JPH10279705A - Flame-retardant polyester elastomer sheet and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant polyester elastomer sheet having high flame retardancy without generating a hydrogen halide gas and excellent in recyclability, blocking resistance, color tone, oil resistance, heat resistance, light resistance and frictional resistance, and to provide an interior material, especially an automotive interior material or a housing interior material, and an electric wire-coating material using the polyester elastomer sheet. SOLUTION: This flame-retardant sheet good in recyclability is obtained by molding a polyester resin composition comprising (A) 100 pts.wt. of a block copolymer comprising 70-20 wt.% of polybutylene terephthalate units and 30-80 wt.% of polytetramethylene glycol units, (B) 1.0-40 pts.wt. of melamine cyanurate and (C) 0-10 pts.wt. of an antidropping agent by a conventional molding method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant polyester sheet and its use. Specifically, it has high flame retardancy without generating hydrogen halide gas harmful to the human body, and has excellent recyclability, blocking resistance, color tone, oil resistance, heat resistance, light resistance, and wear resistance TECHNICAL FIELD The present invention relates to a conductive polyester elastomer sheet and an interior material using the same, particularly an automobile interior material, a house interior material, and a wire covering material.

[0002]

2. Description of the Related Art At present, soft vinyl chloride, vinyl chloride-based elastomer, chlorinated polyolefin-based elastomer, polyurethane and the like are widely used as materials for housing interior materials such as automobile interior materials and wall finishing materials and electric wire coating materials. Have been. In recent years, however, the social climate has been increasing regarding the impact on the global environment and the human body, and recyclability has become increasingly important from the viewpoint of resource reuse. In the automobile industry, there is an urgent need to replace other plastics that are friendly to the environment and the human body, such as the elimination of halogen-containing materials, the elimination of thermosetting resin materials, the high recycling of parts, the reduction of combustion calories, and the improvement of fuel efficiency through weight reduction. Has become. For this reason, there has been a tendency to gradually replace vinyl chloride resins with halogen-free resins such as polypropylene and polyolefin elastomers.

[0003] For example, a vinyl resin is mainly used for a chair skin material among interior materials. Vinyl leather is often lined or sewn with polyester fiber to improve strength and improve texture and feel, and is often brushed with polyester fiber yarn, which is an obstacle to recycling. ing. When the skin material is recycled, if it is cut as it is and used for melt molding again, the polyester fiber etc. and the skin material vinyl chloride resin or polyolefin resin are incompatible,
There is a drawback that remarkable deterioration in physical properties and appearance is caused, and it is practically difficult to repeatedly use it for recycling. For this reason, in the recycling process, it is necessary to separate the skin material (vinyl resin) from the backing or sewn polyester fiber. However, it is costly. It was extremely difficult.

[0004] Further, in the process of manufacturing the multilayer sheet, even in the recycle molding of the ear portion caused by trimming (cutting of the sheet edge portion), the conventional vinyl resin and polyester resin multilayer sheet suffers from problems of various physical properties and appearance deterioration due to recycling. Had. In addition, high levels of flame retardancy are often required for applications such as automotive interior materials, housing interior materials, and electric wire coating materials, but polyolefin resins themselves have extremely low flame retardancy, making them highly flame retardant. At present, organic halogen-based flame retardants and antimony trioxide as a flame retardant auxiliary are used in combination. However, a polyolefin resin to which an organic halogen-based flame retardant is added or a vinyl chloride resin which itself is a halogen-containing compound generates toxic hydrogen halide gas during combustion or is generated by thermal decomposition during molding. There is a problem that the processing equipment and the mold are damaged by corrosion and the like due to the generated hydrogen halide. further,
Since a large amount of black smoke and toxic halogen-containing gas is generated at the time of a fire, there is a drawback that evacuation and fire-fighting activities are hindered. In addition, recently, there has been a report pointing out the danger of generating dioxin as a thermal decomposition product of a halogen-containing compound, and from the viewpoint of environmental protection, the use of halogen-containing compounds has been reduced. Hydrous inorganic compounds such as magnesium hydroxide and aluminum hydroxide are known as non-bromine or non-chlorine flame retardants, but hydrous inorganic compounds are more flame-retardant than non-bromine or non-chlorine flame retardants. Since the effect is low, it is necessary to add a large amount to the resin in order to exhibit high flame retardancy, which has a drawback that the mechanical properties and moldability of the product are remarkably deteriorated.

Further, various phosphorus compounds are also known as non-bromine or non-chlorine flame retardants. Red phosphorus has a high flame retardant effect, so it is possible to express high flame retardancy by adding a relatively small amount, but the product is colored red, and the mechanical properties of the polyester resin are extremely deteriorated under high temperature and high humidity. There was also a problem in practical aspects. It is also known to use a phosphate ester flame retardant, but since the flame retardant effect is insufficient compared to bromine or chlorine flame retardants, polyester resin is required to express high levels of flame retardancy. On the other hand, a large decrease in the crystallinity of the polyester resin due to this greatly deteriorates the mechanical properties and moldability, or the polyester resin in the case of phosphate ester flame retardant under high temperature and high humidity. Had the disadvantage that the hydrolysis resistance was extremely reduced. In addition, a large amount of phosphate ester-based flame retardant added to exhibit high flame retardancy not only violently plate-outs to molds and the like during molding, but also bleeds out to the product surface, resulting in poor appearance and flame retardancy. This was the cause of the deterioration over time.

When soft vinyl chloride is used as an interior material for automobiles, a large amount of a low-molecular plasticizer added to the soft vinyl chloride sublimates under high temperatures in summer or the like and adheres to the inside of the window glass. There is a disadvantage that fogging phenomenon that causes fogging occurs. Furthermore, plasticizers generated from flame-retardant soft vinyl chloride used in wall finishing materials for house interiors and the like have recently become a social problem as so-called sick-house syndrome, which adversely affects the human body.

On the other hand, polyester elastomers are not only excellent in flexibility, but also excellent in heat resistance, chemical resistance, etc., and are easily molded and do not require addition of a plasticizer. It is promising as a soft sheet or wire covering material. However, as it is, the blocking property (adhesion) between sheets or electric wires is extremely strong, and it is extremely difficult to rewind without the use of release paper, etc. There was a problem that efficient collection such as a method of performing the collection was not possible. Further, when blocking occurs once between the polyester elastomer sheet and the electric wire, the sheet and the electric wire are strongly adhered to each other, and it is extremely difficult to remove the sheet and the electric wire. When attempting to forcibly peel off the blocking polyester elastomer sheet / wire, there is a disadvantage that the sheet / wire surface is roughened and peeling occurs partially or widely. This has been one of the obstacles to the application of the polyester elastomer as a sheet-like product and a wire covering material.

Further, when a conventional polyester elastomer sheet is heat-molded into a product having a deep drawing portion and a relatively deep uneven portion, a thin translucent portion is likely to be generated mainly on side surfaces and corner portions, and the opaque portion is formed. There was also a drawback that the color tone difference from the sheet surface wanted to lower the sheet appearance.

[0009]

Under such circumstances, the present invention has been made to solve the above-mentioned disadvantages of the prior art. That is, an object of the present invention is to make the polyester elastomer flame-retardant with a non-halogen flame retardant, thereby drastically suppressing the generation of corrosive gas during molding and irritating gas / black smoke during combustion, and Flame-retardant sheet-like interior materials with excellent mechanical properties, color tone, blocking resistance, heat resistance, light resistance, wear resistance, and good recyclability, especially automotive interior materials, housing interior materials, and flame-retardant electric wire coatings It is to provide materials.

[0010]

According to the present invention, as a result of intensive studies on the above-mentioned problems, it has been found that a polyester elastomer containing a component having a specific structure in a specific ratio has excellent flame retardancy, recyclability, and mechanical properties. The inventors have found that they have physical properties, color tone, blocking resistance, heat resistance, light resistance, and abrasion resistance, and have reached the present invention.

That is, the gist of the present invention is that component (B) cyanuric acid is added to 100 parts by weight of a polyester elastomer resin comprising 70 to 20% by weight of polybutylene terephthalate unit and 30 to 80% by weight of polytetramethylene glycol unit. Good recyclability, characterized by being obtained by molding a polyester resin composition containing from 1.0 to 40 parts by weight of the melamine acid component (C) from 0 to 10 parts by weight of the component (C) anti-dripping agent. Exists in flame retardant sheet.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) polyester elastomer resin constituting the sheet and the wire covering material of the present invention is mainly composed of a hard segment comprising polyester having terephthalic acid and 1,4-butanediol as essential components and the number thereof. A block copolymer composed of a soft segment composed of polytetramethylene glycol having an average molecular weight of 300 to 5,000 is exemplified.

The polyester component, which is the hard segment of the polyester elastomer, contains terephthalic acid and 1,4
-Butanediol is an essential component, but may further contain other dicarboxylic acid and / or diol components as long as the effects of the present invention are not impaired. Examples of dicarboxylic acid components other than terephthalic acid include isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,
Aromatic dicarboxylic acids such as 4'-dicarboxylic acid, diphenoxyethane dicarboxylic acid, sodium 3-sulfoisophthalate, 1,4-cyclohexanedicarboxylic acid, succinic acid, oxalic acid, adipic acid, sebacic acid, dodecanediic acid, dimer acid And the like.

Examples of diol components other than 1,4-butanediol include aliphatic diols such as ethylene glycol, trimethine glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol and decamethylene glycol, and 1,1-cyclohexanedimethyl. Alicyclic diols such as phenol, 1,4-cyclohexanedimethanol and tricyclodecanedimethanol, xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) propane, 2,2-bis} Diols containing an aromatic group such as 4- (2-hydroxyethoxy) phenyl} propane, bis {4- (2-hydroxy) phenyl} sulfone, and 1,1-bis {4- (2-hydroxyethoxy) phenyl} cyclohexane And the like.

The soft segment of the polyester elastomer used in the present invention has a number average molecular weight of 300 to 5
Although it is composed of 000 polytetramethylene glycol, other diol components may be further contained as long as the effects of the present invention are not impaired. As the diol component, polyethylene glycol, poly (1,2-
Polyoxyalkylene glycols such as propylene oxide) glycol, poly (1,3-propylene oxide) glycol, ethylene oxide, a copolymer of propylene oxide, and a copolymer of ethylene oxide and tetrahydrofuran.

The number average molecular weight of polytetramethylene glycol is usually from 300 to 5,000, more preferably from 400 to 4,000, particularly preferably from 500 to 300.
0. If the number average molecular weight of the polytetramethylene glycol is too high, extrudability may be reduced due to an increase in melt viscosity, compatibility with the hard segment may be reduced, and the surface appearance of the sheet and the wire covering material may be deteriorated. If it is too low, the tensile strength, tensile elongation, elastic recovery and the like may be significantly reduced.

The proportion of polytetramethylene glycol in the polyester elastomer of the present invention is 30 to 80 wt.
%. If the proportion of polytetramethylene glycol is too small, flexibility at room temperature or low temperature may be reduced, or the flex resistance may be reduced. Conversely, if the proportion is too large, heat resistance, light resistance, moldability, color tone (initial color tone) Aging), blocking resistance, etc. may be significantly reduced.

The component (B) melamine cyanurate constituting the sheet and the wire covering material of the present invention includes cyanuric acid (2,4,6-trihydroxy-1,3,5-triazine) and melamine (2,4). , 6-triamino-1,3,5
-Triazine), for example, by mixing a cyanuric acid solution and an aqueous melamine solution,
The reaction can be carried out under stirring at a temperature of 00 ° C., and the resulting precipitate can be obtained by filtration. The particle size of the melamine cyanurate is usually from 0.01 to 1000 μm, preferably from 0.01 to 500 μm, particularly 0.1 μm.
~ 250 microns is preferred. Some of the amino groups or hydroxyl groups of melamine cyanurate may be substituted with another substituent such as an epoxy group. In addition, in the present invention, melamine cyanurate has an effect of reducing blocking between sheets and improving weather resistance in addition to imparting flame retardancy and improving color tone.

The amount of the melamine cyanurate is usually from 1.0 to 100 parts by weight of the polyester elastomer.
It is 40 parts by weight, preferably 1.5 to 30 parts by weight, particularly preferably 2.0 to 20 parts by weight. If the amount of melamine cyanurate is too large, the mechanical properties are remarkably reduced, or melamine cyanurate bleeds out on the surface of the molded product, which is not preferable.If the amount is too small, sufficient flame retardancy cannot be obtained. In addition, the color tone and light resistance are deteriorated, and the effect of preventing blocking is also lowered.

The method for producing the sheet and the wire covering material of the present invention is not particularly limited and can be easily achieved by a known conventional method. For example, after dry blending using a blender or a mixer, Melting using a molding machine with a die, extrusion molding as a sheet or wire covering material, dry blending using a blender or mixer, etc., then melt-mixing with a screw extruder and extruding as a strand A method of extruding into a sheet using a sheet forming machine, a method of extruding into a sheet using a sheet forming machine, a method of coating an electric wire using a forming machine for electric wire coating, a method of using a molding machine of an injection molding die, Examples include a method using a molding machine. Usually, the mixture is melt-mixed with a screw extruder and then pelletized, and then a T-die molding machine or a sagittal molding machine is used. Kyuradai molding machine, a method of molding using a wire coating molding machine is preferable. Further, after manufacturing a master batch resin containing a high concentration of melamine cyanurate and an anti-drip agent using a screw extruder, blending the master batch resin with a polyester elastomer resin to prepare a desired melamine cyanurate concentration, May be used.

The sheet and the wire covering material of the present invention are not particularly limited with respect to the sheet width and the covering material surface area, but are limited in the sheet thickness and the covering layer thickness. The thickness of the sheet of the present invention for achieving the effects of the present invention is usually 0.015 mm to 8.0 mm, preferably 0.05 mm to 5.0 mm, and particularly 0.1 mm to 5.0 mm.
3.0 mm. If the thickness is too small, the mechanical properties, color tone, light resistance, and sheet formability are inferior. On the other hand, if the thickness is too large, the flame retardancy of the molded product may be significantly reduced.

The sheet obtained in this way is in accordance with JIS
-In the D1201 combustion test, the average burning speed was 200
It is preferable to have flame retardancy that simultaneously satisfies the following conditions: nm / min or less, burning time 15.0 seconds or less, and burning distance 30.0 mm or less.

The sheet of the present invention can be extruded into a sheet, cooled and solidified, and then subjected to a stretching treatment to improve mechanical properties and abrasion resistance. The stretching direction may be uniaxial or biaxial. In the case of biaxial stretching, a stretching method such as a sequential stretching method or a simultaneous biaxial stretching method can be used. Although the stretching ratio is not particularly limited, it is usually preferably 2.0 to 10 times in terms of area ratio. In order to increase dimensional stability, it is preferable to further heat-treat the sheet thereafter. The heat treatment conditions are not particularly limited, but the heating conditions are usually preferably from 80 to 200 ° C. for 1.0 to 120 seconds. If the heating conditions are too high or the heating time is too long, the sheet will be deformed, colored, deteriorated, and the like. Conversely, if the heating temperature is too low or the heating time is too short, the heat treatment effect is low, which is not preferable.

The sheet of the present invention can be further subjected to heat molding to be used as a car interior material or a house interior material.
The method for producing these interior materials is not particularly limited, and can be easily achieved by a known method. For example, a method in which a sheet extruded from a die is continuously press-molded while the temperature does not decrease, a method in which a sheet extruded from a die is cooled and cut into fixed length units, and then reheated and molded. .

The sheet and the wire covering material of the present invention are excellent in recyclability. The sheet is made of a virgin resin (a resin having no history of being processed as a molded article) and a recycled resin (an ear portion (a sheet end portion) generated by trimming after being molded once, or a molten resin after being used for a long time. Even if some of the cut pellets are mixed, the initial effect of the present invention is not significantly reduced. In order to exhibit the effects of the present invention, the virgin resin is usually at least 20% by weight, preferably at least 40% by weight, particularly at least 60% by weight. If the amount of virgin resin is too small, the mechanical properties and color tone deteriorate, which is not preferable.

The sheet and the wire covering material of the present invention
Even if other polyesters such as polyethylene terephthalate and polybutylene terephthalate are partially mixed during recycling, the initial effects of the present invention are not significantly reduced. In order to achieve the effect of the present invention, the amount of the other polyester mixed is 60% by weight or less, preferably 50% by weight or less, and particularly 40% by weight or less. If the amount of other polyesters is too large, the flame retardancy, flexibility, color tone, and surface appearance of the molded product are significantly reduced.

The sheet of the present invention may further contain 0.1 to 10 parts by weight of a component (C) anti-dripping agent in addition to the above components. The component (C) anti-dripping agent refers to a compound having a property of preventing dripping of a resin accompanying a flame during combustion and improving flame retardancy. Specific examples include talc, mica, montmorillonite, silica, silicone oil, asbestos, fluorine-containing polymers, silicone oil, and the like. Among them, a layered silicate, a fluorine-containing polymer, or the like is preferably used as a preferable compound from the viewpoint of the flame retardancy of the composition.

In the present invention, it is more preferable to use a layered silicate as the component (C) from the viewpoint of improving the fluidity at the time of melting and the flame retardancy. Examples of usable layered silicate compounds include, in addition to the layered silicate itself, modified layered silicates (layered silicates having a quaternary organic onium cation inserted between layers), and layered silicates having a functional group having reactivity with a polyester elastomer. Silicates (abbreviated as functionalized layered silicates) and modified layered silicates to which reactive functional groups are added (abbreviated as functionalized modified layered silicates) can be mentioned. Dispersibility of layered silicate in polyester resin composition From the viewpoints of compatibility, and the ability to prevent dripping, layered silicates and functionalized layered silicates are preferred, and in particular, functional groups to which reactive functional groups such as epoxy groups, amino groups, oxazoline groups, carboxyl groups, and acid anhydrides are added. Layered silicate can be suitably used. The method for imparting a functional group is not particularly limited, but a method of treating with a functionalizing reagent (silane coupling agent) is simple and preferable.

Specific examples include chlorosilanes having an epoxy group such as 3-glycidyloxypropyldimethylchlorosilane, β- (3,4-epoxycyclohexyl) ethyldimethylchlorosilane, 3-glycidyloxypropyltrichlorosilane, trichlorosilylacetic acid, 3
Chlorosilanes having a carboxyl group such as trichlorosilylpropionic acid and 5-carboxyhexyldimethylchlorosilane; chlorosilanes having a mercapto group such as 3-mercaptopropyldimethyltrichlorosilane, 3-mercaptopropyltrichlorosilane and 4-mercaptophenyldimethylchlorosilane , 3-aminopropyltriethoxysilane, N- (2-aminoethyl)-
Alkoxysilanes having an amino group such as 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-
Glycidyloxypropyltrimethoxysilane, β-
Examples thereof include alkoxysilanes having an epoxy group such as 3,4-epoxycyclohexyl) ethyltrimethoxysilane. Among them, 3-glycidyloxypropyldimethylchlorosilane, β- (3,4-epoxycyclohexyl) ethyldimethylchlorosilane, Chlorosilanes having an epoxy group such as glycidyloxypropyltrichlorosilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3 −
Alkoxysilanes having an amino group such as aminopropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane, β- (3,4-epoxysilohexyl) ethyltrimethoxysilane, etc. Alkoxysilanes having an epoxy group of
Glycidyloxypropyldimethylchlorosilane, β-
Chlorosilanes having an epoxy group such as (3,4-epoxycyclohexyl) ethyldimethylchlorosilane, 3-glycidyloxypropyltrichlorosilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-
Glycidyloxypropyltrimethoxysilane, β-
Alkoxysilanes having an epoxy group such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane are more preferable, and in particular, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane, β- (3 And alkoxysilanes having an epoxy group such as (4-epoxycyclohexyl) ethyltrimethoxysilane. There is no particular limitation on the method of contacting these functionalized reagents with the layered silicate,
Usually, it is preferable to carry out the reaction without solvent or by mixing in a polar solvent. The functionalizing agents may be used alone or in combination.

When a modified layered silicate is used, there is no particular limitation on the quaternary onium cation used as the quaternary onium cation inserted between the layers of the layered silicate. , Trimethyloctylammonium, trimethyldecylammonium,
Trimethyl alkyl ammonium such as trimethyl dodecyl ammonium, trimethyl tetradecyl ammonium, trimethyl hexadecyl ammonium, trimethyl octadecyl ammonium, dimethyl dioctyl ammonium, dimethyl didecyl ammonium, dimethyl didodecyl ammonium, dimethyl ditetradecyl ammonium, dimethyl dihexadecyl ammonium, dimethyl And dimethyldialkylammonium such as dioctadecylammonium.

Specific examples of the layered silicate used in the present invention include smectite clay minerals such as montmorillonite, hectorite, fluorine hectorite, saponite, beidellite, subtinsite, Li-type fluorine teniolite, Na-type fluorine teniolite, Swellable synthetic mica such as Na-type tetrasilicon fluorine mica, Li-type tetrasilicon fluorine mica, vermiculite, fluorine vermiculite, halloysite, etc., may be used, and may be natural or synthesized. Among them, smectite-based clay minerals such as montmorillonite and hectorite, and swellable synthetic mica such as Li-type fluorine teniolite, Na-type fluorine teniolite, and Na-type tetrasilicon fluorine mica are preferable, and montmorillonite and Na-type fluorine teniolite are particularly preferable.

In the present invention, the amount of the layered silicate (C) to be added is generally 10 parts by weight or less, preferably 8 parts by weight or less, particularly preferably 5 parts by weight or less based on 100 parts by weight of the component (A). . If the layered silicate (C) is too much, the mechanical properties and the surface appearance of the product are extremely lowered, and the melt viscosity at the time of molding is undesirably increased.

Examples of the fluorine-containing polymer (C) include poly
Tetrafluoroethylene, tetrafluoroethylene / p
-Fluoroalkyl vinyl ether copolymer, tetraf
Fluoroethylene / hexafluoropropylene copolymer,
Tetrafluoroethylene / ethylene copolymer, bifluoride
Fluorine such as nilidene and polychlorotrifluoroethylene
Polyolefins are preferred, with polytetrafluoro
Roethylene, tetrafluoroethylene / perfluoroa
Alkyl vinyl ether copolymer, tetrafluoroethylene
/ Hexafluoropropylene copolymer, tetrafluoro
More preferably, ethylene / ethylene copolymer is used.
Polytetrafluoroethylene, tetrafluoroethylene
/ Hexafluoropropylene copolymer is preferably used
You. Further, the fluorine-containing polymer used in the present invention is 3
The melt viscosity at 50 ° C. is 1.0 × 10^Three~ 1.0 ×
10¹⁶(Poise) is preferable, and among them, 1.0
× 10^Four~ 1.0 × 10^Fifteen(Poise), especially 1.
0x10¹¹~ 1.0 × 10 ¹³(Poise)
Appropriately used. If the melt viscosity is too low, the droplets from combustion
Insufficient effect of lowering prevention and flame retardancy, but too high
Are preferred because they significantly increase the melt viscosity during molding.
I don't.

The addition amount of the fluorine-containing polymer (C) is usually 10 parts by weight or less, preferably 5 parts by weight or less, particularly preferably 3 parts by weight or less based on 100 parts by weight of the component (A). If the content of the fluorine-containing polymer (C) is too large, the mechanical properties and the surface properties of the molded article are remarkably reduced, and the melt viscosity at the time of molding is undesirably increased.

The viscosity of the component (C) silicone oil used in the present invention is from 1,000 to 30,000 at 25 ° C.
(Cs) is preferred. If the viscosity is too low, the effect of preventing dripping during combustion is insufficient, and the flame retardancy is greatly reduced. Conversely, if the viscosity is too high, the fluidity of the composition is significantly reduced due to the thickening effect. The amount of silicone oil (C) added is usually
It is 10 parts by weight or less, preferably 6 parts by weight or less, particularly preferably 3 parts by weight or less based on 100 parts by weight of the component (A). If the amount of the component (C) is more than 10 parts by weight, the mechanical properties are remarkably deteriorated, and the melt viscosity at the time of molding may be remarkably increased.

The sheet and wire covering material of the present invention can achieve the desired flame retardancy without particularly adding an antimony compound or an oxygen-containing compound which is harmful to the human body as an auxiliary flame retardant. Also other conventional components such as light stabilizers, ultraviolet absorbers, antioxidants, antistatic agents, adhesion promoters, crystallization promoters, lubricants, colorants, plasticizers, thickeners, release agents, impact It is preferable to form the composition by various molding methods, which can contain a property improving agent, a reinforcing filler, a smoke suppressant, and the like. These additives can be added together with the raw materials at the time of molding, or can be applied to the surface. Further, it may be molded as a sheet having a multilayer structure composed of another resin and a wire covering material.

The sheet of the present invention is excellent in flame retardancy, recyclability, mechanical properties, color tone, blocking resistance, heat resistance, light resistance, abrasion resistance, and chemical resistance. It can be suitably used for interior materials, wire covering materials, and the like. In particular, conventional interior materials for automobiles, interior materials for homes, and wire coating materials have the problem of generating harmful substances such as hydrogen halide and dioxin during fire and heat processing, and also have the problem of plasticizer sublimation in summer. However, by using the sheet of the present invention, the generation of the above harmful substances is suppressed. Although the sheet of the present invention has high recyclability itself,
When used as an interior material, it has high compatibility with polyester fibers widely used for sewing and lining, and therefore has high recyclability as an integrally molded part with other polyester resins.

[0038]

The present invention will be described in more detail with reference to the following examples. In the examples, “parts” indicates “parts by weight”.

(1) Flame retardancy The flame retardancy of the sheet was determined according to the organic material combustion test for automobile interior (JIS D-1201) by cutting the obtained sheet into a length of 350 mm and a width of 100 mm, and burning rate and burning rate. The flame retardancy was evaluated by measuring the time, the burning distance, the influence of the sheet burning of the three stacked filter papers (top, middle and bottom) placed below. The flame retardancy as an electric wire covering material is as follows. The produced electric wire covering sample having a length of 20 cm is fixed at one end in a horizontal state, and the flame of a gas burner (flame size of 3/4 inch) is applied to the other side for 15 seconds. Immediately after the application, the flame was removed, and the burning state (burning speed, burning distance, burning time, burning state, presence or absence of drippings) was observed.

(2) Mechanical Property Tests Tensile strength and elongation were measured by conducting a tensile test at a tensile speed of 40 mm / min at 23 ° C. and 65% RH.

(3) Initial Color Tone The color tone was measured on a sheet using an SM color computer (manufactured by Suga Test Instruments Co., Ltd.) and expressed as a b value (the larger the b value, the stronger the yellow coloration).

(4) Bleed-out The bleed-out of additives and the like from the sheet is 10% after molding.
Observed visually on the day.

(5) Evaluation of Blocking Property In a T-die extruder, about 3 m of a sheet having a thickness of about 1 mm and a width of 12 to 15 cm, which had been sufficiently cooled after passing through two rolls at 35 ° C., was 12 cm in diameter, 40 cm in width, and weighed. 1.25
kg of metal pipe type roll, 23 ℃ / 50
It was left for 24 hours in an atmosphere of% RH. Then, after fixing the sheet end of the outermost layer of the roll at a height of 3.2 m,
The hand was gently released from the roll, and the blocking condition was evaluated based on the time required for all the sheets to come off from the roll when the roll portion dropped (measurement time was a maximum of 1 minute). That is, the shorter the required time, the better the blocking resistance. In the examples, 0 to 10 seconds are represented by ○, 11 seconds to less than 60 seconds are represented by Δ, and 60 seconds or more are represented by ×.

(6) Thermal Stability Test After the sheet was stored in a gear oven heated to 120 ° C. for 7 days (168 hours), a dumbbell piece was cut off.
Thermal stability was evaluated from changes in tensile strength and color tone. The tensile strength retention was calculated based on the following equation. Strength retention (%) = (tensile strength after test / tensile strength before test) × 100

(7) Light fastness test The sheet was tested for 10 days in a Ducycle Sunshine Super Long Life Weather Meter (manufactured by Suga Test Instruments Co., Ltd.).
After light irradiation (sunshine carbon arc lamp light) for 0 hour, a dumbbell piece was cut out, and the light resistance was evaluated from the tensile strength and color tone. The tensile strength retention was calculated based on the following equation. Strength retention (%) = (tensile strength after test / tensile strength before test) × 100

(8) Abrasion Resistance Test The taper abrasion test was performed according to ASTM D256.
The load was 1 kg and the wear wheels used were CS-17. 200
The abrasion resistance was evaluated by measuring the amount of abrasion caused by sliding 0 times.

(9) Recyclability (Examples 24 to 30) (a) The sheet having a thickness of about 1.0 mm prepared in Example 1 was irradiated with light for 7 days (168 hours) using a Dew Cycle Sunshine Super Long Life Weather Meter. Then, it was cut into a size of about 2.0 mm × 2.0 mm to 5.0 mm × 5.0 mm. The virgin of Example 1 was blended with the pellet before molding in an arbitrary ratio, and a T-die molding machine (a single-screw extruder equipped with a T-die (Kobe Steel Ltd., screw diameter 30 m)
m and the die / barrel temperature were both 225 ° C.) into a hopper to form a sheet. Evaluations such as a tensile test and color tone were performed.

(B) The sheet having a thickness of about 1.0 mm produced in Example 1 was directly used as about 2.0 mm × 2.0 m to 5.0 m.
After cutting to a size of mx 5.0 mm, the mixture was blended with the virgin pellets of Example 1 at an arbitrary ratio, and was then charged into a hopper of a T-die molding machine to form a sheet. Evaluations such as a tensile test and color tone were performed.

(C) Immediately after molding the sheet having a thickness of about 1.0 mm of Example 1, the sheet having a thickness of about 2.0 mm × 2.0 mm to 5. mx 5.0
mm, and blended with polyethylene terephthalate pellets (Novapex GS500 IV = 0.80 dl / g, manufactured by Mitsubishi Chemical Corporation) at 130 ° C. for 4 hours at an arbitrary ratio, and then put into a T-die molding machine hopper. After the sheet was formed (the barrel temperature was 270 ° C.), the tensile test, the color tone, and the like were evaluated.

Example 1 Polytetramethylene glycol unit (number average molecular weight = about 1016, hereinafter PTMG
Abbreviated as 1000. 100) polyester elastomer (hereinafter abbreviated as TPEE) resin pellets having a content of 62% by weight
10 parts by weight of melamine cyanurate (manufactured by Mitsubishi Engineering-Plastics Corporation, hereinafter abbreviated as MCA) are blended, and this is blended with a 30 mm vent-type twin-screw extruder (manufactured by Japan Steel Works, Ltd., twin-screw extrusion). Machine lab TEX3
0) using a barrel temperature of 220 ° C and a screw rotation speed of 1
The mixture was melt-kneaded at 50 rpm, extruded into strands, cooled in a water tank, and then pelletized by a strand cutter. The obtained pellet (A) is heated at 100 ° C. under reduced pressure for 1 hour.
After drying for 2 hours, the pellets were formed into a sheet using a single screw extruder equipped with a T die (manufactured by Kobe Steel Co., Ltd., screw diameter 30 mm, die / barrel temperature 220 ° C., roll temperature 30 ° C.), and a thickness of 1 mm. A .02 mm sheet was obtained. A combustion test (JIS D-1) was performed on the obtained sheet sample (A).
201), measurements such as a tensile test, an initial color tone, a heat resistance test, a light resistance test, and a wear test were performed.

Example 2 Example 1 was repeated except that 2.0 parts by weight of swellable synthetic fluoromica (trade name: Somasif ME100, manufactured by Corp Chemical Co., Ltd.) were added.
Same as.

Example 3 The procedure of Example 1 was repeated except for using 8.0 parts by weight of swellable synthetic fluoromica (trade name: Somasif ME100, manufactured by Corp Chemical Co., Ltd.).

Example 4 Example 1 was repeated except that the layered silicate compound was changed to 2.0 parts by weight of montmorillonite (Kunipia F, manufactured by Kunimine Mining Co., Ltd.) in Example 2.
Same as.

Example 5 Example 5 was repeated except that the layered silicate compound in Example 2 was changed to 3.0 parts by weight of organic bentonite (trade name: Orben M, manufactured by Shiraishi Mining Co., Ltd., ash content: 67.2% by weight). Same as Example 1.

Example 6 The same procedure as in Example 2 was repeated except that the layered silicate compound was treated with 2.0 parts by weight of a functionalized layered silicate (swellable synthetic fluoromica mosaic ME100 whose surface was treated with 3-glycidyloxypropylmethyldiethoxysilane). An experiment was conducted in the same manner as in Example 1 except that the pellet (B) and a sheet (B) having a thickness of 1.07 mm were obtained.

Example 7 An experiment was performed in the same manner as in Example 6, except that 8.0 parts by weight of the functionalized layered silicate was used.

Example 8 In Example 1, polytetrafluoroethylene (trade name: F2, manufactured by Daikin Industries, Ltd.)
01) Same as Example 1 except that 2.0 parts by weight was added.

Example 9 The procedure of Example 8 was repeated except that 8.0 parts by weight of polytetrafluoroethylene was added.

Example 10 In Example 1, the silicone oil (KF102, 750 manufactured by Shin-Etsu Silicon Co., Ltd.) was used.
0cSt) Same as Example 1 except that 2.0 parts by weight was added.

Example 11 Example 11 was the same as Example 11 except that 8.0 parts by weight of silicone oil was added.
Same as.

Example 12 PTMG1000 content 42
The same experiment as in Example 1 was performed, except that the TPEE pellets were used in a weight%.

Example 13 The same experiment as in Example 12 was carried out except that 2.0 parts by weight of the functionalized layered silicate (used in Example 6) was added.

Example 14 The same experiment as in Example 12 was carried out except that polytetrafluoroethylene (used in Example 8) was changed to 2.0 parts by weight.

Example 15 PTMG (number average molecular weight =
1984, hereinafter abbreviated as PTMG2000. The same experiment as in Example 1 was performed except that TPEE pellets having a content of 77% by weight were used.

Example 16 The same experiment as in Example 15 was carried out except that 2.0 parts by weight of the functionalized layered silicate (used in Example 6) was added.

Example 17 The same experiment as in Example 1 was carried out except that melamine cyanurate was used in an amount of 2.5 parts by weight.

Example 18 The same experiment as in Example 17 was carried out, except that 2.0 parts by weight of the functionalized layered silicate (used in Example 6) was added.

Example 19 The same experiment as in Example 1 was conducted except that melamine cyanurate was used in an amount of 30 parts by weight.

Example 20 The same experiment as in Example 19 was carried out except that the functionalized layered silicate (used in Example 6) was changed to 2.0 parts by weight.

Example 21 The same experiment as in Example 6 was performed except that the sheet thickness was changed to 0.18 mm.

Example 22 The same experiment as in Example 6 was conducted except that the sheet thickness was changed to 3.42 mm. The sheet extruded from the T die was taken out on a metal plate at 30 ° C. without being rolled up by a roll, and was obtained by immediately sandwiching it between two metal plates.

Example 23 An experiment was performed in the same manner as in Example 6, except that the sheet thickness was changed to 6.52 mm. The sheet extruded from the T die was taken out on a metal plate at 30 ° C. without being rolled up by a roll, and was obtained by immediately sandwiching it between two metal plates.

Example 24 The sheet having a thickness of about 1 mm obtained in Example 1 was held for 7 days (168 hours) by a sunshine weather meter, and then cut into small pieces.
The obtained cut product (A2) was mixed with the pellet (A0) before sheeting obtained in Example 1 and (A0) :( A2) = 3.
0:70 parts by weight, a single screw extruder equipped with a T die (manufactured by Shinko Co., Ltd., screw diameter 30 m)
m and the die / barrel temperature were both 225 ° C.). The measurement of each evaluation item was performed about the obtained sheet sample.

Example 25 The sheet having a thickness of about 1 mm obtained in Example 6 was held for 7 days (168 hours) by a sunshine weather meter, and then cut into small pieces.
The obtained cut material (B2) was mixed with the pellet (B0) before sheeting obtained in Example 6 and (B0) :( B2) = 3.
Example 18 was carried out in the same manner as in Example 18 except that the blending was performed so that the ratio became 0:70 parts by weight.

Example 26 A sheet having a thickness of about 1 mm and a width of 130 mm obtained in Example 1 was cut off at 15 mm at both ends and finely cut. The obtained cut material (A1) is obtained by mixing the pellets (A0) before sheeting obtained in Example 1 with:
(A0) :( A1) = 30: 70 parts by weight, and a single screw extruder equipped with a T die (Shinko Co., Ltd.)
Extruded at a screw diameter of 30 mm and a die / barrel temperature of 225 ° C.) to form a sheet with a thickness of 1.05 mm. The measurement of each evaluation item was performed about the obtained sheet sample.

Example 27 A sheet having a thickness of about 1 mm and a width of 130 mm obtained in Example 6 was cut off at both ends by 15 mm and cut into small pieces. Except that the obtained cut product (B1) was blended with the compound pellet (B0) before sheeting obtained in Example 6 so that the ratio of (B0) :( B1) = 30: 70 parts by weight. Same as Example 26.

Example 28 The pellet (A0) obtained in Example 1 was dried under reduced pressure at 120 ° C. for 6 hours, and then polyethylene terephthalate pellets (Novapex GS500 manufactured by Mitsubishi Chemical Corporation) (C). (A0): (C)
The same experiment as in Example 1 was performed except that the blending was performed so that the ratio was 75:25 parts by weight.

Example 29 Example 28 (A0):
The same experiment as in Example 28 was performed, except that the blending was carried out so that (C) = 50: 50 parts by weight.

Example 30 The same experiment as in Example 29 was performed, except that the ratio of the pellet (B0) :( C) obtained in Example 6 was 50:50 parts by weight.

[Example 31] 6. Obtained in Example 23
After cutting a 52 mm thick sheet to a size of 12 cm × 12 cm, a 3 × sheet was cut using a biaxial stretching machine (manufactured by Long Corporation).
A three-fold biaxial stretching treatment (stretching condition: after preheating at 85 ° C. for 60 seconds, a stretching speed of 5000% / min) was performed. The obtained stretched sheet was heat-set at 145 ° C. for 1 minute. The evaluation was performed in the same manner as in Example 1.

Example 32 PTMG 1000 content 62
100% by weight of TPEE resin pellets by weight, MCA
10 parts by weight were blended and the barrel temperature was adjusted to 2 using a 30 mm vent type twin screw extruder (used in Example 1).
The mixture was melt-kneaded at 20 ° C. and a screw rotation speed of 150 rpm, extruded into strands, cooled in a water tank, and pelletized by a strand cutter. The obtained pellets were dried under reduced pressure at 100 ° C. for 12 hours, and the pellets were subjected to a single screw extruder equipped with a T die (manufactured by Kobe Steel Co., Ltd., screw diameter 30 mm, die / barrel temperature 220 ° C., roll temperature 30 ° C.). )) To form a sheet having a thickness of 0.09 mm. After winding the obtained sheet around a conducting wire (about 6 mm in diameter and 30 cm in length), a Teflon sheet was further wound. Thereafter, the mixture was heated for 3 minutes while blowing a nitrogen stream into an electric furnace heated to 280 ° C. After cooling to room temperature, the Teflon sheet is removed and the wire coated sample having an average diameter of 12 mm (the average thickness of the resin layer is about 3 mm)
was gotten. A combustion test was performed on the obtained wire-coated sample.

Example 33 PTMG 1000 content 62
100% by weight of TPEE resin pellets by weight, MCA
10 parts by weight, functionalized layered silicate (used in Example 4)
Same as Example 26 except that 3 parts by weight were blended. An electric wire coated sample having an average diameter of 12 mm (the average thickness of the resin layer was about 3 mm) was obtained. A combustion test was performed on the obtained wire-coated sample.

Comparative Example 1 A polyester elastomer resin pellet having a PTMG1000 content of 62% by weight
After drying at 10 ° C. for 6 hours, the pellet was subjected to a single screw extruder equipped with a T die (manufactured by Kobe Steel Co., Ltd., screw diameter 30 mm,
The sheet was formed at a die / barrel temperature of 225 ° C.) to obtain a sheet having a thickness of 1.05 mm. The measurement of each evaluation item was performed similarly to Example 1. Flame retardancy, color tone, heat aging resistance, light resistance and abrasion resistance were significantly reduced, and the sheet had severe blocking.

Comparative Example 2 The same experiment as in Example 1 was carried out except that the amount of melamine cyanurate was changed to 0.5 part by weight. Flame retardancy, color tone, heat aging resistance, light resistance and abrasion resistance were significantly reduced, and the sheet had severe blocking.

Comparative Example 3 The amount of melamine cyanurate was 7
The same experiment as in Example 1 was performed except that the amount was changed to 0 parts by weight.
Physical properties were remarkably reduced, the sheet surface became dull, and bleed-out occurred.

[Comparative Example 4] PTMG100 in Example 1
The same experiment as in Example 1 was conducted, except that the polyester elastomer resin pellets having a 0 content of 85% by weight were used and the amount of melamine cyanurate added was 35 parts by weight. Flame retardance,
In addition to reduced physical properties, heat aging resistance and light resistance, the sheet had severe blocking.

Comparative Example 5 The same experiment as in Example 1 was performed except that 10 parts by weight of the phosphoric ester compound of the following formula (1) was used instead of melamine cyanurate. Flame retardancy, physical properties, heat aging resistance, light resistance, abrasion resistance, color tone, bleed-out, and blocking were observed.

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Comparative Example 6 An experiment was conducted in the same manner as in Example 1 except that 10 parts by weight of melamine was used instead of melamine cyanurate. Flame resistance, color tone, heat aging resistance, light resistance have been significantly reduced, as well as bleed out,
There was blocking.

Comparative Example 7 Example 1 was repeated except that 10 parts by weight of PBBPA (polypentabromobenzyl acrylate) was added in place of melamine cyanurate.
The same experiment was performed. In addition to flame retardancy, color tone, heat aging resistance, and light resistance, there was blocking.

Comparative Example 8 In Example 1, PBBPA / antimony trioxide (=) was used in place of melamine cyanurate.
(3.2 / 1.8 weight ratio), and the same experiment as in Example 1 was performed except that 10 parts by weight was added. Flame retardancy, physical properties, color tone, heat aging resistance, light resistance were reduced, and there was also blocking.

Comparative Example 9 The same experiment as in Example 1 was conducted, except that 10 parts by weight of magnesium hydroxide was added instead of melamine cyanurate. In addition to flame retardancy, physical properties, color tone, heat aging resistance, and light resistance, there was blocking.

Comparative Example 10 The same experiment as in Example 6 was performed except that the functionalized layered silicate was changed to 30 parts by weight. The mechanical properties were significantly reduced, and the melt viscosity during sheet molding was significantly increased.

Comparative Example 11 An experiment was conducted in the same manner as in Example 8, except that polytetrafluoroethylene was changed to 30 parts by weight. The mechanical properties were significantly reduced, and the melt viscosity during sheet molding was significantly increased.

Comparative Example 12 The same experiment as in Example 10 was performed except that the silicone oil was changed to 30 parts by weight in Example 10. The mechanical properties were significantly reduced, and the melt viscosity during sheet molding was significantly increased.

Comparative Example 13 Polyethylene terephthalate (D) was blended with polyolefin-based thermoplastic elastomer (Mitsubishi Monsanto Kasei Kasei Santoprene uncolored standard grade) (F) at a ratio of (F) :( D) = 50: 50. Thereafter, the pellet was formed into a sheet by a single screw extruder equipped with a T die to obtain a sheet having a thickness of about 1.0 mm. Flame retardancy, physical properties, color tone, heat aging resistance, and light resistance decreased.

Comparative Example 14 Polyethylene resin (HDPE manufactured by Mitsubishi Chemical Corporation, melt flow rate according to JIS K-6760; 0.15 g / 10 min) pellet (D) 100
Example 32 was repeated except that 100 parts by weight of aluminum hydroxide and 100 parts by weight of aluminum hydroxide were blended. An electric wire covering sample having an average diameter of 13 mm (the resin layer has an average thickness of about 3
mm). A combustion test was performed on the obtained wire-coated sample. The sample was burned. In addition to the sample completely burned (20 cm), a large amount of black smoke was generated, and the resin accompanying the flame was dropped during combustion.

Comparative Example 15 Ethylene / vinyl acetate copolymer resin (melt flow rate according to EVA, JIS K-6730, manufactured by Mitsubishi Chemical Corporation; 0.5 g / 10 minutes) Pellets 1
Example 26 was repeated except that 00 parts by weight and 100 parts by weight of magnesium hydroxide were blended. Average 13mm
(The thickness of the resin layer is about 3 mm on average). A combustion test was performed on the obtained wire-coated sample. The sample was burned. The sample was burned down (20cm) and a lot of black smoke was generated.
During the combustion, the resin accompanying the flame dripped.

[Comparative Example 16] 0.1 m of polyvinyl chloride resin (plasticizer added with 60 parts by weight of dioctyl phthalic acid)
Example 26 was carried out in the same manner as in Example 26 except that a wire covering sample was prepared using an m-thick film. An electric wire coating sample having an average diameter of 13 mm (the average thickness of the resin layer was about 3 mm) was obtained. A combustion test was performed on the obtained wire-coated sample. Although the combustion of the sample was stopped at 13 cm, a large amount of black smoke was generated, and a large amount of resin accompanying the flame was dropped during the combustion.

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[Table 1]

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[Table 2]

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[Table 3]

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[Table 4]

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[Table 5]

[0105]

[Table 6]

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[Table 7]

[0107]

[Table 8]

[0108]

[Table 9]

[0109]

[Table 10]

[0110]

[Table 11]

[0111]

According to the present invention, it has high flame retardancy without generating hydrogen halide gas harmful to the human body, and has recyclability, blocking resistance, color tone, oil resistance, heat resistance, light resistance, A remarkable effect is obtained in that a flame-retardant polyester elastomer sheet excellent in abrasion resistance and an interior material using the same, particularly an automobile interior material, a house interior material, and a wire covering material can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI B29L 31:58

Claims (11)

[Claims] 1. Component (B) melamine cyanurate per 100 parts by weight of a block copolymer comprising 70 to 20% by weight of polybutylene terephthalate unit and 30 to 80% by weight of polytetramethylene glycol unit. A flame-retardant sheet with good recyclability, which is obtained by molding a polyester resin composition containing 0 to 40 parts by weight of a component (C) anti-dripping agent by 0 to 10 parts by weight by an ordinary method. . 2. The sheet according to claim 1, wherein the component (C) is a layered silicate compound. 3. The sheet according to claim 1, wherein the component (C) is a fluorine-containing polymer. 4. The sheet according to claim 1, wherein the component (C) is a silicone oil. 5. The sheet according to claim 1, wherein the polyester resin composition contains at least 40% by weight of a recycled resin. 6. The sheet according to claim 5, wherein the recycled resin is a resin containing 60% by weight or less of another kind of polyester resin. 7. In a JIS D-1201 combustion test,
The average burning speed is 200 mm / min or less, and the burning time is 15.
The sheet according to any one of claims 1 to 6, which has flame retardancy that simultaneously satisfies a burning distance of 30.0 mm or less for 0 seconds or less, and has a thickness of 0.015 mm to 8.0 mm. 8. An interior material obtained by stretching the sheet according to claim 1. 9. An automotive interior material obtained by further heating and molding the sheet according to claim 1. 10. A housing interior material obtained by further heating and molding the sheet according to claim 1. 11. The component (A) according to claim 1, wherein:
An electric wire covering material having the composition of (B) or (C).