WO2018131211A1 - Composition and molded object - Google Patents
Composition and molded object Download PDFInfo
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- WO2018131211A1 WO2018131211A1 PCT/JP2017/033004 JP2017033004W WO2018131211A1 WO 2018131211 A1 WO2018131211 A1 WO 2018131211A1 JP 2017033004 W JP2017033004 W JP 2017033004W WO 2018131211 A1 WO2018131211 A1 WO 2018131211A1
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Classifications
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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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Abstract
Description
本発明に係る組成物の一態様は、
ヨウ素価が2~150である熱可塑性樹脂(A)と、水とを含有する組成物であって、
前記組成物100質量部に対して、前記水を100~2000ppm含有し、
前記熱可塑性樹脂(A)が共役ジエン化合物に由来する繰り返し単位を有し、
前記熱可塑性樹脂(A)の、結晶融解ピーク温度が50℃~95℃であり、かつ、結晶融解熱量が10J/g~40J/gであることを特徴とする。 [Application Example 1]
One aspect of the composition according to the present invention is:
A composition comprising a 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.
上記適用例の組成物において、
さらに、ブロッキング防止剤(B)を含有し、
前記熱可塑性樹脂(A)の含有量をMa(質量部)、前記ブロッキング防止剤(B)の含有量をMb(質量部)としたときに、Ma/Mb=200~4000であることができる。 [Application Example 2]
In the composition of the above application example,
Furthermore, it contains an antiblocking agent (B),
When the content of the thermoplastic resin (A) is Ma (parts by mass) and the content of the antiblocking agent (B) is Mb (parts by mass), Ma / Mb = 200 to 4000. .
上記適用例の組成物において、
ポリエチレンワックス、ポリプロピレンワックス、脂肪酸アミド、脂肪酸エステル及び脂肪酸金属塩からなる群より選ばれる少なくとも1種をさらに含むことができる。 [Application Example 3]
In the 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.
上記適用例の組成物において、
前記熱可塑性樹脂(A)が、
2×104以上8×104未満の分子量区間に0.3~10質量%、及び
8×104以上1×106以下の分子量区間に90~99.7質量%存在する分布を有することができる。 [Application Example 4]
In the composition of the above application example,
The 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.
上記適用例の組成物において、
前記熱可塑性樹脂(A)が、芳香族ビニル化合物に由来する繰り返し単位をさらに有することができる。 [Application Example 5]
In the composition of the above application example,
The thermoplastic resin (A) may further have a repeating unit derived from an aromatic vinyl compound.
上記適用例の組成物は、共押出し法に用いられることができる。 [Application Example 6]
The composition of the above application example can be used in a coextrusion method.
本発明に係る成形体の一態様は、
上記適用例の組成物を用いて作成されることを特徴とする。 [Application Example 7]
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.
本実施形態に係る組成物は、ヨウ素価が2~150である熱可塑性樹脂(A)(以下、単に「成分(A)」ともいう。)と、水とを含有する組成物であって、前記組成物100質量部に対して前記水を100~2000ppm含有し、前記熱可塑性樹脂(A)が共役ジエン化合物に由来する繰り返し単位を有し、前記熱可塑性樹脂(A)の、結晶融解ピーク温度が50℃~95℃であり、かつ、結晶融解熱量が10J/g~40J/gであることを特徴とする。
以下、本実施形態に係る組成物に含有される各成分について詳細に説明する。 1. Composition The composition according to this embodiment 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.
Hereinafter, each component contained in the composition according to the present embodiment will be described in detail.
本実施形態に係る組成物に含まれる熱可塑性樹脂(A)は、ヨウ素価が2~150であり、共役ジエン化合物に由来する繰り返し単位を含有し、結晶融解ピーク温度が50℃~95℃であり、かつ、結晶融解熱量が10J/g~40J/gである熱可塑性樹脂であり、成形体を作製するために用いられる。 1.1. Thermoplastic resin (A)
The 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.
成分(A)は、共役ジエン化合物に由来する繰り返し単位を有する。共役ジエン化合物としては、例えば1,3-ブタジエン、2-メチル-1,3-ブタジエン、2,3-ジメチル-1,3-ブタジエン、2-クロル-1,3-ブタジエンなどを挙げることができ、これらのうちから選択される1種以上であることができる。共役ジエン化合物としては、1,3-ブタジエンが特に好ましい。 1.1.1. Repeating unit derived from a conjugated diene compound Component (A) has a repeating unit derived from a conjugated diene compound. Examples of 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. As the conjugated diene compound, 1,3-butadiene is particularly preferable.
成分(A)は、芳香族ビニル化合物に由来する繰り返し単位をさらに有してもよい。芳香族ビニル化合物としては、例えばスチレン、tert-ブチルスチレン、α-メチルスチレン、p-メチルスチレン、p-エチルスチレン、ジビニルベンゼン、1,1-ジフェニルスチレン、ビニルナフタレン、ビニルアントラセン、N,N-ジエチル-p-アミノエチルスチレン、ビニルピリジン等を挙げることができる。これらの中でも、スチレンが特に好ましい。 1.1.2. Repeating Unit Derived from Aromatic Vinyl Compound Component (A) may further have a repeating unit derived from an aromatic vinyl compound. Examples of aromatic vinyl compounds include styrene, tert-butylstyrene, α-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.
成分(A)は、上記以外の繰り返し単位を有してもよい。上記以外の繰り返し単位としては、例えば、不飽和カルボン酸エステルに由来する繰り返し単位、不飽和カルボン酸に由来する繰り返し単位、α,β-不飽和ニトリル化合物に由来する繰り返し単位等が挙げられる。 1.1.3. Other 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 α, β-unsaturated nitrile compound.
本実施形態における熱可塑性樹脂(A)としては、特に限定されないが、芳香族ビニル化合物に由来する繰り返し単位からなるブロックと、主に共役ジエン化合物に由来する繰り返し単位からなるブロック共重合体や、共役ジエン化合物に由来しビニル結合量が低い繰り返し単位のブロックと、共役ジエン化合物に由来しビニル結合量が高い繰り返し単位のブロックとを有するブロック共重合体の水素添加物が好ましく用いられる。具体的にはブタジエンやイソプレンなどの共役ジエン化合物のブロック共重合体、スチレンとブタジエンやイソプレンなどの共役ジエン化合物とのブロック共重合体、あるいはその水素添加物が好ましく、耐久性の観点からブタジエン-ブタジエン-ブタジエンブロック共重合体、スチレン-ブタジエン-ブタジエンブロック共重合体、スチレン-ブタジエン-スチレンブロック共重合体の水素添加物がより好ましい。このような熱可塑性樹脂(A)は、特許第3303467号公報、特許第3282364号公報、特開2010-255007号公報や国際公開第2007/126081号に記載されている方法により合成することができる。 1.1.4. The structure, properties and synthesis method of the thermoplastic resin (A) The 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. Specifically, 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. From the viewpoint of durability, 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. .
[1]2×104以上8×104未満の分子量区間に成分(A)が0.3~5質量%、好ましくは0.5~4.5質量%存在すること。
[2]8×104以上1×106以下の分子量区間に成分(A)が90~99.7質量%、好ましくは95~99.5質量%存在すること。 Moreover, it is preferable that the molecular weight distribution of a component (A) satisfy | fills the requirements of following [1] and [2].
[1] 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.
[2] 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.
本実施形態に係る組成物は、ブロッキング防止剤(B)(以下、単に「成分(B)」ともいう。)を含有することができる。本実施形態に係る組成物は、ポリエチレンワックス、ポリプロピレンワックス、脂肪酸アミド、脂肪酸エステル及び脂肪酸金属塩からなる群より選ばれる少なくとも1種を含有することができる。このような化合物を組成物が含有することにより、ホッパーなどでのブロッキング(詰まり)を抑制して成形体の生産性をさらに向上させることができる。 1.2. Antiblocking agent (B)
The composition according to this embodiment may contain an anti-blocking agent (B) (hereinafter also simply referred to as “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. When the composition contains such a compound, blocking (clogging) with a hopper or the like can be suppressed, and the productivity of the molded body can be further improved.
本実施形態に係る組成物は、組成物100質量部に対して水を100~2000ppm含有するが、130~1000ppm含有することが好ましく、150~600ppm含有することがより好ましい。水分含有率が前記範囲内にあると、組成物を成形する際に、成形加工性に優れ、良好な外観の成形体を製造することができる。水分含有率が前記範囲を超えると、水分が射出成形機のシリンダー内で加熱され熱可塑性エラストマー中で気泡となり、成形品表面で破泡してHazeの悪化や外観不良(シリバーストリーク)になる可能性がある。 1.3. Water 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. When the moisture content is in the above range, 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.
本実施形態に係る組成物には、上記の各成分の他、必要に応じて、ラジカル発生剤、老化防止剤、充填剤、着色剤、難燃剤、粘着付与剤等の公知の成分を添加してもよい。 1.4. Other components In the 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.
本実施形態に係る成形体は、公知の方法により上述の組成物を用いて作成される。例えば成形体が粘着フィルムである場合、基材層と、当該基材層の片面又は両面に形成された粘着層とを備えたフィルムとなる。以下、基材層及び基材用組成物、粘着フィルムの製造方法について説明する。 2. Molded body The molded body according to the present embodiment is produced using the above-described composition by a known method. For example, when a molded object is an adhesive film, it becomes a film provided with the base material layer and the adhesive layer formed in the single side | surface or both surfaces of the said base material layer. Hereinafter, the manufacturing method of a base material layer, the composition for base materials, and an adhesive film is demonstrated.
基材層を作製するための基材用組成物は、熱可塑性樹脂を含有することが好ましい。熱可塑性樹脂の中でも、オレフィン系樹脂が好ましい。 <Base material layer and base material composition>
It is preferable that the composition for base materials for producing a base material layer contains a thermoplastic resin. Of the thermoplastic resins, olefin resins are preferred.
本実施形態に係る粘着フィルムは、基材層と、当該基材層の片面又は両面に形成された粘着層とを備えた、いわゆる積層構造を有するフィルムである。したがって、本実施形態に係る粘着フィルムは、(1)塗布法;予め作製された基材層の片面又は両面に粘着剤用組成物を塗布して粘着層を形成した後に巻き取る方法、(2)共押出し法;基材用組成物と粘着剤用組成物とを、溶融共押出装置等を使用して共押出成形することにより、基材層の片面又は両面に粘着層を形成する方法、などの方法により製造することができる。なお、粘着剤用組成物としては、上述した本実施形態に係る組成物を使用することができる。 <Method for producing adhesive film>
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 | surface or both surfaces of the said base material layer. Therefore, the pressure-sensitive adhesive film according to this embodiment is obtained by (1) a coating method; a method in which a pressure-sensitive adhesive composition is formed on one surface or both surfaces of a base material layer prepared in advance and then wound up, and (2) ) Coextrusion method; a method of forming an adhesive layer on one or both sides of a substrate layer by coextruding the composition for a substrate and the composition for an adhesive using a melt coextrusion apparatus or the like, It can be manufactured by such a method. In addition, as a composition for adhesives, the composition which concerns on this embodiment mentioned above can be used.
以下、本発明を実施例に基づいて具体的に説明するが、本発明はこれらの実施例に限定されるものではない。実施例、比較例中の「部」および「%」は、特に断らない限り質量基準である。 3. EXAMPLES Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. “Part” and “%” in Examples and Comparative Examples are based on mass unless otherwise specified.
窒素置換された反応容器に、脱気・脱水されたシクロヘキサン800部、1,3-ブタジエン20部、及びテトラヒドロフラン0.03部を仕込み、重合開始温度70℃にてn-ブチルリチウム0.09部を加えて、昇温重合を行った。重合転化率が99%以上に達した後、反応液を25℃に冷却し、水素添加前の重合体を作成した。引き続き、1,3-ブタジエン80部、及びテトラヒドロフラン5部を加えて、さらに昇温重合を行った。重合転化率が99%以上に達した後、ジクロロメチルシラン0.06部を加えて、さらに昇温重合を行った。その後、反応容器内に、ジエチルアルミニウムクロライド0.04部及びビス(シクロペンタジエニル)チタニウムフルフリルオキシクロライド0.06部を加え、撹拌した。水素ガス供給圧0.7MPa-Gauge、反応温度80℃で水素添加反応を開始し、3時間後に反応溶液を60℃・常圧とし、反応容器より抜き出すことにより、熱可塑性樹脂A-1を得た。 3.1.1. 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. 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. A hydrogenation reaction is started at a hydrogen gas supply pressure of 0.7 MPa-Gauge and a reaction temperature of 80 ° C., and after 3 hours, the reaction solution is brought to 60 ° C. and normal pressure, and is taken out from the reaction vessel to obtain a thermoplastic resin A-1. It was.
窒素置換された反応容器に、脱気・脱水されたシクロヘキサン800部、1,3-ブタジエン20部、及びテトラヒドロフラン0.03部を仕込み、重合開始温度70℃にてn-ブチルリチウム0.09部を加えて、昇温重合を行った。重合転化率が99%以上に達した後、反応液を45℃に冷却し、1,3-ブタジエン80部、及びテトラヒドロフラン1部を加えて、さらに昇温重合を行った。重合転化率が99%以上に達した後、ジクロロメチルシラン0.06部を加えて、さらに昇温重合を行った。その後、反応容器内に、ジエチルアルミニウムクロライド0.04部及びビス(シクロペンタジエニル)チタニウムフルフリルオキシクロライド0.06部を加え、撹拌した。その後、合成例1と同様に水素添加反応を行い熱可塑性樹脂A-2を得た。 3.1.2. 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. 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.
水素添加反応時間を2時間としたこと以外は合成例1と同様の方法にて、熱可塑性樹脂A-3を得た。 3.1.3. Synthesis example 3
A thermoplastic resin A-3 was obtained in the same manner as in Synthesis Example 1 except that the hydrogenation reaction time was 2 hours.
水素添加反応時間をそれぞれ2時間、1時間、40分に変更した以外は合成例2と同様の方法により、熱可塑性樹脂A-4、A-5、A-6を得た。 3.1.4. Synthesis Examples 4, 5, 6
Thermoplastic resins A-4, A-5, and A-6 were obtained in the same manner as in Synthesis Example 2, except that the hydrogenation reaction time was changed to 2 hours, 1 hour, and 40 minutes, respectively.
窒素置換された反応容器に、脱気・脱水されたシクロヘキサン600部、1,3-ブタジエン20部、及びテトラヒドロフラン0.03部を仕込み、重合開始温度70℃にてn-ブチルリチウム0.10部を加えて、昇温重合を行った。重合転化率が99%以上に達した後、反応液を10℃に冷却し、次いで、1,3-ブタジエン80部、及びテトラヒドロフラン15部を加えて、さらに昇温重合を行った。重合転化率が99%以上に達した後、テトラクロロシラン0.06部を加えて、さらに昇温重合を行った。その後、反応容器内に、ジエチルアルミニウムクロライド0.03部及びビス(シクロペンタジエニル)チタニウムフルフリルオキシクロライド0.06部を加え、撹拌した。その後、合成例1と同様の方法により水素添加反応を1時間行い熱可塑性樹脂A-7を得た。 3.1.5. 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. 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.
窒素置換された反応容器に、脱気・脱水されたシクロヘキサン600部、1,3-ブタジエン20部、及びテトラヒドロフラン0.03部を仕込み、重合開始温度70℃にてn-ブチルリチウム0.06部を加えて、昇温重合を行った。重合転化率が99%以上に達した後、反応液を10℃に冷却し、次いで、n-ブチルリチウム0.05部、1,3-ブタジエン80部、及びテトラヒドロフラン15部を加えて、さらに昇温重合を行った。重合転化率が99%以上に達した後、テトラクロロシラン0.06部を加えて、さらに昇温重合を行った。その後、反応容器内に、ジエチルアルミニウムクロライド0.03部及びビス(シクロペンタジエニル)チタニウムフルフリルオキシクロライド0.06部を加え、撹拌した。その後、合成例1と同様に水素添加反応を行い熱可塑性樹脂A-8を得た。 3.1.6. 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. 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.
窒素置換された反応容器に、脱気・脱水されたシクロヘキサン600部、1,3-ブタジエン20部、及びテトラヒドロフラン0.03部を仕込み、重合開始温度70℃にてn-ブチルリチウム0.10部を加えて、昇温重合を行った。重合転化率が99%以上に達した後、反応液を10℃に冷却し、次いで、1,3-ブタジエン50部、スチレン30部、及びテトラヒドロフラン15部を加えて、さらに昇温重合を行った。重合転化率が99%以上に達した後、テトラクロロシラン0.06部を加えて、さらに昇温重合を行った。その後、反応容器内に、ジエチルアルミニウムクロライド0.03部及びビス(シクロペンタジエニル)チタニウムフルフリルオキシクロライド0.06部を加え、撹拌した。その後、合成例1と同様に水素添加反応を行い熱可塑性樹脂A-9を得た。 3.1.7. 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. . 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.
窒素置換された反応容器に、脱気・脱水されたシクロヘキサン800部、1,3-ブタジエン40部、及びテトラヒドロフラン0.03部を仕込み、重合開始温度70℃にてn-ブチルリチウム0.09部を加えて、昇温重合を行った。重合転化率が99%以上に達した後、反応液を10℃に冷却し、1,3-ブタジエン60部、及びテトラヒドロフラン15部を加えて、さらに昇温重合を行った。重合転化率が99%以上に達した後、ジクロロメチルシラン0.06部を加えて、さらに昇温重合を行った。その後、反応容器内に、ジエチルアルミニウムクロライド0.04部及びビス(シクロペンタジエニル)チタニウムフルフリルオキシクロライド0.06部を加え、撹拌した。その後、合成例1と同様に水素添加反応を行い熱可塑性樹脂A-10を得た。 3.1.8. 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. 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.
窒素置換された反応容器に、脱気・脱水されたシクロヘキサン500部、スチレン6部、及びテトラヒドロフラン13部を仕込み、重合開始温度40℃にてn-ブチルリチウム0.10部を加えて、昇温重合を行った。重合転化率が99%以上に達した後、反応液を10℃に冷却し、次いで、1,3-ブタジエン94部を加えて、さらに昇温重合を行った。重合転化率が99%以上に達した後、ジクロロジメチルシラン0.07部を加えて、さらに昇温重合を行った。その後、反応容器内に、ジエチルアルミニウムクロライド0.03部及びビス(シクロペンタジエニル)チタニウムフルフリルオキシクロライド0.06部を加え、撹拌した。その後、合成例1と同様に水素添加反応を行い熱可塑性樹脂A-11を得た。 3.1.9. 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. 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-11.
窒素置換された反応容器に、脱気・脱水されたシクロヘキサン800部、1,3-ブタジエン15部、及びテトラヒドロフラン0.03部を仕込み、重合開始温度70℃にてn-ブチルリチウム0.09部を加えて、昇温重合を行った。重合転化率が99%以上に達した後、反応液を15℃に冷却し、1,3-ブタジエン70部、及びテトラヒドロフラン15部を加えて、さらに昇温重合を行った。重合転化率が99%以上に達した後、スチレン15部を加えて、さらに昇温重合を行った。その後、反応容器内に、ジエチルアルミニウムクロライド0.04部及びビス(シクロペンタジエニル)チタニウムフルフリルオキシクロライド0.06部を加え、撹拌した。その後、合成例1と同様に水素添加反応を行い熱可塑性樹脂A-12を得た。 3.1.10. 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. 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.
水素添加反応時間を15分間としたこと以外は合成例11と同様の方法にて、熱可塑性樹脂A-13を得た。 3.1.13. Synthesis Example 13
A thermoplastic resin A-13 was obtained in the same manner as in Synthesis Example 11 except that the hydrogenation reaction time was 15 minutes.
水素添加反応時間を12時間としたこと以外は合成例10と同様の方法にて、熱可塑性樹脂A-14を得た。 3.1.14. Synthesis Example 14
A thermoplastic resin A-14 was obtained in the same manner as in Synthesis Example 10 except that the hydrogenation reaction time was 12 hours.
作製した熱可塑性樹脂の全結合スチレン含量、ビニル結合含量、ヨウ素価、結晶融解ピーク温度、結晶融解熱量及び分子量は以下の手法で測定した。結果を表1、2に示す。 3.2. Evaluation of 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.
水素添加前の重合体を四塩化炭素に溶解し、270MHz、1H-NMRスペクトルから全結合スチレン含量を算出した。結果を表1、2に示す。 3.2.1. Evaluation of total bound styrene content The polymer before hydrogenation was dissolved in carbon tetrachloride, and the total bound styrene content was calculated from a 270 MHz, 1 H-NMR spectrum. The results are shown in Tables 1 and 2.
水素添加前の重合体を赤外分析法を用い、ハンプトン法によりビニル結合(1,2結合及び3,4結合)を算出した。結果を表1、2に示す。 3.2.2. Evaluation of vinyl bond (1,2 bond and 3,4 bond) content The vinyl bond (1,2 bond and 3,4 bond) was calculated by the Hampton method using the infrared analysis method of the polymer before hydrogenation. The results are shown in Tables 1 and 2.
熱可塑性樹脂を「JIS K 0070:1992」に記載の方法に準じてヨウ素価を算出した。結果を表1、2に示す。 3.2.3. Evaluation of iodine value The iodine value of a thermoplastic resin was calculated according to the method described in "JIS K 0070: 1992". The results are shown in Tables 1 and 2.
示差走査熱量計(DSC)を用いて熱可塑性樹脂を200℃で10分保持した後、-80℃まで10℃/分の速度で昇温した時の熱流量(結晶融解熱量(J/g))におけるピーク温度を、結晶融解ピーク温度(℃)とした。結果を表1、2に示す。 3.2.4. Evaluation of Crystal Melting Peak Temperature / Crystal Melting Calorie Heat when a thermoplastic resin is held at 200 ° C. for 10 minutes using a differential scanning calorimeter (DSC) and then heated to −80 ° C. at a rate of 10 ° C./min. The peak temperature at the flow rate (crystal melting heat (J / g)) was defined as the crystal melting peak temperature (° C.). The results are shown in Tables 1 and 2.
熱可塑性樹脂のGPC分析を行った。具体的には、ゲルパーミエーションクロマトグラフィー(GPC、商品名「HLC-8120GPC」、東ソー・ファインケム社製、カラム:東ソー社製、GMH-XL)を用いて、ポリスチレン換算で数平均分子量(Mn)、質量平均分子量(Mw)、及び分子量分布(Mn/Mw)を求めた。溶媒にはテトラヒドロフランを用いた。 3.2.5. Molecular weight evaluation of 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.
作製した熱可塑性樹脂にステアリン酸カルシウムを0.05部添加し、池貝社製40mm単軸押し出し機に投入して溶融混練りしストランド状に押出し水中で冷却固化したのち、技研工機社製ストランドカッターにてペレット化し円柱状の未乾燥ペレットを得た。
未乾燥ペレット100質量部とステアリン酸カルシウム(和光純薬工業(株)製)0.10質量部をスーパーミキサーSMV-20に添加し、撹拌速度300rpmにて5分撹拌し未乾燥ペレット表面にステアリン酸カルシウムを塗布した。その後、目開き6.0mmのステンレス製3.5メッシュでふるいわけ、さらに目開き1.5mmのステンレス製12メッシュでふるいわけた。12メッシュを通過しない大きさのものを乾燥機(商品名「並行流回分式乾燥機」、佐竹化学機械工業(株)製)を用いて乾燥温度80℃の条件で乾燥し、水分含有量を500ppmに調整した組成物(ペレット)を作成した。なお、このようにして作製した組成物の水分含有量はJIS K7251 「プラスチック-水分含有率の求め方」に記載される水分気化法に準拠して測定することができる。 3.3. 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. After that, it was sieved with a stainless steel 3.5 mesh having an aperture of 6.0 mm, and further sieved with a stainless steel 12 mesh having an aperture of 1.5 mm. Dry the one that does not pass 12 mesh under the condition of a drying temperature of 80 ° C. using a drier (trade name “Parallel Flow Drier”, manufactured by Satake Chemical Machinery Co., Ltd.). A composition (pellet) adjusted to 500 ppm was prepared. The water content of the composition thus prepared can be measured in accordance with the water vaporization method described in JIS K7251 “Plastics—How to Obtain Water Content”.
ブロッキングは、乾燥機から回収する際の作業性悪化や押出機ホッパー投入時のエラー原因となるため少ないことが望ましい。このため、以下の方法により組成物(ペレット)のブロッキング状態を確認し、以下の指標に従い評価した。結果を表3に示す。
・「A」:ペレットの互着は認められず、優秀であると判断できる。
・「B」:数珠状ペレットが若干認められるが、解すことでペレット間の互着が解消されるため、生産性に劣るが、実用できるため良好と判断できる。
・「C」:ペレットが互着し一体化し、一体化したペレットは解すことができず、実用に供することができないため不良と判断できる。 3.3.1. Evaluation of Blocking of Composition (Pellets) Since blocking is a cause of deterioration in workability when recovered from the dryer and an error when the extruder hopper is charged, it is desirable that blocking be small. For this reason, the blocking state of the composition (pellet) was confirmed by the following method and evaluated according to the following indices. The results are shown in Table 3.
“A”: Pellets are not attached to each other, and it can be determined that they are excellent.
-"B": Although some bead-shaped pellets are recognized, since mutual adherence between the pellets is solved by solving, it is inferior in productivity, but can be judged to be good because it can be used practically.
"C": The pellets are attached to each other and integrated, and the integrated pellet cannot be unraveled and cannot be put to practical use, so it can be determined to be defective.
粘着剤として使用する際に成形体と被着体は所定の圧力で圧着されるが、成形体の変形量が大きいと被着体との接触面積を充分確保でき良好な粘着性能が期待できることから、硬度が低いことが望ましい。このため、以下の方法に従い組成物(ペレット)の硬度評価を行い、以下の指標に従い評価した。結果を表3に示す。 3.3.2. Hardness evaluation of the composition (pellet) When used as an adhesive, the molded body and the adherend are pressure-bonded at a predetermined pressure. If the deformation of the molded body is large, a sufficient contact area with the adherend can be secured. It is desirable that the hardness is low because good adhesive performance can be expected. Therefore, the hardness of the composition (pellet) was evaluated according to the following method and evaluated according to the following index. The results are shown in Table 3.
・「AA」:硬度が50未満であり、被着体との貼合において被着体と接触面積を大幅に向上できるため、極めて優秀であると判断できる。
・「A」:硬度が50超え65未満であり、被着体との貼合において被着体と接触面積を向上できるため、優秀であると判断できる。
・「B」:硬度が65超え75未満であり、被着体との貼合において被着体と接触面積が少ないが、実用できるため良好と判断できる。
・「C」:硬度が75超えであり、被着体に対する形状変化を起こすことができず、実用に供することができないため不良と判断できる。 The 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.
光学部材の加工工程や外観検査での視認性を考慮するとHaze値が低いことが望ましい。このため、以下の指標に従い評価した。結果を表3に示す。 3.3.3. Haze evaluation of composition (pellet) It is desirable that the haze value is low in consideration of the visibility in the processing step and appearance inspection of the optical member. For this reason, it evaluated according to the following parameters | indexes. The results are shown in Table 3.
・「A」:Hazeが15未満であり、視認性が極めて優秀であると判断できる。
・「B」:Hazeが15超え20未満であり、視認性に劣るが、実用できるため良好と判断できる。
・「C」:Hazeが20超えであり、視認性が不良であるため、実用に供することができず不良と判断できる。 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.
基材層としてポリエチレン(三菱化学(株)製、商品名「YF30」)、接着層として上記で作製した組成物(ペレット)を使用し、フィードブロックタイプのTダイを備えた二層共押出装置により、基材層の厚みが100μm、粘着層の厚みが10μmとなるように、シリンダー温度190℃、ダイス温度190℃の成形条件にて基材層と粘着層とを共押出し成形して、粘着フィルムを製造した。 3.3.4. Manufacture of molded body (adhesive film) and heat resistance and molding appearance evaluation Polyethylene (Mitsubishi Chemical Co., Ltd., trade name “YF30”) is used as the base layer, and the composition (pellet) prepared above is used as the adhesive layer. In a two-layer coextrusion apparatus equipped with a feed block type T-die, under the molding conditions of a cylinder temperature of 190 ° C. and a die temperature of 190 ° C. so that the thickness of the base layer is 100 μm and the thickness of the adhesive layer is 10 μm The base material layer and the adhesive layer were coextruded to produce an adhesive film.
・「A」:溶出成分Aと溶出成分BのGPC強度比、GPC形状共に変化がほとんど認められず、ゲル成分が極めて微量である。異物量が極めて少ないため、優秀であると判断できる。
・「B」:溶出成分Aと溶出成分BのGPC強度比に変化がほとんど認められずゲル成分は微量であるが、GPC形状から多量体生成が認められた。多量体の形成は認められるものの、ゲル成分は微量であることから、異物量が少なく実用できるため良好と判断できる。
・「C」:溶出成分BのGPC強度が極めて小さく、多量化によるゲル成分が極めて多いため実用に供することができず不良と判断できる。
ペレット化やフィルム化工程時に生成する異物はフィルムの欠陥や歩留り不良の原因となり少ないことが望ましい。尚、GPCの評価には、ポリマーラボラトリー社製高温GPC測定システム「PL-GPC220」、カラムはポリマーラボラトリー社製カラム「MIXED-B」、測定温度は135℃で実施した。 On the other hand, the 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. On the other hand, 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.
“A”: Almost no change was observed in the GPC intensity ratio and the GPC shape of the elution component A and elution component B, and the gel component was very small. Since the amount of foreign matter is extremely small, it can be judged that it is excellent.
"B": Almost no change was observed in the GPC intensity ratio between the eluted component A and the eluted component B, and the gel component was insignificant, but multimer formation was observed from the GPC shape. Although formation of a multimer is recognized, since the gel component is very small, it can be judged to be good because it can be used practically with a small amount of foreign matter.
“C”: 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.
・「A」:フィルム表面に、気泡などの異常は認められず、優秀と判断できる。
・「B」:フィルム表面に若干の気泡が存在したが、実用できるため良好と判断できる。
・「C」:フィルム表面に気泡が多く認められ、実用に供することができず不良と判断できる。
粘着フィルムの粘着性能や粘着フィルム使用過程での視認性を考慮すると、フィルム表面の気泡による表面荒れや濁りが小さいことが望ましい。 Moreover, the surface of the adhesive film produced above was observed with an optical microscope and evaluated as follows. The results are shown in Table 3.
“A”: No abnormality such as bubbles is observed on the film surface, and it can be determined that the film is excellent.
"B": Although some bubbles existed on the film surface, it can be judged good because it can be used practically.
"C": Many air bubbles are observed on the film surface, which cannot be used practically and can be judged as defective.
Considering the adhesive performance of the adhesive film and the visibility in the process of using the adhesive film, it is desirable that the surface roughness and turbidity due to bubbles on the film surface be small.
組成物15gとシクロヘキサン85gをセパラに投入し80℃に加温して溶解させた。その後、シクロヘキサン溶液を250mLポリビンに回収し40℃に冷却し、40℃で24時間静置した。静置後のポリマー溶液の外観と溶液粘度から、溶液貯蔵安定性を以下のように判断した。尚、溶液粘度の測定には東機産業社のビスコメーターTVB10Mを用い、測定温度は40℃にて実施した。
・「A」:ポリビンを90度傾けた際、ポリマー溶液が流動した。溶液の粘度が3,000mPa・s以下であり溶液の流動性が高く、溶液貯蔵安定性が優秀と判断した。溶液貯蔵安定性が優秀であるため、配管での移送や容器への移液が容易であり、キャストやコーティングなどウェットプロセスを容易に行うことができるため、優秀である。
・「B」:ポリビンを90度傾けた際、ポリマー溶液が流動した。溶液の粘度が3,000mPa・s以上であったため、溶液の流動性がやや低いものの、溶液貯蔵安定性が良好と判断した。溶液貯蔵安定性が良好であるため、ウェットプロセスに適用できるため、良好である。
・「C」:ポリビンを90度傾けた際、ポリマー溶液が流動しなかった。溶液が流動せず、溶液の粘度を測定することができなかったため、溶液貯蔵安定性が不良と判断した。 3.3.5. 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.
鏡面板上に作製した組成物(ペレット)と2mm厚みのスペーサーを配置し、岩城工業社製熱プレス成型機「AT-37」を用いて、190℃30分熱プレスすることで、2mm厚みのプレスシートを得た。作製したプレスシートを10mm×30mmに切出し、30℃環境下でオレイン酸50gに72時間浸漬した。浸漬後のプレスシートをピンセットで取出し、プレスシート外観と寸法変化量から耐溶剤性を以下のように判断した。なお、寸法変化量は以下のようにして評価した。
寸法変化量(%)=((浸漬後のシート面積-浸漬前のシート面積)/浸漬前のシート面積)×100
・「A」:寸法変化量が200%以下であり、ピンセットを用いてプレスシート形状を維持したまま取り出すことができ、耐溶剤性が優秀であると判断した。成形品に溶剤が付着した際の膨潤に対する耐性が高く、物性変化が抑えられ、形状保持性にも優れるため、各種成形品の素材として優秀である。
・「B」:寸法変化量が200%以上であり、ピンセットを用いてプレスシート形状を維持したまま取り出すことができ、耐溶剤性が良好であると判断した。成形品に溶剤が付着した際に膨潤による物性変化は起こるものの、溶剤の保持性や形状維持性が優れるので、各種成形品の素材として良好である。
・「C」:ピンセットを用いてプレスシートを取り出す際にシート形状が崩れ、寸法変化量を測定できず、耐溶剤性が不良と判断した。耐溶剤性が不良であるため、成形品に溶剤が付着した際に成形品形状を維持できず、物性変化が大きいため、各種成形品の素材として不良である。 3.3.6. 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.
Dimensional change (%) = ((sheet area after immersion−sheet area before immersion) / sheet area before immersion) × 100
"A": The amount of dimensional change was 200% or less, and it was determined that the press sheet shape could be removed using tweezers while maintaining the press sheet shape, and the solvent resistance was excellent. It is excellent as a material for various molded products because it has high resistance to swelling when a solvent adheres to the molded products, suppresses changes in physical properties, and excels in shape retention.
“B”: The amount of dimensional change was 200% or more, and it was determined that the press sheet shape could be taken out using tweezers while maintaining the press sheet shape, and the solvent resistance was good. Although a change in physical properties due to swelling occurs when a solvent adheres to a molded product, it is excellent as a material for various molded products because of excellent solvent retention and shape maintenance.
-"C": When taking out the press sheet using tweezers, the sheet shape collapsed, the dimensional change could not be measured, and the solvent resistance was judged to be poor. Since the solvent resistance is poor, the shape of the molded product cannot be maintained when the solvent adheres to the molded product, and the physical properties change greatly, so that it is a poor material for various molded products.
熱可塑性樹脂A-2~A-14を用いて、ブロッキング防止剤(B)の種類と量、水分量を表3~4の成分と量に変更した以外は実施例1と同様の方法で組成物(ペレット)を作製し、実施例1と同様に評価した。結果を表3~4に示す。
なお、水分量は組成物(ペレット)の乾燥時間を適時変更して調整した。 3.4. Examples 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.
実施例1~12によれば、本発明に係る組成物は、ペレット作製における生産性や作業性に優れ、被着体に対する高い粘着力を示し、押出フィルム成形時のゲル異物量や外観に優れ、フィルム使用時の視認性に優れた、押出成形体を製造することができた。
比較例1~8によれば、水分量が多いと押出フィルム成形時の外観不良が起こり、水分量が少ないとペレット乾燥時のブロッキングが起こり、熱可塑性樹脂のヨウ素価が高いと得率の低下やブロッキングや耐溶剤性の悪化、更には押出フィルムの異物が発生し、熱可塑性樹脂のヨウ素価が低いと硬度やHaze、溶液貯蔵安定性の悪化が起こることがわかった。 3.5. Results According to Examples 1 to 12, 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.
Claims (7)
- ヨウ素価が2~150である熱可塑性樹脂(A)と、水とを含有する組成物であって、
前記組成物100質量部に対して、前記水を100~2000ppm含有し、
前記熱可塑性樹脂(A)が共役ジエン化合物に由来する繰り返し単位を有し、
前記熱可塑性樹脂(A)の、結晶融解ピーク温度が50℃~95℃であり、かつ、結晶融解熱量が10J/g~40J/gである、組成物。 A composition comprising a 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,
A composition of the thermoplastic resin (A) having 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. - さらに、ブロッキング防止剤(B)を含有し、
前記熱可塑性樹脂(A)の含有量をMa(質量部)、前記ブロッキング防止剤(B)の含有量をMb(質量部)としたときに、Ma/Mb=200~4000である、請求項1に記載の組成物。 Furthermore, it contains an antiblocking agent (B),
Ma / Mb = 200 to 4000, where Ma (part by mass) is the content of the thermoplastic resin (A) and Mb (part by mass) is the content of the antiblocking agent (B). 2. The composition according to 1. - ポリエチレンワックス、ポリプロピレンワックス、脂肪酸アミド、脂肪酸エステル及び脂肪酸金属塩からなる群より選ばれる少なくとも1種をさらに含む、請求項1に記載の組成物。 The composition according to claim 1, further comprising at least one selected from the group consisting of polyethylene wax, polypropylene wax, fatty acid amide, fatty acid ester, and fatty acid metal salt.
- 前記熱可塑性樹脂(A)が、
2×104以上8×104未満の分子量区間に0.3~10質量%、及び
8×104以上1×106以下の分子量区間に90~99.7質量%存在する分布を有する、請求項1ないし請求項3のいずれか一項に記載の組成物。 The thermoplastic resin (A) is
Having a distribution of 0.3 to 10% by weight in a molecular weight section of 2 × 10 4 or more and less than 8 × 10 4 and 90 to 99.7% by weight in a molecular weight section of 8 × 10 4 or more and 1 × 10 6 or less, The composition according to any one of claims 1 to 3. - 前記熱可塑性樹脂(A)が、芳香族ビニル化合物に由来する繰り返し単位をさらに有する、請求項1ないし請求項4のいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 4, wherein the thermoplastic resin (A) further has a repeating unit derived from an aromatic vinyl compound.
- 共押出し法に用いるための、請求項1ないし請求項5のいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 5, for use in a coextrusion method.
- 請求項1ないし請求項5のいずれか一項に記載の組成物を用いて作成された成形体。 A molded body produced using the composition according to any one of claims 1 to 5.
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JP2005170985A (en) * | 2003-12-08 | 2005-06-30 | Jsr Corp | Pressure-sensitive adhesive film |
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JPH06228521A (en) * | 1993-01-29 | 1994-08-16 | Nippon Zeon Co Ltd | Block copolymer composition for hot-melt pressure-sensitive adhesive and hot-melt pressure-sensitive adhesive composition |
JPH07165993A (en) * | 1993-12-16 | 1995-06-27 | Sumitomo Rubber Ind Ltd | Rubber composition |
JPH09235524A (en) * | 1996-02-28 | 1997-09-09 | Sekisui Chem Co Ltd | Surface protecting film |
JPH10152585A (en) * | 1996-11-22 | 1998-06-09 | Jsr Corp | Thermoplastic elastomer composition |
JP2002020713A (en) * | 2000-07-11 | 2002-01-23 | Sekisui Chem Co Ltd | Surface protective film |
JP2002194176A (en) * | 2000-10-19 | 2002-07-10 | Idemitsu Petrochem Co Ltd | Resin composition |
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JP3939738B1 (en) * | 2006-04-12 | 2007-07-04 | 出光ユニテック株式会社 | Adhesive material, method for producing the same, adhesive material using the same, and method for producing laminate |
JP5158151B2 (en) | 2010-08-19 | 2013-03-06 | Jsr株式会社 | Adhesive film |
TWI655236B (en) * | 2013-12-27 | 2019-04-01 | 日本瑞翁股份有限公司 | Block copolymer composition, manufacturing method and film thereof |
WO2015178260A1 (en) * | 2014-05-20 | 2015-11-26 | 旭化成ケミカルズ株式会社 | Crumb of block copolymer and adhesive composition |
JP2017043673A (en) * | 2015-08-25 | 2017-03-02 | 旭化成株式会社 | Resin composition and sheet thereof |
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JP2000136248A (en) * | 1998-08-28 | 2000-05-16 | Toray Ind Inc | Thermoplastic elastomer pellet and production of molded product |
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