WO2020110921A1 - Hot melt composition - Google Patents

Hot melt composition Download PDF

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Publication number
WO2020110921A1
WO2020110921A1 PCT/JP2019/045727 JP2019045727W WO2020110921A1 WO 2020110921 A1 WO2020110921 A1 WO 2020110921A1 JP 2019045727 W JP2019045727 W JP 2019045727W WO 2020110921 A1 WO2020110921 A1 WO 2020110921A1
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Prior art keywords
molecular weight
hot melt
melt composition
styrene
mass
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PCT/JP2019/045727
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French (fr)
Japanese (ja)
Inventor
有利 日笠
悠 染谷
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積水フーラー株式会社
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Priority to JP2020521613A priority Critical patent/JP6812049B2/en
Publication of WO2020110921A1 publication Critical patent/WO2020110921A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/12Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02Vinyl aromatic monomers and conjugated dienes

Definitions

  • the present invention relates to a hot melt composition.
  • absorbent articles containing sanitary materials such as disposable diapers and sanitary napkins have been widely used.
  • a stretchable laminate composed of stretchable members is used to prevent slippage when worn.
  • a rubber thread in which a natural rubber or a synthetic polymer is formed into a thread is known. Since the rubber thread shows a good stress when stretched, it is effective in preventing the absorbent article from slipping off when worn.
  • a linear pressure is applied to the human body, which causes a feeling of pressure when wearing and a rash.
  • the rubber thread is easily broken during the production of the sanitary material, which often makes it difficult to manufacture the sanitary material.
  • a stretchable film containing a thermoplastic elastomer is known as a stretchable member of a stretchable laminate provided in an absorbent article.
  • a stretchable film having excellent moisture permeability and flexibility and suitable for absorbent articles such as sanitary products is provided.
  • the stretchable film the above-mentioned problems when using the rubber thread is solved, but when producing, the composition for producing the stretchable film has a high viscosity, and thus an extruder is required. Therefore, there is a problem that the hot melt adhesive application device which is usually used cannot be used and the productivity of sanitary materials is poor.
  • Patent Document 1 discloses a block copolymer containing an elastic polymer segment and a polystyrene polymer segment, which are one or more polymers selected from hydrogenated polymers of butadiene polymers or isoprene polymers, or ethylene propylene polymers.
  • a hot melt stretchable adhesive composition including coalescence is disclosed. According to the hot-melt stretchable adhesive composition, it can be applied using a normal hot-melt applicator, and since it has both adhesiveness and stretchability, it can be used as a base material such as a nonwoven fabric. By laminating, a hot melt adhesive that can easily form a gather portion is provided.
  • the hot-melt stretchable adhesive composition of Patent Document 1 cannot provide the necessary stretch at the time of putting on and taking off when applied to a disposable hygiene product, particularly a paper diaper, and the stretchable adhesive composition is Since the expansion and contraction recovery property is not sufficient, there is a problem that the stress decreases during wearing and the paper diaper is displaced.
  • a hot melt composition containing (A) a styrene block copolymer and (B) a plasticizer, Viscosity at 180°C is 2,000-60,000mPa ⁇ s, The polystyrene equivalent molecular weight distribution measured by gel permeation chromatography has one or more peaks in the high molecular weight region of 500,000 to 150,000 and the low molecular weight region of 120,000 to 50,000, respectively. Satisfies the following formula (1), A hot melt composition characterized by the above.
  • Formula (1) ⁇ Mp(H)n ⁇ h(H)n ⁇ / ⁇ Mp(L)m ⁇ h(L)m ⁇ >1.5
  • Mp(H) represents the molecular weight indicating the peak top value in the molecular weight range of 500,000 to 150,000
  • h(H) represents the peak height in the molecular weight range of 500,000 to 150,000
  • n represents
  • Mp(L) represents the molecular weight indicating the peak top value in the molecular weight range of 120,000 to 50,000
  • h(L) represents the peak height in the molecular weight range of 120,000 to 50,000
  • m represents the peak number.
  • the styrene block copolymer is at least one selected from the group consisting of styrene-butadiene-styrene copolymer (SBS) and styrene-isoprene-styrene copolymer (SIS).
  • Hot melt composition 4.
  • the hot melt composition of the present invention is excellent in stretchability and stretch recovery after stretching, and can be applied by a commonly used hot melt adhesive application device.
  • the hot melt composition of the present invention is a hot melt composition containing (A) a styrene block copolymer and (B) a plasticizer, and has a viscosity at 180° C. of 2,000 to 60,000. mPa ⁇ s, and the polystyrene-equivalent molecular weight distribution measured by gel permeation chromatography has one or more peaks in each of the high molecular weight region of 500,000 to 150,000 and the low molecular weight region of 120,000 to 50,000. However, it is a hot melt composition satisfying the following formula (1).
  • Mp(H) represents a molecular weight showing a peak top value in a region of a molecular weight of 500,000 to 150,000
  • h(H) represents a peak height in a region of a molecular weight of 500,000 to 150,000.
  • n represents the peak number.
  • Mp(L) represents the molecular weight indicating the peak top value in the molecular weight range of 120,000 to 50,000
  • h(L) represents the peak height in the molecular weight range of 120,000 to 50,000
  • m represents the peak number.
  • the numbers of the peaks represented by n and m are numbered from 1 in order from the highest molecular weight showing the peak top value, such as 1, 2,...
  • the molecular weights on the horizontal axis are the high molecular weight side on the left side and the low molecular weight side on the right side as viewed in the drawing. That is, in the above formula (1), Mp(H)n represents the molecular weight showing the peak top value of the nth peak from the high molecular weight side among the peaks in the region of the molecular weight of 500,000 to 150,000.
  • h(H)n represents the peak height of the nth peak from the high molecular weight side among the peaks in the region of molecular weight of 500,000 to 150,000.
  • Mp(L)m represents the molecular weight showing the peak top value of the m-th peak from the high molecular weight side among the peaks in the molecular weight range of 120,000 to 50,000.
  • h(L)m represents the peak height of the m-th peak from the high molecular weight side among the peaks in the molecular weight range of 120,000 to 50,000.
  • the hot melt composition of the present invention can be suitably used as a member used for a stretchable laminate provided on a sanitary material or the like.
  • a member used for the stretchable laminate a thread rubber made of natural rubber or synthetic polymer in a thread shape is known.
  • the elastic member used for the gathered portion of the conventional sanitary material is formed by joining a base material such as a non-woven fabric and a plurality of rubber threads. Since the stretchable member formed in this way has good stretchability, when it is used in an absorbent article, it is less likely to shift when worn, and the wearer can feel secure. However, the stretchable laminate formed as described above may feel a strong tightening feeling because the linear pressure due to the linear rubber thread is applied to the wearer's waistline.
  • the stretchable film has a high viscosity and is not a hot melt type, it cannot be applied using a hot melt application device that is usually used, and the sanitary material manufacturing process becomes complicated.
  • the hot-melt stretchable adhesive composition As the stretchable member, it is possible to create a stretchable laminate that is tightened by surface pressure using an ordinary hot-melt coating device.
  • the conventional hot melt stretchable adhesive composition cannot provide the required elongation at the time of attachment/detachment, and the stretchable adhesive composition does not have sufficient stretch recovery property after stretching, so that stress during wear is reduced.
  • the diaper is misaligned.
  • the hot melt composition of the present invention is used for the stretchable member of the stretchable laminate of sanitary material, it can be applied by a hot melt application device that is usually used, so that the sanitary material manufacturing process is not complicated.
  • a sanitary material equipped with a stretchable laminate using the hot melt composition as a stretchable member is prevented from slipping off when worn, which is safe for the wearer. It can give a feeling.
  • the hot melt composition of the present invention will be described in detail below.
  • the hot melt composition of the present invention contains a styrene block copolymer.
  • the styrene block copolymer means a block copolymer of a vinyl aromatic hydrocarbon and a conjugated diene compound.
  • a vinyl aromatic hydrocarbon is an aromatic hydrocarbon compound having a vinyl group.
  • the vinyl aromatic hydrocarbon include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, ⁇ -methylstyrene, vinylnaphthalene and vinylanthracene. And the like. Among these, styrene is preferable.
  • the vinyl aromatic hydrocarbon may be used alone or in combination of two or more kinds.
  • the conjugated diene compound is a diolefin compound having at least one pair of conjugated double bonds.
  • Specific examples of the conjugated diene compound include 1,3-butadiene, 2-methyl-1,3-butadiene (or isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1 , 3-hexadiene and the like, among which 1,3-butadiene and 2-methyl-1,3-butadiene are preferable.
  • the conjugated diene compound may be used alone or in combination of two or more kinds.
  • the styrene block copolymer is not particularly limited, and styrene-butadiene-styrene copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), styrene-ethylene/butylene-styrene copolymer (SEBS) , Styrene-butadiene/butylene-styrene copolymer (SBBS), styrene-ethylene/propylene-styrene copolymer (SEPS), styrene-ethylene/ethylene/propylene-styrene copolymer (SEEPS), styrene-ethylene/butylene -Olefin Crystal Copolymer (SEBC).
  • SBS styrene-butadiene-styrene copolymer
  • SIS styrene-isoprene-styrene copo
  • the hot melt composition of the present invention exhibits better extensibility and further excellent stretch recovery property after extension.
  • it is composed of styrene-butadiene-styrene copolymer (SBS) and styrene-isoprene-styrene copolymer (SIS). It preferably contains at least one selected from the group, and more preferably contains a styrene-isoprene-styrene copolymer (SIS).
  • the styrene content of the styrene-isoprene-styrene copolymer is preferably 10% by mass or more, more preferably 20% by mass or more, based on 100% by mass of the styrene-isoprene-styrene copolymer.
  • the stretch recovery property of the hot melt composition after stretching is further improved.
  • the styrene content of the styrene-isoprene-styrene copolymer is preferably 50% by mass or less, more preferably 40% by mass or less, with 100% by mass of the styrene-isoprene-styrene copolymer.
  • the upper limit of the styrene content is within the above range, the hot melt composition becomes softer and more excellent extensibility can be exhibited.
  • the “styrene content” of the styrene block copolymer means the content ratio (mass %) of the styrene block in the styrene block copolymer.
  • the method for calculating the styrene content in the styrene block copolymer in the present specification is not particularly limited, and examples thereof include a method using a proton nuclear magnetic resonance method or an infrared spectroscopy method according to JIS K6239. ..
  • a commercially available product can be used as the styrene-isoprene-styrene copolymer.
  • Examples of commercially available products include Quintac3390 manufactured by Nippon Zeon, Quintac3520 manufactured by Nippon Zeon, D1161 manufactured by Kraton Polymers, and VECTOR4411 manufactured by TSRC.
  • the styrene-isoprene-styrene copolymer may be used alone or in combination of two or more.
  • a styrene-isoprene-styrene copolymer having a high styrene content and a styrene-isoprene-styrene copolymer having a low styrene content may be mixed and used.
  • the styrene content of the styrene-butadiene-styrene copolymer is preferably 20% by mass or more, and more preferably 25% by mass or more, based on 100% by mass of the styrene-butadiene-styrene copolymer.
  • the stretch recovery property of the hot melt composition after stretching is further improved.
  • the styrene content of the styrene-butadiene-styrene copolymer is preferably 45% by mass or less, and more preferably 40% by mass or less, based on 100% by mass of the styrene-butadiene-styrene copolymer.
  • the upper limit of the styrene content is within the above range, the hot melt composition becomes softer and more excellent extensibility can be exhibited.
  • a commercially available product can be used as the styrene-butadiene-styrene copolymer.
  • Examples of commercially available products include Toughprene 126 manufactured by Asahi Kasei.
  • the styrene-butadiene-styrene copolymer may be used alone or in combination of two or more.
  • a styrene-butadiene-styrene copolymer having a high styrene content and a styrene-butadiene-styrene copolymer having a low styrene content may be mixed and used.
  • the content of the styrenic block copolymer in the hot melt composition of the present invention is preferably 40 mass% or more, more preferably 43 mass% or more, and even more preferably 45 mass% or more, based on 100 mass% of the hot melt composition. More preferable. Further, the content of the styrene-based block copolymer in the hot melt composition of the present invention is preferably 65 mass% or less, more preferably 63 mass% or less, and 60 mass% based on 100 mass% of the hot melt composition. The following are more preferable. When the content of the styrene-based block copolymer is within the above range, the hot melt composition of the present invention can exhibit more sufficient stretchability and stretch recovery property after stretching.
  • the styrene content of the styrene block copolymer in the hot melt composition of the present invention is preferably 10% by mass or more, more preferably 12% by mass or more, based on 100% by mass of the styrene block copolymer.
  • the stretch recovery property of the hot melt composition after stretching is further improved.
  • the styrene content of the styrene block copolymer in the hot melt composition of the present invention is preferably 35% by mass or less, more preferably 25% by mass or less, with 100% by mass of the styrene block copolymer. ..
  • the hot melt composition becomes softer and more excellent extensibility can be exhibited.
  • the hot melt composition of the present invention contains a plasticizer.
  • the plasticizer (B) is preferably liquid at 25° C., that is, one which exhibits fluidity at 25° C.
  • the pour point of the plasticizer (B) is preferably 23°C or lower, more preferably 10°C or lower.
  • the pour point is a value measured by a measuring method according to JIS K2269.
  • the plasticizer is not particularly limited, and examples thereof include paraffin-based process oil, naphthene-based process oil, aromatic process oil, liquid paraffin, and hydrocarbon-based synthetic oil.
  • paraffinic process oils, naphthenic process oils, liquid paraffins, and hydrocarbon synthetic oils are preferable from the viewpoint of excellent heating stability, and paraffinic process oils and naphthenic oils are preferable from the viewpoint of compatibility with the above polymers.
  • Process oil is more preferred.
  • a commercially available product can be used as the paraffinic process oil.
  • Examples of commercially available products include PW-32 manufactured by Idemitsu Kosan Co., Ltd. and PS-32 manufactured by Idemitsu Kosan Co., Ltd.
  • a commercially available product can be used as the naphthene-based process oil.
  • Examples of commercially available products include Diana Fresia N28 manufactured by Idemitsu Kosan, Diana Fresia U46 manufactured by Idemitsu Kosan, and Nyflex222B manufactured by Nynas.
  • liquid paraffin Commercial products can be used as the liquid paraffin. Examples of commercially available products include P-100 manufactured by MORESCO and Kaydol manufactured by Sonneborn.
  • hydrocarbon-based synthetic oil examples include Lucant HC-10 manufactured by Mitsui Chemicals and Lucant HC-40 manufactured by Mitsui Chemicals.
  • the above plasticizers may be used alone or in combination of two or more.
  • the content of the plasticizer (B) in the hot melt composition of the present invention is preferably 10 mass% or more, more preferably 20 mass% or more, still more preferably 30 mass% or more, based on 100 mass% of the hot melt composition. preferable.
  • the content of the plasticizer (B) in the hot melt composition of the present invention is preferably 55 mass% or less, more preferably 50 mass% or less, and 45 mass% or less, with 100 mass% of the hot melt composition. Is more preferable and 40% by mass or less is particularly preferable.
  • the upper limit of the content of the plasticizer (B) is within the above range, the hot melt composition does not become too soft, and even better extensibility is exhibited.
  • the hot melt composition of the present invention may contain other additives as long as the object of the present invention is not essentially impaired.
  • other additives include antioxidants, ultraviolet absorbers, tackifying resins, liquid rubbers, waxes, and fine particle fillers.
  • Antioxidants include 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate, 2, 2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 2,4-bis(octylthiomethyl)-o-cresol, 2 -T-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2,4-di-t-amyl-6-[1-(3,5 -Di-t-amyl-2-hydroxyphenyl)ethyl]phenyl acrylate, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)]acrylate, tetrakis[methylene-3-(3,3 5-d
  • the content of the antioxidant in the hot melt composition of the present invention is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and 0.1% by mass based on 100% by mass of the hot melt composition. % Or more is more preferable.
  • the thermal stability of the hot melt composition is further improved.
  • the content of the antioxidant in the hot melt composition of the present invention is preferably 2% by mass or less, more preferably 1.5% by mass or less, still more preferably 1% by mass or less.
  • the upper limit of the content of the antioxidant is within the above range, the odor of the hot melt composition is further reduced.
  • UV absorber 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-t-butylphenyl)benzotriazole, 2-(2' -Hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole and other benzotriazole UV absorbers; 2-hydroxy-4-methoxybenzophenone and other benzophenone UV absorbers; salicylate ester UV absorbers; cyanoacrylate-based UV absorbers; hindered amine-based light stabilizers.
  • the ultraviolet absorbers may be used alone or in combination of two or more.
  • the content of the ultraviolet absorber in the hot-melt composition of the present invention is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and 0.1% by mass, based on 100% by mass of the hot-melt composition. % Or more is more preferable.
  • the weather resistance of the hot melt composition is further improved.
  • the content of the ultraviolet absorber in the hot-melt composition of the present invention is preferably 2% by mass or less, more preferably 1.5% by mass or less, and more preferably 1% by mass, based on 100% by mass of the hot-melt composition. More preferable.
  • the upper limit of the content of the ultraviolet absorber is within the above range, the odor of the hot melt composition is further reduced.
  • the tackifying resin is preferably a petroleum resin, a partially hydrogenated petroleum resin, and a fully hydrogenated petroleum resin in terms of the odor of the hot melt composition and excellent heat stability, and a partially hydrogenated petroleum resin and a completely hydrogenated resin. Additive petroleum resin is more preferred. These tackifying resins may be used alone or in combination of two or more.
  • the ring-and-ball type softening point temperature of the tackifying resin is preferably 80° C. or higher, more preferably 90° C. or higher from the viewpoint that the stretchability and thermal stability of the hot melt composition are further excellent.
  • the ring-and-ball type softening point temperature of the tackifying resin is preferably 125° C. or lower, more preferably 120° C. or lower in that the hot melt composition can be made more flexible and the brittleness can be further suppressed. ..
  • the ring and ball softening point temperature of the tackifying resin is a value measured in accordance with JIS K2207.
  • the content of the tackifying resin in the hot melt composition of the present invention is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, based on 100% by mass of the hot melt composition.
  • the hot melt composition does not become too hard and the stretch recovery property after stretching is further improved.
  • wax examples include paraffin wax, Fischer-Tropsch wax, vinyl acetate wax, polyethylene wax, polypropylene wax, acrylic acid wax, and maleic acid modified wax.
  • paraffin wax and Fischer-Tropsch wax are preferable from the viewpoint of compatibility with the hot melt composition. These waxes may be used alone or in combination of two or more.
  • the softening point of the wax is preferably 25°C or higher, more preferably 30°C or higher, even more preferably 40°C or higher.
  • the softening point is a value measured by a measuring method according to ASTM D-3954.
  • the content of the wax in the hot melt composition of the present invention is preferably 30 mass% or less, more preferably 20 mass% or less, still more preferably 15 mass% or less, based on 100 mass% of the hot melt composition.
  • the hot melt composition does not become too hard and the stretch recovery property after stretching is further improved.
  • liquid rubber examples include liquid polybutene, liquid polybutadiene, liquid polyisoprene, and hydrogenated resins thereof.
  • the liquid rubber may be used alone or in combination of two or more.
  • the content of the liquid rubber in the hot melt composition of the present invention is preferably 1 mass% or more, more preferably 2 mass% or more, still more preferably 3 mass% or more, based on 100 mass% of the hot melt composition.
  • the content of the liquid rubber in the hot melt composition of the present invention is preferably 20 mass% or less, more preferably 15 mass% or less, still more preferably 10 mass%, based on 100 mass% of the hot melt composition.
  • the hot melt composition does not become too soft, and more excellent extensibility is exhibited.
  • the fine particle filler is not particularly limited, and examples thereof include calcium carbonate, kaolin, talc, titanium oxide, mica, and styrene beads.
  • the fine particle filler may be used alone or in combination of two or more.
  • the hot melt composition of the present invention has a melt viscosity at 180° C. of 2,000 to 60,000 mPa ⁇ s. If the melt viscosity is less than 2,000 mPa ⁇ s, the stretch recovery property after use is not sufficiently exhibited. When the melt viscosity exceeds 60,000 mPa ⁇ s, it becomes difficult to apply with a hot melt application device which is usually used.
  • the melt viscosity of the hot melt composition at 180° C. is preferably 3,000 mPa ⁇ s or more, more preferably 5,000 mPa ⁇ s or more, and further preferably 8,000 mPa ⁇ s or more.
  • the melt viscosity at 180° C. of the hot melt composition is preferably 50,000 mPa ⁇ s or less, more preferably 45,000 mPa ⁇ s or less, still more preferably 40,000 mPa ⁇ s or less.
  • the “melt viscosity” is the viscosity of the hot melt composition which is in a heated and melted state at a constant temperature.
  • a hot melt composition is heated and melted, and the viscosity of the molten state at 180° C. is measured using a Brookfield RVT viscometer (spindle No. 29). Is mentioned.
  • the hot-melt composition of the present invention has a polystyrene-equivalent molecular weight distribution measured by gel permeation chromatography of one or more in the high molecular weight region of 500,000 to 150,000 and the low molecular weight region of 120,000 to 50,000. It has a peak and satisfies the following formula (1).
  • Formula (1) ⁇ Mp(H)n ⁇ h(H)n ⁇ / ⁇ Mp(L)m ⁇ h(L)m ⁇ >1.5
  • Mp(H) represents the molecular weight indicating the peak top value in the molecular weight range of 500,000 to 150,000
  • h(H) represents the peak height in the molecular weight range of 500,000 to 150,000
  • n represents , Represents the peak number.
  • Mp(L) represents the molecular weight indicating the peak top value in the molecular weight range of 120,000 to 50,000
  • h(L) represents the peak height in the molecular weight range of 120,000 to 50,000
  • m represents the peak number.
  • the numbers of the peaks represented by n and m are numbered from 1 in order from the highest molecular weight showing the peak top value, such as 1, 2,...
  • the molecular weights on the horizontal axis are the high molecular weight side on the left side and the low molecular weight side on the right side as viewed in the drawing. That is, in the above formula (1), Mp(H)n represents the molecular weight showing the peak top value of the nth peak from the high molecular weight side among the peaks in the region of the molecular weight of 500,000 to 150,000.
  • h(H)n represents the peak height of the nth peak from the high molecular weight side among the peaks in the region of molecular weight of 500,000 to 150,000.
  • Mp(L)m represents the molecular weight showing the peak top value of the m-th peak from the high molecular weight side among the peaks in the molecular weight range of 120,000 to 50,000.
  • h(L)m represents the peak height of the m-th peak from the high molecular weight side among the peaks in the molecular weight range of 120,000 to 50,000.
  • the right side of the above formula (1) is preferably 2.0, and more preferably 2.5.
  • the stretchability and the stretch recovery property after stretching are further improved.
  • the value on the right side of the formula (1) is 50 or less.
  • the molecular weight of the hot melt composition of the present invention is a measurement value obtained by converting it with standard polystyrene using a gel permeation chromatography measuring device.
  • the molecular weight in the present invention can be measured, for example, by the following measuring device and measuring conditions.
  • Measuring device Waters product name "ACQUITY APC” Measurement conditions: Column-ACQUITY APCXT45 1.7 ⁇ m x 1-ACQUITY APCXT125 2.5 ⁇ m x 1-ACQUITY APCXT450 2.5 ⁇ m x 1
  • Mobile phase Tetrahydrofuran 0.8 mL/min
  • Sample concentration 0.2 mass%
  • Detector Differential Refractive Index (RI)
  • Detector Standard substance Polystyrene (Made by Waters, molecular weight: 266-1,800,000) Column temperature: 40°C RI detector temperature: 40°C
  • Example 1 The polystyrene equivalent molecular weight distribution measured by gel permeation chromatography has two peaks in the high molecular region (molecular weight 500,000 to 150,000) and in the low molecular region (molecular weight 120,000 to 50,000).
  • a hot-melt composition having one peak, where the molecular weight and peak height showing the respective peak top values are as follows.
  • Example 2 The polystyrene equivalent molecular weight distribution measured by gel permeation chromatography has one peak in the high molecular region (molecular weight 500,000 to 150,000) and in the low molecular region (molecular weight 120,000 to 50,000).
  • the molecular weight on the horizontal axis is the high molecular weight side on the left side of the drawing and the low molecular weight side on the right side.
  • the polystyrene-equivalent molecular weight distribution measured by gel permeation chromatography is either in the high molecular region (molecular weight 500,000 to 150,000) or in the low molecular region (molecular weight 120,000 to 50,000). In the hot melt composition having no peak in the region, the value on the left side of the formula (1) cannot be calculated.
  • the extensibility of the hot melt composition of the present invention is preferably 500% or more, more preferably 600% or more, still more preferably 750% or more.
  • the extensibility of the hot melt composition is 500% or more, breakage when the hot melt composition is expanded when wearing a sanitary material is suppressed.
  • the stretchable laminate is produced by stretching the hot melt composition, the stretching ratio can be suitably changed while suppressing breakage of the hot melt composition.
  • the extensibility of the hot melt composition of the present invention is measured by the following measuring method after preparing a coating sample of the hot melt composition by the following method.
  • the hot-melt composition is applied at a coating temperature of 180° C. onto a PET film which has been subjected to a release treatment by slot coating.
  • the coating amount is 50 g/m 2 and the coating width is 100 mm.
  • another PET film that has been subjected to a mold release treatment is laminated and pressure-bonded at room temperature to form a laminate.
  • the obtained laminate is stored for 24 hours in an atmosphere of 23° C. and a relative humidity of 50%, and the hot melt composition is cooled to room temperature to prepare a coated sample of the hot melt composition.
  • a coated sample of the hot melt composition is cut into a strip having a width of 50 mm in the coating direction and a length of 100 mm in the direction perpendicular to the coating direction to prepare a test piece.
  • the test piece was fixed with a jig to a tensile tester set to a jig width of 50 mm so that the direction perpendicular to the coating direction of the hot melt composition was positioned vertically, and the test piece was pulled at a tensile speed of 500 mm/min. Pull to the point of break.
  • the displacement at which the test piece ruptures is defined as the elongation at break (%) and is used as the evaluation standard for the extensibility of the hot melt composition.
  • the permanent set of the hot melt composition of the present invention is preferably 60% or more, more preferably 85% or more, further preferably 90% or more, particularly preferably 95% or more.
  • the stretch recovery property of the hot melt composition after stretching is further improved.
  • the permanent set of the hot melt composition of the present invention is measured by the following measuring method using the coated sample of the hot melt composition.
  • a coated sample of the hot melt composition is cut into a strip having a width of 50 mm in the coating direction and a length of 100 mm in the direction perpendicular to the coating direction to prepare a test piece. Then, the test piece was fixed with a jig to a tensile tester set to a jig width of 50 mm so that the direction perpendicular to the coating direction of the hot melt composition was positioned vertically, and the test piece was pulled at a pulling speed of 500 mm/min. Is stretched to the point where the strain displacement becomes 300%. Then, it is returned to the initial position at a speed of 500 mm/min.
  • the hot melt composition of the present invention is manufactured by a known method. For example, it is produced by introducing (A) a styrene block copolymer, (B) a plasticizer, various additives and the like into a double-arm type kneader heated to 150° C. and melt-kneading while heating.
  • the use of the hot melt composition is not particularly limited, and examples thereof include so-called sanitary materials such as paper diapers, sanitary napkins, and hospital gowns.
  • the hot melt composition of the present invention is suitably used as a stretchable film and a stretchable member of a stretchable laminate including a stretchable member.
  • a stretchable laminate include a stretchable laminate having the above hot-melt composition on at least one side of a nonwoven fabric.
  • the use of the laminate is not particularly limited, and it can be suitably used for so-called sanitary materials such as paper diapers and sanitary napkins.
  • the raw materials used in the examples and comparative examples are as follows.
  • SIS styrene-isoprene-styrene copolymer
  • (B) Plasticizer ⁇ (B1) Paraffinic process oil: PS-32 (pour point -17.5°C) manufactured by Idemitsu Kosan Co., Ltd. -(B2) naphthenic process oil: Nyflex222B manufactured by Nynas (pour point -35°C)
  • Antioxidant -Phenolic antioxidant IRGANOX1010 manufactured by BASF
  • the properties of the obtained hot melt composition were evaluated under the following measurement conditions.
  • a 0.1 wt% tetrahydrofuran solution of the hot melt composition was prepared and measured by converting it to standard polystyrene using a gel permeation chromatography measuring device.
  • the measuring device and the measuring conditions are as follows.
  • Measuring device Waters product name "ACQUITY APC” Measurement conditions: Column-ACQUITY APCXT45 1.7 ⁇ m x 1-ACQUITY APCXT125 2.5 ⁇ m x 1-ACQUITY APCXT450 2.5 ⁇ m x 1
  • Mobile phase Tetrahydrofuran 0.8 mL/min
  • Sample concentration 0.2 mass%
  • Detector Differential Refractive Index (RI)
  • Detector Standard substance Polystyrene (Made by Waters, molecular weight: 266-1,800,000) Column temperature: 40°C RI detector temperature: 40°C
  • Mp(H) represents the molecular weight indicating the peak top value in the region of molecular weight 500,000 to 150,000
  • h(H) represents the peak height in the region of molecular weight 500,000 to 150,000
  • n represents Represents the peak number
  • Mp(L) represents the molecular weight indicating the peak top value in the molecular weight range of 120,000 to 50,000
  • h(L) represents the peak height in the molecular weight range of 120,000 to 50,000
  • m represents the peak number.
  • the n and m peaks are numbered from 1 in order from the highest molecular weight indicating peak top value, such as 1, 2,...
  • the hot melt composition was applied at a coating temperature of 180° C. by slot coating on a release-treated PET film.
  • the coating amount was 50 g/m 2 and the coating width was 100 mm.
  • another PET film subjected to the mold release treatment was laminated and pressure-bonded at room temperature to form a laminate.
  • the obtained laminate was stored for 24 hours in an atmosphere of 23° C. and a relative humidity of 50%, and the hot melt composition was cooled to room temperature to prepare a coated sample of the hot melt composition.
  • test sample was prepared by cutting a coated sample of the hot melt composition into strips each having a width of 50 mm in the coating direction and a length of 100 mm in the direction perpendicular to the coating direction.
  • the test piece was fixed with a jig to a tensile tester set to a jig width of 50 mm so that the direction perpendicular to the coating direction of the hot melt composition was positioned vertically, and the test piece was pulled at a tensile speed of 500 mm/min. Pulled to the point of break.
  • the displacement at which the test piece broke was defined as the breaking elongation (%), and was used as the evaluation standard for the extensibility of the hot melt composition.
  • Elongation at break is 750% or more
  • B Elongation at break is 600% or more and less than 750%
  • B Elongation at break is 500% or more and less than 600%
  • X Elongation at break is less than 500%
  • test sample was prepared by cutting a coated sample of the hot melt composition into strips each having a width of 50 mm in the coating direction and a length of 100 mm in the direction perpendicular to the coating direction. Then, the test piece was fixed with a jig to a tensile tester set to a jig width of 50 mm so that the direction perpendicular to the coating direction of the hot melt composition was positioned vertically, and the test piece was pulled at a pulling speed of 500 mm/min. Was stretched to the point where the strain displacement was 300%. Then, it was returned to the initial position at a speed of 500 mm/min.
  • the step of pulling to the point where the strain displacement becomes 300% and returning to the initial position is set as one cycle, and two cycles are repeated for the same test piece.
  • the integrated value at the time of pulling in the first cycle is S1
  • the integrated value at the time of pulling in the second cycle is S2, and
  • X Permanent strain is less than 60%.

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Abstract

The present invention provides a hot melt composition having excellent extending ability and post-extension stretch recovery ability, and coatable with ordinarily used hot melt adhesive coating devices. The present invention provides a hot melt composition containing (A) a styrene-based block copolymer and (B) a plasticizer, the hot melt composition being characterized in that the viscosity at 180°C is 2,000 to 60,000 mPa·s, the molecular weight distribution as measured by gel permeation chromatography and converted to polystyrene has one or more peaks in a high molecular weight region of 500,000 to 150,000 molecular weight and in a low molecular weight region of 120,000 to 50,000 molecular weight, respectively, and satisfies formula (1). Formula (1): {ΣMp(H)n×h(H)n}/{ΣMp(L)m×h(L)m}>1.5 (In formula (1), Mp(H) represents a molecular weight exhibiting a peak top value in the molecular weight region of 500,000 to 150,000, h(H) represents a peak height in the molecular weight region of 500,000 to 150,000, and n represents a peak number. In addition, Mp(L) represents a molecular weight exhibiting a peak top value in the molecular weight region of 120,000 to 50,000, h(L) represents a peak height in the molecular weight region of 120,000 to 50,000, and m represents a peak number.)

Description

ホットメルト組成物Hot melt composition
 本発明は、ホットメルト組成物に関する。 The present invention relates to a hot melt composition.
 近年、紙おむつや生理用ナプキン等の衛生材料を含む吸収性物品が広く使用されている。これらの吸収性物品には、着用時のずれ落ち防止のために、伸縮性を有する部材で構成された伸縮性積層体が用いられている。 In recent years, absorbent articles containing sanitary materials such as disposable diapers and sanitary napkins have been widely used. In these absorbent articles, a stretchable laminate composed of stretchable members is used to prevent slippage when worn.
 伸縮性積層体に用いられる伸縮性を有する部材に、天然ゴムや合成高分子を糸状にした糸ゴムが知られている。糸ゴムは伸長時に良好な応力を示すため吸収性物品の着用時のずれ落ち防止に効果的である。しかしながら、伸縮性積層体に用いられる伸縮性を有する部材として上述の糸ゴムを用いた場合、人の身体に線圧がかかるため、着用時の圧迫感やかぶれの原因になるという問題がある。また、衛生材料には細い糸ゴムが複数本使用されるため、衛生材料の製造時に糸ゴムが切れやすく、しばしば衛生材料の製造が困難となるという問題がある。 As the elastic member used for the elastic laminate, a rubber thread in which a natural rubber or a synthetic polymer is formed into a thread is known. Since the rubber thread shows a good stress when stretched, it is effective in preventing the absorbent article from slipping off when worn. However, when the above-mentioned rubber thread is used as the elastic member used for the elastic laminate, a linear pressure is applied to the human body, which causes a feeling of pressure when wearing and a rash. In addition, since a plurality of thin rubber threads are used for the sanitary material, the rubber thread is easily broken during the production of the sanitary material, which often makes it difficult to manufacture the sanitary material.
 また、吸収性物品に設けられる伸縮性積層体の伸縮部材として熱可塑性エラストマーを含む伸縮性フィルムが知られている。当該伸縮性フィルムによれば、透湿性、柔軟性に優れた、生理用品など吸収性物品に好適な伸縮性フィルムが提供される。当該伸縮性フィルムによれば、糸ゴムを用いた際の上述の問題は解消されるが、製造する際に、伸縮性フィルムを製造するための組成物が高粘度であるので押し出し装置が必要となるため、通常用いられるホットメルト接着剤塗布装置が使用できず、衛生材料の生産性が劣るという問題がある。 Also, a stretchable film containing a thermoplastic elastomer is known as a stretchable member of a stretchable laminate provided in an absorbent article. According to the stretchable film, a stretchable film having excellent moisture permeability and flexibility and suitable for absorbent articles such as sanitary products is provided. According to the stretchable film, the above-mentioned problems when using the rubber thread is solved, but when producing, the composition for producing the stretchable film has a high viscosity, and thus an extruder is required. Therefore, there is a problem that the hot melt adhesive application device which is usually used cannot be used and the productivity of sanitary materials is poor.
 そこで、ホットメルト接着剤塗布装置で使用できる伸縮性材料としてホットメルト伸縮性接着剤組成物が提案されている(例えば、特許文献1参照)。特許文献1には、ブタジエン重合体もしくはイソプレン重合体の水素添加重合体、又はエチレンプロピレン重合体より選択された1種以上の重合体である弾性重合体セグメントとポリスチレン重合体セグメントを含むブロック共重合体を含むホットメルト伸縮性接着剤組成物が開示されている。当該ホットメルト伸縮性接着剤組成物によれば、通常のホットメルトアプリケーターを使用して塗工可能であり、且つ、それ自体が接着性と伸縮性を合わせて有するので、不織布等の基材と積層することで、容易にギャザー部を形成することができるホットメルト接着剤が提供される。 Therefore, a hot-melt stretchable adhesive composition has been proposed as a stretchable material that can be used in a hot-melt adhesive application device (see, for example, Patent Document 1). Patent Document 1 discloses a block copolymer containing an elastic polymer segment and a polystyrene polymer segment, which are one or more polymers selected from hydrogenated polymers of butadiene polymers or isoprene polymers, or ethylene propylene polymers. A hot melt stretchable adhesive composition including coalescence is disclosed. According to the hot-melt stretchable adhesive composition, it can be applied using a normal hot-melt applicator, and since it has both adhesiveness and stretchability, it can be used as a base material such as a nonwoven fabric. By laminating, a hot melt adhesive that can easily form a gather portion is provided.
特許第2919385号公報Japanese Patent No. 2919385
 しかしながら、特許文献1のホットメルト伸縮性接着剤組成物は、使い捨て衛生製品、特に紙おむつに適用した場合、着脱時に必要な伸びが提供できず、また当該伸縮性接着剤組成物は、伸長後の伸縮回復性が十分でないため、着用中に応力が低下し、紙おむつのズレが生じるという問題がある。 However, the hot-melt stretchable adhesive composition of Patent Document 1 cannot provide the necessary stretch at the time of putting on and taking off when applied to a disposable hygiene product, particularly a paper diaper, and the stretchable adhesive composition is Since the expansion and contraction recovery property is not sufficient, there is a problem that the stress decreases during wearing and the paper diaper is displaced.
 本発明は上記事情を鑑み、伸長性及び伸長後の伸縮回復性に優れ、且つ、通常用いられるホットメルト接着剤塗布装置で塗布可能なホットメルト組成物を提供することを目的とする。 In view of the above circumstances, it is an object of the present invention to provide a hot melt composition which is excellent in stretchability and stretch recovery after stretching and which can be applied by a commonly used hot melt adhesive coating device.
 本発明者らは、上記目的を達成すべく鋭意研究を重ねた結果、特定組成のホットメルト組成物によれば上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventors have found that a hot melt composition having a specific composition can achieve the above object, and have completed the present invention.
 すなわち、本発明は、下記のホットメルト組成物に関する。
1.(A)スチレン系ブロック共重合体、及び、(B)可塑剤を含有するホットメルト組成物であって、
 180℃での粘度が2,000~60,000mPa・sであり、
 ゲルパーミエーションクロマトグラフィーにより測定したポリスチレン換算の分子量分布が、分子量500,000~150,000の高分子領域、及び、分子量120,000~50,000の低分子領域に、それぞれ1つ以上のピークを有し、
 下記式(1)を満たす、
ことを特徴とするホットメルト組成物。
式(1):{ΣMp(H)n×h(H)n}/{ΣMp(L)m×h(L)m}>1.5
(式(1)中、Mp(H)は、分子量500,000~150,000の領域のピークトップ値を示す分子量を表し、h(H)は、分子量500,000~150,000の領域のピーク高さを表し、nは、ピークの番号を表す。また、Mp(L)は、分子量120,000~50,000の領域のピークトップ値を示す分子量を表し、h(L)は、分子量120,000~50,000の領域のピーク高さを表し、mは、ピークの番号を表す。)
2.(A)成分の含有量は、ホットメルト組成物を100質量%として40~65質量%である、項1に記載のホットメルト組成物。
3.スチレン系ブロック共重合体は、スチレン-ブタジエン-スチレン共重合体(SBS)及びスチレン-イソプレン-スチレン共重合体(SIS)からなる群より選択される少なくとも1種である、項1又は2に記載のホットメルト組成物。
4.不織布の少なくとも片面側に、項1~3のいずれかに記載のホットメルト組成物を有する伸縮性積層体。
That is, the present invention relates to the following hot melt composition.
1. A hot melt composition containing (A) a styrene block copolymer and (B) a plasticizer,
Viscosity at 180℃ is 2,000-60,000mPa・s,
The polystyrene equivalent molecular weight distribution measured by gel permeation chromatography has one or more peaks in the high molecular weight region of 500,000 to 150,000 and the low molecular weight region of 120,000 to 50,000, respectively.
Satisfies the following formula (1),
A hot melt composition characterized by the above.
Formula (1): {ΣMp(H)n×h(H)n}/{ΣMp(L)m×h(L)m}>1.5
(In the formula (1), Mp(H) represents the molecular weight indicating the peak top value in the molecular weight range of 500,000 to 150,000, h(H) represents the peak height in the molecular weight range of 500,000 to 150,000, and n represents , Mp(L) represents the molecular weight indicating the peak top value in the molecular weight range of 120,000 to 50,000, h(L) represents the peak height in the molecular weight range of 120,000 to 50,000, m represents the peak number.)
2. Item 2. The hot melt composition according to item 1, wherein the content of the component (A) is 40 to 65 mass% based on 100 mass% of the hot melt composition.
3. Item 3. The styrene block copolymer is at least one selected from the group consisting of styrene-butadiene-styrene copolymer (SBS) and styrene-isoprene-styrene copolymer (SIS). Hot melt composition.
4. A stretchable laminate having the hot melt composition according to any one of items 1 to 3 on at least one side of the nonwoven fabric.
 本発明のホットメルト組成物は、伸長性及び伸長後の伸縮回復性に優れ、且つ、通常用いられるホットメルト接着剤塗布装置で塗布可能である。 The hot melt composition of the present invention is excellent in stretchability and stretch recovery after stretching, and can be applied by a commonly used hot melt adhesive application device.
本発明のホットメルト組成物のゲルパーミエーションクロマトグラフィーにより測定したポリスチレン換算の分子量分布により、式(1)の値を計算する一例を示す模式図である。It is a schematic diagram which shows an example which calculates the value of Formula (1) by the molecular weight distribution of polystyrene conversion measured by the gel permeation chromatography of the hot melt composition of this invention. 本発明のホットメルト組成物のゲルパーミエーションクロマトグラフィーにより測定したポリスチレン換算の分子量分布により、式(1)の値を計算する一例を示す模式図である。It is a schematic diagram which shows an example which calculates the value of Formula (1) by the molecular weight distribution of polystyrene conversion measured by the gel permeation chromatography of the hot melt composition of this invention.
1.ホットメルト組成物
 本発明のホットメルト組成物は、(A)スチレン系ブロック共重合体、及び、(B)可塑剤を含有するホットメルト組成物であって、180℃での粘度が2,000~60,000mPa・sであり、ゲルパーミエーションクロマトグラフィーにより測定したポリスチレン換算の分子量分布が、分子量500,000~150,000の高分子領域、及び、分子量120,000~50,000の低分子領域に、それぞれ1つ以上のピークを有し、下記式(1)を満たすホットメルト組成物である。
式(1):{ΣMp(H)n×h(H)n}/{ΣMp(L)m×h(L)m}>1.5
ここで、式(1)中、Mp(H)は、分子量500,000~150,000の領域のピークトップ値を示す分子量を表し、h(H)は、分子量500,000~150,000の領域のピーク高さを表し、nは、ピークの番号を表す。また、Mp(L)は、分子量120,000~50,000の領域のピークトップ値を示す分子量を表し、h(L)は、分子量120,000~50,000の領域のピーク高さを表し、mは、ピークの番号を表す。本発明のホットメルト組成物は、上記構成を備えるので、伸張性および伸張後の伸縮回復性に優れ、通常用いられるホットメルト接着塗布装置で塗布可能である。
1. Hot Melt Composition The hot melt composition of the present invention is a hot melt composition containing (A) a styrene block copolymer and (B) a plasticizer, and has a viscosity at 180° C. of 2,000 to 60,000. mPa·s, and the polystyrene-equivalent molecular weight distribution measured by gel permeation chromatography has one or more peaks in each of the high molecular weight region of 500,000 to 150,000 and the low molecular weight region of 120,000 to 50,000. However, it is a hot melt composition satisfying the following formula (1).
Formula (1): {ΣMp(H)n×h(H)n}/{ΣMp(L)m×h(L)m}>1.5
Here, in the formula (1), Mp(H) represents a molecular weight showing a peak top value in a region of a molecular weight of 500,000 to 150,000, and h(H) represents a peak height in a region of a molecular weight of 500,000 to 150,000. n represents the peak number. In addition, Mp(L) represents the molecular weight indicating the peak top value in the molecular weight range of 120,000 to 50,000, h(L) represents the peak height in the molecular weight range of 120,000 to 50,000, and m represents the peak number. Represent Since the hot-melt composition of the present invention has the above-mentioned constitution, it is excellent in stretchability and stretch recovery after stretching, and can be applied by a commonly used hot-melt adhesive coating device.
 なお、上記n及びmで表わされるピークの番号は、それぞれ、ピークトップ値を示す分子量が高い方から順に、1、2、・・・のように、1から番号を付与する。また、後述する図1及び図2において、横軸の分子量は、紙面に向かって左側が高分子量側であり、右側が低分子量側である。すなわち、上記式(1)中、Mp(H)nは、分子量500,000~150,000の領域のピークのうち、高分子量側からn番目のピークのピークトップ値を示す分子量を表す。また、上記式(1)中、h(H)nは、分子量500,000~150,000の領域のピークのうち、高分子量側からn番目のピークのピーク高さを表す。また、上記式(1)中、Mp(L)mは、分子量120,000~50,000の領域のピークのうち、高分子量側からm番目のピークのピークトップ値を示す分子量を表す。更に、上記式(1)中、h(L)mは、分子量120,000~50,000の領域のピークのうち、高分子量側からm番目のピークのピーク高さを表す。 Note that the numbers of the peaks represented by n and m are numbered from 1 in order from the highest molecular weight showing the peak top value, such as 1, 2,... In addition, in FIG. 1 and FIG. 2 described later, the molecular weights on the horizontal axis are the high molecular weight side on the left side and the low molecular weight side on the right side as viewed in the drawing. That is, in the above formula (1), Mp(H)n represents the molecular weight showing the peak top value of the nth peak from the high molecular weight side among the peaks in the region of the molecular weight of 500,000 to 150,000. Further, in the above formula (1), h(H)n represents the peak height of the nth peak from the high molecular weight side among the peaks in the region of molecular weight of 500,000 to 150,000. Further, in the above formula (1), Mp(L)m represents the molecular weight showing the peak top value of the m-th peak from the high molecular weight side among the peaks in the molecular weight range of 120,000 to 50,000. Further, in the above formula (1), h(L)m represents the peak height of the m-th peak from the high molecular weight side among the peaks in the molecular weight range of 120,000 to 50,000.
 上記本発明のホットメルト組成物は、衛生材料等に設けられる伸縮性積層体に用いられる部材として好適に用いることができる。一般に、伸縮性積層体に用いられる部材としては、天然ゴムや合成高分子を糸状にした糸ゴムが知られている。従来の衛生材のギャザー部位に用いられる伸縮性部材は、不織布などの基材と、複数本の糸ゴムを接合することで形成される。このように形成された伸縮性部材は良好な伸縮性を有するため、吸収性物品に用いることで、着用時のずれがおきにくく、着用者に安心感を与えることができる。しかし、上述のようにして形成された伸縮性積層体は、線状の糸ゴムによる線圧が着用者の胴回りにかかるため、強い締め付け感を感じる場合がある。 The hot melt composition of the present invention can be suitably used as a member used for a stretchable laminate provided on a sanitary material or the like. In general, as a member used for the stretchable laminate, a thread rubber made of natural rubber or synthetic polymer in a thread shape is known. The elastic member used for the gathered portion of the conventional sanitary material is formed by joining a base material such as a non-woven fabric and a plurality of rubber threads. Since the stretchable member formed in this way has good stretchability, when it is used in an absorbent article, it is less likely to shift when worn, and the wearer can feel secure. However, the stretchable laminate formed as described above may feel a strong tightening feeling because the linear pressure due to the linear rubber thread is applied to the wearer's waistline.
 面圧で胴回りを締め付ける、伸縮性フィルムを用いた伸縮性部材を用いることにより、着用者にかかる圧力が分散されるため、良好な締め付け感を達成することができる。しかしながら、伸縮性フィルムは高粘度であり、且つ、ホットメルト型ではないため、通常用いられるホットメルト塗布装置を用いて塗布することができず、衛生材料の製造工程が煩雑化する。 By using an elastic member that uses a stretchable film to tighten the waistline with the surface pressure, the pressure applied to the wearer is dispersed, and a good tightening feeling can be achieved. However, since the stretchable film has a high viscosity and is not a hot melt type, it cannot be applied using a hot melt application device that is usually used, and the sanitary material manufacturing process becomes complicated.
 ホットメルト伸縮性接着剤組成物を伸縮性部材として用いることにより、通常のホットメルト塗布装置を用いて面圧で締め付ける伸縮性積層体を作成することができる。しかし、従来のホットメルト伸縮性接着剤組成物では着脱時に必要な伸びが提供できず、また当該伸縮性接着剤組成物は、伸長後の伸縮回復性が十分でないため、着用中に応力が低下し、紙おむつのズレが生じるという問題がある。 By using the hot-melt stretchable adhesive composition as the stretchable member, it is possible to create a stretchable laminate that is tightened by surface pressure using an ordinary hot-melt coating device. However, the conventional hot melt stretchable adhesive composition cannot provide the required elongation at the time of attachment/detachment, and the stretchable adhesive composition does not have sufficient stretch recovery property after stretching, so that stress during wear is reduced. However, there is a problem that the diaper is misaligned.
 これに対し、本発明のホットメルト組成物を衛生材料の伸縮性積層体の伸縮性部材に用いれば、通常用いられるホットメルト塗布装置で塗布可能であるため、衛生材料の製造工程は煩雑にならず、且つ、着用後も応力を維持するため、当該ホットメルト組成物を伸縮部材として用いた伸縮性積層体を搭載した衛生材料は、着用時のずれ落ちが抑制されており、着用者に安心感を与えることができる。 On the other hand, if the hot melt composition of the present invention is used for the stretchable member of the stretchable laminate of sanitary material, it can be applied by a hot melt application device that is usually used, so that the sanitary material manufacturing process is not complicated. In order to maintain stress even after wearing, a sanitary material equipped with a stretchable laminate using the hot melt composition as a stretchable member is prevented from slipping off when worn, which is safe for the wearer. It can give a feeling.
 以下、本発明のホットメルト組成物について詳細に説明する。 The hot melt composition of the present invention will be described in detail below.
(A)スチレンブロック共重合体
 本発明のホットメルト組成物は、スチレン系ブロック共重合体を含む。スチレン系ブロック共重合体とは、ビニル系芳香族炭化水素と共役ジエン化合物とのブロック共重合体をいう。
(A) Styrene Block Copolymer The hot melt composition of the present invention contains a styrene block copolymer. The styrene block copolymer means a block copolymer of a vinyl aromatic hydrocarbon and a conjugated diene compound.
 ビニル系芳香族炭化水素は、ビニル基を有する芳香族炭化水素化合物である。ビニル系芳香族炭化水素としては、具体的には、スチレン、o-メチルスチレン、p-メチルスチレン、p-tert-ブチルスチレン、1,3-ジメチルスチレン、α-メチルスチレン、ビニルナフタレン、ビニルアントラセンなどが挙げられ、これらの中でもスチレンが好ましい。ビニル系芳香族炭化水素は、単独で用いられてもよいし、二種以上が併用されて用いられてもよい。 A vinyl aromatic hydrocarbon is an aromatic hydrocarbon compound having a vinyl group. Specific examples of the vinyl aromatic hydrocarbon include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene and vinylanthracene. And the like. Among these, styrene is preferable. The vinyl aromatic hydrocarbon may be used alone or in combination of two or more kinds.
 共役ジエン化合物は、少なくとも一対の共役二重結合を有するジオレフィン化合物である。共役ジエン化合物としては、具体的には、1,3-ブタジエン、2-メチル-1,3-ブタジエン(又はイソプレン)、2,3-ジメチル-1,3-ブタジエン、1,3-ペンタジエン、1,3-ヘキサジエンなどが挙げられ、これらの中でも1,3-ブタジエン、2-メチル-1,3-ブタジエンが好ましい。共役ジエン化合物は、単独で用いられてもよいし、二種以上が併用されて用いられてもよい。 The conjugated diene compound is a diolefin compound having at least one pair of conjugated double bonds. Specific examples of the conjugated diene compound include 1,3-butadiene, 2-methyl-1,3-butadiene (or isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1 , 3-hexadiene and the like, among which 1,3-butadiene and 2-methyl-1,3-butadiene are preferable. The conjugated diene compound may be used alone or in combination of two or more kinds.
 スチレン系ブロック共重合体としては特に限定されず、スチレン-ブタジエン-スチレン共重合体(SBS)、スチレン-イソプレン-スチレン共重合体(SIS)、スチレン-エチレン/ブチレン-スチレン共重合体(SEBS)、スチレン-ブタジエン/ブチレン-スチレン共重合体(SBBS)、スチレン-エチレン/プロピレン-スチレン共重合体(SEPS)、スチレン-エチレン/エチレン/プロピレン-スチレン共重合体(SEEPS)、スチレン-エチレン/ブチレン-オレフィン結晶共重合体(SEBC)が挙げられる。上記スチレン系ブロック共重合体を用いることにより、本発明のホットメルト組成物がより良好な伸長性を示し、伸長後の伸縮回復性もより一層優れたものとなる。これらの中でも、より一層伸長後の伸縮回復性に優れ、より一層伸長性を両立できる観点から、スチレン-ブタジエン-スチレン共重合体(SBS)及びスチレン-イソプレン-スチレン共重合体(SIS)からなる群より選択される少なくとも1種を含むことが好ましく、スチレン-イソプレン-スチレン共重合体(SIS)を含むことが更に好ましい。 The styrene block copolymer is not particularly limited, and styrene-butadiene-styrene copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), styrene-ethylene/butylene-styrene copolymer (SEBS) , Styrene-butadiene/butylene-styrene copolymer (SBBS), styrene-ethylene/propylene-styrene copolymer (SEPS), styrene-ethylene/ethylene/propylene-styrene copolymer (SEEPS), styrene-ethylene/butylene -Olefin Crystal Copolymer (SEBC). By using the above styrene-based block copolymer, the hot melt composition of the present invention exhibits better extensibility and further excellent stretch recovery property after extension. Among these, from the viewpoint of being more excellent in stretch recovery after elongation and capable of achieving both elongation, it is composed of styrene-butadiene-styrene copolymer (SBS) and styrene-isoprene-styrene copolymer (SIS). It preferably contains at least one selected from the group, and more preferably contains a styrene-isoprene-styrene copolymer (SIS).
 スチレン-イソプレン-スチレン共重合体のスチレン含有量は、当該スチレン-イソプレン-スチレン共重合体を100質量%として、10質量%以上が好ましく、20質量%以上がより好ましい。スチレン含有量の下限が上記範囲であると、ホットメルト組成物の伸長後の伸縮回復性がより一層向上する。また、スチレン-イソプレン-スチレン共重合体のスチレン含有量は、当該スチレン-イソプレン-スチレン共重合体を100質量%として、50質量%以下が好ましく、40質量%以下がより好ましい。スチレン含有量の上限が上記範囲であると、ホットメルト組成物がより柔らかくなり、より一層良好な伸長性を発現することができる。 The styrene content of the styrene-isoprene-styrene copolymer is preferably 10% by mass or more, more preferably 20% by mass or more, based on 100% by mass of the styrene-isoprene-styrene copolymer. When the lower limit of the styrene content is within the above range, the stretch recovery property of the hot melt composition after stretching is further improved. The styrene content of the styrene-isoprene-styrene copolymer is preferably 50% by mass or less, more preferably 40% by mass or less, with 100% by mass of the styrene-isoprene-styrene copolymer. When the upper limit of the styrene content is within the above range, the hot melt composition becomes softer and more excellent extensibility can be exhibited.
 なお、本明細書において、スチレン系ブロック共重合体の「スチレン含有量」とは、スチレン系ブロック共重合体中のスチレンブロックの含有割合(質量%)をいう。 In the present specification, the “styrene content” of the styrene block copolymer means the content ratio (mass %) of the styrene block in the styrene block copolymer.
 また、本明細書における、スチレン系ブロック共重合体中のスチレン含有量の算出方法は特に限定されず、例えば、JIS K6239に準じたプロトン核磁気共鳴法や赤外分光法を用いる方法が挙げられる。 The method for calculating the styrene content in the styrene block copolymer in the present specification is not particularly limited, and examples thereof include a method using a proton nuclear magnetic resonance method or an infrared spectroscopy method according to JIS K6239. ..
 スチレン-イソプレン-スチレン共重合体としては市販されている製品を用いることができる。市販品としては、日本ゼオン社製Quintac3390、日本ゼオン社製Quintac3520、クレイトンポリマー社製D1161、TSRC社製VECTOR4411などが挙げられる。 A commercially available product can be used as the styrene-isoprene-styrene copolymer. Examples of commercially available products include Quintac3390 manufactured by Nippon Zeon, Quintac3520 manufactured by Nippon Zeon, D1161 manufactured by Kraton Polymers, and VECTOR4411 manufactured by TSRC.
 スチレン-イソプレン-スチレン共重合体は、1種単独で用いてもよいし、2種以上を混合して用いてもよい。例えば、スチレン含有量が高いスチレン-イソプレン-スチレン共重合体と、スチレン含有量が低いスチレン-イソプレン-スチレン共重合体とを、混合して用いてもよい。 The styrene-isoprene-styrene copolymer may be used alone or in combination of two or more. For example, a styrene-isoprene-styrene copolymer having a high styrene content and a styrene-isoprene-styrene copolymer having a low styrene content may be mixed and used.
 上記スチレン-ブタジエン-スチレン共重合体のスチレン含有量は、当該スチレン-ブタジエン-スチレン共重合体を100質量%として、20質量%以上が好ましく、25質量%以上がより好ましい。スチレン含有量の下限が上記範囲であると、ホットメルト組成物の伸長後の伸縮回復性がより一層向上する。また、スチレン-ブタジエン-スチレン共重合体のスチレン含有量は、当該スチレン-ブタジエン-スチレン共重合体を100質量%として、45質量%以下が好ましく、40質量%以下がより好ましい。スチレン含有量の上限が上記範囲であると、ホットメルト組成物がより柔らかくなり、より一層良好な伸長性を発現することができる。 The styrene content of the styrene-butadiene-styrene copolymer is preferably 20% by mass or more, and more preferably 25% by mass or more, based on 100% by mass of the styrene-butadiene-styrene copolymer. When the lower limit of the styrene content is within the above range, the stretch recovery property of the hot melt composition after stretching is further improved. Further, the styrene content of the styrene-butadiene-styrene copolymer is preferably 45% by mass or less, and more preferably 40% by mass or less, based on 100% by mass of the styrene-butadiene-styrene copolymer. When the upper limit of the styrene content is within the above range, the hot melt composition becomes softer and more excellent extensibility can be exhibited.
 スチレン-ブタジエン-スチレン共重合体としては、市販されている製品を用いることができる。市販品としては、旭化成社製のタフプレン126等が挙げられる。 A commercially available product can be used as the styrene-butadiene-styrene copolymer. Examples of commercially available products include Toughprene 126 manufactured by Asahi Kasei.
 スチレン-ブタジエン-スチレン共重合体は、1種単独で用いてもよいし、2種以上を混合して用いてもよい。例えば、スチレン含有量が高いスチレン-ブタジエン-スチレン共重合体と、スチレン含有量が低いスチレン-ブタジエン-スチレン共重合体とを、混合して用いてもよい。 The styrene-butadiene-styrene copolymer may be used alone or in combination of two or more. For example, a styrene-butadiene-styrene copolymer having a high styrene content and a styrene-butadiene-styrene copolymer having a low styrene content may be mixed and used.
 本発明のホットメルト組成物中のスチレン系ブロック共重合体の含有量は、ホットメルト組成物を100質量%として、40質量%以上が好ましく、43質量%以上がより好ましく、45質量%以上が更に好ましい。また、本発明のホットメルト組成物中のスチレン系ブロック共重合体の含有量は、ホットメルト組成物を100質量%として、65質量%以下が好ましく、63質量%以下がより好ましく、60質量%以下が更に好ましい。スチレン系ブロック共重合体の含有量が上記範囲内であると、本発明のホットメルト組成物が、より一層十分な伸張性及び伸張後の伸縮回復性を発現することができる。 The content of the styrenic block copolymer in the hot melt composition of the present invention is preferably 40 mass% or more, more preferably 43 mass% or more, and even more preferably 45 mass% or more, based on 100 mass% of the hot melt composition. More preferable. Further, the content of the styrene-based block copolymer in the hot melt composition of the present invention is preferably 65 mass% or less, more preferably 63 mass% or less, and 60 mass% based on 100 mass% of the hot melt composition. The following are more preferable. When the content of the styrene-based block copolymer is within the above range, the hot melt composition of the present invention can exhibit more sufficient stretchability and stretch recovery property after stretching.
 本発明のホットメルト組成物中のスチレン系ブロック共重合体のスチレン含有量は、当該スチレン系ブロック共重合体を100質量%として、10質量%以上が好ましく、12質量%以上がより好ましい。スチレン含有量の下限が上記範囲であると、ホットメルト組成物の伸長後の伸縮回復性がより一層向上する。また、本発明のホットメルト組成物中のスチレン系ブロック共重合体のスチレン含有量は、当該スチレン系ブロック共重合体を100質量%として、35質量%以下が好ましく、25質量%以下がより好ましい。スチレン含有量の上限が上記範囲であると、ホットメルト組成物がより柔らかくなり、より一層良好な伸長性を発現することができる。 The styrene content of the styrene block copolymer in the hot melt composition of the present invention is preferably 10% by mass or more, more preferably 12% by mass or more, based on 100% by mass of the styrene block copolymer. When the lower limit of the styrene content is within the above range, the stretch recovery property of the hot melt composition after stretching is further improved. Further, the styrene content of the styrene block copolymer in the hot melt composition of the present invention is preferably 35% by mass or less, more preferably 25% by mass or less, with 100% by mass of the styrene block copolymer. .. When the upper limit of the styrene content is within the above range, the hot melt composition becomes softer and more excellent extensibility can be exhibited.
(B)可塑剤
 本発明のホットメルト組成物は、可塑剤を含む。可塑剤(B)は、25℃で液状、すなわち、25℃で流動性を示すものが好ましい。また、可塑剤(B)の流動点は、23℃以下が好ましく、10℃以下がより好ましい。
(B) Plasticizer The hot melt composition of the present invention contains a plasticizer. The plasticizer (B) is preferably liquid at 25° C., that is, one which exhibits fluidity at 25° C. The pour point of the plasticizer (B) is preferably 23°C or lower, more preferably 10°C or lower.
 本明細書において、流動点は、JIS K2269に準拠した測定方法により測定される値である。 In the present specification, the pour point is a value measured by a measuring method according to JIS K2269.
 (B)可塑剤としては特に限定されず、例えば、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、芳香族系プロセスオイル、流動パラフィン、炭化水素系合成オイル等が挙げられる。なかでも、加熱安定性が優れる観点から、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、流動パラフィン、及び炭化水素系合成オイルが好ましく、上記ポリマーとの相溶性の観点から、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がより好ましい。 (B) The plasticizer is not particularly limited, and examples thereof include paraffin-based process oil, naphthene-based process oil, aromatic process oil, liquid paraffin, and hydrocarbon-based synthetic oil. Of these, paraffinic process oils, naphthenic process oils, liquid paraffins, and hydrocarbon synthetic oils are preferable from the viewpoint of excellent heating stability, and paraffinic process oils and naphthenic oils are preferable from the viewpoint of compatibility with the above polymers. Process oil is more preferred.
 パラフィン系プロセスオイルとしては、市販品を用いることができる。市販品としては、例えば、出光興産社製PW-32、出光興産社製PS-32等が挙げられる。 A commercially available product can be used as the paraffinic process oil. Examples of commercially available products include PW-32 manufactured by Idemitsu Kosan Co., Ltd. and PS-32 manufactured by Idemitsu Kosan Co., Ltd.
 ナフテン系プロセスオイルとしては、市販品を用いることができる。市販品としては、例えば、出光興産社製ダイアナフレシアN28、出光興産社製ダイアナフレシアU46、Nynas社製Nyflex222B等が挙げられる。 A commercially available product can be used as the naphthene-based process oil. Examples of commercially available products include Diana Fresia N28 manufactured by Idemitsu Kosan, Diana Fresia U46 manufactured by Idemitsu Kosan, and Nyflex222B manufactured by Nynas.
 流動パラフィンとしては、市販品を用いることができる。市販品としては、MORESCO社製P-100、Sonneborn社製Kaydol等が挙げられる。 Commercial products can be used as the liquid paraffin. Examples of commercially available products include P-100 manufactured by MORESCO and Kaydol manufactured by Sonneborn.
 炭化水素系合成オイルとしては、市販品を用いることができる。市販品としては、三井化学社製ルーカントHC-10、三井化学社製ルーカントHC-40等が挙げられる。 Commercially available products can be used as the hydrocarbon-based synthetic oil. Examples of commercially available products include Lucant HC-10 manufactured by Mitsui Chemicals and Lucant HC-40 manufactured by Mitsui Chemicals.
 上記可塑剤は、1種単独で用いてもよいし、2種以上を混合して用いてもよい。 The above plasticizers may be used alone or in combination of two or more.
 本発明のホットメルト組成物中の可塑剤(B)の含有量は、ホットメルト組成物を100質量%として、10質量%以上が好ましく、20質量%以上がより好ましく、30質量%以上が更に好ましい。可塑剤(B)の含有量の下限が上記範囲であると、ホットメルト組成物の粘度上昇がより一層抑制され、通常用いられるホットメルト塗布装置で塗布可能である。また、本発明のホットメルト組成物中の可塑剤(B)の含有量は、ホットメルト組成物を100質量%として、55質量%以下が好ましく、50質量%以下がより好ましく、45質量%以下が更に好ましく、40質量%以下が特に好ましい。可塑剤(B)の含有量の上限が上記範囲であると、ホットメルト組成物が柔らかくなり過ぎず、より一層良好な伸長性を発現する。 The content of the plasticizer (B) in the hot melt composition of the present invention is preferably 10 mass% or more, more preferably 20 mass% or more, still more preferably 30 mass% or more, based on 100 mass% of the hot melt composition. preferable. When the lower limit of the content of the plasticizer (B) is within the above range, the viscosity increase of the hot melt composition is further suppressed, and the hot melt composition can be applied by a commonly used hot melt application device. Further, the content of the plasticizer (B) in the hot melt composition of the present invention is preferably 55 mass% or less, more preferably 50 mass% or less, and 45 mass% or less, with 100 mass% of the hot melt composition. Is more preferable and 40% by mass or less is particularly preferable. When the upper limit of the content of the plasticizer (B) is within the above range, the hot melt composition does not become too soft, and even better extensibility is exhibited.
他の添加剤
 本発明のホットメルト組成物は、本発明の目的を本質的に妨げない範囲で、他の添加剤を含有していてもよい。上記他の添加剤としては、酸化防止剤、紫外線吸収剤、粘着付与樹脂、液状ゴム、ワックス、微粒子充填剤等が挙げられる。
Other Additives The hot melt composition of the present invention may contain other additives as long as the object of the present invention is not essentially impaired. Examples of the above-mentioned other additives include antioxidants, ultraviolet absorbers, tackifying resins, liquid rubbers, waxes, and fine particle fillers.
 酸化防止剤としては、2,6-ジ-t-ブチル-4-メチルフェノール、n-オクタデシル-3-(4'-ヒドロキシ-3',5'-ジ-t-ブチルフェニル)プロピオネート、2,2'-メチレンビス(4-メチル-6-t-ブチルフェノール)、2,2'-メチレンビス(4-エチル-6-t-ブチルフェノール)、2,4-ビス(オクチルチオメチル)-o-クレゾール、2-t-ブチル-6-(3-t-ブチル-2-ヒドロキシ-5-メチルべンジル)-4-メチルフェニルアクリレート、2,4-ジ-t-アミル-6-〔1-(3,5-ジ-t-アミル-2-ヒドロキシフェニル)エチル〕フェニルアクリレート、2-[1-(2-ヒドロキシ-3,5-ジ-tert-ぺンチルフェニル)]アクリレート、テトラキス〔メチレン-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〕メタン等のヒンダードフェノール系酸化防止剤;ジラウリルチオジプロピオネート、ラウリルステアリル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)等のイオウ系酸化防止剤;トリス(ノニルフェニル)ホスファイト、トリス(2,4-ジ-t-ブチルフェニル)ホスファイト等のリン系酸化防止剤等が挙げられる。酸化防止剤は、1種単独で用いてもよいし、2種以上を混合して用いてもよい。 Antioxidants include 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate, 2, 2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 2,4-bis(octylthiomethyl)-o-cresol, 2 -T-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2,4-di-t-amyl-6-[1-(3,5 -Di-t-amyl-2-hydroxyphenyl)ethyl]phenyl acrylate, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)]acrylate, tetrakis[methylene-3-(3,3 5-di-t-butyl-4-hydroxyphenyl)propionate] methane and other hindered phenolic antioxidants; dilauryl thiodipropionate, lauryl stearyl thiodipropionate, pentaerythritol tetrakis (3-lauryl thiopropionate) And sulfur-based antioxidants such as tris(nonylphenyl)phosphite and tris(2,4-di-t-butylphenyl)phosphite. The antioxidants may be used alone or in combination of two or more.
 本発明のホットメルト組成物中の酸化防止剤の含有量は、ホットメルト組成物を100質量%として、0.01質量%以上が好ましく、0.05質量%以上がより好ましく、0.1質量%以上が更に好ましい。酸化防止剤の含有量の下限が上記範囲であると、ホットメルト組成物の熱安定がより一層向上する。また、本発明のホットメルト組成物中の酸化防止剤の含有量は、2質量%以下が好ましく、1.5質量%以下がより好ましく、1質量%以下が更に好ましい。酸化防止剤の含有量の上限が上記範囲であると、ホットメルト組成物の臭気がより一層低減される。 The content of the antioxidant in the hot melt composition of the present invention is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and 0.1% by mass based on 100% by mass of the hot melt composition. % Or more is more preferable. When the lower limit of the content of the antioxidant is within the above range, the thermal stability of the hot melt composition is further improved. Further, the content of the antioxidant in the hot melt composition of the present invention is preferably 2% by mass or less, more preferably 1.5% by mass or less, still more preferably 1% by mass or less. When the upper limit of the content of the antioxidant is within the above range, the odor of the hot melt composition is further reduced.
 紫外線吸収剤としては、2-(2'-ヒドロキシ-5'-メチルフェニル)ベンゾトリアゾール、2-(2'-ヒドロキシ-3',5'-t-ブチルフェニル)ベンゾトリアゾール、2-(2'-ヒドロキシ-3',5'-ジ-t-ブチルフェニル)-5-クロロベンゾトリアゾール等のベンゾトリアゾール系紫外線吸収剤;2-ヒドロキシ-4-メトキシベンゾフェノン等のベンゾフェノン系紫外線吸収剤;サリチル酸エステル系紫外線吸収剤;シアノアクリレート系紫外線吸収剤;ヒンダードアミン系光安定剤が挙げられる。紫外線吸収剤は、1種単独で用いてもよいし、2種以上を混合して用いてもよい。 As the ultraviolet absorber, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-t-butylphenyl)benzotriazole, 2-(2' -Hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole and other benzotriazole UV absorbers; 2-hydroxy-4-methoxybenzophenone and other benzophenone UV absorbers; salicylate ester UV absorbers; cyanoacrylate-based UV absorbers; hindered amine-based light stabilizers. The ultraviolet absorbers may be used alone or in combination of two or more.
 本発明のホットメルト組成物中の紫外線吸収剤の含有量は、ホットメルト組成物を100質量%として、0.01質量%以上が好ましく、0.05質量%以上がより好ましく、0.1質量%以上が更に好ましい。紫外線吸収剤の含有量の下限が上記範囲であると、ホットメルト組成物の耐候性がより一層向上する。また、本発明のホットメルト組成物中の紫外線吸収剤の含有量は、ホットメルト組成物を100質量%として、2質量%以下が好ましく、1.5質量%以下がより好ましく、1質量%が更に好ましい。紫外線吸収剤の含有量の上限が上記範囲であると、ホットメルト組成物の臭気がより一層低減する。 The content of the ultraviolet absorber in the hot-melt composition of the present invention is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and 0.1% by mass, based on 100% by mass of the hot-melt composition. % Or more is more preferable. When the lower limit of the content of the ultraviolet absorber is within the above range, the weather resistance of the hot melt composition is further improved. Further, the content of the ultraviolet absorber in the hot-melt composition of the present invention is preferably 2% by mass or less, more preferably 1.5% by mass or less, and more preferably 1% by mass, based on 100% by mass of the hot-melt composition. More preferable. When the upper limit of the content of the ultraviolet absorber is within the above range, the odor of the hot melt composition is further reduced.
 粘着付与樹脂としては、天然ロジン、変性ロジン、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、天然テルペンのコポリマー、天然テルペンの三次元ポリマー、天然テルペンのコポリマーの水素化誘導体、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;C5系石油樹脂、C9系石油樹脂、C5C9系石油樹脂、ジシクロペンタジエン系石油樹脂等の石油樹脂、また、それら石油樹脂に水素を添加した部分水添石油樹脂、完全水添石油樹脂等が挙げられる。粘着付与樹脂としては、ホットメルト組成物の臭気、熱安定性に優れている点で、石油樹脂、部分水添石油樹脂、及び完全水添石油樹脂が好ましく、部分水添石油樹脂、及び完全水添石油樹脂がより好ましい。これら粘着付与樹脂は1種単独で用いてもよいし、2種以上を混合して用いてもよい。 As the tackifying resin, natural rosin, modified rosin, glycerol ester of natural rosin, glycerol ester of modified rosin, pentaerythritol ester of natural rosin, pentaerythritol ester of modified rosin, natural terpene copolymer, three-dimensional polymer of natural terpene, Hydrogenated derivatives of natural terpene copolymers, terpene resins, hydrogenated derivatives of phenol-based modified terpene resins; petroleum resins such as C5 petroleum resins, C9 petroleum resins, C5C9 petroleum resins and dicyclopentadiene petroleum resins; Partially hydrogenated petroleum resins obtained by adding hydrogen to these petroleum resins, fully hydrogenated petroleum resins and the like can be mentioned. The tackifying resin is preferably a petroleum resin, a partially hydrogenated petroleum resin, and a fully hydrogenated petroleum resin in terms of the odor of the hot melt composition and excellent heat stability, and a partially hydrogenated petroleum resin and a completely hydrogenated resin. Additive petroleum resin is more preferred. These tackifying resins may be used alone or in combination of two or more.
 粘着付与樹脂の環球式軟化点温度は、ホットメルト組成物の伸縮性、熱安定性がより一層優れる点で、80℃以上が好ましく、90℃以上がより好ましい。また、粘着付与樹脂の環球式軟化点温度は、ホットメルト組成物により一層柔軟性を持たせ、より一層脆弱化を抑制することができる点で、125℃以下が好ましく、120℃以下がより好ましい。なお、本明細書において、粘着付与樹脂の環球式軟化点温度は、JIS K2207に準拠して測定される値である。 The ring-and-ball type softening point temperature of the tackifying resin is preferably 80° C. or higher, more preferably 90° C. or higher from the viewpoint that the stretchability and thermal stability of the hot melt composition are further excellent. The ring-and-ball type softening point temperature of the tackifying resin is preferably 125° C. or lower, more preferably 120° C. or lower in that the hot melt composition can be made more flexible and the brittleness can be further suppressed. .. In addition, in this specification, the ring and ball softening point temperature of the tackifying resin is a value measured in accordance with JIS K2207.
 本発明のホットメルト組成物中の粘着付与樹脂の含有量は、ホットメルト組成物を100質量%として30質量%以下が好ましく、20質量%以下がより好ましく、15質量%以下がさらに好ましい。粘着付与樹脂の含有量が30質量%以下であるとホットメルト組成物が硬くなりすぎず、伸長後の伸縮回復性がより一層向上する。 The content of the tackifying resin in the hot melt composition of the present invention is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, based on 100% by mass of the hot melt composition. When the content of the tackifying resin is 30% by mass or less, the hot melt composition does not become too hard and the stretch recovery property after stretching is further improved.
 ワックスとしては、パラフィンワックス、フィッシャートロプスワックス、酢酸ビニルワックス、ポリエチレンワックス、ポリプロピレンワックス、アクリル酸ワックス、マレイン酸変成ワックス等が挙げられる。ワックスとしては、ホットメルト組成物との相溶性の観点から、パラフィンワックス、フィッシャートロプスワックスが好ましい。これらワックスは1種単独で用いてもよいし、2種以上を混合して用いてもよい。 Examples of the wax include paraffin wax, Fischer-Tropsch wax, vinyl acetate wax, polyethylene wax, polypropylene wax, acrylic acid wax, and maleic acid modified wax. As the wax, paraffin wax and Fischer-Tropsch wax are preferable from the viewpoint of compatibility with the hot melt composition. These waxes may be used alone or in combination of two or more.
 ワックスの軟化点は25℃以上が好ましく、30℃以上がより好ましく、40℃以上が更に好ましい。本明細書において、軟化点は、ASTM D-3954に準拠した測定方法により測定される値である。 The softening point of the wax is preferably 25°C or higher, more preferably 30°C or higher, even more preferably 40°C or higher. In the present specification, the softening point is a value measured by a measuring method according to ASTM D-3954.
 本発明のホットメルト組成物中のワックスの含有量は、ホットメルト組成物を100質量%として30質量%以下が好ましく、20質量%以下がより好ましく、15質量%以下がさらに好ましい。ワックスの含有量が30質量%以下であるとホットメルト組成物が硬くなりすぎず、伸長後の伸縮回復性がより一層向上する。 The content of the wax in the hot melt composition of the present invention is preferably 30 mass% or less, more preferably 20 mass% or less, still more preferably 15 mass% or less, based on 100 mass% of the hot melt composition. When the content of the wax is 30% by mass or less, the hot melt composition does not become too hard and the stretch recovery property after stretching is further improved.
 液状ゴムとしては、液状ポリブテン、液状ポリブタジエン、液状ポリイソプレン及びこれらの水添樹脂が挙げられる。液状ゴムは、1種単独で用いてもよいし、2種以上を混合して用いてもよい。 Examples of liquid rubber include liquid polybutene, liquid polybutadiene, liquid polyisoprene, and hydrogenated resins thereof. The liquid rubber may be used alone or in combination of two or more.
 本発明のホットメルト組成物中の液状ゴムの含有量は、ホットメルト組成物を100質量%として、1質量%以上が好ましく、2質量%以上がより好ましく、3質量%以上が更に好ましい。液状ゴムの含有量の下限が上記範囲であると、ホットメルト組成物の溶融粘度が低下し、塗工適性がより一層向上する。また、本発明のホットメルト組成物中の液状ゴムの含有量は、ホットメルト組成物を100質量%として、20質量%以下が好ましく、15質量%以下がより好ましく、10質量%が更に好ましい。液状ゴムの含有量の上限が上記範囲であると、ホットメルト組成物が柔らかくなりすぎず、より一層良好な伸長性を発現する。 The content of the liquid rubber in the hot melt composition of the present invention is preferably 1 mass% or more, more preferably 2 mass% or more, still more preferably 3 mass% or more, based on 100 mass% of the hot melt composition. When the lower limit of the content of the liquid rubber is within the above range, the melt viscosity of the hot melt composition is lowered and the coating suitability is further improved. The content of the liquid rubber in the hot melt composition of the present invention is preferably 20 mass% or less, more preferably 15 mass% or less, still more preferably 10 mass%, based on 100 mass% of the hot melt composition. When the upper limit of the content of the liquid rubber is within the above range, the hot melt composition does not become too soft, and more excellent extensibility is exhibited.
 微粒子充填剤としては、特に限定されず、例えば、炭酸カルシウム、カオリン、タルク、酸化チタン、雲母、スチレンビーズ等が挙げられる。微粒子充填剤は、1種単独で用いてもよいし、2種以上を混合して用いてもよい。 The fine particle filler is not particularly limited, and examples thereof include calcium carbonate, kaolin, talc, titanium oxide, mica, and styrene beads. The fine particle filler may be used alone or in combination of two or more.
ホットメルト組成物の物性
 本発明のホットメルト組成物は、180℃における溶融粘度が2,000~60,000mPa・sである。溶融粘度が2,000mPa・s未満であると、使用後の伸縮回復性が十分に発現されない。溶融粘度が60,000mPa・sを超えると、通常用いられるホットメルト塗布装置で塗布することが困難となる。ホットメルト組成物の180℃における溶融粘度は、3,000mPa・s以上が好ましく、5,000mPa・s以上がより好ましく、8,000mPa・s以上が更に好ましい。また、ホットメルト組成物の180℃における溶融粘度は、50,000mPa・s以下が好ましく、45,000mPa・s以下がより好ましく、40,000mPa・s以下が更に好ましい。
Physical Properties of Hot Melt Composition The hot melt composition of the present invention has a melt viscosity at 180° C. of 2,000 to 60,000 mPa·s. If the melt viscosity is less than 2,000 mPa·s, the stretch recovery property after use is not sufficiently exhibited. When the melt viscosity exceeds 60,000 mPa·s, it becomes difficult to apply with a hot melt application device which is usually used. The melt viscosity of the hot melt composition at 180° C. is preferably 3,000 mPa·s or more, more preferably 5,000 mPa·s or more, and further preferably 8,000 mPa·s or more. The melt viscosity at 180° C. of the hot melt composition is preferably 50,000 mPa·s or less, more preferably 45,000 mPa·s or less, still more preferably 40,000 mPa·s or less.
 本明細書において、「溶融粘度」は、一定の温度で加熱溶融状態となったホットメルト組成物の粘度である。180℃における溶融粘度の測定方法としては、例えば、ホットメルト組成物を加熱溶融し、180℃における溶融状態の粘度を、ブルックフィールドRVT型粘度計(スピンドルNo.29)を用いて測定する測定方法が挙げられる。 In the present specification, the “melt viscosity” is the viscosity of the hot melt composition which is in a heated and melted state at a constant temperature. As a method of measuring the melt viscosity at 180° C., for example, a hot melt composition is heated and melted, and the viscosity of the molten state at 180° C. is measured using a Brookfield RVT viscometer (spindle No. 29). Is mentioned.
 本発明のホットメルト組成物は、ゲルパーミエーションクロマトグラフィーにより測定したポリスチレン換算の分子量分布が、分子量500,000~150,000の高分子領域、及び、分子量120,000~50,000の低分子領域に、それぞれ1つ以上のピークを有し、下記式(1)を満たす。
式(1):{ΣMp(H)n×h(H)n}/{ΣMp(L)m×h(L)m}>1.5
The hot-melt composition of the present invention has a polystyrene-equivalent molecular weight distribution measured by gel permeation chromatography of one or more in the high molecular weight region of 500,000 to 150,000 and the low molecular weight region of 120,000 to 50,000. It has a peak and satisfies the following formula (1).
Formula (1): {ΣMp(H)n×h(H)n}/{ΣMp(L)m×h(L)m}>1.5
 上記式(1)中、Mp(H)は、分子量500,000~150,000の領域のピークトップ値を示す分子量を表し、h(H)は、分子量500,000~150,000の領域のピーク高さを表し、nは、ピークの番号を表す。また、Mp(L)は、分子量120,000~50,000の領域のピークトップ値を示す分子量を表し、h(L)は、分子量120,000~50,000の領域のピーク高さを表し、mは、ピークの番号を表す。 In the above formula (1), Mp(H) represents the molecular weight indicating the peak top value in the molecular weight range of 500,000 to 150,000, h(H) represents the peak height in the molecular weight range of 500,000 to 150,000, and n represents , Represents the peak number. In addition, Mp(L) represents the molecular weight indicating the peak top value in the molecular weight range of 120,000 to 50,000, h(L) represents the peak height in the molecular weight range of 120,000 to 50,000, and m represents the peak number. Represent
 なお、上記n及びmで表わされるピークの番号は、それぞれ、ピークトップ値を示す分子量が高い方から順に、1、2、・・・のように、1から番号を付与する。また、後述する図1及び図2において、横軸の分子量は、紙面に向かって左側が高分子量側であり、右側が低分子量側である。すなわち、上記式(1)中、Mp(H)nは、分子量500,000~150,000の領域のピークのうち、高分子量側からn番目のピークのピークトップ値を示す分子量を表す。また、上記式(1)中、h(H)nは、分子量500,000~150,000の領域のピークのうち、高分子量側からn番目のピークのピーク高さを表す。また、上記式(1)中、Mp(L)mは、分子量120,000~50,000の領域のピークのうち、高分子量側からm番目のピークのピークトップ値を示す分子量を表す。更に、上記式(1)中、h(L)mは、分子量120,000~50,000の領域のピークのうち、高分子量側からm番目のピークのピーク高さを表す。 Note that the numbers of the peaks represented by n and m are numbered from 1 in order from the highest molecular weight showing the peak top value, such as 1, 2,... In addition, in FIG. 1 and FIG. 2 described later, the molecular weights on the horizontal axis are the high molecular weight side on the left side and the low molecular weight side on the right side as viewed in the drawing. That is, in the above formula (1), Mp(H)n represents the molecular weight showing the peak top value of the nth peak from the high molecular weight side among the peaks in the region of the molecular weight of 500,000 to 150,000. Further, in the above formula (1), h(H)n represents the peak height of the nth peak from the high molecular weight side among the peaks in the region of molecular weight of 500,000 to 150,000. Further, in the above formula (1), Mp(L)m represents the molecular weight showing the peak top value of the m-th peak from the high molecular weight side among the peaks in the molecular weight range of 120,000 to 50,000. Further, in the above formula (1), h(L)m represents the peak height of the m-th peak from the high molecular weight side among the peaks in the molecular weight range of 120,000 to 50,000.
 上記式(1)の右辺は、2.0が好ましく、2.5がより好ましい。上記式(1)の右辺が上記値であることにより、より一層伸長性及び伸長後の伸縮回復性が向上する。また、一般的なホットメルト組成物の場合、式(1)の右辺の値は50以下である。 The right side of the above formula (1) is preferably 2.0, and more preferably 2.5. When the right side of the formula (1) has the above value, the stretchability and the stretch recovery property after stretching are further improved. In the case of a general hot melt composition, the value on the right side of the formula (1) is 50 or less.
 本発明のホットメルト組成物の分子量は、ゲルパーミエーションクロマトグラフィー測定装置を用いて、標準ポリスチレンで換算することにより得られる測定値である。 The molecular weight of the hot melt composition of the present invention is a measurement value obtained by converting it with standard polystyrene using a gel permeation chromatography measuring device.
 本発明における分子量は、例えば、下記測定装置及び測定条件にて測定することができる。
測定装置:Waters社製 商品名「ACQUITY APC」
測定条件:カラム
・ACQUITY APCXT45 1.7μm×1本
・ACQUITY APCXT125 2.5μm×1本
・ACQUITY APCXT450 2.5μm×1本
 移動相:テトラヒドロフラン 0.8mL/分
 サンプル濃度:0.2質量%
 検出器:示差屈折率(RI)検出器
 標準物質:ポリスチレン(Waters社製 分子量:266~1,800,000)
 カラム温度:40℃
 RI検出器温度:40℃
The molecular weight in the present invention can be measured, for example, by the following measuring device and measuring conditions.
Measuring device: Waters product name "ACQUITY APC"
Measurement conditions: Column-ACQUITY APCXT45 1.7 μm x 1-ACQUITY APCXT125 2.5 μm x 1-ACQUITY APCXT450 2.5 μm x 1 Mobile phase: Tetrahydrofuran 0.8 mL/min Sample concentration: 0.2 mass%
Detector: Differential Refractive Index (RI) Detector Standard substance: Polystyrene (Made by Waters, molecular weight: 266-1,800,000)
Column temperature: 40°C
RI detector temperature: 40°C
 上記式(1)の計算の例を図を用いて以下に示す。 An example of the calculation of the above formula (1) is shown below using the figure.
例1(図1)
 ゲルパーミエーションクロマトグラフィーにより測定したポリスチレン換算の分子量分布が、高分子領域(分子量500,000~150,000)に2つピークを有し、低分子領域(分子量120,000~50,000)に1つピークを有するホットメルト組成物であって、それぞれのピークトップ値を示す分子量及びピーク高さが以下の場合。
 Mp(H)1=220,000、Mp(H)2=160,000、Mp(L)1=100,000、h(H)1=1,500、h(H)2=2,000、h(L)1=1,750
式(1)の左辺の値は、
(220,000×1,500+160,000×2,000)/(100,000×1,750)=3.71
となる。なお、図1において、横軸の分子量は、紙面に向かって左側が高分子量側であり、右側が低分子量側である。
Example 1 (Fig. 1)
The polystyrene equivalent molecular weight distribution measured by gel permeation chromatography has two peaks in the high molecular region (molecular weight 500,000 to 150,000) and in the low molecular region (molecular weight 120,000 to 50,000). A hot-melt composition having one peak, where the molecular weight and peak height showing the respective peak top values are as follows.
Mp(H)1=220,000, Mp(H)2=160,000, Mp(L)1=100,000, h(H)1=1,500, h(H)2=2,000, h(L)1=1,750
The value on the left side of equation (1) is
(220,000 x 1,500 + 160,000 x 2,000)/(100,000 x 1,750) = 3.71
Becomes In FIG. 1, the molecular weight on the horizontal axis is the high molecular weight side on the left side of the drawing, and the low molecular weight side on the right side.
例2(図2)
 ゲルパーミエーションクロマトグラフィーにより測定したポリスチレン換算の分子量分布が、高分子領域(分子量500,000~150,000)に1つピークを有し、低分子領域(分子量120,000~50,000)に1つピークを有するホットメルト組成物であって、それぞれのピークトップ値を示す分子量及びピーク高さが以下の場合。
 Mp(H)1=180,000、Mp(L)1=105,000、h(H)1=2,200、h(H)1=3,000
式(1)の左辺の値は、
(180,000×2,200)/(105,000×3,000)=1.26となる。なお、図2において、横軸の分子量は、紙面に向かって左側が高分子量側であり、右側が低分子量側である。
Example 2 (Figure 2)
The polystyrene equivalent molecular weight distribution measured by gel permeation chromatography has one peak in the high molecular region (molecular weight 500,000 to 150,000) and in the low molecular region (molecular weight 120,000 to 50,000). A hot-melt composition having one peak, where the molecular weight and peak height showing the respective peak top values are as follows.
Mp(H)1=180,000, Mp(L)1=105,000, h(H)1=2,200, h(H)1=3,000
The value on the left side of equation (1) is
(180,000×2,200)/(105,000×3,000)=1.26. In FIG. 2, the molecular weight on the horizontal axis is the high molecular weight side on the left side of the drawing and the low molecular weight side on the right side.
 なお、ゲルパーミエーションクロマトグラフィーにより測定したポリスチレン換算の分子量分布が、高分子領域(分子量500,000~150,000)、又は、低分子領域(分子量120,000~50,000)のいずれかの領域にピークを有しないホットメルト組成物では、式(1)の左辺の値は算出することができない。 The polystyrene-equivalent molecular weight distribution measured by gel permeation chromatography is either in the high molecular region (molecular weight 500,000 to 150,000) or in the low molecular region (molecular weight 120,000 to 50,000). In the hot melt composition having no peak in the region, the value on the left side of the formula (1) cannot be calculated.
 本発明のホットメルト組成物の伸長性は500%以上が好ましく、600%以上がより好ましく、750%以上が更に好ましい。ホットメルト組成物の伸長性が500%以上であると、衛生材料着用時にホットメルト組成物が伸長された際の破断が抑制される。また、ホットメルト組成物を延伸させて伸縮性積層体を作成する場合、ホットメルト組成物の破断を抑制しつつ、延伸率を好適に変更することができる。 The extensibility of the hot melt composition of the present invention is preferably 500% or more, more preferably 600% or more, still more preferably 750% or more. When the extensibility of the hot melt composition is 500% or more, breakage when the hot melt composition is expanded when wearing a sanitary material is suppressed. Further, when the stretchable laminate is produced by stretching the hot melt composition, the stretching ratio can be suitably changed while suppressing breakage of the hot melt composition.
 本発明のホットメルト組成物の伸長性は、以下の方法によりホットメルト組成物の塗工サンプルを調製した上で、当該塗工サンプルを用いて以下の測定方法により測定される。 The extensibility of the hot melt composition of the present invention is measured by the following measuring method after preparing a coating sample of the hot melt composition by the following method.
ホットメルト組成物の塗工サンプル作成方法
 ホットメルト組成物を180℃の塗工温度で、離型処理されたPETフィルム上にスロット塗工で塗布する。塗布量は50g/m、塗布幅は100mmとする。次いで、離型処理された別のPETフィルムを積層し、室温下で圧着させることで積層体を作成する。得られた積層体を23℃、相対湿度50%雰囲気下で24時間保管し、ホットメルト組成物を室温に冷却して、ホットメルト組成物の塗工サンプルを調製する。
Method for preparing coating sample of hot-melt composition The hot-melt composition is applied at a coating temperature of 180° C. onto a PET film which has been subjected to a release treatment by slot coating. The coating amount is 50 g/m 2 and the coating width is 100 mm. Then, another PET film that has been subjected to a mold release treatment is laminated and pressure-bonded at room temperature to form a laminate. The obtained laminate is stored for 24 hours in an atmosphere of 23° C. and a relative humidity of 50%, and the hot melt composition is cooled to room temperature to prepare a coated sample of the hot melt composition.
伸長性の測定方法
 ホットメルト組成物の塗工サンプルを、塗工方向に対して幅50mm、塗工方向に対して垂直な方向に100mmの短冊状に切断し、試験片を調製する。次いで、治具幅50mmに設定した引張試験機へホットメルト組成物の塗工方向と垂直な方向が上下に位置するように試験片を治具で固定し、引張速度500mm/分で試験片が破断する点まで引っ張る。試験片が破断した変位を破断伸び(%)とし、ホットメルト組成物の伸長性の評価基準とする。
Method of measuring extensibility A coated sample of the hot melt composition is cut into a strip having a width of 50 mm in the coating direction and a length of 100 mm in the direction perpendicular to the coating direction to prepare a test piece. Next, the test piece was fixed with a jig to a tensile tester set to a jig width of 50 mm so that the direction perpendicular to the coating direction of the hot melt composition was positioned vertically, and the test piece was pulled at a tensile speed of 500 mm/min. Pull to the point of break. The displacement at which the test piece ruptures is defined as the elongation at break (%) and is used as the evaluation standard for the extensibility of the hot melt composition.
 本発明のホットメルト組成物の永久歪みは60%以上が好ましく、85%以上がより好ましく、90%以上がさらに好ましく、95%以上が特に好ましい。ホットメルト組成物の永久歪みが60%以上であると、ホットメルト組成物の伸長後の伸縮回復性がより一層良好となる。 The permanent set of the hot melt composition of the present invention is preferably 60% or more, more preferably 85% or more, further preferably 90% or more, particularly preferably 95% or more. When the permanent set of the hot melt composition is 60% or more, the stretch recovery property of the hot melt composition after stretching is further improved.
 本発明のホットメルト組成物の永久歪みは、上記ホットメルト組成物の塗工サンプルを用いて、以下の測定方法により測定される。 The permanent set of the hot melt composition of the present invention is measured by the following measuring method using the coated sample of the hot melt composition.
永久歪みの測定方法
 ホットメルト組成物の塗工サンプルを、塗工方向に対して幅50mm、塗工方向に対して垂直な方向に100mmの短冊状に切断し、試験片を調製する。次いで、治具幅50mmに設定した引張り試験機に、ホットメルト組成物の塗工方向と垂直な方向が上下に位置するように試験片を治具で固定し、引張速度500mm/分で試験片の歪み変位が300%となる点まで引張る。次いで、速度500mm/分で初期の位置まで戻す。歪み変位が300%となる点まで引張り、初期の位置に戻す工程を1サイクルとして、同一の試験片について2サイクル繰り返す。横軸を歪み変位(%)、縦軸を応力(N/mm2)としたグラフにおいて、1サイクル目の引張り時における積分値をS1、2サイクル目の引張時における積分値をS2とし、以下の式により永久歪み(%)を算出する。
 永久歪み(%)=(S2/S1)×100
Method for Measuring Permanent Strain A coated sample of the hot melt composition is cut into a strip having a width of 50 mm in the coating direction and a length of 100 mm in the direction perpendicular to the coating direction to prepare a test piece. Then, the test piece was fixed with a jig to a tensile tester set to a jig width of 50 mm so that the direction perpendicular to the coating direction of the hot melt composition was positioned vertically, and the test piece was pulled at a pulling speed of 500 mm/min. Is stretched to the point where the strain displacement becomes 300%. Then, it is returned to the initial position at a speed of 500 mm/min. The process of pulling to the point where the strain displacement becomes 300% and returning to the initial position is set as one cycle, and two cycles are repeated for the same test piece. In the graph in which the horizontal axis is strain displacement (%) and the vertical axis is stress (N/mm2), the integrated value at the time of pulling in the first cycle is S1, and the integrated value at the time of pulling in the second cycle is S2. The permanent strain (%) is calculated by the formula.
Permanent strain (%)=(S2/S1)×100
ホットメルト組成物の製造方法および用途
 本発明のホットメルト組成物は公知の方法で製造される。例えば、(A)スチレン系ブロック共重合体、(B)可塑剤、各種添加剤等を150℃に加熱した双腕型混練機へ投入し、加熱しながら溶融混練することによって製造される。
Manufacturing Method and Use of Hot Melt Composition The hot melt composition of the present invention is manufactured by a known method. For example, it is produced by introducing (A) a styrene block copolymer, (B) a plasticizer, various additives and the like into a double-arm type kneader heated to 150° C. and melt-kneading while heating.
 当該ホットメルト組成物の用途としては特に限定されず、例えば、紙おむつ、生理用ナプキン、病院用ガウンなどいわゆる衛生材料等が挙げられる。 The use of the hot melt composition is not particularly limited, and examples thereof include so-called sanitary materials such as paper diapers, sanitary napkins, and hospital gowns.
 本発明のホットメルト組成物は、伸縮性フィルム、及び、伸縮部材を含む伸縮性積層体の伸縮部材として好適に用いられる。このような伸縮性積層体としては、例えば、不織布の少なくとも片面側に、上記ホットメルト組成物を有する伸縮性積層体が挙げられる。 The hot melt composition of the present invention is suitably used as a stretchable film and a stretchable member of a stretchable laminate including a stretchable member. Examples of such a stretchable laminate include a stretchable laminate having the above hot-melt composition on at least one side of a nonwoven fabric.
 積層体の用途としては特に限定されず、例えば、紙おむつ、生理用ナプキンなどいわゆる衛生材料に好適に用いることができる。 The use of the laminate is not particularly limited, and it can be suitably used for so-called sanitary materials such as paper diapers and sanitary napkins.
 以下、本発明の実施例について説明する。本発明は、下記の実施例に限定されない。 Hereinafter, examples of the present invention will be described. The present invention is not limited to the examples below.
 なお、実施例及び比較例で用いた原料は以下のとおりである。 The raw materials used in the examples and comparative examples are as follows.
(A)スチレン系ブロック共重合体
・(A1)スチレン-イソプレン-スチレン(SIS)共重合体:日本ゼオン社製 Quintac3390(スチレン含有量48質量%、Mp=105,000、172,000)
・(A2)スチレン-イソプレン-スチレン(SIS)共重合体:TSRC社製 VECTOR4411(スチレン含有量44質量%、Mp=79,000)
・(A3)スチレン-イソプレン-スチレン(SIS)共重合体:クレイトンポリマー社製 D1161(スチレン含有量15質量%、Mp=96,000、214,000)
・(A4)スチレン-イソプレン-スチレン(SIS)共重合体:日本ゼオン社製 Quintac3520(スチレン含有量15質量%、Mp=144,000、350,000)
(A) Styrene-based block copolymer :
-(A1) Styrene-isoprene-styrene (SIS) copolymer: Quintac3390 manufactured by Zeon Corporation (styrene content 48% by mass, Mp=105,000, 172,000)
-(A2) styrene-isoprene-styrene (SIS) copolymer: VECTOR4411 manufactured by TSRC (styrene content 44% by mass, Mp=79,000)
-(A3) Styrene-isoprene-styrene (SIS) copolymer: D1161 manufactured by Kraton Polymer Co., Ltd. (styrene content 15% by mass, Mp=96,000, 214,000)
(A4) styrene-isoprene-styrene (SIS) copolymer: Quintac 3520 manufactured by Zeon Corporation (styrene content 15% by mass, Mp=144,000, 350,000)
(B)可塑剤
・(B1)パラフィン系プロセスオイル:出光興産社製 PS-32(流動点-17.5℃)
・(B2)ナフテン系プロセスオイル:Nynas社製 Nyflex222B(流動点-35℃)
(B) Plasticizer :
・(B1) Paraffinic process oil: PS-32 (pour point -17.5°C) manufactured by Idemitsu Kosan Co., Ltd.
-(B2) naphthenic process oil: Nyflex222B manufactured by Nynas (pour point -35°C)
酸化防止剤
・フェノール系酸化防止剤 BASF社製 IRGANOX1010
Antioxidant :
-Phenolic antioxidant IRGANOX1010 manufactured by BASF
実施例及び比較例
 上述した原料を、それぞれ表1に示した配合量で、加熱装置を備えた攪拌混練機中に投入した。150℃で90分間加熱しながら混練して、ホットメルト組成物を製造した。
Examples and Comparative Examples The raw materials described above were charged in the amounts shown in Table 1 into a stirring and kneading machine equipped with a heating device. A hot melt composition was produced by kneading while heating at 150° C. for 90 minutes.
 得られたホットメルト組成物について、以下の測定条件により特性を評価した。 The properties of the obtained hot melt composition were evaluated under the following measurement conditions.
(180℃溶融粘度)
 ホットメルト組成物を加熱溶融し、180℃における溶融状態の粘度を、ブルックフィールドRVT型粘度計(スピンドルNo.29)を用いて測定し、下記評価基準に従って評価した。
○:180℃溶融粘度が2,000~60,000mPa・sである
×:180℃溶融粘度が60,000mPa・sを超えるか、又は、2,000mPa・s未満である
(180°C melt viscosity)
The hot melt composition was heated and melted, and the viscosity of the molten state at 180° C. was measured using a Brookfield RVT viscometer (spindle No. 29) and evaluated according to the following evaluation criteria.
◯: Melt viscosity at 180°C is 2,000 to 60,000 mPa·s ×: Melt viscosity at 180°C exceeds 60,000 mPa·s or less than 2,000 mPa·s
(分子量)
 ホットメルト組成物の0.1wt%テトラヒドロフラン溶液を作製し、ゲルパーミエーションクロマトグラフィー測定装置を用いて、標準ポリスチレンで換算することにより測定した。測定装置および測定条件は以下の通りである。
測定装置:Waters社製 商品名「ACQUITY APC」
測定条件:カラム
・ACQUITY APCXT45 1.7μm×1本
・ACQUITY APCXT125 2.5μm×1本
・ACQUITY APCXT450 2.5μm×1本
 移動相:テトラヒドロフラン 0.8mL/分
 サンプル濃度:0.2質量%
 検出器:示差屈折率(RI)検出器
 標準物質:ポリスチレン(Waters社製 分子量:266~1,800,000)
 カラム温度:40℃
 RI検出器温度:40℃
(Molecular weight)
A 0.1 wt% tetrahydrofuran solution of the hot melt composition was prepared and measured by converting it to standard polystyrene using a gel permeation chromatography measuring device. The measuring device and the measuring conditions are as follows.
Measuring device: Waters product name "ACQUITY APC"
Measurement conditions: Column-ACQUITY APCXT45 1.7 μm x 1-ACQUITY APCXT125 2.5 μm x 1-ACQUITY APCXT450 2.5 μm x 1 Mobile phase: Tetrahydrofuran 0.8 mL/min Sample concentration: 0.2 mass%
Detector: Differential Refractive Index (RI) Detector Standard substance: Polystyrene (Made by Waters, molecular weight: 266-1,800,000)
Column temperature: 40°C
RI detector temperature: 40°C
 得られた分子量ピークデータより、下記式(1)の左辺を算出した。
式(1):{ΣMp(H)n×h(H)n}/{ΣMp(L)m×h(L)m}>1.5
 式(1)中、Mp(H)は、分子量500,000~150,000の領域のピークトップ値を示す分子量を表し、h(H)は、分子量500,000~150,000の領域のピーク高さを表し、nは、ピークの番号を表す。また、Mp(L)は、分子量120,000~50,000の領域のピークトップ値を示す分子量を表し、h(L)は、分子量120,000~50,000の領域のピーク高さを表し、mは、ピークの番号を表す。なお、上記n及びmのピークの番号は、それぞれ、ピークトップ値を示す分子量が高い方から順に、1、2、・・・のように、1から番号を付与する。
The left side of the following formula (1) was calculated from the obtained molecular weight peak data.
Formula (1): {ΣMp(H)n×h(H)n}/{ΣMp(L)m×h(L)m}>1.5
In the formula (1), Mp(H) represents the molecular weight indicating the peak top value in the region of molecular weight 500,000 to 150,000, h(H) represents the peak height in the region of molecular weight 500,000 to 150,000, and n represents Represents the peak number. In addition, Mp(L) represents the molecular weight indicating the peak top value in the molecular weight range of 120,000 to 50,000, h(L) represents the peak height in the molecular weight range of 120,000 to 50,000, and m represents the peak number. Represent The n and m peaks are numbered from 1 in order from the highest molecular weight indicating peak top value, such as 1, 2,...
ホットメルト組成物の塗工サンプルの調製方法
 ホットメルト組成物を180℃の塗工温度で、離型処理されたPETフィルム上にスロット塗工で塗布した。塗布量は50g/m、塗布幅は100mmとした。次いで、離型処理された別のPETフィルムを積層し、室温下で圧着させることで積層体を作成した。得られた積層体を23℃、相対湿度50%雰囲気下で24時間保管し、ホットメルト組成物を室温に冷却して、ホットメルト組成物の塗工サンプルを調製した。
Method for Preparing Hot Melt Composition Coating Sample The hot melt composition was applied at a coating temperature of 180° C. by slot coating on a release-treated PET film. The coating amount was 50 g/m 2 and the coating width was 100 mm. Next, another PET film subjected to the mold release treatment was laminated and pressure-bonded at room temperature to form a laminate. The obtained laminate was stored for 24 hours in an atmosphere of 23° C. and a relative humidity of 50%, and the hot melt composition was cooled to room temperature to prepare a coated sample of the hot melt composition.
(伸長性)
 ホットメルト組成物の塗工サンプルを、塗工方向に対して幅50mm、塗工方向に対して垂直な方向に100mmの短冊状に切断し、試験片を調製した。次いで、治具幅50mmに設定した引張試験機へホットメルト組成物の塗工方向と垂直な方向が上下に位置するように試験片を治具で固定し、引張速度500mm/分で試験片が破断する点まで引っ張った。試験片が破断した変位を破断伸び(%)とし、ホットメルト組成物の伸長性の評価基準とした。測定結果に基づいて、下記評価基準に従って評価した。
◎:破断伸びが750%以上である
○:破断伸びが600%以上750%未満である
△:破断伸びが500%以上600%未満である
×:破断伸びが500%未満である
(Extensibility)
A test sample was prepared by cutting a coated sample of the hot melt composition into strips each having a width of 50 mm in the coating direction and a length of 100 mm in the direction perpendicular to the coating direction. Next, the test piece was fixed with a jig to a tensile tester set to a jig width of 50 mm so that the direction perpendicular to the coating direction of the hot melt composition was positioned vertically, and the test piece was pulled at a tensile speed of 500 mm/min. Pulled to the point of break. The displacement at which the test piece broke was defined as the breaking elongation (%), and was used as the evaluation standard for the extensibility of the hot melt composition. It evaluated based on the measurement result according to the following evaluation criteria.
A: Elongation at break is 750% or more B: Elongation at break is 600% or more and less than 750% B: Elongation at break is 500% or more and less than 600% X: Elongation at break is less than 500%
(永久歪み)
 ホットメルト組成物の塗工サンプルを、塗工方向に対して幅50mm、塗工方向に対して垂直な方向に100mmの短冊状に切断し、試験片を調製した。次いで、治具幅50mmに設定した引張り試験機に、ホットメルト組成物の塗工方向と垂直な方向が上下に位置するように試験片を治具で固定し、引張速度500mm/分で試験片の歪み変位が300%となる点まで引張った。次いで、速度500mm/分で初期の位置まで戻した。歪み変位が300%となる点まで引張り、初期の位置に戻す工程を1サイクルとして、同一の試験片について2サイクル繰り返した。横軸を歪み変位(%)、縦軸を応力(N/mm)としたグラフにおいて、1サイクル目の引張り時における積分値をS1、2サイクル目の引張時における積分値をS2とし、以下の式により永久歪み(%)を算出した。
 永久歪み(%)=(S2/S1)×100
測定結果に基づいて、下記評価基準に従って評価した。
◎:永久歪みが95%以上である
○:永久歪みが85%以上95%未満である
△:永久歪みが60%以上85%未満である
×:永久歪みが60%未満である
(Permanent distortion)
A test sample was prepared by cutting a coated sample of the hot melt composition into strips each having a width of 50 mm in the coating direction and a length of 100 mm in the direction perpendicular to the coating direction. Then, the test piece was fixed with a jig to a tensile tester set to a jig width of 50 mm so that the direction perpendicular to the coating direction of the hot melt composition was positioned vertically, and the test piece was pulled at a pulling speed of 500 mm/min. Was stretched to the point where the strain displacement was 300%. Then, it was returned to the initial position at a speed of 500 mm/min. The step of pulling to the point where the strain displacement becomes 300% and returning to the initial position is set as one cycle, and two cycles are repeated for the same test piece. In the graph in which the horizontal axis is strain displacement (%) and the vertical axis is stress (N/mm 2 ), the integrated value at the time of pulling in the first cycle is S1, the integrated value at the time of pulling in the second cycle is S2, and The permanent set (%) was calculated by the following equation.
Permanent strain (%)=(S2/S1)×100
It evaluated based on the measurement result according to the following evaluation criteria.
A: Permanent strain is 95% or more. O: Permanent strain is 85% or more and less than 95%. B: Permanent strain is 60% or more and less than 85%. X: Permanent strain is less than 60%.
 結果を表1に示す。
Figure JPOXMLDOC01-appb-T000001
The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001

Claims (4)

  1.  (A)スチレン系ブロック共重合体、及び、(B)可塑剤を含有するホットメルト組成物であって、
     180℃での粘度が2,000~60,000mPa・sであり、
     ゲルパーミエーションクロマトグラフィーにより測定したポリスチレン換算の分子量分布が、分子量500,000~150,000の高分子領域、及び、分子量120,000~50,000の低分子領域に、それぞれ1つ以上のピークを有し、
     下記式(1)を満たす、
    ことを特徴とするホットメルト組成物。
    式(1):{ΣMp(H)n×h(H)n}/{ΣMp(L)m×h(L)m}>1.5
    (式(1)中、Mp(H)は、分子量500,000~150,000の領域のピークトップ値を示す分子量を表し、h(H)は、分子量500,000~150,000の領域のピーク高さを表し、nは、ピークの番号を表す。また、Mp(L)は、分子量120,000~50,000の領域のピークトップ値を示す分子量を表し、h(L)は、分子量120,000~50,000の領域のピーク高さを表し、mは、ピークの番号を表す。)
    A hot melt composition comprising (A) a styrene block copolymer and (B) a plasticizer,
    Viscosity at 180℃ is 2,000-60,000mPa・s,
    The polystyrene equivalent molecular weight distribution measured by gel permeation chromatography has one or more peaks in the high molecular weight region of 500,000 to 150,000 and the low molecular weight region of 120,000 to 50,000, respectively.
    Satisfies the following formula (1),
    A hot melt composition characterized by the above.
    Formula (1): {ΣMp(H)n×h(H)n}/{ΣMp(L)m×h(L)m}>1.5
    (In the formula (1), Mp(H) represents the molecular weight indicating the peak top value in the molecular weight range of 500,000 to 150,000, h(H) represents the peak height in the molecular weight range of 500,000 to 150,000, and n represents , Mp(L) represents the molecular weight indicating the peak top value in the molecular weight range of 120,000 to 50,000, h(L) represents the peak height in the molecular weight range of 120,000 to 50,000, m represents the peak number.)
  2.  (A)成分の含有量は、ホットメルト組成物を100質量%として40~65質量%である、請求項1に記載のホットメルト組成物。 The hot melt composition according to claim 1, wherein the content of the component (A) is 40 to 65 mass% based on 100 mass% of the hot melt composition.
  3.  スチレン系ブロック共重合体は、スチレン-ブタジエン-スチレン共重合体(SBS)及びスチレン-イソプレン-スチレン共重合体(SIS)からなる群より選択される少なくとも1種である、請求項1又は2に記載のホットメルト組成物。 The styrene-based block copolymer is at least one selected from the group consisting of styrene-butadiene-styrene copolymer (SBS) and styrene-isoprene-styrene copolymer (SIS). The hot melt composition described.
  4.  不織布の少なくとも片面側に、請求項1~3のいずれかに記載のホットメルト組成物を有する伸縮性積層体。 An elastic laminate having the hot melt composition according to any one of claims 1 to 3 on at least one side of the nonwoven fabric.
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