Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
  • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/001—Combinations of extrusion moulding with other shaping operations
  • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
  • B29C48/07—Flat, e.g. panels
  • B29C48/08—Flat, e.g. panels flexible, e.g. films
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
  • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
  • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/41—Compounds containing sulfur bound to oxygen
  • C08K5/42—Sulfonic acids; Derivatives thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
  • B29C51/14—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor using multilayered preforms or sheets
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
  • B29K2023/10—Polymers of propylene
  • B29K2023/12—PP, i.e. polypropylene
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
  • B29K2023/16—EPM, i.e. ethylene-propylene copolymers; EPDM, i.e. ethylene-propylene-diene copolymers; EPT, i.e. ethylene-propylene terpolymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
  • B29K2105/0008—Anti-static agents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
  • B29K2995/0003—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular electrical or magnetic properties, e.g. piezoelectric
  • B29K2995/0005—Conductive
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
  • B29K2995/0003—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular electrical or magnetic properties, e.g. piezoelectric
  • B29K2995/001—Electrostatic
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
  • B29K2995/0037—Other properties
  • B29K2995/0093—Other properties hydrophobic
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2031/00—Other particular articles
  • B29L2031/712—Containers; Packaging elements or accessories, Packages
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
  • B32B2264/10—Inorganic particles
  • B32B2264/102—Oxide or hydroxide
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
  • B32B2264/10—Inorganic particles
  • B32B2264/104—Oxysalt, e.g. carbonate, sulfate, phosphate or nitrate particles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
  • B32B2307/21—Anti-static
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/30—Properties of the layers or laminate having particular thermal properties
  • B32B2307/31—Heat sealable
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/514—Oriented
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/546—Flexural strength; Flexion stiffness
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/726—Permeability to liquids, absorption
  • B32B2307/7265—Non-permeable
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/732—Dimensional properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2323/00—Polyalkenes
  • B32B2323/10—Polypropylene
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2439/00—Containers; Receptacles
  • B32B2439/70—Food packaging
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/005—Additives being defined by their particle size in general
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/017—Additives being an antistatic agent

Definitions

• the present invention relates to a resin sheet and a molded body. Specifically, the present invention relates to a composite laminate made of a thermoplastic resin such as polyolefin, and relates to a thermoplastic resin sheet and a molded article excellent in interlayer adhesion, heat seal strength, pressure resistance, rigidity, oil resistance, water repellency and the like.
• a thermoplastic resin such as polyolefin
• conductive carbon black is most widely used.
• carbon black is a fine particle, it easily detaches from the surface of the base material, and there is a problem that the fine particles of the carbon black that is detached contaminate the contents of the container.
• various conductive polymer materials have been proposed as conductive materials to replace conductive carbon black, these conductive polymer materials are expensive and are required to be used in large quantities.
• dissociable inorganic salts such as lithium perchlorate have been proposed as conductive materials that can replace conductive polymer materials, but these dissociable inorganic salts can be used for thermoplastic resins or conductive paints constituting containers. Affinity with the film-forming material is low, and it is difficult to uniformly disperse in the resin or film. Moreover, when it is used in an amount that can provide sufficient conductivity, the dissociable inorganic salt is detached from the container body or the conductive coating film, and the separated inorganic salt is inferior in practicality like the carbon black.
• an antistatic agent for olefin polymer film various compounds having a hydroxy group in the molecule, such as fatty acid ester of polyhydric alcohol, polyoxyalkylene alkyl ether, hydroxyalkyl-substituted aliphatic amine, hydroxyalkyl-substituted fatty acid amide, etc. And mixtures thereof are known (for example, see Patent Documents 1 and 2).
• nitrogen-containing compounds there is concern about the generation of acrylamide during heating, and those that do not contain nitrogen are insufficient in antistatic performance.
• a mixture of a compound having a hydroxy group in the molecule as described above and an organic sulfonate is known (see, for example, Patent Documents 3 and 4).
• the container formed with the polypropylene resin is used preferably.
• the polypropylene resin easily changes in crystal structure depending on molding conditions, and this change affects the speed of developing antistatic properties.
• the surface that comes into contact with the mold exhibits rapid antistatic properties by rapid cooling, while the opposite surface is slowly cooled to delay the development of antistatic properties.
• Polypropylene resin itself uses a co-block polymer because the number of traps of free electrons varies depending on the difference in crystallization due to addition of homo / random copolymer / rubber components (see, for example, Patent Document 6). There is a problem that shortages are a concern.
• water repellency may be required for resin sheets and molded products.
• the ion-release antistatic agent used in conventional containers is hydrophilic, water adheres to the container and it is difficult to obtain a clear water supply amount. Met. Therefore, water repellency is imparted by adding inorganic fine particles to the resin sheet surface (see, for example, Patent Document 7).
• this method cannot be used in materials that do not allow impurities to be mixed, such as food containers, because inorganic fine particles may be peeled off or decomposed and eluted into water.
• an object of the present invention is to provide a thermoplastic resin having water repellency, which can impart high antistatic properties to a molded product in a non-mold surface of a mold and a deep-drawing portion having a high drawing ratio as well as a mold contact surface.
• a sheet and a molded product formed from the resin sheet are provided.
• thermoplastic resin As a result of intensive studies, the present inventors have combined a thermoplastic resin, a specific antistatic agent, and an inorganic additive, so that the molded product can be used in a mold non-contact surface and a molded product such as a container, such as a container.
• the present inventors have found a thermoplastic resin composition that can impart excellent antistatic properties as well as a contact surface and can impart water repellency to a surface having an antistatic agent that is generally hydrophilic, and has completed the present invention.
• the present invention comprises two or more layers including a skin layer and a main layer, the skin layer includes a thermoplastic resin and an antistatic agent, and the main layer includes a thermoplastic resin and an inorganic additive.
• the skin layer has a thickness of 10 ⁇ m or more and 50 ⁇ m or less, and when stretched, the water droplet contact angle in the skin layer is 90 ° or more.
• the surface resistivity of the skin layer is desirably 9 ⁇ 10 13 ⁇ or less.
• thermoplastic resin contained in the skin layer and the main layer is a polyolefin polymer.
• the antistatic agent contains a sulfonate as a substantial component.
• the average particle diameter of the inorganic additive is desirably 20 ⁇ m or less.
• the antistatic resin composition of the present invention When the antistatic resin composition of the present invention is used, a molded product having excellent antistatic properties in the same manner as the mold contact surface can be obtained even in the mold non-contact surface and the deep drawing portion having a high drawing ratio in the secondary molding. can get. Further, even when stretched or oriented, high antistatic properties can be maintained, and the entire molded product can be uniformly antistatic. Furthermore, since the protrusions are generated on the skin layer, the water repellency and the antistatic property which cannot be achieved with the conventional antistatic material can be exhibited. Moreover, since the resin sheet of the present invention has high antistatic properties and water repellency, it is useful as a transport container for semiconductors and electronic parts, a chemical container, a food container, and an interior / exterior material.
• thermoplastic resin for example, a polyolefin polymer is used.
• a polypropylene polymer is particularly desirable in terms of rigidity and heat resistance.
• the crystalline polypropylene polymer used in the present invention is a homopolymer of propylene (polypropylene), a majority weight of propylene and other ⁇ -olefins (for example, ethylene, 1-butene, 1-pentene, 1-hexene, 4 -Methyl-1-pentene, 1-octene, etc.), vinyl esters (eg, vinyl acetate), aromatic vinyl monomers (eg, styrene), vinyl silanes (eg, vinyltrimethoxysilane, vinyltrimethylsilane), etc. It may be a binary block or more, a random or graft copolymer, or a mixture thereof.
• homopolymers and copolymers can be used properly.
• a polymer having a propylene content of about 90 to 100 mol% for example, a propylene homopolymer can be used.
• a copolymer can be used.
• the form of the copolymer may be either a block copolymer or a random copolymer.
• the block copolymer has a low elastic modulus, and when formed into a sheet, the rigidity and the waist are likely to decrease. Therefore, the entire polypropylene resin is preferably a non-block copolymer.
• the polypropylene resin may be an atactic polymer, and the stereoregularity thereof is not particularly limited, and examples thereof include a metallocene structure generated by an isotactic, syndiotactic, or metallocene catalyst.
• polypropylene resins having an isotactic structure which has been conventionally used are preferred from the viewpoint of simplicity and economy.
• propylene / ethylene / random copolymers and propylene / ethylene / block copolymers containing a crystalline polypropylene part and an ethylene / propylene / random copolymer part have antistatic properties, surface whitening prevention properties, and moldability.
• a propylene / ethylene-block copolymer are particularly preferable from the viewpoint of balance of physical properties.
• the crystalline polypropylene homopolymer part is 30 to 100% by weight, preferably 35 to 95% by weight, particularly preferably 40 to 90% by weight, and the weight average molecular weight (Mw) is 200.
• the rigidity is insufficient, the impact strength is insufficient if it is more than the above range.
• the content ratio of the ethylene / propylene-random copolymer portion is less than the above range, the impact strength is insufficient, whereas when it is more than the above range, the rigidity is insufficient.
• the moldability When the weight average molecular weight (Mw) is larger than the above range, the moldability is lowered, and when it is smaller than the above range, the impact strength is lowered. If the melt index (MI) of the entire propylene / ethylene-block copolymer is smaller than the above range, the moldability (fluidity, overall appearance) is inferior, while if it is too large, the impact strength is insufficient.
• MI melt index
• polypropylene resins can be used alone or in combination of two or more.
• a polyethylene resin masterbatch may be included for the convenience of adding fillers and pigments.
• the polyethylene resin is preferably low density polyethylene (LDPE) or linear low density polyethylene (LLDPE), and particularly preferably linear low density polyethylene.
• LDPE low density polyethylene
• LLDPE linear low density polyethylene
• linear low density polyethylene When linear low density polyethylene is used, it is possible to enhance the antistatic property at the stretched portion (orientation portion), particularly the early manifestation and effect of the antistatic property at a high drawing ratio in the molded product. Moreover, even in the non-contact part of the mold, the antistatic property can be exhibited early as in the contact part, and the difference in antistatic property between the front surface and the back surface of the molded product can be reduced.
• the linear low density polyethylene tends to form a continuous phase at least in the vicinity of the sheet surface (for example, a depth of 5 ⁇ m from the sheet surface).
• linear low density polyethylene and polypropylene form a bicontinuous structure (network structure) in the vicinity of the sheet surface. Inside the sheet, it appears that a sea-island structure is formed in which polypropylene is the matrix and linear low density polyethylene is the dispersed phase.
• the linear low density polyethylene is a polyethylene having a few branched chains obtained by a low pressure polymerization method, and is a copolymer of ethylene and ⁇ -olefin.
• ⁇ -olefin include ⁇ -olefins other than ethylene, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, and the like.
• An example is ⁇ -C3-12 olefin.
• ⁇ -olefins Of these ⁇ -olefins, ⁇ -C3-10 olefins are preferable, ⁇ -C3-8 olefins are more preferable, and linear ⁇ -C5-8 olefins (for example, 1-hexane, 1-octene, etc.) are preferable. ). These ⁇ -olefins can be used alone or in combination of two or more.
• the melt index (MI) of the polypropylene resin is about 0.1 to 10 g / 10 minutes, preferably about 0.2 to 10 g / 10 minutes, and more preferably about 0.4 to 3 g / 10 minutes. If the melt index MI is too high, the elastic modulus and rigidity are lowered, and it is easy to draw down during thermoforming, making secondary molding difficult. In addition, the thickness of the molded product becomes not only uneven, but also causes wrinkles. If the melt index MI is too low, the seal adhesion is improved, but extrusion molding becomes difficult.
• Antistatic agent When the thermoplastic resin and the antistatic agent are combined, a resin composition having excellent antistatic properties can be obtained.
• the antistatic agent include antistatic agents such as nonionic antistatic agents, anionic antistatic agents, cationic antistatic agents, and amphoteric antistatic agents.
• Nonionic antistatic agents include polyhydric alcohol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers [for example, polyoxyethylene (oxyethylene group average addition mole number 1 to 30), N, N-bis (2-hydroxyethyl) alkylamine (so-called alkyldiethanolamine), polyoxyethylene alkylamine, N, N-bis (2-hydroxyethyl) fatty acid amide, polyoxyethylene alkylamine fatty acid ester, alkyldiethanolamide, polyoxyethylene Alkyl amide etc. are mentioned.
• anionic antistatic agent examples include alkyl sulfonates [for example, C6-24 alkyl sulfonates (particularly, C8-18 alkyl sulfonates)], alkylbenzene sulfonates, alkyl diphenyl ether disulfonates, alkyl sulfates. Salts, alkyl sulfonate phosphonium salts, alkyl phosphates and the like. Examples of the salt include salts with ammonia, amines, alkali metals (for example, sodium) and alkaline earth metals.
• Examples of cationic antistatic agents include tetraalkylammonium salts and trialkylbenzylammonium salts.
• Examples of the salt include salts with halogen atoms (for example, chlorine atom, bromine atom), perchloric acid and the like.
• amphoteric antistatic agents examples include alkyl betaines, alkyl imidazolium betaines, and hydroxyalkyl imidazoline sulfates.
• anionic antistatic agents particularly those mainly composed of glycerin fatty acid ester sulfonates, are generally used from the viewpoint of compatibility with polyolefin resins, cost, and thermal stability. Since nitrogen and the like are not included, it is preferable when safety and a high antistatic effect are required.
• antistatic agents can be used alone or in combination of two or more.
• the antistatic agent of the present invention contains a sulfonate as a substantial component.
• the substantial component means that the sulfonate is usually in the range of 90 wt% or more and less than 100 wt%, preferably in the range of 95 wt% or more and less than 100 wt%, more preferably 97 wt%. It means to contain in the range below 100 weight%.
• sulfonate examples include monoalkyl sulfate, alkyl polyoxyethylene sulfate, and alkylbenzene sulfonate.
• a glycerin fatty acid ester compound having an aliphatic hydrocarbon group having 1 to 40 carbon atoms in the molecular skeleton can be mentioned.
• those having an aliphatic hydrocarbon group having 3 to 40 carbon atoms are preferred, and those having an aliphatic hydrocarbon group having 6 to 35 carbon atoms are more preferred.
• the antistatic agent of the present invention comprises a sulfonate as a substantial component, and further contains a specific metal ion at a concentration of 0.1 to 1000 ppm, preferably 0.5 to 500 ppm.
• the specific metal ion means one or two or more selected from alkali metal ions and alkaline earth metal ions, and in the case of two or more, means the total thereof (hereinafter simply referred to as metal ions). ).
• alkali metal ions include lithium ions, sodium ions, potassium ions, rubidium ions, cesium ions, and francium ions.
• alkaline earth metal ions examples include beryllium ions, magnesium ions, calcium ions, strontium ions, and barium.
• An ion and a radium ion are mentioned, Of these, an alkali metal ion is preferable, and a sodium ion and / or a potassium ion is more preferable.
• a sulfonate phosphonium salt having an aliphatic hydrocarbon group having 1 to 18 carbon atoms or an aromatic hydrocarbon group in the side chain may be contained.
• the antistatic agent of the present invention comprises sodium sulfonate as a substantial component and contains metal ions at a concentration of 0.1 to 500 ppm, preferably 0.5 to 300 ppm.
• the pH is more preferably 4.5 to 7.5 under specific conditions, and 5.5 to 7.0 is particularly preferable.
• composition of the skin layer constituting the thermoplastic resin sheet according to the present invention will be described. Although details of the skin layer will be described later, the composition of the skin layer is 0.01 to 5.0 parts by weight, preferably 0.05 to 5.0 parts by weight of the antistatic agent of the present invention described above per 100 parts by weight of the synthetic polymer material. It is contained in an amount of 3.0 parts by weight, more preferably 0.2 to 1.5 parts by weight.
• the composition of the skin layer is prepared by 1) a method of adding the antistatic agent of the present invention in the polymerization step of the synthetic polymer material, and 2) a method of adding the antistatic agent of the present invention during the molding process of the synthetic polymer material. Etc. can be adopted.
• the weight average molecular weight of the antistatic agent is 4000 or less, preferably 150 to 3000, and more preferably about 200 to 2000.
• a high molecular weight antistatic agent for the purpose of adjusting the antistatic effect, a high molecular weight antistatic agent, metal oxide, carbon black, conductivity-imparting agent, higher alcohol and the like may be added to the thermoplastic resin of the present invention.
• anti-smudge agents for the purpose of adjusting the antistatic effect, a high molecular weight antistatic agent, metal oxide, carbon black, conductivity-imparting agent, higher alcohol and the like may be added to the thermoplastic resin of the present invention.
• anti-smudge agents for the purpose of adjusting the antistatic effect, a high molecular weight antistatic agent, metal oxide, carbon black, conductivity-imparting agent, higher alcohol and the like may be added to the thermoplastic resin of the present invention.
• anti-smudge agents for the purpose of adjusting the antistatic effect, a high molecular weight antistatic agent, metal oxide, carbon black, conductivity-imparting agent, higher alcohol and the like may be added to the thermoplastic resin of the present invention.
• Inorganic additives include talc, mica, carbon black, silica, dolomite powder, silicate, quartz from the viewpoint of mechanical properties such as cost reduction from reducing the amount of resin used, fire resistance, rigidity and impact resistance, etc.
• examples thereof include powder, diatomaceous earth, alumina, aluminum hydroxide, magnesium hydroxide, and calcium carbonate.
• Mg 3 Si 4 O 10 (OH) 2 as a main component is preferable.
• the average particle size is 20 ⁇ m or less, preferably 1.0 to 18 ⁇ m, more preferably about 2.5 to 15 ⁇ m, and is more preferable in terms of forming water-repellent irregularities on the bulk surface and improving water repellency. .
• white pigments examples include zinc white, lead white, lithopone, titanium oxide, precipitated barium sulfate and barite powder.
• a white pigment titanium oxide which is a food additive compliant with the Food Sanitation Law, there is 99% or more of high-purity titanium oxide.
• the white pigment of titanium oxide is most suitable for food use from the viewpoint of hygiene, hygiene management, and food impression.
• the chemical formula one containing TiO 2 as a main component is preferable.
• the average particle diameter is 1 ⁇ m or less, preferably 0.01 to 0.8 ⁇ m or less, and more preferably about 0.05 to 0.3 ⁇ m, and is more preferable in terms of improving bulk light shielding performance. Since the shielding property does not become so high when the amount of addition increases to some extent, it is preferable to determine it in consideration of the cost.
• thermoplastic resin sheet of the present invention is a laminated sheet composed of a plurality of layers.
• the total thickness of the thermoplastic resin sheet is about 0.1 to 3.0 mm, preferably about 0.2 to 2.0 mm, and more preferably about 0.5 to 1.2 mm.
• thermoplastic resin sheet of the present invention at least one outermost layer is composed of a skin layer.
• the thermoplastic resin sheet of the present invention can be prepared by a method such as a co-extrusion method, heat lamination or dry lamination, and does not necessarily require an adhesive. Note that the amount of the expensive antistatic agent used can be reduced by forming the surface layer with the skin layer and making the intermediate layer a layer not containing the antistatic agent.
• the method for producing the thermoplastic resin sheet of the present invention is not particularly limited, and the pellets of the resin composition are supplied to an ordinary extrusion molding machine and melt-kneaded to obtain a die [flat shape, T shape (T die)]. , Cylindrical shape (circular die), etc.] and can be formed into a sheet shape.
• the sheet configuration at this time is preferably two types, two layers, or two types, three layers.
• the skin layer that is the outermost layer contains a thermoplastic resin and an antistatic agent, and the main layer that becomes the other layer (for example, an intermediate layer) is blended so as to contain a thermoplastic resin and an inorganic additive.
• the main layer may be blended so as to further contain a white pigment.
• the thickness of the skin layer is 10 to 50 ⁇ m, preferably 12 to 40 ⁇ m, more preferably about 15 to 35 ⁇ m.
• the thickness of the main layer is 0.02 to 5.0 mm, preferably 0.05 to 3.0 mm, more preferably about 0.1 to 2.0 mm.
• the protrusion shape is formed because the inorganic additive blended in the main layer serves as a nucleus and the cooling shrinkage of the resin is different.
• the protrusion shape may be transferred by an embossed roll, sea island-like precipitation using a difference in shrinkage of two or more resins, or spinodal decomposition.
• the resin sheet may be stretched (uniaxial stretching, biaxial stretching, etc.), but is usually an unstretched sheet in which a draw (drawing) is applied in the extrusion direction.
• the extruded sheet is usually cooled by a cooling roll (chill roll) and can be wound up.
• the melting temperature is about 150 to 250 ° C., preferably about 200 to 240 ° C.
• the obtained resin sheet may be further coated with an antistatic agent, a conductivity imparting agent such as carbon black or a metal oxide, a release agent, or the like on one or both sides.
• the polyolefin resin sheet of the present invention can be secondary molded by conventional thermal molding such as free blow molding, vacuum molding, bending, pressure forming, match molding, hot plate molding, and the like.
• secondary molded products include packaging materials, food containers, chemical containers, trays, embossed tapes, carrier tapes, and the like.
• the antistatic property in the thermoforming region where stretching and orientation occur can be greatly improved. More specifically, when the housing recess is thermoformed, the antistatic agent on the bottom wall and the inner and outer surfaces of the housing recess affected by heat bleeds, so that the antistatic property can be expressed at an early stage and can be sustained.
• the surface of the sheet or secondary molded product may be subjected to surface treatment (for example, discharge treatment such as corona discharge or glow discharge, acid treatment, wrinkle treatment, etc.).
• surface treatment for example, discharge treatment such as corona discharge or glow discharge, acid treatment, wrinkle treatment, etc.
• the additive shape of the main layer is transferred to the skin layer by high deep drawing or stretching, it is useful for improving water repellency.
• the thermoplastic resin sheet according to the present invention has the effect of imparting excellent antistatic properties to the synthetic polymer material without impairing its original hue and transparency. Further, since the antistatic agent can be efficiently added only to the surface by forming the skin layer, there is an effect that the manufacturing cost can be reduced. Furthermore, by making the skin layer thinner and adding an inorganic additive to the main layer, it is effective in generating protrusions on the surface during thermoforming and improving the strength of the molded body.
• the composition of the skin layer of the present invention has excellent antistatic properties while maintaining the original hue and transparency of the synthetic polymer material, and the main layer contributes greatly to the formation of protrusions and the improvement of rigidity. effective.
• the molded body according to the present invention is excellent in antistatic properties, rigidity, impact properties, and water repellency. For example, when instant noodles / instant food containers are used, the adhesion of the contents to the cup wall surface is suppressed. Furthermore, since it has water repellency, it is possible to clearly grasp the water level.
• melt index (MI, unit: g / 10 min)
• the melt index MI was measured according to a method defined in JISK7210. The measurement temperature is 230 ° C., and the test load is 21.18N.
• Weight ratio X (% by weight) of propylene-ethylene random copolymer portion to total block copolymer in propylene-ethylene block copolymer is the amount of heat of crystal melting of each of the propylene homopolymer portion and the total block copolymer.
• the particles Prior to mixing, the particles are measured with a laser diffraction / scattering particle size distribution meter in a powder state before mixing.
• a laser diffraction / scattering particle size distribution meter As the measuring device, for example, LA-920 type manufactured by HORIBA, Ltd. is preferable because of its excellent measurement accuracy.
• the measuring apparatus uses “Loresta GP” MCP-T600 manufactured by Mitsubishi Chemical Corporation and “HIRESTA UP” electrode UR-100 probe manufactured by Mitsubishi Chemical Corporation, and a sample is placed in an atmosphere of 23 ° C./50% RH, and 500 V A voltage was applied, and the surface resistivity was measured after charging for 1 minute (voltage application time: 1 minute). The numerical value of the surface resistivity is indicated by ⁇ / ⁇ .
• ⁇ is 1.0 ⁇ 10 16 ⁇ / ⁇ or less, preferably 1.0 ⁇ 10 14 to 1.0 ⁇ 10 8 ⁇ / ⁇ is ⁇ , and more preferably 1.0 ⁇ 10 12 to 1.0.
• ⁇ 10 9 ⁇ / ⁇ is ⁇ , which is excellent in antistatic effect and antistatic ability recovery.
• the seal adhesive strength is an index of the sealing property between the container and the lid.
• the initial strength is about 20N, preferably about 15N at the lowest, and the one with a significant decrease over time causes the seal to peel off during transportation. It is not preferable for practical use.
• “Initial weight” ⁇ “weight dropped” “attached weight” was classified according to the result of attached weight. A: 0.01 g or less, very good. A: 0.05 g or less and 0.01 g or more, and generally good. X: It is 0.05 g or more, which is not preferable.
• thermoplastic resin sheet PP (A-1), PP (A-2), PP (A-3)
• the propylene homopolymer and the ethylene / propylene block copolymer shown in Table 1 were used. Consists of a propylene homopolymer made of propylene homopolymer with a weight average molecular weight of 380,000.
• the block copolymer is pelletized from a gas phase polymerization method using a Ziegler catalyst and added during sheet production Used in the way.
• the main component of the antistatic agent is sodium sulfonate, and PP (A-2) is mixed with 18% by weight of the above-mentioned antistatic agent and 3% by weight of anti-blocking agent in a blender, and then extruded and kneaded to form pellets. did.
• a master batch in which the antistatic component was concentrated to a high concentration was prepared and used in a method of adding at the time of sheet production.
• Evolue linear low density polyethylene
• the main component of the white pigment is titanium oxide, which is represented by the chemical formula TiO 2 , measured with LA-920 type manufactured by Horiba, Ltd., and having a mean particle size of 15.0 ⁇ m.
• a master batch in which the white pigment component was concentrated to a high concentration was prepared, and this was used as a white pigment added during sheet production.
• Table 2 shows the sheet composition ratio and the composition thickness
• PP means polypropylene.
• PP and antistatic agent were mixed in advance with a Henschel mixer and then charged into an extruder fed to the skin layer side.
• the “inorganic additive” was dried at 80 ° C. for about 3 hours, and “PP” and “white pigment” were mixed in advance with a Henschel mixer and then fed into an extruder fed to the main layer side.
• the extruder As the extruder, a single screw extruder having a screw diameter of 135 mm and a screw length of 4500 mm was used on the skin layer side, and a single screw extruder having a screw diameter of 50 mm and a screw length of 2835 mm was used on the main layer side.
• the skin layer raw material After melt-kneading at an extruder cylinder temperature of 240 ° C., the skin layer raw material is supplied to the outer layer of the multifeed block laminated T die, the main layer raw material is supplied to the inner layer (opposite surface of the cooling roll) of the laminated die, Two types and two layers of laminated sheets having the main layer configuration were coextruded.
• a sheet was formed while casting was performed so that the main layer was in contact with a 35 ° C. cooling roll at a die temperature of 230 ° C. and rapidly solidified.
• the constituent thickness ratio of the skin / main layer was controlled by the extrusion amount ratio, and the die pressure was controlled and adjusted to be a constant pressure by the gear pump.
• the thickness flare in the TD direction was controlled by a heat bolt method and adjusted so as to be within ⁇ 8% of the center thickness.
• the sheet was cooled with a cooling roll to produce a sheet having a width of 650 mm and a thickness of 0.9 mm.
• the air gap was 1.1 mm
• the take-up speed was 12.0 m / min
• the take-up sheet total thickness was adjusted to 0.9 mm.
• the sheet was adjusted for 24 hours or more in a constant temperature and humidity state (temperature 23 ⁇ 2 ° C., humidity 50 ⁇ 5%), and the antistatic performance of the obtained sheet was measured. Details of the measurement results are shown
• the sheet produced according to the method described above was processed into a molded body using a vacuum / pressure forming machine FVS-500 manufactured by Wakisaka Engineering Co., Ltd. Specifically, the sheet obtained above is fixed to a square stainless steel frame of about 650 mm ⁇ 650 mm, and then heated with a far-red heater (temperature setting: 550 ° C.) for 20 seconds, so that the female mold is male.
• cup sample (dimensions: outer long side 130mm ⁇ inner short side 120mm ⁇ height 95mm, inner long side 115mm ⁇ short side 105mm, flange width one side 7mm, wall thickness : 0.2-0.3 mm, rectangular container).
• the molded cup sample was adjusted for 24 hours or more in a constant temperature and humidity state (temperature 23 ⁇ 2 ° C., humidity 50 ⁇ 5%), and a part thereof was cut out and subjected to water repellency, antistatic property and seal measurement. Details of the measurement results are shown in Table 3.

Landscapes

• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Laminated Bodies (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
• Wrappers (AREA)

Priority Applications (7)

Applications Claiming Priority (2)

Publications (1)

Family

ID=52828219

Family Applications (1)

Country Status (10)

Cited By (1)

Families Citing this family (6)

Citations (4)

Family Cites Families (17)

• 2013
  • 2013-10-17 JP JP2013216168A patent/JP5893598B2/ja active Active
• 2014
  • 2014-10-17 WO PCT/JP2014/077698 patent/WO2015056781A1/ja not_active Ceased
  • 2014-10-17 TW TW103135945A patent/TWI625233B/zh active
  • 2014-10-17 MY MYPI2016701385A patent/MY176223A/en unknown
  • 2014-10-17 KR KR1020167009864A patent/KR20160075516A/ko not_active Withdrawn
  • 2014-10-17 BR BR112016008533-7A patent/BR112016008533B1/pt active IP Right Grant
  • 2014-10-17 US US15/029,522 patent/US10953640B2/en active Active
  • 2014-10-17 CN CN201480056594.6A patent/CN105658431B/zh active Active
  • 2014-10-17 SG SG11201603031UA patent/SG11201603031UA/en unknown
• 2016
  • 2016-04-15 PH PH12016500709A patent/PH12016500709B1/en unknown

Patent Citations (4)

Also Published As

Similar Documents

Legal Events