Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
  • C09D123/26—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic
  • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/04—Non-macromolecular additives inorganic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
  • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment

Definitions

• the present invention relates to a resin composition.
• thermoplastic resins are used as products in various forms by taking advantage of their property of being deformed by heat and being molded not only into flat shapes such as sheets and films, but also into certain shapes such as spheres, cylinders, and boxes.
• thermoplastic resins are basically transparent, relatively soft, and easily scratched, so their surfaces are often printed or painted to protect them or improve their aesthetic appearance.
• Thermoplastic resins include polar resins and non-polar resins.
• non-polar resins polyolefin resins such as polypropylene and polyethylene have been widely adopted in recent years because they are inexpensive and have many excellent properties such as moldability, chemical resistance, water resistance, electrical properties, and safety.
• polar resins such as acrylic resins and polyester resins
• polyolefin resins are non-polar and crystalline, making it difficult to firmly adhere ink, paint, or adhesive to their surfaces. be.
• a modified polyolefin resin has been proposed as a resin that has adhesive properties for a nonpolar resin base material using such a polyolefin resin (see Patent Document 1).
• modified polyolefin resin composition disclosed in Patent Document 1 has adhesion to non-polar substrates at room temperature, it meets market requirements in terms of heat-resistant adhesion and water vapor barrier properties. Since it was not at that level, further improvements were required.
• an object of the present invention is to provide a resin composition that has heat-resistant adhesion to non-polar substrates, water vapor barrier properties, and handling properties.
• the present invention provides the following [1] to [8].
• [1] Contains a modified polyolefin resin to which an ⁇ , ⁇ -unsaturated carboxylic acid and/or a derivative thereof is grafted, and a clay mineral, and the content of the clay mineral is 5% by weight based on 100% by weight of the modified polyolefin resin. ⁇ 50% by weight of the resin composition.
• [2] The resin composition according to [1], wherein the clay mineral is a synthetic clay mineral treated with an organic compound.
• [3] The resin composition according to [1] or [2], wherein the modified polyolefin resin is grafted with a (meth)acrylic acid ester.
• the modified polyolefin resin contains at least one modified polyolefin resin selected from the group consisting of ethylene-propylene copolymer, propylene-1-butene copolymer, and ethylene-propylene-1-butene copolymer.
• the present invention comprises a modified polyolefin resin grafted with an ⁇ , ⁇ -unsaturated carboxylic acid and/or a derivative thereof, and a clay mineral, wherein the content of the clay mineral is based on 100% by weight of the modified polyolefin resin.
• the resin composition has a content of 5 to 50% by weight.
• AA to BB represents AA or more and BB or less.
• melting point is a value measured by a differential scanning calorimeter (hereinafter referred to as "DSC”).
• weight average molecular weight is a value measured by gel permeation chromatography (GPC) using a polystyrene standard.
• the modified polyolefin resin has a structure in which an ⁇ , ⁇ -unsaturated carboxylic acid and/or a derivative thereof is graft-polymerized onto a polyolefin resin.
• the weight average molecular weight of the modified polyolefin resin is not particularly limited, but is preferably from 10,000 to 300,000, more preferably from 30,000 to 200,000, even more preferably from 50,000 to 180,000. When the molecular weight is 10,000 or more, the cohesive force of the resin is improved and sufficient adhesion can be exhibited. On the other hand, when the molecular weight is 300,000 or less, the solution properties are excellent.
• the weight average molecular weight can be adjusted by, for example, the weight average molecular weight of the base resin of the polyolefin resin, the amount of the modifying component used, and the like.
• the melting point (Tm) of the modified polyolefin resin measured by a differential scanning calorimeter (DSC) is preferably 50 to 100°C, more preferably 50 to 90°C. When the melting point is 50°C or higher, sufficient adhesion can be exhibited. On the other hand, when the melting point is 100° C. or lower, adhesion and solution stability at low temperatures are good, and sufficient storage stability at low temperatures can be exhibited.
• the melting point can be adjusted, for example, by the type of base resin of the polyolefin resin.
• Tm measurement by DSC can be performed, for example, under the following conditions.
• a DSC measurement device T Instruments Co., Ltd., DISCOVERY DSC2500
• approximately 5 mg of a sample prepared in the same manner as the Tem measurement sample was heated at 200°C for 10 minutes and kept in a molten state.
• the temperature was lowered at a rate of 10°C/min and stably maintained at -50°C. Thereafter, the temperature was further increased to 200°C at a rate of 10°C/min to measure the melting peak temperature, and this temperature was evaluated as the melting point (°C).
• the polyolefin resin is not particularly limited, but includes, for example, a polyolefin resin obtained by copolymerizing ethylene or ⁇ -olefin using a Ziegler-Natta catalyst or a metallocene catalyst as a polymerization catalyst. More specifically, the polyolefin resin includes at least one selected from the group consisting of polypropylene, ethylene-propylene copolymer, propylene-1-butene copolymer, and ethylene-propylene-1-butene copolymer.
• polystyrene resin is preferred, and more preferably contains at least one selected from the group consisting of ethylene-propylene copolymer, propylene-1-butene copolymer, and ethylene-propylene-1-butene copolymer.
• the polyolefin resins may be used alone or in combination of two or more. In the latter case, the blending ratio of each resin is not particularly limited.
• polyolefin resin a polyolefin resin obtained using a metallocene catalyst as a polymerization catalyst is preferable.
• Polyolefin resins obtained using metallocene catalysts as polymerization catalysts have characteristics such as narrow molecular weight distribution, excellent random copolymerizability, narrow composition distribution, and a wide range of comonomers that can be copolymerized.
• metallocene catalyst known ones can be used.
• Polypropylene refers to a polymer whose basic unit is propylene.
• Ethylene-propylene copolymer refers to a copolymer whose basic units are ethylene and propylene.
• the propylene-1-butene copolymer refers to a copolymer whose basic units are propylene and 1-butene.
• Ethylene-propylene-1-butene copolymer refers to a copolymer whose basic units are propylene, 1-butene, and ethylene.
• Polypropylene, ethylene-propylene copolymer, propylene-1-butene copolymer, and ethylene-propylene-1-butene copolymer may contain small amounts of olefin components other than their respective basic units. Such an olefin component may be mixed, for example, in the process up to the production of modified polyolefin resin.
• the content of the above olefin component in polypropylene, ethylene-propylene copolymer, propylene-1-butene copolymer, and ethylene-propylene-1-butene copolymer is an amount that does not significantly impair the inherent performance of the resin. good.
• the component composition of the polyolefin resin is not particularly limited, but the propylene component in the total polyolefin resin is preferably 50 mol% or more.
• Ethylene-propylene copolymer, propylene-1-butene copolymer, and ethylene-propylene-1-butene copolymer are sometimes collectively referred to as a propylene-based random copolymer.
• the weight average molecular weight of the polyolefin resin may be appropriately set in accordance with the weight average molecular weight of the modified polyolefin resin.
• the weight average molecular weight of the modified polyolefin resin is preferably 10,000 to 300,000, more preferably 30,000 to 200,000, and even more preferably 50,000 to 180,000
• the resulting modified polyolefin resin It is preferable to adjust the weight average molecular weight of the polyolefin resin so that the weight average molecular weight falls within the range. More specifically, it is preferable to adjust the weight average molecular weight of the polyolefin resin to an appropriate range, for example, 300,000 or less, by degrading it in the presence of heat or radicals.
• the weight average molecular weight of the polyolefin resin is a value measured by gel permeation chromatography (GPC, standard material: polystyrene) in the same manner as above. Moreover, the measurement conditions are the same as above.
• the lower limit of the melting point of the polyolefin resin is preferably 50°C or higher, more preferably 60°C or higher.
• the melting point of the polyolefin resin is 50° C. or higher, sufficient coating film strength can be exhibited when the modified polyolefin resin is used for inks, paints, and the like. Therefore, adhesion to the base material can be sufficiently exhibited.
• the upper limit thereof is preferably 100°C or less, more preferably 90°C or less. When the melting point of the polyolefin resin is 100° C.
• the melting point of the polyolefin resin is preferably 50 to 100°C, more preferably 60 to 90°C. Note that the melting point of the polyolefin resin is a value measured by DSC in the same manner as above. Moreover, the measurement conditions are the same as above.
• a modified polyolefin can be obtained by modifying the above polyolefin resin with an ⁇ , ⁇ -unsaturated carboxylic acid and/or a derivative thereof and a (meth)acrylic acid ester.
• ⁇ , ⁇ -unsaturated carboxylic acid means an ⁇ , ⁇ -unsaturated compound having a carboxy group.
• Derivatives of ⁇ , ⁇ -unsaturated carboxylic acids mean anhydrides, mono- or diesters, amides, imides, etc. of the unsaturated compounds.
• Examples of ⁇ , ⁇ -unsaturated carboxylic acids or derivatives thereof include fumaric acid, maleic acid, itaconic acid, mesaconic acid, citraconic acid, aconitic acid, and anhydrides thereof; monomethyl fumarate, monoethyl fumarate, fumaric acid.
• Fumaric acid monoesters such as monopropyl, monobutyl fumarate, fumaric acid diesters such as dimethyl fumarate, diethyl fumarate, dipropyl fumarate, dibutyl fumarate, monomethyl maleate, monoethyl maleate, monopropyl maleate, monobutyl maleate
• Examples include maleic acid monoesters such as dimethyl maleate, diethyl maleate, dipropyl maleate, dibutyl maleate, maleic acid diesters, maleimide, and N-phenylmaleimide.
• ⁇ , ⁇ -unsaturated carboxylic acids and/or derivatives thereof can be used singly or in combination of two or more. In the latter case, the blending ratio of each compound is not particularly limited.
• ⁇ , ⁇ -unsaturated carboxylic acids and/or derivatives thereof may include ⁇ , ⁇ -unsaturated dicarboxylic acids (e.g., fumaric acid, maleic acid, itaconic acid, mesaconic acid, citraconic acid) and/or derivatives thereof.
• it contains one or more selected from the group consisting of itaconic acid, maleic acid, and anhydrides thereof, and more preferably contains one or more selected from the group consisting of itaconic anhydride, maleic anhydride, and maleic acid. is more preferable, and even more preferably one or more selected from the group consisting of itaconic anhydride, maleic anhydride, and maleic acid, with maleic anhydride being particularly preferable.
• the grafting amount of ⁇ , ⁇ -unsaturated carboxylic acid and/or its derivative in the modified polyolefin resin is preferably 0.10% by weight or more, more preferably 1.0% by weight or more, and further preferably 2.0% by weight or more. preferable.
• the upper limit is preferably 20.0% by weight or less, more preferably 10.0% by weight or less, and even more preferably 5.0% by weight or less.
• the content is 20.0% by weight or less, the production of low molecular weight, highly polar by-products that significantly impair the mechanical properties of the composition can be suppressed.
• the grafting amount of ⁇ , ⁇ -unsaturated carboxylic acid or its derivative in the modified polyolefin resin is preferably 0.10 to 20.0% by weight, more preferably 1.0 to 10.0% by weight, and 1.0 to 20.0% by weight. More preferably 5.0% by weight.
• the amount of grafting of the ⁇ , ⁇ -unsaturated carboxylic acid or its derivative in the modified polyolefin resin can be determined by an alkaline titration method as a mass percentage when the modified polyolefin resin is taken as 100% by weight.
• ⁇ , ⁇ -unsaturated carboxylic acids or derivatives thereof that do not graft polymerize to the polyolefin resin, that is, unreacted substances, are removed during the process of producing the modified polyolefin resin, for example, by extraction with a poor solvent. You can.
• the modified polyolefin resin is preferably modified with ⁇ , ⁇ -unsaturated dicarboxylic acid and/or its derivative as ⁇ , ⁇ -unsaturated carboxylic acid and/or its derivative, but ⁇ , ⁇ -unsaturated dicarboxylic acid
• ⁇ , ⁇ -unsaturated monocarboxylic acids eg, acrylic acid, methacrylic acid
• they may also be modified with ⁇ , ⁇ -unsaturated monocarboxylic acids (eg, acrylic acid, methacrylic acid) and/or derivatives thereof.
• ⁇ , ⁇ -unsaturated monocarboxylic acids and/or derivatives thereof include (meth)acrylic esters.
• a (meth)acrylic acid ester is a compound containing at least one (meth)acryloyl group in the molecule.
• (meth)acryloyl group means an acryloyl group and/or a methacryloyl group.
• R 1 represents a hydrogen atom or a methyl group, preferably a methyl group.
• R 2 represents C n H 2n+1 .
• n represents an integer of 1 to 18, preferably an integer of 1 to 15, and more preferably an integer of 1 to 13.
• (Meth)acrylic acid esters include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, glycidyl (meth)acrylate, octyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylamino Examples include ethyl (meth)acrylate, 1-hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, and ace
• methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, ) acrylate is preferred, and octyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, and tridecyl (meth)acrylate are more preferred.
• One type of (meth)acrylic acid ester may be used, or a combination of two or more types may be used. In the latter case, the blending ratio of each compound is not particularly limited.
• the grafting amount of (meth)acrylic ester in the modified polyolefin resin is preferably 0.1 to 20.0% by weight, more preferably 0.5 to 10.0% by weight, and 1.0 to 5.0% by weight. is even more preferable.
• the grafting amount of the (meth)acrylic acid ester of the modified polyolefin resin can be determined by 1 H-NMR as a mass percentage when the modified polyolefin resin is taken as 100% by weight.
• the method for producing the modified polyolefin resin of the present invention is not particularly limited. An example is shown below.
• a polyolefin resin is prepared.
• Polyolefin resins are produced by polymerizing ⁇ -olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene in the presence of a catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. It can be prepared by: A commercially available product may be used as the polyolefin resin.
• the modification method can be performed by a known method, for example, a graft polymerization method.
• a radical generator may be used during the graft polymerization reaction.
• the method for obtaining modified polyolefin resin is a solution method in which the modified component is heated and dissolved in a solvent such as toluene, and a radical generator is added; the modified component and radical generator are added to equipment such as a Banbury mixer, kneader, or extruder.
• An example is a melt-kneading method in which the mixture is mixed and kneaded.
• the modifying components may be added all at once or sequentially.
• the radical generator can be appropriately selected from known ones and used. Among these, organic peroxide compounds are preferred. Examples of organic peroxide compounds include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, benzoyl peroxide, dilauryl peroxide, cumene hydroperoxide, and t-butyl hydroperoxide.
• the preferred range of the amount of the radical generator added to 100% by mass of the modifying component is as follows.
• the lower limit of the amount added is preferably 1% by mass or more, more preferably 10% by mass or more.
• the upper limit of the amount added is preferably 200% by mass or less, more preferably 100% by mass or less. It is economical that the amount of the radical generator added is 200% by mass or less.
• Unreacted substances which are modifying components that do not graft polymerize to the polyolefin resin, may be removed, for example, by extraction with a poor solvent. In this way, a graft polymer is obtained.
• the clay minerals used in the present invention are not particularly limited, but may be those derived from natural products, those obtained by processing natural products such as refining, or synthetic products treated with organic compounds (synthetic clay minerals). It may be a mineral), and a synthetic product treated with an organic compound (synthetic clay mineral) is particularly preferred.
• synthetic products include substances (eg, composites) in which some of the cations contained in clay minerals are replaced with quaternary ammonium cations derived from quaternary ammonium salts.
• the clay mineral used in the present invention preferably has a layered or plate-like shape.
• clay minerals used in the present invention include kaolinites such as kaolinite and hallosite; smectites such as montmorillonite, beidellite, nontronite, saponite, hectorite, stevensite, and mica; and vermiculites; Examples include chlorite; talc; among others, smectites are preferred, and montmorillonite and mica are particularly preferred. These can be used alone or in combination.
• montmorillonite is contained as a main component in bentonite, and therefore, as montmorillonite, one obtained by refining bentonite can be used.
• the quaternary ammonium salt is not particularly limited, and includes, for example, those represented by NR 4 + X ⁇ .
• R is each independently a hydrogen atom, an alkyl group, a hydroxyalkyl group (-R a OH, R a represents an alkylene group), -(R b O) n H (R b represents an alkylene group, n represents an integer from 1 to 20) or an aryl group, and X ⁇ represents a counter ion.
• R is each independently a hydrogen atom, an alkyl group, a hydroxyalkyl group (-R a OH, R a represents an alkylene group), -(R b O) n H (R b represents an alkylene group, n represents an integer from 1 to 20) or an aryl group, and X ⁇ represents a counter ion.
• a plurality of R's may be the same or different.
• the alkyl group that can be used as R
• the alkylene group that can be taken as R a or R b is preferably an ethylene group.
• n is preferably an integer of 1 to 20, more preferably an integer of 1 to 10, even more preferably an integer of 1 to 5, and particularly preferably 1.
• X ⁇ is preferably a halogen ion, such as Cl ⁇ or Br ⁇ .
• the heat resistance temperature of the clay mineral used in the present invention is preferably 150 to 500°C, more preferably 200 to 400°C, even more preferably 230 to 350°C, and particularly preferably 250 to 300°C.
• the heat-resistant temperature is in the range of 150 to 500°C, sufficient heat-resistant adhesion can be exhibited.
• the heat resistance temperature of clay minerals is a value measured by TG/DTA, and can be measured under the following conditions, for example.
• TG/DTA measuring device
• approximately 10 mg of sample was held at 20°C and then heated to 500°C at a rate of 10°C/min. The temperature rose. Thereafter, the temperature was raised to 500° C. and the temperature at which the weight began to decrease was measured, and this temperature was evaluated as the heat resistance temperature (° C.).
• the interplanar spacing of the clay mineral used in the present invention is preferably 20 ⁇ or more, more preferably 25 ⁇ or more, even more preferably 28 ⁇ or more, and particularly preferably 30 ⁇ or more.
• the interplanar spacing is 20 ⁇ or more, exfoliation of the clay mineral is likely to progress during the preparation of the resin composition, and water vapor barrier properties are improved.
• the interplanar spacing in this specification can be measured, for example, under the following conditions.
• Equipment PANalytical XPERT-PRO-MPD X-ray tube: Anode Cu Output: 45kV, 40mA Measurement range: 2.0-29.8° Scan speed: 0.0268°
• the content of clay mineral in the resin composition of the present invention is 5 to 50% by weight, preferably 15 to 40% by weight, and more preferably 15 to 30% by weight, based on 100% by weight of the modified polyolefin resin. . If the clay mineral content is less than 5% by weight, water vapor barrier properties and heat-resistant adhesion properties will not be exhibited. Moreover, if the content of clay mineral is more than 50% by weight, the viscosity when the resin composition is dissolved becomes high, impairing the handling property.
• the resin composition of the present invention has a relatively low viscosity and excellent handling properties.
• the viscosity of the resin composition of the present invention is not particularly limited, but for example, when measured at 25°C with a B-type viscometer, it is preferably 800 mPa ⁇ s or less, more preferably 500 mPa ⁇ s or less, and Preferably it is 200 mPa ⁇ s or less, even more preferably 100 mPa ⁇ s or less, particularly preferably 50 mPa ⁇ s or less, and the lower limit may be, for example, 1 mPa ⁇ s or more, preferably 10 mPa ⁇ s or more.
• the resin composition of the present invention has relatively low water vapor permeability and excellent water vapor barrier properties.
• the water vapor permeability of the resin composition of the present invention is not particularly limited, but for example, when measured at 40°C and 90% RH based on JIS K 7129-1 (humidity sensor method), it is preferably 50 g. /m 2 /day or less, more preferably 45 g/m 2 /day or less, further preferably 40 g/m 2 /day or less, particularly preferably 36 g/m 2 /day or less.
• Examples of other components include solvents, crosslinking agents, curing agents, stabilizers, adhesive components, diluents, antioxidants, light stabilizers, ultraviolet absorbers, pigments, dyes, and inorganic fillers. You can choose according to your needs.
• the solvent may be either an organic solvent or an aqueous solvent.
• organic solvents include aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate; acetone, methyl ethyl ketone, methyl butyl ketone, etc.
• Examples include ketone solvents; alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, and ethylcyclohexane; aliphatic hydrocarbon solvents such as nonane and decane.
• aqueous solvents include water; glycol solvents such as ethylene glycol, ethyl cellosolve, butyl cellosolve; methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl Aliphatic alcohol solvents such as alcohol and 2-ethyl-hexanol; glycol monoether solvents such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, and propylene glycol monobutyl ether; Can be mentioned.
• glycol solvents such as ethylene glycol, ethyl cellosolve, butyl cellosolve
• methanol, ethanol, n-propyl alcohol isopropyl alcohol
• n-butyl alcohol isobutyl alcohol, sec
• solvents may be used alone or may be included in the resin composition as a mixed solvent of two or more. From the viewpoint of environmental issues, it is preferable to select a solvent other than an aromatic hydrocarbon solvent, and a mixed solvent of an alicyclic hydrocarbon solvent and an ester solvent or a ketone solvent is more preferable.
• the crosslinking agent may be any compound that can form a crosslinked structure by reacting with groups such as hydroxyl groups, carboxyl groups, and amino groups present in the composition. (the crosslinking agent is dispersed in water by some method). Examples of the crosslinking agent include blocked isocyanate compounds, aliphatic or aromatic epoxy compounds, amine compounds, and amino resins. The crosslinking agents may be used alone or in combination of two or more.
• the stabilizer examples include compounds containing an epoxy ring, such as epoxy stabilizers.
• the epoxy stabilizer include epoxy compounds having an epoxy equivalent of about 100 to 500 and containing one or more epoxy groups in one molecule. More specifically, the following compounds may be mentioned: Epoxidized soybean oil or epoxidized linseed oil, which is obtained by epoxidizing a vegetable oil with natural unsaturated groups with a peracid such as peracetic acid; oleic acid, tall oil fatty acid, soybean oil Epoxidized fatty acid esters made by epoxidizing unsaturated fatty acids such as fatty acids; Epoxidized alicyclic compounds represented by epoxidized tetrahydrophthalate; For example, bisphenol A glycidyl ether, which is a condensation of bisphenol A or polyhydric alcohol with epichlorohydrin.
• ethylene glycol glycidyl ether propylene glycol glycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether; butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, sec-butyl Monoepoxy compounds represented by phenylglycidyl ether, tert-butylphenylglycidyl ether, phenol polyethylene oxide glycidyl ether, etc.
• the stabilizer may be a compound that does not contain an epoxy ring, such as metal soaps such as calcium stearate and lead stearate, which are used as stabilizers for polyvinyl chloride resin; dibutyltin dilaurate, dibutyl malate, etc.
• Organometallic compounds examples include hydrotalcite compounds.
• Stabilizers that do not contain epoxy rings may also be used, such as metal soaps such as calcium stearate and lead stearate, which are used as stabilizers for polyvinyl chloride resin; organic metals such as dibutyltin dilaurate and dibutyl malate.
• Compounds include hydrotalcite compounds.
• the content of the stabilizer is preferably 0.1% by weight or more, more preferably 1% by weight or more, still more preferably 2% by weight or more, based on 100% by weight of the modified polyolefin resin. Thereby, the stabilizing effect can be expressed satisfactorily.
• the upper limit is preferably 15% by weight or less, more preferably 12% by weight or less, still more preferably 10% by weight or less. Thereby, good adhesion to a base material such as polyolefin can be achieved.
• adhesive component examples include known adhesive components such as polyester adhesives, polyurethane adhesives, and acrylic adhesives.
• a resin composition can be obtained by adding a clay mineral to the above-mentioned modified polyolefin resin and kneading the mixture.
• the temperature during kneading of the clay mineral may be lower than or equal to the heat resistance temperature of the clay mineral used, and from the viewpoint of manufacturability, it may be preferably lower than 200°C, more preferably lower than 150°C. If the temperature during kneading is 200° C. or higher, the delamination properties of the clay mineral may decrease, and the water vapor barrier properties of the resulting resin composition may decrease.
• the temperature during kneading is 150° C. or higher, there is a problem of increased manufacturing cost.
• the lower limit of the temperature during kneading of clay minerals is not particularly limited, but may be, for example, 70° C. or higher.
• the resin composition of the present invention has excellent adhesion between non-polar resins such as polyolefin base materials and between non-polar resins and metals, so primers, adhesives (for example, metal adhesives, resin adhesives, etc.), It can be used in various applications such as paints, inks, and binders (eg, paint binders, ink binders, etc.), and is particularly useful in adhesive applications for packaging materials that require water vapor barrier properties.
• the resin composition of the present invention can be used as a material for layers constituting a laminate.
• the laminate may include a layer containing a modified polyolefin resin or composition, a metal layer, and a resin layer.
• the metal include aluminum, aluminum alloy, nickel, and stainless steel.
• resins include non-polar resins such as polyolefin resins (e.g., polyethylene resins such as low-density polyethylene resins, linear low-density polyethylene resins, and high-density polyethylene resins; polypropylene resins such as unstretched polypropylene resins), polyurethane-based resins, etc.
• polyamide resins acrylic resins, and polyester resins.
• the arrangement of the layers in the laminate is not particularly limited, but there may be an embodiment in which the metal layer and the resin layer are located with a layer containing a modified polyolefin resin or composition sandwiched between them, and a first resin layer and a second resin layer with the metal layer sandwiched in between.
• An example is an embodiment in which a layer containing a modified polyolefin resin composition is sandwiched between the metal layer and each resin layer.
• Applications of the laminate include refill pouches and packaging materials for toiletry products.
• EP ethylene-propylene random copolymer
• Example 2 As a clay mineral, Kunibis-110 (manufactured by Kunimine Kogyo Co., Ltd., synthetic montmorillonite, heat resistant temperature 236°C, interplanar spacing 28 ⁇ ) is added instead of MAE to prevent the extruder from stopping due to overload due to high melt viscosity.
• a resin composition (2) was obtained in the same manner as in Example 1, except that the temperature setting of the twin-screw extruder when kneading with the modified polyolefin resin (a) was changed from 100°C to 170°C.
• Example 3 A resin composition ( 3) was obtained.
• Example 4 As a clay mineral, MEB-3/2HT (manufactured by Katakura Co-op Agri Co., Ltd., synthetic mica, heat resistant temperature 257°C, interplanar spacing 36 ⁇ ) was added instead of MAE, and the extruder was overloaded due to high melt viscosity. Resin composition (4) was obtained in the same manner as in Example 1, except that the set temperature of the twin-screw extruder when kneading with modified polyolefin resin (a) was changed from 100 °C to 130 °C to prevent stoppage. Ta.
• Example 5 The resin composition was prepared in the same manner as in Example 1, except that MEE-O-DS (manufactured by Katakura Co-op Agri Co., Ltd., synthetic mica, heat resistant temperature 215°C, interplanar spacing 25 ⁇ ) was added as the clay mineral instead of MAE.
• MEE-O-DS manufactured by Katakura Co-op Agri Co., Ltd., synthetic mica, heat resistant temperature 215°C, interplanar spacing 25 ⁇
• Product (5) was obtained.
• Example 1 The modified polyolefin resin (a) of Example 1 was used as a resin composition (6) without adding any clay mineral.
• the temperature set in the twin-screw extruder is preferably less than 150°C.
• the measuring device used was L80-5000 manufactured by Lyssy.
• the measurement conditions were 40° C. and 90% RH, and the sample was set so that the coated surface was on the detector side (low humidity side).
• the standard was JIS K 7129-1 (humidity sensor method).
• the resin composition of the present invention has excellent heat-resistant adhesion, water vapor barrier properties, and handling properties.

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• 2023
  • 2023-03-16 JP JP2024508262A patent/JPWO2023176941A1/ja active Pending
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