CN106753092B - Hot-melt adhesive composition and water-absorbing article obtained using same - Google Patents

Hot-melt adhesive composition and water-absorbing article obtained using same Download PDF

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Publication number
CN106753092B
CN106753092B CN201611128003.9A CN201611128003A CN106753092B CN 106753092 B CN106753092 B CN 106753092B CN 201611128003 A CN201611128003 A CN 201611128003A CN 106753092 B CN106753092 B CN 106753092B
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styrene
melt adhesive
adhesive composition
hot melt
block copolymer
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CN106753092A (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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Biomedical Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Epidemiology (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Vascular Medicine (AREA)
  • Polymers & Plastics (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Absorbent Articles And Supports Therefor (AREA)

Abstract

The present invention provides a hot melt adhesive composition comprising 100 parts by weight of at least one thermoplastic block copolymer (A) selected from the group consisting of a styrene-isoprene-styrene block copolymer having a styrene component content of 15 to 35% by weight, a styrene-butadiene-styrene block copolymer having a styrene component content of 15 to 35% by weight, and a styrene-butadiene/butylene-styrene block copolymer having a styrene component content of 15 to 35% by weight, 0.05 to 10 parts by weight of a liquid rubber (B) having a carboxyl group and/or a carboxylic anhydride group in the molecule, and a tackifier resin (C).

Description

Hot-melt adhesive composition and water-absorbing article obtained using same
The present application is a divisional application of a patent application having a chinese application No. 201480001723.1 and having an invention name of "hot melt adhesive composition and water-absorbent article obtained using the same" and an application date of 2014, 07, 04.
Technical Field
The present invention relates to a hot melt adhesive composition, and more particularly to a hot melt adhesive composition suitably used for producing water-absorbent articles such as disposable diapers.
Background
The assembly of water-absorbent articles such as disposable diapers and sanitary napkins is carried out as follows: polyolefin resin films, nonwoven fabrics, tissue paper, natural rubber, and the like are bonded together with a hot melt adhesive.
As the hot melt adhesive used for the water-absorbent article, a rubber hot melt adhesive containing a styrene block copolymer as a main component and an olefin hot melt adhesive containing an ethylene-propylene-butene copolymer or an ethylene-vinyl acetate copolymer as a main component are used. Among them, rubber hot melt adhesives are widely used because they are superior in adhesiveness, cohesive force and creep resistance to olefin hot melt adhesives.
In assembling the water-absorbent article, when a porous base material such as a nonwoven fabric or a tissue is bonded with a rubber-based hot-melt adhesive, the rubber-based hot-melt adhesive melted by heating and the porous base material are pressed together, the rubber-based hot-melt adhesive melted by heating and the porous base material are bonded together by the cohesive force (adhesive force) of the rubber-based hot-melt adhesive, and the rubber-based hot-melt adhesive melted by heating flows into the pores of the porous base material. Then, the porous base material is bonded by cooling and solidifying the rubber-based hot-melt adhesive.
On the other hand, a porous substrate (such as tissue paper) made of a natural material such as a cellulose material or a cotton material, or a nonwoven fabric subjected to hydrophilization treatment is a hydrophilic porous substrate. The surface of such a hydrophilic porous substrate has high polarity, but the affinity between the hydrophilic porous substrate and the rubber hot-melt adhesive is low because the polarity of the rubber hot-melt adhesive is low. Therefore, even if the rubber hot-melt adhesive melted by heating is pressure-bonded to the hydrophilic porous substrate, the rubber hot-melt adhesive does not easily flow into the pores of the hydrophilic porous substrate, and the contact area between the rubber hot-melt adhesive and the hydrophilic porous substrate is reduced, and therefore, the adhesive action by the intermolecular force or the anchor effect is reduced. In such a case, although the hydrophilic porous substrate bonded with the rubber-based hot-melt adhesive can obtain a practically durable adhesive strength in a dry state, the hydrophilic porous substrate bonded with the rubber-based hot-melt adhesive has a problem that the adhesive strength is significantly reduced when the hydrophilic porous substrate is wet with a liquid such as urine and becomes a wet state. Therefore, in the rubber hot melt adhesive, in order to maintain excellent adhesive strength even to a hydrophilic porous substrate which is in a wet state, it is necessary to improve wet adhesiveness.
Accordingly, patent document 1 discloses a hot melt adhesive composition containing a wax modified with a carboxylic acid and/or a carboxylic acid anhydride in addition to a styrene-based block copolymer. The wax modified with a carboxylic acid and/or a carboxylic acid anhydride can impart polarity to the hot melt adhesive composition, thereby improving the affinity of the hot melt adhesive composition for the hydrophilic porous substrate and improving the wet adhesiveness of the hot melt adhesive composition.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2007 and 169531
Disclosure of Invention
Technical problem to be solved by the invention
However, the hot melt adhesive composition of cited document 1 has a low melt viscosity and can exhibit excellent fluidity at a high temperature of 150 ℃ or higher by adding the wax, but rapidly solidifies at a temperature lower than the low temperature, and thus has a high melt viscosity and a low fluidity. Therefore, if the heating melting temperature of the hot-melt adhesive composition during application is lowered or the time (open time) until the hydrophilic porous substrate is bonded after application of the hot-melt adhesive composition is increased, the hydrophilic porous substrate is bonded to the hot-melt adhesive composition whose curing has progressed significantly and whose fluidity is lowered, and the hot-melt adhesive composition is less likely to flow into the pores of the hydrophilic porous substrate, and the contact area between the rubber-based hot-melt adhesive and the hydrophilic porous substrate is reduced. Therefore, the hot melt adhesive composition of cited document 1 is required to exhibit sufficient adhesive strength to a hydrophilic porous substrate in a wet state even when applied at a low temperature.
Furthermore, the wax modified with a carboxylic acid and/or a carboxylic acid anhydride has low compatibility with other components contained in the hot melt adhesive composition. Therefore, the thermal stability of the hot melt adhesive composition is lowered by using such wax. When a hot melt adhesive composition having low thermal stability is left in a heated and molten state for a long time, the hot melt adhesive composition is discolored, or gelation or carbonization occurs, resulting in poor coating.
Accordingly, an object of the present invention is to provide a hot melt adhesive composition which exhibits excellent adhesive strength to a hydrophilic porous substrate in a wet state even at a relatively low temperature and is excellent in thermal stability.
Technical solution for solving technical problem
The hot melt adhesive composition of the present invention comprises 100 parts by weight of a thermoplastic block copolymer (A), 0.05 to 10 parts by weight of a liquid rubber (B), and a tackifying resin (C),
the thermoplastic block copolymer (A) contains at least one selected from 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%,
the liquid rubber (B) has a carboxyl group and/or a carboxylic anhydride group in the molecule.
[ thermoplastic Block copolymer (A) ]
Examples of the thermoplastic block copolymer (a) include: styrene-isoprene-styrene block copolymers, styrene-butadiene-styrene block copolymers, and styrene-butadiene/butylene-styrene block copolymers. By using these copolymers, a hot melt adhesive composition which can exhibit excellent adhesive strength to a hydrophilic porous substrate in a wet state can be provided. The thermoplastic block copolymer may be used alone or in combination of two or more.
The content of the styrene component in the styrene-isoprene-styrene block copolymer is limited to 15 to 35 wt%, preferably 20 to 30 wt%. A styrene-isoprene-styrene block copolymer having an excessively high styrene content may increase the curing rate of the hot melt adhesive composition after heating and melting, and may reduce the wet adhesiveness of the hot melt adhesive composition. In addition, a styrene-isoprene-styrene block copolymer having an excessively low styrene content may cause a decrease in cohesive force of the hot melt adhesive composition itself and insufficient adhesive force.
The content of the styrene component in the styrene-butadiene-styrene block copolymer is limited to 15 to 35% by weight, preferably 20 to 30% by weight. A styrene-butadiene-styrene block copolymer having an excessively high styrene content may increase the curing rate of the hot melt adhesive composition after heating and melting, and may reduce the wet adhesiveness of the hot melt adhesive composition. In addition, a styrene-butadiene-styrene block copolymer having an excessively low styrene content may cause a decrease in cohesive force of the hot melt adhesive composition itself, resulting in insufficient adhesive force.
The content of the styrene component in the styrene-butadiene/butylene-styrene block copolymer is limited to 15 to 35% by weight, preferably 20 to 30% by weight. A styrene-butadiene/butylene-styrene block copolymer having an excessively high styrene content may increase the curing rate of the hot melt adhesive composition after heating and melting, and may reduce the wet adhesiveness of the hot melt adhesive composition. In addition, a styrene-butadiene/butylene-styrene block copolymer having an excessively low styrene content may cause a decrease in cohesive force of the hot melt adhesive composition itself, resulting in insufficient adhesive force.
The styrene content of the thermoplastic block copolymer (A) is limited to 15 to 35 wt%, preferably 20 to 30 wt%, based on the total amount of the thermoplastic block copolymer (A). The thermoplastic block copolymer (a) having an excessively high styrene content may increase the curing rate of the hot melt adhesive composition after heating and melting, and may reduce the wet adhesiveness of the hot melt adhesive composition. In addition, the thermoplastic block copolymer (a) having an excessively low styrene content may reduce cohesive force of the hot melt adhesive composition itself and may result in insufficient adhesive strength.
The weight average molecular weight (Mw) of the styrene-isoprene-styrene block copolymer is preferably 50,000 to 300,000, more preferably 70,000 to 250,000, and particularly preferably 100,000 to 200,000. When the weight average molecular weight (Mw) of the styrene-isoprene-styrene block copolymer is too small, the cohesive force of the hot melt adhesive composition itself may be reduced, and the adhesive strength may be insufficient. In addition, a styrene-isoprene-styrene block copolymer having an excessively large weight average molecular weight (Mw) may cause an excessively high melt viscosity of the hot melt adhesive composition and impair flowability.
The weight average molecular weight (Mw) of the styrene-butadiene-styrene block copolymer is preferably 50,000 to 300,000, more preferably 70,000 to 250,000, and particularly preferably 100,000 to 200,000. A styrene-butadiene-styrene block copolymer having an excessively small weight average molecular weight (Mw) may reduce cohesive force of the hot melt adhesive composition itself, resulting in insufficient adhesive force. In addition, a styrene-butadiene-styrene block copolymer having an excessively large weight average molecular weight (Mw) may cause an excessively high melt viscosity of the hot melt adhesive composition and impair flowability.
The weight average molecular weight (Mw) of the styrene-butadiene/butylene-styrene block copolymer is preferably 50,000 to 300,000, more preferably 70,000 to 250,000, and particularly preferably 100,000 to 200,000. A styrene-butadiene/butylene-styrene block copolymer having an excessively small weight average molecular weight (Mw) may cause a decrease in cohesive force of the hot melt adhesive composition itself, resulting in insufficient adhesive force. In addition, a styrene-butadiene/butylene-styrene block copolymer having an excessively large weight average molecular weight (Mw) may cause an excessively high melt viscosity of the hot melt adhesive composition and impair flowability.
The weight average molecular weight (Mw) of the thermoplastic block copolymer (A) is preferably 50,000 to 300,000, more preferably 70,000 to 250,000, and particularly preferably 100,000 to 200,000. The thermoplastic block copolymer (a) having an excessively small weight average molecular weight (Mw) may reduce cohesive force of the hot melt adhesive composition itself, resulting in insufficient adhesive force. In addition, the thermoplastic block copolymer (a) having an excessively large weight average molecular weight (Mw) may cause an excessively high melt viscosity of the hot melt adhesive composition and impair flowability.
In the present invention, the weight average molecular weights of the styrene-isoprene-styrene block copolymer, the styrene-butadiene/butylene-styrene block copolymer, and the thermoplastic block copolymer (a) are measured in terms of standard polystyrene using a gel permeation chromatography measuring apparatus.
[ liquid rubber (B) ]
The hot melt adhesive composition of the present invention contains a liquid rubber (B) having a polar group in the molecule. Examples of the polar group include: carboxyl (-COOH), and carboxylic anhydride (-CO-O-CO-). The liquid rubber (B) may have either one of a carboxyl group and a carboxylic anhydride group, or both of them.
In the present invention, the term "liquid rubber" means rubber that is 1.01X 10 at 23 ℃ C5A rubber which is liquid under Pa (1 atm).
The liquid rubber (B) can improve the affinity of the polar group for a porous base material (such as tissue paper) made of a natural material such as a cellulose-based material or a cotton-based material, or a hydrophilic porous base material such as a nonwoven fabric subjected to a hydrophilization treatment, and can facilitate the flow of the rubber-based hot-melt adhesive composition after being heated and melted into the pores of the hydrophilic porous base material. Further, even if the hot melt adhesive composition contains the liquid rubber (B), the hot melt adhesive composition has a low melt viscosity after heating and melting and exhibits excellent fluidity, and since it is gradually solidified with a decrease in temperature, a sharp increase in melt viscosity and a decrease in fluidity can be significantly suppressed. Therefore, even if the hot melt adhesive composition is applied at a low temperature and has a long exposure time or the temperature of the hot melt adhesive composition is low, the hot melt adhesive composition can maintain excellent fluidity, and by pressing and bonding a hydrophilic porous base material to such a hot melt adhesive composition, the hot melt adhesive composition flows into the pores of the hydrophilic porous base material, and the contact area between the hot melt adhesive composition and the hydrophilic porous base material can be increased. Therefore, the hot melt adhesive composition of the present invention can exhibit excellent adhesive strength to the hydrophilic porous substrate, and can maintain such excellent adhesive strength even when the hydrophilic porous substrate is in a wet state.
Further, the liquid rubber (B) can improve the thermal stability of the hot melt adhesive composition. Therefore, even if the hot melt adhesive composition of the present invention is stored in a tank in a heated and melted state for a long period of time after being heated and melted, the hot melt adhesive composition can be highly inhibited from being colored, gelled, or carbonized.
Examples of the liquid rubber (B) include: a liquid rubber in which a main chain is composed of a homopolymer of α -olefin, an ethylene- α -olefin copolymer, an ethylene-propylene-diene copolymer, a hydrogenated product of an ethylene-propylene-diene copolymer, an ethylene-butene copolymer, polyisoprene, polybutadiene, polypentadiene, polycyclopentadiene, a styrene-butadiene block copolymer, an acrylonitrile-butadiene copolymer, or a hydrogenated product of an acrylonitrile-butadiene copolymer, and which has a polar group at a terminal or a side chain of the main chain. The liquid rubber (B) may be used alone or in combination of two or more.
Among them, the main chain of the liquid rubber (B) is preferably composed of polyisoprene, polybutadiene, or a styrene-butadiene block copolymer, and more preferably composed of polyisoprene. Since such a liquid rubber (B) has excellent compatibility with the thermoplastic block copolymer (a), it is possible to improve not only the fluidity and thermal stability of the hot-melt adhesive composition after heating and melting, but also the wet adhesiveness.
The number average molecular weight (Mn) of the liquid rubber (B) is preferably 1,000 to 150,000, more preferably 10,000 to 100,000. The liquid rubber (B) having an excessively small number average molecular weight (Mn) may reduce cohesive force of the hot melt adhesive composition, and may have insufficient wet adhesiveness. In addition, the liquid rubber (B) having an excessively large number average molecular weight (Mn) may cause an excessively high melt viscosity of the hot melt adhesive composition and a decrease in fluidity.
In the present invention, the number average molecular weight (Mn) of the liquid rubber (B) is a value obtained by conversion to standard polystyrene using a gel permeation chromatography measuring apparatus.
As the liquid rubber (B) having a polar group in the molecule, commercially available products can be used. Examples of the liquid polyisoprene having a carboxyl group include: the product name of Kuraray is "Kurarene LIR-410" and the like. Examples of the liquid polyisoprene having a carboxylic anhydride group include: the product name of Kuraray is "Kurarene LIR-403" and the like. Examples of the liquid acrylonitrile butadiene copolymer having a carboxyl group include: products manufactured by BF Goodrich company are named "CTBN 1300X 8" and the like.
The content of the liquid rubber (B) in the hot melt adhesive composition is limited to 0.05 to 10 parts by weight, preferably 1 to 10 parts by weight, and more preferably 3 to 10 parts by weight, based on 100 parts by weight of the thermoplastic block copolymer (A). The hot-melt adhesive composition having an excessively low content of the liquid rubber (B) may have low wet adhesion. In addition, the hot melt adhesive composition containing an excessively high content of the liquid rubber (B) may have low thermal stability.
[ tackifying resin (C) ]
The hot melt adhesive composition of the present invention may further contain a tackifier resin (C). Examples of the tackifier resin (C) include: natural rosin, modified rosin, hydrogenated rosin, glycerol ester of natural rosin, glycerol ester of modified rosin, pentaerythritol ester of natural rosin, pentaerythritol ester of modified rosin, pentaerythritol ester of hydrogenated rosin, copolymer of natural terpene, 3-dimensional polymer of natural terpene, hydrogenated derivative of copolymer of hydrogenated terpene, polyterpene resin, hydrogenated derivative of phenolic modified terpene resin, aliphatic petroleum hydrocarbon resin, hydrogenated derivative of aliphatic petroleum hydrocarbon resin, aromatic petroleum hydrocarbon resin, hydrogenated derivative of aromatic petroleum hydrocarbon resin, cycloaliphatic petroleum hydrocarbon resin, hydrogenated derivative of cycloaliphatic petroleum hydrocarbon resin. Among them, hydrogenated derivatives of aliphatic petroleum hydrocarbon resins are preferred.
The softening point of the tackifier resin (C) is preferably 80 to 120 ℃, more preferably 100 to 120 ℃. The wet adhesiveness of the hot melt adhesive can be further improved by the tackifier resin (C) having a softening point within the above range.
In the present invention, the softening point of the tackifier resin (C) is a value measured by the method of JISK 6863.
The content of the tackifier resin (C) in the hot melt adhesive composition is preferably 10 to 500 parts by weight, more preferably 40 to 400 parts by weight, most preferably 150 to 300 parts by weight, based on 100 parts by weight of the thermoplastic block copolymer (A). A hot melt adhesive composition having an excessively low content of the tackifier resin (C) may have a low adhesive strength. In addition, a hot melt adhesive composition having an excessively high content of the tackifier resin (C) may become a hard and brittle cured product after curing, resulting in a decrease in low-temperature adhesiveness of the hot melt adhesive composition.
The hot melt adhesive composition of the present invention may contain other additives in addition to the thermoplastic block copolymer (a), the liquid rubber (B) and the tackifier resin (C). Other additives include: a plasticizer (D), an antioxidant, an ultraviolet absorber, a filler, and the like.
[ plasticizer (D) ]
Examples of the plasticizer (D) include: paraffinic process oils, naphthenic process oils, and aromatic process oils. Among these, paraffinic process oils and naphthenic process oils are more preferable, and paraffinic process oils are particularly preferable. These plasticizers provide a hot-melt adhesive composition having excellent wet adhesive strength. These plasticizers may be used alone, or 2 or more of them may be used in combination.
The paraffin process oil contains aliphatic chain hydrocarbons. The number of carbon atoms of the aliphatic chain hydrocarbon contained in the paraffin process oil is not particularly limited, but is preferably 16 to 40, more preferably 20 to 30.
The number average molecular weight (Mn) of the paraffin process oil is preferably 100 to 1500, more preferably 250 to 1000. Paraffin-based process oil having an excessively small number average molecular weight (Mn) may reduce cohesive force of the hot melt adhesive composition, resulting in insufficient wet adhesion. In addition, paraffin-based process oil having an excessively large number average molecular weight (Mn) may cause an excessively high melt viscosity of the hot melt adhesive composition, and may reduce coatability.
As the paraffin process oil, commercially available products can be used. Examples of commercially available products include: the trade name of "NASolvent" manufactured by Nippon fat and oil, the trade name of "PW-380" manufactured by Shixinghua, the trade name of "Diana Freesia S32" manufactured by Shixinghua, the trade name of "PS-32" manufactured by Shixinghua, the trade name of "IP-Solvent 2835" manufactured by Shixingdi, and the trade name of "Neothiozole" manufactured by Sanko chemical industries, etc.
The naphthenic process oil is not particularly limited as long as it contains aliphatic cyclic hydrocarbons, and the aliphatic cyclic hydrocarbons contained in the naphthenic process oil preferably have 3 or more carbon atoms, and more preferably 3 to 8 carbon atoms.
The number average molecular weight (Mn) of the naphthenic process oil is preferably 100 to 1500, more preferably 250 to 1000. The naphthenic process oil having an excessively small number average molecular weight (Mn) may reduce cohesive force of the hot-melt adhesive composition and may cause insufficient wet adhesion. In addition, the naphthenic process oil having an excessively large number average molecular weight (Mn) may cause an excessively high melt viscosity of the hot melt adhesive composition, and may reduce coatability.
As the naphthenic process oil, commercially available products can be used. Examples of commercially available products include: the trade name "Diana Freesia N28" manufactured by Daghington, the trade name "Diana Freesia U46" manufactured by Daghington, and the trade name "Diana Process Oil NR" manufactured by Daghington.
In the present invention, the number average molecular weights (Mn) of the paraffinic process oil and the naphthenic process oil are measured in terms of standard polystyrene using a gel permeation chromatography measuring apparatus.
The content of the plasticizer (D) in the hot melt adhesive composition is preferably 25 to 250 parts by weight, more preferably 50 to 150 parts by weight, based on 100 parts by weight of the thermoplastic block copolymer (a). When the content of the plasticizer (D) is too high, the hot melt adhesive composition may have reduced creep resistance or reduced cohesive force to lower wet adhesion. In addition, a hot melt adhesive composition having an excessively low content of the plasticizer (D) may have an excessively high curing rate after heating and melting, and may have reduced adhesiveness, particularly wet adhesiveness.
[ antioxidant ]
Examples of the antioxidant include: 2, 6-di-tert-butyl-4-methylphenol, n-octadecyl-3- (4' -hydroxy-3 ',5' -di-tert-butylphenyl) propionate, 2' -methylenebis (4-methyl-6-tert-butylphenol), 2' -methylenebis (4-ethyl-6-tert-butylphenol), 2, 4-bis (octylthiomethyl) -o-cresol, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, 2, 4-di-tert-pentyl-6- [1- (3, 5-di-tert-pentyl-2-hydroxyphenyl) ethyl ] phenylacrylate, methyl-p-butyl-2-hydroxy-methyl-phenyl-methacrylate, methyl-ethyl-2, 4-di-tert-pentyl-6- [1- (3,5-, Hindered phenol antioxidants such as 2- [1- (2-hydroxy-3, 5-di-t-pentylphenyl) ] acrylate and tetrakis [ methylene-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] methane; sulfur antioxidants such as dilaurylthiodipropionate, laurylstearylthiodipropionate and pentaerythritol tetrakis (3-laurylthiopropionate); phosphorus antioxidants such as tris (nonylphenyl) phosphite and tris (2, 4-di-t-butylphenyl) phosphite. The antioxidant may be used singly or in combination of two or more.
[ ultraviolet absorbers ]
Examples of the ultraviolet absorber include: benzotriazole ultraviolet absorbers such as 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, 2- (2 '-hydroxy-3', 5 '-tert-butylphenyl) benzotriazole, and 2- (2' -hydroxy-3 ',5' -di-tert-butylphenyl) -5-chlorobenzotriazole; benzophenone ultraviolet absorbers such as 2-hydroxy-4-methoxybenzophenone; salicylate ultraviolet absorbers, cyanoacrylate ultraviolet absorbers; hindered amine light stabilizers. One kind of the ultraviolet absorber may be used alone, or two or more kinds may be used in combination.
[ Filler ]
Examples of the filler include: mica, calcium carbonate, kaolin, talc, titanium oxide, diatomaceous earth, urea resin, styrene beads, calcined clay, starch, and the like.
[ Water-absorbent article ]
The hot melt adhesive composition of the present invention is used for bonding various members such as woven fabrics, nonwoven fabrics, tissue papers, elastic members, polyolefin resin films, and the like. As described above, the hot melt adhesive composition of the present invention can exhibit excellent wet adhesiveness to a porous substrate (such as tissue) made of a natural material such as a cellulose-based material or a cotton-based material, or a hydrophilic porous substrate such as a hydrophilized nonwoven fabric, and therefore can be preferably used for adhering constituent members in the production of a water-absorbent article.
The water-absorbent article is not particularly limited, and includes a first component, a second component, and the hot-melt adhesive composition of the present invention. The first component and the second component can be bonded and integrated by a hot-melt adhesive composition. At least one of the first component and the second component is preferably a hydrophilic porous substrate.
The first component and the component 2 may be any components used in the water-absorbent article, and examples thereof include: elastic members such as rubber, woven fabrics, nonwoven fabrics, paper, polyolefin resin films, and hydrophilic porous substrates. These constituent members may be used alone or in combination of two or more. Examples of the hydrophilic porous substrate include a porous substrate made of cellulose or cotton, a porous substrate subjected to hydrophilization treatment, and the like. Examples of the porous substrate made of cellulose or cotton include tissue paper. Examples of the porous substrate subjected to hydrophilization treatment include: a nonwoven fabric or woven fabric subjected to hydrophilization treatment.
The water-absorbent article is intended to absorb blood, body fluids such as urine, sweat, pus, gastric juice, saliva, nasal mucus, and other liquids. Examples of the other liquid include water, beverages, and waste liquids. Examples of the water-absorbent article include: paper diapers, sanitary napkins, incontinence pads, portable toilets, portable waste disposal bags, animal feces and urine disposal sheets, hospital gowns, surgical gowns, wound dressings, first aid bandages, and meat or fish freshness retaining materials. Among them, paper diapers are preferable.
A paper diaper is basically constituted by a liquid-impermeable back sheet made of a polyolefin-based resin film or the like, a liquid-permeable top sheet made of a nonwoven fabric or the like, and an absorbent body disposed therebetween. In order to prevent the absorbent body from becoming sticky after absorbing urine or the like, the absorbent body is used in a state where the surface thereof is covered with absorbent paper such as thin paper. In addition, the water-absorbent article is configured to be attached with an elastic member such as rubber so as to be stretchable and contractible, and to be in close contact with the abdomen and waist of the wearer, thereby preventing leakage of excrement. In the production of such a paper diaper, the hot melt adhesive of the present invention is preferably used for bonding and integrating hydrophilic porous base materials such as tissue paper, bonding and integrating a hydrophilic porous base material such as tissue paper and another porous base material such as nonwoven fabric, or bonding and integrating a hydrophilic porous base material such as tissue paper and another constituent member such as a polyolefin resin film or an elastic member.
The method for bonding and integrating the constituent members with each other by the hot melt adhesive composition of the present invention is not particularly limited, and a known method can be used. For example, the following methods can be used: after applying the hot-melt adhesive composition melted by heating to one component, the other component is laminated on the applied hot-melt adhesive composition, and then they are pressure-bonded.
The heating melting temperature of the hot melt adhesive composition is preferably 135 to 180 ℃. In a conventional hot melt adhesive composition, the temperature of heating and melting is usually 150 ℃ or higher in order to reduce the melt viscosity and obtain sufficient fluidity. However, the following may occur: when the temperature of the hot melt adhesive composition is lowered to less than 150 ℃, the melt viscosity of the hot melt adhesive composition rapidly increases to lower the fluidity, and therefore, it is difficult to apply the hot melt adhesive composition, or when the heating melting temperature of the hot melt adhesive composition at the time of application is lowered or the time of exposure is prolonged, the applied hot melt adhesive composition is difficult to flow into the pores of a hydrophilic porous substrate such as a nonwoven fabric or a tissue, and sufficient wet adhesiveness with the hydrophilic porous substrate cannot be obtained.
However, the hot melt adhesive composition of the present invention has a low melt viscosity and can be easily applied even at a low temperature such as a heat melting temperature of less than 150 ℃, particularly 135 to 145 ℃. In addition, the hot melt adhesive composition of the present invention is inhibited from rapidly solidifying with a decrease in temperature, and can maintain excellent fluidity even at relatively low temperatures. Therefore, even if the hot melt adhesive composition is heated to a temperature of less than 150 ℃, particularly 135 to 145 ℃ during application or the exposure time after application is long, the hot melt adhesive composition can flow into the pores of the hydrophilic porous substrate, a sufficient contact area between the hot melt adhesive composition and the hydrophilic porous substrate can be obtained, and excellent adhesive strength can be maintained even for a wet hydrophilic porous substrate.
The method of applying the hot melt adhesive composition after heating and melting is not particularly limited, and a known method can be used. Examples thereof include: slot coater coating, roll coater coating, spiral coating in which coating is performed spirally, omega coating and controlled slot coating in which coating is performed in a wave shape, slot coating and curtain coating in which coating is performed in a planar shape, and dot coating in which coating can be performed in a dot shape, and the like.
Effects of the invention
The hot melt adhesive composition of the present invention can be cured slowly with a decrease in temperature after melting by heating. Therefore, even if the hot-melt adhesive composition is heated to a lower melting temperature, or the time until the adherend is bonded to the hot-melt adhesive composition after application is longer, or the temperature is lowered, the hot-melt adhesive composition can maintain excellent fluidity and can easily flow into the pores of the pressure-bonded hydrophilic porous substrate.
In the water-absorbent article using the hot-melt adhesive composition of the present invention, even if the components thereof are wetted with body fluid such as urine or blood, the hot-melt adhesive composition can maintain excellent adhesion strength between the components. Therefore, when the hot melt adhesive composition of the present invention is used for a water-absorbent article such as a disposable diaper, leakage of urine or the like to the outside can be suppressed to a high degree.
Detailed Description
The present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.
Examples
In the examples and comparative examples described later, the thermoplastic block copolymers (a1) to (a11), the liquid rubbers (B1) to (B4), the waxes, the tackifier resins (C1) to (C3), the plasticizers (D1) to (D2), and the antioxidants used for producing the hot melt adhesive composition are described in detail below.
Thermoplastic block copolymer (a):
styrene-isoprene-styrene Block copolymer (A1) [ non-polar group, styrene content 16 wt%, weight average molecular weight (Mw)171,000, product name "Quintac 3433N" manufactured by Zeon corporation ]
Styrene-isoprene-styrene Block copolymer (A2) [ non-polar group, styrene content 25 wt%, weight average molecular weight (Mw)125,000, product name "Quintac 3280" manufactured by Zeon corporation of Japan ]
Styrene-isoprene-styrene Block copolymer (A3) [ non-polar group, styrene component content 14 wt%, weight average molecular weight (Mw)125,000, product name "Quintac 3421" manufactured by Zeon corporation of Japan ]
Styrene-isoprene-styrene Block copolymer (A4) [ non-polar group, styrene component content 48 wt%, weight average molecular weight (Mw)100,000, product name "Quintac 3390" manufactured by Zeon corporation ]
Styrene-butadiene-styrene Block copolymer (A5) [ non-polar group, styrene content 30 wt%, weight-average molecular weight (Mw)122,300, product name "Asaprene T-436" manufactured by Asahi Kasei Chemicals Ltd ]
Styrene-butadiene-styrene Block copolymer (A6) [ non-polar group, styrene content 35 wt%, weight-average molecular weight (Mw)100,000, product name "Asaprene T-438" manufactured by Asahi Kasei Chemicals Ltd ]
Styrene-butadiene-styrene Block copolymer (A7) [ non-polar group, styrene content 45 wt%, weight-average molecular weight (Mw)70,000, product name "Asaprene T-439" manufactured by Asahi Kasei Chemicals Ltd ]
Styrene-butadiene/butylene-styrene block copolymer (A8) [ non-polar group, styrene content 30 wt%, weight-average molecular weight (Mw)100,000, product name "Tuftec P1500" manufactured by Asahi Kasei Chemicals Ltd ]
Styrene-butadiene/butylene-styrene block copolymer (A9) [ non-polar group, styrene content 67 wt%, weight average molecular weight (Mw)100,000, product name "Tuftec P2000" manufactured by Asahi Kasei Chemicals Ltd ]
Styrene-ethylene/propylene-styrene Block copolymer (A10) [ non-polar group, styrene content 30 wt%, weight average molecular weight (Mw)55,000, manufactured by Kuraray Co., Ltd., product name "Septon 2002 ]
Styrene-ethylene/butylene-styrene block copolymer (A11) [ non-polar group, styrene content 30 wt%, weight-average molecular weight (Mw)200,000, product name "Tuftec H1041" manufactured by Asahi Kasei Chemicals Ltd ]
In tables 1 and 2, the styrene-isoprene-styrene block copolymer is abbreviated as "SIS copolymer", the styrene-butadiene-styrene block copolymer is abbreviated as "SBS copolymer", the styrene-butadiene/butylene-styrene block copolymer is abbreviated as "SBBS copolymer", the styrene-ethylene/propylene-styrene block copolymer is abbreviated as "SEPS copolymer", and the styrene-ethylene/butylene-styrene block copolymer is abbreviated as "SEBS copolymer".
Liquid rubber (B):
liquid polyisoprene (B1) having a carboxyl group [ liquid rubber whose main chain is composed of polyisoprene and which has a carboxyl group at the terminal or side chain of the main chain: number average molecular weight (Mn)30,000, at 23 deg.C, 1.01X 105Liquid at Pa (1atm), melting point of 0 deg.C or lower, and product name "Kuraprene LIR-410" manufactured by Kuraray "]
Liquid polyisoprene (B2) having a carboxylic acid anhydride group [ liquid rubber whose main chain is composed of polyisoprene and which has a carboxylic acid anhydride group at the terminal or side chain of the main chain: number average molecular weight (Mn)34,000, at 23 deg.C, 1.01X 105Liquid at Pa (1atm), melting point of 0 deg.C or lower, and product name "Kuraprene LIR-403" manufactured by Kuraray "]
Liquid polybutadiene (B3) having a carboxylic acid anhydride group [ liquid rubber whose main chain is composed of polybutadiene and which has a carboxylic acid anhydride group at the terminal of the main chain or in the side chain: number average molecular weight (Mn) of 31,000, 23 ℃ and 1.01X 105Liquid at Pa (1atm), melting point of 0 deg.C or lower, manufactured by Clay Valley corporation, product name "Ricon 130MA 20"]
Liquid polyisoprene (B4) [ non polar group: number average molecular weight (Mn)54,000, at 23 deg.C, 1.01X 105Liquid at Pa (1atm), melting point of 0 deg.C or lower, and product name "Kuraprene LIR-50" manufactured by Kuraray "]
Wax:
polyethylene (PE) wax having a carboxylic anhydride group [ number average molecular weight (Mn)1,400, 1.01X 10 at 23 ℃5Solid at Pa (1atm), melting point of 104 deg.CManufactured by Innospec corporation under the product name "Viscomax 261"]
Tackifying resin (C):
hydrogenated derivative of aliphatic Petroleum Hydrocarbon resin (C1) (softening Point 100 ℃ C., crude chemical product, product name "Arkon M-100")
Hydrogenated derivative of aliphatic petroleum hydrocarbon resin (C2) (softening point 80 ℃, manufactured by General Co., Ltd., product name "E5380")
Hydrogenated derivative of aliphatic Petroleum Hydrocarbon resin (C3) [ softening Point 120 ℃ C., product name "I-MARV P120" manufactured by Shikukoku Kaisha)
Plasticizer (D):
paraffin Process Oil (D1) (number average molecular weight (Mn)980, product name "Diana Process Oil PW-90" manufactured by gloss Oil Co., Ltd.)
Naphthenic process oil (D2) (number average molecular weight (Mn) 100-1500, product name "Shell Flex 371N" manufactured by Shell chemical Co.)
[ antioxidant ]
Phenol type antioxidant (product name "IRGANOX 1010" manufactured by BASF corporation)
(examples 1 to 14 and comparative examples 1 to 9)
The thermoplastic block copolymers (a1) to (a11), the liquid rubbers (B1) to (B4), the wax, the tackifier resins (C1) to (C3), the plasticizers (D1) to (D2), and the antioxidant were charged into a kneader equipped with a heating device in the blending amounts shown in tables 1 and 2, and then kneaded while heating at 150 ℃ for one hour to produce a hot melt adhesive composition.
(evaluation)
The hot-melt adhesive compositions prepared in examples and comparative examples were evaluated for wet adhesive strength and thermal stability according to the following points.
These results are shown in tables 1 and 2.
(Wet bond Strength: tissue-paper)
The hot melt adhesive composition was melted by heating it to 140 ℃ and then sprayed by a spiral at 3g/m2The coating amount of (2) is applied to a thin paper (paper weight is 18 to 21 g/m)270 to 90 μm thick) ofOn one side, 1 second after the application, another tissue paper was laminated on the side of the tissue paper coated with the hot melt adhesive composition. Then, they were heated at 23 ℃ at 50gf/cm2The pressure of (3) was applied under pressure for 0.01 second, thereby obtaining a laminate. The laminate was cut to obtain a long test piece 20mm in width by 150mm in length.
Next, the test piece was stored at 23 ℃ under an atmosphere of 50% relative humidity for 24 hours and immersed in water at 23 ℃ for 1 minute. Then, the test piece was taken out of the water and wiped with water, thereby obtaining a test piece in a wet state. Then, the test piece in a wet state was subjected to a T-die peel test at a pulling rate of 100 mm/min in accordance with JIS K6854, and the adhesive strength (X10) was measured- 2N/20 mm). The obtained adhesive strength is shown in the column of "wet adhesive strength" in tables 1 to 2.
(thermal stability 1)
The degree of coloration of the hot melt adhesive composition after the hot melt adhesive composition was heated to 140 ℃ and melted, and before the heat test, was measured by the color test method for chemical products specified in JIS K0071. Next, 20g of the hot melt adhesive composition was placed in a glass bottle, and the glass bottle was directly placed in a hot air dryer at 190 ℃ without being covered with a cap, and after leaving for 72 hours, the Gardner color number was measured according to the color test method for chemical products specified in JIS K0071 with respect to the degree of coloration of the hot melt adhesive composition. The difference between the Gardner color values before and after heating at 190 ℃ is shown in tables 1 and 2.
(thermal stability 2)
The hot melt adhesive composition was heated to 140 ℃ to melt, 50g of the hot melt adhesive composition was placed in a glass bottle, the glass bottle was directly placed in a hot air dryer at 190 ℃ without being capped, and after 1 week of standing, the hot melt adhesive composition after the heating test was visually checked to confirm whether gelation and carbonization occurred. In tables 1 and 2, "good" and "poor" are as follows.
"good": gelation and carbonization did not occur.
"poor": gelation or carbonization occurs.
Figure BDA0001175570710000151
Figure BDA0001175570710000161
(cross-reference to related applications)
The present application claims priority based on japanese patent application No. 2013-142181 filed on 5.7.2013 and japanese patent application No. 2013-158480 filed on 31.7.2013, the disclosures of which are incorporated in the present specification by reference to their entireties.
Industrial applicability
The hot melt adhesive composition of the present invention can be preferably used for water-absorbent articles which can be preferably used for absorbing blood or body fluids such as urine, sweat, pus, gastric juice, saliva, nasal secretion mucus, and the like.

Claims (2)

1. Use of a composition as a hot melt adhesive composition for hydrophilic porous substrates, the composition comprising: 100 parts by weight of a thermoplastic block copolymer (A), 0.05 to 10 parts by weight of a liquid rubber (B), and a tackifying resin (C),
the thermoplastic block copolymer (A) contains at least one selected from 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%,
the liquid rubber (B) has a carboxyl group and/or a carboxylic anhydride group in the molecule, and the main chain is polybutadiene.
2. Use of the composition according to claim 1 as a hot melt adhesive composition for a hydrophilic porous substrate, wherein the composition contains a liquid rubber (B) and the liquid rubber (B) is 0.05 parts by weight or more and less than 5 parts by weight relative to 100 parts by weight of the thermoplastic block copolymer (a).
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