WO2018174068A1 - Article stratifié - Google Patents

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WO2018174068A1
WO2018174068A1 PCT/JP2018/011105 JP2018011105W WO2018174068A1 WO 2018174068 A1 WO2018174068 A1 WO 2018174068A1 JP 2018011105 W JP2018011105 W JP 2018011105W WO 2018174068 A1 WO2018174068 A1 WO 2018174068A1
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polymer layer
polymer
laminate
latex
young
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PCT/JP2018/011105
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English (en)
Japanese (ja)
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健太郎 早坂
実紗 山本
伊賀　隆志
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日本ゼオン株式会社
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Priority to JP2019507696A priority Critical patent/JPWO2018174068A1/ja
Publication of WO2018174068A1 publication Critical patent/WO2018174068A1/fr

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  • the present invention relates to a laminate comprising a substrate and a polymer layer formed from a polymer latex. Moreover, this invention relates also to the method for measuring the softness
  • Patent Document 1 a sample is taken from a protective glove, and the flexibility is evaluated by measuring the bending rigidity of the collected sample using a bending tester.
  • the softness was appropriately evaluated because the correlation between the results and the feeling of use (softness) when actually worn was low. Therefore, in the past, there was a situation in which the flexibility cannot be properly evaluated for a thin sample such as a laminate such as a protective glove, so what kind of laminate would be excellent in flexibility. It has not been clarified whether it will be a product, and it has been difficult to produce a laminate having excellent flexibility.
  • the present invention has been made in view of such a situation, and an object thereof is to provide a laminate having excellent flexibility.
  • the present inventors have permeated the substrate out of the polymer layers in a laminate comprising a substrate and a polymer layer formed from a polymer latex.
  • the thickness of the portion and the thickness of the portion of the polymer layer that covers the surface of the base material are controlled so as to be in a predetermined state, and the laminate in the portion where the polymer layer is laminated on the base material.
  • a laminate comprising a substrate and a polymer layer formed from a polymer latex, wherein the polymer layer partially penetrates the substrate.
  • the ratio of the thickness t 1 of the osmotic polymer layer to the thickness t 2 of the surface polymer layer (t 1 / t) where t 2 is the thickness of the surface polymer layer from the surface of the substrate. 2 ) is 0.15 to 5.0, and a laminate having a Young's modulus of 800 kPa or less at a portion where the polymer layer is laminated on the substrate is provided.
  • the thickness t 1 of the osmotic polymer layer is preferably 0.05 to 0.6 mm.
  • the polymer latex for forming the polymer layer has a Young's modulus of the film molded body of 10,000 kPa or less when the volatile matter is removed to form a film molded body. preferable.
  • the polymer latex for forming the polymer layer contains a conjugated diene rubber having a conjugated diene monomer unit content of 52 to 78% by weight as the polymer. Is preferred.
  • the polymer latex for forming the polymer layer is a conjugated polymer in which the content of the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit is 20 to 40% by weight. It is preferable to contain a diene rubber.
  • the polymer latex for forming the polymer layer is a conjugated diene-based polymer having a carboxyl group-containing ethylenically unsaturated monomer unit content of 2 to 10% by weight as the polymer. It is preferable to contain rubber.
  • a method for measuring the flexibility of a rubber film molded body or a laminate having a rubber layer, wherein an indenter is pushed into the film molded body or the laminated body with a predetermined pushing load Provided is a method for measuring the flexibility of a rubber film molded body or a laminate having a rubber layer, in which the flexibility is measured based on the indentation load and the displacement due to the indentation when the indenter is indented.
  • the film molded body or the laminated body is used in contact with a human body.
  • a laminate having excellent flexibility can be provided.
  • FIG. 1 (A) is a cross-sectional view of a fiber base material before forming a polymer layer
  • FIG. 1 (B) is formed by laminating a polymer layer on the fiber base material shown in FIG. 1 (A).
  • FIG. 2 is a diagram illustrating an example of an indentation test apparatus 20 that can be used in the measurement method of the present invention.
  • FIG. 3 is a characteristic curve showing the relationship between the indentation load on the measurement sample 10 and the displacement caused by the indentation of the measurement sample 10.
  • FIG. 4 is a graph plotting the measurement results of the Young's modulus of the film molded body and the Young's modulus of the protective gloves in association with the results of the sensory test.
  • FIG. 5 is a graph plotting Young's modulus and bending test results in association with sensory test results.
  • the laminate of the present invention is a laminate comprising a substrate and a polymer layer formed from a polymer latex, The polymer layer partially covers the base material in a state of permeating the base material, Wherein one of the polymer layers, which is a penetration portion to the substrate osmopolymers layer, the thickness from the surface of the substrate and t 1, the surface polymer layer is a portion that covers the substrate, When the thickness from the surface of the base material is t 2 , the ratio of the thickness t 1 of the osmotic polymer layer to the thickness t 2 of the surface polymer layer (t 1 / t 2 ) is 0.15 to 5.0, The Young's modulus in the portion where the polymer layer is laminated on the base material is 800 kPa or less.
  • the laminate of the present invention comprises a substrate and a polymer layer.
  • the laminated body of this invention can be used for the use for which a softness
  • a laminated body which has a polymer layer the laminated body which has a fiber base material and polymer layer used in contact with human bodies, such as a protective glove, is illustrated and demonstrated.
  • the fiber base material is not particularly limited as long as it is made of fiber, but natural fibers such as cotton, wool, hemp, and wool, and synthetic fibers such as polyester, polyurethane, acrylic, and nylon may be used as a material. Among these, nylon is preferably used.
  • the fiber base material may be knitted or sewn, and may be a woven fabric or a non-woven fabric.
  • the thickness of the fiber base material (base material layer average thickness d of the fiber base material described later) is not particularly limited, but is preferably 0.05 to 3.00 mm, more preferably 0.10 to 2.00 mm, and still more preferably. 0.15 to 1.5 mm.
  • the linear density of the fiber base material is not particularly limited, but is preferably 50 to 500 denier.
  • the gauge number of the fiber base material is not particularly limited, but is preferably 7 to 18 gauge. Here, the number of gauges refers to the number of knitting machine needles between 1 inch.
  • a polymer latex containing a polymer is brought into contact with the fiber substrate to which the coagulant solution is adhered. It can be obtained by solidifying the polymer in the combined latex to form a polymer layer on the fiber substrate. In this case, the coagulant solution adhering to the fiber base material penetrates between the fibers constituting the fiber base material. In this state, when the polymer latex is brought into contact with the fiber base material into which the coagulant solution has permeated, a part of the polymer latex penetrates between the fibers constituting the fiber base material, and the polymer inside is solidified. By doing so, as shown in FIG.
  • a polymer layer is formed on the surface of the fiber substrate, and a part of the polymer layer constitutes the fiber substrate. It penetrates to the gap between the fibers.
  • 1A is a cross-sectional view of the fiber base material before forming the polymer layer
  • FIG. 1B is a view in which the polymer layer is laminated on the fiber base material shown in FIG. It is sectional drawing of the laminated body formed.
  • the polymer layer formed by coagulating the polymer in the polymer latex may have a multilayer laminated structure by performing the above method a plurality of times.
  • the polymer layer covers the fiber base material in a state where a part of the polymer layer penetrates between the fibers constituting the fiber base material.
  • transmitted the clearance gap between the fibers from the surface of a fiber base material among the polymer layers which comprise a laminated body is made into a permeation
  • covers a fiber base material from the surface of a base material is shown as a surface polymer layer.
  • the polymer layer will be described as appropriately consisting of a osmotic polymer layer and a surface polymer layer. Usually, the osmotic polymer layer and the surface polymer layer are integrally formed. It becomes.
  • the ratio of the thickness t 1 of the osmotic polymer layer to the thickness t 2 of the surface polymer layer may be 0.15 to 5.0, and the durability From the viewpoint of highly balancing flexibility and comfort when worn, it is preferably 0.2 to 0.5, more preferably 0.25 to 4.80, and still more preferably 0.30 to 4.60.
  • the thickness t 1 of the penetrating polymer layer is preferably 0.05 to 0.6 mm, more preferably 0.10 to 0.00 mm, from the viewpoint of durability when the laminate is used as a protective glove or the like. It is 55 mm, more preferably 0.10 to 0.50 mm.
  • the thickness t 1 of the osmotic polymer layer is preferably 0.01 to 3.00 mm, more preferably 0.02 to 2.5 mm, from the viewpoint of durability when the laminate is used as a protective glove or the like. More preferably, it is 0.03 to 2.0 mm.
  • the thickness of the osmotic polymer layer with respect to the average thickness d of the base material layer of the fiber base material from the viewpoint of highly balancing the durability, flexibility, and comfort during wearing when the laminate is used as a protective glove or the like.
  • the ratio of t 1 (t 1 / d) is preferably 0.1 to 0.95, and more preferably from 0.1 to 0.9 and more preferably 0.15 to 0.8.
  • the total thickness of the laminate (total of the surface polymer layer thickness t 2 and the fiber substrate base layer average thickness d) is preferably 0.75 to 3.70 mm, more preferably 0.75. ⁇ 3.5 mm.
  • the thickness may be different between the portion where the fiber overlap is dense and the portion where the fiber overlap is sparse.
  • the base material layer average thickness d of a base material shall be calculated
  • the polymer constituting the polymer latex used for obtaining the laminate of the present invention is not particularly limited. Natural rubber; conjugated diene rubber obtained by polymerizing or copolymerizing conjugated dienes such as butadiene and isoprene Among these, conjugated diene rubbers are preferable.
  • conjugated diene rubber include so-called nitrile rubber, isoprene rubber, styrene-butadiene rubber, chloroprene rubber and the like obtained by copolymerizing nitrile, and among these, nitrile rubber is particularly preferable.
  • the nitrile rubber is not particularly limited, and a nitrile rubber obtained by copolymerizing an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer and other copolymerizable monomers used as necessary can be used.
  • the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer is not particularly limited, and an ethylenically unsaturated compound having a nitrile group and preferably having 3 to 18 carbon atoms can be used.
  • Examples of such ⁇ , ⁇ -ethylenically unsaturated nitrile monomers include acrylonitrile, methacrylonitrile, halogen-substituted acrylonitrile and the like, and among these, acrylonitrile is particularly preferable.
  • These ⁇ , ⁇ -ethylenically unsaturated nitrile monomers may be used alone or in combination of two or more.
  • the content of the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit in the nitrile rubber is preferably 10 to 45% by weight, more preferably 20 to 40% by weight, still more preferably based on the total monomer units. It is 21 to 38% by weight, particularly preferably 22 to 37% by weight.
  • a conjugated diene monomer unit is provided from the viewpoint of imparting rubber elasticity and more effectively preventing cracks from occurring in the polymer layer of the obtained laminate.
  • the thing containing is preferable.
  • the conjugated diene monomer forming the conjugated diene monomer unit include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, chloroprene and the like having 4 to 4 carbon atoms. 6 conjugated diene monomers are preferred, 1,3-butadiene and isoprene are more preferred, and 1,3-butadiene is particularly preferred.
  • these conjugated diene monomers may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the content ratio of the conjugated diene monomer unit is preferably 40 to 80% by weight, more preferably 52 to 78% by weight, still more preferably 54 to 76% by weight, based on all monomer units constituting the nitrile rubber. Particularly preferred is 56 to 74% by weight.
  • Nitrile rubber is also a monomer that forms ⁇ , ⁇ -ethylenically unsaturated nitrile monomer units and other ethylenically unsaturated monomers that are copolymerizable with monomers that form conjugated diene monomer units.
  • An acid monomer may be included.
  • Such other copolymerizable ethylenically unsaturated acid monomer is not particularly limited, and examples thereof include a carboxyl group-containing ethylenically unsaturated monomer, a sulfonic acid group-containing ethylenically unsaturated monomer, Examples thereof include phosphoric acid group-containing ethylenically unsaturated monomers.
  • the carboxyl group-containing ethylenically unsaturated monomer is not particularly limited, but ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; fumaric acid, maleic acid, itaconic acid, maleic anhydride, anhydrous And ethylenically unsaturated polyvalent carboxylic acids such as itaconic acid and anhydrides thereof; partially esterified products of ethylenically unsaturated polyvalent carboxylic acids such as methyl maleate and methyl itaconic acid; and the like.
  • monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid
  • fumaric acid, maleic acid, itaconic acid, maleic anhydride anhydrous And ethylenically unsaturated polyvalent carboxylic acids such as itaconic acid and anhydrides thereof
  • the sulfonic acid group-containing ethylenically unsaturated monomer is not particularly limited, but vinyl sulfonic acid, methyl vinyl sulfonic acid, styrene sulfonic acid, (meth) allyl sulfonic acid, (meth) acrylic acid-2-sulfonic acid ethyl And 2-acrylamido-2-hydroxypropanesulfonic acid.
  • the phosphoric acid group-containing ethylenically unsaturated monomer is not particularly limited, but includes (meth) acrylic acid-3-chloro-2-propyl phosphate, (meth) acrylic acid-2-ethyl phosphate, 3-allyloxy. Examples include -2-hydroxypropane phosphoric acid.
  • These other copolymerizable ethylenically unsaturated acid monomers can also be used as alkali metal salts or ammonium salts, and can be used alone or in combination of two or more. .
  • carboxyl group-containing ethylenically unsaturated monomers are preferable, ethylenically unsaturated monocarboxylic acids are more preferable, and methacrylic acid is particularly preferable.
  • the content ratio of the ethylenically unsaturated acid monomer unit is preferably 2 to 10% by weight, more preferably 2.5 to 9.0% by weight, and still more preferably 3.0 to 8.0% by weight. .
  • the polymer latex can be obtained, for example, by emulsion polymerization of a monomer mixture containing the above monomers.
  • emulsion polymerization commonly used polymerization auxiliary materials such as an emulsifier, a polymerization initiator, and a molecular weight modifier can be used.
  • the polymer latex used for obtaining the laminate of the present invention a film in the case of forming a film molded body by removing volatile components from the viewpoint that a laminate having excellent flexibility can be suitably obtained.
  • a molded product having a Young's modulus of 10,000 kPa or less it is preferable to use a molded product having a Young's modulus of 10,000 kPa or less.
  • the Young's modulus of the film molded body may be 10,000 kPa or less, preferably 9,500 kPa or less, more preferably 9,000 kPa or less, further preferably 8,000 kPa or less, and particularly preferably 7, 000 kPa or less.
  • the lower limit of the Young's modulus of the film molded body is not particularly limited, but is usually 0.01 kPa or more, preferably 0.02 kPa or more.
  • the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit is preferably 20 to 40% by weight, more preferably 21 to 38% by weight, More preferably, it is contained in the range of 22 to 37% by weight, and the conjugated diene monomer unit is preferably 52 to 78% by weight, more preferably 54 to 76% by weight, still more preferably 56 to 74% by weight.
  • the unit of the carboxyl group-containing ethylenically unsaturated monomer is preferably 2 to 10% by weight, more preferably 2.5 to 9.0% by weight. Further, it is particularly preferable to contain in the range of 3.0 to 8.0% by weight. In this case, as the monomer constituting each monomer unit, those described above can be used.
  • the Young's modulus in the case of forming a film molded body by removing volatile matter can be further reduced.
  • flexibility of the laminated body obtained can be improved more appropriately.
  • by making the content rate of a conjugated diene monomer unit into the said range it can suppress more effectively that a gel generate
  • the polymer layer is prevented from becoming a non-uniform film due to the generation of such a gel, and cracks are generated in the polymer layer of the obtained laminate.
  • the laminate can be excellent in solvent resistance and texture. Furthermore, by including the unit of the carboxyl group-containing ethylenically unsaturated monomer in the above content ratio, the Young's modulus in the case of forming a film molded body by removing the volatile matter can be further reduced. Thus, the flexibility of the obtained laminate can be improved more appropriately.
  • a polymer constituting the polymer latex having a methylethylketone insoluble content is preferably 90% by weight or less, more preferably 85% by weight or less, and further preferably 80% by weight or less. Is preferred.
  • a latex blended with a compounding agent such as a crosslinking agent or a thickener may be used as polymer latex. That is, as polymer latex, you may mix
  • blend compounding agents such as a crosslinking agent and a thickener
  • the Young's modulus of the film molded body in the case where the film molded body is removed to form a film molded body may be 10,000 kPa or less.
  • the crosslinking agent it is preferable to use a sulfur-based crosslinking agent.
  • a sulfur type crosslinking agent Sulfur, such as powder sulfur, sulfur white, precipitation sulfur, colloidal sulfur, surface treatment sulfur, insoluble sulfur; sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, dibenzothia Sulfur-containing compounds such as zildisulfide, caprolactam disulfide, phosphorus-containing polysulfide, and polymer polysulfides; sulfur-donating compounds such as tetramethylthiuram disulfide, selenium dimethyldithiocarbamate, and 2- (4′-morpholinodithio) benzothiazole; Is mentioned.
  • These crosslinking agents may be used alone or in combination of two or more.
  • crosslinking accelerator vulcanization accelerator
  • zinc oxide a crosslinking accelerator (vulcanization accelerator) and zinc oxide.
  • the crosslinking accelerator (vulcanization accelerator) is not particularly limited.
  • dithiocarbamine such as diethyldithiocarbamic acid, dibutyldithiocarbamic acid, di-2-ethylhexyldithiocarbamic acid, dicyclohexyldithiocarbamic acid, diphenyldithiocarbamic acid, and dibenzyldithiocarbamic acid.
  • zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, 2-mercaptobenzothiazole, 2-mercaptobenzothiazole zinc is preferred.
  • These crosslinking accelerators may be used alone or in combination of two or more.
  • the viscosity of the polymer latex may be adjusted so that a thickener is added from the viewpoint of controlling the thickness t 1 of the penetrating polymer layer and the thickness t 2 of the surface polymer layer.
  • a thickener for example, Vinyl compounds, such as polyvinyl alcohol and polyvinyl pyrrolidone; Cellulose derivatives, such as hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethylcellulose salt; Polycarboxylic acid compound and its sodium salt; Polyethylene And polyoxyethylene derivatives such as glycol ethers.
  • the 1% viscosity of the thickener used is preferably 20 mPa ⁇ s or more, more preferably 50 mPa ⁇ s or more, and even more preferably 200 mPa ⁇ s or more.
  • the 1% viscosity of the thickener is obtained by dissolving the thickener in water to obtain an aqueous solution having a concentration of 1% by weight, and measuring the viscosity at 25 ° C. using a B-type viscometer at a rotation speed of 10 rpm. Can be obtained.
  • the particle size of the insoluble component when the thickener to be used is dissolved in water is preferably 30 ⁇ m or less, more preferably 28 ⁇ m or less, and still more preferably 25 ⁇ m or less.
  • the content of the thickener in the polymer latex is preferably 0.1 to 5.0% by weight, more preferably 0.1 to 4.0% by weight. %, And further 0.1 to 3.0% by weight.
  • the method of adding the polymer latex to the thickener is not particularly limited, but when a polymer latex to which a crosslinking agent is added is used, it is prevented that aggregates are generated in the polymer latex. From the viewpoint of enabling better transfer of the polymer latex, a method of adding a thickener after aging the polymer latex, or a portion of the thickener before aging the polymer latex It is preferable to use a method in which a thickener is further added after aging, and a method in which a thickener is added after aging of the polymer latex is particularly preferable.
  • the laminated body of this invention does not specifically limit as a method to manufacture the laminated body of this invention.
  • the following methods can be used. That is, in a laminate having a fiber base material and a polymer layer, for example, a coagulant solution is attached to the fiber base material, and then a polymer latex is brought into contact with the fiber base material to which the coagulant solution is attached.
  • the method of obtaining the laminated body which consists of a fiber base material and a polymer layer by forming a polymer layer on a fiber base material by coagulating a polymer can be used.
  • stacked several times after polymer layer formation may be sufficient.
  • the method for attaching the polymer latex to the fiber substrate is not particularly limited, and examples thereof include a method of immersing the fiber substrate in the polymer latex.
  • the fiber base material when attaching the coagulant solution to the fiber base material, it is preferable to immerse the fiber base material in the coagulant solution in a state where the fiber base material is previously covered with a molding die of a desired shape, It is preferable to immerse the polymer latex in the fiber base material to which the coagulant solution is attached.
  • mold which covers a fiber base material Various things, such as a product made from porcelain, glass, metal, and plastics, can be used.
  • the shape of the molding die may be a desired shape according to the shape of the final product.
  • the mold for various gloves such as a mold having a shape from the wrist to the fingertip, is used as a mold for covering the fiber substrate. Is preferably used.
  • the drying temperature at this time is not particularly limited and may be selected according to the solvent to be used, but is preferably 10 to 80 ° C., more preferably 15 to 70 ° C.
  • the drying time is not particularly limited, but is preferably 1 to 600 seconds, more preferably 5 to 300 seconds.
  • the polymer latex is brought into contact with the fiber base material to which the coagulant solution is adhered in this manner, so that the polymer in the polymer latex is coagulated to form a polymer layer on the fiber base material. .
  • the method of bringing the polymer latex into contact with the fiber base material to which the coagulant solution is attached is not particularly limited, and examples thereof include a method in which the fiber base material to which the coagulant solution is attached is immersed in the polymer latex.
  • the fiber base material to which the coagulant solution is attached is immersed in the polymer latex
  • the fiber base material to which the coagulant solution is attached is put on the polymer latex in a state where the fiber base material is put on a molding die having a desired shape. It is preferable to immerse.
  • the fiber base material is coated with the coagulant solution as described above in a state where the fiber base material is previously covered with a molding die having a desired shape, and then the coagulant solution is adhered to the fiber base material. Is preferably immersed in a polymer latex while being covered with a molding die.
  • the drying temperature at this time is not particularly limited, but is preferably 10 to 80 ° C., more preferably 15 to 80 ° C.
  • the drying time is not particularly limited, but is preferably 5 seconds to 120 minutes, more preferably 10 seconds to 60 minutes.
  • the fiber base material may be dipped in polymer latex and dried, and then polymer latex may be further dipped and laminated multiple times.
  • crosslinking agent when blended in the polymer latex, it may be crosslinked by heating as necessary.
  • the laminate is obtained by detaching the fiber base material on which the polymer layer is formed from the molding die. Can do.
  • the desorption method it is possible to adopt a method of peeling from the mold by hand, or peeling by water pressure or compressed air pressure.
  • the laminated body which has a fiber base material and a polymer layer as an example of the laminated body which has a polymer layer can be obtained.
  • the laminate of the present invention measures the Young's modulus at the portion where the polymer layer is laminated on the substrate (that is, the measurement is performed on the substrate and the polymer layer at the place where the polymer layer is laminated on the substrate).
  • the Young's modulus obtained by carrying out is 800 kPa or less, preferably 750 kPa or less, more preferably 700 kPa or less, further preferably 600 kPa or less, and particularly preferably 500 kPa or less.
  • the Young's modulus within the above range, the obtained laminate can be remarkably excellent in flexibility when used as protective gloves or the like.
  • the lower limit of the Young's modulus in the part of the laminate in which the polymer layer is laminated on the base material is not particularly limited, but is usually 0.01 kPa or more, preferably 0.02 kPa or more.
  • the present inventors have found a method that can appropriately measure the Young's modulus for a thin sample such as a laminated body such as a protective glove by a method described later, and in this way.
  • the Young's modulus measured in this way was found to be highly correlated with the flexibility of the laminate. Based on such knowledge, the present invention obtains a laminate that is remarkably excellent in flexibility by controlling the Young's modulus of the laminate in which the polymer layer is laminated on the base material within the above range. It is something that can be done.
  • the method of controlling the Young's modulus in the portion where the polymer layer is laminated on the base material within the above range is not particularly limited, but the type and composition of the polymer constituting the polymer latex are not limited.
  • the method of adjusting, the method of adjusting the type and amount of the thickener added to the polymer latex, and the ratio of the thickness t 1 of the osmotic polymer layer to the thickness t 2 of the surface polymer layer (t 1 / t 2 ) Examples of the method include controlling each of the above ranges.
  • a method using a polymer latex having a Young's modulus of 10,000 kPa or less in the case of forming a film molded body by removing volatile components is also suitable.
  • the Young's modulus of the laminate of the present invention is measured based on the indentation load and the displacement due to indentation when the indenter is pushed into the laminate having a polymer layer with a predetermined indentation load. be able to. Since the Young's modulus measured by this method serves as an index indicating flexibility, according to this method, the flexibility of a laminate having a rubber layer such as the laminate of the present invention can be measured.
  • the method for measuring the Young's modulus of the laminate of the present invention will be described.
  • the Young's modulus of the film molded body obtained using the polymer latex that is, the film molded body obtained using the polymer latex, etc.
  • the flexibility of the rubber film molding can also be measured in the same manner.
  • the indenter is pushed with at least one indentation load into the laminate having the polymer layer, and when the indenter is indented with at least one indentation load. It is sufficient to measure the Young's modulus based on the displacement, but from the viewpoint that the Young's modulus can be measured more appropriately, the indentation load when the indenter is pushed in with different indentations and indented with different indentations It is preferable to measure the Young's modulus based on the corresponding displacement due to the pressing.
  • FIG. 2 is a diagram showing an example of an indentation test apparatus 20 that can be used for measuring Young's modulus.
  • the measurement method of Young's modulus in the case of using the indentation test apparatus 20 shown in FIG. 2 will be described as an example.
  • the measurement method of Young's modulus is a method using the indentation test apparatus 20 shown in FIG. It is not particularly limited.
  • the indentation test apparatus 20 shown in FIG. 2 includes a suction table 30 for placing a measurement sample 10 to be measured for Young's modulus on a measurement table 21, and above the measurement table 21 and the suction table 30.
  • a support arm 22 that holds the spherical indenter 29 is provided. Further, the support arm 22 is provided with a horizontal arm 23, and the spherical indenter 29 is moved in the in-plane direction of the measurement table 21 and the suction table 30 by the horizontal drive mechanism provided in the horizontal arm 23, that is, in the drawing.
  • the indentation test apparatus 20 can perform tests on various portions of the measurement sample 10.
  • a stage 26 is provided so as to be movable in the Z direction in the figure via a coarse moving vertical moving mechanism 24 and a fine moving vertical moving mechanism 25.
  • a spherical indenter 29 is connected to the stage 26 via a load cell 27 and a load shaft 28.
  • the coarse movement vertical movable mechanism 24 can be provided with a movable mechanism using a ball nut, for example, and the stage 26 can be moved in the Z direction in the figure by the rotation of the motor.
  • the fine moving vertical moving mechanism 25 can be provided with a voice coil motor as a moving mechanism, for example, and the stage 26 can be moved in the Z direction with a fine pitch with high accuracy.
  • the spherical indenter 29 is moved by the fine moving vertical movable mechanism 25 via the stage 26.
  • the indenter 29 can be pushed into the measurement sample 10 with a fine pitch with high accuracy.
  • the indentation load at this time can be detected by the load cell 27.
  • the fine movement vertical movable mechanism 25 includes, for example, an optical position detection mechanism using a laser, and the like, and thereby, with a high degree of accuracy, the amount of pressing with respect to the measurement sample 10, that is, the displacement due to the pressing of the measurement sample 10. (Displacement in the thickness direction) can be detected.
  • the suction table 30 has a plurality of suction holes formed in the vicinity of a measurement location (that is, a location where the spherical indenter 29 abuts) on the surface thereof, and is connected to a suction pump (not shown).
  • the measurement sample 10 can be fixed by suction from a plurality of suction holes. In the present invention, the measurement can be performed with high accuracy by performing the measurement while being fixed by suction.
  • the laminated body that is the object of measurement often suffers from sagging of the sample during measurement and cannot be measured satisfactorily.
  • the suction table 30 by performing measurement while being fixed by suction, it is possible to effectively prevent the occurrence of such a defect, thereby realizing highly accurate measurement.
  • a resin tape is applied to a portion corresponding to the plurality of suction holes of the suction table 30 out of the surface opposite to the measurement surface. It is preferable that the measurement is performed by placing it on the suction table 30 after it is in a pasted state.
  • the spherical indenter 29 is driven by the coarse moving vertical movable mechanism 24 through the stage 26, and the spherical indenter 29 is moved to the vicinity of the surface of the measurement sample 10 fixed on the suction table 30 by suction. Thereafter, the spherical indenter 29 is gradually pushed into the measurement sample 10 at a fine pitch through the stage 26 of the vertical moving mechanism 25 for fine movement, and the indentation load on the measurement sample 10 detected by the load cell 27 at this time,
  • the measurement sample as shown in FIG. 3 can be detected by continuously detecting the amount of pushing detected by the position detection mechanism provided in the fine moving vertical moving mechanism 25, that is, the displacement caused by the pushing of the measurement sample 10.
  • a characteristic curve showing the relationship between the indentation load with respect to 10 and the displacement due to indentation of the measurement sample 10 can be obtained.
  • a SUS product can be used as the spherical indenter 29, and the diameter is preferably 40 mm or less, more preferably 20 mm or less.
  • the indentation speed during measurement is preferably 0.1 to 10 mm / s, more preferably 0.1 to 2 mm / s, and the maximum load in measurement is 0.5 to 50 N. Is preferable, and 0.5 to 20 N is more preferable.
  • the Young's modulus of the measurement sample 10 can be obtained based on the characteristic curve showing the relationship between the indentation load on the measurement sample 10 shown in FIG. 3 and the displacement caused by the indentation of the measurement sample 10 obtained by the measurement.
  • a method for calculating the Young's modulus of the measurement sample 10 will be described.
  • the flexibility coefficient ⁇ can be obtained by the least square method or the like
  • the Young's modulus E of the measurement sample 10 can be obtained from the following equation (3) obtained by modifying the above equation (2).
  • the measurement sample 10 as a measurement object is the laminate of the present invention, and these are thin as described above. Therefore, when the spherical indenter 29 is pushed in, it is accompanied by pushing. Since the increase in the indentation load becomes significant, the above formula (1) based on the Hertz elastic contact theory cannot be applied with high accuracy in many cases. Therefore, when the thickness is thin like this, it is preferable to apply the following formula (4).
  • the pressing load F and the pressing amount related to the pressing of the spherical indenter 29 are used. (That is, the displacement of the measurement sample 10) ⁇ can be expressed appropriately.
  • ⁇ is a coefficient representing the influence of the thinness of the measurement sample 10 on the load. Therefore, in the present invention, even when the measurement sample 10 is a thin sample like the laminate of the present invention, the indentation load on the measurement sample 10 shown in FIG.
  • the coefficient ⁇ representing the influence on the load and the flexibility coefficient ⁇ can be obtained using the characteristic curve indicating the relationship with the displacement due to the pressing of the sample. Further, the Young of the measurement sample 10 can be obtained from the above equation (4).
  • the rate E can be determined.
  • the method for measuring the Young's modulus of the laminate of the present invention has been described.
  • the Young's modulus of the film molded body in the case of forming a film molded body by removing volatile components as the polymer latex is 10,000 kPa.
  • the above method may be used also when measuring the Young's modulus of the film molded body. That is, the volatile matter of the polymer latex is removed by a known method such as heating to obtain a film molded body, and the Young's modulus of the obtained film molded body may be measured according to the above method.
  • the thickness of the film molded body produced here is a thickness that is difficult to measure the Young's modulus by the conventional method, specifically, usually 3.0 mm or less, preferably 2.5 mm or less. it can.
  • the solid content obtained from the polymer latex can be measured as long as the solid content is in a bulk state, but the polymer latex is thin like a film molding. When used as a sample, it was difficult to measure the Young's modulus.
  • the Young's modulus can be measured even for a thin film molded body produced using a polymer latex.
  • the indenter when the indenter is pushed in with a predetermined pushing load, the rubber film molded body or the laminate having the rubber layer to be measured, when the indenter is pushed in, Since the flexibility is measured based on the indentation load and the displacement caused by the indentation, the flexibility of the rubber film molded body or the laminate having the rubber layer can be appropriately measured. More specifically, the indenter Based on the indentation load and the displacement due to the indentation, the Young's modulus of the rubber film molded body or the laminate having the rubber layer is obtained. By using it as an index, the flexibility of a rubber film molded body or a laminate having a rubber layer can be appropriately measured.
  • the content ratio of butadiene units was calculated by measuring the iodine value of nitrile rubber (according to JIS K 6235).
  • the content ratio of the acrylonitrile unit was calculated by measuring the nitrogen content in the nitrile rubber by the Kjeldahl method according to JIS K6384.
  • Methyl ethyl ketone insoluble polymer latex was poured onto a framed glass plate and allowed to stand for 48 hours at a humidity of 23 ° C. and a relative humidity of 50% to obtain a dry film having a thickness of 1 mm.
  • About 0.2 g of the obtained dried film was precisely weighed, and this was defined as the weight (W1) of the film before immersion.
  • W1 weight of the film before immersion.
  • the film before immersion was placed in an 80 mesh cage wire mesh and immersed in 100 mL of methyl ethyl ketone for 24 hours in a state of being placed in the cage wire mesh.
  • a 1% viscosity thickener of a thickener is dissolved in water to make an aqueous solution having a concentration of 1% by weight, and a viscosity measured at 25 ° C. using a B-type viscometer at a rotation speed of 60 rpm is 1% viscosity. As sought.
  • Insoluble component particle size of thickener The particle size of the insoluble component was determined by dissolving the thickener in water to a concentration of 1% by weight using a grind gauge (JIS-K5101) to JIS-K5600-5-2. The particle diameter measured by the linear method is shown. Specifically, the aqueous solution is placed on a particle size gauge, and the scraper is pulled toward the front so as to be perpendicular to the gauge, and the scale at the position where three or more lines of 10 mm or more appear continuously is read. The particle size of the insoluble component was determined by the wire method evaluation. In addition, the particle diameter measured by the said method does not exclude what the insoluble component whose particle diameter exceeds 30 micrometers contains in trace amount in a solution at all.
  • the absolute value of the difference between two average values obtained by measuring twice is 95% probability and 20% of the gauge range. It is expected to be (targeted). Therefore, in the range of accuracy and reproducibility required by JIS, an insoluble component having a particle diameter exceeding 30 ⁇ m may exist in the aqueous solution.
  • the thickness t 1 of the osmotic polymer layer and the thickness t 2 of the surface polymer layer For the protective gloves (laminated body), by observing the cross section where the polymer layer of the palm portion of 12 cm from the tip of the middle finger was laminated using an optical microscope (product name “VHX-200”, manufactured by Keyence Corporation), The thickness t 1 of the osmotic polymer layer and the thickness t 2 of the surface polymer layer were measured. A specific measurement method will be described with reference to FIG. 1.
  • the thickness t 1 of the osmotic polymer layer is measured at 10 points from the surface of the fiber base to the deepest part of the infiltrated rubber. The number average value was calculated by calculating.
  • the thickness t 2 of the surface polymer layer from the surface of the fiber substrate, the distance to the surface of the polymer layer was measured 10 locations were determined by calculating the number average value of the measurement results.
  • Sensory test gloves (laminated body) are worn by 10 people, and their flexibility is evaluated by the following five grades. The average score is obtained, and the average score is the highest. The closest score was used as the evaluation score in each example (for example, when the average value was 4.1, “4: soft” or the like). 5: Very soft 4: Soft 3: Slightly soft 2: Hard 1: Very hard
  • the resin tape is attached to the portions corresponding to the plurality of suction holes of the suction table 30 of the measurement sample, and the spherical indenter is applied from the polymer layer side while performing suction by the suction table 30.
  • the measurement was performed by pushing.
  • a polymer tape is applied to the surface opposite to the surface (measurement surface) on which the polymer layer of the measurement sample is formed, and suction is performed by the suction table 30 while the polymer is being suctioned. Measurement was performed by pushing a spherical indenter from the layer side.
  • a sample for measurement was obtained by cutting the palm portion of the bending stiffness protective glove (laminate) into a shape of 60 mm ⁇ 60 mm. Then, when the measurement sample was bent using a bending tester (product name “KES-FB2” manufactured by Kato Tech Co., Ltd.) with the test conditions set to SENS20 and bending 2 cm ⁇ 1 , the rubber layer was attached to the inner surface. The bending stiffness was measured by bending in the direction. The measurement was performed 5 times, and the average value was defined as the bending rigidity of each example.
  • a bending tester product name “KES-FB2” manufactured by Kato Tech Co., Ltd.
  • the abrasion resistance abrasion test was evaluated using a Martindale abrasion tester (product name “STM633”, manufactured by SATRA) in accordance with the method described in EN388. Specifically, for the protective gloves (laminated body), friction was repeated while applying a predetermined load, and the number of frictions until breakage was obtained. According to the number of frictions until breakage, it is divided into levels from level 0 to level 4, and the higher the level, the better the wear resistance. LEVEL 4: 8,000 or more revolutions LEVEL 3: 2,000 or more revolutions and less than 8,000 revolutions LEVEL 2: 500 or more revolutions and less than 2,000 revolutions LEVEL 1: 100 or more revolutions and 500 Less than rotation LEVEL 0: Number of rotations less than 100
  • the reactor was kept at 5 ° C., and 0.1 parts of cumene hydroperoxide (polymerization initiator), a reducing agent, and a chelating agent were charged in appropriate amounts, and the polymerization reaction was continued for about 16 hours with stirring. Subsequently, 0.1 part of a 10 wt% hydroquinone aqueous solution (polymerization terminator) was added to stop the polymerization reaction at a polymerization conversion rate of 85%, and then the residual monomer was removed using a rotary evaporator at a water temperature of 60 ° C. Thereafter, it was concentrated to obtain a nitrile rubber latex (A-1) (solid content concentration of about 30% by weight).
  • A-1 solid content concentration of about 30% by weight
  • Production Example 2 (Production of nitrile rubber latex (A-2))
  • the amount of acrylonitrile used is 20 to 27 parts
  • the amount of t-dodecyl mercaptan (molecular weight modifier) is 0.6 to 0.5 parts
  • the amount of 1,3-butadiene is 75 to 68 parts.
  • a nitrile rubber latex (A-2) was obtained in the same manner as in Production Example 1, except that the respective changes were made. The results are shown in Table 2.
  • Production Example 3 (Production of nitrile rubber latex (A-3))
  • the amount of acrylonitrile used is 20 to 37 parts
  • the amount of t-dodecyl mercaptan (molecular weight modifier) is 0.6 to 0.3 parts
  • the amount of 1,3-butadiene is 75 to 58 parts.
  • a nitrile rubber latex (A-3) was obtained in the same manner as in Production Example 1, except that the respective changes were made. The results are shown in Table 2.
  • Production Example 4 (Production of nitrile rubber latex (A-4))
  • the amount of acrylonitrile used is 20 to 15 parts
  • the amount of t-dodecyl mercaptan (molecular weight modifier) is 0.6 to 0 parts
  • the amount of 1,3-butadiene is 75 to 80 parts.
  • a nitrile rubber latex (A-4) was obtained in the same manner as in Production Example 1 except that each was changed, and the measurement was performed in the same manner. The results are shown in Table 2.
  • Production Example 5 (Production of nitrile rubber latex (A'-5))
  • the amount of acrylonitrile used is 20 to 42 parts
  • the amount of t-dodecyl mercaptan (molecular weight modifier) is 0.6 to 0.4 parts
  • the amount of 1,3-butadiene is 75 to 53 parts.
  • a nitrile rubber latex (A′-5) was obtained in the same manner as in Production Example 1, except that each was changed. The results are shown in Table 2.
  • Production Example 6 (Production of nitrile rubber latex (A'-6))
  • the amount of acrylonitrile used is 20 to 30 parts
  • the amount of methacrylic acid is 5 to 12 parts
  • the amount of t-dodecyl mercaptan (molecular weight modifier) is 0.6 to 0.5 parts
  • 1 A nitrile rubber latex (A′-6) was obtained and measured in the same manner as in Production Example 1 except that the amount of 1,3-butadiene was changed from 75 parts to 58 parts. The results are shown in Table 2.
  • Example 1 Preparation of latex composition for dip molding
  • the latex (A-2) of the nitrile rubber produced in Production Example 2 was prepared, and each 100 parts of the nitrile rubber in the latex of the nitrile rubber was converted into solid content.
  • water of each compounding agent was prepared so that colloidal sulfur (manufactured by Hosoi Chemical Co., Ltd.) 1.0 part, zinc dibutyldithiocarbamate (manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.) 0.5 part, and zinc oxide 2.0 parts.
  • a dispersion was prepared, and the prepared aqueous dispersion was added to obtain a latex composition.
  • a predetermined amount of the aqueous dispersion of each compounding agent was slowly added while the latex was stirred. Thereafter, the solid content concentration of the latex composition was adjusted, and then aging (also referred to as pre-vulcanization) was performed at a temperature of 30 ° C. for 48 hours.
  • carboxymethylcellulose (B-1) (trade name “WS-C”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as a thickener for the latex composition after aging (insoluble component particle size: 20 ⁇ m, 1% Viscosity: 250 mPa ⁇ s, degree of etherification: 0.6 to 0.7) was added at a rate of 0.7% by weight, and a B-type viscometer was used at a temperature of 25 ° C. and a solid content concentration of 45% by weight.
  • a latex composition for dip molding was obtained by adjusting the viscosity measured at a rotation speed of 10 rpm to 2,800 mPa ⁇ s.
  • a metal glove mold covered with a glove-shaped fiber substrate (material: nylon, substrate layer average thickness d of fiber substrate: 0.7 mm, 13 gauge) It was immersed in the solution for 5 seconds, pulled up from the coagulant solution, and then dried under conditions of a temperature of 30 ° C. for 60 seconds. Thereafter, the metal glove mold was dipped in the above dip molding latex composition for 3 seconds, pulled up from the dip molding latex composition, and then dried under the conditions of a temperature of 30 ° C. for 30 minutes. Next, the nitrile rubber in the polymer layer was subjected to a crosslinking treatment by performing a heat treatment under conditions of a temperature of 100 ° C. for 60 minutes.
  • protective gloves were obtained by peeling the fiber base material on which the polymer layer was formed from the metal glove mold.
  • the measurement of the thickness t 1 of the penetrating polymer layer, the measurement of the thickness t 2 of the surface polymer layer, the sensory test, the measurement of Young's modulus, the wear resistance, And the appearance was evaluated. The results are shown in Table 1.
  • Example 2 As a thickener to be added to the latex composition, carboxymethylcellulose (B-2) (trade name “Daicel1150”, manufactured by Daicel Finechem) instead of carboxymethylcellulose (B-1) (insoluble component particle size: 28 ⁇ m, 1 % Viscosity: 300 mPa ⁇ s, degree of etherification: 0.6 to 0.8) at a ratio of 0.65 wt%, the viscosity of the latex composition for dip molding was adjusted to 3,000 mPa ⁇ s. Except for the above, protective gloves (laminated body) were obtained in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1.
  • Example 3 As a thickener to be added to the latex composition, carboxymethylcellulose (B-3) (trade name “Daicel1190”, manufactured by Daicel Finechem) instead of carboxymethylcellulose (B-1) (insoluble component particle size: 25 ⁇ m, 1 % Viscosity: 1,800 mPa ⁇ s, degree of etherification: 0.6 to 0.8) at a ratio of 0.4% by weight, the viscosity of the latex composition for dip molding is 3,200 mPa ⁇ s. Except having adjusted, it carried out similarly to Example 1, obtained the protective glove (laminated body), and evaluated similarly. The results are shown in Table 1.
  • Example 4 After pulling up from the coagulant solution, a protective glove (laminated body) was obtained and evaluated in the same manner as in Example 1 except that it was dried at a temperature of 30 ° C. for 20 seconds. The results are shown in Table 1.
  • Comparative Example 2 As a thickener to be added to the latex composition, carboxymethyl cellulose (B′-5) (trade name “Daicel 1120”, manufactured by Daicel Finechem) instead of carboxymethyl cellulose (B-1) (insoluble component particle size: 15 ⁇ m, The viscosity of the latex composition for dip molding is adjusted to 2,500 mPa ⁇ s by using 1.5% by weight of 1% viscosity: 20 mPa ⁇ s, degree of etherification: 0.6 to 0.8). A protective glove (laminate) was obtained in the same manner as in Example 1 except that the evaluation was performed in the same manner. The results are shown in Table 1.
  • Comparative Examples 1 to 3 when the Young's modulus of the laminate was too high, the laminate had a poor sensory test evaluation result and was inferior in flexibility (Comparative Examples 1 to 3).
  • Comparative Example 1 by the thickness t 1 of the osmopolymer layer of the laminate is thicker, the Young's modulus of the laminate becomes higher, by which the evaluation results of the sensory test is deteriorated, flexibility It was particularly inferior.
  • Example 5 Preparation of Dip Molding Latex Composition
  • Colloidal sulfur made by Hosoi Chemical Industry Co., Ltd.
  • the liquid was added to obtain a latex composition.
  • aqueous dispersion of each compounding agent a predetermined amount of the aqueous dispersion of each compounding agent was slowly added while the latex was stirred.
  • the solid content concentration of the latex composition was adjusted, and then aging (also referred to as pre-vulcanization) was performed at a temperature of 30 ° C. for 48 hours. Then, a thickener (trade name “Aron A-7100”, manufactured by Toagosei Co., Ltd.) was added to the latex composition after aging at a ratio of 0.4% by weight, and the temperature was 25 ° C. and the solid content concentration was 45.
  • a latex composition for dip molding was obtained by using a B-type viscometer under the condition of wt% and adjusting the viscosity measured at a rotational speed of 10 rpm to 3,000 mPa ⁇ s.
  • a metal glove mold covered with a glove-shaped fiber substrate (material: nylon, substrate layer average thickness d of fiber substrate: 0.7 mm, 13 gauge) It was immersed in the solution for 5 seconds, pulled up from the coagulant solution, and then dried under conditions of a temperature of 30 ° C. for 60 seconds. Thereafter, the metal glove mold was dipped in the above dip molding latex composition for 3 seconds, pulled up from the dip molding latex composition, and then dried under the conditions of a temperature of 30 ° C. for 30 minutes. Next, the nitrile rubber in the polymer layer was subjected to a crosslinking treatment by performing a heat treatment under conditions of a temperature of 100 ° C. for 60 minutes.
  • protective gloves were obtained by peeling the fiber base material on which the polymer layer was formed from the metal glove mold.
  • the measurement of the thickness t 1 of the penetrating polymer layer, the measurement of the thickness t 2 of the surface polymer layer, the sensory test, the measurement of Young's modulus, and the evaluation of the appearance Went are shown in Table 2.
  • Example 6 A protective glove (laminate) was obtained in the same manner as in Example 5 except that the nitrile rubber latex (A-2) produced in Production Example 2 was used instead of the nitrile rubber latex (A-1). The same evaluation was performed. The results are shown in Table 2.
  • Example 7 A protective glove (laminate) was obtained in the same manner as in Example 5 except that the nitrile rubber latex (A-3) produced in Production Example 3 was used instead of the nitrile rubber latex (A-1). The same evaluation was performed. The results are shown in Table 2.
  • Example 8 A protective glove (laminate) was obtained in the same manner as in Example 5 except that the nitrile rubber latex (A-4) produced in Production Example 5 was used instead of the nitrile rubber latex (A-1). The same evaluation was performed. The results are shown in Table 2.
  • Comparative Example 4 A protective glove (laminate) was prepared in the same manner as in Example 5 except that the nitrile rubber latex (A′-5) produced in Production Example 5 was used instead of the nitrile rubber latex (A-1). Obtained and evaluated in the same manner. The results are shown in Table 2.
  • Comparative Example 5 A protective glove (laminate) was prepared in the same manner as in Example 5 except that the nitrile rubber latex (A′-6) produced in Production Example 6 was used instead of the nitrile rubber latex (A-1). Obtained and evaluated in the same manner. The results are shown in Table 2.
  • FIG. 4 shows a graph in which the measurement results of the Young's modulus of the film molded body and the Young's modulus of the protective gloves are plotted in association with the results of the sensory test. That is, exemplifying Example 5, the sensory test was 5, the Young's modulus of the film molded body was 2,100 kPa, and the Young's modulus of the protective glove was 211 kPa, so the measurement results of the Young's modulus of the film molded body are shown.
  • the Young's modulus of the film molded body and the Young's modulus of the laminate obtained according to the measurement method described above are in good agreement with the results of the sensory test for protective gloves.
  • the lower the Young's modulus of the film molded body and the Young's modulus of the laminated body the better the result of the sensory test.
  • the higher the Young's modulus of the film molded body and the Young's modulus of the laminated body the worse the result of the sensory test.
  • the Young's modulus of the film molded body and the Young's modulus of the laminate obtained according to the measurement method described above are appropriate as an index of the flexibility of the protective gloves. It can be confirmed that it can be used.
  • Example 9 Preparation of Dip Molding Latex Composition
  • a nitrile rubber latex (A-2) produced in Production Example 2 was prepared as a polymer latex, and 100 parts of nitrile rubber in the nitrile rubber latex was prepared. Respectively, in terms of solid content, 1.0 part of colloidal sulfur (manufactured by Hosoi Chemical Co., Ltd.), 0.5 part of zinc dibutyldithiocarbamate (manufactured by Ouchi Shinsei Chemical Co., Ltd.), and 2.0 parts of zinc oxide.
  • the aqueous dispersion of each compounding agent was prepared, and the prepared aqueous dispersion was added to obtain a latex composition.
  • aqueous dispersion of each compounding agent when adding the aqueous dispersion of each compounding agent, a predetermined amount of the aqueous dispersion of each compounding agent was slowly added while the latex was stirred. Thereafter, the solid content concentration of the latex composition was adjusted, and then aging (also referred to as pre-vulcanization) was performed at a temperature of 30 ° C. for 48 hours. Then, Aron A-7100 (manufactured by Toa Gosei Co., Ltd.) is added as a thickener to the latex composition after aging at a ratio of 0.4% by weight, and the temperature is 25 ° C. and the solid content concentration is 45% by weight.
  • a latex composition for dip molding was obtained by using a B-type viscometer and adjusting the viscosity measured at 10 rpm to 3,000 mPa ⁇ s.
  • a metal glove mold covered with a glove-shaped fiber substrate (material: nylon, substrate layer average thickness d of fiber substrate: 0.7 mm, 13 gauge) It was immersed in the solution for 5 seconds, pulled up from the coagulant solution, and then dried at a temperature of 30 ° C. for 1 minute. Thereafter, the metal glove mold was dipped in the above dip molding latex composition for 3 seconds, pulled up from the dip molding latex composition, and then dried under the conditions of a temperature of 30 ° C. for 30 minutes. Next, the nitrile rubber in the rubber layer was subjected to a crosslinking treatment by performing a heat treatment under conditions of a temperature of 100 ° C. for 60 minutes.
  • a crosslinking treatment by performing a heat treatment under conditions of a temperature of 100 ° C. for 60 minutes.
  • protective gloves were obtained by peeling the fiber base material on which the rubber layer was formed from the metal glove mold.
  • the measurement of the thickness t 1 of the osmotic rubber layer, the measurement of the thickness t 2 of the surface rubber layer, the sensory test, the measurement of Young's modulus, the bending rigidity, and the wear resistance was measured. The results are shown in Table 3.
  • Example 10 As a thickener added to the latex composition after aging, Aron A-7100 (manufactured by Toa Gosei Co., Ltd.) is used in a proportion of 0.3% by weight, so that the viscosity of the dip molding latex composition is 2,000 mPas. -Except having adjusted to s, it carried out similarly to Example 9, obtained the protective glove (laminated body), and evaluated similarly. The results are shown in Table 3.
  • Example 11 A protective glove (laminate) was obtained in the same manner as in Example 9 except that the drying condition after lifting the metal glove mold from the coagulant solution was 30 ° C. for 30 seconds. Went. The results are shown in Table 3.
  • Example 12 As a thickener added to the latex composition after aging, Aron A-7100 (manufactured by Toa Gosei Co., Ltd.) is used at a ratio of 0.6% by weight, so that the viscosity of the dip-molding latex composition is 5,000 mPas. -Adjusting to s and obtaining a protective glove (laminate) in the same manner as in Example 9 except that the time for immersing the metal glove mold in the dip-forming latex composition was changed to 5 seconds, Evaluation was performed in the same manner. The results are shown in Table 3.
  • Comparative Example 6 A protective glove (laminate) was obtained and evaluated in the same manner as in Example 9 except that the drying conditions after the metal glove mold was pulled up from the coagulant solution were set to a temperature of 30 ° C. and 90 seconds. Went. The results are shown in Table 3.
  • Comparative Example 7 After pulling up the metal glove mold from the coagulant solution, drying it at a temperature of 30 ° C. for 60 seconds, and then immersing the metal glove mold in the latex composition for dip molding, that is, the metal glove mold Was dipped in a latex composition for dip molding for 3 seconds, pulled up, and then subjected to protective gloves (as in Example 9) except that the operation of drying at a temperature of 30 ° C. for 30 minutes was repeated twice. A laminate was obtained and evaluated in the same manner. The results are shown in Table 3.
  • Table 3 shows the measurement results of Examples 9 to 12 and Comparative Examples 6 and 7. Further, FIG. 5 shows the Young's modulus and the results of the bending test plotted in correspondence with the results of the sensory test. That is, exemplifying Example 9, the sensory test was 4, the Young's modulus was 359 kPa, and the bending stiffness was 0.340 gf ⁇ cm 2 / cm.
  • the Young's modulus obtained according to the measurement method of the present invention was in good agreement with the results of the sensory test. That is, the worse the sensory test result, the higher the Young's modulus, and the better the sensory test result, the lower the Young's modulus, and there is a certain correlation between them. It can be confirmed that the Young's modulus obtained according to the measuring method can be appropriately used as an index of flexibility. On the other hand, the result of the bending stiffness was inconsistent with the result of the sensory test and was not appropriate as an index of flexibility.

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  • Gloves (AREA)
  • Laminated Bodies (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un article stratifié comportant un substrat et une couche de polymère formée à partir de latex polymère, la couche de polymère recouvrant le substrat dans un état dans lequel une partie de la couche de polymère a infiltré le substrat ; le rapport (t1/t2) de l'épaisseur t1 d'une couche de polymère d'infiltration, qui est la partie de la couche de polymère qui s'infiltre dans le substrat, par rapport à l'épaisseur t2 d'une couche de polymère de surface, qui est la partie de la couche de polymère qui recouvre le substrat, est de 0,15 à 5,0, où t1 est l'épaisseur de la couche de polymère d'infiltration à partir de la surface du substrat, et t2 est l'épaisseur de la couche de polymère de surface à partir de la surface du substrat ; et le module d'Young de la partie du substrat sur lequel la couche de polymère est stratifiée est de 800 kPa ou moins.
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WO2021241407A1 (fr) 2020-05-27 2021-12-02 日本ゼオン株式会社 Composition de latex pour moulage par immersion et article moulé par immersion

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WO2021241407A1 (fr) 2020-05-27 2021-12-02 日本ゼオン株式会社 Composition de latex pour moulage par immersion et article moulé par immersion

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