WO2020004598A1 - Hot melt adhesive containing specific propylene resin composition - Google Patents

Hot melt adhesive containing specific propylene resin composition Download PDF

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Publication number
WO2020004598A1
WO2020004598A1 PCT/JP2019/025745 JP2019025745W WO2020004598A1 WO 2020004598 A1 WO2020004598 A1 WO 2020004598A1 JP 2019025745 W JP2019025745 W JP 2019025745W WO 2020004598 A1 WO2020004598 A1 WO 2020004598A1
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WO
WIPO (PCT)
Prior art keywords
melt adhesive
hot melt
nucleating agent
polypropylene resin
adhesive according
Prior art date
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PCT/JP2019/025745
Other languages
French (fr)
Japanese (ja)
Inventor
望 藤井
金丸　正実
麻未 古賀
武治 田島
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出光興産株式会社
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Publication of WO2020004598A1 publication Critical patent/WO2020004598A1/en

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    • 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
    • C09J123/02—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 not modified by chemical after-treatment
    • C09J123/10—Homopolymers or copolymers of propene
    • 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
    • C09J123/02—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 not modified by chemical after-treatment
    • C09J123/10—Homopolymers or copolymers of propene
    • C09J123/12—Polypropene

Definitions

  • the present invention relates to a hot melt adhesive, and more particularly, to a hot melt adhesive containing a specific propylene-based resin composition.
  • Hot melt adhesives are solventless adhesives, which are applied to an adherend by heating and melting, then solidify by cooling, and exhibit adhesiveness. BACKGROUND ART In recent years, hot melt adhesives have been widely used in various fields because they are excellent in high-speed coating properties, quick-curing properties, solvent-free properties, barrier properties, energy saving properties, economy, and the like.
  • polypropylene polymers are widely used as base polymers for hot melt adhesives from the viewpoint of thermal stability.
  • low molecular weight polypropylene polymerized by metallocene catalyst has high fluidity, excellent coatability when used as a hot melt adhesive, excellent adhesive strength of low polar substances such as polypropylene, and heat stability during heat melting. Because of its excellent properties, it can be suitably used as a base polymer for various hot melt adhesives (Patent Documents 1 to 3).
  • the hot melt adhesive using this has a relatively slow solidification time, has good adherence to the adherend, and has good adhesion.
  • the adhesive because it is hard to solidify, for example, when laminating and bonding a porous substrate such as a nonwoven fabric, the adhesive exudes from the adhesive application surface side to the opposite surface, so-called back side A phenomenon called omission is likely to occur.
  • an object of the present invention is to provide a hot melt adhesive having an excellent solidification rate.
  • the present disclosure relates to the following. ⁇ 1> Using a differential scanning calorimeter (DSC), a sample is held at ⁇ 10 ° C. for 5 minutes in a nitrogen atmosphere, and then heated at a rate of 10 ° C./min.
  • DSC differential scanning calorimeter
  • a hot melt adhesive comprising a polypropylene resin (A) having a calorific value ( ⁇ HD) of more than 0 J / g and 80 J / g or less and a nucleating agent (B), wherein the content of the nucleating agent (B) Is from 5 mass ppm to 50,000 mass ppm with respect to 100 parts by mass of the polypropylene resin (A).
  • ⁇ HD calorific value
  • B nucleating agent
  • the melting point (Tm-D) defined as the observed peak top is not observed or is 0 ° C or more and 120 ° C or less.
  • Tm-D The hot melt adhesive according to ⁇ 1> or ⁇ 2>, wherein the polypropylene resin (A) has a weight average molecular weight (Mw) of 5,000 to 300,000.
  • Mw weight average molecular weight
  • ⁇ 4> The hot melt adhesive according to any one of the above ⁇ 1> to ⁇ 3>, wherein a half-crystallization time of the polypropylene resin (A) at 25 ° C. is 3 minutes or more.
  • ⁇ 5> The hot melt adhesive according to any one of ⁇ 1> to ⁇ 4> above, wherein the polypropylene resin (A) is a propylene homopolymer.
  • the polypropylene-based resin (A) contains at least one structural unit selected from the group consisting of ethylene and ⁇ -olefins having 4 to 30 carbon atoms in an amount of more than 0 mol% and 20 mol% or less.
  • the hot melt adhesive according to any one of ⁇ 4> to ⁇ 4>.
  • the nucleating agent (B) is at least one selected from the group consisting of an acetal nucleating agent, an amide nucleating agent and an organic metal salt nucleating agent. The hot melt adhesive according to one.
  • nucleating agent (B) is at least one selected from the group consisting of a sorbitol-based nucleating agent and a nonitol-based nucleating agent. adhesive.
  • nucleating agent (B) is at least one selected from the group consisting of a carboxamide nucleating agent and a triamide nucleating agent. adhesive.
  • nucleating agent (B) is a metal phenylphosphonate-based nucleating agent.
  • ⁇ 11> The hot melt adhesive according to ⁇ 10>, wherein there is substantially no visible white spot-like aggregation caused by the nucleating agent.
  • ⁇ 12> The hot melt adhesive according to any one of ⁇ 1> to ⁇ 11>, further including a tackifier (D).
  • ⁇ 13> The hot melt adhesive according to any one of ⁇ 1> to ⁇ 12>, further including an oil (E).
  • E oil
  • ⁇ 14> The hot melt adhesive according to any one of ⁇ 1> to ⁇ 13>, further including a linear hydrocarbon wax (F).
  • ⁇ 15> The hot melt adhesive according to any one of ⁇ 1> to ⁇ 14>, further comprising an ethylene polymer (G).
  • the hot melt adhesive of the present invention has an excellent solidification rate.
  • the term “A to B” regarding the description of numerical values means “A or more and B or less” (when A ⁇ B) or “A or less B or more” (when A> B). .
  • a combination of preferred embodiments is a more preferred embodiment.
  • melting endotherm ⁇ H-D
  • melting point Tm-D
  • weight average molecular weight Mw
  • Mn molecular weight distribution
  • the hot melt adhesive of this embodiment is a hot melt adhesive containing a polypropylene resin (A) having a melting endotherm ( ⁇ HD) of more than 0 J / g and 80 J / g or less and a nucleating agent (B).
  • a hot melt adhesive wherein the content of the nucleating agent (B) is 5 mass ppm or more and 50,000 mass ppm or less based on 100 parts by mass of the polypropylene resin (A).
  • the polypropylene resin (A) is preferably contained as a base polymer of the hot melt adhesive.
  • the base polymer of the hot melt adhesive may further contain a specific ethylene polymer (G) in addition to the polypropylene resin (A).
  • the polypropylene resin (A) used in the present embodiment is obtained by holding a sample at ⁇ 10 ° C. for 5 minutes in a nitrogen atmosphere using a differential scanning calorimeter (DSC), and then heating the sample at 10 ° C./min.
  • This is a polypropylene resin having a melting endotherm ( ⁇ HD) obtained from the obtained melting endothermic curve of more than 0 J / g and 80 J / g or less. If the melting endotherm ( ⁇ H ⁇ D) exceeds 80 J / g, the interfacial adhesive strength may decrease.
  • the melting endotherm ( ⁇ H-D) is preferably 20 J / g or more, more preferably 25 J / g or more, further preferably 27 J / g or more, and still more preferably, from the viewpoint of the adhesive strength and flexibility of the hot melt adhesive. Is 30 J / g or more, and preferably 50 J / g or less, more preferably 45 J / g or less, and still more preferably 40 J / g or less.
  • the above-mentioned melting endotherm ( ⁇ H ⁇ D) is defined as the highest temperature of the melting endotherm curve obtained by the DSC measurement using a line connecting the low-temperature side point with no calorific value change and the high-temperature side point with no calorific value change as a baseline.
  • the melting endotherm ( ⁇ HD) can be controlled by appropriately adjusting the monomer concentration and the reaction pressure.
  • the DSC used for the measurement must have been calibrated in advance on the same day.
  • the calibration described here indicates a temperature calibration using indium (In) and lead (Pb) as a standard sample and a calorimetric calibration using In as a standard sample.
  • the extrapolation melting onset temperatures of In and Pb were ⁇ 0.3 ° C.
  • the polypropylene resin (A) preferably satisfies the following (1).
  • (1) Using a differential scanning calorimeter (DSC), the sample was kept at ⁇ 10 ° C. for 5 minutes in a nitrogen atmosphere, and then heated at a rate of 10 ° C./min.
  • the melting point (Tm-D) defined as the observed peak top is not observed or is 0 ° C or more and 120 ° C or less.
  • the melting point (Tm-D) of the polypropylene resin (A) is not observed or is 0 ° C or more and 120 ° C or less from the viewpoint of the adhesive strength of the hot melt adhesive.
  • a melting point is observed, from the same viewpoint, it is more preferably at least 30 ° C, still more preferably at least 45 ° C, still more preferably at least 60 ° C, particularly preferably at least 75 ° C, and more preferably
  • the temperature is 100 ° C. or lower, more preferably 90 ° C. or lower, even more preferably 85 ° C. or lower.
  • the melting point can be controlled by appropriately adjusting the monomer concentration and the reaction pressure.
  • the weight average molecular weight (Mw) of the polypropylene resin (A) is preferably 5,000 or more, more preferably 15,000 or more, and still more preferably 30,000 or more, from the viewpoint of adhesive strength. From the viewpoint of coatability, it is preferably 300,000 or less, more preferably 200,000 or less, and still more preferably 150,000 or less.
  • the weight average molecular weight (Mw) is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.
  • the molecular weight distribution (Mw / Mn) of the polypropylene resin (A) is preferably 3.0 or less, more preferably 2.8 or less, further preferably 2.6 or less, and still more preferably 2.5 or less, And it is 1.5 or more, More preferably, it is 1.6 or more, More preferably, it is 1.7 or more, More preferably, it is 1.8 or more.
  • the molecular weight distribution (Mw / Mn) is a value calculated from the weight average molecular weight Mw and the number average molecular weight Mn in terms of polystyrene measured by gel permeation chromatography (GPC).
  • the semi-crystallization time when the polypropylene resin (A) is rapidly cooled to 25 ° C. from the molten state is preferably 3 minutes or more from the viewpoint of adhesiveness or from the molten state by a differential scanning calorimeter (DSC). No crystallization peak measured in the process of cooling at ⁇ 10 ° C./min is observed. It is more preferably at least 10 minutes, even more preferably at least 15 minutes, particularly preferably at least 20 minutes.
  • the half-crystallization time of the polypropylene resin (A) was measured by using a differential scanning calorimeter (DSC) (manufactured by Perkin-Elmer Co., Ltd., trade name: “DSC-7”) at 10 ° C.
  • DSC differential scanning calorimeter
  • the temperature is raised to 220 ° C. at 320 ° C./min and held for 5 minutes, then cooled to 25 ° C. at 320 ° C./min, and held for 60 minutes to measure the time change of the calorific value during the isothermal crystallization process.
  • the integrated value of the calorific value from the start of isothermal crystallization to the completion of crystallization is 100%
  • the time from the start of isothermal crystallization until the integrated value of the calorific value becomes 50% is the isothermal half-crystallization. Is defined as the conversion time (t 1/2 ).
  • the polypropylene-based resin (A) is not particularly limited as long as the above-mentioned melting endotherm ( ⁇ HD) satisfies the above range.
  • ⁇ HD melting endotherm
  • the propylene polymer is preferably selected from the group consisting of: Among them, a propylene homopolymer and a propylene-ethylene random copolymer are more preferable, and a propylene homopolymer is more preferable.
  • the polypropylene resin (A) is a copolymer
  • it contains at least one structural unit selected from the group consisting of ethylene and ⁇ -olefins having 4 to 30 carbon atoms, in an amount of more than 0 mol% and not more than 20 mol%.
  • This is preferable from the viewpoint of suppressing the occurrence of bumps due to crosslinking and increasing the flexibility of the resin composition. From such a viewpoint, it is more preferably at least 0.5 mol%, further preferably at least 1.0 mol%, and more preferably at most 18.5 mol%, further preferably at most 15.0 mol%, It is even more preferably at most 10.0 mol%.
  • the structural unit of the olefin having 2 carbon atoms is preferably 0 mol%. It is more than 20 mol%, more preferably more than 0 mol% and 18 mol% or less, further preferably more than 0 mol% and 16 mol% or less, even more preferably more than 0 mol% and 14 mol% or less.
  • the content of ⁇ -olefins having 4 or more carbon atoms is preferably more than 0 mol% and 30 mol% or less, more preferably 0 mol% or less. It is more than 25 mol% and more preferably more than 0 mol% and 20 mol% or less.
  • a commercially available product can be used as the polypropylene resin (A). Specific examples include “S400”, “S410”, “S600”, and “S901” of “L-MODU” (registered trademark) (manufactured by Idemitsu Kosan Co., Ltd.).
  • Commercially available amorphous poly- ⁇ -olefins (APAO) include “Rextac” manufactured by LLC, “Vestoplast” manufactured by Evonik, “Eastflex”, “Aerafin” manufactured by Eastman, etc. Name).
  • propylene elastomers include “Tuffmer XM”, “Tuffmer PN”, and “Tuffmer SN” manufactured by Mitsui Chemicals, Inc .; “Prime TPO” manufactured by Prime Polymer Co., Ltd .; and Dow Chemical Co., Ltd. "Versify”; “Vistamaxx” and “Linxar” manufactured by ExxonMobil, “Licosene” manufactured by Clariant; "Adflex” manufactured by Bathell, and the like (all are trade names).
  • the polypropylene resin (A) can be obtained by polymerizing a monomer in the presence of a polymerization catalyst such as a Ziegler-Natta type catalyst or a metallocene catalyst.
  • a polymerization catalyst such as a Ziegler-Natta type catalyst or a metallocene catalyst.
  • the polypropylene resin (A) is preferably a polypropylene resin obtained with a metallocene catalyst.
  • the metallocene catalyst is a kind of homogeneous catalyst, and the resulting polymer is a uniform polymer having a narrow molecular weight distribution and a narrow composition distribution.
  • the content of the polypropylene resin (A) in the hot melt adhesive is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass, based on 100% by mass of the resin component (base polymer). %, More preferably 15% by mass or more, particularly preferably 25% by mass.
  • the upper limit is not particularly limited, but may be 100% by mass, 90% by mass or less, 85% by mass or less, or 80% by mass or less.
  • the polypropylene resin (A) in the hot melt adhesive may be of one type or two or more types.
  • the hot melt adhesive of the present embodiment contains a nucleating agent (B). Since the polypropylene-based resin (A) has a low crystallization rate, a hot-melt adhesive using the same has a relatively slow solidification time, good adherence to an adherend, and excellent adhesion. On the other hand, since it is difficult to solidify, a phenomenon called so-called strike-through, in which the adhesive exudes from the adhesive-coated surface to the opposite surface, is likely to occur.
  • the hot melt adhesive of the present embodiment contains the nucleating agent (B), whereby the crystallization speed of the polypropylene resin (A) is improved, and the solidification speed is excellent. As a result, the strike-through of the adhesive during the application of the adhesive can be suppressed.
  • the nucleating agent (B) is preferably one that induces crystallization quickly without lowering the physical properties of the polypropylene resin (A) and raises the crystallization temperature required for crystallization to start.
  • Specific examples of the nucleating agent (B) include acetal-based nucleating agents such as sorbitol and nonitol; amide-based nucleating agents such as carboxamide, triamide, and bisamide; metal phosphate salts, metal carboxylate salts, and metal phenylphosphonate.
  • the nucleating agent (B) is at least one selected from the group consisting of acetal nucleating agents, amide nucleating agents, and organic metal salt nucleating agents. Is preferred. Further, these may be used in combination.
  • the nucleating agent (B) may be added as a master batch within a range that does not affect the properties of the polypropylene resin (A).
  • the effect of improving the crystallization rate of the above nucleating agent varies depending on the temperature conditions during kneading and the concentration to be added, it is desirable to optimize the conditions according to each nucleating agent.
  • the effect of improving the crystallization rate when kneaded at preferably 260 to 320 ° C., more preferably 280 to 300 ° C. Becomes larger.
  • “Irgclear XT386” manufactured by BASF is preferably 5 to 1,000 ppm by mass, more preferably 10 to 500 ppm by mass, and still more preferably 50 to 200 ppm by mass with respect to 100 parts by mass of the polypropylene resin (A). When added at a concentration of ppm by mass, the effect of improving the crystallization rate is increased. Furthermore, “Eco Promote C” manufactured by Nissan Chemical Industries, Ltd. or the like is preferably in a good dispersion state, whereby the effect of improving the crystallization rate is increased.
  • the acetal-based nucleating agent is preferably at least one selected from the group consisting of sorbitol-based nucleating agents and nonitol-based nucleating agents.
  • sorbitol derivatives for example, 1,3: 2,4-bis-O-benzylidene-D-glucitol-dibenzylidene sorbitol, 1,3: 2,4-bis-O- (4-methylbenzylidene) -D-sorbitol , 1,3: 2,4-bis-O- (3,4-dimethylbenzylidene) sorbitol, bis (4-propylbenzylidene) propylsorbitol, nonitol, 1,2,3-trideoxy-4,6: 5,7 -Bis-o-[(4-propylphenyl) methylene] and mixtures thereof.
  • the amide nucleating agent is preferably at least one selected from the group consisting of a carboxamide nucleating agent and a triamide nucleating agent, and a carboxamide nucleating agent is particularly preferred.
  • the amide nucleating agent include N, N'-dicyclohexyl-2,6-naphthalenedicarboxamide, 1,3,5-tris [2,2-dimethylpropyl-amino] benzene, N, N ', N "-tris [2-Methylcyclohexane-1-yl] -propane-1,2,3-triylcarboxamide, N, N′-ethylenebisstearic acid amide, etc.
  • amide-based nucleating agents include Shin-Nippon Rika ( “Nrgester NU-100” manufactured by BASF, “Irgclear @ XT386” manufactured by BASF, and “Likaclear PC1” manufactured by Nippon Rika Co., Ltd.
  • the organic metal salt nucleating agent is in the form of fine powder and is used by dispersing it in a resin.
  • the organic metal salt nucleating agent include a phosphoric acid ester metal salt, a carboxylic acid metal salt, and a phenylphosphonic acid metal salt.
  • phosphoric acid is preferred from the viewpoint of improving the crystallization rate of the polypropylene resin (A).
  • Ester metal salts and phenylphosphonic acid metal salt nucleating agents are preferred, and phenylphosphonic acid metal salt nucleating agents are particularly preferred.
  • organic metal salt-based nucleating agents include "ADKSTAB @ NA-11", “ADKSTAB @ NA-21” and “ADKSTAB @ NA-27” manufactured by ADEKA, “Hostanox 4030” manufactured by Clariant, and “Milken Chemical”. HPN-68L "Eco-promote C” manufactured by Nissan Chemical Industries, Ltd. and the like.
  • the content of the nucleating agent (B) in the hot melt adhesive is determined from the viewpoint of improving the crystallization speed of the polypropylene resin (A) without deteriorating the physical properties of the polypropylene resin (A).
  • A) It is at least 5 ppm by mass, preferably at least 10 ppm by mass, more preferably at least 50 ppm by mass with respect to 100 parts by mass, and 50,000 parts by mass from the viewpoint of dispersibility in the polypropylene resin (A).
  • ppm preferably 20,000 mass ppm or less, more preferably 5,000 mass ppm or less, still more preferably 1,000 mass ppm or less, further preferably 500 mass ppm or less, and still more preferably 200 mass ppm or less.
  • the hot melt adhesive of the present invention is preferably substantially free from visible white spot-like aggregation caused by the nucleating agent when visually observed.
  • the hot melt adhesive of the present embodiment may further contain a tackifier (D).
  • a tackifier (D) for example, a solid, semi-solid or liquid at room temperature composed of a hydrogenated derivative of an aliphatic hydrocarbon petroleum resin, a rosin derivative resin, a polyterpene resin, a petroleum resin, an oil-soluble phenol resin, or the like. And the like.
  • tackifiers Commercially available products of the tackifier (D) include the following.
  • Examples of the tackifiers produced using crude oil and the raw material obtained in the naphtha refining process include “I-MARV” (manufactured by Idemitsu Kosan Co., Ltd.), “ALCON” (manufactured by Arakawa Chemical Industry Co., Ltd.), “Quinton” ( Nippon Zeon Co., Ltd.), “T-REZ” (JXTG Energy Co., Ltd.), “Escorez”, “Opera” (all from ExxonMobil Chemical), “Eastotac", “Regalite”, “Regalrez”, “Plastolyn” (all from Eastman), “Sukolez” (Kolon), “Wingtack", “Norsolene” (all from Cray Valley) and the like can be mentioned (all are trade names).
  • Examples of the tackifier manufactured using an essential oil obtained from orange or the like as a raw material include “Clearon” (manufactured by Yashara Chemical Co., Ltd.) and “Sylvalite” and “Sylvares” (manufactured by Arizona Chemical). (All are trade names).
  • Examples of tackifiers manufactured using raw materials such as rosin include “Haritac”, “Neotol” (manufactured by Harima Chemicals, Inc.), “Ester Gum”, and “Pencel” (manufactured by Arakawa Chemical Industries, Ltd.). (Both are trade names).
  • the content of the tackifier (D) in the hot-melt adhesive is preferably based on 100 parts by mass of the resin component (base polymer) in the hot-melt adhesive from the viewpoint of improving tackiness and applicability. Is 20 parts by mass or more, more preferably 30 parts by mass or more, still more preferably 40 parts by mass or more, even more preferably 50 parts by mass or more, and preferably 200 parts by mass or less, more preferably 150 parts by mass or less, More preferably, it is 120 parts by mass or less, even more preferably 100 parts by mass or less.
  • the softening point of the tackifier (D) is not particularly limited. However, if the softening point is too high, the viscosity of the hot-melt adhesive at the time of coating increases, so that the coatability deteriorates and the softening point is too low. In addition, the thermal stability of the hot melt adhesive becomes poor, and seizure occurs in the melter, which adversely affects the adhesiveness and odor.
  • the softening point of the tackifier (D) is preferably 80 ° C. or higher, more preferably 85 ° C. or higher, even more preferably 90 ° C. or higher, and preferably 130 ° C. or lower, more preferably It is 120 ° C. or lower, more preferably 110 ° C. or lower.
  • the hot melt adhesive of the present embodiment may further contain an oil (E).
  • the oil (E) is not particularly limited, and mineral oils such as paraffin-based process oil, naphthene-based process oil and isoparaffin-based oil, aromatic mineral oil-based hydrocarbons, polybutene, polyisobutylene, polybutadiene, and poly ( ⁇ ) -Olefin) and other synthetic resin-based hydrocarbons such as low molecular weight products, alkylbenzenes, castor oil, linseed oil, rapeseed oil, fatty oil-based softeners such as coconut oil, dibutyl phthalate, dioctyl phthalate, dioctyl adipate, dioctyl sebacate, etc.
  • Ester plasticizers and the like are preferred, and at least one selected from the group consisting of mineral oil-based hydrocarbons, paraffin-based process oils, and naphthene-based process oils is preferred, and paraffin-based hydrocarbons have a carbon number of 50% of the total carbon number. Oil is particularly preferred.
  • the weight average molecular weight of the mineral oil-based hydrocarbon is preferably from 50 to 2,000, particularly preferably from 100 to 1,500, and the pour point is preferably from -40 to 0 ° C, particularly preferably from -30 to 0 ° C.
  • the (COC method) is preferably at 200 to 400 ° C., particularly 250 to 350 ° C.
  • the pour point is a value measured according to JIS K2269, and the flash point is a value measured according to JIS K2265.
  • the kinematic viscosity of the oil (E) at 40 ° C. is preferably 5 cSt or more and 800 cSt or less, more preferably 10 cSt or more and 500 cSt or less.
  • the kinematic viscosity is a value measured according to ISO3104.
  • paraffin-based process oils include “Diana Process Oil PW-32”, “Diana Process Oil PW-90”, “Diana Process Oil PW-150”, and “Diana Process Oil PS-” manufactured by Idemitsu Kosan Co., Ltd. 32, “Diana Process Oil PS-90", “Diana Process Oil PS-430”; “Kaydol Oil” and “ParaLux Oil” manufactured by Chevron USA (all are trade names).
  • IP Solvent 1016 Commercially available isoparaffinic oils include “IP Solvent 1016”, “IP Solvent 1620”, “IP Solvent 2028”, “IP Solvent 2835”, “IP Clean LX” manufactured by Idemitsu Kosan Co., Ltd .; And “NA Solvent” series (both are trade names).
  • the hot melt adhesive of the present embodiment contains an oil (E)
  • the content is determined from the viewpoint of improving the tackiness of the hot melt adhesive, applicability, and improving the wettability to an adherend due to a decrease in viscosity.
  • the resin component (base polymer) in the hot melt adhesive preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and preferably 200 parts by mass or less. It is preferably at most 100 parts by mass, more preferably at most 50 parts by mass.
  • the hot melt adhesive of the present embodiment may further contain a linear hydrocarbon wax (F) having a melting endotherm ( ⁇ HD) of more than 120 J / g and 300 J / g or less.
  • the melting endotherm ( ⁇ HD) of the linear hydrocarbon wax (F) is more preferably 140 J / g or more, still more preferably 160 J / g or more, and more preferably 280 J, from the viewpoint of solidification rate. / G or less, more preferably 250 J / g or less.
  • the melting endotherm ( ⁇ HD) of the linear hydrocarbon wax (F) is measured in the same manner as the above-mentioned melting endotherm ( ⁇ HD) of the polypropylene resin (A).
  • the melting point (Tm-D) of the linear hydrocarbon wax (F) is preferably at least 50 ° C, more preferably at least 80 ° C, and preferably at most 150 ° C, more preferably at most 130 ° C.
  • the melting point (Tm-D) of the linear hydrocarbon wax (F) is measured in the same manner as the above-mentioned melting point (Tm-D) of the polypropylene resin (A).
  • straight-chain hydrocarbon wax examples include paraffin wax, higher fatty acid wax, higher fatty acid ester wax, Fischer-Tropsch wax, polyethylene wax, polypropylene wax and the like (however, the ethylene polymer (G) described below). Excludes that apply.)
  • linear hydrocarbon wax (F) Commercial products of the linear hydrocarbon wax (F) include the following.
  • examples of the Fischer-Tropsch wax include “Sasol” manufactured by Sasol, and examples of the paraffin wax include “Paraffin Wax” manufactured by Nippon Seiro Co., Ltd.
  • examples of the low-density polyethylene-based wax include “Hi Wax” NL series manufactured by Mitsui Chemicals, Inc. and the like are listed (all are trade names).
  • the content of the linear hydrocarbon-based wax (F) in the hot melt adhesive of the present embodiment is 100% in terms of the content of the resin component (base polymer) in the hot melt adhesive from the viewpoint of improving flexibility and coating properties.
  • the amount is preferably 10,000 parts by mass or less, more preferably 5,000 parts by mass or less, still more preferably 500 parts by mass or less, and still more preferably 100 parts by mass or less with respect to parts by mass.
  • the content of the wax increases, the viscosity of the thermoplastic resin composition decreases. Therefore, it is preferable to appropriately determine the content of the linear hydrocarbon wax (F) according to the use of the hot melt adhesive made of the thermoplastic resin composition.
  • the hot melt adhesive of the present embodiment may contain an ethylene polymer (G) having a melting endotherm ( ⁇ HD) of 0 J / g or more and 120 J / g or less.
  • the ethylene polymer (G) is preferably contained as a base polymer of the hot melt adhesive.
  • the melting endothermic amount ( ⁇ HD) of the ethylene polymer (G) is preferably 20 J / g or more, more preferably 40 J / g or more, and preferably 100 J / g or less, from the viewpoint of flexibility. More preferably, it is 80 J / g or less.
  • the melting endotherm ( ⁇ HD) of the ethylene polymer (G) is measured in the same manner as the above-mentioned melting endotherm ( ⁇ HD) of the polypropylene resin (A).
  • the melting point (Tm-D) of the ethylene polymer (G) is preferably 30 ° C. or higher, more preferably 50 ° C. or higher, and preferably less than 85 ° C., more preferably, from the viewpoint of applicability. 80 ° C. or less.
  • the melting point (Tm-D) of the ethylene-based polymer (G) is measured in the same manner as the melting point (Tm-D) of the polypropylene-based resin (A).
  • Ethylene polymer (G) is an ethylene homopolymer or an ethylene copolymer.
  • the ethylene-based copolymer refers to a copolymer of ethylene and a copolymerizable monomer copolymerizable with ethylene.
  • the copolymerizable monomer include ⁇ -olefins; carboxylic acids (esters) such as vinyl acetate, (meth) acrylic acid, (meth) acrylate, maleic acid, and maleic ester; maleic anhydride, phthalic anhydride, and anhydride.
  • Carboxylic acid anhydrides such as succinic acid; and the like.
  • copolymerizable monomers may be copolymerized with ethylene alone, or two or more copolymerizable monomers may be copolymerized.
  • ethylene copolymer examples include an ethylene / ⁇ -olefin copolymer, an ethylene / carboxylic acid copolymer, an ethylene / carboxylic acid ester copolymer, and an ethylene / carboxylic anhydride copolymer.
  • (meth) acrylic acid refers to a concept including both methacrylic acid and acrylic acid.
  • Specific examples of (meth) acrylates include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, acryl Isooctyl acid, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate and the like can be mentioned.
  • the ethylene polymer (G) at least one selected from the group consisting of ⁇ -olefins having 3 to 30 carbon atoms (preferably having 3 to 10 carbon atoms) from the viewpoint of the adhesiveness and odor of the hot melt adhesive. It is preferable to contain more than 0 mol% and no more than 40 mol% of structural units.
  • the ethylene-based polymer (G) is preferably an ethylene / ⁇ -olefin copolymer, and is preferably a copolymer of ethylene and an ⁇ -olefin having 3 to 30 (preferably 3 to 10) carbon atoms. preferable. Further, an ethylene / ⁇ -olefin copolymer obtained by polymerization with a metallocene catalyst is preferable.
  • ⁇ -olefin examples include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, and 1-hexadecene , 1-octadecene, 1-eicosene and the like. In the present embodiment, one or more of these can be used. Propylene or 1-octene is preferred among these ⁇ -olefins.
  • the ethylene-based polymer (G) used in the present embodiment is more preferably an ethylene-1-octene copolymer from the viewpoint of adhesiveness, and still more preferably contains 5 to 20 structural units derived from 1-octene. It is an ethylene-1-octene copolymer containing mol%.
  • the hot melt adhesive of the present embodiment contains an ethylene / ⁇ -olefin copolymer obtained by polymerization with a metallocene catalyst, the suitability for spiral coating at low temperatures is improved, and the adhesion to a polyethylene film or a nonwoven fabric is further improved. Excellent.
  • G Commercial products of the ethylene-based polymer (G) include the “Exact” series (manufactured by ExxonMobil), the “Affinity @ polymer” series, and the “Infuse” series (both manufactured by Dow Chemical Company). "Affinity @ GA1875", “Affinity @ GA1900”, “Affinity @ GA1950”, “Affinity @ GP1570”, “Infuse @ 9807”, “Infuse9817” (manufactured by Dow Chemical Company) (all are trade names).
  • the content of the ethylene-based polymer (G) in the hot melt adhesive is preferably 10,000 parts by mass based on 100 parts by mass of the polypropylene-based resin (A) from the viewpoint of improving flexibility and coatability. Or less, more preferably 7,500 parts by mass or less, and still more preferably 5,000 parts by mass or less.
  • the content of the ethylene polymer (G) in the resin component (base polymer) increases, the strength decreases. Therefore, it is preferable to appropriately determine the content of the ethylene polymer (G) according to the use of the hot melt adhesive.
  • the content of the polypropylene resin (A) in the total amount of 100% by mass of the polypropylene resin (A) and the ethylene polymer (G) is preferably 25% by mass or more, more preferably 50% by mass or more, and furthermore It is preferably at least 75% by mass.
  • the hot melt adhesive of the present embodiment may further contain various additives such as a plasticizer, an inorganic filler, an antioxidant and the like, as needed, as long as the effects of the present invention are not impaired.
  • plasticizer examples include phthalates, adipic esters, fatty acid esters, glycols, epoxy polymer plasticizers, and the like.
  • inorganic filler talc, calcium carbonate, barium carbonate, wollastonite, silica, clay, mica, kaolin, titanium oxide, diatomaceous earth, urea resin, styrene beads, starch, barium sulfate, calcium sulfate, magnesium silicate, Examples thereof include magnesium carbonate, alumina, and quartz powder.
  • antioxidants examples include trisnonylphenyl phosphite, distearylpentaerythritol diphosphite, "Adecastab 1178" (manufactured by ADEKA Corporation), “Stamlyzer TNP” (manufactured by Sumitomo Chemical Co., Ltd.), and “Ilgafos 168" (BASF Phosphorus antioxidants such as “Sandstab P-EPQ” (manufactured by Sando), 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3- (3 ′, 5 ′) Phenolic antioxidants such as -di-t-butyl-4'-hydroxyphenyl) propionate, “SUMILIZER BHT” (manufactured by Sumitomo Chemical Co., Ltd.) and “Irganox 1010" (manufactured by BASF), dilauryl-3,3 '
  • the hot melt adhesive of the present embodiment may further contain a wax other than the linear hydrocarbon wax (F).
  • the wax other than the linear hydrocarbon wax (F) include animal wax, vegetable wax, carnauba wax, candelilla wax, wood wax, beeswax, mineral wax, petroleum wax, microcrystalline wax, petrolatum, higher fatty acid wax, and higher-grade wax. Fatty acid ester waxes and the like.
  • the hot melt adhesive of the present embodiment it is possible to partially crosslink by adding a crosslinking agent or a crosslinking assistant.
  • the crosslinking agent include organic peroxides, sulfur, sulfur compounds, and phenolic vulcanizing agents such as phenolic resins. Of these, organic peroxides are preferred. Specific examples of the organic peroxide include 2,5-dimethyl-2,5-di (t-butylperoxy) -hexane and 2,5-dimethyl-2,5-di (t-butylperoxy) -3.
  • 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane and 2,5-dimethyl-2,5-di- (t -Butylperoxy) -3-hexyne 1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl -4,4-bis (t-butylperoxy) valerate is preferred, and 1,3-bis (t-butylperoxyisopropyl) benzene is most preferred.
  • crosslinking assistant examples include N-methyl-N, 4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, divinylbenzene, trimethylolpropane tri (meth) acrylate, ethylene di (meth) acrylate, and diethylene glycol di (meth) acrylate.
  • crosslinking aids triallyl cyanurate, ethylene glycol dimethacrylate, divinylbenzene, and bismaleimide are preferable. These are easy to handle, have good compatibility with the polypropylene resin (A), which is the main component of the object to be crosslinked, and have an action of solubilizing organic peroxides. Since it acts as an oxide dispersant, a resin composition having a uniform crosslinking effect by heat treatment and a balance between flexibility and physical properties can be obtained.
  • the cross-linking agent and the cross-linking assistant may be used alone or in combination of two or more.
  • a crosslinking agent and a crosslinking aid are used, the degree of crosslinking is adjusted arbitrarily in the range of 0.1 to 5 parts by mass based on 100 parts by mass of the total of components (A) to (G). be able to.
  • an unsaturated silane compound is used as a crosslinking aid, crosslinking can be further advanced by contact with moisture in the presence of a silanol condensation catalyst.
  • the hot melt adhesive of this embodiment is obtained by adding a nucleating agent (B) to a polypropylene resin (A), and further, if necessary, a tackifier (D), an oil (E), and a linear hydrocarbon-based resin.
  • a nucleating agent (B) to a polypropylene resin (A)
  • a tackifier (D) to an oil (E)
  • a linear hydrocarbon-based resin At least one selected from the group consisting of wax (F), ethylene-based polymer (G) and various additives is added and dry-blended using a Henschel mixer or the like, and a single-screw or twin-screw extruder, plast mill or Banbury is used. It can be produced by melt-kneading with a mixer or the like.
  • the temperature during melt-kneading can be appropriately determined according to the type of the nucleating agent (B) used.
  • the temperature during melt kneading is preferably 150 ° C. Or less, more preferably 100 ° C. or less.
  • the temperature at the time of melt-kneading is preferably 250 ° C. or higher, since the effect of improving the crystallization rate when kneaded and dispersed at a high temperature in a hot melt adhesive is large. 280 ° C. or more.
  • the hot melt adhesive of the present embodiment has an excellent solidification rate.
  • a hot melt adhesive having an improved solidification rate is useful in various applications.
  • the hot melt adhesive composed of the thermoplastic resin composition of the present embodiment can be suitably used for, for example, sanitary materials, bookbinding, fibers, cans, filters, low pressure molding, and bag making. .
  • the packaging field fixing cartons, cardboard, cushioning materials, repairing automatic packaging boxes, fixing samples, packaging after unpacking, packing desiccants in food packaging, etc.
  • electrical materials Fixing electronic parts on C-board, temporary fixing, anti-vibration reinforcement, filling of connector empty space, board insulation, wire fixing, encapsulation), film adhesive processing, non-slip (film coating such as DM), housing, building materials ( Siding, tile, flooring, carpet, fabric, wallpaper, sample adhesion), architecture / interior (adhesion of insulation material, kitchen tarpaulin, prevention of fraying when cutting tatami, roof, veranda FRP, crack, tile), furniture, woodwork (Tables, chairs, sofas, beds, mirror cabinets, fixing of reinforcements, bonding of fabric, fixing of frills, Buddhist altars, binding, etc.), hobby, small Adhesives, accessories, traditional crafts, automotive industry (adhesion of dashboard anti-vibration reinforcement, adhesion of head / lamp case, door interior materials
  • the hot-melt adhesive In the case of woodworking, in a bonding method in which a hot-melt adhesive is applied to an adherend and then wound once with a roll, if the hot-melt adhesive does not solidify quickly, the rolls are all bonded and integrated. Faster solidification allows for winding.
  • the bonding between the pocket coils is made on an automated automated assembly machine. After the pocket coils are adhered to each other, it is necessary to develop the adhesive strength early in order to prevent displacement, and it is useful to improve the solidification speed.
  • the hot melt adhesive may be applied and affixed using a hand gun. At this time, the set time is shortened, and thus the adhesive strength immediately after lamination is improved.
  • B1 "Gelall D”, a sorbitol-based nucleating agent manufactured by Shin Nippon Rika Co., Ltd.
  • B2 "Gerol MD”, a sorbitol-based nucleating agent manufactured by Shin Nippon Rika Co., Ltd.
  • B3 "Gerol DXR”, New Japan Sorbitol-based nucleating agent manufactured by Rika Co., Ltd.
  • E1 "Diana Process Oil PW-90": paraffinic oil, manufactured by Idemitsu Kosan Co., Ltd., kinematic viscosity at 40.degree.
  • G ⁇ Ethylene polymer (G)>
  • the heat was obtained as a crystallization heat ( ⁇ Hc) from a crystallization heat curve obtained.
  • the crystallization temperature (Tc) was determined from the peak top of the obtained crystallization exothermic curve.
  • the melting endotherm ( ⁇ H ⁇ D or ⁇ Hm) and the crystallization calorific value (cHc) are obtained by using a line connecting a low-temperature side point with no calorific value change and a high-temperature side point with no calorific value change as a baseline.
  • a line portion including a peak of a melting endothermic curve and a crystallization exothermic curve obtained by DSC measurement using a differential scanning calorimeter (manufactured by Perkin-Elmer Co., Ltd., “DSC-7”) is surrounded by the base line. It is calculated by calculating the area.
  • Weight average molecular weight (Mw) The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC). For the measurement, the following apparatus and conditions were used, and a weight average molecular weight in terms of polystyrene was obtained.
  • ⁇ GPC measurement device Column: "TOSO GMHHR-H (S) HT” manufactured by Tosoh Corporation Detector: RI detection for liquid chromatogram "WATERS 150C” manufactured by Waters Corporation ⁇ Measurement conditions> Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C Flow rate: 1.0 mL / min Sample concentration: 2.2 mg / mL Injection volume: 160 ⁇ L Calibration curve: Universal Calibration Analysis program: HT-GPC (Ver. 1.0)
  • the measurement was carried out using a differential scanning calorimeter (DSC) (manufactured by Perkin-Elmer Co., Ltd., trade name: "DSC-7") by the following method.
  • DSC differential scanning calorimeter
  • 10 mg of a sample is held at 25 ° C. for 5 minutes, heated to 220 ° C. at 320 ° C./min and held for 5 minutes, then cooled to 25 ° C. at 320 ° C./min, and held for 60 minutes to be isothermal.
  • the time change of the calorific value during the crystallization process was measured.
  • Examples 1 to 22 and Comparative Example 1 The components of the types and compounding amounts shown in Tables 1 and 2 were melt-kneaded using a plast mill at the temperature shown in Tables 1 and 5 for 5 minutes at 100 rpm to prepare a resin composition.
  • the nucleating agent (B5) was kneaded at 300 ° C.
  • the nucleating agent (B10) was kneaded at 80 ° C.
  • Examples 23 to 27 and Comparative Examples 2 to 6 The components shown in Table 3 were charged into a heat-resistant glass bottle having a capacity of 100 mL so that the total amount was 60 g, and the content was melted by heating at 200 ° C. for 30 minutes. Thereafter, the contents were stirred with a spatula for 5 minutes and heated at 200 ° C. for 10 minutes. The above operation was repeated five times to obtain a hot melt adhesive made of the thermoplastic resin composition. After taking out the obtained hot melt adhesive into a vat coated with polytetrafluoroethylene, the solidification time was measured by the following method. In Example 27 and Comparative Example 6, the open time was measured by the following method. Table 3 shows the results.
  • the open time refers to the adhesive holding time from when the adhesive is applied to the adherend until the temperature decreases and the adhesive disappears.
  • a hot melt adhesive melted by heating to 180 ° C. is applied to a K liner cardboard at a coating amount of 2.8 to 3.2 g / m, and after a predetermined time, an adhesive pressure of 2 kg / 25 cm 2 and a set time of 2 seconds Under the following conditions.
  • the adhesive test piece was allowed to stand for 24 hours in an environment of 23 ° C. and 50% humidity, and was peeled off by hand. Of the five measurements, the longest elapsed time when four or more test pieces with a material destruction rate of 80% or more were defined as open time (seconds).

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Abstract

A hot melt adhesive which contains (A) a polypropylene resin that has a melting endotherm (∆H - D) of more than 0 J/g but 80 J/g or less as determined from the melting endothermic curve that is obtained with use of a differential scanning calorimeter (DSC) by holding a sample at -10°C for 5 minutes in a nitrogen atmosphere and subsequently heating the sample at 10°C/min, and (B) a nucleator. This hot melt adhesive is configured such that the content of the nucleator (B) is from 5 ppm by mass to 50,000 ppm by mass (inclusive) relative to 100 parts by mass of the polypropylene resin (A).

Description

特定のプロピレン系樹脂組成物を含むホットメルト接着剤Hot melt adhesive containing specific propylene resin composition
　本発明は、ホットメルト接着剤に関し、詳しくは、特定のプロピレン系樹脂組成物を含むホットメルト接着剤に関する。 The present invention relates to a hot melt adhesive, and more particularly, to a hot melt adhesive containing a specific propylene-based resin composition.
　ホットメルト接着剤は、無溶剤の接着剤であり、加熱溶融することで被着体に塗工後、冷却することで固化して接着性を発現する。近年、ホットメルト接着剤は、高速塗工性、速硬化性、無溶剤性、バリヤ性、省エネルギー性、経済性等に優れるため、各種分野において利用が拡大している。 Hot melt adhesives are solventless adhesives, which are applied to an adherend by heating and melting, then solidify by cooling, and exhibit adhesiveness. BACKGROUND ART In recent years, hot melt adhesives have been widely used in various fields because they are excellent in high-speed coating properties, quick-curing properties, solvent-free properties, barrier properties, energy saving properties, economy, and the like.
　ホットメルト接着剤のベースポリマーとしては、熱安定性の観点からプロピレン系重合体が広く使用されている。中でもメタロセン系触媒により重合された低分子量ポリプロピレンは、流動性が高く、ホットメルト接着剤として使用した場合の塗布性に優れ、ポリプロピレン等の低極性物質の接着強度に優れ、加熱溶融時の熱安定性に優れることから、各種ホットメルト接着剤のベースポリマーとして好適に使用できる（特許文献１～３）。 プ ロ ピ レ ン Propylene polymers are widely used as base polymers for hot melt adhesives from the viewpoint of thermal stability. Above all, low molecular weight polypropylene polymerized by metallocene catalyst has high fluidity, excellent coatability when used as a hot melt adhesive, excellent adhesive strength of low polar substances such as polypropylene, and heat stability during heat melting. Because of its excellent properties, it can be suitably used as a base polymer for various hot melt adhesives (Patent Documents 1 to 3).
国際公開第２０１４／１９２７６７号WO 2014/192767 特開２０１３－０６４０５６号公報JP 2013-064056 A 特表２０１６－５２４００２号公報JP-T-2016-524002
　上記のメタロセン系触媒により重合された低分子量ポリプロピレンは結晶化速度が遅いため、これを用いたホットメルト接着剤は、固化時間が比較的遅く、被着体への追従性が良好で接着性には優れるが、その反面、固化しにくいために、例えば不織布等の多孔質基材を積層接着する場合、接着剤の塗布面側からその反対側の面に向かって接着剤が染み出る、いわゆる裏抜けと呼ばれる現象が生じやすい。また、素早い接着強度の発現が求められる建材、包装用途には適さなくなる可能性がある。
　したがって、本発明が解決しようとする課題は、固化速度に優れるホットメルト接着剤を提供することである。 Because the low molecular weight polypropylene polymerized by the above metallocene catalyst has a low crystallization rate, the hot melt adhesive using this has a relatively slow solidification time, has good adherence to the adherend, and has good adhesion. On the other hand, because it is hard to solidify, for example, when laminating and bonding a porous substrate such as a nonwoven fabric, the adhesive exudes from the adhesive application surface side to the opposite surface, so-called back side A phenomenon called omission is likely to occur. In addition, there is a possibility that it is not suitable for building materials and packaging applications that require rapid development of adhesive strength.
Therefore, an object of the present invention is to provide a hot melt adhesive having an excellent solidification rate.
　本発明者らは、上記の課題を解決するべく鋭意検討した結果、下記の発明により当該課題を解決できることを見出した。すなわち、本願開示は、以下に関する。
＜１＞示差走査型熱量計（ＤＳＣ）を用い、試料を窒素雰囲気下－１０℃で５分間保持した後、１０℃／分で昇温させることにより得られた融解吸熱カーブから得られる融解吸熱量（ΔＨ－Ｄ）が０Ｊ／ｇを超え８０Ｊ／ｇ以下であるポリプロピレン系樹脂（Ａ）及び核剤（Ｂ）を含有するホットメルト接着剤であって、前記核剤（Ｂ）の含有量が、前記ポリプロピレン系樹脂（Ａ）１００質量部に対して、５質量ｐｐｍ以上５０，０００質量ｐｐｍ以下である、ホットメルト接着剤。
＜２＞前記ポリプロピレン系樹脂（Ａ）が下記（１）を満たす、上記＜１＞に記載のホットメルト接着剤。
（１）示差走査型熱量計（ＤＳＣ）を用い、試料を窒素雰囲気下－１０℃で５分間保持した後、１０℃／分で昇温させることにより得られた融解吸熱カーブの最も高温側に観測されるピークトップとして定義される融点（Ｔｍ－Ｄ）が、観測されないか又は０℃以上１２０℃以下である。
＜３＞前記ポリプロピレン系樹脂（Ａ）の重量平均分子量（Ｍｗ）が５，０００以上３００，０００以下である、上記＜１＞又は＜２＞に記載のホットメルト接着剤。
＜４＞前記ポリプロピレン系樹脂（Ａ）の２５℃における半結晶化時間が３分以上である、上記＜１＞～＜３＞のいずれか１つに記載のホットメルト接着剤。
＜５＞前記ポリプロピレン系樹脂（Ａ）がプロピレン単独重合体である、上記＜１＞～＜４＞のいずれか１つに記載のホットメルト接着剤。
＜６＞前記ポリプロピレン系樹脂（Ａ）が、エチレン及び炭素数４～３０のα－オレフィンからなる群より選ばれる少なくとも１つの構成単位を０モル％を超え２０モル％以下含む、上記＜１＞～＜４＞のいずれか１つに記載のホットメルト接着剤。
＜７＞前記核剤（Ｂ）が、アセタール系核剤、アミド系核剤及び有機金属塩系核剤からなる群より選ばれる少なくとも１種である、上記＜１＞～＜６＞のいずれか１つに記載のホットメルト接着剤。
＜８＞前記核剤（Ｂ）が、ソルビトール系核剤及びノニトール系核剤からなる群より選ばれる少なくとも１種である、上記＜１＞～＜７＞のいずれか１つに記載のホットメルト接着剤。
＜９＞前記核剤（Ｂ）が、カルボキサミド系核剤及びトリアミド系核剤からなる群より選ばれる少なくとも１種である、上記＜１＞～＜７＞のいずれか１つに記載のホットメルト接着剤。
＜１０＞前記核剤（Ｂ）が、フェニルホスホン酸金属塩系核剤である、上記＜１＞～＜７＞のいずれか１つに記載のホットメルト接着剤。
＜１１＞核剤に起因した目視可能な白点状の凝集が実質的にない、上記＜１０＞に記載のホットメルト接着剤。
＜１２＞更に、粘着性付与剤（Ｄ）を含む、上記＜１＞～＜１１＞のいずれか１つに記載のホットメルト接着剤。
＜１３＞更に、オイル（Ｅ）を含む、上記＜１＞～＜１２＞のいずれか１つに記載のホットメルト接着剤。
＜１４＞更に、直鎖炭化水素系ワックス（Ｆ）を含む、上記＜１＞～＜１３＞のいずれか１つに記載のホットメルト接着剤。
＜１５＞更に、エチレン系重合体（Ｇ）を含む、上記＜１＞～＜１４＞のいずれか１つに記載のホットメルト接着剤。 Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the following problems can be solved. That is, the present disclosure relates to the following.
<1> Using a differential scanning calorimeter (DSC), a sample is held at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then heated at a rate of 10 ° C./min. A hot melt adhesive comprising a polypropylene resin (A) having a calorific value (ΔHD) of more than 0 J / g and 80 J / g or less and a nucleating agent (B), wherein the content of the nucleating agent (B) Is from 5 mass ppm to 50,000 mass ppm with respect to 100 parts by mass of the polypropylene resin (A).
<2> The hot melt adhesive according to <1>, wherein the polypropylene resin (A) satisfies the following (1).
(1) Using a differential scanning calorimeter (DSC), the sample was kept at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then heated at a rate of 10 ° C./min. The melting point (Tm-D) defined as the observed peak top is not observed or is 0 ° C or more and 120 ° C or less.
<3> The hot melt adhesive according to <1> or <2>, wherein the polypropylene resin (A) has a weight average molecular weight (Mw) of 5,000 to 300,000.
<4> The hot melt adhesive according to any one of the above <1> to <3>, wherein a half-crystallization time of the polypropylene resin (A) at 25 ° C. is 3 minutes or more.
<5> The hot melt adhesive according to any one of <1> to <4> above, wherein the polypropylene resin (A) is a propylene homopolymer.
<6> The above <1>, wherein the polypropylene-based resin (A) contains at least one structural unit selected from the group consisting of ethylene and α-olefins having 4 to 30 carbon atoms in an amount of more than 0 mol% and 20 mol% or less. The hot melt adhesive according to any one of <4> to <4>.
<7> Any one of the above <1> to <6>, wherein the nucleating agent (B) is at least one selected from the group consisting of an acetal nucleating agent, an amide nucleating agent and an organic metal salt nucleating agent. The hot melt adhesive according to one.
<8> The hot melt according to any one of <1> to <7>, wherein the nucleating agent (B) is at least one selected from the group consisting of a sorbitol-based nucleating agent and a nonitol-based nucleating agent. adhesive.
<9> The hot melt according to any one of <1> to <7>, wherein the nucleating agent (B) is at least one selected from the group consisting of a carboxamide nucleating agent and a triamide nucleating agent. adhesive.
<10> The hot melt adhesive according to any one of the above <1> to <7>, wherein the nucleating agent (B) is a metal phenylphosphonate-based nucleating agent.
<11> The hot melt adhesive according to <10>, wherein there is substantially no visible white spot-like aggregation caused by the nucleating agent.
<12> The hot melt adhesive according to any one of <1> to <11>, further including a tackifier (D).
<13> The hot melt adhesive according to any one of <1> to <12>, further including an oil (E).
<14> The hot melt adhesive according to any one of <1> to <13>, further including a linear hydrocarbon wax (F).
<15> The hot melt adhesive according to any one of <1> to <14>, further comprising an ethylene polymer (G).
　本発明のホットメルト接着剤は、固化速度に優れる。 ホ ッ ト The hot melt adhesive of the present invention has an excellent solidification rate.
　以下、本発明について詳細に説明する。なお、本明細書において、数値の記載に関する「Ａ～Ｂ」という用語は、「Ａ以上Ｂ以下」（Ａ＜Ｂの場合）又は「Ａ以下Ｂ以上」（Ａ＞Ｂの場合）を意味する。本発明において、好ましい態様の組み合わせは、より好ましい態様である。 Hereinafter, the present invention will be described in detail. In this specification, the term “A to B” regarding the description of numerical values means “A or more and B or less” (when A <B) or “A or less B or more” (when A> B). . In the present invention, a combination of preferred embodiments is a more preferred embodiment.
　本明細書において、融解吸熱量（ΔＨ－Ｄ）、融点（Ｔｍ－Ｄ）、重量平均分子量（Ｍｗ）及び分子量分布（Ｍｗ／Ｍｎ）は、実施例に記載の方法により求められた値と定義する。 In this specification, the melting endotherm (ΔH-D), melting point (Tm-D), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) are defined as the values obtained by the method described in Examples. I do.
　本実施形態のホットメルト接着剤は、融解吸熱量（ΔＨ－Ｄ）が０Ｊ／ｇを超え８０Ｊ／ｇ以下であるポリプロピレン系樹脂（Ａ）及び核剤（Ｂ）を含有するホットメルト接着剤であって、前記核剤（Ｂ）の含有量が、前記ポリプロピレン系樹脂（Ａ）１００質量部に対して、５質量ｐｐｍ以上５０，０００質量ｐｐｍ以下である、ホットメルト接着剤である。ポリプロピレン系樹脂（Ａ）は、ホットメルト接着剤のベースポリマーとして含まれることが好ましい。また、ホットメルト接着剤のベースポリマーは、更にポリプロピレン系樹脂（Ａ）以外に、特定のエチレン系重合体（Ｇ）を含んでいてもよい。 The hot melt adhesive of this embodiment is a hot melt adhesive containing a polypropylene resin (A) having a melting endotherm (ΔHD) of more than 0 J / g and 80 J / g or less and a nucleating agent (B). A hot melt adhesive wherein the content of the nucleating agent (B) is 5 mass ppm or more and 50,000 mass ppm or less based on 100 parts by mass of the polypropylene resin (A). The polypropylene resin (A) is preferably contained as a base polymer of the hot melt adhesive. The base polymer of the hot melt adhesive may further contain a specific ethylene polymer (G) in addition to the polypropylene resin (A).
＜ポリプロピレン系樹脂（Ａ）＞
　本実施形態で用いられるポリプロピレン系樹脂（Ａ）は、示差走査型熱量計（ＤＳＣ）を用い、試料を窒素雰囲気下－１０℃で５分間保持した後、１０℃／分で昇温させることにより得られた融解吸熱カーブから得られる融解吸熱量（ΔＨ－Ｄ）が０Ｊ／ｇを超え８０Ｊ／ｇ以下であるポリプロピレン系樹脂である。融解吸熱量（ΔＨ－Ｄ）が８０Ｊ／ｇを超えると、界面接着強度が低下するおそれがある。融解吸熱量（ΔＨ－Ｄ）は、ホットメルト接着剤の接着強度及び柔軟性の観点から、好ましくは２０Ｊ／ｇ以上、より好ましくは２５Ｊ／ｇ以上、更に好ましくは２７Ｊ／ｇ以上、より更に好ましくは３０Ｊ／ｇ以上であり、そして、好ましくは５０Ｊ／ｇ以下、より好ましくは４５Ｊ／ｇ以下、更に好ましくは４０Ｊ／ｇ以下である。
　上記融解吸熱量（ΔＨ－Ｄ）は、熱量変化の無い低温側の点と熱量変化の無い高温側の点とを結んだ線をベースラインとして、ＤＳＣ測定により得られた融解吸熱カーブの最も高温側に観測されるピークを含むライン部分と当該ベースラインとで囲まれる面積を求めることで算出される。なお、融解吸熱量（ΔＨ－Ｄ）は、モノマー濃度や反応圧力を適宜調整することで制御することができる。
　このとき、測定に用いるＤＳＣは同日中に事前の校正を施されたものでなくてはならない。ここで記述した校正とは、インジウム（Ｉｎ）及び鉛（Ｐｂ）を標準試料とした温度校正並びにＩｎを標準試料とした熱量校正を指すものである。校正においては、Ｉｎ及びＰｂの補外融解開始温度が文献値（Ｉｎ：１５８．６０℃、Ｐｂ：３２７．４７℃）に対し±０．３℃、Ｉｎの熱量が文献値（２８．４５Ｊ／ｇ）に対し±０．２Ｊ／ｇの範囲内となるように調整する。 <Polypropylene resin (A)>
The polypropylene resin (A) used in the present embodiment is obtained by holding a sample at −10 ° C. for 5 minutes in a nitrogen atmosphere using a differential scanning calorimeter (DSC), and then heating the sample at 10 ° C./min. This is a polypropylene resin having a melting endotherm (ΔHD) obtained from the obtained melting endothermic curve of more than 0 J / g and 80 J / g or less. If the melting endotherm (ΔH−D) exceeds 80 J / g, the interfacial adhesive strength may decrease. The melting endotherm (ΔH-D) is preferably 20 J / g or more, more preferably 25 J / g or more, further preferably 27 J / g or more, and still more preferably, from the viewpoint of the adhesive strength and flexibility of the hot melt adhesive. Is 30 J / g or more, and preferably 50 J / g or less, more preferably 45 J / g or less, and still more preferably 40 J / g or less.
The above-mentioned melting endotherm (ΔH−D) is defined as the highest temperature of the melting endotherm curve obtained by the DSC measurement using a line connecting the low-temperature side point with no calorific value change and the high-temperature side point with no calorific value change as a baseline. It is calculated by obtaining the area surrounded by the line portion including the peak observed on the side and the base line. The melting endotherm (ΔHD) can be controlled by appropriately adjusting the monomer concentration and the reaction pressure.
At this time, the DSC used for the measurement must have been calibrated in advance on the same day. The calibration described here indicates a temperature calibration using indium (In) and lead (Pb) as a standard sample and a calorimetric calibration using In as a standard sample. In the calibration, the extrapolation melting onset temperatures of In and Pb were ± 0.3 ° C. with respect to the literature values (In: 158.60 ° C., Pb: 327.47 ° C.), and the calorific value of In was the literature value (28.45 J / g) is adjusted to be within the range of ± 0.2 J / g.
　ポリプロピレン系樹脂（Ａ）は、下記（１）を満たすことが好ましい。
（１）示差走査型熱量計（ＤＳＣ）を用い、試料を窒素雰囲気下－１０℃で５分間保持した後、１０℃／分で昇温させることにより得られた融解吸熱カーブの最も高温側に観測されるピークトップとして定義される融点（Ｔｍ－Ｄ）が、観測されないか又は０℃以上１２０℃以下である。 The polypropylene resin (A) preferably satisfies the following (1).
(1) Using a differential scanning calorimeter (DSC), the sample was kept at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then heated at a rate of 10 ° C./min. The melting point (Tm-D) defined as the observed peak top is not observed or is 0 ° C or more and 120 ° C or less.
　ポリプロピレン系樹脂（Ａ）の融点（Ｔｍ－Ｄ）は、ホットメルト接着剤の接着強度の観点から、観測されないか又は０℃以上１２０℃以下であることが好ましい。融点が観測される場合には、同様の観点から、より好ましくは３０℃以上、更に好ましくは４５℃以上、より更に好ましくは６０℃以上、特に好ましくは７５℃以上であり、そして、より好ましくは１００℃以下、更に好ましくは９０℃以下、より更に好ましくは８５℃以下である。
　なお、融点は、モノマー濃度や反応圧力を適宜調整することで制御可能である。 It is preferable that the melting point (Tm-D) of the polypropylene resin (A) is not observed or is 0 ° C or more and 120 ° C or less from the viewpoint of the adhesive strength of the hot melt adhesive. When a melting point is observed, from the same viewpoint, it is more preferably at least 30 ° C, still more preferably at least 45 ° C, still more preferably at least 60 ° C, particularly preferably at least 75 ° C, and more preferably The temperature is 100 ° C. or lower, more preferably 90 ° C. or lower, even more preferably 85 ° C. or lower.
The melting point can be controlled by appropriately adjusting the monomer concentration and the reaction pressure.
　また、ポリプロピレン系樹脂（Ａ）の重量平均分子量（Ｍｗ）は、接着強度の観点から、好ましくは５，０００以上、より好ましくは１５，０００以上、更に好ましくは３０，０００以上であり、そして、塗工性の観点から好ましくは３００，０００以下、より好ましくは２００，０００以下、更に好ましくは１５０，０００以下である。
　本発明において、重量平均分子量（Ｍｗ）は、ゲルパーミエイションクロマトグラフィ（ＧＰＣ）法により測定したポリスチレン換算の重量平均分子量である。 In addition, the weight average molecular weight (Mw) of the polypropylene resin (A) is preferably 5,000 or more, more preferably 15,000 or more, and still more preferably 30,000 or more, from the viewpoint of adhesive strength. From the viewpoint of coatability, it is preferably 300,000 or less, more preferably 200,000 or less, and still more preferably 150,000 or less.
In the present invention, the weight average molecular weight (Mw) is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.
　ポリプロピレン系樹脂（Ａ）の分子量分布（Ｍｗ／Ｍｎ）は、好ましくは３．０以下、より好ましくは２．８以下、更に好ましくは２．６以下、より更に好ましくは２．５以下であり、そして、好ましくは１．５以上、より好ましくは１．６以上、更に好ましくは１．７以上、より更に好ましくは１．８以上である。分子量分布（Ｍｗ／Ｍｎ）を上記範囲内とすることで、樹脂組成物の柔軟性をより高め、樹脂組成物のべたつきをより抑制することができる。
　なお、本実施形態において、分子量分布（Ｍｗ／Ｍｎ）は、ゲルパーミエイションクロマトグラフィ（ＧＰＣ）法により測定したポリスチレン換算の重量平均分子量Ｍｗ及び数平均分子量Ｍｎより算出した値である。 The molecular weight distribution (Mw / Mn) of the polypropylene resin (A) is preferably 3.0 or less, more preferably 2.8 or less, further preferably 2.6 or less, and still more preferably 2.5 or less, And it is 1.5 or more, More preferably, it is 1.6 or more, More preferably, it is 1.7 or more, More preferably, it is 1.8 or more. By setting the molecular weight distribution (Mw / Mn) within the above range, the flexibility of the resin composition can be further increased, and the stickiness of the resin composition can be further suppressed.
In the present embodiment, the molecular weight distribution (Mw / Mn) is a value calculated from the weight average molecular weight Mw and the number average molecular weight Mn in terms of polystyrene measured by gel permeation chromatography (GPC).
　ポリプロピレン系樹脂（Ａ）の溶融状態から２５℃に急冷した際の半結晶化時間は、接着性の観点から、好ましくは３分以上であるか又は示差走査型熱量計（ＤＳＣ）で溶融状態から－１０℃／ｍｉｎで冷却する過程で測定される結晶化ピークが観測されない。より好ましくは１０分以上、更に好ましくは１５分以上であり、特に好ましくは２０分以上である。
　ポリプロピレン系樹脂（Ａ）の半結晶化時間は、示差走査型熱量計（ＤＳＣ）（パーキン・エルマー社製、商品名：「ＤＳＣ－７」）を用い、試料１０ｍｇを２５℃で５分間保持し、３２０℃／分で２２０℃に昇温し５分間保持した後、３２０℃／分で２５℃に冷却し、６０分間保持することにより、等温結晶化過程における、発熱量の時間変化を測定することでも得られる。ここで、等温結晶化開始時から結晶化完了時までの発熱量の積分値を１００％とした時、等温結晶化開始時から発熱量の積分値が５０％となるまでの時間を等温半結晶化時間（ｔ1/2）として定義する。 The semi-crystallization time when the polypropylene resin (A) is rapidly cooled to 25 ° C. from the molten state is preferably 3 minutes or more from the viewpoint of adhesiveness or from the molten state by a differential scanning calorimeter (DSC). No crystallization peak measured in the process of cooling at −10 ° C./min is observed. It is more preferably at least 10 minutes, even more preferably at least 15 minutes, particularly preferably at least 20 minutes.
The half-crystallization time of the polypropylene resin (A) was measured by using a differential scanning calorimeter (DSC) (manufactured by Perkin-Elmer Co., Ltd., trade name: “DSC-7”) at 10 ° C. for 5 minutes at 25 ° C. The temperature is raised to 220 ° C. at 320 ° C./min and held for 5 minutes, then cooled to 25 ° C. at 320 ° C./min, and held for 60 minutes to measure the time change of the calorific value during the isothermal crystallization process. Can also be obtained. Here, assuming that the integrated value of the calorific value from the start of isothermal crystallization to the completion of crystallization is 100%, the time from the start of isothermal crystallization until the integrated value of the calorific value becomes 50% is the isothermal half-crystallization. Is defined as the conversion time (t 1/2 ).
　ポリプロピレン系樹脂（Ａ）は、上述の融解吸熱量（ΔＨ－Ｄ）が上記範囲を満たせば、特に限定されないが、例えば、プロピレン単独重合体、プロピレン－エチレンブロック共重合体、プロピレン－ブテンブロック共重合体、プロピレン－α－オレフィンブロック共重合体、プロピレン－エチレンランダム共重合体、プロピレン－ブテンランダム共重合体、プロピレン－α－オレフィンランダム共重合体、又はプロピレン－α－オレフィングラフト共重合体等から選択されるプロピレン系重合体であることが好ましい。中でも、プロピレン単独重合体やプロピレン－エチレンランダム共重合体がより好ましく、プロピレン単独重合体が更に好ましい。 The polypropylene-based resin (A) is not particularly limited as long as the above-mentioned melting endotherm (ΔHD) satisfies the above range. For example, propylene homopolymer, propylene-ethylene block copolymer, propylene-butene block copolymer Polymer, propylene-α-olefin block copolymer, propylene-ethylene random copolymer, propylene-butene random copolymer, propylene-α-olefin random copolymer, propylene-α-olefin graft copolymer, etc. The propylene polymer is preferably selected from the group consisting of: Among them, a propylene homopolymer and a propylene-ethylene random copolymer are more preferable, and a propylene homopolymer is more preferable.
　ポリプロピレン系樹脂（Ａ）が共重合体である場合は、エチレン及び炭素数４～３０のα－オレフィンからなる群より選ばれる少なくとも１つの構成単位を、０モル％を超えて２０モル％以下含むことが、架橋によるブツ発生を抑制し、樹脂組成物の柔軟性を高める観点から好ましい。このような観点から、より好ましくは０．５モル％以上、更に好ましくは１．０モル％以上であり、そして、より好ましくは１８．５モル％以下、更に好ましくは１５．０モル％以下、より更に好ましくは１０．０モル％以下である。 When the polypropylene resin (A) is a copolymer, it contains at least one structural unit selected from the group consisting of ethylene and α-olefins having 4 to 30 carbon atoms, in an amount of more than 0 mol% and not more than 20 mol%. This is preferable from the viewpoint of suppressing the occurrence of bumps due to crosslinking and increasing the flexibility of the resin composition. From such a viewpoint, it is more preferably at least 0.5 mol%, further preferably at least 1.0 mol%, and more preferably at most 18.5 mol%, further preferably at most 15.0 mol%, It is even more preferably at most 10.0 mol%.
　また、ポリプロピレン系樹脂（Ａ）は、炭素数が２のオレフィンを含有する共重合体の場合には、炭素数が２のオレフィン（すなわち、エチレンモノマー）の構成単位が、好ましくは０モル％を超え２０モル％以下、より好ましくは０モル％を超え１８モル％以下、更に好ましくは０モル％を超え１６モル％以下、より更に好ましくは０モル％を超え１４モル％以下である。また、炭素数が４以上のαオレフィンを含有する共重合体の場合には、炭素数が４以上のα－オレフィン含有量が、好ましくは０モル％を超え３０モル％以下、より好ましくは０モル％を超え２５モル％以下、更に好ましくは０モル％を超え２０モル％以下である。 When the polypropylene resin (A) is a copolymer containing an olefin having 2 carbon atoms, the structural unit of the olefin having 2 carbon atoms (that is, ethylene monomer) is preferably 0 mol%. It is more than 20 mol%, more preferably more than 0 mol% and 18 mol% or less, further preferably more than 0 mol% and 16 mol% or less, even more preferably more than 0 mol% and 14 mol% or less. In the case of a copolymer containing α-olefins having 4 or more carbon atoms, the content of α-olefins having 4 or more carbon atoms is preferably more than 0 mol% and 30 mol% or less, more preferably 0 mol% or less. It is more than 25 mol% and more preferably more than 0 mol% and 20 mol% or less.
　ポリプロピレン系樹脂（Ａ）としては市販品を用いることができる。具体例としては、「Ｌ－ＭＯＤＵ」（登録商標）（出光興産（株）製）の「Ｓ４００」、「Ｓ４１０」、「Ｓ６００」、「Ｓ９０１」が挙げられる。非晶質ポリα－オレフィン（ＡＰＡＯ）の市販品として、ＬＬＣ社製の「ＲＥＸｔａｃ」、エボニック社製の「Ｖｅｓｔｏｐｌａｓｔ」、Ｅａｓｔｍａｎ社製の「Ｅａｓｔｏｆｌｅｘ」、「Ａｅｒａｆｉｎ」等も挙げられる（いずれも商品名）。プロピレン系エラストマーの市販品として、三井化学（株）製の「タフマーＸＭ」、「タフマーＰＮ」、「タフマーＳＮ」；（株）プライムポリマー製の「プライムＴＰＯ」；ダウ・ケミカル（株）製の「Ｖｅｒｓｉｆｙ」；エクソンモービル社製の「Ｖｉｓｔａｍａｘｘ」、「Ｌｉｎｘａｒ」、クラリアント社製の「Ｌｉｃｏｃｅｎｅ」；バセル社製の「Ａｄｆｌｅｘ」等も挙げられる（いずれも商品名）。 市 販 A commercially available product can be used as the polypropylene resin (A). Specific examples include “S400”, “S410”, “S600”, and “S901” of “L-MODU” (registered trademark) (manufactured by Idemitsu Kosan Co., Ltd.). Commercially available amorphous poly-α-olefins (APAO) include “Rextac” manufactured by LLC, “Vestoplast” manufactured by Evonik, “Eastflex”, “Aerafin” manufactured by Eastman, etc. Name). Commercially available propylene elastomers include “Tuffmer XM”, “Tuffmer PN”, and “Tuffmer SN” manufactured by Mitsui Chemicals, Inc .; “Prime TPO” manufactured by Prime Polymer Co., Ltd .; and Dow Chemical Co., Ltd. "Versify"; "Vistamaxx" and "Linxar" manufactured by ExxonMobil, "Licosene" manufactured by Clariant; "Adflex" manufactured by Bathell, and the like (all are trade names).
　ポリプロピレン系樹脂（Ａ）は、チーグラーナッタ型の触媒やメタロセン触媒等の重合触媒の存在下で単量体を重合させて得ることができる。中でも、ポリプロピレン系樹脂（Ａ）は、メタロセン触媒により得られるポリプロピレン系樹脂であることが好ましい。メタロセン触媒は均一系触媒の一種であり、得られる重合体は狭い分子量分布や狭い組成分布を有する均一な重合体となる。 The polypropylene resin (A) can be obtained by polymerizing a monomer in the presence of a polymerization catalyst such as a Ziegler-Natta type catalyst or a metallocene catalyst. Among them, the polypropylene resin (A) is preferably a polypropylene resin obtained with a metallocene catalyst. The metallocene catalyst is a kind of homogeneous catalyst, and the resulting polymer is a uniform polymer having a narrow molecular weight distribution and a narrow composition distribution.
　ホットメルト接着剤中におけるポリプロピレン系樹脂（Ａ）の含有量は、樹脂成分（ベースポリマー）１００質量％に対して、好ましくは１質量％以上、より好ましくは５質量％以上、更に好ましくは１０質量％以上、より更に好ましくは１５質量％以上、特に好ましくは２５質量％である。上限は特に限定されないが、１００質量％であってもよく、９０質量％以下であってもよく、８５質量％以下であってもよく、８０質量％以下であってもよい。
　また、ホットメルト接着剤中におけるポリプロピレン系樹脂（Ａ）は１種類でもよく、２種類以上を用いてもよい。 The content of the polypropylene resin (A) in the hot melt adhesive is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass, based on 100% by mass of the resin component (base polymer). %, More preferably 15% by mass or more, particularly preferably 25% by mass. The upper limit is not particularly limited, but may be 100% by mass, 90% by mass or less, 85% by mass or less, or 80% by mass or less.
Further, the polypropylene resin (A) in the hot melt adhesive may be of one type or two or more types.
（核剤（Ｂ））
　本実施形態のホットメルト接着剤は、核剤（Ｂ）を含有する。前記ポリプロピレン系樹脂（Ａ）は結晶化速度が遅いため、これを用いたホットメルト接着剤は、固化時間が比較的遅く、被着体への追従性が良好で接着性には優れるが、その反面、固化しにくいために、接着剤の塗布面側からその反対側の面に向かって接着剤が染み出る、いわゆる裏抜けと呼ばれる現象が生じやすい。本実施形態のホットメルト接着剤は、核剤（Ｂ）を含有することで、ポリプロピレン系樹脂（Ａ）の結晶化速度が向上し、固化速度に優れる。その結果として、接着剤塗布時における接着剤の裏抜けを抑制することができる。 (Nucleating agent (B))
The hot melt adhesive of the present embodiment contains a nucleating agent (B). Since the polypropylene-based resin (A) has a low crystallization rate, a hot-melt adhesive using the same has a relatively slow solidification time, good adherence to an adherend, and excellent adhesion. On the other hand, since it is difficult to solidify, a phenomenon called so-called strike-through, in which the adhesive exudes from the adhesive-coated surface to the opposite surface, is likely to occur. The hot melt adhesive of the present embodiment contains the nucleating agent (B), whereby the crystallization speed of the polypropylene resin (A) is improved, and the solidification speed is excellent. As a result, the strike-through of the adhesive during the application of the adhesive can be suppressed.
　核剤（Ｂ）は、ポリプロピレン系樹脂（Ａ）の物性を低下させることなく、速やかに結晶化を誘発し、結晶化が始まるのに必要な結晶化温度を高くするものが好ましい。
　核剤（Ｂ）の具体例としては、ソルビトール系及びノニトール系等のアセタール系核剤；カルボキサミド、トリアミド、ビスアミド等のアミド系核剤；リン酸エステル金属塩、カルボン酸金属塩、フェニルホスホン酸金属塩等の有機金属塩系核剤；タルク、炭酸カルシウム等の無機微粒子系核剤等が挙げられる。ポリプロピレン系樹脂（Ａ）の結晶化速度を向上させる観点から、核剤（Ｂ）は、アセタール系核剤、アミド系核剤及び有機金属塩系核剤からなる群より選ばれる少なくとも１種であることが好ましい。また、これらを組み合わせ使用してもよい。また、ポリプロピレン系樹脂（Ａ）の特性に影響を与えない範囲で核剤（Ｂ）のマスターバッチとして添加してもよい。
　上記の核剤は混練する際の温度条件や添加する濃度によって結晶化速度の向上効果が変化するため、それぞれの核剤に合わせて条件を最適化することが望ましい。
　例えば、以下に挙げる、新日本理化（株）製の「エヌジェスターＮＵ－１００」の場合は、好ましくは２６０～３２０℃、より好ましくは２８０～３００℃で混練した場合に結晶化速度の向上効果が大きくなる。また、ＢＡＳＦ社製の「Ｉｒｇａｃｌｅａｒ　ＸＴ３８６」は、前記ポリプロピレン系樹脂（Ａ）１００質量部に対して好ましくは５～１，０００質量ｐｐｍ、より好ましくは１０～５００質量ｐｐｍ、更に好ましくは５０～２００質量ｐｐｍの濃度で添加した場合に、結晶化速度の向上効果が大きくなる。さらに、日産化学工業（株）製の「エコプロモートＣ」等は、好ましくは良分散状態とすることで結晶化速度の向上効果が大きくなる。 The nucleating agent (B) is preferably one that induces crystallization quickly without lowering the physical properties of the polypropylene resin (A) and raises the crystallization temperature required for crystallization to start.
Specific examples of the nucleating agent (B) include acetal-based nucleating agents such as sorbitol and nonitol; amide-based nucleating agents such as carboxamide, triamide, and bisamide; metal phosphate salts, metal carboxylate salts, and metal phenylphosphonate. Organic metal salt nucleating agents such as salts; inorganic fine particle nucleating agents such as talc and calcium carbonate; From the viewpoint of improving the crystallization rate of the polypropylene resin (A), the nucleating agent (B) is at least one selected from the group consisting of acetal nucleating agents, amide nucleating agents, and organic metal salt nucleating agents. Is preferred. Further, these may be used in combination. The nucleating agent (B) may be added as a master batch within a range that does not affect the properties of the polypropylene resin (A).
Since the effect of improving the crystallization rate of the above nucleating agent varies depending on the temperature conditions during kneading and the concentration to be added, it is desirable to optimize the conditions according to each nucleating agent.
For example, in the case of “Ngester NU-100” manufactured by Shin-Nippon Rika Co., Ltd., the effect of improving the crystallization rate when kneaded at preferably 260 to 320 ° C., more preferably 280 to 300 ° C. Becomes larger. Further, “Irgclear XT386” manufactured by BASF is preferably 5 to 1,000 ppm by mass, more preferably 10 to 500 ppm by mass, and still more preferably 50 to 200 ppm by mass with respect to 100 parts by mass of the polypropylene resin (A). When added at a concentration of ppm by mass, the effect of improving the crystallization rate is increased. Furthermore, "Eco Promote C" manufactured by Nissan Chemical Industries, Ltd. or the like is preferably in a good dispersion state, whereby the effect of improving the crystallization rate is increased.
　アセタール系核剤としては、ソルビトール系核剤及びノニトール系核剤からなる群より選ばれる少なくとも１種であることが好ましい。ソルビトール誘導体として、例えば、１，３：２，４－ビス－Ｏ－ベンジリデン－Ｄ－グルシトール－ジベンジリデンソルビトール、１，３：２，４－ビス－Ｏ－（４－メチルベンジリデン）－Ｄ－ソルビトール、１，３：２，４－ビス－Ｏ－（３，４－ジメチルベンジリデン）ソルビトール、ビス（４－プロピルベンジリデン）プロピルソルビトール、ノニトール、１，２，３－トリデオキシ－４，６：５，７－ビス－ｏ－［（４－プロピルフェニル）メチレン］及びそれらの混合物が挙げられる。アセタール系核剤の市販品として、新日本理化（株）製の「ゲルオールＤ」、「ゲルオールＭＤ」、「ゲルオールＤＸＲ」、ミリケンケミカル社製の「Ｍｉｌｌａｄ　３９０５」、「Ｍｉｌｌａｄ　３９４０」、「Ｍｉｌｌａｄ　３９８８」「Ｍｉｌｌａｄ　ＮＸ８０００」等が挙げられる。 The acetal-based nucleating agent is preferably at least one selected from the group consisting of sorbitol-based nucleating agents and nonitol-based nucleating agents. As sorbitol derivatives, for example, 1,3: 2,4-bis-O-benzylidene-D-glucitol-dibenzylidene sorbitol, 1,3: 2,4-bis-O- (4-methylbenzylidene) -D-sorbitol , 1,3: 2,4-bis-O- (3,4-dimethylbenzylidene) sorbitol, bis (4-propylbenzylidene) propylsorbitol, nonitol, 1,2,3-trideoxy-4,6: 5,7 -Bis-o-[(4-propylphenyl) methylene] and mixtures thereof. As commercial products of acetal-based nucleating agents, "Gelol D", "Gelol MD", "Gelol DXR" manufactured by Shin Nippon Rika Co., Ltd., "Millad 3905", "Millad 3940", "Millad 3988" manufactured by Milliken Chemical Co., Ltd. "Millad NX8000" and the like.
　アミド系核剤としては、カルボキサミド系核剤及びトリアミド系核剤からなる群より選ばれる少なくとも１種であることが好ましく、カルボキサミド系が特に好ましい。アミド系核剤として、例えばＮ，Ｎ’－ジシクロヘキシル－２，６－ナフタレンジカルボキサミド、１，３，５－トリス［２，２－ジメチルプロピル－アミノ］ベンゼン、Ｎ，Ｎ’，Ｎ”－トリス［２－メチルシクロヘキサン－１－イル］－プロパン－１，２，３－トリイルカルボキサミド、Ｎ，Ｎ’－エチレンビスステアリン酸アミドが挙げられる。アミド系核剤の市販品として、新日本理化（株）製の「エヌジェスターＮＵ－１００」、ＢＡＳＦ社製の「Ｉｒｇａｃｌｅａｒ　ＸＴ３８６」、新日本理化（株）製の「リカクリアＰＣ１」等が挙げられる。 The amide nucleating agent is preferably at least one selected from the group consisting of a carboxamide nucleating agent and a triamide nucleating agent, and a carboxamide nucleating agent is particularly preferred. Examples of the amide nucleating agent include N, N'-dicyclohexyl-2,6-naphthalenedicarboxamide, 1,3,5-tris [2,2-dimethylpropyl-amino] benzene, N, N ', N "-tris [2-Methylcyclohexane-1-yl] -propane-1,2,3-triylcarboxamide, N, N′-ethylenebisstearic acid amide, etc. Commercially available amide-based nucleating agents include Shin-Nippon Rika ( “Nrgester NU-100” manufactured by BASF, “Irgclear @ XT386” manufactured by BASF, and “Likaclear PC1” manufactured by Nippon Rika Co., Ltd.
　有機金属塩系核剤は、微粉状であり、樹脂中に分散させて使用する。有機金属塩系核剤としては、リン酸エステル金属塩、カルボン酸金属塩、フェニルホスホン酸金属塩等が挙げられ、中でも、ポリプロピレン系樹脂（Ａ）の結晶化速度を向上させる観点から、リン酸エステル金属塩及びフェニルホスホン酸金属塩系核剤が好ましく、フェニルホスホン酸金属塩系核剤が特に好ましい。有機金属塩系核剤の市販品として、（株）ＡＤＥＫＡ製の「ＡＤＫＳＴＡＢ　ＮＡ－１１」、「ＡＤＫＳＴＡＢ　ＮＡ－２１」及び「ＡＤＫＳＴＡＢ　ＮＡ－２７」、Ｃｌａｒｉａｎｔ製「Ｈｏｓｔａｎｏｘ４０３０」、ミリケンケミカル社製の「ＨＰＮ－６８Ｌ」日産化学工業（株）製の「エコプロモートＣ」等が挙げられる。 The organic metal salt nucleating agent is in the form of fine powder and is used by dispersing it in a resin. Examples of the organic metal salt nucleating agent include a phosphoric acid ester metal salt, a carboxylic acid metal salt, and a phenylphosphonic acid metal salt. Among them, phosphoric acid is preferred from the viewpoint of improving the crystallization rate of the polypropylene resin (A). Ester metal salts and phenylphosphonic acid metal salt nucleating agents are preferred, and phenylphosphonic acid metal salt nucleating agents are particularly preferred. Commercially available organic metal salt-based nucleating agents include "ADKSTAB @ NA-11", "ADKSTAB @ NA-21" and "ADKSTAB @ NA-27" manufactured by ADEKA, "Hostanox 4030" manufactured by Clariant, and "Milken Chemical". HPN-68L "Eco-promote C" manufactured by Nissan Chemical Industries, Ltd. and the like.
　ホットメルト接着剤中における核剤（Ｂ）の含有量は、ポリプロピレン系樹脂（Ａ）の物性を低下させることなく、ポリプロピレン系樹脂（Ａ）の結晶化速度を向上させる観点から、ポリプロピレン系樹脂（Ａ）１００質量部に対して、５質量ｐｐｍ以上、好ましくは１０質量ｐｐｍ以上、より好ましくは５０質量ｐｐｍ以上であり、そして、ポリプロピレン系樹脂（Ａ）に対する分散性の観点から、５０，０００質量ｐｐｍ以下、好ましくは２０，０００質量ｐｐｍ以下、より好ましくは５，０００質量ｐｐｍ以下、更に好ましくは１，０００質量ｐｐｍ以下、更に好ましくは５００質量ｐｐｍ以下、更に好ましくは２００質量ｐｐｍ以下である。本発明のホットメルト接着剤は、目視観察したときに、核剤に起因した目視可能な白点状の凝集が実質的にないことが好ましい。 The content of the nucleating agent (B) in the hot melt adhesive is determined from the viewpoint of improving the crystallization speed of the polypropylene resin (A) without deteriorating the physical properties of the polypropylene resin (A). A) It is at least 5 ppm by mass, preferably at least 10 ppm by mass, more preferably at least 50 ppm by mass with respect to 100 parts by mass, and 50,000 parts by mass from the viewpoint of dispersibility in the polypropylene resin (A). ppm, preferably 20,000 mass ppm or less, more preferably 5,000 mass ppm or less, still more preferably 1,000 mass ppm or less, further preferably 500 mass ppm or less, and still more preferably 200 mass ppm or less. The hot melt adhesive of the present invention is preferably substantially free from visible white spot-like aggregation caused by the nucleating agent when visually observed.
（粘着性付与剤（Ｄ））
　本実施形態のホットメルト接着剤は、粘着性付与剤（Ｄ）を更に含有してもよい。
　粘着性付与剤（Ｄ）としては、例えば、脂肪族系炭化水素石油樹脂の水素化誘導体、ロジン誘導体樹脂、ポリテルペン樹脂、石油樹脂、油溶性フェノール樹脂などからなる常温で固体、半固体あるいは液状のもの等を挙げることができる。具体的には、天然ロジン、変性ロジン、水添ロジン、天然ロジンのグリセロールエステル、変性ロジンのグリセロールエステル、天然ロジンのペンタエリスリトールエステル、変性ロジンのペンタエリスリトールエステル、水添ロジンのペンタエリスリトールエステル、天然テルペンのコポリマー、天然テルペンの３次元ポリマー、水添テルペンのコポリマーの水素化誘導体、ポリテルペン樹脂、フェノール系変性テルペン樹脂の水素化誘導体、脂肪族石油炭化水素樹脂、脂肪族石油炭化水素樹脂の水素化誘導体、芳香族石油炭化水素樹脂、芳香族石油炭化水素樹脂の水素化誘導体、環状脂肪族石油炭化水素樹脂、環状脂肪族石油炭化水素樹脂の水素化誘導体を例示することができる。これらは単独で又は二種以上を組み合わせて用いてもよい。本発明では、ベースポリマーとの相溶性を考慮して、水素添加物を用いることが好ましい。中でも、熱安定性に優れる石油樹脂の水素化物がより好ましい。 (Tackifier (D))
The hot melt adhesive of the present embodiment may further contain a tackifier (D).
As the tackifier (D), for example, a solid, semi-solid or liquid at room temperature composed of a hydrogenated derivative of an aliphatic hydrocarbon petroleum resin, a rosin derivative resin, a polyterpene resin, a petroleum resin, an oil-soluble phenol resin, or the like. And the like. Specifically, natural rosin, modified rosin, hydrogenated rosin, glycerol ester of natural rosin, glycerol ester of modified rosin, pentaerythritol ester of natural rosin, pentaerythritol ester of modified rosin, pentaerythritol ester of hydrogenated rosin, natural Terpene copolymers, three-dimensional polymers of natural terpenes, hydrogenated derivatives of hydrogenated terpene copolymers, polyterpene resins, hydrogenated derivatives of phenolic modified terpene resins, aliphatic petroleum hydrocarbon resins, hydrogenation of aliphatic petroleum hydrocarbon resins Derivatives, aromatic petroleum hydrocarbon resins, hydrogenated derivatives of aromatic petroleum hydrocarbon resins, cycloaliphatic petroleum hydrocarbon resins, hydrogenated derivatives of cycloaliphatic petroleum hydrocarbon resins can be exemplified. These may be used alone or in combination of two or more. In the present invention, it is preferable to use a hydrogenated product in consideration of compatibility with the base polymer. Above all, hydrides of petroleum resins having excellent thermal stability are more preferable.
　粘着性付与剤（Ｄ）の市販品としては、以下を挙げることができる。
　原油及びナフサ精製過程で得られる原料を用いて製造した粘着性付与剤としては、「アイマーブ」（出光興産（株）製）、「アルコン」（荒川化学工業（株）製）、「クイントン」（日本ゼオン（株）製）、「Ｔ－ＲＥＺ」（ＪＸＴＧエネルギー（株）製）、「Ｅｓｃｏｒｅｚ」、「Ｏｐｐｅｒａ」（以上、ＥｘｘｏｎＭｏｂｉｌ　Ｃｈｅｍｉｃａｌ社製）、「Ｅａｓｔｏｔａｃ」、「Ｒｅｇａｌｉｔｅ」、「Ｒｅｇａｌｒｅｚ」、「Ｐｌａｓｔｏｌｙｎ」（以上、Ｅａｓｔｍａｎ社製）、「Ｓｕｋｏｌｅｚ」（Ｋｏｌｏｎ社製）及び「Ｗｉｎｇｔａｃｋ」、「Ｎｏｒｓｏｌｅｎｅ」（以上、Ｃｒａｙ　Ｖａｌｌｅｙ社製）等を挙げることができる（いずれも商品名）。
　オレンジ等から得られる精油を原料として用いて製造した粘着性付与剤としては、「クリアロン」（ヤスハラケミカル（株）製）及び「Ｓｙｌｖａｌｉｔｅ」、「Ｓｙｌｖａｒｅｓ」（Ａｒｉｚｏｎａ　Ｃｈｅｍｉｃａｌ社製）等を挙げることができる（いずれも商品名）。
　ロジン等の原料を用いて製造した粘着性付与剤としては、「ハリタック」、「ネオトール」（ハリマ化成（株）製）及び「エステルガム」、「ペンセル」（荒川化学工業（株）製）等を挙げることができる（いずれも商品名）。 Commercially available products of the tackifier (D) include the following.
Examples of the tackifiers produced using crude oil and the raw material obtained in the naphtha refining process include “I-MARV” (manufactured by Idemitsu Kosan Co., Ltd.), “ALCON” (manufactured by Arakawa Chemical Industry Co., Ltd.), “Quinton” ( Nippon Zeon Co., Ltd.), "T-REZ" (JXTG Energy Co., Ltd.), "Escorez", "Opera" (all from ExxonMobil Chemical), "Eastotac", "Regalite", "Regalrez", "Plastolyn" (all from Eastman), "Sukolez" (Kolon), "Wingtack", "Norsolene" (all from Cray Valley) and the like can be mentioned (all are trade names).
Examples of the tackifier manufactured using an essential oil obtained from orange or the like as a raw material include "Clearon" (manufactured by Yashara Chemical Co., Ltd.) and "Sylvalite" and "Sylvares" (manufactured by Arizona Chemical). (All are trade names).
Examples of tackifiers manufactured using raw materials such as rosin include "Haritac", "Neotol" (manufactured by Harima Chemicals, Inc.), "Ester Gum", and "Pencel" (manufactured by Arakawa Chemical Industries, Ltd.). (Both are trade names).
　ホットメルト接着剤における粘着性付与剤（Ｄ）の含有量は、粘着性向上及び塗布性の観点から、ホットメルト接着剤中における樹脂成分（ベースポリマー）の含有量１００質量部に対して、好ましくは２０質量部以上、より好ましくは３０質量部以上、更に好ましくは４０質量部以上、より更に好ましくは５０質量部以上であり、そして、好ましくは２００質量部以下、より好ましくは１５０質量部以下、更に好ましくは１２０質量部以下、より更に好ましくは１００質量部以下である。 The content of the tackifier (D) in the hot-melt adhesive is preferably based on 100 parts by mass of the resin component (base polymer) in the hot-melt adhesive from the viewpoint of improving tackiness and applicability. Is 20 parts by mass or more, more preferably 30 parts by mass or more, still more preferably 40 parts by mass or more, even more preferably 50 parts by mass or more, and preferably 200 parts by mass or less, more preferably 150 parts by mass or less, More preferably, it is 120 parts by mass or less, even more preferably 100 parts by mass or less.
　また、粘着性付与剤（Ｄ）の軟化点は特に限定されるものではないが、軟化点が高すぎると塗布時のホットメルト接着剤の粘度増加により塗布性が悪くなり、軟化点が低すぎるとホットメルト接着剤の熱安定性が悪くなり、メルター内で焼け付きが発生して接着性や臭気に悪影響を与える。以上の理由から、粘着性付与剤（Ｄ）の軟化点は、好ましくは８０℃以上、より好ましくは８５℃以上、更に好ましくは９０℃以上であり、そして、好ましくは１３０℃以下、より好ましくは１２０℃以下、更に好ましくは１１０℃以下である。 The softening point of the tackifier (D) is not particularly limited. However, if the softening point is too high, the viscosity of the hot-melt adhesive at the time of coating increases, so that the coatability deteriorates and the softening point is too low. In addition, the thermal stability of the hot melt adhesive becomes poor, and seizure occurs in the melter, which adversely affects the adhesiveness and odor. For the reasons described above, the softening point of the tackifier (D) is preferably 80 ° C. or higher, more preferably 85 ° C. or higher, even more preferably 90 ° C. or higher, and preferably 130 ° C. or lower, more preferably It is 120 ° C. or lower, more preferably 110 ° C. or lower.
（オイル（Ｅ））
　本実施形態のホットメルト接着剤は、オイル（Ｅ）を更に含有してもよい。
　オイル（Ｅ）としては、特に限定されず、パラフィン系プロセスオイル、ナフテン系プロセスオイル、イソパラフィン系オイル等の鉱物油、芳香族系の鉱物油系炭化水素、ポリブテン、ポリイソブチレン、ポリブタジエン、ポリ（α－オレフィン）等の低分子量物等の合成樹脂系炭化水素、アルキルベンゼンやひまし油、あまに油、ナタネ油、ヤシ油等の脂肪油系軟化剤、ジブチルフタレート、ジオクチルフタレート、ジオクチルアジペート、ジオクチルセバケート等のエステル系可塑剤等が例示できる。中でも、鉱物油系炭化水素、パラフィン系プロセスオイル及びナフテン系プロセスオイルからなる群より選ばれる少なくとも１種であることが好ましく、パラフィン系炭化水素の炭素数が全炭素数の５０％を占めるパラフィン系オイルが特に好ましい。 (Oil (E))
The hot melt adhesive of the present embodiment may further contain an oil (E).
The oil (E) is not particularly limited, and mineral oils such as paraffin-based process oil, naphthene-based process oil and isoparaffin-based oil, aromatic mineral oil-based hydrocarbons, polybutene, polyisobutylene, polybutadiene, and poly (α) -Olefin) and other synthetic resin-based hydrocarbons such as low molecular weight products, alkylbenzenes, castor oil, linseed oil, rapeseed oil, fatty oil-based softeners such as coconut oil, dibutyl phthalate, dioctyl phthalate, dioctyl adipate, dioctyl sebacate, etc. Ester plasticizers and the like. Among them, at least one selected from the group consisting of mineral oil-based hydrocarbons, paraffin-based process oils, and naphthene-based process oils is preferred, and paraffin-based hydrocarbons have a carbon number of 50% of the total carbon number. Oil is particularly preferred.
　鉱物油系炭化水素の重量平均分子量は５０～２，０００、特に１００～１，５００のものが好ましく、流動点は－４０～０℃、特に－３０～０℃であるのが好ましく、引火点（ＣＯＣ法）は２００～４００℃、特に２５０～３５０℃であることが好ましい。
　なお、流動点は、ＪＩＳ　Ｋ２２６９に準拠して測定した値であり、引火点は、ＪＩＳ　Ｋ２２６５に準拠して測定した値である。 The weight average molecular weight of the mineral oil-based hydrocarbon is preferably from 50 to 2,000, particularly preferably from 100 to 1,500, and the pour point is preferably from -40 to 0 ° C, particularly preferably from -30 to 0 ° C. The (COC method) is preferably at 200 to 400 ° C., particularly 250 to 350 ° C.
The pour point is a value measured according to JIS K2269, and the flash point is a value measured according to JIS K2265.
　また、オイル（Ｅ）の４０℃における動粘度は、５ｃＳｔ以上８００ｃＳｔ以下であるのが好ましく、１０ｃＳｔ以上５００ｃＳｔ以下であるのがより好ましい。
　なお、動粘度は、ＩＳＯ３１０４に準拠して測定した値である。 The kinematic viscosity of the oil (E) at 40 ° C. is preferably 5 cSt or more and 800 cSt or less, more preferably 10 cSt or more and 500 cSt or less.
The kinematic viscosity is a value measured according to ISO3104.
　パラフィン系プロセスオイルの市販品としては、出光興産（株）製の「ダイアナプロセスオイルＰＷ－３２」、「ダイアナプロセスオイルＰＷ－９０」、「ダイアナプロセスオイルＰＷ－１５０」、「ダイアナプロセスオイルＰＳ－３２」、「ダイアナプロセスオイルＰＳ－９０」、「ダイアナプロセスオイルＰＳ－４３０」；シェブロンＵＳＡ社製の「Ｋａｙｄｏｌオイル」、「ＰａｒａＬｕｘオイル」等が挙げられる（いずれも商品名）。 Commercially available paraffin-based process oils include “Diana Process Oil PW-32”, “Diana Process Oil PW-90”, “Diana Process Oil PW-150”, and “Diana Process Oil PS-” manufactured by Idemitsu Kosan Co., Ltd. 32, "Diana Process Oil PS-90", "Diana Process Oil PS-430"; "Kaydol Oil" and "ParaLux Oil" manufactured by Chevron USA (all are trade names).
　イソパラフィン系オイルの市販品としては、出光興産（株）製の「ＩＰソルベント１０１６」、「ＩＰソルベント１６２０」、「ＩＰソルベント２０２８」、「ＩＰソルベント２８３５」、「ＩＰクリーンＬＸ」；日油（株）製の「ＮＡソルベント」シリーズ等が挙げられる（いずれも商品名）。 Commercially available isoparaffinic oils include "IP Solvent 1016", "IP Solvent 1620", "IP Solvent 2028", "IP Solvent 2835", "IP Clean LX" manufactured by Idemitsu Kosan Co., Ltd .; And "NA Solvent" series (both are trade names).
　本実施形態のホットメルト接着剤がオイル（Ｅ）を含有する場合、その含有量は、ホットメルト接着剤の粘着性向上、塗布性、及び粘度低下による被着体への濡れ性向上の観点から、ホットメルト接着剤中における樹脂成分（ベースポリマー）の含有量１００質量部に対して、好ましくは５質量部以上、より好ましくは１０質量部以上であり、そして、好ましくは２００質量部以下、より好ましくは１００質量部以下、更に好ましくは５０質量部以下である。 When the hot melt adhesive of the present embodiment contains an oil (E), the content is determined from the viewpoint of improving the tackiness of the hot melt adhesive, applicability, and improving the wettability to an adherend due to a decrease in viscosity. , Based on 100 parts by mass of the resin component (base polymer) in the hot melt adhesive, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and preferably 200 parts by mass or less. It is preferably at most 100 parts by mass, more preferably at most 50 parts by mass.
（直鎖炭化水素系ワックス（Ｆ））
　本実施形態のホットメルト接着剤は、融解吸熱量（ΔＨ－Ｄ）が１２０Ｊ／ｇを超え３００Ｊ／ｇ以下である直鎖炭化水素系ワックス（Ｆ）を更に含有してもよい。
　直鎖炭化水素系ワックス（Ｆ）の融解吸熱量（ΔＨ－Ｄ）は、固化速度の観点から、より好ましくは１４０Ｊ／ｇ以上、更に好ましくは１６０Ｊ／ｇ以上であり、そして、より好ましくは２８０Ｊ／ｇ以下、更に好ましくは２５０Ｊ／ｇ以下である。なお、直鎖炭化水素系ワックス（Ｆ）の融解吸熱量（ΔＨ－Ｄ）は、上述したポリプロピレン系樹脂（Ａ）の融解吸熱量（ΔＨ－Ｄ）と同様にして測定される。 (Linear hydrocarbon wax (F))
The hot melt adhesive of the present embodiment may further contain a linear hydrocarbon wax (F) having a melting endotherm (ΔHD) of more than 120 J / g and 300 J / g or less.
The melting endotherm (ΔHD) of the linear hydrocarbon wax (F) is more preferably 140 J / g or more, still more preferably 160 J / g or more, and more preferably 280 J, from the viewpoint of solidification rate. / G or less, more preferably 250 J / g or less. The melting endotherm (ΔHD) of the linear hydrocarbon wax (F) is measured in the same manner as the above-mentioned melting endotherm (ΔHD) of the polypropylene resin (A).
　直鎖炭化水素系ワックス（Ｆ）の融点（Ｔｍ－Ｄ）は、好ましくは５０℃以上、より好ましくは８０℃以上であり、そして、好ましくは１５０℃以下、より好ましくは１３０℃以下である。なお、直鎖炭化水素系ワックス（Ｆ）の融点（Ｔｍ－Ｄ）は、上述したポリプロピレン系樹脂（Ａ）の融点（Ｔｍ－Ｄ）と同様にして測定される。 The melting point (Tm-D) of the linear hydrocarbon wax (F) is preferably at least 50 ° C, more preferably at least 80 ° C, and preferably at most 150 ° C, more preferably at most 130 ° C. The melting point (Tm-D) of the linear hydrocarbon wax (F) is measured in the same manner as the above-mentioned melting point (Tm-D) of the polypropylene resin (A).
　直鎖炭化水素系ワックスとしては、例えば、パラフィンワックス、高級脂肪酸ワックス、高級脂肪酸エステルワックス、フィッシャー・トロプシュワックス、ポリエチレンワックス、ポリプロピレンワックス等を例示できる（ただし、後述するエチレン系重合体（Ｇ）に該当するものを除く。）。 Examples of the straight-chain hydrocarbon wax include paraffin wax, higher fatty acid wax, higher fatty acid ester wax, Fischer-Tropsch wax, polyethylene wax, polypropylene wax and the like (however, the ethylene polymer (G) described below). Excludes that apply.)
　直鎖炭化水素系ワックス（Ｆ）の市販品としては、以下を挙げることができる。
　フィッシャー・トロプシュワックスとしては、サゾール社製の「Ｓａｓｏｌ」等が挙げられ、パラフィンワックスとしては、日本精蝋株式会社製の「Ｐａｒａｆｆｉｎ　Ｗａｘ」等が挙げられる。さらに、低密度ポリエチレン系ワックスとしては、三井化学株式会社製の「ハイワックス」ＮＬシリーズ等が挙げられる（いずれも商品名）。 Commercial products of the linear hydrocarbon wax (F) include the following.
Examples of the Fischer-Tropsch wax include "Sasol" manufactured by Sasol, and examples of the paraffin wax include "Paraffin Wax" manufactured by Nippon Seiro Co., Ltd. Further, as the low-density polyethylene-based wax, "Hi Wax" NL series manufactured by Mitsui Chemicals, Inc. and the like are listed (all are trade names).
　本実施形態のホットメルト接着剤における直鎖炭化水素系ワックス（Ｆ）の含有量は、柔軟性向上及び塗布性向上の観点から、ホットメルト接着剤中における樹脂成分（ベースポリマー）の含有量１００質量部に対して、好ましくは１０，０００質量部以下、より好ましくは５，０００質量部以下、更に好ましくは５００質量部以下、更に好ましくは１００質量部以下である。ワックスの含有量が多くなると、熱可塑性樹脂組成物の粘度が低くなる。そのため、熱可塑性樹脂組成物からなるホットメルト接着剤の用途に応じて、直鎖炭化水素系ワックス（Ｆ）の含有量を適宜決定することが好ましい。 The content of the linear hydrocarbon-based wax (F) in the hot melt adhesive of the present embodiment is 100% in terms of the content of the resin component (base polymer) in the hot melt adhesive from the viewpoint of improving flexibility and coating properties. The amount is preferably 10,000 parts by mass or less, more preferably 5,000 parts by mass or less, still more preferably 500 parts by mass or less, and still more preferably 100 parts by mass or less with respect to parts by mass. When the content of the wax increases, the viscosity of the thermoplastic resin composition decreases. Therefore, it is preferable to appropriately determine the content of the linear hydrocarbon wax (F) according to the use of the hot melt adhesive made of the thermoplastic resin composition.
＜エチレン系重合体（Ｇ）＞
　本実施形態のホットメルト接着剤は、融解吸熱量（ΔＨ－Ｄ）が０Ｊ／ｇ以上１２０Ｊ／ｇ以下であるエチレン系重合体（Ｇ）を含有してもよい。エチレン系重合体（Ｇ）は、ホットメルト接着剤のベースポリマーとして含まれることが好ましい。
　エチレン系重合体（Ｇ）の融解吸熱量（ΔＨ－Ｄ）は、柔軟性の観点から、好ましくは２０Ｊ／ｇ以上、より好ましくは４０Ｊ／ｇ以上であり、そして、好ましくは１００Ｊ／ｇ以下、より好ましくは８０Ｊ／ｇ以下である。なお、エチレン系重合体（Ｇ）の融解吸熱量（ΔＨ－Ｄ）は、上述したポリプロピレン系樹脂（Ａ）の融解吸熱量（ΔＨ－Ｄ）と同様にして測定される。 <Ethylene polymer (G)>
The hot melt adhesive of the present embodiment may contain an ethylene polymer (G) having a melting endotherm (ΔHD) of 0 J / g or more and 120 J / g or less. The ethylene polymer (G) is preferably contained as a base polymer of the hot melt adhesive.
The melting endothermic amount (ΔHD) of the ethylene polymer (G) is preferably 20 J / g or more, more preferably 40 J / g or more, and preferably 100 J / g or less, from the viewpoint of flexibility. More preferably, it is 80 J / g or less. The melting endotherm (ΔHD) of the ethylene polymer (G) is measured in the same manner as the above-mentioned melting endotherm (ΔHD) of the polypropylene resin (A).
　また、エチレン系重合体（Ｇ）の融点（Ｔｍ－Ｄ）は、塗布性の観点から、好ましくは３０℃以上、より好ましくは５０℃以上であり、そして、好ましくは８５℃未満、より好ましくは８０℃以下である。なお、エチレン系重合体（Ｇ）の融点（Ｔｍ－Ｄ）は、上述したポリプロピレン系樹脂（Ａ）の融点（Ｔｍ－Ｄ）と同様にして測定される。 Further, the melting point (Tm-D) of the ethylene polymer (G) is preferably 30 ° C. or higher, more preferably 50 ° C. or higher, and preferably less than 85 ° C., more preferably, from the viewpoint of applicability. 80 ° C. or less. The melting point (Tm-D) of the ethylene-based polymer (G) is measured in the same manner as the melting point (Tm-D) of the polypropylene-based resin (A).
　エチレン系重合体（Ｇ）は、エチレン単独重合体又はエチレン系共重合体である。エチレン系共重合体とは、エチレンと、エチレンと共重合し得る共重合性モノマーとの共重合体をいう。共重合性モノマーとしては、α－オレフィン；酢酸ビニル、（メタ）アクリル酸、（メタ）アクリル酸エステル、マレイン酸、マレイン酸エステル等のカルボン酸（エステル）；無水マレイン酸、無水フタル酸、無水コハク酸等のカルボン酸無水物；等を例示できる。これら共重合性モノマーはエチレンと単独で共重合されてもよいし、２種以上の共重合性モノマーが共重合されてもよい。エチレン系共重合体としては、エチレン／α－オレフィンコポリマー、エチレン／カルボン酸共重合体、エチレン／カルボン酸エステル共重合体、エチレン／カルボン酸無水物共重合体を例示できる。 Ethylene polymer (G) is an ethylene homopolymer or an ethylene copolymer. The ethylene-based copolymer refers to a copolymer of ethylene and a copolymerizable monomer copolymerizable with ethylene. Examples of the copolymerizable monomer include α-olefins; carboxylic acids (esters) such as vinyl acetate, (meth) acrylic acid, (meth) acrylate, maleic acid, and maleic ester; maleic anhydride, phthalic anhydride, and anhydride. Carboxylic acid anhydrides such as succinic acid; and the like. These copolymerizable monomers may be copolymerized with ethylene alone, or two or more copolymerizable monomers may be copolymerized. Examples of the ethylene copolymer include an ethylene / α-olefin copolymer, an ethylene / carboxylic acid copolymer, an ethylene / carboxylic acid ester copolymer, and an ethylene / carboxylic anhydride copolymer.
　なお、本明細書では、（メタ）アクリル酸とは、メタクリル酸及びアクリル酸の双方を含む概念をいう。（メタ）アクリル酸エステルの具体例としては、アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ－プロピル、アクリル酸ｎ－ブチル、アクリル酸イソブチル、アクリル酸２－エチルヘキシル、アクリル酸２－ヒドロキシエチル、アクリル酸イソオクチル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸グリシジル等が挙げられる。 In the present specification, (meth) acrylic acid refers to a concept including both methacrylic acid and acrylic acid. Specific examples of (meth) acrylates include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, acryl Isooctyl acid, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate and the like can be mentioned.
　エチレン系重合体（Ｇ）としては、ホットメルト接着剤の接着性及び臭気の観点から、炭素数３～３０（好ましくは炭素数３～１０）のα－オレフィンからなる群より選ばれる少なくとも１つの構成単位を０モル％を超え４０モル％以下含むことが好ましい。エチレン系重合体（Ｇ）は、エチレン／α－オレフィンコポリマーであることが好ましく、エチレンと炭素数３～３０（好ましくは炭素数３～１０）のα－オレフィンとの共重合体であることが好ましい。また、メタロセン触媒で重合して得られたエチレン／α－オレフィンコポリマーであることが好ましい。α－オレフィンの具体例としては、プロピレン、１－ブテン，１－ペンテン，４－メチル－１－ペンテン，１－ヘキセン，１－オクテン，１－デセン，１－ドデセン，１－テトラデセン，１－ヘキサデセン，１－オクタデセン，１－エイコセン等が挙げられる。本実施形態においては、これらのうち一種又は二種以上を用いることができる。これらのα－オレフィンの中でもプロピレンもしくは１－オクテンが好ましい。本実施形態に用いられるエチレン系重合体（Ｇ）は、接着性の観点から、より好ましくはエチレン－１－オクテン共重合体であり、更に好ましくは１－オクテンから導かれる構成単位を５～２０モル％含有するエチレン－１－オクテン共重合体である。本実施形態のホットメルト接着剤は、メタロセン触媒で重合して得られたエチレン／α－オレフィンコポリマーを含む場合、低温でのスパイラル塗工適性が向上し、ポリエチレンフィルムや不織布との接着性も更に優れる。 As the ethylene polymer (G), at least one selected from the group consisting of α-olefins having 3 to 30 carbon atoms (preferably having 3 to 10 carbon atoms) from the viewpoint of the adhesiveness and odor of the hot melt adhesive. It is preferable to contain more than 0 mol% and no more than 40 mol% of structural units. The ethylene-based polymer (G) is preferably an ethylene / α-olefin copolymer, and is preferably a copolymer of ethylene and an α-olefin having 3 to 30 (preferably 3 to 10) carbon atoms. preferable. Further, an ethylene / α-olefin copolymer obtained by polymerization with a metallocene catalyst is preferable. Specific examples of the α-olefin include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, and 1-hexadecene , 1-octadecene, 1-eicosene and the like. In the present embodiment, one or more of these can be used. Propylene or 1-octene is preferred among these α-olefins. The ethylene-based polymer (G) used in the present embodiment is more preferably an ethylene-1-octene copolymer from the viewpoint of adhesiveness, and still more preferably contains 5 to 20 structural units derived from 1-octene. It is an ethylene-1-octene copolymer containing mol%. When the hot melt adhesive of the present embodiment contains an ethylene / α-olefin copolymer obtained by polymerization with a metallocene catalyst, the suitability for spiral coating at low temperatures is improved, and the adhesion to a polyethylene film or a nonwoven fabric is further improved. Excellent.
　エチレン系重合体（Ｇ）の市販品としては、「Ｅｘａｃｔ」シリーズ（エクソンモービル社製）、「Ａｆｆｉｎｉｔｙ　ｐｏｌｙｍｅｒ」シリーズ、「Ｉｎｆｕｓｅ」シリーズ（ともにダウ・ケミカル社製）等があり、より好ましくは、「Ａｆｆｉｎｉｔｙ　ＧＡ１８７５」、「Ａｆｆｉｎｉｔｙ　ＧＡ１９００」、「Ａｆｆｉｎｉｔｙ　ＧＡ１９５０」、「Ａｆｆｉｎｉｔｙ　ＧＰ１５７０」、「Ｉｎｆｕｓｅ　９８０７」、「Ｉｎｆｕｓｅ９８１７」（ダウ・ケミカル社製）が挙げられる（いずれも商品名）。 Commercial products of the ethylene-based polymer (G) include the “Exact” series (manufactured by ExxonMobil), the “Affinity @ polymer” series, and the “Infuse” series (both manufactured by Dow Chemical Company). "Affinity @ GA1875", "Affinity @ GA1900", "Affinity @ GA1950", "Affinity @ GP1570", "Infuse @ 9807", "Infuse9817" (manufactured by Dow Chemical Company) (all are trade names).
　ホットメルト接着剤におけるエチレン系重合体（Ｇ）の含有量は、柔軟性向上及び塗布性向上の観点から、ポリプロピレン系樹脂（Ａ）の含有量１００質量部に対して、好ましくは１０，０００質量部以下、より好ましくは７，５００質量部以下、更に好ましくは５，０００質量部以下である。
　樹脂成分（ベースポリマー）中におけるエチレン系重合体（Ｇ）の含有量が多くなると、強度が低下する。そのため、ホットメルト接着剤の用途に応じて、エチレン系重合体（Ｇ）の含有量を適宜決定することが好ましい。 The content of the ethylene-based polymer (G) in the hot melt adhesive is preferably 10,000 parts by mass based on 100 parts by mass of the polypropylene-based resin (A) from the viewpoint of improving flexibility and coatability. Or less, more preferably 7,500 parts by mass or less, and still more preferably 5,000 parts by mass or less.
When the content of the ethylene polymer (G) in the resin component (base polymer) increases, the strength decreases. Therefore, it is preferable to appropriately determine the content of the ethylene polymer (G) according to the use of the hot melt adhesive.
　ポリプロピレン系樹脂（Ａ）及びエチレン系重合体（Ｇ）の合計量１００質量％中における前記ポリプロピレン系樹脂（Ａ）の含有量は、好ましくは２５質量％以上、より好ましくは５０質量％以上、更に好ましくは７５質量％以上である。 The content of the polypropylene resin (A) in the total amount of 100% by mass of the polypropylene resin (A) and the ethylene polymer (G) is preferably 25% by mass or more, more preferably 50% by mass or more, and furthermore It is preferably at least 75% by mass.
（その他の添加剤）
　また、本実施形態のホットメルト接着剤は、本発明の効果を阻害しない範囲内で、必要に応じて可塑剤、無機フィラー、酸化防止剤等の各種添加剤を更に含有してもよい。 (Other additives)
Further, the hot melt adhesive of the present embodiment may further contain various additives such as a plasticizer, an inorganic filler, an antioxidant and the like, as needed, as long as the effects of the present invention are not impaired.
　可塑剤としては、フタル酸エステル類、アジピン酸エステル類、脂肪酸エステル類、グリコール類、エポキシ系高分子可塑剤等を例示できる。 Examples of the plasticizer include phthalates, adipic esters, fatty acid esters, glycols, epoxy polymer plasticizers, and the like.
　無機フィラーとしては、タルク、炭酸カルシウム、炭酸バリウム、ウォラストナイト、シリカ、クレー、雲母、カオリン、酸化チタン、ケイソウ土、尿素系樹脂、スチレンビーズ、澱粉、硫酸バリウム、硫酸カルシウム、ケイ酸マグネシウム、炭酸マグネシウム、アルミナ、石英粉末等を例示できる。 As the inorganic filler, talc, calcium carbonate, barium carbonate, wollastonite, silica, clay, mica, kaolin, titanium oxide, diatomaceous earth, urea resin, styrene beads, starch, barium sulfate, calcium sulfate, magnesium silicate, Examples thereof include magnesium carbonate, alumina, and quartz powder.
　酸化防止剤としては、トリスノニルフェニルホスファイト、ジステアリルペンタエリスリトールジホスファイト、「アデカスタブ１１７８」（株式会社ＡＤＥＫＡ製）、「スタミライザーＴＮＰ」（住友化学株式会社製）、「イルガフォス１６８」（ＢＡＳＦ社製）、「ＳａｎｄｓｔａｂＰ－ＥＰＱ」（サンド社製）、等のリン系酸化防止剤、２，６－ジ－ｔ－ブチル－４－メチルフェノール、ｎ－オクタデシル－３－（３’，５’－ジ－ｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート、「スミライザーＢＨＴ」（住友化学株式会社製）、「イルガノックス１０１０」（ＢＡＳＦ社製）等のフェノール系酸化防止剤、ジラウリル－３，３’－チオジプロピオネート、ペンタエリスリトールテトラキス（３－ラウリルチオプロピオネート）、「スミライザーＴＰＬ」（住友化学株式会社製）、「ＤＬＴＰ「ヨシトミ」」（三菱ケミカル株式会社製）、「アンチオックスＬ」（日油株式会社製）等のイオウ系酸化防止剤などを例示できる。 Examples of antioxidants include trisnonylphenyl phosphite, distearylpentaerythritol diphosphite, "Adecastab 1178" (manufactured by ADEKA Corporation), "Stamlyzer TNP" (manufactured by Sumitomo Chemical Co., Ltd.), and "Ilgafos 168" (BASF Phosphorus antioxidants such as “Sandstab P-EPQ” (manufactured by Sando), 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3- (3 ′, 5 ′) Phenolic antioxidants such as -di-t-butyl-4'-hydroxyphenyl) propionate, "SUMILIZER BHT" (manufactured by Sumitomo Chemical Co., Ltd.) and "Irganox 1010" (manufactured by BASF), dilauryl-3,3 '-Thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate) ), "SUMILIZER TPL" (manufactured by Sumitomo Chemical Co., Ltd.), "DLTP" Yoshitomi "" (manufactured by Mitsubishi Chemical Corporation), "Antiox L" (manufactured by NOF CORPORATION), etc. Can be exemplified.
　また、本実施形態のホットメルト接着剤は、直鎖炭化水素系ワックス（Ｆ）以外のワックスを更に含有してもよい。直鎖炭化水素系ワックス（Ｆ）以外のワックスとしては、動物ワックス、植物ワックス、カルナウバワックス、キャンデリラワックス、木蝋、蜜蝋、鉱物ワックス、石油ワックス、マイクロクリスタリンワックス、ペトロラタム、高級脂肪酸ワックス、高級脂肪酸エステルワックス等が挙げられる。 ホ ッ ト In addition, the hot melt adhesive of the present embodiment may further contain a wax other than the linear hydrocarbon wax (F). Examples of the wax other than the linear hydrocarbon wax (F) include animal wax, vegetable wax, carnauba wax, candelilla wax, wood wax, beeswax, mineral wax, petroleum wax, microcrystalline wax, petrolatum, higher fatty acid wax, and higher-grade wax. Fatty acid ester waxes and the like.
　さらに、本実施形態のホットメルト接着剤においては、架橋剤や架橋助剤等を添加して部分架橋させることも可能である。
　架橋剤としては、有機パーオキサイド、イオウ、イオウ化合物、フェノール樹脂等のフェノール系加硫剤等が挙げられる。これらの中では、有機パーオキサイドが好ましい。有機パーオキサイドの具体例としては、２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）－ヘキサン、２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）－３－ヘキシン；２，５－ジメチル－２，５－ジ（ベンゾイルパーオキシ）－ヘキサン；ｔ－ブチルパーオキシベンゾエート；ジクミルパーオキサイド；ｔ－ブチルクミルパーオキサイド；ジイソプロピルベンゼンハイドロパーオキサイド；１，３－ビス（ｔ－ブチルパーオキシイソプロピル）ベンゼン；ベンゾイルパーオキサイド；１，１－ジ（ｔ－ブチルパーオキシ）－３，３，５－トリメチルシクロヘキサン、ジ－ｔ－ブチルパーオキサイド、ｎ－ブチル－４，４－ビス（ｔ－ブチルパーオキシ）バレレート、ｐ－クロロベンゾイルパーオキサイド、２，４－ジクロロベンゾイルパーオキサイド、ｔ－ブチルパーオキシイソプロピルカーボネート、ジアセチルパーオキサイド、ラウロイルパーオキサイド等が挙げられる。これらの中では、臭気性、スコーチ安定性の点で、２，５－ジメチル－２，５－ジ－（ｔ－ブチルパーオキシ）ヘキサン、２，５－ジメチル－２，５－ジ－（ｔ－ブチルパーオキシ）－３－ヘキシン、１，３－ビス（ｔ－ブチルパーオキシイソプロピル）ベンゼン、１，１－ビス（ｔ－ブチルパーオキシ）－３，３，５－トリメチルシクロヘキサン、ｎ－ブチル－４，４－ビス（ｔ－ブチルパーオキシ）バレレートが好ましく、中でも、１，３－ビス（ｔ－ブチルパーオキシイソプロピル）ベンゼンが最も好ましい。 Further, in the hot melt adhesive of the present embodiment, it is possible to partially crosslink by adding a crosslinking agent or a crosslinking assistant.
Examples of the crosslinking agent include organic peroxides, sulfur, sulfur compounds, and phenolic vulcanizing agents such as phenolic resins. Of these, organic peroxides are preferred. Specific examples of the organic peroxide include 2,5-dimethyl-2,5-di (t-butylperoxy) -hexane and 2,5-dimethyl-2,5-di (t-butylperoxy) -3. -Hexyne; 2,5-dimethyl-2,5-di (benzoylperoxy) -hexane; t-butylperoxybenzoate; dicumyl peroxide; t-butylcumyl peroxide; diisopropylbenzene hydroperoxide; -Bis (t-butylperoxyisopropyl) benzene; benzoyl peroxide; 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, di-t-butylperoxide, n-butyl- 4,4-bis (t-butylperoxy) valerate, p-chlorobenzoyl peroxide, 2,4-dichloro Benzoyl peroxide, t- butyl peroxy isopropyl carbonate, diacetyl peroxide, lauroyl peroxide and the like. Among these, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane and 2,5-dimethyl-2,5-di- (t -Butylperoxy) -3-hexyne, 1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl -4,4-bis (t-butylperoxy) valerate is preferred, and 1,3-bis (t-butylperoxyisopropyl) benzene is most preferred.
　また、架橋助剤としては、例えば、Ｎ－メチル－Ｎ，４－ジニトロソアニリン、ニトロソベンゼン、ジフェニルグアニジン、ジビニルベンゼン、トリメチロールプロパントリ（メタ）アクリレート、エチレンジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、アリル（メタ）アクリレート、ジアリルフタレート、トリアリルシアヌレート、キノンジオキシム、ｐ，ｐ’－ジベンゾイルキノンジオキシム、ビスマレイミド、フェニレンビスマレイミド、トリメチロールプロパン－Ｎ，Ｎ’－ｍ－フェニレンジマレイミド、ポリエチレングリコールジメタクリレート、ビニルブチラート、ビニルステアレート、不飽和シラン化合物、硫黄等が挙げられる。このような架橋助剤を用いることにより、均一かつ緩和な架橋反応が期待できる。 Examples of the crosslinking assistant include N-methyl-N, 4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, divinylbenzene, trimethylolpropane tri (meth) acrylate, ethylene di (meth) acrylate, and diethylene glycol di (meth) acrylate. A) acrylate, allyl (meth) acrylate, diallyl phthalate, triallyl cyanurate, quinone dioxime, p, p'-dibenzoylquinone dioxime, bismaleimide, phenylenebismaleimide, trimethylolpropane-N, N'-m- Examples include phenylenedimaleimide, polyethylene glycol dimethacrylate, vinyl butyrate, vinyl stearate, unsaturated silane compounds, and sulfur. By using such a crosslinking aid, a uniform and mild crosslinking reaction can be expected.
　これらの架橋助剤の中では、トリアリルシアヌレート、エチレングリコールジメタクリレート、ジビニルベンゼン、ビスマレイミドが好ましい。これらは、取扱いが容易であり、被架橋処理物の主成分であるポリプロピレン系樹脂（Ａ）との相溶性が良好であり、かつ、有機過酸化物を可溶化する作用を有し、有機過酸化物の分散剤として働くため、熱処理による架橋効果が均質で、柔軟性と物性とのバランスのとれた樹脂組成物が得られる。 で は Among these crosslinking aids, triallyl cyanurate, ethylene glycol dimethacrylate, divinylbenzene, and bismaleimide are preferable. These are easy to handle, have good compatibility with the polypropylene resin (A), which is the main component of the object to be crosslinked, and have an action of solubilizing organic peroxides. Since it acts as an oxide dispersant, a resin composition having a uniform crosslinking effect by heat treatment and a balance between flexibility and physical properties can be obtained.
　架橋剤及び架橋助剤は、それぞれ１種を用いてもよく、２種以上を組み合わせて用いてもよい。
　架橋剤及び架橋助剤を使用する場合は、（Ａ）～（Ｇ）成分の合計量１００質量部に対して、０．１～５質量部の範囲で任意に使用し、架橋度を調整することができる。
　なお、架橋助剤として不飽和シラン化合物を使用した場合には、更にシラノール縮合触媒の存在下で水分と接触させて架橋を進行させることができる。 The cross-linking agent and the cross-linking assistant may be used alone or in combination of two or more.
When a crosslinking agent and a crosslinking aid are used, the degree of crosslinking is adjusted arbitrarily in the range of 0.1 to 5 parts by mass based on 100 parts by mass of the total of components (A) to (G). be able to.
When an unsaturated silane compound is used as a crosslinking aid, crosslinking can be further advanced by contact with moisture in the presence of a silanol condensation catalyst.
［ホットメルト接着剤の製造方法］
　本実施形態のホットメルト接着剤は、ポリプロピレン系樹脂（Ａ）に核剤（Ｂ）を添加し、更に必要に応じて、粘着性付与剤（Ｄ）、オイル（Ｅ）、直鎖炭化水素系ワックス（Ｆ）、エチレン系重合体（Ｇ）及び各種添加剤からなる群より選ばれる少なくとも１種を添加し、ヘンシェルミキサー等を用いてドライブレンドし、単軸又は二軸押出機、プラストミルやバンバリーミキサー等により溶融混練することで製造することができる。 [Production method of hot melt adhesive]
The hot melt adhesive of this embodiment is obtained by adding a nucleating agent (B) to a polypropylene resin (A), and further, if necessary, a tackifier (D), an oil (E), and a linear hydrocarbon-based resin. At least one selected from the group consisting of wax (F), ethylene-based polymer (G) and various additives is added and dry-blended using a Henschel mixer or the like, and a single-screw or twin-screw extruder, plast mill or Banbury is used. It can be produced by melt-kneading with a mixer or the like.
　溶融混練時の温度は、使用する核剤（Ｂ）の種類に応じて適宜決定することができる。例えば、フェニルホスホン酸金属塩を使用する場合は、ホットメルト接着剤中に低温で混練して分散させたときに結晶化速度の向上効果が大きいので、溶融混練時の温度は、好ましくは１５０℃以下、より好ましくは１００℃以下である。一方、アミド系核剤を使用する場合は、ホットメルト接着剤中に高温で混練して分散させたときに結晶化速度の向上効果が大きいので、溶融混練時の温度は、好ましくは２５０℃以上、より好ましくは２８０℃以上である。 温度 The temperature during melt-kneading can be appropriately determined according to the type of the nucleating agent (B) used. For example, when a metal phenylphosphonate is used, since the effect of improving the crystallization rate when kneaded and dispersed at a low temperature in a hot melt adhesive is large, the temperature during melt kneading is preferably 150 ° C. Or less, more preferably 100 ° C. or less. On the other hand, when an amide-based nucleating agent is used, the temperature at the time of melt-kneading is preferably 250 ° C. or higher, since the effect of improving the crystallization rate when kneaded and dispersed at a high temperature in a hot melt adhesive is large. 280 ° C. or more.
　本実施形態のホットメルト接着剤は、固化速度に優れる。固化速度が向上したホットメルト接着剤は、各種用途において有用である。
　本実施形態の熱可塑性樹脂組成物からなるホットメルト接着剤は、例えば、衛生材料用、製本用、繊維用、製缶用、フィルター用、低圧成形用、製袋用に好適に用いることができる。具体的には、包装分野（カートン、ダンボール、緩衝材の固定、紙器自動包装ラインの補修、サンプル固定、梱包チェック開梱後の包装、食品包装内の乾燥剤の包装等）、電気材料用（Ｃボードに電子部品固定、補強仮止め、防振補強、コネクター空きスペース充填、基板絶縁、ワイヤーの固定、カプセル化）、フィルム粘着加工、滑り止め（ＤＭ等のフィルム塗工）、住宅、建材（サイディング、タイル、床材、カーペット、生地、壁紙、見本接着）、建築・インテリア（断熱材フォームの接着、台所防水シート、畳表切断時ほつれ防止、屋根、ベランダＦＲＰ、クラック、タイル）、家具、木工（テーブル、椅子、ソファー、ベッド、鏡台キャビネット、補強材固定、布地の接着、フリルの固定、仏壇、バインディング等）、ホビー、小物類の接着、アクセサリー、伝統工芸品、自動車工業（ダッシュボード防振補強材の接着、ヘッド・ランプケースの接着、ドアー内装材、断熱防音防振材、フィルター、組立工程上の仮留め、天井材、ソファー、トランク用カーペット及びマット）、衛材分野（オムツ、生理用品の組み立て）、医療（シーツ、手術着、マスクの組み立て）、テキスタイルラミネート、自動車のフロアマットに代表されるアッセンブリー用途や、不織布又は高吸水性高分子（ＳＡＰ）の固定に代表される衛生材料用途等に好適に用いることができる。 The hot melt adhesive of the present embodiment has an excellent solidification rate. A hot melt adhesive having an improved solidification rate is useful in various applications.
The hot melt adhesive composed of the thermoplastic resin composition of the present embodiment can be suitably used for, for example, sanitary materials, bookbinding, fibers, cans, filters, low pressure molding, and bag making. . Specifically, for the packaging field (fixing cartons, cardboard, cushioning materials, repairing automatic packaging boxes, fixing samples, packaging after unpacking, packing desiccants in food packaging, etc.), for electrical materials ( Fixing electronic parts on C-board, temporary fixing, anti-vibration reinforcement, filling of connector empty space, board insulation, wire fixing, encapsulation), film adhesive processing, non-slip (film coating such as DM), housing, building materials ( Siding, tile, flooring, carpet, fabric, wallpaper, sample adhesion), architecture / interior (adhesion of insulation material, kitchen tarpaulin, prevention of fraying when cutting tatami, roof, veranda FRP, crack, tile), furniture, woodwork (Tables, chairs, sofas, beds, mirror cabinets, fixing of reinforcements, bonding of fabric, fixing of frills, Buddhist altars, binding, etc.), hobby, small Adhesives, accessories, traditional crafts, automotive industry (adhesion of dashboard anti-vibration reinforcement, adhesion of head / lamp case, door interior materials, thermal insulation and vibration-insulating materials, filters, temporary fixing in the assembly process, ceiling materials , Sofas, carpets and mats for trunks), sanitary materials (assembly of diapers and sanitary products), medical care (assembly of sheets, surgical gowns, masks), textile laminates, assembly uses such as automobile floor mats, and nonwoven fabrics Alternatively, it can be suitably used for sanitary material applications typified by fixation of superabsorbent polymers (SAP).
　例えば、衛生材料用途の場合、不織布へ塗布した際に染み抜けが抑制される。また、被着体同士の張り合わせ時に塗布した際、初期の接着強度（グリーン強度）が向上する。それによって、張り合わせ工程のインライン中での張り合わせ位置のずれを防止できる。
　包装用途の場合、配合物を造粒して箱に詰め合わせした際、ペレットが速く固まることで荷重による変形が抑制され、ペレット同士のブロッキングを抑制できる。
　木工用途の場合、被着体にホットメルト接着剤を塗布した後に一度ロールで巻き取る接着方法では、ホットメルト接着剤の固化が速くないとロール巻きがすべて接着して一体化してしまう。固化が速くなることで、巻き取りが可能になる。
　マットレス用途の場合、ポケットコイル同士の接着はオートメーション化された自動組み立て機で製造される。ポケットコイル同士が接着した後は、ズレ防止のために早期に接着強度が発現する必要があり、固化速度向上が有用となる。
　その他のアッセンブリー用途の場合、ハンドガンを使用してホットメルト接着剤を塗布・貼り付けすることがあるが、その際、セットタイムが短くなるので、張り合わせ直後からの接着強度が向上する。 For example, in the case of a sanitary material application, when applied to a nonwoven fabric, penetration through is suppressed. Further, when applied at the time of laminating the adherends, the initial adhesive strength (green strength) is improved. Thereby, it is possible to prevent the displacement of the bonding position during the in-line of the bonding process.
In the case of a packaging use, when the compound is granulated and packed in a box, the pellets are rapidly solidified, so that deformation due to load is suppressed, and blocking between the pellets can be suppressed.
In the case of woodworking, in a bonding method in which a hot-melt adhesive is applied to an adherend and then wound once with a roll, if the hot-melt adhesive does not solidify quickly, the rolls are all bonded and integrated. Faster solidification allows for winding.
For mattress applications, the bonding between the pocket coils is made on an automated automated assembly machine. After the pocket coils are adhered to each other, it is necessary to develop the adhesive strength early in order to prevent displacement, and it is useful to improve the solidification speed.
In the case of other assembly uses, the hot melt adhesive may be applied and affixed using a hand gun. At this time, the set time is shortened, and thus the adhesive strength immediately after lamination is improved.
　次に実施例により、本発明を具体的に説明するが、本発明は、これらの例によってなんら限定されるものではない。
　実施例及び比較例で使用した原料は以下の通りである。 Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
The raw materials used in the examples and comparative examples are as follows.
＜ポリプロピレン系樹脂（Ａ）＞
・Ａ１：「エルモーデュ　Ｓ４００」：メタロセン触媒により得られたポリプロピレン系樹脂、出光興産（株）製、融解吸熱量（ΔＨ－Ｄ）＝３６Ｊ／ｇ、融点（Ｔｍ－Ｄ）＝８０℃、重量平均分子量（Ｍｗ）＝４５，０００、２５℃における半結晶化時間＝２１．５分 <Polypropylene resin (A)>
A1: "Elmodu S400": a polypropylene resin obtained with a metallocene catalyst, manufactured by Idemitsu Kosan Co., Ltd., melting endotherm (ΔHD) = 36 J / g, melting point (Tm-D) = 80 ° C., weight average Molecular weight (Mw) = 45,000, half-crystallization time at 25 ° C. = 21.5 minutes
＜核剤（Ｂ）＞
・Ｂ１：「ゲルオールＤ」、新日本理化（株）製、ソルビトール系核剤
・Ｂ２：「ゲルオールＭＤ」、新日本理化（株）製、ソルビトール系核剤
・Ｂ３：「ゲルオールＤＸＲ」、新日本理化（株）製、ソルビトール系核剤
・Ｂ４：「Ｍｉｌｌａｄ　ＮＸ８０００」、ミリケンケミカル社製、ノニトール系核剤
・Ｂ５：「エヌジェスターＮＵ－１００」、新日本理化（株）製、カルボキサミド系核剤
・Ｂ６：「Ｉｒｇａｃｌｅａｒ　ＸＴ３８６」、ＢＡＳＦ社製、トリアミド系核剤
・Ｂ７：Ｎ，Ｎ’－エチレンビスステアリン酸アミド、富士フイルム和光純薬（株）製
・Ｂ８：「ＡＤＫＳＴＡＢ　ＮＡ－２７」、（株）ＡＤＥＫＡ製、リン酸エステル金属塩系核剤
・Ｂ９：「Ｈｙｐｅｒｆｏｒｍ　ＨＰＮ－６８Ｌ」、ミリケンケミカル社製、カルボン酸金属塩系核剤
・Ｂ１０：「エコプロモートＣ」、日産化学工業（株）製、フェニルホスホン酸金属塩系核剤 <Nucleating agent (B)>
B1: "Gelall D", a sorbitol-based nucleating agent manufactured by Shin Nippon Rika Co., Ltd. B2: "Gerol MD", a sorbitol-based nucleating agent manufactured by Shin Nippon Rika Co., Ltd. B3: "Gerol DXR", New Japan Sorbitol-based nucleating agent manufactured by Rika Co., Ltd. B4: "Millad NX8000", manufactured by Milliken Chemical Co., Ltd., nonitol-based nucleating agent B5: "Ngester NU-100", manufactured by Nippon Rika Co., Ltd., carboxamide-based nucleating agent -B6: "Irgclear XT386", manufactured by BASF, a triamide-based nucleating agent-B7: N, N'-ethylenebisstearic acid amide, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.-B8: "ADKSTAB NA-27", ( ADEKA CORPORATION, Phosphate ester metal salt nucleating agent B9: "Hyperform HPN-68L", manufactured by Milliken Chemical Co., Ltd. Metal salt-based nucleating agent · B10: "Ekopuro moat C", manufactured by Nissan Chemical Industries, Ltd., phenylphosphonic acid metal salt-based nucleating agent
＜粘着性付与剤（Ｄ）＞
・Ｄ１：「Ｅｓｃｏｒｅｚ　５３００」：ＤＣＰＤ系水添石油樹脂、エクソンモービルケミカル社製、軟化点＝１００℃
・Ｄ２：「Ｅａｓｔｏｔａｃ　Ｈ－１３０Ｗ」：Ｃ５系水添石油樹脂、イーストマンケミカル社製、軟化点＝１２５℃ <Tackifier (D)>
D1: "Escorez 5300": DCPD-based hydrogenated petroleum resin, manufactured by ExxonMobil Chemical Company, softening point = 100 ° C
D2: “Eastotac H-130W”: C5 hydrogenated petroleum resin, manufactured by Eastman Chemical Company, softening point = 125 ° C.
＜オイル（Ｅ）＞
・Ｅ１：「ダイアナプロセスオイルＰＷ－９０」：パラフィン系オイル、出光興産株式会社製、４０℃における動粘度９０ｃＳｔ <Oil (E)>
E1: "Diana Process Oil PW-90": paraffinic oil, manufactured by Idemitsu Kosan Co., Ltd., kinematic viscosity at 40.degree.
＜直鎖炭化水素系ワックス（Ｆ）＞
・Ｆ１：「Ｓａｓｏｌ　Ｈ－１」：フィッシャー・トロプッシュワックス、サゾール社製、融解吸熱量（ΔＨ－Ｄ）＝２２０Ｊ／ｇ、融点（Ｔｍ－Ｄ）＝１１０℃
・Ｆ２：「Ｐａｒａｆｆｉｎ　Ｗａｘ　－　１５０」：パラフィンワックス、日本精蝋（株）製、融解吸熱量（ΔＨ－Ｄ）＝１３０Ｊ／ｇ、融点（Ｔｍ－Ｄ）＝６５℃ <Linear hydrocarbon wax (F)>
F1: “Sasol H-1”: Fischer-Tropsch wax, manufactured by Sasol Co., Ltd., melting endotherm (ΔHD) = 220 J / g, melting point (Tm−D) = 110 ° C.
F2: "Paraffin Wax-150": paraffin wax, manufactured by Nippon Seiro Co., Ltd., melting endotherm (ΔHD) = 130 J / g, melting point (Tm-D) = 65 ° C.
＜エチレン系重合体（Ｇ）＞
・Ｇ１：「Ａｆｆｉｎｉｔｙ　ＧＡ　１９００」：エチレン－オクテンランダム共重合体、ダウ・ケミカル社製、融解吸熱量（ΔＨ－Ｄ）＝６０Ｊ／ｇ、融点（Ｔｍ－Ｄ）＝７０℃
・Ｇ２：「Ｉｎｆｕｓｅ　９８０７」：エチレン－オクテンマルチブロック共重合体、ダウ・ケミカル社製、融解吸熱量（ΔＨ－Ｄ）＝２０Ｊ／ｇ、融点（Ｔｍ－Ｄ）＝１２０℃ <Ethylene polymer (G)>
G1: “Affinity GA 1900”: ethylene-octene random copolymer, manufactured by Dow Chemical Company, melting endotherm (ΔHD) = 60 J / g, melting point (Tm−D) = 70 ° C.
G2: “Infuse 9807”: ethylene-octene multiblock copolymer, manufactured by Dow Chemical Company, melting endotherm (ΔHD) = 20 J / g, melting point (Tm−D) = 120 ° C.
〔ＤＳＣ測定〕
　示差走査型熱量計（パーキン・エルマー社製、「ＤＳＣ－７」）を用い、試料１０ｍｇを窒素雰囲気下－１０℃で５分間保持した後、１０℃／分で２２０℃まで昇温させることにより得られた融解吸熱カーブから融解吸熱量（ΔＨ－Ｄ又はΔＨｍ）として求めた。また、得られた融解吸熱カーブの最も高温側に観測されるピークのピークトップから融点（Ｔｍ－Ｄ）を求めた。
　２２０℃で５分間保持したのち、－１０℃／分で－１０℃まで降温させることにより得られた結晶化発熱カーブから結晶化発熱量（△Ｈｃ）として求めた。また、得られた結晶化発熱カーブのピークトップから結晶化温度（Ｔｃ）を求めた。
　なお、融解吸熱量（ΔＨ－Ｄ又はΔＨｍ）、結晶化発熱量（△Ｈｃ）は、熱量変化の無い低温側の点と熱量変化の無い高温側の点とを結んだ線をベースラインとして、示差走査型熱量計（パーキン・エルマー社製、「ＤＳＣ－７」）を用いた、ＤＳＣ測定により得られた融解吸熱カーブ、結晶化発熱カーブのピークを含むライン部分と当該ベースラインとで囲まれる面積を求めることで算出される。 [DSC measurement]
Using a differential scanning calorimeter (manufactured by Perkin-Elmer, "DSC-7"), 10 mg of a sample was kept at -10 ° C for 5 minutes in a nitrogen atmosphere, and then heated to 220 ° C at 10 ° C / minute. The melting endotherm (ΔHD or ΔHm) was obtained from the obtained melting endotherm curve. Further, the melting point (Tm-D) was determined from the peak top of the peak observed on the highest temperature side of the obtained melting endothermic curve.
After holding at 220 ° C. for 5 minutes, the temperature was lowered to −10 ° C. at −10 ° C./min, and the heat was obtained as a crystallization heat (ΔHc) from a crystallization heat curve obtained. The crystallization temperature (Tc) was determined from the peak top of the obtained crystallization exothermic curve.
In addition, the melting endotherm (ΔH−D or ΔHm) and the crystallization calorific value (ｃHc) are obtained by using a line connecting a low-temperature side point with no calorific value change and a high-temperature side point with no calorific value change as a baseline. A line portion including a peak of a melting endothermic curve and a crystallization exothermic curve obtained by DSC measurement using a differential scanning calorimeter (manufactured by Perkin-Elmer Co., Ltd., “DSC-7”) is surrounded by the base line. It is calculated by calculating the area.
〔重量平均分子量（Ｍｗ）〕
　ゲルパーミエイションクロマトグラフィ（ＧＰＣ）法により、重量平均分子量（Ｍｗ）を測定した。測定には、下記の装置および条件を使用し、ポリスチレン換算の重量平均分子量を得た。
＜ＧＰＣ測定装置＞
カラム　　　　　：東ソー（株）製「ＴＯＳＯ　ＧＭＨＨＲ－Ｈ（Ｓ）ＨＴ」
検出器　　　　　：液体クロマトグラム用ＲＩ検出　ウォーターズ・コーポレーション製「ＷＡＴＥＲＳ　１５０Ｃ」
＜測定条件＞
　溶媒　　　　　：１，２，４－トリクロロベンゼン
　測定温度　　　：１４５℃
　流速　　　　　：１．０ｍＬ／分
　試料濃度　　　：２．２ｍｇ／ｍＬ
　注入量　　　　：１６０μＬ
　検量線　　　　：Ｕｎｉｖｅｒｓａｌ　Ｃａｌｉｂｒａｔｉｏｎ
　解析プログラム：ＨＴ－ＧＰＣ（Ｖｅｒ．１．０） [Weight average molecular weight (Mw)]
The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC). For the measurement, the following apparatus and conditions were used, and a weight average molecular weight in terms of polystyrene was obtained.
<GPC measurement device>
Column: "TOSO GMHHR-H (S) HT" manufactured by Tosoh Corporation
Detector: RI detection for liquid chromatogram "WATERS 150C" manufactured by Waters Corporation
<Measurement conditions>
Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C
Flow rate: 1.0 mL / min Sample concentration: 2.2 mg / mL
Injection volume: 160 μL
Calibration curve: Universal Calibration
Analysis program: HT-GPC (Ver. 1.0)
〔半結晶化時間〕
　示差走査型熱量計（ＤＳＣ）（パーキン・エルマー社製、商品名：「ＤＳＣ－７」）を用い、下記方法にて測定した。
（１）試料１０ｍｇを２５℃で５分間保持し、３２０℃／分で２２０℃に昇温し５分間保持した後、３２０℃／分で２５℃に冷却し、６０分間保持することにより、等温結晶化過程における、発熱量の時間変化を測定した。
（２）等温結晶化開始時から結晶化完了時までの発熱量の積分値を１００％とした時、等温結晶化開始時から発熱量の積分値が５０％となるまでの時間を等温半結晶化時間（ｔ1/2）とした。 (Semi-crystallization time)
The measurement was carried out using a differential scanning calorimeter (DSC) (manufactured by Perkin-Elmer Co., Ltd., trade name: "DSC-7") by the following method.
(1) 10 mg of a sample is held at 25 ° C. for 5 minutes, heated to 220 ° C. at 320 ° C./min and held for 5 minutes, then cooled to 25 ° C. at 320 ° C./min, and held for 60 minutes to be isothermal. The time change of the calorific value during the crystallization process was measured.
(2) Assuming that the integrated value of the calorific value from the start of isothermal crystallization to the completion of crystallization is 100%, the time from the start of isothermal crystallization until the integrated value of the calorific value becomes 50% is the isothermal half-crystallization. (T 1/2 ).
〔引張弾性率の測定〕
　ＪＩＳ　Ｋ７１１３に準拠して、下記条件にて引張破断強度及び引張破断伸度を測定した。
・試験片：ＪＩＳ　Ｋ７１１３－２号　１／２サイズダンベル（厚み：１ｍｍ）
・測定温度：２３℃
・引張速度：１００ｍｍ／分
・チャック間距離：４０ｍｍ (Measurement of tensile modulus)
Based on JIS K7113, the tensile strength at break and tensile elongation at break were measured under the following conditions.
-Test piece: JIS K7113-1-2 1/2 size dumbbell (thickness: 1 mm)
・ Measurement temperature: 23 ° C
・ Pulling speed: 100mm / min ・ Distance between chucks: 40mm
〔軟化点〕
　ＪＡＩ７－１９９１に準拠して、Ｒｉｎｇ　ａｎｄ　Ｂａｌｌ法により測定した。 (Softening point)
It was measured by the Ring and Ball method in accordance with JAI7-1991.
実施例１～２２及び比較例１
　表１及び２に記載の種類及び配合量の各成分を、プラストミルを用いて、表１及び２に記載の温度で５分間、１００ｒｐｍの条件下で溶融混練し、樹脂組成物を調製した。なお、核剤（Ｂ５）を３００℃で混練した実施例１０～１１及び核剤（Ｂ１０）を８０℃で混練した実施例２１～２２では、二軸押出機（Ｌ／Ｄ＝３５、回転数；３００ｒｐｍ、吐出量；２５ｋｇ／ｈ）を用いて混練した。 Examples 1 to 22 and Comparative Example 1
The components of the types and compounding amounts shown in Tables 1 and 2 were melt-kneaded using a plast mill at the temperature shown in Tables 1 and 5 for 5 minutes at 100 rpm to prepare a resin composition. In Examples 10 to 11 in which the nucleating agent (B5) was kneaded at 300 ° C. and in Examples 21 and 22 in which the nucleating agent (B10) was kneaded at 80 ° C., the twin-screw extruder (L / D = 35, rotation speed) ; 300 rpm, discharge rate; 25 kg / h).
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
実施例２３～２７及び比較例２～６
　容量１００ｍＬの耐熱ガラス瓶に、表３に記載の成分を合計量が６０ｇとなるように仕込み、２００℃に３０分間かけて加熱して内容物を融解させた。その後、内容物をスパチュラで５分間撹拌して、２００℃で１０分間加熱した。以上の操作を５回繰り返して、熱可塑性樹脂組成物からなるホットメルト接着剤を得た。得られたホットメルト接着剤について、ポリテトラフルオロエチレンでコーティングされたバットに取り出した後、以下に示す方法で固化時間を測定した。また、実施例２７及び比較例６については、以下に示す方法でオープンタイムを測定した。結果を表３に示す。 Examples 23 to 27 and Comparative Examples 2 to 6
The components shown in Table 3 were charged into a heat-resistant glass bottle having a capacity of 100 mL so that the total amount was 60 g, and the content was melted by heating at 200 ° C. for 30 minutes. Thereafter, the contents were stirred with a spatula for 5 minutes and heated at 200 ° C. for 10 minutes. The above operation was repeated five times to obtain a hot melt adhesive made of the thermoplastic resin composition. After taking out the obtained hot melt adhesive into a vat coated with polytetrafluoroethylene, the solidification time was measured by the following method. In Example 27 and Comparative Example 6, the open time was measured by the following method. Table 3 shows the results.
（レオメーターを用いた固化時間の測定）
　レオメーター（Ａｎｔｏｎ－Ｐａａｒ社製、「ＭＣＲ３０１」）を用いて、Ｐ＆Ｐプレートでギャップ１ｍｍ、周波数１Ｈｚ、歪みはトルクが検出下限以上になるように任意に設定し、１５０℃から（１４１×ｅ-0.002×経過時間）℃／ｍｉｎで２５℃まで降温した後、２５℃を保持した時、降温を開始した時間を０秒とした時、粘度が１×１０5Ｐａ・ｓを超える時間を「レオメーターを用いた固化時間」と定義した。 (Measurement of solidification time using rheometer)
Rheometer (Anton-Paar, Inc., "MCR301") using, P & P plate gap 1 mm, frequency 1 Hz, strain is arbitrarily set so that the torque is equal to or higher than the detection limit, from 150 ℃ (141 × e - After the temperature was lowered to 25 ° C. at a rate of 0.002 × elapsed time / ° C./min, and when the temperature was kept at 25 ° C., the time when the temperature was started was set to 0 second, the time when the viscosity exceeded 1 × 10 5 Pa · s was referred to as “Rheo Solidification time using a meter ".
（硬度計を用いた固化時間の測定）
　直径５０ｍｍ、深さ１５ｍｍのアルミニウム製カップにホットメルト接着剤を２０ｇ秤量した後、１８０℃で３０分間加熱融解した。加熱終了後、ホットメルト接着剤がアルミニウム製カップに入った状態のまま、その表面に冷却スプレーを１０秒間吹き掛けた後、アルミニウム製カップを１Ｌの氷水中に投入して冷却した。１．５分後に氷水中から取り出し、氷水中から取り出してから３０秒後から、硬度計（西東京精密株式会社製「ＷＲ－１０４Ａ」）を用い、経過時間とショアＡ硬度との関係を調べた。氷水に浸した時間を０秒とした時、ショアＡ硬度が９０を超える時間を「硬度計を用いた固化時間」と定義して求めた。 (Measurement of solidification time using a hardness meter)
After weighing 20 g of the hot melt adhesive in an aluminum cup having a diameter of 50 mm and a depth of 15 mm, the mixture was heated and melted at 180 ° C. for 30 minutes. After the heating was completed, a cooling spray was sprayed on the surface of the aluminum cup while the hot melt adhesive was in the aluminum cup for 10 seconds, and the aluminum cup was put into 1 L of ice water to cool. 1.5 minutes later, the sample was taken out of the ice water, and after 30 seconds from the ice water, the relationship between the elapsed time and the Shore A hardness was examined using a hardness meter (“WR-104A” manufactured by Nishi Tokyo Seimitsu Co., Ltd.). Was. Assuming that the time of immersion in ice water was 0 seconds, the time when the Shore A hardness exceeded 90 was defined as "solidification time using a hardness meter".
（オープンタイム）
　オープンタイムとは、被着材に塗布したときから温度が下がって粘着性がなくなるまでの粘着保持時間をいう。
　１８０℃に加熱して溶融させたホットメルト接着剤を、Ｋライナーダンボールに塗工量２．８～３．２ｇ／ｍで塗布し、所定時間経過後に接着圧２ｋｇ／２５ｃｍ2、セットタイム２秒の条件で貼り合わせた。接着試験片を２３℃、湿度５０％の環境下で２４時間静置し、手で剥離させた。５回測定したうち、材料破壊率８０％以上の試験片が４個以上となる最長の経過時間をオープンタイム（秒）とした。 (Open time)
The open time refers to the adhesive holding time from when the adhesive is applied to the adherend until the temperature decreases and the adhesive disappears.
A hot melt adhesive melted by heating to 180 ° C. is applied to a K liner cardboard at a coating amount of 2.8 to 3.2 g / m, and after a predetermined time, an adhesive pressure of 2 kg / 25 cm 2 and a set time of 2 seconds Under the following conditions. The adhesive test piece was allowed to stand for 24 hours in an environment of 23 ° C. and 50% humidity, and was peeled off by hand. Of the five measurements, the longest elapsed time when four or more test pieces with a material destruction rate of 80% or more were defined as open time (seconds).
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003

Claims (15)

  1. 　示差走査型熱量計（ＤＳＣ）を用い、試料を窒素雰囲気下－１０℃で５分間保持した後、１０℃／分で昇温させることにより得られた融解吸熱カーブから得られる融解吸熱量（ΔＨ－Ｄ）が０Ｊ／ｇを超え８０Ｊ／ｇ以下であるポリプロピレン系樹脂（Ａ）及び核剤（Ｂ）を含有するホットメルト接着剤であって、前記核剤（Ｂ）の含有量が、前記ポリプロピレン系樹脂（Ａ）１００質量部に対して、５質量ｐｐｍ以上５０，０００質量ｐｐｍ以下である、ホットメルト接着剤。 Using a differential scanning calorimeter (DSC), the sample was kept at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then heated at a rate of 10 ° C./min. -D) a hot melt adhesive containing a polypropylene resin (A) having a nucleating agent (B) content of more than 0 J / g and not more than 80 J / g, wherein the content of the nucleating agent (B) is A hot melt adhesive having a content of 5 mass ppm or more and 50,000 mass ppm or less based on 100 parts by mass of the polypropylene resin (A).
  2. 　前記ポリプロピレン系樹脂（Ａ）が下記（１）を満たす、請求項１に記載のホットメルト接着剤。
    （１）示差走査型熱量計（ＤＳＣ）を用い、試料を窒素雰囲気下－１０℃で５分間保持した後、１０℃／分で昇温させることにより得られた融解吸熱カーブの最も高温側に観測されるピークトップとして定義される融点（Ｔｍ－Ｄ）が、観測されないか又は０℃以上１２０℃以下である。     The hot melt adhesive according to claim 1, wherein the polypropylene resin (A) satisfies the following (1).
    (1) Using a differential scanning calorimeter (DSC), the sample was kept at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then heated at a rate of 10 ° C./min. The melting point (Tm-D) defined as the observed peak top is not observed or is 0 ° C or more and 120 ° C or less.
  3. 　前記ポリプロピレン系樹脂（Ａ）の重量平均分子量（Ｍｗ）が５，０００以上３００，０００以下である、請求項１又は２に記載のホットメルト接着剤。 The hot melt adhesive according to claim 1 or 2, wherein the polypropylene resin (A) has a weight average molecular weight (Mw) of 5,000 to 300,000.
  4. 　前記ポリプロピレン系樹脂（Ａ）の２５℃における半結晶化時間が３分以上である、請求項１～３のいずれか１つに記載のホットメルト接着剤。 (4) The hot melt adhesive according to any one of (1) to (3), wherein a half-crystallization time at 25 ° C. of the polypropylene resin (A) is 3 minutes or more.
  5. 　前記ポリプロピレン系樹脂（Ａ）がプロピレン単独重合体である、請求項１～４のいずれか１つに記載のホットメルト接着剤。 ホ ッ ト The hot melt adhesive according to any one of claims 1 to 4, wherein the polypropylene resin (A) is a propylene homopolymer.
  6. 　前記ポリプロピレン系樹脂（Ａ）が、エチレン及び炭素数４～３０のα－オレフィンからなる群より選ばれる少なくとも１つの構成単位を０モル％を超え２０モル％以下含む、請求項１～４のいずれか１つに記載のホットメルト接着剤。 5. The polypropylene resin (A) according to claim 1, wherein the polypropylene resin (A) contains at least one structural unit selected from the group consisting of ethylene and α-olefins having 4 to 30 carbon atoms in an amount of more than 0 mol% and 20 mol% or less. The hot melt adhesive according to any one of the above.
  7. 　前記核剤（Ｂ）が、アセタール系核剤、アミド系核剤及び有機金属塩系核剤からなる群より選ばれる少なくとも１種である、請求項１～６のいずれか１つに記載のホットメルト接着剤。 The hot water according to any one of claims 1 to 6, wherein the nucleating agent (B) is at least one selected from the group consisting of an acetal nucleating agent, an amide nucleating agent, and an organic metal salt nucleating agent. Melt adhesive.
  8. 　前記核剤（Ｂ）が、ソルビトール系核剤及びノニトール系核剤からなる群より選ばれる少なくとも１種である、請求項１～７のいずれか１つに記載のホットメルト接着剤。 The hot melt adhesive according to any one of claims 1 to 7, wherein the nucleating agent (B) is at least one selected from the group consisting of a sorbitol nucleating agent and a nonitol nucleating agent.
  9. 　前記核剤（Ｂ）が、カルボキサミド系核剤及びトリアミド系核剤からなる群より選ばれる少なくとも１種である、請求項１～７のいずれか１つに記載のホットメルト接着剤。 The hot melt adhesive according to any one of claims 1 to 7, wherein the nucleating agent (B) is at least one selected from the group consisting of a carboxamide nucleating agent and a triamide nucleating agent.
  10. 　前記核剤（Ｂ）が、フェニルホスホン酸金属塩系核剤である、請求項１～７のいずれか１つに記載のホットメルト接着剤。 ホ ッ ト The hot melt adhesive according to any one of claims 1 to 7, wherein the nucleating agent (B) is a phenylphosphonic acid metal salt-based nucleating agent.
  11. 　核剤に起因した目視可能な白点状の凝集が実質的にない、請求項１０に記載のホットメルト接着剤。 The hot melt adhesive according to claim 10, wherein substantially no visible white spot-like aggregation caused by the nucleating agent is present.
  12. 　更に、粘着性付与剤（Ｄ）を含む、請求項１～１１のいずれか１つに記載のホットメルト接着剤。 (12) The hot melt adhesive according to any one of (1) to (11), further comprising a tackifier (D).
  13. 　更に、オイル（Ｅ）を含む、請求項１～１２のいずれか１つに記載のホットメルト接着剤。 The hot melt adhesive according to any one of claims 1 to 12, further comprising an oil (E).
  14. 　更に、直鎖炭化水素系ワックス（Ｆ）を含む、請求項１～１３のいずれか１つに記載のホットメルト接着剤。 (14) The hot melt adhesive according to any one of (1) to (13), further comprising a linear hydrocarbon wax (F).
  15. 　更に、エチレン系重合体（Ｇ）を含む、請求項１～１４のいずれか１つに記載のホットメルト接着剤。 (15) The hot melt adhesive according to any one of (1) to (14), further comprising an ethylene polymer (G).
PCT/JP2019/025745 2018-06-28 2019-06-27 Hot melt adhesive containing specific propylene resin composition WO2020004598A1 (en)

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JP2016524002A (en) * 2013-05-23 2016-08-12 ボスティック，インコーポレイテッド Hot melt adhesive based on low melting point polypropylene homopolymer
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JP2018504473A (en) * 2014-12-04 2018-02-15 エクソンモービル ケミカル パテンツ インコーポレイテッド Multimodal polymer blend, hot melt adhesive containing the same and use thereof

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JP2016524002A (en) * 2013-05-23 2016-08-12 ボスティック，インコーポレイテッド Hot melt adhesive based on low melting point polypropylene homopolymer
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