CN104411796B - Hot-melt adhesive agent composition, and water-absorbable article manufactured using same - Google Patents

Hot-melt adhesive agent composition, and water-absorbable article manufactured using same Download PDF

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Publication number
CN104411796B
CN104411796B CN201480001723.1A CN201480001723A CN104411796B CN 104411796 B CN104411796 B CN 104411796B CN 201480001723 A CN201480001723 A CN 201480001723A CN 104411796 B CN104411796 B CN 104411796B
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hot
styrene
melt adhesive
compositionss
melt
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CN104411796A (en
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岛村和赖
吉田裕贵
村本祯
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Sekisui Fuller Co Ltd
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Sekisui Fuller Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives 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
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/84—Accessories, not otherwise provided for, for absorbent pads
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L13/00—Compositions of rubbers containing carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J113/00—Adhesives based on rubbers containing carboxyl groups

Abstract

A hot-melt adhesive agent composition according to the present invention is characterized by comprising: 100 parts by weight of a thermoplastic block copolymer (A) that comprises at least one component selected from the group consisting of a styrene-isoprene-styrene block copolymer having a styrene component content of 15 to 35 wt%, a styrene-butadiene-styrene block copolymer having a styrene component content of 15 to 35 wt% and a styrene-butadiene/butylene-styrene block copolymer having a styrene component content of 15 to 35 wt%; 0.05 to 10 parts by weight of a liquid rubber (B) having a carboxyl group and/or a carboxylic acid anhydride group in the molecule; and an adhesiveness-imparting resin (C).

Description

Hot-melt adhesive compositionss and use absorbent article obtained from it
Technical field
The present invention relates to a kind of hot-melt adhesive compositionss, more particularly to one kind can be suitably used for manufacturing diaper etc. The hot-melt adhesive compositionss of absorbent article.
Background technology
The assembling of the absorbent article such as diaper or sanitary napkin is carried out as follows: using hot-melt adhesive by polyolefin The adhering components such as resin film, non-woven fabrics, thin paper and natural rubber are together.
As the hot-melt adhesive used in absorbent article, it is used using SBC as main one-tenth Point rubber based hot melt bonding agent and using ene-propylene-butene copolymer or ethylene-vinyl acetate copolymer as main The olefines hot-melt adhesive of composition.Wherein, compared to olefines hot-melt adhesive, the cementability of rubber based hot melt bonding agent, Cohesiveness and creep resistant are excellent, therefore, are widely used.
In the assembling of absorbent article, using rubber based hot melt bonding agent come the porous base such as bonding non-woven fabrics or thin paper In the case of material, the rubber based hot melt bonding agent making heated melting is together with porous substrate pressure viscosity, (viscous using its cohesiveness Make a concerted effort) so that the rubber based hot melt bonding agent of heated melting is bonded together with porous substrate, and make the rubber of heated melting Glue class hot-melt adhesive flows into the pore of porous substrate.Then, to be entered by making rubber based hot melt bonding agent cool and solidify The bonding of row porous substrate.
On the other hand, the porous substrate (thin paper etc.) or real being made up of the natural material such as cellulose material or cotton class material Having applied non-woven fabrics of hydrophilicity-imparting treatment etc. is hydrophilic porous base material.The surface of such hydrophilic porous base material is highly polar, However, the polarity of rubber based hot melt bonding agent is low, therefore, the affinity of hydrophilic porous base material and rubber based hot melt bonding agent Low.Therefore, even if making the rubber based hot melt bonding agent of heating melting and hydrophilic porous base material pressure viscosity, rubber based hot melt bonding agent In the pore being not easy to flow to hydrophilic porous base material, the contact area of rubber based hot melt bonding agent and hydrophilic porous base material Reduce, therefore, reduced by the bonding effect that molecular separating force or anchoring effect produce.In this case, by rubber based hot melt Although the hydrophilic porous base material of bonding agent bonding available adhesive strength being capable of resistance to practicality. in the state of drying, by rubber The hydrophilic porous base material of glue class hot-melt adhesive bonding, in the case of the body fluid moistening such as being urinated and becoming moisture state, can produce The raw significantly reduced problem of adhesive strength.Therefore, for rubber based hot melt bonding agent, in order to being changed into the hydrophilic of moisture state Property porous substrate also can maintain excellent adhesive strength, need to improve moistening cementability.
Therefore, Patent Document 1 discloses a kind of hot-melt adhesive compositionss, it is except containing styrenic block altogether Beyond polymers, also contain the wax with carboxylic acid and/or carboxylic acid anhydride modified.According to carboxylic acid and/or carboxylic acid anhydride modified Hot-melt adhesive compositionss can be given polarity by wax, thus, it is possible to improve hot-melt adhesive compositionss with respect to hydrophilic porous The affinity of base material, can improve the moistening cementability of hot-melt adhesive compositionss.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2007-169531 publication
Content of the invention
Invent technical problem to be solved
Although however, the hot-melt adhesive compositionss of citation 1 are passed through to add above-mentioned wax, the high temperature more than 150 DEG C When melt viscosity low and excellent mobility can be shown, but drastically solidified at a temperature of lower than it, melt viscosity becomes Height, mobility reduces.Therefore, if the heating melt temperature of hot-melt adhesive compositionss reduces or coating hot-melt adhesive when applying After compositionss arrive fit hydrophilic porous base material time (sphere time) elongated, then can lead to solidification significantly carried out and Fit in the hot-melt adhesive compositionss of mobility step-down hydrophilic porous base material, hot-melt adhesive compositionss are difficult close relative of flowing Flowing in the pore of aqueouss porous substrate, the contact area of rubber based hot melt bonding agent and hydrophilic porous base material reduces.Therefore, Even if the hot-melt adhesive compositionss requiring citation 1 also can be hydrophilic to moisture state in the case of carrying out low-temperature coating Property porous substrate play sufficient adhesive strength.
And then, with the wax of carboxylic acid and/or carboxylic acid anhydride modified and contained other compositions in hot-melt adhesive compositionss The compatibility low.Therefore, the heat stability of hot-melt adhesive compositionss is because being reduced using such wax.If heat stability is low Hot-melt adhesive compositionss placed for a long time with heating molten condition, then hot-melt adhesive compositionss variable color or because produce gel Change or carbonization and leading to apply bad.
Therefore, it is an object of the invention to, even if provide a kind of at a lower temperature also can be to the hydrophilic of moisture state Porous substrate shows excellent adhesive strength, and the hot-melt adhesive compositionss of excellent heat stability.
For solving the technical scheme of technical problem
The hot-melt adhesive compositionss of the present invention, comprise thermoplastic block copolymers (a) 100 weight portion, liquid rubber (b) 0.05～10 weight portion and tackifying resin (c),
Described thermoplastic block copolymers (a) contain selected from styrene content content be 15～35 weight % styrene- Isoprene-styrene block copolymer, styrene content content are the s-B-S of 15～35 weight % The content of block copolymer and styrene content is that the styrene-butadiene/butylene-styrene block of 15～35 weight % is common At least one in polymers,
Described liquid rubber (b) has carboxyl and/or acid anhydride in intramolecular.
[thermoplastic block copolymers (a)]
As thermoplastic block copolymers (a), can enumerate: styrene isoprene styrene block copolymer (SIS), benzene Ethylene-butadiene-styrene block copolymer and styrene-butadiene/butylene-styrene block copolymer.By using this A little copolymers, it is possible to provide a kind of hot melt that the hydrophilic porous base material of moisture state can be shown with excellent adhesive strength glues Connect agent compositionss.One kind in addition, thermoplastic block copolymers can be used alone is it is also possible to be applied in combination more than two kinds.
The content of the styrene content in styrene isoprene styrene block copolymer (SIS) is defined in 15～35 weights Amount %, preferably 20～30 weight %.The styrene isoprene styrene block copolymer (SIS) of the too high levels of styrene content The curing rate of the hot-melt adhesive compositionss after being likely to result in heating melting accelerates, and makes the moistening of hot-melt adhesive compositionss Cementability reduces.In addition, the too low styrene isoprene styrene block copolymer (SIS) of the content of styrene content is possible to The cohesiveness leading to hot-melt adhesive compositionss itself reduces, and bonding force is insufficient.
The content of the styrene content in styrene butadiene styrene block copolymer (SBS) is defined in 15～35 weight %, Preferably 20～30 weight %.The styrene butadiene styrene block copolymer (SBS) of the too high levels of styrene content is possible to lead The curing rate causing the hot-melt adhesive compositionss after heating melting accelerates, and makes the moistening cementability fall of hot-melt adhesive compositionss Low.In addition, the too low styrene butadiene styrene block copolymer (SBS) of the content of styrene content is likely to result in hot melt gluing The cohesiveness connecing agent compositionss itself reduces, and bonding force is insufficient.
The content of the styrene content in styrene-butadiene/butylene-styrene block copolymer is defined in 15～35 weights Amount %, preferably 20～30 weight %.The styrene-butadiene of the too high levels of styrene content/butylene-styrene block copolymerization The curing rate that thing is likely to result in heating the hot-melt adhesive compositionss after melting accelerates, and makes the wet of hot-melt adhesive compositionss Profit cementability reduces.In addition, the too low styrene-butadiene of the content of styrene content/butylene-styrene block copolymer has The cohesiveness that hot-melt adhesive compositionss itself may be led to reduces, and bonding force is insufficient.
Styrene content content in thermoplastic block copolymers (a) is with respect to the total amount of thermoplastic block copolymers (a) It is defined in 15～35 weight %, preferably 20～30 weight %.The thermoplastic block copolymers (a) of the too high levels of styrene content The curing rate of the hot-melt adhesive compositionss after being likely to result in heating melting accelerates, and makes the moistening of hot-melt adhesive compositionss Cementability reduces.In addition, the too low thermoplastic block copolymers (a) of the content of styrene content are likely to result in hot-melt adhesive The cohesiveness of compositionss itself reduces, and bonding force is insufficient.
The weight average molecular weight (mw) preferably 50,000～300,000 of styrene isoprene styrene block copolymer (SIS), More preferably 70,000～250,000, particularly preferred 100,000～200,000.The too small styrene of weight average molecular weight (mw)-different Isoprene-styrene block copolymer is likely to result in making the cohesiveness of hot-melt adhesive compositionss itself to reduce, and bonding force is not Fully.In addition, the excessive styrene isoprene styrene block copolymer (SIS) of weight average molecular weight (mw) is likely to result in hot melt The melt viscosity of adhesive composite becomes too high and damages mobility.
The weight average molecular weight (mw) preferably 50,000～300,000 of styrene butadiene styrene block copolymer (SBS), more Preferably 70,000～250,000, particularly preferred 100,000～200,000.Too small styrene-the fourth two of weight average molecular weight (mw) The cohesiveness that alkene-styrene block copolymer is likely to result in hot-melt adhesive compositionss itself reduces, and bonding force is insufficient.Separately Outward, the excessive styrene butadiene styrene block copolymer (SBS) of weight average molecular weight (mw) is likely to result in hot-melt adhesive combination The melt viscosity of thing becomes too high and damages mobility.
The weight average molecular weight (mw) preferably 50,000～300 of styrene-butadiene/butylene-styrene block copolymer, 000, more preferably 70,000～250,000, particularly preferred 100,000～200,000.The too small benzene second of weight average molecular weight (mw) The cohesiveness that alkene-butadiene/butylene-styrene block copolymer is likely to result in hot-melt adhesive compositionss itself reduces, and glues Relay is insufficient.In addition, the excessive styrene-butadiene of weight average molecular weight (mw)/butylene-styrene block copolymer is possible to The melt viscosity leading to hot-melt adhesive compositionss becomes too high and damages mobility.
The weight average molecular weight (mw) preferably 50,000～300,000, more preferably 70,000 of thermoplastic block copolymers (a)～ 250,000, particularly preferred 100,000～200,000.The too small thermoplastic block copolymers (a) of weight average molecular weight (mw) have can The cohesiveness that hot-melt adhesive compositionss itself can be led to reduces, and bonding force is insufficient.In addition, weight average molecular weight (mw) is excessive The melt viscosity that thermoplastic block copolymers (a) are likely to result in hot-melt adhesive compositionss becomes too high and damages mobility.
In addition, in the present invention, so-called styrene isoprene styrene block copolymer (SIS), styrene-butadiene-benzene Ethylene block copolymer, styrene-butadiene/butylene-styrene block copolymer and the weight of thermoplastic block copolymers (a) Average molecular weight, refers to measure device using gel permeation chromatography respectively, by measuring obtained from being converted with polystyrene standard Value.
[liquid rubber (b)]
The hot-melt adhesive compositionss of the present invention contain the liquid rubber (b) in intramolecular with polar group.As pole Property group, can enumerate: carboxyl (- cooh) and acid anhydride (- co-o-co-).Liquid rubber (b) can have carboxyl and carboxylic Any one of anhydride group, it is possible to have both.
In addition, in the present invention, so-called " liquid rubber " refer to 23 DEG C, 1.01 × 105It is in a liquid state under pa (1atm) Rubber.
Liquid rubber (b) makes to being made up of natural materials such as cellulose material or cotton-like material by its polar group Porous substrate (thin paper etc.) or the affinity raising implementing the hydrophilic porous base material such as non-woven fabrics of hydrophilicity-imparting treatment, can make Rubber based hot melt adhesive composite after heating melting easily flows in the pore of hydrophilic porous base material.In addition, hot melt Even if adhesive composite contains liquid rubber (b), after heating melting, melt viscosity is also very low and shows excellent flowing Property, and lentamente solidified with temperature reduction due to it, therefore can significantly inhibit melt viscosity and steeply rise and make mobility Reduce.Therefore, though hot-melt adhesive compositionss during coating heating melt temperature is low, sphere time is elongated, or hot melt glues The temperature connecing agent compositionss becomes relatively low, and hot-melt adhesive compositionss also can maintain excellent mobility, by such heat The hydrophilic porous base material of pressure viscosity in fusible dose of compositionss, hot-melt adhesive compositionss flow to the pore of hydrophilic porous base material Inside, can improve hot-melt adhesive compositionss and the contact area of hydrophilic porous base material.Therefore, the hot melt adhesion of the present invention Agent compositionss can show excellent adhesive strength to hydrophilic porous base material, even and if, becoming in hydrophilic porous base material In the case of moisture state, also can maintain so excellent adhesive strength.
In addition, utilizing liquid rubber (b), the heat stability of hot-melt adhesive compositionss can also be improved.Therefore, make this After the hot-melt adhesive compositionss heating melting of invention, even if long-term in the state of heating melting store in tank, also can be relatively Highland suppression hot-melt adhesive compositionss colour, gelation or carbonization.
As liquid rubber (b), can enumerate: main chain by the homopolymer of alpha-olefin, ethene-alpha-olefin copolymer, ethylene- Propylene copolymer, ethylene-propylene-diene copolymer, the hydride of ethylene-propylene-diene copolymer, ethylene-butene copolymer, Polyisoprene, polybutadiene, polyprene, dicyclopentadiene, styrene-butadiene block copolymer, acrylonitrile-butadiene The hydride of copolymer or acrylonitrile-butadiene copolymer is constituted, and the end in above-mentioned main chain or side chain have polar group Liquid rubber.One kind in addition, liquid rubber (b) can be used alone is it is also possible to be applied in combination more than two kinds.
Wherein, the main chain of liquid rubber (b) is preferably common by polyisoprene, polybutadiene or Styrene-Butadiene block Polymers is constituted, and is more preferably made up of polyisoprene.Such liquid rubber (b) is due to above-mentioned thermoplastic block copolymers A () has the excellent compatibility, therefore, not only can improve the mobility of hot-melt adhesive compositionss after heating melting and heat is steady Qualitative, also can improve moistening cementability.
The number-average molecular weight (mn) preferably 1,000～150,000, more preferably 10,000～100,000 of liquid rubber (b). The cohesiveness that the too small liquid rubber (b) of number-average molecular weight (mn) is likely to result in hot-melt adhesive compositionss reduces, and moistens viscous Connecing property is insufficient.In addition, the excessive liquid rubber (b) of number-average molecular weight (mn) is likely to result in the molten of hot-melt adhesive compositionss Melt-viscosity becomes too high and so that mobility is reduced.
In addition, in the present invention, the number-average molecular weight (mn) of so-called liquid rubber (b) refers to survey using gel permeation chromatography Determine device, by the measured value obtaining with polystyrene standard conversion.
In addition, as the liquid rubber (b) in intramolecular with polar group, it is possible to use commercially available product.For example as tool There is the liquid polyisoprene of carboxyl, can enumerate: the product entitled " kuraprene lir-410 " that kuraray company produces Deng.As the liquid polyisoprene with acid anhydride, can enumerate: the product that kuraray company produces is entitled " kuraprene lir-403 " etc..As the propylene liguid nitrile butadiene copolymer with carboxyl, can enumerate: bf Product entitled " ctbn1300x8 " that goodrich company produces etc..
As the content of liquid rubber (b) in hot-melt adhesive compositionss, with respect to thermoplastic block copolymers (a) 100 Weight portion is defined in 0.05～10 weight portion, preferably 1～10 weight portion, more preferably 3～10 weight portions.The containing of liquid rubber (b) It is low that the too low hot-melt adhesive compositionss of amount are likely to result in moistening cementability.In addition, the heat of the too high levels of liquid rubber (b) It is low that fusible dose of compositions are likely to result in heat stability.
[tackifying resin (c)]
The hot-melt adhesive compositionss of the present invention can also contain tackifying resin (c).As tackifying resin (c), Ke Yiju Go out: natural rosin, modified rosin, hydrogenated rosin, the glyceride of natural rosin, the glyceride of modified rosin, the season of natural rosin Doutrate, the pentaerythritol ester of modified rosin, the pentaerythritol ester of hydrogenated rosin, the copolymer of natural terpenes, natural terpenes 3-dimensional polymer, the hydrogenated derivatives of the copolymer of hydriding terpene, polyterpene resin, the hydrogenation of phenolic modified terpene resin spreads out Biology, aliphatic petroleum hydrocarbon resin, the hydrogenated derivatives of aliphatic petroleum hydrocarbon resin, aromatic base crude oil hydrocarbon resin, aromatic series stone The hydrogenated derivatives of petroleum hydrocarbon resin, annular aliphatic petroleum hydrocarbon resin, the hydrogenated derivatives of annular aliphatic petroleum hydrocarbon resin.Its In, the hydrogenated derivatives of preferred aliphat petroleum hydrocarbon resin.
Preferably 80～120 DEG C of the softening point of tackifying resin (c), more preferably 100～120 DEG C.Using softening point in above-mentioned model Tackifying resin (c) in enclosing, can further improve the moistening cementability of hot-melt adhesive.
In addition, in the present invention, the softening point of tackifying resin (c) is using the value recording according to the method for jisk 6863.
The content of the tackifying resin (c) in hot-melt adhesive compositionss is with respect to thermoplastic block copolymers (a) 100 weight Part preferably 10～500 weight portions, more preferably 40～400 weight portions, most preferably 150～300 weight portions.The containing of tackifying resin (c) It is low that the too low hot-melt adhesive compositionss of amount are likely to result in bonding force.In addition, the hot melt of the too high levels of tackifying resin (c) glues Connect the solidfied material that agent compositionss are possible to become after hardening hard and crisp, lead to the low adhesion of hot-melt adhesive compositionss to drop Low.
The hot-melt adhesive compositionss of the present invention remove thermoplastic block copolymers (a), liquid rubber (b) and tackifying resin Beyond (c), other additives can also be contained.As other additives, can enumerate: plasticizer (d), antioxidant, ultraviolet Light absorbers and filler etc..
[plasticizer (d)]
As plasticizer (d), for example, can enumerate: paraffin generic operation oil, cycloalkanes generic operation oil and aromatic series generic operation oil Deng.Wherein, more preferably paraffin generic operation oil and cycloalkanes generic operation are oily, particularly preferred paraffin generic operation oil.Using these plasticizers, The hot-melt adhesive compositionss that moistening adhesive strength is excellent can be provided.In addition, these plasticizers can be used alone it is also possible to combine Using two or more.
Paraffin generic operation oil contains aliphatic chain hydrocarbon.The carbon atom of contained aliphatic chain hydrocarbon in paraffin generic operation oil Number is not particularly limited, but preferably 16～40, more preferably 20～30.
The number-average molecular weight (mn) preferably 100～1500, more preferably 250～1000 of paraffin generic operation oil.Number-average molecular weight (mn) cohesiveness that too small paraffin generic operation oil is likely to result in hot-melt adhesive compositionss reduces, and moistening cementability does not fill Point.In addition, the excessive paraffin generic operation oil of number-average molecular weight (mn) is likely to result in the melt viscosity of hot-melt adhesive compositionss Too high and make screening characteristics reduce.
As paraffin generic operation oil, it is possible to use commercially available product.As commercially available product, for example, can enumerate: Japanese oils and fatss manufacture Trade name " nasolvent ", go out light emerging produce manufacture trade name " pw-380 ", Chu Guangxingchan company manufacture trade name For " diana fresia s32 ", the trade name " ps-32 " of Chu Guangxingchan company manufacture, go out what light petrochemistry (strain) manufactured Trade name " neothiozole " that trade name " ip-solvent 2835 ", three photochemistry industry manufacture etc..
As long as cycloalkanes generic operation oil comprises aliphatic category cyclic hydrocarbon, it is not particularly limited, institute in cycloalkanes generic operation oil The carbon number of the aliphatic category cyclic hydrocarbon containing is preferably more than 3, more preferably 3～8.
The number-average molecular weight (mn) preferably 100～1500, more preferably 250～1000 of cycloalkanes generic operation oil.Number-average molecular weight (mn) too small cycloalkanes generic operation oil is likely to result in making the cohesiveness of hot-melt adhesive compositionss to reduce, and moistening cementability does not fill Point.In addition, the excessive cycloalkanes generic operation oil of number-average molecular weight (mn) is likely to result in the melt viscosity of hot-melt adhesive compositionss Too high and make screening characteristics reduce.
As cycloalkanes generic operation oil, it is possible to use commercially available product.As commercially available product, for example, can enumerate: Chu Guangxingchan company Trade name " the diana fresia that the trade name " diana fresia n28 " of manufacture, Chu Guangxingchan company manufacture Trade name " diana process oil nr " of u46 " and the manufacture of Chu Guangxingchan company etc..
In addition, in the present invention, the number-average molecular weight (mn) of so-called paraffin generic operation oil and cycloalkanes generic operation oil refers to point Do not measure device using gel permeation chromatography, by the measured value obtaining with polystyrene standard conversion.
As the content of the plasticizer (d) in hot-melt adhesive compositionss, with respect to thermoplastic block copolymers (a) 100 Weight portion preferably 25～250 weight portion, more preferably 50～150 weight portions.The hot-melt adhesive group of the too high levels of plasticizer (d) Compound is likely to result in creep resistant reduction or cohesiveness reduces and so that moistening cementability is reduced.In addition, the containing of plasticizer (d) Measuring the curing rate after too low hot-melt adhesive compositionss are likely to result in heating melting becomes too high and makes cementability, especially It is that moistening cementability reduces.
[antioxidant]
As antioxidant, can enumerate: 2,6- di-tert-butyl-4-methy phenols, n-octadecane base -3- (4'- hydroxyl - 3', 5'- di-tert-butyl-phenyl) propionic ester, 2,2' methylene bis (4- methyl-6-tert-butylphenol), 2,2' methylene bis (4- Ethyl -6- tert-butyl phenol), 2,4- double (pungent butylthiomethyl)-orthoresol, the 2- tert-butyl group -6- (the 3- tert-butyl group -2- hydroxy-5-methyl Base benzyl) -4- aminomethyl phenyl acrylate, 2,4- bis- tertiary pentyl -6- (1- (3,5- bis- tertiary pentyl -2- hydroxy phenyl) ethyl) benzene Base acrylate, 2- [1- (2- hydroxyl -3,5- di-tert-pentyl-phenyl)] acrylate, four (methylene -3- (3,5- di-t-butyl - 4- hydroxy phenyl) propionic ester) hindered phenol anti-oxidants such as methane；Dilauryl thiodipropionate, lauryl stearyl sulfur For sulfur class antioxidants such as dipropionate, tetramethylolmethanes four (3- lauryl thiopropionate)；Three (nonyl phenyl) phosphite ester, Phosphorus antioxidants such as three (2,4- di-tert-butyl-phenyl) phosphite ester etc..Antioxidant can be used alone one kind it is also possible to group Close and use more than two kinds.
[UV absorbent]
As UV absorbent, can enumerate: 2- (2'- hydroxyl -5'- aminomethyl phenyl) benzotriazole, 2- (2'- hydroxyl - 3', 5'- tert-butyl-phenyl) benzo three such as benzotriazole, 2- (2'- hydroxyl -3', 5'- di-tert-butyl-phenyl) -5- chlorobenzotriazole Azole UV absorbent；The benzophenone ultraviolet absorbent such as ESCALOL 567；Salicylic acid esters are purple Ultraviolet absorbers, cyanoacrylate ultraviolet absorbent；Hindered amine light stabilizer.In addition, UV absorbent can be single Solely using a kind of it is also possible to and with more than two kinds.
[filler]
As filler, for example, can enumerate: Muscovitum, Calcium Carbonate, Kaolin, Talcum, titanium oxide, kieselguhr, ureas tree Fat, styrene beads, burn till clay, starch etc..
[absorbent article]
The hot-melt adhesive compositionss of the present invention are used for weaving cotton cloth, non-woven fabrics, thin paper, elastomeric element, polyolefin resin The various parts such as film carry out bonding.As described above, the hot-melt adhesive compositionss of the present invention are to by cellulose material or cotton class The natural materials such as material constitute porous substrate (thin paper etc.) or implement the hydrophilic porous base such as non-woven fabrics of hydrophilicity-imparting treatment Material also can play excellent moistening cementability, thus, it may be preferable to for bonding component parts in the manufacture of absorbent article.
Absorbent article is not particularly limited, and the hot melt with the first component parts, the second component parts and the present invention glues Connect agent compositionss.First component parts are bonded and integrated by available hot-melt adhesive compositionss with the second component parts.And, At least one party in first component parts and the second component parts is preferably hydrophilic porous base material.
As the component parts of the first component parts and the 2nd, as long as the component parts used in absorbent article being Can, for example can enumerate: the elastomeric element such as rubber, weave cotton cloth, non-woven fabrics, paper, polyolefin resin film and hydrophilic porous base material. These component parts can be used alone one kind it is also possible to be applied in combination more than two kinds.In addition, as hydrophilic porous base material, can To enumerate the porous substrate being made up of cellulose or cotton and to implement porous substrate of hydrophilicity-imparting treatment etc..As by cellulose or The porous substrate that cotton is constituted, for example, can enumerate thin paper etc..In addition, as the porous substrate being implemented with hydrophilicity-imparting treatment, permissible Enumerate: be implemented with the non-woven fabrics of hydrophilicity-imparting treatment or weave cotton cloth.
The purpose of absorbent article is, absorb the body fluid such as blood or urine, antiperspirant, pus, gastric juice, saliva, nose secreting mucus with And other liquid.As other liquid, can enumerate, water, beverage and waste liquid etc..As absorbent article, for example, can enumerate: Diaper, sanitary napkin, sanitary towel, incontinence shield, Portable bathroom, portable type pollution treatment bag, animal are urinated with dung Process piece, hospital's robe, operation gown of a doctor, Perserving materials of wound covering material, first-aid dressing and meat or fish etc. etc..Its In, preferably enumerate diaper.
The liquid permeability that opaque liquid tergite that diaper is substantially made up of polyolefin resin film etc., non-woven fabrics etc. are made Top flat and configuration between them absorber constitute.In order to decrease uptake body absorb urine etc. rear tacky, absorber with The absorbent paper such as thin paper use in the state of covering its surface.In addition, absorbent article is using by being elastically provided with rubber The elastomeric elements such as glue carry out abdominal part with wearer and waist is close to and prevent the structure that Excreta spills.In such diaper In manufacture, in order to by hydrophilic porous for thin paper etc. base material be bonded to each other integration, by hydrophilic porous for thin paper etc. base material and nonwoven Other porous substrate such as cloth is bonded and integrated or by hydrophilic porous for thin paper etc. base material and polyolefin resin film or elastomeric element It is bonded and integrated Deng other component parts, preferably use the hot-melt adhesive of the present invention.
As using the present invention hot-melt adhesive compositionss by component parts be bonded to each other integration method, there is no spy Do not limit, it is possible to use known method.For example can make with the following method etc.: by the hot-melt adhesive compositionss after heating melting After being coated on component parts, after another component parts being superimposed on the hot-melt adhesive compositionss of coating, they are pressed Viscous.
Preferably 135～180 DEG C of the heating melt temperature of hot-melt adhesive compositionss.In existing hot-melt adhesive compositionss In, obtain sufficient mobility in order to reduce melt viscosity, generally heating melt temperature is set to more than 150 DEG C.However, having There may be a case when: if the temperature of hot-melt adhesive compositionss decreases below 150 DEG C, hot-melt adhesive compositionss Melt viscosity steeply rise and make mobility reduce, accordingly, it is difficult to coating hot-melt adhesive compositionss, if or coating when hot melt The heating melt temperature step-down of adhesive composite or sphere time are elongated, then the hot-melt adhesive compositionss applying are difficult to flow Move to the pore of the hydrophilic porous base material such as non-woven fabrics or thin paper it is impossible to obtain abundant and hydrophilic porous base material between Moistening cementability.
Even if however, the hot-melt adhesive compositionss of the present invention heating melt temperature be less than 150 DEG C, particularly 135～ Under 145 DEG C of such relatively low temperature, melt viscosity is also low and can easily apply.In addition, the hot-melt adhesive combination with regard to the present invention For thing, situation about drastically solidifying with the reduction of temperature is suppressed, even if excellent mobility also can be maintained under compared with low temperature. Therefore, though coating when hot-melt adhesive compositionss heating melt temperature be less than 150 DEG C, particularly as little as 135～145 DEG C or coating after sphere time elongated, hot-melt adhesive compositionss can also flow in the pore of hydrophilic porous base material Portion, can get hot-melt adhesive compositionss and the sufficient contact area of hydrophilic porous base material, even if the parent to moisture state Aqueouss porous substrate also can maintain excellent adhesive strength.
As the coating method of the hot-melt adhesive compositionss after heating melting, it is not particularly limited, can use known Method.For example can enumerate: slit type coater coating, roll coater coating, the spiral coating being helically coated, wave Be coated shape ω coating and control slit coating, be coated to planar slit spraying and curtain spraying and Point type coating that can be coated to point-like etc..
Invention effect
The hot-melt adhesive compositionss of the present invention lentamente can solidify so that the temperature after heat tracing melting reduces.Cause This, even if the heating melt temperature of hot-melt adhesive compositionss reduces or until the hot melt after coating by adherend laminating Time on adhesive composite is elongated or temperature reduces, and hot-melt adhesive compositionss also can maintain excellent mobility, can hold Change places in the pore of hydrophilic porous base material flowing to pressure viscosity.
In absorbent article using the hot-melt adhesive compositionss of such present invention, though its component parts because Urine or the body fluid such as blood and moisten, the excellent bonding between component parts also can be maintained strong by hot-melt adhesive compositionss Degree.Therefore, when the hot-melt adhesive compositionss by the present invention are used for the absorbent articles such as diaper, urine etc. can be suppressed higher Spill to outside.
Specific embodiment
Below, using embodiment, the present invention is more specifically illustrated, but the present invention is not limited to this.
Embodiment
In embodiment described later and comparative example, thermoplastic block used in the manufacture with regard to hot-melt adhesive compositionss Copolymer (a1)～(a11), liquid rubber (b1)～(b4), wax, tackifying resin (c1)～(c3), plasticizer (d1)～(d2) and Antioxidant, records detailed description respectively below.
Thermoplastic block copolymers (a):
Styrene isoprene styrene block copolymer (SIS) (a1) [non-polar group, styrene content content 16 weight Amount %, weight average molecular weight (mw) 171,000, Japanese zeon company manufacture, ProductName " quintac3433n "]
Styrene isoprene styrene block copolymer (SIS) (a2) [non-polar group, styrene content content 25 weight Amount %, weight average molecular weight (mw) 125,000, Japanese zeon company manufacture, ProductName " quintac3280 "]
Styrene isoprene styrene block copolymer (SIS) (a3) [non-polar group, styrene content content 14 weight Amount %, weight average molecular weight (mw) 125,000, Japanese zeon company manufacture, ProductName " quintac3421 "]
Styrene isoprene styrene block copolymer (SIS) (a4) [non-polar group, styrene content content 48 weight Amount %, weight average molecular weight (mw) 100,000, Japanese zeon company manufacture, ProductName " quintac3390 "]
Styrene butadiene styrene block copolymer (SBS) (a5) [non-polar group, styrene content content 30 weight Amount %, weight average molecular weight (mw) 122,300, chemical company of Asahi Chemical Industry manufacture, ProductName " asaprenet-436 "]
Styrene butadiene styrene block copolymer (SBS) (a6) [non-polar group, styrene content content 35 weight Amount %, weight average molecular weight (mw) 100,000, chemical company of Asahi Chemical Industry manufacture, ProductName " asaprenet-438 "]
Styrene butadiene styrene block copolymer (SBS) (a7) [non-polar group, styrene content content 45 weight Amount %, weight average molecular weight (mw) 70,000, chemical company of Asahi Chemical Industry manufacture, ProductName " asaprenet-439 "]
Styrene-butadiene/butylene-benzene second block copolymer (a8) [non-polar group, styrene-content 30 weight Amount %, weight average molecular weight (mw) 100,000, chemical company of Asahi Chemical Industry manufacture, ProductName " tuftecp1500 "]
Styrene-butadiene/butylene-benzene second block copolymer (a9) [non-polar group, styrene-content 67 weight Amount %, weight average molecular weight (mw) 100,000, chemical company of Asahi Chemical Industry manufacture, ProductName " tuftecp2000 "]
Styrene-ethylene/propylene-styrene block copolymer (a10) [non-polar group, styrene content content 30 Weight %, weight average molecular weight (mw) 55,000, kuraray company manufacture, ProductName " septon2002 "]
Styrene-ethylene/butylene-benzene second block copolymer (a11) [non-polar group, styrene-content 30 weight %, Weight average molecular weight (mw) 200,000, chemical company of Asahi Chemical Industry manufacture, ProductName " tuftech1041 "]
In addition, in table 1 and 2, styrene isoprene styrene block copolymer (SIS) is abbreviated as " sis copolymer ", Styrene butadiene styrene block copolymer (SBS) is abbreviated as " sbs copolymer ", by styrene-butadiene/butylene-styrene Block copolymer is abbreviated as " sbbs copolymer ", styrene-ethylene/propylene-styrene block copolymer is abbreviated as " seps is common Polymers ", styrene-ethylene/butylene-styrene block copolymer is abbreviated as " sebs copolymer ".
Liquid rubber (b):
[main chain is made up of polyisoprene and the end in main chain or side to have the liquid polyisoprene (b1) of carboxyl Chain has a liquid rubber of carboxyl: number-average molecular weight (mn) 30,000,23 DEG C, 1.01 × 105It is liquid under pa (1atm), melt Less than 0 DEG C of point, kuraray company manufacture, ProductName " kuraprene lir-410 "]
[main chain is made up of polyisoprene and the end in main chain to have the liquid polyisoprene (b2) of acid anhydride Or side chain has a liquid rubber of acid anhydride: number-average molecular weight (mn) 34,000,23 DEG C, 1.01 × 105Under pa (1atm) For below liquid, 0 DEG C of fusing point, kuraray company manufacture, ProductName " kuraprene lir-403 "]
[main chain is made up of polybutadiene and the end in main chain or side to have the liquid polybutadiene (b3) of acid anhydride Chain has a liquid rubber of acid anhydride: 31,000,23 DEG C of number-average molecular weight (mn), 1.01 × 105It is liquid under pa (1atm) Below state, 0 DEG C of fusing point, clay valley company manufacture, ProductName " ricon130ma20 "]
Liquid polyisoprene (b4) [non-polar group: number-average molecular weight (mn) 54,000,23 DEG C, 1.01 × 105It is that liquid, 0 DEG C of fusing point be following, the manufacture of kuraray company under pa (1atm), ProductName " kuraprene lir-50 "]
Wax:
Have acid anhydride polyethylene (pe) wax [number-average molecular weight (mn) 1,400,23 DEG C, 1.01 × 105pa (1atm) it is solid, 104 DEG C of fusing point, the manufacture of innospec company under, ProductName " viscowax261 "]
Tackifying resin (c):
[100 DEG C of softening point, waste river chemistry manufacture the hydrogenated derivatives (c1) of aliphatic petroleum hydrocarbon resin, ProductName “arkon m-100”]
[80 DEG C of softening point, general company manufacture the hydrogenated derivatives (c2) of aliphatic petroleum hydrocarbon resin, ProductName “e5380”]
Aliphatic petroleum hydrocarbon resin hydrogenated derivatives (c3) [120 DEG C of softening point, go out light emerging produce manufacture, ProductName " i- marv p120”]
Plasticizer (d):
(number-average molecular weight (mn) 980, Chu Guang oil company manufacture paraffin generic operation oil (d1), ProductName " diana The oily pw-90 of process oil operation ")
(number-average molecular weight (mn) 100～1500, shell chemical company manufacture cycloalkanes generic operation oil (d2), ProductName “shell flex 371n”)
[antioxidant]
Phenol antioxidant (basf company manufactures, ProductName " irganox1010 ")
(embodiment 1～14 and comparative example 1～9)
By above-mentioned thermoplastic block copolymers (a1)～(a11), liquid rubber (b1)～(b4), wax, tackifying resin (c1) ～(c3), plasticizer (d1)～(d2) and antioxidant are put into heater with the use level shown in table 1 and 2 respectively After in stirring kneading machine, heating one hour at 150 DEG C, while mixing, manufactures hot-melt adhesive compositionss.
(evaluation)
According to following shown main points, the hot-melt adhesive compositionss evaluation making in embodiment and comparative example is moistened viscous Connect intensity and heat stability.
These results are shown in table 1 and 2.
(moistening adhesive strength: thin paper-thin paper)
By by hot-melt adhesive compositionss be heated to 140 DEG C so that it is melted after, by spiral spray with 3g/m2Coating Amount is coated on thin paper, and (paper weighs 18～21g/m2, 70～90 μm of thickness) one side, coating latter 1 second after, being coated with to this thin paper Face lamination other thin paper of hot-melt adhesive compositionss.Then, by they at 23 DEG C with 50gf/cm2Pressure pressurization pressure viscosity 0.01 second, thus obtain duplexer.This duplexer is cut off, thus obtains the test film of the strip of wide 20mm × long 150mm.
Then, test film is taken care of 24 hours under 23 DEG C, relative humidity 50% atmosphere, in 23 DEG C of water, impregnate 1 point Clock.Then, test film is taken out from water, wipe water, thus obtain the test film of moisture state.And, according to jis K6854, divides the test film to moisture state to carry out t mould disbonded test to pull speed 100mm/, measures adhesive strength (× 10- 2n/20mm).The adhesive strength obtaining is shown in " moistening adhesive strength " hurdle of table 1～2.
(heat stability 1)
For by hot-melt adhesive compositionss be heated to 140 DEG C so that it is melted after and heat run before hot melt adhesion The coloring degree of agent compositionss, the color test method according to the chemical productss of defined in jis k0071 measures gardner color Value.Then, hot-melt adhesive compositionss 20g are put into vial, do not add a cover on vial but be directly placed into 190 DEG C of heat In wind drying machine, after placing 72 hours, with regard to the coloring degree of hot-melt adhesive compositionss, according to defined in jis k0071 Chemical productss color test method measure Gardner color value.By the differential of the Gardner color value before and after 190 DEG C of heating in Table 1 and 2.
(heat stability 2)
Hot-melt adhesive compositionss are heated to 140 DEG C makes it melt, and this hot-melt adhesive compositions 50g is put into glass Glass bottle, does not add a cover on vial but is directly placed in 190 DEG C of air drier, after placing 1 week, visually confirms heating examination Hot-melt adhesive compositionss after testing, are confirmed whether to produce gelation and carbonization.In table 1 and 2, " good " is " bad " as follows respectively Described.
" good ": do not produce gelation and carbonization.
" bad ": produce gelation or carbonization.
(association request cross-referenced)
The Japanese patent application that the application was filed an application based on July 5th, 2013 No. 2013-142181 and 2013 7 The moon Japanese patent application the 2013-158480th filed an application for 31st and CLAIM OF PRIORITY, the disclosure of which passes through It is introduced in this specification with reference to their full content.
Industrial applicibility
The hot-melt adhesive compositionss of the present invention are preferably used for absorbent article, and described absorbent article is preferably used for Absorb the body fluid such as blood or urine, antiperspirant, pus, gastric juice, saliva, nose secreting mucus.

Claims (3)

1. a kind of hot-melt adhesive compositionss, it comprises: thermoplastic block copolymers (a) 100 weight portion, liquid rubber (b) 0.05～10 weight portion and tackifying resin (c),
Styrene-isoamyl that it is 15～35 weight % selected from styrene content content that described thermoplastic block copolymers (a) are contained Styrene block copolymer, styrene content content are the s-B-S block of 15～35 weight % Copolymer and styrene-butadiene/butylene-styrene block copolymer that styrene content content is 15～35 weight % In at least one,
Described liquid rubber (b) has carboxyl and/or acid anhydride in intramolecular, and main chain is polyisoprene.
2. hot-melt adhesive compositionss according to claim 1, wherein, the softening point of tackifying resin (c) is 80～120 ℃.
3. a kind of absorbent article, its usage right require 1 described in adhesive composite and obtain.
CN201480001723.1A 2013-07-05 2014-07-04 Hot-melt adhesive agent composition, and water-absorbable article manufactured using same Active CN104411796B (en)

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