JP2012131968A - Reflector plate with metal film formed thereon - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a reflector plate with a metal film formed thereon, showing excellent molding processability, adhesiveness of the metal film and falling-ball impact resistance.SOLUTION: In the reflector plate, a metal film is formed on a molded article produced by molding a polyphenylene sulfide resin composition. In the reflector plate with a metal film formed thereon, the polyphenylene sulfide resin composition is prepared by compounding (a) a polyphenylene sulfide resin, (b) an amorphous resin and (c) an alkoxysilane compound having an isocyanate group, the (a) polyphenylene sulfide resin forms a continuous phase (sea phase), the (b) amorphous resin forms a dispersion phase (island phase) dispersed as particles having a number average dispersion particle diameter of 1 nm or more and less than 1,000 nm, and the number of particles having a particle diameter of 1,000 nm or more in the dispersion particles of the (b) amorphous resin is 1.0% or less of the number of the whole particles.

Description

  The present invention is a reflecting plate in which a metal film is formed on a molded product obtained by molding a polyphenylene sulfide resin composition, and the metal film can be directly formed on the molded product. The present invention relates to a reflector having a metal film formed with excellent resistance to falling ball impact resistance.

  Polyphenylene sulfide (hereinafter may be abbreviated as PPS) resin has excellent properties as engineering plastics such as excellent heat resistance, chemical resistance, electrical insulation, moisture and heat resistance, and is mainly used for injection molding and extrusion molding. It is used for various electric / electronic parts, machine parts and automobile parts.

  Specifically, PPS resin is used as a light reflecting component because of the above-mentioned characteristics, but since a large amount of inorganic filler needs to be blended for the purpose of improving dimensional stability, surface smoothness is deteriorated. Before the metal film is formed, an undercoat process called an undercoat is required, and the melt viscosity becomes high, resulting in inferior molding processability, and the improvement thereof is strongly desired.

  Up to now, there have been some related to reflectors having a metal film made of PPS resin and polyetherimide (hereinafter abbreviated as PEI) resin or polyethersulfone (hereinafter abbreviated as PES) resin. A report has been made.

  For example, Patent Document 1 discloses a resin composition comprising polyarylene sulfide, polyetherimide, aminoalkoxysilane or epoxyalkoxysilane, and a lamp reflector using the resin composition. However, there is no description about using an alkoxysilane compound having an isocyanate group as a compatibilizing agent. Further, by finely dispersing the polyetherimide within the range of the number average dispersed particle diameter of 1 nm or more and less than 1000 nm, the number of polyetherimide particles having a particle diameter of 1000 nm or more is set to 1.0% or less of the total number of particles. Since the dimensional stability of the molded product is dramatically improved, there is no need to add a large amount of inorganic filler, and there is no description about the fact that a metal film can be directly formed without undercoating. . In addition, for the kneading method, only a general method is described. In this case, the polyetherimide is finely dispersed in the range of the number average dispersed particle diameter of 1 nm or more and less than 1000 nm, and the particle diameter is 1000 nm or more. It is substantially difficult to make the number of polyetherimide particles of 1.0% or less of the total number of particles.

  Patent Document 2 discloses a resin composition comprising polyarylene sulfide, polyetherimide, carbon black, and fibrous filler, and a lamp reflector using the resin composition. However, in Patent Document 2, since the fibrous filler is contained in a large amount of at least 25 parts by weight or more, the surface smoothness of the molded product is deteriorated, and the metal film cannot be directly formed without undercoating. . Further, by finely dispersing the polyetherimide within the range of the number average dispersed particle diameter of 1 nm or more and less than 1000 nm, the number of polyetherimide particles having a particle diameter of 1000 nm or more is set to 1.0% or less of the total number of particles. In addition, since the dimensional stability of the molded product is dramatically improved, there is no need to add a large amount of an inorganic filler, and there is no description that a metal film can be directly formed without undercoating. .

  Patent Document 3 discloses a polyarylene sulfide, an amorphous thermoplastic resin having a glass transition temperature of 140 ° C. or higher, graphite, a resin composition comprising a fibrous filler, and a lamp reflector comprising the resin composition. However, in Patent Document 3, since the fibrous filler is contained in a large amount of at least 15 parts by weight or more, the surface smoothness of the molded product is deteriorated and it is difficult to directly form the metal film. Further, the amorphous resin is finely dispersed in the range of the number average dispersed particle diameter of 1 nm or more and less than 1000 nm, and the number of amorphous resin particles having a particle diameter of 1000 nm or more is 1.0% or less of the total number of particles. Therefore, there is no need to add a large amount of an inorganic filler, so that a metal film can be directly formed without undercoating. Absent.

  Patent Document 4 discloses polyphenylene sulfide resin, polyetherimide resin or polyethersulfone resin, and polyphenylene sulfide having an isocyanate group-containing alkoxysilane and having a number average dispersed particle diameter of the polyetherimide resin or polyethersulfone resin of 1000 nm or less. A resin composition is disclosed. However, with regard to dispersed particles of polyetherimide resin or polyethersulfone resin, the dimensional stability of the molded product is dramatically improved by making the number of particles having a particle diameter of 1000 nm or more 1.0% or less of the total number of particles. Therefore, there is no need to add a large amount of an inorganic filler, and there is no description about that a metal film can be directly formed without undercoating. In addition, there is no description about improving the adhesive strength between the molded body and the metal film and improving the falling ball impact strength by controlling the dispersed particles of the polyetherimide resin or the polyethersulfone resin in this way. It wasn't.

  As described above, in any patent document, a polyetherimide resin or a polyethersulfone resin is finely dispersed in a range of a number average dispersed particle diameter of 1 nm or more and less than 1000 nm, and a polyetherimide resin having a particle diameter of 1000 nm or more or By making the number of polyethersulfone resin particles 1.0% or less of the total number of particles, the dimensional stability of the molded product is drastically improved, and it is not necessary to add a large amount of inorganic filler, so that surface smoothness is eliminated. However, there is no description on the technical idea that the metal film can be directly formed without undercoating. In addition, it has excellent adhesion to the metal film, improves the falling ball impact strength, and it is not necessary to add a large amount of an inorganic filler, so that there is no description about improving melt fluidity and improving moldability. It wasn't.

Japanese Patent Laid-Open No. 4-130158 (Claims) JP 2003-147200 A (Claims) JP 2003-268236 A (Claims) International Publication No. 2007/108384 (Claims)

  The present invention drastically improves dimensional stability without sacrificing the heat resistance, chemical resistance, flame retardancy, and mechanical strength inherent in polyphenylene sulfide resin, so inorganic fillers are added at all or in large amounts. Therefore, it is possible to directly form a metal film on a molded product, and to obtain a reflecting plate on which a metal film is formed, which is excellent in molding processability, metal film adhesion, and falling ball impact resistance. Is an issue.

  Therefore, as a result of intensive studies to solve the above problems, the present inventors have used an alkoxysilane compound having an isocyanate group as a compatibilizing agent, and in the polyphenylene sulfide resin, a polyetherimide resin or a polyethersulfone resin is 1 nm or more. While finely dispersing with a number average dispersed particle size of less than 1000 nm, the number of particles having a particle size of 1000 nm or more is 1.0% or less of the total number of particles of the polyetherimide resin or polyethersulfone resin dispersed particles. By controlling, the dimensional stability of the molded body made of the polyphenylene sulfide resin composition is dramatically improved even if it contains no inorganic filler or is added in a very small amount. Discovered that the film can be formed directly and reached the present invention It was.

That is, the present invention is as follows.
1. A reflecting plate in which a metal film is formed on a molded article obtained by molding a polyphenylene sulfide resin composition, wherein the polyphenylene sulfide resin composition is (a) polyphenylene sulfide, with the total of (a) and (b) being 100% by weight. (C) with respect to 100 parts by weight of a resin composition consisting of 99 to 60% by weight of resin, (b) 1 to 40% by weight of at least one amorphous resin selected from polyetherimide resin and polyethersulfone resin A polyphenylene sulfide resin composition comprising 0.1 to 10 parts by weight of an alkoxysilane compound having an isocyanate group, wherein the (a) polyphenylene sulfide resin forms a continuous phase (sea phase) in the morphology, (B) Dispersion in which an amorphous resin is dispersed with a number average dispersed particle diameter of 1 nm or more and less than 1000 nm The metal film is characterized in that the number of particles having a particle diameter of 1000 nm or more is 1.0% or less of the total number of particles with respect to the dispersed particles of the (b) amorphous resin. Formed reflector,
2. (B) The non-crystalline resin is dispersed with a number average dispersed particle diameter of 1 nm or more and less than 500 nm, and the reflector having the metal film according to 1,
3. Furthermore, (d) an inorganic filler is blended in a range of more than 0 parts by weight and less than 15 parts by weight with respect to a total of 100 parts by weight of the (a) polyphenylene sulfide resin and the (b) amorphous resin. A reflecting plate on which the metal film according to any one of 1 to 2 is formed,
4). (A) The reflection having a metal film as defined in any one of 1 to 3, wherein the polyphenylene sulfide resin has a melt viscosity (300 ° C., shear rate of 1000 / s) of 300 Pa · s or less. Board,
5. The amount of lower alcohol having 1 to 4 carbon atoms generated when the pellets of the polyphenylene sulfide resin composition are heated and melted at 350 ° C. for 30 minutes under vacuum is 0.6 mmol relative to the weight of the polyphenylene sulfide resin composition. % Or less, the reflector formed with the metal film according to any one of 1 to 4,
6). The polyphenylene sulfide resin composition comprises (a) 90 to 1% by weight of the polyphenylene sulfide resin, (b) the polyetherimide resin and the polyethersulfone resin, where the total of (a) and (b) is 100% by weight. 10 to 99% by weight of at least one amorphous resin selected, and 0.1 to 10 parts by weight of the alkoxysilane compound (c) having an isocyanate group with respect to 100 parts by weight of the total of (a) and (b). A reflector comprising the metal film according to any one of 1 to 5, which is obtained by previously melt-kneading the resin composition comprising: (a) the polyphenylene sulfide resin and further melt-kneading;
7). When the total of (a) and (b) is 100% by weight, at least one amorphous material selected from (a) polyphenylene sulfide resin 90 to 1% by weight, (b) polyetherimide resin and polyethersulfone resin. A resin composition comprising 0.1 to 10 parts by weight of the alkoxysilane compound having an isocyanate group (c) with respect to 10 parts by weight of the conductive resin and 100 parts by weight of the total of (a) and (b) is previously melted. After kneading, by further melt-kneading with the (a) polyphenylene sulfide resin, the total of (a) and (b) is 100% by weight, and (a) 99-60% by weight of the polyphenylene sulfide resin, ) A tree comprising 1 to 40% by weight of at least one amorphous resin selected from polyetherimide resins and polyethersulfone resins A polyphenylene sulfide resin composition comprising 0.1 to 10 parts by weight of the alkoxysilane compound having an isocyanate group (c) is produced with respect to 100 parts by weight of the composition, and the polyphenylene sulfide resin composition is molded. A method for producing a reflector having a metal film according to any one of 1 to 5, wherein the metal film is formed after
It is.

  According to the present invention, since the dimensional stability is greatly improved, it is not necessary to add an inorganic filler at all or in a large amount, so that a metal film can be formed directly without undercoating. In addition, it is possible to obtain a reflecting plate on which a metal film is formed, which is excellent in molding processability, metal film adhesion, and impact resistance against falling balls.

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

(A) Polyphenylene sulfide resin (a) 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, (a) the 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.

  Although there is no restriction | limiting in the melt viscosity of (a) PPS resin used by this invention, From a viewpoint with which a thin injection molded object is easy to be obtained, it is preferable that it is 300 Pa * s (300 degreeC, shear rate 1000 / s) or less. 200 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 (a) PPS resin used for this invention is demonstrated below, if (a) 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 (a) 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]
(A) 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 (a) PPS resin in a shorter time, it is also one of preferred embodiments to use a polymerization aid. Here, the polymerization assistant means (a) 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 (a) 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]
(A) In the production method of PPS resin, the sulfiding agent is usually used in the form of a hydrate, but before adding the polyhalogenated aromatic compound, the mixture containing the organic polar solvent and the sulfiding 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]
(A) 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]
(A) 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]
(A) The PPS resin may be produced through the above polymerization and recovery steps, and then subjected to acid treatment, hot water treatment, washing with an organic solvent, and alkali metal or alkaline earth metal treatment.

  When acid treatment is performed, it is as follows. (A) The acid used for the acid treatment of the PPS resin is not particularly limited as long as it does not have the function of decomposing the (a) 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 (a) those that decompose and deteriorate the PPS resin such as nitric acid are not preferable.

  As the acid treatment method, there is a method of immersing (a) the PPS resin in an acid or an acid aqueous solution, and it is possible to appropriately stir or heat as necessary. 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 (a) PPS resin is preferably washed several times with water or warm water in order to remove the remaining 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 (a) PPS resin by acid treatment.

  When performing hot water treatment, it is as follows. (A) 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 (a) PPS resin is small, it is not preferable.

  The water used is preferably distilled water or deionized water in order to exhibit the effect of preferable chemical modification of the (a) PPS resin by hot water washing. There is no particular restriction on the operation of the hot water treatment, and a predetermined amount of (a) PPS resin is put into a predetermined amount of water and heated and stirred in a pressure vessel, or a method of continuous hot water treatment is performed. Is called. (A) The ratio of the PPS resin and water is preferably larger, but usually a bath ratio of (a) 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. Furthermore, it is preferable that the (a) PPS resin that has finished this hot water treatment operation is washed several times with warm water in order to remove the remaining components.

  When washing with an organic solvent, it is as follows. (A) The organic solvent used for washing the PPS resin is not particularly limited as long as it does not have the action of decomposing (a) 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 such as (a) immersing a PPS resin in an organic solvent, and if necessary, stirring or heating can be appropriately performed. There is no restriction | limiting in particular about the washing | cleaning temperature at the time of wash | cleaning (a) 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 reflector having excellent light distribution performance, by repeating organic solvent cleaning and hot water of about 80 ° C. or hot water cleaning described above several times, residuals that cause fogging, surface sticking, etc. A method of removing the oligomer is preferred. Further, from the viewpoint of improving the reactivity with (c) an alkoxysilane compound having an isocyanate group which is a compatibilizing agent, an acid treatment method is preferred.

  In addition, (a) 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, (a) the PPS resin is preferably a substantially linear PPS that does not undergo high molecular weight by thermal oxidation crosslinking treatment in order to achieve the object of the present invention. In the present invention, a plurality of (a) PPS resins having different melt viscosities may be mixed and used.

(B) At least one amorphous resin selected from polyetherimide resin and polyethersulfone resin As the amorphous resin, at least one resin selected from polyetherimide resin and polyethersulfone resin is used. be able to. The polyetherimide referred to in the present invention is a polymer containing an aliphatic, alicyclic or aromatic ether unit and a cyclic imide group as repeating units, and is not particularly limited as long as it is a polymer having melt moldability. . 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 SABIC Innovative Plastics under the trademark “Ultem”.

  The molecular weight of the polyetherimide is not particularly limited, but the surface appearance of the resin composition molded article according to the present invention is that the weight average molecular weight is 30,000 or more, preferably 50,000 or more, and more preferably 60,000 or more. This is preferable from the viewpoint of improving the orientation performance of the reflecting plate on which the finally obtained metal film is formed. The upper limit of the weight average molecular weight is not particularly limited as long as it is within a range in which melt molding can be performed, and is preferably 100,000 or less.

  The weight average molecular weight referred to here is an LC-10ADvp device manufactured by Shimadzu Corporation, the mobile phase is dimethylformamide / lithium chloride (95.5 wt% / 0.5 wt%), and the stationary phase is a SHODEX KF-805L column. It is a relative average molecular weight calculated with PMMA as a standard substance.

  The polyether sulfone as referred to in the present invention is a resin having a sulfone bond and an ether bond in a repeating skeleton. The following can be illustrated as a typical structure.

  Generally, it is marketed under the trademark of “Victrex” PES and “Sumika Excel”.

(C) Alkoxysilane compound having isocyanate group In the present invention, (b) an amorphous resin is finely dispersed in (a) PPS resin with a number average dispersed particle size of 1 nm or more and less than 1000 nm, thereby forming a molded product. The dimensional stability of the is greatly improved. In order to finely disperse the amorphous resin (b) with such a number average dispersed particle size, it is necessary to add an alkoxysilane compound having an isocyanate group as a compatibilizing agent.

  Examples of the alkoxysilane compound having an isocyanate group useful in the present invention include γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatepropylmethyldiethoxysilane, γ- Illustrative examples include isocyanatepropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, and γ-isocyanatopropyltrichlorosilane.

  Among them, (a) PPS resin and (b) γ-isocyanatopropyltriethoxysilane and γ-isocyanatopropyltrimethoxysilane are particularly preferable because of excellent reactivity with the amorphous resin.

  The blending ratio of (a) PPS resin and (b) amorphous resin in the present invention is (a) / (b) = 99 to 60% by weight, where the total of (a) and (b) is 100% by weight. 1 to 40% by weight, more preferably (a) / (b) = 97 to 70% by weight / 3 to 30% by weight, (a) / (b) = 95 to 80% by weight / 5 The range of ˜20% by weight is more preferable. (B) If the amorphous resin is less than 1% by weight, sufficient dimensional stability cannot be obtained. (B) If the amorphous resin exceeds 40% by weight, the melt fluidity is remarkably hindered, and the material cost Is unfavorable because it increases.

  The blending amount of the alkoxysilane compound having an isocyanate group (c) in the present invention is in the range of 0.05 to 10 parts by weight with respect to a total of 100 parts by weight of (a) PPS resin and (b) amorphous resin. The range of 0.1 to 5 parts by weight is more preferable, and the range of 0.2 to 3 parts by weight is more preferable. (C) When the amount of the alkoxysilane compound having an isocyanate group is less than 0.05 parts by weight, it becomes difficult to finely disperse the amorphous resin with a number average dispersed particle diameter of 1 nm or more and less than 1000 nm. . On the other hand, when the amount of (c) the alkoxysilane compound having an isocyanate group exceeds 10 parts by weight, the melt fluidity is remarkably hindered and the material cost increases.

  The reflecting plate on which the metal film of the present invention is formed is a reflecting plate that is greatly improved in dimensional stability, and excellent in adhesion to the metal film and anti-falling ball impact resistance. In order to express such characteristics, in the morphology (phase structure) of the polyphenylene sulfide resin composition, (a) the PPS resin forms a sea phase (continuous phase or matrix), and (b) the amorphous resin is an island phase. It is necessary to form (dispersed phase).

  In addition, (b) the number average dispersed particle size of the amorphous resin needs to be 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. (B) If the number average dispersed particle size of the amorphous resin is in the range of 1000 nm or more, the effect of improving the dimensional stability of the molded product obtained by molding the polyphenylene sulfide resin composition becomes insufficient, so warp deformation is likely to occur. Become. In addition, the specific surface area of the (b) amorphous resin in the polyphenylene sulfide resin composition is reduced, resulting in a decrease in the proportion of the (b) amorphous resin that can be in contact with the metal film and a decrease in adhesion to the metal film. In addition, since a sufficient impact strength improvement effect cannot be obtained, it becomes easy to break when dropped or impacted. On the other hand, when the number average dispersed particle diameter of the (b) amorphous resin is less than 1 nm, it is not preferable from the viewpoint of productivity.

  The number average dispersed particle diameter here is (a) PPS resin melting peak temperature + 40 ° C. molding temperature (vertical) 100 mm × (horizontal) 70 mm × (thickness) 3 mm (gate shape: film gate, mold mirror surface) A specular square plate having a roughness of 0.03 s) was formed, and a thin piece having a thickness of 0.1 μm or less was cut at −20 ° C. from the central portion of the cross section obtained by cutting the central portion in a direction perpendicular to the resin flow direction. In addition, with an H-7100 type transmission electron microscope (resolution (particle image) 0.38 nm, magnification of 500 to 600,000 times) manufactured by Hitachi, Ltd., any 100 pieces when observed at a magnification of 20,000 times, (B) For the dispersed portion of the amorphous resin, first, the maximum diameter and the minimum diameter are measured, the average value is set as the dispersed particle diameter, and then the average value is obtained.

  Furthermore, in the reflecting plate on which the metal film of the present invention is formed, the dimensional stability is drastically improved even when the inorganic filler is not contained or even a small amount of a specific amount or less. In order to express such characteristics, the number of particles having a particle diameter of 1000 nm or more needs to be 1.0% or less of the total number of particles in (b) the amorphous resin dispersed particles, and 0.5% or less. And more preferably 0%. (B) If the number of particles having a particle size of 1000 nm or more exceeds 1.0% due to insufficient dispersion of the amorphous resin or aggregation and coalescence during melt molding, the number average dispersed particle size is temporarily Even if it is in the range of 1 nm or more and less than 1000 nm, the effect of improving the dimensional stability of the molded product becomes insufficient, and warpage deformation after heat treatment is likely to occur.

  The number of (b) amorphous resin particles having a particle diameter of 1000 nm or more is the same as the above-mentioned number average dispersed particle diameter (a) PPS resin melting peak temperature + molding temperature of 40 ° C. (vertical) 100 mm × ( Horizontal) 70 mm x (thickness) 3 mm (gate shape: film gate, mold mirror surface roughness: 0.03 s), a cross-section obtained by molding a mirror-surface square plate and cutting its central portion in a direction perpendicular to the resin flow direction A thin piece of 0.1 μm or less was cut at −20 ° C. from the center of the above, and an H-7100 transmission electron microscope (resolution (particle image) 0.38 nm, magnification: 500 to 600,000 times) manufactured by Hitachi, Ltd. With respect to any 100 dispersed particles of (b) amorphous resin observed at a magnification of 20,000 times, first, the maximum diameter and the minimum diameter are measured, and the average value is defined as the dispersed particle diameter. Of which, the dispersed particle diameter is 1000 nm. It is as defined as the percentage of the number of a top particle.

  In addition, it is desirable that the morphology (phase structure) of the polyphenylene sulfide resin composition is stable in the reflector having the metal film of the present invention. That is, after injection molding once, the molded piece is pulverized and injection molded again, and (a) the PPS resin forms a sea phase (continuous phase or matrix), and (b) an amorphous resin. It is preferable to form an island phase (dispersed phase). Further, (b) the number average dispersed particle size of the amorphous resin 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. Furthermore, (b) the number of particles having a particle diameter of 1000 nm or more in the amorphous resin dispersed particles is 1.0% or less, more preferably 0.5% or less, and further 0% of the total number of particles. Most preferred.

  The phase structure of the PPS resin composition used in the present invention is dissolved in a soluble solvent or the like common to (a) PPS resin and (b) amorphous resin, and once subjected to molecular compatibility, followed by spinodal decomposition. (B) A method of uniformly controlling the dispersed particle size of the amorphous resin can also be exemplified, but from the viewpoint of productivity, the (b) amorphous resin is not melted by spin kneading without going through spinodal decomposition. A method of controlling the phase structure so that the dispersed particle diameter has a specific distribution is preferable.

(D) Inorganic filler (d) An inorganic filler can also be mix | blended and used for the PPS resin composition used for the reflecting plate in which the metal film of this invention was formed. 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 silica, calcium carbonate, and mica are preferable, and calcium carbonate and mica are more preferable from the viewpoint of achieving a balance between surface smoothness and mechanical properties of a resin molded product. 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.

  The blending amount of the inorganic filler (d) is preferably in the range of more than 0 parts by weight and less than 15 parts by weight with respect to 100 parts by weight of the total of (a) PPS resin and (b) amorphous resin, and more than 0 parts by weight. The range of not more than parts by weight is more preferable, and more than 0 parts by weight and not more than 5 parts by weight is still more preferable. (D) The blending of the inorganic filler is effective for improving the dimensional stability, heat resistance, and rigidity, but a large amount of blending of 15 parts by weight or more deteriorates the surface smoothness, so an undercoat is necessary. Since it becomes impossible to form a metal film directly, it is not preferable. In addition, the addition of an inorganic filler increases the melt viscosity, which deteriorates the moldability and makes it difficult to obtain a particularly thin molded product.

Other Additives In addition, the polyphenylene sulfide resin composition used for the reflecting plate on which the metal film of the present invention is formed is blended with a resin other than (b) an amorphous resin as long as the effects of the present invention are not impaired. You may do it. Specific examples thereof include polyamide resin, polybutylene terephthalate resin, polyethylene terephthalate resin, modified polyphenylene ether resin, polysulfone resin, polyallyl sulfone resin, polyketone resin, polyarylate resin, liquid crystal polymer, polyether ketone resin, polythioether ketone. Examples thereof include resins, polyether ether ketone resins, polyimide resins, polyamideimide resins, tetrafluoropolyethylene resins, and olefin polymers and copolymers that do not contain an epoxy group such as ethylene / 1-butene copolymer.

  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 soap such as polyethylene wax, ethylenediamine / stearic acid / sebacic acid polycondensate, release agent such as silicone compound, anti-coloring agent such as hypophosphite, (3,9-bis [2- (3 -(3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane) Phenolic antioxidant, (bis (2,4-di-cumylphenyl) pentaerythritol-di-phospha In addition to phosphorus-based antioxidants such as water), usual additives such as water, lubricants, ultraviolet light inhibitors, colorants, and foaming agents can be blended. If any of the above compounds exceeds 20% by weight of the total composition, (a) the original properties of the PPS resin are impaired, which is not preferable, and it is preferable to add 10% by weight or less, more preferably 1% by weight or less.

  For the polyphenylene sulfide resin composition used for the reflector having the metal film of the present invention, the amount of lower alcohol having 1 to 4 carbon atoms generated when heated and melted at 350 ° C. for 30 minutes under vacuum is polyphenylene sulfide. It is preferably 0.6 mmol% or less, more preferably 0.4 mmol% or less, still more preferably 0.3 mmol% or less, and even more preferably 0.25 mmol% or less with respect to the weight of the sulfide resin composition. Particularly preferred. In addition, the C1-C4 lower alcohol said here is what is produced | generated when the unreacted alkoxysilane in the alkoxysilane compound which has (c) isocyanate group added as a compatibilizing agent hydrolyzes. It is. By setting the alcohol generation amount to 0.6 mmol% or less, volatile components generated when the polyphenylene sulfide resin composition is molded is reduced, and it becomes possible to impart smoothness and specularity to the surface of the molded product. In the range where the amount of alcohol generated exceeds 0.6 mmol%, not only the smoothness and specularity of the surface of the molded product can be obtained, but also the adhesion between the surface of the molded product and the metal film is reduced by the formed void. It is not preferable.

  The amount of alcohol generated is collected and quantified by vacuum-sealing polyphenylene sulfide resin composition pellets dried in hot air overnight at 130 ° C. in a glass ampule and heating it in a tubular furnace. A glass ampoule having an abdomen of 100 mm × 25 mm, a neck of 255 mm × 12 mm, and a wall thickness of 1 mm is used. As a specific method for determining the amount of alcohol generated, only the abdomen of a glass ampoule in which 3 g of polyphenylene sulfide resin composition pellets are vacuum-sealed is placed in a 350 ° C. tubular furnace (Asahi Rika Seisakusho ceramic electric tubular furnace ARF-30K). By inserting and heating for 30 minutes, the volatilized gas is cooled and deposited at the neck of the ampoule not heated by the tubular furnace. After the neck is cut out, the attached gas is dissolved and recovered in 4 g of N-methyl-2-pyrrolidone (NMP). Next, the NMP solution of the collected gas is separated and quantified by a gas chromatographic method using GC-14A manufactured by Shimadzu Corporation to obtain the amount of alcohol generated.

Production Method of Resin Composition As a production method of the polyphenylene sulfide resin composition used for the reflector having the metal film of the present invention, it is generally known such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, and a mixing roll. As a representative example, a method of supplying raw materials to the melt kneader and (a) melt kneading at a processing temperature of 5 to 100 ° C. of the melting peak temperature of the PPS resin can be given. At this time, it is preferable to use a twin-screw extruder and relatively increase the shearing force in terms of finely dispersing the number average dispersed particle diameter of the amorphous resin in the range of 1 nm to less than 1000 nm. . Specifically, L / D (L: screw length, D: screw diameter) is 20 or more, preferably 30 or more, and there are 3 or more kneading parts per screw, and more preferably 5 or more. Using a twin screw extruder, the screw rotation speed is 200 to 1000 rotations / minute, preferably 300 to 1000 rotations / minute, and the resin temperature during mixing is (a) the melting peak temperature of the PPS resin +10 to 70 ° C. Thus, a method of kneading can be preferably used. The upper limit of L / D is not particularly limited, but 60 or less is preferable from the viewpoint of economy. The upper limit of the kneading portion is not particularly limited, but is preferably 10 or less from the viewpoint of productivity.

  Further, as a method for producing a polyphenylene sulfide resin composition used for a reflector having a metal film according to the present invention, melt kneading while stretching and flowing can be exemplified as a preferred method. Here, 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, since the dispersion efficiency is higher than that of the shear flow generally used at the time of melt kneading, it is essentially incompatible with (a) PPS resin and (b) amorphous resin. When it is desired to alloy different resins and to make the island component highly finely dispersed, for example, it is necessary to carry out some reaction, and in the extension flow method, it 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 addition, when melt kneading is performed using an extruder, the inflow effect pressure drop before and after the zone for melt kneading while stretching and flowing (extension flow zone) 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, when melt kneading is performed using an extruder, in order to provide an extension flow field suitable for the present invention, the total number of zones (extension flow zones) in which melt kneading is performed while extending and flowing over the entire length of the screw of the extruder. Is preferably in the range of 5 to 60%, more preferably 10 to 55%, and still more preferably 15 to 50%.

  In addition, when melt kneading is performed using an extruder, the length of a zone (extension flow zone) for melt kneading while stretching and flowing in the screw of the extruder is Lk, and the screw diameter is D, kneadability, From the viewpoint of 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.

  When performing melt-kneading using an extruder, a specific method of a zone for melt-kneading while stretching and flowing includes a kneading disk, and the top of the kneading disk on the disk front side and the top on the rear surface side thereof. It is a twist kneading disk with a spiral angle θ that is in the range of 0 ° <θ <90 ° in the half-rotation direction of the screw or a flight screw. As a preferred example, a resin passage having a reduced cross-sectional area from the side toward the rear end side is formed, or a cross-sectional area through which the molten resin passes in the extruder is temporarily reduced. Can be mentioned.

  Moreover, when melt-kneading 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, 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 (dimensional stability, mechanical properties, etc.) of the thermoplastic resin composition are improved. It is hard to be done. 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.

  Regarding the mixing order of the raw materials, a method in which all the raw materials are blended and then melt-kneaded by the above method, a method in which some raw materials are blended and melt-kneaded by the above-described method, and this and the remaining raw materials are further blended and melt-kneaded Alternatively, after blending some raw materials, a method of mixing the remaining raw materials using a side feeder during melt-kneading with a twin-screw extruder can be mentioned, but the dimensional stability of the present invention has been dramatically improved. In order to obtain a reflector having a metal film, a resin composition comprising (a) a PPS resin, (b) an amorphous resin, and (c) an alkoxysilane compound having an isocyanate group is previously melt-kneaded (b ) After preparing a high concentration of amorphous resin, it is important to (a) further melt and knead and dilute with PPS resin.

  (A) PPS resin, (b) amorphous resin and (c) (a) PPS resin and (b) amorphous resin when melt-kneaded in advance a resin composition comprising an alkoxysilane compound having an isocyanate group The blending ratio is in the range of (a) / (b) = 90-1% by weight / 10-99% by weight, with the total of (a) and (b) being 100% by weight, and (a) / (b) = 85-10 wt% / 15-90 wt% is preferred, (a) / (b) = 80-30 wt% / 20-70 wt% is more preferred, (a) / (b) = A range of 70 to 50% by weight / 30 to 50% by weight is more preferable. When (b) the amorphous resin is less than 10% by weight, the reaction between (a) the PPS resin, (b) the amorphous resin, and (c) the alkoxysilane compound having an isocyanate group does not proceed sufficiently. ) Regarding the dispersed particles of the amorphous resin, the number of particles having a particle diameter of 1000 nm or more tends to exceed 1.0% of the total number of particles, which is not preferable.

  Further, the melt viscosity of the (a) PPS resin when the resin composition comprising (a) a PPS resin, (b) an amorphous resin, and (c) an alkoxysilane compound having an isocyanate group is previously melt-kneaded is particularly limited. However, it is preferably 150 Pa · s or more, and more preferably 200 Pa · s or more, from the viewpoint that shearing force is easily involved during kneading. The melt viscosity referred to here is a value measured using a Capillograph manufactured by Toyo Seiki Co., Ltd. under conditions of 300 ° C. and a shear rate of 1000 / s.

  The blending ratio of (c) an alkoxysilane compound having an isocyanate group when a resin composition comprising (a) a PPS resin, (b) an amorphous resin, and (c) an alkoxysilane compound having an isocyanate group is previously melt-kneaded is: , (A) PPS resin and (b) A total of 100 parts by weight of amorphous resin is in the range of 0.05 to 10 parts by weight, more preferably in the range of 0.1 to 5 parts by weight. A range of ˜3 parts by weight is more preferred. (C) When the amount of the alkoxysilane compound having an isocyanate group is less than 0.05 parts by weight, it becomes difficult to finely disperse the amorphous resin with a number average dispersed particle diameter of 1 nm or more and less than 1000 nm. . On the other hand, if the amount of (c) the alkoxysilane compound having an isocyanate group exceeds 10 parts by weight, gas is frequently generated and the melt fluidity is remarkably hindered.

  The blending amount of (a) PPS resin when the resin composition previously melt-kneaded and (a) PPS resin is further melt-kneaded is such that the finally obtained PPS resin composition is (a) and (b) (C) having an isocyanate group with respect to 100 parts by weight of a resin composition comprising (a) 99 to 60% by weight of a polyphenylene sulfide resin and (b) 1 to 40% by weight of an amorphous resin. If an alkoxysilane compound will be 0.1-10 weight part, there will be no restriction | limiting in particular.

  At this time, the melt viscosity of the resin composition previously melt-kneaded and (a) the PPS resin to be melt-kneaded can be freely selected, thereby controlling the fluidity of the finally produced polyphenylene sulfide resin composition. Is also possible. From the viewpoint of improving thin-wall moldability by good fluidization, the melt viscosity of the (a) PPS resin during further melt-kneading is preferably 150 Pa · s or less, and more preferably 100 Pa · s or less. The melt viscosity referred to here is a value measured using a Capillograph manufactured by Toyo Seiki Co., Ltd. under conditions of 300 ° C. and a shear rate of 1000 / s.

  In addition, after melt-kneading a resin composition comprising (a) a PPS resin, (b) an amorphous resin, and (c) an alkoxysilane compound having an isocyanate group in advance, (a) when further melt-kneading with the PPS resin. (A) PPS resin, (b) Amorphous resin, and (c) A resin composition comprising an alkoxysilane compound having an isocyanate group is previously melt-kneaded and pelletized, and then blended with (a) PPS resin. Further, it may be melt kneaded, or a resin composition comprising (a) a PPS resin, (b) an amorphous resin, and (c) an alkoxysilane compound having an isocyanate group is previously melt melt kneaded using a side feeder. (A) PPS resin can be supplied from the middle of the extruder and further melt-kneaded.

  When (d) an inorganic filler is blended, (a) a PPS resin, (b) an amorphous resin, and (c) a resin composition comprising an alkoxysilane compound having an isocyanate group is previously melt-kneaded, or ( a) It can be blended with any of the PPS resin and further melt kneaded. From the viewpoint of improving the dispersibility of (b) the amorphous resin, (a) the PPS resin and (b) the amorphous resin And (c) a resin composition comprising an alkoxysilane compound having an isocyanate group is melt-kneaded in advance, and (a) it is preferably blended when further melt-kneaded with the PPS resin.

  With respect to the polyphenylene sulfide resin composition used for the reflecting plate on which the metal film of the present invention is formed, (b) from the viewpoint of finely dispersing the number average dispersed particle size of the amorphous resin in the range of 1 nm to less than 1000 nm, From the viewpoint of reducing the amount of lower alcohol having 1 to 4 carbon atoms generated when heated and melted at 350 ° C. for 30 minutes under vacuum to 0.6 mmol% or less with respect to the weight of the polyphenylene sulfide resin composition. A preferable production method is to once melt-knead and then melt-knead once more. The upper limit of the number of kneading is not particularly limited, but after melt-kneading once, kneading once to three times is preferable from the viewpoint of (b) fine dispersion of the amorphous resin, alcohol reducing effect and economical efficiency. .

  Furthermore, from the viewpoint of obtaining a polyphenylene sulfide resin composition with a small amount of alcohol generated, 0.02 water is added to 100 parts by weight of the total of (a) PPS resin and (b) amorphous resin during melt kneading. A method of adding a part or more is also mentioned as a preferable production method. As a result of the hydrolysis of the alkoxysilane compound being accelerated by this method, the amount of alcohol generated from the resulting polyphenylene sulfide resin composition can be further reduced. Furthermore, not only the amount of alcohol but also impurities derived from oligomers and by-products are easily devolatilized and removed, which further improves melt molding processability, surface roughness of the molded product, specularity, and adhesion to metal films. To do. The method of adding water is not particularly limited, but a method of side-feeding water using a liquid feeding device such as a gear pump or a plunger pump from the middle of the extruder, or once melting and kneading and further melting once or more. When kneading, a preferable method is to mix water or side feed from the middle of the extruder.

  About the addition amount of water, 0.02 part or more is preferable, More preferably, it is 0.5 part or more, Furthermore, 1.0 part or more is preferable. The upper limit of the amount of water added is not particularly limited, but is preferably less than 5 parts from the viewpoint of kneadability and pressure increase in the extruder due to water vapor.

  The timing of adding water is not particularly limited, but is preferably after (c) an alkoxysilane compound having an isocyanate group has reacted with (a) a polyphenylene sulfide resin or (b) an amorphous resin, and once melt-kneaded. It is particularly preferable to add it later when it is further melt-kneaded once or more.

  In order to obtain a polyphenylene sulfide resin composition with a small amount of alcohol generated, a method of reinforcing kneading force by arranging five or more kneading parts, a method of using an extruder with a long kneading length, and the like are preferable. It is not necessarily limited to the method of kneading twice or more or the method of adding water.

  In the present invention, (a) in the PPS resin, (b) the amorphous resin is finely dispersed with a number average dispersed particle diameter of 1 nm or more and less than 1000 nm, and (b) the dispersed particles of the amorphous resin By controlling the number of particles with a diameter of 1000 nm or more to be 1.0% or less of the total number of particles, the dimensional stability is drastically improved even if inorganic fillers are not included or a very small amount is added. Thus, it has been found that a metal film can be directly formed without an undercoat. In order to exhibit such characteristics, the surface roughness (center line) after treating the PPS resin composition mirror surface molded product (metal mold surface roughness: 0.03 s) before forming the metal film at 180 ° C. for 24 hours. (Average roughness) Ra is preferably 40 nm or less. When the surface roughness (centerline average roughness) Ra after the heat treatment treated at 180 ° C. for 24 hours exceeds 40 nm, the warp deformation when the reflecting plate on which the metal film is formed is exposed to the use environment increases. This means that even if the metal film is formed directly at an angle, an excellent alignment performance (image clarity) cannot be obtained. The lower limit of the surface roughness (centerline average roughness) is not particularly limited, but 1 nm or more can be exemplified as a preferable range.

  The surface roughness (centerline average roughness) Ra was determined by subjecting a specular square plate (longitudinal) 100 mm × (horizontal) 70 mm × (thickness) 3 mm to 180 ° C. × 24 hr. For the mirror surface portion, the center line average roughness Ra defined in JISB0601 was measured at any 10 locations with a surface roughness measuring instrument manufactured by Mitutoyo Corporation, and the average value was defined as the surface roughness after heat treatment. .

  In the present invention, (a) in the PPS resin, (b) the amorphous resin is finely dispersed with a number average dispersed particle diameter of 1 nm or more and less than 1000 nm, and (b) the dispersed particles of the amorphous resin By controlling the number of particles having a diameter of 1000 nm or more to be 1.0% or less of the total number of particles, the dimensional stability is remarkably improved. Therefore, even if an inorganic filler is not contained or added, Since warping deformation can be sufficiently suppressed with a small amount, it has a feature of excellent melt fluidity. In order to express such characteristics, the rod flow length at a resin temperature of 320 ° C. is preferably 50 mm or more, more preferably 70 mm or more, and further preferably 90 mm or more. When the rod flow length is less than 50 mm, it means that the melt flowability of the PPS resin composition is low, and it is difficult to obtain a thin molded product, which is disadvantageous from the viewpoint of weight reduction. The upper limit value of the rod flow length is not particularly limited, but 150 mm or less can be exemplified as a preferable range.

  The rod flow length was set under the conditions of using an injection molding machine Promat 40/20 manufactured by Sumitomo Heavy Industries, Ltd. with a resin temperature of 320 ° C., a mold temperature of 130 ° C., an injection speed setting of 99%, and an injection pressure setting of 45%. , (Length) 150 mm × (width) 12.6 mm × (thickness) 0.5 mm (gate position: width side of molded piece, gate shape: film gate) The filling end length in the longitudinal direction is measured from the gate position side, and the average value is defined as the rod flow length.

Formation of Metal Film A reflector formed with the metal film of the present invention is a molded product obtained by molding the above-described polyphenylene sulfide resin composition by a known method such as injection molding, extrusion molding, compression molding, blow molding, injection compression molding or the like. Although it is a reflecting plate which formed the metal film, it is especially preferable that it is a reflecting plate which formed the metal film in the molded article shape | molded by injection molding in the temperature range of 280 degreeC-340 degreeC.

  As a method for forming a metal film, metals such as aluminum, copper, nickel, cobalt, nickel-cobalt alloy, silver, etc., wet methods such as electroplating and electroless plating, vacuum deposition, sputtering, ion plating, etc. A method of forming a film by a dry method can be mentioned, and among them, a method of vacuum deposition after degreasing the surface of a molded product with isopropyl alcohol or the like is preferable from the viewpoint of cost and workability.

  Since the polyphenylene sulfide resin composition molded article used for the reflecting plate on which the metal film of the present invention is formed does not contain an inorganic filler or is a small amount of a specific amount or less, it has excellent surface smoothness. However, a primer (undercoat) treatment or a surface roughening treatment may be performed as necessary. Examples of the primer include epoxy, acrylic, urethane, acrylurethane, and melamine. Examples of the surface roughening treatment include UV treatment, corona discharge treatment, and plasma treatment.

  If necessary, a transparent protective film having good heat resistance may be provided on the metal film. Specific examples of the protective film include a coating type top coat, a plasma polymerization film, and a vapor deposition film.

  The reflector formed with the metal film of the present invention has an unknown attribute that it has excellent dimensional stability, melt molding processability, adhesion to the metal film, and good impact resistance to falling balls. Downlight covers and reflectors for fixtures, reflectors and lamp covers for projectors, reflectors and lamp parts used in LED packages, reflectors for backlight condensing such as LCD TVs and LCD panels, guide lights and advertising lights Reflectors used for display lamps, headlamps for automobiles and motorcycles, lamp reflectors for fog lamps or rear lamps, reflectors for room lamps, lamp housings, lamp units, reflectors for medical device illumination, UV spot irradiators, etc. Reflectors for physics and chemistry equipment, lighting fixtures for photography (strobes) Compactors, are useful, such as the illuminated push switch and reflectors for photoelectric switch.

  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.

[Injection molding of square plate]
Using an injection molding machine SE75-DUZ manufactured by Sumitomo Heavy Industries, under the conditions of a resin temperature of 320 ° C. and a mold temperature of 130 ° C. (vertical) 100 mm × (horizontal) 70 mm × (thickness) 3 mm (gate shape: film gate , A mirror square plate having a mold mirror surface roughness of 0.03 s) was molded.

[Number average dispersed particle size]
The center part of the injection-molded square plate is cut in a direction perpendicular to the resin flow direction, and a thin piece of 0.1 μm or less is cut at −20 ° C. from the center part of the cross section. 7100-type transmission electron microscope (resolution (particle image) 0.38 nm, magnification: 500 to 600,000 times) Any 100 (b) amorphous resins observed at 20,000 times magnification For the dispersed portion, first, the maximum diameter and the minimum diameter were measured, the average value was used as the dispersed particle diameter, and then the number average dispersed particle diameter, which was the average value thereof, was obtained.

[Number of amorphous resin particles having a particle diameter of 1000 nm or more (%)]
The center part of the injection-molded square plate is cut in a direction perpendicular to the resin flow direction, and a thin piece of 0.1 μm or less is cut at −20 ° C. from the center part of the cross section. 100 arbitrary (b) amorphous resins when observed at 70000 magnification with a 7100 type transmission electron microscope (resolution (particle image) 0.38 nm, magnification: 500 to 600,000 times) For each of the dispersed particles, first, the maximum diameter and the minimum diameter were measured, and the average value was used as the dispersed particle diameter, and the percentage of the number of particles having the dispersed particle diameter of 1000 nm or more with respect to the total number of particles was determined.

[Alcohol generation]
A glass ampoule having an abdomen of 100 mm × 25 mm, a neck of 255 mm × 12 mm, and a wall thickness of 1 mm was weighed with 3 g of PPS resin composition pellets dried with hot air overnight at 130 ° C. and then vacuum-sealed. Only the abdomen of this glass ampoule was inserted into a ceramic electric tubular furnace ARF-30K manufactured by Asahi Rika Seisakusho and heated at 350 ° C. for 30 minutes. After taking out the ampule, the neck of the ampoule which was not heated by the tubular furnace and to which volatile gas adhered was cut out with a file. Next, the attached gas was dissolved and recovered in 4 g of NMP, and then the amount of alcohol was estimated by gas chromatography using GC-14A manufactured by Shimadzu Corporation.

[Surface appearance]
By visually observing the injection-molded specular square plate, superiority or inferiority was determined as follows.
◎ Good with no cloudiness or floating of filler.
○ Although it is at a practical level, inconspicuous cloudiness and floating of fillers are recognized.
X Cloudiness, floating of filler, etc., practicality is low.

[Surface roughness before heat treatment (centerline average roughness Ra)]
With respect to the mirror surface portion of the injection-molded mirror surface square plate, the center line average roughness Ra defined in JISB0601 is measured at any 10 locations with a surface roughness measuring instrument manufactured by Mitutoyo Corporation, and the average value thereof is measured. Was the surface roughness before heat treatment. The lower the value, the better the surface smoothness.

[Surface roughness after heat treatment (centerline average roughness Ra)]
After heat-treating the injection-molded mirror-surface square plate in a hot air dryer at 180 ° C. for 24 hours, the mirror surface portion of the mirror-surface square plate is arbitrarily surface-measured by Mitutoyo Corp. The centerline average roughness Ra defined in JISB0601 was measured, and the average value was defined as the surface roughness after heat treatment. The lower the numerical value, the better the surface smoothness, and the smaller the difference from the surface roughness before heat treatment, the lower the warpage deformation during the heat treatment.

[Aluminum deposition]
About the mirror surface part of the said injection-molded mirror surface square plate, after degreasing with isopropyl alcohol, vapor deposition of metallic aluminum was performed using the vacuum deposition apparatus by Hitachi, Ltd. The thickness of the metal film was approximately 0.1 μm.

[Untreated product adhesion test]
Depth reaching the dough so that 100 squares with a 1 mm interval can be made on the vapor deposition surface of the mirror-finished square plate molded metal aluminum vapor deposition using a commercially available NT cutter (blade 9 mm wide, 35 ° inclined blade). After making a cut with, attach a tape (Nichiban cello tape (registered trademark), width 18 mm) with adhesive strength of 3.4 to 3.9 N / cm), and hold both ends of the tape in the vertical direction. Torn off. At this time, the superiority or inferiority was determined as follows according to the number of cells remaining without peeling.
◎ 100-91
○ 90-81
△ 80 ~ 41
X40-0.

[Cold heat-treated product adhesion test]
The mirror-finished square plate molded article on which the metal aluminum is deposited is subjected to three cycles of cold heat treatment with 90 ° C. × 1 hour → room temperature × 15 minutes → −20 ° C. × 1 hour → room temperature × 15 minutes as one cycle, After being allowed to stand for a long time, the superiority or inferiority of the adhesiveness was determined in the same manner as in the untreated product adhesion test described above.

[Moisture heat treated product adhesion test]
The metal plate-deposited square plate molded article is treated for 100 hours in a high-humidity and high-temperature tank set at 60 ° C. and a relative humidity of 95%, and then left at room temperature for 12 hours. The superiority or inferiority of the adhesion was determined in the same manner as the property test.

[Falling ball impact test]
The square plate molded product on which the metal aluminum is vapor-deposited is placed on a (vertical) 70 mm × (horizontal) 70 mm × (height) 50 mm cradle, and a 200 g hard ball is dropped from the height of 100 cm into the middle of the molded product. The superiority or inferiority was determined as follows by confirming the presence or absence of cracks and cracks.
○ No destruction.
△ Only cracks.
× Destruction with cracks.

[Bar flow length evaluation]
Using a Sumitomo Heavy Industries injection molding machine Promat 40/20, under the conditions of a resin temperature of 320 ° C., a mold temperature of 130 ° C., an injection speed setting of 99%, and an injection pressure setting of 45%, (length) 150 mm × A molded piece of (width) 12.6 mm × (thickness) 0.5 mm (gate position: width side of molded piece, gate shape: film gate) was continuously injection-molded 10 times. Each of the obtained molded pieces was measured for the filling end length in the longitudinal direction from the gate position side, and the average value was taken as the rod flow length. The larger the value of the rod flow length, the higher the fluidity of the resin composition.

[Weight average molecular weight measurement of polyetherimide]
Using a Shimadzu LC-10ADvp apparatus, the mobile phase was dimethylformamide / lithium chloride (95.5 wt% / 0.5 wt%), the stationary phase was two SHODEX KF-805L columns, and PMMA was used as the standard substance. The weight average molecular weight (relative average) of polyetherimide was measured.

[Reference Example 1] (a) Polymerization of PPS resin (a-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 861.00 g (10.5 mol), and ion-exchanged water 10500 g, and gradually heated to 245 ° C. over about 3 hours while passing 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 resin a-1 had a melt viscosity of 60 Pa · s (300 ° C., shear rate 1000 / s).

[Reference Example 2] (a) Polymerization of PPS resin (a-2)
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 resin a-2 had a melt viscosity of 200 Pa · s (300 ° C., shear rate 1000 / s).

[Reference Example 3] (b) At least one amorphous resin selected from polyetherimide resin and polyethersulfone resin b-1: polyetherimide resin having a weight average molecular weight of 53,000 (manufactured by SABIC Innovative Plastics) "ULTEM" 1010)
b-2: Polyethersulfone resin (Sumitomo Chemical "Sumika Excel" 3600G)
b-3: polyetherimide resin having a weight average molecular weight of 62,000 (“ULTEM” 1000 manufactured by SABIC Innovative Plastics)

[Reference Example 4] (c) Alkoxysilane compound having an isocyanate group c-1: 3-isocyanatopropyltriethoxysilane (KBE-9007 manufactured by Shin-Etsu Chemical Co., Ltd.)

[Reference Example 5] Alkoxysilane compound having no isocyanate group c′-1: γ-aminopropyltriethoxysilane (KBE-903 manufactured by Shin-Etsu Chemical Co., Ltd.)
c′-2: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBM-303 manufactured by Shin-Etsu Chemical Co., Ltd.)

[Reference Example 6] (d) Inorganic filler d-1: Calcium carbonate (KSS-1000 manufactured by Calfine)

[Examples 1 to 6]
Each component shown in the first kneading in Tables 1 and 2 was dry-blended in the proportions shown in Tables 1 and 2 and then a TEX30α twin screw extruder (screw diameter 30 mm) manufactured by Nippon Steel Works, Inc. equipped with a vacuum vent. , L / D = 45, 5 kneading sections, fully meshing screw rotating in the same direction), screw rotation speed 300rpm, discharge rate 20Kg / hr, cylinder temperature so that the die discharge resin temperature becomes 330 ° C Was set and melt kneaded. The strand discharged from the die was rapidly cooled in a water bath and then pelletized by a strand cutter. The resulting pellet was opaque. Next, this pellet (first kneaded resin composition) and (a) PPS resin were dry blended so as to have the ratio shown in the second kneading in Tables 1 and 2, and then melt kneaded under the same conditions as described above. The strand discharged from the die was rapidly cooled in a water bath and then pelletized by a strand cutter. The resulting pellet was opaque. The composition of the finally obtained PPS resin composition was as shown in the final composition in Tables 1 and 2. The resin composition pellets dried overnight at 130 ° C. were evaluated for the amount of alcohol gas generated and the rod flow length, and the number average dispersed particle size, the number of particles exceeding 1000 nm, and the surface in the molded mirror plate obtained by injection molding Appearance and surface roughness were evaluated. In addition, various adhesion tests and falling ball impact tests were performed on mirror-finished square plate molded products on which aluminum was deposited. The results were as shown in Tables 1 and 2.

[Example 7]
Each component shown in the first kneading in Table 2 was dry blended in the proportions shown in Table 2, and then a TEX30α twin screw extruder (screw diameter 30 mm, L / D = 45) manufactured by Nippon Steel Works, equipped with a vacuum vent. Melt kneading using a kneading part at 5 locations and a fully meshing screw rotating in the same direction at a screw speed of 300 rpm and a discharge rate of 20 kg / hr. did. The strand discharged from the die was rapidly cooled in a water bath and then pelletized by a strand cutter. The resulting pellet was opaque. 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). Further, by subtracting the pressure difference (ΔP ₀ ) in the extension flow zone from the pressure difference (ΔP) before the twist kneading disc, the inflow effect pressure drop before and after the extension flow zone was obtained. cm ² . Next, this pellet (first kneaded resin composition) and (a) PPS resin were dry blended so as to have the ratio shown in the second kneading in Table 2, and further melt kneaded under the same conditions as described above. The strand discharged from the die was rapidly cooled in a water bath and then pelletized by a strand cutter. The resulting pellet was opaque. The composition of the finally obtained PPS resin composition is as shown in the final composition of Table 2. Various evaluations were performed in the same manner as in Example 2. The results were as shown in Table 2.

[Example 8]
In the second kneading, the resin composition obtained by the first kneading (first kneading resin composition) and (a) in addition to the PPS resin, the ion exchange water is dried so as to have a ratio shown in the second kneading in Table 2. Except for blending, a PPS resin composition was obtained by melt-kneading in the same manner as in Example 2. The composition of the finally obtained PPS resin composition is as shown in the final composition of Table 2. Various evaluations were performed in the same manner as in Example 2. The results were as shown in Table 2.

[Example 9]
In the second kneading, in addition to the resin composition (first kneading resin composition) obtained in the first kneading and (a) the PPS resin, (d) the inorganic filler has the ratio shown in the second kneading in Table 2. A PPS resin composition was obtained by melt-kneading in the same manner as in Example 2 except that dry blending was performed. The composition of the finally obtained PPS resin composition is as shown in the final composition of Table 2. Various evaluations were performed in the same manner as in Example 2. The results were as shown in Table 2.

[Comparative Example 1]
Each component shown in the first kneading in Table 3 was dry blended at the ratio shown in Table 3, and then a TEX30α twin screw extruder (screw diameter 30 mm, L / D = 45) manufactured by Nippon Steel Works, equipped with a vacuum vent. Melt kneading using a kneading part at 5 locations and a fully meshing screw rotating in the same direction at a screw speed of 300 rpm and a discharge rate of 20 kg / hr. And pelletized with a strand cutter. The composition of the finally obtained PPS resin composition is as shown in the final composition in Table 3. Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 3.

[Comparative Example 2]
Each component shown in the first kneading in Table 3 was dry blended at the ratio shown in Table 3, and then a TEX30α twin screw extruder (screw diameter 30 mm, L / D = 45) manufactured by Nippon Steel Works, equipped with a vacuum vent. Melt kneading using a kneading part at 5 locations and a fully meshing screw rotating in the same direction at a screw speed of 300 rpm and a discharge rate of 20 kg / hr. And pelletized with a strand cutter. Next, this pellet (first kneaded resin composition) was further melt-kneaded under the conditions described above and pelletized with a strand cutter. The composition of the finally obtained PPS resin composition is as shown in the final composition in Table 3. Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 3.

[Comparative Example 3]
In both the first kneading and the second kneading, melt kneading was carried out in the same manner as in Example 2 except that the melt kneading conditions were set at two kneading portions and the screw rotation speed of 150 rpm, and pelletized with a strand cutter. The composition of the finally obtained PPS resin composition was as shown in the final composition in Table 3. Various evaluations were performed in the same manner as in Example 2. The results are shown in Table 3.

[Comparative Examples 4 and 5]
(C) Except that the compatibilizer species were c′-1 and c′-2, respectively, the mixture was melt-kneaded in the same manner as in Example 2 and pelletized with a strand cutter. The composition of the finally obtained PPS resin composition was as shown in the final composition in Tables 3 and 4, and various evaluations were performed in the same manner as in Example 2. The results were as shown in Tables 3 and 4.

  The results of Examples 1-9 and Comparative Examples 1-5 will be described in comparison.

  In any of the examples, after (a) a PPS resin, (b) an amorphous resin, and (c) an alkoxysilane compound having an isocyanate group are melt-kneaded, (a) a method of melt-kneading with the PPS resin. By adopting, the surface appearance is good, the surface roughness is small after heat treatment and the smoothness is excellent, and even if the metal film is directly formed without undercoat, it can be used as a light reflecting mirror surface It was a thing.

  In Examples 1 to 6, an alkoxysilane compound having an isocyanate group was used as a compatibilizing agent, and as a result of melt kneading under high shear conditions, (b) the amorphous resin was finely dispersed to a number average dispersed particle size of less than 1000 nm. It was. In particular, in Examples 2 to 6 using a-2 as the (a) PPS resin used in the first kneading, (b) the amorphous resin was further finely dispersed as compared with Example 1, The number of (b) amorphous resins having a particle diameter exceeding 1000 nm was 0%, the surface roughness after heat treatment was small, and the dimensional stability was excellent.

  In Example 7, by further combining the extension flow technique, (b) the amorphous resin is further finely dispersed and the amount of generated alcohol gas is reduced and the surface roughness is reduced as compared with Example 2. became.

  In Example 8, by adding water during the second kneading, the amount of alcohol gas generated was reduced and the surface roughness was reduced compared to Example 2.

  In Example 9, the surface roughness after the heat treatment was equivalent to the surface roughness before the heat treatment, and the dimensional stability was further improved as compared with Example 2. Since the dimensional stability can be further improved by adding a very small amount of filler in this way, the surface appearance remains good.

  On the other hand, in Comparative Example 1 in which (a) a PPS resin, (b) an amorphous resin, and (c) an alkoxysilane compound having an isocyanate group are melt-kneaded, the comparative example 1 is compared with the corresponding Example 1 (b) The number average dispersed particle size of the crystalline resin increases, and (b) the number of amorphous resins with a particle size exceeding 1000 nm also exceeds 1.0%. As a result, the surface roughness Ra after heat treatment is large, and the dimensional stability The result was inferior.

  In Comparative Example 2 in which (a) PPS resin, (b) amorphous resin, and (c) alkoxysilane compound having an isocyanate group were simply melt-kneaded twice, compared to Comparative Example 1, (b) Although the number average dispersed particle size of the crystalline resin was reduced, the number of (b) amorphous resins having a particle size exceeding 1000 nm still exceeded 1.0%. For this reason, the surface roughness Ra after the heat treatment was large, resulting in poor dimensional stability.

  In Comparative Example 3, as in Example 2, (a) PPS resin, (b) amorphous resin, and (c) alkoxysilane compound having an isocyanate group were previously melt-kneaded, and then (a) PPS resin and melted. Although the method of kneading was adopted, the kneading force was small, so that the number average dispersed particle size of (b) amorphous resin was large, and the number of (b) amorphous resin having a particle size exceeding 1000 nm was large.

  In Comparative Examples 4 and 5, unlike Example 2, (c) particles exceeding 1000 nm were obtained as a result of using c′-1: aminosilane and c′-2: epoxysilane instead of the alkoxysilane compound having an isocyanate group. The number of (b) amorphous resins in diameter increased, and the surface roughness Ra after heat treatment increased.

Claims (7)

A reflecting plate in which a metal film is formed on a molded article obtained by molding a polyphenylene sulfide resin composition, wherein the polyphenylene sulfide resin composition is (a) polyphenylene sulfide, with the total of (a) and (b) being 100% by weight. (C) with respect to 100 parts by weight of a resin composition consisting of 99 to 60% by weight of resin, (b) 1 to 40% by weight of at least one amorphous resin selected from polyetherimide resin and polyethersulfone resin A polyphenylene sulfide resin composition comprising 0.1 to 10 parts by weight of an alkoxysilane compound having an isocyanate group, wherein the (a) polyphenylene sulfide resin forms a continuous phase (sea phase) in the morphology, (B) Dispersion in which an amorphous resin is dispersed with a number average dispersed particle diameter of 1 nm or more and less than 1000 nm The metal film is characterized in that the number of particles having a particle diameter of 1000 nm or more is 1.0% or less of the total number of particles with respect to the dispersed particles of the (b) amorphous resin. Formed reflector. 2. The reflector having a metal film according to claim 1, wherein the (b) amorphous resin is dispersed with a number average dispersed particle diameter of 1 nm or more and less than 500 nm. Furthermore, (d) an inorganic filler is blended in a range of more than 0 parts by weight and less than 15 parts by weight with respect to a total of 100 parts by weight of the (a) polyphenylene sulfide resin and the (b) amorphous resin. A reflecting plate on which the metal film according to claim 1 is formed. The metal film according to any one of claims 1 to 3, wherein (a) the polyphenylene sulfide resin has a melt viscosity (under conditions of 300 ° C and a shear rate of 1000 / s) of 300 Pa · s or less. Reflector. The amount of lower alcohol having 1 to 4 carbon atoms generated when the pellets of the polyphenylene sulfide resin composition are heated and melted at 350 ° C. for 30 minutes under vacuum is 0.6 mmol relative to the weight of the polyphenylene sulfide resin composition. % Or less, The reflecting plate formed with the metal film according to claim 1. The polyphenylene sulfide resin composition comprises (a) 90 to 1% by weight of the polyphenylene sulfide resin, (b) the polyetherimide resin and the polyethersulfone resin, where the total of (a) and (b) is 100% by weight. 10 to 99% by weight of at least one amorphous resin selected, and 0.1 to 10 parts by weight of the alkoxysilane compound (c) having an isocyanate group with respect to 100 parts by weight of the total of (a) and (b). 6. A reflector formed with a metal film according to any one of claims 1 to 5, which is obtained by previously kneading and kneading a resin composition comprising: (a) the polyphenylene sulfide resin and further kneading. When the total of (a) and (b) is 100% by weight, at least one amorphous material selected from (a) polyphenylene sulfide resin 90 to 1% by weight, (b) polyetherimide resin and polyethersulfone resin. A resin composition comprising 0.1 to 10 parts by weight of the alkoxysilane compound having an isocyanate group (c) with respect to 10 parts by weight of the conductive resin and 100 parts by weight of the total of (a) and (b) is previously melted. After kneading, by further melt-kneading with the (a) polyphenylene sulfide resin, the total of (a) and (b) is 100% by weight, and (a) 99-60% by weight of the polyphenylene sulfide resin, ) A tree comprising 1 to 40% by weight of at least one amorphous resin selected from polyetherimide resins and polyethersulfone resins A polyphenylene sulfide resin composition comprising 0.1 to 10 parts by weight of the alkoxysilane compound having an isocyanate group (c) is produced with respect to 100 parts by weight of the composition, and the polyphenylene sulfide resin composition is molded. A method for producing a reflector having a metal film according to any one of claims 1 to 5, wherein the metal film is formed later.