JP2001270953A - Thermoplastic polyester molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic polyester molded article for metal deposition having good mold releasability in molding, furthermore exhibiting good adhesion strength to a vapor-deposited metal and being excellent in heat resistance, particularly in heat cycle properties. SOLUTION: The thermoplastic polyester molded article comprises a metal vapor-deposited on the surface of a article obtained by molding a resin composition comprising (A) 100 pts.wt. of the thermoplastic polyester resin and, blended therewith, (B) 0-400 pts.wt. of a polycarbonate resin and (C) 0.02-10 pts.wt. of an alkaline earth metal salt of a 26C or higher fatty acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a metal-deposited product, particularly a housing for automobiles, office automation, home appliances, electric and electronic fields,
The present invention relates to a molded article of a thermoplastic polyester resin which is suitably used for parts and the like and has excellent adhesiveness to metal, particularly excellent adhesiveness to aluminum.

[0002]

2. Description of the Related Art Thermoplastic polyester resins have excellent mechanical properties and
It is widely used in various applications such as electronic parts, automobile and other opportunity parts, office automation, home appliances, and other products and parts. In addition, particularly in the fields of automobiles and home electric appliances, in order to impart a metallic feeling to the molded article or to obtain a light reflection effect, metal,
In particular, an aluminum thin film may be used by bonding. However, when a metal is directly vapor-deposited on a molded product, the adhesion to the vapor-deposited metal is poor, and the metal is easily peeled off even when the metal is vapor-deposited. Therefore, chromic acid treatment, solvent treatment, plasma, corona discharge treatment, etc. have been performed to improve the adhesiveness, including undercoat treatment, but there were problems in safety and health, workability, economy, etc. . In addition, there are thermoplastic polyester molded products in which good adhesion is obtained by directly depositing a metal, but in such a case, the moldability, particularly the mold releasability at the time of molding is poor, which is also practical. The situation was not available.

[0003]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned drawbacks of the prior art, and has good releasability during molding and good adhesion strength to a metal deposition film when metal is deposited. It is an object of the present invention to provide a thermoplastic polyester molded article for vapor deposition having excellent heat resistance, particularly heat cycleability.

[0004]

Means for Solving the Problems The present inventors have solved the above-mentioned problems and have found that a thermoplastic resin having a good mold release property at the time of molding and a good adhesive strength to a metal-deposited film when metal is deposited. As a result of diligent, research, and examination to develop polyester molded products,
Finally, the present invention has been completed. That is, the present invention
(A) 100 parts by weight of a thermoplastic resin polyester resin, (B) 0 to 400 parts by weight of a polycarbonate resin and (C) 0.02 to 10 parts by weight of an alkaline earth metal salt of a higher fatty acid having 26 or more carbon atoms. On the surface of the molded product obtained by molding the thermoplastic polyester resin composition, a thermoplastic polyester molded product characterized in that metal is deposited, on the surface of the molded product obtained by molding the thermoplastic polyester resin composition And the above-mentioned thermoplastic polyester molded article on which a metal is directly deposited without performing surface treatment such as undercoating, and the above-mentioned thermoplastic polyester molded article on which the deposited metal is aluminum.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. Examples of the thermoplastic polyester resin which is the component (A) used in the present invention include polyethylene terephthalate, polybutylene terephthalate, a copolymer containing 60 mol% or more, preferably 65 mol% or more, and / or an alloy thereof. Is mentioned. As the copolymerization component, a conventionally known acid component and / or glycol component can be used. That is, as the copolymer component,
For example, isophthalic acid, naltarene 1,4- or 2,
Acid components such as 6-dicarboxylic acid, cyclohexanedicarboxylic acid, diphenylether 4,4-dicarboxylic acid, adipic acid, sebacic acid, propylene glycol, diethylene glycol, cyclohexanedimethanol, tricyclodecane dimethylol, bisphenol A ethylene oxide adduct, Glycol components such as polyethylene glycol, and oxyacids such as p-hydroxybenzoic acid and p-hydroxyoxybenzoic acid are included. The polyester has an intrinsic viscosity of preferably 0.4 or more, more preferably 0.45 or more, measured at 30 ° C. in a phenol / tetrachloroethane mixed solvent (6/4 weight ratio) solution. The polyester may have a partially branched structure as long as the moldability is not impaired.

In some cases, the polycarbonate as the component (B) used in the present invention is preferably a polycarbonate derived from dioxydiarylalkane, which is an aromatic polycarbonate, or a copolymer thereof. Particularly preferred are polycarbonates and copolymers such as polycarbonates having a norbornane ring.

The amount of the polycarbonate as the component (B) is from 0 to 400 parts by weight, preferably from 0 to 300 parts by weight, particularly preferably from 0 to 200 parts by weight, per 100 parts by weight of the thermoplastic polyester resin. It is. If the content of the polycarbonate exceeds 400 parts by weight, the heat resistance (the deflection temperature under load) decreases, which is not preferable.

The alkaline earth metal salt of a higher fatty acid having a carbon number of 26 or more (hereinafter referred to as a higher fatty acid salt) which is a component (C) used in the present invention includes calcium montanic acid or cellotinic acid. In addition to salts, magnesium salts, barium salts, beryllium salts, strontium salts, etc., calcium salts of higher fatty acids obtained by adding fatty acids to α-olefins, magnesium salts, barium salts,
Beryllium salts, strontium salts and the like. As the α-olefin used here, an α-olefin mixture having 30 or more carbon atoms (average carbon number 43 calculated from iodine value) or an α-olefin mixture having 20 to 28 carbon atoms (average carbon number 23) is used. Preferably, propionic acid is preferred as the fatty acid. As the higher fatty acid obtained by adding and reacting the above components, a mixture of α-methyl fatty acids having 33 or more carbon atoms (average carbon number of 46 calculated from iodine value) or α-methyl fatty acids having 23 to 31 carbon atoms can be used. A mixture (average carbon number 26) is mentioned. Of course, fatty acids other than propionic acid such as butyric acid and valeric acid can also be used.

In the present invention, the higher fatty acid salt is used in an amount of 0.02 to 10 per 100 parts by weight of the thermoplastic polyester resin.
% By weight, preferably 0.05 to 5.0 parts by weight, particularly preferably 0.1 to 1.0 part by weight. The amount used is 0.
If the amount is less than 02 parts by weight, the effect of the present invention is insufficient, and if it exceeds 10 parts by weight, the mechanical properties of the thermoplastic polyester serving as a matrix are lowered, which is not preferable.

[0010] The polyester resin composition of the present invention may contain, if necessary, a fibrous reinforcing agent, an indefinite filler, a stabilizer, a colorant,
Flame retardants, foaming agents, plasticizers, lubricants, antistatic agents, release agents,
Various additives such as a crosslinking agent and metal powder can be blended.

The method for obtaining the thermoplastic polyester resin composition used in the present invention is not particularly limited, and a usual method can be employed. For example,
A method in which (C) a higher fatty acid salt is melt-mixed in a polymerization vessel during or after the production of (A) a thermoplastic polyester resin by an extruder, a mill roll, a Banbury mixer, or the like. Similar effects can be obtained by mixing N solid (A) thermoplastic polyester resin, (B) polycarbonate resin and (C) higher fatty acid salt before molding and using them directly for molding.

As a method for obtaining a molded article from the composition, a conventionally known method can be mentioned, and is not particularly limited, but is generally an injection molding method. In addition,
The shape of the molded article is not particularly limited.

Next, as a method for depositing a metal on the molded article, a vacuum deposition method, that is, a high vacuum (10 ^-4 to 10 ^{-6) is used.}
An example is a method of introducing a vapor deposited metal into an apparatus maintained at Torr and depositing the vapor on the surface of a molded product. Also,
A spattering method in which a metal is sputtered using glow discharge and vapor deposition, and an ion plating method in which a substrate is etched by argon ionized and accelerated by ionization and vapor deposition can be also preferably used. The metal to be deposited is aluminum, titanium, chromium,
Nickel, copper, silver, gold, zinc, germanium, tin, selenium and the like can be mentioned, but aluminum is preferred in terms of workability, reflectance, economy and the like. In this case, the thickness of the aluminum deposition layer is generally 500 to 1000 °, but is not particularly limited, and a preferable thickness is selected as needed.

The molded article of the present invention has good releasability at the time of molding while maintaining the excellent performance inherent to the thermoplastic polyester resin, and allows direct molding of metal without performing surface treatment such as undercoat on the molded article surface. It has good adhesion strength to a metal deposited film when deposited, and has greatly improved heat resistance, especially heat cycleability.

[0015]

The present invention will be described below in detail with reference to preferred embodiments of the present invention, but the present invention is not limited thereto. "Parts" in the text and examples
Means part by weight. The evaluation of the release resistance value and the adhesive strength to the metal thin film was performed by the following methods.

(1) Release resistance: Various polyester resin compositions are melted and kneaded, and a compound chip of each composition is mixed with 1
After drying under reduced pressure at 40 ° C for 4 hours, the molding machine (cylinder temperature 265-265-265-250 ° C, mold temperature 80
(C °, injection holding pressure time: 10 seconds, cooling time: 15 seconds). If the release resistance value is 100 kgf or more, deformation or the like occurs at the time of release, which is not preferable. (2) Adhesive strength to metal thin film: After leaving for 24 hours after the vapor deposition, and heat cycle (treatment in an atmosphere of -40 ° C for 2 hours, followed by treatment in an atmosphere of 170 ° C for 2 hours, 10 cycles of heat cycle) After standing for 24 hours after the treatment, a cross-cut peeling test (100 pieces) at 1 mm intervals was performed using Nichiban cellophane tape. The evaluation was shown as a percentage (%) of the number of grids remaining on the surface of the molded product with respect to the total number of grids. If the bonding strength is less than 100% at the initial stage and less than 80% after the heat cycle, it is not preferable because of poor adhesion.

Examples 1 to 3 As the component (A) thermoplastic polyester resin, polyethylene terephthalate resin (intrinsic viscosity 0.62) (hereinafter referred to as P
ET) and polybutylene terephthalate (intrinsic viscosity number 0.80) (hereinafter abbreviated as PBT) as a component (B) polycarbonate resin from bisphenol A type polycarbonate resin ((viscosity average molecular weight 25000) (hereinafter abbreviated as PC) ) As component (C) high fatty acid salt calcium montanate (Clariant Japan K.K. Ho)
stamontCaV102 calcium content 4.5
%) (Hereinafter abbreviated as CaV) was preliminarily mixed with the composition shown in Table 1, and then charged into a hopper of a twin-screw extruder and melt-kneaded at a cylinder temperature of 260 to 280 ° C. to obtain compound chips.

After drying the compound chip at 140 ° C. for 4 hours, a plate for metal vapor deposition (150 × 70 × 3 mmt) was obtained by an injection molding machine, and the plate was vacuumed at 5 × 10 ^-5 Torr using a bell jar vapor deposition machine. Was used to deposit aluminum on one side of the plate. At this time, the adhesive strength of the deposited aluminum film was evaluated after standing at room temperature for 24 hours after the deposition and after standing for 24 hours at room temperature after the heat cycle treatment. In addition, the mold release resistance value at the time of molding of a mold for evaluating mold release resistance (a cup-shaped product) was also evaluated. The evaluation results are also shown in Table 1.

Comparative Example 1 The procedure of Example 2 was repeated except that the component (C) higher fatty acid salt was not added. Table 1 shows the evaluation results.

Comparative Example 2 In Example 2, the component (C) higher fatty acid salt was not added, and instead, ethylene glycol diester montanate (HoechstWax manufactured by Clariant Japan K.K.) was used.
E The same procedure as in Example 2 was performed except that calcium content was 0% (hereinafter abbreviated as waxE). Table 1 shows the evaluation results.
Shown in

Comparative Example 3 In Example 2, the component (C) higher fatty acid salt was not added, and instead, calcium stearate (hereinafter referred to as St-Ca) was used.
The procedure was the same as in Example 2 except that (abbreviated as). Table 1 shows the evaluation results.

[0022]

[Table 1]

[0023]

As is clear from Table 1, the molded article of the present invention has a mold release resistance of 100 kgf or less, and has a grid strength of 100% both at the initial stage and after the heat cycle. As described above, the molded article of the present invention has a good release property at the time of molding, has a good adhesive strength with a metal deposition film when metal is deposited, and has excellent heat resistance, especially heat cycle property, so its use is expanded. Can greatly contribute to the industry.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C23C 14/14 C23C 14/14 B F term (Reference) 4F006 AA35 AA36 AB73 BA01 CA04 CA08 DA01 4F100 AB01B AB10B AH08A AK41A AK42 AK45A AL05A BA02 DA01 EH36 EH66B GB32 GB41 GB48 JB16A JL02 JL11 YY00A 4J002 BB203 CF06W CF07W CG01X EG036 GQ00 4K029 AA11 BA03 BC00 BC10 CA01

Claims (3)

[Claims] (A) Thermoplastic polyester resin 100
(B) polycarbonate resin 0 to 400 parts by weight
A metal is vapor-deposited on the surface of a molded product obtained by molding a thermoplastic polyester resin composition containing 0.1 parts by weight and (C) 0.02 to 10 parts by weight of an alkaline earth metal salt of a higher fatty acid having 26 or more carbon atoms. A thermoplastic polyester molded article, characterized in that: 2. The thermoplastic polyester molded article according to claim 1, wherein a metal is directly deposited on the surface of the molded article obtained by molding the thermoplastic polyester resin composition without performing a surface treatment such as an undercoat. . 3. The thermoplastic polyester molded article according to claim 1, wherein the metal to be deposited is aluminum.