JP5005161B2 - Polyphenylene ether resin sheet - Google Patents

Description

  The present invention relates to a polyphenylene ether resin sheet having excellent heat resistance, no delamination, excellent bending resistance and moisture resistance, and a small heat shrinkage rate.

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 a disadvantage that its moldability is poor due to its high melt viscosity. is doing. On the other hand, in order to improve these moldability, moldability has been improved by alloying polyphenylene ether with polystyrene or the like, but there is a problem that heat resistance is lowered.
On the other hand, it has been proposed to improve the melt processability of polyphenylene ether by blending liquid crystal polyester with a polymer such as polyphenylene ether, but it relates to injection molding that requires a high share rate of 100 to 1000 (1 / second). Thus, there is no description of extrusion molding with a low share rate, and the physical properties are not sufficient. (See Patent Document 1)

Although there is a description of a sheet in which a liquid crystal polymer is added to a thermoplastic resin, the sheet is substantially made of polyester or polycarbonate, and the heat resistance, the non-removability of the layer and the moisture resistance are not sufficient. (See Patent Document 2)
For the purpose of improving solder heat resistance, it has been proposed to blend various polyarylene oxides with liquid crystal polyester, and further, it has been proposed to blend polyphenylene ether modified with amines and liquid crystal polyester. However, there was no description about the moldability of the extruded sheet, and the physical properties were not sufficient. (See Patent Document 3 and Patent Document 4)
In addition, a method for improving strength and rigidity recycling retention has been proposed, but there is no description on the sheet, and physical properties are not sufficient. (See Patent Document 5)

Further, a sheet in which a liquid crystal polyester is blended with polyphenylene ether has been proposed, but the heat resistance and the lack of a layer are not sufficient. (See Patent Document 6 and Patent Document 7)
In addition, a silane coupling agent is blended with LCP and PPE to reduce the anisotropy of mechanical properties, but there is no description of the sheet, and physical properties are not sufficient. (See Patent Document 8)
Moreover, although the composition of LPE and PPE which prescribed | regulated specific molecular weight distribution was proposed, there is no description about a sheet | seat and it was not enough about delamination or bending resistance. (See Patent Document 9)

JP 56-115357 A Japanese Patent No. 3117136 Japanese Patent Laid-Open No. 2-97555 JP-A-6-122762 JP-A-5-86288 JP 2002-241515 A JP 2002-241601 A JP-A-5-117505 JP 2002-265776 A

  An object of the present invention is to provide a polyphenylene ether resin sheet having excellent heat resistance, no delamination, excellent bending resistance and moisture resistance, and a small heat shrinkage rate.

  As a result of earnestly examining the technology for achieving the above-mentioned problems, the present inventors have obtained a resin composition comprising a polyphenylene ether-based resin, a liquid crystal polyester, and a compound containing an I-valent, II-valent, III-valent or IV-valent metal element. By forming a sheet using an extrusion molding machine as a raw material, it is possible to obtain a sheet made of a polyphenylene ether resin having excellent heat resistance, no delamination, excellent bending resistance and moisture resistance, and a low heat shrinkage rate. As a result, the present invention has been completed.

（Ｒ_１、Ｒ_４は、それぞれ独立して、水素、第一級もしくは第二級の低級アルキル、フェニル、アミノアルキル、炭化水素オキシを表わす。Ｒ_２、Ｒ_３は、それぞれ独立して、水素、第一級もしくは第二級の低級アルキル、フェニルを表わす。）
（Ｂ）液晶ポリエステルの合計量１００重量部に対して、（Ａ）該ポリフェニレンエーテル系樹脂５１〜９９．９重量部、（Ｂ）液晶ポリエステル０．１〜４９重量部並びに、
（Ｃ）Ｚｎ元素を含有する化合物および／またはＭｇ（ＯＨ） _２ ０．１〜３重量部および／または（Ｄ）アミノ基、ウレイド基、エポキシ基、イソシアネート基およびメルカプト基からなる群より選ばれる少なくとも一種の官能基を含有するシラン化合物０．１〜５重量部を含有する樹脂組成物からなる耐熱性に優れ、層剥離のないポリフェニレンエーテル系樹脂製シート。
（２）（Ｃ）成分がＺｎ元素を含有する化合物であることを特徴とする請求項１に記載のポリフェニレンエーテル系樹脂製シート。
（３）（Ｃ）成分がＺｎＯおよび／またはＭｇ（ＯＨ）_２であることを特徴とする上記（１）に記載のポリフェニレンエーテル系樹脂製シート、 That is, the present invention
(1) (A) Polyphenylene having a repeating unit structure of the following (formula 1) and having a reduced viscosity (0.5 g / dl, chloroform solution, measured at 30 ° C.) in the range of 0.15 to 1.0 dl / g With ether resin

(R ₁ and R ₄ each independently represent hydrogen, primary or secondary lower alkyl, phenyl, aminoalkyl, hydrocarbon oxy. R ₂ and R ₃ each independently represent hydrogen Represents primary or secondary lower alkyl or phenyl.)
(B) With respect to 100 parts by weight of the total amount of liquid crystal polyester, (A) 51 to 99.9 parts by weight of the polyphenylene ether resin, (B) 0.1 to 49 parts by weight of liquid crystal polyester,
(C) 0.1 to 3 parts by weight of a compound containing Zn element and / or Mg (OH) ₂ and / or (D) selected from the group consisting of amino group, ureido group, epoxy group, isocyanate group and mercapto group A polyphenylene ether resin sheet having excellent heat resistance and no delamination, comprising a resin composition containing 0.1 to 5 parts by weight of a silane compound containing at least one functional group.
(2) The polyphenylene ether resin sheet according to claim 1, wherein the component (C) is a compound containing Zn element.
(3) The polyphenylene ether-based resin sheet according to (1) above, wherein the component (C) is ZnO and / or Mg (OH) ₂ ;

( 4 ) The above (1) to (3), wherein 0.1 to 5 parts by weight of (E) silicone polymer is contained with respect to 100 parts by weight of the total amount of components (A) and (B ). Polyphenylene ether resin sheet according to any of the above,
( 5 ) (E) The polyphenylene ether-based resin sheet according to ( 4 ) above, wherein the silicone polymer has an amino group and is a liquid having a viscosity of 10 mm ² / s or more at 25 ° C.
( 6 ) The polyphenylene ether-based resin sheet according to any one of the above (1) to ( 5 ) obtained by molding by an extruded tubular method,
( 7 ) The sheet made of the polyphenylene ether resin according to any one of (1) to ( 5 ) obtained by molding by a T-die extrusion method,
It is.

  According to the present invention, it is possible to provide a sheet made of a polyphenylene ether resin having excellent heat resistance, no delamination, excellent bending resistance and moisture resistance, and a small heat shrinkage rate.

Hereinafter, the present invention will be specifically described.
The (A) polyphenylene ether resin of the present invention has a repeating unit structure of the following (formula 1), and has a reduced viscosity (0.5 g / dl, chloroform solution, measured at 30 ° C.) of 0.15 to 1.0 dl. Homopolymer and / or copolymer in the range of / 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.

(R ₁ and R ₄ each independently represent hydrogen, primary or secondary lower alkyl, phenyl, aminoalkyl, hydrocarbon oxy. R ₂ and R ₃ each independently represent hydrogen Represents primary or secondary lower alkyl or phenyl.)

  Specific examples of the polyphenylene ether resin 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, and 2,6-dimethylphenol and other phenols (for example, And a polyphenylene ether copolymer such as a copolymer with 2,3,6-trimethylphenol or 2-methyl-6-butylphenol). Of these, 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-phenylene ether).

As an example of the method for producing (A) polyphenylene ether used in the present invention, there is a method of oxidative polymerization of 2,6-xylenol using a complex of cuprous salt and amine described in US Pat. No. 3,306,874 as a catalyst. is there.
The methods described in U.S. Pat. Nos. 3,306,875, 3,257,357 and 3,257,358, JP-B-52-17880, JP-A-50-51197, and JP-A-63-152628 are also included. (A) It is preferable as a method for producing polyphenylene ether.
The (A) polyphenylene ether-based resin of the present invention may be used as it is after the polymerization process, or using an extruder or the like, under a nitrogen gas atmosphere or a non-nitrogen gas atmosphere, under devolatilization or non-devolatilization. You may use it by pelletizing by melt-kneading below.

  The (A) polyphenylene ether resin of the present invention includes polyphenylene ethers functionalized with various dienophile compounds. Various dienophile compounds include, for example, maleic anhydride, maleic acid, fumaric acid, phenylmaleimide, itaconic acid, acrylic acid, methacrylic acid, methyl allylate, methyl methacrylate, glycidyl acrylate, glycidyl methacrylate, stearyl acrylate, styrene, and the like. Can be mentioned. Furthermore, as a method of functionalizing with these dienophile compounds, an extruder or the like may be used in the presence or absence of a radical generator, and functionalization may be performed in a molten state under devolatilization or non-devolatilization. Alternatively, it may be functionalized in the non-molten state, that is, in the temperature range from room temperature to the melting point in the presence or absence of a radical generator. In this case, the melting point of polyphenylene ether is defined by the peak top temperature of the peak observed in the temperature-heat flow graph obtained when the temperature is raised at 20 ° C./min in the differential thermal scanning calorimeter (DSC) measurement. If there are a plurality of peak top temperatures, the peak top temperature is defined as the highest temperature.

  The polyphenylene ether resin (A) of the present invention is a polyphenylene ether resin alone or a mixture of a polyphenylene ether resin and an aromatic vinyl polymer, and further includes a mixture of other resins. Examples of the aromatic vinyl polymer include atactic polystyrene, high impact polystyrene, syndiotactic polystyrene, acrylonitrile-styrene copolymer, and the like. When a mixture of a polyphenylene ether resin and an aromatic vinyl polymer is used, the polyphenylene ether resin is 70 wt% or more, preferably 80 wt% or more based on the total amount of the polyphenylene ether resin and the aromatic vinyl polymer. is there.

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

  Here, the structural units (A) and (B) are respectively a structural unit of a polyester generated from p-hydroxybenzoic acid and a structural unit generated from 2-hydroxy-6-naphthoic acid. By using the structural units (a) and (b), it is possible to obtain the thermoplastic resin composition of the present invention having an excellent balance of mechanical properties such as excellent heat resistance, fluidity and rigidity. X in the structural units (c) and (d) can be independently selected from the following (formula 2), one or more of them.

In the structural formula (c), preferred are structural units formed from ethylene glycol, hydroquinone, 4,4′-dihydroxybiphenyl, 2,6-dihydroxynaphthalene and bisphenol A, and more preferred are ethylene glycol, Structural units formed from 4,4'-dihydroxybiphenyl and hydroquinone, and particularly preferred are structural units formed from ethylene glycol and 4,4'-dihydroxybiphenyl.
In the structural formula (d), preferred are structural units formed from each of terephthalic acid, isophthalic acid and 2,6-dicarboxynaphthalene, and more preferred are structural units formed from each of terephthalic acid and isophthalic acid. It is.

In the structural formula (c) and the structural formula (d), at least one or two or more of the structural units listed above 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 Examples include structural units formed from '-dihydroxybiphenyl, 3) structural units formed from hydroquinone / 4, structural units formed from 4,4'-dihydroxybiphenyl, and the like.
In the structural formula (d), 1) a structural unit generated from terephthalic acid / a structural unit generated from isophthalic acid, 2) a structural unit generated from terephthalic acid / 2, a structural unit generated from 2,6-dicarboxynaphthalene , Etc. Here, the amount of terephthalic acid is preferably 40 wt% or more, more preferably 60 wt% or more, and particularly preferably 80 wt% or more in the two components. 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 proportion 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.

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

The liquid crystal polyester component (B) of the present invention is formed from other aromatic dicarboxylic acids, aromatic diols, and aromatic hydroxycarboxylic acids within a small range that does not impair the features and effects of the present invention as necessary. Structural units can be introduced.
The temperature at which the liquid crystal state at the time of melting of the component (B) of the present invention (hereinafter referred to as the liquid crystal start temperature) is preferably 150 to 350 ° C, more preferably 180 to 320 ° C. Setting the liquid crystal start temperature within this range is preferable because less black foreign matter is present in the resulting resin sheet.

The compound (C) containing Zn element and / or Mg element of the present invention is an inorganic compound or organic compound containing Zn element and / or Mg element . The component (C) of the present invention is a compound essentially comprising a Zn element and / or a Mg element as a main component . No delamination, from the viewpoint of greatly improving the toughness of the sheet, more preferably from Z n elements and / or Mg element, and particularly preferably Zn element.

(C) As the compound containing Zn element and / or Mg element , oxides, hydroxides, alkoxide salts, aliphatic carboxylates and acetates of the above metal elements are preferable. Examples of preferable oxides include ZnO, MgO, TiO ₄ , TiO ₂ , PbO, CdO, SnO, SbO, Sb ₂ O ₃ , NiO, Al ₂ O ₃ , GeO, and the like. Examples of preferred hydroxides include 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 and the} like. Examples of preferable alkoxide salts include Ti (O ⁱ Pr) ₄ and Ti (O ⁿ Bu) ₄ . Examples of preferred aliphatic carboxylates include zinc stearate, magnesium stearate, titanium stearate, lead stearate, cadmium stearate, tin stearate, antimony stearate, nickel stearate, aluminum stearate, germanium stearate. Etc. Examples of preferred acetates include zinc acetate, magnesium acetate, titanium acetate, lead acetate, cadmium acetate, tin acetate, antimony acetate, nickel acetate, aluminum acetate, germanium acetate, titanium acetate and the like.

Among these, more preferable examples include ZnO, Mg (OH) ₂ , Ti (O ⁱ Pr) ₄ , Ti (O ⁿ Bu) ₄ , zinc acetate, zinc stearate, and aluminum stearate. Furthermore, ZnO and / or Mg (OH) ₂ are preferable from the viewpoint of no delamination, and ZnO is particularly preferable. Moreover, these (C) components may contain the impurity in the range which does not impair the effect of this invention.
The (D) silane compound of the present invention is a functional group-containing silane compound, which contains at least one functional group selected from the group consisting of an amino group, a ureido group, an epoxy group, an isocyanate group, and a mercapto group. A compound. The functional group-containing silane compound usually only needs to contain any one of these functional groups in the molecule, but in some cases, two or more of these functional groups are contained in the molecule. It may be what you do.

  Moreover, the silane compound used in the present invention is usually an alkoxysilane containing a functional group as described above in the molecule. Specific examples of the functional group-containing silane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxy. Silane compounds containing amino groups such as silane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-phenyl-γ-aminopropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ Silane compounds containing a ureido group such as ureidopropylmethyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropylmethyltriethoxysilane, γ- (2-ureidoethyl) aminopropyltrimethoxysilane; Glycidoxypropyl Methoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β -Silane compounds containing an epoxy group such as (3,4-epoxycyclohexyl) ethyltriethoxysilane; γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanate Isocyanes such as propylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, and γ-isocyanatopropyltrichlorosilane A silane compound containing a radical group; γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylethyldiethoxysilane, γ-mercaptopropylmethyldiethoxysilane, β-mercaptoethyltrimethoxysilane, silane compounds containing mercapto groups such as β-mercaptoethyltriethoxysilane and β-mercaptoethyldimethoxysilane;

  The blending amount of the (A) polyphenylene ether resin in the present invention is 51 to 99.9 parts by weight, preferably 60 to 100 parts by weight based on the total amount of (A) polyphenylene ether resin and (B) liquid crystal polyester. 99 parts by weight, more preferably 70 to 98 parts by weight. When the blending amount is more than 99.9 parts by weight, the fluidity is greatly reduced, and it is necessary to increase the set temperature of the extruder from the viewpoint of torque (extruder load), which is included in the sheet. The amount of black foreign matter is increased. When the blending amount is less than 51 parts by weight, the thickness unevenness of the sheet is deteriorated, and the layer is markedly cut. Here, the black foreign matter is called a black spot, a shadow, or a char, and has an unfavorable influence on sheet physical properties.

In the present invention, the blending amount of the liquid crystal polyester as the component (B) is set to 0. -491 parts by weight, preferably 1-40 parts by weight, more preferably 2-30 parts by weight. When the blending amount is more than 49 parts by weight, the thickness unevenness of the sheet is reduced due to the anisotropy of the liquid crystal polymer. When the blending amount is less than 0.1 parts by weight, the fluidity is greatly lowered, and the black foreign matter in the sheet is increased.
The compounding amount of the component (C) in the present invention is preferably 0.1 to 3 parts by weight, more preferably 0.2 to 3 parts by weight with respect to 100 parts by weight of the total of (A) and (B). Particularly preferred is 0.4 to 3 parts by weight. When the content of the component (C) is less than 0.1 weight, delamination of the sheet becomes remarkable. When the content is more than 10 parts by weight, the specific gravity increases and the heat resistance may be lowered.

The blending amount of the component (D) in the present invention is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 3 parts by weight with respect to 100 parts by weight of the total of (A) and (B). Particularly preferred is 0.3 to 1 part by weight. When the content of the component (D) is less than 0.1 weight, delamination of the sheet becomes remarkable, and when the content is more than 5 parts by weight, the composition of the present invention cannot be obtained stably or moisture resistance is increased. It may cause a decline in sex.
In this invention, (C) component and (D) component can also be used together and is a preferable aspect.

The (E) silicone polymer used in the present invention has four types of siloxane units (M units: R ₃ SiO _0.5 , D units: R ₂ SiO _1.0 , T units: RSiO _1.5 , Q units: SiO _2.0 ) is an organopolysiloxane obtained by polymerization. From the viewpoint of flame retardancy, the silicone polymer used in the present invention preferably contains at least one group selected from an amino group, a hydroxyl group, an epoxy group, and a phenyl group in the molecule. Or the thing containing a hydroxyl group is more preferable. Further, those containing an amino group are particularly preferred. The amino group is preferably a primary amine, secondary amine, tertiary amine or quaternary amine, but from the viewpoint of flame retardancy, a primary amine or secondary amine is more preferable. Moreover, you may contain both a primary amine and a secondary amine in a molecule | numerator. When the amino group is contained in the molecule, the amino equivalent is preferably 300 or more, more preferably 500 or more, and even more preferably 1000 or more, from the viewpoint of flame retardancy and appearance.

The silicone polymer of the present invention is a liquid having a viscosity of 10 mm ² / s or more at 25 ° C. The viscosity, from the viewpoint of bleed-out, preferably at least 10 mm ² / s, more preferably not less than 100 mm ² / s, and particularly preferably equal to or greater than 150 mm ² / s. The larger the viscosity, the better. However, from the viewpoint of workability, the upper limit is usually about 20,000 mm ² / s. Since the (E) silicone polymer of the present invention is a liquid, the D unit is often 50 mol% or more, more preferably 70 mol% or more, further 90 mol% or more, and more preferably 95 mol% or more.
At least one group selected from an amino group, a hydroxyl group, an epoxy group, and a phenyl group may be bonded to the main chain of the silicone polymer or may be bonded to the terminal.
The amount of the (E) silicone polymer used in the present invention is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 4 parts per 100 parts by weight of the total amount of (A) and (B). Part by weight, particularly preferably 0.5 to 2 parts by weight. This blending amount is preferably 0.1 parts by weight or more from the viewpoint of flame retardancy, and is preferably 5 parts by weight or less from the viewpoint of appearance deterioration and bleed out of the silicone polymer.

  In the present invention, in addition to the above-described components, other additional components, such as antioxidants, flame retardants (organic phosphate ester compounds, phosphazene-based compounds), as necessary, as long as the characteristics and effects of the present invention are not impaired. Compound), elastomer (ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene / non-conjugated diene copolymer, ethylene / ethyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, Ethylene / vinyl acetate / glycidyl methacrylate copolymer and ethylene / propylene-g-maleic anhydride copolymer, olefin copolymer such as ABS, polyester polyether elastomer, polyester polyester elastomer, vinyl aromatic compound-conjugated diene Compound block copolymer, vinyl aromatic compound Hydrogenated product of conjugated diene compound block copolymer), plasticizer (oil, low molecular weight polyethylene, epoxidized soybean oil, polyethylene glycol, fatty acid ester, etc.), flame retardant aid, weather resistance (light) improver, polyolefin A nucleating agent and various colorants may be added.

In the present invention, when kneading (A), (B), (C), (D), and (E), the kneading order is not particularly limited, but kneading all at once can simplify the process. And desirable from the viewpoint of improving physical properties. However, when (C) and (D) are used in combination, (C) and (D) may be kneaded simultaneously with (A) and (B). Therefore, it is desirable to knead (C) and then knead (D), or knead (D) and then knead (C).
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. Although the melt kneading temperature in this case is not particularly limited, it can usually be arbitrarily selected from 150 to 350 ° C.

The sheet of the present invention has a thickness of 0.001 to 2.0 mm, preferably 0.005 to 0.50 mm, and more preferably 0.005 to 0.20 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 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 off. Is extremely important in creating.

On the other hand, the polyphenylene ether resin sheet of the present invention can 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 polyphenylene ether resin sheet of the present invention thus obtained has excellent heat resistance, no delamination, excellent bending resistance and moisture resistance, low thermal shrinkage, flame resistance, mechanical strength. In addition, it has excellent electrical properties such as insulation, dielectric constant, dielectric loss tangent and the like, and also has excellent hydrolysis resistance. Therefore, it can be used for applications requiring these characteristics. For example, printed circuit board materials, printed circuit board peripheral parts, semiconductor packages, data system magnetic tape, APS photographic film, film capacitors, insulating materials such as motors and transformers, speaker diaphragms, automotive sheet sensors, insulating tapes for wire cables, TAB Tape, generator slot liner interlayer insulating material, toner agitator, insulating washer such as lithium ion battery, and the like.

  The present invention will be described below based on examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

[Production Example 1]
<Production example of polyphenylene ether (PPE-1)>
It is a powdery poly (2,6-dimethyl-1,4-phenylene ether) having a reduced viscosity of 0.42 obtained by oxidative polymerization of 2,6-dimethylphenol.

[Production Example 2]
<Production Example of Liquid Crystalline Polyester (LCP-1)>
Under a nitrogen atmosphere, p-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, and acetic anhydride were charged, heated, melted, and polycondensed to obtain a liquid crystal polyester (LCP-1) having the following theoretical structural formula. Obtained. In addition, the component ratio of a composition represents molar ratio.

Sheet molding and physical property evaluation of each resin composition were performed according to the following methods.
(1) Sheet molding The obtained pellet was subjected to extrusion sheet molding by a tubular method using an extruder having a screw diameter of 50 mm set at a cylinder temperature of 290 ° C and a cylindrical die temperature of 290 ° C. The pressure of the air to blow was set so that the thickness would be 100 μm.
(2) Heat resistance The sheet was placed in a hot air oven at 150 ° C. for 5 hours, and the heat resistance was evaluated based on the following criteria.
○: Deformation of the sheet is not recognized.
X: Deformation of the sheet was observed.

(3) No delamination The edge portion of the obtained sheet was cut with 10 scissors with a length of about 10 mm at intervals of 5 mm, and 20 points in the cross section of the cut sheet were visually observed, and the following judgment was made. Based on the criteria, the absence of delamination was evaluated.
○: No peeling at all.
(Triangle | delta): Layer peeling was recognized by 1-3 places.
X: Layer peeling was observed at four or more locations.

(4) Bending resistance The sheet was cut into 120 × 30 corners, completely bent at about half of the longitudinal direction (about 60 mm from the end), then returned to its original position, and further bent to the opposite side. This cycle was repeated 10 times, and the bending resistance was determined according to the following criteria.
○: Neither crack nor breakage was observed.
(Triangle | delta): Although it does not fracture | rupture, the crack was recognized.
X: Breakage was observed within 10 times.

(5) Moisture resistance The sheet obtained in the above (1) is cut into a size of 100 × 200 mm square, and using a constant temperature and humidity chamber (PL-3FP, manufactured by Tabai Espec Co., Ltd.), 90 ° C. and 80% relative humidity. After being exposed to a warm and humid environment for 24 hours, the weight increase rate (Δw) was determined according to the following formula. The average value of two sheets was taken.
Weight increase rate (Δw) (%) = (w ₁ −w ₀ ) / w ₀ × 100
(W ₁ : sheet weight (g) after sufficiently humidifying the water droplets on the sheet surface after heating and humidification, w ₀ : drying in a hot air dryer at 100 ° C. for 2 hours before heating and humidifying, desiccator Weight of sheet cooled to room temperature (g))
A smaller weight increase rate (Δw) means better moisture absorption resistance.

(6) Thermal shrinkage The sheet obtained in (1) above was cut into a size of 150 mm × 150 mm so that each piece was parallel to MD and TD, and placed in an oven set at 190 ° C. for 5 minutes. Set, take out and let cool. The dimension before and after heating was measured for each of MD and TD, and determined according to the following formula.
Thermal contraction rate (%) = (length of side before heating−length of side after heating) / (length of side before heating) × 100
Here, MD is a direction in which the resin flows from the die of the tubular extruder, and TD indicates a direction perpendicular to the MD.

[Example 1]
Polyphenylene ether (PPE-1), liquid crystal polyester (LCP-1) and zinc oxide (ZnO, special grade, manufactured by Wako Pure Chemical Industries, Ltd.) at a ratio (parts by weight) shown in Table 1 at 250 to 310 ° C. It melt-kneaded using the set twin-screw extruder with a vent port (ZSK-25; product made by WERNER & PFLEIDERER), and obtained as a pellet. Using this pellet, a sheet was formed by the method described above. The average thickness of the obtained sheet was 102 μm. Sheet evaluation was performed according to the method shown above. The results are shown in Table 1.

[Example 2]
As the component (D), an amino group-containing silane compound (Silane 1, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.) is used. Except for blending in the proportions (parts by weight) shown in Table 1, the same procedure as in Example 1 was performed to obtain pellets, which were sheet-formed. The average thickness of the obtained sheet was 103 μm. The physical properties of these sheets were evaluated according to the method shown above. The results are shown in Table 1.

[Example 3]
As component (E), a silicone polymer (silicone 1, amino-modified silicone, SF8417, manufactured by Toray Dow Corning Silicone Co., Ltd., viscosity (25 ° C.): 1,200 mm ² / s liquid, amino equivalent: 1,800 ), And the same procedure as in Example 1 was performed except that the respective components were blended in the proportions (parts by weight) shown in Table 1. Pellets were obtained and sheet-formed. The average thickness of the obtained sheet was 105 μm. The physical properties of these sheets were evaluated according to the method shown above. The results are shown in Table 1.

[Example 4]
As component (A), in addition to polyphenylene ether (PPE-1), high impact polystyrene (HIPS, H9405, manufactured by PS Japan Co., Ltd.) was used, and each component was blended in the proportions (parts by weight) shown in Table 1. Except for this, the same procedure as in Example 1 was performed to obtain pellets, which were then sheet-formed. The average thickness of the obtained sheet was 98 μm. The physical properties of these sheets were evaluated according to the method shown above. The results are shown in Table 1.

[Comparative Example 1]
A sheet molding process was performed in the same manner as in Example 1 except that heat-resistant and flame-retardant modified polyphenylene ether (Zylon 500Z (registered trademark), manufactured by Asahi Kasei Chemicals Corporation) was used as the pellet raw material. The average thickness of the obtained sheet was 110 μm. The physical properties of these sheets were evaluated according to the method shown above. The results are shown in Table 1. Regarding the thermal shrinkage rate, the deformation of the sheet was large and could not be measured.

[Comparative Example 2]
(C) Except not having used the component, it carried out similarly to Example 1, and obtained the pellet and carried out sheet forming process. The average thickness of the obtained sheet was 106 μm. The physical properties of these sheets were evaluated according to the method shown above. The results are shown in Table 1.

[Comparative Example 3]
As a sheet, a polyimide sheet (PI, Kapton 500H (registered trademark), manufactured by Toray DuPont Co., Ltd., thickness: 125 μm) was evaluated for physical properties according to the method described above. The results are shown in Table 1.

[Comparative Example 4]
As a sheet, a polyethylene terephthalate sheet (PET, Lumirror (registered trademark), manufactured by Toray Industries, Inc., thickness 100 μm) was evaluated for physical properties according to the method described above. The results are shown in Table 1.

  From Table 1, it can be seen that the polyphenylene ether-based resin sheet obtained by the present invention is excellent in heat resistance, has no delamination, is excellent in bending resistance and moisture resistance, and has a small heat shrinkage rate. Even when compared with a single polymer polyimide sheet or polyethylene terephthalate sheet, the sheet of the present invention is surprisingly small in heat shrinkage in addition to being excellent in moisture resistance.

  The polyphenylene ether resin sheet of the present invention has excellent heat resistance, no delamination, excellent bending resistance and moisture resistance, low thermal shrinkage, flame resistance, mechanical strength, insulation and dielectric constant. For example, printed circuit board materials, printed circuit board peripheral parts, semiconductor packages, data magnetic tape, APS photographic film, film capacitors, motors. Insulating materials such as transformers, speaker diaphragms, automotive sheet sensors, wire cable insulation tape, TAB tape, generator slot liner interlayer insulation materials, toner agitators, insulation washers such as lithium ion batteries, etc. Suitable for household appliances OA materials, automotive materials, industrial materials.

Claims (7)

(A) A polyphenylene ether resin having a repeating unit structure of the following (formula 1) and having a reduced viscosity (0.5 g / dl, chloroform solution, measured at 30 ° C.) in the range of 0.15 to 1.0 dl / g. When

(R ₁ and R ₄ each independently represent hydrogen, primary or secondary lower alkyl, phenyl, aminoalkyl, hydrocarbon oxy. R ₂ and R ₃ each independently represent hydrogen Represents primary or secondary lower alkyl or phenyl.)
(B) With respect to 100 parts by weight of the total amount of liquid crystal polyester, (A) 51 to 99.9 parts by weight of the polyphenylene ether resin, (B) 0.1 to 49 parts by weight of liquid crystal polyester,
(C) 0.1 to 3 parts by weight of a compound containing Zn element and / or Mg (OH) ₂ and / or (D) selected from the group consisting of amino group, ureido group, epoxy group, isocyanate group and mercapto group A polyphenylene ether resin sheet having excellent heat resistance and no delamination, comprising a resin composition containing 0.1 to 5 parts by weight of a silane compound containing at least one functional group. The polyphenylene ether-based resin sheet according to claim 1, wherein the component (C) is a compound containing Zn element. (C) A component is ZnO and / or Mg (OH) ₂ , The polyphenylene ether-type resin sheet of Claim 1 characterized by the above-mentioned. The polyphenylene according to any one of claims 1 to 3, comprising 0.1 to 5 parts by weight of (E) silicone polymer with respect to 100 parts by weight of the total amount of component (A) and component (B). Ether-based resin sheet. (E) The polyphenylene ether-based resin sheet according to claim 4, wherein the silicone polymer has an amino group and is a liquid having a viscosity of 10 mm ² / s or more at 25 ° C. The polyphenylene ether resin sheet according to any one of claims 1 to 5, which is obtained by molding by an extrusion tubular method.   The polyphenylene ether-based resin sheet according to any one of claims 1 to 5, which is obtained by molding by a T-die extrusion method.