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WO2022196121A1 - Composition de résine composite acrylique-oléfine, une composition de résine non aqueuse, procédé de production d'une composition de résine non aqueuse, procédé de production d'une composition de résine composite acrylique-oléfine, composition de revêtement, composition d'encre, composition d'agent adhésif, film et matériau de formation - Google Patents

Composition de résine composite acrylique-oléfine, une composition de résine non aqueuse, procédé de production d'une composition de résine non aqueuse, procédé de production d'une composition de résine composite acrylique-oléfine, composition de revêtement, composition d'encre, composition d'agent adhésif, film et matériau de formation Download PDF

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Publication number
WO2022196121A1
WO2022196121A1 PCT/JP2022/003079 JP2022003079W WO2022196121A1 WO 2022196121 A1 WO2022196121 A1 WO 2022196121A1 JP 2022003079 W JP2022003079 W JP 2022003079W WO 2022196121 A1 WO2022196121 A1 WO 2022196121A1
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WIPO (PCT)
Prior art keywords
resin composition
composition
composite resin
resin
mass
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Ceased
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PCT/JP2022/003079
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English (en)
Japanese (ja)
Inventor
陽 佐藤
光挙 岡部
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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Priority to CN202280007955.2A priority Critical patent/CN116583563A/zh
Priority to JP2023506824A priority patent/JP7559925B2/ja
Publication of WO2022196121A1 publication Critical patent/WO2022196121A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Ethene-propene or ethene-propene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/06—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on 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
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

  • the present invention relates to an acrylic olefin composite resin composition and its manufacturing method, a non-aqueous resin composition and its manufacturing method, a coating composition, an ink composition, an adhesive composition, a film and a molding material.
  • Polyolefin resins which are polymers of olefin monomers, are widely used in a wide variety of applications because they have excellent mechanical properties and chemical resistance, are low cost, and are easy to mold. Furthermore, polyolefin resins are excellent in recyclability, and their applications are expanding further against the backdrop of recent global environmental problems. However, due to the low polarity of polyolefin resins, it is generally believed that adhesion to polyolefin base materials is difficult.
  • Methods for improving the adhesion to polyolefin base materials include methods of chemically treating the surface of polyolefin base materials with chemicals, and methods of oxidizing the surface by corona discharge treatment, plasma treatment, flame treatment, etc. It has been known. However, these methods have the problem that special equipment is required and the effect of improving adhesiveness is not sufficient.
  • Patent Document 1 discloses a resin solution containing a graft copolymer obtained by graft-polymerizing a specific monomer to an olefin-based polymer as a chlorine-free resin having high adhesiveness to a polyolefin-based substrate. is described. However, since the resin solution described in Patent Document 1 separates over time, there is a problem with storage stability.
  • Patent Literature 2 describes a solid resin containing a graft copolymer obtained by graft-polymerizing a specific monomer to an olefin-based polymer and having no concerns about storage stability.
  • the method described in Patent Document 2 does not have good solubility in the solvent used, so there is a problem in using it for applications such as inks, paints, and adhesives that require solubility in solvents.
  • the present invention provides an acrylic olefin composite resin composition having excellent adhesion to polyolefin substrates and excellent storage stability, and a non-aqueous system comprising a composite resin composition having excellent adhesion to polyolefin substrates and storage stability.
  • An object of the present invention is to provide resin compositions and methods for producing them.
  • the gist of the present invention is the following [1] to [21].
  • the acrylic olefin composite resin C contains a structural unit derived from the (meth)acrylic monomer a and a structure derived from the olefin resin B,
  • An acrylic olefin composite resin composition D having a moisture content of 0.01% by mass or more and 10% by mass or less.
  • the acrylic-olefin composite resin composition D of [1] further comprising an acrylic resin A containing a structural unit derived from the (meth)acrylic monomer a, and the olefin resin B.
  • the mass ratio of the total mass of the structural units derived from all the monomers constituting the olefin resin B to the total mass of the structural units derived from the (meth)acrylic monomer a is 1 to 100%.
  • the non-aqueous resin composition E of [7] further containing an organic solvent.
  • SP value solubility parameter
  • the acrylic olefin composite resin composition D of any one of [1] to [6] is mixed with an organic solvent containing 50% by mass or more of an organic solvent having an SP value of less than 9.2, and the acrylic olefin composite resin composition is obtained.
  • a method for producing an acrylic olefin composite resin composition D containing an acrylic olefin composite resin C having a structural unit derived from a (meth)acrylic monomer a and a structure derived from an olefin resin B A method for producing an acrylic olefin composite resin composition D, comprising suspension polymerization of the (meth)acrylic monomer a in the presence of the olefin resin B.
  • a coating composition comprising the acrylic olefin composite resin composition D of any one of [1] to [6].
  • An adhesive composition comprising the acrylic olefin composite resin composition D of any one of [1] to [6].
  • a film or molded material containing the acrylic olefin composite resin composition D of any one of [1] to [6].
  • a coating composition comprising the non-aqueous resin composition E according to any one of [7] to [12].
  • An ink composition containing the non-aqueous resin composition E according to any one of [7] to [12].
  • An adhesive composition comprising the non-aqueous resin composition E according to any one of [7] to [12].
  • an acrylic olefin composite resin composition having excellent adhesion to polyolefin substrates and excellent storage stability, and a composite resin composition having excellent adhesion to polyolefin substrates and storage stability are included.
  • Non-aqueous resin compositions and methods for producing them can be provided.
  • (meth)acryl means a generic term for "acryl” and “methacryl”.
  • (Meth)acrylate is a generic term for "acrylate” and “methacrylate”.
  • the acrylic olefin composite resin composition D (hereinafter also referred to as “composite resin composition D") of the present invention contains acrylic olefin composite resin C (hereinafter also referred to as “resin C”), and resin C is , (Meth)acrylic monomer a (hereinafter also referred to as “monomer a”) containing structural units derived from and olefin resin B (hereinafter also referred to as “resin B”) derived structure,
  • the moisture content of the composite resin composition D is 0.01% or more and 10% or less.
  • Composite resin composition D contains, in addition to resin C, acrylic resin A (hereinafter referred to as “resin A”), and resin B are preferably further included.
  • the existence state of the structure derived from the resin B and the structural unit derived from the monomer a in the resin C is, for example, A state in which the structure derived from resin B and the structural unit derived from monomer a are bonded by chemical bonds such as covalent bonds, ionic bonds, and hydrogen bonds; A state of existing as secondary particles which are aggregates of primary particles of resin B and primary particles of resin having structural units derived from monomer a; A state in which a resin having a structure derived from resin B and a structural unit derived from monomer a exists in a core-shell structure; A state in which a resin having a structure derived from resin B and a structural unit derived from monomer a exists in a microphase-separated structure such as a sea-island structure or an interconnected structure.
  • the structure derived from resin B and the constituent units derived from monomer a are bound by covalent bonds, ionic bonds, hydrogen bonds, and the like.
  • a state in which they are bonded by chemical bonds, and a state in which they exist as secondary particles that are aggregates of primary particles of the resin B and primary particles of the resin having structural units derived from the monomer a are preferable; structure and monomers derived from the resin B.
  • the constituent units derived from body a are bonded by chemical bonds such as covalent bonds, ionic bonds and hydrogen bonds.
  • the composite resin composition D may be in the form of particles, for example, particles obtained by pulverizing lumps, powders, solids such as pellets, particles in a suspended state, and particles in an emulsified state. good.
  • Composite resin composition D is preferably in the form of particles obtained by pulverizing lumps, or in the form of particles in a suspended state, from the viewpoint of handleability when dissolved in an organic solvent.
  • Resin A and Resin C have at least one structural unit derived from monomer a.
  • Examples of the monomer a include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, ) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, i-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) Alkyl (meth)acrylates having a linear or branched hydrocarbon skeleton such as acrylates, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, 4-t-butylcyclohexyl
  • alkyl (meth)acrylates having a linear or branched hydrocarbon skeleton and alkyl (meth)acrylates having an alicyclic skeleton It preferably contains at least one of methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl ( It more preferably contains at least one of meth)acrylate and isobornyl (meth)acrylate, and more preferably contains both methyl (meth)acrylate and n-butyl (meth)acrylate.
  • Monomer a may be used alone or in combination of two or more.
  • the resin A and the resin C may have a structural unit derived from a monomer other than the monomer a in the copolymerization component.
  • monomers other than monomer a include aromatic vinyl monomers such as styrene, ⁇ -methylstyrene, p-methylstyrene, vinyltoluene, and chlorostyrene; Vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, ⁇ -cyanoacrylate, dicyanovinylidene, and fumaronitrile; monomers having a carboxyl group such as crotonic acid, isocrotonic acid, cinnamic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, glutaconic acid; sulfonic acid group-containing monomers such as vinylsulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid; Polyfunctional monomers such as divinylbenzene, divin
  • the resin A preferably contains 50% by mass or more, more preferably 80% by mass or more, of structural units derived from the monomer a.
  • the mass ratio of the structural unit derived from the monomer a in the resin A is at least the above lower limit, the storage stability of the composite resin composition D tends to be improved.
  • the resin A may have any structure such as random copolymer, graft copolymer, block copolymer, linear, or branched.
  • the weight average molecular weight Mw of resin A measured by gel permeation chromatography (GPC) is preferably 5000 or more and 500000 or less from the viewpoint of heat resistance, adhesion to polyolefin base materials and storage stability of composite resin composition D. , 10000 or more and 300000 or less. If it is more than the said lower limit, there exists a tendency for adhesiveness to improve. When the content is equal to or less than the above upper limit, the storage stability of the composite resin composition D tends to be improved.
  • the glass transition temperature (Tg) of resin A is preferably 0° C. or higher and 150° C. or lower, and preferably 15° C. or higher and 100° C. or lower, from the viewpoint of heat resistance, adhesion to polyolefin substrates, and storage stability of composite resin composition D. More preferably, the temperature is 25° C. or higher and 80° C. or lower. If it is at least the above lower limit, there is a tendency for the adhesiveness to improve. When the content is equal to or less than the above upper limit, the storage stability of the composite resin composition D tends to be improved.
  • glass transition temperature (Tg) (unit: °C) is calculated by the Fox formula shown in formula (1) below.
  • Tgi Tg (°C) of homopolymer of monomer i
  • Tg (°C) Tg (°C) of homopolymer of monomer i
  • Resin A and resin C can be produced by commonly known polymerization methods such as bulk polymerization, solution polymerization and suspension polymerization. Among these, suspension polymerization is preferable in that a resin in the form of spherical particles, which is easy to handle, can be obtained. Resin A and resin C can be produced, for example, by the following suspension polymerization method.
  • the method for producing Resin A and Resin C preferably includes a polymerization step, a first dehydration step, a washing step, a second dehydration step, and a drying step.
  • the polymerization step is a step of suspension polymerization of the monomer a and, if necessary, a monomer other than the monomer a to obtain the resin A or the resin C.
  • a known method can be employed as the suspension polymerization method. For example, in a container having a polymerization temperature control function and a stirring function, the monomer a and, if necessary, a monomer other than the monomer a is polymerized in water in the presence of a polymerization aid.
  • Polymerization aids include, for example, polymerization initiators, chain transfer agents, dispersants, and dispersion aids.
  • polymerization initiators include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), benzoyl peroxide and lauroyl peroxide.
  • chain transfer agents include t-dodecylmercaptan, n-dodecylmercaptan, octylthioglycolate, and ⁇ -methylstyrene dimer.
  • Dispersants include, for example, surfactants capable of stably dispersing monomers in water.
  • Copolymers of sulfopropyl methacrylate and methyl methacrylate, copolymers of sodium methacrylate and methacrylic acid, polyvinyl alcohol, polyvinylpyrrolidone, hydroxyethyl cellulose and hydroxypropyl cellulose can be mentioned.
  • Dispersing aids include, for example, sodium sulfate, sodium carbonate, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium chloride, calcium acetate, magnesium sulfate, and manganese sulfate.
  • the resins obtained by suspension polymerization (for example, resin A, resin B, and resin C) are obtained in a slurry state. By dehydrating the slurry, bead-like resin particles that are nearly spherical are usually obtained.
  • the dehydration step includes a first dehydration step in which the slurry after the suspension polymerization is dehydrated with a dehydrator or the like to separate the resin (for example, resin A, resin B, resin C) from the reaction solution, and the resin after the washing step ( For example, there is a second dehydration step in which particles of resin A, resin B, and resin C) are dehydrated with a dehydrator or the like to separate resin particles (for example, particles of resin A, resin B, and resin C) from the washing liquid. .
  • dehydrator can be used in each dehydration step, and for example, a centrifugal dehydrator, a dehydrator having a mechanism for removing water by suction on a perforated belt, or the like can be appropriately selected and used.
  • a centrifugal dehydrator a dehydrator having a mechanism for removing water by suction on a perforated belt, or the like can be appropriately selected and used.
  • One dehydrator may be used, two of the same model may be prepared and used in each dehydration step, or a plurality of different dehydrator models may be used. It is possible to appropriately select a model that meets the purpose in terms of product quality, equipment investment cost, productivity, operating cost, and the like. If the balance between product quality and production speed is emphasized, a dedicated dehydrator may be used in each dehydration step.
  • the washing step increases the purity of the resin (eg resin A, resin B, resin C).
  • a washing liquid is added to the resin particles dehydrated in the first dehydration step, and the resin is slurried again and stirred and mixed.
  • a second dehydration step such as a method of subsequently adding a washing liquid for washing, may be performed later. Also, these washing methods may be combined to wash the resin (for example, resin A, resin B, and resin C).
  • the kind and amount of the cleaning liquid may be selected so that the purpose of the cleaning process is achieved.
  • the cleaning agent include water (ion-exchanged water, distilled water, purified water, etc.), an aqueous solution in which sodium salt is dissolved, and methanol.
  • the drying step is a step of drying particles of the resin (for example, resin A, resin B, and resin C) after the second dehydration step. Water remains on the surface of the resin particles after the second dehydration step.
  • drying is preferable in order to further reduce the water content of the resin.
  • Various dryers can be used for drying, for example, a dryer that heats and dries under reduced pressure, a dryer that simultaneously dries resin particles while air-flying them in a tube using heated air, There is a dryer in which heated air is blown from the lower side of a perforated plate, and the resin particles on the upper side are dried while flowing.
  • Resin B has a structural unit derived from at least one olefinic monomer b (hereinafter also referred to as "monomer b").
  • the resin B may have a reactive group.
  • reactive groups include carboxyl groups, epoxy groups, isocyanate groups, sulfonic acid groups, hydroxyl groups, and amino groups.
  • the reactive group may be an acid anhydride structure of a carboxyl group.
  • Examples of the monomer b include ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, cyclopentene, cyclohexene and norbornene.
  • the resin B for example, a homopolymer of the monomer b; copolymers of ethylene and propylene; At least one of ethylene and propylene, and a monomer copolymerizable with ethylene and propylene (e.g., ⁇ -olefin having 4 or more carbon atoms (e.g., butene-1, pentene-1, hexene-1, heptene-1, octene -1, cyclopentene, cyclohexene, norbornene)); Copolymer of two or more ⁇ -olefins having 4 or more carbon atoms; A copolymer of an ⁇ -olefin having 2 or more carbon atoms and an aromatic monomer or a hydrogenated product thereof; A conjugated diene block copolymer or a hydrogenated product thereof may be mentioned.
  • Monomer b may be used alone or in combination of two or more.
  • the mass ratio of the structural units derived from the olefinic monomer b to the total mass of the structural units constituting the resin B is preferably 50% by mass or more, more preferably 65% by mass or more, and even more preferably 75% by mass or more. , and preferably 100% by mass or less.
  • the content is equal to or less than the above lower limit, there is a tendency for the adhesiveness to the polyolefin base material to be improved.
  • Resin B is preferably a polymer having a propylene-derived structural unit from the viewpoint of adhesion to polyolefin-based substrates, such as polypropylene, ethylene-propylene copolymer, ethylene-propylene-butene copolymer, propylene-butene copolymer. Polymers are more preferred, and polypropylene and ethylene-propylene copolymers are even more preferred.
  • the mass ratio of the propylene-derived structural unit in the polymer having the propylene-derived structural unit is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and preferably 100% by mass or less. . When the content is equal to or less than the above lower limit, there is a tendency for the adhesiveness to the polyolefin base material to be improved.
  • the resin B may have any structure such as random copolymer, graft copolymer, block copolymer, linear or branched.
  • the melting point (Tm) of Resin B is preferably 125° C. or lower, more preferably 110° C. or lower, still more preferably 95° C. or lower, and preferably 50° C. or higher. If it is at least the above lower limit, there is a tendency for the adhesion to polyolefin base materials to improve. When the content is equal to or less than the above upper limit, the storage stability of the composite resin composition D tends to be improved.
  • the "melting point (Tm)" (unit: °C) is measured by differential scanning calorimetry (DSC).
  • the weight average molecular weight Mw of Resin B measured by gel permeation chromatography is preferably 3,000 or more and 500,000 or less, more preferably 6,000 or more and 200,000 or less, more preferably 10,000, from the viewpoint of heat resistance and adhesion to polyolefin base materials. 100000 or more is more preferable. If it is more than the said lower limit, there exists a tendency for adhesiveness to improve. When the amount is equal to or less than the above upper limit, there is a tendency that solvent solubility is improved.
  • the method for producing Resin B is not particularly limited, but for example, it can be produced by polymerizing an olefin by a method such as radical polymerization, cationic polymerization, anionic polymerization, or coordination polymerization. Each of these polymerization methods may be a living polymerization method.
  • catalysts used for coordination polymerization include Ziegler-Natta catalysts and single-site catalysts.
  • single-site catalysts can have sharp molecular weight distributions and stereoregularity distributions by designing ligands.
  • single-site catalysts include metallocene catalysts and Brookhart catalysts.
  • Metallocene catalysts include, for example, C1 symmetric type, C2 symmetric type, C2V symmetric type, and CS symmetric type, and can be appropriately selected depending on the stereoregularity of the desired polyolefin.
  • the method of polymerizing resin B is not particularly limited, and may be any method such as solution polymerization, suspension polymerization, bulk polymerization, and gas phase polymerization.
  • examples of polymerization solvents include aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane, heptane and octane; and alicyclic carbonization such as cyclohexane and methylcyclohexane.
  • Aroma hydrocarbons such as toluene and xylene
  • aliphatic hydrocarbons such as hexane, heptane and octane
  • alicyclic carbonization such as cyclohexane and methylcyclohexane.
  • Halogenated hydrocarbons esters; ketones; and ethers.
  • Aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons are preferred, and toluene, xylene, heptane and cyclohexane are more preferred.
  • One type of polymerization solvent may be used alone, or two or more types may be used in combination.
  • the production method thereof includes, for example, a method in which an olefin resin and a radically polymerizable monomer having a reactive group are reacted by heating and stirring in a solution, and an olefin resin and a reactive group.
  • a method of reacting by melting, heating and stirring a radically polymerizable monomer having A method of graft polymerizing a radically polymerizable monomer having the above to an olefin resin.
  • the polymerization solvent exemplified in the production method of resin B by solution polymerization or suspension polymerization can be used.
  • the content of the reactive group is preferably 0.01 to 1 mmol/g, more preferably 0.05 to 0.5 mmol/g, more preferably 0.05 to 0.5 mmol/g, per 1 g of the resin B. 1 to 0.3 mmol/g is more preferable.
  • Resin C can be produced by subjecting a mixture of a monomer mixture containing monomer a and resin B to radical polymerization in the presence of a radical polymerization initiator.
  • the resin A may also be produced at the same time by radically polymerizing only the monomer mixture containing the monomer a.
  • a composite resin composition D which is composed of three types of resin compositions, the resin A, the unreacted resin B, and the resin C, may be obtained.
  • composite resin composition D a resin composition of resin A, resin B and resin C is preferable.
  • the composite resin composition D is a resin composition of the resin A, the resin B and the resin C, the monomer a and the resin B which are the raw materials of the resin A depending on the desired physical properties of the composite resin composition D
  • the mass ratio of the resin A, the resin B and the resin C in the composite resin composition D can be adjusted.
  • the mass ratio of the resin A in the composite resin composition D is preferably 45% by mass or more and 95% by mass or less, more preferably 55% by mass or more and 90% by mass or less. If it is at least the above lower limit, the storage stability tends to be improved when dispersed in a solvent. When the content is equal to or less than the above upper limit, the adhesion to polyolefin substrates tends to be improved.
  • the mass ratio of the resin B in the composite resin composition D is preferably 5% by mass or more and 55% by mass or less, more preferably 10% by mass or more and 45% by mass or less. If it is at least the above lower limit, the adhesiveness to the polyolefin base material tends to be improved. If it is less than the above upper limit, the storage stability tends to improve when dispersed in a solvent.
  • the mass ratio of the resin C in the composite resin composition D is preferably 0.001% by mass or more and 10% by mass or less, and 0.01% by mass or more and 4% by mass. The following is more preferable, and 0.05% by mass or more and 2% by mass or less is even more preferable. If it is at least the above lower limit, the storage stability tends to be improved when the composite resin composition D is dispersed in a solvent. If it is equal to or less than the above upper limit, the viscosity tends to decrease when the composite resin composition D is dispersed in a solvent.
  • the mass ratio of resin A, resin B and resin C contained in composite resin composition D can be measured by a known method using 1 H-NMR, 13 C-NMR or the like.
  • a polymerization method for obtaining Resin C known polymerization methods such as radical polymerization such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, anionic polymerization, group transfer polymerization (GTP), and coordination anionic polymerization are employed.
  • radical polymerization such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, anionic polymerization, group transfer polymerization (GTP), and coordination anionic polymerization
  • GTP group transfer polymerization
  • GTP group transfer polymerization
  • coordination anionic polymerization are employed.
  • Bulk polymerization and suspension polymerization are preferred from the viewpoint of ease of resin recovery, and suspension polymerization is more preferred from the viewpoint of particle size control.
  • a method for producing resin C by suspension polymerization includes, for example, a mixture of a monomer mixture containing monomer a in water and resin B, a dispersant, a radical polymerization initiator, and optionally a chain transfer agent.
  • an aqueous suspension is prepared by adding an aqueous suspension, and the monomer is dispersed into droplets of about 0.05 to 2.5 mm while stirring, and the polymerization proceeds under heating.
  • the polymerization temperature is preferably 0° C. or higher and 200° C. or lower, more preferably 20° C. or higher and 150° C. or lower, even more preferably 50° C. or higher and 100° C. or lower.
  • the content is equal to or less than the above upper limit, there is a tendency that the dispersion stability of the polymer is improved. If it is at least the above lower limit, there is a tendency that the solubility of the resin C in the solvent is improved.
  • Method 1 Resin B is added to a monomer mixture containing monomer a and heated and stirred to form a mixture of the monomer mixture containing monomer a and resin B, and then a radical polymerization initiator and A method in which water and a dispersant are added and stirred to polymerize.
  • Method 2 A mixture of monomer a, a mixture of monomers other than monomer a, and resin B are added to water and heated and stirred to form a mixture of the monomer mixture containing monomer a and resin B. After that, a radical polymerization initiator and a dispersant are added and stirred to polymerize.
  • a chain transfer agent may be added to the mixture of the monomer mixture and Resin B.
  • radical polymerization initiator used for producing the aqueous suspension of Resin C examples include organic peroxides and azo compounds, with organic peroxides being preferred.
  • a radical polymerization initiator may be used alone or in combination of two or more.
  • organic peroxides used as radical polymerization initiators include o-methylbenzoyl peroxide, bis-3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, cyclohexanone peroxide, benzoyl peroxide, and methyl ethyl ketone.
  • azo compounds used as radical polymerization initiators include 2,2′-azobisisobutyronitrile, 2,2′-azobis(2-methylbutyronitrile), 2,2′-azobis(2,4 -dimethylvaleronitrile), 2,2′-azobis(2,4-dimethyl-4-methoxyvaleronitrile).
  • t-butyl peroxypivalate t-butyl peroxyneoheptanoate, t-butyl peroxyneodecanoate, t-butyl peroxy-2-ethylhexanoate, t -butyl peroxylaurate, t-butyl peroxyacetate, t-butyl peroxy isobutyrate, t-butyl peroxy isononanoate, t-butyl peroxybenzoate, t-butyl peroxy-3,5,5 -trimethylhexanoate, t-butylperoxymaleic acid, t-butylperoxyisopropylmonocarbonate, t-butylperoxy-2-ethylhexylmonocarbonate, di-t-butylperoxyhexahydroterephthalate, 1,6- Di-(t-butylperoxycarbonyloxy)hexane
  • t-butylperoxy-2-ethylhexanoate t-butylperoxylaurate, t-butylperoxyisobutyrate, di-t-butylperoxyhexahydroterephthalate , 1,6-di-(t-butylperoxycarbonyloxy)hexane is more preferred.
  • the amount of the radical polymerization initiator used is preferably 0.0001 to 10 parts by mass, and 0.01 to 5 parts by mass with respect to a total of 100 parts by mass of the monomer mixture containing the monomer a and the resin B. More preferably, 0.1 to 2 parts by mass is even more preferable. If it is more than the said lower limit, there exists a tendency for adhesiveness to improve. If it is below the said upper limit, there exists a tendency for solvent solubility to improve.
  • the hydrogen abstraction ability is an index indicating the ease of occurrence of a hydrogen abstraction reaction, which is one of the reactions involving radical species generated from the organic peroxide.
  • the hydrogen abstraction ability of an organic peroxide is determined by the method described in various documents (e.g., Polymer Journal, 29, 366 (1997), Polymer Journal, 29, 940 (1997), Polymer Journal, 29, 733 (1997)). can be measured.
  • Chain transfer agents used in the preparation of the aqueous suspension of Resin C include, for example, hydrogen, mercaptans, ⁇ -methylstyrene dimers, terpenoids, and cobalt chain transfer agents.
  • a chain transfer agent may be used individually by 1 type, and may use 2 or more types together.
  • Chain transfer agents include, for example, n-octylmercaptan, n-dodecylmercaptan, tert-dodecylmercaptan, n-octylmercaptan, n-tetradecylmercaptan, n-hexylmercaptan, and 2-ethylhexyl thioglycolate.
  • the amount of the chain transfer agent used is preferably 0.01 parts by mass or more and 10 parts by mass or less, and 0.05 parts by mass or more with respect to a total of 100 parts by mass of the mixture of monomers containing the monomer a and the resin B. 5 parts by mass or less is more preferable, and 0.1 to 2 parts by mass is even more preferable. If it is at least the above lower limit, the solubility in solvents tends to improve. When the content is equal to or less than the above upper limit, the adhesion to polyolefin substrates tends to be improved.
  • Examples of dispersing agents used for producing an aqueous suspension of Resin C include poly(meth)acrylic acid metal salts, copolymer alkali metal salts of (meth)acrylic acid and methyl (meth)acrylate; degree of saponification 70-100% polyvinyl alcohol; methyl cellulose; From the viewpoint of dispersibility, a copolymer alkali metal salt of (meth)acrylic acid and methyl (meth)acrylate, and polyvinyl alcohol are preferable, and a copolymer alkali metal salt of (meth)acrylic acid and methyl (meth)acrylate. is more preferred. Dispersants may be used singly or in combination of two or more.
  • the amount of the dispersant used is preferably 0.001 to 10% by mass, more preferably 0.005 to 5% by mass, with respect to the total 100 parts by mass of the mixture of monomers containing the monomer a and the resin B. , 0.01 to 2 mass % is more preferable. If it is at least the above lower limit, there is a tendency for the dispersibility during suspension polymerization to be good. When the content is equal to or less than the above upper limit, the solubility in solvents tends to be improved.
  • electrolytes such as sodium carbonate, sodium sulfate, and sodium hydrogen carbonate may be used.
  • the method of adding the electrolyte includes, for example, method 1 and method 2 described above, a method in which the electrolyte is dissolved in water in advance and used for polymerization, and a method in which the monomer is added together with water in a solid state. A method of putting it into a solution and using it for polymerization can be mentioned.
  • the same method as the method for obtaining the resin C can be mentioned.
  • the same production method as the production method for obtaining resin C can be used.
  • the monomer a and the resin B that can be used in the production of the composite resin composition D the monomer a and the resin B used in the production method for obtaining the composite resin C can be used.
  • the mass average particle size of the composite resin composition D of the present invention is preferably 10 ⁇ m to 2500 ⁇ m, more preferably 100 ⁇ m to 2000 ⁇ m, and even more preferably 150 ⁇ m to 1500 ⁇ m. If it is at least the above lower limit, the adhesive area between the resins is reduced, and as a result, the resins are less likely to fuse with each other, and the storage stability of the composite resin composition D is improved. When the content is equal to or less than the above upper limit, the solvent solubility of the composite resin composition D is improved.
  • the mass average particle size can be calculated by shaking 20 g of the granular resin for 5 minutes and classifying it using a standard sieve.
  • the mass ratio of the total mass of the structural units derived from all the monomers constituting the resin B to the total mass of the structural units derived from the monomer a is preferably 1 to 100%. ⁇ 90% is more preferred, and 20-80% is even more preferred. If it is at least the above lower limit, the adhesiveness to the polyolefin base material tends to be improved. When the content is equal to or less than the above upper limit, the storage stability of the composite resin composition D tends to be improved.
  • the water content of composite resin composition D is 0.01% or more and 10% or less, preferably 0.05% or more and 5% or less, and more preferably 0.1% or more and 3% or less.
  • the content is equal to or less than the above upper limit, the adhesion to polyolefin substrates is improved. If it is at least the above lower limit, the composite granular resin is less likely to be charged, and the risk of dust explosion is reduced.
  • Methods for adjusting the moisture content of the composite resin composition D include, for example, a method of adjusting drying conditions such as the degree of pressure reduction, drying temperature, and drying time when drying the composite resin composition D, and a method of adjusting moisture content such as a dehydrating agent. to the composite resin composition D.
  • Examples of the dehydrating agent used in the method for adjusting the water content of the composite resin composition D include inorganic compounds such as anhydrous sodium sulfate, anhydrous magnesium sulfate, and phosphorus pentoxide; Examples include organic compounds.
  • the method of adding a moisture adjusting agent such as a dehydrating agent to the composite resin composition D is to reduce the concentration of the active ingredient in the composite resin composition D to reduce the effect obtained in the present invention, and to reduce the effect of the moisture adjusting agent such as a dehydrating agent.
  • a method for adjusting the water content of the composite resin composition D it is simple and preferable to adjust the drying conditions such as the degree of pressure reduction, the drying temperature, and the drying time when drying the composite resin composition D.
  • composition E contains the composite resin composition D of the present invention. Since the composition E contains the composite resin composition D of the present invention, the dispersibility of the composition E is improved, and the storage stability of the composition E is improved. Composition E preferably further contains an organic solvent. When the composition E contains an organic solvent, the composition E may be in a state in which the composite resin composition D is completely dissolved in the organic solvent, or in a state in which the composite resin composition D is partially dissolved and dispersed in the organic solvent.
  • organic solvent that can dissolve part or all of the composite resin composition D may be used as the organic solvent.
  • organic solvents examples include aromatic hydrocarbons such as xylene (solubility parameter (SP value): 8.8) and toluene (SP value: 8.9); Alicyclic hydrocarbons such as methylcyclocyclohexane (SP value: 7.8) and cyclohexane (SP value: 8.2); Ketones such as acetone (SP value: 9.9), methyl ethyl ketone (SP value: 9.3), methyl propyl ketone (SP value: 8.7), methyl isobutyl ketone (SP value: 8.4); ethyl acetate (SP value: 9.1), n-propyl acetate (SP value: 8.8), n-butyl acetate (SP value: 8.5), i-propyl acetate (SP value: 8.4), Esters such as i-butyl acetate (SP value: 8.3); Methanol (SP value: 14.5), ethanol (SP value: 12.7), n-butanol (SP
  • alcohols such as n-hexanol (SP value: 10.7); Glycols such as ethylene glycol (SP value: 14.6) and propylene glycol (SP value: 12.6); Ethylene glycol monomethyl ether acetate (SP value: 9.2), propylene glycol monomethyl ether acetate (SP value: 8.2), diethylene glycol monobutyl ether acetate (SP value: 8.5), diethylene glycol monoethyl ether acetate (SP value: 8.5) Glycol esters such as; Diethylene glycol monomethyl ether (SP value: 10.2), diethylene glycol monoethyl ether (SP value: 10.2), diethylene glycol monobutyl ether (SP value: 9.5), propylene glycol monomethyl ether (SP value: 10.1), etc.
  • Glycol esters such as; Diethylene glycol monomethyl ether (SP value: 10.2), diethylene glycol monoethyl ether (SP value: 10.2), diethylene glycol monobuty
  • the organic solvent preferably contains both an organic solvent with an SP value of 8.0 or less and an organic solvent with an SP value of 9.2 or more.
  • Organic solvents with an SP value of 8.0 or less are preferably compounds having a cycloalkane structure, and organic solvents with an SP value of 9.2 or more are preferably ketone solvents.
  • solubility parameter is a solubility parameter expressed in units of (cal/cm 3 ) 1/2 , and is described in Polymer Engineering and Science, Vol. 14, 147 (1974).
  • the content of organic solvents having an SP value of 8.0 or less relative to the total mass of all organic solvents is preferably 5% by mass or more and 80% by mass or less, more preferably 20% by mass or more and 72% by mass or less, and 25% by mass or more and 65% by mass. % by mass or less is more preferable. If it is at least the above lower limit, the adhesiveness to the polyolefin base material tends to be improved. When the content is equal to or less than the above upper limit, the storage stability of composition E tends to be improved.
  • the content of an organic solvent having an SP value of 9.2 or more with respect to the total mass of all organic solvents is preferably 10% by mass or more and 70% by mass or less, more preferably 15% by mass or more and 60% by mass or less, and 25% by mass or more and 40% by mass. % by mass or less is more preferable. If it is at least the above lower limit, the storage stability of composition E tends to be improved. When the content is equal to or less than the above upper limit, the adhesion to polyolefin substrates tends to be improved.
  • composition E examples include the following method.
  • Method 3 A method of stirring a mixture of composite resin composition D and an organic solvent.
  • Method 4 After mixing part or all of the composite resin composition D with an organic solvent containing 50% by mass or more of an organic solvent having an SP value of less than 9.2, the mixture of the composite resin composition D is mixed with the SP value A method of coexisting with an organic solvent of 9.2 or more.
  • Method 4 is preferred because the composition E after dissolution or dispersion is less likely to separate and the composition E has good storage stability.
  • the production of composition E may be carried out at room temperature or under heating.
  • the combination of organic solvents used when part or all of the composite resin composition D is mixed includes: At least one organic solvent having an SP value of 8.0 or less is preferably included. At this time, the ratio of the organic solvent having an SP value of 8.0 or less to the organic solvent used when part or all of the composite resin composition D is mixed is preferably 25% by mass or more and 100% by mass or less. It is more preferably 95% by mass or less, and even more preferably 45% by mass or more and 90% by mass or less. If it is at least the above lower limit, the adhesiveness to the polyolefin base material tends to be improved. When the content is equal to or less than the above upper limit, the storage stability of composition E tends to be improved.
  • the content of the organic solvent having an SP value of 9.2 or more is preferably 10% by mass or more and 70% by mass or less, more preferably 15% by mass or more and 60% by mass or less, relative to the total mass of all organic solvents. It is preferably 25% by mass or more and 40% by mass or less. If it is at least the above lower limit, the storage stability of composition E tends to be improved. When the content is equal to or less than the above upper limit, the adhesion to polyolefin substrates tends to be improved.
  • the organic solvent having an SP value of less than 9.2 should be at least one of the above-described hydrocarbons and alicyclic hydrocarbons, an ester and It preferably contains at least one of ketones, more preferably contains an alicyclic hydrocarbon and either an ester or a ketone, still more preferably contains an alicyclic hydrocarbon and an ester, and a cycloalkane It is particularly preferred to include compounds having structures and esters.
  • the organic solvent having an SP value of 8.0 or less in Method 3 and Method 4 is preferably the above-described hydrocarbon or alicyclic hydrocarbon, more preferably a compound having a cycloalkane structure, and still more preferably methylcyclohexane.
  • the organic solvent having an SP value of 9.2 or more in Method 3 and Method 4 the above-described ketones, alcohols and glycols are preferred, ketones are more preferred, and acetone and methyl ethyl ketone are even more preferred.
  • Composition E of the present invention may contain other resins in addition to Resin A, Resin B and Resin C within a range that does not impair adhesion to the substrate.
  • Other resins include, for example, polyaromatic vinyl compounds such as polystyrene; polyester resins; polyurethane resins; alkyd resins; epoxy resins; vinyl chloride vinyl acetate copolymer resins such as vinyl chloride resins, vinyl chloride vinyl acetate copolymer resins, and vinyl acetate resins;
  • composition E of the present invention if necessary, for example, a conductivity imparting agent such as carbon black and ferrite; an inorganic filler; a lubricant; a plasticizer; an organic peroxide; Antioxidants; UV absorbers; weather resistance imparting agents; radiation resistance imparting agents; thermal stability imparting agents; surface conditioners; can be added by common compounding methods.
  • Composite resin composition D and composition E of the present invention have excellent adhesiveness to the surface of substrates made of polyolefin resins, which has been difficult to adhere to with conventional techniques.
  • Substrates made of polyolefin resin include, for example, polyethylene film (PE), non-oriented polypropylene film (CPP), oriented polypropylene film (OPP), ethylene-vinyl acetate copolymer film (EVA), ethylene-vinyl alcohol Films such as polymer films (EVOH) and polyvinyl chloride films (PVC); -Molded articles for automobile parts and molded articles for home electric appliances made of polyolefin resins such as butene copolymers and propylene-butene copolymers;
  • the composite resin composition D and the composition E of the present invention can be used as a substrate other than the substrate made of the polyolefin resin described above, such as polyethylene terephthalate film (PET), amorphous polyethylene terephthalate film (A-PE
  • Plastic films such as films, polybutylene terephthalate (PBT) resin films, unstretched nylon films, biaxially stretched nylon films, polyvinylidene chloride films, polyvinyl alcohol films, polystyrene films; acrylic resins such as copolymers, polyester resins, resin alloys composed of polypropylene and synthetic rubber, polyamide resins, unsaturated polyester resins, polybutylene terephthalate resins, polycarbonate resins, polystyrene resins, etc.; Metal substrates such as uncoated steel plates, steel plates plated with oxide film of zinc or aluminum; excellent adhesion to non-ferrous metal substrates such as copper plate, aluminum plate, aluminum foil, aluminum alloy plate, titanium plate, etc. have sex.
  • PBT polybutylene terephthalate
  • the substrate to be printed using the composite resin composition D and composition E of the present invention is a substrate molded by any known molding method such as injection molding, compression molding, hollow molding, extrusion molding, and rotational molding.
  • the base material may be subjected to a surface treatment for improving adhesiveness such as corona treatment, plasma treatment, undercoat treatment, primer coat treatment, or the like.
  • a pigment may be added to the base material, or a metal or the like may be deposited on the surface of the base material.
  • Examples of the base material having a metal vapor-deposited on the surface of the base material include films obtained by vapor-depositing a metal such as aluminum, gold, silver, copper, nickel, zinc, titanium, cobalt, indium, and chromium on a film; aluminum oxide; A film in which silicon oxide is vapor-deposited can be mentioned.
  • the adhesive composition of the present invention contains at least one of the composite resin composition D and composition E of the present invention.
  • adhesive compositions include, for example, hot-melt adhesives and heat-sealing adhesives.
  • Heat-sealing adhesives are adhesives used to hermetically seal packaging containers for foods, pharmaceuticals, industrial products, daily necessities, cosmetics, etc. with lids. Used for paper, non-woven fabric, glass, etc.
  • the aluminum foil may be a single layer of aluminum foil, may be an aluminum foil having a primer layer (for example, a resin layer containing a vinyl chloride-vinyl acetate copolymer), or may be an aluminum foil and a sealant film.
  • a laminate for example, a laminate having an aluminum foil, an adhesive layer, and a sealant film in this order
  • the adhesive composition of the present invention is preferably used as an adhesive layer interposed between the sealant film and the container.
  • the adhesive composition After the adhesive composition is applied to the substrate, it may be dried by heating.
  • the drying conditions are preferably in the range of 100 to 200° C. for 5 to 1000 seconds.
  • the thickness of the adhesive composition after drying by heating is appropriately set according to the lid material and container to be adhered, and is preferably 0.1 to 40 ⁇ m, more preferably 1 to 20 ⁇ m, even more preferably 3 to 15 ⁇ m.
  • the coating composition of the present invention contains at least one of the composite resin composition D and composition E of the present invention.
  • the coating method for applying the coating composition includes, for example, a spray coating method, a brush coating method, a dip coating method, a roll coating method, and a flow coating method.
  • the temperature and time for drying the applied coating composition can be appropriately selected depending on the type and content of the solvent in the coating composition, specifically the evaporation rate of the solvent and the drying conditions.
  • the drying temperature is preferably room temperature to 200° C. from the viewpoint of the heat resistance of the substrate.
  • the drying temperature is preferably equal to or lower than the heat resistance temperature of the base material.
  • the drying time is preferably 1 minute or longer, more preferably 30 minutes or longer, and preferably 24 hours or shorter.
  • the ink composition of the present invention contains at least one of composite resin composition D and composition E.
  • the hues of the coloring agent that can be used in the ink composition include, for example, white as the basic process color, yellow, crimson, indigo, and black; (green) and purple; transparent yellow, peony, vermillion, brown, gold, silver, and pearl; and almost transparent medium for adjusting color density (including extender pigment if necessary) as base colors.
  • the ink composition can be mixed with a white colorant to form a white ink and mixed with other inks.
  • organic pigments, inorganic pigments, and dyes can be mixed as necessary.
  • examples of white inorganic pigments include titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, and silica. It is preferable to use titanium oxide as a pigment for white ink from the viewpoint of coloring power, hiding power, chemical resistance and weather resistance.
  • examples of non-white inorganic pigments include pigments such as carbon black, aluminum, and mica (mica).
  • examples of colored colorants include organic pigments, inorganic pigments, and dyes used in general inks, paints, and recording agents.
  • organic pigments that can be used in combination with the ink composition include azo-based, phthalocyanine-based, anthraquinone-based, perylene-based, perinone-based, quinacridone-based, thioindigo-based, dioxazine-based, isoindolinone-based, quinophthalone-based, azomethineazo-based, and dictopyrrolo pigments.
  • examples include pyrrole-based and isoindoline-based pigments. From the viewpoints of cost and lightfastness, as organic pigments, copper phthalocyanine is used for indigo ink, and C.I. I. Pigment No Yellow 83 is preferably used.
  • the content of the colorant in the ink composition is preferably 1 to 50% by mass based on the total mass of the ink composition from the viewpoint of ensuring coloring power. Colorants may be used singly or in combination of two or more.
  • a dispersant in combination, since the colorant can be stably dispersed in the ink composition.
  • Anionic, nonionic, cationic or amphoteric surfactants can be used as dispersants.
  • the content of the dispersant in the ink composition is preferably 0.05% by mass or more and 5% by mass or less with respect to the total mass of the ink composition, and 0.1% by mass. % or more and 2 mass % or less is more preferable.
  • a dispersing agent may be used individually by 1 type, and may use 2 or more types together.
  • a printing ink composition containing the ink composition of the present invention can be used in general printing methods such as gravure printing and flexographic printing. Also, the printing ink composition can be used at a viscosity and concentration suitable for various printing methods.
  • the acrylic olefin composite resin composition D of the present invention can also be used for films or molded materials.
  • Applications of the film or molding material include, for example, automobile members, household appliance members, medical members, construction members, and packaging materials.
  • the molding material may optionally contain UV absorbers, antioxidants, weather resistance imparting agents, plasticizers, lubricants, antistatic agents, colorants, pigments, and flame retardants that are commonly used in the field of resin compositions. , a dispersant, and other additives may be added.
  • methods for molding the molding material include injection molding, blow molding, vacuum/pressure molding, T-die extrusion, profile extrusion, calendar molding, and inflation molding. Injection molding is preferred because of good moldability and high productivity.
  • Tetrahydrofuran (containing dibutylhydroxytoluene as a stabilizer) was used as the eluent, the flow rate was 0.35 mL/min, the inlet temperature was 40°C, the oven temperature was 40°C, and the RI detector temperature was 40°C. As a sample, 10 ⁇ L of a resin concentration adjusted with tetrahydrofuran to 0.2% by mass was injected.
  • the mass average particle size was measured by classifying 20 g of the granular resin by shaking it for 5 minutes using a standard sieve.
  • MMA methyl methacrylate
  • a dropping pump was used to continuously drop MMA at a rate of 0.24 parts by mass/minute for 75 minutes to add a total of 18 parts by mass.
  • the resulting mixture was held at a polymerization temperature of 60° C. for 6 hours and then cooled to room temperature to obtain a dispersant (1).
  • the solid content concentration of the dispersant (1) was 10% by mass.
  • the inside of the polymerization apparatus was sufficiently replaced with nitrogen, and the dispersion obtained while continuing stirring was heated to 80°C and held for 2 hours, then heated to 90°C and held for 1 hour to remove the granular resin.
  • a suspension containing The obtained suspension was filtered with a filter cloth, and the filtrate was washed with deionized water, dehydrated, and dried at 40° C. for 16 hours to obtain a particulate acrylic resin A (resin 8).
  • Table 1 shows the weight-average molecular weight, mass-average particle size, and water content of acrylic resin A (resin 8).
  • MMA methyl methacrylate (manufactured by Mitsubishi Chemical Corporation, Acryester M)
  • nBMA n-butyl methacrylate (manufactured by Mitsubishi Chemical Corporation, Acryester B)
  • MAA methacrylic acid (manufactured by Mitsubishi Chemical Corporation, methacrylic acid)
  • PBO t-butyl peroxy-2-ethylhexanoate (manufactured by NOF Corporation, Perbutyl O)
  • PHO t-hexylperoxy-2-ethylhexanoate (manufactured by NOF Corporation, Perhexyl O)
  • MSD ⁇ -methylstyrene dimer (Nofmer MSD manufactured by NOF Corporation)
  • nDM n-dodecyl mercaptan (manufactured by Kanto Chemical Co., Ltd., 1-dodecanethiol)
  • PP1602 ethylene-propylene glycol glycol
  • the resin liquid immediately after being evaluated for solubility in a solvent was coated on the primer surface of a hard aluminum foil with a bar coater so that the thickness after drying was 5 ⁇ m, and dried at 180° C. for 3 minutes.
  • a CPP film (Super Foil E0025NA, manufactured by Mitsubishi Chemical Co., Ltd.) is superimposed on the coated surface, and a heat seal tester (TP-701, manufactured by Tester Sangyo Co., Ltd.) is used at 180 ° C. and 0.5 kgf / cm 2 for 2 seconds. Sealed.
  • Example 19 and 20 A hard aluminum foil (manufactured by Takeuchi Metal Foil Industry Co., Ltd., A1N30H-H18) is coated with a resin solution immediately after being evaluated for solubility in a solvent so that the thickness after drying is 5 ⁇ m with a bar coater. and dried at 180° C. for 3 minutes.
  • a CPP film Super Foil E0025NA, manufactured by Mitsubishi Chemical Co., Ltd.
  • a heat seal tester TP-701, manufactured by Tester Sangyo Co., Ltd.
  • Examples 1 to 20 contain a resin C having a structural unit derived from the monomer a and a structure derived from the resin B, and the water content is 0.01% or more and 10% or less. Since the composite resin composition D was used, the storage stability and adhesion to the polyolefin substrate were excellent.
  • the resin A is used without using the composite resin composition D, which contains a resin C having a structural unit derived from the monomer a and a structure derived from the resin B and has a water content of 0.01% or more and 10% or less.
  • Comparative Example 1 used had poor adhesion to polyolefin substrates.
  • Comparative Example 2 in which resin A and resin B were mixed, was inferior in solubility in solvents and adhesiveness to olefin substrates.
  • Comparative Example 3 using an acrylic olefin composite resin composition containing a resin C having a structural unit derived from the monomer a and a structure derived from the resin B, but having a water content not in the range of 0.01% or more and 10% or less After 24 hours, two layers were separated and the storage stability was poor.
  • the acrylic olefin composite resin composition of the present invention is excellent in adhesion to polyolefin base materials and storage stability, and can be used in printing inks, UV inks, adhesives, adhesives, hot melt adhesives, ceramic sintering agents, It can be suitably used in fields such as paints, primers, heat sealing agents, molding materials, and toners.

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Abstract

L'invention concerne une composition de résine composite acrylique-oléfine qui présente une excellente stabilité au stockage et une excellente adhésivité par rapport à un matériau de base à la polyoléfine. La composition de résine composite acrylique-oléfine selon la présente invention contient une résine composite acrylique-oléfine C. La résine composite acrylique-oléfine C comprend une unité structurale dérivée d'un monomère (meth)acrylique a, et une structure dérivée d'une résine d'oléfine B. La teneur en eau de la composition de résine composite acrylique-oléfine est de 0,01 à 10 % en masse.
PCT/JP2022/003079 2021-03-16 2022-01-27 Composition de résine composite acrylique-oléfine, une composition de résine non aqueuse, procédé de production d'une composition de résine non aqueuse, procédé de production d'une composition de résine composite acrylique-oléfine, composition de revêtement, composition d'encre, composition d'agent adhésif, film et matériau de formation Ceased WO2022196121A1 (fr)

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CN202280007955.2A CN116583563A (zh) 2021-03-16 2022-01-27 丙烯酸烯烃复合树脂组合物、非水系树脂组合物、非水系树脂组合物的制造方法、丙烯酸烯烃复合树脂组合物的制造方法、涂布组合物、油墨组合物、粘接剂组合物、膜及成型材料
JP2023506824A JP7559925B2 (ja) 2021-03-16 2022-01-27 アクリルオレフィン複合樹脂組成物、非水系樹脂組成物、非水系樹脂組成物の製造方法、アクリルオレフィン複合樹脂組成物の製造方法、コーティング組成物、インキ組成物、接着剤組成物、フィルム及び成形材

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PCT/JP2022/003079 Ceased WO2022196121A1 (fr) 2021-03-16 2022-01-27 Composition de résine composite acrylique-oléfine, une composition de résine non aqueuse, procédé de production d'une composition de résine non aqueuse, procédé de production d'une composition de résine composite acrylique-oléfine, composition de revêtement, composition d'encre, composition d'agent adhésif, film et matériau de formation

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JPS59187012A (ja) * 1983-04-06 1984-10-24 Toray Ind Inc 熱可塑性樹脂の製造方法
JP2004067729A (ja) * 2002-08-01 2004-03-04 Mitsubishi Chemicals Corp プロピレン系共重合体、それを含む組成物及び接着剤
JP2004269866A (ja) * 2003-02-18 2004-09-30 Mitsubishi Chemicals Corp プロピレン系重合体類を含むコーティング組成物及び使用方法

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