JPH07102160A - Polycarbonate resin composition for simultaneous injection molding and transfer - Google Patents

Abstract

PURPOSE:To obtain a polycarbonate composition free from problems such as the flow and crack of decorative ink, etc., and useful for nameplate of automobile meters, etc., by compounding an aromatic polycarbonate resin with a specific amount of an ester compound of a bisphenol compound and an aliphatic carboxylic acid. CONSTITUTION:This polycarbonate resin composition is produced by compounding (A) 100 pts.wt. of an aromatic polycarbonate resin with (B) 0.1-10 pts.wt. of an ester compound of (i) a bisphenol compound and (ii) a 2-36C, preferably 8-22C aliphatic carboxylic acid (e.g. butyric acid or capric acid), preferably a compound of the formula I (R1 and R2 is 1-35C aliphatic hydrocarbon group) produced by using bisphenol A as the component (i) or a compound of the formula II (R3 and R4 are 1-5C aliphatic hydrocarbon group; m and n are integer of >=0 and m+n>=1, preferably m and n are 1-5) produced by using an alkylene oxide adduct of bisphenol A as the component (i).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate resin composition used in simultaneous injection-molding transfer, in which surface decoration and surface function impartation are performed simultaneously with injection molding.

[0002]

2. Description of the Related Art The so-called injection molding simultaneous transfer method is a method of setting a transfer foil in a mold in advance and performing transfer simultaneously with injection molding. In the transfer molding of plastic products, the process is shortened and unattended. Taking advantage of the advantages that it can be realized and the diversification of design, etc., its applications are expanding more and more in recent years mainly for electric / electronic parts and automobile parts.

Conventionally, the method of transferring at the same time as molding is applied to polyethylene, polypropylene, polystyrene, ABS resin, AS resin, polymethylmethacrylate resin and the like, and imparts various surface functions such as surface decoration and scratch resistance. A method for transfer-molding a transfer foil on the surface thereof has been technically established and has been industrially produced. On the other hand, polycarbonate resin has high transparency and is excellent in impact strength, heat resistance, etc.
It is used in many applications such as automobile parts, medical / security, building materials, and household products. Therefore, the injection molding simultaneous transfer method,
If it can be applied to a polycarbonate resin, its field of use will be further expanded, and it will be possible to obtain a highly functional product having a higher design.

[0004]

However, when attempting simultaneous injection molding with polycarbonate resin using a transfer foil, the ink to be decorated and the performance-imparting film due to high resin temperature and shear stress during molding. In addition, it causes problems such as flow and cracks and wrinkles on the transfer foil, and it is difficult to obtain a product in good condition.

A possible solution to such a problem is to reduce the molecular weight of the polycarbonate resin to lower the resin temperature and shear stress. However, in order to reduce the molecular weight, the impact resistance, which is a characteristic of polycarbonate, is significantly impaired, and the resin inlet has a relatively high residual stress such as the gate part and the flow end where the residual stress is high. However, there is a drawback that cracks occur in a short time, so that it may cause great restrictions on the gate position, mold design, and product design, or may cause defects.

[0006]

DISCLOSURE OF THE INVENTION The inventors of the present invention have diligently studied to obtain a polycarbonate resin composition which enables simultaneous injection molding by injection molding without suffering from such problems and restrictions. The inventors have found that a composition that meets the purpose can be obtained by adding an ester compound of a bisphenol compound and an aliphatic carboxylic acid having 2 to 36 carbon atoms to the present invention, and arrived at the present invention.

That is, the gist of the present invention is to mix 0.1 to 10 parts by weight of an ester compound of a bisphenol compound and an aliphatic carboxylic acid having 2 to 36 carbon atoms with 100 parts by weight of an aromatic polycarbonate resin. And a polycarbonate resin composition for simultaneous injection molding transfer. The present invention will be specifically described below.

The simultaneous injection molding transfer in the present invention means a pattern layer such as a printing ink, a pattern layer such as a metal thin film layer, a hard coat layer, or an antistatic property, an ultraviolet absorbing property, on the surface of a thermoplastic resin film or sheet. Heat ray absorption,
Transfer foil with various layers such as antifogging property, electromagnetic interference prevention property, conductive property, insulation property, and other surface function-imparting film layers is inserted into a molding die to be molded simultaneously with injection molding. On the other hand, it is a method of decorating the surface or imparting surface function.

This will be explained with reference to the drawings. As shown in FIG. 1, a transfer foil comprising a thermoplastic film 3 and a layer 4 comprising a release layer, a surface decoration or surface function imparting film layer, an adhesive layer and the like. Is attached or left stationary in the mold 1 so that the surface of the thermoplastic film 3 is in contact with the surface of the mold, and then a polycarbonate resin is press-fitted into the mold cavity by injection molding by the injection machine 2 and cooled and solidified. After molding, only the thermoplastic film or sheet 3 is removed to obtain a polycarbonate resin molded product having a surface decoration and a surface function imparting film layer.

This method is advantageous in that the process can be shortened and unmanned as compared with the conventional method in which printing, painting, coating, vapor deposition and the like are performed on the surface of the product after injection molding, and it has gloss. Taking advantage of the diversification of design such as surface, deep print finish, partial decoration and function addition, fine unevenness and three-dimensional curved surface, electrical and electronic parts, automobiles In recent years, its applications have been expanding, focusing on parts.

The aromatic polycarbonate resin used in the present invention is obtained by a phosgene method in which various dihydroxydiaryl compounds are reacted with phosgene, or a transesterification method in which a dihydroxydiaryl compound is reacted with a carbonic acid ester such as diphenyl carbonate. A typical example of the polymer or copolymer is a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).

As the dihydroxydiaryl compound, in addition to bisphenol A, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl)
Butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4- Hydroxy-3-t
-Butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4- Bis (hydroxyaryl) alkanes such as hydroxy-3,5-dichlorophenyl) propane, bis such as 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane (Hydroxyaryl) cycloalkanes, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-
Dihydroxy diaryl ethers such as dimethyl diphenyl ether, 4,4'-dihydroxy diphenyl sulfide, dihydroxy diaryl sulfides such as 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfide, 4,4'-dihydroxy diphenyl sulfoxide , 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, such as dihydroxydiaryl sulfoxides, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-
Examples thereof include dihydroxydiarylsulfonic acid such as dimethyldiphenyl sulfone.

These may be used alone or in admixture of two or more, but in addition to them, piperazine, dipiperidyl, hydroquinone, resorcin, and 4,4'-dihydroxydiphenyls may be mixed and used. The viscosity average molecular weight of the polycarbonate resin used in the present invention is 170
00-30000, preferably 17000-22000
Are preferred.

The bisphenol compound used in the ester compound of the bisphenol compound of the present invention and the aliphatic carboxylic acid having 2 to 36 carbon atoms (hereinafter sometimes simply referred to as an ester compound) has a bisphenol skeleton. Any compound can be used, but specifically, bisphenols such as 2,2
-Bis (4-hydroxyphenyl) propane (bisphenol A), bis (4-hydroxyphenyl) methane,
1,1-bis (4-hydroxyphenyl) ethane, 2,
2-bis (4-hydroxyphenyl) butane, 2,2-
Bis (4-hydroxyphenyl) octane, bis (4-
Hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane,
1,1-bis (4-hydroxy-3-t-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-) Bis (hydroxyaryl) alkanes such as dibromophenyl) propane and 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane,
1,1-bis (4-hydroxyphenyl) cyclopentane, bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxydiphenyl ether,
Dihydroxy diaryl ethers such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-dihydroxydiphenyl sulfide,
Dihydroxydiaryl sulfides such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide Examples thereof include dihydroxydiaryl sulfoxides, 4,4'-dihydroxydiphenyl sulfone, and dihydroxydiaryl sulfones such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone.

The aliphatic carboxylic acid has 2 to 3 carbon atoms.
6, preferably 8 to 22 are used. Specific examples include butyric acid, capric acid, lauric acid, palmitic acid, stearic acid, oleic acid, behenic acid and montanic acid. Among them, it is preferable to use bisphenol A as the bisphenol and use a compound represented by the following general formula (A).

[0016]

[Chemical 1]

(R ₁ and R ₂ represent an aliphatic hydrocarbon group having 1 to 35 carbon atoms.) As the bisphenol compound, it is also preferable to use an alkylene oxide adduct of bisphenol. Compounds obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, oxetane and tetrahydrofuran, or a mixture thereof to the above-mentioned bisphenols can be mentioned.

In the present invention, an ester compound of an alkylene oxide compound of these bisphenols and an aliphatic carboxylic acid having 2 to 36 carbon atoms is preferably used, and the following general formula (bisphenol A using bisphenol A is used. It is particularly preferable to use the compounds represented by B). In addition, these ester compounds are used individually or in mixture of 2 or more types.

[0019]

[Chemical 2]

(R ₁ and R ₂ are aliphatic hydrocarbon groups having 1 to 35 carbon atoms, R ₃ and R ₄ are aliphatic hydrocarbon groups having 1 to 5 carbon atoms, and m and n are 0 or more. It is an integer and m + n ≧ 1. Preferably, m and n are each 1 to 5.) The aromatic polycarbonate resin and the ester compound used in the present invention are blended in the following ratios.

That is, the aromatic polycarbonate resin 100
0.1 to 10 parts by weight, preferably 0.
It is in the range of 5 to 6 parts by weight. If the blending amount is less than 0.1 part by weight, the effect of improving the processability at the time of simultaneous injection molding and transfer molding is insufficient, while if the blending amount exceeds 10 parts by weight, the heat resistance and mechanical properties of the resulting composition are improved. Is reduced, which is not preferable.

Further, in addition to the above-mentioned compounds, the materials of the present invention include various well-known additives such as paraffin wax, lubricants such as fatty acid esters, hindered phenols, phosphoric acid esters and phosphorous acid esters. Antioxidant, impact resistance improver such as acrylic rubber, weather resistance agent, flame retardant, foaming agent, antistatic agent, pigment, dye and the like may be contained. In addition, the material of the present invention is not limited to other resin materials such as polyethylene terephthalate, polybutylene terephthalate and ABS as long as the effects of the present invention are not impaired.
It can be mixed and used.

[0023]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples without departing from the gist thereof. The transfer foil used in this example is as follows. Transfer foil X: A release layer is formed on the surface of a base material film made of polyethylene terephthalate and having a thickness of 50 μm,
Then, a transfer foil is obtained by printing a pattern of burrs at 5 mm intervals with a printing ink such as a urethane-based paint, and further applying a resin for forming an acrylic-urethane-based resin adhesive layer.

Transfer foil Y: A hard coat film made of an acrylic electron beam cross-linking resin is applied on the surface of a base material film made of polyethylene terephthalate and having a thickness of 50 μm, and then an electron beam of 180 KeV, 5 Mrad is irradiated from the base material side. Then, the resin is cured, and then a transfer foil is obtained by applying an adhesive layer forming resin made of an acrylic-urethane resin. The evaluation method of the injection-molding simultaneous transfer molded article in this example is as follows.

(1) Appearance of Molded Product With respect to the transfer foil X, the turbulence of the goggles due to the ink flow was visually observed. The symbols in Table 2 are as follows. ◯: No turbulence Δ: There is turbulence ×: Disturbance is severe For the transfer foil Y, the presence or absence of cracks in the transfer layer was visually observed. The symbols in Table 2 are as follows. ○: No cracks ×: Cracks

(2) High-speed impact test High Rate Imp manufactured by Rheometric Co., USA
act Tester; using RIT8000, 100
Destruction when a flat plate test piece of 3 mm square was mounted on a sample fixing jig as shown in FIG. 2 and punched at a test speed of 3 m / sec using a load cell with a tip radius of 3/8 inch. Energy was measured. The test room temperature is 23
℃ was made.

(3) Heat shock test A heat shock test piece was left in a cooling bath at -20 ° C for 1 hour and then left in a hot air bath at 80 ° C for 1 hour within 10 seconds. The presence or absence of cracks in the peripheral portion of the gate of the rear polycarbonate resin base material and the end surface of the molded product was visually observed. The symbols in Table 2 are
It is as follows. ○: No cracks occurred ×: Cracks occurred

Examples 1 to 4 and Comparative Examples 1 and 2 As an aromatic polycarbonate, a bisphenol A type polycarbonate resin having an average molecular weight of 19,000 (manufactured by Mitsubishi Kasei Co., Ltd., trade name: NOVAREX 7022A, NOVAREX) Is a registered trademark), and the ester compound of the present invention having the structure shown in Table 1 below are mixed at a mixing ratio shown in Table 2 below, and then the mixture is mixed with a vented extruder having a cylinder diameter of 40 mm.
The mixture was melt-mixed at a resin temperature of 280 to 300 ° C. and pelletized.

Further, the pellets were placed in an atmosphere of 120 ° C. for 5 minutes.
After drying for an hour, the transfer foil X is loaded into a flat plate mold of 100 mm square and 3 mm thickness, and then an injection molding machine (manufactured by Toshiba Machine Co., IS
80 EPN), molding temperature 280 ° C., mold temperature 80
Injection molding at ℃, after cooling, remove the molded product from the mold,
A transfer molded product was obtained. The evaluation results of this molded product are shown in Table 2.

(Comparative Example 3) As an aromatic polycarbonate, a bisphenol A type polycarbonate resin having an average molecular weight of 15,000 (trade name: Novarex 7020AD2, manufactured by Mitsubishi Kasei Co., Ltd., is a registered trademark) was used. As in Example 1, a transfer molded article was prepared from the transfer foil X and the same evaluation was performed. The results are also shown in Table 2.

(Example 5 and Comparative Example 4) As in Example 1, as an aromatic polycarbonate, an average molecular weight of 19,
000 bisphenol A type polycarbonate resin (NOVAREX 7022A) and the ester compound shown in Table 1 were mixed at the compounding ratio shown in Table 2 and then pelletized.
Using these, the transfer foil Y was used to obtain transfer molded articles in the same manner as in Example 1 and evaluated. The evaluation results are shown in Table 2.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

INDUSTRIAL APPLICABILITY By using the resin composition of the present invention, simultaneous injection molding transfer can be performed without causing defects such as flow or crack in the ink to be decorated and the performance-imparting film, and wrinkles in the transfer foil. By doing so, it is possible to easily decorate the surface of the polycarbonate molded article and impart the surface function thereto. That is, it becomes easy to apply the injection molding simultaneous transfer method to the polycarbonate resin, the application field of the polycarbonate resin further expands, and it becomes possible to obtain a highly functional product having a higher design.

Therefore, the resin composition of the present invention is, for example,
In the automotive field, meter nameplates, various lamp lenses, interior / exterior parts such as window glass, electrical / electronic parts nameplates, VTR / computer equipment housings, lighting equipment lenses and parts, OA equipment faxes, laser beams Printers, floppy disk drive parts and various nameplates, camera / clock parts for precision machinery parts, artificial dialysis cases, artificial heart-lung cases, etc. for medical security applications, window glass and light roofing materials for building materials, toys, tableware, etc. It can be preferably used for household products such as.

[Brief description of drawings]

FIG. 1 is a diagram showing an outline of an injection molding simultaneous transfer method of the present invention.

FIG. 2 is a diagram showing an outline of a high-speed impact test shown in Example 1 of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Mold 2 Injection machine 3 Transfer foil base film 4 Transfer layer including function-imparting coating layer 5 Load cell 6 Tip radius (R = 3/8 inch) 7 Sample fixing jig 8 Test piece 9 Transfer layer 10 φ1 inch penetration hole

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroyuki Imaizumi 370 Enzo, Chigasaki City, Kanagawa Mitsubishi Kasei Co., Ltd. Chigasaki Plant

Claims (1)

[Claims] 1. A composition comprising 0.1 to 10 parts by weight of an ester compound of a bisphenol compound and an aliphatic carboxylic acid having 2 to 36 carbon atoms with 100 parts by weight of an aromatic polycarbonate resin. , A polycarbonate resin composition for simultaneous injection molding transfer.