TWI252164B - Laminated sheet structure - Google Patents

Abstract

A laminated sheet structure comprising a substrate layer and at least one surface layer laminated on at least one surface of the substrate layer; which is characterized in that the materials of the substrate layer comprise polystyrene and styrene/butadiene/styrene copolymer.

Description

1252164 发明, INSTRUCTION DESCRIPTION: TECHNICAL FIELD The present invention relates generally to a polymer gelation technique, and more particularly to a multilayer film structure. [Prior Art] Plastics have many advantages such as light weight, no oxidative rust, easy processing, various types, low energy consumption, recyclable, τ I ^, industrialized production, etc., and are widely used in daily necessities to automobiles. , the manufacture of aircraft. The combination of plastic and other types of plastic, rubber, and inorganic materials, depending on the degree of compatibility, is called polymer compounding, polymer blending, or composite materials. Polymer gelation mainly has the following advantages: (1) from research and development to: short-term and less investment in industrialization; and (7) high degree of freedom in material design in response to different needs. & Today's plastic materials are moving toward polymer bonding. ^ In general, polymer gelation can be used to improve the performance of plastics, such as change = impact resistance, heat, chemical resistance and strength characteristics; can also be thief plastic: new: functional 'such as flame retardant, Transparency, electrical and versatility. The plastic is made of a material that is matched with the required performance or function to achieve the purpose of performance and multi-function.层 之 之 层 层 层 层 包含 包含 包含 包含 层 层 层 层 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The conventional material is polystyrene (PS)' and the surface layer material is polystyrene (such as polymethyl phthalic acid (PMMA), polycarbonate) or propylene.

〇: '87\8765!.D〇C 1252164 A plastic such as a nitrile-butadiene-styrene copolymer (ABS), and optionally a material which imparts multiple properties or versatility to the substrate layer. However, the conventional multi-layer film has poor folding resistance and can be folded back at an angle of 80 degrees, and can only be folded back once, and the impact strength cannot meet the needs of the industry today. Especially for these transparent plastics, such as polystyrene (PS), styrene #/butadiene/styrene (SBS), polymethyl methacrylate (PMMA) and other similar materials, due to their transparency, It is quite difficult to form plastics with other properties or functions, and it is necessary to consider the inflection rate in order to maintain transparency. For example, in order to improve the impact resistance of a transparent plastic, a rubber component may be dispersed therein, but the molded article loses transparency due to light scattering between the substrate resin and the rubber particles. Therefore, it is necessary for the industry to develop a plastic that has a high degree of folding resistance and can be used for other functions. SUMMARY OF THE INVENTION One is highly resistant to folding and can be both oceanic. The present invention relates to a multilayer. The object of the present invention is to provide a novel plastic of other functional properties. , the mouth structure comprises a substrate layer and at least a surface layer, the surface layer layer and the 10,000 layer layer and at least one surface; wherein the material of the substrate layer comprises polyphenylene Benzene/butadiene/phenethyl hydrazine copolymer. Whether the multilayer film structure has a folding resistance and a folding resistance of the substrate layer. According to the invention, the substrate layer serves as a main portion of the multilayer film structure, which can be used to provide the multilayer film. Functionality of the structure. The present invention is characterized by an improvement in the "substrate layer" material in the multilayer film structure. According to the present invention, the soil layer < material comprises polystyrene and stupid ethylene / butyl

O:\87\8765! DOC 1252164 phenyl/phenylene copolymer'. Preferably, the material of the substrate layer comprises 20 to 75% polystyrene and 25 to 8 % styrene/butyl A diene/styrene copolymer. More preferably, the material of the substrate layer comprises 25 to 4% by weight of polyphenylene bromide and 60 to 75% of styrene/butadiene/phenylethylene copolymer. «Another Aspect of the Invention' The substrate layer material of the present invention further comprises a styrene/butadiene copolymer. Preferably, the material of the substrate layer comprises Μ to 45% polystyrene, 5 〇 to Benzene succinimide/phenylethyl conjugate copolymer and 1 to 10% styrene/butadiene copolymer . More preferably, the material of the substrate layer comprises 30 to 40% of polystyrene, 53 to 6 % of styrene/butane benzene copolymer and 5 to 1% of styrene/butyl Ene copolymer. More preferably, the material of the substrate layer comprises 37% polystyrene, 53% styrene/butadiene/styrene copolymer and 1% stupid ethylene/butadiene copolymer. According to the invention, the material of the surface layer can be any surface layer material known in the art, such as plastic, acrylic (such as polymethylpropionic acid), carbonated and acrylonitrile, butadiene-phenylene copolymer. Things. In order to provide the multi-layered film structure of the present invention with multiple properties and versatility, other materials may be included in the material of the surface layer as needed. For example, in order to make the multilayer film structure antistatic, the surface layer material may further comprise an antistatic agent. Preferably, the antistatic agent comprises a transient type or a polymer type, and the volume resistivity is about 1〇. 1 to 丨〇〗 2 Ω · cm 'The polymer type antistatic agent includes, but is not limited to, Inherent Dissipative Polymer (IDP) and intrinsic conjugated Inherent Conductive Polymer (ICP) , such as polyethylene glycol yeast? Fc S-area amine, polyesteramine and poly(ethylene oxide/propylene oxide) copolymer. On the other hand, in order to make the multilayer film structure flame resistant, the surface layer material may be additionally

〇Λ87\8765Ι DOC 1252164 contains a flame retardant that meets UL94 V〇 to V2 specifications, including but not limited to polyolefins and their polymers, polyvinyl chloride and its polymers, nylon and its polymers. Polycarbonate and its polymers, polymethyl propyl hydrazine and its polymers, polyesters and polymers thereof. In still another aspect, in order to impart a pen-like property to the multilayer film structure, the surface layer material may further comprise a conductive agent, which includes, but is not limited to, carbon black. According to the invention, the surface layer is laminated on at least one surface of the substrate layer. In one embodiment of the invention, the multilayer film structure comprises a surface layer laminated on a surface of the substrate layer; preferably, the surface layer has a thickness of 1 〇/ of the thickness of the edge multilayer film. Up to 15%, and the thickness of the substrate layer is from 85% to 99% of the thickness of the multilayer film. In another embodiment of the present invention, the multilayer film structure comprises two surface layers respectively stacked on the upper two surfaces of the substrate layer. Preferably, each of the surface layers has a thickness of 1% of the thickness of the multilayer film. 15%, and the thickness of the base layer of the child occupies 7〇% to %% of the thickness of the multilayer film; more preferably, each of the surface layer thickness accounts for 1% to 5% of the thickness of the multilayer film, and the thickness of the substrate layer occupies The thickness of the multilayer film ranges from 90 〇/〇 to 98%. A substrate layer and a surface layer according to the present invention can be obtained by those skilled in the art and can be obtained by the prior art. For example, it may be to extrude a sheet or to eject a sheet _ $ out or out of the technique to familiarize yourself with the technique < well known to those skilled in the art. The $ "film... is constructed by co-extruding the separately produced substrate layer and surface layer. And / 丨, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , In order to obtain _ ^ S ^ ^ ^, a substrate layer and a garment layer are co-extruded, and then one side of the substrate is coextruded with the other surface layer to form 1,252,164 pieces. This coextrusion technique is also well known to those skilled in the art. The multilayer film structure of the invention has the advantages of high folding endurance, and can be folded back at least twice, and has good impact resistance characteristics. In addition, the substrate layer according to the present invention has a high tortuosity. The transparent material of the rate: the diversity of the mouth is required, but can be widely used in the manufacture of various appliances, = ordering plates, containers, integrated circuit tubes, 'integrated circuit trays, packaging, such as: two components, wafer cassettes, Electronic component tray, heat-sealed molding carrier: Its:: [Embodiment] The following examples are used to explain in detail. This is only an illusion that & - ^ 隹 does not mean that the invention is limited to the contents disclosed in this temple. Example 1······················································································· ", 彳τ its tortuosity rate, impact

Har (W , $ δ degree and Rockwell hardness (Rockwell

Hardness), the results are shown in the table:

O:\87\87651 DOC 1252164 Table 1 Substrate layer number 1 2 3 4 5 6 7 8 9 10 Material type" content (%) Polystyrene PG33 (25) 氺氺30 - 37 - (40) 氺氺35 - 37 - Polystyrene PG383 (25) 氺氺- 30 - 37 (40) 氺氺- 35 - 37 styrene/butadiene/styrene PB5903 75 60 60 53 53 60 60 60 58 58 styrene / butyl Ene copolymer PB5300 - 10 10 10 10 - 5 5 5 5 Folding resistance (times) 5 6 7 8 10 2 4 5 4 5 Tortuous ratio 1.56 1.57 1.57 1.57 1.57 1.57 1.57 1.57 1.56 1.56 Impact strength (1/8") 6.25 5.35 4.56 4.44 4.25 1.25 3.35 3.56 3.44 3.25 Impact strength (1/4") 6.88 5.85 4.8 4.66 4.35 1.88 3.85 3.8 3.66 3.35 Rockwell hardness 80 84 82 83 82 90 84 83 85 84 Average molecular weight (kD) 97.5 97 97 80.3 89.55 96 101.5 105.25 96.3 105.55 *Model refers to the product model of Chi Mei Industrial Co., Ltd. ** Brackets can be selected from polystyrene PG33 or polystyrene PG383. The substrate layer in Table 1 can be shot or extruded by the injection machine. The machine is extruded. The injection machine used is SM25#SM150#, and the mold is set to be an antistatic crystal tray with a temperature of 220 °C. 230 ° C, the injection pressure is 50%, the speed is 40 meters / minute, the cycle is 25 to 35 seconds, the maximum stroke is 110mm * 40mm. The extruder used is 3 #巴嘴 extruder 11 5 mm or 1 #巴The mouth extrusion machine is 105 mm, the operating temperature is from 145 °C to 195 °C, the discharge pressure is about 700 bar, the roller temperature is about 65/65/60 °C, the vacuum is about 650 Mh/kg, and the mesh is about 50/80/80 mesh. The surface layer is made of polycarbonate type PC-115 (product type of Chi Mei Industrial Co., Ltd.) or methyl methacrylate type PM-2 1丨 (product type of Chi Mei Industrial Co., Ltd.) 0:\S7'87651 DOC -10- 1252164 Example 2: Two-layer multilayer film structure In the case of Example 1, the substrate layer No. 5 and the PC-115 surface layer were prepared, and then a base was used. The sheet layer and a surface layer were co-extruded to obtain a two-layered multilayer film structure of "surface layer-substrate layer", and the thickness ratio thereof is shown in Table 2 below, and 180 was performed for the multilayer film structure, respectively. The folding resistance test of the foldback and the measurement of the resistance value, the impact strength and the Rockwell hardness are shown in Table 2 below.

Surface layer/substrate layer (thickness ratio) 5/95 4/96 3/97 Folding resistance (times) Resistance (Ώ/cm) Strength (1/8") Strength (1/4 inch) I hardness L〇i-10 1.20 '1.80 —86 10-10 4.00 4.80 85 7 ιο^Το 4.50 5·50— 84 — 1/99

As is apparent from Table 2, the multilayer film structure (Editor 1 to 5) of the present invention having a surface layer content of from 1 to 5% is excellent in folding resistance and excellent in impact strength and hardness. Example 3: Two-layer multilayer film structure In the second example, the substrate layer No. 5 and the surface layer of CM-2 11 were obtained, and then a substrate layer and a surface layer were co-extruded to obtain a "surface layer". The two-layered multilayer film structure of the substrate layer is shown in Table 3 below and is 180 for the multilayer film structure, respectively. The folding resistance test of the foldback, and the measurement of the resistance value, the impact strength and the Rockwell hardness are shown in Table 3 below. Ο \87\87651 DOC -11 - 1252164

As is clear from Table 3, the multilayer film structure (single number 6 to 1 〇) of the present invention having a surface layer content of 5% has good folding resistance and excellent impact strength and hardness. Example 4: Three-layer multilayer film structure A substrate layer No. 4 and a pC-115 surface layer in Example 1 were obtained, and then a substrate layer and a surface layer were co-extruded, and then the substrate layer was laminated. The other side was coextruded with the other surface layer to obtain a three-layered multilayer film structure of "surface layer_substrate layer_surface layer", and the thickness ratio thereof is shown in Table 4 below, and 180 was performed for the multilayer film structure, respectively. The folding resistance test and the measurement of the resistance value, impact strength and Rockwell hardness are shown in Table 4 below.

Up to 5% of the multilayer film of the present invention and excellent impact strength Z5555___ surface layer / substrate layer / surface layer edge ratio) Fold (times) i resistance (Ω / cm) Μ strength (1/F)

Strength (1/M is known from Table 4 (No. 11 to

〇, '87\87651 DOC -12- 1252164 and hardness. Example 5: Three-layer multilayer film structure 2. The substrate layer No. 4 and the surface layer of CM-211 in Example 1 were obtained, and then a substrate layer and a surface layer were co-extruded, and then the substrate layer was The other side is coextruded with the other surface layer to obtain the "surface layer-substrate layer-surface·one/曰" core two-arm multilayer film structure. The thickness ratio thereof is shown in the following Table 5, and the respective layers of the multilayer film, 纟The resistance structure of the 180° foldback test was measured, and the resistance value, impact strength and Rockwell hardness were measured. The results are shown in Table 5 below. Multilayer film number 16 17 18 — ~T9~ Surface layer / substrate layer / surface layer ratio) 5/90/5 4/92/4 3/94/3 2/96/2 ----___ TmrT^ ιό^ Ϊο^ : 3⁄4 degrees (times) 5 6 Resistance value (Ω/cm) HV-IO6 ΙΟ'-ΙΟ6 10 丨-l〇f Strength (1/8") 2.00 2.15 2.50 3.50 4j〇^' Color! Strength (1/4,,) 2.05 2.20 2.80 3.80 More 86 85 84 83 As can be seen from Table 4, the multilayer film structure (Nos. 16 to 20) of the present invention having a surface layer content of 1 to 5%, the folding resistance Good, and has excellent impact strength and hardness. The above-described embodiments are merely illustrative of the principles and effects of the invention and are not intended to limit the invention. Therefore, modifications and variations of the embodiments described above will be made without departing from the spirit of the invention. The scope of the invention should be as set forth in the appended claims.

O:\87\8765l DOC -13 -

Claims (1)

修 修 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 a layer, the surface layer being laminated on at least one surface of the substrate layer; wherein the material of the substrate layer comprises polystyrene and a styrene/butadiene/styrene copolymer; wherein the material of the substrate layer is It comprises 20 to 75% polystyrene and 25 to 80% styrene/butadiene/styrene copolymer. 2. The multilayer film structure according to claim 1, wherein the material of the substrate layer comprises 25 to 40% of polystyrene and 60 to 75% of styrene/butadiene/styrene copolymer. Things. 3. The multilayer film structure according to claim 1, wherein the material of the substrate layer further comprises a styrene/butadiene copolymer. 4. The multilayer film structure according to claim 3, wherein the material of the substrate layer comprises 20 to 45% polystyrene, 50 to 80% styrene/butadiene/styrene copolymer and 1 to 10% of a styrene/butadiene copolymer. 5. The multilayer film structure according to claim 4, wherein the material of the substrate layer comprises 30 to 40% polystyrene, 53 to 60% styrene/butadiene/styrene copolymer and 5 to 10% of a styrene/butadiene copolymer. The multilayer film structure according to claim 1, comprising a surface layer on one surface of the substrate layer. 7. The multilayer film structure of claim 6, wherein the surface layer thickness ranges from 1% to 15% of the thickness of the multilayer film, and the substrate layer thickness ranges from 85% to 99% of the thickness of the multilayer film. O:\87\87651-940920.DOC 1252164 8. The multilayer film structure according to the scope of the patent application, comprising two surface layers respectively laminated on the lower two surfaces of the substrate layer. 9. The multilayer film structure of claim 8 wherein each of said surface layer thicknesses comprises from 1% to 15% of the thickness of said multilayer film and said substrate layer thicknesses comprise from 70% to 98% of the thickness of said multilayer film. The multilayer film structure according to claim 9, wherein each of the surface layer has a thickness of 1% to 5% of the thickness of the multilayer film, and the thickness of the substrate layer accounts for 90% to 98% of the thickness of the multilayer film. . 11. A multilayer film structure comprising a substrate layer and at least one surface layer laminated on at least one surface of the substrate layer; wherein the material of the substrate layer comprises 37% polyphenylene晞, 53% styrene / butyl bismuth / styrene copolymer and 10% styrene / dibutyl copolymer. 12. A multilayered gland structure comprising: a substrate layer and a surface layer laminated on a surface of the substrate layer; wherein the material of the substrate layer comprises 37% poly a styrene, 53% styrene/butadiene/phenethyl methacrylate copolymer and a 10% styrene/butadiene copolymer; the surface layer material comprises polystyrene, and the surface layer thickness accounts for 1 of the thickness of the multilayer film From % to 15%, the thickness of the substrate layer is from 85% to 99% of the thickness of the multilayer film. 13. A multilayer film structure comprising a substrate layer and a two surface layer, the surface layer being laminated on the upper two surfaces of the substrate layer; wherein the material of the substrate layer comprises 37% polystyrene , 53% styrene/butadiene/styrene copolymer and 1% styrene/butadiene copolymer; and each of the surface layers has a thickness of 1 ° / of the thickness of the multilayer film. To 15%, the thickness of the substrate layer is from 70% to 98% of the thickness of the multilayer film. O:\87\87651-940920.DOC 1252164 14· A multilayer film structure comprising a substrate layer and two surface layers, the surface layer being laminated on the lower two surfaces of the substrate layer; characterized in that the base The material of the sheet layer comprises 37% polystyrene '53% styrene/butadiene/styrene copolymer and 10% styrene/butadiene copolymer; and each of the surface layer thickness accounts for 1 of the thickness of the multilayer film. From 0.01 to 15 Å, the thickness of the substrate layer is from 70% to 98% of the thickness of the multilayer film. 1 5 . The multilayer film according to any one of claims 4 to 4 wherein the surface layer material is selected from the group consisting of polystyrene, polymethyl methacrylate and polycarbonate. . 16. The multilayer film structure of any one of clauses 1 to 14, wherein the surface layer material further comprises an electrostatic agent, a flame retardant or a conductive agent. 1 = According to the scope of the patent scope, the multilayer film structure of the item - 14 is used to manufacture plates, containers, integrated circuit tubes, integrated circuit trays, =:t sub-components, wafer cassettes , electronic parts tray or heat seal molding \: \87\87651 -940920.DOC