WO2002062900A1 - Thermoplastic resin composition and molded article - Google Patents

Abstract

A thermoplastic resin composition produced by compounding 100 parts by weight of a resin composition comprising (a) 30 to 99.5 wt.% thermoplastic resin and (b) 0.5 to 70 wt.% glass with (c) 1 to 25 parts by weight of a plasticizer and (d) 0.05 to 10 parts by weight of a brightening agent. From the thermoplastic resin composition, a molding having a deep surface appearance and capable of bearing a three-dimensional pattern (silk-like) can be formed by a simple method.

Description

 Specification

 Thermoplastic resin composition and molded article

Technical field

 The present invention relates to a thermoplastic resin composition, and more particularly, to a thermoplastic resin composition having a deep surface appearance of a molded article and capable of forming a three-dimensional pattern (silk-like), and molding the same. Related to molded articles. Background art

 Among thermoplastic resins, polycarbonate resins are widely used in various fields as engineering plastics because of their excellent mechanical strength, heat resistance, and transparency. By the way, in recent years, in the fields of electric and electronic equipment, office equipment, home electric appliances, building materials, automobile parts, etc., designability such as shape, color, appearance, etc. has been regarded as important, and it is required to impart designability to the material. Have been.

 With respect to imparting a design property to the material, many techniques relating to a resin composition capable of forming an appearance such as a pearly tone or a metallic tone by blending a glossy pigment are generally disclosed. Furthermore, in order to give a sense of depth and a sense of quality, a method of (1) applying a material coating to the molded product and then applying a clear coating, (2) blending glossy particles with glass fiber reinforced polycarbonate resin with excellent transparency (Japanese Patent Laid-Open Publication No. Hei 6-212068).

 Regarding the method ①, in the case of such a coating, in addition to degreasing and washing of the surface of the molded article, undercoating, intermediate coating, and topcoating, complicated processes such as dust removal, drying, and baking, and expensive equipment and paints are used. I need. 'In addition, the cycle time of the process will be longer. 'There is a problem that this is the main cause of cost increase.

For method (2), glass fiber reinforced polycarbonate with excellent transparency There is a problem in that a limited glass having a difference in the refractive index from the polycarbonate resin which is equal to or less than a specific value must be used in order to obtain a specific value. The present invention has been made in view of the above circumstances, and provides a thermoplastic resin composition that has a deep feeling in the surface appearance of a molded article and can form a three-dimensional pattern (silk-like) by a simple method. The purpose is to do so. Disclosure of the invention

 As a result of various studies, the present inventors have found that a thermoplastic resin composition obtained by blending a plasticizer and a glittering material with a resin composition of a thermoplastic resin and glass can effectively achieve the object of the present invention. And completed the present invention based on these findings.

 That is, the gist of the present invention is as follows.

1. (a) Thermoplastic resin 30 to 99.5 mass. / o, (b) 100 to 100 parts by mass of a resin composition consisting of 0.5 to 70% by mass of glass, (c) 1 to 25 parts by mass of a plasticizer and (d) 0.05 to 5 parts by mass of a luminous material. ~ 1 ◦ A thermoplastic resin composition blended by mass.

 2. The thermoplastic resin composition according to the above 1, wherein the thermoplastic resin as the component (a) mainly contains a polycarbonate resin.

 3. The thermoplastic resin composition according to the above 1 or 2, wherein the glass of the component (b) is at least one selected from glass fibers, glass flakes, and glass pads.

 4. The thermoplastic resin composition according to any one of the above items 1 to 3, wherein the plasticizer of the component (c) is selected from a phosphorus compound and a higher fatty acid ester.

 5. The thermoplastic resin composition according to any one of the above items 1 to 4, wherein the glitter material of the component (d) is at least one selected from pearl pigments, metallic pigments and glass flakes coated with metal. object.

6. Mold the thermoplastic resin composition according to any one of the above 1 to 5 Molded products.

BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the present invention will be described in detail.

 As the thermoplastic resin (a) constituting the thermoplastic resin composition of the present invention, polycarbonate resin, polystyrene resin, rubber-modified polystyrene resin, styrene-butadiene-acrylonitrile copolymer (ABS) Resin), acrylic resin, methacrylic resin, styrene-at-a-mouth-to-tolyl copolymer (AS resin), terpene resin, polyolefin resin, vinyl chloride resin, polyester resin, methyl methacrylate-methyl acrylate Alkyl-dimethylsiloxane copolymers (elastomers) and mixtures thereof can be mentioned. Among them, a thermoplastic resin mainly containing a polycarbonate resin is preferable. Particularly, a thermoplastic resin containing 65% by mass or more of polycarbonate is preferable.

 The above-mentioned polycarbonate resin is not particularly limited in its chemical structure and production method, and various resins can be used. For example, an aromatic polycarbonate resin produced by a reaction between a divalent phenol and a carbonate precursor is suitably used.

Is in this divalent phenol, various ones can be used, for example, 2, 2 _ bis (4-arsenate Dorokishifueniru) Puronoヽ⁰ emissions, bis (4-arsenide de Rokishifue two Honoré) methane, 1, 1 one bis (4-arsenide Dorokishifue two Honoré) Etan, 2, 2-bis (4-arsenide Dorokishi _ 3, 5-Jimechinorefue two Honoré) Purono, ⁰ emissions, 4, 4, Jihi Dorokishijifue two Honoré, bis (4 - arsenate (Droxoxyphene) cyclohexane, bis (4-hydroxy phenyl) ether, bis (4—hydroxyphene) snorefied, bis (4-hydroxydoxyphene) snorefon, bis (4-hydroxydoxyphene) Nore) Snorre Hoxide, Bis (4-hydroxydroxyphenol) Ketone, Hydroquinone, Preferred examples include resorcinol and potassium hydroxide. Among these divalent phenols, bis (hydroxyphenol) alkane, particularly 2,2-bis (4-hydroxyphenyl) propane [bisphenol A] is preferred. These divalent phenols may be used alone or as a mixture of two or more.

 Further, as the carbonate precursor, carbonyl halide, carbonyl ester, haloformate, or the like can be used. More specifically, there are phosgene, dihaloformate of divalent phenol, diphenolenocarbonate, dimethinorecarbonate, getinolecarbonate and the like.

 As the chemical structure of the polycarbonate resin, those whose molecular chains have a linear structure, a cyclic structure, or a branched structure can be used. Among them, as a polycarbonate resin having a branched structure, 1,1,1-tris (4-hydroxyphenyl) ethane,, a ,, α "—tris (4—hydroxy) are used as branching agents. (Droxyfile) 1-1,3,5-Trisisopropinolebenzene, phlorognolesin, trimellitic acid, isatin bis (ο-cresol), etc., are preferably used. As the resin, a polyester-carbonate resin produced using an ester precursor such as a bifunctional carboxylic acid such as terephthalic acid or an ester-forming derivative thereof can also be used. A mixture of polycarbonate resins having the same can also be used.

The viscosity-average molecular weight of these polycarbonate resins is usually from 10,000 to 500,000, preferably from 13,000 to 35,000, more preferably from 15,500. .000 to 25,000. This viscosity average molecular weight (Μ ν) was measured using an Ubbelohde viscometer at 20 ° C. The viscosity of the methylene solution was measured, and the intrinsic viscosity [77] was determined from this.

] = 1. 2 3 X 1 0 5 M v. It is a value calculated by the formula of ^'83 . For controlling the molecular weight of such a polycarbonate resin, phenol, p-tert-butynolephenone, ρ-dodecinolephenole, p-tert-octylphenol, p-cumylphenol, and the like are used.

 Further, a polycarbonate-polyorganosiloxane copolymer can be used as the polycarbonate resin. This copolymer is prepared, for example, by dissolving a polycarbonate oligomer and a polyorganosiloxane having a reactive group at a terminal in a solvent such as methylene chloride, and adding thereto a sodium hydroxide of divalent phenol. Aqueous solution can be added and interfacial polycondensation reaction is performed using a catalyst such as triethylamine. In this case, as the polyorganosiloxane structure portion, those having a polydimethylsiloxane structure, a polydiethylenesiloxane structure, a polymethinolephenylsiloxane structure, or a polydiphenylsiloxane structure are preferably used.

The polycarbonate-polyorganosiloxane copolymer has a degree of polymerization of the polycarbonate portion of 3 to 100 and a degree of polymerization of the polinoreganosiloxane portion of about 2 to 500. Is preferably used. The content ratio of the polyorganosiloxane moiety in the polycarbonate-polyorganosiloxane copolymer is 0.5 to 10% by mass. / ₀ , preferably 3 to 6% by mass is suitable. Further, the viscosity-average molecular weight of the polycarbonate-polyorganosiloxane copolymer is 50,000 to 100,000, preferably 100,000 to 300,000. Are preferably used.

Next, the component (b) to be added to the thermoplastic resin will be described. (b) Glass As the component (b) constituting the thermoplastic resin composition of the present invention, various kinds or forms can be used as long as it is glass. Is a composition of this good Una glass, for _{example, S i 0 2 5 5~ 6} 0 mass _{^{0 / o, A 1 2 0}} 3 1 0~ 1 2 wt%, C a O 2 0~ 2 5 mass . /. , M g O 0~ 5 wt%, T i O ₂ 0~ 5 wt. /. , ZnO 0-5 mass. /. , N a ₂ O 0.:! To 5% by mass and K ₂ O 0.1 to 5% by mass. Further, as the form, for example, glass fiber, glass flake, glass powder, etc. can be used, and these may be used alone or in combination of two or more. Among these, glass fibers widely used for resin reinforcement may be any of alkali-containing glass, low-alkali glass, and alkali-free glass. The fiber length is 0.05 to 8 mm, preferably 2 to 6 mm, and the fiber diameter is 3 to 30 μιη, preferably 5 to 25 / m. The form of the glass fiber is not particularly limited, and examples thereof include various types such as roving, milled fiber, and chopped strand. These glass fibers can be used alone or in combination of two or more. Furthermore, these glasses are surface-treated with silane-based coupling materials such as aminosilane, epoxysilane, vinylsilane, and methacrylsilane, epoxy complex compounds, and boron compounds in order to increase the affinity with the resin. May be done. A preferred example of such a glass is ECR glass manufactured by Asahi Fiberglass.

The ratio of the component (a) to the component (b) is 0.5 to 70% by mass of the component (b) with respect to 30 to 99.5% by mass of the component (a). When a (a) with component 3 less than 0 wt%, the amount of glass is large, is formed pattern as a surface appearance difficulty no longer exceeds 9 9.5 mass _^0/0, the amount of glass And it is difficult to form a sufficient pattern for the surface appearance. Is not preferred. Preferred details, and against the component (a) 7 0-9 9-5 wt%, component (b) from 0.5 to 3 0 mass ^_0/0.

 Next, the component (c) and the component (d) to be blended in the resin composition comprising the component (a) and the component (b) will be described.

 (c) Plasticizer

 The plasticizer of the component (C) constituting the thermoplastic resin composition of the present invention is not particularly limited as long as it exhibits a viscosity reducing effect upon melting, and is preferably a phosphorus compound or a higher fatty acid ester. Can be cited.

 Specific examples of the phosphorus compounds include trimethyl phosphate, trietinole phosphate, triptinole phosphate, trioctyl phosphate, tripoxetinole phosphate, and the like. Triphenylene phosphate, Tricinolephosphate phosphate, Cresinoresinophosphate phosphate, Tricinolephenephosphate phosphate, Tri (2-ethylenoxyphosphate) phosphate, Disopropyl phenyl phosphate phosphate, Trixyleninolephosphoric acid, tris (isopropynolephate) phosphate, triptinole phosphate, bisphenol A bisphosphite, hydroquinone bisphosphite, resolecin bisphosphate, resole / resinole

(Dipheno-phosphate), trioxybenzene triphosphate, cresyl diphenyl phosphate and the like.

 As commercial products, TPP (triphenyl phosphate), TXP (trixylenyl phosphate), CR-733S (resorcinol (diphenyl phosphate) manufactured by Daihachi Chemical Industry Co., Ltd. )], PX 200

[1,3-phenylene-tetrakis (2,6 "-dimethylphenyl) phosphate, PX 201 [1,4-phenylene-tetrakis (2,6-dimethinolephenyl) phosphate , PX 202 [4, 4, 1 fu Adencastab PFR (phenyl 'resorcinol polyphosphate), ADK STAB FP600 (bisphenol A bis (diphenyl phosphate)), manufactured by Asahi Denka Kogyo Co., Ltd. )]].

 Examples of the higher fatty acid ester include a partial ester or a whole ester of a monovalent or polyvalent alcohol having 1 to 10 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Specifically, glycerin monostearate, glycerin distearate, glycerin tristearate, glycerinte traurate, sorbitan monostearate, pentaerythritol tonolemonostearate, pentaerythritol tolte torstearate, pentaerythritol Tolte traperalargonate, propylene glycol monostearate, stearinolestearate, palmityl phenol dimitrate, butinolestearate, methinorelaurate, isopropyl palmitate, 2-ethylhexyl stearate, etc. It is a thing.

 The amount of the plasticizer (C) is from 1 to 25 parts by mass, preferably from 5 to 15 parts by mass, per 100 parts by mass of the resin composition comprising the components (a) and (b). It is. If the amount is less than 1 part by mass, it is difficult to obtain a transparent feeling on the surface, and if it exceeds 25 parts by mass, the impact resistance of the molded product is undesirably reduced.

 (d) Bright materials

Examples of the brilliant component (d) constituting the thermoplastic resin composition of the present invention include pearl pigments, metallic pigments, and glass flakes coated with metal. Specific examples of pearl pigments include metal oxidized mica-based pigments such as titanium mica coated with titanium oxide, mica coated with bismuth trichloride, and natural pearl pigments such as fish scale foil. But it can.

 Specific examples of the metallic pigment include metal powders such as aluminum, gold, silver, copper, nickel, titanium, and stainless steel, and metal sulfides such as nickel sulfide, cobalt sulfide, and manganese sulfide. be able to.

 Examples of the metal of the glass flake coated with the metal include gold, silver, platinum, palladium, nickel, copper, chromium, and tin.

 The amount of the brilliant component (d) is 0.05 to 10 parts by mass, preferably 0.5 part by mass, per 100 parts by mass of the resin composition comprising the components (a) and (b). To 5 parts by mass. When the amount is less than 0.05 parts by mass, it is difficult to form a pattern as the surface appearance, and when the amount exceeds 10 parts by mass, the amount of the glittering material protruding from the surface increases, and the appearance is impaired. Absent. The thermoplastic resin composition of the present invention appropriately contains, in addition to the above components, general thermoplastic resins and additives used in the composition according to the characteristics required for the molded article. Can be done. Examples of such additives include antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, antibacterial agents, compatibilizers, flame retardants, and anti-dripping agents.

Next, regarding the method for producing the thermoplastic resin composition of the present invention, the above-mentioned components (a) to (d) and various additives used as needed are mixed together in accordance with the required properties of the molded article. What is necessary is just to mix and knead in a ratio. The mixers and kneaders used here are pre-mixed with commonly used equipment, for example, a ribbon blender, a drum tumbler, a Henschel mixer, etc., and are mixed with a Banbury mixer, a single screw screw extruder, A screw screw extruder, a multi-screw screw extruder, a coneder, etc. can be used. The heating temperature at the time of kneading is appropriately selected usually in the range of 240 to 300 ° C. As the melt-kneading molding, it is preferable to use an extruder, particularly a vent-type extruder. The thermoplastic resin composition of the present invention may be prepared by using the above-described melt-kneading molding machine or an injection molding method, an injection compression molding method, an extrusion molding method, a blow molding method, a press molding method using the obtained pellet as a raw material. Various molded products can be manufactured by a foam molding method or the like. In this case, a method in which each component is melt-kneaded to produce a pellet-shaped molding raw material, and then, an injection molding using this pellet, or a method of producing an injection-molded article by injection compression molding is particularly preferable. . Also, if a gas injection molding method is adopted as this injection molding method, a molded product which is excellent in appearance without shrinkage and which is reduced in weight can be obtained.

 The molded article obtained from the thermoplastic resin composition obtained in this manner has a deep surface and a three-dimensional pattern (silk-like), and is particularly suitable for electric and electronic equipment, office equipment, and home electric appliances. Used in fields such as products, building materials, and automotive parts.

 Next, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. [Examples 1 to 10 and Comparative Examples 1 and 2]

 The mixing ratios shown in Table 1 [(a) component, (b) component are% by mass, (c) component and (d) component are based on 100 parts by mass of the sum of (a) component and (b) component. Parts by mass), the components were mixed and melt-kneaded at 260 ° C. with a 4 O mm single screw extruder (VS40, manufactured by Tanabe Plastic Machinery Co., Ltd.) to form pellets. Next, the obtained pellets were injection-molded using a 45-ton injection molding machine (manufactured by Toshiba Machine Co., Ltd., IS45PV) to obtain a 90 x 50 mm thickness 3 m: m, 2 mm , 1 mm three-stage thick plate specimens were obtained. The physical properties of the obtained test pieces were evaluated as follows, and the results are shown in Table 1.

The raw materials and physical property evaluation methods used are shown below. 〔raw materials〕

 (a) Thermoplastic resin

 a-1: Polycarbonate resin; Bisphenol A as raw material, melt flow rate (MFR) [JIS K72010, temperature: 300 ° C, load: 1.1.7 N] is 20 g / Polycarbonate resin having a viscosity average molecular weight of 19,000 for 10 minutes [Idemitsu Petrochemical Co., Ltd .: Toughlon A190]

 a-2: Polycarbonate resin; bisphenol A as raw material, melt flow rate (MFR) [JISK72010, temperature: 300 ° C, load: 1.1.7 N]: 8 g / l Polycarbonate resin having a viscosity average molecular weight of 25,000 for 0 minutes [Idemitsu Petrochemical Co., Ltd .: Toughlon A250]

 a-3: Elastomer; methinoacrylate methacrylate alkyl-dimethyl oxalate copolymer, manufactured by Mitsubishi Rayon Co., Ltd .: methaprene S—200 1]

 a—4: Terpene resin; Aromatic terpene resin [Yasuhara Chemical Co., Ltd .: Y S resin TR—105]

 (b) Glass material

b—1: Glass fiber; refractive index (n 1.545, fiber diameter 13 μm, fiber length 3 mm [Made of Asahi Fire Per Glass Co., Ltd .: MA409C]

b-2: glass flakes; [Nippon Sheet Glass Co., Ltd .: REFG101] (c) Plasticizer

c-1: phenyl 'resorcinol polyphosphate [Asahi Denka Kogyo KK: ADK STAB PFR]

 (d) Bright materials

d-1: Pearl pigment; Pearl My power [Merck Japan: I rio din 1 0 3)

d-2: Metallic pigment; aluminum powder [Toyo Aluminum Co., Ltd .: P010]

 (Physical property evaluation method)

Flexural modulus: Compliant with JISK 7203 (MPa)

IZOD impact strength: Conforms to JISK 7110 (23 ° C, 3.2 mm) (k J / m ² )

Appearance: Evaluated visually.

Feeling of depth: Good, X bad

Three-dimensional pattern feeling: ◎ best, 〇 good, X poor

Table 1

 Wei example 1 Difficult example 2 Fine row 3 Fine row 4 Fine row 5 Fine row 6

(a) a— 1 79.0 79.0 79.0 7.9.0 84.5 84.5 a—2 ——————— Quality a— 3 4.5 5.4.5 4.5.4.5 4.5 4.5 ri'a—4 5.5 5.5.5 5.5.5 5.5.5 5.5.5

%

 (b) b-1 11.0 11.0 11.0 11.0 5.5 5.5 b—2

 (c) c-1 11.0 11.0 11.0 11.0 11.0 11.0Quantity (d) d-1 0.6.2 2.1.1.1.1 copy d-2 1.1 1.1 Object bending elastic modulus 4,300 4,300 4,300 4,300 3,300 3,300 Property I ZOD boat 7 7 7 7 7 7 Outside o 〇 〇 〇 〇 〇 View o ◎ 〇 〇 〇 〇

雞 Example 8 Fine row 9 Difficult example 10 赚 Row 1 1 ： Yu 2

(a) a-1 84.5 84.5 68.0 68.0 79.0

 a— 2 90.0 a— 3 4.5.4.5 4.4.5.4.5.5 a—4 5.5.5.5.5.5.5.5.5 ri

 (b) b-1 22.0 11.0 10.0%

 b-2 5.5 5.5 5.5 22.0

Quality (c) c-1 11.0 11.0 11.0 11.0 11.0 m. (D) d-1 1.1 1.1 1.1

Part d-2 1.1

Object Bending rate 3,300 3,300 6,300 6,300 4'300 3,900 Property I ZOD hall plating 5 5 7 7 10 9 Outside O o O 〇 〇 X View 〇 〇 〇 XX XX

Industrial applicability

 Advantageous Effects of Invention According to the present invention, it is possible to provide a thermoplastic resin composition having a deep feeling on the surface appearance of a molded article and capable of forming a three-dimensional pattern (silk-like) by a simple method.

Claims

The scope of the claims  1. (a) 30 to 99.5% by mass of a thermoplastic resin; (b) 0.5 to 70% by mass of a glass; 100 parts by mass of a resin composition; A thermoplastic resin composition comprising from 0.05 to 25 parts by mass and (d) 0.05 to 10 parts by mass of a glittering material.  2. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin as the component (a) mainly contains a polycarbonate resin.  3. The thermoplastic resin composition according to claim 1, wherein the glass of the component (b) is at least one selected from the group consisting of glass fiber, glass flake and glass powder.  4. The thermoplastic resin composition according to any one of claims 1 to 3, wherein the plasticizer (c) is selected from a phosphorus compound and a higher fatty acid ester. 5. The thermoplastic resin composition according to any one of claims 1 to 4, wherein the brilliant component (d) is at least one selected from pearl pigments, metallic pigments, and glass flakes coated with metal. object.  6. A molded article obtained by molding the thermoplastic resin composition according to any one of claims 1 to 5.