JP2012096360A - Reflecting plate with metal film formed - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a reflecting plate in which a metal film is formed in a molding prepared by molding a polyetherimide resin composition which is eminently improved in flowability without spoiling the heat resistance, mechanical strength, and dimensional stability of original properties of a polyetherimide resin.SOLUTION: In the reflecting plate, the metal film is formed in the molding prepared by molding a thermoplastic resin composition which comprises >40 wt.% and ≤99 wt.% of the polyetherimide resin (a) and ≥1 wt.% and <60 wt.% of a polyphenylene sulfide resin (b) [the total amount of (a) and (b) is 100 wt.%] and is melt/kneaded while being stretched and made to flow.

Description

  The present invention relates to a reflector plate in which a metal film is formed on a molded product obtained by molding a thermoplastic resin composition having excellent heat resistance, mechanical strength, and dimensional stability and having dramatically improved melt fluidity.

  Polyetherimide (hereinafter abbreviated as PEI) resin is a super engineering plastic excellent in heat resistance, mechanical strength, flame retardancy, dimensional stability and the like. Especially for mechanical strength, it exhibits tensile strength that cannot be obtained with general-purpose engineering plastics, and has the characteristics of maintaining high strength comparable to general-purpose engineering plastics even at high temperatures around 190 ° C. It is used in various fields such as parts. In addition, PEI resin has a small surface roughness, and can directly form a film on various metals such as aluminum without undercoating called an undercoat, and is also used for various reflecting mirror surfaces. .

  However, since the PEI resin is amorphous, its fluidity is lower than that of general-purpose crystalline engineering plastics such as nylon and PBT, and an improvement in thin moldability is strongly desired.

  For this reason, several techniques related to a thermoplastic resin composition comprising a PEI resin and a polyphenylene sulfide (hereinafter abbreviated as PPS) resin have been reported so far.

  For example, Patent Document 1 discloses a resin composition composed of an alkoxysilane having a polyarylene sulfide, a polyetherimide, an amino group, an epoxy group, and a mercapto group having a tetrahydrofuran extraction rate of 3% by weight or less. However, there is no description about improving the fluidity of polyetherimide by blending polyarylene sulfide with polyetherimide. In addition, although a silane coupling agent having an amino group, an epoxy group, or a mercapto group is added as a compatibilizing agent, the reaction between the compatibilizing agent and polyetherimide or polyarylene sulfide is insufficient. Since the solubility is not good and the interface peels easily, the Izod impact value is low, and there is a defect that warp deformation occurs when heat treatment is performed. Furthermore, the method for producing the resin composition is a general melt-kneading method, and there is no description about a technique for melt-kneading polyetherimide and polyarylene sulfide while stretching and flowing as described in the present application. As described above, in the disclosed technique of Patent Document 1, it is difficult to improve the fluidity of polyetherimide without sacrificing the mechanical strength and dimensional stability inherent in polyetherimide.

  Patent Document 2 discloses a resin composition comprising a polyphenylene sulfide resin, a polyetherimide resin, an amino group, and a silane coupling agent having an epoxy group. However, there is no description about improving the fluidity of the polyetherimide resin by blending the polyphenylene sulfide resin with the polyetherimide resin. In addition, although a silane coupling agent having an amino group or an epoxy group is added as a compatibilizing agent, the reaction between the compatibilizing agent and the polyetherimide resin or polyphenylene sulfide resin is insufficient. Since the solubility is not good and the interface peels easily, the bending strength is low, and there is a defect that warpage deformation occurs when heat treatment is performed. Furthermore, the method for producing the resin composition is a general melt-kneading method, and there is no description about a technique for melt-kneading a polyetherimide resin and a polyphenylene sulfide resin while stretching and flowing as described in the present application. Absent. As described above, in the disclosed technique of Patent Document 2, it is difficult to improve the fluidity of the polyetherimide resin without sacrificing the mechanical strength and dimensional stability inherent in the polyetherimide resin.

  Patent Document 3 discloses a resin composition comprising a polyetherimide resin, a poly (arylene sulfide) resin, and an epoxy compound. However, in any of the examples, the poly (arylene sulfide) resin has a composition exceeding 60% by weight, and the polyether (arylene sulfide) resin is blended in the polyetherimide resin in the range of less than 60% by weight to obtain a polyether. No mention is made of improving the fluidity of the imide resin. In addition, although an epoxy compound is added as a compatibilizing agent, the compatibility between the compatibilizing agent and the polyetherimide resin or poly (arylene sulfide) resin is insufficient, so the compatibility is not good, and the peeling of the interface As a result, the mechanical properties are deteriorated, and warping deformation occurs during the heat treatment. Furthermore, the method for producing the resin composition is a general melt-kneading method, and there is no description about a technique for melt-kneading polyetherimide and poly (arylene sulfide) while stretching and flowing as described in the present application. . As described above, in the disclosed technique of Patent Document 3, it is difficult to improve the fluidity of the polyetherimide resin without sacrificing the mechanical strength, heat distortion temperature, and dimensional stability inherent in the polyetherimide resin. .

  Patent Document 4 discloses a resin composition comprising a polyphenylene sulfide resin having an oligomer content of 1% by weight or less extracted with a polyetherimide resin and methylene chloride. According to this, the fluidity of the resin composition is improved by adding the polyphenylene sulfide resin. However, the compatibility between the polyetherimide resin and the polyphenylene sulfide resin is not sufficient, and peeling at the interface is likely to occur.Therefore, the tensile fracture strength with weld is greatly reduced, and warping deformation is caused during heat treatment. there were. The method for producing the resin composition is a general melt-kneading method, and does not describe any technique for melt-kneading the polyetherimide and the polyarylene sulfide while stretching and flowing as described in the present application. As described above, in the technique disclosed in Patent Document 4, it is difficult to improve the fluidity of the polyetherimide resin without sacrificing the mechanical strength and dimensional stability inherent in the polyetherimide resin.

Japanese Patent Laid-Open No. 4-130158 (Claims) JP-A-5-86293 (Claims) JP-A-8-176439 (Claims) Japanese Patent Laid-Open No. 11-80545 (Claims)

  It is an object of the present invention to obtain a reflecting plate in which a metal film is formed on a molded product obtained by molding a thermoplastic resin composition having excellent heat resistance, mechanical strength, and dimensional stability and dramatically improved melt fluidity. And

As a result of intensive studies to solve the above-described problems, the reflector having the metal film of the present invention has the following configuration.
1. The total amount of (a) and (b) is 100% by weight, (a) a polyetherimide resin more than 40% by weight and 99% by weight or less, (b) a polyphenylene sulfide resin of 1% by weight to less than 60% by weight A reflecting plate in which a metal film is formed on a molded product obtained by molding a thermoplastic resin composition melt-kneaded while
2. 1 wherein the thermoplastic resin composition is produced with an inflow effect pressure drop of 10 to 1000 kg / cm ² before and after a zone (extension flow zone) in which the thermoplastic resin composition melts and kneads while stretching and flowing. A reflecting plate on which the metal film described above is formed,
3. The thermoplastic resin composition is manufactured by setting the ratio of the total length of the zone (extension flow zone) in which the thermoplastic resin composition is melt-kneaded by an extruder and melted and kneaded while stretching and flowing to the entire length of the extruder screw to be 5 to 60%. A reflecting plate on which the metal film according to any one of 1 and 2 is formed,
4). When the length of a zone in which the thermoplastic resin composition melts and kneads while stretching and flowing (extension flow zone) in the screw of the extruder is Lk and the screw diameter is D, Lk / D = 0.2 The reflector formed with the metal film according to any one of 1 to 3, which is manufactured as
5. The thermoplastic resin composition includes (c) a compound having at least one group selected from an epoxy group, an amino group, an isocyanate group, a hydroxyl group, and a mercapto group. A reflector with a metal film,
6). (C) The reflection having a metal film according to 5, wherein the compound having at least one group selected from an epoxy group, an amino group, an isocyanate group, a hydroxyl group, and a mercapto group is an alkoxysilane compound. Board,
It is.

  Since the present invention has sufficiently improved the compatibility between the polyetherimide resin and the polyphenylene sulfide resin, the thermoplastic resin has excellent heat resistance, mechanical strength and dimensional stability, and drastically improved melt fluidity. A reflecting plate in which a metal film is formed on a molded product obtained by molding the composition is obtained. Since the reflection plate formed with the metal film thus obtained can be thinned, it is useful in that it greatly contributes to the weight reduction of the entire product requiring the reflection plate.

  Hereinafter, embodiments of the present invention will be described in detail.

(A) Polyetherimide resin The polyetherimide resin referred to in the present invention is a polymer containing an aliphatic, alicyclic or aromatic ether unit and a cyclic imide group as a repeating unit, and has melt moldability. If it is a polymer, it will not specifically limit. Further, as long as the effect of the present invention is not impaired, the main chain of the polyetherimide is a cyclic imide, a structural unit other than an ether bond, such as an aromatic, aliphatic, alicyclic ester unit, oxycarbonyl unit, etc. May be contained.

  As a specific polyetherimide, a polymer represented by the following general formula is preferably used.

Wherein R1 is a divalent aromatic residue having 6 to 30 carbon atoms, R2 is a divalent aromatic residue having 6 to 30 carbon atoms, 2 to 20 2 selected from the group consisting of an alkylene group having 2 carbon atoms, a cycloalkylene group having 2 to 20 carbon atoms, and a polydiorganosiloxane group chain-terminated with an alkylene group having 2 to 8 carbon atoms As R1 and R2, for example, those having an aromatic residue represented by the following formula group are preferably used.

  In the present invention, from the viewpoint of melt moldability and cost, 2,2-bis [4- (2,3-dicarboxyphenoxy) phenyl] propane dianhydride and m-phenylene having a structural unit represented by the following formula Diamine or a condensate with p-phenylenediamine is preferably used. This polyetherimide is commercially available from Savic Innovative Plastics under the trademark “Ultem”.

  Although there is no restriction | limiting in particular in the molecular weight of (a) polyetherimide resin used by this invention, The thing of 30,000-120,000 in the weight average molecular weight measured by GPC-MALLS is 40,000-110,000, Especially 5 Using a PEI resin in the range of 10,000 to 100,000 can be preferably used from the viewpoint of enabling highly fine dispersion of the PPS resin and expressing more excellent mechanical properties. With a PEI resin having a weight average molecular weight of 30,000 or less, it is difficult to achieve a reduction in the strength of the molded product and a high degree of fine dispersion of the PPS resin. Further, PEI resins having a weight average molecular weight of 120,000 or more tend to be inferior in terms of fluidity when a molded product is obtained by injection molding.

In addition, the weight average molecular weight said here is a gel permeation chromatograph equipped with a DAWN-DSP type multi-angle light scattering photometer (manufactured by Wyatt Technology) by dissolving PEI resin in dimethylformamide and using dimethylformamide as a solvent. A value obtained by measuring a weight average molecular weight (absolute molecular weight) using a pump: 515 type, manufactured by Waters, column: TSK-gel-GMH _XL , manufactured by Tosoh Corporation.

(B) Polyphenylene sulfide resin (b) PPS resin used in the present invention is a polymer having a repeating unit represented by the following structural formula,

From the viewpoint of heat resistance, a polymer containing 70 mol% or more, more preferably 90 mol% or more of a polymer containing a repeating unit represented by the above structural formula is preferred. In addition, (b) PPS resin may be composed of a repeating unit having the following structure in an amount of less than 30 mol% of the repeating unit.

  Since the PPS copolymer having a part of such a structure has a low melting point, such a resin composition is advantageous in terms of moldability.

  The melt viscosity of the (b) PPS resin used in the present invention is not limited, but is preferably 200 Pa · s (300 ° C., shear rate 1000 / s) or less from the viewpoint of easily obtaining a thin injection molded product. 150 Pa · s or less is more preferable, and 100 Pa · s or less is more preferable. The lower limit is preferably 1 Pa · s or more from the viewpoint of melt molding processability and gas generation amount.

  In addition, the melt viscosity in this invention is the value measured using the Toyo Seiki Co., Ltd. capilograph on the conditions of 300 degreeC and the shear rate of 1000 / s.

  Although the manufacturing method of (b) PPS resin used for this invention is demonstrated below, if (b) PPS resin of the said structure is obtained, it will not be limited to the following method.

  First, the contents of the polyhalogen aromatic compound, sulfidizing agent, polymerization solvent, molecular weight regulator, polymerization aid and polymerization stabilizer used in the production method will be described.

[Polyhalogenated aromatic compounds]
A polyhalogenated aromatic compound refers to a compound having two or more halogen atoms in one molecule. Specific examples include p-dichlorobenzene, m-dichlorobenzene, o-dichlorobenzene, 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene, 1,2,4,5-tetrachlorobenzene, hexa Polyhalogenated aroma such as chlorobenzene, 2,5-dichlorotoluene, 2,5-dichloro-p-xylene, 1,4-dibromobenzene, 1,4-diiodobenzene, 1-methoxy-2,5-dichlorobenzene Group compounds, and preferably p-dichlorobenzene is used. Further, it is possible to combine two or more different polyhalogenated aromatic compounds into a copolymer, but it is preferable to use a p-dihalogenated aromatic compound as a main component.

  The polyhalogenated aromatic compound is used in an amount of 0.9 to 2.0 mol, preferably 0.95 to 1. mol per mol of sulfidizing agent, from the viewpoint of obtaining a (b) PPS resin having a viscosity suitable for processing. A range of 5 moles, more preferably 1.005 to 1.2 moles can be exemplified.

[Sulfiding agent]
Examples of the sulfiding agent include alkali metal sulfides, alkali metal hydrosulfides, and hydrogen sulfide.

  Specific examples of the alkali metal sulfide include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide and a mixture of two or more of these, and sodium sulfide is preferably used. These alkali metal sulfides can be used as hydrates or aqueous mixtures or in the form of anhydrides.

  Specific examples of the alkali metal hydrosulfide include, for example, sodium hydrosulfide, potassium hydrosulfide, lithium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide and a mixture of two or more of these. Preferably used. These alkali metal hydrosulfides can be used as hydrates or aqueous mixtures or in the form of anhydrides.

  In addition, an alkali metal sulfide prepared in situ in a reaction system from an alkali metal hydrosulfide and an alkali metal hydroxide can also be used. Moreover, an alkali metal sulfide can be prepared from an alkali metal hydrosulfide and an alkali metal hydroxide and transferred to a polymerization tank for use.

  Alternatively, an alkali metal sulfide prepared in situ in a reaction system from an alkali metal hydroxide such as lithium hydroxide or sodium hydroxide and hydrogen sulfide can also be used. Moreover, an alkali metal sulfide can be prepared from an alkali metal hydroxide such as lithium hydroxide or sodium hydroxide and hydrogen sulfide, and transferred to a polymerization tank for use.

  The amount of the sulfidizing agent charged means a residual amount obtained by subtracting the loss from the actual charged amount when a partial loss of the sulfiding agent occurs before the start of the polymerization reaction due to dehydration operation or the like.

  An alkali metal hydroxide and / or an alkaline earth metal hydroxide can be used in combination with the sulfidizing agent. Specific examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, and a mixture of two or more thereof. Specific examples of the metal hydroxide include, for example, calcium hydroxide, strontium hydroxide, barium hydroxide, and sodium hydroxide is preferably used.

  When an alkali metal hydrosulfide is used as the sulfiding agent, it is particularly preferable to use an alkali metal hydroxide at the same time, but the amount used is 0.95 to 1. A range of 20 mol, preferably 1.00 to 1.15 mol, more preferably 1.005 to 1.100 mol can be exemplified.

[Polymerization solvent]
An organic polar solvent is preferably used as the polymerization solvent. Specific examples include N-alkylpyrrolidones such as N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, caprolactams such as N-methyl-ε-caprolactam, and 1,3-dimethyl-2-imidazolide. Non-, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric acid triamide, dimethyl sulfone, tetramethylene sulfoxide and the like, and mixtures thereof, and the like are all included. It is preferably used because of its high reaction stability. Of these, N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP) is particularly preferably used.

  The amount of the organic polar solvent used is selected in the range of 2.0 to 10 mol, preferably 2.25 to 6.0 mol, more preferably 2.5 to 5.5 mol per mol of the sulfidizing agent.

[Molecular weight regulator]
(B) A monohalogen compound (not necessarily an aromatic compound) is combined with the polyhalogenated aromatic compound for the purpose of forming a terminal of the PPS resin or adjusting the polymerization reaction or the molecular weight. Can be used together.

[Polymerization aid]
In order to obtain a relatively high degree of polymerization (b) PPS resin in a shorter time, it is also one of preferred embodiments to use a polymerization aid. Here, the polymerization assistant means (b) a substance having an action of increasing the viscosity of the PPS resin to be obtained. Specific examples of such polymerization aids include, for example, organic carboxylates, water, alkali metal chlorides, organic sulfonates, alkali metal sulfates, alkaline earth metal oxides, alkali metal phosphates and alkaline earths. Metal phosphates and the like. These may be used alone or in combination of two or more. Of these, organic carboxylates, water, and alkali metal chlorides are preferable. Further, alkali metal carboxylates are preferable as organic carboxylates, and lithium chloride is preferable as alkali metal chlorides.

  The alkali metal carboxylate is a general formula R (COOM) n (wherein R is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, an alkylaryl group, or an arylalkyl group). M is an alkali metal selected from lithium, sodium, potassium, rubidium and cesium, and n is an integer of 1 to 3). Alkali metal carboxylates can also be used as hydrates, anhydrides or aqueous solutions. Specific examples of the alkali metal carboxylate include, for example, lithium acetate, sodium acetate, potassium acetate, sodium propionate, lithium valerate, sodium benzoate, sodium phenylacetate, potassium p-toluate, and mixtures thereof. Can be mentioned.

  The alkali metal carboxylate is an organic acid and one or more compounds selected from the group consisting of alkali metal hydroxides, alkali metal carbonates, and alkali metal bicarbonates, and are allowed to react by adding approximately equal chemical equivalents. You may form by. Among the alkali metal carboxylates, lithium salts are highly soluble in the reaction system and have a large auxiliary effect, but are expensive, and potassium, rubidium and cesium salts are insufficiently soluble in the reaction system. Therefore, sodium acetate, which is inexpensive and has an appropriate solubility in the polymerization system, is most preferably used.

  When using these alkali metal carboxylates as polymerization aids, the amount used is usually in the range of 0.01 to 2 moles per mole of charged alkali metal sulfide, and in the sense of obtaining a higher degree of polymerization. The range of 0.1-0.6 mol is preferable, and the range of 0.2-0.5 mol is more preferable.

  Moreover, the addition amount in the case of using water as a polymerization aid is usually in the range of 0.3 mol to 15 mol with respect to 1 mol of the charged alkali metal sulfide, and in the sense of obtaining a higher degree of polymerization, 0.6 to The range of 10 mol is preferable, and the range of 1 to 5 mol is more preferable.

  Of course, two or more kinds of these polymerization aids can be used in combination. For example, when an alkali metal carboxylate and water are used in combination, a higher molecular weight can be obtained in a smaller amount.

  There is no particular designation as to the timing of addition of these polymerization aids, which may be added at any time during the previous step, polymerization start, polymerization in the middle to be described later, or may be added in multiple times. When using an alkali metal carboxylate as a polymerization aid, it is more preferable to add it at the start of the previous step or at the start of the polymerization from the viewpoint of easy addition. When water is used as a polymerization aid, it is effective to add the polyhalogenated aromatic compound during the polymerization reaction after charging.

[Polymerization stabilizer]
A polymerization stabilizer can also be used to stabilize the polymerization reaction system and prevent side reactions. The polymerization stabilizer contributes to stabilization of the polymerization reaction system and suppresses undesirable side reactions. One measure of the side reaction is the generation of thiophenol, and the addition of a polymerization stabilizer can suppress the generation of thiophenol. Specific examples of the polymerization stabilizer include compounds such as alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides, and alkaline earth metal carbonates. Among these, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide are preferable. Since the alkali metal carboxylate described above also acts as a polymerization stabilizer, it is one of the polymerization stabilizers. In addition, when an alkali metal hydrosulfide is used as a sulfidizing agent, it has been described above that it is particularly preferable to use an alkali metal hydroxide at the same time. Oxides can also be polymerization stabilizers.

  These polymerization stabilizers can be used alone or in combination of two or more. The polymerization stabilizer is usually in a proportion of 0.02 to 0.2 mol, preferably 0.03 to 0.1 mol, more preferably 0.04 to 0.09 mol, relative to 1 mol of the charged alkali metal sulfide. Is preferably used. If this ratio is small, the stabilizing effect is insufficient. Conversely, if the ratio is too large, it is economically disadvantageous or the polymer yield tends to decrease.

  The addition timing of the polymerization stabilizer is not particularly specified, and may be added at any time during the previous step, at the start of polymerization, or during the polymerization described later, or may be added in multiple times. It is more preferable because it is easy to add at the start of the process or at the start of the polymerization.

  Next, a preferred method for producing the (b) PPS resin used in the present invention will be described in detail in the order of a pre-process, a polymerization reaction process, a recovery process, and a post-treatment process. Of course, the process is limited to this process. It is not something.

[pre-process]
(B) In the method for producing a PPS resin, the sulfidizing agent is usually used in the form of a hydrate. Before adding the polyhalogenated aromatic compound, the mixture containing the organic polar solvent and the sulfidizing agent is increased. It is preferable to warm and remove excess water out of the system.

  As described above, a sulfidizing agent prepared from an alkali metal hydrosulfide and an alkali metal hydroxide in situ in the reaction system or in a tank different from the polymerization tank is also used as the sulfidizing agent. Can do. Although there is no particular limitation on this method, desirably an alkali metal hydrosulfide and an alkali metal hydroxide are added to the organic polar solvent in an inert gas atmosphere at a temperature ranging from room temperature to 150 ° C., preferably from room temperature to 100 ° C. In addition, there is a method in which the temperature is raised to at least 150 ° C. or more, preferably 180 to 260 ° C. under normal pressure or reduced pressure, and water is distilled off. A polymerization aid may be added at this stage. Moreover, in order to accelerate | stimulate distillation of a water | moisture content, you may react by adding toluene etc.

  The amount of water in the polymerization system in the polymerization reaction is preferably 0.3 to 10.0 moles per mole of the charged sulfidizing agent. Here, the amount of water in the polymerization system is an amount obtained by subtracting the amount of water removed from the polymerization system from the amount of water charged in the polymerization system. In addition, the water to be charged may be in any form such as water, an aqueous solution, and crystal water.

[Polymerization reaction step]
(B) A PPS resin is produced by reacting a sulfidizing agent and a polyhalogenated aromatic compound in an organic polar solvent within a temperature range of 200 ° C. or higher and lower than 290 ° C.

  When starting the polymerization reaction step, the organic polar solvent, the sulfidizing agent, and the polyhalogenated aromatic compound are desirably mixed in an inert gas atmosphere at room temperature to 240 ° C., preferably 100 to 230 ° C. . A polymerization aid may be added at this stage. The order in which these raw materials are charged may be out of order or may be simultaneous.

  The mixture is usually heated to a temperature in the range of 200 ° C to 290 ° C. Although there is no restriction | limiting in particular in a temperature increase rate, Usually, the speed of 0.01-5 degreeC / min is selected, and the range of 0.1-3 degreeC / min is more preferable.

  In general, the temperature is finally raised to a temperature of 250 to 290 ° C., and the reaction is usually carried out at that temperature for 0.25 to 50 hours, preferably 0.5 to 20 hours.

  In the stage before reaching the final temperature, for example, a method of reacting at 200 to 260 ° C. for a certain time and then raising the temperature to 270 to 290 ° C. is effective in obtaining a higher degree of polymerization. Under the present circumstances, as reaction time in 200 to 260 degreeC, the range of 0.25 to 20 hours is normally selected, Preferably the range of 0.25 to 10 hours is selected.

  In order to obtain a polymer having a higher degree of polymerization, it may be effective to perform polymerization in multiple stages. When the polymerization is performed in a plurality of stages, it is effective that the conversion of the polyhalogenated aromatic compound in the system at 245 ° C. reaches 40 mol% or more, preferably 60 mol%.

The conversion rate of the polyhalogenated aromatic compound (herein abbreviated as PHA) is a value calculated by the following formula. The residual amount of PHA can usually be determined by gas chromatography.
(A) When polyhalogenated aromatic compound is added excessively in a molar ratio with respect to the alkali metal sulfide, the conversion rate = [PHA charge (mol) −PHA remaining amount (mol)] / [PHA charge (mol) -PHA excess (mole)]
(B) In cases other than (A) above, conversion rate = [PHA charge (mol) −PHA remaining amount (mol)] / [PHA charge (mol)]

[Recovery process]
(B) In the method for producing a PPS resin, after the polymerization is completed, a solid is recovered from a polymerization reaction product containing a polymer, a solvent, and the like. Any known method may be adopted as the recovery method.

  For example, after completion of the polymerization reaction, a method of slowly cooling and recovering the particulate polymer may be used. Although there is no restriction | limiting in particular in the slow cooling rate in this case, Usually, it is about 0.1 degreeC / min-3 degreeC / min. It is not necessary to perform slow cooling at the same rate in the entire process of the slow cooling step, such as a method of gradually cooling at a rate of 0.1 to 1 ° C / min until the polymer particles are crystallized and precipitated, and then at a rate of 1 ° C / min or more. It may be adopted.

Moreover, it is also one of the preferable methods to perform said collection | recovery on quenching conditions, As a preferable method of this collection method, the flash method is mentioned. In the flash method, the polymerization reaction product is flushed from a high temperature and high pressure (usually 250 ° C. or more, 8 kg / cm ² or more) into an atmosphere of normal pressure or reduced pressure, and the polymer is recovered in the form of powder simultaneously with the solvent recovery. This is a method, and the term “flash” here means that a polymerization reaction product is ejected from a nozzle. Specific examples of the atmosphere to be flushed include nitrogen or water vapor at normal pressure, and the temperature is usually in the range of 150 ° C to 250 ° C.

[Post-processing process]
(B) The PPS resin may be subjected to acid treatment, hot water treatment, washing with an organic solvent, alkali metal or alkaline earth metal treatment after being produced through the above polymerization and recovery steps.

  When acid treatment is performed, it is as follows. (B) The acid used for the acid treatment of the PPS resin is not particularly limited as long as it does not have the action of decomposing the (B) PPS resin, such as acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid, and propyl acid. Among them, acetic acid and hydrochloric acid are more preferably used, but (b) those that decompose and deteriorate the PPS resin such as nitric acid are not preferable.

  As the acid treatment method, there is a method such as (b) immersing the PPS resin in an acid or an aqueous solution of the acid, and if necessary, stirring or heating can be appropriately performed. For example, when acetic acid is used, a sufficient effect can be obtained by immersing the PPS resin powder in an aqueous PH4 solution heated to 80 to 200 ° C. and stirring for 30 minutes. The PH after processing may be 4 or more, for example, about PH 4-8. The acid-treated (b) PPS resin is preferably washed several times with water or warm water in order to remove residual acid or salt. The water used for washing is preferably distilled water or deionized water in the sense that it does not impair the effect of the preferred chemical modification of the (b) PPS resin by acid treatment.

  When performing hot water treatment, it is as follows. (B) In the hot water treatment of the PPS resin, the temperature of the hot water is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, further preferably 150 ° C. or higher, and particularly preferably 170 ° C. or higher. If it is less than 100 degreeC, since the effect of the preferable chemical modification | denaturation of (b) PPS resin is small, it is unpreferable.

  The water used is preferably distilled water or deionized water in order to exhibit the effect of preferable chemical modification of the (b) PPS resin by hot water washing. There is no particular limitation on the operation of the hot water treatment, and a predetermined amount of (b) PPS resin is charged into a predetermined amount of water, heated and stirred in a pressure vessel, or a continuous hydrothermal treatment method. Is called. (B) The ratio of the PPS resin to water is preferably higher, but usually a bath ratio of (b) 200 g or less of PPS resin is selected for 1 liter of water.

  Further, since the decomposition of the terminal group is not preferable, the treatment atmosphere is desirably an inert atmosphere in order to avoid this. Further, the (b) PPS resin that has finished this hot water treatment operation is preferably washed several times with warm water in order to remove the remaining components.

  When washing with an organic solvent, it is as follows. (B) The organic solvent used for washing the PPS resin is not particularly limited as long as it does not have an action of decomposing (b) the PPS resin. For example, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, Nitrogen-containing polar solvents such as 1,3-dimethylimidazolidinone, hexamethylphosphoramide, piperazinones, sulfoxide / sulfon solvents such as dimethyl sulfoxide, dimethyl sulfone, sulfolane, ketones such as acetone, methyl ethyl ketone, diethyl ketone, acetophenone Solvents, ether solvents such as dimethyl ether, dipropyl ether, dioxane, tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchlorethylene, monochloroethane, dichloroethane, Halogen solvents such as trachlorethane, perchlorethane, chlorobenzene, alcohol / phenol solvents such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, polypropylene glycol and the like Aromatic hydrocarbon solvents such as benzene, toluene, xylene and the like can be mentioned. Among these organic solvents, use of N-methyl-2-pyrrolidone, acetone, dimethylformamide, chloroform and the like is particularly preferable. These organic solvents are used alone or in combination of two or more.

  As a method of washing with an organic solvent, there is a method of immersing (b) the PPS resin in an organic solvent, and it is possible to appropriately stir or heat as necessary. There is no restriction | limiting in particular about the washing | cleaning temperature at the time of wash | cleaning (b) PPS resin with an organic solvent, Arbitrary temperature of about normal temperature-about 300 degreeC can be selected. Although the cleaning efficiency tends to increase as the cleaning temperature increases, a sufficient effect is usually obtained at a cleaning temperature of room temperature to 150 ° C. It is also possible to wash under pressure in a pressure vessel at a temperature above the boiling point of the organic solvent. There is no particular limitation on the cleaning time. Depending on the cleaning conditions, in the case of batch-type cleaning, a sufficient effect can be obtained usually by cleaning for 5 minutes or more. It is also possible to wash in a continuous manner.

  As a method of treating alkali metal or alkaline earth metal, before the previous step, during the previous step, after the previous step, a method of adding an alkali metal salt or alkaline earth metal salt, before the polymerization step, during the polymerization step, during the polymerization step Examples include a method of adding an alkali metal salt or an alkaline earth metal salt into the polymerization vessel later, or a method of adding an alkali metal salt or an alkaline earth metal salt at the first, middle or last stage of the washing step. Among them, the easiest method includes a method of adding an alkali metal salt or an alkaline earth metal salt after removing residual oligomers or residual salts by washing with an organic solvent or washing with warm water or hot water. Alkali metals and alkaline earth metals are preferably introduced into PPS in the form of alkali metal ions such as acetates, hydroxides and carbonates, and alkaline earth metal ions. It is preferable to remove excess alkali metal salt and alkaline earth metal salt by washing with warm water. The concentration of alkali metal ions and alkaline earth metal ions when introducing the alkali metal and alkaline earth metal is preferably 0.001 mmol or more, more preferably 0.01 mmol or more, relative to 1 g of PPS. As temperature, 50 degreeC or more is preferable, 75 degreeC or more is more preferable, and 90 degreeC or more is especially preferable. Although there is no upper limit temperature, it is usually preferably 280 ° C. or lower from the viewpoint of operability. The bath ratio (the weight of the cleaning solution with respect to the dry PPS weight) is preferably 0.5 or more, more preferably 3 or more, and still more preferably 5 or more.

  In the present invention, from the viewpoint of obtaining a reflecting plate on which a metal film having excellent light distribution performance is formed, the organic film cleaning and hot water at about 80 ° C. or the above-mentioned hot water cleaning are repeated several times, thereby being adhered to the metal film. A method of removing residual oligomers that cause defects or cloudiness is preferred. From the viewpoint of improving the reactivity with the compound having (c) an epoxy group, an amino group, an isocyanate group, a hydroxyl group, and a mercapto group, which is a compatibilizer, an acid treatment method is preferred.

  In addition, (b) the PPS resin can be used after having been polymerized to have a high molecular weight by heating in an oxygen atmosphere and thermal oxidation crosslinking treatment by heating with addition of a crosslinking agent such as peroxide.

  When the dry heat treatment is performed for the purpose of increasing the molecular weight by thermal oxidation crosslinking, the temperature is preferably 160 to 260 ° C, more preferably 170 to 250 ° C. The oxygen concentration is preferably 5% by volume or more, more preferably 8% by volume or more. Although there is no restriction | limiting in particular in the upper limit of oxygen concentration, About 50 volume% is a limit. The treatment time is preferably 0.5 to 100 hours, more preferably 1 to 50 hours, and further preferably 2 to 25 hours. The heat treatment apparatus may be a normal hot air dryer or a heating apparatus with a rotary type or a stirring blade. However, for efficient and more uniform processing, a heating apparatus with a rotary type or a stirring blade is used. More preferably it is used.

  In addition, it is possible to carry out dry heat treatment for the purpose of suppressing thermal oxidative crosslinking and removing volatile matter. The temperature is preferably 130 to 250 ° C, and more preferably 160 to 250 ° C. In this case, the oxygen concentration is preferably less than 5% by volume, and more preferably less than 2% by volume. The treatment time is preferably 0.5 to 50 hours, more preferably 1 to 20 hours, and further preferably 1 to 10 hours. The heat treatment apparatus may be a normal hot air dryer or a heating apparatus with a rotary type or a stirring blade. However, for efficient and more uniform processing, a heating apparatus with a rotary type or a stirring blade is used. More preferably it is used.

  However, from the viewpoint of improving mechanical properties such as impact strength, the (b) PPS resin is preferably a substantially linear PPS that does not undergo high molecular weight by thermal oxidation crosslinking treatment. In the present invention, a plurality of (b) PPS resins having different melt viscosities may be mixed and used.

(C) Compound having one or more groups selected from an epoxy group, an amino group, an isocyanate group, a hydroxyl group, and a mercapto group In the present invention, (c) an epoxy group, an amino group, It is preferable to add a compound having one or more groups selected from an isocyanate group, a hydroxyl group, and a mercapto group as a compatibilizing agent.

  Epoxy group-containing compounds include bisphenol A, resorcinol, hydroquinone, pyrocatechol, bisphenol F, saligenin, 1,3,5-trihydroxybenzene, bisphenol S, trihydroxy-diphenyldimethylmethane, 4,4′-dihydroxybiphenyl, 1 , 5-dihydroxynaphthalene, cashew phenol, glycidyl ethers of bisphenols such as 2,2,5,5-tetrakis (4-hydroxyphenyl) hexane, those using halogenated bisphenol instead of bisphenol, butanediol di Glycidyl ether epoxy compounds such as glycidyl ether, glycidyl ester compounds such as glycidyl phthalate, glycidyl amine compounds such as N-glycidyl aniline, etc. Glycidyl epoxy resins, epoxidized polyolefins, linear epoxy compounds such as epoxidized soybean oil, vinylcyclohexene dioxide, such as a non-glycidyl epoxy resins ring system such as dicyclopentadiene dioxide and the like.

  In addition, other novolac type epoxy resins are also included. The novolac type epoxy resin has two or more epoxy groups and is usually obtained by reacting a novolac type phenol resin with epichlorohydrin. Moreover, a novolac type phenol resin is obtained by a condensation reaction of phenols and formaldehyde. Although there is no restriction | limiting in particular as phenols of a raw material, Phenol, o-cresol, m-cresol, p-cresol, bisphenol A, resorcinol, p-tertiary butylphenol, bisphenol F, bisphenol S, and these condensates are mentioned.

  Moreover, the olefin copolymer which has an epoxy group is also mentioned. Examples of the olefin copolymer having an epoxy group (epoxy group-containing olefin copolymer) include an olefin copolymer obtained by introducing a monomer component having an epoxy group into an olefinic (co) polymer. . Moreover, the copolymer which epoxidized the double bond part of the olefin polymer which has a double bond in a principal chain can also be used.

  Examples of functional group-containing components for introducing a monomer component having an epoxy group into an olefinic (co) polymer include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, glycidyl citraconic acid, etc. And a monomer containing an epoxy group.

  The method for introducing these epoxy group-containing components is not particularly limited, and methods such as copolymerization with α-olefin and the like, or graft introduction to an olefin (co) polymer using a radical initiator can be used.

  The introduction amount of the monomer component containing an epoxy group is 0.001 to 40 mol%, preferably 0.01 to 35 mol% with respect to the whole monomer as a raw material of the epoxy group-containing olefin copolymer. It is appropriate to be within the range.

  As an epoxy group-containing olefin copolymer particularly useful in the present invention, an olefin copolymer having an α-olefin and a glycidyl ester of an α, β-unsaturated carboxylic acid as a copolymerization component is preferably exemplified. As said alpha olefin, ethylene is mentioned preferably. These copolymers further include α, β-unsaturated carboxylic acids such as acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and the like. It is also possible to copolymerize the alkyl ester, styrene, acrylonitrile and the like.

  Such an olefin copolymer may be any random, alternating, block, or graft copolymerization mode.

  An olefin copolymer obtained by copolymerizing an glycidyl ester of an α-olefin and an α, β-unsaturated carboxylic acid is, among others, a glycidyl ester 1 of 60 to 99% by weight of an α-olefin and an α, β-unsaturated carboxylic acid. An olefin copolymer obtained by copolymerizing ˜40% by weight is particularly preferable.

  Specific examples of the glycidyl ester of α, β-unsaturated carboxylic acid include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate. Among them, glycidyl methacrylate is preferably used.

  As a specific example of an olefin copolymer having an α-olefin and a glycidyl ester of α, β-unsaturated carboxylic acid as an essential copolymerization component, an ethylene / propylene-g-glycidyl methacrylate copolymer ("g" Representing graft, the same applies hereinafter), ethylene / butene-1-g-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate copolymer-g-polystyrene, ethylene-glycidyl methacrylate copolymer-g-acrylonitrile-styrene copolymer Polymer, ethylene-glycidyl methacrylate copolymer-g-PMMA, ethylene / glycidyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / methyl acrylate / glycidyl methacrylate copolymer, ethylene / methyl methacrylate / Glycidi methacrylate Copolymers thereof.

  Furthermore, the alkoxysilane which has an epoxy group is mentioned. Specific examples of such compounds include epoxy group-containing alkoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. A compound etc. can be illustrated.

  Examples of the amino group-containing compound include alkoxysilanes having an amino group. Specific examples of such compounds include amino group-containing alkoxysilanes such as γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, and γ-aminopropyltrimethoxysilane. Compound etc. are mentioned.

  As the compound containing an isocyanate group, aromatic diisocyanates such as diphenylmethane diisocyanate, tolylene diisocyanate, 1,4-diisocyanate benzene, xylylene diisocyanate, and 2,6-naphthalene diisocyanate are particularly heat resistant and resin compositions with less gas generation. Can be preferably used in that it is obtained. Furthermore, as alicyclic diisocyanate, for example, methylene bis (cyclohexyl isocyanate), isophorone diisocyanate, methylcyclohexane 2,4-diisocyanate, methylcyclohexane 2,6-diisocyanate, cyclohexane 1,4-diisocyanate, hexahydroxylylene diisocyanate, hexahydrotolylene diisocyanate Isocyanates, octahydro 1,5-naphthalene diisocyanate and the like can also be used. Also, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatepropylethyldiethoxysilane Illustrative are isocyanate group-containing alkoxysilane compounds such as silane and γ-isocyanatopropyltrichlorosilane.

  Among them, in order to develop high compatibility and excellent mechanical properties, a compound containing at least one epoxy group and an isocyanate group, an alkoxysilane containing an epoxy group, and an alkoxysilane containing an isocyanate group are preferable. Can also be exemplified as a more preferable form.

  The blending ratio of (a) PEI resin and (b) PPS resin in the present invention is (a) / (b) = over 40% by weight and not more than 99% by weight, with the total of (a) and (b) being 100% by weight. / 1 wt% or more and less than 60 wt%, preferably (a) / (b) = 97-70 wt% / 3-30 wt%, (a) / (b) = 95-80 wt A range of% / 5 to 20% by weight is more preferable. (B) If the PPS resin is less than 1% by weight, a sufficient fluidity improving effect cannot be obtained, and if (b) the PPS resin is in the range of 60% by weight or more, the mechanical properties, thermal deformation temperature, and dimensions of the thermoplastic resin composition are obtained. In addition to significantly impairing stability, it is not preferable because warpage deformation is likely to occur when the molded product is heat-treated.

  The compounding amount of the compound having one or more groups selected from (c) epoxy group, amino group, isocyanate group, hydroxyl group and mercapto group in the present invention is a total of 100 weights of (a) PEI resin and (b) PPS resin. The amount is preferably in the range of 0.05 to 10 parts by weight, more preferably in the range of 0.1 to 5 parts by weight, and still more preferably in the range of 0.2 to 3 parts by weight. (C) When the compounding amount of the compound having one or more groups selected from an epoxy group, amino group, isocyanate group, hydroxyl group, and mercapto group is less than 0.05 parts by weight, (a) PEI resin and (b) PPS The effect of further improving the compatibility of the resin becomes poor. On the other hand, in the range where the compounding amount of the compound having one or more groups selected from (c) an epoxy group, an amino group, an isocyanate group, a hydroxyl group, and a mercapto group exceeds 10 parts by weight, the melt fluidity is remarkably impaired. In addition, it is not preferable because the material cost increases.

  If necessary, the thermoplastic resin composition of the present invention can be used by blending (d) an inorganic filler as long as the effects of the present invention are not impaired. Specific examples of the inorganic filler (d) include glass fiber, carbon fiber, carbon nanotube, carbon nanohorn, potassium titanate whisker, zinc oxide whisker, calcium carbonate whisker, wollastonite whisker, aluminum borate whisker, aramid fiber, alumina fiber, Fibrous fillers such as silicon carbide fiber, ceramic fiber, asbestos fiber, stone-kow fiber, metal fiber, or fullerene, talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, silica, bentonite, Silicates such as asbestos and alumina silicate, metal compounds such as silicon oxide, magnesium oxide, alumina, zirconium oxide, titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite Sulfates such as calcium sulfate and barium sulfate, hydroxides such as calcium hydroxide, magnesium hydroxide and aluminum hydroxide, glass beads, glass flakes, glass powder, ceramic beads, boron nitride, silicon carbide, carbon black and silica, Non-fibrous fillers such as graphite are used, among which glass fiber, silica, and calcium carbonate are preferable, and calcium carbonate and silica are particularly preferable from the viewpoint of the effects of the anticorrosive material and the lubricant. These (d) inorganic fillers may be hollow, and two or more kinds may be used in combination. These (d) inorganic fillers may be used after pretreatment with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, and an epoxy compound. Of these, calcium carbonate, silica, and carbon black are preferable from the viewpoint of the anticorrosive material, the lubricant, and the effect of imparting conductivity.

  The blending amount of the inorganic filler is preferably a range of 30 parts by weight or less with respect to a total of 100 parts by weight of the (a) polyetherimide resin and the (b) polyphenylene sulfide resin, and is preferably less than 10 parts by weight. A range of less than parts by weight is more preferred, and a range of 0.8 parts by weight or less is even more preferred. Although there is no particular lower limit, 0.01 parts by weight or more is preferable. While the blending of the inorganic filler is effective for improving the elastic modulus of the material, a large amount of blending exceeding 30 parts by weight is not preferable because it causes a large decrease in toughness. The content of the inorganic filler can be appropriately changed depending on the application from the balance between toughness and rigidity.

  Furthermore, in the thermoplastic resin composition of the present invention, a resin other than the polyetherimide resin and polyphenylene sulfide resin may be added and blended within a range not impairing the effects of the present invention. Specific examples thereof include polyamide resin, polybutylene terephthalate resin, polyethylene terephthalate resin, modified polyphenylene ether resin, polyether sulfone resin, polysulfone resin, polyallyl sulfone resin, polyketone resin, polyarylate resin, liquid crystal polymer, polyether ketone. Examples thereof include resins, polythioether ketone resins, polyether ether ketone resins, polyimide resins, polyamideimide resins, and tetrafluoropolyethylene resins.

  Moreover, the following compounds can be added for the purpose of modification. Plasticizers such as polyalkylene oxide oligomer compounds, thioether compounds, ester compounds, organophosphorus compounds, crystal nucleating agents such as organophosphorus compounds, polyetheretherketone, montanic acid waxes, lithium stearate, aluminum stearate Metal soaps such as ethylenediamine / stearic acid / sebacic acid polycondensate, release agents such as silicone compounds, anti-coloring agents such as hypophosphite, water, lubricants, UV protection agents, coloring agents, foaming A usual additive such as an agent can be blended. If any of the above compounds exceeds 20% by weight of the total composition, the inherent properties of (a) the polyetherimide resin and (b) the polyphenylene sulfide resin are undesirably undesirably 10% by weight or less, more preferably 1% by weight. The following addition is good.

In the present invention, since the compatibility between the polyetherimide resin and the polyphenylene sulfide resin is sufficiently improved, the melt fluidity can be obtained without sacrificing the mechanical strength, heat distortion temperature, and dimensional stability inherent in the polyetherimide resin. Is significantly improved, and a reflector having a metal film with improved thin moldability and light weight is obtained. In order to express such properties, (a) the glass transition temperature of the polyetherimide resin itself is Tg ₀ (° C.), (a) a thermoplastic resin composition comprising a polyetherimide resin and (b) a polyphenylene sulfide resin. (A) When the glass transition temperature derived from the polyetherimide resin is Tg ₁ (° C.), it is preferable to satisfy the following formula.
Tg ₀ -Tg ₁ ≧ 2 (° C.)

In the above formula, the glass transition temperature Tg ₁ derived from (a) polyetherimide resin in the thermoplastic resin composition comprising (a) polyetherimide resin and (b) polyphenylene sulfide resin is It is shown that the glass transition temperature Tg is lower by 2 ° C. or more than the glass transition temperature Tg _0, which means that (a) polyetherimide resin and (b) polyphenylene sulfide resin are compatible or partially compatible. Means that
When the value of Tg ₀ -Tg ₁ is less than 2 ° C., the compatibility between (a) the polyetherimide resin and (b) the polyphenylene sulfide resin is poor. Deformation temperature and dimensional stability may decrease. Although the upper limit of the value of Tg ₀ -Tg ₁ is not particularly defined, it is preferably less than 70 ° C. in consideration of the amount of (b) polyphenylene sulfide resin added. (A) 20 ≧ Tg ₀ −Tg ₁ ≧ 2 is preferable in order to impart excellent melt fluidity without sacrificing the mechanical strength, heat distortion temperature, and dimensional stability inherent in the polyetherimide resin. Furthermore, 15 ≧ Tg ₀ −Tg ₁ ≧ 3 is more preferable.

  The glass transition temperature can be measured with a differential scanning calorimeter or the like.

In addition, regarding (a) the glass transition temperature Tg ₀ (° C.) of the polyetherimide resin itself, various reflectors that dissolve the polyetherimide resin such as DMSO and DMF after pulverizing the reflector on which the metal film is formed It is also possible to measure what is extracted and purified with a solvent using a differential scanning calorimeter.

  In the present invention, since the compatibility between the polyetherimide resin and the polyphenylene sulfide resin is sufficiently improved, the melt fluidity can be obtained without sacrificing the mechanical strength, heat distortion temperature, and dimensional stability inherent in the polyetherimide resin. Is significantly improved, and a reflector having a metal film with improved thin moldability and light weight is obtained. In order to express such characteristics, in the morphology (phase structure) of the thermoplastic resin composition, (a) the PEI resin forms a sea phase (continuous phase or matrix), and (b) the PPS resin forms an island phase (dispersed). It is mentioned as an example of a preferable aspect to form a phase.

  Furthermore, (b) the number average dispersed particle size of the PPS resin has a constant distribution and is preferably 1 nm or more and less than 1000 nm, more preferably 10 nm or more and less than 500 nm, and further preferably 50 nm or more and less than 300 nm. Is particularly preferred. When the number average dispersed particle size of the (b) PPS resin is in the range of 1000 nm or more, the specific surface area of the (b) PPS resin in the thermoplastic resin composition becomes small, so that sufficient melt fluidity cannot be obtained.

  Moreover, it is desirable that the thermoplastic resin composition of the present invention has a stable morphology (phase structure). That is, even in a molded piece that has been once injection molded and then pulverized and injection molded again, (a) the PEI resin forms a sea phase (continuous phase or matrix), and (b) the PPS resin is an island. It is preferable to form a phase (dispersed phase). Furthermore, (b) the number average dispersed particle size of the PPS resin is preferably 1 nm or more and less than 1000 nm, more preferably 10 nm or more and less than 500 nm, and even more preferably 50 nm or more and less than 300 nm.

  In addition, the number average dispersed particle diameter referred to here is (a) a square plate having a width of 50 mm, a length of 80 mm, and a thickness of 3 mm (gate shape: film gate) is molded at the molding temperature of the PEI resin, and the central portion thereof is made of resin. A thin piece of 0.1 μm or less was cut at −20 ° C. from the center of the cross section cut in a direction perpendicular to the flow direction, and a Hitachi H-7100 transmission electron microscope (resolution (particle image) 0. First, the maximum diameter and the minimum diameter of 100 disperse portions of (b) PPS resin when observed at a magnification of 10,000 to 20,000 times at 38 nm and a magnification of 500 to 600,000 times) Is the number average dispersed particle size obtained by measuring the average value as the dispersed particle size and then obtaining the average value.

  In the present invention, since the compatibility between the polyetherimide resin and the polyphenylene sulfide resin is sufficiently improved, the melt fluidity can be obtained without sacrificing the mechanical strength, heat distortion temperature, and dimensional stability inherent in the polyetherimide resin. Is significantly improved, and a reflector having a metal film with improved thin moldability and light weight is obtained. In order to exhibit such characteristics, it is preferable that the arithmetic average surface roughness Ra after the reflector having the metal film formed thereon is treated at 180 ° C. for 24 hours is 0.2 mm or less. When the surface roughness Ra exceeds 0.2 mm, it means that the warp deformation of the reflecting plate on which the metal film is formed is large, and excellent orientation performance (even if the thin formability and light weight are improved) (Image clarity) is not obtained, which is not preferable. The lower limit of the surface roughness Ra is not particularly limited, but a preferable range is 0.01 mm or more.

  The surface roughness Ra is a surface roughness manufactured by ACCRTECH Co., Ltd. after heat-treating a specular square plate having a width of 50 mm, a length of 80 mm, and a height of 3 mm under the conditions of 180 ° C. × 24 hr. It can be defined as an average value measured using a measuring device.

  In the present invention, since the compatibility between the polyetherimide resin and the polyphenylene sulfide resin is sufficiently improved, the melt fluidity can be obtained without sacrificing the mechanical strength, heat distortion temperature, and dimensional stability inherent in the polyetherimide resin. Is significantly improved, and a reflector having a metal film with improved thin moldability and light weight is obtained. In order to exhibit such characteristics, it is preferable that the tensile break strength of the ASTM No. 4 dumbbell test piece having a weld line near the center of the test piece is 50 MPa or more. When the weld tensile strength at break is less than 50 MPa, it is not preferable because breakage from the weld portion is likely to occur even if the thin formability and lightness are improved.

  The weld tensile strength at break was measured on an ASTM No. 4 dumbbell test piece having a weld line near the center of the test piece under the conditions of a strain rate of 10 mm / min and a distance between marked lines of 50 mm.

  In the present invention, since the compatibility between the polyetherimide resin and the polyphenylene sulfide resin is sufficiently improved, the melt fluidity can be obtained without sacrificing the mechanical strength, heat distortion temperature, and dimensional stability inherent in the polyetherimide resin. Is significantly improved, and a reflector having a metal film with improved thin moldability and light weight is obtained. In order to exhibit such characteristics, the heat distortion temperature under a load of 1.82 MPa is preferably 180 ° C. or higher, and more preferably 190 ° C. or higher. When the heat distortion temperature is less than 180 ° C., it is not preferable because it cannot withstand heat generation under a long-term continuous use environment and deformation easily occurs.

  The heat distortion temperature was measured under a load of 1.82 MPa according to ASTM D648 on a test piece having a width of 12.7 mm, a length of 127 mm, and a height of 6.4 mm.

Kneading method When producing the thermoplastic resin composition of the present invention, it is necessary to melt and knead while stretching and flowing. The extension flow is a flow method in which molten resin is stretched in two flows flowing in opposite directions. On the other hand, generally used shear flow is a flow method in which molten resin undergoes deformation in two flows having different velocities in the same direction.

  In the extension flow, compared to the shear flow generally used in melt-kneading, the dispersion efficiency is high, so that essentially incompatible resins such as PEI resin and PPS resin are alloyed. When it is desired to highly finely disperse the components, for example, it is necessary to carry out some kind of reaction, and it has been found that the extension flow method of the present invention can be efficiently performed.

As a method of melt kneading while stretching and flowing, melt kneading using an extruder is preferably used. Examples of the extruder include a single screw extruder, a twin screw extruder, and a multi-screw extruder having three or more axes. Among them, a single screw extruder and a twin screw extruder are preferably used, and a twin screw extruder is particularly preferably used. Further, the screw of such a twin screw extruder is not particularly limited, and a fully meshed type, an incomplete meshed type, a non-meshed type screw, etc. can be used. It is a type. Further, the rotation direction of the screw may be either the same direction or a different direction, but from the viewpoint of kneading property and reactivity, the rotation direction is preferably the same direction. In the present invention, the most preferred screw is a co-rotating fully meshed type. Further, in the present invention, when melt kneading is performed using an extruder, the inflow effect pressure drop before and after the zone (extension flow zone) for melt kneading while stretching and flowing is preferably 10 to 1000 kg / cm ^2. . The inflow effect pressure drop before and after the zone (extension flow zone) for melt kneading while stretching and flowing means the pressure difference (ΔP ₀ ) in the extension flow zone from the pressure difference (ΔP) before the extension flow zone. It can be obtained by subtracting. When the inflow effect pressure drop before and after the extension flow zone is less than 10 kg / cm ^2, it is preferable because the rate of extension flow formation in the extension flow zone is low and the pressure distribution becomes non-uniform. Absent. Further, when the inflow effect pressure drop before and after the extension flow zone is larger than 1000 kg / cm ² , the back pressure in the extruder becomes too large, and it is not preferable because stable production becomes difficult. The inflow effect pressure drop across the zone to melt-kneading while stretched flow (stretched flow zone) is preferably in the range of 30~600kg / cm ^2, more preferably in the range of 50~600kg / cm ^2, even 100 A range of ˜500 kg / cm ² is most preferred.

  In addition, in the present invention, when melt kneading is performed using an extruder, in order to provide an extension flow field suitable for the present invention, a zone in which melt kneading is performed while extending and flowing with respect to the full length of the screw of the extruder (extension flow). The ratio of the total length of the zone) is preferably in the range of 5 to 60%, more preferably in the range of 10 to 55%, and still more preferably in the range of 15 to 50%.

  Further, in the present invention, when melt kneading is performed using an extruder, the length of one melt flow kneading zone (extension flow zone) in the screw of the extruder is Lk, and the screw diameter is D. From the viewpoints of kneading properties and reactivity, Lk / D is preferably 0.2 to 10. More preferably, it is 0.3-9, More preferably, it is 0.5-8. In the present invention, the zone (extension flow zone) in which the twin-screw extruder melts and kneads while stretching and flowing is preferably not disposed unevenly at a specific position in the screw. In particular, it is more preferable from the viewpoints of kneadability and reactivity that the zone (extension flow zone) in which melt-kneading while stretching and flowing is arranged at three or more locations in the extruder screw.

  In the present invention, when performing melt kneading using an extruder, the specific method of the zone for melt kneading while stretching and flowing includes a kneading disk, and the top and rear surfaces of the kneading disk at the disk front end side. A twist kneading disk in which the spiral angle θ, which is the angle with the top of the side, is in the range of 0 ° <θ <90 ° in the half-rotation direction of the screw, or a flight screw, and the flight of such a flight screw A resin passage with a reduced cross-sectional area from the screw front side to the rear end side is formed in the part, or a resin passage in which the cross-sectional area through which the molten resin passes in the extruder is temporarily reduced Is a preferred example.

  Moreover, in this invention, when melt-kneading is performed using an extruder, it is preferable that the extrusion amount of the thermoplastic resin composition with respect to 1 rpm of screws is 0.01 kg / h or more. The extrusion amount is an extrusion rate of the thermoplastic resin composition discharged from the extruder, and is a weight (kg) extruded per hour. If the amount of extrusion of the thermoplastic resin composition with respect to 1 rpm of the screw is less than 0.01 kg / h, the amount of extrusion with respect to the number of rotations is not sufficient, and the residence time in the extruder becomes too long, causing thermal deterioration. In addition, the filling rate of the resin in the extruder becomes small, and there may be a problem that sufficient kneading cannot be performed. The rotational speed of the screw is not particularly limited as long as it is within the above range, but is usually 10 rpm or more, preferably 50 rpm or more, and more preferably 80 rpm or more. The amount of extrusion is not particularly limited as long as it is within the above range, but is usually 0.1 kg / h or more, preferably 0.15 kg / h or more, more preferably 0.2 kg / h or more.

  Moreover, in this invention, when melt-kneading using an extruder, it is preferable that the residence time in the extruder of a thermoplastic resin composition is 0.1 to 20 minutes. The residence time means that the thermoplastic resin composition is extruded from the discharge port of the extruder from the position of the screw base to which the raw material is supplied, and the colorant and the like are added together with the raw material. This is the time until the maximum degree of coloration of the extrudate by the colorant. When the residence time is less than 0.1 minute, the reaction time in the extruder is short, the reaction is not sufficiently promoted, and the properties of the thermoplastic resin composition (balance of heat resistance, impact resistance, etc.) are improved. In addition, it is difficult to realize an improvement in the characteristic of absorbing an impact that has made the unique viscoelastic characteristic remarkably manifest. When the residence time is longer than 20 minutes, there is a possibility that the resin is thermally deteriorated due to the long residence time. The residence time in the present invention is preferably 0.3 to 15 minutes, more preferably 0.5 to 5 minutes.

  A method of kneading such that the resin temperature at the time of mixing is (b) the melting peak temperature of the PPS resin +10 to 70 ° C. can be preferably used. More preferably, the temperature of the cylinder part of the extruder is set so that (a) the melting temperature of the PEI resin +10 to 40 ° C., especially (b) the melting peak temperature of the PPS resin +10 to 30 ° C. It is important to obtain the effect of.

  There is no particular restriction on the mixing order of the raw materials, and all the raw materials are blended and then melt-kneaded by the above method, and some raw materials are blended and then melt-kneaded by the above method, and this and the remaining raw materials are blended. Any method may be used, such as a method of melt-kneading or a method of mixing a part of raw materials and mixing the remaining raw materials using a side feeder during melt-kneading with a twin-screw extruder. As for the small amount additive component, other components can be kneaded by the above-mentioned method and pelletized, then added before molding and used for molding.

  Moreover, after melt-kneading (a) PEI resin and (b) PPS resin once, melt-kneading once more is mentioned as a preferable method. Although the upper limit of the number of kneading is not particularly limited, it is preferable from the viewpoint of toughness improvement effect and economical efficiency that once kneaded once and then kneaded once to three times.

  Note that (b) the PPS resin ratio is set to a high concentration, once melt-kneaded to obtain a PPS resin composition, and further melt-kneaded once or more, (a) the PEI resin is blended, a) It is also possible to dilute the PPS resin to the desired ratio. In addition, when melt kneading once or more, it is also possible to freely control the fluidity of the finally formed thermoplastic resin composition by blending (a) PEI resin having different melt viscosities. In addition, a reflecting plate or the like on which a relatively complicated metal film is formed can be easily manufactured by injection molding or the like.

  In the present invention, since the compatibility between the polyetherimide resin and the polyphenylene sulfide resin is sufficiently improved, the melt fluidity can be obtained without sacrificing the mechanical strength, heat distortion temperature, and dimensional stability inherent in the polyetherimide resin. Is significantly improved, and a reflector having a metal film with improved thin moldability and light weight is obtained. From such characteristics, downlight covers and reflectors for home appliance lighting equipment, reflectors and lamp covers for projectors, reflectors and lamp parts used in LED packages, reflectors for backlight collection such as liquid crystal televisions and liquid crystal display boards, Reflectors used for indicator lights such as guide lights and advertising lights, headlamps for automobiles and motorcycles, lamp reflectors for fog lamps or rear lamps, reflectors for room lamps, lamp housings, lamp units, reflectors for lighting medical devices It is useful for reflectors for physics and chemistry equipment such as UV spot irradiators, reflectors for photographic lighting equipment (strobes), reflectors for illuminated push switches and photoelectric switches, and the like.

  The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples.

  In the following examples, material characteristics were evaluated by the following methods.

[Glass transition temperature measurement]
The PEI resin alone and the thermoplastic resin composition pellets were heated and melt-pressed at 340 ° C. for 4 minutes at 50 kg / cm ² , and then immersed in ice water to form an amorphous film having a thickness of about 100 μm. Next, about 10 mg of this amorphous film was charged into an aluminum pan, and thermal characteristics were measured under the following heating and cooling conditions using a DSC7 manufactured by PerkinElmer.
Hold at 50 ° C. for 1 minute at a temperature increase rate of 20 ° C./min. Increase to 340 ° C. Increase at a temperature of 340 ° C. for 1 minute. Reduce to 100 ° C. at a temperature decrease rate of 20 ° C./min. (A) Glass transition temperature of polyetherimide resin alone Tg ₀ (° C.), (a) the glass transition temperature derived from the polyether imide resin in the thermoplastic resin composition comprising (a) a polyetherimide resin and (b) a polyphenylene sulfide resin, and Tg ₁ (° C.) A value of _0- Tg ₁ was calculated.

[injection molding]
Using a Sumitomo-Nestal injection molding machine SG75H-M III, at a resin temperature of 350 ° C. and a mold temperature of 150 ° C., an ASTM No. 1 dumbbell test piece, a test piece of width 12.7 mm × length 127 mm × height 6.4 mm, Notched and unnotched Izod impact test specimens having a width of 12.7 mm, a length of 60 mm, and a height of 3.2 mm were molded. Also, an ASTM No. 4 dumbbell test piece having gates at both ends and a weld line near the center of the test piece was molded. Further, a specular square plate having a width of 50 mm, a length of 80 mm, and a height of 3 mm was formed.

[Bending strength measurement]
ASTM D790 was used under the conditions of an injection molded width 12.7 mm × length 127 mm × height 6.4 mm, an atmosphere of 23 ° C. and a relative humidity of 50%, a span of 100 mm, and a strain rate of 3 mm / min. The bending strength was measured according to the above.

[Izod impact test]
The Izod impact strength of the injection-molded notched and unnotched Izod impact test pieces of width 12.7 mm × length 60 mm × height 3.2 mm was measured according to ASTM D256.

[Weld tensile strength]
For the ASTM No. 4 dumbbell test piece having a weld line near the center of the test piece, the weld tensile strength was measured under the conditions of a strain rate of 10 mm / min and a distance between marked lines of 50 mm.

[Heat deformation temperature]
The test piece having a width of 12.7 mm, a length of 127 mm, and a height of 6.4 mm was evaluated for the heat distortion temperature under a load of 1.82 MPa according to ASTM D648.

[Surface roughness Ra after 180 ° C treatment]
The injection-molded mirror surface square plate having a width of 50 mm, a length of 80 mm, and a height of 3 mm was degreased with isopropyl alcohol, and then metal aluminum was deposited using a vacuum deposition apparatus manufactured by Hitachi, Ltd. The thickness of the metal film was approximately 0.1 μm. Next, after heat-treating this aluminum-deposited specular square plate under the conditions of 180 ° C. × 24 hr, the arithmetic average roughness Ra was measured for at least 20 locations of the specular square plate using a surface roughness measuring device manufactured by ACCRTECH. The average value was defined as the surface roughness Ra after 180 ° C. treatment. When this value becomes large, it means that the specular square plate after being processed at 180 ° C. is warped and deformed.

[Reference Example 1] (a) PEI resin (PEI-1)
“Ultem” 1010 manufactured by Subic Innovative Plastics.

[Reference Example 2] (b) Polymerization of PPS resin (PPS-1)
In a 70 liter autoclave equipped with a stirrer, 8267.37 g (70.00 mol) of 47.5% sodium hydrosulfide, 2957.21 g (70.97 mol) of 96% sodium hydroxide, N-methyl-2-pyrrolidone (NMP ) 11434.50 g (115.50 mol), sodium acetate 2583.00 g (31.50 mol), and ion-exchanged water 10500 g, gradually heated to 245 ° C. over about 3 hours under nitrogen at normal pressure, After distilling out 14780.1 g of water and 280 g of NMP, the reaction vessel was cooled to 160 ° C. The residual water content in the system per 1 mol of the charged alkali metal sulfide was 1.06 mol including the water consumed for the hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.02 mol per mol of the charged alkali metal sulfide.

  Next, 10235.46 g (69.63 mol) of p-dichlorobenzene and 900.00 g (91.00 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and stirred at 240 rpm while stirring at 0.6 ° C. / The temperature was raised to 238 ° C. at a rate of minutes. After reacting at 238 ° C. for 95 minutes, the temperature was raised to 270 ° C. at a rate of 0.8 ° C./min. After performing the reaction at 270 ° C. for 100 minutes, 1260 g (70 mol) of water was injected over 15 minutes and cooled to 250 ° C. at a rate of 1.3 ° C./minute. Then, after cooling to 200 ° C. at a rate of 1.0 ° C./min, it was rapidly cooled to near room temperature.

  The contents were taken out, diluted with 26300 g of NMP, the solvent and solid matter were filtered off with a sieve (80 mesh), and the resulting particles were washed with 31900 g of NMP and filtered off. This was washed several times with 56000 g of ion-exchanged water and filtered, then washed with 70000 g of 0.05 wt% aqueous acetic acid and filtered. After washing with 70000 g of ion-exchanged water and filtering, the resulting hydrous PPS particles were dried with hot air at 80 ° C. and dried under reduced pressure at 120 ° C. The obtained PPS-1 had a melt viscosity of 200 Pa · s (310 ° C., shear rate of 1000 / s).

[Reference Example 3] (c) Compound having at least one group selected from epoxy group, amino group, isocyanate group, hydroxyl group and mercapto group c-1: 3-isocyanatopropyltriethoxysilane (KBE manufactured by Shin-Etsu Chemical Co., Ltd.) -9007)
c-2: 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane (KBM-303 manufactured by Shin-Etsu Chemical Co., Ltd.)
c-3: γ-aminopropyltriethoxysilane (KBE-903 manufactured by Shin-Etsu Chemical Co., Ltd.)
c-4: Epoxy cresol novolak resin (DIC-made N-695)

[Examples 1-7, Comparative Examples 1-2]
The raw materials shown in Tables 1 and 2 were mixed at the blending ratios shown in Tables 1 and 2, and the same direction rotation complete with a screw diameter of 30 mm and L / D = 45 while performing volatile content removal and nitrogen flow with a vacuum pump. Engagement type twin screw extruder (manufactured by Nippon Steel Works, TEX-30α): The screw uses two screws with two threads, the cylinder temperature is 300 ° C, the screw rotation speed is 300 rpm, and the extrusion rate is 20 kg / h. The mixture was melt kneaded and discharged from the discharge port, and then pelletized with a strand cutter. The ratio (%) of the total length of the zone (extension flow zone) for melt kneading while stretching and flowing with respect to the total length of the screw is defined as (total length of extension flow zone) / (total length of screw) × 100, 29 %. Moreover, as a screw structure, from the position of L / D = 14,23,30, the top part of the kneading disc front-end | tip side made into Lk / D = 4.0, 4.0, 5.0, respectively, and the rear surface side are each set. A twist kneading disk having a spiral angle θ of 20 ° in the direction of half rotation of the screw was provided (this screw configuration is designated as A-1). Table 1 shows the results of calculating the inflow effect pressure drop before and after the extension flow zone by subtracting the pressure difference (ΔP ₀ ) in the extension flow zone from the pressure difference (ΔP) before the twist kneading disc. The results are shown in Table 2. The obtained pellets were dried at 130 ° C. overnight and then subjected to injection molding to evaluate various physical properties.

[Example 8]
As the screw configuration, from the position of L / D = 14, 23, 30, 35, the top of the kneading disk tip side and the rear surface with Lk / D = 4.0, 2.0, 2.0, 1.0 A twist kneading disk having a spiral angle θ of 20 ° in the direction of half rotation of the screw is provided (this screw configuration is A-2), and melt kneading while extending and flowing over the entire length of the screw Melting and kneading was carried out in the same manner as in Example 1 except that the ratio (%) of the total length of the zones (extension flow zones) to be set was 20%. Table 1 shows the results of calculating the inflow effect pressure drop before and after the extension flow zone by subtracting the pressure difference (ΔP ₀ ) in the extension flow zone from the pressure difference (ΔP) before the twist kneading disc. It was described in. The obtained pellets were dried at 130 ° C. overnight and then subjected to injection molding to evaluate various physical properties.

[Comparative Examples 3 to 6]
The raw materials shown in Table 2 are mixed at the blending ratio shown in Table 2, and the unidirectionally rotating fully meshed twin screw extruder with a screw diameter of 30 mm and L / D = 45 while removing the volatile matter by a vacuum pump and flowing nitrogen. (Nippon Steel Works Co., Ltd., TEX-30α): Two screws, two-threaded, are used, and melt kneading is performed at a cylinder temperature of 300 ° C., a screw speed of 300 rpm, and an extrusion rate of 20 kg / h. After discharging from the discharge port, it was pelletized with a strand cutter. As a screw configuration, general kneading disks (L / D = 4.0, 4.0, 5.0) are provided from the positions of L / D = 14, 23, 30 (this screw configuration is B- 1), the ratio (%) of the total length of the zone (extension flow zone) for melting and kneading while stretching and flowing with respect to the total length of the screw is 0%, and melt kneading without melt and kneading while stretching and flowing. Melt kneading was carried out in the same manner as in Example 1. In addition, by subtracting the pressure difference (ΔP ₀ ) in the kneading zone from the pressure difference (ΔP) before the kneading disc, the inflow effect pressure drop before and after the kneading zone was obtained. / Cm ^{2 or} less. The obtained pellets were dried at 130 ° C. overnight and then subjected to injection molding to evaluate various physical properties.

  In Examples 1 to 8, even if the PPS resin is alloyed with the PEI resin by adopting a specific melt-kneading method, the mechanical properties, heat distortion temperature, and dimensions equal to or higher than those of Comparative Example 1 (PEI simple substance). While exhibiting stability (hardness to warp deformation), the molding lower limit pressure was lowered, and the fluidity during melt molding was improved. On the other hand, Comparative Examples 3 to 6 show a certain good flow effect, but do not employ a specific melt-kneading method as in the present invention, so notched impact strength, weld tensile strength, surface after 180 ° C. treatment Roughness etc. were inferior. As described above, in the present application, since the compatibility between the polyetherimide resin and the polyphenylene sulfide resin is sufficiently improved, the mechanical strength, heat distortion temperature, and dimensional stability inherent in the polyetherimide resin are not sacrificed. It has been found that the melt fluidity is greatly improved, and it is useful as a reflector having a metal film for which thin-wall formability and weight reduction are desired.

Claims (6)

The total amount of (a) and (b) is 100% by weight, (a) a polyetherimide resin is more than 40% by weight and 99% by weight or less, and (b) a polyphenylene sulfide resin is 1% by weight to less than 60% by weight. A reflective plate in which a metal film is formed on a molded product obtained by molding a thermoplastic resin composition melt-kneaded while being kneaded. The thermoplastic resin composition is produced with an inflow effect pressure drop of 10 to 1000 kg / cm ² before and after a zone (extension flow zone) in which the thermoplastic resin composition melts and kneads while stretching and flowing. A reflector on which the metal film according to 1 is formed. The thermoplastic resin composition is manufactured by setting the ratio of the total length of the zone (extension flow zone) in which the thermoplastic resin composition is melt-kneaded by an extruder and melted and kneaded while stretching and flowing to the entire length of the extruder screw to be 5 to 60%. A reflector having a metal film according to claim 1, wherein the reflector is a metal plate. When the length of a zone in which the thermoplastic resin composition melts and kneads while stretching and flowing (extension flow zone) in the screw of the extruder is Lk and the screw diameter is D, Lk / D = 0.2 The reflector formed with the metal film according to any one of claims 1 to 3, wherein the reflector is manufactured as No. 10 to No. 10. The thermoplastic resin composition includes (c) a compound having at least one group selected from an epoxy group, an amino group, an isocyanate group, a hydroxyl group, and a mercapto group. A reflecting plate on which the metal film is formed. 6. The metal film according to claim 5, wherein the compound (c) having at least one group selected from an epoxy group, an amino group, an isocyanate group, a hydroxyl group, and a mercapto group is an alkoxysilane compound. Reflector.