Classifications

• • 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
• • 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
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
  • C08K5/098—Metal salts of carboxylic acids
• • 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
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
  • C08K5/101—Esters; Ether-esters of monocarboxylic acids
• • 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
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/20—Carboxylic acid amides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/02—Homopolymers or copolymers of hydrocarbons
  • C08L25/04—Homopolymers or copolymers of styrene
  • C08L25/08—Copolymers of styrene
  • C08L25/10—Copolymers of styrene with conjugated dienes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L47/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
  • C08L91/06—Waxes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
  • C09J153/02—Vinyl aromatic monomers and conjugated dienes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J191/00—Adhesives based on oils, fats or waxes; Adhesives based on derivatives thereof
  • C09J191/06—Waxes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J201/00—Adhesives based on unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils

Definitions

• the present invention relates to a composition and a molded body produced using the composition.
• a surface protective film is used to protect the lens surface of a prism sheet used in a liquid crystal display. Since this surface protective film is for protecting the lens surface of the prism sheet from scratches and dirt in the manufacturing process, it is peeled off after the manufacturing process is completed and does not remain in the final product. Therefore, the surface protective film has (1) low hardness; a sufficient contact area with the adherend can be secured, (2) good visibility; work process and appearance inspection are easy, (3) It must have heat-resistant properties, such as stable shape even at high temperatures, no generation of foreign matters, and (4) good molded appearance characteristics.
• a molded body made of, for example, an ethylene-vinyl acetate copolymer (EVA) or a conjugated diene polymer is formed on one surface of a base material layer made of a thermoplastic resin such as an olefin resin. What is formed is known.
• EVA ethylene-vinyl acetate copolymer
• a conjugated diene polymer is formed on one surface of a base material layer made of a thermoplastic resin such as an olefin resin. What is formed is known.
• a method for producing a pressure-sensitive adhesive film such as a surface protective film
• a method in which a pressure-sensitive adhesive is applied to a base material layer for example, refer to Patent Document 1
• a method in which the base material layer and a molded body are collectively formed by a coextrusion method for example, refer to Patent Document 2 and Patent Document 3.
• a method of producing a molded body by a co-extrusion method has been attracting attention in recent years because it is simple and can suppress the production cost.
• some aspects of the present invention solve at least a part of the above-described problems, thereby improving the productivity by suppressing blocking with a hopper and the like, and producing a molded body having excellent characteristics described above.
• a composition having excellent moldability is provided.
• the present invention has been made to solve at least a part of the above-described problems, and can be realized as the following aspects or application examples.
• thermoplastic resin (A) having an iodine value of 2 to 150 and water, Containing 100 to 2000 ppm of the water with respect to 100 parts by mass of the composition;
• the thermoplastic resin (A) has a repeating unit derived from a conjugated diene compound,
• the thermoplastic resin (A) has a crystal melting peak temperature of 50 ° C. to 95 ° C. and a heat of crystal melting of 10 J / g to 40 J / g.
• composition of the above application example It may further include at least one selected from the group consisting of polyethylene wax, polypropylene wax, fatty acid amide, fatty acid ester and fatty acid metal salt.
• thermoplastic resin (A) is It has a distribution of 0.3 to 10% by mass in the molecular weight section of 2 ⁇ 10 4 or more and less than 8 ⁇ 10 4 and 90 to 99.7% by mass in the molecular weight section of 8 ⁇ 10 4 or more and 1 ⁇ 10 6 or less. Can do.
• thermoplastic resin (A) may further have a repeating unit derived from an aromatic vinyl compound.
• composition of the above application example can be used in a coextrusion method.
• One aspect of the molded body according to the present invention is: It is produced using the composition of the said application example, It is characterized by the above-mentioned.
• composition of the present invention blocking in a hopper or the like can be suppressed when the pellet is introduced into a process for producing a pellet obtained by molding the composition or a production apparatus for producing a molded body. As a result, the productivity of the molded body is improved. Further, according to the composition of the present invention, it is possible to produce a molded body having a low hardness, excellent visibility, heat resistance, and excellent molded product characteristics such as a good molded appearance. Workability is also good.
• (meth) acryl is a concept encompassing both “acryl” and “methacryl”.
• ⁇ (meth) acrylate is a concept encompassing both “ ⁇ acrylate” and “ ⁇ methacrylate”.
• composition is a composition containing a thermoplastic resin (A) having an iodine value of 2 to 150 (hereinafter also simply referred to as “component (A)”) and water. And 100 to 2000 parts by mass of the composition containing 100 to 2000 ppm of water, the thermoplastic resin (A) has a repeating unit derived from a conjugated diene compound, and the thermoplastic resin (A) The melting peak temperature is 50 ° C. to 95 ° C., and the heat of crystal melting is 10 J / g to 40 J / g.
• thermoplastic resin (A) contained in the composition according to this embodiment has an iodine value of 2 to 150, contains a repeating unit derived from a conjugated diene compound, and has a crystal melting peak temperature of 50 ° C. to 95 ° C. It is a thermoplastic resin having a crystal melting heat quantity of 10 J / g to 40 J / g, and is used for producing a molded body.
• Component (A) has a repeating unit derived from a conjugated diene compound, but can further have a repeating unit derived from an aromatic vinyl compound as necessary.
• the repeating unit constituting the component (A) and the structure and properties of the component (A) will be described in order.
• Component (A) has a repeating unit derived from a conjugated diene compound.
• the conjugated diene compound include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene and the like. , One or more selected from these.
• 1,3-butadiene is particularly preferable.
• the content ratio of the repeating unit derived from the conjugated diene compound is preferably 30 to 100 parts by mass, and 35 to 100 parts by mass when the total repeating unit of the component (A) is 100 parts by mass. More preferably, it is a part.
• the content ratio of the repeating unit derived from the conjugated diene compound is in the above range, it becomes easy to produce a molded article having excellent viscoelasticity and strength.
• Aromatic Vinyl Component (A) may further have a repeating unit derived from an aromatic vinyl compound.
• aromatic vinyl compounds include styrene, tert-butylstyrene, ⁇ -methylstyrene, p-methylstyrene, p-ethylstyrene, divinylbenzene, 1,1-diphenylstyrene, vinylnaphthalene, vinylanthracene, N, N—
• Examples include diethyl-p-aminoethyl styrene and vinyl pyridine. Among these, styrene is particularly preferable.
• the content of the repeating unit derived from the aromatic vinyl compound is preferably 0 to 70 parts by mass when the total repeating unit of the component (A) is 100 parts by mass, More preferably, it is part by mass.
• repeating units Component (A) may have other repeating units.
• Examples of the repeating unit other than the above include a repeating unit derived from an unsaturated carboxylic acid ester, a repeating unit derived from an unsaturated carboxylic acid, and a repeating unit derived from an ⁇ , ⁇ -unsaturated nitrile compound.
• the unsaturated carboxylic acid ester is preferably a (meth) acrylic acid ester.
• (meth) acrylic acid esters include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, (meth ) N-butyl acrylate, i-butyl (meth) acrylate, n-amyl (meth) acrylate, i-amyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth ) 2-ethylhexyl acrylate, n-octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acryl
• unsaturated carboxylic acid examples include mono- or dicarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and the like. One type selected from these That can be the end. In particular, at least one selected from acrylic acid, methacrylic acid and itaconic acid is preferable.
• ⁇ , ⁇ -unsaturated nitrile compound examples include acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -ethylacrylonitrile, vinylidene cyanide, and one or more selected from these. Can be. Of these, at least one selected from acrylonitrile and methacrylonitrile is preferable, and acrylonitrile is particularly preferable.
• the component (A) may further have a repeating unit derived from the compound shown below.
• examples of such compounds include fluorine-containing compounds having an ethylenically unsaturated bond such as vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene; ethylenically unsaturated carboxylic acids such as (meth) acrylamide and N-methylolacrylamide.
• Acid alkyl amides Monoalkyl esters; Monoamides; Aminoethylacrylamide, dimethylaminomethylmethacrylamide, Methylaminopropylmethacrylamide Examples thereof include aminoalkylamides of ethylenically unsaturated carboxylic acids such as, and can be one or more selected from these.
• thermoplastic resin (A) in the present embodiment is not particularly limited, but is mainly composed of a block composed of repeating units derived from an aromatic vinyl compound and a conjugated diene compound.
• a block copolymer comprising a repeating unit derived from the above, a block of a repeating unit derived from a conjugated diene compound and having a low vinyl bond, and a block of a repeating unit derived from a conjugated diene compound and having a high vinyl bond.
• a polymer hydrogenated product is preferably used.
• a block copolymer of a conjugated diene compound such as butadiene or isoprene, a block copolymer of styrene and a conjugated diene compound such as butadiene or isoprene, or a hydrogenated product thereof is preferable.
• butadiene- A hydrogenated product of a butadiene-butadiene block copolymer, a styrene-butadiene-butadiene block copolymer, or a styrene-butadiene-styrene block copolymer is more preferable.
• Such a thermoplastic resin (A) can be synthesized by the methods described in Japanese Patent No. 3303467, Japanese Patent No. 3282364, Japanese Patent Application Laid-Open No. 2010-255007, and International Publication No. 2007/126081. .
• the content of the repeating unit derived from the aromatic vinyl compound in such a styrene-conjugated diene block copolymer is usually 5 to 40% by mass, preferably 10 to 35% by mass.
• the adhesive force can be further increased, and there is a tendency that no adhesive residue occurs due to cohesive failure.
• the iodine value of component (A) needs to be 2 to 150, preferably 2 to 100, more preferably 2 to 70.
• the iodine value is a value representing the amount of halogen that reacts with 100 g of the target substance in terms of grams of iodine, so the unit of iodine value is “g / 100 g”.
• the iodine value is 2 to 150 means “the iodine value is 2 to 150 g / 100 g”.
• thermoplastic resins are affected by the fact that the main chain contains many unsaturated bonds and the entanglement density of the main chain decreases, and the crystallinity decreases when the ethylene chain is broken by unsaturated bonds. This is thought to be due to a decrease in shape retention.
• the heat resistance tends to be deteriorated, and it may not be able to withstand a high temperature processing step such as coextrusion. This is considered to be the effect that the unsaturated bond contained in the thermoplastic resin reacts at a high temperature.
• thermoplastic resin (A) in the present invention can be measured according to the method described in “JIS K 0070: 1992”.
• the melt flow rate of the component (A) contained in the composition measured at 230 ° C. and 21.2 N load (MFR) is preferably from 0.1 to 100 g / 10 min, more preferably from 1.0 to 50 g / 10 min, and particularly preferably from 2.0 to 30 g / 10 min. If the MFR is less than 0.1 g / 10 min, the load during extrusion may be excessive. On the other hand, if the MFR exceeds 100 g / 10 min, there is a tendency to cause problems in extrusion moldability such as drawdown.
• the mass average molecular weight (Mw) of the component (A) is preferably 1 ⁇ 10 5 to 1 ⁇ 10 6 , and more preferably 2 ⁇ 10 5 to 5 ⁇ 10 5 .
• mass average molecular weight here refers to the mass average molecular weight of polystyrene conversion measured by GPC (gel permeation chromatography).
• a component (A) satisfies the requirements of following [1] and [2].
• Component (A) is present in a molecular weight section of 2 ⁇ 10 4 or more and less than 8 ⁇ 10 4 in an amount of 0.3 to 5% by mass, preferably 0.5 to 4.5% by mass.
• Component (A) is present in a molecular weight section of 8 ⁇ 10 4 or more and 1 ⁇ 10 6 or less in an amount of 90 to 99.7% by mass, preferably 95 to 99.5% by mass.
• Component (A) has at least one melting peak (crystal melting peak) in the range of 50 to 95 ° C.
• This melting peak temperature is measured by differential scanning calorimetry (DSC method). Specifically, using a differential scanning calorimeter (DSC), the sample component (A) was held at 200 ° C. for 10 minutes, then cooled to ⁇ 80 ° C. at a rate of 10 ° C./minute, and then ⁇ 80 This is the peak temperature of the heat flow rate (heat of crystal melting) when the temperature is raised at a rate of 10 ° C./min after being held at ° C. for 10 minutes.
• the heat of crystal melting at the melting peak is 10 to 40 J / g, preferably 15 to 35 J / g.
• the content ratio of the component (A) in the composition according to this embodiment is preferably 50 to 100% by mass, more preferably 55 to 100% by mass, particularly when the total mass of the composition is 100% by mass. Preferably, it is 60 to 100% by mass.
• the composition according to this embodiment may contain an anti-blocking agent (B) (hereinafter also simply referred to as “component (B)”).
• component (B) The composition according to this embodiment can contain at least one selected from the group consisting of polyethylene wax, polypropylene wax, fatty acid amide, fatty acid ester, and fatty acid metal salt.
• Anti-blocking agents (B) include fluoropolymers, polyethylene wax, polypropylene wax, ethylene-propylene copolymer wax, Fischer-Tropsch wax and their partial oxides or copolymers with ethylenically unsaturated carboxylic acids.
• Synthetic hydrocarbon waxes such as: modified waxes such as montan wax derivatives, paraffin wax derivatives, microcrystalline wax derivatives; hydrogenated waxes such as hardened castor oil and hardened castor oil derivatives; cetyl alcohol, stearic acid, 12-hydroxystearic acid, etc.
• fatty acid esters such as glyceryl stearate, polyethylene glycol stearate, stearyl stearate and isopropyl palmitate; fatty acid esters such as stearamide De; calcium stearate, fatty acid metal salts of lithium stearate; phthalic anhydride imide, chlorinated hydrocarbons, and the like.
• At least one selected from the group consisting of polyethylene wax, polypropylene wax, fatty acid amide, fatty acid ester, and fatty acid metal salt is preferable.
• these components are added to the composition according to the present embodiment, blocking with a hopper or the like can be more effectively suppressed in a manufacturing apparatus for manufacturing a pellet manufacturing process or a molded body.
• the content ratio of the component (B) in the pressure-sensitive adhesive composition according to this embodiment is preferably 0.02 parts by mass or more and 0.5 parts by mass or less with respect to 100 parts by mass in total of the components (A). It is more preferable that it is 0.03 mass part or more and 0.4 mass part or less.
• the thermoplastic resin (A) in the composition according to this embodiment is Ma (parts by mass) and the content of the antiblocking agent (B) is Mb (parts by mass)
• the thermoplastic resin (A) The amount ratio (Ma / Mb) of the blocking inhibitor (B) is preferably 200 to 4000, more preferably 250 to 3500.
• the composition according to this embodiment contains 100 to 2000 ppm of water with respect to 100 parts by mass of the composition, preferably 130 to 1000 ppm, more preferably 150 to 600 ppm.
• a molded article having excellent appearance and good appearance can be produced when the composition is molded. If the moisture content exceeds the above range, the moisture is heated in the cylinder of the injection molding machine and becomes bubbles in the thermoplastic elastomer, and bubbles are broken on the surface of the molded product, resulting in deterioration of the haze and poor appearance (siriburst leak). there is a possibility.
• the “water content of the composition” is synonymous with the water content of the pellets of the composition.
• the moisture content of the composition in the present invention is a value measured in accordance with JIS K7251 “Plastics—How to determine moisture content”.
• the moisture content of the composition should be controlled by heating the composition at a temperature and time suitable for the thermoplastic elastomer used, using a pellet dryer such as a dehumidifying dryer, vacuum dryer or hot air dryer. Can do.
• a pellet dryer such as a dehumidifying dryer, vacuum dryer or hot air dryer.
• the drying temperature is high and the drying time is long, the amount of water can be greatly reduced.
• the pellets of the composition may cause blocking or change in quality such as bleed out.
• the moisture content can be controlled by controlling the drying temperature and the drying time.
• composition according to the present embodiment in addition to the above-described components, as necessary, known components such as a radical generator, an anti-aging agent, a filler, a colorant, a flame retardant, and a tackifier. May be added.
• the radical generator generates radicals by irradiating with radiation such as heating or ultraviolet rays when producing a molded body, and crosslinks the component (A) to adjust the degree of crosslinking, thereby adjusting the hardness of the molded body. And heat resistance can be controlled.
• a photo radical generator that generates radicals by irradiation with light such as ultraviolet rays is preferable.
• Specific examples of the photo radical generator include hydroxy ketones, benzyl dimethyl ketals, amino ketones, acyl phosphine oxides, benzophenones and the like. These photo radical generators can be used singly or in combination of two or more.
• the radical generator is particularly preferably an oligomer type photoradical generator.
• the oligomer type photo radical generator is a low molecular weight polymer of a monomer having a functional group capable of generating radicals by irradiation with light such as ultraviolet rays.
• Such an oligomer type photo radical generator has a plurality of radical generation points in one molecule, so it is not easily affected by cross-linking inhibition by oxygen and can be cross-linked with a small amount. In particular, it is preferably used because it does not scatter in a solvent-free hot melt state and is not extracted from the polymer.
• oligomer type photo radical generator examples include an oligomer obtained by polymerizing acrylated benzophenone (trade name “Ebecryl P36” manufactured by UCB), 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy- An oligomer obtained by polymerizing a reaction product of a primary hydroxyl group of 2-methyl-1-propan-1-one (trade name “Irgacure 2959” manufactured by BASF Corporation) and 2-isocyanatoethyl methacrylate, 2-hydroxy-2-methyl- [4 -(1-Methylvinyl) phenyl] propanol oligomer (manufactured by Lamberti, trade name “EsacureKIP150”) and the like.
• the molecular weight of these oligomer-type photoradical generators is preferably up to about 50,000.
• antioxidants such as hindered phenols and phosphites
• UV absorbers such as benzotriazoles, benzophenones, and salicylic acid esters
• light stabilizers such as hindered amines are suitably added.
• inorganic fillers such as talc, silica and calcium carbonate, and organic fillers such as carbon fiber and amide fiber can be used.
• the molded body according to the present embodiment is produced using the above-described composition by a known method.
• a molded object is an adhesive film
• the manufacturing method of a base material layer, the composition for base materials, and an adhesive film is demonstrated.
• the composition for base materials for producing a base material layer contains a thermoplastic resin.
• thermoplastic resins olefin resins are preferred.
• polyethylene, polypropylene, and polybutene copolymers can be suitably used.
• polyethylene, polypropylene, and polybutene copolymers can be suitably used.
• These thermoplastic resins can be used alone or in combination of two or more.
• the composition for a substrate contains a thermoplastic resin as a main component, but for the purpose of preventing deterioration, for example, an antioxidant, an ultraviolet absorber, a light stabilizer such as a hindered amine light stabilizer, an antistatic agent, and the like.
• a thermoplastic resin for example, an antioxidant, an ultraviolet absorber, a light stabilizer such as a hindered amine light stabilizer, an antistatic agent, and the like.
• fillers such as calcium oxide, magnesium oxide, silica, zinc oxide, and titanium oxide, pigments, anti-tarnish agents, lubricants, anti-blocking agents, and the like can be appropriately added.
• the MFR of the thermoplastic resin contained in the base material composition measured at 230 ° C. and 21.2 N load is preferably 0.01 to 100 g / 10 minutes, preferably 0.1 to 80 g / 10 minutes. It is more preferable that Moreover, the thermoplastic resin contained in the base composition may be composed of only one kind of thermoplastic resin, or may be composed of a mixture of two or more kinds of thermoplastic resins.
• the base material layer may be a single layer or a multilayer of two or more layers. It is also possible to select a foam layer as the base material layer.
• the adhesive film which concerns on this embodiment is a film which has what is called a laminated structure provided with the base material layer and the adhesive layer formed in the single side
• a composition for adhesives the composition which concerns on this embodiment mentioned above can be used.
• the above-mentioned pressure-sensitive adhesive composition is applied to one or both sides of a base material layer having a thickness of about 2 to 150 ⁇ m, and ultraviolet (UV) or electron beam (EB) is applied as necessary. ), Etc., to form a pressure-sensitive adhesive layer having a thickness of 5 to 200 ⁇ m.
• UV ultraviolet
• EB electron beam
• it can also be set as the adhesive film for transcription
• the pressure-sensitive adhesive composition to the base material layer it can be applied in a state where the viscosity is reduced by heating if necessary.
• a hot melt coater, a comma roll, a gravure coater, A roll coater, kiss coater, slot die coater, squeeze coater or the like can be used.
• a pressure-sensitive adhesive film When producing a pressure-sensitive adhesive film by co-extrusion of the substrate composition and the pressure-sensitive adhesive composition, irradiate energy rays such as ultraviolet rays (UV) or electron beams (EB) as necessary. It can be produced by crosslinking to form an adhesive layer having a thickness of 5 to 200 ⁇ m.
• energy rays such as ultraviolet rays (UV) or electron beams (EB)
• UV ultraviolet rays
• EB electron beams
• the ultraviolet irradiation can be performed using an appropriate ultraviolet ray source such as a high-pressure mercury lamp, a low-pressure mercury lamp, an excimer laser, or a metal halide lamp.
• Dose of ultraviolet light is determined according to the degree of crosslinking in need, preferably 10mJ / cm 2 ⁇ 5000mJ / cm 2, more preferably 100mJ / cm 2 ⁇ 5000mJ / cm 2.
• a filter or a polyester sheet that cuts ultraviolet rays on the short wavelength side may be used as necessary.
• the temperature at the time of ultraviolet irradiation is not particularly limited, and heating conditions from room temperature to 140 ° C. can be appropriately selected.
• an electron beam source for example, a method using thermal electrons generated from a commercially available tungsten filament, a cold cathode method in which metal is generated through a high voltage pulse, and collision between ionized gaseous molecules and a metal electrode.
• a secondary electron system using secondary electrons generated can be given.
• the electron dose is determined according to the required degree of crosslinking, but is preferably 10 to 1000 kGy, more preferably 100 to 500 kGy.
• electron beam (EB) irradiation is more preferable than ultraviolet (UV) irradiation in terms of the ease of crosslinking of the adhesive layer.
• the pressure-sensitive adhesive layer irradiated with an electron beam is advantageous in that the generation of a gel component can be made extremely small, and the generation of a foreign substance derived from the gel component can be suppressed.
• the radical generator may be decomposed at the extrusion temperature, and there are production problems such as the necessity of producing in a light-shielding environment.
• the adhesive properties and heat resistance are improved by irradiating the adhesive layer formed of the adhesive composition with energy rays such as ultraviolet rays (UV) or electron beams (EB).
• energy rays such as ultraviolet rays (UV) or electron beams (EB).
• An adhesive layer can be prepared.
• the solvent-soluble content of the block copolymer is preferably 5 to 60% by mass, preferably 10 to 50% by mass.
• the degree of crosslinking may be adjusted as appropriate by selecting the amount of radical generator used or selecting the amount of energy ray irradiation.
• radical generators In place of radical generators, if sulfur, sulfur vulcanizing agents, or vulcanization accelerators generally used for rubber crosslinking are used, a large amount of sulfide ions and sulfate ions are generated and bleed out from the adhesive layer. Since it may be, it is not preferable. In addition, it may be difficult to obtain sufficient heat resistance by crosslinking using a peroxide.
• the adhesive film manufactured in this way can be used in shapes, such as a tape form and a sheet form, as needed.
• Synthesis example 1 A reaction vessel purged with nitrogen was charged with 800 parts of degassed and dehydrated cyclohexane, 20 parts of 1,3-butadiene and 0.03 part of tetrahydrofuran, and 0.09 part of n-butyllithium at a polymerization initiation temperature of 70 ° C. Was added, and the temperature rising polymerization was performed. After the polymerization conversion rate reached 99% or more, the reaction solution was cooled to 25 ° C. to prepare a polymer before hydrogenation. Subsequently, 80 parts of 1,3-butadiene and 5 parts of tetrahydrofuran were added, and further temperature rising polymerization was performed.
• Synthesis example 2 A reaction vessel purged with nitrogen was charged with 800 parts of degassed and dehydrated cyclohexane, 20 parts of 1,3-butadiene and 0.03 part of tetrahydrofuran, and 0.09 part of n-butyllithium at a polymerization initiation temperature of 70 ° C. Was added, and the temperature rising polymerization was performed. After the polymerization conversion rate reached 99% or more, the reaction liquid was cooled to 45 ° C., 80 parts of 1,3-butadiene and 1 part of tetrahydrofuran were added, and further temperature-initiated polymerization was performed.
• thermoplastic resin A-2 After the polymerization conversion rate reached 99% or more, 0.06 part of dichloromethylsilane was added, and the temperature rising polymerization was further performed. Thereafter, 0.04 part of diethylaluminum chloride and 0.06 part of bis (cyclopentadienyl) titanium furfuryloxychloride were added to the reaction vessel and stirred. Thereafter, a hydrogenation reaction was carried out in the same manner as in Synthesis Example 1 to obtain a thermoplastic resin A-2.
• thermoplastic resin A-3 was obtained in the same manner as in Synthesis Example 1 except that the hydrogenation reaction time was 2 hours.
• Synthesis example 7 A reaction vessel purged with nitrogen was charged with 600 parts of degassed and dehydrated cyclohexane, 20 parts of 1,3-butadiene, and 0.03 part of tetrahydrofuran, and 0.10 parts of n-butyllithium at a polymerization start temperature of 70 ° C. Was added, and the temperature rising polymerization was performed. After reaching a polymerization conversion rate of 99% or more, the reaction solution was cooled to 10 ° C., and then 80 parts of 1,3-butadiene and 15 parts of tetrahydrofuran were added, followed by further temperature rising polymerization.
• thermoplastic resin A-7 After the polymerization conversion rate reached 99% or more, 0.06 part of tetrachlorosilane was added, and the temperature rising polymerization was further performed. Thereafter, 0.03 part of diethylaluminum chloride and 0.06 part of bis (cyclopentadienyl) titanium furfuryloxychloride were added to the reaction vessel and stirred. Thereafter, a hydrogenation reaction was carried out for 1 hour in the same manner as in Synthesis Example 1 to obtain a thermoplastic resin A-7.
• Synthesis example 8 A reaction vessel purged with nitrogen was charged with 600 parts of degassed and dehydrated cyclohexane, 20 parts of 1,3-butadiene, and 0.03 part of tetrahydrofuran, and 0.06 part of n-butyllithium at a polymerization start temperature of 70 ° C. Was added, and the temperature rising polymerization was performed. After the polymerization conversion reached 99% or more, the reaction solution was cooled to 10 ° C., and then 0.05 parts of n-butyllithium, 80 parts of 1,3-butadiene and 15 parts of tetrahydrofuran were added, and the temperature was further increased. Warm polymerization was performed.
• thermoplastic resin A-8 After the polymerization conversion rate reached 99% or more, 0.06 part of tetrachlorosilane was added, and the temperature rising polymerization was further performed. Thereafter, 0.03 part of diethylaluminum chloride and 0.06 part of bis (cyclopentadienyl) titanium furfuryloxychloride were added to the reaction vessel and stirred. Thereafter, a hydrogenation reaction was carried out in the same manner as in Synthesis Example 1 to obtain a thermoplastic resin A-8.
• Synthesis Example 9 A reaction vessel purged with nitrogen was charged with 600 parts of degassed and dehydrated cyclohexane, 20 parts of 1,3-butadiene, and 0.03 part of tetrahydrofuran, and 0.10 parts of n-butyllithium at a polymerization start temperature of 70 ° C. Was added, and the temperature rising polymerization was performed. After the polymerization conversion rate reached 99% or more, the reaction solution was cooled to 10 ° C., and then 50 parts of 1,3-butadiene, 30 parts of styrene and 15 parts of tetrahydrofuran were added, and further temperature rising polymerization was performed. .
• thermoplastic resin A-9 After the polymerization conversion rate reached 99% or more, 0.06 part of tetrachlorosilane was added, and the temperature rising polymerization was further performed. Thereafter, 0.03 part of diethylaluminum chloride and 0.06 part of bis (cyclopentadienyl) titanium furfuryloxychloride were added to the reaction vessel and stirred. Thereafter, a hydrogenation reaction was carried out in the same manner as in Synthesis Example 1 to obtain a thermoplastic resin A-9.
• Synthesis Example 10 A reaction vessel purged with nitrogen was charged with 800 parts of degassed and dehydrated cyclohexane, 40 parts of 1,3-butadiene, and 0.03 part of tetrahydrofuran, and 0.09 part of n-butyllithium at a polymerization initiation temperature of 70 ° C. Was added, and the temperature rising polymerization was performed. After the polymerization conversion rate reached 99% or more, the reaction solution was cooled to 10 ° C., 60 parts of 1,3-butadiene and 15 parts of tetrahydrofuran were added, and further temperature-initiated polymerization was performed.
• thermoplastic resin A-10 After the polymerization conversion rate reached 99% or more, 0.06 part of dichloromethylsilane was added, and the temperature rising polymerization was further performed. Thereafter, 0.04 part of diethylaluminum chloride and 0.06 part of bis (cyclopentadienyl) titanium furfuryloxychloride were added to the reaction vessel and stirred. Thereafter, a hydrogenation reaction was carried out in the same manner as in Synthesis Example 1 to obtain a thermoplastic resin A-10.
• Synthesis Example 11 A nitrogen-substituted reaction vessel was charged with 500 parts of degassed and dehydrated cyclohexane, 6 parts of styrene, and 13 parts of tetrahydrofuran, and 0.10 parts of n-butyllithium was added at a polymerization initiation temperature of 40 ° C. Polymerization was performed. After the polymerization conversion rate reached 99% or more, the reaction solution was cooled to 10 ° C., and then 94 parts of 1,3-butadiene was added to carry out further temperature rising polymerization. After the polymerization conversion rate reached 99% or more, 0.07 part of dichlorodimethylsilane was added, and the temperature rising polymerization was further performed.
• thermoplastic resin A-11 a thermoplastic resin A-11.
• Synthesis Example 12 A nitrogen-substituted reaction vessel was charged with 800 parts of degassed and dehydrated cyclohexane, 15 parts of 1,3-butadiene, and 0.03 part of tetrahydrofuran, and 0.09 part of n-butyllithium at a polymerization initiation temperature of 70 ° C. Was added, and the temperature rising polymerization was performed. After the polymerization conversion rate reached 99% or more, the reaction solution was cooled to 15 ° C., 70 parts of 1,3-butadiene and 15 parts of tetrahydrofuran were added, and further temperature-initiated polymerization was performed.
• thermoplastic resin A-12 After the polymerization conversion rate reached 99% or more, 15 parts of styrene was added, and the temperature rising polymerization was further performed. Thereafter, 0.04 part of diethylaluminum chloride and 0.06 part of bis (cyclopentadienyl) titanium furfuryloxychloride were added to the reaction vessel and stirred. Thereafter, a hydrogenation reaction was carried out in the same manner as in Synthesis Example 1 to obtain a thermoplastic resin A-12.
• thermoplastic resin A-13 was obtained in the same manner as in Synthesis Example 11 except that the hydrogenation reaction time was 15 minutes.
• thermoplastic resin A-14 was obtained in the same manner as in Synthesis Example 10 except that the hydrogenation reaction time was 12 hours.
• thermoplastic resin The total bonded styrene content, vinyl bond content, iodine value, crystal melting peak temperature, crystal melting heat amount and molecular weight of the produced thermoplastic resin were measured by the following methods. The results are shown in Tables 1 and 2.
• thermoplastic resin GPC analysis of the thermoplastic resin was performed. Specifically, using gel permeation chromatography (GPC, trade name “HLC-8120GPC”, manufactured by Tosoh Finechem Corporation, column: manufactured by Tosoh Corporation, GMH-XL), the number average molecular weight (Mn) in terms of polystyrene. , Mass average molecular weight (Mw), and molecular weight distribution (Mn / Mw) were determined. Tetrahydrofuran was used as the solvent.
• GPC gel permeation chromatography
• the total area of the molecular weight distribution curve was calculated from the chromatogram measured in the molecular weight evaluation of the thermoplastic resin.
• the peak area S1 of the molecular weight section of 2 ⁇ 10 4 or more and less than 8 ⁇ 10 4 and the peak area S2 of the molecular weight section of 8 ⁇ 10 4 or more and 1 ⁇ 10 6 or less were calculated.
• S1 a content ratio of molecular weight of 2 ⁇ 10 4 or more and less than 8 ⁇ 10 4
• the content ratio of molecular weight 8 ⁇ 10 4 or more and 1 ⁇ 10 6 or less was calculated by dividing S2 by the total area.
• Example 1 0.05 parts of calcium stearate is added to the thermoplastic resin produced, put into a 40 mm single screw extruder manufactured by Ikegai, melt kneaded, extruded into a strand, cooled and solidified in water, and then a strand cutter manufactured by Giken Koki Co., Ltd. To obtain a cylindrical undried pellet. 100 parts by weight of undried pellets and 0.10 parts by weight of calcium stearate (manufactured by Wako Pure Chemical Industries, Ltd.) are added to Supermixer SMV-20 and stirred at a stirring speed of 300 rpm for 5 minutes. Was applied.
• composition (pellet) prepared on the mirror plate and a 2 mm-thick spacer were placed and heat-pressed at 190 ° C. for 30 minutes using a hot press molding machine “AT-37” manufactured by Iwaki Industry Co., Ltd. A press sheet was obtained.
• the prepared sheets were overlapped to a thickness of 6 mm, and the value after 15 seconds was read using a type A durometer described in JIS6253.
• AA Hardness is less than 50, and it is possible to determine that it is extremely excellent because the contact area with the adherend can be greatly improved in bonding with the adherend.
• -"A” Hardness is more than 50 and less than 65, and it can be judged that it is excellent because it can improve the contact area with the adherend in bonding with the adherend.
• B Hardness is more than 65 and less than 75, and the contact area with the adherend is small in bonding with the adherend, but it can be judged as good because it can be used practically.
• C Hardness is over 75, shape change with respect to the adherend cannot be caused, and it cannot be used practically, so it can be determined as defective.
• the sheet prepared above was measured according to JIS-K7136 (2000) using “HAZEMETER HM-150” manufactured by Murakami Color Research Laboratory. “A”: Haze is less than 15, and it can be determined that the visibility is extremely excellent. “B”: Haze is more than 15 and less than 20, and is inferior in visibility, but can be judged good because it can be used practically. “C”: Haze is over 20 and the visibility is poor, so it cannot be put to practical use and can be judged as defective.
• composition (pellet) prepared above was cut, weighed 20.0 mg, immersed in 20 mL of orthodichlorobenzene at 135 ° C. for 1 hour, and filtered to collect the eluted component A.
• the prepared adhesive film was cut and weighed 20.0 mg, immersed in 20 mL of orthodichlorobenzene at 135 ° C. for 1 hour, and filtered to collect the eluted component B.
• GPC measurement of the elution components A and B was performed, the presence or absence of the gel component in the film forming step was evaluated as follows, and the heat resistance of the composition (pellet) was evaluated. The results are shown in Table 3.
• the GPC intensity of the eluted component B is extremely small, and the gel component due to the increase in quantity is extremely large. It is desirable that the amount of foreign matter generated during the pelletization or film forming process causes a film defect or a yield failure and is small.
• the GPC was evaluated at a high temperature GPC measurement system “PL-GPC220” manufactured by Polymer Laboratories, a column “MIXED-B” manufactured by Polymer Laboratories, and a measurement temperature of 135 ° C.
• Solution storage stability 15 g of the composition and 85 g of cyclohexane were added to Separa and dissolved by heating to 80 ° C. Thereafter, the cyclohexane solution was recovered in 250 mL polyvin, cooled to 40 ° C., and allowed to stand at 40 ° C. for 24 hours. From the appearance of the polymer solution after standing and the solution viscosity, the solution storage stability was judged as follows. The solution viscosity was measured using a viscometer TVB10M manufactured by Toki Sangyo Co., Ltd. at a measurement temperature of 40 ° C. “A”: The polymer solution flowed when the polybin was tilted 90 degrees.
• the viscosity of the solution was 3,000 mPa ⁇ s or less, the fluidity of the solution was high, and the solution storage stability was judged to be excellent. Since the solution storage stability is excellent, it can be easily transferred by piping or transferred to a container, and can be easily performed by a wet process such as casting or coating.
• B When the polybin was tilted 90 degrees, the polymer solution flowed. Since the viscosity of the solution was 3,000 mPa ⁇ s or more, it was judged that the solution storage stability was good although the fluidity of the solution was slightly low. Since the solution storage stability is good, it can be applied to a wet process.
• C When the polybin was tilted 90 degrees, the polymer solution did not flow. Since the solution did not flow and the viscosity of the solution could not be measured, the solution storage stability was judged to be poor.
• Solvent resistance A composition (pellet) prepared on a mirror face plate and a spacer having a thickness of 2 mm are placed, and by using a hot press molding machine “AT-37” manufactured by Iwaki Industry Co., Ltd., heat-pressed at 190 ° C. for 30 minutes, A 2 mm thick press sheet was obtained.
• the produced press sheet was cut into 10 mm ⁇ 30 mm and immersed in 50 g of oleic acid for 72 hours in an environment of 30 ° C.
• the press sheet after immersion was taken out with tweezers, and the solvent resistance was judged from the appearance of the press sheet and the amount of dimensional change as follows. The dimensional change was evaluated as follows.
• Example 2 to 12 Comparative Examples 1 to 8 Composition was the same as in Example 1 except that thermoplastic resins A-2 to A-14 were used and the type and amount of antiblocking agent (B) and the amount of water were changed to the components and amounts shown in Tables 3 to 4.
• a product (pellet) was prepared and evaluated in the same manner as in Example 1. The results are shown in Tables 3-4. The water content was adjusted by changing the drying time of the composition (pellet) as appropriate.
• the compositions according to the present invention are excellent in productivity and workability in pellet production, exhibit high adhesive strength to adherends, and have a gel foreign matter amount and appearance during extrusion film formation. It was possible to produce an extruded product that was excellent and excellent in visibility when the film was used. According to Comparative Examples 1 to 8, if the amount of water is large, poor appearance during extrusion film forming occurs, if the amount of water is small, blocking occurs when pellets are dried, and the yield decreases when the iodine value of the thermoplastic resin is high. Further, it was found that when the iodine value of the thermoplastic resin is low, the hardness, haze, and solution storage stability are deteriorated.
• the present invention is not limited to the above embodiment, and various modifications can be made.
• the present invention includes configurations that are substantially the same as the configurations described in the embodiments (for example, configurations that have the same functions, methods, and results, or configurations that have the same objects and effects).
• the present invention also includes a configuration in which a non-essential part of the configuration described in the above embodiment is replaced with another configuration.
• the present invention includes a configuration that achieves the same effects as the configuration described in the above embodiment or a configuration that can achieve the same object.
• the present invention includes a configuration obtained by adding a known technique to the configuration described in the above embodiment.

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