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WO2024248150A1 - Composition de résine durcissable - Google Patents

Composition de résine durcissable Download PDF

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Publication number
WO2024248150A1
WO2024248150A1 PCT/JP2024/020107 JP2024020107W WO2024248150A1 WO 2024248150 A1 WO2024248150 A1 WO 2024248150A1 JP 2024020107 W JP2024020107 W JP 2024020107W WO 2024248150 A1 WO2024248150 A1 WO 2024248150A1
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Prior art keywords
resin composition
curable resin
polyolefin
modified polyolefin
composition according
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English (en)
Japanese (ja)
Inventor
真也 渡邉
珠世 佐々井
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Toyobo Co Ltd
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Toyobo Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment

Definitions

  • the present invention relates to a curable resin composition.
  • hot melt adhesives are used in fields such as building materials, automobile interior materials, and electrical component assembly because they can bond in a short time and do not contain solvents.
  • automobile interior materials ceilings, doors, seats, etc.
  • the molded products are mainly polyolefin molded products (polypropylene, polyethylene, etc.), and the skin materials are mainly polyolefin skin materials.
  • Automotive interior materials are manufactured by bonding these molded products and skin materials with hot melt adhesives using methods such as press bonding and vacuum molding.
  • Curable resin compositions are widely used as materials for hot melt adhesives (see, for example, Patent Documents 1 and 2).
  • Patent Document 1 describes a curable resin composition in which a silane coupling agent is blended with a styrene block copolymer graft-polymerized with an acrylic monomer.
  • Patent Document 2 describes a curable resin composition that includes a reaction product between a modified polyolefin resin modified with an unsaturated carboxylic acid and/or a derivative thereof, and a compound having a functional group reactive to the modified polyolefin resin and a reactive silyl group.
  • the present invention has been made in consideration of the above, and aims to provide a curable resin composition that has excellent coatability in a molten state and excellent heat creep resistance after the curing reaction.
  • the inventors discovered that the following specific curable resin composition has excellent coatability in a molten state and excellent heat creep resistance after the curing reaction, and thus completed the present invention.
  • a curable resin composition A curable resin composition containing modified polyolefin A and modified polyolefin B,
  • the modified polyolefin A has a chemical structure obtained by grafting a moisture-curable functional group onto the polyolefin a
  • the modified polyolefin B has a chemical structure obtained by grafting a moisture-curable functional group onto the polyolefin b
  • the curable resin composition of the present invention exhibits excellent coatability in a molten state and excellent heat creep resistance after the curing reaction.
  • FIG. 1 is a diagram showing an adhesive sample in an evaluation method for heat creep resistance.
  • FIG. 2 is a diagram showing the relationship between a measurement sample and a weight in the evaluation method for heat creep resistance.
  • the curable resin composition of the present invention is a curable resin composition containing modified polyolefin A and modified polyolefin B.
  • a total of 100 parts by mass of modified polyolefin A and modified polyolefin B is immersed in xylene at 100° C. for 1 hour. It is preferable that 25 to 40 parts by mass of the composition remain undissolved when the composition is immersed in xylene at 120° C. for 1 hour, and that 0.1 to 5 parts by mass of the composition remain undissolved when the composition is immersed in xylene at 120° C. for 1 hour.
  • the resin composition may further contain, in addition to the modified polyolefin A and modified polyolefin B, a moisture curing accelerator C, a moisture curing catalyst D, a diluent, a tackifier, a wax, an antioxidant, etc.
  • the curable resin composition can be produced by melting and kneading the components thereof, and may be cooled and solidified, and then granulated or powdered, or may be dissolved or dispersed in a solvent to form a liquid. good.
  • the modified polyolefin A in the present invention is composed of a chemical structure obtained by grafting a moisture-curable functional group to polyolefin a.
  • the modified polyolefin B in the present invention is composed of a chemical structure obtained by grafting a moisture-curable functional group to polyolefin b.
  • the chemical structure obtained by grafting means a chemical structure in a grafted state, and for example, the modified polyolefin A can also be expressed as "a chemical structure in which a moisture-curable functional group is grafted to polyolefin a".
  • the polyolefin a or the polyolefin b may, for example, be a homopolymer of an ⁇ -olefin polymerized from a monomer component such as ethylene, propylene, 1-butene, isobutene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, or 1-eicosene; a copolymer of an ⁇ -olefin other than ethylene and ethylene, such as an ethylene-propylene copolymer, an ethylene-propylene-butylene copolymer, or an ethylene-propylene-isobutylene copolymer; an ⁇ -olefin copolymer such as an ethylene-propylene-isobutylene copolymer; Examples of such copolymers include copolymers of fin
  • propylene homopolymers ethylene-propylene copolymers, ethylene-propylene-butylene copolymers, ethylene-propylene-isobutylene copolymers, and the like are preferred, with propylene homopolymers being more preferred.
  • the polyolefin a is preferably a polypropylene-based polymer, and more preferably a homopolypropylene.
  • the melting point of the polyolefin a is preferably 100 to 190°C, more preferably 120 to 170°C, and even more preferably 130 to 160°C.
  • the glass transition temperature of the polyolefin a is preferably -20 to 5°C, more preferably -15 to 0°C, and even more preferably -10 to 0°C.
  • the melt viscosity of the polyolefin a at 140°C is preferably 20,000 cps or less, more preferably 15,000 cps or less, and even more preferably 10,000 cps or less, with a lower limit of about 1,000 cps, although this is not restrictive.
  • the polyolefin a preferably satisfies two or more of the above composition, melting point, glass transition temperature, and melt viscosity ranges, and more preferably satisfies all of them.
  • the polyolefin b is particularly preferably an ethylene-butylene-propylene copolymer.
  • the melting point of the polyolefin b is preferably 100 to 190°C, more preferably 130 to 170°C, and even more preferably 120 to 150°C.
  • the glass transition temperature of the polyolefin b is preferably -20 to 20°C, more preferably -20 to 15°C, and even more preferably -20 to -10°C.
  • the polyolefin b preferably satisfies two or more of the above composition, melting point, and glass transition temperature ranges, and more preferably satisfies all of them.
  • the modified polyolefin A and modified polyolefin B can be produced by known methods, for example, by grafting moisture-curable functional groups onto the polyolefin a and polyolefin b in the presence of a radical initiator or by electron beam irradiation.
  • the graft reaction may be carried out on the polyolefin a and polyolefin b individually, or on a mixture of the polyolefin a and polyolefin b.
  • radical initiators include peroxide initiators such as dicumyl peroxide, t-butylperoxyisopropyl carbonate, di-t-butylperoxide, t-butylperbenzoate, benzoylperoxide, cumenehydroperoxide, t-butylperoctoate, methylethylketoneperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, laurylperoxide, t-butylperacetate, t-butyl- ⁇ -cumylperoxide, di-t-butylperoxide, t-butylperoxyisopropylcarbonate ...oxyisopropylcarbonate, di-t-butylperoxide, t-butylperoxyisopropylcarbonate, di-t-butylperoxide, di-t-butylperoxide, di-t-butylperoxide, di
  • Examples of the moisture-curable functional group used in the synthesis of modified polyolefin A and modified polyolefin B include an isocyanate group, a hydrolyzable silyl group, and the like.
  • a compound having a moisture-curable functional group may be grafted to the polyolefin a and the polyolefin b, and as the compound, a silane-modified monomer containing a hydrolyzable silyl group and an ethylenically unsaturated group can be suitably used from the viewpoint of controlling reactivity.
  • Such a silane-modified monomer is, for example, represented by the following formula (1): X n R 3-n -Si-Y...(1) (Y is an ethylenically unsaturated group, X is a hydrolyzable silyl group, R is an alkyl group, and n is an integer of 1 to 3.) Examples of the above-mentioned are represented by the following formula:
  • the hydrolyzable group in the above formula (1) may be, for example, a halogen, an alkoxy group, an alkenyloxy group, an acyloxy group, an amino group, an aminooxy group, an oxime group, an amide group, etc.
  • the above alkoxy group is preferably a methoxy group.
  • the number of these hydrolyzable groups bonded to one silicon atom is selected from the range of 1, 2, and 3.
  • the hydrolyzable group bonded to one silicon atom may be one type or multiple types.
  • a hydrolyzable group and a non-hydrolyzable group may be bonded to one silicon atom.
  • n is preferably 3.
  • the ethylenically unsaturated group contained in the silane-modified monomer may be, for example, a vinyl group, an aryl group, an acrylic group, a methacrylic group, etc.
  • Preferred silane-modified monomers having an ethylenically unsaturated group are vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane.
  • the amount of radical initiator used in producing modified polyolefin A and modified polyolefin B is preferably 0.5 to 10 parts by mass, more preferably 0.75 to 8 parts by mass, and even more preferably 1 to 5 parts by mass, per 100 parts by mass of the total amount of polyolefin a and polyolefin b (the amount of that one when only one of them is used as a raw material).
  • the amount of radical initiator is 0.5 parts by mass or more, the graft reaction proceeds sufficiently, and the room temperature adhesive strength, adhesive strength in a high temperature environment, and creep properties of the cured curable resin composition or hot melt adhesive using the curable resin composition are improved.
  • the amount of radical initiator is 10 parts by mass or less, side reactions such as homopolymerization of the silane-modified monomer or decomposition reaction of the polyolefin are suppressed.
  • the amount of the silane-modified monomer used in producing modified polyolefin A and modified polyolefin B is preferably 0.5 to 10 parts by mass, more preferably 0.75 to 8 parts by mass, and particularly preferably 1 to 8 parts by mass, per 100 parts by mass of the total amount of polyolefin a and polyolefin b (when only one of them is used as a raw material, the amount of that one).
  • the amount of the silane-modified monomer used is 0.5 parts by mass or more, the graft polymerization reaction proceeds sufficiently, and the heat creep resistance properties and adhesive strength after curing of the curable resin composition and the hot melt adhesive using the curable resin composition are further improved.
  • the amount of the silane-modified monomer used is 10 parts by mass or less, side reactions such as homopolymerization of the silane-modified monomer and decomposition reaction of polyolefin a are further suppressed.
  • the melt viscosity of the modified polyolefin A at 140°C is preferably 35,000 mPa ⁇ s or less, more preferably 25,000 mPa ⁇ s or less, even more preferably 15,000 mPa ⁇ s or less, and most preferably 10,000 mPa ⁇ s or less, with a lower limit of about 1,000 mPa ⁇ s, although this is not critical.
  • the melt viscosity of the modified polyolefin A at 140°C is 35,000 mPa ⁇ s or less, the curable resin composition and the hot melt adhesive using the curable resin composition can be easily applied to the adherend.
  • the melt viscosity of the curable resin composition of the present invention containing the modified polyolefin A and the modified polyolefin B is 35,000 mPa ⁇ s or less, preferably 34,000 mPa ⁇ s or less, more preferably 33,000 mPa ⁇ s or less, and the lower limit is not limited but is about 30,000 mPa ⁇ s. Since the melt viscosity of the curable resin composition at 140°C is 35,000 mPa ⁇ s or less, the curable resin composition and the hot melt adhesive using the curable resin composition can be easily applied to an adherend.
  • the melt viscosity of the modified polyolefin A and the curable resin composition is a value measured using a B-type viscometer (for example, Brookfield's DVNXRVTJG type).
  • the measurement conditions and determination method are as follows. 11 g of sample was placed in the measurement chamber of the B-type viscometer (Brookfield's DVNXRVTJG type), heated to 200°C to melt the sample, and then cooled to 140°C, and measured in accordance with the melt viscosity test method for hot melt adhesives of JIS K6862.
  • the spindle No. used for the measurement was No. 27, and the rotation speed was set to 5 rpm.
  • the melting point (Tm) of the modified polyolefin A is preferably 120°C to 170°C, more preferably 130°C to 160°C.
  • Tm The melting point of the modified polyolefin A is 120°C or higher, the adhesive strength at around room temperature and in a high-temperature environment of the curable resin composition cured under any environment or the hot melt adhesive using the curable resin composition, as well as the creep characteristics in a high-temperature environment, are improved.
  • the melting point of the modified polyolefin A is 170°C or lower, the curable resin composition and the hot melt adhesive using the curable resin composition can be applied without affecting the adherend.
  • the melting point (Tm) of the modified polyolefin B is preferably 120°C to 170°C, more preferably 120°C to 150°C.
  • Tm The melting point of the modified polyolefin B is 120°C or higher, the adhesive strength at around room temperature and in a high-temperature environment of the curable resin composition cured under any environment or the hot melt adhesive using the curable resin composition, as well as the creep characteristics in a high-temperature environment, are improved.
  • the melting point of the modified polyolefin B is 170°C or lower, the curable resin composition and the hot melt adhesive using the curable resin composition can be applied without affecting the adherend.
  • the melting points (Tm) of modified polyolefin A and modified polyolefin B are values determined by DSC measurement using a differential scanning calorimeter (DSC, for example, DuPont's V4.OB2000 model).
  • the measurement conditions and determination method were as follows. 10 mg of sample was heated from 25°C to 200°C at 25°C/min in a nitrogen atmosphere, held at 200°C for 5 minutes, and then cooled to 25°C at 25°C/min. The sample was then heated from 25°C to 200°C at 25°C/min. The peak top of the endothermic peak observed on the highest temperature side of the heat of fusion absorption curve detected during this heating process was taken as the melting point (Tm).
  • Modified polyolefin A and modified polyolefin B may or may not have an observable glass transition point.
  • the glass transition temperature (Tg) is preferably 15°C or lower, and more preferably -20°C to 10°C.
  • Tg glass transition temperature
  • the glass transition temperatures of modified polyolefin A and modified polyolefin B are 15°C or lower, the curable resin composition does not become too hard even in a low-temperature environment, and can maintain adhesion to the substrate.
  • the glass transition temperatures (Tg) of modified polyolefin A and modified polyolefin B were determined from the temperature dependence of dynamic viscoelasticity.
  • the measurement conditions and determination method were as follows. Using a "DVA-200" manufactured by IT Measurement & Control Co., Ltd., the storage modulus (E') and loss modulus (E") were measured with a sample thickness of approximately 0.5 mm, attachment mode: tension-compression mode, frequency: 10 Hz, temperature: -100°C to 200°C, and heating rate: 4°C/min, and the loss tangent (tan ⁇ ) was calculated.
  • the peak top temperature of the loss tangent tan ⁇ (loss modulus E"/storage modulus E') in the dynamic viscoelasticity measurement was determined as the glass transition temperature (Tg) [°C].
  • the number average molecular weight of the modified polyolefin A is preferably 2,000 to 10,000, more preferably 4,000 to 6,000.
  • the number average molecular weight of the modified polyolefin A is 2,000 or more, the adhesive strength at room temperature and in a high-temperature environment of the cured curable resin composition or the hot melt adhesive using the curable resin composition, as well as the creep characteristics in a high-temperature environment, are improved.
  • the number average molecular weight of the modified polyolefin A is 10,000 or less, the curable resin composition and the hot melt adhesive using the curable resin composition can be easily applied to an adherend.
  • the number average molecular weight of the modified polyolefin B is preferably 50,000 to 100,000, and more preferably 80,000 to 100,000.
  • the number average molecular weight of the modified polyolefin B is 50,000 or more, the room temperature adhesive strength and adhesive strength in a high temperature environment, as well as creep characteristics, of the cured curable resin composition or hot melt adhesive using the curable resin composition are improved.
  • the number average molecular weight of the modified polyolefin B is 100,000 or less, the curable resin composition and the hot melt adhesive using the curable resin composition can be easily applied to an adherend.
  • the number average molecular weights of Modified Polyolefin A and Modified Polyolefin B are polystyrene equivalent values determined by GPC (gel permeation chromatography, in accordance with DIN 55 672).
  • the measurement conditions and determination method were as follows.
  • GPC measuring device HLC-8321GPC/HT (manufactured by Tosoh Corporation) Column: Waters Styragel HT3, 4, 6E Detector: RI Solvent: ortho-dichlorobenzene (containing 0.5 mg/mL butylated hydroxyl toluene) Measurement temperature: 140°C Flow rate: 0.3mL/min. Sample concentration: 1.2-1.7 mg/mL Injection volume: 200 ⁇ L Analysis program: GPC data processing system (TOSOH)
  • the polyolefin b and/or modified polyolefin B preferably have a controlled nanocrystalline structure.
  • the polyolefin b is preferably a thermoplastic polyolefin-based elastomer in which the crystal/amorphous structure of the polymer is controlled on the nano-order and the crystal has a mesh structure on the nano-order.
  • TAFMER registered trademark
  • PN-2070, PN-3560, PN-2060, and PN-20300 manufactured by Mitsui Chemicals, Inc. are mentioned as suitable examples, but are not limited to these.
  • the nanocrystalline structure-controlled polyolefin resin in the present invention has a crystal size controlled on the nano-order, whereas the crystal size of conventional polyolefins is on the micron order. Therefore, compared with conventional polyolefin resins, the polyolefin resin is often superior in transparency, heat resistance, flexibility, rubber elasticity, etc.
  • the modified polyolefin B has a controlled nanocrystalline structure, and thus the flexibility at low temperatures (0°C) of the obtained curable resin composition and the hot melt adhesive using the curable resin composition is significantly improved. By improving flexibility at low temperatures, the adhesive surface is less likely to peel off when the hot melt adhesive cools and solidifies during the bonding process and when the adhesive is used in a cold environment.
  • the breaking elongation at low temperature (0°C) of the obtained curable resin composition and the hot melt adhesive using the curable resin composition in an uncured state is not particularly limited, but is preferably 300% or more, more preferably 350% or more, and even more preferably 400% or more. If the breaking elongation is 300% or more, the adhesive surface tends to become difficult to peel off as the hot melt adhesive cools and solidifies in the bonding process.
  • the breaking elongation at low temperature (0°C) after the obtained curable resin composition and the hot melt adhesive using the curable resin composition are cured and aged is not particularly limited, but is preferably 200% or more, more preferably 250% or more, and even more preferably 300% or more. If the breaking elongation is 200% or more, the adhesive surface tends to be less likely to peel off when used in a cold environment.
  • modified polyolefin B is preferably 5 to 15 parts by mass, more preferably 7 to 13 parts by mass, and even more preferably 9 to 11 parts by mass, per 100 parts by mass of modified polyolefin A.
  • the flexibility of the curable resin composition and the hot melt adhesive using the curable resin composition in a low-temperature environment is improved.
  • the adhesive strength at room temperature and in a high-temperature environment of the cured curable resin composition or the hot melt adhesive using the curable resin composition, as well as the creep characteristics in a high-temperature environment are improved.
  • modified polyolefin A and modified polyolefin B combined When 100 parts by mass of modified polyolefin A and modified polyolefin B combined is immersed in xylene at 100°C for 1 hour, it is preferable that 25 to 40 parts by mass remain undissolved, and when immersed in xylene at 120°C for 1 hour, 0.1 to 5 parts by mass remain undissolved. When within the above range, excellent coatability in the molten state and excellent heat creep resistance are exhibited.
  • the curable resin composition of the present invention may contain a moisture curing accelerator C.
  • Preferred examples of the moisture curing accelerator C include, but are not limited to, an acid-modified polyolefin CA and a rosin compound CB having an acid functional group.
  • the moisture curing accelerator C may be used alone or in combination of two or more kinds.
  • the moisture curing accelerator C preferably has an acid functional group and satisfies at least one of a melting point of 70 to 100°C and a softening point of 100 to 140°C.
  • the acid-modified polyolefin CA is preferably, but not limited to, one obtained by grafting at least one of ⁇ , ⁇ -unsaturated carboxylic acids and their acid anhydrides (acid functional groups) onto a polyolefin resin.
  • Polyolefin resin refers to polymers mainly composed of a hydrocarbon skeleton, such as homopolymers of olefin monomers such as ethylene, propylene, butene, butadiene, isoprene, etc., copolymers with other monomers, and hydrogenated or halides of the above homopolymers and copolymers.
  • the acid-modified polyolefin CA is preferably one obtained by grafting at least one of ⁇ , ⁇ -unsaturated carboxylic acids and their acid anhydrides onto at least one of polyethylene, polypropylene, and propylene- ⁇ -olefin copolymers.
  • Propylene- ⁇ -olefin copolymers are copolymers of propylene with an ⁇ -olefin as the main component.
  • the ⁇ -olefin for example, one or more of ethylene, 1-butene, 1-heptene, 1-octene, 4-methyl-1-pentene, vinyl acetate, etc. can be used. Among these ⁇ -olefins, ethylene and 1-butene are preferred.
  • the propylene component is 50 mol% or more, and more preferably 70 mol% or more.
  • Examples of at least one of ⁇ , ⁇ -unsaturated carboxylic acids and their acid anhydrides include maleic acid, itaconic acid, citraconic acid, and their acid anhydrides. Among these, acid anhydrides are preferred, and maleic anhydride is more preferred. Specific examples include maleic anhydride-modified polypropylene, maleic anhydride-modified propylene-ethylene copolymer, maleic anhydride-modified propylene-butene copolymer, maleic anhydride-modified propylene-ethylene-butene copolymer, etc., and these acid-modified polyolefins can be used alone or in combination of two or more kinds.
  • the method for producing acid-modified polyolefin CA is not particularly limited, and examples include radical grafting reaction (i.e., a reaction in which radical species are generated in the main chain polymer and the radical species is used as the polymerization initiation point to graft polymerize unsaturated carboxylic acid and acid anhydride).
  • radical grafting reaction i.e., a reaction in which radical species are generated in the main chain polymer and the radical species is used as the polymerization initiation point to graft polymerize unsaturated carboxylic acid and acid anhydride.
  • acid-modified polyolefin CA examples include PMA-T, PMA-F2, PMA-HM (all trade names, chlorinated maleic acid-modified polyolefin, manufactured by Toyobo Co., Ltd.), PMA-KH, PMA-L, PMA-LZ (all trade names, maleic acid-modified polyolefin, manufactured by Toyobo Co., Ltd.), UMEX 1001, UMEX 1010, UMEX 100TS, UMEX 5500 (all trade names, manufactured by Sanyo Chemical Industries, Ltd.), etc.
  • the melting point (Tm) of the acid-modified polyolefin CA is preferably in the range of 70°C to 100°C. By keeping it below the upper limit, excellent coating properties and good heat creep resistance properties are obtained.
  • the melting point (Tm) was determined by DSC measurement using a differential scanning calorimeter (V4.OB2000 model, manufactured by DuPont). 10 mg of the sample was heated from 25°C to 200°C at 25°C/min in a nitrogen atmosphere, held at 200°C for 5 minutes, and then cooled to 25°C at 25°C/min. The temperature was then raised from 25°C to 200°C at 25°C/min. The peak top of the endothermic peak observed on the highest temperature side of the heat of fusion absorption curve detected during this heating process was taken as the melting point (Tm).
  • rosin compounds CB having acid functional groups include unsaturated acid modified rosins obtained by adding unsaturated acids such as maleic acid, fumaric acid, and acrylic acid by Diels-Alder addition reaction, more specifically maleopimaric acid obtained by adding maleic acid to rosin, fumaropimaric acid obtained by adding fumaric acid, and acrylopimaric acid obtained by adding acrylic acid.
  • esterified rosins include alkyl esters of rosin, glycerin esters obtained by esterifying rosin with glycerin, and pentaerythritol esters obtained by esterifying rosin with pentaerythritol.
  • rosin compounds CB having acid functional groups include Hariestar DS-70L, Haritac R-80, Haritac FK100, Haritac FK125, Haritac SE10, Haritac F85, Haritac PH, Haritac F-75, Haritac FG-90, Harimacc T-80, Harimacc M-453, Haritac 4740, Hariestar MSR-4, Haritac 28JA, Haritac PCJ, and Harimacc AS-5 (all trade names, manufactured by Harima Chemical Co., Ltd.) ), Pine Crystal KE-100, Pine Crystal KE-311, Pine Crystal KE-590, Pine Crystal KE-359, Pine Crystal KE-604, Pine Crystal KE-140, Pine Crystal D-6011 (all trade names, manufactured by Arakawa Chemical Industries, Ltd.), Super Ester A-75, Super Ester A-100, Super Ester A-115, Super Ester A-125 (all trade names, manufactured by Arakawa Chemical Industries, Ltd.), etc.
  • the softening point of the rosin compound CB having an acid functional group is preferably 100°C to 140°C. By keeping it below the upper limit, excellent coating properties and good heat creep resistance are achieved.
  • the softening point of the rosin compound refers to the value measured using an RSP-202 (manufactured by RIGO Corporation) in accordance with the JIS K6863 softening point test method for hot melt adhesives.
  • the moisture curing accelerator C is preferably contained in an amount of 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 5 to 10 parts by mass, per 100 parts by mass of the total of modified polyolefin A and modified polyolefin B.
  • the curable resin composition of the present invention may contain a moisture curing catalyst D.
  • the moisture curing catalyst D is not particularly limited as long as it can promote the reaction of the moisture curing functional group of the modified polyolefin A and/or modified polyolefin B, typically the dehydration condensation reaction of the hydrolyzable silyl group.
  • Examples of the moisture curing catalyst D include organic bases, organic acids, carboxylic acids, and organometallic compounds (including organic titanates and complexes, or carboxylates of lead, cobalt, iron, nickel, zinc, and tin).
  • Examples of the organic base include tertiary amines, etc.
  • the organometallic compounds include dibutyltin dilaurate, dioctyltin maleate, dibutyltin diacetate, dibutyltin dioctate, stannous acetate, stannous octanoate, lead naphthenate, zinc caprylate, and cobalt naphthenate.
  • the moisture curing catalyst D may be used alone or in combination of two or more types.
  • the content of the moisture curing catalyst D is preferably 0.0001 to 10.0 parts by mass, more preferably 0.0005 to 5.0 parts by mass, and particularly preferably 0.001 to 0.5 parts by mass, relative to 100 parts by mass of the curable resin composition. If the content is 0.0001 to 10.0 parts by mass, the curable resin composition and the hot melt adhesive using the curable resin composition can be easily applied to an adherend.
  • the curable resin composition of the present invention may further contain one or more diluents.
  • the diluents are generally used to reduce the viscosity of the curable resin composition.
  • Such diluents can be used in an amount of typically less than about 50 parts by weight, preferably less than about 40 parts by weight, and more preferably less than about 35 parts by weight, per 100 parts by weight of the curable resin composition of the present invention.
  • Specific examples of such diluents include, but are not limited to, white mineral oil (e.g., Kaydol® oil available from Witco), Shellflex® 371 naphthenic oil (available from Shell Oil Company), and Calsol 5550 (a naphthenic oil from Calumet Lubricants).
  • the curable resin composition of the present invention may further contain one or more tackifiers.
  • the proportion of the tackifier in 100% by mass of the curable resin composition is usually less than 50% by mass, preferably less than 40% by mass, and more preferably less than 35% by mass.
  • the tackifier resin includes, but is not limited to, aliphatic, alicyclic and aromatic hydrocarbons and modified hydrocarbons and their hydrogenated products; terpenes and modified terpenes and their hydrogenated products; rosin and rosin derivatives and their hydrogenated products; and mixtures thereof.
  • tackifier a wide variety of known commercially available products can be used, for example, Eastotac H-100, Eastotac H-115, Eastotac H130, and Eastotac H142 (all trade names, manufactured by Eastman Chemical Co., Ltd.), Escorez 5300, Escorez 5400, Escorez 5600, and Escorez 5637 (all trade names, manufactured by ExxonMobil Chemical Co., Ltd.), Wingtack Extra and Hercolite 2100 (all trade names, manufactured by Goodyear Chemical Co., Ltd.), Zonatac 105 and Zonatac 501 Lite (all trade names, manufactured by Arizona Examples of such products include those manufactured by Epson Corporation.
  • the curable resin composition of the present invention may further contain one or more waxes. If wax is present, it is present in an amount of less than 30%, preferably less than 20%, and more preferably less than 15% by weight based on 100% by weight of the curable resin composition.
  • Useful waxes include paraffin waxes, microcrystalline waxes, high density and low molecular weight polyethylene waxes, pyrolysis waxes, by-product polyethylene waxes, Fischer-Tropsch waxes, oxidized Fischer-Tropsch waxes, functionalized waxes (e.g., hydroxystearamide waxes and fatty amide waxes), and the like. It is common in the art to use the term "synthetic high melting point waxes" to include high density, low molecular weight polyethylene waxes, by-product polyethylene waxes, and Fischer-Tropsch waxes.
  • the curable resin composition of the present invention may further contain one or more antioxidants.
  • the content ratio of the antioxidant in 100% by mass of the curable resin composition is usually 0.5% by mass or less, preferably 0.2% by mass or less.
  • antioxidant a wide variety of known antioxidants can be used, and examples thereof include hindered phenol-based antioxidants (Irganox (registered trademark) 565, 1010 and 1076 manufactured by Ciba-Geigy); phosphorous acid-based antioxidants (Irgafos (registered trademark) 168 manufactured by Ciba-Geigy); Cyanox (registered trademark) LTDP manufactured by Cytec Industries; and Ethanox (registered trademark) 1330 manufactured by Albemarle.
  • hindered phenol-based antioxidants Irganox (registered trademark) 565, 1010 and 1076 manufactured by Ciba-Geigy
  • phosphorous acid-based antioxidants Irgafos (registered trademark) 168 manufactured by Ciba-Geigy
  • Ethanox registered trademark 1330 manufactured by Albemarle.
  • the moisture curing conditions of the curable resin composition are not particularly limited, and conditions that are usually adopted when forming an adhesive layer using a moisture-curable hot melt adhesive may be used.
  • the curing conditions of the curable resin composition layer are not particularly limited, but the curing temperature is preferably 20 to 80°C, and more preferably 50°C to 80°C.
  • the curing time is preferably 1 to 14 days, and more preferably 7 to 14 days.
  • the humidity is preferably 20% RH to 80% RH, and more preferably 50% RH to 80% RH, but it is also preferable to immerse the layer in water at the curing temperature for the curing time.
  • the present invention provides the following aspects.
  • Item 1 A curable resin composition containing modified polyolefin A and modified polyolefin B,
  • the modified polyolefin A has a chemical structure obtained by grafting a moisture-curable functional group onto the polyolefin a
  • the modified polyolefin B has a chemical structure obtained by grafting a moisture-curable functional group onto the polyolefin b
  • the polyolefin b has a nanocrystalline structure
  • the melt viscosity of the curable resin composition is 35,000 cps or less at 140°C.
  • a curable resin composition is 35,000 cps or less at 140°C.
  • Item 2 The curable resin composition according to item 1, wherein the polyolefin b is an ethylene-butylene-propylene copolymer.
  • Item 3 The curable resin composition according to item 1 or 2, wherein the polyolefin b has a melting point of 100 to 190° C.
  • Item 4 The curable resin composition according to any one of items 1 to 3, wherein the polyolefin b has a glass transition temperature of ⁇ 20 to 20° C.
  • Item 5. The curable resin composition according to any one of items 1 to 4, wherein the modified polyolefin B is contained in an amount of 5 to 15 parts by mass relative to 100 parts by mass of the modified polyolefin A.
  • Item 6 The curable resin composition according to any one of items 1 to 5, wherein the polyolefin a is polypropylene.
  • Item 8 The curable resin composition according to any one of items 1 to 7, wherein the polyolefin a has a glass transition temperature of ⁇ 20 to 5° C.
  • Item 9 The curable resin composition according to any one of items 1 to 8, wherein the polyolefin a has a melt viscosity at 140° C. of 20,000 cps or less.
  • Item 11 The curable resin composition according to item 10, wherein the moisture curing accelerator C has an acid functional group and satisfies at least one of a melting point of 70 to 100 ° C. and a softening point of 100 to 140 ° C.
  • Item 12 The curable resin composition according to item 10 or 11, wherein the moisture curing accelerator C is an acid-modified polyolefin.
  • Item 14 The curable resin composition according to item 10 or 11, wherein the moisture curing accelerator C is a rosin compound having an acid functional group.
  • Item 15 The curable resin composition according to any one of items 1 to 9, further comprising 0.0001 to 10.0 parts by mass of a moisture curing catalyst D relative to a total of 100 parts by mass of the modified polyolefin A and the modified polyolefin B, and the moisture curing catalyst D is an organic metal compound.
  • Item 17 A hot melt adhesive comprising the curable resin composition according to any one of items 1 to 16.
  • Polyolefin a-1 Eastoflex P1010 (melting point: 152°C, glass transition temperature: -4°C, number average molecular weight: 5000, manufactured by Eastman Chemical Company)
  • Polyolefin a-2 Lmodu s400 (melting point: 80°C, glass transition temperature: 6°C, number average molecular weight: 25,000, manufactured by Idemitsu Kosan Co., Ltd.)
  • Polyolefin b-1 TAFMER PN2070 (melting point: 140°C, glass transition temperature: -14°C, number average molecular weight: 90200, has a nanocrystalline structure, manufactured by Mitsui Chemicals, Inc.)
  • Polyolefin b-2 TAFMER DF940 (melting point: 77°C, does not have a nanocrystalline structure, manufactured by Mitsui Chemicals, Inc.)
  • Moisture curing accelerator C-1 PMA-L (acid value: 7-8 mgKOH/g, melting point: 70°C, manufactured by Toyobo Co., Ltd.)
  • Moisture curing accelerator C-2 Haritac 4740 (acid value: 25 to 35 mg KOH/g, softening point: 115 to 125°C, manufactured by Harima Chemicals Co., Ltd.)
  • Moisture curing accelerator C-3 Haritac MSR-4 (acid value: 120 to 150 mg KOH/g, softening point: 120 to 135°C, manufactured by Harima Chemicals Co., Ltd.)
  • Moisture curing accelerator C-4 Hariestar AS-5 (acid value: 185-210 mgKOH/g, softening point: 160°C, manufactured by Harima Chemicals Co., Ltd.)
  • Moisture curing accelerator C-5 Pine Crystal KE-604 (acid value: 230-245 mg KOH/g, softening point: 124-134°
  • Moisture curing catalyst D-1 Neostan U-100 (manufactured by Nitto Kasei Co., Ltd.)
  • Modified Polyolefin composition X is a composition that does not contain moisture curing accelerator C and moisture curing catalyst D.
  • Modified Polyolefin Composition Y is a composition containing moisture curing accelerator C or moisture curing catalyst D.
  • Modified polyolefin composition X and moisture curing accelerator C or moisture curing catalyst D in the blending ratios shown in Tables 2 and 3 were added to a benchtop kneader (PBV-0.1 manufactured by Irie Shokai Co., Ltd.), and the mixture was heated at 170°C for 1 hour while being uniformly mixed and dissolved to obtain modified polyolefin composition Y.
  • PBV-0.1 manufactured by Irie Shokai Co., Ltd. a benchtop kneader
  • 11 g of sample was placed in a measurement chamber, heated to 200°C to melt, and then cooled to 140°C, and measured in accordance with the melt viscosity test method for hot melt adhesives of JIS K6862.
  • the spindle No. used for the measurement was No. 27, and the rotation speed was set to 5 rpm.
  • the modified polyolefin composition Y was pressurized and formed into a film under conditions of 10 MPa and 30 seconds in a 140°C environment using a spacer having a thickness of 200 ⁇ m to obtain a film-formed sample.
  • the obtained film-formed sample was cut into a width of 25 mm and a length of 25 mm.
  • the cut-out sample was placed between the following adherend 1 and adherend 2 together with a 100 ⁇ m spacer, and pressed under conditions of 0.1 MPa and 30 seconds in a 160°C environment to prepare an adhesion sample (FIG. 1).
  • "SA-302 tabletop test press" manufactured by Tester Sangyo Co., Ltd. was used to prepare the film-formed sample and the adhesion sample, and a PP plate (thickness: 2 mm) was used as the adherend 1, and cotton canvas No. 9 was used as the adherend 2.
  • the prepared adhesive sample was cured in 60°C hot water for 7 days, and then aged in an environment of 23°C and 50% RH for 1 day to obtain a measurement sample.
  • a weight was placed so that a 100g load was applied vertically to the end of the adhesive surface of the obtained measurement sample ( Figure 2).
  • Figure 2 After 24 hours in a temperature environment of 90°C, 100°C, 110°C, 120°C, or 130°C, if the peel length was less than 10 mm, it was marked as " ⁇ ", and if it was 10 mm or more, it was marked as " ⁇ ". If the judgement was " ⁇ " at 110°C or higher, it could be judged that the heat creep resistance was sufficiently high for practical use.
  • the modified polyolefin composition X or the modified polyolefin Y was pressurized and formed into a film under conditions of 10 MPa and 30 seconds in a 140° C. environment to obtain a film-formed sample.
  • the obtained film-formed sample was cut into a width of 10 mm and a length of 50 mm.
  • the cut-out samples derived from the modified polyolefin composition X were left as they were, while those derived from the modified polyolefin Y were cured in hot water at 60° C. for 7 days and then aged in a 23° C., 50% RH environment for 1 day.
  • the composition and properties of the modified polyolefin composition are shown in Tables 1 to 3. From the results in Tables 2 and 3, it was confirmed that the curable resin composition of the present invention has excellent coatability in a molten state and excellent heat creep resistance properties after the curing reaction. In contrast, it was confirmed that the heat creep resistance properties deteriorated when modified polyolefin B was not included (Comparative Example 1). It was confirmed that the breaking elongation and heat creep resistance properties deteriorated when modified polyolefin B did not have a nanocrystalline structure (Comparative Example 3 using polyolefin b-2). It was confirmed that problems with coatability occurred when the melt viscosity at 140°C exceeded 35,000 cps (Comparative Examples 2, 4, and 5).
  • the curable resin composition of the present invention has excellent coatability and heat creep resistance after the curing reaction, making it suitable for use as a hot melt adhesive.
  • the curable resin composition of the present invention has excellent coatability in a molten state, making it easy to apply and attach to an adherend, and it cures quickly after cooling and solidifying, exhibiting excellent heat creep resistance.
  • the curable resin composition of the present invention can be used for a variety of applications, including adhesives, sealants, waterproofing materials, paints and coatings, lining materials, sealing materials, adhesive tapes, adhesive sheets, pressure-sensitive adhesives, and adhesive processed products.
  • Adherend 1 Adhesive layer 3. Adherent 2 4. Weights

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Abstract

La présente invention concerne une composition de résine durcissable qui présente une excellente aptitude au revêtement à l'état fondu et présente d'excellentes caractéristiques de fluage même dans un environnement à haute température.　La présente invention concerne spécifiquement une composition de résine durcissable qui contient une polyoléfine modifiée A et une polyoléfine modifiée B : la polyoléfine modifiée A ayant une structure chimique qui est obtenue par greffage d'un groupe fonctionnel durcissable à l'humidité sur une polyoléfine a ; la polyoléfine modifiée B ayant une structure chimique qui est obtenue par greffage d'un groupe fonctionnel durcissable à l'humidité sur une polyoléfine b ; la polyoléfine b ayant une structure nanocristalline ; et la viscosité à l'état fondu de la composition de résine durcissable étant de 35 000 cps ou moins à 140°C.
PCT/JP2024/020107 2023-06-01 2024-05-31 Composition de résine durcissable Pending WO2024248150A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010106069A (ja) * 2008-10-28 2010-05-13 Mitsui Chemicals Inc 変性プロピレン重合体およびその組成物、並びにそれを含む積層体
JP2016512855A (ja) * 2013-03-20 2016-05-09 ビック・コーメトラ・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング 官能化された熱可塑性エラストマーの製造方法
WO2018100672A1 (fr) * 2016-11-30 2018-06-07 日立化成株式会社 Composition d'adhésif thermofusible, procédé d'utilisation de composition d'adhésif thermofusible, matériau d'intérieur d'automobile, matériau de surface pré-enduite pour intérieur d'automobile, et procédé de production de matériau d'intérieur d'automobile
WO2018179609A1 (fr) * 2017-03-30 2018-10-04 日立化成株式会社 Composition adhésive
JP2023128798A (ja) * 2022-03-04 2023-09-14 Ｍｃｐｐイノベーション合同会社 シラン変性ポリオレフィン、シラン変性ポリオレフィン組成物、シラン架橋ポリオレフィン、並びにこれらを用いた成形体、架橋成形体、及び三次元網状繊維集合体
JP2023128806A (ja) * 2022-03-04 2023-09-14 Ｍｃｐｐイノベーション合同会社 シラン変性ポリプロピレン、シラン変性ポリプロピレン組成物、シラン架橋ポリプロピレン、及びこれらを用いた成形体、架橋成形体、三次元網状繊維集合体並びに三次元網状繊維集合体の架橋成形体

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010106069A (ja) * 2008-10-28 2010-05-13 Mitsui Chemicals Inc 変性プロピレン重合体およびその組成物、並びにそれを含む積層体
JP2016512855A (ja) * 2013-03-20 2016-05-09 ビック・コーメトラ・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング 官能化された熱可塑性エラストマーの製造方法
WO2018100672A1 (fr) * 2016-11-30 2018-06-07 日立化成株式会社 Composition d'adhésif thermofusible, procédé d'utilisation de composition d'adhésif thermofusible, matériau d'intérieur d'automobile, matériau de surface pré-enduite pour intérieur d'automobile, et procédé de production de matériau d'intérieur d'automobile
WO2018179609A1 (fr) * 2017-03-30 2018-10-04 日立化成株式会社 Composition adhésive
JP2023128798A (ja) * 2022-03-04 2023-09-14 Ｍｃｐｐイノベーション合同会社 シラン変性ポリオレフィン、シラン変性ポリオレフィン組成物、シラン架橋ポリオレフィン、並びにこれらを用いた成形体、架橋成形体、及び三次元網状繊維集合体
JP2023128806A (ja) * 2022-03-04 2023-09-14 Ｍｃｐｐイノベーション合同会社 シラン変性ポリプロピレン、シラン変性ポリプロピレン組成物、シラン架橋ポリプロピレン、及びこれらを用いた成形体、架橋成形体、三次元網状繊維集合体並びに三次元網状繊維集合体の架橋成形体

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