JP4758757B2 - Extruded film forming method - Google Patents

Description

  The present invention relates to a method for extruding a polyphenylene ether resin having excellent heat resistance and flame retardancy and excellent surface smoothness. In particular, the present invention relates to a film manufacturing method.

  Polyphenylene ether resin has excellent properties such as heat resistance, hot water resistance, dimensional stability and mechanical and electrical properties, but there are few examples of use for films, and polyphenylene ether resin films that are practically used are The heat resistance is low because it contains a substantial amount of polystyrene and a large amount of flame retardant. High heat-resistant films that make use of the inherent heat resistance of polyphenylene ether resins cause high temperature molding in the manufacturing process and high adhesion to metal, resulting in the formation of mesani near the die lip and deposits inside the die. As a result, there was a problem that a die line was generated on the film.

  In order to solve these problems, Patent Documents 1 and 2 disclose that R and / or corner cutting of a die tip corner and a step to the die tip are provided for the purpose of reducing die lines when extruding polyester. It has been proposed to grant.

  Patent Documents 3 and 4 propose using a die in which the vicinity of the die of the extruder is coated with fluororesin or vanadium carbide for the purpose of reducing the mean when the nylon and glass fiber are compounded. However, there is no description about polyphenylene ether resin or film.

  On the other hand, Patent Document 5 discloses that blending a polymer such as polyphenylene ether with liquid crystal polyester has an effect of suppressing sag when the composition is made into a film.

  However, any of these techniques is still insufficient as a method for forming a polyphenylene ether-based resin film.

JP-A-9-207194 Japanese Patent Laid-Open No. 9-207195 Japanese Patent Laid-Open No. 5-220812 JP-A-11-138616 JP 2002-241515 A

  An object of the present invention is to provide a polyphenylene ether-based resin film that has excellent heat resistance and flame retardancy, no die line, and excellent surface smoothness. An object of the present invention is to provide a molding method capable of molding with good production stability.

  As a result of earnestly examining the technology for achieving the above-mentioned problems, the present inventors have found that when a polyphenylene ether-based resin is melt-extruded into a film shape, the tip of the die is molded using a die having an acute angle. It has been found that a polyphenylene ether resin film having excellent surface smoothness with no die line can be obtained, and the present invention has been completed.

That is, according to the first aspect of the present invention, when at least (A) the polyphenylene ether-based resin is melt-extruded, the angle formed by the streamline at the center of the resin at the die tip and the outer wall surface of the die at the die tip is 75. A die that is not more than ° (however, the maximum height (Ryb) in JIS B 0601 (1994) as the surface roughness of the outer wall surface of the die at the tip of the die is the maximum height of the surface roughness of the inner surface of the die that contacts the molten resin) The arithmetic average roughness (Rab) of the surface roughness of the outer surface of the die that is larger than (Rya) or the surface roughness of the outer surface of the die at the die tip is in contact with the molten resin (Raa) A die that satisfies the condition that it is larger than a die) .

In the extruded film forming method of the present invention,
The film thickness is 0.005 to 0.20 mm;
The die inner surface of the die that is in contact with the molten resin is coated with at least one material selected from the group consisting of metals, metal oxides, metal nitrides, polymers, carbon-based materials, ceramics,
(A) melt extrusion molding a resin composition containing 0.1 to 30 parts by mass of (B) liquid crystalline polyester with respect to 100 parts by mass of a polyphenylene ether resin;
Is included as a preferred embodiment.

  According to the present invention, a polyphenylene ether-based resin film having excellent heat resistance and flame retardancy, no die line, and excellent surface smoothness can be molded by extrusion molding. There was no occurrence, and it was possible to produce the film stably.

  Hereinafter, the present invention will be specifically described.

  In the extrusion molding of the present invention, at least (A) polyphenylene ether resin is used as the resin material.

  The (A) polyphenylene ether resin used in the present invention has a repeating unit structure represented by the following structural formula (1), and the reduced viscosity (0.5 g / dl, chloroform solution, measured at 30 ° C.) is 0. A homopolymer and / or copolymer in the range of 15 to 1.0 dl / g. A more preferred reduced viscosity is in the range of 0.20 to 0.70 dl / g, most preferably in the range of 0.40 to 0.60.

In the above formula, R ₁ and R ₄ each independently represent any of hydrogen, primary or secondary lower alkyl, phenyl, aminoalkyl, and hydrocarbonoxy. R ₂ and R ₃ each independently represent hydrogen, primary or secondary lower alkyl, or phenyl.

  Specific examples of the (A) polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), and poly (2,6-dimethyl-1,4-phenylene ether). (2-methyl-6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like, and 2,6-dimethylphenol and other phenols A polyphenylene ether copolymer such as a copolymer with 2,3,6-trimethylphenol or 2-methyl-6-butylphenol is also included. Of these, poly (2,6-dimethyl-1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable, and poly (2,6-dimethyl-1 , 4-phenylene ether).

  The (A) polyphenylene ether-based resin may be used as it is after the polymerization step, or may be pelletized using an extruder or the like.

  The polyphenylene ether resin (A) used in the present invention includes polyphenylene ethers functionalized with various dienophile compounds. Examples of various dienophile compounds include maleic anhydride, maleic acid, fumaric acid, phenylmaleimide, itaconic acid, acrylic acid, methacrylic acid, methyl allylate, methyl methacrylate, glycidyl acrylate, glycidyl methacrylate, stearyl acrylate, styrene, and the like. Can be mentioned.

  The polyphenylene ether resin (A) used in 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, acrylonitrile-styrene copolymer, and the like. When a mixture of a polyphenylene ether resin and an aromatic vinyl polymer is used, the polyphenylene ether resin is 70 wt% or more, preferably 80 wt% or more based on the total amount of the polyphenylene ether resin and the aromatic vinyl polymer. is there.

  The extrusion molding method of the present invention refers to a molding method in which the component (A) is melted and subsequently extruded. Specifically, the melt extruder may be a molding machine having a function of melting and extruding, and may be any machine that can operate continuously even if the melting function and the extrusion function are different apparatuses. For example, generally known melt extruders include, but are not limited to, single screw extruders and twin screw extruders. In addition, the resin composition containing the component (A) and the component (B) to be described later, and the component (C) and / or the component (D) to be described later is once melt-kneaded in an extruder and pelletized. It may be put into an extrusion molding machine, or each component may be fed into a hopper of a shaping extrusion molding machine.

  The die used in the present invention is a shaping die used for extrusion molding. Specific examples of die types include narrow-sense T dies, coat-hanger dies, fish-tail dies and other broad-sense dies, circular dies used for inflation molding, profile dies used for deformed shapes, and wire coating molding. Crosshead dies that are used, multilayer dies that are used to form multilayer sheets, and the like, but are not limited to these examples.

  The die used in the present invention is characterized in that the angle formed by the streamline at the center of the resin at the die tip and the outer wall surface of the die is an acute angle of 75 ° or less. FIG. 1 is a schematic cross-sectional view of the die tip during the extrusion molding process of the present invention. As shown in FIG. 1, the angle 3 formed by the streamline 1 at the center of the resin at the die tip and the outer wall surface 2 of the die at the die tip is 75 ° or less. A preferable range of the angle is 60 ° or less. More preferably, it is 45 ° or less. Further, the tip corner portion 4 may be subjected to R processing, corner cut processing, or the like. Furthermore, the die outer wall surface 5 other than the die tip is not particularly limited.

  In the die used in the present invention, the inner surface of the die that is in contact with the molten resin is coated with at least one material selected from the group consisting of metals, metal oxides, metal nitrides, polymers, carbon-based materials, and ceramics. Preferably it is. These are preferably selected to have low reactivity.

Examples of the metal used for coating the inner surface of the die in the present invention include gold, nickel, aluminum, and SUS304. As the metal oxide, chromium oxide and nickel oxide are preferable, and nickel oxide is particularly preferable. Furthermore, examples of the metal nitride include chromium nitride and titanium nitride. Polymers include thermosetting resins such as polyimide, silicone resin, phenolic resin, melamine resin, urea resin, unsaturated polyester resin, fluororesin, reinforced polyetheretherketone, high heat resistance thermoplastic such as polyamideimide Resins are preferred. More preferably, the thermosetting resin is polyimide or a crosslinked silicone resin, and the thermoplastic resin is polytetrafluoroethylene (PTFE). Examples of the carbon-based material include a carbon-based material (DLC) mainly composed of amorphous carbon containing sp ³ carbon. Examples of the ceramic include Si ₃ N ₄ , Ti—N—Al, SiO ₂ —Cr ₂ O ₃ , and TiN.

  In the present invention, as the resin material, in addition to the above (A) polyphenylene ether-based resin alone, at least (B) liquid crystalline polyester is contained in an amount of 0.1 to 30 parts by mass with respect to 100 parts by mass of the (A) polyphenylene ether-based resin. The resin composition to be used is preferably used.

  The (B) liquid crystal polyester used in the present invention is a polyester called a thermotropic liquid crystal polymer, and known ones can be used. For example, a thermotropic liquid crystal polyester mainly composed of p-hydroxybenzoic acid and polyethylene terephthalate, a thermotropic liquid crystal polyester mainly composed of p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid, and p-hydroxybenzoic acid. Examples thereof include thermotropic liquid crystal polyesters having acid and 4,4′-dihydroxybiphenyl and terephthalic acid as main structural units, and are not particularly limited. The liquid crystal polyester (B) used in the present invention includes a repeating unit represented by the following structural formula (A) and / or a repeating unit represented by (B), and a repeating unit represented by (C) as necessary. And / or what consists of a repeating unit shown by (d) is preferable.

  Here, the repeating units represented by (i) and (b) are respectively a repeating unit of polyester produced from p-hydroxybenzoic acid and a repeating unit produced from 2-hydroxy-6-naphthoic acid. X in the repeating units represented by the above (c) and (d) can independently select one or more types of structures represented by the following structural formula.

  The repeating unit represented by the structural formula (c) is preferably a repeating unit generated from each of ethylene glycol, hydroquinone, 4,4′-dihydroxybiphenyl, 2,6-dihydroxynaphthalene and bisphenol A, and more preferably Is a repeating unit produced from each of ethylene glycol, 4,4′-dihydroxybiphenyl and hydroquinone, and particularly preferred is a repeating unit produced from each of ethylene glycol and 4,4′-dihydroxybiphenyl.

  The repeating unit represented by the structural formula (d) is preferably a repeating unit formed from each of terephthalic acid, isophthalic acid and 2,6-dicarboxynaphthalene, and more preferably each of terephthalic acid and isophthalic acid. Is a repeating unit generated from

As the repeating units represented by the structural formula (c) and the structural formula (d), at least one or two or more of the repeating units listed above can be used in combination. Specifically, when two or more types are used in combination, in the structural formula (c)
1) Repeating unit generated from ethylene glycol / Repeating unit generated from hydroquinone,
2) Repeating units generated from ethylene glycol / 4 repeating units generated from 4,4′-dihydroxybiphenyl,
3) Repeating units generated from hydroquinone / 4 repeating units generated from 4,4′-dihydroxybiphenyl,
And so on.

In addition, as the repeating unit represented by the structural formula (d),
1) Repeating unit generated from terephthalic acid / Repeating unit generated from isophthalic acid,
2) Repeating unit generated from terephthalic acid / 2 Repeating unit generated from 2,6-dicarboxynaphthalene,
And so on.

  Here, the amount of terephthalic acid is preferably 40 wt% or more, more preferably 60 wt% or more, and particularly preferably 80 wt% or more in the two components. By setting the amount of terephthalic acid to 40 wt% or more of the two components, a resin composition having relatively good fluidity and heat resistance can be obtained. The ratio of the repeating units (a), (b), (c), and (d) in the liquid crystal polyester (B) component is not particularly limited. However, the repeating units (c) and (d) are basically in equimolar amounts.

A repeating unit represented by the following structural formula (e) consisting of repeating units (c) and (d) can also be used as a repeating unit in the component (B). In particular,
1) Repeating units generated from ethylene glycol and terephthalic acid,
2) Repeating units generated from hydroquinone and terephthalic acid,
3) a structural unit formed from 4,4′-dihydroxybiphenyl and terephthalic acid,
4) a structural unit formed from 4,4′-dihydroxybiphenyl and isophthalic acid,
5) Structural units generated from bisphenol A and terephthalic acid,
And so on.

  The liquid crystal polyester component (B) used in the present invention may contain other aromatic dicarboxylic acids, aromatic diols, and aromatic hydroxycarboxylic acids within a small range that does not impair the features and effects of the present invention, if necessary. Structural units generated from can be introduced.

  The temperature at which the liquid crystal polyester component (B) used in the present invention starts to show a liquid crystal state at the time of melting (hereinafter referred to as “liquid crystal start temperature”) is preferably 150 to 350 ° C., more preferably 180 to 320 ° C. . It is preferable to set the liquid crystal start temperature within this range because black foreign substances are reduced in the obtained resin film.

  It is preferable that (B) liquid crystalline polyester used for this invention contains 0.1-30 mass parts with respect to 100 mass parts of (A) polyphenylene ether-type resin. Furthermore, 1-20 mass parts is preferable from a heat resistant and fluidity | liquidity viewpoint of a resin composition, and 2-10 mass parts is especially preferable.

In the “(A) resin composition containing 0.1 to 30 parts by mass of liquid crystalline polyester with respect to (A) 100 parts by mass of polyphenylene ether-based resin” used in the present invention, (A) component 100 is further included. It is preferable to include 0.1 to 20 parts by mass of (C) a compound containing a metal element of I, II, III, or IV relative to parts by mass. More preferably, the component (C) is ZnO and / or Mg (OH) ₂ . Further, it is more preferable that 0.1 to 5 parts by mass of (D) a silane compound having an amino group is included with respect to 100 parts by mass of component (A).

  The polyphenylene ether-based resin film of the present invention has a thickness of 0.001 to 2.0 mm, preferably 0.005 to 0.50 mm, and more preferably 0.005 to 0.20 mm. Sometimes called a sheet.

  In the present invention, in addition to the above-mentioned components, other additional components, such as antioxidants, flame retardants (organic phosphate ester compounds, phosphazene-based compounds), as necessary, as long as the characteristics and effects of the present invention are not impaired. Compound), elastomer (ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene / non-conjugated diene copolymer, ethylene / ethyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, Ethylene / vinyl acetate / glycidyl methacrylate copolymer and ethylene / propylene-g-maleic anhydride copolymer, styrene copolymer such as ABS, polyester polyether elastomer, polyester polyester elastomer, vinyl aromatic compound-conjugated diene Compound block copolymer, vinyl aromatic compound-conjugate Hydrogenated products of ene compound block copolymers), plasticizers (oil, low molecular weight polyethylene, epoxidized soybean oil, polyethylene glycol, fatty acid esters, etc.), flame retardant aids, weather resistance (light) improvers, for polyolefins Nucleating agents and various colorants may be added.

  In the present invention, when the components (A), (B), (C), and (D) are kneaded, the order and method of kneading are not particularly limited.

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

  The present invention will be described below based on film forming examples. However, the present invention is not limited to film forming unless it exceeds the gist. The same applies to the target resin and the covering material.

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

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

[Production Example 3]
Production Example of Polyphenylene Ether Resin Composition (a) 100 parts by mass of polyphenylene ether (PPE-1), 6 parts by mass of liquid crystalline polyester (LCP-1), and zinc oxide (ZnO, UnionPay A (registered trademark), Toho Zinc Co., Ltd. )) 0.8 parts by weight of the top feed to the twin-screw extruder with a vent port (ZSK-25; WERNER & PFLIDELER, D = 25mm, L / D = 42) set at a barrel set temperature of 290 ° C. The mixture was melt-kneaded while vacuum devolatilization with a two-stage vent at a discharge rate of 10 kg / hr and a screw rotation speed of 300 rpm to obtain pellets.

[Production Example 4]
Production Example of Polyphenylene Ether Resin Composition (b) As raw materials, 85 parts by mass of polyphenylene ether (PPE-1), 10 parts by mass of high impact polystyrene (H9405, manufactured by PS Japan Co., Ltd.), GP polystyrene (685, PS Japan) Except having been 5 mass parts, it carried out similarly to manufacture example 3, and obtained the pellet.

  The extrusion molding method and die line evaluation method in this example are shown below.

[Extrusion method]
The obtained pellets were used at a cylinder temperature of 300 ° C. using a single screw extrusion molding machine (manufactured by Union Plastic Co., Ltd., screw diameter 40 mm, L / D28) and coat hanger die (width 400 mm, die lip interval 0.8 mm). Extruded into a film. The number of rotations of the screw and the take-up roll was adjusted so that the thickness was 125 μm.

[Die line evaluation method]
The above extrusion molding was carried out, and the die line resulting from the main accumulated in the vicinity of the die lip was visually observed.
A: The above die line was not observed even after continuous molding for 2 hours or more.
○: In continuous molding for 1.5 hours or less, the die line was not observed, but was slightly observed after 1.5 hours.
Δ: In the continuous molding for 1 hour or less, the above die line was not observed, but was observed after 1 hour.
X: A die line was observed within 1 hour.

[Example 1]
The angle formed by the flow line at the center of the resin at the die tip and the outer wall surface of the die (hereinafter referred to as “tip angle”) is 75 °, and the surface treatment material in the vicinity of the die lip (hereinafter referred to as “coating material”) Using a die with hard chrome, the polyphenylene ether resin composition (hereinafter referred to as “resin composition”) (a) was subjected to extrusion molding by the above extrusion molding method. Die line generation status results were evaluated according to the die line evaluation method.

[Example 2]
Example 1 is the same as Example 1 except that the tip angle of the die is 60 °.

[Example 3]
Example 1 is the same as Example 1 except that the tip angle of the die is 45 °.

[Example 4]
Example 3 is the same as Example 3 except that the resin composition (b) was used instead of the resin composition (a).

[Example 5]
Example 3 is the same as Example 3 except that the covering material is gold.

[Example 6]
Example 3 is the same as Example 3 except that the coating material is nickel.

[Example 7]
Example 3 is the same as Example 3 except that the covering material is PTEF.

[Example 8]
Example 3 is the same as Example 3 except that the coating material is titanium nitride.

[Example 9]
Example 3 is the same as Example 3 except that the coating material is nickel oxide.

[Example 10]
Example 3 is the same as Example 3 except that the coating material is chromium nitride.

[Example 11]
Example 3 is the same as Example 3 except that the covering material is DLC.

[Example 12]
Example 4 is the same as Example 4 except that the covering material is DLC.

[Comparative Example 1]
Example 1 is the same as Example 1 except that the tip angle of the die is 90 °.

[Comparative Example 2]
Instead of the resin composition (a), high-density polyethylene (Suntech S360 (registered trademark), manufactured by Asahi Kasei Chemicals Corporation) is used, and the molding temperature is 250 ° C., which is the same as Comparative Example 1.

[Comparative Example 3]
The same as Comparative Example 1 except that the covering material is gold.

[Comparative Example 4]
The same as Comparative Example 1 except that the covering material is nickel.

[Comparative Example 5]
It is the same as that of the comparative example 1 except a coating | covering material being PTFE.

[Comparative Example 6]
The same as Comparative Example 1 except that the covering material is titanium nitride.

表１から明らかように、本発明によれば、ダイラインのない表面平滑性に優れたポリフェニレンエーテル系樹脂フィルムを成形することができ、メヤニの発生がなく、生産安定性に優れるフィルムの製造方法を提供できることがわかる。

As is apparent from Table 1, according to the present invention, a polyphenylene ether-based resin film having no die line and excellent in surface smoothness can be formed, and there is no generation of mess, and a method for producing a film excellent in production stability is provided. You can see that it can be provided.

It is a schematic sectional drawing of the die | tip front-end | tip part vicinity used for this invention.

Explanation of symbols

1 Streamline at the center 2 Outer wall surface of the die tip 3 Angle formed by the streamline at the center and the outer wall surface of the die (tip angle)
4 Die tip corner 5 Die outer wall 6 Resin 7 Die

Claims (4)

When at least (A) polyphenylene ether-based resin is melt-extruded, a die having an angle between a streamline at the center of the resin at the die tip and a die outer wall surface at the die tip of 75 ° or less (however, The maximum height (Ryb) in JIS B 0601 (1994) as the surface roughness of the die outer wall surface at the tip is greater than the maximum height (Rya) of the surface roughness of the die inner surface with which the molten resin contacts, or The condition that the arithmetic average roughness (Rab) of the surface roughness of the outer surface of the die at the die tip is larger than the arithmetic average roughness (Raa) of the surface roughness of the inner surface of the die in contact with the molten resin is satisfied. Extruded film forming method characterized by using a die) .   The extruded film forming method according to claim 1, wherein the film thickness is 0.005 to 0.20 mm.   The die inner surface of the die that contacts the molten resin is coated with at least one material selected from the group consisting of metals, metal oxides, metal nitrides, polymers, carbon-based materials, and ceramics. Or the extrusion film forming method of 2. 4. The resin composition containing at least 0.1 to 30 parts by weight of (B) liquid crystalline polyester is melt-extruded with respect to 100 parts by weight of (A) polyphenylene ether-based resin. extrusion film molding method according to any one of claims.

Images