JPH10101896A - Acrylonitrile-butadiene-styrene-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject resin composition free from unevenness of color, excellent in surface property, smoothness and adhesiveness and useful for color sheet, etc., by including an acrylonitrile-butadiene-styrene-based resin, (meth) acrylic resin, etc., and coloring pigment at a specific ratio. SOLUTION: This resin composition contains (A) 100 pts.wt. acrylonitrile- butadiene-styrene-based resin, (B) 0.1-5 pts.wt. one or more kinds of compounds selected from (meth)acrylic resin and/or phosphate-based metal salts and organic phosphates and (C) preferably 0.5-20 pts.wt. pigment for coloring, e.g. carbon black in an amount effective for imparting light screening property. Furthermore, the resin composition is formed into >=0.1mm thickness having <=30% total light transmittance by calendering.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an acrylonitrile-butadiene-styrene resin (hereinafter abbreviated as ABS resin) composition for sheet molding which suppresses light transmittance, and more particularly, to an optical composition by calendering. The present invention relates to an ABS-based resin composition suitable for producing a sheet having suppressed permeability and a practical color sheet obtained by calendering the composition.

[0002]

2. Description of the Related Art ABS resins have excellent mechanical and electrical properties and are excellent in chemical resistance, ink adhesion and adhesiveness. It is widely used in various fields such as furniture, home appliances, building materials and automobile parts due to conductive carrier tape, lamination of various plastics and metals, and coating for adding functions. However, the ABS resin has inherently poor releasability from a metal roll, and particularly when a pigment is contained, the releasability from a metal roll is further deteriorated.
Due to lack of peel tension from
Since air marks are easily generated on the sheet and uneven color and uneven thickness of the sheet are brought about, various color sheets of ABS resin can be produced by a calendaring method with excellent productivity. It has been substantially difficult to produce more efficiently. Therefore, conventionally, an ABS resin color sheet has been produced exclusively by an extrusion molding method or an injection molding method with low productivity.

[0003]

SUMMARY OF THE INVENTION In view of the above-mentioned situation of the production of an ABS resin sheet, the present inventors have developed an ABS resin sheet having excellent physical properties and performance. In order to develop a manufacturing method by processing, many trial production experiments were repeated, paying particular attention to the improvement of the releasability from the surface of a calendar roll which is a metal roll. Therefore, an object of the present invention is to provide an ABS having excellent smoothness by calendaring.
An object of the present invention is to develop a production method for smoothly drawing a color sheet of a system resin from a roll. Another object of the present invention is to provide an ABS resin capable of industrially and advantageously producing a color sheet without color unevenness and having a suppressed total light transmittance without impairing the excellent properties of the ABS resin. It is to provide a resin composition. Other objects and features of the present invention will become more apparent from the following description.

[0004]

That is, the present invention has the gist of the constituent elements described in claim 1 of the claims. Thus, the present invention, which is added to suppress the total light transmittance, heats the ABS resin composition containing carbon black and other coloring inorganic pigments which deteriorate the calendar roll releasability. As means for improving the releasability from the calendered roll,
A specific range of acrylic resin, a specific range of at least one phosphate compound selected from phosphate metal salts and organic phosphates, or a combination of both components in BS resin. Is characteristic.

[0005] As coloring pigments for suppressing the total light transmittance, carbon black and other inorganic coloring pigments are used.
It is selectively used depending on the desired color tone, but carbon black is usually used alone for producing black sheet. In this case, an amount in the range of 0.5 to 20 parts by weight per 100 parts by weight of the ABS resin is selectively blended depending on the object to be applied of the obtained sheet or the desired light shielding property.
When a non-black sheet-forming color pigment is blended, the ABS resin 10 may be used depending on the desired color tone and the degree of light shielding.
An addition amount in the range of 2 to 30 parts by weight per 0 parts by weight is used. In that case, according to the total light transmittance suppression degree,
A small amount of about 0.5 part by weight or less of carbon black can be used in combination.

The ABS resin according to the composition of the present invention is a terpolymer containing acrylonitrile, butadiene and styrene as monomer components.
It is composed of butadiene alone or a mixture of a rubber (styrene-butadiene rubber) copolymerized with styrene and acrylonitrile and a styrene-acrylonitrile copolymer. Typical production methods are a polymer blend method (a simple mixing method and a latex mixing method) and a graft method (emulsion polymerization method, bulk polymerization method and bulk suspension polymerization method). The ABS resin of the present invention is essentially composed of acrylonitrile, butadiene, and a styrene monomer component. However, in order to improve transparency or heat resistance, it is desirable to use methacrylic acid methyl ester or α-methylstyrene for the purpose. Accordingly, an appropriate amount of another monomer component may be contained.

The ABS resin used in the composition of the present invention contains acrylonitrile, butadiene and styrene as main constituent monomer components in an amount of 10 to 30: 5 to 4 respectively.
Those containing at a weight ratio of 0:45 to 70 are preferably used.
The average molecular weight calculated by the permeation chromatography method has a number average value (Mn) of 4.0 × 10 ⁴ to
9.0 × 10 ⁴ range, weight average value (Mw) 9.0 × 10 ⁴ ~
In the range of 3.0 × 10 ⁵ , the molecular weight distribution (Mw / Mn) is 1.7
Those having a range of from 5.0 to 5.0 are preferably used. As such an ABS resin, for example, K-2540 (trade name, manufactured by Sumika Avis Latex) can be typically mentioned.

As the acrylic resin contained in the composition of the present invention, an acrylic acid and methacrylic acid polymer described in "Self-regulation standards for food containers and packaging made of vinyl chloride resin" is used. These include, for example, polyacrylates, polymethacrylates, acrylic acid / methacrylate copolymers, copolymers of acrylates and methacrylates, acrylates and / or methacrylates and one of the following monomers: Copolymers with species or more. Examples of this monomer include acrylic acid, glycidyl methacrylate, acrylonitrile, vinyl chloride, butadiene, vinyl acetate, vinylidene chloride, itaconic acid, dibryl itaconate, styrene, methacrylic acid, α-
Examples include methylstyrene and cyclohexylmaleimide. As typical resins that can be easily obtained, for example, acrylic resin (manufactured and sold by Mitsubishi Rayon Co., Ltd. (trade name: L-1000, weight average molecular weight Mw =
2.0 × 10 ⁵ to 4.0 × 10 ⁵ ).

In the composition of the present invention, the above (meth)
Acrylic acid-based resin is different from the ABS-based resin in that A
The mixing ratio is in the range of 0.1 to 5 parts by weight per 100 parts by weight of the BS resin. When carbon black alone is used as the color pigment, if the amount of the (meth) acrylic resin is less than 0.1 part by weight, the releasability of the heated calendar roll is improved, that is, It is not suitable because the effect of addition cannot be obtained and the sheet stretched extremely in the take-off step in the calendering produces uneven thickness. On the other hand, if the added amount exceeds 5 parts by weight, the surface smoothness of the sheet is undesirably reduced. When an inorganic pigment for coloring other than carbon black is used as the coloring pigment, the (meth) acrylic acid-based resin is added to the ABS resin 10 in relation to the amount of the coloring pigment to be added.
The range of 0.5 to 5 parts by weight per 0 parts by weight is preferably used. If the amount added is less than 0.5 parts by weight, the calendar
Since the releasability from the roll is insufficient and the thickness distribution of the sheet deteriorates, the effect of addition cannot be obtained.

Further, in the composition of the present invention, a phosphate ester compound selected from a phosphate metal salt and an organic phosphate in combination with a (meth) acrylic resin is used. The phosphate metal salts are metal salts of acidic phosphoric esters, and include, for example, metal salts of monoalkyl esters and dialkyl esters of acidic phosphoric acid. Examples of the metal forming these salts include calcium, magnesium, barium, zinc and the like. A typical example is LBT-1830 (zinc stearyl acid phosphite) manufactured and sold by Sakai Chemical Industry Co., Ltd. Organic phosphoric acid esters include, for example, nonylphenylpolyoxyethylenes. Practically desirable organic phosphoric acid esters include, for example, trade name: Akishima Chemical Industry Co., Ltd .: N
O. 1737 (tridecyl polyoxyethylene) is a representative example.

At least one of these phosphoric esters is used in an amount of 0.1 to 5 parts by weight per 100 parts by weight of the ABS resin, and is used in combination with a (meth) acrylic resin. When used,
It is not preferable that the total fee deviates from the above range.
In the case of a black sheet using carbon black alone as a coloring pigment, if the amount is less than 0.1 part by weight, the calender roll releasability is not improved, and the addition amount exceeds 5 parts by weight. And the surface smoothness of the sheet is reduced. When an inorganic pigment for coloring other than carbon black is used as the coloring pigment, if less than 0.5 part by weight, the calender powder may be used.
Insufficient release properties and poor sheet thickness distribution make it impossible to obtain the effect of addition. If the addition amount exceeds 5 parts by weight, the surface smoothness deteriorates. When an inorganic pigment for coloring is used, it is used in an amount of 0.5 to 5 parts by weight per 100 parts by weight of the ABS resin. If the amount is less than 0.5 parts by weight, the roll releasability of the calendar is insufficient, and the thickness distribution of the obtained sheet is poor.

The acrylic resin and the phosphate compound may be used in combination with the ABS resin, or only one of them may be used. Further, the phosphoric ester compounds may be used alone or in combination of two or more, but it is necessary to avoid that the total amount thereof departs from the above range. is there.

The pigments used in the ABS resin composition of the present invention are carbon black as a black pigment and other color pigments.
Pigments known as pigments for coloring plastic materials are included, for example, azo lake pigments, insoluble azo pigments,
Organic coloring pigments such as condensed azo pigments, metal complex azo pigments, phthalocyanine pigments, quinacridone pigments, dioxazine pigments, helinone pigments, anthraquinone pigments, isoindolinone pigments, quinophthalone pigments, and perylene pigments; Red iron oxide, yellow iron oxide, titanium yellow, chromium oxide, cobalt blue, titanium white,
Inorganic pigments such as cadmium yellow, cadmium red, ultramarine, crepe, talc, navy blue, graphite, chrome bar million, zinc chloroformate, alumina white, precipitated barium sulfate, calcium carbonate, aluminum powder, brass powder, and mica are exemplified. You.

Further, the composition of the present invention may contain generally known inorganic pigments not intended for coloring, for example, white pigments such as zinc oxide, titanium oxide, and a mixture of titanium oxide and calcium sulfate; calcium carbonate, barium sulfate, and the like. Calcium sulfate,
Aluminum silicate, clay, kaolin, bentonite,
Fillers such as mica, calcium silicate, magnesium silicate (talc), silica, diatomaceous earth, calcium oxide, magnesium oxide, magnesium hydroxide, aluminum hydroxide; or metal powders such as aluminum, iron, brass, etc .:
Can also be used.

In the composition of the present invention, carbon black alone is used as a pigment to be added and blended to form black A
To obtain a BS resin sheet, use ABS resin 100
0.5 to 20 parts by weight of carbon black is used per part by weight, and when a non-black colored sheet is obtained using a coloring pigment, an ABS pigment as an inorganic pigment other than carbon black is used. It is desirable to use two or more parts by weight per 100 parts by weight of the resin. When a coloring pigment other than carbon black is used, a small amount of about 0.5 part by weight or less of carbon black is added to reduce the light transmittance depending on the kind and the amount of the pigment used. be able to.

[0016]

Next, the present invention will be described in more detail with reference to specific examples. The percentages and parts in the specific examples are by weight unless otherwise specified.

【Example】

Examples 1 to 14 and Comparative Examples 1 to 11 Resins and other substances used: ABS resin: K-2540 manufactured by Sumitomo Avis Latex, Inc. Acrylic resin: L- manufactured by Mitsubishi Rayon Co., Ltd. 1000 Phosphate metal salt: LBT-1 manufactured by Sakai Chemical Industry Co., Ltd.
No. 830 Organic phosphoric acid ester: NO. 173
7

Using the above materials, the amounts of the various compositions shown in Tables 1 and 2 below are uniformly mixed and prepared with a Henschel mixer, and the resulting composition is inverted L-shaped four-roll calender.
Using a processing machine, at a roll temperature of 210 ° C and a thickness of 0.1
mm, and processed into a sheet with a width of 1,000 mm. At this time, the roll peeling property, the smoothness of the obtained sheet, the surface property of the sheet, the presence or absence of uneven color tone, and the total light transmittance were observed and measured by the methods described in the evaluation items below. Was evaluated. Table 1 and Table 2 show the results of the evaluation together with the content of the ABS resin composition.
It was also described in.

Evaluation items: Calender roll peelability: good: good, poor peelability makes stable production difficult ... x Sheet smoothness: maximum and minimum thickness in sheet width direction Difference of 7% or less: ○, 7% or more × × Sheet surface: Good surface without any mark or deaeration on sheet ・ ・ ・ ○ -Mark and degassing and poor surface quality ... × Unevenness of color: Same color tone in all parts of sheet ... None Partial difference in color tone in sheet ... Yes Total light transmittance: 30% or less of total light transmittance of sheet according to JIS-K7105.

[0019]

[Table 1]

[0020]

[Table 2]

[0021]

The ABS resin composition for calendering of the present invention can be used for sheet molding by a calendar method.
It has good separation properties, does not impair the excellent properties inherent in the ABS resin, has excellent sheet surface properties and smoothness, has no color unevenness, and has high light-shielding black and other colored sheets. Obtained by sex. Further, the obtained sheet is excellent in ink adhesion and adhesion, and is used as a conductive tray or carrier tape for precision electronic components such as ICs, or as a laminate or a functional additive for various plastics and metals. With such coatings, it can be applied to a wide range of uses such as furniture, home appliances, building materials and automobile parts.

Claims (4)

[Claims] 1. An acrylonitrile-butadiene-styrene resin is prepared by adding 0.1 to 5 parts by weight of a (meth) acrylic acid resin and / or a phosphate metal salt and an organic phosphate to 100 parts by weight of the resin. An acrylonitrile-butadiene-styrene-based resin composition for calendering, which comprises at least one selected coloring agent and an effective amount of a coloring pigment for imparting light-shielding properties. 2. The coloring pigment is used in an amount of 0.5 to 0.5 parts by weight per 100 parts by weight of an acrylonitrile-butadiene-styrene resin.
The resin composition according to claim 1, which is 20 parts by weight of carbon black. 3. The pigment according to claim 1, wherein the coloring pigment is 2 to 30 parts by weight per 100 parts by weight of the acrylonitrile-butadiene-styrene resin.
The resin composition according to claim 1, comprising 0 to 0.5 parts by weight of an inorganic pigment other than carbon and carbon black in parts by weight. 4. The resin composition according to claim 1, which has a total light transmittance of 30% or less by calendering.
A color sheet formed to a thickness of at least mm.