JP2004211084A - Polyphenylene ether resin sheet - Google Patents

Abstract

An object of the present invention is to provide a polyphenylene ether-based resin sheet having excellent heat resistance, no delamination, excellent bending resistance and moisture resistance, and a small heat shrinkage.
SOLUTION: (A) 51 to 99.9 parts by weight of polyphenylene ether-based resin, (B) liquid crystal polyester 0.1 with respect to 100 parts by weight in total of (A) polyphenylene ether-based resin and (B) liquid crystal polyester. And (C) 0.1 to 10 parts by weight of a compound containing a metal element having a valence of I, II, III or IV and / or 0.1 to 5 parts by weight of a (D) silane compound. A sheet made of a polyphenylene ether-based resin comprising a resin composition to be contained.
[Selection diagram] No selection diagram

Description

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

In general, polyphenylene ether is a resin having excellent properties such as heat resistance, hot water resistance, dimensional stability, and mechanical and electrical properties.On the other hand, polyphenylene ether has a drawback of poor moldability due to its high melt viscosity. are doing. On the other hand, in order to improve these moldability, moldability has been improved by alloying polyphenylene ether or the like with polyphenylene ether, but there is a problem that heat resistance is reduced.
On the other hand, it has been proposed to blend a polymer such as polyphenylene ether into a liquid crystal polyester to improve the melt processability of polyphenylene ether, but it relates to injection molding with a high shear rate of 100 to 1000 (1 / second). There is no description about extrusion molding with a low shear rate, and the physical properties are not sufficient. (See Patent Document 1)

There is a description of a sheet in which a liquid crystal polymer is added to a thermoplastic resin, but the sheet is substantially made of polyester or polycarbonate as a matrix, and the heat resistance, the lack of a layer, and the moisture resistance are not sufficient. (See Patent Document 2)
It has been proposed to mix various polyarylene oxides with liquid crystal polyester for the purpose of improving solder heat resistance, and furthermore, it has been proposed to mix liquid crystal polyester with amine-modified polyphenylene ether. However, there was no description about the moldability of the extruded sheet, and the physical properties were not sufficient. (See Patent Documents 3 and 4)
In addition, a method has been proposed for increasing the strength and rigidity in maintaining the recycled property, but there is no description in the sheet and the physical properties are not sufficient. (See Patent Document 5)

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

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

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

  The present inventors have conducted intensive studies on a technique for achieving the above object, and as a result, have found that a resin composition containing a compound containing a polyphenylene ether-based resin, a liquid crystal polyester, and an I-, II-, III- or IV-valent metal element is formulated. By forming a sheet using an extruder as a raw material, it is possible to obtain a polyphenylene ether-based resin sheet having excellent heat resistance, no delamination, excellent bending resistance and moisture resistance, and a small heat shrinkage. They have found and completed the present invention.

That is, the present invention
(1) 51 to 99.9 parts by weight of (A) polyphenylene ether-based resin and 0.1 to 0.1 parts by weight of (B) liquid-crystalline polyester, based on 100 parts by weight of the total of (A) polyphenylene ether-based resin and (B) liquid crystal polyester. 49 parts by weight and (C) 0.1 to 10 parts by weight of a compound containing a metal element having a valence of I, II, III or IV and / or 0.1 to 5 parts by weight of a silane compound (D) Polyphenylene ether-based resin sheet comprising a resin composition to be
(2) The polyphenylene ether-based resin sheet according to (1), wherein the metal element of the component (C) is a Zn element and / or a Mg element.
(3) The polyphenylene ether-based resin sheet according to (2), wherein the component (C) is ZnO and / or Mg (OH) ₂ .

(4) The above (1) to (3), wherein the silicone polymer is contained in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the total of the components (A) and (B). Polyphenylene ether-based resin sheet according to any one,
(5) The polyphenylene ether-based resin sheet according to (4), wherein (E) the silicone polymer has an amino group and has 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), which is obtained by molding by an extrusion tubular method,
(7) The polyphenylene ether-based resin sheet according to any one of the above (1) to (5) obtained by molding by a T-die extrusion method,
It is.

  According to the present invention, it has become possible to provide a polyphenylene ether-based resin sheet having excellent heat resistance, no delamination, excellent bending resistance and moisture resistance, and a small heat shrinkage.

Hereinafter, the present invention will be specifically described.
The polyphenylene ether resin (A) of the present invention has a repeating unit structure represented by 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. / G in the range of homopolymer and / or copolymer. 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, hydrocarbonoxy. R ₂ and R ₃ each independently represent hydrogen Represents a primary or secondary lower alkyl or phenyl.)

  Specific examples of the polyphenylene ether-based 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. Further, 2,6-dimethylphenol and other phenols (for example, Polyphenylene ether copolymers such as copolymers with 2,3,6-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) is more preferable. , 4-phenylene ether) are preferred.

As an example of the method for producing the polyphenylene ether (A) used in the present invention, a method of oxidative polymerization of 2,6-xylenol using a complex of a cuprous salt and an amine as a catalyst described in US Pat. No. 3,308,874 is used. is there.
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 used. (A) It is preferable as a method for producing polyphenylene ether.
The polyphenylene ether-based resin (A) of the present invention may be used as it is after the polymerization process, or may be extruded or the like under a nitrogen gas atmosphere or a non-nitrogen gas atmosphere, under devolatilization or non-devolatilization. It may be pelletized and used by melt-kneading below.

  The polyphenylene ether-based resin (A) of the present invention also includes a polyphenylene ether functionalized with various dienophile compounds. Various dienophile compounds include, for example, compounds such as maleic anhydride, maleic acid, fumaric acid, phenylmaleimide, itaconic acid, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, glycidyl acrylate, glycidyl methacrylate, stearyl acrylate, and styrene. No. Further, as a method of functionalization with these dienophile compounds, an extruder or the like may be used in the presence or absence of a radical generator in a molten state under devolatilization or non-devolatilization. Alternatively, the functionalization may be performed in a non-molten state in the presence or absence of a radical generator, that is, in a temperature range from room temperature to melting point. At this time, the melting point of the polyphenylene ether is defined as a peak top temperature of a peak observed in a temperature-heat flow graph obtained when the temperature is increased at 20 ° C./min in a measurement by a differential scanning calorimeter (DSC). If there are a plurality of peak top temperatures, the highest temperature is defined.

  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. Examples of the aromatic vinyl polymer include atactic polystyrene, high-impact polystyrene, syndiotactic polystyrene, and acrylonitrile-styrene copolymer. When a mixture of the polyphenylene ether resin and the aromatic vinyl polymer is used, the content of 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. is there.

  The liquid crystal polyester (B) of the present invention is a polyester called a thermotropic liquid crystal polymer, and a known polyester can be used. For example, a thermotropic liquid crystal polyester having p-hydroxybenzoic acid and polyethylene terephthalate as main constitutional units, a thermotropic liquid crystal polyester having p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid as main constitutional units, p-hydroxybenzoic acid Thermotropic liquid crystal polyester having an acid, 4,4'-dihydroxybiphenyl and terephthalic acid as main constitutional units is exemplified, and there is no particular limitation. As the liquid crystal polyester (B) used in the present invention, those comprising 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 a structural unit of a polyester generated from p-hydroxybenzoic acid and a structural unit generated 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 structural units (c) and (d) can be independently selected from one or two or more types from the following (Formula 2).

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

In the structural formulas (c) and (d), at least one or two or more of the above 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 formed from ethylene glycol / a structural unit formed from hydroquinone, 2) a structural unit formed from ethylene glycol / 4, 4 Structural units generated from '-dihydroxybiphenyl, 3) structural units generated from hydroquinone / 4 structural units generated from 4,4'-dihydroxybiphenyl, and the like.
Further, 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, a structural unit formed from 2,6-dicarboxynaphthalene And the like. 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 usage ratio 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 be used as the structural unit in the component (B). Specifically, 1) a structural unit formed from ethylene glycol and terephthalic acid, 2) a structural unit formed from hydroquinone and terephthalic acid, 3) a structural unit formed from 4,4'-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.

The liquid crystal polyester component (B) of the present invention may be formed from other aromatic dicarboxylic acids, aromatic diols, or aromatic hydroxycarboxylic acids, if necessary, in a small amount that does not impair the features and effects of the present invention. Structural units can be introduced.
The temperature at which the component (B) of the present invention starts to show a liquid crystal state upon melting (hereinafter referred to as a liquid crystal onset temperature) is preferably 150 to 350 ° C, more preferably 180 to 320 ° C. It is preferable to set the liquid crystal onset temperature within this range, since black foreign matters are reduced in the obtained resin sheet.

  The compound (C) containing a metal element having a valence of I, II, III or IV in the present invention is an inorganic compound or an organic compound containing a metal. The component (C) of the present invention is a compound essentially containing a metal element as a main component. Specific examples of the metal element which can have I valence, II valence, III valence or IV valence in the component (C) 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. From the viewpoint of substantially eliminating the delamination and greatly improving the toughness of the sheet, the metal element having a valence of I, II, III, or IV is more preferably Zn and / or Mg, and is preferably Zn. Particularly preferred.

(C) As the compound containing a metal element having a valence of I, II, III or IV, oxides, hydroxides, alkoxide salts, aliphatic carboxylate salts and acetate salts of the above metal elements are preferable. Examples of preferred _{oxides, ZnO, MgO, TiO 4,} TiO 2, PbO, CdO, SnO, SbO, Sb 2 O 3, NiO, Al 2 O 3, etc. 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 and Sn (OH) ₂ , Sb (OH) ₂ , Sb (OH) ₃ , Ni (OH) ₂ , Al (OH) ₃ , Ge (OH) _{2 and the} like. Examples of preferred alkoxide _{^{salts, Ti (O i Pr) 4}} , etc. ^Ti (O n _{Bu) 4} and the like. Examples of preferred aliphatic carboxylate include zinc stearate, magnesium stearate, titanium stearate, lead stearate, cadmium stearate, tin stearate, antimony stearate, nickel stearate, aluminum stearate, germanium stearate. And the like. 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.

More preferred examples among ^{_{these, ZnO, Mg (OH) 2}} , Ti (O i Pr) 4, Ti (O n Bu) 4, zinc acetate, zinc stearate, aluminum stearate, and the like. Further, from the viewpoint of no delamination, ZnO and / or Mg (OH) ₂ are preferable, and ZnO is particularly preferable. These components (C) may contain impurities as long as the effects of the present invention are not impaired.
The (D) silane compound of the present invention is a silane compound having a functional group, which is a silane compound containing at least one functional group selected from the group consisting of an amino group, a ureide group, an epoxy group, an isocyanate group and a mercapto group. Compound. Usually, the functional group-containing silane compound may contain any one of these functional groups in the molecule, but in some cases, may contain two or more of these functional groups in the molecule. It may be something to do.

  The silane compound used in the present invention is usually an alkoxysilane containing the above-described functional group 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 an amino group 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 Isocyanates such as propylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, and γ-isocyanatopropyltrichlorosilane. A silane compound containing a γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylethyldiethoxysilane, γ-mercaptopropylmethyldiethoxysilane, β-mercaptoethyltrimethoxysilane, silane compounds containing a mercapto group such as β-mercaptoethyltriethoxysilane and β-mercaptoethyldimethoxysilane; and the like.

  In the present invention, the compounding amount of the (A) polyphenylene ether-based resin is 51 to 99.9 parts by weight, preferably 60 to 100 parts by weight based on 100 parts by weight of the total amount of the (A) polyphenylene ether-based resin and (B) the liquid crystal polyester. It is 99 parts by weight, more preferably 70 to 98 parts by weight. If the compounding 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 (load of the extruder). Black foreign matter increases. When the amount is less than 51 parts by weight, the thickness unevenness of the sheet is deteriorated, and the layer is remarkably peeled. Here, the black foreign matter is called black spots, dark spots or chars, and has an unfavorable effect on the sheet properties.

In the present invention, the compounding amount of the liquid crystal polyester of the component (B) is 0.1% based on 100 parts by weight of the total amount of the components (A) and (B). The amount is from 49 to 49 parts by weight, preferably from 1 to 40 parts by weight, and more preferably from 2 to 30 parts by weight. When the amount is more than 49 parts by weight, the thickness of the sheet is reduced due to the anisotropy of the liquid crystal polymer. If the amount is less than 0.1 part by weight, the fluidity is greatly reduced, and the number of black foreign substances in the sheet increases.
The compounding amount of the component (C) in the present invention is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight based on 100 parts by weight of the total of (A) and (B). It is particularly preferably 0.4 to 3 parts by weight. If the content of the component (C) is less than 0.1 part by weight, the delamination of the sheet becomes remarkable, and if the content is more than 10 parts by weight, the specific gravity becomes large and the heat resistance may be lowered.

The compounding amount of the component (D) in the present invention is preferably 0.1 to 5 parts by weight, and more preferably 0.2 to 3 parts by weight based on 100 parts by weight of the total of (A) and (B). It is particularly preferably 0.3 to 1 part by weight. If the content of the component (D) is less than 0.1 part by weight, the delamination of the sheet becomes remarkable, and if it is more than 5 parts by weight, the composition of the present invention cannot be obtained stably or the moisture resistance In some cases, it may lead to a decrease in performance.
In the present invention, the component (C) and the component (D) can be used in combination, which is a preferable embodiment.

The (E) silicone polymer used in the present invention comprises four types of siloxane units (M unit: R ₃ SiO _0.5 , D unit: R ₂ SiO _1.0 , T unit: RSiO _1.5 , Q unit: 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 amino groups, hydroxyl groups, epoxy groups, and phenyl groups in the molecule. Or those containing a hydroxyl group are more preferred. Further, those containing an amino group are particularly preferred. The amino group is preferably a primary amine, a secondary amine, a tertiary amine or a quaternary amine, but from the viewpoint of flame retardancy, a primary amine or a secondary amine is more preferred. Further, both primary amine and secondary amine may be contained in the molecule. When an amino group is contained in the molecule, the amino equivalent is preferably 300 or more, more preferably 500 or more, and even more preferably 1,000 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 higher the viscosity, the better. However, from the viewpoint of workability, the upper limit is usually about 20,000 mm ² / s. Since the silicone polymer (E) of the present invention is a liquid, the D unit is often at least 50 mol%, more preferably at least 70 mol%, further at least 90 mol%, further preferably at least 95 mol%.
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 a terminal.
The amount of the silicone polymer (E) used in the present invention is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 4 parts by weight, based on 100 parts by weight of the total of (A) and (B). Parts by weight, particularly preferably 0.5 to 2 parts by weight. The compounding amount is preferably at least 0.1 part by weight from the viewpoint of flame retardancy, and is preferably at most 5 parts by weight from the viewpoint of appearance reduction and bleed out of the silicone polymer.

  In the present invention, in addition to the above components, other additional components such as an antioxidant and a flame retardant (organic phosphate compound, phosphazene compound) may be used as needed within a range not to impair the features and effects of the present invention. 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 copolymers such as ABS, polyester polyether elastomer, polyester polyester elastomer, vinyl aromatic compound-conjugated diene Compound block copolymer, vinyl aromatic compound Hydrogenated conjugated diene compound block copolymer), plasticizer (oil, low molecular weight polyethylene, epoxidized soybean oil, polyethylene glycol, fatty acid esters, etc.), flame retardant aid, weather (light) resistance improver, polyolefin Nucleating agents and various coloring agents may be added.

In the present invention, when (A), (B), (C), (D), and (E) are kneaded, the order of kneading is not particularly limited. And from the viewpoint of improving physical properties. However, when (C) and (D) are used in combination, (C) and (D) may be simultaneously kneaded with (A) and (B), but from the viewpoint of further suppressing delamination of the sheet. Therefore, it is desirable to knead (C) and knead (D) or knead (D) and knead (C).
The resin composition of the present invention can be produced by various methods. For example, a hot-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 melt-kneading temperature at this time is not particularly limited, but it can be arbitrarily selected usually 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 it is called a film.
The polyphenylene ether-based resin sheet of the present invention can be obtained from the resin composition obtained above as a raw material by extrusion sheet molding, or the components of the present invention can be directly charged into an extrusion sheet molding machine, and the blend and sheet can be obtained. It can also be obtained by performing molding at the same time.
The polyphenylene ether-based resin sheet of the present invention can be manufactured 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 is made uniform, and the sheet without delamination is formed. Is extremely important in creating

On the other hand, the polyphenylene ether-based resin sheet of the present invention can be produced by T-die extrusion molding. In this case, the film may be used without stretching, may be stretched uniaxially, or may be stretched biaxially. When it is desired to increase the strength of the sheet, it can be achieved by stretching.
The polyphenylene ether-based resin sheet of the present invention thus obtained has excellent heat resistance, no delamination, excellent bending resistance and moisture resistance, low heat shrinkage, flame retardancy, and mechanical strength. It also has excellent characteristics such as insulation, dielectric constant, dielectric loss tangent, etc., and excellent hydrolysis resistance. Therefore, it can be used for applications requiring these characteristics. For example, printed circuit board materials, printed circuit board peripheral components, semiconductor packages, data magnetic tapes, APS photographic films, film capacitors, insulating materials such as motors and transformers, speaker diaphragms, automotive sheet sensors, wire cable insulating tapes, TAB Tape, a generator slot liner interlayer insulating material, a toner agitator, an insulating washer such as a lithium ion battery, and the like.

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

[Production Example 1]
<Production example of polyphenylene ether (PPE-1)>
Powdered 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 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 obtain a liquid crystal polyester (LCP-1) having the following theoretical structural formula. Obtained. In addition, the component ratio of a composition represents a molar ratio.

Sheet molding and physical property evaluation of each resin composition were performed according to the following methods.
(1) Sheet Forming The obtained pellets were formed into an extruded sheet by a tubular method using an extruder with 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 be blown was set so that the thickness became 100 μm.
(2) Heat resistance The sheet was placed in a hot air oven at 150 ° C. for 5 hours, and heat resistance was evaluated based on the following criteria.
：: No deformation of the sheet was observed.
×: Deformation of the sheet was observed.

(3) No delamination The edges of the obtained sheet were cut with scissors of about 10 mm in length at intervals of 5 mm using scissors, and 20 sections 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 was observed at all.
Δ: Peeling was observed at 1 to 3 places.
×: Layer delamination was observed at four or more locations.

(4) Bending resistance The sheet was cut into a 120 x 30 square, completely bent at about half of the longitudinal direction (about 60 mm from the end), then returned to the 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.
：: No crack or break was observed.
Δ: No break, but crack was observed.
×: Breakage was observed within 10 times.

(5) Moisture resistance The sheet obtained in the above (1) was cut into a size of 100 × 200 mm square, and was heated at 90 ° C. and 80% relative humidity using a constant temperature and humidity chamber (PL-3FP, manufactured by Tabai Espec Corp.). After being exposed to a heated and humidified environment for 24 hours, the weight increase rate (Δw) was determined according to the following equation. 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 wiping water droplets on the sheet surface after heating and humidification; w ₀ : Drying in a hot air dryer for 2 hours at 100 ° C. before heating and humidification; (Sheet weight (g) cooled to room temperature inside)
The smaller the value of the weight increase rate (Δw), the better the moisture absorption resistance.

(6) 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 placed in an oven set at 190 ° C. for 5 minutes. Set, remove and allow to cool. The dimensions of 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) × 100
Here, MD is a direction in which the resin flows from a die of the tubular extrusion molding machine, 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 rate (parts by weight) shown in Table 1 at 250 to 310 ° C. The mixture was melt-kneaded using a set twin-screw extruder with a vent port (ZSK-25; manufactured by Werner & Pfleiderer) to obtain pellets. Using the pellets, 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), a silane compound containing an amino group (silane 1, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.) was used. Except for blending in the proportions (parts by weight) shown in Table 1, the same procedure as in Example 1 was carried out to obtain pellets and to perform sheet forming. The average thickness of the obtained sheet was 103 μm. These sheets were evaluated for physical properties according to the methods described above. The results are shown in Table 1.

[Example 3]
As the component (E), a silicone polymer (silicone 1, amino-modified silicone, SF8417, manufactured by Dow Corning Toray Silicone Co., Ltd., viscosity (25 ° C.): liquid having a viscosity of 1,200 mm ² / s, amino equivalent: 1,800 ) And the components were blended in the proportions (parts by weight) shown in Table 1 to obtain pellets and perform sheet forming. The average thickness of the obtained sheet was 105 μm. These sheets were evaluated for physical properties according to the methods described above. The results are shown in Table 1.

[Example 4]
As the 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 ratio (parts by weight) shown in Table 1. Except for the above, the same procedure as in Example 1 was carried out to obtain pellets and sheet forming. The average thickness of the obtained sheet was 98 μm. These sheets were evaluated for physical properties according to the methods described above. The results are shown in Table 1.

[Comparative Example 1]
A sheet was formed in the same manner as in Example 1 except that a heat-resistant and flame-retardant modified polyphenylene ether (Zylon 500Z (registered trademark), manufactured by Asahi Kasei Chemicals Corporation) was used as a pellet material. The average thickness of the obtained sheet was 110 μm. These sheets were evaluated for physical properties according to the methods described above. The results are shown in Table 1. Regarding the heat shrinkage, the sheet was so deformed that it could not be measured.

[Comparative Example 2]
A pellet was obtained and processed into a sheet in the same manner as in Example 1 except that the component (C) was not used. The average thickness of the obtained sheet was 106 μm. These sheets were evaluated for physical properties according to the methods described above. The results are shown in Table 1.

[Comparative Example 3]
As a sheet, a polyimide sheet (PI, Kapton 500H (registered trademark), manufactured by Du Pont-Toray Co., Ltd., thickness 125 μm) was evaluated for physical properties in accordance with 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 methods described above. The results are shown in Table 1.

  Table 1 shows that the polyphenylene ether-based resin sheet obtained by the present invention has excellent heat resistance, no delamination, excellent bending resistance and moisture resistance, and a small heat shrinkage. Compared to a polyimide sheet or a polyethylene terephthalate sheet which is a single polymer, the sheet of the present invention is surprisingly low in heat shrinkage in addition to being excellent in moisture resistance.

  The polyphenylene ether-based resin sheet of the present invention has excellent heat resistance, no delamination, excellent bending resistance and moisture resistance, low heat shrinkage, flame retardancy, mechanical strength, insulation and dielectric constant. Because of its excellent electrical properties such as heat dissipation and dielectric loss tangent, and its excellent hydrolysis resistance, for example, printed circuit board materials, printed circuit board peripheral parts, semiconductor packages, data magnetic tapes, APS photographic films, film capacitors, motors And transformers, speaker diaphragms, automotive seat sensors, wire cable insulation tape, TAB tape, generator slot liner interlayer insulation materials, toner agitators, insulation washers for lithium ion batteries, and other electronic and electrical parts materials Suitable for home appliance OA materials, automotive materials, and industrial materials.

Claims (7)

  (A) 51 to 99.9 parts by weight of (A) polyphenylene ether-based resin and 0.1 to 49 parts by weight of (B) liquid-crystalline polyester, based on 100 parts by weight of the total amount of (A) polyphenylene ether-based resin and (B) liquid crystal polyester. And a resin composition containing (C) 0.1 to 10 parts by weight of a compound containing a metal element having a valence of I, II, III or IV and / or 0.1 to 5 parts by weight of a silane compound (D) Sheet made of polyphenylene ether resin.   The polyphenylene ether-based resin sheet according to claim 1, wherein the metal element (C) is a Zn element and / or a Mg element. The polyphenylene ether resin sheet according to claim 2, wherein the component (C) is ZnO and / or Mg (OH) ₂ .   The polyphenylene according to any one of claims 1 to 3, further comprising (E) 0.1 to 5 parts by weight of the silicone polymer based on 100 parts by weight of the total of the components (A) and (B). Ether resin sheet. (E) a silicone polymer having an amino group, and at 25 ° C., polyphenylene ether resin sheet according to claim 4, wherein the viscosity of 10 mm 2 / ^s or more liquids.   The polyphenylene ether-based 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.