JP2002241515A - Resin composition sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyphenylene ether-based resin composition sheet excellent in sheet formability, flame retardancy, appearance, rigidity at high temperatures and thickness uniformity, and having low shrinkage, and to provide a method for producing the above resin composition sheet. SOLUTION: This resin composition sheet is produced by using (A) 51-99. 9 pts.wt. of a polyphenylene ether-based resin and (B) 0.1-49 pts.wt. of a liquid crystalline polyester, and is characterized by being <3% in thermal shrinkage and <5% in thickness unevenness Dt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sheet made of a polyphenylene ether-based resin composition which is excellent in sheet formability, and has excellent rigidity, flame retardancy and appearance when heated, and a method for producing the same.

[0002]

2. Description of the Related Art In general, polyphenylene ether is a resin having excellent properties such as heat resistance, hot water resistance, dimensional stability and mechanical and electrical properties, but has poor moldability due to its high melt viscosity. There is a disadvantage that.
On the other hand, in order to improve the moldability, the moldability has been improved by alloying polystyrene or the like with polyphenylene ether, but there was a problem that the heat resistance was reduced.

On the other hand, for example, Japanese Patent Application Laid-Open No. 56-115357 proposes blending a polymer such as polyphenylene ether with liquid crystal polyester to improve the melt processability of polyphenylene ether.
It relates to injection molding with a high shear rate of 00 (1 / sec), there is no description about extrusion molding with a low shear rate, and the physical properties are not sufficient. Japanese Patent No. 3117136 describes a sheet in which a liquid crystal polymer is added to a thermoplastic resin. However, the sheet is essentially made of polyester or polycarbonate as a matrix, and has insufficient rigidity when heated.

Japanese Patent Application Laid-Open No. 2-97555 proposes blending various kinds of polyarylene oxides with a liquid crystal polyester for the purpose of improving solder heat resistance. It has been proposed to mix a polyphenylene ether modified with amines and a liquid crystal polyester, but none of them described the moldability of the extruded sheet and the physical properties were not sufficient. Further, Japanese Patent Application Laid-Open No. 5-86288 proposes a method for improving the strength and rigidity of the recycled material, but there is no description in the sheet, and the physical properties are not sufficient.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a sheet made of a polyphenylene ether-based resin composition which is excellent in sheet formability and which is excellent in rigidity upon heating, flame retardancy and appearance, and a method for producing the same.

[0006]

Means for Solving the Problems As a result of intensive studies on the technology for achieving the above object, the present inventors have obtained a sheet comprising a polyphenylene ether-based resin and a liquid crystal polyester, and having a specific heat shrinkage and thickness unevenness. As a result, the present inventors have found that a sheet having excellent sheet formability, heat rigidity, flame retardancy, and appearance can be obtained, and have completed the present invention.

That is, the present invention provides: (A) Polyphenylene ether resin 51-9
9.9 parts by weight and (B) 0.1 to 4 liquid crystal polyester
1. A sheet made of a polyphenylene ether-based resin composition, comprising 9 parts by weight, having a heat shrinkage of less than 3% and thickness unevenness of less than 5%. The above 1 wherein the dielectric breakdown strength is 30 kV / mm or more
2. A sheet made of the polyphenylene ether-based resin composition described in 2. above, 3. The sheet made of the polyphenylene ether-based resin composition according to the above 1 or 2, wherein the surface temperature of the rolling roll immediately after the T-die of the extruder is in the range of 120 to 200 ° C. when the extruded sheet is formed. And a method for producing the same.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. The (A) polyphenylene ether-based resin of the present invention is a repeating unit structure represented by the following formula (1)

[0009]

Embedded image

(R ₁ and R ₄ each independently represent hydrogen, primary or secondary lower alkyl, phenyl, aminoalkyl or hydrocarbonoxy. R ₂ and R ₃ each independently represent Hydrogen, represents a primary or secondary lower alkyl or phenyl), and has a reduced viscosity (0.5 g / dl, chloroform solution, measured at 30 ° C.)
Is a homopolymer and / or a copolymer in the range of 0.15 to 1.0 dl / g. A more preferred reduced viscosity is in the range of 0.20 to 0.70 dl / g, most preferably in the range of 0.40 to 0.60.

Specific examples include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether) and poly (2-methyl- 6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like. Further, 2,6-dimethylphenol and other phenols (for example, Polyphenylene ether copolymers such as copolymers with 3,6-trimethylphenol and 2-methyl-6-butylphenol) are also included. Among them, poly (2,6-dimethyl-
1,4-phenylene ether), and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable, and poly (2,6-dimethyl-1,4) is more preferable.
-Phenylene ether) is preferred.

US Pat. No. 3,306,687 is an example of a method for producing the polyphenylene ether (A) used in the present invention.
There is a method in which 2,6-xylenol is oxidatively polymerized using a complex of a cuprous salt and an amine described in the specification of Patent No. 4 as a catalyst. U.S. Pat. Nos. 3,306,875 and 325
Nos. 7357 and 3257358, JP-B-52-17880, JP-A-50-51197 and JP-A-63-152628 also describe (A) a method for producing polyphenylene ether. preferable. The polyphenylene ether-based resin (A) of the present invention may be used as it is after the polymerization process, or may be extruded under a nitrogen gas atmosphere or a non-nitrogen gas atmosphere, under devolatilization or non-devolatilization. It may be pelletized by melt-kneading below.

The polyphenylene ether resin (A) of the present invention also includes a polyphenylene ether functionalized with various dienophile compounds. Examples of the dienophile compound include compounds such as maleic anhydride, maleic acid, fumaric acid, phenylmaleimide, itaconic acid, acrylic acid, methacrylic acid, methylarylate, methylmethacrylate, glycidyl acrylate, glycidyl methacrylate, stearyl acrylate, and styrene. . Further, as a method of functionalization with these dienophile compounds, a method of functionalizing in a molten state with or without devolatilization using an extruder or the like in the presence or absence of a radical generator, or a radical generator A method of functionalization in a non-molten state in the presence or absence of a non-molten state is exemplified.

The polyphenylene ether resin (A) of the present invention includes a polyphenylene ether resin alone or a mixture of a polyphenylene ether resin and an aromatic vinyl polymer, and a mixture of other resins. The aromatic vinyl polymer, for example, atactic polystyrene, syndiotactic polystyrene,
An acrylonitrile-styrene copolymer is exemplified. When a mixture of the polyphenylene ether resin and the aromatic vinyl polymer is used, the polyphenylene ether resin is at least 70 wt%, preferably at least 80 wt%, based on the total amount of the polyphenylene ether resin and the aromatic vinyl polymer. More preferably, it is 90 wt% or more.

The liquid crystal polyester (B) of the present invention is a polyester called a thermotropic liquid crystal polymer, and known polyesters can be used. For example, a thermotropic liquid crystal polyester having p-hydroxybenzoic acid and polyethylene terephthalate as main constituent units, a thermotropic liquid crystal polyester having p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid as main constituent units, p-
Examples thereof include, but are not particularly limited to, thermotropic liquid crystal polyesters having hydroxybenzoic acid, 4,4'-dihydroxybiphenyl, and terephthalic acid as main constituent units. As the liquid crystal polyester (B) used in the present invention, those composed of the following structural units (a) and (b), and if necessary, (c) and / or (d) are preferably used.

[0016]

Embedded image

The structural units (a) and (b) are a structural unit of a polyester formed from p-hydroxybenzoic acid and a structural unit formed from 2-hydroxy-6-naphthoic acid, respectively. By using the structural units (a) and (b), it is possible to obtain the thermoplastic resin composition of the present invention having excellent balance of mechanical properties such as excellent heat resistance, fluidity and rigidity. X in the above structural units (c) and (d)
Can be arbitrarily selected from formula (2) below.

[0018]

Embedded image

Preferred in the structural formula (C) are structural units formed from ethylene glycol, hydroquinone, 4,4'-dihydroxybiphenyl, 2,6-dihydroxynaphthalene, and bisphenol A, respectively.
More preferably, ethylene glycol, 4,4'-
Dihydroxybiphenyl and hydroquinone are particularly preferable, and ethylene glycol and 4,4'-dihydroxybiphenyl are particularly preferable. In the structural formula (d), preferred are structural units formed from terephthalic acid, isophthalic acid, and 2,6-dicarboxynaphthalene, and more preferred are terephthalic acid and isophthalic acid.

In the structural formulas (c) and (d), at least one or more of the above-mentioned structural units can be used in combination. Specifically, when two or more kinds are used in combination, in the structural formula (C), 1) a structural unit generated from ethylene glycol / a structural unit generated from hydroquinone, 2) a structural unit generated from ethylene glycol / 4, 4 Structural units formed from '-dihydroxybiphenyl, 3) structural units formed from hydroquinone /
And structural units generated from 4,4'-dihydroxybiphenyl.

In the structural formula (d), 1) a structural unit formed from terephthalic acid / a structural unit formed from isophthalic acid, 2) a structural unit formed from terephthalic acid / 2, formed from 2,6-dicarboxynaphthalene And other structural units. Here, the amount of terephthalic acid in the two components is preferably at least 40 wt%, more preferably at least 60 wt%, particularly preferably at least 80 wt%. By setting the amount of terephthalic acid to 40 wt% or more of the two components, a resin composition having relatively good fluidity and heat resistance can be obtained. The use division of the structural units (a), (b), (c), and (d) in the liquid crystal polyester (B) component is not particularly limited. However, the structural units (c) and (d) are basically in equimolar amounts.

The structural unit (e) composed of the structural units (c) and (d) can be used as the structural unit in the component (B). Specifically, 1) a structural unit generated from ethylene glycol and terephthalic acid, 2) a structural unit generated from hydroquinone and terephthalic acid, 3) 4,
Structural units formed from 4'-dihydroxybiphenyl and terephthalic acid, 4) structural units formed from 4,4'-dihydroxybiphenyl and isophthalic acid, 5) structural units formed from bisphenol A and terephthalic acid, and the like. it can.

[0023]

Embedded image

The liquid crystalline polyester component (B) of the present invention may contain other aromatic dicarboxylic acids, aromatic diols, and aromatic hydroxy carboxylic acids, if necessary, in a small amount that does not impair the features and effects of the present invention. Structural units generated from acids can be introduced. The temperature at which the component (B) of the present invention starts to exhibit a liquid crystal state upon melting (hereinafter, referred to as liquid crystal onset temperature) is preferably 150 to 350 ° C, more preferably 180 to 320 ° C. By setting the liquid crystal onset temperature in this range, the obtained resin composition has a favorable balance of color tone, heat resistance, and moldability.

The (B) liquid crystal polyester component 2 of the present invention
The dielectric loss tangent (tan δ) at 5 ° C. and 1 MHz is preferably 0.03 or less, more preferably 0.02 or less.
5 or less. The smaller the value of the dielectric loss tangent is, the smaller the dielectric loss becomes, and when this resin composition is used as a raw material for electric / electronic parts, electric noise generated is preferably suppressed. In particular, at a temperature of 25 ° C. under a high frequency range, that is, in a range of 1 to 10 GHz, a dielectric loss tangent (tan) is obtained.
δ) is preferably 0.03 or less, more preferably 0.025 or less.

The apparent melt viscosity of the liquid crystal polyester component (B) of the present invention (the liquid crystal onset temperature + 30 ° C and the shear rate 10
0 / sec) is preferably 10 to 3,000 Pa · s, more preferably 10 to 2,000 Pa · s, and particularly preferably 10 to 1,000 Pa · s. Adjusting the apparent melt viscosity to this range makes the fluidity of the obtained composition favorable.

In the present invention, the compounding amount of the polyphenylene ether resin (A) is 51 to 99.9 parts by weight, preferably 60 to 99 parts by weight, and more preferably 70 to 9 parts by weight.
8 parts by weight. If the amount is more than 99.9 parts by weight, the fluidity is greatly reduced, and the T-die portion is liable to be apt to be formed, resulting in a decrease in molding stability. This compounding amount is 5
When the amount is less than 1 part by weight, the thickness unevenness of the sheet and the heat shrinkability are deteriorated. Here, the term "decomposition" refers to a decomposed oligomer or a crosslinked product of a resin which is deposited as a foreign substance in a portion of the T-die in the vicinity of where the molten resin is discharged during extrusion molding. This occasionally adversely affects the production stability by adhering to the sheet from time to time.

The compounding amount of the liquid crystal polyester as the component (B) in the present invention is 0.1 to 49 parts by weight, preferably 1 to 49 parts by weight.
The amount is from 40 to 40 parts by weight, more preferably from 2 to 30 parts by weight. If the compounding amount is more than 49 parts by weight, the anisotropy of the liquid crystal polymer causes deterioration in sheet thickness unevenness and heat shrinkage. If the compounding amount is less than 0.1 part by weight, the fluidity is greatly reduced, and the flow rate is greatly reduced, and the discharge amount must be reduced in relation to the load of the extruder, resulting in reduced production. There's a problem.

In the present invention, in addition to the above components, other additional components such as an antioxidant and a flame retardant (organic phosphoric acid ester-based compound) may be used as necessary, provided that the characteristics and effects of the present invention are not impaired. , Phosphazene compounds, silicon compounds), elastomers, plasticizers (oil, low molecular weight polyethylene, epoxidized soybean oil, polyethylene glycol, fatty acid esters, etc.), flame retardant aids, weather (light) resistance improvers, polyolefins Nucleating agents, slip agents, various coloring agents, release agents, etc. may be added.

The resin composition of the present invention can be produced by various methods. For example, a heat-melt kneading method using a single-screw extruder, a twin-screw extruder, a roll, a kneader, a Brabender plastograph, a Banbury mixer, or the like can be mentioned. Among them, a melt-kneading method using a twin-screw extruder is most preferable. The melting and kneading temperature at this time is not particularly limited, but can be arbitrarily selected usually from 150 to 350 ° C. The sheet of the present invention has a thickness of 0.010 to
1.0 mm, preferably 0.050-0.
It is 50 mm and is sometimes called a film.

The sheet made of the polyphenylene ether-based resin composition of the present invention is obtained by extruding a sheet from the resin composition obtained above as a raw material. T-die extrusion,
Inflation molding is preferable, and T-die extrusion molding is more preferable from the viewpoint of the heat shrinkage and uneven thickness. It may be used without stretching, may be stretched uniaxially, or may be stretched biaxially. In the method for producing a sheet of the present invention, it is preferable that the surface temperature of the rolling roll immediately after the T-die of the extruder is selected from the range of 120 to 200 ° C. The surface temperature is more preferably 130 to 180
° C, and still more preferably 150 to 170 ° C. Also, it is preferable that the set temperature be small
The temperature is within ± 10 ° C., preferably within ± 5 ° C., and more preferably within ± 2 ° C. The smaller the flap, the more preferable in terms of uneven thickness and heat shrinkage.

The heat shrinkage of the present invention is determined by measuring a sheet cut at a size of 150 mm × 150 mm at 150 ° C. so that each piece is parallel to MD (flow direction) and TD (perpendicular to the flow direction). After cooling, the temperature was adjusted in an atmosphere of 23 ° C. and a humidity of 50% for 24 hours, and the dimensions of MD and TD before and after heating were measured, and the values were determined according to the following formula. Heat shrinkage (%) = (1− (length of side after heating / length of side before heating)) × 100

The thickness unevenness Dt of the present invention can be obtained by measuring nine thicknesses of a sheet cut into a size of 150 mm × 150 mm so that each piece is parallel to the MD and the TD, and obtaining the following formula. it can. Dt (%) = ( _Tmax − _Tav ) / _Tav × 100 _Tmax : The largest of the nine thicknesses. T _av : Average value of thickness at 9 places.

The essence of the present invention is that, when the heat shrinkage and the thickness unevenness Dt of the sheet are limited to a specific range, the appearance, rigidity, and thermal rigidity of the sheet can be simultaneously satisfied at a high level. It is in the point. That is, when performing sheet forming of the polyphenylene ether-based resin composition of the present invention, the surface temperature of the rolling roll immediately after the T-die of the extruder is selected from the range of 120 to 200 ° C., and the heat shrinkage of the sheet is By controlling the thickness to be less than 3% and the thickness unevenness Dt to be less than 5%, a sheet capable of simultaneously satisfying a high level of appearance, rigidity, and rigidity when heated can be obtained.

The dielectric breakdown strength of the present invention can be determined by using a sheet sample and measuring according to JIS K6911. Further, the sheet of the present invention is a sheet made of a polyphenylene ether-based resin, and is characterized by having excellent dielectric breakdown strength. Its dielectric strength is 30 kV / mm or more, preferably 40 kV / mm.
mm or more, more preferably 50 kV / mm or more, even more preferably 60 kV / mm or more.

The sheet of the present invention thus obtained is excellent in flame retardancy, appearance, rigidity when heated, and also excellent in dielectric breakdown strength. Therefore, it can be used for the following applications where these characteristics are required. Home appliances and O represented by personal computers, mobile phones, refrigerators, facsimile machines, copiers, etc.
A mechanical component in a product related to A, a printed circuit board, or an insulating component called an insulating washer of a lithium ion battery.

As described above, in the present invention, (A)
By using a resin composition in which the component and the component (B) are blended and extruding by using a rolling roll in a specific temperature range, the resin composition is excellent in flame retardancy, appearance, rigidity at heating, and thickness uniformity. Low heat shrinkage and excellent dielectric strength. Although the reason is not always clear, it can be considered as follows. The polyphenylene ether resin itself has a inherently high melt viscosity, has a high torque in the extruder, is accompanied by a higher shear heat, and is exposed to higher temperatures, so that undesired crosslinking of the polyphenylene ether resin, etc. Cause side reactions. However, by blending the liquid crystal polyester which is the component (B) of the present invention, the melt viscosity can be reduced, the shear heat generation is suppressed, and the linear molecular chain inherently possessed by the polyphenylene ether resin can be retained. Even more surprisingly, in the present invention, the occurrence of glazing is extremely reduced, but this is because the liquid crystal polyester has an anisotropy at the time of melting, a slip phenomenon occurs when the molten resin passes through the T-die, This is considered to be due to the suppression of stagnation and side reactions such as crosslinking. It is considered that, due to these, flame retardancy, appearance, rigidity at heat, and thickness uniformity are further excellent, heat shrinkage is small, and dielectric breakdown strength is excellent.

Hereinafter, the present invention will be described with reference to examples. However, the present invention is not limited to the following examples as long as the gist is not exceeded. Components used in Examples (Polyphenylene ether) PPE-1: Powder-like poly (2,6-) having a reduced viscosity of 0.42 obtained by oxidative polymerization of 2,6-dimethylphenol.
Dimethyl-1,4-phenylene ether). (Liquid crystal polyester) LCP-1: Under a nitrogen atmosphere, p-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, and acetic anhydride are charged, heated and melted, and polycondensed to have the following theoretical structural formula. A liquid crystal polyester was obtained. In addition, the component ratio of a composition represents a molar ratio.

[0039]

Embedded image

LCP-2: p- under a nitrogen atmosphere
By charging hydroxybenzoic acid, polyethylene terephthalate, acetic anhydride, heating and melting, and polycondensation,
A liquid crystalline polyester having the following theoretical structural formula was obtained. In addition, the component ratio of a composition represents a molar ratio.

[0041]

Embedded image

The sheet molding and physical property evaluation of each resin composition were performed as follows.
It carried out according to the following method. (1) Sheet molding The obtained pellets were discharged at a discharge rate of 60 kg / hr and a take-up speed of 4.2 to 4.8 m using a single screw extruder having a screw diameter of 65 mm and a cylinder temperature of 300 ° C and a T-die temperature of 300 ° C. / Min, die clearance 0.5mm,
Extruded sheet molding was performed under the conditions of a rolling roller clearance of 0.25 to 0.30 mm.

(2) Formability (2-1) Sheet Formability When extruded sheet was formed under the conditions of the above (1), the sheet formability was determined according to the following criteria. ：: The torque of the extruder was not problematic, and a sheet having a uniform thickness was continuously and stably formed for 30 minutes or more. Δ: There was no problem with the torque of the extruder, but resin pools were generated at the rolling rolls, and it was difficult to form a uniform sheet. ×: There was a problem in the torque of the extruder, and molding was not possible.

(2-2) Sharpness The sharpness generated at the T-die portion during extrusion molding was deposited on the lip portion of the T-die, sometimes adhered to the sheet side, and mixed into the sheet as brown foreign matter. Therefore, the amount was determined based on the following criteria. Good: No brown foreign matter was detected in the sheet formed continuously for 30 minutes. ×: 1 brown foreign matter in sheet formed continuously for 30 minutes
Or more were detected.

(3) Flame Retardancy (3-1) Maximum Burning Time The sheet obtained under the conditions of the above (1) is 200 mm in length.
× Cut to size of 50mm width, Underwriters Labor
A combustion test was performed based on UL-94 film standards of atories. That is, the sheet was wound and fixed in a cylindrical shape having a diameter of 13 mm, the upper loop was closed, and the flame was brought into contact with the lower portion in a vertical state. A combustion test was performed on five test pieces, and after the flame contact for 3 seconds, the burning time from when the flame was released until the flame disappeared was set to t ₁ (second). After the flame contact for 3 seconds again, the flame was released. The burning time from when the flame disappeared until the flame disappeared was defined as t ₂ (second). The maximum burning time was selected from the five t ₁ and t ₂ , that is, a total of ten points.

(3-2) Total Burning Time At the time of the above burning test, the burning time of five points t ₁ and t ₂ , ie, a total of 10 burning times were totaled. (3-3) Burning distance A marking line was drawn at a distance of 125 mm from the lowermost part of the cylindrical sample, and judgment was made according to the following judgment criteria. ：: Self-extinguishing at 10 points below the marked line. X: Some burned above the marked line even at one point.

(4) Appearance The surface of the sheet obtained in the above (1) was determined according to the following criteria. ：: The surface is smooth, there is no silver streaks, and no small dents are observed. ×: Silver streaks or small dents were observed on the surface.

(5) Tensile properties (rigidity under heat) Using an autograph (AG-5000, manufactured by Shimadzu Corporation), the sheet obtained in the above (1) was cut into a 6 mm-wide tangled shape. A tensile test was performed at a chuck distance of 80 mm and a test speed of 50 mm / min, and the tensile strength (TS) was measured. MD and TD length direction
Each measurement was performed. Measurement temperature atmosphere is 23 ° C, 150
Each measurement was carried out.

(6) Uneven thickness (Dt) The sheet obtained in the above (1) was subjected to MD (flow direction) and T
D (150 mm x 150 mm) so that each piece is parallel to
The thickness at each location was measured using a micro gauge and determined according to the following equation. Dt (%) = ( _Tmax − _Tav ) / _Tav × 100 _Tmax : The largest of the nine thicknesses. T _av : Average value of thickness at 9 places.

(7) Heat Shrinkage The sheet obtained in the above (1) is cut into a size of 150 mm × 150 mm so that each piece is parallel to MD and TD, and is placed in an oven set at 150 ° C. After cooling, the temperature is adjusted in an atmosphere of 23 ° C. and a humidity of 50% for 24 hours. The dimensions of the MD and TD before and after heating were measured, and determined according to the following equations. Heat shrinkage (%) = (length of side before heating−length of side after heating) / (length of side before heating) × 1
00

(8) Dielectric breakdown strength The sheet obtained in the above (1) is 100 mm × 100 mm
The measurement was performed using a withstand voltage tester (Model SD-12, manufactured by Toshiba Corporation) in accordance with JIS K6911. The measurement temperature atmosphere is 23 ° C.

[0052]

Example 1 A twin-screw extruder (ZSK-25) with a vent port set at 250 to 300 ° C. at a ratio (parts by weight) of polyphenylene ether (PPE-1) and liquid crystal polyester (LCP-1) shown in Table 1. ; WERNER & PFLE
The mixture was melt-kneaded using IDERER Co., Ltd.) to obtain pellets. Using this pellet, by the method shown above,
The sheet was formed. The surface temperature of the rolling roll is 130 ° C
Was controlled. A sheet was obtained stably, and almost no occurrence of turbidity in the T-die portion was recognized. The average thickness of the sheet was 0.38 mm. These sheets were evaluated for physical properties according to the methods described above. Table 1 shows the results.
It was shown to.

[0053]

Example 2 Liquid crystal polyester (LCP-1 and LC
Pellets were obtained by melt-kneading in the same manner as in Example 1 except that P-2) and the ratio (parts by weight) shown in Table 1 were used. Using the pellets, a sheet was formed by the method described above. The surface temperature of the rolling roll was controlled at 150 ° C. A sheet was obtained stably, and almost no occurrence of turbidity in the T-die portion was recognized. The average thickness of the sheet is 0.
It was 35 mm. These sheets were evaluated for physical properties according to the methods described above. The results are shown in Table 1.

[0054]

Example 3 As polyphenylene ether resin, polyphenylene ether (PPE-1) and high impact polystyrene (H9405, manufactured by A & M Co.,
S ”. ) Was performed in the same manner as in Example 1 except that the proportions shown in Table 1 were used to obtain pellets, and sheet forming was performed. The surface temperature of the rolling roll was controlled at 130 ° C. A sheet was obtained stably, and almost no occurrence of turbidity in the T-die portion was recognized. The average thickness of the sheet was 0.36 mm. These sheets were evaluated for physical properties according to the methods described above. The results are shown in Table 1.

[0055]

Comparative Example 1 Modified polyphenylene ether (Zylon X9102, manufactured by Asahi Kasei Corporation) which is a heat-resistant grade 100
Sheet molding was carried out in the same manner as in Example 1 except that parts by weight were used as raw materials. Occurrence of blindness was observed in the T-die portion. The average thickness of the sheet was 0.34 mm. These sheets were evaluated for physical properties according to the methods described above. The results are shown in Table 1.

[0056]

Comparative Example 2 Polyphenylene ether (PPE-1) 1
In a manner similar to that of Example 1, 100 parts by weight of the raw materials were melt-kneaded to obtain pellets. Using the pellets, sheet forming was attempted by the method described above, but under the same conditions, sheet forming could not be performed because the torque load of the extruder was excessive.

[0057]

[Table 1]

[0058]

Comparative Example 3 A sheet was formed in the same manner as in Example 1 except that the pellets obtained in Example 1 were used and the surface temperature of the rolling roll was set at 90 ° C. Since the sheet was rapidly cooled by the rolling roll, a gap was formed between the contracted sheet and the rolling roll, and the sheet could not be formed stably.

[0059]

Comparative Example 4 A sheet was formed in the same manner as in Example 1 except that the pellets obtained in Example 1 were used and the surface temperature of the rolling roll was set to 220 ° C. The thickness of the obtained sheet was 0.31 mm. According to the method (7), the heat shrinkage was measured. The heat shrinkage of MD was 5.2%, and the heat shrinkage of TD was 3.3%.

[0060]

Industrial Applicability According to the present invention, there is provided a sheet made of a polyphenylene ether-based resin composition having excellent sheet moldability, excellent flame retardancy, appearance, rigidity at heating, uniform thickness, and low heat shrinkage, and a method for producing the same. It became possible.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08L 67:00) C08L 67:00) B29K 67:00 B29K 67:00 71:00 71:00 B29L 7: 00 B29L 7:00 F term (reference) 4F071 AA43 AA51 AF39 AF39Y AF61 AF61Y AH12 AH13 AH16 BA01 BB06 BC01 BC12 4F207 AA24 AA32 AC01 AG01 AR06 KA01 KA17 KF01 KL76 KL84 KM16 KW26 4J002 CF002 CF05020 CF002

Claims (3)

[Claims] 1. A polyphenylene ether resin (A)
1 to 99.9 parts by weight and (B) a liquid crystalline polyester.
A sheet made of a polyphenylene ether-based resin composition comprising 1 to 49 parts by weight, having a heat shrinkage of less than 3% and a thickness unevenness of less than 5%. 2. The sheet made of the polyphenylene ether-based resin composition according to claim 1, which has a dielectric breakdown strength of 30 kV / mm or more. 3. When forming an extruded sheet, the surface temperature of the rolling roll immediately after the T-die of the extruder is adjusted to 120 to 200.
The method for producing a sheet made of a polyphenylene ether-based resin composition according to claim 1 or 2, wherein the temperature is in the range of ° C.