WO2018037849A1 - Modified polyolefin-based resin - Google Patents

Modified polyolefin-based resin 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
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French (fr)
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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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/en
Publication of WO2018037849A1 publication Critical patent/WO2018037849A1/en

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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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Abstract

Provided is a modified polyolefin-based resin which has excellent adhesiveness to polyolefin-based substrates and has excellent adhesiveness to polycarbonate-based substrates and to polystyrene-based substrates. The modified polyolefin-based resin is obtained by modifying a polyolefin resin, as ingredient (A), with modifying ingredients, the modifying ingredients comprising ingredient (B), which is one or more compounds selected from among α,β-unsaturated carboxylic acids and the anhydrides thereof, and ingredient (C), which is a compound having a benzene ring.

Description

変性ポリオレフィン系樹脂Modified polyolefin resin
　本発明は、変性ポリオレフィン系樹脂に関する。 The present invention relates to a modified polyolefin resin.
　ポリプロピレン、ポリエチレン等のポリオレフィン系樹脂は、熱可塑性の汎用樹脂であり、安価で成形性、耐薬品性、耐光性、耐水性、電気特性など多くの優れた性質を有するため、従来からシート、フィルム、成形物等として、幅広い分野で使用されている。しかし、これらポリオレフィン系樹脂からなる基材（以下、「ポリオレフィン系基材」ともいう。）は、ポリウレタン系樹脂、ポリアミド系樹脂、アクリル系樹脂、ポリエステル樹脂、金属等の極性基材とは異なり、極性が低く、且つ結晶性であるため、難付着性の基材であり、極性が低い物質の接着や塗装、及び極性の高い物質の接着や塗装が困難であるという欠点を有する。 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. However, 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.
　ポリオレフィン系基材の接着性を向上させる方法としては、従来から基材に対する表面処理が行われている。表面処理として、研磨による粗面化、又、酸化剤、コロナ放電、プラズマ処理、火炎処理による極性基の導入があるが、これらは接着性向上の効果が次第に低減する欠点を有するため、一般に普及していない。 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.
　そのため、基材に対し接着性を有する前処理剤を予め基材表面に塗工する方法が考案されている。このような前処理剤は、用途によって様々な呼び名があり、例えば、接着剤、バインダー、プライマー等と呼ばれる。前処理剤としては、例えば所定の性質を有する樹脂が用いられ、熱により溶融させてバインダー等とするホットメルト系、樹脂を溶剤に溶解させる溶剤系、樹脂が界面活性剤等を用いて乳化されている水系等の前処理剤が提供されている。 Therefore, a method has been devised in which a pretreatment agent having adhesiveness to the substrate is previously applied to the substrate surface. Such a pretreatment agent has various names depending on applications, and is called, for example, an adhesive, a binder, a primer, or the like. As 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.
　前処理剤の具体例としては、特開２００３－３２１５８８号公報（特許文献１）に記載されたカルボキシル基含有塩素化ポリプロピレン系ランダム共重合体を含むバインダー樹脂組成物が挙げられ、この樹脂組成物をバインダー及びプライマー用のコーティング組成物として用いて、ポリオレフィン系基材と、塩化ビニル基材、ポリカーボネート（ＰＣ）系基材、ポリエチレンテレフタレート（ＰＥＴ）基材、アクリロニトリル－ブタジエン－スチレン樹脂（ＡＢＳ）基材、ポリアミド（ナイロン）系樹脂基材等との親和性を高め、接着性の向上を図る方法が開示されている。 Specific examples of 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). As 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.
　また、カルボン酸やカルボン酸無水物をグラフトした非塩素系変性ポリオレフィン樹脂が開発されている。例えば特開２００１－２７９０４８号公報（特許文献２）には、不飽和カルボン酸誘導体及び／又はその無水物でグラフト変性された変性ポリオレフィン樹脂組成物が開示され、この変性ポリオレフィン樹脂組成物をコーティング組成物として用いることにより、ポリプロピレン基材との親和性を高め、接着性の向上を図る方法が開示されている。 In addition, non-chlorinated modified polyolefin resins grafted with carboxylic acids and carboxylic anhydrides have been developed. For example, 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.
特開２００３－３２１５８８号公報JP 2003-321588 A 特開２００１－２７９０４８号公報JP 2001-279048 A
　近年、前処理剤を多様な用途に適用するために、塩素化の有無に関係なく、各種基材への良好な接着性を発揮する樹脂組成物の開発が求められている。
　しかし特許文献１では、塩素化された樹脂が使用されており、近年の環境問題の観点から脱ハロゲン化が望まれる分野に使用されるのに好ましいとされる非塩素化樹脂に関するものではない。
　また特許文献２では、ポリオレフィン系基材であるポリプロピレン基材及び各種極性基材への接着性が向上しているが、ポリカーボネート系樹脂やポリスチレン（ＰＳ）系樹脂等からなる基材には未だ十分な接着性が得られていなかった。
　そこで本発明の目的は、包装材等の様々な産業用途で多用されるポリオレフィン系基材への接着性に優れ、且つポリカーボネート系基材及びポリスチレン系基材との接着性に優れた変性ポリオレフィン系樹脂を提供することにある。 In recent years, in order to apply a pretreatment agent to various uses, development of a resin composition that exhibits good adhesiveness to various substrates is required regardless of the presence or absence of chlorination.
However, 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.
In 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.
Therefore, 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.
　本発明者らは、鋭意検討した結果、ポリオレフィン系樹脂を、ベンゼン環を有する化合物を含む、特定の変性成分によりポリオレフィン樹脂を変性してなる変性ポリオレフィン系樹脂により、上記課題を解決できることを見出し、本発明を完成した。 As a result of intensive studies, the present inventors have found that the above problems can be solved by a modified polyolefin resin obtained by modifying a polyolefin resin with a specific modifying component, including a compound having a benzene ring, The present invention has been completed.
　すなわち、本発明は以下を提供する。
［１］　成分（Ａ）：ポリオレフィン樹脂を変性成分により変性してなり、
　変性成分が、成分（Ｂ）：α，β－不飽和カルボン酸及びその酸無水物から選ばれる１種以上、並びに
　成分（Ｃ）：ベンゼン環を有する化合物
を含む、変性ポリオレフィン系樹脂。
［２］　変性成分が、さらに
　成分（Ｄ）：（メタ）アクリル酸エステル
を含む、［１］に記載の変性ポリオレフィン系樹脂。
［３］　成分（Ｄ）が、式（Ｉ）で表される（メタ）アクリル酸エステルを含む、［２］に記載の変性ポリオレフィン系樹脂。
ＣＨ２＝ＣＲ１ＣＯＯＲ２・・・（Ｉ）
（式（Ｉ）中、Ｒ１は水素原子又はメチル基を表し、Ｒ２は、－ＣｎＨ２ｎ＋１で表される基を表し、ｎは８～１８の整数である。）
［４］　成分（Ｃ）が、ベンジル基を有する化合物である、［１］～［３］のいずれか１つに記載の変性ポリオレフィン系樹脂。
［５］　成分（Ａ）が、プロピレン－エチレン系共重合体又はプロピレン－ブテン系共重合体である、［１］～［４］のいずれか１つに記載の変性ポリオレフィン系樹脂。
［６］　重量平均分子量が、５，０００以上２００，０００未満である、［１］～［５］のいずれか１つに記載の変性ポリオレフィン系樹脂。
［７］　成分（Ｃ）の含有量が、成分（Ａ）１００重量部に対して、０．１～２０重量部である、［１］～［６］のいずれか１つに記載の変性ポリオレフィン系樹脂。
［８］　［１］～［７］のいずれか１つに記載の変性ポリオレフィン系樹脂を含むヒートシール剤。
［９］　［１］～［７］のいずれか１つに記載の変性ポリオレフィン系樹脂を含む接着剤。
［１０］　［１］～［７］のいずれか１つに記載の変性ポリオレフィン系樹脂を含むプライマー。
［１１］　［１］～［７］のいずれか１つに記載の変性ポリオレフィン系樹脂を含む塗料用バインダー。
［１２］　［１］～［７］のいずれか１つに記載の変性ポリオレフィン系樹脂を含むインキ用バインダー。
［１３］　成分（Ａ）：ポリオレフィン樹脂を変性成分により変性して変性ポリオレフィン系樹脂を得ることを含み、
　変性成分が、
　成分（Ｂ）：α，β－不飽和カルボン酸及びその酸無水物から選ばれる１種以上、並びに
　成分（Ｃ）：ベンゼン環を有する化合物を含む、変性ポリオレフィン系樹脂の製造方法。
［１４］　変性が、成分（Ｂ）による変性、成分（Ｃ）による変性の順で行われる、［１３］に記載の変性ポリオレフィン系樹脂の製造方法。
［１５］　変性成分が、成分（Ｄ）：（メタ）アクリル酸エステルをさらに含む、［１３］又は［１４］に記載の変性ポリオレフィン系樹脂の製造方法。
［１６］　成分（Ｂ）による変性及び成分（Ｄ）による変性が同時に行われる、［１５］に記載の変性ポリオレフィン系樹脂の製造方法。 That is, the present invention provides the following.
[1] Component (A): A polyolefin resin is modified with a modifying component,
A modified polyolefin resin, wherein the modifying component comprises at least one selected from component (B): α, β-unsaturated carboxylic acid and acid anhydride thereof, and component (C): a compound having a benzene ring.
[2] The modified polyolefin resin according to [1], wherein the modified component further includes a component (D): (meth) acrylic acid ester.
[3] The modified polyolefin resin according to [2], wherein the component (D) includes 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)
[4] The modified polyolefin resin according to any one of [1] to [3], wherein the component (C) is a compound having a benzyl group.
[5] The modified polyolefin resin according to any one of [1] to [4], wherein the component (A) is a propylene-ethylene copolymer or a propylene-butene copolymer.
[6] The modified polyolefin resin according to any one of [1] to [5], which has a weight average molecular weight of 5,000 or more and less than 200,000.
[7] The modified polyolefin according to any one of [1] to [6], wherein the content of component (C) is 0.1 to 20 parts by weight with respect to 100 parts by weight of component (A) Resin.
[8] A heat sealant comprising the modified polyolefin resin according to any one of [1] to [7].
[9] An adhesive comprising the modified polyolefin resin according to any one of [1] to [7].
[10] A primer comprising the modified polyolefin resin according to any one of [1] to [7].
[11] A paint binder comprising the modified polyolefin resin according to any one of [1] to [7].
[12] An ink binder comprising the modified polyolefin resin according to any one of [1] to [7].
[13] Component (A): comprising 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 α, β-unsaturated carboxylic acids and acid anhydrides thereof, and 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.
　また本発明は、以下の態様も提供する。
［１７］　成分（Ｄ）が、式（Ｉ）で表される（メタ）アクリル酸エステルを含む、［１５］又は［１６］に記載の変性ポリオレフィン系樹脂の製造方法。
ＣＨ２＝ＣＲ１ＣＯＯＲ２・・・（Ｉ）
（式（Ｉ）中、Ｒ１は水素原子又はメチル基を表し、Ｒ２は、－ＣｎＨ２ｎ＋１で表される基を表し、ｎは８～１８の整数である。）
［１８］　成分（Ｃ）が、ベンジル基を有する化合物である、［１３］～［１７］のいずれか１つに記載の変性ポリオレフィン系樹脂の製造方法。
［１９］　成分（Ａ）が、プロピレン－エチレン系共重合体又はプロピレン－ブテン系共重合体である、［１３］～［１８］のいずれか１つに記載の変性ポリオレフィン系樹脂の製造方法。
［２０］　成分（Ｃ）の含有量が、成分（Ａ）１００重量部に対して、０．１～２０重量部である、［１３］～［１９］のいずれか１つに記載の変性ポリオレフィン系樹脂の製造方法。 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.
[19] The method for producing a modified polyolefin resin according to any one of [13] to [18], wherein the component (A) is a propylene-ethylene copolymer or a propylene-butene copolymer.
[20] The modified polyolefin according to any one of [13] to [19], wherein the content of component (C) is 0.1 to 20 parts by weight with respect to 100 parts by weight of component (A) Method for production of resin.
　本発明によれば、ポリオレフィン系基材への接着性に優れ、且つポリカーボネート系基材及びポリスチレン系基材との接着性に優れた変性ポリオレフィン系樹脂を提供することができる。 According to the present invention, it is possible to provide a modified polyolefin resin having excellent adhesion to a polyolefin substrate and excellent adhesion to a polycarbonate substrate and a polystyrene substrate.
１．本発明の変性ポリオレフィン系樹脂
　本発明の変性ポリオレフィン系樹脂は、成分（Ａ）：ポリオレフィン樹脂を変性成分により変性してなり、
　変性成分が、
　成分（Ｂ）：α，β－不飽和カルボン酸及びその酸無水物から選ばれる１種以上、並びに
　成分（Ｃ）：ベンゼン環を有する化合物
を含む。 1. Modified polyolefin resin of the present invention The 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 α, β-unsaturated carboxylic acids and acid anhydrides thereof, and Component (C): a compound having a benzene ring.
＜変性＞
　本明細書において、変性には、変性成分がポリオレフィン樹脂にグラフト重合しているグラフト変性、変性成分が、ポリオレフィン樹脂又はポリオレフィン樹脂を変性している変性成分に付加している、付加変性が含まれる。
　変性ポリオレフィン系樹脂は、変性成分により変性されているポリオレフィン樹脂である。 <Modification>
In the present specification, 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.
＜成分（Ａ）＞
　成分（Ａ）としてのポリオレフィン樹脂は、特に限定されず、１種のオレフィンの単独重合体であっても、２種以上のオレフィンの共重合体であってよい。ポリオレフィン樹脂を構成するモノマー単位のオレフィンとしては、例えば、α－オレフィンが挙げられ、炭素数２～６のα－オレフィン（例、１－ブテン、１－ペンテン、１－ヘキセン、１－ヘプテン、１－オクテン）が好ましい。
　ポリオレフィン樹脂として、例えば、エチレン又はプロピレンの単独重合体、エチレンとプロピレンとの共重合体、エチレンとその他の１種以上のオレフィンとの共重合体、プロピレンとその他の１種以上のオレフィンとの共重合体が挙げられ、好ましくは、エチレンとプロピレンとの共重合体、エチレンと炭素数２～６のα－オレフィンとの共重合体、及びプロピレンと炭素数２～６のα－オレフィンとの共重合体から選ばれる１種以上であり、エチレン－プロピレン共重合体、プロピレン－１－ブテン共重合体、及びエチレン－プロピレン－１－ブテン共重合体から選ばれる１種以上がより好ましい。ポリオレフィン樹脂が共重合体である場合、ランダム共重合体であっても、ブロック共重合体であってもよい。
　また、成分（Ａ）は、２種以上のポリオレフィン樹脂の組み合わせであってもよい。 <Component (A)>
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. Examples of the olefin of the monomer unit constituting the polyolefin resin include α-olefins, and α-olefins having 2 to 6 carbon atoms (eg, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1 -Octene) is preferred.
Examples of the polyolefin resin 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 α-olefin having 2 to 6 carbon atoms, and a copolymer of propylene and an α-olefin having 2 to 6 carbon atoms. 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. 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.
＜変性成分＞
（成分（Ｂ））
　成分（Ｂ）はα，β－不飽和カルボン酸及びその酸無水物から選ばれる１種以上である。
　α，β－不飽和カルボン酸としては、例えば、マレイン酸、フマル酸、シトラコン酸、メサコン酸、イタコン酸、アコニット酸、及び（メタ）アクリル酸が挙げられる。
　α，β－不飽和カルボン酸の酸無水物としては、例えば、無水マレイン酸、無水シトラコン酸、無水イタコン酸、無水アコニット酸、無水ハイミック酸、及び無水（メタ）アクリル酸が挙げられる。 <Modified component>
(Ingredient (B))
Component (B) is at least one selected from α, β-unsaturated carboxylic acids and acid anhydrides thereof.
Examples of the α, β-unsaturated carboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, aconitic acid, and (meth) acrylic acid.
Examples of the acid anhydride of α, β-unsaturated carboxylic acid include maleic anhydride, citraconic anhydride, itaconic anhydride, aconitic anhydride, hymic anhydride, and (meth) acrylic anhydride.
　成分（Ｂ）は、好ましくはα，β－不飽和カルボン酸の酸無水物を含み、より好ましくは無水マレイン酸を含む。成分（Ｂ）は、α，β－不飽和カルボン酸及びその酸無水物から選ばれる１種以上であり、α，β－不飽和カルボン酸１種以上とその酸無水物１種以上との組み合わせ、α，β－不飽和カルボン酸２種以上の組み合わせ、α，β－不飽和カルボン酸の酸無水物２種以上の組み合わせであってもよい。
　本明細書において、「（メタ）アクリル酸」とは、メタクリル酸又はアクリル酸を意味する。 Component (B) preferably comprises an acid anhydride of an α, β-unsaturated carboxylic acid, more preferably maleic anhydride. Component (B) is one or more selected from α, β-unsaturated carboxylic acids and acid anhydrides thereof, and a combination of one or more α, β-unsaturated carboxylic acids and one or more acid anhydrides thereof. , A combination of two or more α, β-unsaturated carboxylic acids, or a combination of two or more acid anhydrides of α, β-unsaturated carboxylic acid.
In this specification, “(meth) acrylic acid” means methacrylic acid or acrylic acid.
　変性に際して、成分（Ｂ）の配合量は成分（Ａ）に対して、好ましくは０．１重量％以上であり、より好ましくは０．５重量％以上である。これにより、得られる変性ポリオレフィン系樹脂が、金属などの極性の被着体に対する良好な接着性を有するとともに、後述の成分（Ｃ）との反応性が高まる。上限は、好ましくは１０重量％以下であり、より好ましくは５重量％以下であり、さらに好ましくは４重量％以下である。これにより、成分（Ｂ）が無駄なく成分（Ａ）と反応し、また被着体に対する良好な接着性を保持することができる。 In the modification, 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). Thereby, while 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. Preferably it is 10 weight% or less, More preferably, it is 5 weight% or less, More preferably, it is 4 weight% or less. Thereby, 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 | maintained.
　変性ポリオレフィン系樹脂中の成分（Ｂ）による変性重量（グラフト重量）は、変性ポリオレフィン系樹脂を１００重量％とした場合に、好ましくは０．１重量％以上であり、より好ましくは０．５重量％以上である。上限は、好ましくは１０重量％以下であり、より好ましくは５重量％以下であり、さらに好ましくは４重量％以下である。変性ポリオレフィン系樹脂中の成分（Ｂ）による変性重量（グラフト重量）は、変性ポリオレフィン系樹脂を１００重量％とした場合に、好ましくは０．１～１０重量％であり、より好ましくは０．５～４重量％である。変性重量（グラフト重量）が０．１重量％以上であることにより、得られる変性ポリオレフィン系樹脂が、金属などの極性の被着体に対する良好な接着性を有し、後述の成分（Ｃ）との反応性を確保することができる。変性重量（グラフト重量）が１０重量％以下であることにより、樹脂被着体に対する良好な接着性を保持することができる。 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. 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.
　変性ポリオレフィン系樹脂における成分（Ｂ）による変性重量％は、公知の方法で測定することができる。例えば、アルカリ滴定法或いはフーリエ変換赤外分光法によって求めることができる。 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.
（成分（Ｃ））
　成分（Ｃ）は、ベンゼン環を有する化合物である。成分（Ｃ）は、好ましくは、成分（Ａ）と反応して、ポリオレフィン樹脂にベンゼン環を導入できる化合物である。ベンゼン環を有する化合物としては、例えば、アニリン、フェノール、ベンゼンチオール、ベンジル基を有する化合物（例、ベンジルアミン、ベンジルアルコール、及びベンジルメルカプタン）が挙げられる。中でも、取り扱いが容易であり、反応性が高いため、ベンジル基を有する化合物が好ましく、ベンジルアミン及びベンジルアルコールから選ばれる１種以上がより好ましい。
　成分（Ｃ）は、ベンゼン環を有する化合物１種であっても、２種以上の組み合わせであってもよい。 (Ingredient (C))
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. Examples of the compound having a benzene ring include aniline, phenol, benzenethiol, and a compound having a benzyl group (eg, benzylamine, benzyl alcohol, and benzyl mercaptan). Especially, since it is easy to handle and has high reactivity, 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.
　本発明の変性ポリオレフィン系樹脂は、ポリオレフィン系基材のみならず、ポリカーボネート系基材及びポリスチレン系基材に対し高い接着性を有する。
　その理由については、次の通りに推察される。すなわちベンゼン環はπ結合を有するために、ポリオレフィン樹脂を成分（Ｃ）：ベンゼン環を有する化合物を含む変性成分により変性した場合、変性ポリオレフィン系樹脂は、その構造中にベンゼン環を含み、分子内に共役系が形成される。他方、ポリカーボネート系基材及びポリスチレン系基材は、構造中にベンゼン環を有する。変性ポリオレフィン系樹脂に形成された共役系と、基材の構造中に含まれるベンゼン環との相互作用により、本発明の変性ポリオレフィン系樹脂は、ポリカーボネート系基材及びポリスチレン系基材に対する接着性が高まると推察される。 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 π 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. On the other hand, the polycarbonate base material and the polystyrene base material have a benzene ring in the structure. 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.
　変性に際して、成分（Ｃ）の配合量（含有量）は成分（Ａ）に対して、好ましくは０．１重量％以上であり、より好ましくは０．５重量％以上である。これにより、十分な接着効果を発揮することができる。上限は、好ましくは２０重量％以下であり、より好ましくは１０重量％以下である。これにより、成分（Ｃ）が無駄なく成分（Ａ）と反応し、また被着体に対する良好な接着性を保持することができる。 In the modification, 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.
　変性ポリオレフィン系樹脂中の成分（Ｃ）の変性（付加）重量は、変性ポリオレフィン系樹脂を１００重量％とした場合に、好ましくは０．１重量％以上であり、より好ましくは０．５重量％以上である。上限は、好ましくは２０重量％以下であり、より好ましくは１０重量％以下である。変性ポリオレフィン系樹脂中の成分（Ｃ）の変性（付加）重量は、変性ポリオレフィン系樹脂を１００重量％とした場合に、好ましくは０．１～２０重量％であり、より好ましくは、０．５～１０重量％である。変性重量が０．１重量％以上であると、変性ポリオレフィン系樹脂が、被着体に対する良好な接着性を有する。２０重量％以下であると被着体に対する接着性を良好に保持することができる。 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. When the modified weight is 0.1% by weight or more, the modified polyolefin resin has good adhesion to the adherend. The adhesiveness with respect to a to-be-adhered body can be hold | maintained favorably as it is 20 weight% or less.
　変性ポリオレフィン系樹脂における成分（Ｃ）による変性重量％は、公知の方法で測定することができる。例えば、フーリエ変換赤外分光法によって求めることができる。 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.
（その他の変性成分）
　成分（Ａ）を変性する変性成分は、成分（Ｂ）及び成分（Ｃ）以外に、用途や目的に応じて、本発明の効果を損なわない範囲で、他の成分を含んでいてもよい。 (Other modified components)
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.
（成分（Ｄ））
　成分（Ａ）を変性する変性成分は、好ましくは成分（Ｄ）：（メタ）アクリル酸エステルを含む。
　（メタ）アクリル酸エステルとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ヒドロキシエチル（メタ）アクリレート、イソボルニル（メタ）アクリレート、グリシジル（メタ）アクリレート、オクチル（メタ）アクリレート、ラウリル（メタ）アクリレート、トリデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェニル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、アセトアセトキシエチル（メタ）アクリレート等が挙げられる。
　なお、本明細書において、「（メタ）アクリレート」とは、メタクリレート又はアクリレートを意味する。
　成分（Ｄ）は、１種単独でも２種以上の組み合わせであってもよい。 (Component (D))
The modifying component that modifies component (A) preferably comprises component (D): (meth) acrylic acid ester.
Examples of (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) acrylate, N, N-dimethylaminoethyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate Rate, and the like.
In the present specification, “(meth) acrylate” means methacrylate or acrylate.
Component (D) may be a single type or a combination of two or more types.
　成分（Ｄ）は、式（Ｉ）で表される（メタ）アクリル酸エステルを含むことが好ましく、式（Ｉ）で表される（メタ）アクリル酸エステルであることがより好ましい。
　ＣＨ２＝ＣＲ１ＣＯＯＲ２　・・・（Ｉ）
（式（Ｉ）中、Ｒ１は水素原子又はメチル基を表し、Ｒ２は、－ＣｎＨ２ｎ＋１で表される基を表し、ｎは８～１８の整数である。） 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)
　成分（Ｄ）が式（Ｉ）で表される（メタ）アクリル酸エステルを含むことにより、変性ポリオレフィン系樹脂の分子量が、成分（Ａ）：ポリオレフィン樹脂の分子量から低下することを抑制するとともに、変性ポリオレフィン系樹脂の溶剤溶解性、変性ポリオレフィン系樹脂溶液の低温安定性、変性ポリオレフィン系樹脂と、変性ポリオレフィン系樹脂と共に接着剤等に配合される他樹脂との相溶性、変性ポリオレフィン系樹脂の接着性を向上させることができる。成分（Ｄ）が式（Ｉ）で表される（メタ）アクリル酸エステルを含む場合、式（Ｉ）で表される（メタ）アクリル酸エステルは１種単独でも２種以上の組み合わせであってもよく、式（Ｉ）で表される（メタ）アクリル酸エステル２種以上を任意の割合で混合して使用してよい。 By containing the (meth) acrylic acid ester represented by the formula (I) as the component (D), 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. When 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. Alternatively, two or more (meth) acrylic acid esters represented by the formula (I) may be mixed and used in an arbitrary ratio.
　Ｒ１は、好ましくはメチル基を表す。ｎは、好ましくは８～１５の整数であり、より好ましくは８～１４の整数であり、さらに好ましくは８～１３の整数である。
　式（Ｉ）で表される（メタ）アクリル酸エステルは、好ましくはステアリル（メタ）アクリレート、ラウリル（メタ）アクリレート、及びオクチル（メタ）アクリレートから選ばれる１種以上であり、より好ましくはステアリルメタクリレート、ラウリルメタクリレート、及びオクチルメタクリレートから選ばれる１種以上であり、さらに好ましくは、ラウリルメタクリレート及びオクチルメタクリレートから選ばれる１種以上である。 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.
　変性に際して、成分（Ｄ）の配合量は成分（Ａ）に対して、好ましくは０．１重量％以上であり、より好ましくは０．５重量％以上である。これにより、変性ポリオレフィン系樹脂の分子量分布を十分狭い範囲に保つことができる。すなわち、高分子量部分を減少させることにより、溶剤溶解性、溶液の低温安定性及び他樹脂との相溶性を良好に保持することができる。また、低分子量部分を減少させることにより、接着力を向上させることができる。
　上限は、好ましくは１０重量％以下であり、より好ましくは４重量％以下である。これにより、成分（Ｄ）が未反応物として残存することを抑制し、被着体に対する接着性を良好に保持することができる。 At the time of modification, 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). Thereby, 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. Moreover, 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.
　変性ポリオレフィン系樹脂中の成分（Ｄ）による変性（グラフト）重量は、変性ポリオレフィン系樹脂を１００重量％とした場合に、好ましくは０．１重量％以上であり、より好ましくは０．５重量％以上である。上限は、好ましくは１０重量％以下であり、より好ましくは４重量％以下である。したがって、変性ポリオレフィン系樹脂中の成分（Ｄ）の変性（グラフト）重量は、変性ポリオレフィン系樹脂を１００重量％とした場合に、好ましくは０．１～１０重量％であり、より好ましくは、０．５～４重量％である。変性重量（グラフト重量）が０．１重量％以上であることにより、変性ポリオレフィン系樹脂の分子量分布を十分狭い範囲に保つことができる。すなわち、高分子量部分を減少させることにより、溶剤溶解性、溶液の低温安定性及び他樹脂との相溶性を良好に保持することができる。また、低分子量部分を減少させることにより、接着力を向上させることができる。変性重量（グラフト重量）が１０重量％以下であることにより、樹脂被着体に対する接着性を良好に保持することができる。 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. Accordingly, 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. When 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. 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. Moreover, adhesive force can be improved by reducing a low molecular weight part. When the modified weight (graft weight) is 10% by weight or less, it is possible to maintain good adhesion to the resin adherend.
　成分（Ｄ）の変性（グラフト）重量％は、公知の方法で測定することができる。例えば、フーリエ変換赤外分光法或いは１Ｈ－ＮＭＲによって求めることができる。 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.
（他の任意の変性成分）
　変性成分は、成分（Ｂ）、成分（Ｃ）、及び成分（Ｄ）以外の変性成分を、１種単独で、又は２種以上の組み合わせで含んでいてもよい。
　成分（Ｂ）、成分（Ｃ）、及び成分（Ｄ）以外の変性成分としては、例えば、成分（Ｂ）及び成分（Ｄ）以外の、α，β－不飽和カルボン酸の誘導体が挙げられる。該α，β－不飽和カルボン酸の誘導体としては、例えば、α，β－不飽和カルボキサミドが挙げられる。α，β－不飽和カルボキサミドとしては、例えば、（メタ）アクリル酸のアミド（例、Ｎ－メチル（メタ）アクリルアミド、ヒドロキシエチル（メタ）アクリルアミド、（メタ）アクリロイルモルホリン）が挙げられる。
　本明細書において、（メタ）アクリルアミドとは、メタクリルアミド又はアクリルアミドを意味し、（メタ）アクリロイルとはメタクリロイル又はアクリロイルを意味する。 (Other optional modifying components)
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.
Examples of the modifying component other than the component (B), the component (C), and the component (D) include α, β-unsaturated carboxylic acid derivatives other than the component (B) and the component (D). Examples of the derivatives of the α, β-unsaturated carboxylic acid include α, β-unsaturated carboxamides. Examples of α, β-unsaturated carboxamides include amides of (meth) acrylic acid (eg, N-methyl (meth) acrylamide, hydroxyethyl (meth) acrylamide, (meth) acryloylmorpholine).
In the present specification, (meth) acrylamide means methacrylamide or acrylamide, and (meth) acryloyl means methacryloyl or acryloyl.
　変性成分は、成分（Ｅ）：塩素を含んでいてもよいが、変性成分は、好ましくは成分（Ｅ）を含まない。これにより、本発明の変性ポリオレフィン系樹脂を、塩素に由来する成分の残存が好ましくない物質の接着にも好適に使用できる。
　変性成分が、成分（Ｂ）、成分（Ｃ）、及び成分（Ｄ）以外の変性成分を含む場合、成分（Ｂ）、成分（Ｃ）、及び成分（Ｄ）以外の変性成分による各変性重量の合計が、成分（Ｂ）による変性重量、成分（Ｃ）による変性重量、及び成分（Ｄ）による変性重量の合計を超えないことが好ましい。 The modifying component may contain component (E): chlorine, but the modifying component preferably does not contain component (E). As a result, 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.
When the modifying component contains a modifying component other than the component (B), the component (C), and the component (D), 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).
　本発明の変性ポリオレフィン系樹脂は、成分（Ａ）を変性成分により変性してなるものであり、本発明の目的及び効果を阻害しない限りにおいて、変性成分のみを構成単位とするポリマー、変性成分のモノマー、変性されていないポリオレフィン樹脂などの、変性ポリオレフィン系樹脂以外の物質を含む形態であってもよい。 The modified polyolefin-based resin of the present invention is obtained by modifying the component (A) with a modifying component. As long as the object and effect of the present invention are not impaired, a polymer containing only the modifying component as a structural unit, The form containing substances other than modified polyolefin resin, such as a monomer and unmodified polyolefin resin, may be sufficient.
＜変性ポリオレフィン系樹脂の製造方法＞
　本発明の変性ポリオレフィン系樹脂は、公知の方法により製造することができる。
　本発明の変性ポリオレフィン系樹脂製造の際には成分（Ｆ）：ラジカル発生剤を用いてもよい。 <Method for producing modified polyolefin resin>
The modified polyolefin resin of the present invention can be produced by a known method.
In the production of the modified polyolefin resin of the present invention, component (F): a radical generator may be used.
　成分（Ｆ）としてのラジカル発生剤は、特に限定されず、公知のラジカル発生剤の中より適宜選択してよい。成分（Ｆ）として、有機過酸化物系化合物が好ましい。有機過酸化物系化合物としては、例えば、ジ－ｔ－ブチルパーオキサイド、ジクミルパーオキサイド、ｔ－ブチルクミルパーオキサイド、ベンゾイルパーオキサイド、ジラウリルパーオキサイド、クメンハイドロパーオキサイド、ｔ－ブチルハイドロパーオキサイド、１，４－ビス［（ｔ－ブチルパーオキシ）イソプロピル］ベンゼン、１，１－ビス（ｔ－ブチルパーオキシ）－３，５，５－トリメチルシクロヘキサン、１，１－ビス（ｔ－ブチルパーオキシ）－シクロヘキサン、シクロヘキサノンパーオキサイド、ｔ－ブチルパーオキシベンゾエート、ｔ－ブチルパーオキシイソブチレート、ｔ－ブチルパーオキシ－３，５，５－トリメチルヘキサノエート、ｔ－ブチルパーオキシ－２－エチルヘキサノエート、ｔ－ブチルパーオキシイソプロピルカーボネート、クミルパーオキシオクトエート等が挙げられ、ジ－ｔ－ブチルパーオキサイド、ジクミルパーオキサイド、及びジラウリルパーオキサイドから選ばれる１種以上が好ましい。成分（Ｆ）は、１種単独でもよいし、２種以上の組み合わせであってもよい。 The radical generator as the component (F) is not particularly limited, and may be appropriately selected from known radical generators. As the component (F), an organic peroxide compound is preferable. Examples of organic peroxide compounds include di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, benzoyl peroxide, dilauryl peroxide, cumene hydroperoxide, and t-butyl hydroperoxide. Oxide, 1,4-bis [(t-butylperoxy) isopropyl] benzene, 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, 1,1-bis (t-butyl) Peroxy) -cyclohexane, cyclohexanone peroxide, t-butylperoxybenzoate, t-butylperoxyisobutyrate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-2 -Ethyl hexanoate, t-butyl peroxyiso 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.
　本発明の変性ポリオレフィン系樹脂製造の際の成分（Ｆ）の配合量は、成分（Ｂ）、成分（Ｃ）、及び任意で成分（Ｄ）の配合量の合計（重量）に対し、好ましくは１～１００重量％であり、より好ましくは、１０～５０重量％である。１重量％以上であることにより、十分なグラフト効率を保持することができる。１００重量％以下であることにより、変性ポリオレフィン系樹脂の重量平均分子量の低下を抑制することができる。 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.
　変性ポリオレフィン系樹脂を得る方法として、例えば、成分（Ａ）と変性成分（例、成分（Ｂ）、成分（Ｃ）、及び成分（Ｄ））との混合物を、溶媒（例、トルエン等の有機溶媒）に加熱溶解し、成分（Ｆ）を添加する溶液法、及び、バンバリーミキサー、ニーダー、押出機等の混練機を使用して、成分（Ａ）、変性成分（例、成分（Ｂ）、成分（Ｃ）、及び成分（Ｄ））、及び成分（Ｆ）を、加熱下で溶融混練して反応させる溶融混練法が挙げられる。 As a method for obtaining 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). 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.
　成分（Ａ）を変性成分により変性する際、変性成分に含まれる各成分による変性の順序は特に限定されず、各変性成分による変性をすべて同時に行ってもよく、一部の変性成分による変性を、残りの変性成分による変性の前、又は後に行ってもよく、各変性成分による変性を、順次行ってもよい。
　変性成分による成分（Ａ）の変性は、好ましくは、成分（Ｂ）による変性、成分（Ｃ）による変性の順で行われる。
　変性成分が、成分（Ｄ）を含む場合、好ましくは成分（Ｂ）による変性及び成分（Ｄ）による変性が同時に行われる。 When modifying component (A) with a modifying component, 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).
When the modifying component contains the component (D), the modification with the component (B) and the modification with the component (D) are preferably performed simultaneously.
　変性成分が成分（Ｄ）を含む場合、成分（Ａ）を、成分（Ｂ）及び成分（Ｄ）により成分（Ｆ）を用いてグラフト変性した後、成分（Ｃ）により変性する方法が好ましい。本方法では、成分（Ａ）の変性箇所に成分（Ｃ）が付加反応により導入されると推測される。 When the 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. In this method, it is presumed that component (C) is introduced into the modified site of component (A) by an addition reaction.
　変性ポリオレフィン系樹脂中の成分（Ｂ）による変性重量、成分（Ｄ）による変性重量、及び成分（Ｃ）による変性重量のうちのいずれかが０．１～１０重量％であることが好ましく、成分（Ｂ）による変性重量、成分（Ｄ）による変性重量、及び成分（Ｃ）による変性重量の全てが０．１～１０重量％であることがより好ましい。 It is preferable that 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.
　本発明の変性ポリオレフィン系樹脂の重量平均分子量は、好ましくは５，０００～３００，０００であり、より好ましくは８，０００～２００，０００又はより好ましくは５，０００以上２００，０００未満であり、さらに好ましくは１０，０００～１５０，０００である。重量平均分子量が５，０００以上であることにより、充分な接着強度を得ることができる。
　３００，０００以下であることにより、溶剤への溶解が良好で、比較的良好な流動性を得ることができる。なお、実施例を含む本発明における重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）（標準物質：ポリスチレン）によって測定し、算出された値である。
　例えば、ＧＰＣは、下記の条件で行うことができる。
　測定機器：ＨＬＣ－８３２０ＧＰＣ（東ソー株式会社製）
　溶離液：テトラヒドロフラン
　カラム：ＴＳＫｇｅｌ（東ソー株式会社製） 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. When the weight average molecular weight is 5,000 or more, sufficient adhesive strength can be obtained.
By being 300,000 or less, dissolution in a solvent is good and relatively good fluidity can be obtained. In addition, 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).
For example, GPC can be performed under the following conditions.
Measuring instrument: HLC-8320GPC (manufactured by Tosoh Corporation)
Eluent: Tetrahydrofuran Column: TSKgel (manufactured by Tosoh Corporation)
　本発明の変性ポリオレフィン系樹脂の示差走査型熱量計（以下、ＤＳＣ）による融点（以下、Ｔｍともいう。）は、使用条件にもよるが、５０℃～１２０℃が好ましい。融点が５０℃以上であることにより、充分な接着強度を得ることができる。一方、融点が１２０℃以下であることにより、基材の形状の変形を発生させない比較的低温での接着性が良好であり、溶液安定性が良好であり、低温での十分な保管安定性を得ることができる。 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. When the melting point is 50 ° C. or higher, sufficient adhesive strength can be obtained. On the other hand, when 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.
　本発明におけるＤＳＣによるＴｍの測定は、例えば以下の条件で行うことができる。ＪＩＳ　Ｋ７１２１－１９８７に準拠し、ＤＳＣ測定装置（セイコー電子工業製）を用い、約５ｍｇの試料を１５０℃で１０分間加熱して融解状態を保持後、１０℃／分の速度で降温して－５０℃で安定保持した後、更に１０℃／分で１５０℃まで昇温して融解した時の融解ピーク温度を測定し、該温度をＴｍとして評価する。尚、後述の実施例におけるＴｍは前述の条件で測定されたものである。 The measurement of Tm by DSC in the present invention can be performed, for example, under the following conditions. In accordance with JIS K7121-1987, using 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. After stably holding at 50 ° C., 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. In the examples described later, Tm is measured under the conditions described above.
　本発明の変性ポリオレフィン系樹脂は、必要に応じて他の成分と組み合わせて、変性ポリオレフィン系樹脂組成物とすることができる。変性ポリオレフィン系樹脂又は変性ポリオレフィン系樹脂組成物は、ヒートシール剤、接着剤、プライマー、バインダー（例、塗料用バインダー、インキ用バインダー）として使用し得る。
　他の成分としては、例えば、硬化剤、溶媒又は分散媒、酸化防止剤、光安定剤、紫外線吸収剤、顔料、染料、及び無機充填剤が挙げられる。 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).
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.
　硬化剤としては、例えば、ポリイソシアネート化合物、エポキシ化合物、ポリアミン化合物、ポリオール化合物、及びそれらの化合物が有する官能基が保護基で保護された硬化剤が挙げられる。
　硬化剤は樹脂組成物に１種単独で配合されていてもよいし、又は２種以上の組み合わせとして配合されていてもよい。
　樹脂組成物における硬化剤の配合量には、特に限定はないが、例えば、本発明の変性ポリオレフィン系樹脂中のα，β－不飽和カルボン酸又はその酸無水物による変性量により適宜選択してよい。又、硬化剤を配合する場合は、目的に応じて有機スズ化合物、第三級アミン化合物、等の触媒を併用してよい。 Examples of the curing agent 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.
A hardening | curing agent may be mix | blended with the resin composition individually by 1 type, or may be mix | blended as 2 or more types of combinations.
The blending amount of the curing agent in the resin composition is not particularly limited. Good. Moreover, when mix | blending a hardening | curing agent, you may use together catalysts, such as an organotin compound and a tertiary amine compound, according to the objective.
　溶媒又は分散媒としては、特に限定はなく、例えば、芳香族炭化水素（例、トルエン、キシレン）、エステル（例、酢酸エチル、酢酸ブチル、酢酸プロピル）、脂肪族又は脂環式炭化水素（例、シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン、ノナン、デカン）、アルコール（例、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール）、グリコールエーテル（例、プロピレングリコールメチルエーテル、プロピレングリコールエチルエーテル、プロピレングリコール－ｔ－ブチルエーテル）、水が挙げられる。変性ポリオレフィン系樹脂組成物が含む溶媒又は分散媒は、１種単独でも、２種以上の組み合わせでもよい。
　変性ポリオレフィン系樹脂組成物は、水を含む溶媒又は分散媒を含む、水性樹脂組成物とされ得る。 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. 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.
　本発明の変性ポリオレフィン系樹脂を含む樹脂組成物は、所望の効果を阻害しない範囲で、接着剤に用いられる他の成分（例、ポリエステル系接着剤、ポリウレタン系接着剤、アクリル系接着剤等の公知の接着剤）、ヒートシール剤に用いられる他の成分、プライマーに用いられる他の成分、バインダーに用いられる他の成分が配合されていてもよい。 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. Known components), other components used in heat sealants, other components used in primers, and other components used in binders may be blended.
　本発明の変性ポリオレフィン系樹脂は、ポリオレフィン系基材のみならず、極性基の少ないポリカーボネート系基材及びポリスチレン系基材との接着性に優れるので、これらを貼り合わせる接着剤又はヒートシール剤として有用である。本発明の変性ポリオレフィン系樹脂は、例えば、電子部品用エンボスキャリアテープのカバーテープの接着などに用いることができる。 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.
２．本発明の変性ポリオレフィン系樹脂の製造方法
　本発明の変性ポリオレフィン系樹脂の製造方法は、
　成分（Ａ）：ポリオレフィン樹脂を変性成分により変性して変性ポリオレフィン系樹脂を得ることを含み、
　変性成分が、
　成分（Ｂ）：α，β－不飽和カルボン酸及びその酸無水物から選ばれる１種以上、並びに
　成分（Ｃ）：ベンゼン環を有する化合物を含む。 2. Production method of the modified polyolefin resin of the present invention 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 α, β-unsaturated carboxylic acids and acid anhydrides thereof, and Component (C): a compound having a benzene ring.
　成分（Ａ）、並びに変性成分である成分（Ｂ）及び成分（Ｃ）については、上記項目１．において既に説明したとおりである。 Regarding the component (A) and the modified components (B) and (C), the above item 1. As already explained.
　変性成分は、好ましくは成分（Ｄ）：（メタ）アクリル酸エステルをさらに含む。
　成分（Ｄ）については、上記項目１．において既に説明したとおりである。
　成分（Ａ）を変性成分により変性する方法は、特に限定されず、例えば、成分（Ａ）と変性成分との混合物を溶媒（例、トルエン等の有機溶媒）に加熱溶解し、上記成分（Ｆ）を添加する溶液法、並びに成分（Ａ）、変性成分、及び成分（Ｆ）を、加熱下で溶融混練して反応させる溶融混練法が挙げられる。
　成分（Ｆ）の例及び好ましい例は、上記項目１．において既に説明したとおりである。
　これらの方法を実施する装置は特に限定されず、公知の装置により実施してよい。例えば、溶融混練法では、バンバリーミキサー、ニーダー、押出機等の混練機を使用し得る。 The modifying component preferably further comprises component (D): (meth) acrylic acid ester.
Regarding the component (D), the above item 1. As already explained.
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. For example, in the melt-kneading method, a kneader such as a Banbury mixer, a kneader, or an extruder can be used.
　変性成分に含まれる各成分による成分（Ａ）の変性の順序は特に限定されず、各変性成分による変性をすべて同時に行ってもよく、一部の変性成分による変性を、残りの変性成分による変性の前、又は後に行ってもよく、各変性成分による変性を、順次行ってもよい。
　変性成分による成分（Ａ）の変性は、好ましくは、成分（Ｂ）による変性、成分（Ｃ）による変性の順で行われる。
　変性成分が、成分（Ｄ）を含む場合、好ましくは成分（Ｂ）による変性及び成分（Ｄ）による変性が同時に行われる。 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).
When the modifying component contains the component (D), the modification with the component (B) and the modification with the component (D) are preferably performed simultaneously.
　変性成分は、成分（Ｂ）、成分（Ｃ）、及び成分（Ｄ）以外の変性成分を、１種単独で、又は２種以上の組み合わせで含んでいてもよい。成分（Ｂ）、成分（Ｃ）、及び成分（Ｄ）以外の、他の任意の変性成分については、上記項目１．において既に説明したとおりである。 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.
　本発明の製造方法により得られる変性ポリオレフィン系樹脂の、好ましい変性重量、好ましい重量平均分子量、好ましい融点については、上記項目１．において既に説明したとおりである。 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.
　本発明の製造方法により得られる変性ポリオレフィン系樹脂は、上記項目１．においてすでに説明したとおり、必要に応じて他の成分と組み合わせて、変性ポリオレフィン系樹脂組成物とすることができ、変性ポリオレフィン系樹脂又は変性ポリオレフィン系樹脂組成物は、ヒートシール剤、接着剤、プライマー、バインダー（例、塗料用バインダー、インキ用バインダー）として使用し得る。 The modified polyolefin resin obtained by the production method of the present invention is the above item 1. As described above, 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).
　なお、本明細書において、「剤」は「組成物」を含む。 In this specification, “agent” includes “composition”.
　次に本発明を実施例及び比較例により更に詳細に説明するが、本発明はこれらに限定されるものではない。 Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these.
（実施例１）
　プロピレン－エチレン共重合体１００重量部、無水マレイン酸１重量部、ラウリルメタクリレート０．７５重量部、及びジ－ｔ－ブチルパーオキサイド３重量部を１８０℃に設定した二軸押出機を用いて混練反応した。押出機内にて減圧脱気を行い、残留する未反応物を除去して変性物を得た。得られた変性物７５重量部とキシレン４５重量部とを１３５℃で溶解し、撹拌下、ベンジルアミン１重量部を添加し、１３５℃で２時間保持した後、減圧留去によりキシレンを除去し、変性ポリオレフィン系樹脂を得た。得られた変性ポリオレフィン樹脂をメチルシクロヘキサン／酢酸プロピル＝７０／３０（Ｖ／Ｖ）の混合溶媒に固形分２０％となるように溶解したところ、変性ポリオレフィン系樹脂溶液の性状は、固化物が無く、流動性のある状態であり、良好であった。
　得られた変性ポリオレフィン系樹脂の重量平均分子量は７０，０００であった。 (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. When the obtained modified polyolefin resin was dissolved in 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 70,000.
（実施例２）
　プロピレン－エチレン共重合体１００重量部、無水マレイン酸１重量部、ラウリルメタクリレート０．７５重量部、及びジ－ｔ－ブチルパーオキサイド１．５重量部を１７０℃に設定した二軸押出機を用いて混練反応した。押出機内にて減圧脱気を行い、残留する未反応物を除去して変性物を得た。得られた変性物を７５重量部とキシレン４５重量部とを１３５℃で溶解し、撹拌下、ベンジルアミン５重量部を添加し、１３５℃で２時間保持した後、減圧留去によりキシレンを除去し、変性ポリオレフィン系樹脂を得た。得られた変性ポリオレフィン樹脂をメチルシクロヘキサン／酢酸プロピル＝７０／３０（Ｖ／Ｖ）の混合溶媒に固形分２０％となるように溶解したところ、変性ポリオレフィン系樹脂溶液の性状は、固化物が無く、流動性のある状態であり、良好であった。
　得られた変性ポリオレフィン系樹脂の重量平均分子量は６８，０００であった。 (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. Thus, a modified polyolefin resin was obtained. When the obtained modified polyolefin resin was dissolved in 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 68,000.
（実施例３）
　プロピレン－エチレン共重合体１００重量部、無水イタコン酸３重量部、及びジ－ｔ－ブチルパーオキサイド３重量部を１７０℃に設定した二軸押出機を用いて混練反応した。押出機内にて減圧脱気を行い、残留する未反応物を除去して変性物を得た。得られた変性物を７５重量部とキシレン４５重量部とを１３５℃で溶解し、撹拌下、ベンジルメルカプタン５重量部を添加し、１３５℃で２時間保持した後、減圧留去によりキシレンを除去し、変性ポリオレフィン系樹脂を得た。得られた変性ポリオレフィン樹脂をメチルシクロヘキサン／酢酸プロピル＝７０／３０（Ｖ／Ｖ）の混合溶媒に固形分２０％となるように溶解したところ、変性ポリオレフィン系樹脂溶液の性状は、固化物が無く、流動性のある状態であり、良好であった。
得られた変性ポリオレフィン系樹脂の重量平均分子量は７１，０００であった。 (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. When the obtained modified polyolefin resin was dissolved in 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 weight average molecular weight of the modified polyolefin resin obtained was 71,000.
（実施例４）
　プロピレン－エチレン共重合体１００重量部、無水マレイン酸３重量部、オクチルメタクリレート０．２５重量部、及びジ－ｔ－ブチルパーオキサイド４重量部を１６０℃に設定した二軸押出機を用いて混練反応した。押出機内にて減圧脱気を行い、残留する未反応物を除去して変性物を得た。得られた変性物を７５重量部とキシレン４５重量部とを１３５℃で溶解し、撹拌下、ベンジルアミン１重量部を添加し、１３５℃で２時間保持した後、減圧留去によりキシレンを除去し、変性ポリオレフィン系樹脂を得た。得られた変性ポリオレフィン樹脂をメチルシクロヘキサン／酢酸プロピル＝７０／３０（Ｖ／Ｖ）の混合溶媒に固形分２０％となるように溶解したところ、変性ポリオレフィン系樹脂溶液の性状は、固化物が無く、流動性のある状態であり、良好であった。
　得られた変性ポリオレフィン系樹脂の重量平均分子量は７２，０００であった。 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. Thus, a modified polyolefin resin was obtained. When the obtained modified polyolefin resin was dissolved in 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 72,000.
（実施例５）
　プロピレン－エチレン共重合体１００重量部、無水マレイン酸３重量部、オクチルメタクリレート０．２５重量部、及びジ－ｔ－ブチルパーオキサイド３重量部を１６０℃に設定した二軸押出機を用いて混練反応した。押出機内にて減圧脱気を行い、残留する未反応物を除去して変性物を得た。得られた変性物を７５重量部とキシレン４５重量部とを１３５℃で溶解し、撹拌下、ベンジルアミン５重量部を添加し、１３５℃で２時間保持した後、減圧留去によりキシレンを除去し、変性ポリオレフィン系樹脂を得た。得られた変性ポリオレフィン樹脂をメチルシクロヘキサン／酢酸プロピル＝７０／３０（Ｖ／Ｖ）の混合溶媒に固形分２０％となるように溶解したところ、変性ポリオレフィン系樹脂溶液の性状は、固化物が無く、流動性のある状態であり、良好であった。
　得られた変性ポリオレフィン系樹脂の重量平均分子量は７１，０００であった。 (Example 5)
Kneading using a twin screw extruder in which 100 parts by weight of propylene-ethylene copolymer, 3 parts by weight of maleic anhydride, 0.25 parts by weight of octyl methacrylate and 3 parts by weight of di-t-butyl peroxide are set at 160 ° C. 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 5 parts by weight of benzylamine with stirring, hold at 135 ° C. for 2 hours, and then remove xylene by distillation under reduced pressure. Thus, a modified polyolefin resin was obtained. When the obtained modified polyolefin resin was dissolved in 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 weight average molecular weight of the modified polyolefin resin obtained was 71,000.
（実施例６）
　プロピレン－エチレン共重合体１００重量部、無水シトラコン酸５重量部、及びジ－ｔ－ブチルパーオキサイド５重量部を１７０℃に設定した二軸押出機を用いて混練反応した。押出機内にて減圧脱気を行い、残留する未反応物を除去して変性物を得た。得られた変性物を７５重量部とキシレン４５重量部とを１３５℃で溶解し、撹拌下、ベンジルアルコール５重量部を添加し、１３５℃で２時間保持した後、減圧留去によりキシレンを除去し、変性ポリオレフィン系樹脂を得た。得られた変性ポリオレフィン樹脂をメチルシクロヘキサン／酢酸プロピル＝７０／３０（Ｖ／Ｖ）の混合溶媒に固形分２０％となるように溶解したところ、変性ポリオレフィン系樹脂溶液の性状は、固化物が無く、流動性のある状態であり、良好であった。
　得られた変性ポリオレフィン系樹脂の重量平均分子量は７３，０００であった。 (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. When the obtained modified polyolefin resin was dissolved in 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 73,000.
（実施例７）
　プロピレン－エチレン共重合体１００重量部、無水マレイン酸５重量部、ステアリルメタクリレート３．７５重量部、及びジ－ｔ－ブチルパーオキサイド２重量部を１７０℃に設定した二軸押出機を用いて混練反応した。押出機内にて減圧脱気を行い、残留する未反応物を除去して変性物を得た。得られた変性物を７５重量部とキシレン４５重量部とを１３５℃で溶解し、撹拌下、ベンジルアミン１重量部を添加し、１３５℃で２時間保持した後、減圧留去によりキシレンを除去し、変性ポリオレフィン系樹脂を得た。得られた変性ポリオレフィン樹脂をメチルシクロヘキサン／酢酸プロピル＝７０／３０（Ｖ／Ｖ）の混合溶媒に固形分２０％となるように溶解したところ、変性ポリオレフィン系樹脂溶液の性状は、固化物が無く、流動性のある状態であり、良好であった。
　得られた変性ポリオレフィン系樹脂の重量平均分子量は７５，０００であった。 (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. for 2 hours, and then xylene was removed by distillation under reduced pressure. Thus, a modified polyolefin resin was obtained. When the obtained modified polyolefin resin was dissolved in 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.
（実施例８）
　プロピレン－エチレン共重合体１００重量部、無水マレイン酸５重量部、ステアリルメタクリレート３．７５重量部、及びジ－ｔ－ブチルパーオキサイド１．５重量部を１７０℃に設定した二軸押出機を用いて混練反応した。押出機内にて減圧脱気を行い、残留する未反応物を除去して変性物を得た。得られた変性物を７５重量部とキシレン４５重量部とを１３５℃で溶解し、撹拌下、ベンジルアミン５重量部を添加し、１３５℃で２時間保持した後、減圧留去によりキシレンを除去し、変性ポリオレフィン系樹脂を得た。得られた変性ポリオレフィン樹脂をメチルシクロヘキサン／酢酸プロピル＝７０／３０（Ｖ／Ｖ）の混合溶媒に固形分２０％となるように溶解したところ、変性ポリオレフィン系樹脂溶液の性状は、固化物が無く、流動性のある状態であり、良好であった。
　得られた変性ポリオレフィン系樹脂の重量平均分子量は７２，０００であった。 (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. Thus, a modified polyolefin resin was obtained. When the obtained modified polyolefin resin was dissolved in 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 72,000.
（実施例９）
　プロピレン－エチレン共重合体１００重量部、無水イタコン酸１０重量部、ステアリルメタクリレート７．５重量部、及びジ－ｔ－ブチルパーオキサイド２重量部を１８０℃に設定した二軸押出機を用いて混練反応した。押出機内にて減圧脱気を行い、残留する未反応物を除去して変性物を得た。得られた変性物を７５重量部とキシレン４５重量部とを１３５℃で溶解し、撹拌下、ベンジルアルコール５重量部を添加し、１３５℃で２時間保持した後、変性ポリオレフィン系樹脂を得た。得られた変性ポリオレフィン樹脂をメチルシクロヘキサン／酢酸プロピル＝７０／３０（Ｖ／Ｖ）の混合溶媒に固形分２０％となるように溶解したところ、変性ポリオレフィン系樹脂溶液の性状は、固化物が無く、流動性のある状態であり、良好であった。
　得られた変性ポリオレフィン系樹脂の重量平均分子量は７８，０００であった。 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. . When the obtained modified polyolefin resin was dissolved in 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 78,000.
（実施例１０）
　プロピレン－エチレン共重合体１００重量部、無水イタコン酸１０重量部、ステアリルメタクリレート７．５重量部、及びジ－ｔ－ブチルパーオキサイド３重量部を１７０℃に設定した二軸押出機を用いて混練反応した。押出機内にて減圧脱気を行い、残留する未反応物を除去して変性物を得た。得られた変性物を７５重量部とキシレン４５重量部とを１３５℃で溶解し、撹拌下、ベンジルアルコール１０重量部を添加し、１３５℃で２時間保持した後、変性ポリオレフィン系樹脂を得た。得られた変性ポリオレフィン樹脂をメチルシクロヘキサン／酢酸プロピル＝７０／３０（Ｖ／Ｖ）の混合溶媒に固形分２０％となるように溶解したところ、変性ポリオレフィン系樹脂溶液の性状は、固化物が無く、流動性のある状態であり、良好であった。
　得られた変性ポリオレフィン系樹脂の重量平均分子量は７８，０００であった。 (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. for 2 hours to obtain a modified polyolefin resin. . When the obtained modified polyolefin resin was dissolved in 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 78,000.
（比較例１）
　プロピレン－エチレン共重合体１００重量部、マレイン酸３重量部、オクチルメタクリレート２．２５重量部、及びジ－ｔ－ブチルパーオキサイド３重量部を１７０℃に設定した二軸押出機を用いて混練反応した。押出機内にて減圧脱気を行い、残留する未反応物を除去して変性物を得た。得られた変性物を７５重量部とキシレン４５重量部とを１３５℃で溶解し、２時間保持した後、変性ポリオレフィン系樹脂を得た。得られた変性ポリオレフィン樹脂をメチルシクロヘキサン／酢酸プロピル＝７０／３０（Ｖ／Ｖ）の混合溶媒に固形分２０％となるように溶解したところ、変性ポリオレフィン系樹脂溶液の性状は、良好であった。
　得られた変性ポリオレフィン系樹脂の重量平均分子量は７２，０００であった。 (Comparative Example 1)
A kneading reaction using a twin screw extruder in which 100 parts by weight of propylene-ethylene copolymer, 3 parts by weight of maleic acid, 2.25 parts by weight of octyl methacrylate and 3 parts by weight of di-t-butyl peroxide are set at 170 ° C. did. 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 obtained modified product and 45 parts by weight of xylene were dissolved at 135 ° C. and held for 2 hours, and then a modified polyolefin resin was obtained. When the obtained modified polyolefin resin was dissolved in a mixed solvent of methylcyclohexane / propyl acetate = 70/30 (V / V) so as to have a solid content of 20%, the properties of the modified polyolefin resin solution were good. .
The resulting modified polyolefin resin had a weight average molecular weight of 72,000.
（比較例２）
　プロピレン－エチレン共重合体１００重量部、ラウリルメタクリレート２．２５重量部、及びジ－ｔ－ブチルパーオキサイド２重量部を１６０℃に設定した二軸押出機を用いて混練反応した。押出機内にて減圧脱気を行い、残留する未反応物を除去して変性物を得た。得られた変性物を７５重量部とキシレン４５重量部とを１３５℃で溶解し、撹拌下、ベンジルアルコール５重量部を添加し、１３５℃で２時間保持した後、変性ポリオレフィン系樹脂を得た。得られた変性ポリオレフィン樹脂をメチルシクロヘキサン／酢酸プロピル＝７０／３０（Ｖ／Ｖ）の混合溶媒に固形分２０％となるように溶解したところ、変性ポリオレフィン系樹脂溶液の性状は、固化物が無く、流動性のある状態であり、良好であった。
　得られた変性ポリオレフィン系樹脂の重量平均分子量は６５，０００であった。 (Comparative Example 2)
A kneading reaction was performed using 100 parts by weight of a propylene-ethylene copolymer, 2.25 parts by weight of lauryl methacrylate and 2 parts by weight of di-t-butyl peroxide using a twin screw extruder set at 160 ° 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 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. . When the obtained modified polyolefin resin was dissolved in 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 65,000.
（評価方法）
　実施例１～１０、比較例１～２で得られた各樹脂について、下記の方法にしたがって評価を行った。
（ヒートシール強度）
　各樹脂をメチルシクロヘキサン／酢酸プロピル＝７０／３０（Ｖ／Ｖ）の混合溶媒に固形分２０％となるように溶解し、マイヤーバー＃１０にて延伸ポリプロピレン（ｏｒｉｅｎｔｅｄ　ｐｏｌｙｐｒｏｐｙｌｅｎｅ：ＯＰＰ）フイルム（フタムラ化学製）のコロナ処理面に塗布し、ヘアドライヤーで３０秒乾燥後、一晩静置して樹脂塗工フィルムを得た。
　樹脂塗工フィルムフィルムと各基材（ＰＳ板、ＰＣ板、又はＰＥＴ板）とを重ね合わせ、Ｎｏ．２７６ヒートシールテスタ（安田精機製作所製）を用いヒートシールした。ヒートシールは、フィルム側のみを１４０℃に加温し、２ｋｇｆにて６秒間加圧することによって行った。ヒートシールの後３時間静置し、テンシロン万能試験機（エー・アンド・デイ株式会社製、ＲＴＧ－１２１０）にて１８０°方向の剥離試験を実施した。剥離速度は１００ｍｍ／分とした。 (Evaluation methods)
Each resin obtained in Examples 1 to 10 and Comparative Examples 1 and 2 was evaluated according to the following method.
(Heat seal strength)
Each resin was dissolved in a mixed solvent of methylcyclohexane / propyl acetate = 70/30 (V / V) so as to have a solid content of 20%, and stretched polypropylene (OPP) film (Futamura Chemical Co., Ltd.) with Mayer bar # 10. The product was applied to the corona-treated surface of the product, dried with a hair dryer for 30 seconds, and allowed to stand overnight to obtain a resin-coated film.
A resin-coated film film and each substrate (PS plate, PC plate, or PET plate) 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.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１及び２の結果から、実施例１～１０の変性ポリオレフィン系樹脂は、成分（Ｃ）により変性されていない比較例１及び成分（Ｂ）により変性されていない比較例２の変性ポリオレフィン系樹脂と比較して、ＯＰＰフィルムと各基材（ＰＳ板、ＰＣ板、又はＰＥＴ板）とをヒートシールした場合に、顕著にヒートシール強度が向上していることが分かる。
　この結果は、本発明の変性ポリオレフィン系樹脂が、ポリオレフィン系基材、ポリスチレン系基材、ポリカーボネート系基材、ＰＥＴなどのポリエステル系基材に対する優れた接着性を有することを示している。 From the results shown in Tables 1 and 2, 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.

Claims (16)

  1. 　成分（Ａ）：ポリオレフィン樹脂を変性成分により変性してなり、
    　変性成分が、成分（Ｂ）：α，β－不飽和カルボン酸及びその酸無水物から選ばれる１種以上、並びに
    　成分（Ｃ）：ベンゼン環を有する化合物
    を含む、変性ポリオレフィン系樹脂。     Component (A): A polyolefin resin is modified with a modifying component,
    A modified polyolefin resin, wherein the modifying component comprises at least one selected from component (B): α, β-unsaturated carboxylic acid and acid anhydride thereof, and component (C): a compound having a benzene ring.
  2. 　変性成分が、さらに
    　成分（Ｄ）：（メタ）アクリル酸エステル
    を含む、請求項１に記載の変性ポリオレフィン系樹脂。     The modified polyolefin resin according to claim 1, wherein the modified component further comprises a component (D): (meth) acrylic acid ester.
  3. 　成分（Ｄ）が、式（Ｉ）で表される（メタ）アクリル酸エステルを含む、請求項２に記載の変性ポリオレフィン系樹脂。
    ＣＨ２＝ＣＲ１ＣＯＯＲ２・・・（Ｉ）
    （式（Ｉ）中、Ｒ１は水素原子又はメチル基を表し、Ｒ２は、－ＣｎＨ２ｎ＋１で表される基を表し、ｎは８～１８の整数である。）     The modified polyolefin resin according to claim 2, 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)
  4. 　成分（Ｃ）が、ベンジル基を有する化合物である、請求項１～３のいずれか１項に記載の変性ポリオレフィン系樹脂。 The modified polyolefin resin according to any one of claims 1 to 3, wherein the component (C) is a compound having a benzyl group.
  5. 　成分（Ａ）が、プロピレン－エチレン系共重合体又はプロピレン－ブテン系共重合体である、請求項１～４のいずれか１項に記載の変性ポリオレフィン系樹脂。 The modified polyolefin resin according to any one of claims 1 to 4, wherein the component (A) is a propylene-ethylene copolymer or a propylene-butene copolymer.
  6. 　重量平均分子量が、５，０００以上２００，０００未満である、請求項１～５のいずれか１項に記載の変性ポリオレフィン系樹脂。 6. The modified polyolefin resin according to claim 1, having a weight average molecular weight of 5,000 or more and less than 200,000.
  7. 　成分（Ｃ）の含有量が、成分（Ａ）１００重量部に対して、０．１～２０重量部である、請求項１～６のいずれか１項に記載の変性ポリオレフィン系樹脂。 The modified polyolefin resin according to any one of claims 1 to 6, wherein the content of the component (C) is 0.1 to 20 parts by weight with respect to 100 parts by weight of the component (A).
  8. 　請求項１～７のいずれか１項に記載の変性ポリオレフィン系樹脂を含むヒートシール剤。 A heat sealant comprising the modified polyolefin resin according to any one of claims 1 to 7.
  9. 　請求項１～７のいずれか１項に記載の変性ポリオレフィン系樹脂を含む接着剤。 An adhesive comprising the modified polyolefin resin according to any one of claims 1 to 7.
  10. 　請求項１～７のいずれか１項に記載の変性ポリオレフィン系樹脂を含むプライマー。 A primer containing the modified polyolefin resin according to any one of claims 1 to 7.
  11. 　請求項１～７のいずれか１項に記載の変性ポリオレフィン系樹脂を含む塗料用バインダー。 A paint binder comprising the modified polyolefin resin according to any one of claims 1 to 7.
  12. 　請求項１～７のいずれか１項に記載の変性ポリオレフィン系樹脂を含むインキ用バインダー。 An ink binder comprising the modified polyolefin resin according to any one of claims 1 to 7.
  13. 　成分（Ａ）：ポリオレフィン樹脂を変性成分により変性して変性ポリオレフィン系樹脂を得ることを含み、
    　変性成分が、
    　成分（Ｂ）：α，β－不飽和カルボン酸及びその酸無水物から選ばれる１種以上、並びに
    　成分（Ｃ）：ベンゼン環を有する化合物を含む、変性ポリオレフィン系樹脂の製造方法。     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 α, β-unsaturated carboxylic acids and acid anhydrides thereof, and Component (C): A method for producing a modified polyolefin resin comprising a compound having a benzene ring.
  14. 　変性が、成分（Ｂ）による変性、成分（Ｃ）による変性の順で行われる、請求項１３に記載の変性ポリオレフィン系樹脂の製造方法。 The method for producing a modified polyolefin resin according to claim 13, wherein the modification is performed in the order of modification by component (B) and modification by component (C).
  15. 　変性成分が、成分（Ｄ）：（メタ）アクリル酸エステルをさらに含む、請求項１３又は１４に記載の変性ポリオレフィン系樹脂の製造方法。 The method for producing a modified polyolefin resin according to claim 13 or 14, wherein the modified component further comprises a component (D): (meth) acrylic acid ester.
  16. 　成分（Ｂ）による変性及び成分（Ｄ）による変性が同時に行われる、請求項１５に記載の変性ポリオレフィン系樹脂の製造方法。 The method for producing a modified polyolefin resin according to claim 15, wherein the modification with the component (B) and the modification with the component (D) are simultaneously performed.
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JPWO2019188858A1 (en) * 2018-03-26 2021-04-01 日本製紙株式会社 Modified polyolefin resin and its uses
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WO2022202822A1 (en) 2021-03-26 2022-09-29 三井化学株式会社 Adhesive composition and multilayer body
WO2022210053A1 (en) * 2021-04-02 2022-10-06 住友化学株式会社 Modified polyolefin resin
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