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WO2023190929A1 - Résine polyoléfine durcissable par rayonnement d'énergie active et composition de résine aqueuse - Google Patents

Résine polyoléfine durcissable par rayonnement d'énergie active et composition de résine aqueuse Download PDF

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Publication number
WO2023190929A1
WO2023190929A1 PCT/JP2023/013295 JP2023013295W WO2023190929A1 WO 2023190929 A1 WO2023190929 A1 WO 2023190929A1 JP 2023013295 W JP2023013295 W JP 2023013295W WO 2023190929 A1 WO2023190929 A1 WO 2023190929A1
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WO
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Prior art keywords
double bond
polyolefin
unsaturated double
polyolefin resin
resin composition
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PCT/JP2023/013295
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English (en)
Japanese (ja)
Inventor
恵太朗 宮崎
健二 柏原
篤 山根
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Toyobo MC Corp
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Toyobo MC Corp
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Priority to JP2024512824A priority Critical patent/JPWO2023190929A1/ja
Publication of WO2023190929A1 publication Critical patent/WO2023190929A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
    • 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
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • 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
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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 active energy ray-curable polyolefin resins that have excellent adhesion to polyolefin substrates.
  • Polyolefin resins such as polypropylene have excellent properties and are inexpensive, so they are used in large quantities in automobile parts, various films, various molded products, etc. However, since polyolefin resins are crystalline and have non-polar surfaces, they have the problem of being difficult to paint or adhere to.
  • modified polyolefins such as acid-modified polyolefins and acid-modified chlorinated polyolefins have been developed for painting, printing, and film lamination and adhesion of polyolefin resins.
  • water-based modified polyolefins which are environmentally and sanitary-friendly, have been developed.
  • Dispersion compositions have been proposed (eg, Patent Documents 1 and 2).
  • the present invention was devised in view of the problems of the prior art, and it is an object of the present invention to provide an active energy ray-curable polyolefin resin that exhibits high adhesion, water resistance, and peel strength to polyolefin substrates.
  • a polyolefin resin having the following characteristics. It has a carboxyl group and an unsaturated double bond, and the unsaturated double bond is from the group consisting of ⁇ , ⁇ -unsaturated carboxylic acid anhydride (B) and the following (I), (II) and (III).
  • Active energy ray-curable polyolefin resin (A) derived from at least one selected compound (C) (I) Compound (C1) having an unsaturated double bond and an amino group (II) Compound (C2) having an unsaturated double bond and a hydroxyl group (III) Compound (C3) having an unsaturated double bond and an epoxy group.
  • the present invention has the following configuration.
  • Item 1 It has a carboxyl group and an unsaturated double bond, and the unsaturated double bond is from the group consisting of ⁇ , ⁇ -unsaturated carboxylic acid anhydride (B) and the following (I), (II) and (III).
  • An active energy ray-curable polyolefin resin (A) characterized by being derived from at least one selected compound (C).
  • C1 Compound (C1) having an unsaturated double bond and an amino group
  • II Compound (C2) having an unsaturated double bond and a hydroxyl group
  • III Compound (C3) having an unsaturated double bond and an epoxy group.
  • Item 2. Item 2.
  • Item 3. Item 2. A paint for a polyolefin substrate, comprising the active energy ray-curable polyolefin resin (A) according to Item 1 or the aqueous resin composition according to Item 2.
  • Item 4. Item 2. An ink for polyolefin substrates containing the active energy ray-curable polyolefin resin (A) according to Item 1 or the aqueous resin composition according to Item 2.
  • Item 6. Item 2.
  • the active energy ray-curable polyolefin resin (A) of the present invention exhibits excellent adhesion, water resistance, and high peel strength to polyolefin base materials. Therefore, it can be suitably used in paints, inks, adhesives, primers, etc.
  • the polyolefin resin (A) of the present invention (hereinafter, the active energy ray-curable polyolefin resin (A) may simply be referred to as polyolefin resin (A)) has a carboxyl group and an unsaturated double bond.
  • the polyolefin (a) in the present invention is selected from, for example, polypropylene, propylene- ⁇ -olefin copolymer, polyethylene, ethylene- ⁇ -olefin copolymer, poly-1-butene, and 1-butene- ⁇ -olefin copolymer. At least one type of polyolefin is mentioned.
  • the propylene- ⁇ -olefin copolymer is a copolymer of propylene and ⁇ -olefin.
  • the ⁇ -olefin include ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 4-methyl-1-pentene, etc. and ⁇ -olefins having 2 or 4 to 20 carbon atoms.
  • the content of the propylene component in the propylene- ⁇ -olefin copolymer is preferably 50 mol% or more, more preferably 70 mol% or more. When the content of the propylene component is 50 mol % or more, the adhesiveness to the polypropylene base material becomes good.
  • Ethylene- ⁇ -olefin copolymer is a copolymer of ethylene and ⁇ -olefin.
  • the ⁇ -olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 4-methyl-1-pentene, etc. and ⁇ -olefins having 3 to 20 carbon atoms.
  • the content of the ethylene component in the ethylene- ⁇ -olefin copolymer is preferably 75 mol% or more. When the content of the ethylene component is 75 mol% or more, the adhesiveness to the polyethylene base material will be good.
  • the 1-butene- ⁇ -olefin copolymer is a copolymer of 1-butene and ⁇ -olefin.
  • ⁇ -olefins include ethylene, propylene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 4-methyl-1-pentene, etc. Mention may be made of ⁇ -olefins having 2 to 3 or 5 to 20 carbon atoms.
  • the content of the 1-butene component in the 1-butene- ⁇ -olefin copolymer is preferably 65 mol% or more. When the content of the 1-butene component is 65 mol % or more, the adhesiveness to the polypropylene base material or the poly-1-butene base material will be good.
  • the polyolefin (a) may be further chlorinated and modified.
  • a chlorinated polyolefin obtained by chlorinating the above-mentioned polyolefin resin (a) is preferable.
  • the lower limit of the chlorine content is preferably 5% by mass or more, more preferably 8% by mass, from the viewpoint of solution stability and adhesion to the polyolefin base material.
  • the content is more preferably 10% by mass or more, particularly preferably 12% by mass or more, and most preferably 14% by mass or more. When the content is 5% by mass or more, the solution stability becomes good and emulsification becomes easy.
  • the upper limit is preferably 40% by mass or less, more preferably 38% by mass or less, even more preferably 35% by mass or less, particularly preferably 32% by mass or less, and most preferably 30% by mass or less. be. If it is less than 40% by mass, the crystallinity of the chlorinated polyolefin becomes high and the peel strength tends to become strong.
  • the chlorine content of the chlorinated polyolefin can be measured by titration according to JIS K-7229-1995.
  • the polyolefin resin (A) of the present invention has a carboxyl group and an unsaturated double bond.
  • the unsaturated double bond is derived from an ⁇ , ⁇ -unsaturated carboxylic acid anhydride (B) and at least one compound selected from the group consisting of (I), (II), and (III) below.
  • Compound (C1) having an unsaturated double bond and an amino group Compound (C2) having an unsaturated double bond and a hydroxyl group
  • Compound (C3) having an unsaturated double bond and an epoxy group.
  • the carboxyl group and unsaturated double bond that the polyolefin resin (A) of the present invention has can be obtained by graft polymerizing the ⁇ , ⁇ -unsaturated carboxylic acid anhydride (B) onto the polyolefin (a).
  • a compound (C1) having an unsaturated double bond and an amino group, a compound (C2) having an unsaturated double bond and a hydroxyl group, and an unsaturated double bond and epoxy via the unsaturated carboxylic anhydride (B) It is preferably obtained by adding at least one compound selected from the group consisting of compounds having an unsaturated double bond (C3) (hereinafter sometimes abbreviated as a compound having an unsaturated double bond (C)).
  • the carboxyl group that the polyolefin resin (A) has is determined to be an ⁇ , ⁇ -unsaturated carboxyl group when the polyolefin (a) is polymerized with the ⁇ , ⁇ -unsaturated carboxylic acid anhydride (B).
  • the adhesion and peel strength of the coating film obtained from the polyolefin resin (A) become even better.
  • the unsaturated double bond that the polyolefin resin (A) has is converted into a compound ( Addition of C1) is preferable because an amide group is induced.
  • a compound (C2) having an unsaturated double bond and a hydroxyl group or a compound (C3) having an unsaturated double bond and an epoxy group is added via the ⁇ , ⁇ -unsaturated carboxylic anhydride (B). This is preferable because an ester group is thereby induced.
  • the coating film obtained from the polyolefin resin (A) has good adhesion to the polyolefin substrate, water resistance, and peel strength.
  • Examples of the ⁇ , ⁇ -unsaturated carboxylic acid anhydride (B) to be graft copolymerized to the polyolefin (a) include maleic anhydride, citraconic anhydride, itaconic anhydride, aconitic anhydride, and himic anhydride. . Among these, maleic anhydride and itaconic anhydride are preferred.
  • a method for graft copolymerizing polyolefin (a) with ⁇ , ⁇ -unsaturated carboxylic acid anhydride (B) involves heating and melting polyolefin (a) above its melting point in the presence of a radical generator to react.
  • a radical generator to react.
  • known methods include a method (melt method) and a method in which the polyolefin (a) is dissolved in an organic solvent and then heated and stirred in the presence of a radical generator to react (solution method).
  • the content of ⁇ , ⁇ -unsaturated carboxylic acid anhydride (B) is The amount of acid anhydride (B) is preferably 0.5 to 10% by mass based on 100 parts by mass of acid-modified polyolefin modified to polyolefin (a). More preferably, it is 0.7% by mass or more. Further, the content is more preferably 3% by mass or less, and even more preferably 2% by mass or less.
  • the unsaturated double bond that the polyolefin resin (A) of the present invention has is derived from the compound (C) having an unsaturated double bond. It is thought that the presence of unsaturated double bonds causes a crosslinking reaction during curing with active energy rays, and improves cohesive force, thereby improving adhesion to polyolefin substrates, water resistance, and peel strength.
  • the proportion of the compound (C) having an unsaturated double bond containing an alkylene glycol chain is: It is preferably 3% by mass or less based on the compound (C) having all unsaturated double bonds contained in the polyolefin resin (A).
  • Alkylene glycol chains have a high affinity with water and facilitate phase inversion emulsification of the polyolefin resin (A), but they also reduce the affinity with the polyolefin base material, resulting in decreased adhesion and water resistance. There are cases. It is more preferably 2% by mass or less, and even more preferably 1% by mass or less, based on the compound (C) having all unsaturated double bonds contained in the polyolefin resin (A).
  • Examples of the compound (C1) having an unsaturated double bond and an amino group include allylamine and diallylamine.
  • the number of active hydrogens on the nitrogen of the compound (C1) having an unsaturated double bond and an amino group is one or two, and one is more preferable.
  • the number of active hydrogens is 1 or 2
  • the formation of imide bonds in the reaction with the ⁇ , ⁇ -unsaturated carboxylic acid anhydride (B) is further suppressed, and phase inversion when preparing the aqueous resin composition is suppressed. Emulsification becomes easier.
  • reaction temperature is lowered in the manufacturing process of introducing the unsaturated double bond into the polyolefin resin (A). By doing so, the generation of imide bonds can be suppressed.
  • the reaction temperature is preferably 100°C or lower, more preferably 80°C or lower.
  • Compounds (C2) having an unsaturated double bond and a hydroxyl group include, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 1,4-cyclohexane
  • Examples include alcohol compounds such as dimethanol monoacrylate, N-(2-hydroxyethyl)acrylamide, allyl alcohol, and acrylate adducts to polyols such as isocyanuric acid EO-modified diacrylate and pentaerythritol triacrylate.
  • Examples of the compound (C3) having an unsaturated double bond and an epoxy group include glycidyl ether compounds such as glycidyl methacrylate, glycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether, and allyl glycidyl ether.
  • the melting point of the polyolefin resin (A) in the present invention as measured by a differential scanning calorimeter (hereinafter referred to as DSC) is preferably 50°C or more and 85°C or less.
  • the temperature is more preferably 55°C or more and 80°C or less, particularly preferably 60°C or more and 75°C or less.
  • the film formability and cohesive force due to crystallinity in curing with active energy rays are favorable, and the adhesion to the polyolefin substrate, water resistance, and peel strength are favorable.
  • the measurement of the melting point by DSC in the present invention can be performed in accordance with JIS K7121-2012, and can be performed, for example, under the following conditions.
  • a DSC measurement device manufactured by Seiko Electronics Industries
  • approximately 5 mg of the sample was heated at 150°C and kept in a molten state for 10 minutes, then cooled down at a rate of 10°C/min, kept stably at -50°C, and then heated for another 10 minutes.
  • the temperature is increased to 150°C at a rate of 150°C/min, the melting peak temperature is measured, and this temperature is evaluated as the melting point. Note that the melting points in the Examples described below were measured under the conditions described above.
  • the content of the compound (C) having an unsaturated double bond in the polyolefin resin (A) is preferably 0.5 to 20% by mass. More preferably, it is 0.7% by mass or more. Further, it is more preferably 15% by mass or less, and even more preferably 10% by mass or less.
  • content of the compound (C) having an unsaturated double bond is 0.5 to 20% by mass, adhesion to the polyolefin substrate and phase inversion emulsification to water can be improved in a well-balanced manner.
  • the structure of the polyolefin resin (A) of the present invention is an amide formed when a compound (C1) having an unsaturated double bond and an amino group is added via an ⁇ , ⁇ -unsaturated carboxylic acid anhydride (B).
  • a compound (C1) having an unsaturated double bond and an amino group is added via an ⁇ , ⁇ -unsaturated carboxylic acid anhydride (B).
  • Infrared absorption of the ester group and carboxyl group when a compound (C2) having an unsaturated double bond and a hydroxyl group is added via an ⁇ , ⁇ -unsaturated carboxylic anhydride (B) It can be confirmed by spectrum.
  • the weight average molecular weight of the polyolefin resin (A) is preferably 15,000 to 300,000, more preferably 30,000 to 150,000, and even more preferably 30,000 to 120,000. It is preferably 50,000 to 120,000, particularly preferably 50,000 to 120,000. When the weight average molecular weight is within the above range, the ease of phase inversion emulsification of the aqueous resin composition and the adhesion to the polyolefin substrate and peel strength can be improved in a well-balanced manner.
  • the polyolefin resin (A) may further be graft-modified with a radically polymerizable monomer. That is, the modifying component may contain a radically polymerizable monomer together with the ⁇ , ⁇ -unsaturated carboxylic acid anhydride (B) and the compound having an unsaturated double bond (C).
  • Examples of radically polymerizable monomers include (meth)acrylic compounds and vinyl compounds.
  • a (meth)acrylic compound is a compound containing at least one (meth)acryloyl group (meaning an acryloyl group and/or a methacryloyl group) in the molecule.
  • radically polymerizable monomers include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, hydroxyethyl (meth)acrylate, isobornyl (meth)acrylate, and glycidyl ( meth)acrylate, octyl(meth)acrylate, lauryl(meth)acrylate, tridecyl(meth)acrylate, stearyl(meth)acrylate, cyclohexyl(meth)acrylate, benzyl(meth)acrylate, phenyl(meth)acrylate, dimethylaminoethyl( meth)acrylate, diethylaminoethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate,
  • methyl (meth)acrylate, ethyl (meth)acrylate, cyclohexyl (meth)acrylate, and lauryl (meth)acrylate are preferred, and among these methacrylates are more preferred. These can be used alone or in combination of two or more, and the mixing ratio can be freely set.
  • the polyolefin resin (A) of the present invention can be made into an aqueous resin composition by further containing a basic compound (D), and the carboxyl group is neutralized with the basic compound (D) in the aqueous resin composition.
  • the modified polyolefin resin (A) may be dispersed in water.
  • a basic compound is allowed to coexist. By allowing this to exist in the system, it becomes possible to improve the dispersibility of the modified polyolefin resin (A).
  • Basic compounds (D) include inorganic basic compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, triethylamine, N,N-dimethylethanolamine, aminoethanolamine, N-methyl -N,N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, 3-ethoxypropylamine, 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, allylamine, diallylamine, methyliminobis Propylamine, 3-methoxypropylamine, monoethanolamine, diethanolamine, triethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine, 2-amino-2-methyl-1-propanol, 2-dimethylamino-2- Examples include amines such as methyl-1-propanol, ammonia, and the like
  • the amount of the basic compound (D) added is preferably 0.3 to 4.0 times the chemical equivalent, more preferably 0.7 to 2.5 times the chemical equivalent, relative to the carboxyl group of the polyolefin resin (A). If it is less than 0.3 times the chemical equivalent, the effect of the presence of the basic compound may not be observed. On the other hand, if it exceeds 4.0 times the chemical equivalent, there is a risk that the residual amount of the target composition in the dried product may become too large.
  • the basic compound (D) is preferably contained in an amount of 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, and 0.5 parts by mass or more based on 100 parts by mass of the polyolefin resin (A). It is even more preferable to contain it. Moreover, it is more preferable to contain 2 parts by mass or less, and even more preferably to contain 1 part by mass or less. In this case, the dispersibility of the polyolefin resin (A) can be improved, the particle size of the dispersed particles will not become too large, the storage stability will be good, and the amount remaining in the dry product will be suitable.
  • the method for producing the aqueous resin composition in the present invention is not particularly limited, the carboxyl groups in the polyolefin resin (A) are neutralized with a basic compound (D) in an organic solvent, and the aqueous medium is A phase inversion emulsification method in which the organic solvent is removed after addition, heating and stirring, and cooling is preferred.
  • the solid content concentration of the aqueous dispersion of the aqueous resin composition in the present invention is preferably 10 to 60% by mass, and preferably 20 to 50% by mass based on the total amount of the aqueous dispersion, from the viewpoint of handleability of the aqueous dispersion. %, and even more preferably 30 to 40% by mass. In this case, the stability of the aqueous resin composition will be good, and the adhesion to the polyolefin substrate will also be good.
  • the aqueous resin composition according to the present invention may contain a surfactant within a range that does not impair the performance of the present invention.
  • Surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. Among these, it is preferable to use nonionic surfactants and anionic surfactants from the viewpoint of the particle size of the dispersed particles and the water resistance of the coating film obtained from the target composition. is more preferable.
  • nonionic surfactants include polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxypropylene alkylphenyl ether, polyoxyethylene styrenated phenyl ether, and polyoxypropylene styrenated phenyl ether.
  • Ether polyoxyethylene fatty acid ester, polyoxypropylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxypropylene sorbitan fatty acid ester, polyoxyethylene alkylamine ether, polyoxypropylene alkylamine ether, polyoxyethylene lanolin alcohol ether, poly Examples include oxypropylene lanolin alcohol ether, polyoxyethylene lanolin fatty acid ester, polyoxypropylene lanolin fatty acid ester, (polyoxyethylene oxypropylene) block copolymer, and the like.
  • Examples include the Emulmin series (manufactured by Sanyo Chemical Industries, Ltd.), the Neugen series (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and the Brownon series (manufactured by Aoki Yushi Kogyo Co., Ltd.).
  • reactive surfactants having a polymerizable double bond in the molecule can also be used.
  • examples include ADEKA REASOAP ER-10, ER-20, ER-30, and ER-40 (manufactured by ADEKA Co., Ltd.).
  • anionic surfactant examples include higher alkyl sulfate esters, alkylaryl polyoxyethylene sulfate salts, higher fatty acid salts, alkylaryl sulfonates, and alkyl phosphate ester salts.
  • examples include the Neocol series and the Hitenol series (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).
  • reactive surfactants having a polymerizable double bond in the molecule can also be used.
  • examples include Adekaria Soap NE-10, NE-20, NE-30, NE-40, SE-10N (manufactured by ADEKA Co., Ltd.), Aqualon RN-20, RN-30, RN-50, HS. -10, HS-20 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Eleminol JS-2, Eleminol RS-30 (manufactured by Sanyo Chemical Industries, Ltd.), and the like.
  • the above surfactants can be used alone or in combination of two or more.
  • the surfactant per 100 parts by mass of the polyolefin resin (A) from the viewpoint of ease of phase inversion emulsification and water resistance of the coating film. More preferably it is 40 parts by mass or less, and still more preferably 30 parts by mass or less. Moreover, it is more preferably 25 parts by mass or less.
  • the Z average particle diameter of the resin particles in the aqueous resin composition obtained as described above is preferably 10 nm or more and 500 nm or less, more preferably 200 nm or less. If the average particle diameter exceeds 500 nm, defects may occur in the coated film after painting, which adversely affects various physical properties, making it particularly difficult to use as a top coat paint, which is not preferable.
  • the polyolefin resin (A) of the present invention can be used as a clear varnish in the form of a solution or an aqueous dispersion.
  • various paint additives and other resin emulsions can be blended to the extent that they do not inhibit adhesion to polyolefin substrates.
  • film forming aids such as propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, butylpropylene diglycol, antifoaming agents, anti-sag agents, wetting agents, ultraviolet absorbers, etc. can be used.
  • coating film performance such as weather resistance, water resistance, coating film strength, and flexibility can be improved.
  • the aqueous resin composition of the present invention may contain a tackifier such as rosin, dammar, polymerized rosin, hydrogenated rosin, ester rosin, rosin-modified maleic acid resin, polyterpene resin, petroleum resin, cyclopentadiene resin.
  • a phenol resin, a xylene resin, a coumaron indene resin, or the like can be appropriately added as necessary, thereby improving the drying properties of the coating film and the adhesion to the polyolefin substrate.
  • the amount added is preferably 5 to 100 parts by weight, more preferably 10 to 50 parts by weight, based on 100 parts by weight of the solid content of the resin composition.
  • the amount added is less than 5 parts by mass, there is a risk that the effect of the addition will not appear. On the other hand, if it exceeds 100 parts by mass, the amount added is too large and there is a risk that the adhesion will be adversely reduced.
  • the active energy ray-curable polyolefin resin (A) of the present invention has high adhesion to various polyolefin base materials including polypropylene, and can be used as active energy ray-curable paints, inks, adhesives, sealants, primers, etc. Although it can be suitably used, it is not limited to these base materials; for example, other plastics, wood, metal, etc. can also be coated. Examples of the polyolefin base material include films, sheets, molded bodies, and the like. There are no special restrictions on the coating method.
  • the active energy ray-curable polyolefin resin (A) of the present invention can be cured with active energy rays by a known method.
  • an electron beam irradiation device with an accelerating voltage of 20 to 2000 KeV, preferably 150 to 300 KeV is applied.
  • a cured product can be obtained by irradiating in an inert gas atmosphere containing or not containing a small amount of oxygen at a total irradiation dose of 5 to 200 KGy, preferably 20 to 150 KGy.
  • a method of curing in air or an inert gas atmosphere using ultraviolet rays obtained from a mercury lamp, a xenon lamp, etc. a method of curing using energy related to heat such as infrared rays, high frequency, or microwave, that is, a method of curing by heating.
  • energy related to heat such as infrared rays, high frequency, or microwave
  • heat curing or ultraviolet curing it is preferable to add a photopolymerization initiator or a thermal polymerization initiator.
  • one method selected from the above-mentioned curing method using ionizing radiation, curing method using ultraviolet rays, or heat curing method can be used alone, or two or more methods can be used simultaneously, or each method can be used one after the other.
  • thermal or photopolymerization initiators examples include potassium persulfate, ammonium persulfate, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), and 2,2'-azobisisobutyronitrile.
  • Azo initiators such as '-azobis(2,4-dimethylvaleronitrile), 1,1'azobis(cyclohexane-1-carbonitrile), ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, etc., cumene Hydroperoxides such as hydroperpoxide, tert-butyl peroxide, dialkyl peroxides such as di-tert-butyl peroxide and dicumyl peroxide, tert-butyl peroxylaurylate, tert-butyl peroxybenzoate It is possible to use peroxide initiators such as peroxyesters such as.
  • redox system initiation is performed in which these persulfates, peroxides, etc. are used in combination with metal ions such as iron ions, or reducing agents such as sodium sulfoxylate formaldehyde, sodium pyrosulfite, or L-ascorbic acid. Agents can also be used.
  • intermolecular hydrogen abstraction type initiators such as benzophenone, 4,4'-bisdimethylaminobenzophenone, Michler's ketone, dibenzosuberone, 2-ethylanthraquinone, isobutylthioxanthone, benzoin, benzoin, etc.
  • organic phase radical polymerization initiators such as intramolecular bond cleavage type initiators such as Linopropane-1 can be used.
  • examples of the cationic polymerization initiator include diazonium salt type compounds, sulfonium salt type compounds, and iodonium salt type compounds. These compounds may be used in combination. However, when used as an aqueous resin composition, it is easy to use a structure that can also be used in an aqueous system or a liquid type. When using these organic phase initiators as an aqueous resin composition, it is preferable to add them in advance to the organic solvent solution before dispersing the resin solution in water.
  • the amount used may be appropriately selected from the range of 0.2 to 20% based on the solid content excluding colorant, and the range of 0.5 to 10% is particularly preferable.
  • the average particle diameter was measured by intensity distribution using a dynamic light scattering method using "Zetasizer Nano-ZS Model ZEN3600" manufactured by Malvern. A sample in which the solid content of the aqueous dispersion composition was adjusted to a concentration of 0.05 g/L was measured three times at 25°C, and the average value was taken as the average value.
  • the resulting resin was dried under reduced pressure to obtain a solid acid-modified polyolefin (PO-1).
  • PO-1 solid acid-modified polyolefin
  • the total content of the maleic anhydride component and the maleic acid component in which maleic anhydride is ring-opened was 1.1% by mass.
  • the weight average molecular weight as determined by high temperature GPC measurement was 90,000, and the melting point as determined by DSC was 70°C.
  • Production Example 3 (Production of aqueous resin composition (a)) 100 g of the maleic acid-modified polyolefin (PO-1) obtained in Production Example 1 and 60 g of toluene were placed in an autoclave equipped with a stirrer, and after purging with nitrogen for about 5 minutes, the mixture was heated and dissolved at 100°C for 30 minutes. went. Thereafter, 1.9 g of allylamine was added and the reaction was carried out at 80° C. for 2 hours while heating and stirring to obtain a polyolefin resin. Once cooled, a portion of the reaction solution was taken out and an infrared absorption spectrum was measured.
  • aqueous resin composition (b) A polyolefin resin (weight average molecular weight 90,000, melting point 70° C. by DSC) was obtained in the same manner as in Example 1, except that the types, amounts, and reaction temperatures of each component were changed to the compositions shown in Table 1. Furthermore, an aqueous resin composition (b) having a resin concentration (solid content) of 30% by mass and an average particle diameter of resin particles of 90 nm was obtained. In the infrared absorption spectrum measurement of the polyolefin resin, the spectrum around 1780 cm-1 derived from the acid anhydride disappeared, and peaks derived from the amide group and carboxyl group were confirmed at 1655 cm-1 and 1705 cm-1, respectively.
  • aqueous resin composition (c) A polyolefin resin (weight average molecular weight 90,000, melting point 70° C. by DSC) was obtained in the same manner as in Example 1, except that the types, amounts, and reaction temperatures of each component were changed to the compositions shown in Table 1. Furthermore, an aqueous resin composition (c) having a resin concentration (solid content) of 30% by mass and an average particle diameter of resin particles of 80 nm was obtained. In the infrared absorption spectrum measurement of the polyolefin resin, the spectrum around 1780 cm-1 derived from the acid anhydride disappeared, and peaks derived from the ester group and carboxyl group were confirmed at 1732 cm-1 and 1700 cm-1, respectively.
  • aqueous resin composition (d) A polyolefin resin (weight average molecular weight 90,000, melting point 70° C. by DSC) was obtained in the same manner as in Example 1, except that the types, amounts, and reaction temperatures of each component were changed to the compositions shown in Table 1. Furthermore, an aqueous resin composition (d) having a resin concentration (solid content) of 30% by mass and an average particle diameter of resin particles of 90 nm was obtained. In the infrared absorption spectrum measurement of the polyolefin resin, the spectrum around 1780 cm-1 derived from the acid anhydride disappeared, and peaks derived from the ester group and carboxyl group were confirmed at 1730 cm-1 and 1708 cm-1, respectively.
  • aqueous resin composition (e) A polyolefin resin (weight average molecular weight 80,000, melting point 70°C by DSC) was obtained in the same manner as in Example 1 except that the types and amounts of each component were changed to the compositions shown in Table 1. Furthermore, an aqueous resin composition (e) having a resin concentration (solid content) of 30% by mass and an average particle diameter of resin particles of 60 nm was obtained. In the infrared absorption spectrum measurement of the polyolefin resin, the spectrum around 1780 cm-1 derived from the acid anhydride disappeared, and peaks derived from the amide group and carboxyl group were confirmed at 1643 cm-1 and 1708 cm-1, respectively.
  • Production Example 8 (Production of aqueous resin composition (f))
  • 100 g of the acid-modified polyolefin (PO-1) obtained in Production Example 1 60 g of toluene, 60 g of isopropyl alcohol, and polyoxyethylene cetyl were added.
  • 20 g of ether manufactured by NOF Corporation, trade name "Nonion P-210", nonionic surfactant
  • 4.0 g of N,N-dimethylethanolamine was added to this solution and stirred for 15 minutes.
  • aqueous resin composition (f) having a resin concentration (solid content) of 30% by mass and an average particle size of resin particles of 65 nm.
  • Production Example 9 (Production of aqueous resin composition (g)) An aqueous resin composition (g ) was obtained.
  • Production Example 10 (Production of aqueous resin composition (h)) The same method as in Example 1 was carried out except that the type, amount, and reaction temperature of each component were changed to those shown in Table 1, but an aqueous resin composition could not be obtained due to poor emulsification.
  • the spectrum around 1780 cm-1 derived from the acid anhydride disappeared, and the spectrum at 1720 cm-1 derived from the imide group was confirmed.
  • peaks derived from carboxyl groups and amide groups could not be confirmed.
  • Example 1 60 g of aqueous resin composition (a), 40 g of urethane acrylate dispersion (UCECOAT7571 manufactured by ALLNEX), 2 g of propylene glycol monomethyl ether as a film-forming agent, 2 g of "Dynol 604" (manufactured by Air Products Japan Co., Ltd.) as a wetting agent, and light 1.5 g of OMNIRAD1173 (manufactured by IGM RESINS BV) was added as a polymerization initiator and stirred with a magnetic stirrer for 30 minutes to obtain an active energy ray-curable polyolefin resin composition.
  • Example 2 An active energy ray-curable polyolefin resin composition was obtained in the same manner as in Example 1, except that the aqueous resin composition (b) was used.
  • Example 3 An active energy ray-curable polyolefin resin composition was obtained in the same manner as in Example 1, except that the aqueous resin composition (c) was used.
  • Example 4 An active energy ray-curable polyolefin resin composition was obtained in the same manner as in Example 1, except that the aqueous resin composition (d) was used.
  • Example 5 An active energy ray-curable polyolefin resin composition was obtained in the same manner as in Example 1, except that the aqueous resin composition (e) was used.
  • Comparative example 1 An acid-modified polyolefin resin composition was obtained in the same manner as in Example 1, except that the aqueous resin composition (f) was used.
  • Comparative example 2 An active energy ray-curable polyolefin resin composition was obtained in the same manner as in Example 1, except that the aqueous resin composition (g) was used.
  • Peel strength A test plate was prepared in the same manner as in (1) above, except that a 100 ⁇ m thick protective film was spray-painted, and then left in an atmosphere of 25°C and 60% relative humidity for an additional 48 hours, and this was used as a test plate. . Strip-shaped peel pieces were made on this test plate at 1 cm intervals, and a 50 mm, 180° peel test was performed at a speed of 50 mm/min using a tensile tester (Tensilon RTG-1310, manufactured by A&D Co., Ltd.). The stress during tension was defined as the peel strength, and the average value of 5 tests was defined as the measurement result.
  • the peel strength evaluation results were as follows.

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Abstract

La présente invention concerne une résine polyoléfine (A) durcissable par rayonnement d'énergie active qui présente une force de détachement, une résistance à l'eau et une force d'adhérence élevées par rapport à un matériau de base polyoléfine, et qui est caractérisée en ce qu'elle possède un groupe carboxyle et une double liaison insaturée, et qui est caractérisée en ce que la double liaison insaturée est dérivée d'un anhydride carboxylique α,β-insaturé (B) et d'au moins un composé (C) choisi dans le groupe constitué de (I), (II) et (III). (I) Composés (C1) ayant une double liaison insaturée et un groupe amino. (II) Composés (C2) ayant une double liaison insaturée et un groupe hydroxyle. (III) Composés (C3) ayant une double liaison insaturée et un groupe époxy.
PCT/JP2023/013295 2022-03-31 2023-03-30 Résine polyoléfine durcissable par rayonnement d'énergie active et composition de résine aqueuse Ceased WO2023190929A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7535347B1 (ja) 2023-10-31 2024-08-16 ユニチカ株式会社 ポリオレフィン樹脂水性分散体、その製造方法、及び塗膜
WO2025205039A1 (fr) * 2024-03-29 2025-10-02 東洋紡エムシー株式会社 Composition de résine de polyoléfine modifiée et utilisations de ladite composition de résine

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JPH05105841A (ja) * 1991-10-14 1993-04-27 Sanyo Kokusaku Pulp Co Ltd バインダー樹脂組成物
JPH06172422A (ja) * 1992-12-10 1994-06-21 Tonen Chem Corp 反応性ポリプロピレン
JPH0892427A (ja) * 1994-09-27 1996-04-09 Nippon Paper Ind Co Ltd 水性樹脂組成物
JP2002212241A (ja) * 2000-11-14 2002-07-31 Toyo Kasei Kogyo Co Ltd グラフトポリオレフィン、並びにそれを含有するコーティング用樹脂組成物
JP2004520474A (ja) * 2001-02-09 2004-07-08 イーストマン ケミカル カンパニー 紫外線硬化性非塩素系定着剤
JP2004269872A (ja) * 2003-02-21 2004-09-30 Mitsubishi Chemicals Corp ポリプロピレン共重合体、それを含む組成物及びその製法
WO2020040217A1 (fr) * 2018-08-24 2020-02-27 日本製紙株式会社 Résine polyoléfinique modifiée et son procédé de production

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05105841A (ja) * 1991-10-14 1993-04-27 Sanyo Kokusaku Pulp Co Ltd バインダー樹脂組成物
JPH06172422A (ja) * 1992-12-10 1994-06-21 Tonen Chem Corp 反応性ポリプロピレン
JPH0892427A (ja) * 1994-09-27 1996-04-09 Nippon Paper Ind Co Ltd 水性樹脂組成物
JP2002212241A (ja) * 2000-11-14 2002-07-31 Toyo Kasei Kogyo Co Ltd グラフトポリオレフィン、並びにそれを含有するコーティング用樹脂組成物
JP2004520474A (ja) * 2001-02-09 2004-07-08 イーストマン ケミカル カンパニー 紫外線硬化性非塩素系定着剤
JP2004269872A (ja) * 2003-02-21 2004-09-30 Mitsubishi Chemicals Corp ポリプロピレン共重合体、それを含む組成物及びその製法
WO2020040217A1 (fr) * 2018-08-24 2020-02-27 日本製紙株式会社 Résine polyoléfinique modifiée et son procédé de production

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7535347B1 (ja) 2023-10-31 2024-08-16 ユニチカ株式会社 ポリオレフィン樹脂水性分散体、その製造方法、及び塗膜
JP2025075428A (ja) * 2023-10-31 2025-05-15 ユニチカ株式会社 ポリオレフィン樹脂水性分散体、その製造方法、及び塗膜
WO2025205039A1 (fr) * 2024-03-29 2025-10-02 東洋紡エムシー株式会社 Composition de résine de polyoléfine modifiée et utilisations de ladite composition de résine

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