TWI402166B - Composite sheet - Google Patents

Description

Composite sheet

The present invention relates to a composite sheet composed of a resin composition which is suitable, for example, for packaging various electronic parts.

A packaging container for an intermediate product of various industrial articles such as an electronic machine or an automobile is a vacuum formed tray obtained by heat-forming a sheet, an embossed transfer tape, or the like. For the sheet for packaging containers, a sheet of a polystyrene resin or an ABS resin laminated polystyrene resin is used (see, for example, Patent Documents 1 to 3). The tray and the embossed transfer tape are formed by various molding methods such as vacuum forming and hot press forming by a sheet obtained by extrusion molding, etc., and the adhesion between the ABS resin and the polystyrene resin is poor. The method causes a problem of peeling between the layers of the substrate layer and the skin layer.

Moreover, the outer circumference of the tray is formed or the inside thereof according to the situation; the so-called flywheel hole or the hole of the central hole of the embossed conveyance glue, and the end face of the central processing hole is somewhat burred during the processing, and the packaging container is used in the use step. The burrs fall off and become polluted. In recent years, the packaged electronic components have been rapidly miniaturized, and the stricter requirements for reducing the pollution caused by the burrs are caused.

Japanese Patent Laid-Open Publication No. Hei 9-076425 (Patent Document No. Hei 9-076425)

The present invention solves the related problems and provides a plan to simultaneously improve the adhesion between the layers of the sheet to prevent peeling, reduce the burrs generated by the punching process in the manufacturing step of the tray or the embossed conveyance tape, and reduce the content to the contents. A contaminated composite sheet of electronic parts or the like.

The present invention has the following gist in order to solve the above problems.

(1) A composite sheet characterized by a skin layer containing a polystyrene resin and carbon black as a main component is laminated on at least one surface of a base material layer mainly composed of an ABS resin.

(2) The ABS resin is the composite sheet of the above (1) characterized by containing 5 to 23% by mass of a diene rubber.

(3) ABS-based resin containing AB of 23 to 23% by mass of diene rubber, 55 to 80% by mass of aromatic vinyl monomer, and 15 to 27% by mass of vinyl cyanide monomer as main components A composite sheet of the above (1) which is characterized by a resin.

(4) ABS-based resin, which is a graft of 40 to 60% by mass of a diene rubber, 25 to 45% by mass of an aromatic vinyl monomer, and 5 to 25% by mass of a vinyl cyanide monomer as a main component. The copolymer is characterized by having 15 to 60 parts by mass of the copolymer and 40 to 85 parts by mass of a divalent ethylene copolymer containing 60 to 85% by mass of the aromatic vinyl monomer and 15 to 40% by mass of the vinyl cyanide monomer as a main component. A composite sheet of (1) or (2).

(5) 100 parts by mass of ABS resin containing 5 to 30% by mass of a diene rubber, 40 to 80% by mass of an aromatic vinyl monomer, and 10 to 40% by mass of a vinyl cyanide monomer as a main component, and At least one selected from the group consisting of styrene-butadiene-butene-styrene block copolymerized resin, styrene-diene block copolymer resin, and resin for hydrogenation of styrene-diene block copolymer The olefin is characterized by laminating at least one side of a base layer of a thermoplastic resin having a styrene graft copolymerized resin of 1 to 20 parts by mass, and a skin layer containing a polystyrene resin and carbon black as a main component. a composite sheet.

(6) ABS-based resin is a graft copolymerization of 40 to 60% by mass of a diene rubber, 25 to 45% by mass of an aromatic vinyl monomer, and 5 to 25% by mass of a vinyl cyanide monomer as a main component. 15 to 60 parts by mass, which is characterized by 40 to 85 parts by mass of a diethylene copolymer containing 60 to 85% by mass of an aromatic vinyl monomer and 15 to 40% by mass of a vinyl cyanide monomer as a main component. The composite sheet of the above (5).

(7) A container using the composite sheet according to any one of the above (1) to (6).

(8) An embossed conveyance tape using the composite sheet according to any one of the above (1) to (6).

(9) A package of the composite sheet according to any one of the above (1) to (6).

The composite sheet of the present invention is suitable for packaging of electronic parts or the like which are required to be electrostatically treated, and the step of manufacturing the tray or the embossed carrying tape by using the composite sheet of the present invention, the peeling of the skin layer and the substrate layer, and at this time, punching The generation of burrs is small, and the pollution caused by the detachment of the burrs can be reduced.

[The best form for implementing the invention]

The ABS-based resin used in the composite sheet base material layer of the present invention is a three-dimensional copolymer of a diene rubber-aromatic vinyl monomer-cyanide vinyl monomer as a main component, and the meaning is represented by acrylonitrile-butadiene. A three-dimensional copolymer of an ene-styrene is a resin or a resin composition of a main component. Specific examples thereof include a mixture of an acrylonitrile-butadiene-styrene three-dimensional copolymer, an acrylonitrile-butadiene-styrene three-dimensional copolymer and an acrylonitrile-styrene two-dimensional copolymer, and an acrylonitrile-styrene II. The dimensional copolymer alloys the polybutadiene polymer. The invention is ideal for using the acrylonitrile-butadiene-styrene three-dimensional copolymer therein, and more preferably using a mixture of the acrylonitrile-butadiene-styrene three-dimensional copolymer and the acrylonitrile-styrene two-dimensional copolymer. ideal.

The above acrylonitrile-butadiene-styrene three-dimensional copolymer, for example, in the presence of a diene rubber such as a polybutadiene or a styrene-butadiene copolymer, an aromatic vinyl monomer such as styrene Or graft copolymerization of a vinyl cyanide monomer such as acrylonitrile.

ABS resin, a mixture of acrylonitrile-butadiene-styrene three-dimensional copolymer and acrylonitrile-styrene two-dimensional copolymer, acrylonitrile-butadiene-styrene three-dimensional copolymer and acrylonitrile-styrene The copolymer is used in an amount of 40 to 60% by mass of a diene rubber, preferably 40 to 55% by mass, and 25 to 45% by mass of an aromatic vinyl monomer, preferably 30 to 40% by mass, and 5 to 25% by mass. The vinyl cyanide monomer, preferably 5 to 20% by mass, more preferably 5 to 18% by mass, of the graft copolymer is preferred, and the ethylene-based copolymer is an aromatic vinyl monomer 60~ A copolymer of 85 mass%, preferably 65 to 80 mass%, and a vinyl cyanide monomer of 15 to 40% by mass, preferably 20 to 35 mass%, is preferred. a mixing ratio of a mixture of an acrylonitrile-butadiene-styrene three-dimensional copolymer and an acrylonitrile-styrene two-dimensional copolymer, preferably an acrylonitrile-butadiene-styrene three-dimensional copolymer of 15 to 60 parts by mass and acrylonitrile The styrene two-dimensional copolymer is 40 to 85 parts by mass, more preferably 30 to 45 parts by mass of the acrylonitrile-butadiene-styrene three-dimensional copolymer and 55 to 70 parts by mass of the acrylonitrile-styrene two-dimensional copolymer. The graft ratio of the acrylonitrile-butadiene-styrene three-dimensional copolymer is desirably 30 to 90%, more preferably 30 to 60%.

The content of the diene rubber in the ABS resin is preferably 5 to 30% by mass, more preferably 5 to 23% by mass, still more preferably 8 to 20% by mass. When the content of the diene rubber is less than 5% by mass, the strength is lowered, and when it exceeds 30% by mass, the burrs are generated in a large amount.

The content of the vinyl cyanide monomer in the ABS system is 10 to 40% by mass, preferably 15 to 27% by mass, and more preferably 20 to 25% by mass. When the content of the vinyl cyanide monomer is less than the above range, the rigidity is lowered. When the content exceeds this range, peeling easily occurs between the layers of the laminated polystyrene resin. Further, the content of the aromatic vinyl monomer of the residual component in the ABS system is preferably 40 to 80% by mass, more preferably 55 to 80% by mass, and particularly preferably 65 to 72% by mass.

The polystyrene resin used in the skin layer of the present invention is styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, An aromatic vinyl compound such as α-methylstyrene, naphthaleneethylene, nonylethylene or 1,1-diphenylethylidene is a resin containing a monomer as a main component, or an impact-resistant polystyrene resin is ideal. The impact-resistant polystyrene resin is a rubber graft-polymerized polystyrene resin containing butadiene as a main component. These polystyrene resins and impact-resistant polystyrene resins may be used singly or in combination.

The carbon black to be blended in the skin layer is a furnace black, a channel black, or an acetylene black. It is preferably a large specific surface area, and a small amount of the resin is added to obtain a high conductivity. For example, SCF (Super Conductive Furnace), ECF (Electric Cconductive Furnace), ketjin black (product of Japan Lion-AkZO Co., Ltd.), acetylene black or the like. The addition amount to the value of surface resistivity of an ideal addition amount of 10 ² ~ 10 ^{1 0} Ω, the quality of the skin layer 100 and the total amount of the composition in terms of% by mass of carbon black 1 to 50% of over. When the amount is less than 1% by mass, sufficient conductivity is not obtained, and the surface specific resistance is increased. When the amount is more than 50% by mass, the uniform dispersibility of the resin is deteriorated, the moldability is remarkably lowered, and the characteristic value such as mechanical strength is lowered.

In the composite sheet of the present invention, the skin layer (B) is laminated on at least one surface of the base material layer (A). Specifically, it may be a structure of the skin layer (B) / base material layer (A), skin layer (B) / base material layer (A) / skin layer (B). In particular, both sides of the composite sheet are intended to suppress the generation of static electricity, and it is preferable to have a configuration of the skin layer (B) / the substrate layer (A) / the skin layer (B).

The thickness of the entire composite sheet of the present invention is preferably 0.1 to 3.0 mm, more preferably 0.15 to 2.0 mm. In particular, the entire thickness of 0.15 to 0.6 mm can be suitably used for the embossed transfer tape used for the secondary formed electronic component packaging sheet. In addition, the entire packaging thickness of 0.5 mm to 2.0 mm can be suitably used for packaging trays for electronic components and mechanical parts that are secondarily formed. The thickness of the base material layer (A) is preferably 40% to 98% of the total thickness. Further, the thickness of the skin layer (B) is preferably 2 to 30% of the total thickness.

The base material layer may be added in a small amount, and is preferably in a range of 0.1 to 30 parts by mass based on the ABS resin component. When the packaging container is formed by adding a carbon black sheet, the problem that the corner of the molded article becomes thin due to the thickness of the sheet can be solved. The carbon black added to the substrate layer is not particularly limited, and conventional furnace carbon black, channel black, acetylene black, or the like can be used.

In addition to the above-mentioned resin component, the base material layer and/or the skin layer may be added with other resin components as a modifier, and various additives such as a slip agent, a plasticizer, and a processing aid may be added as necessary. The above other resin component may suitably be at least one selected from the group consisting of styrene-butadiene-butylene-styrene block copolymer (hereinafter referred to as SBBS), styrene-diene block copolymer resin, and styrene- A resin in which a diene block copolymer resin is hydrogenated, and a thermoplastic resin in which a polyolefin is graft-copolymerized with styrene.

These resins may be added singly or in combination. By adding such a thermoplastic resin, it is possible to improve the impact strength, and at the same time, it is possible to improve the adhesion between the interlayer and the skin layer, and to suppress the peeling of the interlayer or the generation of burrs or powder generated from the end faces of the sheet. The amount of addition is preferably from 1 to 20 parts by mass, more preferably from 3 to 15 parts by mass, per 100 parts by mass of the total amount of the polystyrene resin and the ABS resin.

The styrene-butadiene-butene-styrene block copolymer is a copolymer having repeating units represented by the following chemical formulas (1), (2) and (3). Further, in the chemical formulas of (1), (2) and (3), a, b, and c are positive integers.

The styrene-butadiene-butene-styrene block copolymer, which has the above-described constitution, is not particularly limited. For example, its manufacturing method is based on the structure and performance of the new styrene-based thermal elastomer (SBBS) (Japanese Ren Xiu Si, et al., 9th Polymer Materials, 125~126, 2000), Japan Special 64 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 6-35, 401, Japanese Unexamined Patent Publication No. Hei 61-28507, and JP-A-61-57524, and the like. The styrene-butadiene-butene-styrene block copolymer can be used as it is in the market. The styrene content in the styrene-butadiene-butene-styrene block copolymer is preferably from 10 to 80% by mass, more preferably from 20 to 70% by mass. Further, the copolymer has a melt index (190 ° C, 2.16 kfg) of 1 to 9 g/10 min, and 2 to 6 g/10 min is more suitable.

The styrene-butadiene block copolymer resin or the diene of the resin hydrogenated in the styrene-butadiene block copolymer is preferably made of butadiene or isoprene. The styrene content of the styrene-butadiene block copolymer resin or the resin hydrogenated in the styrene-butadiene block copolymer is preferably 10 to 80% by mass, more preferably 20 to 70% by mass. The polyolefin of the polyolefin styrene graft block copolymerized resin is a homogeneous polymer or copolymer of ethylene or propylene, and particularly preferably polyethylene, polypropylene, or ethylene-vinyl acetate copolymer.

a polystyrene resin used for the skin layer, a styrene-butadiene-butene-styrene block (SBBS) copolymer, a styrene-butadiene block copolymer resin, and a styrene-butadiene resin may be added. a resin in which an alkylene block copolymer is hydrogenated, a resin in which a polyolefin is grafted with a styrene graft block, a polyolefin resin represented by a homogeneous polymer or copolymer mainly composed of ethylene or propylene, a polyester resin, A resin component other than the ABS resin or the like is used as a modifier. Various additives such as a slip agent, a plasticizer, and a processing aid can be added as necessary.

Representative examples of the olefin resin include a polyethylene resin, a polypropylene resin, an ethylene-α-olefin resin, an ethylene-vinyl acetate copolymer resin, and an ethylene-ethyl acrylate copolymer resin. Representative examples of the polyester resin include a polyethylene terephthalate resin and a polybutylene terephthalate resin.

The composite film of the present invention can be produced by using a conventional extruder, a roll press molding or the like. The method of laminating the respective layers of the sheet, each formed into a sheet or a film shape by a separate extruder, may be laminated in stages by thermal lamination, dry lamination, extrusion lamination, and the like. Further, the other layers may be laminated on the base material layer of the previously formed sheet by extrusion coating or the like. A more inexpensive manufacturing process is desirable for obtaining a laminated film at a time using a multi-tube die or a multi-layer extrusion process in the injection zone.

A free-form electronic component packaging container can be obtained by the above-described sheet forming method using vacuum forming, pressure forming, and hot press forming. The container has less pollution from the end surface of the container and is excellent in mechanical strength, and is particularly suitable for use in a tray for packaging electronic parts or a handling tape.

The invention will now be described in more detail by way of examples.

Example 1~11

The surface layer was uniformly mixed by a high-speed mixer from 70 parts by weight of a polystyrene resin, 20 parts by mass of carbon black, and 10 parts by mass of ethylene-ethyl acrylate. Use of the resulting mixture The 45 mm twin-screw extruder was kneaded and pelletized by a single strand cutting method.

On the one hand, the acrylic-butadiene-styrene three-dimensional copolymer (graft copolymer), the acrylonitrile-styrene two-dimensional copolymer (AS), and the SBBS as necessary, as shown in Table 1, The ratio is shown to be a resin composition which is uniformly mixed as a base material layer by a mixer. The resin composition for the base material layer and the rubber particles for the skin layer are used. 65 mm extruder (L/D=28), 40 mm (L/D=26) extruder 2 parts and injection zone and T-die, formed into skin layer: base material layer: thickness ratio of skin layer is 1:8:1 3 layers with a total thickness of 0.3 mm Sheet.

The evaluation results of the respective examples are shown in Table 3. The evaluation was carried out in the following manner.

(1) Folding strength: Based on JIS-P-8115 (2001), the load was evaluated at a load of 500 g and an angle of 135 degrees.

(2) Tensile strength: Based on JIS-K-7127 (1999), it was evaluated on the 4th.

(3) Surface resistance value: Three points in the sheet direction were measured using a Mega-ohm meter Model-800 (manufactured by EST Co., Ltd.), and the logarithmic mean value was an intrinsic surface resistance value.

(4) DuPont impact strength: Using a DuPont impact tester/manufactured by Toyo Seiki Co., Ltd., a breaking height of 50% of a load of 300 g, 500 g or 1 kg was calculated, and the energy value was calculated from the load at that time. The calculation is based on JIS-k-7211.

(5) Formability: An embossed transfer tape of 24 mm width was formed by an EWG vacuum embossing tape forming machine. Those with good formability were 5, and those with poor formability were evaluated by 1 for 5 segments.

(6) Flushing rate: The flywheel hole of the embossed conveyance tape formed by the EDG molding machine was observed with a measuring microscope (manufactured by Mitutoyo Co., Ltd., Japan). The state without burrs is 0%, and the proportion of the area of the burrs occupied by the flywheel holes is calculated.

(7) Peeling resistance: For the 24 mm embossed handling tape formed by EDG molding machine, the heat-sealed portion of the cover tape is unilaterally 60 at 16 mm intervals. The total surface of 120 is slightly injured by the blade, and then averaged. The condition is heat sealed with a heat seal strength of about 1.0 N. The sample was peeled at 90° at a speed of about 200 mm/min, and the number of surface materials of the sheet attached to the cover tape was S of 0.2 mm or less, M of 0.2 to 1 mm, and L of 1 mm or more. Further, Denka thermo film ALS-AS (manufactured by Nippon Denki Chemical Co., Ltd.) was used as the cover tape.

The resins used in the surface layers of the respective examples are as follows.

Polystyrene resin: Toyo Styrol HI-SQ (manufactured by Toyo Styrene Co., Ltd.) Carbon black: Denka Black granular (manufactured by Nippon Denki Chemical Co., Ltd.) ethylene-ethyl acrylate copolymer DPDJ-6169 (manufactured by Unica, Japan) SBBS: Toughtec P-2000 (manufactured by Asahi Kasei Chemicals Co., Ltd.) Examples 1 to 6 are superior in burrability and peeling resistance to any of Examples 7 to 11.

Further, in Tables 1, 2, and 3, the following symbols respectively show the following meanings.

Graft copolymer: acrylonitrile-butadiene-styrene three-dimensional copolymer AS: acrylonitrile-styrene two-dimensional copolymer AN: acrylonitrile monomer St: styrene monomer Bd: butadiene monomer A~E : SBBS: styrene-butadiene-tert-butyl-styrene block copolymer resin MD: mechanical direction TD: transverse direction

[Industry use area]

The vacuum-molded tray, the pressure-change conveyance tape, and the like which are obtained by heating and molding the composite sheet of the present invention are suitable for use in a packaging container such as an intermediate product such as an electronic machine or an automobile.

Japanese Patent Application No. 2004-269346, filed on Sep. 16, 2004, and Japanese Patent Application No. 2004-269347, filed on Sep. 16, 2004, and Japanese Patent Application No. 2004-269348, filed on Sep. The entire contents of the specification, the scope of the patent application, the drawings and the abstract are incorporated herein by reference.

Claims (5)

A composite sheet characterized in that a skin layer containing a polystyrene resin and carbon black as a main component is laminated on at least one surface of a base material layer mainly composed of an ABS resin, and the ABS resin is contained in an amount of 5 to 23% by mass. Diene rubber, 55 to 80% by mass of aromatic vinyl monomer, and 15 to 27% by mass of vinyl cyanide monomer, and 40 to 60% by mass of diene rubber, 25 to 45% by mass 15 to 60 parts by mass of a graft copolymer of an aromatic vinyl monomer and 5 to 25% by mass of a vinyl cyanide monomer as a main component, and 60 to 85% by mass of an aromatic vinyl monomer and 15 to 40 The mass% of the vinyl cyanide monomer is composed of 40 to 85 parts by mass of the binary ethylene copolymer as a main component. The composite sheet according to claim 1, wherein a skin layer mainly composed of a polystyrene resin and carbon black is laminated on at least one surface of the base material layer, and the base material layer is 100 parts by mass of ABS. The resin is composed of 1 to 20 parts by mass of a thermoplastic resin, and the thermoplastic resin is at least one selected from the group consisting of styrene-butadiene-butylene-styrene block copolymer resin and styrene-diene block. A copolymer resin, a resin hydrogenated on a styrene-diene block copolymer, and a resin graft-polymerized with a styrene in a polyolefin. A composite sheet according to claim 1 or 2, which is used for a container. A composite sheet according to claim 1 or 2, which is used for embossing a handling tape. A composite sheet according to claim 1 or 2, which is used for a package.