JP4471758B2 - Dipping molding composition and solvent paste - Google Patents

Description

  The present invention relates to a dipping molding composition and a solvent paste that are particularly excellent in gas barrier properties and excellent in oil resistance and flexibility.

Conventionally, gloves are one of the molded products obtained by heat treatment of polyvinyl chloride / phthalic acid plasticizer system and polyurethane / organic solvent system pastes, but these molded products have excellent oil resistance and wear resistance. However, since the volume resistivity was 10 ¹² to 10 ¹³ [Ω · cm], the insulating properties were inferior, and it was inevitable to use at 200 V or less.

  In addition, although gloves obtained from natural rubber latex have excellent insulation properties, they have skin allergy problems, rubber odors, and tingling sensations, and they cannot withstand fine work or long work, which may be the cause. In order to reduce the amount of protein contained in natural rubber, fine particles having —OH groups are contained in rubber latex (for example, see Patent Document 1) or protease is added (for example, see Patent Document 2). However, it still has a problem that a satisfactory result cannot be obtained and an additional process is required.

The gas barrier property of water vapor is required for electrical installation work under high humidity. Conventionally, a natural rubber material has been used. However, there was a problem that the water vapor barrier property was poor and the insulation resistance was lowered according to the working time.
When using a solvent, there was a problem of vapor passing through the gloves and putting your hands on it. To prevent or alleviate this symptom, the gas barrier properties of the solvent (benzene, thinner, toluene, xylol, MEK, DMF, etc.) are necessary. Met.
Thus, none of the gas barrier properties, insulating properties, oil resistance, wear resistance, odorless or low odor, no or low allergic properties were satisfied.
JP 2002-348712 A JP 2004-107483 A

  An object of the present invention is to provide a composition for dipping molding, a solvent and a solvent paste, which are particularly excellent in gas barrier properties and excellent in oil resistance and flexibility.

That is, according to the first invention of the present invention,
(A) A dipping molding composition comprising an isobutylene block copolymer composed of an isobutylene compound block and an aromatic vinyl compound block is provided.

  According to the second invention of the present invention, in the first invention, (a) 100 parts by weight of (b) hydrogenated and / or partially hydrogenated copolymer is contained in an amount of 1 to 80 parts by weight. A dipping molding composition is provided.

  According to the third invention of the present invention, in the first or second invention, (a) 100 parts by weight of (c) 1 to 100 parts by weight of a non-aromatic rubber softener is included. A dipping molding composition is provided.

  According to a fourth invention of the present invention, in any one of the first to third inventions, (a) 100 parts by weight includes (d) 1-50 parts by weight of petroleum resin. A dipping molding composition is provided.

  According to the fifth aspect of the present invention, there is provided a dipping molding solvent paste obtained by dissolving 100 parts by weight of the dipping molding composition according to any one of the first to fourth inventions in 80 to 400 parts by weight of a solvent. Provided.

  According to the sixth invention of the present invention, in any one of the first to fifth inventions, oil resistance (volume change rate) at 50 ° C. × 24 hours using liquid paraffin according to JIS K 6258. A dipping molding composition is provided, wherein the composition is 30% or less.

According to the seventh invention of the present invention, in any one of the first to sixth inventions, a 0.5 mm thick dipping molded sheet is used in accordance with JIS K 7126 A method (differential pressure method), and before measurement. There is provided a dipping molding composition characterized in that the gas barrier property against oxygen at 25 ° C. after standing at 25 ° C. for about 6 hours is 6 × 10 ⁻¹⁵ mol · m / m ² · s · Pa or less.

According to the eighth invention of the present invention, in any one of the first to seventh inventions, a 0.5 mm thick dipping molded sheet is used in accordance with the JIS K 7126 A method (differential pressure method) and before measurement. Provided is a dipping molding composition characterized in that the gas barrier property against carbon dioxide at 25 ° C. after standing at 25 ° C. for about 6 hours is 6 × 10 ⁻¹⁵ mol · m / m ² · s · Pa or less. .

Moreover, according to the ninth invention of the present invention, in any one of the first to eighth inventions, measurement is performed using a 0.5 mm thick dipping molded sheet in accordance with JIS K 7129 A method (moisture sensitive sensor method). A dipping molding composition characterized by having a gas barrier property against water vapor of 2 g / m ² · 24 hours or less under conditions of 40 ° C. × 90% RH after standing at 40 ° C. × 90% RH for about 170 hours. Provided.

  According to a tenth aspect of the present invention, in any one of the first to ninth aspects, a dipping molding composition for gas barrier is provided.

  The thermoplastic elastomer composition for dipping molding and the solvent paste of the present invention are optimal for dipping molding, and are particularly excellent in gas barrier properties and oil resistance and flexibility.

Hereinafter, each component of the resin composition of this invention is demonstrated.
Components of thermoplastic elastomer composition for dipping molding excellent in gas barrier properties, oil resistance and flexibility and solvent paste (a) Isobutylene block copolymer composed of isobutylene compound block and aromatic vinyl compound block

  The isobutylene block copolymer used in the present invention may be any having any structure as long as it has a unit mainly composed of isobutylene and a unit mainly composed of an aromatic vinyl compound. However, a triblock body having a structure of (a unit mainly composed of an aromatic vinyl compound, a unit mainly composed of isobutylene, and a unit mainly composed of an aromatic vinyl compound) from the balance of physical properties and ease of synthesis, A diblock body having a structure of a unit mainly composed of isobutylene-a unit mainly composed of an aromatic vinyl compound), or a mixture thereof can be used. There is no particular limitation on the ratio of the unit mainly composed of isobutylene of the block copolymer and the unit mainly composed of the aromatic vinyl compound, but from the balance of physical properties, 95 to 20% by weight of the monomer mainly composed of isobutylene and the aromatic 5 to 80% by weight of a monomer mainly composed of an aromatic vinyl compound is preferable, and further 90 to 60% by weight of a monomer mainly composed of isobutylene and 10 to 40% by weight composed mainly of an aromatic vinyl compound. preferable.

  The weight average molecular weight of the isobutylene block copolymer is not particularly limited, but is preferably 40,000 to 500,000, particularly preferably 60,000 to 400,000. When the weight average molecular weight is less than 40,000, the mechanical properties are deteriorated, and when it exceeds 500,000, the moldability is deteriorated.

  Examples of the aromatic vinyl compound used in the aromatic vinyl polymer block include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, t-butylstyrene, monochlorostyrene, dichlorostyrene, methoxystyrene, and the like. Can be mentioned. Among the above compounds, styrene, α-methylstyrene, and p-methylstyrene are preferable from the balance of cost, physical properties, and productivity, and two or more of them may be selected.

  Specific examples of the isobutylene block copolymer include 103T (number average molecular weight = 92,000, weight average molecular weight = 100,000) or 073T (number average molecular weight = 60,000, weight) manufactured by Kaneka Chemical Co., Ltd. Average molecular weight = 65,000).

The component (b) hydrogenated and / or partially hydrogenated copolymer added as necessary functions as a thickener (viscosity modifier).
As component (b), hydrogenated and / or partially hydrogenated aromatic vinyl compound-conjugated diene compound block copolymer, hydrogenated and / or partially hydrogenated conjugated diene compound block copolymer And hydrogenated and / or partially hydrogenated products of aromatic vinyl compound-conjugated diene compound-based random copolymers. Among these, hydrogenated products and / or partially hydrogenated aromatic vinyl compound-conjugated diene compound block copolymers, hydrogenated products and / or partially hydrogenated conjugated diene compound block copolymers are included. preferable.

As the hydrogenated product and / or partially hydrogenated product of the aromatic vinyl compound-conjugated diene compound block copolymer, at least one polymer block A mainly composed of an aromatic vinyl compound and a conjugated diene compound are used. Mention may be made of a hydrogenated product and / or a partially hydrogenated product of a block copolymer comprising at least one polymer block B as a main component.
Hydrogenated and / or partially hydrogenated block copolymer comprising at least one polymer block A mainly composed of an aromatic vinyl compound and at least one polymer block B mainly composed of a conjugated diene compound The product component is obtained by hydrogenating a block copolymer comprising at least one polymer block A mainly composed of an aromatic vinyl compound and at least one polymer block B mainly composed of a conjugated diene compound. Polymer. For example, a hydrogenated block copolymer of an aromatic vinyl compound-conjugated diene compound having a structure such as A-B, A-B-A, B-A-B-A, or A-B-A-B-A Is obtained.

  The polymer block A mainly composed of an aromatic vinyl compound may be a polymer composed only of an aromatic vinyl compound or a copolymer of an aromatic vinyl compound and less than 50% by weight of a conjugated diene compound. The polymer block B mainly composed of a conjugated diene compound may be a polymer composed solely of a conjugated diene compound or a copolymer of a conjugated diene compound and less than 50% by weight of an aromatic vinyl compound.

  Examples of the aromatic vinyl compound constituting the aromatic vinyl compound-conjugated diene compound block copolymer include one or two of styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, and the like. From the above, styrene is preferable. In addition, as the conjugated diene compound, for example, one or two or more kinds are selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, etc., among which butadiene, isoprene, and These combinations are preferred.

  Hydrogenated and / or partially hydrogenated block copolymer comprising at least one polymer block A mainly composed of an aromatic vinyl compound and at least one polymer block B mainly composed of a conjugated diene compound In the polymer block B mainly composed of a conjugated diene compound, the hydrogenation rate of the physical component is arbitrary, but it is preferably 50% or more, more preferably 55% or more, and still more preferably 60% or more. Further, the microstructure is arbitrary. For example, when the block B is composed of butadiene alone, the polybutadiene block preferably has a 1,2-microstructure of 20 to 50% by weight, particularly preferably 25 to 45%. % By weight. Moreover, the thing which selectively hydrogenated 1,2-microstructure may be sufficient. When block B is composed of a mixture of isoprene and butadiene, the 1,2-microstructure is preferably less than 50%, more preferably less than 25%, and even more preferably less than 15%.

  When block B is composed of isoprene alone, in the polyisoprene block, preferably 70 to 100% by weight of isoprene has a 1,4-microstructure, and preferably at least aliphatic double bonds derived from isoprene. 90% hydrogenated is preferred.

  Moreover, it is preferable that the polymer block A exists in the ratio of 5-70 weight% of the whole component. Furthermore, the weight average molecular weight of the whole component is 350,000 or less, Preferably it is 30,000-250,000. If the weight average molecular weight exceeds 350,000, the moldability deteriorates.

  Specific examples of hydrogenated and / or partially hydrogenated aromatic vinyl compound-conjugated diene compound block copolymers include styrene-ethylene / butene copolymers (SEB) and styrene-ethylene / propylene copolymers. (SEP), styrene-ethylene-butene-styrene copolymer (SEBS), styrene-ethylene-propylene-styrene copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene copolymer (SEEPS), styrene- Butadiene / butylene-styrene copolymer (styrene-butadiene-styrene copolymer partial hydrogenated product, SBBS), styrene-isoprene-styrene copolymer partial hydrogenated product, styrene-isoprene-butadiene-styrene copolymer And a partially hydrogenated product. In the present invention, the hydrogenated product and / or the partial hydrogenated product of the aromatic vinyl compound-conjugated diene compound block copolymer may be used alone or in admixture of two or more.

  A block obtained by hydrogenating a block copolymer comprising at least one polymer block A mainly composed of these aromatic vinyl compounds and at least one polymer block B mainly composed of a conjugated diene compound. As a method for producing a copolymer, a number of methods have been proposed. As a typical method, for example, a lithium catalyst or a Ziegler type catalyst is used by the method described in JP-B-40-23798. It can be obtained by block polymerization in an inert medium. Such a hydrogenation treatment of the block copolymer can be performed in the presence of a hydrogenation catalyst in an inert solvent by a known method.

Examples of the hydrogenated product of the conjugated diene compound block copolymer include a block copolymer having a crystalline ethylene block and an amorphous ethylene-butene block obtained by hydrogenating a block copolymer of butadiene. Examples thereof include a block copolymer (SEBC) having a block composed of a crystalline ethylene block, an amorphous ethylene-butene block and an aromatic vinyl compound obtained by hydrogenating a block copolymer of butadiene (CEBC) and butadiene. It is done. In the present invention, the hydrogenated conjugated diene compound block copolymer may be used alone or in combination of two or more.
The weight average molecular weight of the hydrogenated product of this conjugated diene compound-based block copolymer is preferably 350,000 or less, more preferably 30,000 to 250,000. If the weight average molecular weight exceeds 350,000, the moldability deteriorates.

  Furthermore, as a hydrogenated product of the above aromatic vinyl compound-conjugated diene compound-based random copolymer, for example, hydrogenation of a random copolymer mainly composed of an aromatic vinyl compound (styrene) and a conjugated diene compound (butadiene) Product (H-SBR), and as a specific commercial product, for example, Dynaron 1320P (trade name) manufactured by JSR Corporation may be mentioned.

  The amount of component (b), when added, is 1 to 80 parts by weight, preferably 3 to 50 parts by weight per 100 parts by weight of component (a). If the upper limit is exceeded, the oil resistance and gas barrier properties deteriorate, and at the same time, the viscosity becomes too high and the molding processability deteriorates. If it is less than the lower limit, when it is made into a paste with a solvent such as xylol, MEK, or DMF, the addition effect (thickening effect, bubble generation suppressing effect, uniform film thickness forming effect) is not sufficient.

The component (c) non-aromatic rubber softener added as needed functions as a softener and is added when used for applications requiring an A hardness of 60 or less, preferably 50 or less. The
Examples of the component (c) include non-aromatic mineral oils or liquid or low molecular weight synthetic softeners. Generally, a mineral oil softener for rubber is a mixture of an aromatic ring, a naphthene ring and a paraffin chain, and has a saturated hydrocarbon chain carbon number of 50% or more of the total carbon number. Those that occupy 30 to 40% are called naphthenes, and those that occupy 30% or more aromatic carbons are called aromatics. The mineral oil softener for rubber used in the present invention is preferably the paraffinic and naphthenic types described above. Aromatic softeners are not preferred because of their poor dispersibility.
As the non-aromatic hydrocarbon rubber softening agent, a paraffinic mineral oil softening agent is particularly preferable, and paraffinic ones having a small aromatic ring component are particularly suitable.

  Examples of the compound constituting the paraffinic softener include paraffinic compounds having 4 to 155 carbon atoms, preferably paraffinic compounds having 4 to 50 carbon atoms, and specifically, butane, pentane, hexane. , Heptane, octane, nonane, decane, undecane, dodecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosan, heneicosan, docosan, tricosan, tetracosan, pentacosan, hexacosan, heptacosan, octacosan, triacotan, henakosan, triacontane, N-paraffins (linear saturated hydrocarbons) such as Contan, Dotriacontane, Pentatriacontane, Hexacontane, Heptacontane, etc., Isobutane, Isopentane, Neopentane, Isohexane, Pentane, neohexane, 2,3-dimethylbutane, 2-methylhexane, 3-methylhexane, 3-ethylpentane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3, 3-dimethylpentane, 2,2,3-trimethylbutane, 3-methylheptane, 2,2-dimethylhexane, 2,3-dimethylhexane, 2,4-dimethylhexane, 2,5-dimethylhexane, 3,4 -Dimethylhexane, 2,2,3-trimethylpentane, isooctane, 2,3,4-trimethylpentane, 2,3,3-trimethylpentane, 2,3,4-trimethylpentane, isononane, 2-methylnonane, isodecane, Isoundecane, isododecane, isotridecane, isotetradecane, isopentadecane, isoeo Tadekan, Isonanodekan, isoeicosane, 4-ethyl-5-isoparaffins methyl octane (branched saturated hydrocarbons) and can include derivatives of these saturated hydrocarbons. These paraffins are used in a mixture and are preferably liquid at room temperature.

  Commercially available paraffinic softeners that are liquid at room temperature include NA Solvent (isoparaffinic hydrocarbon oil) manufactured by Nippon Oil & Fats, PW-90 (n-paraffinic process oil) manufactured by Idemitsu Kosan Co., Ltd., and Idemitsu. Examples include IP-solvent 2835 (synthetic isoparaffinic hydrocarbon, 99.8% by weight or more isoparaffin) manufactured by Petrochemical Co., Ltd., and neothiozole (n-paraffinic process oil) manufactured by Sanko Chemical Co., Ltd.

  Moreover, a small amount of unsaturated hydrocarbons and derivatives thereof may coexist in the non-aromatic hydrocarbon softener. Unsaturated hydrocarbons include ethylene, propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2 -Ethylene hydrocarbons such as butene, 1-hexene, 2,3-dimethyl-2-butene, 1-heptene, 1-octene, 1-nonene, 1-decene, acetylene, methylacetylene, 1-butyne, 2- Examples thereof include acetylene hydrocarbons such as butyne, 1-pentyne, 1-hexyne, 1-octyne, 1-nonine and 1-decyne.

  When added, the amount of component (c) is 1 to 100 parts by weight, preferably 3 to 60 parts by weight, per 100 parts by weight of component (a). When the above upper limit is exceeded, the softening agent tends to bleed out, giving the final product tackiness, and also reducing the mechanical properties of the molded product. Moreover, if it is less than the said lower limit, the addition effect (flexibility provision effect) is not enough.

Furthermore, a petroleum resin can be added as a component (d) as needed.
Component (d) is a component that functions to impart further flexibility of the resulting composition, improve mechanical properties, and provide a more balanced flexibility and texture. Component (d) is a resin obtained by copolymerization using unsaturated hydrocarbons obtained in various processes in the petroleum refining industry and petrochemical industry, particularly in the naphtha decomposition process, with C5 fraction as the raw material. Aliphatic petroleum resin, aromatic petroleum resin made from C9 fraction, alicyclic petroleum resin made from dicyclopentadiene, terpene resin, and copolymerization system of these two or more Examples thereof include petroleum resins and hydrogenated petroleum resins obtained by hydrogenating these. The hydrogenated petroleum resin of the above-described resin can be obtained by hydrogenating the above resin by a method known to those skilled in the art. Specifically, Imabe (hydrogenated petroleum resin) manufactured by Idemitsu Petrochemical Co., Ltd., Alcon (hydrogenated petroleum resin) manufactured by Arakawa Chemical Industries, Ltd., and Clearon (hydrogenated terpene resin) manufactured by Yashara Chemical Co., Ltd. Commercial products such as Escorez (aliphatic hydrocarbon resin) manufactured by Tonex Co., Ltd. can be used.

  The amount of component (d) is 1 to 50 parts by weight, preferably 3 to 20 parts by weight, based on 100 parts by weight of component (a) when blended. When the upper limit is exceeded, the dipping formability deteriorates and the stickiness becomes remarkable. On the other hand, if it is less than the lower limit, the flexibility-imparting effect is not sufficient.

The component (e) terpene oil added as necessary has functions of imparting flexibility to the product and reducing the viscosity of the solvent paste.
Terpene oil is derived from essential oils obtained by steam-distilling raw pine fat collected from the red pine and black pine stands mainly in North America and mainland China, and from the turpentine oil or by the orange peel, a by-product of the pulp production of the tree. It is obtained from extracted essential oils or orange oils derived from these essential oils by isomerization reaction or the like, and specifically includes terpene hydrocarbons and terpene ethers having 10 carbon atoms.

  Terpenic hydrocarbons having 10 carbon atoms include myrcene (boiling point 167 ° C.), karene (boiling point 167 ° C.), osymene, pinene (boiling point 155 ° C.), limonene (boiling point 176 ° C.), camphene (boiling point 160 ° C.), terpinolene. (Boiling point 187 ° C.), tricyclene (boiling point 153 ° C.), terpinene (boiling point 170-180 ° C.), fenchen (boiling point 150-155 ° C.), ferrandrene (boiling point 170-175 ° C.), silbestrene (boiling point 175 ° C.), Sabinene (boiling point 163 ° C.), P-menten-1 (carbomentene) (boiling point 176 ° C.), P-menten-3 (boiling point 168 ° C.), P-cymene, P-menthane (boiling point 168 ° C.) and the like. Of these, α-pinene, β-pinene, limonene, P-menten-1, P-menten-3, P-cymene, and P-menthane are particularly preferable.

  Examples of the terpene ether having 10 carbon atoms include 1,4-cineole (boiling point 173 ° C.), 1,8-cineole (boiling point 173 ° C.), pinol (boiling point 180 ° C.), and the like. Among these, at least one selected from 1,4-cineole and 1,8-cineole is particularly preferable.

  When added, the amount of component (e) is 1 to 75 parts by weight, preferably 5 to 50 parts by weight, per 100 parts by weight of component (a). When the upper limit is exceeded, the gas and odor generated during molding become intense, and a bleed feeling is recognized on the product surface. If it is less than the lower limit, the effect of adding (the effect of imparting flexibility to the product, the effect of reducing the viscosity of the solvent paste) is not sufficient.

Component (f): Antioxidant Examples of the antioxidant include 2,6-di-tert-p-butyl-p-cresol, 2,6-di-tert-butylphenol, and 2,4-dimethyl-6. Phenolic antioxidants such as tert-butylphenol, 4,4-dihydroxydiphenyl, tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, phosphite antioxidants, thioether antioxidants, etc. Is mentioned. Of these, phenolic antioxidants and phosphite antioxidants are particularly preferred.

Next, the other components of the thermoplastic elastomer composition for dipping molding for producing a molded article excellent in oil resistance, gas barrier property and flexibility, solution and solvent paste will be described.
In the composition of the present invention, a heat stabilizer, a light stabilizer, an ultraviolet absorber, a crystal nucleating agent, an antiblocking agent, a sealability improving agent, stearic acid, and silicone oil are further added within the range not impairing the object of the present invention. Mold release agents such as polyethylene wax, lubricants such as polyethylene wax, colorants, pigments, inorganic fillers [alumina, talc, calcium carbonate, mica, wollastonite (wollastonite), clay], foaming agents (organic and inorganic) A flame retardant (hydrated metal compound, red phosphorus, ammonium polyphosphate, antimony, silicone) can be blended.
As the foaming agent, Expancel (manufactured by Expancel) and Matsumoto Microsphere (Matsumoto Yushi Seiyaku) are preferred.

  For dipping, 100 parts by weight of the thermoplastic elastomer added with (a) and (b) to (f) added as necessary are dissolved in 80 to 400 parts by weight of a solvent (for example, xylol: manufactured by Gordo solvent). A solvent paste is obtained. The amount is preferably 100 to 300 parts by weight of the solvent. When the upper limit is exceeded, the viscosity decreases, bubbles tend to be generated, and the film thickness becomes thin. If it is less than the said lower limit, a viscosity will become high, paste property will deteriorate, and dipping moldability will deteriorate.

Hereinafter, the manufacturing method of the resin composition of this invention is demonstrated.
In the composition of the present invention, the above component (a) and (b) to (f), which are added as necessary, are kneaded at a temperature of 180 to 200 ° C., a suitable single screw extruder, twin screw extruder, roll, Banbury It can be produced by dissolving pellets or blocks obtained by melt-kneading using a mixer or various kneaders in an organic solvent such as industrial xylol at a solid content of 20 to 55% by weight.
Or it can manufacture by dissolving the said component (a) and (b)-(f) added as needed directly in organic solvents, such as an industrial xylol, at 20-55 weight% of solid content. .

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example and a comparative example, this invention is not limited only to an Example. The evaluation methods and raw materials used in the examples are as follows.

Evaluation Method (1) Specific gravity: Based on JIS K7112, the test piece was measured using a dipping molded sheet having a thickness of about 0.5 mm. The dipping molded sheet is a 1000 cc round bottom flask equipped with a reflux condenser, charged with a magnetic stirrer of 60 mm × φ8 mm, 200 g of the resulting glove composition pellets and 300 g of industrial xylol, and a stirrer maintained at about 95 ° C. Stirring was carried out for 1 hour in a high-temperature tank. The mixture was allowed to stand for 12 hours or more until it reached room temperature, stirred for 10 minutes, and dipped once using a ferrotype plate (130 mm × 130 mm × 1 mm). The ferrotype plate was obtained by leaving it to stand at room temperature for 30 minutes and then performing a heat treatment at 120 ° C. for 30 minutes in an oven.
(2) Hardness: Based on JIS K 7215, the dipping molded sheets were overlapped to a thickness of 4.0 mm and measured with durometer hardness / type A.
(3) Tensile strength, 100% elongation stress, elongation: In accordance with JIS K 6301, a test piece was used by punching a 0.5 mm thick dipping molded sheet into a No. 3 dumbbell mold. The tensile speed was 500 mm / min.
(4) Oil bleed, tackiness: A sheet of about 65 mm x 80 mm x 0.5 mm thickness obtained by dipping molding is sandwiched between kraft papers, and a weight of 70 g in a disk shape is put on a 500 g weight at room temperature (23 ° C). The state of the kraft paper after standing for 168 hours was visually observed and evaluated according to the following criteria.
○: Kraft paper is easily peeled off from the sheet and no trace of oil bleed is observed.
Δ: A trace of oil bleed is observed with the kraft paper slightly adhering to the sheet.
X: Kraft paper is in close contact with the sheet and traces of oil bleed are observed.

(5) Dipping property: A 1000 cc round bottom flask equipped with a reflux condenser was charged with a magnetic stirrer of 60 mm × φ8 mm, 200 g of the thermoplastic elastomer pellets of the present invention and 300 g of industrial xylol, and maintained at about 95 ° C. The mixture was stirred for 1 hour in the high-temperature tank equipped with a stirrer. The mixture was allowed to stand for 12 hours or more until it reached room temperature, stirred for 10 minutes, and dipped once using a ferrotype plate (130 mm × 130 mm × 1 mm). The ferrotype plate was allowed to stand at room temperature for 30 minutes, and then heat-treated in an oven at 120 ° C. for 30 minutes. The film formation state was visually observed and evaluated according to the following criteria.
A: There is no pinhole-like unmelted material and the film thickness is uniform.
○: There is no pinhole-shaped unmelted material, but the film thickness is not uniform.
(Triangle | delta): There exists a pinhole-shaped unmelted material.
X: Film formation is impossible.
(6) Oil resistance (volume change rate): In accordance with JIS K 6258, a test piece was used by punching a dipping molded sheet having a thickness of about 0.5 mm into a No. 3 mold with a dumbbell. Liquid paraffin (Neothiozole: Sanko Chemical Co., Ltd., boiling point: 225 to 247 ° C., specific gravity: 0.761) was used, and the volume change at 50 ° C. × 24 hours was measured.
(7) Gas barrier property: Measured at 25 ° C. using a dipping molded sheet having a thickness of about 0.5 mm according to JIS K 7126 A method (differential pressure method). Before measurement, the sample was allowed to stand at 25 ° C. for about 6 hours, and then gas barrier properties against oxygen and carbon dioxide were measured.
[In order to determine the gas barrier properties of solvents (benzene, thinner, toluene, xylol, MEK, DMF, etc.), pseudo tests were conducted with oxygen and carbon dioxide. ]
(8) Water vapor barrier property: According to JIS K 7129 A method (moisture sensitive sensor method), measurement was performed under the condition of 40 ° C. × 90% RH using a dipping molded sheet having a thickness of about 0.5 mm. Before the measurement, after standing at 40 ° C. × 90% RH for about 170 hours, the gas barrier property against water vapor was measured.

Raw material used Component (a): Styrene-isobutylene-styrene block copolymer [SIBS: SIBSTAR 073T (manufactured by Kaneka Chemical Co., Ltd.)] obtained by living cationic polymerization, styrene content: 30% by weight, number average molecular weight: 60,000, weight average molecular weight: 65,000, molecular weight distribution: 1.08, hardness: 57A, unsaturated bond: 0%.
Component (b-1): Hydrogenated copolymer component, Septon 2104 (SEPS) (trademark; manufactured by Kuraray Co., Ltd.), styrene content 65% by weight, number average molecular weight 70,000, weight average molecular weight 91,000, molecular weight Distribution 1.30, hydrogenation rate 90% or more.
Component (b-2): Hydrogenated copolymer component, Kraton E-1818E (SEBS) (trademark; manufactured by Kraton Polymer Japan Co., Ltd.), styrene content 30% by weight, number average molecular weight 160,000, weight average molecular weight 200 1,000, molecular weight distribution 1.25, hydrogenation rate 90% or more.
Component (b-3): Hydrogenated copolymer component, Septon 4077 (trademark; manufactured by Kuraray Co., Ltd.), styrene content 30% by weight, number average molecular weight 260,000, weight average molecular weight 320,000, molecular weight distribution 23, 90% or more hydrogenation rate.
Component (b-4): Hydrogenated copolymer component, Dynalon DR6201B (CEBC) (trademark; manufactured by JSR Corporation), styrene content 0% by weight, number average molecular weight 180,000, weight average molecular weight 230,000, molecular weight Distribution 1.27, hydrogenation rate 90% or more.

Component (c): Non-aromatic rubber softener NA Solvent NAS-5H (Nippon Yushi Co., Ltd.) Specific gravity: 0.823, Type: Isoparaffin hydrocarbon oil, Viscosity (40 ° C.): 11.0 cSt, Flammable Point: 146 ° C.
Component (d): Petroleum resin, Imabu P-140 (trademark; manufactured by Idemitsu Petrochemical Co., Ltd.), softening point: 140 ° C., average molecular weight: 910, density: 1.03 g / cm ³ .
Component (e): Terpene oil, Woody River # 10 (manufactured by Yashara Chemical Co., Ltd.) Specific gravity: 0.80, viscosity (25): 1.14 cP, boiling point: 167-170 ° C., flash point: 41.5 ° C.
Component (f): additive, antioxidant HP2215 (manufactured by Ciba Specialty Chemicals), component: 15% lactone-based and 85% hindered phenol-based / phosphite-based combined antioxidant.

Examples and Comparative Examples A 1000 cc round bottom flask equipped with a reflux condenser was charged with a magnetic stirrer of 60 mm × φ8 mm, 200 g of thermoplastic elastomer pellets of the present invention and 300 g of industrial xylol, and maintained at about 95 ° C. The mixture was stirred for 1 hour in a high-temperature tank equipped with a stirrer. The mixture was allowed to stand for 12 hours or more until it reached room temperature, stirred for 10 minutes, and dipped once using a ferrotype plate (130 mm × 130 mm × 1 mm). The ferrotype plate was left at room temperature for 30 minutes, and then heat-treated in an oven at 120 ° C. for 30 minutes to obtain a test sheet.

As is clear from Examples 1 to 6 in Table 1, the thermoplastic elastomer composition of the present invention has a gas barrier property against oxygen and carbon dioxide of 6 × 10 ⁻¹⁵ mol · m · m ² · s · Pa or less, The gas barrier property against water vapor was 2 g / m ² · 24 hours or less and had good characteristics. Moreover, the volume resistivity in the thermoplastic elastomer composition of Examples 1-6 was the range of 2 * 10 < ¹⁵ > (ohm * cm) -5 * 10 < ¹⁵ > (ohm * cm), and all had high insulation resistance.
In Examples 2 to 6, the dipping moldability was further improved by adding the component (b).
In Example 6, a flexible composition having a hardness of 50 A or less can be obtained using the optional component (c). At that time, the use of component (d) further imparts flexibility to the product and the adhesive property to polyurethane, and the use of component (e) causes deterioration of the composition due to heat during paste adjustment and dipping molding. Further, the property of reducing the property was imparted.
In Comparative Examples 1 to 4 shown in Table 2, the component (a) was not blended. From Table 2, it is clear that when component (a) is not included, oil resistance and gas barrier properties are not exhibited.

Claims (10)

A dipping characterized by containing an isobutylene block copolymer composed of (a) an isobutylene compound block and an aromatic vinyl compound block that satisfies all of the following conditions (1), (2) and (3): Molding composition.
(1) The isobutylene block copolymer is a triblock body having a structure of (a unit mainly composed of an aromatic vinyl compound, a unit mainly composed of isobutylene and a unit mainly composed of an aromatic vinyl compound).
(2) The isobutylene block copolymer comprises 90 to 60% by weight of a monomer mainly composed of isobutylene and 10 to 40% by weight of a monomer mainly composed of an aromatic vinyl compound.
(3) The isobutylene block copolymer has a weight average molecular weight of 60,000 to 400,000.   2. The dipping molding composition according to claim 1, comprising 1 to 80 parts by weight of (b) hydrogenated and / or partially hydrogenated copolymer with respect to 100 parts by weight of (a).   The composition for dipping molding according to claim 1 or 2, comprising 1 to 100 parts by weight of (c) a non-aromatic rubber softener for 100 parts by weight of (a).   The composition for dipping molding according to any one of claims 1 to 3, comprising 1 to 50 parts by weight of (d) a petroleum resin with respect to 100 parts by weight of (a).   A solvent paste for dipping molding obtained by dissolving 100 parts by weight of the composition according to any one of claims 1 to 4 in 80 to 400 parts by weight of a solvent. According to JIS K 6258, oil resistance (volume change rate) at 50 ° C. × 24 hours using liquid paraffin is 30% or less, according to any one of claims 1 to 4 A composition for dipping molding. Based on JIS K 7126 A method (differential pressure method), 0.5 mm thick dipping molded sheet is used, and the gas barrier property against oxygen at 25 ° C. after standing for 6 hours at 25 ° C. before measurement is 6 × 10 ⁻¹⁵ mol · The composition for dipping molding according to any one of claims 1, 2, 3, 4 and 6, wherein m / m ² · s · Pa or less. Based on JIS K 7126 A method (differential pressure method), a 0.5 mm thick dipping molded sheet is used, and the gas barrier property against carbon dioxide at 25 ° C. after standing at 25 ° C. for about 6 hours is 6 × 10 ⁻¹⁵ mol. The composition for dipping molding according to any one of claims 1, 2, 3, 4, 6 and 7 , wherein m / m ² · s · Pa or less. In accordance with JIS K 7129 A method (moisture sensitive sensor method), using a 0.5 mm thick dipping molded sheet, under conditions of 40 ° C. × 90% RH after standing for about 170 hours at 40 ° C. × 90% RH before measurement. The dipping molding composition according to any one of claims 1, 2, 3, 4, 6, 7 and 8, wherein a gas barrier property against water vapor is 2 g / m ² · 24 hours or less. A gas barrier dipping molding composition comprising the dipping molding composition according to any one of claims 1, 2, 3, 4, 6, 7, 8, or 9 .