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WO2018151190A1 - Adhésif thermofusible et stratifié étirable - Google Patents

Adhésif thermofusible et stratifié étirable Download PDF

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Publication number
WO2018151190A1
WO2018151190A1 PCT/JP2018/005170 JP2018005170W WO2018151190A1 WO 2018151190 A1 WO2018151190 A1 WO 2018151190A1 JP 2018005170 W JP2018005170 W JP 2018005170W WO 2018151190 A1 WO2018151190 A1 WO 2018151190A1
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WIPO (PCT)
Prior art keywords
styrene
melt adhesive
hot melt
copolymer
mass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/005170
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English (en)
Japanese (ja)
Inventor
悠 染谷
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Sekisui Fuller Co Ltd
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Sekisui Fuller Co Ltd
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Priority to JP2018536522A priority Critical patent/JP6716705B2/ja
Publication of WO2018151190A1 publication Critical patent/WO2018151190A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J125/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
    • C09J125/02—Homopolymers or copolymers of hydrocarbons
    • C09J125/04—Homopolymers or copolymers of styrene
    • C09J125/08—Copolymers of styrene
    • 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

Definitions

  • the present invention is excellent in adhesiveness, suppressed from peeling from the base material after stretching, exhibits good stretch recovery after stretching, has excellent thermal stability, and is usually at a relatively low temperature.
  • the present invention relates to a hot-melt adhesive that can be applied by a hot-melt adhesive application device and a stretchable laminate using the hot-melt adhesive.
  • Patent Document 1 discloses a block copolymer comprising an elastic polymer segment and a polystyrene polymer segment, which are one or more polymers selected from hydrogenated polymers of butadiene polymers or isoprene polymers, or ethylene propylene polymers.
  • a hot melt stretchable adhesive composition is disclosed. According to the hot-melt stretchable adhesive composition, it can be applied using a normal hot-melt applicator, and itself has both adhesiveness and stretchability. By laminating, a hot melt adhesive that can easily form a gathered portion is provided.
  • a hot melt adhesive when manufacturing sanitary materials such as disposable diapers and sanitary napkins, it is melted in a tank heated to about 150 to 170 ° C. and heated to about 150 to 170 ° C. It is applied to the substrate in a predetermined shape with a hot melt applicator. At this time, if the operating temperature is further increased, there is a problem that the thermal stability of the hot melt adhesive is lowered, causing thermal degradation, the property is changed, and odor is generated, and the safety of the user is increased. There is a problem of lowering.
  • the present invention is excellent in adhesiveness, suppressed from peeling with the base material after stretching, exhibits good stretch recovery after stretching, and is also excellent in thermal stability. It is an object of the present invention to provide a hot melt adhesive excellent in coating suitability that can be applied with a hot melt adhesive application device that is normally used even at a low temperature, and a stretchable laminate using the hot melt adhesive.
  • the present inventors have found a hot melt adhesive containing a styrene-based block copolymer (A), a tackifier resin (B), and a plasticizer (C). Then, a specific copolymer is used as the styrenic block copolymer (A), and the ratio ( ⁇ 1 / ⁇ 2) of the melt viscosity ( ⁇ 1) at 140 ° C. to the melt viscosity ( ⁇ 2) at 180 ° C. is 5 or less.
  • the hot melt adhesive having a melt viscosity at 180 ° C. of 8,000 mPa ⁇ s or less, the inventors have found that the above object can be achieved, and have completed the present invention.
  • a hot-melt adhesive containing a styrene block copolymer (A), a tackifier resin (B), and a plasticizer (C),
  • the styrenic block copolymer (A) includes styrene-ethylene-butylene / styrene-styrene copolymer, styrene-ethylene-propylene / styrene-styrene copolymer, asymmetric styrene-isoprene-styrene copolymer, and asymmetric Containing at least one selected from the group consisting of styrene-butadiene-styrene copolymers,
  • the hot melt adhesive has a ratio ( ⁇ 1 / ⁇ 2) of a melt viscosity ( ⁇ 1) at 140 ° C.
  • the styrenic block copolymer (A) contains at least one selected from the group consisting of a styrene-ethylene-butylene / styrene-styrene copolymer and an asymmetric styrene-isoprene-styrene copolymer.
  • the hot melt adhesive according to 1. 3. Item 3.
  • the hot melt adhesive according to Item 1 or 2 wherein the content of the plasticizer (C) is 50 to 200 parts by mass with respect to 100 parts by mass of the styrenic block copolymer (A). 4).
  • a stretchable laminate comprising a pair of base materials bonded together by the hot melt adhesive according to any one of Items 1 to 3.
  • the hot melt adhesive of the present invention is excellent in adhesiveness, suppressed from peeling with the base material after stretching, exhibits good stretch recovery after stretching, and has excellent thermal stability, It can be applied with a commonly used hot melt adhesive application device even at a relatively low temperature, and exhibits excellent coating suitability. Moreover, since the stretch laminate of the present invention has a pair of base materials bonded together by the hot melt adhesive, delamination after stretching is suppressed, and good stretch recovery properties after stretching are exhibited. be able to.
  • the hot melt adhesive of the present invention is a hot melt adhesive containing a styrene block copolymer (A), a tackifier resin (B), and a plasticizer (C), wherein the styrene block copolymer ( A) is a styrene-ethylene-butylene / styrene-styrene copolymer, a styrene-ethylene-propylene / styrene-styrene copolymer, an asymmetric styrene-isoprene-styrene copolymer, and an asymmetric styrene-butadiene-styrene copolymer.
  • the hot melt adhesive contains at least one selected from the group consisting of: a melt viscosity ( ⁇ 1) at 140 ° C. and a melt viscosity ( ⁇ 2) at 180 ° C. ( ⁇ 1 / ⁇ 2) of 5 or less. And a hot melt adhesive having a melt viscosity at 180 ° C. of 8,000 mPa ⁇ s or less.
  • the hot melt adhesive of the present invention comprises the above (A) to (C), and in particular, the styrenic block copolymer (A) is a styrene-ethylene-butylene / styrene-styrene copolymer, styrene-ethylene-propylene.
  • / Contains at least one selected from the group consisting of styrene-styrene copolymer, asymmetric styrene-isoprene-styrene copolymer, and asymmetric styrene-butadiene-styrene copolymer. Peeling from the substrate is suppressed, it exhibits good stretch recovery after stretching, is excellent in thermal stability, and is excellent in coating suitability.
  • the hot melt adhesive of the present invention can be suitably used as a member used in gathered parts such as sanitary materials.
  • a member used for the gathered portion thread rubber made of natural rubber or synthetic polymer in a thread form is known.
  • the elastic member used for the gathered part of the conventional sanitary material is formed by joining a base material such as a nonwoven fabric and a plurality of thread rubbers. Since the stretchable member formed in this manner has good stretchability, when used for absorbent articles, it is difficult for the wearer to shift during wearing, giving the wearer a sense of security. However, the gathered portion formed as described above may feel a strong tightening feeling because the linear pressure due to the linear rubber thread is applied to the wearer's waist.
  • the stretchable film has no adhesiveness, and in order to form a stretchable member including a stretchable film, it can be stretched with respect to a substrate such as a non-woven fabric by hot melt adhesive, heat fusion, ultrasonic bonding, etc.
  • the process of joining the conductive film is indispensable, and the process becomes complicated.
  • the hot-melt adhesive of the present invention is a hot-melt adhesive containing a styrenic block copolymer (A), a tackifier resin (B), and a plasticizer (C), wherein the styrenic block
  • the copolymer (A) includes styrene-ethylene-butylene / styrene-styrene copolymer, styrene-ethylene-propylene / styrene-styrene copolymer, asymmetric styrene-isoprene-styrene copolymer, and asymmetric styrene-butadiene- It contains at least one selected from the group consisting of styrene copolymers, and the hot melt adhesive has a ratio ( ⁇ 1 / ⁇ 2) of the melt viscosity ( ⁇ 1) at 140 ° C. and the melt viscosity ( ⁇ 2) at 180 ° C.
  • Styrenic block copolymers (A) are styrene-ethylene-butylene / styrene-styrene copolymer (“SEBS / S”), styrene-ethylene-propylene / styrene-styrene copolymer (“SEPS / S”). And at least one selected from the group consisting of an asymmetric styrene-isoprene-styrene copolymer (“asymmetric SIS”) and an asymmetric styrene-butadiene-styrene copolymer (“asymmetric SBS”).
  • SEBS / S styrene-ethylene-butylene / styrene-styrene copolymer
  • SEPS / S styrene-ethylene-propylene / styrene-styrene copolymer
  • asymmetric SIS asymmetric styrene-
  • the hot melt adhesive of the present invention exhibits good stretchability, and is prevented from being peeled off from the stretched base material. Can show aptitude.
  • Styrene-ethylene-butylene / styrene-styrene copolymers and asymmetric styrene-isoprene-styrene copolymers are preferred in that thermal stability can be further improved and odor can be further reduced, and styrene-ethylene- A butylene / styrene-styrene copolymer is more preferred.
  • the styrene-ethylene-butylene / styrene-styrene copolymer is a styrene-ethylene-butylene-styrene copolymer in which a terminal styrene unit is an end block phase and an ethylene-butylene unit is a mid block phase. Further, it is a copolymer in which styrene is dispersed. By using a copolymer in which styrene is dispersed in the midblock phase, even if the blending amount of styrene-ethylene-butylene / styrene-styrene copolymer in the hot melt adhesive is increased, it is about 140 ° C. or less. Stretch hot that has excellent coating droplet properties because it suppresses the increase in melt viscosity at low temperatures, has good stretchability, is suppressed from peeling after being stretched, and has excellent thermal stability A melt adhesive can be provided.
  • the method for preparing the styrene-ethylene-butylene / styrene-styrene copolymer is not particularly limited, and examples thereof include the method described in US Pat. No. 7,169,848.
  • the styrene content of the styrene-ethylene-butylene / styrene-styrene copolymer is preferably 20% by mass or more, more preferably 30% by mass or more based on 100% by mass of the styrene-ethylene-butylene / styrene-styrene copolymer.
  • the lower limit of the styrene content of the styrene-ethylene-butylene / styrene-styrene copolymer is within the above range, the stretch recovery property after elongation of the hot melt adhesive is further improved.
  • the styrene content of the styrene-ethylene-butylene / styrene-styrene copolymer is preferably 70% by mass or less, more preferably 60% by mass or less, based on 100% by mass of the styrene-ethylene-butylene / styrene-styrene copolymer. preferable.
  • the upper limit of the styrene content of the styrene-ethylene-butylene / styrene-styrene copolymer is within the above range, the hot-melt adhesive becomes softer and better adhesive strength can be expressed.
  • the “styrene content” of the styrenic block copolymer refers to the content ratio (% by mass) of the styrene block in the styrenic block copolymer.
  • the method for calculating the styrene content in the styrene block copolymer in the present specification is not particularly limited, and examples thereof include a method using a proton nuclear magnetic resonance method or infrared spectroscopy according to JIS K6239. .
  • styrene-ethylene-butylene / styrene-styrene copolymer commercially available products can be used. Examples of commercially available products include MD6951 manufactured by Kraton Polymer, A1536 manufactured by Kraton Polymer, and the like.
  • the styrene-ethylene-butylene / styrene-styrene copolymer may be used singly or in combination of two or more.
  • a styrene-ethylene-butylene / styrene-styrene copolymer having a high styrene content and a styrene-ethylene-butylene / styrene-styrene copolymer having a low styrene content may be mixed and used.
  • the styrene-ethylene-propylene / styrene-styrene copolymer is a styrene-ethylene-propylene-styrene copolymer in which a terminal styrene unit is an end block phase and an ethylene-propylene unit is a mid block phase. Further, it is a copolymer in which styrene is dispersed. By using a copolymer in which styrene is dispersed in the midblock phase, even if the blending amount of styrene-ethylene-propylene / styrene-styrene copolymer in the hot melt adhesive is increased, it is about 140 ° C. or less. Stretch hot that has excellent coating droplet properties because it suppresses the increase in melt viscosity at low temperatures, has good stretchability, is suppressed from peeling after being stretched, and has excellent thermal stability A melt adhesive can be provided.
  • the styrene content of the styrene-ethylene-propylene / styrene-styrene copolymer is preferably 20% by mass or more, more preferably 30% by mass or more based on 100% by mass of the styrene-ethylene-propylene / styrene-styrene copolymer.
  • the lower limit of the styrene content of the styrene-ethylene-propylene / styrene-styrene copolymer is within the above range, the stretch recovery property after elongation of the hot melt adhesive is further improved.
  • the styrene content of the styrene-ethylene-propylene / styrene-styrene copolymer is preferably 70% by mass or less, more preferably 60% by mass or less, based on 100% by mass of the styrene-ethylene-propylene / styrene-styrene copolymer. preferable.
  • the upper limit of the styrene content of the styrene-ethylene-propylene / styrene-styrene copolymer is within the above range, the hot-melt adhesive becomes softer and better adhesive strength can be exhibited.
  • the styrene-ethylene-propylene / styrene-styrene copolymer may be used alone or in combination of two or more.
  • a styrene-ethylene-propylene / styrene-styrene copolymer having a high styrene content and a styrene-ethylene-propylene / styrene-styrene copolymer having a low styrene content may be mixed and used. What is necessary is just to calculate the styrene content of the whole styrene-ethylene-propylene / styrene-styrene copolymer by mixing 2 or more types by the average value based on weight.
  • the asymmetric styrene-isoprene-styrene copolymer is an asymmetric styrene-isoprene-styrene copolymer, and “asymmetric” refers to the content of styrene in the styrene phase at both ends of the styrene-isoprene-styrene copolymer. Means different. Using an asymmetric styrene-isoprene-styrene copolymer suppresses an increase in melt viscosity at a low temperature of about 140 ° C.
  • the styrene content of the asymmetric styrene-isoprene-styrene copolymer is preferably 20% by mass or more, more preferably 30% by mass or more, based on 100% by mass of the asymmetric styrene-isoprene-styrene copolymer.
  • the lower limit of the styrene content of the asymmetric styrene-isoprene-styrene copolymer is within the above range, the stretch recovery property after elongation of the hot melt adhesive is further improved.
  • the styrene content of the asymmetric styrene-isoprene-styrene copolymer is preferably 70% by mass or less, more preferably 60% by mass or less, based on 100% by mass of the asymmetric styrene-isoprene-styrene copolymer.
  • the upper limit of the styrene content of the asymmetric styrene-isoprene-styrene copolymer is within the above range, the hot-melt adhesive becomes softer and better adhesive strength can be expressed.
  • asymmetric styrene-isoprene-styrene copolymer used in the present invention commercially available products can be used.
  • Nippon Zeon 3390 and the like can be mentioned.
  • the asymmetric styrene-isoprene-styrene copolymer may be used alone or in combination of two or more.
  • an asymmetric styrene-isoprene-styrene copolymer having a high styrene content and an asymmetric styrene-isoprene-styrene copolymer having a low styrene content may be mixed and used. What is necessary is just to calculate the styrene content of the whole asymmetric styrene-isoprene-styrene copolymer at the time of using 2 or more types mixedly by the average value based on a weight.
  • the asymmetric styrene-butadiene-styrene copolymer is an asymmetric styrene-butadiene-styrene copolymer, and the term “asymmetric” refers to the styrene content in the styrene phases at both ends of the styrene-butadiene-styrene copolymer. Means different. Using an asymmetric styrene-butadiene-styrene copolymer suppresses an increase in melt viscosity at a low temperature of about 140 ° C.
  • the styrene content of the asymmetric styrene-butadiene-styrene copolymer is preferably 20% by mass or more, more preferably 30% by mass or more, based on 100% by mass of the asymmetric styrene-butadiene-styrene copolymer.
  • the lower limit of the styrene content of the asymmetric styrene-butadiene-styrene copolymer is within the above range, the stretch recovery property after elongation of the hot melt adhesive is further improved.
  • the styrene content of the asymmetric styrene-butadiene-styrene copolymer is preferably 70% by mass or less, more preferably 60% by mass or less, based on 100% by mass of the asymmetric styrene-butadiene-styrene copolymer.
  • the upper limit of the styrene content of the asymmetric styrene-butadiene-styrene copolymer is within the above range, the hot-melt adhesive becomes softer and better adhesive strength can be expressed.
  • the asymmetric styrene-butadiene-styrene copolymer may be used alone or in combination of two or more.
  • an asymmetric styrene-butadiene-styrene copolymer having a high styrene content and an asymmetric styrene-butadiene-styrene copolymer having a low styrene content may be mixed and used. What is necessary is just to calculate the styrene content of the whole asymmetric styrene-butadiene-styrene copolymer in the case of using 2 or more types mixedly by the average value based on weight.
  • the styrene block copolymer (A) includes the styrene-ethylene-butylene / styrene-styrene copolymer, styrene-ethylene-propylene / styrene-styrene copolymer, asymmetric styrene-isoprene-styrene copolymer, and asymmetric A styrene block copolymer other than the styrene-butadiene-styrene copolymer may be contained.
  • styrene block copolymers include styrene-butadiene-styrene copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), styrene-butadiene / butylene-styrene copolymer (SBBS), and styrene.
  • SBS styrene-butadiene-styrene copolymer
  • SIS styrene-isoprene-styrene copolymer
  • SBBS butylene-styrene copolymer
  • SEBS styrene-Ethylene-butylene-styrene copolymer
  • SEPS styrene-ethylene-propylene-styrene copolymer
  • SIS ZEON Corporation Quintac 3433
  • SBBS Asahi Kasei Corporation Tuftec P1500
  • SEBS Asahi Kasei Corporation Tuftec H1041
  • SEPS Kuraray Septon 2002
  • the content of the other styrene block copolymer in the styrene block copolymer (A) is preferably 1% by mass or more, preferably 10% by mass or more, based on 100% by mass of the styrene block copolymer (A). Is more preferable.
  • the content of the other styrene block copolymer in the styrene block copolymer (A) is preferably 50% by mass or less, based on 100% by mass of the styrene block copolymer (A), and 40% by mass. % Or less is more preferable.
  • the hot melt adhesive of the present invention has even better adhesion, suppression of peeling from the stretched base material, stretch after stretching. Recoverability can be exhibited, and more excellent thermal stability and coating suitability can be exhibited.
  • the content of the styrenic block copolymer (A) in the hot melt adhesive of the present invention is preferably 25% by mass or more, more preferably 30% by mass or more, and 35% by mass with 100% by mass of the hot melt adhesive. The above is more preferable.
  • the content of the styrenic block copolymer (A) in the hot melt adhesive of the present invention is preferably 65% by mass or less, more preferably 60% by mass or less, based on 100% by mass of the hot melt adhesive. A mass% or less is more preferable.
  • the styrene content of the styrenic block copolymer (A) in the hot melt adhesive of the present invention is preferably 20% by mass or more, and more preferably 30% by mass or more, based on 100% by mass of the styrenic block copolymer (A). More preferred.
  • the lower limit of the styrene content of the styrenic block copolymer (A) is within the above range, the stretch recovery property after elongation of the hot melt adhesive is further improved.
  • the styrene content of the styrene block copolymer (A) is preferably 70% by mass or less, more preferably 60% by mass or less, based on 100% by mass of the styrene block copolymer (A).
  • the upper limit of the styrene content of the styrenic block copolymer (A) is within the above range, the hot-melt adhesive becomes softer, and better adhesive strength can be expressed.
  • the weight average molecular weight (Mw) of the styrenic block copolymer (A) contained in the hot melt adhesive of the present invention is preferably 30,000 or more, more preferably 40,000 or more, and still more preferably 45,000 or more. 50,000 or more is particularly preferable.
  • the weight average molecular weight (Mw) of the styrene block copolymer (A) contained in the hot melt adhesive of the present invention is preferably 200,000 or less, more preferably 150,000 or less, and 125,000 or less. More preferred is 110,000 or less.
  • the upper limit of the weight average molecular weight of the styrenic block copolymer (A) is within the above range, the hot melt adhesive becomes softer and more excellent extensibility can be expressed.
  • the weight average molecular weight (Mw) of the styrene-based block copolymer is a measured value obtained by conversion with standard polystyrene using a gel permeation chromatography measuring device.
  • the weight average molecular weight (Mw) of the styrenic block copolymer can be measured, for example, with the following measuring apparatus and measuring conditions.
  • Measuring device Product name “ACQUITY APC” manufactured by Waters Measurement conditions: Column, ACQUITY APC XT45 1.7 ⁇ m ⁇ 1, ACQUITY APC XT125 2.5 ⁇ m ⁇ 1, ACQUITY APC XT450 2.5 ⁇ m ⁇ 1
  • Mobile phase Tetrahydrofuran 0.8 mL / min
  • Detector Differential refractive index (RI) detector Standard substance: Polystyrene (Molecular weight: 266-1,800,000 manufactured by Waters) Column temperature: 40 ° C RI detector temperature: 40 ° C
  • Tackifying resin (B) The hot melt adhesive of the present invention contains a tackifying resin (B).
  • Tackifying resin (B) includes natural rosin, modified rosin, natural rosin glycerol ester, modified rosin glycerol ester, natural rosin pentaerythritol ester, modified rosin pentaerythritol ester, natural terpene copolymer, natural terpene tertiary Hydrogenated derivatives of original polymers, natural terpene copolymers, terpene resins, hydrogenated derivatives of phenolic modified terpene resins; petroleum resins such as C5 petroleum resins, C9 petroleum resins, C5C9 petroleum resins, dicyclopentadiene petroleum resins Also, partially hydrogenated petroleum resins obtained by adding hydrogen to these petroleum resins, fully hydrogenated petroleum resins and the like can be mentioned.
  • the tackifying resin (B) is preferably a petroleum resin, a partially hydrogenated petroleum resin, or a fully hydrogenated petroleum resin in terms of excellent odor and thermal stability of the hot melt adhesive, and a partially hydrogenated petroleum resin, And fully hydrogenated petroleum resin is more preferred.
  • the above tackifying resins may be used alone or in combination of two or more.
  • the ring-and-ball softening point temperature of the tackifying resin is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, from the viewpoint that the stretchability and thermal stability of the hot melt adhesive are further improved.
  • the ring and ball softening point temperature of the tackifying resin is preferably 125 ° C. or lower, more preferably 120 ° C. or lower, in that the hot-melt adhesive composition can provide more flexibility and further suppress weakening. More preferred.
  • the ring and ball softening point temperature of the tackifier resin is a value measured according to JIS K2207.
  • the content of the tackifier resin (B) in the hot melt adhesive of the present invention is preferably 10 parts by mass or more and more preferably 15 parts by mass or more with respect to 100 parts by mass of the styrenic block copolymer (A). 20 parts by mass or more is more preferable.
  • the hot melt adhesive of the present invention can exhibit even better adhesive strength.
  • 80 mass parts or less are preferable with respect to 100 mass parts of said styrenic block copolymers (A), and, as for content of the tackifying resin (B) in the hot-melt-adhesive of this invention, 60 mass parts or less are preferable.
  • the upper limit of the content of the tackifying resin (B) is within the above range, the content of the styrene block copolymer (A) is relatively increased, and the stretchability and heat of the hot melt adhesive of the present invention are increased. Stability is further improved.
  • tackifier resin (B) Commercially available products can be used as the tackifier resin (B).
  • examples of commercially available products include HA-103 manufactured by TonenGeneral Sekiyu KK, Alcon M-100 manufactured by Arakawa Chemical Co., Ltd., Imabe P100 manufactured by Idemitsu Kosan Co., Ltd., and SCOLEZ SU400 manufactured by Kolon.
  • the hot melt adhesive of the present invention contains a plasticizer (C).
  • the plasticizer (C) is not particularly limited, and examples thereof include paraffinic process oil, naphthenic process oil, aromatic process oil, liquid paraffin, and hydrocarbon synthetic oil. Among these, paraffinic process oil, naphthenic process oil, liquid paraffin, and hydrocarbon synthetic oil are preferable, and paraffinic process oil, liquid paraffin, and hydrocarbon synthetic oil are more preferable. Paraffinic process oil is more preferable in that the coating suitability is further improved.
  • paraffinic process oil examples include Idemitsu Kosan PW-32, Idemitsu Kosan Diana Fresia S32, Idemitsu Kosan PS-32, and the like.
  • the paraffinic process oil By using the paraffinic process oil, the increase in the melt viscosity at a low temperature of the hot melt adhesive is suppressed, and the ratio ( ⁇ 1 / ⁇ 2) between the melt viscosity ( ⁇ 1) at 140 ° C. and the melt viscosity ( ⁇ 2) at 180 ° C. ) Can be further reduced, and coating suitability is further improved.
  • hydrocarbon synthetic oil examples include Lucant HC-10 manufactured by Mitsui Chemicals, Lucant HC-20 manufactured by Mitsui Chemicals, and the like.
  • the above plasticizers may be used alone or in combination of two or more.
  • the content of the plasticizer (C) in the hot melt adhesive of the present invention is preferably 50 parts by mass or more, more preferably 70 parts by mass or more based on 100 parts by weight of the styrene block copolymer (A).
  • the content of the plasticizer (C) in the hot melt adhesive of the present invention is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, based on 100 parts by weight of the styrenic block copolymer (A).
  • the hot melt adhesive of the present invention is in the above range, the hot melt adhesive does not become too soft, and the stretch recovery property after extension of the hot melt adhesive is further increased. improves.
  • the hot melt adhesive of the present invention may contain other additives as long as the object of the present invention is not essentially disturbed.
  • the other additives include waxes, antioxidants, ultraviolet absorbers, and liquid rubber.
  • the wax is not particularly limited.
  • animal wax such as shellac wax and beeswax
  • plant wax such as carnauba wax and beeswax
  • mineral wax such as paraffin wax and macrocrystalline wax
  • Fischer-Tropsch wax ethylene -Synthetic waxes
  • polyolefin waxes are preferable in that the deterioration of the thermal stability of the hot melt adhesive can be further suppressed, and the generation of odor can be further reduced.
  • Waxes may be used alone or in combination of two or more.
  • a commercially available product can be used as the wax.
  • Commercially available polyolefin waxes are Honeywell A-C7, INNOSPEC Viscowax 122, and ethylene-vinyl acetate copolymer (EVA) waxes are Honeywell A-C400, INNOSPEC VISCOWAX 334 may be mentioned.
  • Antioxidants include 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propionate, 2, 2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,4-bis (octylthiomethyl) -o-cresol, 2 -T-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-di-t-amyl-6- [1- (3,5 -Di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl)] acrylate, tetrakis [methylene-3 (3,
  • Examples of the ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-t-butylphenyl) benzotriazole, 2- (2 ′ -Hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole and other benzotriazole ultraviolet absorbers; 2-hydroxy-4-methoxybenzophenone and other benzophenone ultraviolet absorbers; salicylic acid ester Examples include ultraviolet absorbers; cyanoacrylate ultraviolet absorbers; hindered amine light stabilizers. An ultraviolet absorber may be used individually by 1 type, and 2 or more types may be mixed and used for it.
  • liquid rubber examples include liquid polybutene, liquid polybutadiene, liquid polyisoprene, and hydrogenated resins thereof.
  • a liquid rubber may be used individually by 1 type, and may mix and use 2 or more types.
  • the total content of the other additives in the hot melt adhesive of the present invention is preferably 0.1 parts by mass or more, based on 100 parts by mass of the styrenic block copolymer (A), and 0.5 parts by mass. Part or more is more preferable. Further, the total content of the other additives is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, based on 100 parts by mass of the styrene block copolymer (A).
  • the hot melt adhesive of the present invention has even better adhesion, suppression of peeling from the stretched substrate, and stretch recovery after stretching. It is possible to show the properties, and it is possible to show a further excellent thermal stability and coating suitability, and to impart desired performance to the hot melt adhesive of the present invention.
  • the ratio of the melt viscosity ( ⁇ 1) at 140 ° C. to the melt viscosity ( ⁇ 2) at 180 ° C. ( ⁇ 1 / ⁇ 2) of the hot melt adhesive of the present invention is 5 or less. If ⁇ 1 / ⁇ 2 exceeds 5, the melt viscosity of the hot melt adhesive increases when the coating temperature is lowered, and good coating suitability cannot be maintained.
  • ⁇ 1 / ⁇ 2 is preferably 5 or less, and more preferably 4 or less. Further, the lower limit of ⁇ 1 / ⁇ 2 is not particularly limited, and is about 1.5.
  • melt viscosity is the viscosity of a hot melt adhesive that has been heated and melted at a certain temperature.
  • the ratio ( ⁇ 1 / ⁇ 2) between the melt viscosity ( ⁇ 1) at 140 ° C. and the melt viscosity ( ⁇ 2) at 180 ° C. is a value measured by the following measurement method. That is, the hot-melt adhesive is heated and melted, and the melted viscosities at 140 ° C. and 180 ° C. are measured using a Brookfield RVT viscometer (spindle No. 29), which are ⁇ 1 and ⁇ 2, respectively. It is a value measured by calculating the ratio ⁇ 1 / ⁇ 2 of the melt viscosity at 140 ° C. and 180 ° C. based on the measurement result.
  • the hot melt adhesive of the present invention has a melt viscosity ( ⁇ 2) at 180 ° C. of 8000 mPa ⁇ s or less.
  • ⁇ 2 exceeds 8000 mPa ⁇ s, the coating suitability of the hot melt adhesive of the present invention is lowered.
  • ⁇ 2 is preferably 7,500 mPa ⁇ s or less.
  • ⁇ 2 is preferably 3000 mPa ⁇ s or more, and more preferably 4,000 mPa ⁇ s or more.
  • the melt viscosity ( ⁇ 1) at 140 ° C. is preferably 10,000 mPa ⁇ s or more, and more preferably 13,000 mPa ⁇ s or more. Moreover, ⁇ 1 is preferably 30,000 mPa ⁇ s or less, and more preferably 20,000 mPa ⁇ s or less. By setting ⁇ 1 within the above range, the hot melt adhesive of the present invention is further excellent in coating suitability, and the value of ⁇ 1 / ⁇ 2 can be easily adjusted to 5 or less.
  • the stretch recovery property (permanent strain) of the hot melt adhesive of the present invention is preferably 15% or less, and more preferably 10% or less.
  • the stretch recovery property (permanent strain) of the hot melt adhesive of the present invention is measured by the following measuring method.
  • the hot melt adhesive is applied to the spunlace nonwoven fabric F2650 manufactured by Suominen by slot coating at a coating temperature of 160 to 180 ° C.
  • the coating amount is 50 g / m 2 and the coating width is 100 mm.
  • a non-woven fabric F2650 is prepared separately, laminated on the non-woven fabric coated with the hot melt adhesive prepared as described above, and pressure-bonded at room temperature to prepare a laminate.
  • the time from when the hot melt adhesive is applied to the first nonwoven fabric until the second nonwoven fabric is laminated and pressure bonded is 1 second.
  • the laminate is stored for 24 hours under conditions of 23 ° C. and 50% relative humidity, and the hot melt adhesive is cooled.
  • the cooled laminate is cut into strips having a width of 25 mm in the longitudinal direction (coating direction of the hot melt adhesive) and 150 mm in a direction perpendicular to the longitudinal direction to prepare test pieces.
  • a test piece is fixed to a tensile tester set to a jig width of 50 mm with a jig so that the direction perpendicular to the longitudinal direction (coating direction of the hot melt adhesive) is positioned up and down, and tested at a tensile speed of 500 mm / min. Pull to the point where the strain displacement of the piece is 50%. Then, it returns to the initial position at a speed of 500 mm / min. The process of pulling up to 50% strain displacement and then returning to the initial position is one cycle, and the same test piece is repeated two cycles.
  • the adhesiveness of the hot melt adhesive of the present invention is preferably 0.1 N / 25 mm or more, and more preferably 1 N / 25 mm or more. Moreover, the upper limit of the adhesiveness is not particularly limited, and it is preferable that the nonwoven fabric used for the adhesive evaluation is in a “material breakage” state.
  • the adhesiveness of the hot melt adhesive of the present invention is measured by the following measuring method.
  • the hot melt adhesive of the present invention is suitably used for the production of disposable products.
  • the disposable product is not particularly limited, and examples thereof include so-called sanitary materials such as disposable diapers, sanitary napkins, pet sheets, hospital gowns, and lab coats.
  • Stretch laminate is also a stretch laminate in which a pair of base materials are joined by the hot melt adhesive.
  • the method for joining a pair of substrates using the hot melt adhesive of the present invention is not particularly limited, and for example, the following method is used.
  • the hot melt adhesive is heated to a molten state.
  • the heating temperature is preferably 140 ° C. or higher, and more preferably 150 ° C. or higher. Further, the heating temperature is preferably 180 ° C. or lower, and more preferably 170 ° C. or lower.
  • a hot melt adhesive in a molten state is applied to one of the substrates.
  • the hot melt adhesive is cooled and solidified, whereby the pair of base materials can be joined.
  • the substrate is not particularly limited, and examples thereof include a nonwoven fabric, a hydrophilic fiber material, and a polymer composition film.
  • the base material which has a stretching property is preferable from a viewpoint which can manufacture the elastic laminated body which has favorable stretching property.
  • stretchable substrates include stretchable nonwoven fabrics and stretchable polymer composition films.
  • Non-woven fabric is not particularly limited, and generally used non-woven fabrics such as spunbonded non-woven fabric, melt blown non-woven fabric, spunlace non-woven fabric, and air-through non-woven fabric.
  • a stretchable nonwoven fabric that exhibits stretchability in the longitudinal direction, the direction perpendicular to the longitudinal direction, or both is preferable.
  • By using a stretchable nonwoven fabric it is possible to form a stretchable laminate that does not hinder the stretchability of the hot melt adhesive and has a good texture.
  • the stretchable nonwoven fabric is not particularly limited, and a commercially available product can be used.
  • Spunlace nonwoven fabric F6600 manufactured by Suominen Spunlace nonwoven fabric F2650 manufactured by Suominen, and the like can be given.
  • the method for applying the molten hot melt adhesive is not particularly limited, and can be applied by a known method. Examples thereof include slot coater coating, roll coater coating, spiral coating, omega coating, control seam coating, curtain spray coating, and dot coating. Coating methods such as slot coater coating and roll coater coating are applied on a flat surface while the hot melt adhesive is in direct contact with the base material, so a relatively small amount of hot melt adhesive is good. Elasticity can be expressed. On the other hand, in the method of applying hot melt adhesive melted in a fiber shape in a non-contact manner, such as spiral coating, omega coating and curtain spray coating, the hot melt adhesive is applied on the substrate. Since an uncoated region is formed, it is suitable for forming a stretchable laminate having air permeability.
  • the stretchable laminate of the present invention is suitably used as a disposable product.
  • the disposable product is not particularly limited, and examples thereof include so-called sanitary materials such as disposable diapers, sanitary napkins, pet sheets, hospital gowns, and surgical lab coats.
  • the raw material used by the Example and the comparative example is as follows.
  • Styrene block copolymer (A) -Styrenic block copolymer (A1): Styrene-Ethylene-Butylene / Styrene-Styrene (SEBSS) Copolymer MD6951 by Clayton Polymer Co., Ltd. (styrene content 34% by mass, Mw 100,000) -Styrenic block copolymer (A2): Styrene-Ethylene-Butylene / Styrene-Styrene (SEBSS) Copolymer A1536 by Clayton Polymer Co., Ltd.
  • Tackifying resin (B) ⁇ Hydrogenated petroleum resin (B1) HA-103 (softening point 100 ° C) manufactured by TonenGeneral Sekiyu KK ⁇ Hydrogenated petroleum resin (B2) Escorez 5690 (softening point 90 ° C) manufactured by ExxonMobil
  • Plasticizer (C) ⁇ Paraffinic process oil (C1) PW-32 made by Idemitsu Kosan Co., Ltd. ⁇ Hydrocarbon synthetic oil (C2) Lucant HC-10 manufactured by Mitsui Chemicals, Inc. -Liquid paraffin (C3) Kaydol manufactured by Sonneborn ⁇ Naphthenic process oil (C4) Nyflex 222B made by Nynas
  • Antioxidants ⁇ Phenolic antioxidant BASF IRGANOX1010
  • Examples and Comparative Examples The above-mentioned raw materials were respectively charged in the stirring and kneading machine equipped with a heating device in the blending amounts shown in Table 1. A hot melt adhesive was produced by kneading while heating at 145 ° C. for 90 minutes.
  • the characteristics of the obtained hot melt adhesive were evaluated under the following measurement conditions.
  • melt viscosity The hot melt adhesive was heated and melted, and the viscosity in a molten state at 140 ° C. and 180 ° C. was measured using a Brookfield RVT viscometer (spindle No. 29) to be ⁇ 1 and ⁇ 2, respectively. Moreover, based on the measurement result, the ratio ⁇ 1 / ⁇ 2 of melt viscosity at 140 ° C. and 180 ° C. was calculated. It can be evaluated that the closer the value of ⁇ 1 / ⁇ 2 is to 1, the better the coating suitability.
  • the hot melt adhesive was applied to the first nonwoven fabric Spunlace nonwoven fabric F2650 by slot coating or curtain spray coating at a coating temperature of 160 to 180 ° C. The coating amount was 50 g / m 2 and the coating width was 100 mm.
  • a non-woven fabric F2650 to be a second non-woven fabric is separately prepared, laminated on the first non-woven fabric coated with the hot melt adhesive prepared as described above, and press-bonded at room temperature to obtain a laminate.
  • the laminate was stored for 24 hours under conditions of 23 ° C.
  • the hot melt adhesive was cooled.
  • the cooled laminate was cut into strips having a width of 25 mm in the longitudinal direction (coating direction of the hot melt adhesive) and 150 mm in a direction perpendicular to the longitudinal direction to prepare test pieces.
  • a test piece is fixed to a tensile tester set to a jig width of 50 mm with a jig so that the direction perpendicular to the longitudinal direction (coating direction of the hot melt adhesive) is positioned up and down, and tested at a tensile speed of 500 mm / min.
  • the piece was pulled to a point where the strain displacement was 50%. Subsequently, it returned to the initial position at a speed of 500 mm / min.
  • the process of pulling up to 50% strain displacement and then returning to the initial position was defined as 1 cycle, and the same test piece was repeated 2 cycles.
  • adhesive strength is obtained by performing a T-type peel test in a direction perpendicular to the longitudinal direction (coating direction of the hot melt adhesive) at a tensile speed of 300 mm / min. was measured.
  • the non-woven fabric was torn by the T-type peel test, the material was in a fractured state exhibiting sufficient adhesive strength, and thus was evaluated as “material breakage”.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Absorbent Articles And Supports Therefor (AREA)

Abstract

L'invention concerne : un adhésif thermofusible qui possède une excellente adhésivité et une excellente stabilité thermique, tout en étant supprimé dans la séparation d'un substrat après expansion et contraction, et présentant une récupération d'étirabilité après expansion satisfaisante, et qui est excellent en termes d'adéquation dite de revêtement, et qui est ainsi apte à être appliqué par un dispositif d'application d'adhésif thermofusible couramment utilisé, même à des températures relativement basses ; et un stratifié étirable qui est obtenu à l'aide de l'adhésif thermofusible. L'adhésif thermofusible contient un copolymère séquencé de styrène (A), une résine tackifiante (B) et un plastifiant (C), et est caractérisé en ce que : le copolymère séquencé de styrène (A) contient au moins un copolymère choisi dans le groupe constitué par un copolymère de styrène-éthylène-butylène/styrène-styrène, un copolymère de styrène-éthylène-propylène/styrène-styrène, un copolymère de styrène-isoprène-styrène asymétrique et un copolymère de styrène-butadiène-styrène asymétrique. Le rapport de la viscosité à l'état fondu (η1) de l'adhésif thermofusible à 140 °C à la viscosité à l'état fondu (η2) de l'adhésif thermofusible à 180 °C, à savoir η1/η2, est inférieur ou égal à 5 ; et la viscosité à l'état fondu (η2) à 180 °C est inférieure ou égale à 8 000 Pa·s.
PCT/JP2018/005170 2017-02-17 2018-02-15 Adhésif thermofusible et stratifié étirable Ceased WO2018151190A1 (fr)

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WO2019131972A1 (fr) * 2017-12-27 2019-07-04 積水フーラー株式会社 Adhésif thermofusible
JP2019172949A (ja) * 2018-03-28 2019-10-10 株式会社日本触媒 共重合体および樹脂組成物
WO2020110921A1 (fr) * 2018-11-28 2020-06-04 積水フーラー株式会社 Composition thermofusible
CN112772005A (zh) * 2018-09-25 2021-05-07 积水富乐株式会社 电子电路安装基板用热熔涂敷剂
JP2022521103A (ja) * 2019-02-25 2022-04-05 スリーエム イノベイティブ プロパティズ カンパニー 押出可能な感圧接着剤
WO2023195539A1 (fr) * 2022-04-08 2023-10-12 積水フーラー株式会社 Composition thermofusible
JP7646324B2 (ja) 2019-10-31 2025-03-17 積水フーラー株式会社 ホットメルト組成物及び繊維状部材

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WO2019131972A1 (fr) * 2017-12-27 2019-07-04 積水フーラー株式会社 Adhésif thermofusible
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JP7646324B2 (ja) 2019-10-31 2025-03-17 積水フーラー株式会社 ホットメルト組成物及び繊維状部材
WO2023195539A1 (fr) * 2022-04-08 2023-10-12 積水フーラー株式会社 Composition thermofusible

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