JP2007277410A - Sheet formed of polyphenylene ether resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sheet formed of a polyphenylene ether resin that is excellent in heat resistance and transparency. <P>SOLUTION: The sheet formed of a polyphenylene ether resin is composed of a resin composition comprising 75 mass% or more polyphenylene ether wherein the sheet has a total light transmittance of 80% or more and a haze value of 10% or less. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a sheet made of polyphenylene ether resin having excellent heat resistance and transparency.

Polyphenylene ether is used in a wide range of applications because it has excellent mechanical properties, electrical properties, and heat resistance, and also has excellent dimensional stability, but it is inferior in molding processability by itself. It is widely known to blend polystyrene. However, there is a problem that heat resistance and chemical resistance are lowered.
As a technique for improving the fluidity of polyphenylene ether while maintaining heat resistance, a technique for blending liquid crystal polyester (see, for example, Patent Document 1) has been proposed, and a sheet (for example, blending polyphenylene ether and liquid crystal polyester) (for example, Further, a sheet containing a flame retardant (for example, see Patent Document 3) has been proposed, but it was not sufficient in terms of transparency.

Further, a technique for blending a polyphenylene ether-based resin, a specific cage-shaped silsesquioxane partial cleavage structure and a specific silicon compound (see, for example, Patent Document 4) has also been proposed. It was not enough in terms of the occurrence of etc.
Therefore, the present situation is that a sheet made of polyphenylene ether resin having excellent heat resistance and transparency is desired.
JP 56-115357 A JP 2002-241515 A JP 2002-241601 A JP 2004-107511 A

  An object of the present invention is to provide a sheet made of a polyphenylene ether resin that is suitable for uses requiring heat resistance and transparency, and has excellent heat resistance and transparency, which could not be achieved by the technology described above. is there.

As a result of intensive studies, the present inventors have found that the present invention is effective for solving the above-mentioned problems by sheet-molding a resin composition containing 75% by mass or more of polyphenylene ether as a raw material. Reached.
Next, in order to facilitate understanding of the present invention, basic features and preferred embodiments of the present invention will be listed.
(1) A polyphenylene ether-based resin sheet comprising a resin composition containing 75% by mass or more of (A) polyphenylene ether, having a total light transmittance of 80% or more and a haze of 10% or less.
(2) The polyphenylene ether-based resin sheet according to (1) above, which contains an organic compound having a molecular weight of 400 to 2000 (B).
(3) The polyphenylene ether-based resin sheet according to (2), wherein the melting point of the component (B) is 150 ° C. or higher.
(4) The polyphenylene ether-based resin sheet according to (2) and (3), wherein the component (B) is at least one selected from the group consisting of a hindered phenol compound and a phosphite compound.

(5) The polyphenylene ether-based resin sheet according to any one of (1) to (4), wherein the component (B) is 0.05 to 10 parts by mass with respect to 100 parts by mass of the component (A).
(6) The polyphenylene ether-based resin sheet according to any one of (1) to (5), wherein the thickness is 0.01 to 0.5 mm.
(7) The polyphenylene ether-based resin sheet according to any one of (1) to (6), which is obtained by molding by an extruded tubular method or a T-die extrusion method.
(8) The polyphenylene ether-based resin sheet according to any one of the above (1) to (7), which is produced by producing the resin composition supply port with an oxygen concentration of 0 to 3% during sheet molding.
(9) The manufacturing method of the sheet | seat made from polyphenylene ether resin as described in said (7) and (8).

  According to the present invention, it is possible to provide a polyphenylene ether resin sheet having excellent heat resistance and transparency.

Next, each component that can be used in the present invention will be described in detail.
The polyphenylene ether of the component (A) that can be used in the present invention is a homopolymer and / or copolymer composed of the structural unit of the formula (1).

[Wherein O is an oxygen atom, R is independently hydrogen, halogen, primary or secondary lower alkyl, phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, or halohydrocarbonoxy (provided that At least two carbon atoms separating the halogen atom and the oxygen atom). ]
Specific examples of the polyphenylene ether of the present invention include, for example, poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like, and 2,6-dimethylphenol and other phenols (For example, a copolymer with 2,3,6-trimethylphenol or a copolymer with 2-methyl-6-butylphenol as described in JP-B-52-17880) Polyphenylene ether copolymers may also be mentioned. When using a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol as polyphenylene ether, the ratio of each monomer unit is based on the total amount of polyphenylene ether copolymer being 100% by mass. In particular, a copolymer comprising about 80 to about 90% by mass of 2,6-dimethylphenol and about 10 to about 20% by mass of 2,3,6-trimethylphenol is particularly preferable.

Among these, particularly preferred polyphenylene ethers include poly (2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, or these It is a mixture.
The method for producing the polyphenylene ether used in the present invention is not particularly limited as long as it can be obtained by a known method. For example, U.S. Pat. Nos. 3,306,874, 3,306,875, and 3,257,357 are disclosed. And the production methods described in JP-A-3257358, JP-A-50-51197, JP-B52-17880, and 63-152628.

The reduced viscosity (η _{sp / c} : 0.5 g / dl, chloroform solution, measured at 30 ° C.) of the polyphenylene ether that can be used in the present invention is preferably in the range of 0.15 to 0.70 dl / g. More preferably, it is in the range of 0.20 to 0.60 dl / g, more preferably in the range of 0.40 to 0.55 dl / g.
In the present invention, two or more polyphenylene ethers having different reduced viscosities may be blended. For example, a mixture of a polyphenylene ether having a reduced viscosity of 0.45 dl / g or less and a polyphenylene ether having a reduced viscosity of 0.50 dl / g or more, a low molecular weight polyphenylene ether having a reduced viscosity of 0.40 dl / g or less, and a reduced viscosity of 0.50 dl / g or more. A mixture of polyphenylene ethers, etc., of course, is, of course, not limited to these.

In addition, the polyphenylene ether that can be used in the present invention may be a polyphenylene ether modified in whole or in part.
The modified polyphenylene ether here means at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group, or glycidyl in the molecular structure. The polyphenylene ether modified with at least one modifying compound having a group.

  The method for producing the modified polyphenylene ether includes (1) a modified compound without melting the polyphenylene ether at a temperature in the range of 100 ° C. or higher in the presence or absence of a radical initiator and lower than the glass transition temperature of the polyphenylene ether. (2) a method in which a modified compound is melt-kneaded and reacted at a temperature in the range of the glass transition temperature of polyphenylene ether to 360 ° C. in the presence or absence of a radical initiator, and (3) a radical initiator. In the presence or absence, a method of reacting a polyphenylene ether and a modifying compound in a solution at a temperature lower than the glass transition temperature of the polyphenylene ether may be mentioned. Any of these methods may be used, (1) and The method (2) is preferred.

Next, at least one modified compound having at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group, or glycidyl group in the molecular structure Will be described in detail.
Examples of modified compounds having a carbon-carbon double bond, a carboxylic acid group, and an acid anhydride group in the molecule include maleic acid, fumaric acid, chloromaleic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, and these And acid anhydrides. Fumaric acid, maleic acid, and maleic anhydride are particularly preferable, and fumaric acid and maleic anhydride are particularly preferable.
In addition, those in which one or two of the carboxyl groups of the unsaturated dicarboxylic acid are esters can be used.
Examples of the modified compound having a carbon-carbon double bond and a glycidyl group in the molecule include allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, and epoxidized natural fats and oils.

Among these, glycidyl acrylate and glycidyl methacrylate are particularly preferable.
Examples of the modified compound having a carbon-carbon double bond and a hydroxyl group in the molecule include general formula C _n H _2n-3 OH such as allyl alcohol, 4-penten-1-ol, and 1,4-pentadien-3-ol. (n is a positive integer) of unsaturated alcohols of the general formula _{C n H 2n-5 OH,} ( n is a positive integer) _{C n H 2n-7} OH include unsaturated alcohols such as.
The above-described modifying compounds may be used alone or in combination of two or more.

The amount of the modifying compound added when producing the modified polyphenylene ether is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass with respect to 100 parts by mass of the polyphenylene ether.
A preferable amount of the radical initiator when producing the modified polyphenylene ether using the radical initiator is 0.001 to 1 part by mass with respect to 100 parts by mass of the polyphenylene ether.
Further, the addition rate of the modifying compound in the modified polyphenylene ether is preferably 0.01 to 5% by mass. More preferably, it is 0.1-3 mass%.
In the modified polyphenylene ether, an unreacted modified compound and / or a polymer of the modified compound may remain.

  In the present invention, the blending amount of the component (A) needs to be 75% by mass or more based on 100% by mass of the total resin composition from the viewpoint of heat resistance. Preferably, it is 75 mass% or more and less than 100 mass%, More preferably, it is 80 mass% or more and less than 100 mass%, More preferably, it is 90 mass% or more and less than 100 mass%, Most preferably, it is 90 mass% or more and 99 mass% or less, Preferably they are 90 mass% or more and 96.2 mass% or less.

In the present invention, the component (B) preferably contains an organic compound having a molecular weight of 400 to 2,000. The organic compound is a compound mainly composed of carbon element, hydrogen element, and oxygen element, but may contain nitrogen element, phosphorus element, sulfur element and the like.
The molecular weight of the component (B) of the present invention needs to be in the range of 400 to 2,000. It is 400 or more from the viewpoint of occurrence in the eyes and corners during sheet processing, and 2000 or less from the viewpoint of sheet workability. Preferably it is 500-1000, More preferably, it is 550-800, More preferably, it is 600-800.

The component (B) of the present invention preferably has a melting point of 150 ° C. or higher. More preferably, it is 150 degreeC or more and 320 degrees C or less, More preferably, it is 200 degreeC or more and 300 degrees C or less. A melting point of 150 ° C. or higher is preferable from the viewpoint of heat resistance, and a melting point of 320 ° C. or lower is preferable from the viewpoint of transparency.
Examples of these components (B) include hindered phenol compounds, phosphite compounds, hindered amine compounds, and the like. Among these, from the viewpoint of reducing foreign substances, hindered phenol compounds and phosphite compounds are preferable, and hindered phenol compounds are more preferable.

  Specific examples of hindered phenol compounds include 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3,5- Trimethyl-2,4,6-tris (3,5-di-i-propyl-4-hydroxybenzyl) benzene, 1,3,5-trimethyl-2,4,6-tris (3,5-dimethyl-4) -Hydroxybenzyl) benzene, 1,3,5-trimethyl-2,4,6-tris (4-hydroxybenzyl) benzene, 1,3,5-tris (3,5-di-t-butyl-4-hydroxy Benzyl) benzene, 1,3,5-tris (3,5-di-i-propyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3,5-dimethyl-4-hydroxybenzyl) benzene, 1,3,5-tris (4-hydroxy Benzyl) benzene, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), octadecyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate, tetrakismethylene ( 3,5-di-t-butyl-4-hydroxyhydrocinnamate) methane and the like. Of these, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene is preferred.

  Specific examples of the phosphite compound include trioctyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, triisooctyl phosphite, tris (nonylphenyl) phosphite, tris (2, 4-dinonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (octylphenyl) phosphite, diisodecylpentaerythritol diphosphite, dilaurylpentaerythritol diphosphite, distearyl Pentaerythritol diphosphite, diphenylpentaerythritol diphosphite, bis (2-methylphenyl) pentaerythritol diphosphite, bis (3-methylphenyl) pentaerythritol diphosphite Bis (4-methylphenyl) pentaerythritol diphosphite, bis (2,4-dimethylphenyl) pentaerythritol diphosphite, bis (2,6-dimethylphenyl) pentaerythritol diphosphite, bis (2,3,6) -Trimethylphenyl) bentaerythritol diphosphite, bis (2-t-butylphenyl) pentaerythritol diphosphite, bis (3-t-butylphenyl) pentaerythritol diphosphite, bis (4-t-butylphenyl) penta Erythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di -T-butyl-4-methylpheny ) Pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (biphenyl) pentaerythritol diphosphite , Dinaphthyl pentaerythritol diphosphite, etc. Among them, tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite is preferred, and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite is more preferred.

Moreover, these (B) components may be used individually by 1 type, and may use 2 or more types together. In particular, one or more selected from hindered phenol compounds, one or more selected from phosphite compounds, or one or more phosphite compounds selected from hindered phenol compounds are used. It is preferable to use at least one selected from a combination.
The preferable compounding quantity of these (B) components is 0.05-10 mass parts with respect to 100 mass parts of polyphenylene ether. It is 0.05 parts by mass or more from the viewpoint of reducing the generation of foreign matter, and is preferably 10 parts by mass or less from the viewpoint of heat resistance and generation of eyes in the sheet processing. More preferably, it is 0.1-7 mass parts, More preferably, it is 0.2-7 mass parts, More preferably, it is 1-7 mass parts, Most preferably, it is 4-7 mass parts.
Although there is no restriction | limiting in particular in the addition method of these organic compounds, It is preferable to add simultaneously with a polyphenylene ether component.

In addition to the component (A) and the component (B), an inorganic compound can be added to the sheet of the present invention as long as the transparency is not impaired. Preferred inorganic compounds include metal oxides, metal hydroxides, metal sulfides and the like. Examples of metal elements include Li, Na, K, Zn, Cd, Sn, Cu, Ni, Pd, Co, Fe, Ru, Mn, Pb, Mg, Ca, Sr, Ba, Al, Ti, Ge, Sb. Among them, Zn, Mg, Ti, Pb, Cd, Sn, Sb, Ni, Al, and Ge elements are preferable, and Zn, Mg, and Ti elements are more preferable. Specific examples of these metal compounds include ZnO, MgO, TiO ₄ , TiO ₂ , PbO, CdO, SnO, SbO, Sb ₂ O ₃ , NiO, Al ₂ O ₃ , GeO, Zn (OH) ₂ , Mg (OH) ) ₂ , Ti (OH) ₄ , Ti (OH) ₂ , Pb (OH) ₂ , Cd (OH) ₂ , Sn (OH) ₂ , Sb (OH) ₂ , Sb (OH) ₃ , Ni (OH) ₂ , Al (OH) ₃ , Ge (OH) _2, etc., among which ZnO, MgO, and Mg (OH) ₂ are preferable from the viewpoint of the mechanical properties of the sheet.

Although there is no restriction | limiting in particular in the addition method of these inorganic compounds, It is preferable to add simultaneously with a polyphenylene ether component.
Furthermore, in this invention, the styrenic polymer may be included in the range which does not impair heat resistance. Examples of the styrenic polymer in the present invention include homopolystyrene, rubber-modified polystyrene (HIPS), styrene-acrylonitrile copolymer (AS resin), styrene-rubber polymer-acrylonitrile copolymer (ABS resin), and the like. From the viewpoint of transparency, homopolystyrene is preferable. By including the styrenic polymer, the weather resistance and fluidity can be improved in addition to achieving the object of the present invention. A preferable blending amount of the styrenic polymer is less than 25 parts by mass with respect to 100 parts by mass of the polyphenylene ether. Although there is no restriction | limiting in particular in the addition method of these styrene-type polymers, It is preferable to add simultaneously with a polyphenylene ether component.

  In the present invention, an elastomer can be further added as long as heat resistance and transparency are not impaired. Preferred elastomers include block copolymers composed of a polymer block mainly composed of at least one aromatic vinyl compound and a polymer block mainly composed of at least one conjugated diene compound.

  The “mainly” in the polymer block mainly composed of the aromatic vinyl compound of the present invention refers to a block in which at least 50% by mass or more of the block is an aromatic vinyl compound. More preferably, it is 70 mass% or more, More preferably, it is 80 mass% or more, Most preferably, it is 90 mass% or more. The same applies to “mainly” in a polymer block mainly composed of a conjugated diene compound, and refers to a block in which at least 50% by mass or more is a conjugated diene compound. More preferably, it is 70 mass% or more, More preferably, it is 80 mass% or more, Most preferably, it is 90 mass% or more.

In this case, for example, even in the case of a block in which a small amount of a conjugated diene compound or other compound is randomly bonded in the aromatic vinyl compound block, 50% by mass of the block is formed from the aromatic vinyl compound. Thus, it is regarded as a block copolymer mainly composed of an aromatic vinyl compound. The same applies to the case of a conjugated diene compound.
Specific examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyltoluene and the like, and one or more compounds selected from these are used, and among them, styrene is particularly preferable.
Specific examples of the conjugated diene compound include butadiene, isoprene, piperylene, 1,3-pentadiene and the like, and one or more compounds selected from these are used. Of these, butadiene, isoprene and combinations thereof are preferable. .

The microstructure of the conjugated diene compound block portion of the block copolymer is preferably 1,2-vinyl content or a total amount of 1,2-vinyl content and 3,4-vinyl content of 5-80%, more preferably 10-50% 15 to 40% is most preferable.
In the block copolymer of the present invention, the polymer block [A] mainly composed of an aromatic vinyl compound and the polymer block [B] mainly composed of a conjugated diene compound are AB type and ABA type. A block copolymer having a bond type selected from A-B-A-B type is preferable, and a mixture thereof may be used. Among these, the AB type, the ABA type, or a mixture thereof is more preferable, and the ABA type is most preferable.

The block copolymer of an aromatic vinyl compound and a conjugated diene compound that can be used in the present invention is more preferably a hydrogenated block copolymer. The hydrogenated block copolymer is an aliphatic double bond of a polymer block mainly composed of a conjugated diene compound by subjecting the block copolymer of the aromatic vinyl compound and the conjugated diene compound to a hydrogenation treatment. Is controlled in the range of more than 0 and 100%. A preferable hydrogenation rate of the hydrogenated block copolymer is 80% or more, and most preferably 98% or more.
These block copolymers can be used without any problem as a mixture of a non-hydrogenated block copolymer and a hydrogenated block copolymer.

In addition, these aromatic vinyl compound-conjugated diene compound block copolymers are different in bond type, different in aromatic vinyl compound type, different in conjugated diene compound type, unless contrary to the spirit of the present invention, A mixture of 1,2-bonded vinyl content, 1,2-bonded vinyl content and 3,4-bonded vinyl content, or different aromatic vinyl compound component content may be used. .
Further, the block copolymer used in the present invention may be a block copolymer in which all or part of the block copolymer is modified.
The modified block copolymer as used herein refers to at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group in the molecular structure. Alternatively, it refers to a block copolymer modified with at least one modifying compound having a glycidyl group.

  The modified block copolymer can be produced by (1) melt-kneading with a modifying compound at a temperature in the range of the softening point of the block copolymer to 250 ° C. in the presence or absence of a radical initiator. A method of reacting, (2) a method of reacting a block copolymer and a modifying compound in a solution at a temperature below the softening point of the block copolymer in the presence or absence of a radical initiator, and (3) radical initiation. In the presence of the agent, in the absence of the block copolymer at a temperature equal to or lower than the softening point of the block copolymer, a method of reacting without melting the block copolymer and the like, and any of these methods may be used, The method (1) is preferable, and the method (1) performed in the presence of a radical initiator is most preferable.

At least one modification having at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group, or glycidyl group in the molecular structure referred to herein. As the compound, the same modified compounds as described in the modified polyphenylene ether can be used.
Among these block copolymers, from the viewpoint of transparency, a block copolymer in which a polymer block mainly composed of an aromatic vinyl compound is 60% by mass or more with respect to 100% by mass of the entire block copolymer. preferable.
As a compounding quantity of the elastomer in this invention, it is preferable that it is less than 25 mass parts with respect to 100 mass parts of polyphenylene ether. Although there is no restriction | limiting in particular in the addition method of these elastomers, It is preferable to add simultaneously with a polyphenylene ether component.
In the present invention, in addition to the above-described components, additional components may be added as necessary within a range not impairing the effects of the present invention.

Examples of additional components are listed below.
Inorganic filler (glass fiber, metal fiber, carbon fiber, wollastonite, talc, kaolin, mica, zonotolite, etc.), conductivity imparting material (conductive carbon black, carbon nanotube, etc.), plasticizer (oil, low molecular weight polyolefin) Polyethylene glycol, fatty acid esters, etc.) and antistatic agents, various peroxides, antioxidants, ultraviolet absorbers, light stabilizers, and the like.
Specific processing machines for obtaining the composition of the present invention include, for example, a single screw extruder, a twin screw extruder, a roll, a kneader, a Brabender plastograph, a Banbury mixer, etc. A twin-screw extruder provided with an upstream supply port and one or more downstream supply ports is particularly preferable.

A preferable production method for obtaining the composition of the present invention is to use a twin screw extruder equipped with an upstream supply port and a vacuum vent in front of the die, and melt by supplying polyphenylene ether or the like from the upstream supply port. Examples of the method include, but are not limited to, a method of removing volatile components by a vacuum vent after kneading.
In the present invention, the preferred temperature for obtaining the composition can be arbitrarily selected from the range of 250 to 350 ° C. Among these, the range of 250 to 330 ° C. is more preferable.

The sheet of the present invention has a thickness of 0.01 to 2.0 mm, preferably 0.01 to 0.5 mm, and more preferably 0.01 to 0.2 mm. Sometimes called a film.
The polyphenylene ether-based resin sheet of the present invention can be obtained by extrusion sheet molding using the resin composition obtained above as a raw material, and the components of the present invention are directly fed into an extrusion sheet molding machine to blend and sheet It can also be obtained by carrying out the molding simultaneously.
The polyphenylene ether-based resin sheet of the present invention can be produced by an extrusion tubular method, and in some cases a method called an inflation method. In order to prevent the parison coming out of the cylinder from being cooled immediately, the temperature of the parison is appropriately selected from the temperature range of 50 to 290 ° C., and the temperature of the parison can be made uniform so that the sheet does not peel Is extremely important in creating.

On the other hand, the polyphenylene ether resin sheet of the present invention can also be produced by T-die extrusion. In this case, it may be used without stretching, may be uniaxially stretched, or may be obtained by biaxially stretching. When it is desired to increase the strength of the sheet, it can be achieved by stretching.
The preferable temperature for obtaining the polyphenylene ether resin sheet of the present invention can be arbitrarily selected from the range of 250 to 350 ° C. Among these, the range of 250 to 330 ° C. is more preferable.
Moreover, when obtaining the polyphenylene ether resin-made sheet | seat of this invention by extrusion sheet molding, it is preferable to make oxygen concentration of the supply port of a resin composition into 0 to 3%. By setting the oxygen concentration within this range, the generation of foreign matter can be remarkably reduced. More preferably, it is 0 to 2%. A method for reducing the oxygen concentration includes flowing nitrogen into the supply port, but is not limited thereto.

The feature of the polyphenylene ether-based resin sheet of the present invention is that it is excellent in transparency, the total light transmittance measured according to JIS K7361 is 80% or more, and the haze measured according to JIS K7136 is 10% or less. Is essential. More preferably, the total light transmittance is 85% or more and the haze is 5% or less. These total light transmittance and haze can be measured using, for example, a turbidimeter (NDH2000: manufactured by Nippon Denshoku Industries Co., Ltd.).
Since the resin sheet of the present invention thus obtained is excellent in heat resistance and transparency, it can be suitably used for applications requiring these characteristics. For example, printed circuit board materials, printed circuit board peripheral parts, printed circuit board release films, semiconductor packages, data magnetic tapes, APS photographic films, film capacitors, insulating materials such as motors and transformers, speaker diaphragms, automotive seat sensors, Examples thereof include insulating tapes for wire cables, TAB tapes, generator slot liner interlayer insulating materials, toner agitators, and insulating washers such as lithium ion batteries.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to what was shown by this Example.
(Raw materials used)
(1) Polyphenylene ether (hereinafter abbreviated as PPE)
Poly (2,6-dimethyl-1,4-phenylene ether)
Reduced viscosity: 0.42 dl / g, (0.5 g / dl, chloroform solution, measured at 30 ° C.)

(2) Hindered phenol compound (2-1) 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene (hereinafter referred to as compound- Abbreviated 1)
Product Name: ADK STAB (registered trademark) AO-330 (Asahi Denka Kogyo Co., Ltd.)
Molecular weight: 775
Melting point: 244 ° C
(2-2) Tetrakismethylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate) methane (hereinafter abbreviated as compound-2)
Product name: ADK STAB (registered trademark) AO-60 (manufactured by Asahi Denka Kogyo Co., Ltd.)
Molecular weight: 1178
Melting point: 115 ° C

(3) Phosphite ester compound (3-1) Bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (hereinafter abbreviated as compound-3)
Product name: ADK STAB (registered trademark) PEP-36 (manufactured by Asahi Denka Kogyo Co., Ltd.)
Molecular weight: 633
Melting point: 237 ° C

(4) Polystyrene (4-1) Product name: PSJ-Polystyrene (registered trademark) 685 (manufactured by PS Japan) (hereinafter abbreviated as PS)
(4-2) Rubber-reinforced polystyrene (hereinafter abbreviated as HIPS)
Rubber content: 10% by mass, MFR: 2.5 g / 10 min (200 ° C., 5 kg load)

(Evaluation methods)
The evaluation method is described below.
<Total light transmittance and haze>
Sheet molding was performed as in Examples and Comparative Examples, and the obtained sheet was measured using a turbidimeter [NDH2000: manufactured by Nippon Denshoku Industries Co., Ltd.] for total light transmittance according to JIS K7361. Measured according to JIS K7136.

<Deformation after heating>
Sheet molding was performed as in Examples and Comparative Examples, and the obtained sheets were cut into 100 mm × 100 mm and heated in an oven at 180 ° C. for 1 hour. After cooling to room temperature, when an arbitrary corner is fixed to a smooth base, the diagonal part is not floating from the base (no deformation), and the one floating below 1 cm is ○ The case where 1 cm or more and less than 3 cm is Δ, the case where 3 cm or more is used, or the case where the angle cannot be measured due to curling is indicated as x.

<Near eyes when processing sheets>
Sheet molding was performed as in the examples and comparative examples, and the operation was performed for 2 hours. X indicates that eye spots occur between 30 minutes and 30 minutes after the start of operation, ○ indicates that eyes appear between 30 minutes and 1 hour, and ○ indicates that eyes appear between 1 hour and 2 hours. Those which did not occur after time were marked with ◎.

<Foreign matter>
Sheet molding was performed as in Examples and Comparative Examples, and the obtained sheets were cut into 100 mm × 100 mm, and the number of brown or black foreign matters was counted visually.

[Examples 1-14 and Comparative Examples 1-2]
An upstream supply port is provided in the first barrel from the upstream side of the extruder, a vacuum vent is provided in the 10th barrel, and L / D (extruder cylinder length / extruder cylinder diameter) = 44 (number of barrels: 11) using a twin-screw extruder [ZSK-40: manufactured by Coperion (Germany)], the temperature from the upstream supply port to the die was set at 290 ° C., the screw rotation speed was 300 rpm, and the discharge rate was 60 kg / h. PPE, PS, HIPS, Compound-1, Compound-2, and Compound-3 were supplied from the upstream supply port so as to have the ratio described in 1 or Table 2, and melt-kneaded to prepare resin composition pellets. The obtained resin composition was dried at 120 ° C. for 3 hours using a dryer, and a single-screw extruder having a screw diameter of 40 mm set to a cylinder temperature of 310 ° C. and a T-die (width: 40 cm) temperature of 320 ° C. Using this, extrusion sheet molding was performed at a screw rotational speed of 30 rpm and a discharge rate of 6 kg / h. In Example 10, since the torque of the sheet forming machine was increased, the sheet discharge was performed at a discharge rate of 5 kg / h. At this time, the clearance of the T dice and the sheet take-up speed were adjusted so that the thicknesses of the sheets were as shown in Tables 1 and 2, respectively. The eyes were evaluated at the time of forming the sheet, and the obtained sheet was evaluated for total light transmittance, haze, deformation after heating, and foreign matter. The physical property values are shown in Table 1 and Table 2 together with the composition.

  Since the resin sheet of the present invention is excellent in heat resistance and transparency, it can be suitably used for applications requiring these characteristics, and in particular, it can be suitably used for electric / electronic parts.

Claims (9)

(A) A polyphenylene ether-based resin sheet comprising a resin composition containing 75% by mass or more of polyphenylene ether, having a total light transmittance of 80% or more and a haze of 10% or less. (B) The sheet | seat made from a polyphenylene ether resin of Claim 1 containing the organic compound whose molecular weight is 400-2000. The melting point of (B) component is 150 degreeC or more, The sheet | seat made from polyphenylene ether-type resin of Claim 2 characterized by the above-mentioned. The polyphenylene ether-based resin sheet according to claim 2 or 3, wherein the component (B) is at least one selected from the group consisting of a hindered phenol compound and a phosphite compound. The polyphenylene ether-based resin sheet according to claim 1, wherein the component (B) is 0.05 to 10 parts by mass with respect to 100 parts by mass of the component (A). The polyphenylene ether-based resin sheet according to any one of claims 1 to 5, wherein the thickness is 0.01 to 0.5 mm. The polyphenylene ether-based resin sheet according to any one of claims 1 to 6, obtained by molding by an extrusion tubular method or a T-die extrusion method. The polyphenylene ether-based resin sheet according to any one of claims 1 to 7, which is obtained by being produced at an oxygen concentration of 0 to 3% at a resin composition supply port during sheet molding. The manufacturing method of the sheet | seat made from polyphenylene ether resin of Claim 7 or 8.