Curable resin composition

Abstract

The present invention provides a curable resin composition that exhibits excellent coatability in a molten state and excellent thermal creep resistance and adhesive strength after a curing reaction.　Specifically, the present invention provides a curable resin composition containing a modified polyolefin A, a modified polyolefin B, and at least one of an organic polymer C and a tackifier D, wherein: the modified polyolefin A comprises a chemical structure obtained by grafting a moisture-curable functional group onto a polyolefin (a); the modified polyolefin B comprises a chemical structure obtained by grafting a moisture-curable functional group onto a polyolefin (b); the organic polymer C is an unmodified polyolefin-based copolymer having a melt viscosity at 170°C of 3 Pa·s or less; and the tackifier D is a hydrocarbon-based resin having a softening point of 100-150°C.

Description

Curable resin composition

[0001] The present invention relates to a curable resin composition.

[0002] Hot melt adhesives have traditionally been used in fields such as building materials, automotive interior materials, and electrical component assembly because they can bond in a short time and do not contain solvents. For example, automotive interior materials (ceilings, doors, seats, etc.) are composed of molded products and skin materials. Polyolefin molded products (polypropylene, polyethylene, etc.) are mainly used as the molded products, and polyolefin skin materials are mainly used as the skin materials. Automotive interior materials are produced by bonding these molded products and skin materials with hot melt adhesives using methods such as press bonding and vacuum forming.

[0003] 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 comprising a styrene block copolymer graft-polymerized with an acrylic monomer, and a silane coupling agent blended therein. Patent Document 2 describes a curable resin composition comprising a reaction product of a modified polyolefin resin modified with an unsaturated carboxylic acid and / or a derivative thereof, and a compound having a functional group reactive with the modified polyolefin resin and a reactive silyl group.

[0004] Japanese Patent Publication No. 2000-303047 Japanese Patent Publication No. 2010-059319

[0005] However, when the curable resin composition described in Patent Document 1 is applied to a substrate, its high viscosity causes problems with coatability. The curable resin composition described in Patent Document 2 has a problem of poor heat creep resistance. It has also been found that adding a low-viscosity component to improve coatability reduces adhesive strength, heat creep resistance, and the like.

[0006] The present invention has been made in view of the above, and an object of the present invention is to provide a curable resin composition that has excellent coatability in a molten state, and excellent heat creep resistance and adhesive strength after a curing reaction.

[0007] As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have found that a curable resin composition having the following properties has excellent coatability in a molten state, and excellent heat creep resistance and adhesive strength after a curing reaction, and have thus completed the present invention.

[0008] The present invention encompasses, for example, the subject matter described in the following items: Item 1. A curable resin composition containing a modified polyolefin A, a modified polyolefin B, and at least one of an organic polymer C and a tackifier D, wherein the modified polyolefin A has a chemical structure obtained by grafting a moisture-curable functional group onto polyolefin a, the modified polyolefin B has a chemical structure obtained by grafting a moisture-curable functional group onto polyolefin b, the organic polymer C is an unmodified polyolefin-based copolymer having a melt viscosity of 3 Pa s or less at 170°C, and the tackifier D is a hydrocarbon-based resin having a softening point of 100 to 150°C.

[0009] The curable resin composition of the present invention exhibits excellent coatability in a molten state, and excellent heat creep resistance and adhesive strength after the curing reaction.

[0010] 1 is a diagram showing a bonded sample in a method for evaluating heat creep resistance; and FIG. 2 is a diagram showing the relationship between a measurement sample and a weight in a method for evaluating heat creep resistance.

[0011] Hereinafter, a curable resin composition according to an embodiment of the present invention will be described. In the following, the notation "to" indicating a numerical range means "less than" or "exceeding," unless otherwise specified. In other words, "A to B" means "A or more and B or less."

[0012] <Curable Resin Composition> The curable resin composition of the present invention is a curable resin composition containing modified polyolefin A, modified polyolefin B, and at least one of organic polymer C and tackifier D. The curable resin composition of the present invention may further contain a moisture-cure-accelerating component E, a diluent, a wax, an antioxidant, etc. The curable resin composition of the present invention can be produced by melt-kneading the constituent components, and may be cooled and solidified to form granules or powder, or may be dissolved or dispersed in a solvent to form a liquid.

[0013] <Modified Polyolefin A and Modified Polyolefin B> The modified polyolefin A in the present invention has a chemical structure obtained by grafting a moisture-curable functional group onto polyolefin a. The modified polyolefin B in the present invention has a chemical structure obtained by grafting a moisture-curable functional group onto polyolefin b. The chemical structure obtained by grafting refers to the chemical structure in a grafted state, and for example, modified polyolefin A can also be expressed as "a chemical structure in which a moisture-curable functional group is grafted onto polyolefin a."

[0014] Examples of the polyolefin a or the polyolefin b include homopolymers of α-olefins polymerized from monomer components 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, and 1-eicosene; copolymers of ethylene with α-olefins other than ethylene, such as ethylene-propylene copolymers, ethylene-propylene-butylene copolymers, and ethylene-propylene-isobutylene copolymers; Examples of the polyolefin-based polymer include copolymers of α-olefins with other monomers copolymerizable with α-olefins (for example, conjugated or non-conjugated dienes such as butadiene, 1,4-hexadiene, 7-methyl-1,6-octadiene, 1,8-nonadiene, and 1,9-decadiene; cyclic olefins such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, norbornene, and dicyclopentadiene); copolymers of isobutylene and isoprene; polychloroprene; polyisoprene; copolymers of isoprene or butadiene with acrylonitrile and / or styrene; and polybutadiene. Among the polyolefin-based polymers described above, in the present invention, from the viewpoint of the adhesion of the curable resin composition to polyolefins and the like, preferred are propylene homopolymers, ethylene-propylene copolymers, ethylene-propylene-butylene copolymers, and ethylene-propylene-isobutylene copolymers, with propylene homopolymers being more preferred.

[0015] 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 Pa·s or less (20,000 cps or less), more preferably 15 Pa·s or less (15,000 cps or less), and even more preferably 10 Pa·s or less (10,000 cps or less), with a lower limit of about 1 Pa·s (about 1,000 cps), although this is not critical. The polyolefin a preferably satisfies two or more of the above-mentioned composition, melting point, glass transition temperature, and melt viscosity ranges, and more preferably satisfies all of them.

[0016] 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-mentioned composition, melting point, and glass transition temperature ranges, and more preferably satisfies all of them.

[0017] The modified polyolefin A and the modified polyolefin B can be produced by known methods. For example, they can be produced by grafting moisture-curable functional groups onto the polyolefin a and the polyolefin b in the presence of a radical initiator or by electron beam irradiation. The grafting reaction may be carried out on the polyolefin a and the polyolefin b individually, or on a mixture of the polyolefin a and the polyolefin b. Examples of the radical initiator include peroxide initiators such as dicumyl peroxide, t-butylperoxyisopropyl carbonate, di-t-butyl peroxide, t-butyl perbenzoate, benzoyl peroxide, cumene hydroperoxide, t-butyl peroctoate, methyl ethyl ketone peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, lauryl peroxide, t-butyl peracetate, t-butyl-α-cumyl peroxide, and di-t-butyl peroxide. Examples of the radical initiator include dicumyl peroxide, di-t-amyl peroxide, t-amyl peroxybenzoate, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, α,α'-bis(t-butylperoxy)-1,3-diisopropylbenzene, α,α'-bis(t-butylperoxy)-1,4-diisopropylbenzene, 2,5-bis(t-butylperoxy)-2,5-dimethylhexane, and 2,5-bis(t-butylperoxy)-2,5-dimethyl-3-hexyne. These radical initiators can be used alone or in combination of two or more. Among these, dicumyl peroxide and t-butylperoxyisopropyl carbonate are preferred.

[0018] Examples of moisture-curable functional groups used in the synthesis of modified polyolefin A and modified polyolefin B include an isocyanate group and a hydrolyzable silyl group. During the synthesis, a compound having a moisture-curable functional group is grafted onto the polyolefin a and the polyolefin b, and a silane-modified monomer containing a hydrolyzable silyl group and an ethylenically unsaturated group can be suitably used as the compound from the viewpoint of reactivity control. Such a silane-modified monomer can be, for example, a compound represented by the following formula (1): X ｎ R ３－ｎ -Si-Y (1) (wherein 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).

[0019] Examples of the hydrolyzable group in the above formula (1) include halogen, alkoxy groups, alkenyloxy groups, acyloxy groups, amino groups, aminooxy groups, oxime groups, and amide groups. The 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 number of hydrolyzable groups bonded to one silicon atom may be one or more. Furthermore, a hydrolyzable group and a non-hydrolyzable group may be bonded to one silicon atom. As the hydrolyzable group bonded to the silicon group, an alkoxy group (such as a monoalkoxy group, a dialkoxy group, or a trialkoxy group) is preferred because of its ease of handling. In the above formula (1), n ​​is preferably 3. Examples of the ethylenically unsaturated group contained in the silane-modified monomer include a vinyl group, an aryl group, an acrylic group, and a methacrylic group. Preferred silane-modified monomers having an ethylenically unsaturated group include vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane.

[0020] 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 (or the amount of that polyolefin when only one of them is used as a raw material). When the amount of radical initiator is 0.5 parts by mass or more, the graft reaction proceeds sufficiently, improving 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. When 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.

[0021] The amount of 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 (or the amount of that polyolefin when only one of them is used as a raw material). When the amount of silane-modified monomer used is 0.5 parts by mass or more, the graft polymerization reaction proceeds sufficiently, and the heat creep resistance and adhesive strength after aging of the curable resin composition and hot melt adhesive using the curable resin composition are further improved. When the amount of 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.

[0022] The melt viscosity of the modified polyolefin A at 140°C is preferably 35 Pa s or less, more preferably 25 Pa s or less, even more preferably 15 Pa s or less, and most preferably 10 Pa s or less, with a lower limit of about 1 Pa s, although not critical. When the melt viscosity of the modified polyolefin A at 140°C is 35 Pa s or less, the curable resin composition and the hot melt adhesive using the curable resin composition can be easily applied to an adherend.

[0023] The melt viscosity of the curable resin composition of the present invention containing the modified polyolefin A and the modified polyolefin B is preferably 35 Pa s or less, more preferably 34 Pa s or less, and even more preferably 33 Pa s or less, with a non-limiting lower limit of about 30 Pa s. When the melt viscosity of the curable resin composition at 140°C is 35 Pa s or less, the curable resin composition and the hot melt adhesive using the curable resin composition can be easily applied to an adherend.

[0024] The melt viscosity of the modified polyolefin A and the curable resin composition containing the modified polyolefin A is a value measured using a Brookfield DVNXRVTJG viscometer. The measurement conditions and determination method were as follows. 11 g of sample was placed in the measurement chamber of a Brookfield DVNXRVTJG viscometer, the sample was heated to 200°C to melt, and then cooled to 140°C, and the viscosity was measured in accordance with the melt viscosity test method for hot melt adhesives of JIS K6862. The spindle No. 27 was used for the measurement, and the rotation speed was set to 5 rpm.

[0025] The melting point (Tm) of the modified polyolefin A is preferably 120°C to 170°C, more preferably 130°C to 160°C. When 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 or the hot-melt adhesive using the curable resin composition cured under any environment, and the creep properties in a high-temperature environment are improved. When 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.

[0026] The melting point (Tm) of the modified polyolefin B is preferably 120°C to 170°C, more preferably 120°C to 150°C. When 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 or the hot-melt adhesive using the curable resin composition cured under any environment, and the creep properties in a high-temperature environment are improved. When 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.

[0027] The melting points (Tm) of modified polyolefin A and modified polyolefin B were determined by DSC measurement using a differential scanning calorimeter (DSC, for example, DuPont V4.OB2000). The measurement conditions and determination method were as follows: 10 mg of a sample was heated from 25°C to 200°C at a rate of 25°C / min under a nitrogen atmosphere, held at 200°C for 5 minutes, and then cooled to 25°C at a rate of 25°C / min. The sample was then heated from 25°C to 200°C at a rate of 25°C / min. The melting point (Tm) was determined as the peak top of the endothermic peak observed at the highest temperature side of the heat of fusion absorption curve detected during this heating process.

[0028] The modified polyolefin A and the modified polyolefin B may or may not have an observable glass transition point. When a glass transition point is observable, the glass transition temperature (Tg) is preferably 15° C. or lower, more preferably −20° C. to 10° C. When the glass transition temperature of the modified polyolefin A and the modified polyolefin B is 15° C. or lower, they do not become too hard even in a low-temperature environment, and can maintain adhesion to a substrate.

[0029] 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 at 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 δ) was calculated. The peak top temperature of the loss tangent tan δ (loss modulus E'' / storage modulus E') in the dynamic viscoelasticity measurement was taken as the glass transition temperature (Tg) [°C].

[0030] The number average molecular weight of the modified polyolefin A is preferably 2,000 to 10,000, more preferably 4,000 to 6,000. When 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 properties in a high-temperature environment, are improved. When 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.

[0031] The number average molecular weight of the modified polyolefin B is preferably 50,000 to 100,000, more preferably 80,000 to 100,000. When 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. When 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.

[0032] 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 measurement device: HLC-8321GPC / HT (manufactured by Tosoh Corporation) Column: Waters Styragel HT3,4,6E Detector: RI Solvent: ortho-dichlorobenzene (containing 0.5 mg / mL of butylated hydroxyltoluene) Measurement temperature: 140°C Flow rate: 0.3 mL / min Sample concentration: 1.2 to 1.7 mg / mL Injection volume: 200 μL Analysis program: GPC data processing system (TOSOH)

[0033] It is preferable that polyolefin b and / or modified polyolefin B have a controlled nanocrystalline structure. Polyolefin b is preferably a thermoplastic polyolefin-based elastomer in which the crystalline / amorphous structure of the polymer is controlled on the nano-order, and the crystals have a network structure on the nano-order. Suitable examples include, but are not limited to, TAFMER (registered trademark) PN-2070, PN-3560, PN-2060, and PN-20300 manufactured by Mitsui Chemicals, Inc. The nanocrystalline structure-controlled polyolefin resin of the present invention has a crystal size controlled on the nano-order, whereas conventional polyolefins have a crystal size on the micron order. Therefore, compared to conventional polyolefin resins, it is often superior in transparency, heat resistance, flexibility, rubber elasticity, and the like. In the present invention, since modified polyolefin B has a controlled nanocrystalline structure, the flexibility of the resulting curable resin composition and hot melt adhesives using the curable resin composition at low temperatures (0°C) is significantly improved. By improving flexibility at low temperatures, the adhesive surface is less likely to peel when the hot melt adhesive cools and solidifies during the bonding process and when the bonded body is used in a cold environment. On the other hand, when a polyolefin resin without a controlled nanocrystalline structure is used, the flexibility of the resulting curable resin composition and the hot melt adhesive using the curable resin composition at low temperatures (0°C) is poor, and the adhesive surface is more likely to peel.

[0034] The breaking elongation at low temperature (0°C) of the resulting 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. When the breaking elongation is 300% or more, the hot melt adhesive tends to be difficult to peel at the bonding surface during the process of cooling and solidifying in the bonding step.

[0035] The breaking elongation at low temperature (0°C) after curing and aging of the resulting curable resin composition and the hot melt adhesive using the curable resin composition is not particularly limited, but is preferably 200% or more, more preferably 250% or more, and even more preferably 300% or more. When the breaking elongation is 200% or more, the bonded body tends to be less likely to peel at the adhesive surface when used in a cold environment.

[0036] The content of 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. Within this content range, the flexibility of the curable resin composition and the hot melt adhesive using the curable resin composition in a low-temperature environment is improved. Furthermore, the adhesive strength at room temperature and in a high-temperature environment, as well as the creep properties in a high-temperature environment, of the cured curable resin composition or the hot melt adhesive using the curable resin composition are improved.

[0037] <Organic Polymer C> The curable resin composition of the present invention contains at least one of organic polymer C and tackifier D. Here, organic polymer C is an unmodified polyolefin copolymer having a melt viscosity of 3 Pa s or less at 170°C. Specific examples of the unmodified polyolefin polymer include ethylene-propylene copolymer, polybutene, polybutadiene, and poly(α-olefin). Of these, ethylene-propylene copolymer is preferred.

[0038] The melt viscosity of the organic polymer C at 170°C is 3 Pa s or less, preferably 2 Pa s or less, more preferably 1 Pa s or less, and even more preferably 0.5 Pa s or less. When the melt viscosity of the organic polymer C at 170°C is 3 Pa s or less, the application of the curable resin composition and the hot melt adhesive using the curable resin composition to an adherend can be further facilitated, and the adhesion to the adherend can be improved.

[0039] The organic polymer C is preferably contained in an amount of 5 to 45 parts by mass, more preferably 10 to 45 parts by mass, and even more preferably 10 to 25 parts by mass, relative to 100 parts by mass of the total of the modified polyolefin A and the modified polyolefin B.

[0040] The organic polymer C is preferably, but not limited to, a liquid at room temperature. Being a liquid at room temperature means being a liquid at 23° C. By satisfying this condition, the adhesiveness between the curable resin composition and the hot melt adhesive using the curable resin composition and the adherend can be further improved.

[0041] Examples of commercially available organic polymer C include "Licocene PPA 330 TP" manufactured by Clariant K.K., some brands of "Lucant" manufactured by Mitsui Chemicals, Inc., and some brands of "Nippon Oil Polybutene" manufactured by ENEOS Corporation (all of which are trade names).

[0042] <Tackifier D> The curable resin composition of the present invention contains at least one of organic polymer C and tackifier D. Here, tackifier D is a hydrocarbon-based resin having a softening point of 100 to 150°C. Examples of such hydrocarbon-based resins include alicyclic hydrocarbon resins; mixed modified aromatic and aliphatic hydrocarbon resins; terpenes, modified terpenes, and hydrogenated versions thereof; natural rosin, modified rosin, rosin esters, and hydrogenated versions thereof; low-molecular-weight polylactic acid, and mixtures thereof. Among these, hydrogenated alicyclic hydrocarbon resins are preferred. The use of tackifier D can improve the adhesion of the curable resin composition and hot-melt adhesives using the curable resin composition to an adherend.

[0043] The softening point of the tackifier D refers to the ring and ball softening point specified in ASTM method E28-58T. The softening point of the tackifier D is 100 to 150°C, preferably 120 to 150°C, and more preferably 130 to 150°C.

[0044] The tackifier D is preferably contained in an amount of 5 to 45 parts by mass, more preferably 10 to 35 parts by mass, and even more preferably 10 to 25 parts by mass, per 100 parts by mass of the total of the modified polyolefin A and the modified polyolefin B.

[0045] Examples of commercially available tackifiers D include YS Resin PX1250, YS Resin TO125, YS Polystar U130, YS Polystar T130, YS Polystar T145, YS Polystar S145, YS Polystar G125, YS Polystar G150, YS Polystar N125, YS Polystar K125, and YS Polystar TH130, all manufactured by Yasuhara Chemical Co., Ltd.; Arcon P125, Arcon P140, and Arcon M135, all manufactured by Arakawa Chemical Industries, Ltd.; Quinton 1920 and Quinton 2940, all manufactured by Nippon Zeon Co., Ltd.; and T-REZ H series and T-REZ Examples include R series, neopolymer 120, neopolymer 130, neopolymer 140, neopolymer 150, neopolymer 170, neopolymer 120s, neopolymer 130s, neopolymer 140s, neopolymer 150s, and neopolymer 170s.

[0046] <Moisture-Cure Accelerator Component E> The curable resin composition of the present invention may contain a moisture-cure accelerator component E. Preferred examples of the moisture-cure accelerator component E include, but are not limited to, acid-modified polyolefin EA, a rosin compound EB having an acid functional group, and a moisture-cure catalyst EC. The moisture-cure accelerator component E may be used alone or in combination of two or more types. Among these, in the case of acid-modified polyolefin EA and / or a rosin compound EB having an acid functional group, it is preferable that the moisture-cure 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.

[0047] The acid-modified polyolefin EA is preferably, but not limited to, one obtained by grafting at least one of an α,β-unsaturated carboxylic acid and its acid anhydride onto a polyolefin resin. Polyolefin resin refers to a polymer primarily composed of a hydrocarbon skeleton, such as a homopolymer of an olefin monomer, exemplified by ethylene, propylene, butene, butadiene, isoprene, etc., or a copolymer with other monomers, or a hydrogenated or halogenated version of the above homopolymer or copolymer. The acid-modified polyolefin EA is preferably one obtained by grafting at least one of an α,β-unsaturated carboxylic acid and its acid anhydride onto at least one of polyethylene, polypropylene, and propylene-α-olefin copolymer.

[0048] Propylene-α-olefin copolymers are copolymers of propylene as the main component with an α-olefin. As the α-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 α-olefins, ethylene and 1-butene are preferred. The ratio of the propylene component to the α-olefin component in the propylene-α-olefin copolymer is not limited, but the propylene component is preferably 50 mol% or more, and more preferably 70 mol% or more.

[0049] Examples of at least one of the α,β-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, and maleic anhydride-modified propylene-ethylene-butene copolymer, and these acid-modified polyolefins can be used alone or in combination of two or more.

[0050] The method for producing the acid-modified polyolefin EA is not particularly limited, and examples thereof include a radical graft reaction (i.e., a reaction in which radical species are generated in a polymer that becomes a main chain, and an unsaturated carboxylic acid and an acid anhydride are graft-polymerized using the radical species as a polymerization initiation point).

[0051] Preferred examples of the acid-modified polyolefin EA include PMA-T, PMA-F2, PMA-HM (all trade names, chlorinated maleic acid-modified polyolefins, manufactured by Toyobo Co., Ltd.), PMA-KH, PMA-L, PMA-LZ (all trade names, maleic acid-modified polyolefins, manufactured by Toyobo Co., Ltd.), Umex 1001, Umex 1010, Umex 100TS, Umex 5500 (all trade names, manufactured by Sanyo Chemical Industry Co., Ltd.), and the like.

[0052] The melting point (Tm) of the acid-modified polyolefin EA is preferably in the range of 70 to 100°C. By setting it to the upper limit or less, excellent coatability and good heat creep resistance properties are achieved. The melting point (Tm) was determined by DSC measurement using a differential scanning calorimeter (DuPont, V4.OB2000 model). 10 mg of a sample was heated from 25°C to 200°C at a rate of 25°C / min under a nitrogen atmosphere, held at 200°C for 5 minutes, and then cooled to 25°C at a rate of 25°C / min. The temperature was then increased from 25°C to 200°C at a rate of 25°C / min. The melting point (Tm) was determined as 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.

[0053] Preferred examples of the rosin compound EB having an acid functional group include unsaturated acid-modified rosin obtained by adding an unsaturated acid such as maleic acid, fumaric acid, or acrylic acid by a 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, etc. Examples of esterified rosin include alkyl esters of rosin, glycerin esters obtained by esterifying rosin with glycerin, and pentaerythritol esters obtained by esterifying rosin with pentaerythritol, etc.

[0054] Specific examples of rosin compounds EB having an acid functional group include Hariestar DS-70L, Halitack R-80, Halitack FK100, Halitack FK125, Halitack SE10, Halitack F85, Halitack PH, Halitack F-75, Halitack FG-90, Halitack T-80, Halitack M-453, Halitack 4740, Halitack MSR-4, Halitack 28JA, Halitack PCJ, and Halitack AS-5 (all trade names, manufactured by Harima Chemicals 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.), and the like.

[0055] The softening point of the rosin compound EB having an acid functional group is preferably 100 to 140°C. By setting the softening point to the upper limit or less, excellent coatability and good heat creep resistance are achieved. In the present invention, the softening point of the rosin compound refers to a value measured using an RSP-202 (manufactured by RIGO Corporation) in accordance with JIS K6863, the softening point test method for hot melt adhesives.

[0056] The moisture-cure-accelerating component EA and / or EB 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.

[0057] The moisture-curing catalyst EC is not particularly limited as long as it can promote the reaction of the moisture-curable functional group possessed by the modified polyolefin A or modified polyolefin B, typically the dehydration condensation reaction of the hydrolyzable silyl group. Examples of moisture-curing catalysts 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 organic bases include tertiary amines. Examples of organometallic compounds include dibutyltin dilaurate, dioctyltin maleate, dibutyltin diacetate, dibutyltin dioctate, stannous acetate, stannous octoate, lead naphthenate, zinc caprylate, and cobalt naphthenate. The moisture-curing catalysts may be used alone or in combination. When the curable resin composition of the present invention contains a moisture-cure catalyst EC, the content of the moisture-cure catalyst EC (particularly an organometallic compound) 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, per 100 parts by mass of the combined total of the modified polyolefin A and the modified polyolefin B. When 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.

[0058] <Antioxidant> When the curable resin composition of the present invention contains an antioxidant as an optional component, the content 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. As the 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), phosphite-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.

[0059] The moisture curing conditions for the curable resin composition are not particularly limited, and conditions typically employed when forming an adhesive layer using a moisture-curable hot melt adhesive may be used. The curing conditions for the curable resin composition layer are not particularly limited, but the curing temperature is preferably 20 to 80°C, more preferably 50 to 80°C. The curing time is preferably 1 to 14 days, more preferably 7 to 14 days. The humidity is preferably 20% RH to 80% RH, more preferably 50% RH to 80% RH, although immersion in water at the curing temperature for the curing time is also preferred.

[0060] The present invention provides the following aspects of the invention. Item 1. A curable resin composition containing a modified polyolefin A, a modified polyolefin B, and at least one of an organic polymer C and a tackifier D, wherein the modified polyolefin A has a chemical structure obtained by grafting a moisture-curable functional group onto polyolefin a, and the modified polyolefin B has a chemical structure obtained by grafting a moisture-curable functional group onto polyolefin b, the organic polymer C is an unmodified polyolefin copolymer having a melt viscosity of 3 Pa·s or less at 170°C, and the tackifier D is a hydrocarbon resin having a softening point of 100 to 150°C. Item 2. The curable resin composition according to Item 1, wherein the melt viscosity of the curable resin composition at 140°C is 35 Pa·s or less. Item 3. The curable resin composition according to Item 1 or 2, wherein 5 to 15 parts by mass of the modified polyolefin B is contained per 100 parts by mass of the modified polyolefin A. Item 4. The curable resin composition according to any one of Items 1 to 3, comprising 5 to 45 parts by mass of the organic polymer C relative to 100 parts by mass of the total of the modified polyolefin A and the modified polyolefin B. Item 5. The curable resin composition according to any one of Items 1 to 4, wherein the organic polymer C is liquid at room temperature (23°C). Item 6. The curable resin composition according to any one of Items 1 to 5, comprising 5 to 45 parts by mass of the tackifier D relative to 100 parts by mass of the total of the modified polyolefin A and the modified polyolefin B. Item 7. The curable resin composition according to any one of Items 1 to 6, wherein the tackifier D is an alicyclic hydrocarbon resin. Item 8. The curable resin composition according to any one of Items 1 to 7, wherein the polyolefin a is polypropylene. Item 9. The curable resin composition according to any one of Items 1 to 8, wherein the polyolefin a has a melting point of 100 to 190°C. Item 10. Item 11. The curable resin composition according to any one of items 1 to 9, wherein the polyolefin a has a glass transition temperature of -20 to 5°C. Item 12. The curable resin composition according to any one of items 1 to 10, wherein the polyolefin a has a melt viscosity at 140°C of 20 Pa s or less.Item 12. The curable resin composition according to any one of Items 1 to 11, wherein the polyolefin b has a nanocrystalline structure. Item 13. The curable resin composition according to any one of Items 1 to 12, wherein the polyolefin b is an ethylene-butylene-propylene copolymer. Item 14. The curable resin composition according to any one of Items 1 to 13, wherein the polyolefin b has a melting point of 100 to 190°C. Item 15. The curable resin composition according to any one of Items 1 to 14, wherein the polyolefin b has a glass transition temperature of -20 to 20°C. Item 16. The curable resin composition according to any one of Items 1 to 15, wherein the organic polymer C is an ethylene-propylene copolymer. Item 17. The curable resin composition according to any one of Items 1 to 16, further comprising 0.5 to 15 parts by mass of a moisture-cure-accelerating component E per 100 parts by mass of the total of the modified polyolefin A and the modified polyolefin B. Item 18. Item 17. The curable resin composition according to item 17, wherein the moisture-cure-accelerating component E 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 19. The curable resin composition according to item 17 or 18, wherein the moisture-cure-accelerating component E is an acid-modified polyolefin. Item 20. The curable resin composition according to item 19, wherein the acid functional group contained in the acid-modified polyolefin is maleic anhydride. Item 21. The curable resin composition according to item 17 or 18, wherein the moisture-cure-accelerating component E is a rosin compound having an acid functional group. Item 22. The curable resin composition according to any one of items 1 to 16, further comprising 0.0001 to 10.0 parts by mass of moisture-cure-accelerating component E per 100 parts by mass of the total of the modified polyolefin A and the modified polyolefin B, and the moisture-cure-accelerating component E is an organometallic compound. Item 23. A hot-melt adhesive containing the curable resin composition according to any one of items 1 to 22.

[0061] First, each component used in preparing the curable resin composition (hot melt adhesive) will be described.

[0062] <Polyolefin a> Polyolefin a-1: Eastoflex P1010 (melting point: 152°C, glass transition temperature: -4°C, number average molecular weight: 5000, manufactured by Eastman Chemical Company)

[0063] <Polyolefin b> Polyolefin b-1: Tafmer PN2070 (melting point: 140°C, glass transition temperature: -14°C, number average molecular weight: 90200, manufactured by Mitsui Chemicals, Inc.)

[0064] <Organic Polymer C> Organic Polymer C-1: Licocene PPA 330 TP (ethylene-propylene copolymer, (melt viscosity at 170°C: 0.2 Pa·s (200 cps) @ 170°C)) Organic Polymer C-2: Licocene PP1602, ethylene-propylene copolymer, (melt viscosity at 170°C: 6 Pa·s (6000 cps) @ 170°C)

[0065] <Tackifier D> Tackifier D-1: Arcon P140 (hydrogenated hydrocarbon, softening point: 130°C, manufactured by Arakawa Chemical Industries, Ltd.) Tackifier D-2: Arcon P90 (hydrogenated hydrocarbon, softening point: 90°C, manufactured by Arakawa Chemical Industries, Ltd.)

[0066] <Moisture-cure accelerator E> Moisture-cure accelerator EA-1 (acid-modified polyolefin): PMA-L (acid value: 7 to 8 mg KOH / g, melting point: 70°C, manufactured by Toyobo Co., Ltd.) Moisture-cure accelerator EB-1 (rosin compound having an acid functional group): HALITACK 4740 (acid value: 25 to 35 mg KOH / g, softening point: 115 to 125°C, manufactured by Harima Chemicals Co., Ltd.) Moisture-cure accelerator EB-2 (rosin compound having an acid functional group): HALITACK MSR-4 (acid value: 120 to 150 mg KOH / g, softening point: 120 to 135°C, manufactured by Harima Chemicals Co., Ltd.) Moisture-cure accelerator EB-3 (rosin compound having an acid functional group): HARIESTAR AS-5 (acid value: 185 to 210 mg KOH / g, softening point: 160°C, manufactured by Harima Chemicals Co., Ltd.) Moisture-cure accelerator EB-4 (rosin compound having an acid functional group): Pine Crystal KE-604 (acid value: 230 to 245 mg KOH / g, softening point: 124 to 134°C, manufactured by Arakawa Chemical Industries, Ltd.) Moisture-cure accelerator EC-1 (moisture-cure catalyst): Neostan U-100 (manufactured by Nitto Kasei Co., Ltd.)

[0067] <Production of Modified Polyolefin Compositions> 1) Production of Modified Polyolefin Composition W Polyolefin, KBM-503 (3-methacryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Polymer Co., Ltd.), and PERBUTYL (registered trademark) I (t-butyl peroxy isopropyl monocarbonate, manufactured by NOF Corporation) in the blending ratios shown in Table 1 were added through the supply port of a twin-screw extruder (KZW15TW-45 / 60MG-NH(-2200) (screw outer diameter 15 mm, L / D=60) manufactured by Technovel Corporation), and while vacuum degassing was performed from the end of the twin-screw extruder, the mixture was kneaded at a barrel temperature of 160°C and an extrusion rate of 1.0 to 1.5 kg / h to obtain modified polyolefin compositions W (W1, W2).

[0068]

[0069] 2) Preparation of Modified Polyolefin Composition X Modified polyolefin composition X was prepared for use in evaluating the properties of modified polyolefin compositions in a state where moisture curing has hardly occurred. Modified polyolefin composition X is a composition that does not contain moisture curing accelerator components EA and EB and moisture curing catalyst EC.

[0070] The modified polyolefin composition W and the organic polymer C or the tackifier D having the blending ratios shown in Tables 2 and 3 were charged into a benchtop kneader (PBV-0.1 manufactured by Irie Shokai Co., Ltd.), and the mixture was uniformly mixed and dissolved while heating at 170°C for 1 hour, thereby obtaining a modified polyolefin X.

[0071] 3) Preparation of Modified Polyolefin Composition Y Modified polyolefin composition Y was prepared for use in evaluating the properties of the modified polyolefin composition after moisture curing. Modified polyolefin composition Y is a composition containing moisture curing accelerator component EA, EB or moisture curing catalyst EC.

[0072] The modified polyolefin composition W, the organic polymer C or the tackifier D, and the moisture-cure-accelerating component E in the blending ratios shown in Tables 2 and 3 were charged into a tabletop kneader (PBV-0.1 manufactured by Irie Shokai Co., Ltd.), and the mixture was uniformly mixed and dissolved while heating at 170°C for 1 hour, thereby obtaining a modified polyolefin Y.

[0073] <Evaluation Method> Evaluations in the examples and comparative examples were carried out by the following measurement methods.

[0074] 1) Evaluation of Coatability The coatability of the modified polyolefin composition X was evaluated based on its melt viscosity at 140°C. If the melt viscosity at 140°C is 35 Pa·s or less, it is evaluated as having no problems in practical use. ◯: The melt viscosity at 140°C is 35 Pa·s or less. ×: The melt viscosity at 140°C is greater than 35 Pa·s. The melt viscosity was measured using a Brookfield-type viscometer (DVNXRVTJG, manufactured by Brookfield) as follows. 11 g of sample was placed in a measurement chamber, heated to 200°C to melt, and then cooled to 140°C. The measurement was performed 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.

[0075] 2) Measurement of Heat Creep Resistance Modified polyolefin composition Y was pressurized using a 200 μm thick spacer at 10 MPa for 30 seconds in a 140°C environment to form a film sample. The resulting film sample was cut into a width of 25 mm and a length of 25 mm. The cut sample was placed between the following adherends 1 and 2 together with a 100 μm spacer, and pressurized at 0.1 MPa for 30 seconds in a 160°C environment to prepare an adhesive sample (Figure 1). The film sample and adhesive sample were prepared using an "SA-302 Tabletop Test Press" manufactured by Tester Sangyo Co., Ltd., using a PP plate (thickness: 2 mm) as adherend 1 and cotton canvas No. 9 as adherend 2.

[0076] The prepared adhesive sample was cured in 60°C hot water for 7 days and then aged in a 23°C, 50% RH environment for 1 day to obtain a measurement sample. A weight was placed on the edge of the adhesive surface of the obtained measurement sample so that a 100g load was applied vertically (Figure 2). After 24 hours in a temperature environment of 90°C, 100°C, 110°C, 120°C, or 130°C, a peel length of less than 10 mm was evaluated as "Good" and a peel length of 10 mm or more was evaluated as "Poor." Note that if the evaluation was "Good" at 110°C or higher, it was determined that the heat creep resistance was sufficiently high for practical use.

[0077] 3) Measurement of Adhesion Strength Modified polyolefin composition Y was pressurized using a 200 μm thick spacer at 10 MPa for 30 seconds in a 140°C environment to form a film sample. The obtained film sample was cut into a width of 25 mm and a length of 25 mm. The cut sample was placed between the following adherends 1 and 2 together with a 100 μm spacer, and pressed at 0.1 MPa for 30 seconds in a 160°C environment to prepare an adhesive sample. Note that an "SA-302 Tabletop Test Press" manufactured by Tester Sangyo Co., Ltd. was used to prepare the film sample and adhesive sample, and a PP plate (thickness: 2 mm) was used as adherend 1 and cotton canvas No. 9 was used as adherend 2.

[0078] The prepared adhesive sample was cured in 60°C hot water for 7 days, and then aged for 1 day in an environment of 23°C and 50% RH to obtain a measurement sample. The obtained measurement sample was subjected to a 180-degree peel test using a "TENSILON universal material testing machine" RTA-100 manufactured by ORIENTEC under the following conditions: Temperature: 23±2°C (in a constant temperature and humidity chamber) Distance between chucks: 80 mm Peel speed: 300 mm / min The adhesive strength was evaluated based on whether it was improved compared to Comparative Example 1, which was a case in which organic polymer C and tackifier D were not blended but a moisture curing catalyst was blended. ◯: Adhesive strength was improved ×: Adhesive strength was the same or decreased

[0079] 4) Measurement of Breaking Elongation Using a 500 μm thick spacer, modified polyolefin composition X or modified polyolefin Y was pressurized and formed into a film under conditions of 10 MPa for 30 seconds in a 140°C environment, to obtain a film sample. The obtained film sample was cut into a width of 10 mm and a length of 50 mm. Of the cut samples, those derived from modified polyolefin composition X were used as is, while those derived from modified polyolefin Y were cured in 60°C hot water for 7 days and then aged in a 23°C, 50% RH environment for 1 day. Then, a tensile strength test was carried out under the following conditions using an RTA-100 "TENSILON universal material testing machine" manufactured by ORIENTEC Co., Ltd. Temperature: 0±2°C (in a constant temperature and humidity chamber) Distance between chucks: 20 mm Tensile speed: 300 mm / min

[0080] The compositions and properties of the modified polyolefin compositions are shown in Tables 1 to 4. The results in Tables 2 to 4 demonstrate that the curable resin compositions of the present invention have excellent coatability in a molten state and excellent heat creep resistance and adhesive strength after the curing reaction. In contrast, it was confirmed that the adhesive strength was low when neither organic polymer C nor tackifier D was included (Comparative Example 1). It was confirmed that the coatability was poor when the melt viscosity of organic polymer C was too high (Comparative Example 2). It was confirmed that the heat creep resistance was poor when the softening point of tackifier D was too low (Comparative Example 3).

[0081] The curable resin composition of the present invention has excellent coatability in a molten state, and excellent heat creep resistance and adhesive strength after the curing reaction, and can be suitably used as a hot melt adhesive.

[0082]

[0083]

[0084]

[0085] The curable resin composition of the present invention has excellent coatability in a molten state, allowing for easy application and lamination to an adherend, and also cures rapidly after cooling and solidifying, thereby exhibiting excellent heat creep resistance. The curable resin composition of the present invention can be used for a variety of purposes, such as adhesives, sealants, waterproofing materials, paints and coating materials, lining materials, sealing materials, pressure-sensitive adhesives, adhesive tapes, pressure-sensitive adhesive sheets, pressure-sensitive adhesives, and adhesive-processed products.

[0086] 1. Adherend 1 2. Adhesive layer 3. Adherend 2 4. Weight

Claims

1. A curable resin composition containing modified polyolefin A, modified polyolefin B, and at least one of organic polymer C and tackifier D, wherein the modified polyolefin A has a chemical structure obtained by grafting a moisture-curable functional group to polyolefin a, the modified polyolefin B has a chemical structure obtained by grafting a moisture-curable functional group to polyolefin b, the organic polymer C is an unmodified polyolefin-based copolymer having a melt viscosity of 3 Pa·s or less at 170°C, and the tackifier D is a hydrocarbon-based resin having a softening point of 100 to 150°C.

2. The curable resin composition according to claim 1, wherein the melt viscosity of the curable resin composition at 140°C is 35 Pa·s or less.

3. The curable resin composition according to claim 1, wherein the modified polyolefin B is contained in an amount of 5 to 15 parts by mass per 100 parts by mass of the modified polyolefin A.

4. The curable resin composition according to claim 1, comprising 5 to 45 parts by mass of said organic polymer C per 100 parts by mass of the total of said modified polyolefin A and said modified polyolefin B.

5. The curable resin composition according to claim 1, wherein the organic polymer C is liquid at room temperature (23°C).

6. The curable resin composition according to claim 1, comprising 5 to 45 parts by mass of said tackifier D per 100 parts by mass of the total of said modified polyolefin A and said modified polyolefin B.

7. The curable resin composition according to claim 1, wherein said tackifier D is an alicyclic hydrocarbon resin.

8. The curable resin composition according to claim 1, wherein the polyolefin a is polypropylene.

9. The curable resin composition according to claim 1, wherein the melting point of said polyolefin a is 100 to 190°C.

10. The curable resin composition according to claim 1, wherein the polyolefin a has a glass transition temperature of -20 to 5°C.

11. The curable resin composition according to claim 1, wherein the melt viscosity of the polyolefin a at 140°C is 20 Pa·s or less.

12. The curable resin composition according to claim 1, wherein the polyolefin b has a nanocrystalline structure.

13. The curable resin composition according to claim 1, wherein the polyolefin b is an ethylene-butylene-propylene copolymer.

14. The curable resin composition according to claim 1, wherein the melting point of said polyolefin b is 100 to 190°C.

15. The curable resin composition according to claim 1, wherein the polyolefin b has a glass transition temperature of -20 to 20°C.

16. The curable resin composition according to claim 1, wherein the organic polymer C is an ethylene-propylene copolymer.

17. The curable resin composition according to claim 1, further comprising 0.5 to 15 parts by mass of a moisture-curing accelerator component E per 100 parts by mass of the combined total of the modified polyolefin A and the modified polyolefin B.

18. The curable resin composition according to claim 17, wherein the moisture-cure-accelerating component E 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.

19. The curable resin composition according to claim 17, wherein the moisture cure-accelerating component E is an acid-modified polyolefin.

20. The curable resin composition according to claim 19, wherein the acid functional group contained in the acid-modified polyolefin is maleic anhydride.

21. The curable resin composition according to claim 17, wherein the moisture cure accelerator component E is a rosin compound having an acid functional group.

22. The curable resin composition according to claim 1, further comprising 0.0001 to 10.0 parts by mass of a moisture-cure accelerator component E per 100 parts by mass of the combined total of the modified polyolefin A and the modified polyolefin B, the moisture-cure accelerator component E being an organometallic compound.

23. A hot melt adhesive comprising the curable resin composition according to any one of claims 1 to 22.

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