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WO2018037849A1 - Résine à base de polyoléfine modifiée - Google Patents

Résine à base de polyoléfine modifiée Download PDF

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Publication number
WO2018037849A1
WO2018037849A1 PCT/JP2017/027841 JP2017027841W WO2018037849A1 WO 2018037849 A1 WO2018037849 A1 WO 2018037849A1 JP 2017027841 W JP2017027841 W JP 2017027841W WO 2018037849 A1 WO2018037849 A1 WO 2018037849A1
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WO
WIPO (PCT)
Prior art keywords
component
polyolefin resin
modified polyolefin
weight
modified
Prior art date
Application number
PCT/JP2017/027841
Other languages
English (en)
Japanese (ja)
Inventor
早川　潤一
勝 神埜
由生 ▲高▼田
実 矢田
Original Assignee
日本製紙株式会社
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Filing date
Publication date
Application filed by 日本製紙株式会社 filed Critical 日本製紙株式会社
Priority to JP2018535556A priority Critical patent/JP6970095B2/ja
Publication of WO2018037849A1 publication Critical patent/WO2018037849A1/fr

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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
    • C08F8/00—Chemical modification by after-treatment
    • 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
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • 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
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers

Definitions

  • the present invention relates to a modified polyolefin resin.
  • Polyolefin resins such as polypropylene and polyethylene are general-purpose thermoplastic resins that are inexpensive and have many excellent properties such as moldability, chemical resistance, light resistance, water resistance, and electrical properties. It is used in a wide range of fields as molded products.
  • base materials made of these polyolefin resins (hereinafter also referred to as “polyolefin base materials”) are different from polar base materials such as polyurethane resins, polyamide resins, acrylic resins, polyester resins, metals, etc. Because of its low polarity and crystallinity, it is a difficult-to-adhere substrate, and has the disadvantages that it is difficult to adhere or paint a substance with low polarity and to adhere or paint a substance with high polarity.
  • a surface treatment for the base material As a method for improving the adhesion of a polyolefin base material, a surface treatment for the base material has been conventionally performed.
  • Surface treatment includes roughening by polishing, and introduction of polar groups by oxidant, corona discharge, plasma treatment, and flame treatment, but these have the disadvantage that the effect of improving adhesiveness gradually decreases, so it is generally popular. Not done.
  • a method has been devised in which a pretreatment agent having adhesiveness to the substrate is previously applied to the substrate surface.
  • a pretreatment agent has various names depending on applications, and is called, for example, an adhesive, a binder, a primer, or the like.
  • the pretreatment agent for example, a resin having a predetermined property is used, and a hot melt system that is melted by heat to form a binder, a solvent system that dissolves the resin in a solvent, and the resin is emulsified using a surfactant or the like.
  • a pretreatment agent such as an aqueous system is provided.
  • the pretreatment agent include a binder resin composition containing a carboxyl group-containing chlorinated polypropylene random copolymer described in JP-A No. 2003-321588 (Patent Document 1).
  • a coating composition for binders and primers polyolefin base, vinyl chloride base, polycarbonate (PC) base, polyethylene terephthalate (PET) base, acrylonitrile-butadiene-styrene resin (ABS) group
  • a method for improving the adhesiveness by improving the affinity with a material, a polyamide (nylon) resin base material, and the like is disclosed.
  • Non-chlorinated modified polyolefin resins grafted with carboxylic acids and carboxylic anhydrides have been developed.
  • JP-A-2001-279048 Patent Document 2 discloses a modified polyolefin resin composition graft-modified with an unsaturated carboxylic acid derivative and / or an anhydride thereof, and this modified polyolefin resin composition is used as a coating composition.
  • a method for improving the adhesiveness by increasing the affinity with a polypropylene base material by using as a product is disclosed.
  • Patent Document 1 uses a chlorinated resin, and does not relate to a non-chlorinated resin that is preferred for use in a field where dehalogenation is desired from the viewpoint of environmental problems in recent years.
  • Patent Document 2 adhesion to a polypropylene base material and various polar base materials, which are polyolefin base materials, is improved, but it is still sufficient for base materials made of polycarbonate resin or polystyrene (PS) resin. Adhesiveness was not obtained.
  • the object of the present invention is to provide a modified polyolefin type which is excellent in adhesiveness to polyolefin base materials frequently used in various industrial applications such as packaging materials, and excellent in adhesiveness to polycarbonate base materials and polystyrene base materials. It is to provide a resin.
  • component (D): (meth) acrylic acid ester a component (D): (meth) acrylic acid ester.
  • component (D) includes a (meth) acrylic acid ester represented by the formula (I).
  • a heat sealant comprising the modified polyolefin resin according to any one of [1] to [7].
  • An adhesive comprising the modified polyolefin resin according to any one of [1] to [7].
  • a primer comprising the modified polyolefin resin according to any one of [1] to [7].
  • a paint binder comprising the modified polyolefin resin according to any one of [1] to [7].
  • An ink binder comprising the modified polyolefin resin according to any one of [1] to [7].
  • Component (A) comprising modifying a polyolefin resin with a modifying component to obtain a modified polyolefin resin,
  • the denaturing component is
  • Component (C) A method for producing a modified polyolefin resin comprising a compound having a benzene ring.
  • [14] The method for producing a modified polyolefin resin according to [13], wherein the modification is performed in the order of modification with the component (B) and modification with the component (C).
  • [15] The method for producing a modified polyolefin resin according to [13] or [14], wherein the modified component further comprises a component (D): (meth) acrylic acid ester.
  • [16] The method for producing a modified polyolefin resin according to [15], wherein the modification with the component (B) and the modification with the component (D) are simultaneously performed.
  • the present invention also provides the following aspects.
  • [17] The method for producing a modified polyolefin resin according to [15] or [16], wherein the component (D) contains a (meth) acrylic acid ester represented by the formula (I).
  • CH 2 CR 1 COOR 2 (I) (In Formula (I), R 1 represents a hydrogen atom or a methyl group, R 2 represents a group represented by —C n H 2n + 1 , and n is an integer of 8 to 18)
  • [18] The method for producing a modified polyolefin resin according to any one of [13] to [17], wherein the component (C) is a compound having a benzyl group.
  • a modified polyolefin resin having excellent adhesion to a polyolefin substrate and excellent adhesion to a polycarbonate substrate and a polystyrene substrate.
  • Modified polyolefin resin of the present invention is obtained by modifying component (A): polyolefin resin with a modifying component,
  • the denaturing component is Component (B): One or more selected from ⁇ , ⁇ -unsaturated carboxylic acids and acid anhydrides thereof, and Component (C): a compound having a benzene ring.
  • the modification includes graft modification in which the modification component is graft-polymerized to the polyolefin resin, and addition modification in which the modification component is added to the polyolefin resin or the modification component modifying the polyolefin resin.
  • the modified polyolefin resin is a polyolefin resin that has been modified with a modifying component.
  • the polyolefin resin as the component (A) is not particularly limited, and may be a homopolymer of one olefin or a copolymer of two or more olefins.
  • the olefin of the monomer unit constituting the polyolefin resin include ⁇ -olefins, and ⁇ -olefins having 2 to 6 carbon atoms (eg, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1 -Octene) is preferred.
  • polystyrene resin examples include a homopolymer of ethylene or propylene, a copolymer of ethylene and propylene, a copolymer of ethylene and one or more other olefins, and a copolymer of propylene and one or more other olefins. And a copolymer of ethylene and propylene, a copolymer of ethylene and an ⁇ -olefin having 2 to 6 carbon atoms, and a copolymer of propylene and an ⁇ -olefin having 2 to 6 carbon atoms.
  • polystyrene resin One or more selected from polymers, and more preferably one or more selected from ethylene-propylene copolymers, propylene-1-butene copolymers, and ethylene-propylene-1-butene copolymers.
  • polyolefin resin When the polyolefin resin is a copolymer, it may be a random copolymer or a block copolymer.
  • the component (A) may be a combination of two or more polyolefin resins.
  • Component (B) is at least one selected from ⁇ , ⁇ -unsaturated carboxylic acids and acid anhydrides thereof.
  • ⁇ , ⁇ -unsaturated carboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, aconitic acid, and (meth) acrylic acid.
  • acid anhydride of ⁇ , ⁇ -unsaturated carboxylic acid include maleic anhydride, citraconic anhydride, itaconic anhydride, aconitic anhydride, hymic anhydride, and (meth) acrylic anhydride.
  • Component (B) preferably comprises an acid anhydride of an ⁇ , ⁇ -unsaturated carboxylic acid, more preferably maleic anhydride.
  • Component (B) is one or more selected from ⁇ , ⁇ -unsaturated carboxylic acids and acid anhydrides thereof, and a combination of one or more ⁇ , ⁇ -unsaturated carboxylic acids and one or more acid anhydrides thereof.
  • (meth) acrylic acid means methacrylic acid or acrylic acid.
  • the amount of component (B) is preferably 0.1% by weight or more, more preferably 0.5% by weight or more based on component (A).
  • the modified polyolefin resin obtained has favorable adhesiveness with respect to an adherend of polarity, such as a metal
  • the reactivity with the below-mentioned component (C) increases.
  • An upper limit becomes like this.
  • it is 10 weight% or less, More preferably, it is 5 weight% or less, More preferably, it is 4 weight% or less.
  • a component (B) can react with a component (A) without waste, and the favorable adhesiveness with respect to a to-be-adhered body can be hold
  • the modified weight (graft weight) by the component (B) in the modified polyolefin resin is preferably 0.1% by weight or more, more preferably 0.5% by weight when the modified polyolefin resin is 100% by weight. % Or more. An upper limit becomes like this. Preferably it is 10 weight% or less, More preferably, it is 5 weight% or less, More preferably, it is 4 weight% or less.
  • the modified weight (graft weight) due to the component (B) in the modified polyolefin resin is preferably 0.1 to 10% by weight, more preferably 0.5% when the modified polyolefin resin is 100% by weight. ⁇ 4% by weight.
  • the modified weight (graft weight) When the modified weight (graft weight) is 0.1% by weight or more, the resulting modified polyolefin resin has good adhesion to polar adherends such as metals, The reactivity of can be ensured. When the modified weight (graft weight) is 10% by weight or less, good adhesion to the resin adherend can be maintained.
  • the modified weight% by the component (B) in the modified polyolefin resin can be measured by a known method. For example, it can be determined by alkali titration or Fourier transform infrared spectroscopy.
  • Component (C) is a compound having a benzene ring.
  • Component (C) is preferably a compound that can react with component (A) to introduce a benzene ring into the polyolefin resin.
  • the compound having a benzene ring include aniline, phenol, benzenethiol, and a compound having a benzyl group (eg, benzylamine, benzyl alcohol, and benzyl mercaptan).
  • a compound having a benzyl group is preferable, and at least one selected from benzylamine and benzyl alcohol is more preferable.
  • Component (C) may be one type of compound having a benzene ring or a combination of two or more types.
  • the modified polyolefin resin of the present invention has high adhesion to not only polyolefin base materials but also polycarbonate base materials and polystyrene base materials.
  • the reason is guessed as follows. That is, since the benzene ring has a ⁇ bond, when the polyolefin resin is modified with a component (C): a modifying component containing a compound having a benzene ring, the modified polyolefin resin contains a benzene ring in its structure, A conjugated system is formed.
  • the polycarbonate base material and the polystyrene base material have a benzene ring in the structure.
  • the modified polyolefin resin of the present invention Due to the interaction between the conjugated system formed in the modified polyolefin resin and the benzene ring contained in the structure of the substrate, the modified polyolefin resin of the present invention has adhesiveness to the polycarbonate substrate and the polystyrene substrate. Presumed to increase.
  • the blending amount (content) of the component (C) is preferably 0.1% by weight or more, more preferably 0.5% by weight or more based on the component (A). Thereby, sufficient adhesive effect can be exhibited.
  • the upper limit is preferably 20% by weight or less, and more preferably 10% by weight or less. Thereby, a component (C) can react with a component (A) without waste, and can maintain the favorable adhesiveness with respect to a to-be-adhered body.
  • the modified (added) weight of the component (C) in the modified polyolefin resin is preferably 0.1% by weight or more, more preferably 0.5% by weight when the modified polyolefin resin is 100% by weight. That's it.
  • the upper limit is preferably 20% by weight or less, and more preferably 10% by weight or less.
  • the modified (added) weight of component (C) in the modified polyolefin resin is preferably 0.1 to 20% by weight, more preferably 0.5%, based on 100% by weight of the modified polyolefin resin. ⁇ 10% by weight.
  • the modified polyolefin resin has good adhesion to the adherend.
  • the adhesiveness with respect to a to-be-adhered body can be hold
  • the modified weight% by component (C) in the modified polyolefin resin can be measured by a known method. For example, it can be determined by Fourier transform infrared spectroscopy.
  • the modified component that modifies the component (A) may contain other components in addition to the component (B) and the component (C) as long as the effects of the present invention are not impaired, depending on the application and purpose.
  • the modifying component that modifies component (A) preferably comprises component (D): (meth) acrylic acid ester.
  • (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyethyl (meth) acrylate, isobornyl (meth) acrylate, Glycidyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, Diethylaminoethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylic acid ester
  • the component (D) preferably contains a (meth) acrylic acid ester represented by the formula (I), and more preferably a (meth) acrylic acid ester represented by the formula (I).
  • CH 2 CR 1 COOR 2 (I) (In Formula (I), R 1 represents a hydrogen atom or a methyl group, R 2 represents a group represented by —C n H 2n + 1 , and n is an integer of 8 to 18)
  • the molecular weight of the modified polyolefin resin is suppressed from decreasing from the molecular weight of the component (A): polyolefin resin, Solvent solubility of modified polyolefin resin, low temperature stability of modified polyolefin resin solution, compatibility between modified polyolefin resin and other resins blended with adhesives together with modified polyolefin resin, adhesion of modified polyolefin resin Can be improved.
  • the component (D) includes a (meth) acrylic acid ester represented by the formula (I)
  • the (meth) acrylic acid ester represented by the formula (I) is a single type or a combination of two or more types.
  • two or more (meth) acrylic acid esters represented by the formula (I) may be mixed and used in an arbitrary ratio.
  • R 1 preferably represents a methyl group.
  • n is preferably an integer of 8 to 15, more preferably an integer of 8 to 14, and still more preferably an integer of 8 to 13.
  • the (meth) acrylic acid ester represented by the formula (I) is preferably at least one selected from stearyl (meth) acrylate, lauryl (meth) acrylate, and octyl (meth) acrylate, more preferably stearyl methacrylate. , Lauryl methacrylate, and one or more selected from octyl methacrylate, and more preferably one or more selected from lauryl methacrylate and octyl methacrylate.
  • the amount of component (D) is preferably 0.1% by weight or more, more preferably 0.5% by weight or more based on component (A).
  • the molecular weight distribution of the modified polyolefin resin can be kept in a sufficiently narrow range. That is, by reducing the high molecular weight portion, it is possible to maintain good solvent solubility, low temperature stability of the solution, and compatibility with other resins.
  • adhesive force can be improved by reducing a low molecular weight part.
  • the upper limit is preferably 10% by weight or less, and more preferably 4% by weight or less. Thereby, it can suppress that a component (D) remains as an unreacted substance, and can maintain the adhesiveness with respect to a to-be-adhered body favorably.
  • the modified (graft) weight by component (D) in the modified polyolefin resin is preferably 0.1% by weight or more, more preferably 0.5% by weight, when the modified polyolefin resin is 100% by weight. That's it.
  • the upper limit is preferably 10% by weight or less, and more preferably 4% by weight or less.
  • the modified (graft) weight of the component (D) in the modified polyolefin resin is preferably 0.1 to 10% by weight, more preferably 0, when the modified polyolefin resin is 100% by weight. .5-4% by weight.
  • the modified weight (graft weight) is 0.1% by weight or more, the molecular weight distribution of the modified polyolefin resin can be kept in a sufficiently narrow range.
  • the modification (graft) weight% of the component (D) can be measured by a known method. For example, it can be determined by Fourier transform infrared spectroscopy or 1H-NMR.
  • the modified component may contain modified components other than the component (B), the component (C), and the component (D) singly or in combination of two or more.
  • the modifying component other than the component (B), the component (C), and the component (D) include ⁇ , ⁇ -unsaturated carboxylic acid derivatives other than the component (B) and the component (D).
  • the derivatives of the ⁇ , ⁇ -unsaturated carboxylic acid include ⁇ , ⁇ -unsaturated carboxamides.
  • Examples of ⁇ , ⁇ -unsaturated carboxamides include amides of (meth) acrylic acid (eg, N-methyl (meth) acrylamide, hydroxyethyl (meth) acrylamide, (meth) acryloylmorpholine).
  • (meth) acrylamide means methacrylamide or acrylamide
  • (meth) acryloyl means methacryloyl or acryloyl.
  • the modifying component may contain component (E): chlorine, but the modifying component preferably does not contain component (E).
  • the modified polyolefin resin of the present invention can be suitably used for adhesion of substances in which the residual components derived from chlorine are not preferred.
  • each modified weight by the modifying component other than the component (B), the component (C), and the component (D) Is preferably not more than the sum of the weight modified by component (B), the weight modified by component (C), and the weight modified by component (D).
  • the modified polyolefin-based resin of the present invention is obtained by modifying the component (A) with a modifying component.
  • a polymer containing only the modifying component as a structural unit a polymer containing substances other than modified polyolefin resin, such as a monomer and unmodified polyolefin resin, may be sufficient.
  • the modified polyolefin resin of the present invention can be produced by a known method.
  • component (F): a radical generator may be used.
  • the radical generator as the component (F) is not particularly limited, and may be appropriately selected from known radical generators.
  • an organic peroxide compound is preferable.
  • organic peroxide compounds include di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, benzoyl peroxide, dilauryl peroxide, cumene hydroperoxide, and t-butyl hydroperoxide.
  • B pills carbonate include cumylperoxy octoate, etc., di -t- butyl peroxide, dicumyl peroxide, and one or more selected from dilauryl peroxide are preferred.
  • Component (F) may be a single type or a combination of two or more types.
  • the blending amount of component (F) in the production of the modified polyolefin resin of the present invention is preferably relative to the total (weight) of the blending amount of component (B), component (C), and optionally component (D). It is 1 to 100% by weight, and more preferably 10 to 50% by weight. By being 1% by weight or more, sufficient graft efficiency can be maintained. By being 100 weight% or less, the fall of the weight average molecular weight of modified polyolefin resin can be suppressed.
  • a modified polyolefin resin for example, a mixture of a component (A) and a modified component (eg, component (B), component (C), and component (D)) is mixed with a solvent (eg, toluene or other organic material).
  • a solvent eg, toluene or other organic material
  • Solvent is heated and dissolved in a solvent, and a component method (F) is added, and a kneading machine such as a Banbury mixer, a kneader, or an extruder is used, and component (A), modified component (eg, component (B), Examples thereof include a melt kneading method in which the component (C), the component (D)), and the component (F) are reacted by melting and kneading under heating.
  • a component method (F) such as a Banbury mixer, a kneader, or an extruder is used, and component (A), modified component (eg, component (B), Examples thereof include a melt kneading method in which the component (C), the component (D)), and the component (F) are reacted by melting and kneading under heating.
  • the order of modification by each component contained in the modifying component is not particularly limited, and modification by each modifying component may be performed all at the same time. Further, the modification may be performed before or after modification with the remaining modification component, and modification with each modification component may be performed sequentially.
  • the modification of component (A) with the modifying component is preferably performed in the order of modification with component (B) and modification with component (C).
  • the modifying component contains the component (D)
  • the modification with the component (B) and the modification with the component (D) are preferably performed simultaneously.
  • modifying component contains the component (D)
  • a method of modifying the component (A) with the component (B) and the component (D) using the component (F) and then modifying with the component (C) is preferable.
  • component (C) is introduced into the modified site of component (A) by an addition reaction.
  • any one of the weight modified by the component (B), the weight modified by the component (D), and the weight modified by the component (C) in the modified polyolefin resin is 0.1 to 10% by weight. More preferably, the weight modified by (B), the weight modified by component (D), and the weight modified by component (C) are all 0.1 to 10% by weight.
  • the weight average molecular weight of the modified polyolefin resin of the present invention is preferably 5,000 to 300,000, more preferably 8,000 to 200,000, or more preferably 5,000 or more and less than 200,000, More preferably, it is 10,000 to 150,000.
  • the weight average molecular weight is 5,000 or more, sufficient adhesive strength can be obtained.
  • the weight average molecular weight in this invention containing an Example is a value calculated by measuring by gel permeation chromatography (GPC) (standard substance: polystyrene).
  • GPC gel permeation chromatography
  • the melting point (hereinafter also referred to as Tm) of the modified polyolefin resin of the present invention by a differential scanning calorimeter (hereinafter referred to as DSC) is preferably 50 ° C. to 120 ° C., although it depends on the use conditions.
  • Tm differential scanning calorimeter
  • the melting point is 50 ° C. or higher, sufficient adhesive strength can be obtained.
  • the melting point is 120 ° C. or lower, the adhesiveness at a relatively low temperature that does not cause deformation of the shape of the base material is good, the solution stability is good, and sufficient storage stability at a low temperature is achieved. Obtainable.
  • the measurement of Tm by DSC in the present invention can be performed, for example, under the following conditions.
  • a DSC measuring device manufactured by Seiko Denshi Kogyo
  • about 5 mg of sample is heated at 150 ° C. for 10 minutes to maintain the molten state, and then cooled at a rate of 10 ° C./min.
  • the melting peak temperature is measured when the temperature is further raised to 150 ° C. at 10 ° C./min to melt, and the temperature is evaluated as Tm.
  • Tm is measured under the conditions described above.
  • the modified polyolefin resin of the present invention can be combined with other components as necessary to obtain a modified polyolefin resin composition.
  • the modified polyolefin resin or the modified polyolefin resin composition can be used as a heat sealant, an adhesive, a primer, and a binder (eg, a binder for paint and an ink binder).
  • a binder eg, a binder for paint and an ink binder.
  • examples of other components include a curing agent, a solvent or a dispersion medium, an antioxidant, a light stabilizer, an ultraviolet absorber, a pigment, a dye, and an inorganic filler.
  • the curing agent examples include a polyisocyanate compound, an epoxy compound, a polyamine compound, a polyol compound, and a curing agent in which the functional group of these compounds is protected with a protective group.
  • curing agent may be mix
  • the blending amount of the curing agent in the resin composition is not particularly limited. Good.
  • curing agent you may use together catalysts, such as an organotin compound and a tertiary amine compound, according to the objective.
  • the solvent or dispersion medium is not particularly limited, and examples thereof include aromatic hydrocarbons (eg, toluene, xylene), esters (eg, ethyl acetate, butyl acetate, propyl acetate), aliphatic or alicyclic hydrocarbons (eg, , Cyclohexane, methylcyclohexane, ethylcyclohexane, nonane, decane), alcohol (eg, methanol, ethanol, propanol, isopropanol, butanol), glycol ether (eg, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol t-butyl ether) ), Water.
  • aromatic hydrocarbons eg, toluene, xylene
  • esters eg, ethyl acetate, butyl acetate, propyl acetate
  • the solvent or dispersion medium contained in the modified polyolefin resin composition may be a single type or a combination of two or more types.
  • the modified polyolefin resin composition may be an aqueous resin composition containing a solvent or dispersion medium containing water.
  • the resin composition containing the modified polyolefin-based resin of the present invention has other components (eg, polyester-based adhesive, polyurethane-based adhesive, acrylic-based adhesive, etc.) used for the adhesive within a range that does not impair the desired effect.
  • other components eg, polyester-based adhesive, polyurethane-based adhesive, acrylic-based adhesive, etc.
  • heat sealants e.g., heat sealants, other components used in primers, and other components used in binders may be blended.
  • the modified polyolefin resin of the present invention has excellent adhesion to not only polyolefin base materials but also polycarbonate base materials and polystyrene base materials with few polar groups, and is therefore useful as an adhesive or heat sealant for bonding them together. It is.
  • the modified polyolefin resin of the present invention can be used for adhesion of a cover tape of an embossed carrier tape for electronic parts, for example.
  • the production method of the modified polyolefin resin of the present invention comprises: Component (A): modifying a polyolefin resin with a modifying component to obtain a modified polyolefin resin,
  • the denaturing component is Component (B): One or more selected from ⁇ , ⁇ -unsaturated carboxylic acids and acid anhydrides thereof, and
  • the modifying component preferably further comprises component (D): (meth) acrylic acid ester.
  • component (D) the above item 1.
  • the method for modifying the component (A) with the modifying component is not particularly limited. For example, a mixture of the component (A) and the modifying component is heated and dissolved in a solvent (eg, an organic solvent such as toluene), and the above component (F ) And a melt kneading method in which the component (A), the modified component, and the component (F) are reacted by melting and kneading under heating. Examples and preferred examples of the component (F) are as described in the above item 1. As already explained.
  • An apparatus for performing these methods is not particularly limited, and may be performed by a known apparatus.
  • a kneader such as a Banbury mixer, a kneader, or an extruder can be used.
  • the order of modification of component (A) by each component included in the modification component is not particularly limited, and modification by each modification component may be performed simultaneously, and modification by some modification components may be performed by modification with the remaining modification components. Before or after the step, modification with each modification component may be performed sequentially.
  • the modification of component (A) with the modifying component is preferably performed in the order of modification with component (B) and modification with component (C).
  • the modifying component contains the component (D)
  • the modification with the component (B) and the modification with the component (D) are preferably performed simultaneously.
  • the modified component may contain modified components other than the component (B), the component (C), and the component (D) singly or in combination of two or more.
  • Other optional modifying components other than the component (B), the component (C), and the component (D) are described in the above item 1. As already explained.
  • the preferred modified weight, preferred weight average molecular weight, and preferred melting point of the modified polyolefin resin obtained by the production method of the present invention are as described in 1. above. As already explained.
  • the modified polyolefin resin obtained by the production method of the present invention is the above item 1.
  • the modified polyolefin-based resin composition can be combined with other components as necessary, and the modified polyolefin-based resin or the modified polyolefin-based resin composition includes a heat sealant, an adhesive, and a primer. It can be used as a binder (eg, binder for paint, binder for ink).
  • agent includes “composition”.
  • Example 1 Kneading using a twin screw extruder set at 180 ° C. 100 parts by weight of propylene-ethylene copolymer, 1 part by weight of maleic anhydride, 0.75 part by weight of lauryl methacrylate, and 3 parts by weight of di-t-butyl peroxide Reacted.
  • a denatured product was obtained by performing degassing under reduced pressure in the extruder to remove the remaining unreacted material.
  • Dissolve 75 parts by weight of the modified product and 45 parts by weight of xylene at 135 ° C. add 1 part by weight of benzylamine with stirring, hold at 135 ° C. for 2 hours, and then remove xylene by distillation under reduced pressure.
  • a modified polyolefin resin was obtained.
  • the resulting modified polyolefin resin had a weight average molecular weight of 70,000.
  • Example 2 Using a twin screw extruder in which 100 parts by weight of propylene-ethylene copolymer, 1 part by weight of maleic anhydride, 0.75 part by weight of lauryl methacrylate, and 1.5 parts by weight of di-t-butyl peroxide were set at 170 ° C. And kneaded. A denatured product was obtained by performing degassing under reduced pressure in the extruder to remove the remaining unreacted material. Dissolve 75 parts by weight of the modified product and 45 parts by weight of xylene at 135 ° C., add 5 parts by weight of benzylamine with stirring, hold at 135 ° C. for 2 hours, and then remove xylene by distillation under reduced pressure.
  • a modified polyolefin resin was obtained.
  • the resulting modified polyolefin resin had a weight average molecular weight of 68,000.
  • Example 3 A kneading reaction was performed using 100 parts by weight of a propylene-ethylene copolymer, 3 parts by weight of itaconic anhydride and 3 parts by weight of di-t-butyl peroxide using a twin screw extruder set at 170 ° C. A denatured product was obtained by performing degassing under reduced pressure in the extruder to remove the remaining unreacted material. Dissolve 75 parts by weight of the modified product and 45 parts by weight of xylene at 135 ° C, add 5 parts by weight of benzyl mercaptan with stirring, and hold at 135 ° C for 2 hours. Thus, a modified polyolefin resin was obtained.
  • Example 4 Using a twin screw extruder set at 160 ° C., 100 parts by weight of propylene-ethylene copolymer, 3 parts by weight of maleic anhydride, 0.25 parts by weight of octyl methacrylate, and 4 parts by weight of di-t-butyl peroxide are kneaded. Reacted. A denatured product was obtained by performing degassing under reduced pressure in the extruder to remove the remaining unreacted material. 75 parts by weight of the modified product and 45 parts by weight of xylene were dissolved at 135 ° C., 1 part by weight of benzylamine was added with stirring, the mixture was kept at 135 ° C. for 2 hours, and then xylene was removed by distillation under reduced pressure.
  • a modified polyolefin resin was obtained.
  • the resulting modified polyolefin resin had a weight average molecular weight of 72,000.
  • a modified polyolefin resin was obtained.
  • the weight average molecular weight of the modified polyolefin resin obtained was 71,000.
  • Example 6 A kneading reaction was performed using 100 parts by weight of a propylene-ethylene copolymer, 5 parts by weight of citraconic anhydride, and 5 parts by weight of di-t-butyl peroxide using a twin screw extruder set at 170 ° C. A denatured product was obtained by performing degassing under reduced pressure in the extruder to remove the remaining unreacted material. 75 parts by weight of the modified product and 45 parts by weight of xylene were dissolved at 135 ° C., 5 parts by weight of benzyl alcohol was added with stirring, and the mixture was kept at 135 ° C. for 2 hours. Thus, a modified polyolefin resin was obtained.
  • Example 7 Using a twin screw extruder set at 170 ° C., 100 parts by weight of propylene-ethylene copolymer, 5 parts by weight of maleic anhydride, 3.75 parts by weight of stearyl methacrylate, and 2 parts by weight of di-t-butyl peroxide are kneaded. Reacted. A denatured product was obtained by performing degassing under reduced pressure in the extruder to remove the remaining unreacted material. 75 parts by weight of the modified product and 45 parts by weight of xylene were dissolved at 135 ° C., 1 part by weight of benzylamine was added with stirring, the mixture was kept at 135 ° C.
  • modified polyolefin resin was obtained.
  • a mixed solvent of methylcyclohexane / propyl acetate 70/30 (V / V) so as to have a solid content of 20%, the property of the modified polyolefin resin solution was no solidified product. The fluidity state was good.
  • the resulting modified polyolefin resin had a weight average molecular weight of 75,000.
  • Example 8 Using a twin screw extruder in which 100 parts by weight of propylene-ethylene copolymer, 5 parts by weight of maleic anhydride, 3.75 parts by weight of stearyl methacrylate, and 1.5 parts by weight of di-t-butyl peroxide were set at 170 ° C. And kneaded. A denatured product was obtained by performing degassing under reduced pressure in the extruder to remove the remaining unreacted material. Dissolve 75 parts by weight of the modified product and 45 parts by weight of xylene at 135 ° C., add 5 parts by weight of benzylamine with stirring, hold at 135 ° C. for 2 hours, and then remove xylene by distillation under reduced pressure.
  • a modified polyolefin resin was obtained.
  • the resulting modified polyolefin resin had a weight average molecular weight of 72,000.
  • Example 9 Using a twin screw extruder set at 180 ° C., 100 parts by weight of propylene-ethylene copolymer, 10 parts by weight of itaconic anhydride, 7.5 parts by weight of stearyl methacrylate, and 2 parts by weight of di-t-butyl peroxide are kneaded. Reacted. A denatured product was obtained by performing degassing under reduced pressure in the extruder to remove the remaining unreacted material. 75 parts by weight of the resulting modified product and 45 parts by weight of xylene were dissolved at 135 ° C., 5 parts by weight of benzyl alcohol was added with stirring, and the mixture was held at 135 ° C. for 2 hours, to obtain a modified polyolefin resin.
  • Example 10 Using a twin screw extruder set at 170 ° C., 100 parts by weight of a propylene-ethylene copolymer, 10 parts by weight of itaconic anhydride, 7.5 parts by weight of stearyl methacrylate, and 3 parts by weight of di-t-butyl peroxide are kneaded. Reacted. A denatured product was obtained by performing degassing under reduced pressure in the extruder to remove the remaining unreacted material. 75 parts by weight of the resulting modified product and 45 parts by weight of xylene were dissolved at 135 ° C., 10 parts by weight of benzyl alcohol was added with stirring, and the mixture was held at 135 ° C.
  • modified polyolefin resin For 2 hours to obtain a modified polyolefin resin.
  • the resulting modified polyolefin resin had a weight average molecular weight of 78,000.
  • the resulting modified polyolefin resin had a weight average molecular weight of 72,000.
  • a resin-coated film film and each substrate are overlapped, and Heat sealing was performed using a 276 heat seal tester (manufactured by Yasuda Seiki Seisakusho). Heat sealing was performed by heating only the film side to 140 ° C. and pressurizing with 2 kgf for 6 seconds. After heat sealing, it was allowed to stand for 3 hours, and a peel test in the 180 ° direction was performed with a Tensilon universal testing machine (manufactured by A & D Co., Ltd., RTG-1210). The peeling speed was 100 mm / min.
  • the modified polyolefin resins of Examples 1 to 10 were modified polyolefin resin of Comparative Example 1 that was not modified with Component (C) and Comparative Example 2 that was not modified with Component (B). It can be seen that when the OPP film and each substrate (PS plate, PC plate, or PET plate) are heat sealed, the heat seal strength is significantly improved. This result shows that the modified polyolefin resin of the present invention has excellent adhesiveness to polyester base materials such as polyolefin base materials, polystyrene base materials, polycarbonate base materials, and PET.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Sealing Material Composition (AREA)
  • Paints Or Removers (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne une résine à base de polyoléfine modifiée qui a une excellente adhésivité à des substrats à base de polyoléfine et a une excellente adhésivité à des substrats à base de polycarbonate et à des substrats à base de polystyrène. La résine à base de polyoléfine modifiée est obtenue par modification d'une résine polyoléfine, en tant qu'ingrédient (A), avec des ingrédients modificateurs, les ingrédients modificateurs comprenant l'ingrédient (B), qui est un ou plusieurs composés sélectionnés parmi les acides carboxyliques α,β-insaturés et leurs anhydrides, et l'ingrédient (C), qui est un composé ayant un cycle benzénique.
PCT/JP2017/027841 2016-08-24 2017-08-01 Résine à base de polyoléfine modifiée WO2018037849A1 (fr)

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WO2019188858A1 (fr) * 2018-03-26 2019-10-03 日本製紙株式会社 Résine de polyoléfine modifiée et utilisation de celle-ci
US20220010048A1 (en) * 2018-12-21 2022-01-13 Nippon Paper Industries Co., Ltd. Modified polyolefin resin
US20220017671A1 (en) * 2018-12-21 2022-01-20 Nippon Paper Industries Co., Ltd. Modified polyolefin resin
WO2022024476A1 (fr) * 2020-07-27 2022-02-03 日本製紙株式会社 Résine de polyoléfine modifiée et son utilisation
JP2022536587A (ja) * 2019-04-26 2022-08-18 ダウ グローバル テクノロジーズ エルエルシー 接着剤組成物
WO2022202822A1 (fr) 2021-03-26 2022-09-29 三井化学株式会社 Composition adhésive et corps multicouche
WO2022210054A1 (fr) * 2021-04-02 2022-10-06 住友化学株式会社 Dispersion aqueuse
WO2022210053A1 (fr) * 2021-04-02 2022-10-06 住友化学株式会社 Résine de polyoléfine modifiée

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JP7297736B2 (ja) 2018-03-26 2023-06-26 日本製紙株式会社 変性ポリオレフィン樹脂及びその用途
JPWO2019188858A1 (ja) * 2018-03-26 2021-04-01 日本製紙株式会社 変性ポリオレフィン樹脂及びその用途
WO2019188858A1 (fr) * 2018-03-26 2019-10-03 日本製紙株式会社 Résine de polyoléfine modifiée et utilisation de celle-ci
US20220010048A1 (en) * 2018-12-21 2022-01-13 Nippon Paper Industries Co., Ltd. Modified polyolefin resin
US20220017671A1 (en) * 2018-12-21 2022-01-20 Nippon Paper Industries Co., Ltd. Modified polyolefin resin
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JP7320076B2 (ja) 2019-04-26 2023-08-02 ダウ グローバル テクノロジーズ エルエルシー 接着剤組成物
WO2022024476A1 (fr) * 2020-07-27 2022-02-03 日本製紙株式会社 Résine de polyoléfine modifiée et son utilisation
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JP7116265B2 (ja) 2020-07-27 2022-08-09 日本製紙株式会社 変性ポリオレフィン樹脂及びその用途
JPWO2022024476A1 (fr) * 2020-07-27 2022-02-03
WO2022202822A1 (fr) 2021-03-26 2022-09-29 三井化学株式会社 Composition adhésive et corps multicouche
WO2022210053A1 (fr) * 2021-04-02 2022-10-06 住友化学株式会社 Résine de polyoléfine modifiée
WO2022210054A1 (fr) * 2021-04-02 2022-10-06 住友化学株式会社 Dispersion aqueuse

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