JP2011135958A - Bag - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a bag with a beautiful, massive and high-grade piano-black-like appearance and good impact strength and fatigue property while maintaining the innate quality of polycarbonate resin such as good impact strength, heat resistance, and thermal stability. <P>SOLUTION: The bag molded of polycarbonate resin composition is molded of a resin composition composed of a specific polycarbonate resin composition, an organic black dye, and a cyclic poly(alkylene terephthalate) oligomer. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a bag made of a polycarbonate resin composition having excellent jetness and excellent drop impact, scratching, and releasability, and particularly to a bag suitable for a carrying case type bag or a suitcase. More specifically, the present invention relates to a bag having excellent jet blackness, drop impact resistance, scratch resistance, and releasability while retaining the impact resistance, heat resistance, thermal stability, etc., which are the characteristics of polycarbonate resin. Moreover, the bag of the present invention has a beautiful, heavy and high quality appearance.

  Polycarbonate resin is a thermoplastic resin excellent in impact resistance, heat resistance, thermal stability, and the like, and is widely used in fields such as electricity, electronics, ITE, machinery, and automobiles. On the other hand, in the use of straw, while taking advantage of these excellent performances of the resin, it has an excellent jetness (also called piano black) appearance from the viewpoint of design and design of the obtained molded product. It is desired.

  As a technique for imparting jet blackness to a polycarbonate resin composition, a technique for adding carbon black having high concealment (Patent Document 1), a technique for adding silicone oil (Patent Document 2), and the like have been proposed. However, when a carbon black pigment is added, it is difficult to develop high jetness although the concealability is improved. On the other hand, the addition of silicone oil has a problem of whitening during molding.

JP2003-96286 JP 2004-210889 A

  Polycarbonate resin, on the other hand, is a resin with excellent impact resistance. However, in the use of bags, in addition to problems such as cracking and breakage when the product is dropped, it has mold release properties and scratches on the molded product surface. There is a particular need for improvement.

  The object of the present invention is to overcome the above-mentioned problems in the prior art, that is, to overcome the disadvantages of jet black deterioration and whitening when using carbon black or silicone oil, The object is to provide a polycarbonate resin bag having a piano black-like appearance) and having excellent drop impact, scratching, and releasability.

  As a result of diligent research in view of such an object, the present inventors have found that an organic black dye and a cyclic poly (alkylene terephthalate) oligomer having specific optical performance in a polycarbonate resin having transparency, and, if necessary, a rubber component. By blending, it was found that a piano black-like appearance can be obtained without impairing the jetness of the obtained molded product, and the impact resistance upon dropping can be improved, and the present invention has been completed.

That is, the present invention is a mold formed by molding a polycarbonate resin composition,
(1) The polycarbonate resin composition comprises 100 parts by weight of a polycarbonate resin (A) having a viscosity average molecular weight of 21,000 to 35,000, 0.05 to 0.5 parts by weight of an organic black dye (B), and a cyclic poly (alkylene terephthalate) oligomer. (C) consisting of a resin composition containing 1 to 8 parts by weight as an essential component,
(2) The optical characteristics of the organic black dye (B) were obtained by injection molding a resin composition comprising 100 parts by weight of the polycarbonate resin (A) and 0.3 parts by weight of the organic black dye (B). When measuring the light transmittance of a flat plate with a thickness of 2 mm, it has a light transmittance of 50% or more in a wavelength region of 800 to 900 nm,
(3) When the impact strength with a notch is measured according to ASTM D-256 using a 3.2 mm-thick test piece formed by injection molding of the polycarbonate resin composition, it has an impact resistance of 650 J / m or more. (4) When measured with a 15 MPa load according to JIS K7119 using a 3.0 mm thick JIS K7119 II fatigue test piece formed by injection molding of the polycarbonate resin composition, 2 × 10 6 times Having the above fatigue characteristics,
It is intended to provide a bag characterized by that.

  The bag of the present invention has a beautiful, heavy, high-quality piano black-like appearance while maintaining the excellent impact strength, heat resistance, thermal stability, etc. inherent to the polycarbonate resin, and is resistant to dropping. Excellent impact. Therefore, it is particularly suitable for carrying case type bags and suitcases.

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

  Examples of the dihydroxydiaryl compound include bisphenol 4-, 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-hydroxyphenyl-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3) -Tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis ( Bis (hydroxyaryl) alkanes such as 4-hydroxy-3,5-dichlorophenyl) propane, 1,1- (4-hydroxyphenyl) cyclopentane, bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3 Dihydroxy diaryl ethers such as 3,3'-dimethyldiphenyl ether, dihydroxy diaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3 ' Dihydroxy diaryl sulfoxides such as dimethyldiphenyl sulfoxide, dihydroxy diary such as 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone Sulfone, and the like.

  These may be used alone or in combination of two or more. In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4′-dihydroxydiphenyl, and the like may be used in combination.

  Furthermore, the above dihydroxyaryl compound and a trivalent or higher phenol compound as shown below may be used in combination. Trihydric or higher phenols include phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 2,4,6-dimethyl-2,4,6-tri- (4 -Hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -ethane and 2,2-bis- [4 4- (4,4'-dihydroxydiphenyl) -cyclohexyl] -propane and the like.

  The viscosity average molecular weight of the polycarbonate resin (A) is 21000 to 35000, preferably 23,000 to 30000, and more preferably 24,000 to 29000. When the viscosity average molecular weight is less than 21,000, the impact strength is inferior, and when it exceeds 35,000, the melt viscosity is high and molding becomes difficult. Moreover, when manufacturing this polycarbonate resin, a molecular weight regulator, a catalyst, etc. can be used as needed.

The above viscosity average molecular weight is 0.5 wt% polycarbonate resin solution using methylene chloride as a solvent, and the specific viscosity (η _sp ) is measured at a temperature of 20 ° C. using a Cannon-Fenske type viscosity tube. [Η] was obtained and calculated from the following SCHNELL equation.
[Η] = 1.23 × 10 ⁻⁴ M ^0.83

  Examples of the organic black dye (B) used in the present invention include a mixture of organic dyes such as anthraquinone, perinone, perylene, azo, methine, and xylinone. In particular, anthraquinone-based and perinone-based organic dyes are preferably used. Anthraquinone-based organic dyes such as blue, purple and green are preferable, and perinone-based organic dyes such as red and orange are preferable.

  The organic black dye (B) of the present invention is obtained by injection molding a resin composition comprising 100 parts by weight of a polycarbonate resin (A) and 0.3 part by weight of an organic black dye (B) as its optical characteristics. When measuring the light transmittance of a flat plate having a thickness of 2 mm, it is necessary to have a light transmittance of 50% or more in a wavelength region of 800 to 900 nm. The light transmittance is measured according to ASTM D-1003.

  When the light transmittance is less than 50%, an excellent jet black (piano black-like) appearance cannot be obtained, which is not preferable. The light transmittance is preferably 80% or more, more preferably 85% or more.

  Moreover, as a compounding quantity of organic type black dye (B), it is 0.05-0.5 weight part with respect to 100 weight part of polycarbonate resin (A). If the blending amount is less than 0.05 parts by weight, jet blackness and hiding properties are inferior. If the blending amount exceeds 0.5 parts by weight, the thermal stability of the polycarbonate resin (A) is inferior. This is not preferable. A more preferable blending amount is in the range of 0.1 to 0.4 parts by weight, and more preferably 0.2 to 0.3 parts by weight.

The cyclic poly (alkylene terephthalate) oligomer (C) used in the present invention is one having a structural unit represented by the following general formula.

  In the formula, R represents an alkylene group having 2 to 8 carbon atoms, and Ar represents a divalent aromatic group. In particular, those in which R is ethylene or tetramethylene and Ar is m-phenylene or p-phenylene are preferably used.

  The cyclic poly (alkylene terephthalate) oligomer (C) is usually a mixture of cyclic oligomers having a polymerization degree of 2 to 30 and the main component having a polymerization degree of up to 12. Commercially available products include CBT manufactured by Cyclix Corporation.

  The compounding quantity of cyclic poly (alkylene terephthalate) oligomer (C) is 1-8 weight part with respect to 100 weight part of polycarbonate resin (A). If the blending amount is less than 1 part by weight, the effect of improving scratch resistance is small, and if it exceeds 8 parts by weight, the impact strength decreases and the appearance of the molded product also decreases, which is not preferable. More preferably, it is in the range of 2 to 5 parts by weight.

  The rubber component (D) used in the present invention includes acrylonitrile-butadiene-styrene copolymer (ABS resin), methyl methacrylate-butadiene-styrene copolymer (MBS resin), high impact polystyrene (HIPS) and the like. And rubber reinforced styrene copolymers, acrylic or silicone elastomers, and the like.

  The compounding quantity of a rubber component (D) is 1-8 weight part with respect to 100 weight part of polycarbonate resin (A). If the blending amount is less than 1 part by weight, the drop impact strength is small, and if it exceeds 8 parts by weight, jet blackness is lowered, which is not preferable. More preferably, it is in the range of 2 to 5 parts by weight.

  The blending method of the various blending components (A), (B) and (C) of the present invention, and (D) depending on necessity is not particularly limited, and these can be carried out using any mixer such as a tumbler, ribbon blender, high-speed mixer, etc. And then kneading and kneading with a normal single-screw or twin-screw extruder. Moreover, there is no restriction | limiting in particular also about employ | adopting batch mixing and division | segmentation mixing for these compounding components.

  In addition, other known additives such as mold release agents, UV absorbers, antistatic agents, antioxidants, phosphorous heat stabilizers, spreading agents (epoxy soybean oil, liquid paraffin, etc.) may be used at the time of mixing. ) And the like.

  As a method for producing the bag of the present invention, methods such as extrusion molding, compression molding, and hot press molding are employed.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Parts and% are based on weight unless otherwise specified.

The details of the used blending components are as follows.
Polycarbonate resin:
Polycarbonate resin synthesized from bisphenol A and phosgene Caliber 200-4 manufactured by Sumitomo Dow
(Viscosity average molecular weight: 26000, hereinafter abbreviated as PC1)
Sumitomo Dow Caliber 200-20
(Viscosity average molecular weight: 19000, hereinafter abbreviated as PC2)
Organic black dye:
Sumiplast Black HB
(Manufactured by Sumika Chemtex Co., Ltd., hereinafter abbreviated as Colorant 1)
Light transmittance in a wavelength range of 800 to 900 nm * 1: 85%
Sumiplast Black HLG
(Manufactured by Sumika Chemtex Co., Ltd., hereinafter abbreviated as Colorant 2)
Light transmittance in the wavelength region of 800 to 900 nm * 1: 55%
Carbon black:
Furnace type carbon black (XC-305 manufactured by Cabot, hereinafter abbreviated as Colorant 3)
Light transmittance in a wavelength region of 800 to 900 nm * 1: Less than 1% * 1: The light transmittance is injection-molded with a resin composition comprising 100 parts of PC1 and 0.3 parts of colorant 1, 2 or 3. Using the 2 mm thick flat plate obtained in this way,
Measurement was performed in a wavelength range of 800 to 900 nm in accordance with D-1003.
Cyclic poly (alkylene terephthalate) oligomer:
Cyclic poly (butylene terephthalate) oligomer (CBT manufactured by Axia Materials, hereinafter abbreviated as CBT)
Rubber component:
Acrylonitrile-butadiene-styrene copolymer (ABS resin)
(Nippon A & L Co., Ltd. Clarastic S3710, hereinafter abbreviated as ABS)

(Preparation of polycarbonate resin composition pellets)
The above-mentioned various blending components are collectively put into a tumbler at the blending ratios shown in Tables 1 to 3, and after dry mixing for 10 minutes, using a twin screw extruder (KTX37 manufactured by Kobe Steel), a melting temperature of 280 ° C. Kneaded to obtain various pellets of the polycarbonate resin composition.

(Create test pieces for evaluating jetness, scratching and impact strength)
The obtained pellets of various resin compositions were dried at 120 ° C. for 4 hours, and then jet jet under conditions of a cylinder temperature of 320 ° C. and a mold temperature of 100 ° C. using an injection molding machine (J100E-C5 manufactured by Nippon Steel Works). A flat plate (90 × 50 × 2 mm) was used for evaluation of optical properties and scratches, and an ASTM Izod impact test piece (3.2 mm thickness) was used for evaluation of impact strength.

(Preparation of fatigue test specimen)
2. The obtained pellets of various resin compositions are dried at 120 ° C. for 4 hours, and then subjected to conditions of a cylinder temperature of 330 ° C. and a mold temperature of 120 ° C. using an injection molding machine (J100E-C5 manufactured by Nippon Steel Works). A JIS K7119 No. II fatigue test piece having a thickness of 0 mm was prepared.

(Evaluation of jetness)
The evaluation of jetness is performed by irradiating the obtained 2 mm flat plate with the light of the LED light source (GETROS GTR-32T, brightness of 26.6 lumens) (the distance between the light of the flat plate and the LED light source is 10 cm) and visually. The degree of jetness was evaluated. The results are shown in Tables 1-3.
The evaluation criteria are as follows:
Good (◎): Even when illuminated by an LED light source, it glows black.
Good (◯): Even if the LED light source is irradiated, it glows black, but looks slightly whitish.
Defect (x): When an LED light source is irradiated, it glows whitish.

(Evaluation of impact strength)
The impact strength was determined by measuring the notched Izod impact strength (J / m) under the condition of 23 ° C. using the obtained Izod impact test piece in accordance with ASTM D-256. 650 J / m or more was regarded as acceptable. The results are shown in Tables 1-3.

(Evaluation of scratchability)
The evaluation of scratchability was performed as follows.
(1) One commercially available tissue paper is spread and folded five times, and a total of 32 laminates are prepared in advance.
(2) Prepare a jig (stainless steel, height 15 mm x width 15 mm x depth 10 mm, R3 mm saddle) with a linear pressure part of 15 mm, and wind the laminated tissue paper around the jig Put on.
(3) The jig around which the tissue paper obtained in the above (2) was wound was brought into contact with the surface of a flat plate (90 × 50 × 2 mm) for evaluation of scratchability, and a total of 250 g of the tissue was placed on the tissue. After adjusting to become a load, it is reciprocated 50 times at a speed of 50 mm / sec.
(4) Thereafter, the presence or absence of scratches generated on the surface of the flat plate was visually observed and evaluated according to the following criteria.
Good (◎): Good without any scratches.
Good (O): Although there are some scratches, it is not whitened.
Defect (x): The surface is whitened and looks whitish. Or the surface is scratched.
(5) The surface was not whitened or scratched.

(Evaluation of fatigue characteristics)
When the obtained 3.0 mm-thick JIS K7119 No. II fatigue test piece was measured at 15 MPa load according to JIS K7119 using a repeated vibration fatigue tester (model B-70) manufactured by Toyo Seiki Co., Ltd., 2 × 10 The thing which does not generate | occur | produce a crack by the 6th power of was set as the pass.

  When the polycarbonate resin composition satisfied all the constituent requirements of the present invention (Examples 1 to 7), good results were exhibited over all the evaluation items.

On the other hand, in the case where the polycarbonate resin composition does not satisfy the constituent requirements of the present invention, each case has some drawbacks.
Comparative Example 1 was inferior in jet blackness because the blending amount of the organic black dye was less than the specified amount.
In Comparative Example 2, since the blending amount of the organic black dye was larger than the specified amount, the impact strength was reduced.
Since the comparative example 3 used carbon black for the coloring agent, it was inferior in jetness.
In Comparative Example 4, the blending amount of CBT was less than the specified amount, so that the scratch resistance was inferior.
Comparative Example 5 was inferior in impact strength and fatigue characteristics because the blending amount of CBT was larger than specified.
Comparative Example 6 was inferior in impact strength and fatigue properties because the viscosity average molecular weight of the polycarbonate resin was lower than specified.
Comparative Example 7 was inferior in jet blackness, impact strength, scratch resistance, and fatigue properties because the blending amount of ABS was larger than specified.

Claims (6)

A mold formed by molding a polycarbonate resin composition,
(1) The polycarbonate resin composition comprises 100 parts by weight of a polycarbonate resin (A) having a viscosity average molecular weight of 21,000 to 35,000, 0.05 to 0.5 parts by weight of an organic black dye (B), and a cyclic poly (alkylene terephthalate) oligomer. (C) consisting of a resin composition containing 1 to 8 parts by weight as an essential component,
(2) The optical characteristics of the organic black dye (B) were obtained by injection molding a resin composition comprising 100 parts by weight of the polycarbonate resin (A) and 0.3 parts by weight of the organic black dye (B). When measuring the light transmittance of a flat plate with a thickness of 2 mm, it has a light transmittance of 50% or more in a wavelength region of 800 to 900 nm,
(3) When the impact strength with a notch is measured according to ASTM D-256 using a 3.2 mm-thick test piece formed by injection molding of the polycarbonate resin composition, it has an impact resistance of 650 J / m or more. (4) When measured with a 15 MPa load according to JIS K7119 using a 3.0 mm thick JIS K7119 II fatigue test piece formed by injection molding of the polycarbonate resin composition, 2 × 10 6 times Having the above fatigue characteristics,
鞄 characterized by that.   The optical characteristics of the organic black dye (B) are 2 mm thick obtained by injection molding a resin composition comprising 100 parts by weight of the polycarbonate resin (A) and 0.3 parts by weight of the organic black dye (B). 2. The bag according to claim 1, which has a light transmittance of 80% or more in a wavelength region of 800 to 900 nm when the light transmittance of the flat plate is measured.   The optical characteristics of the organic black dye (B) are 2 mm thick obtained by injection molding a resin composition comprising 100 parts by weight of the polycarbonate resin (A) and 0.3 parts by weight of the organic black dye (B). 2. The bag according to claim 1, which has a light transmittance of 85% or more in a wavelength region of 800 to 900 nm when the light transmittance of the flat plate is measured.   The bag according to claim 1, wherein the cyclic poly (alkylene terephthalate) oligomer (C) is a cyclic poly (butylene terephthalate) oligomer.   The rubber component (D) is added to the polycarbonate resin composition in an amount of 1 to 8 parts by weight (per 100 parts by weight of the polycarbonate resin (A)), according to any one of claims 1 to 4. bag.   The soot according to claim 5, wherein the rubber component (D) is acrylonitrile-butadiene-styrene resin.