrinsic viscosity of polyethylene terephthalate constituting the film or sheet is 0.60 or more.

The flame retardant used in the present invention is di- or tri-brominated polystyrene, or a copolymer thereof, and a cross-linked brominated product obtained by introducing a unit having three or more functional groups into these polymers. Polystyrene, brominated oligocarbonate, brominated phenoxy resin, terminal epoxidized resin and the like are used.

The blending amounts of these flame retardants are (A) and (B)
When the total amount of the above is 100 parts by weight, 10 to 30 parts by weight should be mixed.

Further, in order to make the flame retardant effect of the flame retardant more effective, it is preferable to use a flame retardant aid.

As the flame retardant aid, antimony trioxide, antimony tetroxide, antimony pentoxide or a partial or total sodium salt thereof, or a mixture of two or more of the above antimony compounds can be used. The blending amount of the flame retardant aid is 0 to 15 parts by weight, preferably 2 to 10 parts by weight, when the total amount of (A) and (B) is 100 parts by weight.

The crystal nucleating agent to be mixed in the present invention is graphite, carbon black, magnesium oxide, calcium silicate, magnesium silicate, talc, kaolin, calcium carbonate, magnesium carbonate, sodium carbonate, potassium carbonate, zinc oxide, alumina, barium sulfate and An inorganic substance such as calcium sulfate, which is melt-mixed in an amount of 0.1 to 2 parts by weight with respect to 100 parts by weight of polyethylene terephthalate. The preferable mixing ratio of the crystal nucleating agent is 0.3.
If the mixing ratio is less than 0.1 parts by weight, the effect of the crystal nucleating agent is small and the preheating time of the film or sheet when forming the thermoformed body is long, which is preferable from the viewpoint of productivity. Absent. On the other hand, if the amount is more than 2 parts by weight, the crystal nucleating agent is deposited as foreign matter on the film or sheet extruded by the extruder, and the appearance of the sheet is impaired, which is not preferable.

The film of the present invention has a sheet (A),
(B), (E) and (F) and, if necessary, (C) and (D) are kneaded and pelletized by using a single-screw or multi-screw extruder, and the obtained pellets are dried. Then, it is supplied to an extruder or directly supplied to the extruder and kneaded with a screw, and then cooled on a casting drum with a die to form a film or sheet.

The cooling on the casting drum is preferably rapid cooling. By doing so, a substantially amorphous film or sheet can be obtained, and such a film or sheet is easy to thermoform.

Polyethylene terephthalate and Co
Regarding the degree of melt-kneading with —PP, it is preferable to knead and homogenize well so that the dispersed particle diameter of Co-PP is 10 μm or less.

When a multi-layer film or sheet comprising two or more layers of the present invention is discharged from a slit die, two or more kneading means for melt-mixing the composition of the present invention are used. , After melt-mixing, discharge from two (two) or more multi-layer dies,
It can be manufactured by quenching with a cooling drum.

The multilayer film or sheet is (A),
(B), (E) and (F), and further (C) and (D)
It is possible to produce by laminating compositions having different compositions by changing the compounding ratio of.

The thermoformed article of the present invention is a molded article obtained by thermoforming the above polyester film or sheet.
The thermoforming referred to in the present invention is a vacuum forming in which a film or sheet is softened by heating and pressed against a desired mold, air in the gap between the mold and the material is removed, and the film or sheet is brought into close contact with the mold by atmospheric pressure, or is formed into a large size. It is a general term for compressed air molding in which a film or sheet is brought into close contact with a mold by compressed air of atmospheric pressure or more, and molding in which vacuum and compressed air are used together.

In addition, a colorant, an inorganic filler, a polymer for improving barrier properties, an ultraviolet absorber or a stabilizer for improving the heat-melting stability may be contained within a range not impairing the object of the present invention.

[0029]

INDUSTRIAL APPLICABILITY The film or sheet of the present invention is flame-retardant and thermoformable, and the film sheet or a thermoformed product thereof has excellent toughness and is used as a constituent material for electric, electronic devices, automobiles, machine tools and the like. It is useful.

[0030]

The present invention will be described in detail below with reference to examples. The measurement conditions of the main physical properties are as follows.

Intrinsic viscosity: Measured at 35 ° C. in a solution obtained by filtering insoluble matter in orthochlorophenol.

Combustibility: A film or sheet having a predetermined thickness is used, and U is specified by Underwriting Laboratories.
A sample of a predetermined size specified in L94 is cut out, and the combustion grade is measured according to this standard.

Formability: FC-1APA-W manufactured by Asano Laboratory
Equipped with a tray-shaped mold in a mold vacuum / pressure molding machine, and evaluate the characteristics such as mold releasability, sheet dripping, mold traceability, etc. when vacuum molding is performed by changing the sheet heating conditions at a predetermined mold temperature. ..

Toughness: judged by the state of the bent portion when a part of the formed film or sheet or a part of the thermoformed product is bent at a predetermined temperature by 180 ° C. and further bent by 360 ° in the opposite direction.

The present invention will be described in more detail with reference to the following examples.

[0036]

Examples 1 to 3 and Comparative Examples 1 to 3 Polyesters having an intrinsic viscosity of 0.70 and composed of a terephthalic acid component and an ethylene glycol component were dried with hot air at 150 ° C. for 3 hours. Then, in the proportions shown in Table 1, copolymerized polypropylene (Mitsubishi Yuka: MODIC-300F) as a modifier, talc (Hayashi Kasei: talc PKNN) as a crystal nucleating agent, and brominated polystyrene (Nissan Fellow: Pyrocheck) as a flame retardant. 6
8PB) and antimony trioxide (Japan concentrate: PATOX-C) as a flame retardant aid were melt-mixed by an extruder to obtain pellets. The pellets thus obtained were hot-air dried at 130 ° C. for 5 hours. Next, the pellets were melted by an extruder, further passed through a die to form a film, and cast on a cooling drum.

The thickness of the obtained film was about 300 μm. The film was then flame tested according to UL94.

On the other hand, this film was vacuum formed using a Cosmic molding machine manufactured by Asano Laboratory to form a tray having an opening of 18 cm, a length of 12 cm, and a bottom of 17 cm and a width of 11 cm at a depth of 3.5 mm. Molded and examined for moldability. The results obtained are summarized in Table 1.

As compared with Comparative Example 1, Examples 1, 2, and 3 were found to have improved combustibility. Further, it was found that V-0, V-1, and V-2 were obtained depending on the mixed amount of the flame retardant / flame retardant auxiliary.

[0040]

[Table 1]

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Claims (5)

[Claims] 1. A polyester (A) comprising 77 to 100% by weight of ethylene terephthalate as a main repeating unit,
Polypropylene (B) copolymerized with ethylene and maleic anhydride: 23 parts by weight or less, 100 parts by weight in total, 10 to 30 parts by weight of flame retardant (E) and 0 to 15 parts by weight of flame retardant aid (F). A film or sheet comprising the resin composition (I) in which the above is mixed. [Here, the flame retardant (E) is at least one selected from the group consisting of brominated phenoxy resin, brominated epoxy resin, brominated polystyrene, and brominated polycarbonate (including oligomer), and the flame retardant aid (F) ) Is at least one selected from the group consisting of antimony trioxide, antimony tetroxide, antimony pentoxide, and mixtures or sodium salts of these antimony oxide compounds. ] 2. The resin composition (I) according to claim 1.
In addition, a crystal nucleating agent selected from the group of graphite, carbon black, magnesium oxide, calcium silicate, magnesium silicate, talc, kaolin, calcium carbonate, magnesium carbonate, sodium carbonate, zinc oxide, aluminum oxide, barium sulfate and calcium sulfate (C Or a resin composition (II) in which 0.1 to 2% by weight is blended with the polyester (A). 3. The resin composition (I) or the resin composition (II) according to claim 1 or 2, wherein the lubricant, the colorant, the ultraviolet absorber, the heat stabilizer, the antioxidant, and the release agent are used. And a resin composition (III) containing at least one additive (D) selected from the group consisting of a filler and a filler. 4. A mixture ratio of any one of polyester (A), copolymerized polypropylene (B), crystal nucleating agent (C), additive (D), flame retardant (E) and flame retardant auxiliary (F). A multilayer film or sheet comprising at least two layers obtained by laminating different resin compositions. 5. A thermoformed body obtained by thermoforming the single-layer or multi-layer film or sheet according to any one of claims 1 to 4.