WO2011001959A1 - 射出成形品の製造方法 - Google Patents
射出成形品の製造方法 Download PDFInfo
- Publication number
- WO2011001959A1 WO2011001959A1 PCT/JP2010/061021 JP2010061021W WO2011001959A1 WO 2011001959 A1 WO2011001959 A1 WO 2011001959A1 JP 2010061021 W JP2010061021 W JP 2010061021W WO 2011001959 A1 WO2011001959 A1 WO 2011001959A1
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- WIPO (PCT)
- Prior art keywords
- injection
- molded product
- mold
- molding
- insulating layer
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
- B29C33/3828—Moulds made of at least two different materials having different thermal conductivities
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/76—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/26—Moulds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0079—Liquid crystals
Definitions
- the present invention relates to a method for producing an injection molded product using a liquid crystalline resin composition.
- a group of plastics called engineering plastics has high strength and is being replaced by metal parts.
- a group of plastics called liquid crystalline resins melts while maintaining a crystal structure.
- High strength based on this crystal structure is one of the characteristics of the liquid crystalline resin.
- the liquid crystalline resin has a small volume change between melting and solidification because the crystal structure does not change greatly upon solidification. As a result, the liquid crystalline resin has an advantage that the molding shrinkage is small and the dimensional accuracy of the molded product is excellent.
- the liquid crystalline resin composition is used for precision instrument parts by taking advantage of the above-described advantages of high strength and excellent dimensional accuracy.
- a small amount of dust, dust, etc. affect the equipment performance.
- components used in precision instruments and optical instruments, such as camera module parts are usually ultrasonically cleaned using water or the like to remove small dust, oil, dust, etc. adhering to the surface of the parts.
- a molded product formed by molding the liquid crystalline resin composition is relatively easily fibrillated on the surface because the molecular orientation is particularly large in the surface portion. For this reason, if the surface of a molded product peels, it will become a factor of dropout (dust). Therefore, since generation
- Patent Document 1 A resin molded product characterized by having a flat portion of 4 ⁇ m or less is disclosed (Patent Document 1).
- Patent Document 1 it is useful as a component of an electric / electronic device or an optical device, and can prevent generation of surface particles (foreign matter).
- the surface characteristics can be improved.
- Patent Document 1 the generation of foreign matter in Patent Document 1 is a foreign matter that occurs when the surface is washed by gently stirring in pure water for 1 minute. Therefore, in the improvement of the surface characteristics by the method described in Patent Document 1, a satisfactory result cannot be obtained for the suppression of fibrillation during ultrasonic cleaning. That is, in the method described in Patent Document 1, when a resin molded product is exposed to severe conditions such as ultrasonic cleaning, a large amount of foreign matter is generated.
- the mold temperature at the time of molding is higher in order to suppress the generation of dust and the like.
- molding is performed under the condition of a mold temperature of 130 ° C.
- the mold temperature condition is set to a temperature exceeding 100 ° C., the temperature cannot be adjusted with water, and the temperature must be adjusted using oil. For this reason, from the viewpoint of facilitating the production of injection-molded products, it is required to mold the mold at a temperature of 100 ° C. or less.
- the injection-molded product has a particularly large molecular orientation at the surface portion, surface fibrillation is likely to occur and ultrasonic cleaning or the like tends to cause fluff. For this reason, there is a demand for a technique for improving surface characteristics that can be applied to injection molded products.
- the injection molded product formed by injection molding the liquid crystalline resin composition is also required to have an excellent appearance.
- the present invention has been made to solve the above-described problems, and its purpose is to suppress the fibrillation of the surface of an injection-molded product even when the liquid crystalline resin composition is subjected to ultrasonic cleaning, and has an excellent appearance. It is providing the shaping
- the inventors of the present invention have made extensive studies to solve the above problems.
- a mold in which a heat insulating layer is formed on the inner surface of the mold is used, the heat insulating layer thickness t1, the injection speed S, the injection molded product thickness t2, the mold temperature T.
- the present inventors have found that the above problems can be solved by injection molding under molding conditions that satisfy a specific relational expression, and have completed the present invention.
- the present invention provides the following.
- a mold having a heat insulating layer formed on the inner surface of the mold is used, the thickness t1 ( ⁇ m) of the heat insulating layer, the injection speed S (mm / sec), and the injection molded product.
- the manufacturing method of the injection molded product which carries out injection molding on the molding conditions which satisfy
- the injection-molded product obtained by the production method of the present invention does not generate dropouts (dust) due to peeling of the surface of the molded product even by ultrasonic cleaning. For this reason, the injection molded product used for the precision instrument, the optical instrument, etc. manufactured by the manufacturing method of the present invention can be easily ultrasonically cleaned, and the cleaning operation at the time of manufacturing the parts can be performed efficiently. .
- the injection molded product obtained by the production method of the present invention has an excellent appearance.
- the surface of an injection molded product obtained by the production method of the present invention is not easily peeled off, it is easy to maintain a beautiful appearance for a long period of time.
- the production method of the present invention can be performed under conditions where the mold temperature is 100 ° C. or less. For this reason, the temperature adjustment of the metal mold
- the present invention uses a mold in which a heat insulating layer is formed on the inner surface of the mold, and the thickness t1 ( ⁇ m) of the heat insulating layer, the injection speed S (mm / sec), When the thickness t2 (mm) of the injection-molded product and the mold temperature T (° C.) are used, injection molding is performed under molding conditions that satisfy a specific relational expression.
- the present invention will be described in the order of a liquid crystalline resin composition and a method for producing an injection molded product.
- Liquid crystal resin composition The method for producing an injection-molded article of the present invention can be applied to all liquid crystalline resin compositions containing a liquid crystalline resin.
- the liquid crystalline resin refers to a melt processable polymer having a property capable of forming an optically anisotropic molten phase.
- the property of the anisotropic molten phase can be confirmed by a conventional polarization inspection method using an orthogonal polarizer. More specifically, the anisotropic molten phase can be confirmed by using a Leitz polarizing microscope and observing a molten sample placed on a Leitz hot stage under a nitrogen atmosphere at a magnification of 40 times.
- the liquid crystalline resin applicable to the present invention is inspected between crossed polarizers, the polarized light is normally transmitted even in a molten stationary state, and optically anisotropic.
- the liquid crystalline resin as described above is not particularly limited, but is preferably an aromatic polyester or an aromatic polyester amide, and a polyester partially including an aromatic polyester or an aromatic polyester amide in the same molecular chain is also within the range. It is in. They preferably have a logarithmic viscosity (IV) of at least about 2.0 dl / g, more preferably 2.0-10.0 dl / g when dissolved in pentafluorophenol at 60 ° C. at a concentration of 0.1% by weight. .) Are used.
- IV logarithmic viscosity
- the aromatic polyester or aromatic polyester amide as the liquid crystalline resin applicable to the present invention is particularly preferably at least one compound selected from the group of aromatic hydroxycarboxylic acids, aromatic hydroxyamines, and aromatic diamines. Aromatic polyesters and aromatic polyester amides as constituent components.
- a polyester amide comprising one or more of aromatic dicarboxylic acid, alicyclic dicarboxylic acid and derivatives thereof; (4) mainly (a) one or more of aromatic hydroxycarboxylic acids and derivatives thereof; (b) one or more of aromatic hydroxyamines, aromatic diamines and derivatives thereof; and (c). One or more of aromatic dicarboxylic acid, alicyclic dicarboxylic acid and derivatives thereof, and (d) at least one or more of aromatic diol, alicyclic diol, aliphatic diol and derivatives thereof, and And polyester amides composed of Furthermore, you may use a molecular weight modifier together with said structural component as needed.
- Specific examples of the specific compound constituting the liquid crystalline resin applicable to the present invention include aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, 2,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 4,4′-dihydroxybiphenyl, hydroquinone, resorcin, aromatic diols such as compounds represented by the following general formula (A) and the following general formula (B); terephthalic acid, isophthalic acid, 4 , 4′-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid and aromatic dicarboxylic acids such as compounds represented by the following general formula (C); aromatic amines such as p-aminophenol and p-phenylenediamine Can be mentioned.
- aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, 2,6-di
- X a group selected from alkylene (C1 to C4), alkylidene, —O—, —SO—, —SO 2 —, —S—, and —CO—
- the liquid crystalline resin composition used in the present invention includes other resins, nucleating agents, carbon black, inorganic baked pigments and other pigments, antioxidants, stabilizers, plasticizers, and lubricants as long as the effects of the present invention are not impaired.
- the liquid crystal resin composition used in the present invention also includes a composition imparted with desired characteristics by adding additives such as a release agent and a flame retardant.
- the method for producing an injection-molded article of the present invention uses a mold in which a heat insulating layer is formed on the inner surface of the mold in the injection molding of the liquid crystalline resin composition, the thickness t1 ( ⁇ m) of the heat insulating layer, and the injection speed S. (Mm / sec), injection molded product thickness t2 (mm), and mold temperature T (° C.), injection molding is performed under molding conditions that satisfy the following relational expression (I).
- the heat insulating layer formed on the inner surface of the mold is not particularly limited as long as it functions to delay solidification of the liquid crystalline resin composition on the mold surface.
- those having a heat insulating layer formed on a part of the inner surface of the mold are also included in the “mold having the heat insulating layer formed on the inner surface of the mold”.
- the thickness (t1) of the heat insulating layer is not particularly limited as long as it is adjusted so as to satisfy the above formula (I) as described later.
- the thickness of the heat insulating layer formed on the inner surface of the mold may be uniform or may include portions having different thicknesses. When the thickness of the heat insulation layer is not uniform, the average thickness is set to t1.
- the thermal conductivity of the heat insulating layer formed on the inner surface of the mold is particularly preferably 5 W / m ⁇ K or less.
- the heat insulating layer needs to have heat resistance that can withstand the high temperature during molding.
- the heat insulating layer formed on the inner surface of the mold used in the method for producing an injection molded product of the present invention preferably contains a polyimide resin. This is because the polyimide resin has a thermal conductivity of 5 W / m ⁇ K or less and has heat resistance enough to withstand high temperatures during injection molding.
- polyimide resins that can be used include pyromellitic acid (PMDA) -based polyimide, biphenyltetracarboxylic acid-based polyimide, polyamideimide using trimellitic acid, bismaleimide-based resins (bismaleimide / triazine-based, etc.), benzophenone Examples include tetracarboxylic acid-based polyimides, acetylene-terminated polyimides, and thermoplastic polyimides. In particular, a heat insulating layer made of a polyimide resin is preferable. Preferable materials other than polyimide resin include, for example, tetrafluoroethylene resin.
- the method for forming the heat insulating layer on the inner surface of the mold is not particularly limited.
- a solution of a polymer precursor such as a polyimide precursor capable of forming a polymer heat insulating layer is applied to the mold surface, heated to evaporate the solvent, and further heated to polymerize to form a heat insulating layer such as a polyimide film.
- a polymer precursor such as a polyimide precursor capable of forming a polymer heat insulating layer
- die using an adhesive tape-shaped polymer heat insulation film, and forming a heat insulation layer is mentioned. It is also possible to form a polyimide film and further form a chromium (Cr) film or a titanium nitride (TiN) film as a metal-based hard film on
- the manufacturing method of the injection molded product of the present invention is the case where the thickness t1 ( ⁇ m) of the heat insulation layer, the injection speed S (mm / sec), the thickness t2 (mm) of the injection molded product, and the mold temperature T (° C.).
- the injection molding is performed under molding conditions that satisfy the relational expression of the following formula (I).
- the boundary between the surface layer and the skin layer does not exist on at least a part of the surface of the molded product as will be described later.
- the surface peeling of the injection molded product is caused by the peeling of the surface layer formed on the skin layer.
- this surface layer is obtained as an injection molded product having no surface layer on at least a part of the surface of the molded product. It is done. As a result, it is possible to obtain a high-quality injection-molded product that has an excellent appearance and does not peel off even when ultrasonically cleaned.
- the injection molded product obtained by the production method of the present invention is characterized in that at least part of the boundary between the surface layer and the skin layer on the surface of the molded product is eliminated.
- the effect of suppressing surface peeling of the injection molded product is remarkably enhanced.
- the injection molded product having an excellent appearance with very little peeling of the surface of the molded product prevents the liquid crystalline resin composition flowing into the mold from immediately solidifying on the mold surface, and solidifies the resin composition.
- the heat insulating layer has a function of suppressing the resin composition from immediately solidifying on the mold surface when the molten liquid crystalline resin composition flows into the mold.
- the time for filling the resin composition in the mold is shortened by improving the injection speed. That is, the filling of the liquid crystal resin composition into the mold can be finished at a stage where the solidification of the liquid crystal resin composition does not proceed excessively. As a result, it can be suppressed that the molecules before solidification are pulled by the solidified resin composition and the molecular orientation is increased on the surface of the molded product.
- the thickness of the injection molded product is too thick, it takes time to fill the liquid crystalline resin composition into the mold. For this reason, if the thickness of the injection-molded product is too thick, the solidified resin composition tends to cause a phenomenon in which molecules in the portion before solidification are pulled and molecular orientation is increased on the surface of the molded product.
- the feature of the present invention is that the heat insulating layer thickness t1 ( ⁇ m), the injection speed S (mm / sec), the mold temperature T (° C.), and the injection molded product thickness t2 (mm) satisfy the above formula (I). It is found that the boundary between the surface layer and the skin layer on the surface of the injection molded product is eliminated by adjusting to.
- Heat insulation layer thickness t1 ( ⁇ m) will be described.
- Heat insulation layer thickness t1 should just be adjusted so that the said Formula (I) may be satisfy
- a more preferable heat insulating layer thickness t1 is 10 ⁇ m to 300 ⁇ m.
- the injection speed S (mm / sec) will be described.
- the injection speed S may be adjusted so as to satisfy the above formula (I) similarly to the heat insulating layer thickness t1.
- the mold temperature T (° C.) will be described.
- the mold temperature T may be adjusted so as to satisfy the above formula (I) similarly to the heat insulating layer thickness t1 and the like.
- the temperature of the mold can be adjusted with water, and a high-quality injection-molded product can be easily obtained.
- a more preferable mold temperature range is 50 ° C to 100 ° C.
- the injection molded product thickness t2 can be adjusted in a wide range. Specifically, the thickness t2 of the injection molded product can be adjusted from 0.2 mm to 10 mm under the condition satisfying the above formula (I). Under the condition satisfying the above formula (II), t2 can be adjusted from 0.2 mm to 5 mm. In particular, when the thickness t2 of the injection-molded product is in the range of 0.2 mm to 3 mm, the above-mentioned problem is likely to occur. Can be easily obtained.
- FIG. 1 shows a multilayer structure (from a central portion to a surface portion) of an injection molded product obtained by the production method of the present invention.
- the injection molded product obtained by the manufacturing method of this invention does not have the boundary of a surface layer and a skin layer in at least one part of the molded product surface. Therefore, even if the injection molded product obtained by the manufacturing method of the present invention is subjected to ultrasonic cleaning or the like, the portion where surface peeling occurs is reduced as shown in FIG.
- FIG. 2 shows a multilayer structure (from the central part to the surface part) of the injection molded product obtained by the manufacturing method of the prior art.
- a surface layer is present on the entire surface of the injection molded product. Therefore, when ultrasonic cleaning or the like is performed on an injection molded product obtained by the manufacturing method of the prior art, surface peeling occurs on the entire surface as shown in FIG.
- FIG. 3 shows a multilayer structure (from the central portion to the surface portion) of the injection molded product manufactured under the condition satisfying the above formula (II).
- the injection molded products manufactured under the conditions satisfying the above formula (II) tend to have no boundary between the surface layer and the skin layer. . Therefore, even if ultrasonic cleaning or the like is performed, it becomes an injection molded product that hardly causes surface peeling.
- the injection-molded product obtained by the production method of the present invention does not peel off even when subjected to ultrasonic cleaning, and has an excellent appearance. Furthermore, by setting the mold temperature to 100 ° C. or less, a high-quality injection molded product can be easily obtained.
- Liquid crystalline resin 1 “Vectra (registered trademark) E130i” Glass fiber 30% by mass Filling material Melting point 335 ° C., melt viscosity 40 Pa ⁇ s (manufactured by Polyplastics Co., Ltd.)
- Heat insulation layer forming material 1 polyimide resin tape (manufactured by Sumitomo 3M), thermal conductivity 0.2 W / m ⁇ K
- Thermal insulation layer forming material 2 polyimide resin varnish (Fine Chemical Japan), thermal conductivity 0.2 W / m ⁇ K
- Heat insulation layer forming material 3 polyimide resin film (manufactured by Toray DuPont), thermal conductivity 0.2 W / m ⁇ K
- the thermal conductivity of the polyimide resin was calculated by measuring the thermal diffusivity by laser flash method, specific gravity by Archimedes method, and specific heat by DSC.
- the heat insulating layer forming material 1 is affixed to the mold cavity surface of a flat plate mold having a width of 20 mm, a length of 50 mm, and a thickness of 0.5 mm. Molding was performed under molding conditions such as injection speed and mold temperature to obtain an injection molded product.
- the conditions other than the molding conditions shown in the table are as follows. [Molding condition] Cylinder set temperature: 350 ° C Screw rotation speed: 150rpm
- Example 2 After using the liquid crystalline resin 1 as a molding material and spraying the heat insulation layer forming material 2 on the mold cavity surface of a plate molding mold of 40 mm ⁇ ⁇ thickness 1 mm and baking at 250 ° C. for 1 hour, After the polyimide surface was polished and adjusted to the thickness of the heat insulating layer in Table 1, molding was performed at the injection speed and mold temperature in Table 1 to obtain an injection molded product.
- the molding conditions other than those shown in Table 1 are the same as in Example 1.
- Example 3 An injection molded product was produced in the same manner as in Example 2 except that the molding conditions were changed to the conditions shown in Table 1. The molding conditions other than those shown in Table 1 are the same as in Example 1.
- Example 4 A liquid crystalline resin 1 is used as a molding material, and a heat insulating layer forming material 3 is attached to a mold cavity surface of an ISO standard test piece mold with a double-sided tape. Molding was performed to obtain an injection molded product.
- the molding conditions other than those shown in Table 1 are the same as in Example 1.
- Example 5 An injection molded product was produced in the same manner as in Example 4 except that the molding conditions were changed to the conditions shown in Table 1.
- the molding conditions other than those shown in Table 1 are the same as in Example 1.
- the injection molded product obtained by the production method of the present invention was found to be less susceptible to surface peeling, as is clear from the number of peels in the cross-cut peel test evaluation. As described above, the injection molded product obtained by the production method of the present invention is unlikely to peel off, so that a beautiful appearance can be maintained.
- Example 4 it was found that no fibril generation occurred from the ultrasonic cleaning test. In Examples 1 to 3 and 5, it was confirmed that there was no boundary between the surface layer and the skin layer on the surface of the injection molded product. Moreover, although fibril generation on the surface occurred in Example 4, the generation area is very small compared with the generation area of fibrillation generated on the surface of the molded article of the comparative example. Therefore, in Example 4, it was confirmed that a boundary between the surface layer and the skin layer exists in part.
- the production method of the present invention can produce a high-quality injection-molded product even under a mold temperature of 100 ° C. or less.
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Abstract
Description
本発明の射出成形品の製造方法は、液晶性樹脂を含む全ての液晶性樹脂組成物に適用することができる。
液晶性樹脂とは、光学異方性溶融相を形成し得る性質を有する溶融加工性ポリマーを指す。異方性溶融相の性質は、直交偏光子を利用した慣用の偏光検査法により確認することが出来る。より具体的には、異方性溶融相の確認は、Leitz偏光顕微鏡を使用し、Leitzホットステージに載せた溶融試料を窒素雰囲気下で40倍の倍率で観察することにより実施できる。本発明に適用できる液晶性樹脂は直交偏光子の間で検査したときに、たとえ溶融静止状態であっても偏光は通常透過し、光学的に異方性を示す。
(1)主として芳香族ヒドロキシカルボン酸及びその誘導体の1種又は2種以上からなるポリエステル;
(2)主として(a)芳香族ヒドロキシカルボン酸及びその誘導体の1種又は2種以上と、(b)芳香族ジカルボン酸、脂環族ジカルボン酸及びその誘導体の1種又は2種以上と、(c)芳香族ジオール、脂環族ジオール、脂肪族ジオール及びその誘導体の少なくとも1種又は2種以上、とからなるポリエステル;
(3)主として(a)芳香族ヒドロキシカルボン酸及びその誘導体の1種又は2種以上と、(b)芳香族ヒドロキシアミン、芳香族ジアミン及びその誘導体の1種又は2種以上と、(c)芳香族ジカルボン酸、脂環族ジカルボン酸及びその誘導体の1種又は2種以上、とからなるポリエステルアミド;
(4)主として(a)芳香族ヒドロキシカルボン酸及びその誘導体の1種又は2種以上と、(b)芳香族ヒドロキシアミン、芳香族ジアミン及びその誘導体の1種又は2種以上と、(c)芳香族ジカルボン酸、脂環族ジカルボン酸及びその誘導体の1種又は2種以上と、(d)芳香族ジオール、脂環族ジオール、脂肪族ジオール及びその誘導体の少なくとも1種又は2種以上、とからなるポリエステルアミド等が挙げられる。さらに上記の構成成分に必要に応じ分子量調整剤を併用してもよい。
本発明に用いる液晶性樹脂組成物には、本発明の効果を害さない範囲で、他の樹脂、核剤、カーボンブラック、無機焼成顔料等の顔料、酸化防止剤、安定剤、可塑剤、滑剤、離型剤及び難燃剤等の添加剤を添加して、所望の特性を付与した組成物も本発明に用いる液晶性樹脂組成物に含まれる。
本発明の射出成形品の製造方法は、上記液晶性樹脂組成物の射出成形において、金型内表面に断熱層が形成された金型を用い、断熱層の厚みt1(μm)、射出速度S(mm/sec)、射出成形品の厚みt2(mm)、金型温度T(℃)とした場合に、下記式(I)の関係式を満たす成形条件で射出成形する。
本発明の射出成形品を製造する方法においては、金型の内表面(金型の内側の表面)に断熱層が形成された金型を用いる。金型の内側の表面に形成された断熱層により、金型内に流れ込んだ液晶性樹脂組成物は金型表面付近で固まり難くなる。その結果、金型表面で固化した樹脂組成物に接触する固化前の樹脂組成物に含まれる分子が、その固化後の樹脂組成物に引っ張られ成形品表面で分子配向が大きくなることを抑えることができる。
本発明の射出成形品の製造方法は、断熱層の厚みt1(μm)、射出速度S(mm/sec)、射出成形品の厚みt2(mm)、金型温度T(℃)とした場合に、下記式(I)の関係式を満たす成形条件で射出成形を行うことを特徴とする。
液晶性樹脂組成物を成形すると多層構造になる。図1には、本発明の製造方法により得られる射出成形品の多層構造(中央部分から表面部分まで)を示す。図1(a)に示すように、本発明の製造方法により得られる射出成形品は、成形品表面の少なくとも一部において表層とスキン層との境界が存在しない。したがって、本発明の製造方法により得られる射出成形品に超音波洗浄等を行っても図1(b)に示すように表面剥がれが生じる部分は少なくなる。
液晶性樹脂1:「ベクトラ(登録商標)E130i」 ガラス繊維30質量%充填材料 融点335℃、溶融粘度40Pa・s (ポリプラスチックス株式会社製)
断熱層形成材料1:ポリイミド樹脂テープ(住友スリーエム社製)、熱伝導率0.2W/m・K
断熱層形成材料2:ポリイミド樹脂ワニス(ファインケミカルジャパン社製)、熱伝導率0.2W/m・K
断熱層形成材料3:ポリイミド樹脂フィルム(東レ・デュポン社製)、熱伝導率0.2W/m・K
成形用材料として液晶性樹脂1を用い、幅20mm×長さ50mm×厚さ0.5mmの平板成形用金型の金型キャビティー面に、断熱層形成材料1を貼付し、表1中の射出速度、金型温度等の成形条件にて成形を行い、射出成形品を得た。なお、表に示す成形条件以外の条件は下記の通りである。
[成形条件]
シリンダー設定温度:350℃
スクリュー回転数:150rpm
成形用材料として液晶性樹脂1を用い、40mm□×厚さ1mmの平板成形用金型の金型キャビティー面に、断熱層形成材料2をスプレーし、250℃、1時間で焼付けした後、ポリイミド面を研摩し、表1中の断熱層厚みに調整した後、表1中の射出速度、金型温度にて成形を行い、射出成形品を得た。なお、表1に示す以外の成形条件は実施例1と同様である。
成形条件を表1に示す条件に変更した以外は実施例2と同様の方法で射出成形品を製造した。なお、表1に示す以外の成形条件は実施例1と同様である。
成形用材料として液晶性樹脂1を用い、ISO標準試験片金型の金型キャビティー面に、断熱層形成材料3を両面テープにて貼付し、表1中の射出速度、金型温度にて成形を行い、射出成形品を得た。なお、表1に示す以外の成形条件は実施例1と同様である。
成形条件を表1に示す条件に変更した以外は実施例4と同様の方法で射出成形品を製造した。なお、表1に示す以外の成形条件は実施例1と同様である。
成形条件を表1に示す条件に変更した以外は実施例4と同様の方法で射出成形品を製造した。なお、表1に示す以外の成形条件は実施例1と同様である。
金型内に断熱層を形成しなかった以外は実施例1と同様の方法で射出成形品を製造した。
成形条件を表1に示す条件に変更した以外は比較例2と同様の方法で射出成形品を製造した。なお、表1に示す以外の成形条件は実施例1と同様である。
実施例及び比較例の射出成形品について、碁盤目試験評価、超音波洗浄試験評価を行った。
JIS K5400に準じた方法で評価を行い、1mm□の100格子の内の剥離された格子数にて評価を行った。評価結果を表1に示した。
実施例及び比較例の射出成形品を水に浸漬し、1分間超音波洗浄を実施し、表面のフィブリル発生状況を表面の白化現象として測定し、フィブリル発生の有無を評価した。評価結果を表1に示した。
Claims (5)
- 前記断熱層は、熱伝導率が5W/m・K以下である請求項1又は2に記載の射出成形品の製造方法。
- 前記断熱層は、ポリイミド樹脂を含む請求項1から3のいずれかに記載の射出成形品の製造方法。
- 金型温度Tが、100℃以下である請求項1から4のいずれかに記載の射出成形品の製造方法。
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JPH06198667A (ja) * | 1992-12-28 | 1994-07-19 | Asahi Chem Ind Co Ltd | 合成樹脂の射出成形法 |
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