KR20200026705A - Sheet comprising inline-laminated antistatic PMMA film and manufacturing method thereof - Google Patents

Abstract

The present invention provides an antistatic sheet comprising a) a base layer of a transparent ABS resin, PMMA resin or impact-resistant PMMA resin; and b) an antistatic PMMA film laminated inline on both surfaces of the base layer. The antistatic sheet according to the present invention replaces a conventional polymer sheet on which an antistatic coating layer is formed, and is excellent in transparency and mechanical properties while having a very low range of a specific surface resistance value, and thus can be applied as packaging sheets of electronic parts such as semiconductor parts and especially of photomask storage cases, and also enables mass production due to a simple inline laminating process.

Description

Sheet comprising inline-laminated antistatic PMMA film and manufacturing method

The present invention relates to a sheet comprising an in-line laminating antistatic PMMA film and a method of manufacturing the same, and more particularly, to anti-static symmetry of vertically formed on the base layer of the transparent ABS resin, PMMA resin or impact-resistant PMMA resin by in-line laminating A sheet containing a PMMA film and a method for producing the same.

In general, materials used in semiconductor clean rooms may cause problems such as equipment malfunction and surface contamination caused by electrostatic discharge or attraction. In other words, materials used in many manufacturing processes in the semiconductor, flat panel display, disk drives, and medical device industries use non-conductors or insulating materials, which produce or discharge large potential charges and pollute the air during transportation. Since these contaminated materials can have a fatal effect in photolithography, coating, and etching processes, materials used in semiconductor clean rooms should not generate static electricity.

In particular, an antistatic function is required for a material such as a case for storing and transporting a finished semiconductor component. As an antistatic packaging material for packaging a semiconductor component having such an antistatic function, the film or sheet is charged on the surface of the plastic resin substrate which is an insulator. The method of crimping, hard-coating, or inline-coating the prevention film to incorporating an antistatic agent into the plastic resin substrate is adopted.

However, when the antistatic film is pressed, the film itself is pressed and produced in a multi-layer, even though the unit price of the film itself is high, resulting in a decrease in transparency and adhesiveness and a high defective rate in the manufacturing process. In this case, since the offline process is further performed after sheet production, a problem arises in that the unit cost increases and the entire process is delayed, and the antistatic function may deteriorate significantly over time. In addition, even when the in-line coating process is adopted, there is a known disadvantage that the antistatic function may drop sharply after washing.

Meanwhile, as the mixing method, an antistatic sheet formed by adding an antistatic agent such as carbon black to an insulating material having excellent electrical insulation such as polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyethylene terephthalate resin, and the like is known. In the case where the dispersibility of the carbon black is uneven, there may be a problem that the antistatic variation is large depending on the portion of the sheet. In addition, although a polyolefin resin composition has been known which improves the appearance and transparency of a sheet by incorporating a specific block copolymer into a resin composition as a high molecular weight antistatic agent, the cost of sheet production due to the use of a high molecular weight antistatic agent is known. There is a new problem of ascension.

Therefore, the inventors made transparent ABS (acrylonitrile-butadiene-styrene copolymer) resin, PMMA resin or impact resistant PMMA resin as a base layer, and laminated the PMMA antistatic film on both surfaces of the base layer by a simple in-line laminating process. The present invention has been completed by focusing on the fact that the present invention can be applied to packaging sheets such as electronic parts, including semiconductor parts, without complicated separate coating and drying processes.

Patent Document 1. Registered Patent Publication No. 10-0650152 Patent Document 2. Publication No. 10-2005-0053355 Patent Document 3. Publication No. 10-2012-0101592

Accordingly, the present invention has been made in view of the above problems, and an object of the present invention is to provide a vertical anti-symmetric antistatic PMMA film laminated on a base layer of transparent ABS resin, PMMA resin or impact resistant PMMA resin by a simple inline laminating process. To provide a sheet and a method of manufacturing the same, and to apply it as a packaging sheet for electronic components, such as semiconductor components.

The present invention for achieving the above object is a) a base layer of a transparent ABS resin, PMMA resin or impact-resistant PMMA resin; And b) an antistatic PMMA film in-line laminated on both surfaces of the substrate layer.

The antistatic PMMA film of b) is characterized in that the injection molding a master batch consisting of 75 to 85% by weight PMMA resin and 15 to 25% by weight of the antistatic agent.

The antistatic agent is characterized in that the inorganic or organic compound.

The inorganic compound may be ZnO, ZnSb ₂ O ₆ , InSbO ₄ , TiO ₂ , ZrO ₂ , SnO ₂ , Sb ₂ O ₃ , Sb ₂ O ₅ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₃ , BaSO ₄ , SrSO ₄ , MgSO ₄ , MgCO ₃ And CaCO _{3 It} is characterized by one or more selected from the group consisting of.

The organic compound may be a nonionic, anionic, cationic or zwitterionic surfactant or a conductive polymer.

The antistatic sheet is characterized in that for packaging of electronic components.

In addition, the present invention comprises the steps of: I) supplying a transparent ABS resin, PMMA resin or impact-resistant PMMA resin to the extruder to melt, kneading and extruding to form a base layer sheet; And II) transferring the base layer sheet to an inline laminating apparatus to sequentially perform an inline lamination of an antistatic PMMA film on both surfaces of the base layer sheet.

The antistatic sheet according to the present invention replaces the polymer sheet having a conventional antistatic coating layer, and has excellent transparency and mechanical properties, and has a very low surface specific resistance value, and has excellent antistatic properties. Not only can be applied as a packing sheet such as a mask storage case, but also mass production is possible due to a simple in-line laminating process.

1 is a cross-sectional view of the antistatic sheet according to the present invention.

Hereinafter, a sheet including an inline laminating antistatic PMMA film according to the present invention and a manufacturing method thereof will be described in detail with the accompanying drawings.

In the present invention, a) a base layer of a transparent ABS resin, PMMA resin or impact-resistant PMMA resin; And b) an antistatic PMMA film in-line laminated on both surfaces of the substrate layer.

Transparent ABS resin, PMMA resin or impact-resistant PMMA resin can be used as a material for forming the substrate layer. ABS resin, PMMA resin or impact-resistant PMMA resin has good mechanical properties and is suitable as a substrate layer in a multilayer structure sheet. In particular, the use of ABS resin or PMMA resin in a transparent state is preferable because it can visually identify the parts accommodated when applied to packaging sheets such as electronic parts and the like.

As shown in the cross-sectional view of the antistatic sheet shown in Fig. 1, a transparent ABS (acrylonitrile-butadiene-styrene) resin is used as the polymer material constituting the base material layer 10 of the antistatic sheet 100 according to the present invention. Generally, ABS resin is a copolymer having chemical resistance of acrylonitrile, impact resistance of butadiene and excellent processability of styrene, and is widely used as a material for furniture or a bath.

The ABS resin has a structure of a copolymer in which an acrylonitrile monomer and a styrene monomer are grafted to a butadiene rubber polymer, and when the copolymer is prepared in consideration of the use of the copolymer, an acrylonitrile, butadiene and styrene monomer may be used. Although the ratio can be appropriately adjusted, the present invention preferably uses 15 to 35% by weight of acrylonitrile monomer, 5 to 30% by weight of butadiene rubber and 40 to 60% by weight of styrene monomer as the ABS resin.

When the content of the acrylonitrile monomer constituting the ABS resin is less than 15% by weight, the chemical resistance may be lowered. When the content of the acrylonitrile monomer is less than 15% by weight, thermal discoloration may occur during the molding process. In addition, when the content of butadiene rubber is less than 5% by weight, the impact strength is lowered, and when it exceeds 30% by weight, the thermal stability may be lowered. In addition, if the content of the styrene monomer is less than 40% by weight, the workability is inferior, and if it exceeds 60% by weight, there is a disadvantage that the chemical resistance is lowered.

In addition, the butadiene rubber is preferably an average particle diameter of 0.05 ~ 0.5㎛ bar butadiene rubber may have a low impact resistance when the average particle diameter is less than 0.05㎛, if exceeding 0.5㎛ acrylonitrile monomer and styrene in the butadiene rubber polymer chain The degree to which the monomer is grafted is lowered, thereby reducing the molecular weight of the copolymer.

On the other hand, PMMA resin can also be used as the polymer material constituting the base layer 10 of the antistatic sheet 100 according to the present invention, the PMMA resin has the physical properties of PMMA intact as it is by other components This says that it is in an unmodified state. PMMA resin is widely used as a material for plastic products because of its excellent transparency, gloss, and molding processability. Especially, since it has weather resistance and scratch resistance, it is not easily discolored by being adapted to ultraviolet rays, and it is also resistant to scratches of external stimuli. It is suitable as a material used for the base material layer 10 of the antistatic sheet 100 which concerns on this invention.

Further, the impact-resistant PMMA resin may be used as the polymer material constituting the base layer 10 of the antistatic sheet 100 according to the present invention. The impact-resistant PMMA resin contains a rubbery resin component while having a PMMA block in the resin. It may be used in the form of a copolymer or blend. As the copolymer type, a copolymer resin of an MMA (methyl methacrylate) monomer and an ethyl acrylate or butyl acrylate monomer is preferably a copolymer resin in which an acrylic rubber block such as polyacrylate is mixed in a PMMA block. have. Blend forms include PMMA resins and MBS (methyl methacrylate-butadiene-styrene) resins, MABS (methyl methacrylate-acrylonitrile-butadiene-styrene) resins, SBC (thermoplastic styrene block copolymer) resins, or The blend resin of ABS (acrylonitrile-butadiene-styrene) resin can be used preferably, It is more preferable to use PMMA-MBS resin which is especially a blend of PMMA resin and MBS resin.

In addition, the antistatic sheet 100 according to the present invention includes an antistatic PMMA film 20, 30 laminated inline on both surfaces of the substrate layer 10 described above, the antistatic PMMA film is a PMMA resin 75 Preference is given to using those produced by injection molding a master batch consisting of ˜85% by weight and an antistatic agent of 15-25% by weight.

When the content of the antistatic agent constituting the antistatic PMMA film is more than 25% by weight, it is difficult to obtain a uniform film after injection molding because the dispersibility with the raw material PMMA resin is poor in the process of obtaining a master batch, and the excessive charge Transparency may decrease depending on the use of the inhibitor, and when the content of the antistatic agent is less than 15% by weight, the antistatic property may be deteriorated.

In this case, as the antistatic agent, an inorganic or organic compound may be used. The inorganic compound may be a crystalline metal oxide or a fine powdery ZnO, ZnSb ₂ O ₆ , InSbO ₄ , TiO ₂ , ZrO ₂ , SnO ₂ , Sb ₂ At least one selected from the group consisting of O ₃ , Sb ₂ O ₅ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₃ , BaSO ₄ , SrSO ₄ , MgSO ₄ , MgCO ₃ and CaCO ₃ It may be.

In addition, the organic compound may be a nonionic, anionic, cationic or zwitterionic surfactant, such as nonionic interfaces such as ethoxylated alkylamines, glycerin fatty acid esters, sorbitan fatty acid esters or alkyl ethanol amides. Active agents or anionic surfactants such as alkylsulfonates, alkylphosphates or alkylbenzenesulfonates, or cationic surfactants such as tetraalkylammonium salts or trialkylbenzyl ammonium salts, or alkylbetaines, alkylalanine or imidazolines Zwitterionic surfactants can be used, and in particular, the transparency can be selected in consideration of transparency.

In addition, a conductive polymer such as polyaniline, polypyrrole, polythiophene or PEDOT (poly (3,4-ethylenedioxythiophene)) may be used as the organic compound.

In addition, the present invention comprises the steps of: I) supplying a transparent ABS resin, PMMA resin or impact-resistant PMMA resin to the extruder to melt, kneading and extruding to form a base layer sheet; And II) transferring the base layer sheet to an inline laminating apparatus to sequentially perform an inline lamination of an antistatic PMMA film on both surfaces of the base layer sheet.

First, in order to prepare a flat sheet using a thermoplastic resin such as a transparent ABS resin, a PMMA resin, or an impact-resistant PMMA resin, as in the present invention, all known molding methods such as injection molding, extrusion molding and compression molding can be generally used. In the step I), a known extrusion molding method is more preferably used.

On the other hand, in order to obtain an antistatic effect by the antistatic treatment of the thermoplastic resin, by adding an antistatic agent to the thermoplastic resin composition before molding and extruding or injection molding, the antistatic agent is mixed into the thermoplastic resin, or after molding the thermoplastic resin product It is also possible to apply an antistatic agent to the surface of the. The former has an antistatic effect because the antistatic agent is incorporated into the thermoplastic resin product, while the latter has an antistatic agent applied to the surface of the thermoplastic product, and thus the antistatic effect is weak with time due to friction or washing. There is a disadvantage that the production cost can be increased, accompanied by complicated coating and drying process of the antistatic agent.

Therefore, in the present invention, the substrate layer sheet formed in step I) is transferred to an inline laminating apparatus to achieve continuous antistatic effect by sequentially inline laminating antistatic PMMA films on both surfaces of the base layer sheet by a simple inline laminating process. As can be seen, the antistatic sheet 100 obtained according to the manufacturing method of the present invention described above can be applied to packaging sheets, such as electronic components, such as semiconductor components in a very low surface specific resistance value range.

Hereinafter, specific embodiments will be described in detail.

(Example 1)

A sheet (base layer) was formed by supplying 100 kg of transparent ABS resin pellets to the hopper of the extruder, melting and kneading them, and extruding them. On the other hand, a master batch consisting of 80% by weight of PMMA resin and 20% by weight of antistatic agent was injection molded to obtain an antistatic PMMA film. Subsequently, the formed sheet is transferred to an inline laminating apparatus, and an antistatic sheet (antistatic PMMA film / transparent ABS base layer / antistatic PMMA film) is produced by sequentially inline laminating an antistatic PMMA film on both surfaces of the sheet. It was.

(Example 2)

An antistatic sheet (antistatic PMMA film / PMMA base layer / antistatic PMMA film) was prepared in the same manner as in Example 1 except that PMMA resin pellets were used to form a sheet (base layer).

(Example 3)

An antistatic sheet (antistatic PMMA film / impact resistant PMMA base layer / antistatic PMMA film) was prepared in the same manner as in Example 1 except that impact resistant PMMA resin pellets were used to form a sheet (base layer).

(Comparative Example 1)

An antistatic sheet (antistatic PMMA film / transparent ABS substrate layer /) in the same manner as in Example 1, except that an antistatic PMMA film was obtained by injection molding a master batch consisting of 70% by weight of PMMA resin and 30% by weight of antistatic agent. Antistatic PMMA film).

(Comparative Example 2)

An antistatic sheet (antistatic PMMA film / transparent ABS substrate layer /) in the same manner as in Example 1, except that an antistatic PMMA film was obtained by injection molding a master batch consisting of 90% by weight of PMMA resin and 10% by weight of an antistatic agent. Antistatic PMMA film).

(Test example)

Total light transmittance (Tt) and haze (Hz) of the antistatic sheets prepared from Examples 1 to 3 and Comparative Examples 1 and 2 were measured using a haze meter according to ASTM D1003 method, and surface specific resistance was JIS K6911 method. According to the UPMCP-HT450, the surface intrinsic resistance value at the applied voltage of 500V (after the sheet manufacturing and after one year) was measured.

Table 1 shows the total light transmittance (Tt), haze (Hz) and surface specific resistance values measured from the test examples.

Sample Tt (%) Hz (%) Surface specific resistance (Ω / cm) Immediately after sheet manufacturing 1 year later Example 1 85.0 10.0 1.1 x 10 ⁷ 1.2 x 10 ⁷ Example 2 87.1 11.2 1.0 x 10 ⁷ 1.1 x 10 ⁷ Example 3 84.5 12.1 1.1 x 10 ⁷ 1.2 x 10 ⁷ Comparative Example 1 80.2 14.1 1.2 x 10 ⁷ 1.5 x 10 ⁷ Comparative Example 2 84.5 11.5 1.3 x 10 ⁸ 1.5 x 10 ⁸

As can be seen in Table 1, the antistatic sheet of Examples 1 to 3 manufactured according to the present invention exhibits excellent transparency and a surface intrinsic resistance value of 10 ⁷ , which is seen in conventional conventional antistatic sheets. It can be confirmed that the antistatic performance is excellent compared to the surface intrinsic resistance value of the order of 10 ⁹ to 10 ¹⁰ (excellent antistatic performance even in Comparative Examples 1 and 2 different from Example 1 only in the antistatic agent content Since the film is formed, the antistatic performance is superior to the conventional antistatic sheet).

In addition, even after one year has elapsed, the surface intrinsic resistance is almost unchanged, and thus the antistatic effect is maintained even after a long time, so that it can be used stably for a long time. It was found that the resistance value remained in a very low range.

Therefore, the antistatic sheet according to the present invention replaces the polymer sheet having a conventional antistatic coating layer, and has excellent transparency and mechanical properties and a very low surface intrinsic resistance value. Not only can be applied as a packing sheet such as a photomask storage case, but also mass production is possible due to a simple in-line laminating process.

10. Base layer
20 (30). In-line Laminated Antistatic PMMA Film
100. Antistatic Sheet

Claims (7)

a) a base layer of transparent ABS resin, PMMA resin or impact resistant PMMA resin; And
b) an antistatic PMMA film in-line laminated on both surfaces of the substrate layer. [Claim 2] The antistatic sheet according to claim 1, wherein the antistatic PMMA film of b) is injection molded into a master batch consisting of 75 to 85 wt% of the PMMA resin and 15 to 25 wt% of the antistatic agent. The antistatic sheet according to claim 2, wherein the antistatic agent is an inorganic or organic compound. The method of claim 3, wherein the inorganic compound is ZnO, ZnSb ₂ O ₆ , InSbO ₄ , TiO ₂ , ZrO ₂ , SnO ₂ , Sb ₂ O ₃ , Sb ₂ O ₅ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₃ , BaSO ₄ , SrSO ₄ , MgSO ₄ , MgCO ₃ and at least one member selected from the group consisting of CaCO ₃ antistatic sheet. The antistatic sheet according to claim 3, wherein the organic compound is a nonionic, anionic, cationic or zwitterionic surfactant or a conductive polymer. The antistatic sheet according to any one of claims 1 to 5, wherein the antistatic sheet is for packaging electronic components. I) forming a base layer sheet by feeding, melting, kneading and extruding a transparent ABS resin, PMMA resin or impact resistant PMMA resin into an extruder; And
II) transferring the base layer sheet to an inline laminating device to sequentially in-line laminating the antistatic PMMA film on both surfaces of the base layer sheet.

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