JP2008255220A - Polymer alloy extrusion molded sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve drawdown (sagging of a sheet or film by heating) on extrusion molding of a polymer alloy constituted of a polyphenylene sulfide resin and a polyphenylene ether-based resin and to improve the properties (thickness irregularity and surface appearance) of an obtained extrusion molded sheet from the polymer alloy. <P>SOLUTION: This extrusion molded sheet is obtained by subjecting a polymer alloy comprising (a) a matrix phase composed of a polyphenylene sulfide resin, (b) a dispersion phase composed of a polyphenylene ether-based resin, and (d) a styrenic copolymer having at least one of the functional groups of a glycidyl group and an oxazolyl group to extrusion molding, and the above polyphenylene sulfide resin has melt viscosity at 300°C at a shear rate of 100 sec<SP>-1</SP>of 100-500 Pa sec and an oligomer content of not more than 0.7 wt.%, and the above dispersion phase has an average particle diameter of not greater than 10 μm, and the above polymer alloy has melt viscosity at 300°C at a shear rate of 100 sec<SP>-1</SP>of 200-1,200 Pa sec. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an extruded sheet by an extrusion method comprising a polymer alloy having a polyphenylene sulfide resin as a matrix phase and a polyphenylene ether resin as a dispersed phase.

  The sheet of polyphenylene sulfide resin is excellent in heat resistance, chemical resistance, electrical properties and hydrolysis resistance, so as a single sheet or composite sheet in the fields of electronic equipment, electronic parts, automotive electrical parts, generator parts, or These sheets are used in a further shaped shape. On the other hand, since the polyphenylene sulfide resin has a low glass transition temperature of about 90 ° C., the sheet of polyphenylene sulfide resin used in an environment of 90 ° C. or more has a problem that it is likely to be thermally contracted.

  Many proposals have already been made on sheets made of polyphenylene sulfide resin in order to improve the defects caused by the glass transition temperature. For example, it has been proposed that a polymer having a glass transition temperature higher than that of polyphenylene sulfide is blended with polyphenylene sulfide to form a polymer alloy. Some of these proposals disclose a resin composition comprising polyphenylene sulfide / polyphenylene ether and excellent in heat resistance, molding processability and impact resistance. Another part of these proposals is a resin composed of polyphenylene sulfide / polyphenylene ether / thermoplastic elastomer and excellent in heat resistance, flame retardancy, solvent resistance, molding processability, mechanical strength and impact resistance. A composition is disclosed. Furthermore, in still another part of these proposals, a resin composition composed of polyphenylene sulfide / polyphenylene ether, which has greatly improved impact resistance and improved weld strength has been proposed. All of these proposals describe or suggest a method of injection molding a remer alloy containing polyphenylene sulfide. Moreover, the description of "a sheet | seat or a film" is seen by the specification as the use which the resin composition shown by one part literature (for example, patent documents 1-4).

However, when the present inventors molded a sheet by an extrusion method using a resin composition comprising polyphenylene sulfide / polyphenylene ether, drawdown (sag of the sheet or film due to heating) occurred, resulting in uneven thickness and surface appearance. It turns out that the problem of deterioration occurs. In fact, no technical disclosure has been made regarding such a problem when a resin composition comprising polyphenylene sulfide / polyphenylene ether is formed into a sheet by extrusion molding, and a method for improving the problem. .
JP 2002-12764 A Japanese Patent Laid-Open No. 2005-264124 WO2006 / 0697902A1 WO2006 / 082902A1

  The problem to be solved by the present invention is to provide a sheet by an extrusion molding method using a polymer alloy containing a polyphenylene sulfide resin and a polyphenylene ether-based resin and free from drawdown, thickness unevenness, and surface appearance deterioration. is there.

  In order to solve the above-mentioned problem, as a result of earnestly examining the extrusion process at the time of forming into a sheet by an extrusion molding method using a polymer alloy containing a polyphenylene sulfide resin and a polyphenylene ether resin, it has a specific melt viscosity, and A polymer alloy containing a polyphenylene sulfide resin having a specific oligomer amount and a polyphenylene ether resin, and when the polymer alloy having a specific melt viscosity is formed into a sheet by an extrusion molding method, a drawdown (sheet by heating, It was found that film sag is unlikely to occur, and the present invention was completed.

That is, the present invention
[1] (a) a matrix phase composed of polyphenylene sulfide resin;
(B) a dispersed phase comprising a polyphenylene ether resin;
(D) a styrene copolymer having at least one functional group of a glycidyl group and an oxazolyl group;
Extruded sheet obtained by extrusion molding a polymer alloy containing
The polyphenylene sulfide resin has a melt viscosity at 300 ° C. at a shear rate of 100 sec ⁻¹ of 100 to 500 Pa · sec, and an oligomer content of 0.7% by weight or less,
An average particle size of the dispersed phase is 10 μm or less,
An extruded sheet having a melt viscosity at 300 ° C. of 200 to 1200 Pa · sec at a shear rate of 100 sec ⁻¹ of the polymer alloy,
[2] The extruded sheet according to [1], wherein (c) an elastomer is present in the dispersed phase,
[3] The polymer alloy is
(A) 45 to 95% by weight of polyphenylene sulfide resin;
(B) 5 to 55% by weight of a polyphenylene ether resin,
1 to 5 parts by weight of a styrene-based copolymer having at least one functional group of (d) glycidyl group and oxazolyl group with respect to 100 parts by weight of the total of component (a) and component (b);
An extruded sheet according to [1] or [2] above,
[4] The polymer alloy is
(A) 45 to 95% by weight of polyphenylene sulfide resin;
(B) 5 to 55% by weight of a polyphenylene ether resin,
(C) 1-15 parts by weight of elastomer for 100 parts by weight of the total of component (a) and component (b),
(D) 1-5 parts by weight of a styrene copolymer having at least one functional group of a glycidyl group and an oxazolyl group;
The extruded sheet according to any one of [1] to [3] above,
[5] (a) The extruded sheet according to any one of [1] to [4], wherein the polyphenylene sulfide resin is linear polyphenylene sulfide or cross-linked polyphenylene sulfide.
[6] (a) The extruded sheet according to any one of [1] to [4], wherein the polyphenylene sulfide resin contains linear polyphenylene sulfide and cross-linked polyphenylene sulfide;
[7] Any one of [1] to [6], wherein the component (b) is 100% by weight of polyphenylene ether or polyphenylene ether / styrene resin = 1 to 99% by weight / 99 to 1% by weight. Extruded sheet according to
[8] (c) A block copolymer obtained by copolymerizing a vinyl aromatic compound and a conjugated diene compound as an elastomer, a hydrogenated block copolymer obtained by further hydrogenating the block copolymer, And an extruded sheet according to any one of [2] to [7] above, which is at least one selected from the group consisting of ethylene / α-olefin copolymers,
[9] (d) The styrene copolymer is a styrene-glycidyl methacrylate copolymer, a styrene-glycidyl methacrylate-methyl methacrylate copolymer, a styrene-glycidyl methacrylate-acrylonitrile copolymer, a styrene-vinyl oxazoline copolymer, From styrene-vinyloxazoline-acrylonitrile copolymer, graft copolymer in which styrene monomer is grafted on ethylene-glycidyl methacrylate copolymer, and graft copolymer in which styrene monomer and acrylonitrile are grafted on ethylene-glycidyl methacrylate copolymer The extruded sheet according to any one of [3] to [8] above, which is at least one selected from the group consisting of:
[10] The extruded sheet according to any one of [1] to [9], which is a single layer or a multilayer.
[11] The extruded sheet according to any one of [1] to [10], wherein the extruded sheet has a thickness of 1000 μm or less.
[12] A molded body molded using the extruded sheet according to any one of [1] to [11],
I will provide a.

  The term “extruded sheet” used in the present specification refers to an extruded thin film. Depending on the technical field, a sheet having a thickness of 1000 μm or less may be referred to as a sheet, and a sheet having a thickness of 100 μm or less may be referred to as a film, but the extruded sheet of the present invention includes any thickness.

  A polymer alloy having a specific melt viscosity and including a polyphenylene sulfide resin and a polyphenylene ether resin having a specific oligomer amount and having a specific melt viscosity is drawn down when an extrusion sheet is formed by an extrusion method. (Sheet of sheets and films due to heating) hardly occurs.

Hereinafter, the present invention will be described in detail.
A polymer alloy for forming an extruded sheet, which is a polymer alloy for forming an extruded sheet of the present invention, includes a polyphenylene sulfide resin as the component (a) and a polyphenylene ether-based resin as the component (b). The component (a) polyphenylene sulfide resin (hereinafter abbreviated as “PPS”) preferably has 50 mol% of repeating units of arylene sulfide represented by the following general formula (formula 1), more preferably 70 mol. %, More preferably 90 mol% or more of arylene sulfide repeating units.
[—Ar—S—] (Formula 1)
(Ar represents an arylene group, and examples of the arylene group include a p-phenylene group, an m-phenylene group, and a phenylene group that may have a substituent (the substituent is an alkyl having 1 to 10 carbon atoms). Group, and a phenyl group are preferable.), P, p'-diphenylenesulfone group, p, p'-biphenylene group, p, p'-diphenylenecarbonyl group, and naphthylene group.
PPS may be a homopolymer having one type of arylene group as a structural unit, and is a copolymer obtained by mixing two or more different arylene groups from the viewpoint of processability and heat resistance. May be. Among these, PPS having a repeating unit of p-phenylene sulfide as a main constituent element is preferable because it is excellent in processability and heat resistance and is easily available industrially.

  The above-mentioned PPS production method is usually a method in which a halogen-substituted aromatic compound, for example, p-dichlorobenzene is polymerized in the presence of sulfur and sodium carbonate, (1) sodium sulfide; (2) sulfurization in a polar solvent. Examples thereof include sodium hydrogen and sodium hydroxide; (3) hydrogen sulfide and sodium hydroxide; (4) polymerization in the presence of sodium aminoalkanoate, and self-condensation of p-chlorothiophenol. Among them, a method of reacting sodium sulfide and p-dichlorobenzene in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone solvent such as sulfolane is suitable. These production methods are known methods, for example, US Pat. No. 2,513,188, Japanese Examined Patent Publication No. 44-27671, Japanese Examined Patent Publication No. 45-3368, Japanese Examined Patent Publication No. 52-12240, Japanese Unexamined Patent Publication No. Sho 61-61. 225217, U.S. Pat. No. 3,274,165, Japanese Examined Patent Publication No. 46-27255, Belgian Patent No. 29437, and Japanese Patent Laid-Open No. 5-222196, and the like. PPS can be obtained by other prior art methods. The PPS obtained by this polymerization is usually a linear type PPS. After this PPS is polymerized, it is further heat-treated at a temperature below the melting point of PPS (for example, 200 to 250 ° C.) in the presence of oxygen to promote oxidative crosslinking. Those having a moderately increased polymer molecular weight and viscosity are classified as cross-linked PPS. The cross-linked PPS classified here includes semi-cross-linked PPS in which the degree of cross-linking is kept small.

As the polyphenylene sulfide resin of component (a) used in the present invention, any one or two of the above-described linear PPS and cross-linked PPS can be used in combination. In the present invention, the melt viscosity at 300 ° C. at a shear rate of 100 sec ⁻¹ of the polyphenylene sulfide resin of component (a) is 100 to 500 Pa · sec, preferably 100 to 400 Pa · sec, more preferably 150 to 400 Pa · sec. Is a PPS. By using PPS having a melt viscosity of 100 Pa · sec or more, it is possible to prevent a drawdown at the time of extrusion when forming an extruded sheet from a polymer alloy, so that the moldability (film forming property) is excellent and the melt viscosity is 500 Pa. -By using PPS of sec or less, an extruded sheet is produced from a polymer alloy having excellent thickness unevenness and surface appearance.

The melt viscosity can be measured with a capillary rheometer. For example, a capillograph (manufactured by Toyo Seiki Seisakusho Co., Ltd.) is used, and the capillary has a capillary length = 10 mm, a capillary diameter = 1 mm, a temperature of 300 ° C., a shear It can be measured at a speed of 100 sec ⁻¹ .

  Furthermore, in addition to the above-mentioned features, in order to reduce the appearance of the molding generated in the die part of the extruder when the polymer alloy is extruded to obtain the extruded sheet of the present invention, the appearance of the molded sheet surface is not deteriorated. The (a) component oligomer content needs to be 0.7% by weight or less. Here, the oligomer contained in PPS means a substance obtained by extracting the supplied PPS with methylene chloride, and is a substance generally known as an impurity of PPS. The measurement of the oligomer content is obtained by the following method. be able to. That is, 5 g of PPS powder is added to 80 ml of methylene chloride, subjected to Soxhlet extraction for 6 hours, cooled to room temperature, and the extracted methylene chloride solution is transferred to a weighing bottle. Further, the container used for the above extraction is washed in three portions with a total of 60 ml of methylene chloride, and the washing solution is collected in the weighing bottle. Next, the methylene chloride in the weighing bottle is evaporated and removed by heating to about 80 ° C., the residue is weighed, and the amount extracted from the methylene chloride from the amount of the residue, that is, the proportion of the oligomer present in the PPS. Can be requested.

  The polyphenylene ether resin of component (b) used in the present invention has a repeating unit represented by the following bond unit (Formula 2), and is a number average molecular weight in terms of polystyrene measured using GPC (gel permeation chromatography). Is a homopolymer and / or copolymer polyphenylene ether resin (hereinafter abbreviated as PPE) in the range of 1000 or more, preferably 1500 to 50000, more preferably 1500 to 30000.

(Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen, halogen, primary or secondary lower alkyl group having 1 to 7 carbon atoms, phenyl group, haloalkyl group, An aminoalkyl group, a hydrocarbonoxy group, or a group consisting of a halohydrocarbonoxy group in which at least two carbon atoms separate a halogen atom and an oxygen atom.)

  Specific examples of the aforementioned PPE include 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) and poly (2,6-dichloro-1,4-phenylene ether). Furthermore, a polyphenylene ether copolymer such as a copolymer of 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethylphenol or 2-methyl-6-butylphenol) is also included. Among them, poly (2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol is preferable, and poly (2,6-dimethyl-1 , 4-phenylene ether).

  The method for producing such PPE is not particularly limited as long as it is a known method. For example, a complex of cuprous salt and amine by Hay described in US Pat. No. 3,306,874 is used as a catalyst, for example, 2,6-xylenol. Can be easily produced by oxidative polymerization. In addition, the method described in US Pat. Nos. 3,306,875, 3,257,357, 3,257,358, JP-B-52-17880, JP-A-50-51197, and 63-152628 can be easily used. Can be manufactured.

  The PPE of the component (b) used in the present invention can be used even with 100% by weight of the above-mentioned PPE component, but is composed of PPE / styrene resin = 1 to 99% by weight / 99 to 1% by weight. Can also be preferably used. From the viewpoint of improving the heat resistance of PPS, particularly the defects of the amorphous phase, the blending ratio of PPE / styrene resin should be such that its glass transition temperature is equal to or higher than the glass transition temperature of PPS (about 90 ° C.). It is preferable to adjust.

  Such a styrene resin is a rubber polymer dispersed in a matrix made of a homopolymer of a styrene compound, a copolymer of two or more styrene compounds, and a polymer of styrene compounds. Examples thereof include rubber-modified styrene resin (high impact polystyrene). Examples of the styrenic compound that gives these polymers include styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, α-methylstyrene, ethylstyrene, α-methyl-p-methylstyrene, 2, 4 -Dimethyl styrene, monochloro styrene, p-tert-butyl styrene, etc. are mentioned.

  These styrenic compounds may be copolymers obtained by using two or more styrenic compounds, and among them, polystyrene obtained by polymerization using styrene alone is preferred. As these polymers, polystyrene having a stereoregular structure such as atactic polystyrene and syndiotactic polystyrene can be effectively used. The styrene resin used in combination with the PPE includes a styrene-glycidyl methacrylate copolymer, a styrene-glycidyl methacrylate-methyl methacrylate copolymer, and a styrene-glycidyl listed as the copolymer of the component (d) described later. Styrenic copolymers such as methacrylate-acrylonitrile copolymers, styrene-vinyloxazoline copolymers, and styrene-vinyloxazoline-acrylonitrile copolymers, and vinyl aromatic compounds and conjugated dienes listed as elastomers for component (c) A block copolymer obtained by copolymerizing a compound, and a styrene-butadiene block copolymer represented by a hydrogenated block copolymer obtained by further hydrogenation reaction of this block copolymer or a hydrogenated product thereof. Some hydrogenated block copolymers are Rare no.

  The PPE of the component (b) used in the present invention exists as particles dispersed in the matrix of the above (a) PPS, and is important for reinforcing the heat resistance above the glass transition temperature of the amorphous part of the PPS. The role is shown, and the dispersion average particle diameter is 10 μm or less. When the dispersion average particle diameter exceeds 10 μm, the appearance of the obtained extruded sheet is deteriorated or a peeling phenomenon occurs, which is not preferable.

  Next, the styrene copolymer having a functional group as the component (d) used in the present invention is a styrene copolymer having any one functional group of a glycidyl group and an oxazolyl group, and the component (a) It acts as an emulsifying dispersant when mixing PPS of component (b) and PPE of component (b), and the dispersion average particle size of PPE of component (b) which is a dispersed phase of polymer alloy is 10 μm in PPS of component (a). The following effects are exerted, and an excellent effect is exerted in adjusting the melt viscosity of the polymer alloy to be high.

  As the copolymer of component (d), a copolymer of an unsaturated monomer having any one functional group of glycidyl group and oxazolyl group and a monomer having styrene as a main component can be preferably used. As used herein, the monomer having styrene as the main component has no problem if the styrene component is 100% by weight, but when there is another monomer copolymerizable with styrene, the copolymer chain is component (b). In order to maintain the miscibility with PPE, it is necessary to contain at least 65% by weight of styrene monomer, more preferably 75 to 95% by weight. Examples of unsaturated monomers having any one functional group of glycidyl group and oxazolyl group constituting these copolymers include glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, glycidyl ether of hydroxyalkyl (meth) acrylate, poly Examples include alkylene glycol (meth) acrylate glycidyl ether, glycidyl itaconate, and the like. Of these, glycidyl methacrylate is preferred. Moreover, as said oxazolyl group containing unsaturated monomer, 2-isopropenyl-2-oxazoline is industrially available and can be used preferably, for example.

  As the other unsaturated monomer copolymerized with the unsaturated monomer having any one functional group of glycidyl group and oxazolyl group, in addition to styrene as an essential component, vinyl cyanide monomer such as acrylonitrile as a copolymerization component , Vinyl acetate, acrylic acid ester, methacrylic acid ester and the like. The unsaturated monomer having any one functional group of glycidyl group and oxazolyl group is 0.3 to 20% by weight, preferably 1 to 15% by weight, more preferably 3% in the copolymer of component (d). -10% by weight. The amount of the unsaturated monomer having any one functional group of glycidyl group and oxazolyl group of the copolymer of component (d) needs to be 0.3% by weight or more, and if it is 20% by weight or less, The miscibility between the PPS of the component a) and the PPE of the component (b) is improved, and the dispersion average particle size of the PPE of the component (b) dispersed in the resulting polymer alloy can be controlled to 10 μm or less. The melt viscosity of the polymer alloy can be preferably increased for an extruded sheet.

  Examples of copolymer (d) obtained by copolymerizing these copolymerizable unsaturated monomers include styrene-glycidyl methacrylate copolymer, styrene-glycidyl methacrylate-methyl methacrylate copolymer, and styrene-glycidyl methacrylate. -An acrylonitrile copolymer, a styrene-vinyl oxazoline copolymer, a styrene-vinyl oxazoline-acrylonitrile copolymer, etc. are mentioned. As the copolymer of component (d), a copolymer obtained by grafting a styrene monomer or the like onto an ethylene copolymer may be used. For example, a graft obtained by grafting a styrene monomer onto an ethylene-glycidyl methacrylate copolymer. Examples thereof include a copolymer and a graft copolymer obtained by grafting an ethylene-glycidyl methacrylate copolymer with a styrene monomer and acrylonitrile.

The blending amount of the copolymer of component (d) is 1 to 5 parts by weight with respect to a total of 100 parts by weight of the components (a) to (b) described above. If the blending amount of the component (d) is 1 part by weight or more, the miscibility of the PPS of the component (a) and the PPE of the component (b) is improved, and if it is 5 parts by weight or less, the obtained polymer Drawdown when forming an extruded sheet by an extrusion method using an alloy is prevented, resulting in a sheet having an excellent balance between moldability (film forming property) and sheet characteristics (thickness unevenness, surface appearance). As described above, the component (d) is obtained in consideration of the surface appearance when it is formed into an extruded sheet, although it has the effect of emulsifying and dispersing the component (b) to an average particle size of 10 μm or less and increasing the melt viscosity of the polymer alloy. It is necessary to select a suitable blending amount of component (d) and an amount of functional groups so that the melt viscosity at 300 ° C. at a shear rate of 100 sec ⁻¹ of the polymer alloy to be obtained is 200 to 1200 Pa · sec.

  The polymer alloy which is the resin composition for forming an extruded sheet of the present invention includes the above-described component (a), component (b) and component (d). In order to impart the toughness and flexibility of the extruded sheet of the present invention, a polymer alloy to which an elastomer (c) described below is further added is the most preferred polymer alloy for the extruded sheet of the present invention.

  The elastomer as the component (c) used in the present invention includes, for example, a block copolymer obtained by copolymerizing a vinyl aromatic compound and a conjugated diene compound, and water obtained by further hydrogenating the block copolymer. According to the purpose, at least one selected from an additive block copolymer and an ethylene / α-olefin copolymer can be selected and used as the elastomer as the component (c).

Here, the structure of the (c) component vinyl aromatic compound-conjugated diene compound block copolymer and the hydrogenated block copolymer that is a hydrogenated product thereof will be briefly described. In general, a vinyl aromatic compound-conjugated diene compound block copolymer is obtained by block copolymerizing a vinyl aromatic compound and a conjugated diene compound in respective monomer units, and mainly comprising a vinyl aromatic compound (of a vinyl aromatic compound). A block copolymer structure comprising a polymer block A having a content of at least 70% and a polymer block B mainly comprising a conjugated diene compound (having a content of at least 70% of the conjugated diene compound). It is shown. In the block copolymer, the vinyl aromatic compound in the random copolymer portion may be uniformly distributed or distributed in a tapered shape. Further, in the copolymer block, a plurality of portions where the vinyl aromatic compound is uniformly distributed and / or a portion where the vinyl aromatic compound is distributed in a tapered shape may coexist. Furthermore, a plurality of portions having different vinyl aromatic compound contents may coexist in the copolymer block. Polymer block A mainly composed of this vinyl aromatic compound (having a content of at least 70% vinyl aromatic compound) and conjugated diene compound (having a content of at least 70% conjugated diene compound) In general, the block copolymer composed of the polymer block B is exemplified by a block copolymer having the following structure.
(AB) _n , A- (BA) _n- B, B- (AB) _{n + 1} , [(AB) _k ] _{m + 1-} Z, [(AB) _k -A] _{m + 1-} Z, [(BA) _k ] _{m + 1-} Z, [(BA) _k- B] _{m + 1-} Z.
(In the above formula, Z represents a residue of a coupling agent or a residue of an initiator of a polyfunctional organolithium compound. N, k and m are integers of 1 or more, generally 1 to 5. )

  Examples of the vinyl aromatic compound used in the vinyl aromatic compound-conjugated diene compound block copolymer include one or more of styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, diphenylethylene, and the like. Two or more types can be selected, and styrene is particularly preferable. The content of the vinyl aromatic compound in the vinyl aromatic compound-conjugated diene compound block copolymer can usually be suitably selected from 1 to 70% by weight, preferably 5 to 55% by weight, more preferably Is 10 to 55% by weight. Further, as the conjugated diene compound in the block copolymer, for example, one or more kinds are selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like. In particular, butadiene, isoprene and combinations thereof are preferred. Moreover, the microstructure which is a polymerization form of the conjugated diene compound in the vinyl aromatic compound-conjugated diene compound block copolymer can be arbitrarily selected. For example, in butadiene, the 1,2-vinyl bond is 2 to 85%, preferably 100 to 85%, more preferably 35 to 85%. In isoprene, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds is 2-85%, preferably 3-75%, more preferably 3-60%. The 1,2-vinyl bond and 3,4-vinyl bond may be uniformly distributed in the conjugated diene compound polymer block or may be distributed in a tapered shape. In addition, the conjugated diene compound polymer has a 1,2-vinyl bond content or a polymer portion having a different total amount of 1,2-vinyl bond and 3,4-vinyl bond, for example, 1,2-vinyl bond content or 1 , 2-vinyl bonds and 3,4-vinyl bonds may be present in a polymer portion having a total amount of less than 30% and polymer portions having a proportion of 30% or more, and polymer portions having different vinyl bond amounts. A plurality of may coexist.

The number average molecular weight of the precursor vinyl aromatic compound-conjugated diene compound block copolymer (molecular weight in terms of polystyrene by gel permeation chromatography) is usually 1,000 to 1,000,000, preferably 10,000 to 500,000, more preferably. 30000-300000.
The block copolymer described above is obtained by anionic polymerization of a conjugated diene compound and a vinyl aromatic compound in a hydrocarbon solvent using an organic lithium compound as a polymerization initiator. As such hydrocarbon solvent, aliphatic, alicyclic and aromatic hydrocarbons can be used, for example, propane, isobutane, n-hexane, isooctane, cyclopentane, cyclohexane, benzene, toluene and the like. Particularly preferred solvents are n-hexane, cyclohexane, and benzene, and these solvents may be used as one or a mixture of two or more. Moreover, as an organic lithium compound which is a polymerization initiator used for polymerization, mono-organic lithium compounds such as n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, dilithiomethane, Polyfunctional organolithium compounds such as 1,4-dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, 1,2-dilithio-1,2-diphenylmethane, 1,3,5-trilithiobenzene, etc. can be used. Can be used alone or in a mixture of two or more. The amount of these organic lithium compounds used can be appropriately selected by calculation based on a monodisperse polymer (weight average molecular weight / number average molecular weight = 1) according to the number average molecular weight of the polymer containing the target conjugated diene compound. . The amount of 1,2-vinyl bond in the microstructure, the increase in the amount of 3,4-vinyl bond, or the randomness in the vinyl aromatic compound-conjugated diene compound copolymer chain, which is the polymerization mode of the conjugated diene compound described above. In order to adjust, usually polar compounds such as ethers, tertiary amines, alkali metal alkoxides and the like can be used. For example, diethyl ether, ethylene glycol dimethyl ether, ethylene glycol di-n-butyl ether, ethylene glycol n-butyl-tert-butyl ether, ethylene glycol di-tert-butyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetrahydrofuran, α-methoxymethyltetrahydrofuran, dioxane, 1,2-dimethoxybenzene, triethylamine, N, N, N ′, N′-tetramethylethylenediamine, potassium tert-amyl oxide, potassium tert-butyl oxide, and the like. These compounds can be used alone or as a mixture of two or more. The usage-amount of this polar compound is 0 mol or more with respect to 1 mol of organolithium compounds, Preferably it is 0-300 mol. Thus, a vinyl aromatic compound-conjugated diene compound block copolymer is obtained by anionic polymerization of a vinyl aromatic compound and a conjugated diene compound using an organolithium compound.

  Furthermore, the vinyl aromatic compound-conjugated diene compound block copolymer obtained here is present in the polymer by adding a hydrogenation catalyst and hydrogen gas in a hydrocarbon solvent and performing a hydrogenation reaction. By reducing the olefinically unsaturated bond derived from the conjugated diene compound to 90% or less, preferably 55% or less, more preferably 20% or less, a hydrogenated block copolymer can be obtained. The hydrogenation reaction is not limited in its production method as long as it can reduce the olefinic unsaturated bond derived from the conjugated diene compound present in the vinyl aromatic compound-conjugated diene compound block copolymer, and any production method can be used. The method may be used.

  The vinyl aromatic compound-conjugated diene compound block copolymer (c) used in the present invention and the hydrogenated block copolymer that is a hydrogenated product thereof are block copolymers having the structure described above. Generally, a vinyl aromatic compound-conjugated diene compound block copolymer having a functional group obtained by reacting these block copolymers with a compound having a functional group, and a hydrogenated block having a functional group which is a hydrogenated product thereof A copolymer or the like is known, but it is not preferable to use it as a component (c) of a polymer alloy to be formed into an extrusion sheet. This is because when an elastomer having a functional group is used as the component (c), the appearance of the extruded sheet is deteriorated.

  Furthermore, the ethylene / α-olefin copolymer of component (c) is a copolymer of ethylene and at least one kind of α-olefin having 3 to 20 carbon atoms, and has 3 to 20 carbon atoms. Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicocene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1- Pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl 1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene and combinations thereof. Among these α-olefins, a copolymer using an α-olefin having 3 to 12 carbon atoms is preferable. The ethylene / α-olefin copolymer preferably has an α-olefin content of 1 to 30 mol%, more preferably 2 to 25 mol%, and still more preferably 3 to 20 mol%. Further, non-conjugated dienes such as 1,4-hexadiene, dicyclopentadiene, 2,5-norbornadiene, 5-ethylidenenorbornene, 5-ethyl-2,5-norbornadiene, 5- (1′-propenyl) -2-norbornene At least one of these may be copolymerized.

  The ethylene / α-olefin copolymer of component (c) used in the present invention is a copolymer having the structure shown above. Generally, an ethylene / α-olefin copolymer having a functional group obtained by further reacting these ethylene / α-olefin copolymers with a compound having a functional group, a copolymer of ethylene and a functional group-containing monomer, and A copolymer of ethylene / α-olefin / functional group-containing monomer is known, but it is not preferable to use it as a component (c) of a polymer alloy for an extruded sheet. This is because when the elastomer having these functional groups is used as the component (c), the appearance of the extruded sheet is deteriorated.

  The blending amount of the above-mentioned elastomers of the component (c) is preferably 1 to 15 parts by weight, more preferably 3 to 12 parts by weight with respect to 100 parts by weight of the total of the components (a) to (b). It is. When the blending amount is 1 part by weight or more, an extruded sheet having toughness and flexibility is obtained. When the blending amount is 15 parts by weight or less, the sheet extruded from the polymer alloy is excellent in mechanical strength and heat resistance. Sheet.

The most preferred polymer alloy for forming an extruded sheet of the present invention is any of the above-described PPS of component (a), PPE of component (b), elastomer of component (c), and glycidyl group or oxazolyl group of component (d). It is composed of a styrenic copolymer having one functional group, the matrix phase is PPS of component (a), and the dispersed phase is PPE of component (b) dispersed with an average particle size of 10 μm or less. A polymer alloy having a morphology in which the elastomer component of the component (c) is further dispersed in the PPE of the component (b) of the dispersed phase and having a melt viscosity at 300 ° C. at a shear rate of 100 sec ⁻¹ of 200 to 1200 Pa · sec. is there.

  In addition to the above-mentioned components, the polymer alloy for forming an extruded sheet of the present invention may be an inorganic filler such as calcium carbonate or magnesium oxide (excluding titanium oxide), if necessary, as long as the effect is not impaired. Agents; Antioxidants; Stabilizers such as UV absorbers; Crystal nucleating agents; Antistatic agents; Conductive substances (carbon, carbon fiber, carbon nanotubes, etc., excluding graphite); Flame retardants; Colorants such as pigments and dyes Known release agents such as polyethylene wax, polypropylene wax, montanate wax and stearate wax can be appropriately added.

The dispersion form of the (b) component polyphenylene ether resin dispersed in the polymer alloy can be easily measured and confirmed using a transmission electron microscope. For example, a sample is oxidized with a heavy metal compound such as ruthenium tetrachloride, an ultrathin section is cut out with an ultramicrotome, and the section is photographed with a transmission electron microscope and developed as a photograph (for example, 10,000 times). The particle size of the polyphenylene ether resin of component (a) is obtained by capturing the photograph into a scanner with a resolution of 200 dpi or more and dispersing using particle analysis software of an image analyzer (for example, IP-1000 manufactured by Asahi Kasei Corporation). The average particle size was calculated by the following formula.
Average particle diameter = ΣniDri ³ / ΣniDri ²
(Here, ni is the number of particles having a particle diameter Dri in the photograph, and the particle diameter Dri is the particle diameter when the equivalent area is taken from the particle area in the photograph.)

The production method of the polymer alloy is not particularly limited as long as it has the above-described characteristics, but the preferred production method is as follows:
(1) Using a twin screw extruder having at least two vent ports and at least one side supply port and set at a temperature of 280 ° C. to 350 ° C., the component (a) to (d ) A method of supplying and melting and kneading all the components, and then degassing one or more vent ports of the twin-screw extruder at an absolute vacuum pressure of 95 kPa or less and melt-kneading;
(2) When using linear PPS and cross-linked PPS in combination, use a twin screw extruder that has at least two vent ports and at least one side supply port, and the temperature is set between 280 ° C and 350 ° C. Then, from the top of the extruder, after melting and kneading the entire amount of the linear type PPS of the component (a) and the components (b) to (d), the first vent port of the twin screw extruder has an absolute vacuum pressure of 95 kPa or less. A zone for degassing is provided and melt-kneaded, and the cross-linked PPS of component (a) is added from the first side feed port of the twin-screw extruder, and after heat-melt-kneading, A method in which the second vent port is degassed and melt-kneaded at an absolute vacuum pressure of 95 kPa or less.

In the polymer alloy thus obtained, it is important that the melt viscosity at 300 ° C. at a shear rate of 100 sec ⁻¹ is 200 to 1200 Pa · sec, but not only the melt viscosity of the polymer alloy but also the component (a) The melt viscosity at 300 ° C. at a PPS shear rate of 100 sec ⁻¹ must satisfy 100 to 500 Pa · sec. If these two melt viscosities (polymer alloy melt viscosity and PPS melt viscosity) do not satisfy these ranges, drawdown may occur when the sheet is extruded, Extruded sheet characteristics (thickness unevenness, surface appearance) deteriorate, which is not preferable.

  These two polymer alloys whose melt viscosities are controlled within a suitable range prevent drawdown when forming an extruded sheet by an extrusion method, and provide molding processability (film forming property) and characteristics (thickness unevenness, Gives a sheet with an excellent balance of surface appearance.

That is, when the melt viscosity at 300 ° C. at a shear rate of 100 sec ⁻¹ of component (a) is 100 Pa · sec or more and the melt viscosity of the polymer alloy is 200 Pa · sec or more, when forming an extruded sheet. The meltdown at 300 ° C. at a shear rate of 100 sec ⁻¹ of the PPS component (a) is 500 Pa · sec or less and the melt viscosity of the polymer alloy is 1200 Pa · sec or less. By this, it is excellent in the balance of the sheet | seat characteristic (thickness nonuniformity, surface appearance) extruded from a polymer alloy.

  Furthermore, the amount of oligomers contained in (a) PPS to be provided must be 0.7% by weight or less. Even if it is a polymer alloy satisfying the above two melt viscosities, if the amount of the oligomer in the PPS of the component (a) exceeds 0.7% by weight, although it can be extruded as a sheet, an extruder This is not preferable because of the appearance of the surface of the dies, which causes a bad appearance such as damage to the sheet due to the growth of the surface of the generated surface. If the amount of the oligomer is 0.7% by weight or less, it is preferable that the growth of the cane can be reduced and the deterioration of the appearance of the sheet can be prevented.

  In the present invention, an extruded sheet obtained from a polymer alloy can be obtained in a desired thickness by various known extrusion methods using polymer alloy pellets prepared in advance. Moreover, using the extrusion sheet molding machine which has the process of melt-kneading the above-mentioned (a)-(d) component and polymer-alloying, and the process of forming into a sheet simultaneously, desired thickness (1000 micrometers or less and 100 micrometers or less) A sheet can also be obtained.

  A specific extrusion molding method for obtaining the extrusion sheet of the present invention includes a T-die extrusion method. In this case, the extrusion sheet may be produced without stretching or may be uniaxially stretched. Alternatively, biaxial stretching is also possible. In particular, when it is desired to increase the strength of the extruded sheet of the present invention, a stretching method is preferred. Also, in this T-die extrusion molding method, in addition to a single layer sheet of polymer alloy, an extrusion molding method using a multi-layer T-die by a manifold method or a feed block method capable of multi-layering, a polymer alloy and other resins are used. A multilayer sheet can be obtained. It is within the scope of the present invention that at least one of the multilayers is composed of the above-described polymer alloy. Further, a multilayer sheet having a layer made of the above-described polymer alloy and a layer made of a metal such as copper, specifically, a copper-clad laminate is also within the scope of the present invention.

  Furthermore, in addition to the above-described T-die extrusion molding method, a sheet can be produced by using an extrusion molding method called an extrusion tubular molding method or an inflation molding method in order to form a thin sheet. In these production methods, it is possible to control the temperature of the parison by appropriately selecting a suitable temperature from a temperature range of 50 to 290 ° C. so that the polymer alloy parison coming out of the cylinder does not cool immediately. This is extremely important in producing a sheet with uniform sheet thickness and no delamination. In this inflation molding method, in addition to a polymer alloy single-layer sheet, a multilayer sheet made of a polymer alloy and another resin can be obtained using a multilayer die capable of multilayering. Further, the polymer alloy sheet obtained by these methods can be further shaped and used as a polymer alloy sheet-shaped product.

  The extruded sheet of the present invention is excellent in heat resistance, chemical resistance, tear resistance, and heat resistance, and also has a low heat shrinkage, flame resistance, mechanical strength, insulation, dielectric constant and dielectric loss tangent. It has excellent electrical characteristics such as the above, and has excellent hydrolytic resistance. Therefore, the extruded sheet of the present invention can be used for applications requiring these characteristics. For example, printed circuit board materials, printed circuit board peripheral parts, semiconductor packages, semiconductor transport trays, data magnetic tapes, APS photographic films, film capacitors, insulating films, insulating materials such as motors and transformers, speaker diaphragms, automotive film sensors, Examples thereof include an insulating tape for wire cable, a TAB tape, an interlayer insulating material, a toner agitator, and an insulating washer inside a lithium ion battery.

Examples will be described below.
In addition, the used raw material is as follows.

(A) Polyphenylene sulfide resin as component (a-1): According to Example 1 in JP-A-8-253687, a capillograph (manufactured by Toyo Seiki Seisakusho Co., Ltd.) at 300 ° C. at a shear rate of 100 sec ⁻¹ A semi-crosslinked type PPS (a-1) having a melt viscosity of 470 Pa · sec, having a repeating unit of p-phenylene sulfide, and having an oligomer amount of 0.6 wt% determined by methylene chloride extraction was synthesized.
(A-2): Similarly to a-1, the measured melt viscosity has a repeating unit of p-phenylene sulfide of 310 Pa · sec, and the oligomer amount determined by the methylene chloride extraction method is 0.3% by weight. Linear type PPS (a-2) was synthesized.
(A-3): Similar to a-1, it has a repeating unit of p-phenylene sulfide having a measured melt viscosity of 180 Pa · sec, and the amount of oligomer determined by the methylene chloride extraction method is 0.5% by weight. Semi-crosslinked PPS (a-3) was synthesized.
(A-4): Similar to a-1, the measured melt viscosity is 110 Pa · sec, p-phenylene sulfide is a repeating unit, and the amount of oligomer determined by methylene chloride extraction is 0.3% by weight. A type of PPS (a-4) was synthesized.
(A-5): Like a-1, the measured melt viscosity is 75 Pa · sec, has a repeating unit of p-phenylene sulfide, and the amount of oligomer determined by the methylene chloride extraction method is 0.3% by weight linear A type of PPS (a-5) was synthesized.
(A-6): Like a-1, the measured melt viscosity is 38 Pa · sec, has a repeating unit of p-phenylene sulfide, and the amount of oligomer determined by methylene chloride extraction method is 0.5% by weight linear A type of PPS (a-6) was synthesized.
(A-7): Similarly to a-1, the measured melt viscosity is 580 Pa · sec, p-phenylene sulfide is a repeating unit, and the oligomer amount determined by the methylene chloride extraction method is 0.5% by weight. Semi-crosslinked PPS (a-7) was synthesized.
(A-8): Similarly to a-1, the measured melt viscosity is 240 Pa · sec, it has a repeating unit of p-phenylene sulfide, and the oligomer amount determined by the methylene chloride extraction method is 0.8% by weight. Cross-linked PPS (a-8) was synthesized.
(A-9): Similarly to a-1, the measured melt viscosity is 310 Pa · sec, it has a repeating unit of p-phenylene sulfide, and the oligomer amount determined by the methylene chloride extraction method is 1.1% by weight. Cross-linked PPS (a-8) was synthesized.

(B) Component polyphenylene ether resin (b-1): 2,6-xylenol (manufactured by Nippon Klenol Co., Ltd., product name 2,6-xylenol) is oxidatively polymerized, and GPC (gel permeation chromatography) is used. A polyphenylene ether (b-1) having a number average molecular weight of 24,000 measured and converted to polystyrene was synthesized.
(B-2): Number average molecular weight of 2,6-xylenol (manufactured by Nippon Klenol Co., Ltd., product name 2,6-xylenol) by oxidative polymerization, measured using GPC (gel permeation chromatography), and converted to polystyrene. Was synthesized 13,000 polyphenylene ether (b-2).

(C) Elastomer of component (c-1): According to (JP-A-60-79005), it has a structure of polystyrene block-hydrogenated polybutadiene-polystyrene block, the amount of bound styrene is 33%, polybutadiene A hydrogenated block copolymer (c-1) having a 1,2-vinyl bond content of 47%, a polystyrene chain number average molecular weight of 29000 and a polybutadiene portion hydrogenation ratio of 99.8% was synthesized.
(C-2): According to (JP-A-60-79005), it has a polystyrene block-hydrogenated polybutadiene-polystyrene block structure, the amount of bound styrene is 60%, and the polybutadiene portion is 1,2- A hydrogenated block copolymer (c-2) having a vinyl bond content of 55%, a polystyrene chain number average molecular weight of 24,000, and a polybutadiene moiety hydrogenation rate of 99.2% was synthesized.
(C-3): ethylene having a melt flow rate of 0.5 g / 10 min measured under conditions of density 0.86, temperature 230 ° C., and load 21.2 N? An octene copolymer (c-3) was synthesized.

(D) Component Styrene Copolymer (d-1): A styrene-glycidyl methacrylate copolymer (weight average molecular weight 110,000) (d-1) containing 5% by weight of glycidyl methacrylate was synthesized.
(D-2): A styrene-2-isopropenyl-2-oxazoline copolymer (weight average molecular weight 146,000) (d-2) containing 5% by weight of 2-isopropenyl-2-oxazoline was synthesized.

Polymer alloy sheet molding and evaluation were performed according to the following method.
(1) Sheet Molding Polymer alloy pellets are coated with a single-screw extruder (Union Plastic Co., Ltd., screw diameter 40 mm, L / D 28) and a coat hanger die (width 400 mm, die lip spacing 0. 6 mm) and extruded into a sheet at a cylinder temperature and a die temperature of 300 ° C. The molten sheet extruded from the coat hanger die was wound up as a sheet through a cooling roll having a temperature of 120 ° C. The sheet thickness was adjusted by the discharge amount of the extruder and the rotation speed of the take-up roll.

(2) Molten sheet of polymer alloy-drawdown evaluation Extruded from a coat hanger die (width 400mm, die lip interval 0.6mm) positioned perpendicular to the ground at a cylinder temperature and a die temperature of 300 ° C using a single screw extruder. The resulting molten sheet was observed to sag due to its own weight, and a drawdown evaluation of the polymer alloy used was performed based on the following criteria.
○: Drawdown did not occur.
X: Drawdown was observed.

(3) Evaluation of thickness unevenness of polymer alloy sheet The take-up roll was adjusted so that the thickness of the central part of the sheet width was 150 μm, and a polymer alloy sheet was formed to 50 m. The thickness was measured using a digital thickness gauge (Ozaki Mfg. Co., Ltd .: G2-205), and (the average value of the maximum thickness of the sheet width central portion and the minimum thickness of the central portion of the sheet width) / (average thickness value of the central portion of the sheet width) The numerical value expressed in% was evaluated as thickness unevenness (%).
It was judged that the thickness unevenness was larger as the numerical value (%) was larger.

(4) Evaluation of surface appearance of polymer alloy sheet The take-up roll was adjusted so that the thickness of the central part of the sheet width was 150 μm, a polymer alloy sheet was prepared, and a digital variable angle gloss was produced by a method according to JIS-Z8741. Using a meter (Nippon Denshoku Kogyo Co., Ltd .: VGS-1D type), the glossiness of incident light reflected light variable angle 60 ° was measured and evaluated as a surface appearance.
In addition, when the sheet was formed with an extruder, the T-die portion was markedly accumulated, and the samples that deteriorated the appearance of the sheet surface were not measured for glossiness, and it was determined that the occurrence of mesas during film formation was undesirable.

(5) Measurement of Melt Viscosity of Polymer Alloy Using a capillograph (manufactured by Toyo Seiki Seisakusho Co., Ltd.), a capillary having a capillary length = 10 mm, a capillary diameter = 1 mm, a temperature of 300 ° C. and a shear rate of 100 sec ⁻¹ The melt viscosity of the alloy was measured.

(6) Measurement of average particle size of dispersed phase (a) component in polymer alloy Cut ultra-thin sections of polymer alloy pellets with an ultramicrotome, etc., oxidatively stain them with ruthenium tetrachloride, and transmit the stained sections. A photograph is taken with a scanning electron microscope, developed as a 10000-fold photograph, the photograph is taken into a scanner with a resolution of 400 dpi, and dispersed using particle analysis software of an image analyzer (IP-1000 manufactured by Asahi Kasei Co., Ltd.) (a ) The particle size of the component polyphenylene ether resin was measured, and the average particle size was calculated by the following formula.
Average particle diameter = ΣniDri ³ / ΣniDri ²
(Here, ni is the number of particles having a particle diameter Dri in the photograph, and the particle diameter Dri is the particle diameter when the equivalent area is taken from the particle area in the photograph.)

[Examples 1-9, Comparative Examples 1-15]
Using a twin screw extruder (ZSK-40; manufactured by COPERION WERNER & PFLEDERER, Germany) set at a temperature of 290 to 310 ° C. and a screw rotation speed of 300 rpm, the composition ratios shown in Table 1 are obtained from the first raw material supply port of the extruder. Each component was supplied and heated and melt-kneaded, and the first vent port and the second vent port after melt-kneading were deaerated at an absolute vacuum pressure of 95 kPa or less and melt-kneaded to obtain a polymer alloy as pellets. . The polymer alloy obtained here is formed into a sheet using a single screw extruder, and the dispersion average is determined by checking the drawdown, the thickness unevenness of the sheet, the surface appearance, the melt viscosity and the morphology of the polymer alloy used. The particle size was measured. These results are also shown in Tables 1-2.

[Comparative Example 9]
Additional test of JP-A-1-213361 A polyphenylene sulfide resin corresponding to the polyphenylene sulfide resin (PPS: melt viscosity at a shear rate of 1000 sec ⁻¹ at 320 ° C. of about 2600 poise) described in Examples of JP-A-1-213361 The melt viscosity at a temperature of 300 ° C. and a shear rate of 100 sec ⁻¹ was measured and found to be 950 Pa · sec. Using the polyphenylene sulfide resin having this melt viscosity, a polymer alloy was obtained by the same composition and the same method as in Example 1. The melt viscosity of this polymer alloy at a temperature of 300 ° C. and a shear rate of 100 sec ⁻¹ was measured to be 3500 Pa · sec. Using this polymer alloy, the drawdown during extrusion sheet forming was confirmed, but there was no drawdown at all. In addition, the composition corresponding to Example 1 generated a lot of scum during sheet extrusion. The obtained 150 μm sheet was visually uneven, had no gloss, had a glossiness of 28 with an incident light reflected light variable angle of 60 °, and had a sheet thickness unevenness of 37.2%.

[Comparative Example 10]
Additional test of Japanese Patent Laid-Open No. 2-86652 “Product name: Toprene T-4” of polyphenylene sulfide resin used in the compositions of Example 1, Example 4 and Example 6 of Japanese Patent Laid-Open No. 2-86652, The melt viscosity of “trade name: Toprene T-1” at a temperature of 300 ° C. and a shear rate of 100 sec ⁻¹ was 180 Pa · sec and 24 Pa · sec, respectively. In the compositions described in Example 1, Example 4 and Example 6 of JP-A-2-86652, resin compositions were prepared by the methods described in Examples 1 to 3 using the corresponding components. did. The melt viscosity at a temperature of 300 ° C. and a shear rate of 100 sec ⁻¹ of the resin compositions corresponding to Example 1, Example 4 and Example 6 obtained in this additional test were 1800 Pa · sec, 2100 Pa · sec and 1500 Pa · sec, respectively. there were. These resin compositions were used to confirm drawdown during extrusion sheet molding, but there was no drawdown at all. However, there is a lot of scumming at the T-die part, and die lines are generated by the scouring. The resulting 150 μm sheet is visually uneven, has no gloss, and has a glossiness of 43 ° for the incident light reflected light variable angle of 43 °. , 41 and 44. The thickness unevenness of the sheet was 20.6%, 23.5%, and 26.6%, respectively.

[Comparative Example 11]
Additional test of Japanese Patent Application Laid-Open No. 3-20356 The “trade name: Ryton M2588” of the polyphenylene sulfide resin used in Example 1, Example 2 and Example 4 of Japanese Patent Application Laid-Open No. 3-20356 is sheared at a temperature of 300 ° C. The melt viscosity at a speed of 100 sec ⁻¹ was measured and found to be 90 Pa · sec. In the compositions described in Example 1, Example 2 and Example 4 of JP-A-3-20356, resin compositions were prepared by the methods described in Examples 1 to 3 using the corresponding blending components. did. In addition, since no description corresponding to the molecular weight is found in the PPE used in this example, 2,6-xylenol is oxidized and measured using GPC (gel permeation chromatography) and converted to polystyrene. PPE having a number average molecular weight of 24,000 was used. The melt viscosity at a temperature of 300 ° C. and a shear rate of 100 sec ⁻¹ of the resin compositions corresponding to Example 1, Example 2 and Example 4 obtained in this additional test were 1600 Pa · sec, 2400 Pa · sec and 1400 Pa · sec, respectively. there were. These resin compositions were used to confirm drawdown during extrusion sheet molding, but there was no drawdown at all. In addition, there was little occurrence of cracks in the T-die part during sheet extrusion. However, the obtained sheet was visually uneven, had no gloss, and had a glossiness of 35, 29, and 34 at an incident light reflected light variable angle of 60 °, respectively. The thickness unevenness of the obtained sheet was 26.7%, 28.9%, and 21.2%, respectively.

[Comparative Example 12]
Additional test of Japanese Patent Laid-Open No. 9-161737 “Product name: Ryton L2120”, “Product of the polyphenylene sulfide resin used in the compositions of Example 1, Example 4 and Example 6 of Japanese Patent Laid-Open No. 9-161737 “Name: Ryton M2588” was measured for melt viscosity at a temperature of 300 ° C. and a shear rate of 100 sec ⁻¹ and found to be 350 Pa · sec and 90 Pa · sec, respectively. In the compositions described in Example 1, Example 4 and Example 6 of JP-A-9-161737, resin compositions were prepared by the methods described in Examples 1 to 7 using the corresponding components. did. The melt compositions at temperatures of 300 ° C. and shear rates of 100 sec ⁻¹ of the resin compositions corresponding to Example 1, Example 4 and Example 6 obtained in this additional test were 1800 Pa · sec, 2100 Pa · sec and 1400 Pa · sec, respectively. there were. These resin compositions were used to confirm drawdown during extrusion sheet molding, but there was no drawdown at all. In addition, regarding the occurrence of cracks in the T-die part during sheet extrusion, the compositions corresponding to Example 1 and Example 4 generated a lot of cracks in the T-die part, but the resin composition corresponding to Example 6 had a T-die part. There were few occurrences of mains. However, the obtained sheet was visually uneven, had no gloss, and had a glossiness of 42, 40, and 43 at an incident light reflected light variable angle of 60 °, respectively. The thickness unevenness of the obtained 150 μm sheet was 19.7%, 21.3%, and 19.3%, respectively.

[Comparative Example 13]
Supplementary Examination of Japanese Patent Laid-Open No. 2002-12764 (a-1) and (a-2) of the polyphenylene sulfide resins used in the compositions of Example 1, Example 2 and Example 5 of Japanese Patent Laid-Open No. 2002-12764 ) Was measured for a melt viscosity at a temperature of 300 ° C. and a shear rate of 100 sec ⁻¹ and found to be 75 Pa · sec and 74 Pa · sec, respectively. In the compositions described in Example 1, Example 2 and Example 5 of JP-A No. 2002-12764, resin compositions were prepared by the methods described in Examples 1 to 14 using the corresponding components. did. The melt viscosities of the resin compositions corresponding to Example 1, Example 2 and Example 5 obtained in this additional test at a temperature of 300 ° C. and a shear rate of 100 sec ⁻¹ are 650 Pa · sec, 640 Pa · sec and 950 Pa · sec, respectively. there were. When the drawdown at the time of extrusion sheet molding was confirmed using these resin compositions, the composition of Example 1 and Example 2 generated drawdown, and the sheet could not be produced stably. Moreover, the composition of Example 5 was able to obtain a sheet without any drawdown. In addition, regarding the occurrence of a sag in the T-die part during sheet extrusion, the resin compositions corresponding to Example 1, Example 2 and Example 5 generated a small amount of sag in the T-die part. However, the obtained sheet of the composition of Example 5 was visually uneven, had no gloss, and had a glossiness of 20 when the incident light reflected light deflection angle was 60 °. The thickness unevenness of the 150 μm sheet of Example 5 obtained was 28.6%.

[Comparative Example 14]
Additional Examination of WO2006 / 067902 A1 Publication (a-1), (a-2), (a) of the polyphenylene sulfide resin used in the compositions of Example 14, Example 18 and Example 19 of WO2006 / 067902 A1 Publication -3), (b-1), (b-2), and (b-3) were measured for melt viscosity at a temperature of 300 ° C. and a shear rate of 100 sec ⁻¹ , respectively, 75 Pa · sec, 45 Pa · sec, 15 Pa, respectively. · Sec, 74 Pa · sec, 75 Pa · sec and 70 Pa · sec. The resin composition was created by the method as described in Examples 1-31 using each compounding component corresponded to the composition described in Example 14, Example 18, and Example 19 of WO2006 / 067902 A1 gazette. The melt viscosity at a temperature of 300 ° C. and a shear rate of 100 sec ⁻¹ of the resin compositions corresponding to Example 14, Example 18 and Example 19 obtained in this additional test were 600 Pa · sec, 920 Pa · sec and 800 Pa · sec, respectively. there were. When the drawdown at the time of extrusion sheet molding was confirmed using these resin compositions, the compositions of Example 14, Example 18 and Example 19 generated drawdown and could not produce a sheet stably. . In addition, regarding the occurrence of burrs in the T-die part during sheet extrusion, the resin compositions corresponding to Example 14, Example 18 and Example 19 generated less burrs in the T-die part.

[Comparative Example 15]
Additional test of WO2006 / 082902 A1 The polyphenylene sulfide resin used in the composition of the outer layer of Example 5 of WO2006 / 089022 A1 was measured for a melt viscosity at a temperature of 300 ° C. and a shear rate of 100 sec ^−1. Met. A resin composition was prepared by the production method of the present invention using each compounding component corresponding to the composition described in the outer layer of Example 5 of WO2006 / 082902 A1. The melt viscosity at a temperature of 300 ° C. and a shear rate of 100 sec ⁻¹ of the resin composition corresponding to the outer layer of Example 5 obtained in this additional test was 630 Pa · sec. When this resin composition was used to confirm drawdown during extrusion sheet molding, drawdown occurred and the sheet could not be produced stably. In addition, regarding the occurrence of a sag in the T-die part during sheet extrusion, the resin composition corresponding to the outer layer part in Example 5 generated a small amount of sag in the T-die part.
It is understood that the multilayer sheet composed of the outer layer and the inner layer described in Example 5 of this WO2006 / 082902 A1 publication can prevent the drawdown of the multilayer sheet extruded from the T-die by combining the inner layer and the outer layer. The
From these results, the polyphenylene sulfide resin used had a temperature of 300 ° C., a shear viscosity of 100 sec ^{−1 and} a melt viscosity of 100 to 500 Pa · sec, and the average particle of the component (b) polyphenylene ether resin dispersed in the polymer alloy When the diameter is 10 μm or less and the polymer alloy temperature is 300 ° C. and the melt viscosity at a shear rate of 100 sec ⁻¹ satisfies 200 to 1200 Pa · sec, there is no drawdown during extrusion sheet molding, and sheet molding processability ( It has been clarified that a sheet having excellent film forming property and less surface thickness unevenness and excellent surface appearance can be obtained.

  An extruded sheet obtained by extruding a polymer alloy for forming an extruded sheet according to the present invention is a sheet having a thickness of 1000 μm or less that is excellent in molding processability (film forming property) and has a good surface appearance with little thickness unevenness. Printed circuit board materials, printed circuit board peripheral parts, semiconductor packages, semiconductor transport trays, data magnetic tape, APS photographic film, film capacitors, insulating films, insulating materials such as motors and transformers, speaker diaphragms, automotive film sensors Insulation tape for wire cables, TAB tape, interlayer insulation material, toner agitator, sheet for insulation washer, etc. inside lithium ion battery, and material for film region.

Claims (12)

(A) a matrix phase comprising a polyphenylene sulfide resin;
(B) a dispersed phase comprising a polyphenylene ether resin;
(D) a styrene copolymer having at least one functional group of a glycidyl group and an oxazolyl group;
Extruded sheet obtained by extrusion molding a polymer alloy containing
The polyphenylene sulfide resin has a melt viscosity at 300 ° C. at a shear rate of 100 sec ⁻¹ of 100 to 500 Pa · sec, and an oligomer content of 0.7% by weight or less,
An average particle size of the dispersed phase is 10 μm or less,
The extrusion sheet | seat whose 300 degreeC melt viscosity in the shear rate of 100 sec < ^-1 > of the said polymer alloy is 200-1200 Pa.sec.   The extruded sheet according to claim 1, wherein (c) an elastomer is present in the dispersed phase. The polymer alloy is
(A) 45 to 95% by weight of polyphenylene sulfide resin;
(B) 5 to 55% by weight of a polyphenylene ether resin,
1 to 5 parts by weight of a styrene-based copolymer having at least one functional group of (d) glycidyl group and oxazolyl group with respect to 100 parts by weight of the total of component (a) and component (b);
The extruded sheet according to claim 1 or 2, comprising: The polymer alloy is
(A) 45 to 95% by weight of polyphenylene sulfide resin;
(B) 5 to 55% by weight of a polyphenylene ether resin,
(C) 1-15 parts by weight of elastomer for 100 parts by weight of the total of component (a) and component (b),
(D) 1-5 parts by weight of a styrene copolymer having at least one functional group of a glycidyl group and an oxazolyl group;
The extrusion-molded sheet according to any one of claims 1 to 3, comprising:   The extruded sheet according to any one of claims 1 to 4, wherein the (a) polyphenylene sulfide resin is linear polyphenylene sulfide or cross-linked polyphenylene sulfide.   The extruded sheet according to any one of claims 1 to 4, wherein the (a) polyphenylene sulfide resin contains a linear polyphenylene sulfide and a crosslinked polyphenylene sulfide.   The extrusion molded sheet according to any one of claims 1 to 6, wherein the component (b) is polyphenylene ether 100% by weight or polyphenylene ether / styrene resin = 1 to 99% by weight / 99 to 1% by weight. .   (C) a block copolymer obtained by copolymerizing a vinyl aromatic compound and a conjugated diene compound, an hydrogenated block copolymer obtained by further hydrogenation reaction of the block copolymer, and ethylene / The extruded sheet according to any one of claims 2 to 7, which is at least one selected from the group consisting of α-olefin copolymers.   (D) The styrene copolymer is a styrene-glycidyl methacrylate copolymer, a styrene-glycidyl methacrylate-methyl methacrylate copolymer, a styrene-glycidyl methacrylate-acrylonitrile copolymer, a styrene-vinyl oxazoline copolymer, or a styrene-vinyl. An oxazoline-acrylonitrile copolymer, a graft copolymer in which an ethylene-glycidyl methacrylate copolymer is grafted with a styrene monomer, and a graft copolymer in which an ethylene-glycidyl methacrylate copolymer is grafted with a styrene monomer and acrylonitrile. It is at least 1 sort (s) chosen from the inside, The extrusion molding sheet as described in any one of Claims 3-8.   The extruded sheet according to any one of claims 1 to 9, which is a single layer or a multilayer.   The extruded sheet according to any one of claims 1 to 10, wherein the extruded sheet has a thickness of 1000 µm or less.   The molded object shape | molded using the extruded sheet as described in any one of Claims 1-11.