WO2018230210A1 - Hot melt adhesive - Google Patents

Hot melt adhesive Download PDF

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Publication number
WO2018230210A1
WO2018230210A1 PCT/JP2018/018194 JP2018018194W WO2018230210A1 WO 2018230210 A1 WO2018230210 A1 WO 2018230210A1 JP 2018018194 W JP2018018194 W JP 2018018194W WO 2018230210 A1 WO2018230210 A1 WO 2018230210A1
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WO
WIPO (PCT)
Prior art keywords
melt adhesive
hot melt
copolymer
mass
block
Prior art date
Application number
PCT/JP2018/018194
Other languages
French (fr)
Japanese (ja)
Inventor
麻希 佐見津
周平 有田
Original Assignee
株式会社Moresco
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社Moresco filed Critical 株式会社Moresco
Priority to JP2019525207A priority Critical patent/JP6854889B2/en
Priority to CN201880038710.XA priority patent/CN110741058A/en
Publication of WO2018230210A1 publication Critical patent/WO2018230210A1/en

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Classifications

    • 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
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
    • 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 adhesive.
  • a hot melt adhesive is applied to an adherend that is an object to be bonded in a melted state by heating, and the adherends are held in contact with each other via the melted hot melt adhesive.
  • the adherends are bonded to each other.
  • Such hot melt adhesives include, for example, packaging fields such as cardboard and small boxes, sanitary material fields such as paper diapers and sanitary products, bookbinding fields, plywood fields, woodworking fields, automobile fields, home appliance fields, and housing fields, etc. It is used in various fields.
  • the hot melt adhesive is used in a melted state by heating, so that no solvent is required.
  • the hot melt adhesive is preferably used in the sanitary material field, for example, as an adhesive having high safety to the human body.
  • hot-melt adhesives are widely used for fixing and assembling components of disposable sanitary materials such as disposable diapers and sanitary products.
  • hydrophilic sanitary materials such as a paper diaper
  • hydrophilic porous substrates such as a ground pulp used as an absorber of a tissue and a paper diaper.
  • Examples of the adhesive intended to improve the adhesiveness in such a wet state include the adhesives described in Patent Documents 1 to 4.
  • Patent Document 1 discloses a group consisting of a styrene-isoprene-styrene block copolymer, a styrene-butadiene-styrene block copolymer, and a styrene-butadiene / butylene-styrene having a styrene component content of 15 to 35% by mass.
  • Patent Document 1 it is disclosed that it is possible to express excellent adhesive strength to a wet hydrophilic porous substrate even at a relatively low temperature, and that it is excellent in thermal stability. .
  • Patent Document 2 a hot block containing a thermoplastic block copolymer, which is a copolymer of a vinyl aromatic hydrocarbon and a conjugated diene compound, and a wax modified with a carboxylic acid and / or a carboxylic anhydride.
  • a melt adhesive is described. According to Patent Document 2, it is disclosed that wet adhesion is improved, and more preferably, at least one selected from low-temperature adhesion, viscosity, adhesion, odor, and economy is improved.
  • Patent Document 3 discloses a hot for disposable products containing a propylene homopolymer having a melting point of 100 ° C. or less obtained by polymerizing propylene using a metallocene catalyst, and a wax modified with carboxylic acid and / or carboxylic anhydride. A melt adhesive is described. According to Patent Document 3, it is disclosed that it is suitable for high-speed coating and is excellent in adhesiveness in a wet state and low-temperature coating.
  • Patent Document 4 discloses a block copolymer of a vinyl aromatic hydrocarbon and a conjugated diene compound and a thermoplastic block copolymer containing at least one of hydrogenated products thereof, and unsaturated carboxylic acids or anhydrides thereof.
  • a hot melt adhesive containing an acid-modified petroleum resin that has been acid-modified by a product is described. According to Patent Document 4, it is disclosed that wet adhesion is improved with respect to the constituent members without causing deterioration of thermal stability or generation of odor.
  • the hot melt adhesive is required to improve the adhesiveness in a wet state.
  • the occurrence of deformation of the hot melt adhesive may be suppressed. Desired. That is, it is also required to suppress the occurrence of the creep phenomenon in a wet state.
  • the adhesiveness in the wet state can also be improved by suppressing the occurrence of the creep phenomenon in the wet state. For this reason, the hot melt adhesive is required to sufficiently suppress the occurrence of a creep phenomenon in a wet state and to have excellent adhesiveness in a wet state.
  • the present invention has been made in view of such circumstances, and an object of the present invention is to provide a hot melt adhesive that can sufficiently suppress the occurrence of a creep phenomenon in a wet state and is excellent in adhesiveness in a wet state. .
  • thermoplastic polymer includes a first block composed of a conjugated diene compound and a vinyl aromatic.
  • a copolymer comprising a second block comprising a hydrocarbon, and at least one of a hydride of the copolymer, wherein the copolymer has a content of the second block of less than 30% by mass,
  • a hot melt adhesive characterized in that it is 55% by mass or more based on the total amount of the polymer, and the content of the softener is 15 to 30 parts by mass with respect to 100 parts by mass of the hot melt adhesive. Ah .
  • a hot melt adhesive melted by heating is applied to an adherend using a coating machine or the like.
  • the adherends can be adhered to each other.
  • Patent Documents 1 to 4 disclose that the adhesiveness in a wet state can be improved as described above. From this, it is conceivable to use the adhesives described in Patent Documents 1 to 4.
  • the hot melt adhesive is required to improve the adhesiveness in the wet state, and in order to realize this, it is required to sufficiently suppress the occurrence of the creep phenomenon in the wet state.
  • the inventor of the present invention can sufficiently suppress the occurrence of a creep phenomenon in a wet state and provide a hot melt adhesive excellent in adhesiveness in a wet state. I found it to be achieved.
  • the present inventor when using hot melt adhesive in low temperature application and small amount application, even if it can improve the adhesion in the wet state, the reason why the creep phenomenon in the wet state cannot be sufficiently suppressed I guessed as follows.
  • the amount of heat of the hot melt adhesive at the time of coating decreases, and the hot melt adhesive is less likely to soak into the hydrophilic porous substrate that is the adherend. It is considered to be. Thereby, even if the adherends are bonded to each other with the hot melt adhesive, it is considered that the adherend and the hot melt adhesive are in contact only in the vicinity of the surface of the adherend. For this reason, it is considered that the hot melt adhesive is likely to be deformed when a certain time or more elapses in a wet state with a load applied to the hot melt adhesive. That is, it is considered that an interfacial fracture that peels off at the interface between the hot melt adhesive and the adherend tends to occur due to the creep phenomenon.
  • the present inventor has paid attention to increasing the affinity of the hot melt adhesive with the hydrophilic porous substrate so that the hot melt adhesive can easily penetrate into the hydrophilic porous substrate. It was investigated. As a result, the following hot melt adhesives have been conceived.
  • the hot melt adhesive includes a thermoplastic polymer, a tackifier, and a softener.
  • the thermoplastic polymer includes at least one of a copolymer composed of a first block composed of a conjugated diene compound and a second block composed of a vinyl aromatic hydrocarbon, and a hydride of the copolymer. Further, in this copolymer, the content of the second block is less than 30% by mass, and the content of the diblock body of the first block and the second block is 10% by mass or more. It is a polymer. Furthermore, content of the said copolymer and the hydride of the said copolymer is 55 mass% or more with respect to the said thermoplastic polymer whole quantity. In addition, the content of the softening agent is 15 to 30 parts by mass with respect to 100 parts by mass of the hot melt adhesive.
  • This hot melt adhesive contains, as the thermoplastic polymer, at least one of the copolymer and a hydride of the copolymer in a total of 55% by mass or more, and further, a softener is added to the hot melt adhesive.
  • a softener is added to the hot melt adhesive.
  • the second block is a block composed of vinyl aromatic hydrocarbons, so-called hard segments, forms aggregates with other hard segments, and in the copolymer, the bonding points between the molecular chains are determined. It is thought to form. Since the copolymer has a relatively small content of such second blocks, it is considered that the number of bonding points between molecular chains is relatively small.
  • the first block is a block made of a conjugated diene compound and is called a so-called soft segment. By having such a first block, the hot melt adhesive containing the copolymer is considered to be a highly flexible adhesive. Further, the copolymer includes a diblock body of the first block and the second block.
  • this diblock body will have the 2nd block which can become a junction of molecular chains in one edge part, and does not work as a crosslinking agent.
  • the copolymer contains a certain amount or more of a diblock body that does not act as such a crosslinking agent.
  • the hot melt adhesive containing the copolymer is a hydrophilic porous material that is an adherend. It is considered that it easily penetrates into the inside of the base material.
  • the hydride of the copolymer is considered to work in the same manner as the copolymer.
  • the hot melt adhesive is considered to be flexible and easily penetrate into the adherend. Further, since a predetermined amount of the softening agent is contained, it is considered that the hot melt adhesive can be suitably applied even in a small amount. Therefore, the hot melt adhesive can be suitably applied to a hydrophilic porous substrate as an adherend, easily penetrates into the inside, and has flexibility, so that the occurrence of a creep phenomenon in a wet state is preferable. It can be suppressed.
  • the thermoplastic polymer used in the present embodiment includes either one of the copolymer and a hydride of the copolymer, and the total of them includes the total amount of the thermoplastic polymer. If it is 55 mass% or more, it will not specifically limit. Moreover, the content rate of the said hydride of the said copolymer and the said copolymer is 55 mass% or more with respect to the said thermoplastic polymer whole quantity, and it is preferable that it is 75 mass% or more. Further, the thermoplastic polymer may consist of only the copolymer and a hydride of the copolymer, that is, the content of the copolymer and the hydride of the copolymer is 100% by mass. It may be. When the amount of the copolymer is too small, there is a tendency that the effects of including the copolymer, such as easy penetration into the hydrophilic porous substrate that is the adherend, cannot be exhibited sufficiently.
  • the copolymer is a copolymer composed of a first block made of a conjugated diene compound and a second block made of a vinyl aromatic hydrocarbon.
  • the first block is a block made of a conjugated diene compound, that is, a block derived from a conjugated diene compound.
  • the first block include a polymer obtained by polymerizing a conjugated diene compound (a polymer of a conjugated diene compound).
  • the conjugated diene compound is not particularly limited as long as it is a diolefin compound having at least a pair of conjugated double bonds.
  • Specific examples of the conjugated diene compound include butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3. -Hexadiene and the like. Of these, butadiene and isoprene are preferred as the conjugated diene compound.
  • the said exemplary compound may be used independently, and may be used in combination of 2 or more type.
  • the second block is a block made of vinyl aromatic hydrocarbon, that is, a block derived from vinyl aromatic hydrocarbon.
  • the second block include a polymer obtained by polymerizing vinyl aromatic hydrocarbon (polymer of the vinyl aromatic hydrocarbon).
  • the vinyl aromatic hydrocarbon is not particularly limited as long as it is an aromatic hydrocarbon having a vinyl group.
  • Specific examples of the vinyl aromatic hydrocarbon include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, ⁇ -methylstyrene, vinylnaphthalene, and vinyl. Anthracene etc. are mentioned. Of these, styrene is preferred as the vinyl aromatic hydrocarbon.
  • the compound of the said illustration may be used independently, and may be used in combination of 2 or more type.
  • the content of the second block is less than 30% by mass with respect to the copolymer, preferably 5 to 25% by mass, and preferably 15 to 25% by mass. Is more preferable.
  • the content of the second block is a relatively small content within the above range, a highly flexible adhesive can be obtained while suitably functioning as a bonding point between molecular chains.
  • the diblock body content of the first block and the second block is 10% by mass or more, preferably 30 to 90% by mass, and preferably 50 to 80% by mass with respect to the copolymer. % Is more preferable.
  • the copolymer may consist of only the diblock body, that is, the content of the diblock body of the first block and the second block is 100 with respect to the copolymer. It may be mass%.
  • a triblock body etc. will increase and there exists a tendency for the softness
  • the content of the diblock body is within the above range, a highly flexible adhesive can be obtained while suitably functioning as a bonding point between molecular chains.
  • copolymer and the hydride of the copolymer include, for example, a styrene-butadiene block copolymer, a styrene-isoprene block copolymer, a hydrogenated styrene-butadiene block copolymer, and a hydrogenated styrene.
  • -Isoprene block copolymers and the like may contain a triblock body as long as the content of the diblock body is within the above range.
  • the triblock body examples include a styrene-butadiene-styrene block copolymer (SBS) in the case of a styrene-butadiene block copolymer.
  • SBS styrene-butadiene-styrene block copolymer
  • SIS styrene-isoprene-styrene block copolymer
  • SEBS hydrogenated styrene-butadiene block copolymer
  • SEBS styrene-ethylene-butylene-styrene block copolymer
  • styrene-ethylene-propylene-styrene block copolymer SEPS
  • SEPS styrene-ethylene-propylene-styrene block copolymer
  • thermoplastic polymer only needs to contain 55% by mass or more of the copolymer and a hydride of the copolymer, and a thermoplastic polymer other than the copolymer and the hydride of the copolymer (others).
  • the other thermoplastic polymer is not particularly limited as long as it is a thermoplastic polymer used as a component constituting a hot melt adhesive.
  • thermoplastic polymer etc. which are used as a base polymer which is a main component of a hot-melt-adhesive are mentioned.
  • thermoplastic polymer examples include elastomeric, olefinic, ethylene vinyl acetate copolymer (EVA) based, polyester based, polyamide based, and polyacrylic thermoplastic polymers.
  • EVA ethylene vinyl acetate copolymer
  • polyester based examples include polyester based, polyamide based, and polyacrylic thermoplastic polymers.
  • the elastomer-based thermoplastic polymer and the olefin-based thermoplastic polymer are preferable, and the elastomer-based thermoplastic polymer is more preferable.
  • the elastomer-based thermoplastic polymer includes the copolymer and the hydride of the copolymer.
  • the elastomer-based thermoplastic polymer here is other than the copolymer and the hydride of the copolymer.
  • Elastomer-based thermoplastic polymers for example, elastomer-based thermoplastic polymers including blocks other than the first block and the second block.
  • the olefin-based thermoplastic polymer is not particularly limited as long as it is used as an olefin-based thermoplastic polymer in a hot melt adhesive.
  • examples of the olefin-based thermoplastic polymer include polyolefin compounds that are solid at room temperature and polymerized with a Ziegler-Natta catalyst or a single-site catalyst.
  • Specific examples of the olefin-based thermoplastic polymer include polyethylene, polypropylene, poly-1-butene, polyisobutylene, random copolymer or block in any ratio of propylene and at least one of ethylene and 1-butene.
  • Copolymer ethylene-propylene-diene terpolymer in any ratio of ethylene, propylene and diene component, random copolymer or block copolymer of ethylene or propylene and vinyl compound, random polypropylene, block polypropylene , Homopolypropylene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene / 1-octene copolymer, propylene / ethylene copolymer, propylene / ethylene / ⁇ -Butene copolymers, -Butene homopolymer, 1-butene / ethylene copolymer, 1-butene / propylene copolymer, propylene / 1-butene copolymer, ethylene / vinyl acetate copolymer, ethylene / methacrylic acid copolymer, ethylene -A methyl methacrylate cop
  • the olefin-based thermoplastic polymer for example, among the compounds exemplified above, an olefin-based polymer polymerized using an olefin (alkene) such as an ⁇ -olefin as a monomer is preferable.
  • the olefin polymer include poly ⁇ -olefin polymers. More specifically, the poly ⁇ -olefin polymer is preferably an amorphous poly ⁇ -olefin polymer (APAO) or a homopolymer of propylene (propylene homopolymer). More specifically, the propylene homopolymer is preferably a propylene homopolymer obtained by polymerizing propylene using a metallocene catalyst.
  • APAO amorphous poly ⁇ -olefin polymer
  • propylene homopolymer is preferably a propylene homopolymer obtained by polymerizing propylene using a metallocene catalyst.
  • the EVA-based thermoplastic polymer is not particularly limited as long as it is used as an EVA-based thermoplastic polymer in a hot melt adhesive, and examples thereof include a copolymer synthesized from ethylene and vinyl acetate. It is done.
  • the polyester-based thermoplastic polymer is not particularly limited as long as it is used as a polyester-based thermoplastic polymer in the hot melt adhesive.
  • Examples of the polyester-based thermoplastic polymer include polyester polymerized using dimer acid as a monomer.
  • the polyamide-based thermoplastic polymer is not particularly limited as long as it is used as a polyamide-based thermoplastic polymer in the hot melt adhesive, and examples thereof include polyamide.
  • the polyacrylic thermoplastic polymer is not particularly limited as long as it is used as a polyacrylic thermoplastic polymer in a hot melt adhesive, and examples thereof include polyacrylic acid esters and polymethacrylic acid esters. Can be mentioned.
  • thermoplastic polymer As the other thermoplastic polymer, the above-exemplified thermoplastic polymers may be used alone or in combination of two or more.
  • the weight average molecular weight of the thermoplastic polymer such as the copolymer varies depending on the kind of the thermoplastic polymer and is not particularly limited. For example, it is preferably 10,000 to 500,000, and is 50,000 to 300,000. It is more preferable. If the molecular weight of the thermoplastic polymer is too small, the cohesive force tends to decrease, and the stability over time tends to decrease. On the other hand, when the molecular weight of the thermoplastic polymer is too large, the melt viscosity increases and the coatability tends to decrease. In addition, the weight average molecular weight here should just be the weight average molecular weight measured by the general measuring method, for example, the weight average molecular weight measured using gel permeation chromatography (GPC) etc. are mentioned.
  • GPC gel permeation chromatography
  • the tackifier used in the present embodiment is not particularly limited as long as it is a tackifier generally used for hot melt adhesives.
  • tackifiers include rosin resins, terpene resins, and petroleum resins.
  • the rosin resin examples include natural rosin such as gum rosin, tall rosin and wood rosin, disproportionated rosin, polymerized rosin, glycerin ester and pentaerythritol ester of these rosins. Further, the rosin resin may be one in which each of the rosin resins is not hydrogenated, or hydrogenated, that is, a hydrogenated product (hydride) of the rosin resin. Also good.
  • the terpene resin examples include terpene resins, hydrocarbon-modified terpene resins, aromatic-modified terpene resins, and phenol-modified terpene resins.
  • the terpene resin may be one in which each of the terpenes is not hydrogenated, or one obtained by hydrogenation, that is, a hydrogenated product (hydride) of the terpene resin.
  • the terpene resin is preferably an aromatic modified terpene resin hydride, an aromatic modified terpene resin, or a terpene resin hydride, and more preferably an aromatic modified terpene resin hydride.
  • Examples of the petroleum resins include aliphatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, and hydrogenated products (hydrides) thereof. Further, as the petroleum resin hydride, an aliphatic petroleum resin hydride, an alicyclic petroleum resin hydride, and an aromatic petroleum resin hydride are preferable. Examples of the alicyclic petroleum resin hydride include hydrogenated C9 petroleum resin and hydrogenated dicyclopentadiene petroleum resin.
  • the tackifier preferably includes an acid-modified tackifier modified with at least one of carboxylic acid and carboxylic anhydride.
  • the acid-modified tackifier is not particularly limited as long as it is obtained by modifying a tackifier generally used as a tackifier in a hot melt adhesive with at least one of carboxylic acid and carboxylic anhydride.
  • the acid-modified tackifier for example, at least one of carboxylic acid and carboxylic acid anhydride is obtained by grafting to a tackifier, or when a tackifier is synthesized by polymerization, Examples include tackifiers obtained by copolymerizing at least one of carboxylic acid and carboxylic acid anhydride.
  • the tackifier before modification is not particularly limited as long as it is a tackifier generally used for hot melt adhesives, and examples thereof include the tackifiers described above.
  • the carboxylic acid used for the acid modification is not particularly limited.
  • Examples of the carboxylic acid used for the acid modification include maleic acid, fumaric acid, succinic acid, phthalic acid, glutaric acid, itaconic acid, acrylic acid, and methacrylic acid.
  • the carboxylic acid anhydride used for the acid modification is not particularly limited.
  • Examples of the carboxylic acid anhydride used for the acid modification include maleic anhydride (maleic anhydride), succinic anhydride, phthalic anhydride, and glutaric anhydride.
  • the carboxylic acid maleic acid, fumaric acid, and acrylic acid are preferable, and maleic acid is more preferable.
  • the carboxylic acid anhydride is preferably maleic anhydride.
  • maleic anhydride which is a carboxylic acid anhydride is preferable.
  • carboxylic acid and the carboxylic acid anhydride the above carboxylic acids and carboxylic acid anhydrides may be used alone or in combination of two or more.
  • the tackifiers and acid-modified tackifiers exemplified above may be used alone, or two or more kinds may be used in combination.
  • the softener used in the present embodiment is not particularly limited as long as it is a softener generally used for hot melt adhesives.
  • the softener include oils such as mineral oils, synthetic oils, vegetable oils, and fatty acid esters.
  • the mineral oil include process oil and liquid paraffin.
  • the process oil is an oil generally used as a plasticizer such as rubber or thermoplastic elastomer, and is produced in so-called petroleum refining.
  • the process oil is generally a mixture containing an aromatic ring, a naphthene ring, and a paraffin chain, and is roughly classified into a paraffinic process oil, a naphthenic process oil, and an aromatic process oil.
  • Process oils are those in which the number of carbon atoms in the paraffin chain occupies 50% or more of the total number of carbons, paraffin type, in which the naphthene ring carbon number occupies 30% or more, naphthenic type, and in which the aromatic carbon number occupies 30% or more. Differentiated from aromatic.
  • paraffinic process oil examples include paraffinic compounds having 4 to 155 carbon atoms, preferably paraffinic compounds having 4 to 50 carbon atoms.
  • specific examples of the paraffinic process oil include butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosan, heneicosane, docosane, tricosane.
  • Tetracosane pentadecosan, hexacosane, heptacosane, octacosane, nonacosan, triacontane, hentriacontan, dotriacontan, pentatriacontane, hexacontane, and hempacontan, etc.
  • n-paraffin isobutane, isopentane, neopentane, isohexane, isopentane , Neohexane, 2,3-dimethylbutane, various methylhexane, 3-ethylpentane, various dimethylpentane, 2,2,3- Limethylbutane, 3-methylheptane, various dimethylhexanes, various trimethylpentanes, isononane, 2-methylnonane, isodecane, isoundecane, isododecane, isotridecane, isotetradecane, isopentadecane, isooctadecane, isonanodecane, isoeicosane, and 4-ethyl-5- Examples thereof include isoparaffins such as methyloctane and derivatives of these saturated hydrocarbons. These selected paraffinic compounds can be used in a mixture and are liquid at room temperature.
  • synthetic oils include phosphate esters, chlorinated paraffins, ethylene- ⁇ -olefin oligomers, polybutenes, low molecular weight polybutadienes, polyisoprenes, and hydrogenated products thereof that are liquid at room temperature. .
  • vegetable oils include olive oil, carnauba wax, rice germ oil, corn oil, sasanqua oil, camellia oil, castor oil, jojoba seed oil, and eucalyptus leaf oil.
  • fatty acid esters include isopropyl myristate, octyldodecyl ristylate, glycerin triisooctanoate, diisopropyl adipate, diethyl sebacate, cetyl ethylhexanoate, cetyl palmitate, ethylhexyl palmitate, isopropyl palmitate,
  • fatty acid esters include isopropyl myristate, octyldodecyl ristylate, glycerin triisooctanoate, diisopropyl adipate, diethyl sebacate, cetyl ethylhexanoate, cetyl palmitate, ethylhexyl palmitate, isopropyl palmitate,
  • Examples include medium chain fatty acid triglycerides, ethylene glycol salicylate, and glycol distearate.
  • the softener preferably contains an acid-modified softener modified with at least one of carboxylic acid and carboxylic anhydride.
  • the acid-modified softener is not particularly limited as long as it is obtained by modifying a softener generally used as a softener in a hot melt adhesive with at least one of carboxylic acid and carboxylic anhydride.
  • Examples of the acid-modified softening agent include oil having a succinic acid skeleton in the molecule.
  • the softener before modification is not particularly limited as long as it is a softener generally used for hot melt adhesives, and examples thereof include the softeners described above.
  • the carboxylic acid used for the acid modification is not particularly limited.
  • Examples of the carboxylic acid used for the acid modification include maleic acid, fumaric acid, succinic acid, phthalic acid, glutaric acid, itaconic acid, acrylic acid, and methacrylic acid.
  • the carboxylic acid anhydride used for the acid modification is not particularly limited.
  • Examples of the carboxylic acid anhydride used for the acid modification include maleic anhydride (maleic anhydride), succinic anhydride, phthalic anhydride, and glutaric anhydride.
  • the carboxylic acid maleic acid, fumaric acid, and acrylic acid are preferable, and maleic acid is more preferable.
  • the carboxylic acid anhydride is preferably maleic anhydride.
  • maleic anhydride which is a carboxylic acid anhydride is preferable.
  • carboxylic acid and the carboxylic acid anhydride the above carboxylic acids and carboxylic acid anhydrides may be used alone or in combination of two or more.
  • the softener the above-exemplified softener and acid-modified softener may be used alone or in combination of two or more.
  • the contents of the thermoplastic polymer, the tackifier, and the softener are not particularly limited as long as they do not hinder the desired properties of the present invention.
  • the following ranges are mentioned, for example.
  • the content of the thermoplastic polymer is preferably 10 to 50 parts by weight, more preferably 15 to 30 parts by weight, and more preferably 15 to 25 parts by weight with respect to 100 parts by weight of the hot melt adhesive. More preferably it is.
  • the content of the thermoplastic polymer is too small, the cohesive force tends to be insufficient.
  • this content is content with respect to the hot-melt-adhesive whole quantity.
  • the content of the tackifier is preferably 40 to 80 parts by mass, more preferably 50 to 70 parts by mass, and 55 to 65 parts by mass with respect to 100 parts by mass of the hot melt adhesive. More preferably it is.
  • the content of the tackifier is preferably 40 to 80 parts by mass, more preferably 50 to 70 parts by mass, and 55 to 65 parts by mass with respect to 100 parts by mass of the hot melt adhesive. More preferably it is.
  • the content of the softening agent is preferably 15 to 30 parts by mass, more preferably 15 to 27 parts by mass, and more preferably 18 to 27 parts by mass with respect to 100 parts by mass of the hot melt adhesive. It is more preferable that When the content of the softening agent is too small, the creep strength when wet tends to decrease. Moreover, when there is too much content of the said softener, there exists a tendency for cohesion force and adhesive force to fall and for holding power to fall. In addition, this content is content with respect to the hot-melt-adhesive whole quantity.
  • the content of the thermoplastic polymer in the hot melt adhesive is 10 to 50% by mass with respect to the total amount of the hot melt adhesive.
  • the content of the tackifier is preferably 40 to 80% by mass with respect to the total amount of the hot melt adhesive.
  • the content of the softening agent is preferably 15 to 30% by mass with respect to the total mass.
  • the hot melt adhesive according to the present embodiment may contain a material other than the thermoplastic polymer, the tackifier, and the softener, as long as the desired properties of the present invention are not impaired. . Specifically, addition of antioxidants, heat stabilizers, light stabilizers, UV absorbers, fillers, surfactants, coupling agents, colorants, antistatic agents, flame retardants, waxes, plasticizers, etc. An agent may be contained.
  • examples of the antioxidant include phenolic antioxidants and organic sulfur antioxidants.
  • examples of phenolic antioxidants include 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2 -Tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxy Phenyl) propionate] methane and the like.
  • organic sulfur-based antioxidants examples include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, and pentaerythris. Lithyltetrakis (3-lauryl thiopropionate) and the like can be mentioned. As these antioxidants, the above-exemplified antioxidants may be used alone or in combination of two or more.
  • the wax is not particularly limited as long as it is a wax contained in the hot melt adhesive.
  • the wax include synthetic wax, petroleum wax, and natural wax.
  • synthetic waxes include polyolefin waxes such as Fischer-Tropsch wax, polyethylene wax, and polypropylene wax.
  • petroleum waxes include paraffin wax, microcrystalline wax, and petratam.
  • natural waxes include montan wax, wood wax, carbana wax, beeswax, and castor wax. These waxes may be used alone or in combination of two or more.
  • the method for producing the hot melt adhesive according to the present embodiment is not particularly limited as long as it is a production method capable of producing the hot melt adhesive having the above configuration.
  • Examples of a method for producing a hot melt adhesive include a method in which components constituting the hot melt adhesive are heated and melted and stirred and kneaded. By doing so, a hot melt adhesive having a high dispersibility of components constituting the hot melt adhesive can be obtained.
  • the stirring kneader, roll, Banbury mixer, kneader, extruder, etc. which were equipped with the heating apparatus are mentioned, for example.
  • the bonding method using the hot melt adhesive is not particularly limited as long as it can be used as the bonding method using the hot melt adhesive.
  • a hot melt adhesive is melted by heating. And the hot-melt-adhesive of the molten state is apply
  • the hot melt adhesive is cooled and solidified. This solidified hot melt adhesive bonds adherends to each other.
  • the method for applying the hot melt adhesive is not particularly limited as long as the hot melt adhesive can be suitably applied to the adherend.
  • This coating method is roughly classified into, for example, a contact coating method and a non-contact coating method.
  • the contact coating method refers to a coating method in which a hot melt adhesive is applied in a state where an apparatus used for coating such as a coating machine is in contact with an adherend.
  • the non-contact coating method refers to a coating method in which a coating machine or the like is applied without being in contact with an adherend when a hot melt adhesive is applied. Examples of the contact coating method include slot coating (such as a slot coat gun manufactured by Nordson Corporation) and roll coater coating.
  • spiral coating that can be applied in a spiral shape (such as a spiral spray nozzle manufactured by Suntool Co., Ltd.), spray coating that can be applied in a corrugated shape (such as OMEGA COAT manufactured by ITW Dynatech Co., Ltd.) , Spray coating that can be applied in the form of a surface (curtain spray head manufactured by Suntool Co., Ltd.), dot coating that can be applied in the form of dots, etc.
  • the hot melt adhesive according to this embodiment is suitable for spiral coating.
  • Spiral coating is a method in which an adhesive is spirally contacted with air by intermittent or continuous coating.
  • thermoplastic polymer includes a first block composed of a conjugated diene compound and a vinyl aromatic.
  • a copolymer comprising a second block comprising a hydrocarbon, and at least one of a hydride of the copolymer, wherein the copolymer has a content of the second block of less than 30% by mass,
  • a hot melt adhesive characterized in that it is 55% by mass or more based on the total amount of the polymer, and the content of the softener is 15 to 30 parts by mass with respect to 100 parts by mass of the hot melt adhesive. Ah .
  • this hot melt adhesive is excellent in adhesiveness in a wet state.
  • the vinyl aromatic hydrocarbon is preferably styrene
  • the conjugated diene compound is preferably at least one of butadiene and isoprene.
  • a hot melt adhesive that can further suppress the occurrence of a creep phenomenon in a wet state can be obtained.
  • the tackifier preferably includes an acid-modified tackifier modified by at least one of carboxylic acid and carboxylic anhydride.
  • the softener includes an acid-modified softener modified with at least one of carboxylic acid and carboxylic anhydride.
  • thermoplastic adhesive that can sufficiently suppress the occurrence of a creep phenomenon in a wet state and has excellent adhesion in a wet state.
  • Thermoplastic polymer Thermoplastic polymer 1: Styrene-isoprene-styrene block copolymer (SIS) (Quantac 3433 manufactured by Nippon Zeon Co., Ltd., styrene (second block) content: 16 mass%, diblock body content: 60 mass%)
  • Thermoplastic polymer 2 Styrene-isoprene-styrene block copolymer (SIS) (Global Changen 5517, Lee Chang-Ei Chemical Co., Ltd., styrene (second block) content: 15% by mass, diblock body content: 38% by mass)
  • Thermoplastic polymer 4 Styrene-but
  • the content of styrene corresponds to the content of the second block made of a vinyl aromatic hydrocarbon in the case of the thermoplastic polymer.
  • the content of the diblock body corresponds to the content of the diblock body of the first block made of a conjugated diene compound and the second block made of a vinyl aromatic hydrocarbon.
  • Tackifier alicyclic petroleum resin hydride (hydrogenated C9 petroleum resin) (ALCON M-100 manufactured by Arakawa Chemical Industries, Ltd.)
  • Acid-modified tackifier A maleic acid-modified tackifier resin produced as follows: In a reaction vessel made of stainless steel (SUS), an aromatic-modified terpene resin hydride that is a tackifier (manufactured by Yasuhara Chemical Co., Ltd.) 750 g) (Clearon K4100: softening point 100 ° C.) was added and melted at 170 ° C.
  • Oil Oil (Diana Fresia S32 manufactured by Idemitsu Kosan Co., Ltd.)
  • Acid-modified oil Maleic acid-modified oil (oil having a succinic acid skeleton in the molecule) (AS-1532 manufactured by Seiko PMC Co., Ltd.)
  • Wax (Sarawax SX-105 manufactured by Evonik)
  • Antioxidant Primary antioxidant (Irganox 1010 manufactured by BASF)
  • melt viscosity The melt viscosity at 140 ° C. of the hot melt adhesive before curing was measured as follows. Specifically, based on the measurement method described in JIS K 6682, the viscosity of the melt of the hot melt adhesive melted at 140 ° C. was measured with a Brookfield viscometer (spindle No. 27 rotor). . This viscosity is the melt viscosity at 140 ° C. of the hot melt adhesive before curing.
  • melt viscosity at 160 ° C. of the hot melt adhesive before curing was measured by the same method.
  • the melted hot melt adhesive becomes 6 gsm (g / m 2 ) on one side of the tissue by spiral spray. It was applied as follows. One second after application, a tissue was placed on the tissue to which the hot melt adhesive was applied so that the hot melt adhesive was in contact with the tissue. Thereafter, the tissue and the tissue were pressed at 23 ° C. and a pressure of 50 gf / cm 2 for 0.01 seconds. The laminate was cut into 25 mm in the direction perpendicular to the base material (CD) to make a strip-shaped test piece. The test piece was immersed in tap water at 50 ° C.
  • tissue is totally torn, it is evaluated as “ ⁇ ”, and if the tissue is partially torn, it is evaluated as “ ⁇ ”, and the tissue is not torn. Was evaluated as “ ⁇ ”.
  • a tissue corresponds to the material destruction which destroys a test piece, and shows that it is excellent in adhesiveness. In this case, the occurrence of the creep phenomenon in the wet state can be sufficiently suppressed, and the adhesiveness in the wet state is excellent.
  • the tissue was not torn, it corresponds to interface fracture in which the test piece peels without being broken from the interface with the adhesive layer, indicating that the adhesiveness is poor.
  • the manufactured hot melt adhesive was melted by heating to 150 ° C.
  • the melted hot melt adhesive was applied to 4 gsm (g / m 2 ) on one surface of the foamed urethane sheet by a coater. It applied so that it might become.
  • a non-woven fabric was placed on the foamed urethane sheet coated with the hot melt adhesive so that the hot melt adhesive was in contact. Thereafter, the urethane foam sheet and the nonwoven fabric were pressed at 23 ° C. and a pressure of 50 gf / cm 2 for 0.01 seconds.
  • the laminate was cut into 25 mm in the direction perpendicular to the base material (CD) to make a strip-shaped test piece.
  • test piece was immersed in tap water at 40 ° C. for 5 to 6 seconds, then taken out of the water and wiped off to obtain a wet test specimen.
  • Three test specimens were prepared for each hot melt adhesive. Then, a T-type peel test based on JIS K6845 was performed on this test body. Specifically, the strength (N / 25 mm) when this specimen was peeled at a tensile speed of 100 mm / min was measured. This peel test was performed at 23 ° C. and 65% RH.
  • each evaluation result is shown in Table 1 together with the blending amount of the hot melt adhesive.
  • the ratio of the copolymer in the thermoplastic polymer represents the total ratio (mass%) of the thermoplastic polymers 1 to 4 with respect to the total amount of the thermoplastic polymer.
  • content of the softener with respect to 100 mass parts of hot-melt-adhesives shows the mass part of softener with respect to 100 mass parts of hot-melt-adhesives.
  • the hot melt adhesive containing 15 to 30 parts by mass (Examples 1 to 9)
  • both the low-speed peel strength when wet and the shear strength when wet are high. When measuring the shear strength, it was not the interface failure but the material failure.
  • thermoplastic polymer contains other than the above copolymer (Comparative Examples 3, 4, and 7), compared with Examples 1 to 9, the wet shear strength and the wet slow peel strength When measuring the low-speed peel strength when wet and when measuring the shear strength when wet, it was not a material failure but an interface failure. Further, even when the copolymer is contained, when the content of the copolymer in the thermoplastic polymer is less than 55% by mass (Comparative Examples 1, 2, and 5), it is compared with Examples 1 to 9. The wet shear strength and the low wet peel strength were low, and when measuring the wet shear strength, it was not a material failure but an interface failure.
  • thermoplastic polymer containing 55% by mass or more of a copolymer in which the content of styrene constituting the second block is less than 30% by mass and the diblock body is 10% by mass or more.
  • thermoplastic polymer containing 55% by mass or more of a copolymer in which the content of styrene constituting the second block is less than 30% by mass and the diblock body is 10% by mass or more. Furthermore, it was found that by containing 15 to 30% by mass of a softening agent, the occurrence of creep phenomenon in a wet state can be sufficiently suppressed, and the adhesiveness in a wet state is excellent.
  • the first block made of a conjugated diene compound and the second block made of vinyl aromatic hydrocarbon, the content of the second block being less than 30% by mass
  • the first block And a thermoplastic polymer containing 55% by mass or more of a copolymer having a diblock body content of 10% by mass or more with the second block, and further a softener with respect to 100 parts by mass of the hot melt adhesive It has been found that a hot melt adhesive containing 15 to 30 parts by mass can sufficiently suppress the occurrence of creep phenomenon in a wet state and is excellent in adhesiveness in a wet state.
  • a hot melt adhesive that can sufficiently suppress the occurrence of a creep phenomenon in a wet state and has excellent adhesiveness in a wet state.

Abstract

One aspect of the present invention is a hot melt adhesive containing a thermoplastic polymer, a tackifier, and a softening agent, wherein: the thermoplastic polymer contains a copolymer comprising a first block which comprises a conjugated diene-based compound and a second block which comprises a vinyl aromatic hydrocarbon and/or a hydrogenated product of the copolymer; the copolymer is such that the content of the second block is less than 30 mass% and the content of a diblock structure of the first block and the second block is 10 mass% or more; the content of the copolymer and the hydrogenated product thereof is 55 mass% or more relative to the overall quantity of the thermoplastic polymer; and the content of the softening agent is 15-30 parts by mass relative to 100 parts by mass of the hot melt adhesive.

Description

ホットメルト接着剤Hot melt adhesive
 本発明は、ホットメルト接着剤に関する。 The present invention relates to a hot melt adhesive.
 ホットメルト接着剤は、加熱によって溶融された状態で、接着対象物である被着体に塗布し、溶融されたホットメルト接着剤を介して、被着体同士を接触させた状態で保持することにより、被着体同士を接着させるものである。このようなホットメルト接着剤は、例えば、段ボールや小箱等の包装分野、紙おむつや生理用品等の衛生材料分野、製本分野、合板分野、木工分野、自動車分野、家電分野、及び住宅分野等、様々な分野に用いられている。 A hot melt adhesive is applied to an adherend that is an object to be bonded in a melted state by heating, and the adherends are held in contact with each other via the melted hot melt adhesive. Thus, the adherends are bonded to each other. Such hot melt adhesives include, for example, packaging fields such as cardboard and small boxes, sanitary material fields such as paper diapers and sanitary products, bookbinding fields, plywood fields, woodworking fields, automobile fields, home appliance fields, and housing fields, etc. It is used in various fields.
 また、ホットメルト接着剤は、上述したように、加熱によって溶融された状態で用いられるので、溶剤を特に必要としない。このため、ホットメルト接着剤は、人体への安全性が高い接着剤として、例えば、衛生材料分野で好ましく用いられている。具体的には、紙おむつや生理用品等の使い捨て衛生材料において、その構成部材の固定や組み立てにホットメルト接着剤が広く用いられている。 Also, as described above, the hot melt adhesive is used in a melted state by heating, so that no solvent is required. For this reason, the hot melt adhesive is preferably used in the sanitary material field, for example, as an adhesive having high safety to the human body. Specifically, hot-melt adhesives are widely used for fixing and assembling components of disposable sanitary materials such as disposable diapers and sanitary products.
 このような衛生材料分野でホットメルト接着剤を用いた場合、その用途から、体液等の水分と接触する機会が多い。ホットメルト接着剤の中には、水分と接触すると接着性が低下するもの、すなわち、湿潤状態での接着性が低いものがあることが知られている。このようなホットメルト接着剤であると、水分との接触機会が多い分野では、製品の使用時等に構成材料間の接着が維持されず、製品自体が崩壊するおそれがある。具体的には、紙おむつ等の衛生材料には、ティッシュ及び紙おむつの吸収体として使用される粉砕パルプ等の親水性多孔質基材が用いられている。このような親水性多孔質基材がホットメルト接着剤で固定されている場合、この親水性多孔質基材が、尿等の体液で濡れて湿潤状態となると、ホットメルト接着剤による接着強度が著しく低下するおそれがある。このように、接着強度が低下した場合、吸収体として用いられる親水性多孔質基材の固定が不充分となり、足腰の動きに伴って、吸収体が本来の位置からずれ、尿等の体液を適切に吸収できなくなるという問題が生じる。これらのことから、湿潤状態となっている親水性多孔質基材に対しても優れた接着強度を維持できるように、ホットメルト接着剤には、湿潤状態での接着性の維持が求められている。 When using a hot melt adhesive in such a sanitary material field, there are many opportunities to come into contact with moisture such as body fluids because of its use. It is known that some hot melt adhesives have poor adhesive properties when contacted with moisture, that is, poorly wet adhesive properties. In such a hot melt adhesive, in a field where there are many opportunities for contact with moisture, adhesion between the constituent materials is not maintained when the product is used, and the product itself may collapse. Specifically, hydrophilic sanitary materials, such as a paper diaper, use hydrophilic porous substrates, such as a ground pulp used as an absorber of a tissue and a paper diaper. When such a hydrophilic porous substrate is fixed with a hot melt adhesive, when the hydrophilic porous substrate is wet with a body fluid such as urine and becomes wet, the adhesive strength by the hot melt adhesive is increased. There is a risk of significant reduction. Thus, when the adhesive strength decreases, the hydrophilic porous base material used as the absorbent becomes insufficiently fixed, and the absorbent body is displaced from the original position with the movement of the legs and hips. There arises a problem that it cannot be properly absorbed. For these reasons, hot melt adhesives are required to maintain adhesiveness in a wet state so that excellent adhesive strength can be maintained even for a hydrophilic porous substrate in a wet state. Yes.
 このような湿潤状態での接着性を高めること等を目的とした接着剤としては、例えば、特許文献1~4に記載の接着剤が挙げられる。 Examples of the adhesive intended to improve the adhesiveness in such a wet state include the adhesives described in Patent Documents 1 to 4.
 特許文献1には、スチレン成分の含有量が15~35質量%である、スチレン-イソプレン-スチレンブロック共重合体、スチレン-ブタジエン-スチレンブロック共重合体、スチレン-ブタジエン/ブチレン-スチレンよりなる群から選択される少なくとも1種を含む熱可塑性ブロック共重合体100重量部と、カルボキシル基及び/又はカルボン酸無水物基を分子内に有する液状ゴム0.05~10重量部と、粘着付与剤とを含有するホットメルト接着剤組成物が記載されている。特許文献1によれば、比較的低温であっても湿潤状態の親水性多孔質基材に対して優れた接着強度を発現することが可能であり、熱安定性に優れる旨が開示されている。 Patent Document 1 discloses a group consisting of a styrene-isoprene-styrene block copolymer, a styrene-butadiene-styrene block copolymer, and a styrene-butadiene / butylene-styrene having a styrene component content of 15 to 35% by mass. 100 parts by weight of a thermoplastic block copolymer containing at least one selected from the group consisting of 0.05 to 10 parts by weight of a liquid rubber having a carboxyl group and / or a carboxylic acid anhydride group in the molecule, and a tackifier A hot melt adhesive composition containing is described. According to Patent Document 1, it is disclosed that it is possible to express excellent adhesive strength to a wet hydrophilic porous substrate even at a relatively low temperature, and that it is excellent in thermal stability. .
 特許文献2には、ビニル系芳香族炭化水素と共役ジエン化合物との共重合体である熱可塑性ブロック共重合体と、カルボン酸及び/又はカルボン酸無水物で変性されたワックスとを含有するホットメルト接着剤が記載されている。特許文献2によれば、湿潤接着性が改良され、さらに好ましくは低温接着性、粘度、接着性、臭気、経済性から選択される少なくとも1種が改善される旨が開示されている。 In Patent Document 2, a hot block containing a thermoplastic block copolymer, which is a copolymer of a vinyl aromatic hydrocarbon and a conjugated diene compound, and a wax modified with a carboxylic acid and / or a carboxylic anhydride. A melt adhesive is described. According to Patent Document 2, it is disclosed that wet adhesion is improved, and more preferably, at least one selected from low-temperature adhesion, viscosity, adhesion, odor, and economy is improved.
 特許文献3には、メタロセン触媒を用いてプロピレンを重合して得られた融点100℃以下のプロピレンホモポリマーと、カルボン酸及び/又はカルボン酸無水物で変性されたワックスを含有する使い捨て製品用ホットメルト接着剤が記載されている。特許文献3によれば、高速塗工に適し、湿潤状態での接着性及び低温塗工にも優れる旨が開示されている。 Patent Document 3 discloses a hot for disposable products containing a propylene homopolymer having a melting point of 100 ° C. or less obtained by polymerizing propylene using a metallocene catalyst, and a wax modified with carboxylic acid and / or carboxylic anhydride. A melt adhesive is described. According to Patent Document 3, it is disclosed that it is suitable for high-speed coating and is excellent in adhesiveness in a wet state and low-temperature coating.
 特許文献4には、ビニル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およびその水素添加物のうち少なくとも1種を含んでいる熱可塑性ブロック共重合体、及び不飽和カルボン酸類又はその無水物によって酸変性されてなる酸変性石油樹脂を含んでいるホットメルト接着剤が記載されている。特許文献4によれば、熱安定性の低下や臭気の発生をさせることなく、構成部材に対して、湿潤接着性が向上されている旨が開示されている。 Patent Document 4 discloses a block copolymer of a vinyl aromatic hydrocarbon and a conjugated diene compound and a thermoplastic block copolymer containing at least one of hydrogenated products thereof, and unsaturated carboxylic acids or anhydrides thereof. A hot melt adhesive containing an acid-modified petroleum resin that has been acid-modified by a product is described. According to Patent Document 4, it is disclosed that wet adhesion is improved with respect to the constituent members without causing deterioration of thermal stability or generation of odor.
 ホットメルト接着剤は、上述したように、湿潤状態での接着性を高めることが求められる。湿潤状態での接着性を高めるためには、湿潤状態におけるホットメルト接着剤に負荷がかかった状態で一定以上の時間が経過しても、ホットメルト接着剤の変形の発生が抑制されることも求められる。すなわち、湿潤状態におけるクリープ現象の発生が抑制されることも求められる。このような湿潤状態でのクリープ現象の発生を抑制することによっても、湿潤状態での接着性を高めることができる。このため、ホットメルト接着剤は、湿潤状態でのクリープ現象の発生を充分に抑制でき、湿潤状態での接着性に優れることが求められる。 As described above, the hot melt adhesive is required to improve the adhesiveness in a wet state. In order to improve the adhesiveness in the wet state, even when a certain time or more has elapsed with the hot melt adhesive in a wet state being loaded, the occurrence of deformation of the hot melt adhesive may be suppressed. Desired. That is, it is also required to suppress the occurrence of the creep phenomenon in a wet state. The adhesiveness in the wet state can also be improved by suppressing the occurrence of the creep phenomenon in the wet state. For this reason, the hot melt adhesive is required to sufficiently suppress the occurrence of a creep phenomenon in a wet state and to have excellent adhesiveness in a wet state.
特開2015-28118号公報JP2015-28118A 特開2007-169531号公報JP 2007-169531 A 特開2013-64054号公報JP 2013-64054 A 特開2015-91917号公報Japanese Patent Laying-Open No. 2015-91917
 本発明は、かかる事情に鑑みてなされたものであって、湿潤状態でのクリープ現象の発生を充分に抑制でき、湿潤状態での接着性に優れるホットメルト接着剤を提供することを目的とする。 The present invention has been made in view of such circumstances, and an object of the present invention is to provide a hot melt adhesive that can sufficiently suppress the occurrence of a creep phenomenon in a wet state and is excellent in adhesiveness in a wet state. .
 本発明の一局面は、熱可塑性ポリマーと、粘着付与剤と、軟化剤とを含むホットメルト接着剤であって、前記熱可塑性ポリマーは、共役ジエン系化合物からなる第1ブロックとビニル系芳香族炭化水素からなる第2ブロックとからなる共重合体、及び前記共重合体の水素化物の少なくとも一方を含み、前記共重合体は、前記第2ブロックの含有量が30質量%未満であり、前記第1ブロックと前記第2ブロックとのジブロック体の含有量が10質量%以上である共重合体であって、前記共重合体及び前記共重合体の水素化物の含有量が、前記熱可塑性ポリマー全量に対して、55質量%以上であり、前記軟化剤の含有量が、前記ホットメルト接着剤100質量部に対して、15~30質量部であることを特徴とするホットメルト接着剤である。 One aspect of the present invention is a hot melt adhesive containing a thermoplastic polymer, a tackifier, and a softening agent, wherein the thermoplastic polymer includes a first block composed of a conjugated diene compound and a vinyl aromatic. A copolymer comprising a second block comprising a hydrocarbon, and at least one of a hydride of the copolymer, wherein the copolymer has a content of the second block of less than 30% by mass, A copolymer in which the content of the diblock body of the first block and the second block is 10% by mass or more, wherein the content of the copolymer and the hydride of the copolymer is the thermoplasticity. A hot melt adhesive characterized in that it is 55% by mass or more based on the total amount of the polymer, and the content of the softener is 15 to 30 parts by mass with respect to 100 parts by mass of the hot melt adhesive. Ah .
 上記並びにその他の本発明の目的、特徴及び利点は、以下の詳細な記載から明らかになるであろう。 The above and other objects, features and advantages of the present invention will become apparent from the following detailed description.
 ホットメルト接着剤を用いた接着方法では、まず、加熱によって溶融させたホットメルト接着剤を、塗工機等を用いて、被着体に塗布する。この塗布されたホットメルト接着剤に、もう一方の被着体を接触させた状態で保持することによって、被着体同士を接着させることができる。 In the bonding method using a hot melt adhesive, first, a hot melt adhesive melted by heating is applied to an adherend using a coating machine or the like. By holding the other adherend in contact with the applied hot melt adhesive, the adherends can be adhered to each other.
 また、紙おむつ等の衛生材料分野では、その風合いを良くすることが求められている。このため、構成材料を薄くすることで、紙おむつ等の柔軟性を高め、風合いを向上させることが検討されている。しかしながら、構成材料が薄くなると、その耐熱性が低下する傾向がある。このような耐熱性の低い構成材料に、加熱によって溶融されたホットメルト接着剤を塗布すると、構成材料が、溶融したり、変形する等、損傷することがあった。そして、この構成材料の熱による損傷は、塗布するホットメルト接着剤の温度が高かったり、塗布するホットメルト接着剤の量が多かったりすると、発生しやすくなる傾向があった。そこで、このような耐熱性の低い構成材料を用いることができること等を目的として、衛生材料分野では、ホットメルト接着剤の低温塗布及び少量塗布が求められている。また、塗工設備等の性能が向上したことにより、ホットメルト接着剤の低温塗布及び少量塗布が実現できるようになってきている。 In the field of sanitary materials such as disposable diapers, it is required to improve the texture. For this reason, it has been studied to increase the flexibility of paper diapers and the like and improve the texture by making the constituent materials thin. However, as the constituent material becomes thinner, its heat resistance tends to decrease. When a hot-melt adhesive melted by heating is applied to a constituent material having low heat resistance, the constituent material may be damaged, for example, melted or deformed. And the damage by the heat | fever of this constituent material had the tendency for it to generate | occur | produce easily when the temperature of the hot-melt-adhesive to apply | coat is high, or when the quantity of the hot-melt-adhesive to apply | coat is large. Therefore, in order to be able to use such a low heat-resistant constituent material, in the sanitary material field, low temperature application and small amount application of a hot melt adhesive is required. In addition, due to the improved performance of the coating equipment and the like, it has become possible to realize low temperature application and small amount application of a hot melt adhesive.
 これらのことから、低温塗布及び少量塗布であっても、好適に接着可能なホットメルト接着剤が求められるようになってきている。すなわち、塗工機のノズル径を小さくすること等により、塗布されるホットメルト接着剤の量を少なくして、さらに、ホットメルト接着剤を溶融させる温度を下げても、被着体同士の充分な接着性を確保することができるホットメルト接着剤が求められている。特許文献1~4によれば、上述したように、湿潤状態での接着性を高めることができる旨が開示されている。このことから、特許文献1~4に記載の接着剤を用いることが考えられる。 For these reasons, there is a demand for hot melt adhesives that can be suitably bonded even when applied at low temperatures and in small amounts. That is, even if the amount of hot melt adhesive applied is reduced by reducing the nozzle diameter of the coating machine, etc. and the temperature at which the hot melt adhesive is melted is lowered, There is a need for hot melt adhesives that can ensure good adhesion. Patent Documents 1 to 4 disclose that the adhesiveness in a wet state can be improved as described above. From this, it is conceivable to use the adhesives described in Patent Documents 1 to 4.
 しかしながら、本発明者等の検討によれば、ホットメルト接着剤として、特許文献1~4に記載の接着剤を用いると、湿潤状態での接着性を高めることができたとしても、低温塗布及び少量塗布の場合には、その湿潤状態での接着性を充分に高めることができない場合があった。具体的には、特許文献1~4に記載の接着剤を低温塗布及び少量塗布で用いて接着させた場合、紙おむつ等の衛生材料を長時間にわたって使用すると、親水性多孔質基材を固定させていたホットメルト接着剤が湿潤状態になる。このような湿潤状態におけるホットメルト接着剤に負荷がかかった状態で一定以上の時間が経過すると、ホットメルト接着剤が変形してしまう。すなわち、湿潤状態においてクリープ現象が発生してしまうことがあった。このような場合、ホットメルト接着剤で固定されている親水性多孔質基材が本来の位置から移動してしまう。 However, according to the study by the present inventors, when the adhesives described in Patent Documents 1 to 4 are used as hot melt adhesives, even if the adhesiveness in a wet state can be improved, In the case of application in a small amount, the adhesiveness in the wet state may not be sufficiently improved. Specifically, when the adhesives described in Patent Documents 1 to 4 are adhered by low temperature application and small amount application, when a sanitary material such as a paper diaper is used for a long time, the hydrophilic porous substrate is fixed. The hot melt adhesive that has been stored becomes wet. When a certain time or more has elapsed with a load applied to the hot melt adhesive in such a wet state, the hot melt adhesive is deformed. That is, the creep phenomenon may occur in a wet state. In such a case, the hydrophilic porous substrate fixed with the hot melt adhesive moves from the original position.
 そこで、ホットメルト接着剤には、湿潤状態での接着性を高めることが求められ、これを実現するために、湿潤状態でのクリープ現象の発生を充分に抑制できることが求められる。 Therefore, the hot melt adhesive is required to improve the adhesiveness in the wet state, and in order to realize this, it is required to sufficiently suppress the occurrence of the creep phenomenon in the wet state.
 本発明者は、種々検討した結果、湿潤状態でのクリープ現象の発生を充分に抑制でき、湿潤状態での接着性に優れたホットメルト接着剤を提供するといった上記目的は、以下の本発明により達成されることを見出した。 As a result of various studies, the inventor of the present invention can sufficiently suppress the occurrence of a creep phenomenon in a wet state and provide a hot melt adhesive excellent in adhesiveness in a wet state. I found it to be achieved.
 本発明者は、ホットメルト接着剤を低温塗布及び少量塗布で用いた場合、湿潤状態での接着性を高めることができたとしても、湿潤状態でのクリープ現象の発生を充分に抑制できない理由を、以下のように推察した。 The present inventor, when using hot melt adhesive in low temperature application and small amount application, even if it can improve the adhesion in the wet state, the reason why the creep phenomenon in the wet state cannot be sufficiently suppressed I guessed as follows.
 まず、ホットメルト接着剤を低温塗布及び少量塗布で用いた場合、塗工時のホットメルト接着剤の熱量が減少し、ホットメルト接着剤が被着体である親水性多孔質基材にしみこみにくくなると考えられる。これにより、被着体同士がホットメルト接着剤で接着されていても、被着体とホットメルト接着剤とが被着体の表面付近のみで接触することになると考えられる。このため、湿潤状態でホットメルト接着剤に負荷がかかった状態で一定以上の時間が経過すると、ホットメルト接着剤が変形しやすくなると考えられる。すなわち、クリープ現象により、ホットメルト接着剤と被着体との界面で剥離する界面破壊が発生しやすくなると考えられる。 First, when a hot melt adhesive is used for low temperature application and small amount application, the amount of heat of the hot melt adhesive at the time of coating decreases, and the hot melt adhesive is less likely to soak into the hydrophilic porous substrate that is the adherend. It is considered to be. Thereby, even if the adherends are bonded to each other with the hot melt adhesive, it is considered that the adherend and the hot melt adhesive are in contact only in the vicinity of the surface of the adherend. For this reason, it is considered that the hot melt adhesive is likely to be deformed when a certain time or more elapses in a wet state with a load applied to the hot melt adhesive. That is, it is considered that an interfacial fracture that peels off at the interface between the hot melt adhesive and the adherend tends to occur due to the creep phenomenon.
 そこで、本発明者は、ホットメルト接着剤が、親水性多孔質基材にしみこみやすくなるように、ホットメルト接着剤を親水性多孔質基材との親和性を高めることに着目し、その組成を検討した。その結果、以下のようなホットメルト接着剤を想到するに至った。 Therefore, the present inventor has paid attention to increasing the affinity of the hot melt adhesive with the hydrophilic porous substrate so that the hot melt adhesive can easily penetrate into the hydrophilic porous substrate. It was investigated. As a result, the following hot melt adhesives have been conceived.
 以下、本発明に係る実施形態について説明するが、本発明は、これらに限定されるものではない。 Hereinafter, embodiments according to the present invention will be described, but the present invention is not limited thereto.
 本発明の実施形態に係るホットメルト接着剤は、熱可塑性ポリマーと、粘着付与剤と、軟化剤とを含む。そして、前記熱可塑性ポリマーは、共役ジエン系化合物からなる第1ブロックとビニル系芳香族炭化水素からなる第2ブロックとからなる共重合体、及び前記共重合体の水素化物の少なくとも一方を含む。さらに、この共重合体は、前記第2ブロックの含有量が、30質量%未満であり、前記第1ブロックと前記第2ブロックとのジブロック体の含有量が、10質量%以上である共重合体である。さらに、前記共重合体及び前記共重合体の水素化物の含有量は、前記熱可塑性ポリマー全量に対して、55質量%以上である。また、前記軟化剤の含有量は、前記ホットメルト接着剤100質量部に対して、15~30質量部である。 The hot melt adhesive according to an embodiment of the present invention includes a thermoplastic polymer, a tackifier, and a softener. The thermoplastic polymer includes at least one of a copolymer composed of a first block composed of a conjugated diene compound and a second block composed of a vinyl aromatic hydrocarbon, and a hydride of the copolymer. Further, in this copolymer, the content of the second block is less than 30% by mass, and the content of the diblock body of the first block and the second block is 10% by mass or more. It is a polymer. Furthermore, content of the said copolymer and the hydride of the said copolymer is 55 mass% or more with respect to the said thermoplastic polymer whole quantity. In addition, the content of the softening agent is 15 to 30 parts by mass with respect to 100 parts by mass of the hot melt adhesive.
 このホットメルト接着剤は、前記熱可塑性ポリマーとして、前記共重合体及び前記共重合体の水素化物の少なくとも一方を、それらの合計で55質量%以上含み、さらに、軟化剤を、前記ホットメルト接着剤100質量部に対して、15~30質量部含むことによって、湿潤状態でのクリープ現象の発生を抑制できる。 This hot melt adhesive contains, as the thermoplastic polymer, at least one of the copolymer and a hydride of the copolymer in a total of 55% by mass or more, and further, a softener is added to the hot melt adhesive. By including 15 to 30 parts by mass with respect to 100 parts by mass of the agent, the occurrence of creep phenomenon in a wet state can be suppressed.
 このことは、以下のことによると考えられる。 This is thought to be due to the following.
 まず、前記第2ブロックは、ビニル系芳香族炭化水素からなるブロックであり、いわゆるハードセグメントと呼ばれ、他のハードセグメントと集合体を形成し、共重合体において、分子鎖同士の結合点を形成すると考えられる。前記共重合体は、このような第2ブロックの含有量が比較的少ないので、分子鎖同士の結合点が比較的少ないと考えられる。また、前記第1ブロックは、共役ジエン系化合物からなるブロックであり、いわゆるソフトセグメントと呼ばれる。このような第1ブロックを有することによって、前記共重合体を含むホットメルト接着剤は、柔軟性の高い接着剤になると考えられる。また、前記共重合体には、前記第1ブロックと前記第2ブロックとのジブロック体が含まれる。そして、このジブロック体は、分子鎖同士の結合点になりうる第2ブロックが片方の端部に存在することになり、架橋剤として働くものではない。前記共重合体は、このような架橋剤として働くものではないジブロック体が一定量以上含まれていることになる。このように、前記共重合体における、前記第2ブロック及び前記ジブロック体のそれぞれの含有量を調整することによって、前記共重合体を含むホットメルト接着剤は、被着体である親水性多孔質基材の内部に浸透しやすくなると考えられる。また、前記共重合体の水素化物も、前記共重合体と同様に働くと考えられる。このような共重合体及びその水素化物を一定量以上含むので、前記ホットメルト接着剤は、柔軟性があり、被着体の内部に浸透しやすくなると考えられる。また、前記軟化剤を所定量含有させるので、少量塗布でも好適に塗布できるホットメルト接着剤になると考えられる。よって、前記ホットメルト接着剤は、被着体である親水性多孔質基材に、好適に塗布でき、内部に浸透しやすく、柔軟性もあるので、湿潤状態でのクリープ現象の発生を好適に抑制できると考えられる。 First, the second block is a block composed of vinyl aromatic hydrocarbons, so-called hard segments, forms aggregates with other hard segments, and in the copolymer, the bonding points between the molecular chains are determined. It is thought to form. Since the copolymer has a relatively small content of such second blocks, it is considered that the number of bonding points between molecular chains is relatively small. The first block is a block made of a conjugated diene compound and is called a so-called soft segment. By having such a first block, the hot melt adhesive containing the copolymer is considered to be a highly flexible adhesive. Further, the copolymer includes a diblock body of the first block and the second block. And this diblock body will have the 2nd block which can become a junction of molecular chains in one edge part, and does not work as a crosslinking agent. The copolymer contains a certain amount or more of a diblock body that does not act as such a crosslinking agent. Thus, by adjusting the content of each of the second block and the diblock body in the copolymer, the hot melt adhesive containing the copolymer is a hydrophilic porous material that is an adherend. It is considered that it easily penetrates into the inside of the base material. The hydride of the copolymer is considered to work in the same manner as the copolymer. Since such a copolymer and its hydride are contained in a certain amount or more, the hot melt adhesive is considered to be flexible and easily penetrate into the adherend. Further, since a predetermined amount of the softening agent is contained, it is considered that the hot melt adhesive can be suitably applied even in a small amount. Therefore, the hot melt adhesive can be suitably applied to a hydrophilic porous substrate as an adherend, easily penetrates into the inside, and has flexibility, so that the occurrence of a creep phenomenon in a wet state is preferable. It can be suppressed.
 まず、本実施形態において用いられる熱可塑性ポリマーは、上述したように、前記共重合体及び前記共重合体の水素化物のいずれか一方を含み、それらの合計が、前記熱可塑性ポリマー全量に対して、55質量%以上であれば、特に限定されない。また、前記共重合体及び前記共重合体の水素化物の含有率は、上述したように、前記熱可塑性ポリマー全量に対して、55質量%以上であり、75質量%以上であることが好ましい。また、前記熱可塑性ポリマーは、前記共重合体及び前記共重合体の水素化物のみからなっていてもよく、すなわち、前記共重合体及び前記共重合体の水素化物の含有率は、100質量%であってもよい。前記共重合体が少なすぎると、被着体である親水性多孔質基材に浸透させやすくする等の、前記共重合体を含むことによる効果を充分に発揮できない傾向がある。 First, as described above, the thermoplastic polymer used in the present embodiment includes either one of the copolymer and a hydride of the copolymer, and the total of them includes the total amount of the thermoplastic polymer. If it is 55 mass% or more, it will not specifically limit. Moreover, the content rate of the said hydride of the said copolymer and the said copolymer is 55 mass% or more with respect to the said thermoplastic polymer whole quantity, and it is preferable that it is 75 mass% or more. Further, the thermoplastic polymer may consist of only the copolymer and a hydride of the copolymer, that is, the content of the copolymer and the hydride of the copolymer is 100% by mass. It may be. When the amount of the copolymer is too small, there is a tendency that the effects of including the copolymer, such as easy penetration into the hydrophilic porous substrate that is the adherend, cannot be exhibited sufficiently.
 また、前記共重合体は、共役ジエン系化合物からなる第1ブロックとビニル系芳香族炭化水素からなる第2ブロックとからなる共重合体である。 Further, the copolymer is a copolymer composed of a first block made of a conjugated diene compound and a second block made of a vinyl aromatic hydrocarbon.
 前記第1ブロックは、共役ジエン系化合物からなるブロックであり、すなわち、共役ジエン系化合物由来のブロックである。前記第1ブロックとしては、具体的には、共役ジエン系化合物を重合して得られた重合体(共役ジエン系化合物の重合体)等が挙げられる。前記共役ジエン系化合物は、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れば、特に限定されない。前記共役ジエン系化合物としては、具体的には、ブタジエン、2-メチル-1,3-ブタジエン(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、及び1,3-ヘキサジエン等が挙げられる。前記共役ジエン系化合物としては、この中でも、ブタジエン及びイソプレンが好ましい。また、前記共役ジエン系化合物としては、上記例示の化合物を単独で用いてもよいし、2種以上を組み合わせて用いてもよい。 The first block is a block made of a conjugated diene compound, that is, a block derived from a conjugated diene compound. Specific examples of the first block include a polymer obtained by polymerizing a conjugated diene compound (a polymer of a conjugated diene compound). The conjugated diene compound is not particularly limited as long as it is a diolefin compound having at least a pair of conjugated double bonds. Specific examples of the conjugated diene compound include butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3. -Hexadiene and the like. Of these, butadiene and isoprene are preferred as the conjugated diene compound. Moreover, as said conjugated diene type compound, the said exemplary compound may be used independently, and may be used in combination of 2 or more type.
 前記第2ブロックは、ビニル系芳香族炭化水素からなるブロックであり、すなわち、ビニル系芳香族炭化水素由来のブロックである。前記第2ブロックとしては、具体的には、ビニル系芳香族炭化水素を重合して得られた重合体(前記ビニル系芳香族炭化水素の重合体)等が挙げられる。前記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であれば、特に限定されない。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、及びビニルアントラセン等が挙げられる。前記ビニル系芳香族炭化水素としては、この中でも、スチレンが好ましい。また、前記ビニル系芳香族炭化水素としては、上記例示の化合物を単独で用いてもよいし、2種以上を組み合わせて用いてもよい。 The second block is a block made of vinyl aromatic hydrocarbon, that is, a block derived from vinyl aromatic hydrocarbon. Specific examples of the second block include a polymer obtained by polymerizing vinyl aromatic hydrocarbon (polymer of the vinyl aromatic hydrocarbon). The vinyl aromatic hydrocarbon is not particularly limited as long as it is an aromatic hydrocarbon 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 vinyl. Anthracene etc. are mentioned. Of these, styrene is preferred as the vinyl aromatic hydrocarbon. Moreover, as said vinyl-type aromatic hydrocarbon, the compound of the said illustration may be used independently, and may be used in combination of 2 or more type.
 また、前記共重合体は、前記第2ブロックの含有量が、前記共重合体に対して30質量%未満であり、5~25質量%であることが好ましく、15~25質量%であることがより好ましい。前記第2ブロックの含有量が、上記範囲内のような比較的少ない含有量であると、分子鎖同士の結合点として好適に働きつつ、柔軟性の高い接着剤が得られる。 In the copolymer, the content of the second block is less than 30% by mass with respect to the copolymer, preferably 5 to 25% by mass, and preferably 15 to 25% by mass. Is more preferable. When the content of the second block is a relatively small content within the above range, a highly flexible adhesive can be obtained while suitably functioning as a bonding point between molecular chains.
 また、前記第1ブロックと前記第2ブロックとのジブロック体の含有量が、前記共重合体に対して10質量%以上であり、30~90質量%であることが好ましく、50~80質量%であることがより好ましい。また、前記共重合体は、前記ジブロック体のみからなっていてもよく、すなわち、前記第1ブロックと前記第2ブロックとのジブロック体の含有量が、前記共重合体に対して、100質量%であってもよい。前記ジブロック体が少なすぎると、トリブロック体等が増え、得られる接着剤の柔軟性が低下する傾向がある。前記ジブロック体の含有量が上記範囲内であると、分子鎖同士の結合点として好適に働きつつ、柔軟性の高い接着剤が得られる。 The diblock body content of the first block and the second block is 10% by mass or more, preferably 30 to 90% by mass, and preferably 50 to 80% by mass with respect to the copolymer. % Is more preferable. Further, the copolymer may consist of only the diblock body, that is, the content of the diblock body of the first block and the second block is 100 with respect to the copolymer. It may be mass%. When there are too few said diblock bodies, a triblock body etc. will increase and there exists a tendency for the softness | flexibility of the adhesive agent obtained to fall. When the content of the diblock body is within the above range, a highly flexible adhesive can be obtained while suitably functioning as a bonding point between molecular chains.
 また、前記共重合体及び前記共重合体の水素化物の具体例としては、例えば、スチレン-ブタジエンブロックコポリマー、スチレン-イソプレンブロックコポリマー、水素添加されたスチレン-ブタジエンブロックコポリマー、及び水素添加されたスチレン-イソプレンブロックコポリマー等が挙げられる。また、これらの共重合体は、前記ジブロック体の含有量が上記範囲内であれば、トリブロック体を含んでいてもよい。トリブロック体としては、スチレン-ブタジエンブロックコポリマーの場合、例えば、スチレン-ブタジエン-スチレンブロックコポリマー(SBS)等が挙げられる。また、スチレン-イソプレンブロックコポリマーの場合は、例えば、スチレン-イソプレン-スチレンブロックコポリマー(SIS)等が挙げられる。また、水素添加されたスチレン-ブタジエンブロックコポリマーの場合は、例えば、スチレン-エチレン-ブチレン-スチレンブロックコポリマー(SEBS)等が挙げられる。また、水素添加されたスチレン-イソプレンブロックコポリマーの場合は、例えば、スチレン-エチレン-プロピレン-スチレンブロックコポリマー(SEPS)等が挙げられる。 Specific examples of the copolymer and the hydride of the copolymer include, for example, a styrene-butadiene block copolymer, a styrene-isoprene block copolymer, a hydrogenated styrene-butadiene block copolymer, and a hydrogenated styrene. -Isoprene block copolymers and the like. These copolymers may contain a triblock body as long as the content of the diblock body is within the above range. Examples of the triblock body include a styrene-butadiene-styrene block copolymer (SBS) in the case of a styrene-butadiene block copolymer. In the case of a styrene-isoprene block copolymer, for example, styrene-isoprene-styrene block copolymer (SIS) and the like can be mentioned. In the case of a hydrogenated styrene-butadiene block copolymer, for example, styrene-ethylene-butylene-styrene block copolymer (SEBS) and the like can be mentioned. Further, in the case of a hydrogenated styrene-isoprene block copolymer, for example, styrene-ethylene-propylene-styrene block copolymer (SEPS) and the like can be mentioned.
 また、前記熱可塑性ポリマーは、前記共重合体及び前記共重合体の水素化物を55質量%以上含んでいればよく、前記共重合体及び前記共重合体の水素化物以外の熱可塑性ポリマー(他の熱可塑性ポリマー)を含んでいてもよい。前記他の熱可塑性ポリマーとしては、ホットメルト接着剤を構成する成分として用いられる熱可塑性ポリマーであれば、特に限定されない。また、この熱可塑性ポリマーとしては、ホットメルト接着剤の主成分であるベースポリマーとして用いられる熱可塑性ポリマー等が挙げられる。前記熱可塑性ポリマーとしては、具体的には、エラストマー系、オレフィン系、エチレン酢酸ビニルコポリマー(EVA)系、ポリエステル系、ポリアミド系、及びポリアクリル系の熱可塑性ポリマーが挙げられる。この中でも、本実施形態においては、前記エラストマー系の熱可塑性ポリマー及び前記オレフィン系の熱可塑性ポリマーが好ましく、前記エラストマー系の熱可塑性ポリマーがより好ましい。 Further, the thermoplastic polymer only needs to contain 55% by mass or more of the copolymer and a hydride of the copolymer, and a thermoplastic polymer other than the copolymer and the hydride of the copolymer (others). A thermoplastic polymer). The other thermoplastic polymer is not particularly limited as long as it is a thermoplastic polymer used as a component constituting a hot melt adhesive. Moreover, as this thermoplastic polymer, the thermoplastic polymer etc. which are used as a base polymer which is a main component of a hot-melt-adhesive are mentioned. Specific examples of the thermoplastic polymer include elastomeric, olefinic, ethylene vinyl acetate copolymer (EVA) based, polyester based, polyamide based, and polyacrylic thermoplastic polymers. Among these, in the present embodiment, the elastomer-based thermoplastic polymer and the olefin-based thermoplastic polymer are preferable, and the elastomer-based thermoplastic polymer is more preferable.
 エラストマー系の熱可塑性ポリマーには、前記共重合体及び前記共重合体の水素化物も含まれるが、ここでのエラストマー系の熱可塑性ポリマーは、前記共重合体及び前記共重合体の水素化物以外のエラストマー系の熱可塑性ポリマーが挙げられ、例えば、前記第1ブロック及び第2ブロック以外のブロックを含むエラストマー系の熱可塑性ポリマー等が挙げられる。 The elastomer-based thermoplastic polymer includes the copolymer and the hydride of the copolymer. The elastomer-based thermoplastic polymer here is other than the copolymer and the hydride of the copolymer. Elastomer-based thermoplastic polymers, for example, elastomer-based thermoplastic polymers including blocks other than the first block and the second block.
 前記オレフィン系の熱可塑性ポリマーは、ホットメルト接着剤における、オレフィン系の熱可塑性ポリマーとして用いられるものであれば、特に限定されない。また、前記オレフィン系の熱可塑性ポリマーとしては、例えば、チーグラー・ナッタ触媒やシングルサイト触媒で重合した常温で固体のポリオレフィン系化合物等が挙げられる。前記オレフィン系の熱可塑性ポリマーとしては、具体的には、ポリエチレン、ポリプロピレン、ポリ-1-ブテン、ポリイソブチレン、プロピレンとエチレン及び1-ブテンの少なくとも一方とのあらゆる比率でのランダム共重合体又はブロック共重合体、エチレンとプロピレンとジエン成分とのあらゆる比率でのエチレン-プロピレン-ジエン三元共重合体、エチレン又はプロピレンとビニル化合物とのランダム共重合体又はブロック共重合体、ランダムポリプロピレン、ブロックポリプロピレン、ホモポリプロピレン、エチレン・プロピレン共重合体、エチレン・1-ブテン共重合体、エチレン・1-ヘキセン共重合体、エチレン・1-オクテン共重合体、プロピレン・エチレン共重合体、プロピレン・エチレン・α-ブテン共重合体、1-ブテン単独重合体、1-ブテン・エチレン共重合体、1-ブテン・プロピレン共重合体、プロピレン・1-ブテン共重合体、エチレン・酢酸ビニル共重合体、エチレン・メタクリル酸共重合体、エチレン・メタクリル酸メチル共重合体等が挙げられる。前記オレフィン系の熱可塑性ポリマーとしては、例えば、上記例示した化合物の中でも、α-オレフィン等のオレフィン(アルケン)をモノマーとして重合されたオレフィン系ポリマー等が好ましい。前記オレフィン系ポリマーとしては、具体的には、ポリα-オレフィンポリマー等が挙げられる。ポリα-オレフィンポリマーとしては、より具体的には、アモルファス-ポリα-オレフィンポリマー(APAO)、及びプロピレンの単独重合体(プロピレンホモポリマー)等が好ましい。プロピレンホモポリマーとしては、より具体的には、メタロセン触媒を用いてプロピレンを重合して得られたプロピレンホモポリマー等が好ましい。 The olefin-based thermoplastic polymer is not particularly limited as long as it is used as an olefin-based thermoplastic polymer in a hot melt adhesive. Examples of the olefin-based thermoplastic polymer include polyolefin compounds that are solid at room temperature and polymerized with a Ziegler-Natta catalyst or a single-site catalyst. Specific examples of the olefin-based thermoplastic polymer include polyethylene, polypropylene, poly-1-butene, polyisobutylene, random copolymer or block in any ratio of propylene and at least one of ethylene and 1-butene. Copolymer, ethylene-propylene-diene terpolymer in any ratio of ethylene, propylene and diene component, random copolymer or block copolymer of ethylene or propylene and vinyl compound, random polypropylene, block polypropylene , Homopolypropylene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene / 1-octene copolymer, propylene / ethylene copolymer, propylene / ethylene / α -Butene copolymers, -Butene homopolymer, 1-butene / ethylene copolymer, 1-butene / propylene copolymer, propylene / 1-butene copolymer, ethylene / vinyl acetate copolymer, ethylene / methacrylic acid copolymer, ethylene -A methyl methacrylate copolymer etc. are mentioned. As the olefin-based thermoplastic polymer, for example, among the compounds exemplified above, an olefin-based polymer polymerized using an olefin (alkene) such as an α-olefin as a monomer is preferable. Specific examples of the olefin polymer include poly α-olefin polymers. More specifically, the poly α-olefin polymer is preferably an amorphous poly α-olefin polymer (APAO) or a homopolymer of propylene (propylene homopolymer). More specifically, the propylene homopolymer is preferably a propylene homopolymer obtained by polymerizing propylene using a metallocene catalyst.
 前記EVA系の熱可塑性ポリマーは、ホットメルト接着剤における、EVA系の熱可塑性ポリマーとして用いられるものであれば、特に限定されず、例えば、エチレンと酢酸ビニルから合成される共重合体等が挙げられる。 The EVA-based thermoplastic polymer is not particularly limited as long as it is used as an EVA-based thermoplastic polymer in a hot melt adhesive, and examples thereof include a copolymer synthesized from ethylene and vinyl acetate. It is done.
 前記ポリエステル系の熱可塑性ポリマーは、ホットメルト接着剤における、ポリエステル系の熱可塑性ポリマーとして用いられるものであれば、特に限定されない。ポリエステル系の熱可塑性ポリマーとしては、例えば、モノマーとしてダイマー酸を用いて重合されたポリエステル等が挙げられる。 The polyester-based thermoplastic polymer is not particularly limited as long as it is used as a polyester-based thermoplastic polymer in the hot melt adhesive. Examples of the polyester-based thermoplastic polymer include polyester polymerized using dimer acid as a monomer.
 前記ポリアミド系の熱可塑性ポリマーは、ホットメルト接着剤における、ポリアミド系の熱可塑性ポリマーとして用いられるものであれば、特に限定されず、例えば、ポリアミド等が挙げられる。 The polyamide-based thermoplastic polymer is not particularly limited as long as it is used as a polyamide-based thermoplastic polymer in the hot melt adhesive, and examples thereof include polyamide.
 前記ポリアクリル系の熱可塑性ポリマーは、ホットメルト接着剤における、ポリアクリル系の熱可塑性ポリマーとして用いられるものであれば、特に限定されず、例えば、ポリアクリル酸エステル、及びポリメタクリル酸エステル等が挙げられる。 The polyacrylic thermoplastic polymer is not particularly limited as long as it is used as a polyacrylic thermoplastic polymer in a hot melt adhesive, and examples thereof include polyacrylic acid esters and polymethacrylic acid esters. Can be mentioned.
 前記他の熱可塑性ポリマーとしては、上記例示の熱可塑性ポリマーを単独で用いてもよいし、2種以上を組み合わせて用いてもよい。 As the other thermoplastic polymer, the above-exemplified thermoplastic polymers may be used alone or in combination of two or more.
 前記共重合体等の熱可塑性ポリマーの重量平均分子量は、熱可塑性ポリマーの種類等によっても異なり、特に限定されないが、例えば、1万~50万であることが好ましく、5万~30万であることがより好ましい。熱可塑性ポリマーの分子量が小さすぎると、凝集力が低下し、また経時安定性が低下する傾向がある。また、熱可塑性ポリマーの分子量が大きすぎると、溶融粘度が上昇して塗工性が低下する傾向がある。なお、ここでの重量平均分子量は、一般的な測定方法で測定した重量平均分子量であればよく、例えば、ゲル浸透クロマトグラフィー(GPC)を用いて測定した重量平均分子量等が挙げられる。 The weight average molecular weight of the thermoplastic polymer such as the copolymer varies depending on the kind of the thermoplastic polymer and is not particularly limited. For example, it is preferably 10,000 to 500,000, and is 50,000 to 300,000. It is more preferable. If the molecular weight of the thermoplastic polymer is too small, the cohesive force tends to decrease, and the stability over time tends to decrease. On the other hand, when the molecular weight of the thermoplastic polymer is too large, the melt viscosity increases and the coatability tends to decrease. In addition, the weight average molecular weight here should just be the weight average molecular weight measured by the general measuring method, for example, the weight average molecular weight measured using gel permeation chromatography (GPC) etc. are mentioned.
 本実施形態において用いられる粘着付与剤は、ホットメルト接着剤に一般的に用いられる粘着付与剤であれば、特に限定されない。粘着付与剤としては、例えば、ロジン系樹脂、テルペン系樹脂、及び石油系樹脂等が挙げられる。 The tackifier used in the present embodiment is not particularly limited as long as it is a tackifier generally used for hot melt adhesives. Examples of tackifiers include rosin resins, terpene resins, and petroleum resins.
 前記ロジン系樹脂としては、例えば、ガムロジン、トールロジン及びウッドロジン等の天然ロジン、不均斉化ロジン、重合ロジン、これらのロジンのグリセリンエステル及びペンタエリスリトールエステル等が挙げられる。また、このロジン系樹脂は、上記各ロジン系樹脂を、水素添加していないものであってもよいし、水素添加したもの、すなわち、上記ロジン系樹脂の水素添加物(水素化物)であってもよい。 Examples of the rosin resin include natural rosin such as gum rosin, tall rosin and wood rosin, disproportionated rosin, polymerized rosin, glycerin ester and pentaerythritol ester of these rosins. Further, the rosin resin may be one in which each of the rosin resins is not hydrogenated, or hydrogenated, that is, a hydrogenated product (hydride) of the rosin resin. Also good.
 前記テルペン系樹脂としては、テルペン樹脂、炭化水素変性テルペン樹脂、芳香族変性テルペン樹脂、及びフェノール系変性テルペン樹脂等が挙げられる。また、このテルペン系樹脂は、上記各テルペンを、水素添加していないものであってもよいし、水素添加したもの、すなわち、上記テルペン系樹脂の水素添加物(水素化物)であってもよい。また、テルペン系樹脂としては、芳香族変性テルペン樹脂水素化物、芳香族変性テルペン樹脂、テルペン樹脂水素化物が好ましく、芳香族変性テルペン樹脂水素化物がより好ましい。 Examples of the terpene resin include terpene resins, hydrocarbon-modified terpene resins, aromatic-modified terpene resins, and phenol-modified terpene resins. The terpene resin may be one in which each of the terpenes is not hydrogenated, or one obtained by hydrogenation, that is, a hydrogenated product (hydride) of the terpene resin. . The terpene resin is preferably an aromatic modified terpene resin hydride, an aromatic modified terpene resin, or a terpene resin hydride, and more preferably an aromatic modified terpene resin hydride.
 前記石油系樹脂としては、例えば、脂肪族系石油樹脂、脂環族系石油樹脂、芳香族系石油樹脂、及びこれらの水素添加物(水素化物)等が挙げられる。また、石油系樹脂水素化物としては、脂肪族系石油樹脂水素化物、脂環族系石油樹脂水素化物、及び芳香族系石油樹脂水素化物が好ましい。また、脂環族系石油樹脂水素化物としては、例えば、水添C9石油樹脂、及び水添ジシクロペンタジエン系石油樹脂等が挙げられる。 Examples of the petroleum resins include aliphatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, and hydrogenated products (hydrides) thereof. Further, as the petroleum resin hydride, an aliphatic petroleum resin hydride, an alicyclic petroleum resin hydride, and an aromatic petroleum resin hydride are preferable. Examples of the alicyclic petroleum resin hydride include hydrogenated C9 petroleum resin and hydrogenated dicyclopentadiene petroleum resin.
 また、前記粘着付与剤としては、カルボン酸及びカルボン酸無水物の少なくとも一方で変性した酸変性粘着付与剤を含んでいることが好ましい。前記酸変性粘着付与剤は、ホットメルト接着剤において粘着付与剤として一般的に用いられる粘着付与剤を、カルボン酸及びカルボン酸無水物の少なくとも一方で変性したものであれば、特に限定されない。前記酸変性粘着付与剤としては、例えば、カルボン酸及びカルボン酸無水物の少なくとも一方が、粘着付与剤にグラフト付加することで得られる粘着付与剤や、粘着付与剤を重合により合成する際に、カルボン酸及びカルボン酸無水物の少なくとも一方を共重合することで得られる粘着付与剤等が挙げられる。 The tackifier preferably includes an acid-modified tackifier modified with at least one of carboxylic acid and carboxylic anhydride. The acid-modified tackifier is not particularly limited as long as it is obtained by modifying a tackifier generally used as a tackifier in a hot melt adhesive with at least one of carboxylic acid and carboxylic anhydride. As the acid-modified tackifier, for example, at least one of carboxylic acid and carboxylic acid anhydride is obtained by grafting to a tackifier, or when a tackifier is synthesized by polymerization, Examples include tackifiers obtained by copolymerizing at least one of carboxylic acid and carboxylic acid anhydride.
 変性させる前の粘着付与剤としては、ホットメルト接着剤に一般的に用いられる粘着付与剤であれば、特に限定されず、上述した粘着付与剤が挙げられる。 The tackifier before modification is not particularly limited as long as it is a tackifier generally used for hot melt adhesives, and examples thereof include the tackifiers described above.
 前記酸変性に用いるカルボン酸は、特に限定されない。前記酸変性に用いるカルボン酸としては、例えば、マレイン酸、フマル酸、コハク酸、フタル酸、グルタル酸、イタコン酸、アクリル酸、及びメタクリル酸等が挙げられる。 The carboxylic acid used for the acid modification is not particularly limited. Examples of the carboxylic acid used for the acid modification include maleic acid, fumaric acid, succinic acid, phthalic acid, glutaric acid, itaconic acid, acrylic acid, and methacrylic acid.
 前記酸変性に用いるカルボン酸無水物は、特に限定されない。前記酸変性に用いるカルボン酸無水物としては、例えば、無水マレイン酸(マレイン酸無水物)、無水コハク酸、無水フタル酸、及び無水グルタル酸等が挙げられる。 The carboxylic acid anhydride used for the acid modification is not particularly limited. Examples of the carboxylic acid anhydride used for the acid modification include maleic anhydride (maleic anhydride), succinic anhydride, phthalic anhydride, and glutaric anhydride.
 前記カルボン酸としては、マレイン酸、フマル酸、及びアクリル酸が好ましく、マレイン酸がより好ましい。また前記カルボン酸無水物としては、無水マレイン酸が好ましい。また、前記酸変性に用いるものとしては、カルボン酸無水物である無水マレイン酸が好ましい。 As the carboxylic acid, maleic acid, fumaric acid, and acrylic acid are preferable, and maleic acid is more preferable. The carboxylic acid anhydride is preferably maleic anhydride. Moreover, as what is used for the said acid modification, maleic anhydride which is a carboxylic acid anhydride is preferable.
 前記カルボン酸及び前記カルボン酸無水物としては、上記のカルボン酸やカルボン酸無水物を単独で用いてもよいし、2種以上を組み合わせて用いてもよい。 As the carboxylic acid and the carboxylic acid anhydride, the above carboxylic acids and carboxylic acid anhydrides may be used alone or in combination of two or more.
 また、前記粘着付与剤としては、上記例示した粘着付与剤及び酸変性粘着付与剤を単独で用いてもよいし、2種以上を組み合わせて用いてもよい。 Moreover, as the tackifier, the tackifiers and acid-modified tackifiers exemplified above may be used alone, or two or more kinds may be used in combination.
 本実施形態において用いられる軟化剤は、ホットメルト接着剤に一般的に用いられる軟化剤であれば、特に限定されない。軟化剤としては、例えば、鉱物油類、合成油類、植物油類、及び脂肪酸エステル類等のオイル等が挙げられる。 The softener used in the present embodiment is not particularly limited as long as it is a softener generally used for hot melt adhesives. Examples of the softener include oils such as mineral oils, synthetic oils, vegetable oils, and fatty acid esters.
 前記鉱物油類としては、具体的には、プロセスオイル、及び流動パラフィン等が挙げられる。プロセスオイルとは、ゴムや熱可塑性エラストマー等の可塑剤として一般的に用いられるオイルであり、いわゆる石油精製等において生産されるオイルである。プロセスオイルは、一般に、芳香族環、ナフテン環、及びパラフィン鎖を含む混合物であって、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とに大別される。プロセスオイルは、パラフィン鎖炭素数が全炭素数の50%以上を占めるものをパラフィン系、ナフテン環炭素数が30%以上を占めるものをナフテン系、芳香族炭素数が30%以上を占めるものを芳香族系と区別している。パラフィン系プロセスオイルとしては、炭素数4~155のパラフィン系化合物、好ましくは炭素数4~50のパラフィン系化合物が挙げられる。前記パラフィン系プロセスオイルとしては、具体的には、ブタン、ペンタン、ヘキサン、ヘプタン、オクタン、ノナン、デカン、ウンデカン、ドデカン、テトラデカン、ペンタデカン、ヘキサデカン、ヘプタデカン、オクタデカン、ノナデカン、エイコサン、ヘンエイコサン、ドコサン、トリコサン、テトラコサン、ペンタデコサン、ヘキサコサン、ヘプタコサン、オクタコサン、ノナコサン、トリアコンタン、ヘントリアコンタン、ドトリアコンタン、ペンタトリアコンタン、ヘキサコンタン、及びヘンプタコンタン等のn-パラフィン、イソブタン、イソペンタン、ネオペンタン、イソヘキサン、イソペンタン、ネオヘキサン、2,3-ジメチルブタン、各種メチルヘキサン、3-エチルペンタン、各種ジメチルペンタン、2,2,3-トリメチルブタン、3-メチルヘプタン、各種ジメチルヘキサン、各種トリメチルペンタン、イソノナン、2-メチルノナン、イソデカン、イソウンデカン、イソドデカン、イソトリデカン、イソテトラデカン、イソペンタデカン、イソオクタデカン、イソナノデカン、イソエイコサン、及び4-エチル-5-メチルオクタン等のイソパラフィン、これらの飽和炭化水素の誘導体等が挙げられる。選択されるこれらのパラフィン系化合物は、混合物で用いることができ、室温で液状である。 Specific examples of the mineral oil include process oil and liquid paraffin. The process oil is an oil generally used as a plasticizer such as rubber or thermoplastic elastomer, and is produced in so-called petroleum refining. The process oil is generally a mixture containing an aromatic ring, a naphthene ring, and a paraffin chain, and is roughly classified into a paraffinic process oil, a naphthenic process oil, and an aromatic process oil. Process oils are those in which the number of carbon atoms in the paraffin chain occupies 50% or more of the total number of carbons, paraffin type, in which the naphthene ring carbon number occupies 30% or more, naphthenic type, and in which the aromatic carbon number occupies 30% or more. Differentiated from aromatic. Examples of the paraffinic process oil include paraffinic compounds having 4 to 155 carbon atoms, preferably paraffinic compounds having 4 to 50 carbon atoms. Specific examples of the paraffinic process oil include butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosan, heneicosane, docosane, tricosane. , Tetracosane, pentadecosan, hexacosane, heptacosane, octacosane, nonacosan, triacontane, hentriacontan, dotriacontan, pentatriacontane, hexacontane, and hempacontan, etc. n-paraffin, isobutane, isopentane, neopentane, isohexane, isopentane , Neohexane, 2,3-dimethylbutane, various methylhexane, 3-ethylpentane, various dimethylpentane, 2,2,3- Limethylbutane, 3-methylheptane, various dimethylhexanes, various trimethylpentanes, isononane, 2-methylnonane, isodecane, isoundecane, isododecane, isotridecane, isotetradecane, isopentadecane, isooctadecane, isonanodecane, isoeicosane, and 4-ethyl-5- Examples thereof include isoparaffins such as methyloctane and derivatives of these saturated hydrocarbons. These selected paraffinic compounds can be used in a mixture and are liquid at room temperature.
 合成油類としては、具体的には、室温で液状である、リン酸エステル、塩素化パラフィン、エチレン-α-オレフィンオリゴマー、ポリブテン、低分子量ポリブタジエン、ポリイソプレン、及びその水素添加物等が挙げられる。 Specific examples of synthetic oils include phosphate esters, chlorinated paraffins, ethylene-α-olefin oligomers, polybutenes, low molecular weight polybutadienes, polyisoprenes, and hydrogenated products thereof that are liquid at room temperature. .
 植物油類としては、具体的には、オリーブ油、カルナウバロウ、米胚芽油、コーン油、サザンカ油、ツバキ油、ヒマシ油、ホホバ種子油、及びユーカリ葉油などが挙げられる。 Specific examples of vegetable oils include olive oil, carnauba wax, rice germ oil, corn oil, sasanqua oil, camellia oil, castor oil, jojoba seed oil, and eucalyptus leaf oil.
 脂肪酸エステル類としては、具体的には、ミスチル酸イソプロピル、スリスチン酸オクチルドデシル、トリイソオクタン酸グリセリン、アジピン酸ジイソプロピル、セバシン酸ジエチル、エチルヘキサン酸セチル、パルミチン酸セチル、パルミチン酸エチルヘキシル、パルミチン酸イソプロピル、中鎖脂肪酸トリグリセリド、サリチル酸エチレングリコール、及びジステアリン酸グリコール等が挙げられる。 Specific examples of the fatty acid esters include isopropyl myristate, octyldodecyl ristylate, glycerin triisooctanoate, diisopropyl adipate, diethyl sebacate, cetyl ethylhexanoate, cetyl palmitate, ethylhexyl palmitate, isopropyl palmitate, Examples include medium chain fatty acid triglycerides, ethylene glycol salicylate, and glycol distearate.
 また、前記軟化剤としては、カルボン酸及びカルボン酸無水物の少なくとも一方で変性した酸変性軟化剤を含んでいることが好ましい。前記酸変性軟化剤は、ホットメルト接着剤において軟化剤として一般的に用いられる軟化剤を、カルボン酸及びカルボン酸無水物の少なくとも一方で変性したものであれば、特に限定されない。前記酸変性軟化剤としては、例えば、分子内にコハク酸骨格を有するオイル等が挙げられる。 The softener preferably contains an acid-modified softener modified with at least one of carboxylic acid and carboxylic anhydride. The acid-modified softener is not particularly limited as long as it is obtained by modifying a softener generally used as a softener in a hot melt adhesive with at least one of carboxylic acid and carboxylic anhydride. Examples of the acid-modified softening agent include oil having a succinic acid skeleton in the molecule.
 変性させる前の軟化剤としては、ホットメルト接着剤に一般的に用いられる軟化剤であれば、特に限定されず、上述した軟化剤が挙げられる。 The softener before modification is not particularly limited as long as it is a softener generally used for hot melt adhesives, and examples thereof include the softeners described above.
 前記酸変性に用いるカルボン酸は、特に限定されない。前記酸変性に用いるカルボン酸としては、例えば、マレイン酸、フマル酸、コハク酸、フタル酸、グルタル酸、イタコン酸、アクリル酸、及びメタクリル酸等が挙げられる。 The carboxylic acid used for the acid modification is not particularly limited. Examples of the carboxylic acid used for the acid modification include maleic acid, fumaric acid, succinic acid, phthalic acid, glutaric acid, itaconic acid, acrylic acid, and methacrylic acid.
 前記酸変性に用いるカルボン酸無水物は、特に限定されない。前記酸変性に用いるカルボン酸無水物としては、例えば、無水マレイン酸(マレイン酸無水物)、無水コハク酸、無水フタル酸、及び無水グルタル酸等が挙げられる。 The carboxylic acid anhydride used for the acid modification is not particularly limited. Examples of the carboxylic acid anhydride used for the acid modification include maleic anhydride (maleic anhydride), succinic anhydride, phthalic anhydride, and glutaric anhydride.
 前記カルボン酸としては、マレイン酸、フマル酸、及びアクリル酸が好ましく、マレイン酸がより好ましい。また前記カルボン酸無水物としては、無水マレイン酸が好ましい。また、前記酸変性に用いるものとしては、カルボン酸無水物である無水マレイン酸が好ましい。 As the carboxylic acid, maleic acid, fumaric acid, and acrylic acid are preferable, and maleic acid is more preferable. The carboxylic acid anhydride is preferably maleic anhydride. Moreover, as what is used for the said acid modification, maleic anhydride which is a carboxylic acid anhydride is preferable.
 前記カルボン酸及び前記カルボン酸無水物としては、上記のカルボン酸やカルボン酸無水物を単独で用いてもよいし、2種以上を組み合わせて用いてもよい。 As the carboxylic acid and the carboxylic acid anhydride, the above carboxylic acids and carboxylic acid anhydrides may be used alone or in combination of two or more.
 また、前記軟化剤としては、上記例示した軟化剤及び酸変性軟化剤を単独で用いてもよいし、2種以上を組み合わせて用いてもよい。 Further, as the softener, the above-exemplified softener and acid-modified softener may be used alone or in combination of two or more.
 また、前記ホットメルト接着剤において、前記熱可塑性ポリマー、前記粘着付与剤及び前記軟化剤の各含有量は、本発明の目的とする所望の特性を阻害しない範囲であれば、特に限定されない。前記各含有量としては、例えば、以下のような範囲が挙げられる。 In the hot melt adhesive, the contents of the thermoplastic polymer, the tackifier, and the softener are not particularly limited as long as they do not hinder the desired properties of the present invention. As said each content, the following ranges are mentioned, for example.
 前記熱可塑性ポリマーの含有量は、前記ホットメルト接着剤100質量部に対して、10~50質量部であることが好ましく、15~30質量部であることがより好ましく、15~25質量部であることがさらに好ましい。前記熱可塑性ポリマーの含有量が少なすぎると、凝集力が不足する傾向がある。また、前記熱可塑性ポリマーの含有量が多すぎると、溶融粘度が上昇して、塗工性が低下する傾向がある。なお、この含有量は、ホットメルト接着剤全量に対しての含有量である。 The content of the thermoplastic polymer is preferably 10 to 50 parts by weight, more preferably 15 to 30 parts by weight, and more preferably 15 to 25 parts by weight with respect to 100 parts by weight of the hot melt adhesive. More preferably it is. When the content of the thermoplastic polymer is too small, the cohesive force tends to be insufficient. Moreover, when there is too much content of the said thermoplastic polymer, there exists a tendency for melt viscosity to rise and for coating property to fall. In addition, this content is content with respect to the hot-melt-adhesive whole quantity.
 前記粘着付与剤の含有量が、前記ホットメルト接着剤100質量部に対して、40~80質量部であることが好ましく、50~70質量部であることがより好ましく、55~65質量部であることがさらに好ましい。前記粘着付与剤の含有量が少なすぎると、粘着力が低下し、接着強度が低下する傾向がある。また、前記粘着付与剤の含有量が多すぎると、柔軟性や可撓性を喪失し、応力分散性が低下して保持力が低下する傾向がある。なお、この含有量は、ホットメルト接着剤全量に対しての含有量である。 The content of the tackifier is preferably 40 to 80 parts by mass, more preferably 50 to 70 parts by mass, and 55 to 65 parts by mass with respect to 100 parts by mass of the hot melt adhesive. More preferably it is. When there is too little content of the said tackifier, there exists a tendency for adhesive force to fall and for adhesive strength to fall. Moreover, when there is too much content of the said tackifier, a softness | flexibility and flexibility will be lost, there exists a tendency for stress dispersibility to fall and for holding power to fall. In addition, this content is content with respect to the hot-melt-adhesive whole quantity.
 また、前記軟化剤の含有量が、前記ホットメルト接着剤100質量部に対して、15~30質量部であることが好ましく、15~27質量部であることがより好ましく、18~27質量部であることがより好ましい。前記軟化剤の含有量が少なすぎると、湿潤時のクリープ強度が低下する傾向がある。また、前記軟化剤の含有量が多すぎると、凝集力や接着力が低下し、保持力が低下する傾向がある。なお、この含有量は、ホットメルト接着剤全量に対しての含有量である。 In addition, the content of the softening agent is preferably 15 to 30 parts by mass, more preferably 15 to 27 parts by mass, and more preferably 18 to 27 parts by mass with respect to 100 parts by mass of the hot melt adhesive. It is more preferable that When the content of the softening agent is too small, the creep strength when wet tends to decrease. Moreover, when there is too much content of the said softener, there exists a tendency for cohesion force and adhesive force to fall and for holding power to fall. In addition, this content is content with respect to the hot-melt-adhesive whole quantity.
 これらのことから、前記ホットメルト接着剤において、前記熱可塑性ポリマーの含有量は、ホットメルト接着剤全量に対して、10~50質量%であることが好ましい。前記粘着付与剤の含有量は、ホットメルト接着剤全量に対して、40~80質量%であることが好ましい。また、前記軟化剤の含有量は、前記合計質量に対して、15~30質量%であることが好ましい。 For these reasons, it is preferable that the content of the thermoplastic polymer in the hot melt adhesive is 10 to 50% by mass with respect to the total amount of the hot melt adhesive. The content of the tackifier is preferably 40 to 80% by mass with respect to the total amount of the hot melt adhesive. Further, the content of the softening agent is preferably 15 to 30% by mass with respect to the total mass.
 本実施形態に係るホットメルト接着剤には、本発明の目的とする所望の特性を阻害しない範囲で、前記熱可塑性ポリマー、前記粘着付与剤、及び前記軟化剤以外のものを含有してもよい。具体的には、酸化防止剤、熱安定剤、光安定剤、紫外線吸収剤、充填材、界面活性剤、カップリング剤、着色剤、帯電防止剤、難燃剤、ワックス、及び可塑剤等の添加剤を含有してもよい。 The hot melt adhesive according to the present embodiment may contain a material other than the thermoplastic polymer, the tackifier, and the softener, as long as the desired properties of the present invention are not impaired. . Specifically, addition of antioxidants, heat stabilizers, light stabilizers, UV absorbers, fillers, surfactants, coupling agents, colorants, antistatic agents, flame retardants, waxes, plasticizers, etc. An agent may be contained.
 また、酸化防止剤としては、例えば、フェノール系酸化防止剤や有機硫黄系酸化防止剤等が挙げられる。フェノール系酸化防止剤としては、例えば、2,6-ジ-tert-ブチル-4-メチルフェノール、n-オクタデシル-3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート、2-tert-ブチル-6-(3-tert-ブチル-2-ヒドロキシ-5-メチルベンジル)-4-メ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-tert-ブチル-4-ヒドロキシフェニル)プロピオネート]メタン等が挙げられる。有機硫黄系酸化防止剤としては、例えば、ジラウリル-3,3’-チオジプロピオネート、ジミリスチル-3,3’-チオジプロピオネート、ジステアリル-3,3’-チオジプロピオネート、ペンタエリスリチルテトラキス(3-ラウリルチオプロピオネート)等が挙げられる。これらの酸化防止剤は、上記例示した酸化防止剤を単独で用いてもよいし、2種以上を組み合わせて用いてもよい。 Also, examples of the antioxidant include phenolic antioxidants and organic sulfur antioxidants. Examples of phenolic antioxidants include 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2 -Tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxy Phenyl) propionate] methane and the like. Examples of organic sulfur-based antioxidants include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, and pentaerythris. Lithyltetrakis (3-lauryl thiopropionate) and the like can be mentioned. As these antioxidants, the above-exemplified antioxidants may be used alone or in combination of two or more.
 ワックスは、ホットメルト接着剤に含有されるワックスであれば、特に限定されない。ワックスとしては、例えば、合成ワックス、石油ワックス、及び天然ワックス等が挙げられる。また、合成ワックスとしては、例えば、フィッシャートロプシュワックス、ポリエチレンワックスやポリプロピレンワックス等の、ポリオレフィンワックス等が挙げられる。石油ワックスとしては、例えば、パラフィンワックス、マイクロクリスタリンワックス、及びペトラタム等が挙げられる。天然ワックスとしては、例えば、モンタンワックス、木ロウ、カルバナロウ、ミツロウ、及びカスターワックス等が挙げられる。これらのワックスは、上記例示したワックスを単独で用いてもよいし、2種以上を組み合わせて用いてもよい。 The wax is not particularly limited as long as it is a wax contained in the hot melt adhesive. Examples of the wax include synthetic wax, petroleum wax, and natural wax. Examples of synthetic waxes include polyolefin waxes such as Fischer-Tropsch wax, polyethylene wax, and polypropylene wax. Examples of petroleum waxes include paraffin wax, microcrystalline wax, and petratam. Examples of natural waxes include montan wax, wood wax, carbana wax, beeswax, and castor wax. These waxes may be used alone or in combination of two or more.
 本実施形態に係るホットメルト接着剤を製造する方法としては、上記構成のホットメルト接着剤を製造することができる製造方法であれば、特に限定されない。ホットメルト接着剤を製造する方法としては、例えば、ホットメルト接着剤を構成する成分を加熱溶融し、攪拌混練する方法等が挙げられる。そうすることによって、ホットメルト接着剤を構成する成分の分散性の高いホットメルト接着剤が得られる。また、この方法を実現する装置としては、例えば、加熱装置を備えた、攪拌混練機、ロール、バンバリーミキサー、ニーダー、及び押出機等が挙げられる。 The method for producing the hot melt adhesive according to the present embodiment is not particularly limited as long as it is a production method capable of producing the hot melt adhesive having the above configuration. Examples of a method for producing a hot melt adhesive include a method in which components constituting the hot melt adhesive are heated and melted and stirred and kneaded. By doing so, a hot melt adhesive having a high dispersibility of components constituting the hot melt adhesive can be obtained. Moreover, as an apparatus which implement | achieves this method, the stirring kneader, roll, Banbury mixer, kneader, extruder, etc. which were equipped with the heating apparatus are mentioned, for example.
 ホットメルト接着剤を用いた接着方法は、ホットメルト接着剤を用いた接着方法として用いることができる方法であれば、特に限定されない。ホットメルト接着剤を用いた接着方法としては、例えば、ホットメルト接着剤を、加熱によって溶融させる。そして、その溶融状態のホットメルト接着剤を接着対象物である被着体に塗布する。この塗布されたホットメルト接着剤に、もう一方の被着体を接触させた状態で放置することで、このホットメルト接着剤が冷却し、固化される。この固化されたホットメルト接着剤が、被着体同士を接着させる。 The bonding method using the hot melt adhesive is not particularly limited as long as it can be used as the bonding method using the hot melt adhesive. As an adhesion method using a hot melt adhesive, for example, a hot melt adhesive is melted by heating. And the hot-melt-adhesive of the molten state is apply | coated to the to-be-adhered body which is a bonding target object. By leaving the other adherend in contact with the applied hot melt adhesive, the hot melt adhesive is cooled and solidified. This solidified hot melt adhesive bonds adherends to each other.
 ホットメルト接着剤を塗布する方法は、ホットメルト接着剤を被着体に好適に塗布できれば、特に限定されない。この塗布方法としては、例えば、接触塗布方法と非接触塗布方法とに大別される。接触塗布方法とは、ホットメルト接着剤を塗布する際、塗工機等の、塗布に用いる装置を被着体に接触させた状態で塗布する塗布方法をいう。また、非接触塗布方法とは、ホットメルト接着剤を塗布する際、塗工機等を被着体に接触させない状態で塗布する塗布方法をいう。接触塗布方法としては、例えば、スロット塗工(ノードソン株式会社製のスロットコートガン等)及びロールコーター塗工等が挙げられる。また、非接触塗布方法として、例えば、螺旋状に塗布できるスパイラル塗工(株式会社サンツール製のスパイラルスプレーノズル等)、波状に塗布できるスプレー塗工(ITWダイナテック株式会社製のオメガコート等)、面状に塗布できるスプレー塗工(株式会社サンツール製のカーテンスプレーヘッド等)、点状に塗工できるドット塗工等が挙げられる。本実施形態に係るホットメルト接着剤は、スパイラル塗工に適している。スパイラル塗工とは、間欠または連続塗工で接着剤をエアーでらせん状に非接触塗布する方法である。 The method for applying the hot melt adhesive is not particularly limited as long as the hot melt adhesive can be suitably applied to the adherend. This coating method is roughly classified into, for example, a contact coating method and a non-contact coating method. The contact coating method refers to a coating method in which a hot melt adhesive is applied in a state where an apparatus used for coating such as a coating machine is in contact with an adherend. In addition, the non-contact coating method refers to a coating method in which a coating machine or the like is applied without being in contact with an adherend when a hot melt adhesive is applied. Examples of the contact coating method include slot coating (such as a slot coat gun manufactured by Nordson Corporation) and roll coater coating. In addition, as non-contact coating methods, for example, spiral coating that can be applied in a spiral shape (such as a spiral spray nozzle manufactured by Suntool Co., Ltd.), spray coating that can be applied in a corrugated shape (such as OMEGA COAT manufactured by ITW Dynatech Co., Ltd.) , Spray coating that can be applied in the form of a surface (curtain spray head manufactured by Suntool Co., Ltd.), dot coating that can be applied in the form of dots, etc. The hot melt adhesive according to this embodiment is suitable for spiral coating. Spiral coating is a method in which an adhesive is spirally contacted with air by intermittent or continuous coating.
 本明細書は、上述したように、様々な態様の技術を開示しているが、そのうち主な技術を以下に纏める。 This specification discloses various modes of technology as described above, and the main technologies are summarized below.
 本発明の一局面は、熱可塑性ポリマーと、粘着付与剤と、軟化剤とを含むホットメルト接着剤であって、前記熱可塑性ポリマーは、共役ジエン系化合物からなる第1ブロックとビニル系芳香族炭化水素からなる第2ブロックとからなる共重合体、及び前記共重合体の水素化物の少なくとも一方を含み、前記共重合体は、前記第2ブロックの含有量が30質量%未満であり、前記第1ブロックと前記第2ブロックとのジブロック体の含有量が10質量%以上である共重合体であって、前記共重合体及び前記共重合体の水素化物の含有量が、前記熱可塑性ポリマー全量に対して、55質量%以上であり、前記軟化剤の含有量が、前記ホットメルト接着剤100質量部に対して、15~30質量部であることを特徴とするホットメルト接着剤である。 One aspect of the present invention is a hot melt adhesive containing a thermoplastic polymer, a tackifier, and a softening agent, wherein the thermoplastic polymer includes a first block composed of a conjugated diene compound and a vinyl aromatic. A copolymer comprising a second block comprising a hydrocarbon, and at least one of a hydride of the copolymer, wherein the copolymer has a content of the second block of less than 30% by mass, A copolymer in which the content of the diblock body of the first block and the second block is 10% by mass or more, wherein the content of the copolymer and the hydride of the copolymer is the thermoplasticity. A hot melt adhesive characterized in that it is 55% by mass or more based on the total amount of the polymer, and the content of the softener is 15 to 30 parts by mass with respect to 100 parts by mass of the hot melt adhesive. Ah .
 このような構成によれば、湿潤状態でのクリープ現象の発生を充分に抑制でき、湿潤状態での接着性に優れるホットメルト接着剤を提供することができる。よって、このホットメルト接着剤は、湿潤状態での接着性に優れる。 According to such a configuration, it is possible to provide a hot melt adhesive that can sufficiently suppress the occurrence of a creep phenomenon in a wet state and has excellent adhesiveness in a wet state. Therefore, this hot melt adhesive is excellent in adhesiveness in a wet state.
 また、前記ホットメルト接着剤において、前記ビニル系芳香族炭化水素が、スチレンであり、前記共役ジエン系化合物が、ブタジエン及びイソプレンの少なくとも一方であることが好ましい。 In the hot melt adhesive, the vinyl aromatic hydrocarbon is preferably styrene, and the conjugated diene compound is preferably at least one of butadiene and isoprene.
 このような構成によれば、湿潤状態でのクリープ現象の発生をより抑制できるホットメルト接着剤が得られる。 According to such a configuration, a hot melt adhesive that can further suppress the occurrence of a creep phenomenon in a wet state can be obtained.
 また、前記ホットメルト接着剤において、前記粘着付与剤は、カルボン酸及びカルボン酸無水物の少なくとも一方で変性した酸変性粘着付与剤を含むことが好ましい。 In the hot melt adhesive, the tackifier preferably includes an acid-modified tackifier modified by at least one of carboxylic acid and carboxylic anhydride.
 このような構成によれば、湿潤状態でのクリープ現象の発生を充分に抑制でき、さらに、湿潤状態での接着強度がより高められたホットメルト接着剤が得られる。 According to such a configuration, it is possible to sufficiently suppress the occurrence of the creep phenomenon in the wet state, and further, it is possible to obtain a hot melt adhesive having a further increased adhesive strength in the wet state.
 また、前記ホットメルト接着剤において、前記軟化剤は、カルボン酸及びカルボン酸無水物の少なくとも一方で変性した酸変性軟化剤を含むことが好ましい。 In the hot melt adhesive, it is preferable that the softener includes an acid-modified softener modified with at least one of carboxylic acid and carboxylic anhydride.
 このような構成によれば、湿潤状態でのクリープ現象の発生を充分に抑制でき、さらに、湿潤状態での接着強度がより高められたホットメルト接着剤が得られる。 According to such a configuration, it is possible to sufficiently suppress the occurrence of the creep phenomenon in the wet state, and further, it is possible to obtain a hot melt adhesive having a further increased adhesive strength in the wet state.
 本発明によれば、湿潤状態でのクリープ現象の発生を充分に抑制でき、湿潤状態での接着性に優れるホットメルト接着剤を提供することができる。 According to the present invention, it is possible to provide a hot melt adhesive that can sufficiently suppress the occurrence of a creep phenomenon in a wet state and has excellent adhesion in a wet state.
 以下に、実施例により本発明を更に具体的に説明するが、本発明の範囲はこれらに限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples, but the scope of the present invention is not limited thereto.
 まず、本実施例において、ホットメルト接着剤を調製する際に用いる各成分について説明する。 First, each component used in preparing the hot melt adhesive in this example will be described.
 [熱可塑性ポリマー]
 熱可塑性ポリマー1:スチレン-イソプレン-スチレンブロックコポリマー(SIS)(日本ゼオン株式会社製のQuintac3433、スチレン(第2ブロック)の含有量:16質量%、ジブロック体の含有量:60質量%)
 熱可塑性ポリマー2:スチレン-イソプレン-スチレンブロックコポリマー(SIS)(李長栄化学社製のGlobalprene5517、スチレン(第2ブロック)の含有量:15質量%、ジブロック体の含有量:38質量%)
 熱可塑性ポリマー3:スチレン-ブタジエン-スチレンブロックコポリマー(SBS)(分岐状のSBS、JSR株式会社製のTR2830、スチレン(第2ブロック)の含有量:20質量%、ジブロック体の含有量:27質量%)
 熱可塑性ポリマー4:スチレン-ブタジエン-スチレンブロックコポリマー(SBS)(直鎖状のSBS、スチレン(第2ブロック)の含有量:16質量%、ジブロック体の含有量:16質量%)
 熱可塑性ポリマー5:スチレン-ブタジエン-スチレンブロックコポリマー(SBS)(旭化成株式会社製のタフプレン315P、スチレン(第2ブロック)の含有量:20質量%、ジブロック体の含有量:0質量%)
 熱可塑性ポリマー6:スチレン-ブタジエン-スチレンブロックコポリマー(SBS)(旭化成株式会社製のアサプレンT-438、スチレン(第2ブロック)の含有量:35質量%、ジブロック体の含有量:65質量%)
 熱可塑性ポリマー7:スチレン-ブタジエン-スチレンブロックコポリマー(SBS)(旭化成株式会社製のアサプレンT-436、スチレン(第2ブロック)の含有量:30質量%、ジブロック体の含有量:50質量%)
 熱可塑性ポリマー8:スチレン-ブタジエン-スチレンブロックコポリマー(SBS)(旭化成株式会社製のアサプレンT-420、スチレン(第2ブロック)の含有量:30質量%、ジブロック体の含有量:10質量%)
 熱可塑性ポリマー9:スチレン-ブタジエン-スチレンブロックコポリマー(SBS)(旭化成株式会社製のアサプレンT-413、スチレン(第2ブロック)の含有量:30質量%、ジブロック体の含有量:75質量%)
 熱可塑性ポリマー10:スチレン-ブタジエン-スチレンブロックコポリマー(SBS)(クレイトン社製のD-1118、スチレン(第2ブロック)の含有量:30質量%、ジブロック体の含有量:65質量%)
[Thermoplastic polymer]
Thermoplastic polymer 1: Styrene-isoprene-styrene block copolymer (SIS) (Quantac 3433 manufactured by Nippon Zeon Co., Ltd., styrene (second block) content: 16 mass%, diblock body content: 60 mass%)
Thermoplastic polymer 2: Styrene-isoprene-styrene block copolymer (SIS) (Global Changen 5517, Lee Chang-Ei Chemical Co., Ltd., styrene (second block) content: 15% by mass, diblock body content: 38% by mass)
Thermoplastic polymer 3: Styrene-butadiene-styrene block copolymer (SBS) (branched SBS, TR2830 manufactured by JSR Corporation, content of styrene (second block): 20% by mass, content of diblock body: 27 mass%)
Thermoplastic polymer 4: Styrene-butadiene-styrene block copolymer (SBS) (linear SBS, styrene (second block) content: 16 mass%, diblock body content: 16 mass%)
Thermoplastic polymer 5: Styrene-butadiene-styrene block copolymer (SBS) (Tahprene 315P manufactured by Asahi Kasei Corporation, content of styrene (second block): 20% by mass, content of diblock: 0% by mass)
Thermoplastic polymer 6: Styrene-butadiene-styrene block copolymer (SBS) (ASAPRENE T-438 manufactured by Asahi Kasei Corporation, content of styrene (second block): 35% by mass, content of diblock: 65% by mass )
Thermoplastic polymer 7: Styrene-butadiene-styrene block copolymer (SBS) (Asaprene T-436 manufactured by Asahi Kasei Corporation, content of styrene (second block): 30% by mass, content of diblock: 50% by mass )
Thermoplastic polymer 8: Styrene-butadiene-styrene block copolymer (SBS) (Asaprene T-420 manufactured by Asahi Kasei Corporation, content of styrene (second block): 30% by mass, content of diblock: 10% by mass )
Thermoplastic polymer 9: styrene-butadiene-styrene block copolymer (SBS) (Asaprene T-413 manufactured by Asahi Kasei Corporation, content of styrene (second block): 30% by mass, content of diblock: 75% by mass )
Thermoplastic polymer 10: styrene-butadiene-styrene block copolymer (SBS) (D-1118 made by Kraton, content of styrene (second block): 30% by mass, content of diblock body: 65% by mass)
 ここで、スチレンの含有量は、上記熱可塑性ポリマーの場合、ビニル系芳香族炭化水素からなる第2ブロックの含有量に相当する。そして、ジブロック体の含有量は、共役ジエン系化合物からなる第1ブロックとビニル系芳香族炭化水素からなる第2ブロックとのジブロック体の含有量に相当する。 Here, the content of styrene corresponds to the content of the second block made of a vinyl aromatic hydrocarbon in the case of the thermoplastic polymer. The content of the diblock body corresponds to the content of the diblock body of the first block made of a conjugated diene compound and the second block made of a vinyl aromatic hydrocarbon.
 [粘着付与剤]
 粘着付与剤:脂環族系石油樹脂水素化物(水添C9石油樹脂)(荒川化学工業株式会社製のアルコンM-100)
 酸変性粘着付与剤:以下のようにして製造されたマレイン酸変性粘着付与樹脂
 ステンレス鋼(SUS)製の反応釜中に、粘着付与剤である芳香族変性テルペン樹脂水素化物(ヤスハラケミカル株式会社製のクリアロンK4100:軟化点100℃)750gを投入し、170℃で溶融させた。その後、反応釜内を窒素雰囲気下にし、反応釜中の溶融物に、無水マレイン酸22.5gとジクミルパーオキサイド5gとメタクリル酸ブチル22.5gとを1時間かけて滴下した。滴下完了後、170℃で30分間攪拌した後、反応釜内を減圧することにより、未反応物及びジクミルパーオキサイドの分解した低分子量化合物の除去を1時間行った。そうすることにより、淡黄色の固体が得られた。この固体が、無水マレイン酸で変性されている芳香族変性テルペン樹脂水素化物であり、酸変性粘着付与剤(マレイン酸変性粘着付与樹脂)である。この得られた酸変性粘着付与剤は、140℃での溶融粘度が3500mPa・sであり、重量平均分子量が1260であった。
[Tackifier]
Tackifier: alicyclic petroleum resin hydride (hydrogenated C9 petroleum resin) (ALCON M-100 manufactured by Arakawa Chemical Industries, Ltd.)
Acid-modified tackifier: A maleic acid-modified tackifier resin produced as follows: In a reaction vessel made of stainless steel (SUS), an aromatic-modified terpene resin hydride that is a tackifier (manufactured by Yasuhara Chemical Co., Ltd.) 750 g) (Clearon K4100: softening point 100 ° C.) was added and melted at 170 ° C. Thereafter, the inside of the reaction kettle was placed in a nitrogen atmosphere, and 22.5 g of maleic anhydride, 5 g of dicumyl peroxide, and 22.5 g of butyl methacrylate were added dropwise to the melt in the reaction kettle over 1 hour. After completion of the dropwise addition, the mixture was stirred at 170 ° C. for 30 minutes, and then the reaction vessel was depressurized to remove unreacted substances and low molecular weight compounds in which dicumyl peroxide was decomposed for 1 hour. By doing so, a pale yellow solid was obtained. This solid is an aromatic-modified terpene resin hydride modified with maleic anhydride and an acid-modified tackifier (maleic acid-modified tackifier resin). The obtained acid-modified tackifier had a melt viscosity of 3500 mPa · s at 140 ° C. and a weight average molecular weight of 1260.
 [軟化剤]
 オイル:オイル(出光興産株式会社製のダイアナフレシアS32)
 酸変性オイル:マレイン酸変性オイル(分子内にコハク酸骨格を有するオイル)(星光PMC株式会社製のAS-1532)
[Softener]
Oil: Oil (Diana Fresia S32 manufactured by Idemitsu Kosan Co., Ltd.)
Acid-modified oil: Maleic acid-modified oil (oil having a succinic acid skeleton in the molecule) (AS-1532 manufactured by Seiko PMC Co., Ltd.)
 [添加剤]
 ワックス:(エボニック社製のSarawaxSX-105)
 酸化防止剤:一次酸化防止剤(BASF社製のイルガノックス1010)
[Additive]
Wax: (Sarawax SX-105 manufactured by Evonik)
Antioxidant: Primary antioxidant (Irganox 1010 manufactured by BASF)
 [ホットメルト接着剤の製造方法]
 上記各成分を、下記表1に示す配合量(組成:質量部)となるように、以下のような手順で混練してホットメルト接着剤を作成した。攪拌混練機中に、粘着付与剤、軟化剤、及び添加剤を投入し、150~190℃になるように加熱した状態で攪拌することによって、充分に溶融させた。その溶融物の中に、熱可塑性ポリマーを投入し、150~190℃になるように加熱した状態で混練することにより、熱可塑性ポリマーも充分に溶融させ、溶融物の中に均一に分散させた。その後、その溶融物の中に、酸変性粘着付与剤を投入し、攪拌混練した。その際、可能な限り、ホットメルト接着剤の均一性が高まるまで混練した。そうすることで、ホットメルト接着剤を製造した。
[Method for producing hot melt adhesive]
The above components were kneaded according to the following procedure so as to obtain the blending amounts (composition: parts by mass) shown in Table 1 below to prepare a hot melt adhesive. A tackifier, a softener, and an additive were put into a stirring kneader, and the mixture was sufficiently melted by stirring while being heated to 150 to 190 ° C. The thermoplastic polymer was charged into the melt and kneaded while being heated to 150 to 190 ° C., so that the thermoplastic polymer was sufficiently melted and uniformly dispersed in the melt. . Thereafter, an acid-modified tackifier was added into the melt and stirred and kneaded. At that time, kneading was performed as much as possible until the uniformity of the hot melt adhesive was increased. By doing so, a hot melt adhesive was produced.
 [評価]
 (塗工性:溶融粘度)
 以下のようにして、硬化前のホットメルト接着剤の140℃での溶融粘度を測定した。具体的には、JIS K 6682に記載の測定方法に準拠し、ホットメルト接着剤の140℃で溶融させた溶融液の粘度を、ブルックフィールド粘度計(スピンドルNo.27のロータ)により、測定した。この粘度が、硬化前のホットメルト接着剤の140℃での溶融粘度である。
[Evaluation]
(Coating property: melt viscosity)
The melt viscosity at 140 ° C. of the hot melt adhesive before curing was measured as follows. Specifically, based on the measurement method described in JIS K 6682, the viscosity of the melt of the hot melt adhesive melted at 140 ° C. was measured with a Brookfield viscometer (spindle No. 27 rotor). . This viscosity is the melt viscosity at 140 ° C. of the hot melt adhesive before curing.
 また、同様の方法により、硬化前のホットメルト接着剤の160℃での溶融粘度を測定した。 Also, the melt viscosity at 160 ° C. of the hot melt adhesive before curing was measured by the same method.
 (湿潤時低速剥離強度)
 製造されたホットメルト接着剤を150℃に加熱することにより溶融させた後、溶融されたホットメルト接着剤を、スパイラルスプレーによって、ティッシュの一方の面上に、6gsm(g/m)となるように塗布した。塗布してから1秒後に、ホットメルト接着剤が塗布されたティッシュ上に、このホットメルト接着剤が接触するように、ティッシュを置いた。その後、このティッシュとティッシュとを、23℃で、圧力50gf/cmで、0.01秒間プレスした。この積層体を、基材進行に対して垂直方向(CD)方向に25mmに切断することによって、短冊状の試験片とした。そして、この試験片を、50℃の水道水に5~6秒間浸漬させた後、水中から取り出し、水を拭き取ることによって、湿潤状態の試験体とした。そして、この試験体を、各ホットメルト接着剤毎に3個用意した。そして、この試験体にJIS K6845に準拠したT型剥離試験を行った。具体的には、この試験体を、引張速度10mm/分で剥離した時の強度(N/25mm)を測定した。この剥離試験は、23℃、65%RHで行った。
(Low speed peel strength when wet)
After the manufactured hot melt adhesive is melted by heating to 150 ° C., the melted hot melt adhesive becomes 6 gsm (g / m 2 ) on one side of the tissue by spiral spray. It was applied as follows. One second after application, a tissue was placed on the tissue to which the hot melt adhesive was applied so that the hot melt adhesive was in contact with the tissue. Thereafter, the tissue and the tissue were pressed at 23 ° C. and a pressure of 50 gf / cm 2 for 0.01 seconds. The laminate was cut into 25 mm in the direction perpendicular to the base material (CD) to make a strip-shaped test piece. The test piece was immersed in tap water at 50 ° C. for 5 to 6 seconds, then taken out of the water and wiped off to obtain a wet test specimen. Three test specimens were prepared for each hot melt adhesive. Then, a T-type peel test based on JIS K6845 was performed on this test body. Specifically, the strength (N / 25 mm) when this specimen was peeled at a tensile speed of 10 mm / min was measured. This peel test was performed at 23 ° C. and 65% RH.
 また、この剥離試験を行った結果、ティッシュが全体的に破れた場合は、「◎」と評価し、ティッシュが部分的に破れた場合は、「○」と評価し、ティッシュが破れなかった場合は、「×」と評価した。なお、ティッシュが破れた場合は、試験片が破壊される材料破壊に相当し、接着性に優れていることを示す。この場合、湿潤状態でのクリープ現象の発生を充分に抑制でき、湿潤状態での接着性に優れることを示す。また、ティッシュが破れなかった場合は、試験片が接着剤層との界面から破壊されることなく剥離する界面破壊に相当し、接着性に劣っていることを示す。 Also, as a result of this peel test, if the tissue is totally torn, it is evaluated as “◎”, and if the tissue is partially torn, it is evaluated as “○”, and the tissue is not torn. Was evaluated as “×”. In addition, when a tissue is torn, it corresponds to the material destruction which destroys a test piece, and shows that it is excellent in adhesiveness. In this case, the occurrence of the creep phenomenon in the wet state can be sufficiently suppressed, and the adhesiveness in the wet state is excellent. Moreover, when the tissue was not torn, it corresponds to interface fracture in which the test piece peels without being broken from the interface with the adhesive layer, indicating that the adhesiveness is poor.
 (湿潤時せん断強度)
 製造されたホットメルト接着剤を150℃に加熱することにより溶融させた後、溶融されたホットメルト接着剤を、コータによって、発泡ウレタンシートの一方の面上に、4gsm(g/m)となるように塗布した。塗布してから1秒後に、ホットメルト接着剤が塗布された発泡ウレタンシート上に、このホットメルト接着剤が接触するように、不織布を置いた。その後、この発泡ウレタンシートと不織布とを、23℃で、圧力50gf/cmで、0.01秒間プレスした。この積層体を、基材進行に対して垂直方向(CD)方向に25mmに切断することによって、短冊状の試験片とした。そして、この試験片を、40℃の水道水に5~6秒間浸漬させた後、水中から取り出し、水を拭き取ることによって、湿潤状態の試験体とした。そして、この試験体を、各ホットメルト接着剤毎に3個用意した。そして、この試験体にJIS K6845に準拠したT型剥離試験を行った。具体的には、この試験体を、引張速度100mm/分で剥離した時の強度(N/25mm)を測定した。この剥離試験は、23℃、65%RHで行った。
(Shear strength when wet)
After the manufactured hot melt adhesive was melted by heating to 150 ° C., the melted hot melt adhesive was applied to 4 gsm (g / m 2 ) on one surface of the foamed urethane sheet by a coater. It applied so that it might become. One second after application, a non-woven fabric was placed on the foamed urethane sheet coated with the hot melt adhesive so that the hot melt adhesive was in contact. Thereafter, the urethane foam sheet and the nonwoven fabric were pressed at 23 ° C. and a pressure of 50 gf / cm 2 for 0.01 seconds. The laminate was cut into 25 mm in the direction perpendicular to the base material (CD) to make a strip-shaped test piece. The test piece was immersed in tap water at 40 ° C. for 5 to 6 seconds, then taken out of the water and wiped off to obtain a wet test specimen. Three test specimens were prepared for each hot melt adhesive. Then, a T-type peel test based on JIS K6845 was performed on this test body. Specifically, the strength (N / 25 mm) when this specimen was peeled at a tensile speed of 100 mm / min was measured. This peel test was performed at 23 ° C. and 65% RH.
 また、この剥離試験を行った結果、発泡ウレタンシートが全体的に破れた場合は、「◎」と評価し、発泡ウレタンシートが部分的に破れた場合は、「○」と評価し、発泡ウレタンシートが破れなかった場合は、「×」と評価した。なお、発泡ウレタンシートが破れた場合は、試験片が破壊される材料破壊に相当し、接着性に優れていることを示す。この場合、湿潤状態でのクリープ現象の発生を充分に抑制でき、湿潤状態での接着性に優れることを示す。また、発泡ウレタンシートが破れなかった場合は、試験片が接着剤層との界面から破壊されることなく剥離する界面破壊に相当し、接着性に劣っていることを示す。 As a result of this peel test, when the foamed urethane sheet was torn as a whole, it was evaluated as “◎”, and when the foamed urethane sheet was partially torn, it was evaluated as “◯”, and the urethane foam sheet was evaluated. When the sheet was not torn, it was evaluated as “x”. In addition, when a foaming urethane sheet is torn, it corresponds to the material destruction by which a test piece is destroyed, and shows that it is excellent in adhesiveness. In this case, the occurrence of the creep phenomenon in the wet state can be sufficiently suppressed, and the adhesiveness in the wet state is excellent. Moreover, when a urethane foam sheet was not torn, it corresponds to the interface fracture which peels without a test piece being destroyed from the interface with an adhesive bond layer, and shows that it is inferior to adhesiveness.
 各評価結果を、ホットメルト接着剤の配合量とともに、表1に示す。なお、表1中の、熱可塑性ポリマーにおける共重合体の比率は、熱可塑性ポリマー全量に対する、熱可塑性ポリマー1~4の合計の比率(質量%)を示す。また、ホットメルト接着剤100質量部に対する軟化剤の含有量は、ホットメルト接着剤100質量部に対する軟化剤の質量部を示す。 Each evaluation result is shown in Table 1 together with the blending amount of the hot melt adhesive. In Table 1, the ratio of the copolymer in the thermoplastic polymer represents the total ratio (mass%) of the thermoplastic polymers 1 to 4 with respect to the total amount of the thermoplastic polymer. Moreover, content of the softener with respect to 100 mass parts of hot-melt-adhesives shows the mass part of softener with respect to 100 mass parts of hot-melt-adhesives.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
 表1からわかるように、共役ジエン系化合物からなる第1ブロックとビニル系芳香族炭化水素からなる第2ブロックとからなり、前記第2ブロックの含有量が30質量%未満であって、前記第1ブロックと前記第2ブロックとのジブロック体の含有量が10質量%以上である共重合体を55質量%以上含む熱可塑性ポリマーを含み、さらに、軟化剤をホットメルト接着剤100質量部に対して15~30質量部を含むホットメルト接着剤の場合(実施例1~9)は、湿潤時低速剥離強度も湿潤時せん断強度も高く、湿潤時低速剥離強度を測定するときも、湿潤時せん断強度を測定するときも、界面破壊ではなく、材料破壊であった。 As can be seen from Table 1, the first block made of a conjugated diene compound and the second block made of a vinyl aromatic hydrocarbon, the content of the second block being less than 30% by mass, A thermoplastic polymer containing 55% by mass or more of a copolymer having a diblock body content of 1 block and the second block of 10% by mass or more is further included, and a softener is added to 100 parts by mass of the hot melt adhesive. On the other hand, in the case of the hot melt adhesive containing 15 to 30 parts by mass (Examples 1 to 9), both the low-speed peel strength when wet and the shear strength when wet are high. When measuring the shear strength, it was not the interface failure but the material failure.
 これに対して、熱可塑性ポリマーとして、前記共重合体以外を含む場合(比較例3、4、7)は、実施例1~9と比較して、湿潤時せん断強度も、湿潤時低速剥離強度も低く、湿潤時低速剥離強度を測定するときも、湿潤時せん断強度を測定するときも、材料破壊ではなく、界面破壊であった。また、前記共重合体を含んでいても、前記熱可塑性ポリマーにおける前記共重合体の含有率が55質量%未満である場合(比較例1、2、5)は、実施例1~9と比較して、湿潤時せん断強度も、湿潤時低速剥離強度も低く、湿潤時せん断強度を測定するとき、材料破壊ではなく、界面破壊であった。 On the other hand, when the thermoplastic polymer contains other than the above copolymer (Comparative Examples 3, 4, and 7), compared with Examples 1 to 9, the wet shear strength and the wet slow peel strength When measuring the low-speed peel strength when wet and when measuring the shear strength when wet, it was not a material failure but an interface failure. Further, even when the copolymer is contained, when the content of the copolymer in the thermoplastic polymer is less than 55% by mass (Comparative Examples 1, 2, and 5), it is compared with Examples 1 to 9. The wet shear strength and the low wet peel strength were low, and when measuring the wet shear strength, it was not a material failure but an interface failure.
 これらのことから、前記第2ブロックを構成するスチレンの含有量が30質量%未満であって、前記ジブロック体が10質量%以上である共重合体が、55質量%以上含む熱可塑性ポリマーを用いることによって、湿潤状態でのクリープ現象の発生を充分に抑制でき、湿潤状態での接着性に優れることがわかった。 From these facts, a thermoplastic polymer containing 55% by mass or more of a copolymer in which the content of styrene constituting the second block is less than 30% by mass and the diblock body is 10% by mass or more. By using it, it was found that the occurrence of the creep phenomenon in the wet state can be sufficiently suppressed and the adhesiveness in the wet state is excellent.
 ホットメルト接着剤100質量部に対する軟化剤の含有量が15質量部未満の場合(比較例6)は、実施例1~9と比較して、湿潤時せん断強度も、湿潤時低速剥離強度も低く、湿潤時低速剥離強度を測定するときも、湿潤時せん断強度を測定するときも、材料破壊ではなく、界面破壊であった。また、ホットメルト接着剤100質量部に対する軟化剤の含有量が30質量部を超える場合(比較例8)は、実施例1~9と比較して、湿潤時せん断強度も、湿潤時低速剥離強度も低く、湿潤時せん断強度を測定するとき、材料破壊ではなく、界面破壊であった。 When the content of the softening agent relative to 100 parts by mass of the hot-melt adhesive is less than 15 parts by mass (Comparative Example 6), both the shear strength when wet and the low-speed peel strength when wet are low. When measuring the low-speed peel strength when wet and when measuring the shear strength when wet, it was not material failure but interface failure. Further, when the content of the softening agent with respect to 100 parts by mass of the hot melt adhesive exceeds 30 parts by mass (Comparative Example 8), compared with Examples 1 to 9, the wet shear strength is low and the wet low-speed peel strength is However, when measuring the shear strength when wet, it was not material failure but interface failure.
 これらのことから、前記第2ブロックを構成するスチレンの含有量が30質量%未満であって、前記ジブロック体が10質量%以上である共重合体が、55質量%以上含む熱可塑性ポリマーを用い、さらに、軟化剤を15~30質量%含有させることによって、湿潤状態でのクリープ現象の発生を充分に抑制でき、湿潤状態での接着性に優れることがわかった。 From these facts, a thermoplastic polymer containing 55% by mass or more of a copolymer in which the content of styrene constituting the second block is less than 30% by mass and the diblock body is 10% by mass or more. Furthermore, it was found that by containing 15 to 30% by mass of a softening agent, the occurrence of creep phenomenon in a wet state can be sufficiently suppressed, and the adhesiveness in a wet state is excellent.
 以上のことから、共役ジエン系化合物からなる第1ブロックとビニル系芳香族炭化水素からなる第2ブロックとからなり、前記第2ブロックの含有量が30質量%未満であって、前記第1ブロックと前記第2ブロックとのジブロック体の含有量が10質量%以上である共重合体を55質量%以上含む熱可塑性ポリマーを含み、さらに、軟化剤をホットメルト接着剤100質量部に対して15~30質量部を含むホットメルト接着剤であれば、湿潤状態でのクリープ現象の発生を充分に抑制でき、湿潤状態での接着性に優れることがわかった。 From the above, the first block made of a conjugated diene compound and the second block made of vinyl aromatic hydrocarbon, the content of the second block being less than 30% by mass, the first block And a thermoplastic polymer containing 55% by mass or more of a copolymer having a diblock body content of 10% by mass or more with the second block, and further a softener with respect to 100 parts by mass of the hot melt adhesive It has been found that a hot melt adhesive containing 15 to 30 parts by mass can sufficiently suppress the occurrence of creep phenomenon in a wet state and is excellent in adhesiveness in a wet state.
 この出願は、2017年6月12日に出願された日本国特許出願特願2017-114990を基礎とするものであり、その内容は、本願に含まれるものである。 This application is based on Japanese Patent Application No. 2017-114990 filed on June 12, 2017, the contents of which are included in the present application.
 本発明を表現するために、上述において実施形態を通して本発明を適切且つ十分に説明したが、当業者であれば上述の実施形態を変更および/または改良することは容易に為し得ることであると認識すべきである。したがって、当業者が実施する変更形態または改良形態が、請求の範囲に記載された請求項の権利範囲を離脱するレベルのものでない限り、当該変更形態または当該改良形態は、当該請求項の権利範囲に包括されると解釈される。 In order to express the present invention, the present invention has been described above and properly through the embodiments. However, those skilled in the art can easily change and / or improve the above-described embodiments. Should be recognized. Therefore, unless the modifications or improvements implemented by those skilled in the art are at a level that departs from the scope of the claims recited in the claims, the modifications or improvements are not covered by the claims. To be construed as inclusive.
 本発明によれば、湿潤状態でのクリープ現象の発生を充分に抑制でき、湿潤状態での接着性に優れるホットメルト接着剤が提供される。 According to the present invention, there is provided a hot melt adhesive that can sufficiently suppress the occurrence of a creep phenomenon in a wet state and has excellent adhesiveness in a wet state.

Claims (4)

  1.  熱可塑性ポリマーと、粘着付与剤と、軟化剤とを含むホットメルト接着剤であって、
     前記熱可塑性ポリマーは、共役ジエン系化合物からなる第1ブロックとビニル系芳香族炭化水素からなる第2ブロックとからなる共重合体、及び前記共重合体の水素化物の少なくとも一方を含み、
     前記共重合体は、前記第2ブロックの含有量が30質量%未満であって、前記第1ブロックと前記第2ブロックとのジブロック体の含有量が10質量%以上である共重合体であり、
     前記共重合体及び前記共重合体の水素化物の含有量が、前記熱可塑性ポリマー全量に対して、55質量%以上であり、
     前記軟化剤の含有量が、前記ホットメルト接着剤100質量部に対して、15~30質量部であることを特徴とするホットメルト接着剤。
    A hot melt adhesive comprising a thermoplastic polymer, a tackifier, and a softener,
    The thermoplastic polymer includes at least one of a copolymer comprising a first block comprising a conjugated diene compound and a second block comprising a vinyl aromatic hydrocarbon, and a hydride of the copolymer.
    The copolymer is a copolymer in which the content of the second block is less than 30% by mass and the content of the diblock body of the first block and the second block is 10% by mass or more. Yes,
    The copolymer and the hydride content of the copolymer are 55% by mass or more based on the total amount of the thermoplastic polymer,
    The hot-melt adhesive is characterized in that the content of the softening agent is 15 to 30 parts by mass with respect to 100 parts by mass of the hot-melt adhesive.
  2.  前記ビニル系芳香族炭化水素が、スチレンであり、
     前記共役ジエン系化合物が、ブタジエン及びイソプレンの少なくとも一方である請求項1に記載のホットメルト接着剤。
    The vinyl aromatic hydrocarbon is styrene,
    The hot melt adhesive according to claim 1, wherein the conjugated diene compound is at least one of butadiene and isoprene.
  3.  前記粘着付与剤は、カルボン酸及びカルボン酸無水物の少なくとも一方で変性した酸変性粘着付与剤を含む請求項1又は請求項2に記載のホットメルト接着剤。 The hot-melt adhesive according to claim 1 or 2, wherein the tackifier includes an acid-modified tackifier modified with at least one of carboxylic acid and carboxylic anhydride.
  4.  前記軟化剤は、カルボン酸及びカルボン酸無水物の少なくとも一方で変性した酸変性軟化剤を含む請求項1~3のいずれか1項に記載のホットメルト接着剤。 The hot melt adhesive according to any one of claims 1 to 3, wherein the softener includes an acid-modified softener modified with at least one of carboxylic acid and carboxylic anhydride.
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Publication number Priority date Publication date Assignee Title
WO2021039118A1 (en) * 2019-08-29 2021-03-04 株式会社Moresco Hot-melt adhesive composition and hygiene product
JPWO2021039118A1 (en) * 2019-08-29 2021-03-04
CN114341307A (en) * 2019-08-29 2022-04-12 株式会社Moresco Hot melt adhesive composition and sanitary article
JP7271681B2 (en) 2019-08-29 2023-05-11 株式会社Moresco Hot-melt adhesive compositions and sanitary products
CN114341307B (en) * 2019-08-29 2023-10-20 株式会社Moresco Hot melt adhesive composition and sanitary article

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