WO2024004673A1 - ホットメルト接着剤組成物、自動車内装用プレコート表皮材、自動車内装材、及び接着体の製造方法 - Google Patents
ホットメルト接着剤組成物、自動車内装用プレコート表皮材、自動車内装材、及び接着体の製造方法 Download PDFInfo
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- WO2024004673A1 WO2024004673A1 PCT/JP2023/022213 JP2023022213W WO2024004673A1 WO 2024004673 A1 WO2024004673 A1 WO 2024004673A1 JP 2023022213 W JP2023022213 W JP 2023022213W WO 2024004673 A1 WO2024004673 A1 WO 2024004673A1
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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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/10—Homopolymers or copolymers of propene
- C09J123/12—Polypropene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
- B29C65/40—Applying molten plastics, e.g. hot melt
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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
-
- 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
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such 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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
-
- 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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/35—Heat-activated
Definitions
- the present disclosure relates to a hot melt adhesive composition, a precoated skin material for automobile interiors using the same, and an automobile interior material.
- Hot melt adhesives are solid at room temperature, are heated and melted and applied to base materials, and are cooled and solidified to bond the base materials together. Hot melt adhesives have advantages over solvent-based adhesives, such as reduced VOC and improved productivity due to the omission of a drying process, and are used in various applications, such as automobile manufacturing.
- Patent Document 1 discloses a hot melt adhesive composition containing a hydrocarbon-based cyclic polymer, an ⁇ -olefin-based polymer, and a tackifier resin.
- Patent Document 2 describes an ⁇ -olefin copolymer polymerized using a multi-site catalyst, an ⁇ -olefin copolymer polymerized using a single-site catalyst, an ethylene-polar group-containing monomer copolymer, and a hydrogenated
- a hot melt adhesive composition is disclosed that includes a polypropylene-based tackifying resin and a polypropylene-based wax in specific proportions.
- Patent Document 1 and Patent Document 2 do not discuss the process of peeling the hot melt adhesive from the mold.
- Conventional hot melt adhesives take time to solidify from a molten state, and during that time, the hot melt adhesive cannot be easily peeled from the mold, resulting in poor workability. Additionally, when conventional hot melt adhesives are used, there are problems from a workability perspective, as the hot melt adhesive remains after being peeled off from the mold, requiring manual peeling and cleaning. It can be.
- the present disclosure provides a hot melt that has good adhesion to resin base materials, particularly polyolefin base materials such as polypropylene, and also has workability (mold releasability) that allows it to be easily peeled from a mold.
- resin base materials particularly polyolefin base materials such as polypropylene
- workability molding releasability
- the purpose is to provide adhesives.
- the crystalline polyolefin (A) contains an ethylene-propylene copolymer.
- the amorphous polyolefin (B) has a softening point of 100° C. or higher.
- the amorphous polyolefin (B) contains at least one selected from the group consisting of an ethylene-propylene binary copolymer and an ethylene-propylene-butene ternary copolymer.
- [Section 6] Item 6.
- Item 7 The hot melt adhesive composition according to any one of Items 1 to 6, comprising a tackifier (D).
- the tackifier (D) has a softening point of 90°C or higher.
- the tackifier (D) contains at least one selected from the group consisting of hydrogenated petroleum resins, terpene resins, and terpene phenol resins.
- the tackifier (D) contains at least one selected from the group consisting of hydrogenated petroleum resins, terpene resins, and terpene phenol resins.
- [Section 15] A skin material for automotive interiors, and a hot melt adhesive layer formed from the hot melt adhesive composition according to any one of Items 1 to 14 on the back side of the skin material for automotive interiors. Pre-coated skin material.
- [Section 16] An automobile interior material comprising an automobile interior molded article and the precoated skin material for automobile interior according to item 15, which is adhered to the automobile molded article via the hot melt adhesive layer.
- [Section 17] A method for manufacturing an adhesive body, the method comprising: The adhesive body is adhered to the first base material through a first base material and a hot melt adhesive layer formed from the hot melt adhesive composition according to any one of Items 1 to 14. having a second base material, A method for producing an adhesive body, comprising a step of bringing a mold into contact with the hot melt adhesive composition.
- the hot melt adhesive of the present disclosure has particularly good adhesion to polyolefin substrates such as polypropylene, and also has good mold releasability and is excellent in workability.
- the hot melt adhesive composition of the present disclosure includes a crystalline polyolefin (A), an amorphous polyolefin (B), and a polypropylene wax (C).
- the hot melt adhesive composition of the present disclosure may optionally contain a tackifier (D), an antioxidant (E), an inorganic filler (F), an elastomer ( G), a plasticizer (H), and other additives (I).
- the hot melt adhesive composition of the present disclosure includes a crystalline polyolefin (A).
- the crystalline polyolefin (A) is a polyolefin with high crystallinity. Crystalline polyolefin (A) is distinguished from other components described herein in terms of crystallinity, Shore A hardness, and/or molecular weight. Typically, the crystallinity of the crystalline polyolefin (A) is 20% or more. Typically, the Shore A hardness of the crystalline polyolefin (A) is 80 or higher. Typically, the crystalline polyolefin (A) has a weight average molecular weight of 40,000 or more.
- the degree of crystallinity of the crystalline polyolefin (A) may be 20% or more, 25% or more, 30% or more, or 35% or more.
- the crystallinity of the crystalline polyolefin (A) may be 100% or less, 98% or less, 95% or less, 90% or less, or 85% or less. It is preferable that the degree of crystallinity is equal to or higher than the above lower limit value from the viewpoint of better achieving the effects of the present disclosure.
- the degree of crystallinity can be measured, for example, by differential scanning calorimetry, polymer X-ray diffraction, or the like.
- crystalline in the present disclosure may mean a property in which a clear endothermic peak originating from a crystalline portion is observed in differential scanning calorimetry, while “amorphous” refers to In measurement, it may also mean the property that no clear endothermic peak originating from the crystalline portion is observed.
- the Shore A hardness of the crystalline polyolefin (A) may be 80 or more, 85 or more, 90 or more, or 95 or more, preferably 85 or more, and more preferably 90 or more.
- the Shore A hardness of the crystalline polyolefin (A) may be 100 or less, 99 or less, 98 or less, or 97 or less.
- Shore A hardness can be used as an indicator of the cohesive force of a resin, and can be one of the indicators of adhesiveness at room temperature and hot. It is preferable that the content be within the above range from the viewpoint of better achieving the effects of the present disclosure.
- the melting point of the crystalline polyolefin (A) may be 60°C or higher, 70°C or higher, 80°C or higher, 90°C or higher, 100°C or higher, or 110°C or higher, preferably 80°C or higher.
- the melting point of the crystalline polyolefin (A) may be 150°C or lower, 140°C or lower, 130°C or lower, 120°C or lower, 110°C or lower, 100°C or lower, or 90°C or lower, preferably 120°C or lower, for example 110°C or lower. °C or lower, or 100°C or lower. It is preferable that the content be within the above range from the viewpoint of better achieving the effects of the present disclosure.
- the glass transition temperature of the crystalline polyolefin (A) may be -150°C or higher, -125°C or higher, -100°C or higher, -75°C or higher, -50°C or higher, or -25°C or higher.
- the glass transition temperature of the crystalline polyolefin (A) may be 20°C or lower, 10°C or lower, 0°C or lower, -10°C or lower, or -20°C or lower, preferably 0°C or lower, more preferably -10°C. It is as follows. It is also preferable from the viewpoint of low-temperature adhesion that the glass transition temperature is below the above upper limit.
- the crystalline polyolefin (A) is typically thermoplastic.
- the MFR of the crystalline polyolefin (A) may be 3 g/10 minutes or more, 5 g/10 minutes or more, 7 g/10 minutes or more, 10 g/10 minutes or more, 12 g/10 minutes or more, or 15 g/10 minutes or more, Preferably it is 5 g/10 minutes or more, more preferably 7 g/10 minutes or more.
- the MFR of the crystalline polyolefin (A) may be 40 g/10 minutes or less, 30 g/10 minutes or less, 20 g/10 minutes or less, 15 g/10 minutes or less, or 10 g/10 minutes or less. It is preferable that the MFR is in a range equal to or higher than the above lower limit from the viewpoint of low melt viscosity and coating stability. MFR can be measured based on JIS K7210.
- the weight average molecular weight of the crystalline polyolefin (A) may be 40,000 or more, 50,000 or more, 75,000 or more, 100,000 or more, 200,000 or more, 300,000 or more, or 500,000 or more. , 100,000 or more is preferred.
- the weight average molecular weight of the crystalline polyolefin (A) is 5,000,000 or less, 2,000,000 or less, 1,500,000 or less, 1,200,000 or less, 1,000,000 or less, 800,000 or less , 600,000 or less, 400,000 or less, or 200,000 or less, preferably 1,000,000 or less, such as 600,000 or less. It is preferable that the weight average molecular weight is within the above range from the viewpoint of better achieving the effects of the present disclosure.
- Crystalline polyolefin (A) is a polymer having repeating units derived from olefins.
- the crystalline polyolefin (A) is preferably an ⁇ -olefin polymer having repeating units derived from an ⁇ -olefin, particularly an ⁇ -olefin copolymer.
- the crystalline polyolefin (A) may be a homopolymer, a copolymer, or a mixture thereof.
- the form of the copolymer may be random copolymerization, block copolymerization, graft copolymerization, or the like.
- repeating units contained in the crystalline polyolefin (A) include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1 - Derived from nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, etc. These repeating units may be used alone or in combination of two or more.
- the crystalline polyolefin (A) preferably contains repeating units derived from propylene among the above-mentioned repeating units, for example repeating units derived from propylene and repeating units derived from other ⁇ -olefins (e.g. ethylene). May contain both units and.
- the repeating units constituting the crystalline polyolefin (A) are 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, or 70 mol% % or more, preferably 30 mol% or more.
- the crystalline polyolefin (A) include ethylene homopolymer, propylene homopolymer, ethylene-propylene copolymer, propylene-1-butene copolymer, ethylene-1-butene copolymer, and ethylene-1-octene.
- Examples include copolymers of olefins such as copolymers, ethylene-1-hexene copolymers, and ethylene-propylene-1-butene copolymers, and preferred examples include ethylene-propylene copolymers. These may be used alone or in combination of two or more.
- Examples of typical commercially available crystalline polyolefins (A) include the product names "Tafmer XM-7090", “Tafmer XM-7080", “Tafmer XM-7070”, and “Tafmer , Tafmar series such as “Tafmar XM-5080", “Tafmar XM-5070", “Tafmar BL-2491M”, “Tafmar DF110”; , ExxonMobil's Vistamaxx series such as “Vistamaxx8880", “Vistamaxx3000", and “Vistamaxx3980FL”, and Idemitsu Kosan's "L-MODU S901", “L-MODU S600", “L-MODU S400”, etc. It will be done.
- the crystalline polyolefin (A) may be used alone or in combination of two or more types.
- the hot melt adhesive composition of the present disclosure includes an amorphous polyolefin (B).
- the amorphous polyolefin (B) is a polyolefin that does not have crystallinity or has a small amount of crystallinity, and can impart flexibility.
- the amorphous polyolefin (B) is distinguished from other components described herein in terms of crystallinity, molecular weight, and the like.
- the crystallinity of the amorphous polyolefin (B) is less than 20%.
- the amorphous polyolefin (B) has a weight average molecular weight of 40,000 or more.
- the degree of crystallinity of the amorphous polyolefin (B) may be 0% or more, 3% or more, or 5% or more.
- the crystallinity of the amorphous polyolefin (B) may be less than 20%, 15% or less, 10% or less, 5% or less, 3% or less, or 1% or less. It is preferable that the degree of crystallinity is less than or equal to the above upper limit value from the viewpoint of better achieving the effects of the present disclosure.
- the degree of crystallinity can be measured, for example, by differential scanning calorimetry, polymer X-ray diffraction, or the like.
- the softening point of the amorphous polyolefin (B) may be 70°C or higher, 80°C or higher, 90°C or higher, 100°C or higher, 110°C or higher, 120°C or higher, or 130°C or higher, preferably 80°C or higher,
- the temperature is 100°C or higher.
- the softening point of the amorphous polyolefin (B) may be 180°C or lower, 170°C or lower, 160°C or lower, 150°C or lower, 140°C or lower, 130°C or lower, 120°C or lower, or 110°C or lower, preferably
- the temperature is 160°C or lower, for example 140°C or lower. It is preferable that the content be within the above range from the viewpoint of better achieving the effects of the present disclosure.
- the softening point can be measured by the ring and ball method.
- the glass transition temperature of the amorphous polyolefin (B) may be -150°C or higher, -125°C or higher, -100°C or higher, -75°C or higher, -50°C or higher, or -25°C or higher.
- the glass transition temperature of the crystalline polyolefin (A) may be 20°C or lower, 10°C or lower, 0°C or lower, -10°C or lower, or -20°C or lower, preferably 0°C or lower, more preferably -10°C. It is as follows. It is also preferable from the viewpoint of low-temperature adhesion that the glass transition temperature is below the above upper limit.
- the amorphous polyolefin (B) is typically thermoplastic.
- the MFR of the amorphous polyolefin (B) may be 3 g/10 minutes or more, 5 g/10 minutes or more, 7 g/10 minutes or more, 10 g/10 minutes or more, 12 g/10 minutes or more, or 15 g/10 minutes or more. , preferably 5 g/10 minutes or more, more preferably 7 g/10 minutes or more.
- the MFR of the amorphous polyolefin (B) may be 40 g/10 minutes or less, 30 g/10 minutes or less, 20 g/10 minutes or less, 15 g/10 minutes or less, or 10 g/10 minutes or less. It is preferable that the MFR is in a range equal to or higher than the above lower limit from the viewpoint of low melt viscosity and coating stability. MFR can be measured based on JIS K7210.
- the weight average molecular weight of the amorphous polyolefin (B) is 40,000 or more, 50,000 or more, 75,000 or more, 100,000 or more, 200,000 or more, 300,000 or more, or 500,000 or more. Generally, 100,000 or more is preferred.
- Amorphous polyolefin (B) is 5,000,000 or less, 2,000,000 or less, 1,500,000 or less, 1,200,000 or less, 1,000,000 or less, 800,000 or less, 600, 000 or less, 400,000 or less, or 200,000 or less, preferably 1,000,000 or less, such as 600,000 or less. It is preferable that the weight average molecular weight is within the above range from the viewpoint of better achieving the effects of the present disclosure.
- the amorphous polyolefin (B) is a polymer having repeating units derived from olefins.
- the amorphous polyolefin (B) is preferably an ⁇ -olefin polymer having repeating units derived from an ⁇ -olefin, particularly an ⁇ -olefin copolymer.
- the amorphous polyolefin (B) may be a homopolymer, a copolymer, or a mixture thereof.
- the form of the copolymer may be random copolymerization, block copolymerization, graft copolymerization, or the like.
- repeating units contained in the amorphous polyolefin (B) include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, From 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, and 1-eicosene, etc. Examples include derived repeating units, and these may be used alone or in combination of two or more.
- the amorphous polyolefin (B) preferably contains repeating units derived from propylene among the above-mentioned repeating units, for example, repeating units derived from propylene and other repeating units derived from ⁇ -olefins (e.g. ethylene). It may contain both repeating units and.
- the repeating units constituting the amorphous polyolefin (B) are 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, or 70 mol% or more It may be mol% or more, preferably 30 mol% or more.
- amorphous polyolefin (B) examples include ethylene homopolymer, propylene homopolymer, ethylene-propylene copolymer, propylene-1-butene copolymer, ethylene-1-butene copolymer, ethylene-1- Examples include copolymers of olefins such as octene copolymers, ethylene-1-hexene copolymers, and ethylene-propylene-1-butene copolymers; preferred examples include ethylene-propylene binary copolymers. and/or a terpolymer of ethylene-propylene-butene. These may be used alone or in combination of two or more.
- Examples of typical commercially available amorphous polyolefins include the product names "Bestplast 308", “Bestplast 508", “Bestplast 520", “Bestplast 608", and “Bestplast” manufactured by Evonik.
- RT series such as product names "RT2280", “RT2385”, “RT2585”, and “RT2780” manufactured by REXtac.
- the hot melt adhesive composition of the present disclosure includes a polypropylene wax (C).
- Polypropylene wax (C) is a wax having repeating units derived from propylene.
- the polypropylene wax (C) generally has a low molecular weight (less than 40,000), and can impart coatability and wettability to adherends by lowering the viscosity of the hot melt adhesive. Further, the polypropylene wax (C) can promote crystallization and solidification of the crystalline polyolefin (A), improve the solidification rate of the hot melt adhesive, and improve mold releasability.
- the softening point of the polypropylene wax (C) is 90°C or higher, 100°C or higher, 110°C or higher, 120°C or higher, 130°C or higher, 140°C or higher, or 150°C or higher, preferably 110°C or higher, more preferably 120°C.
- the temperature is above, more preferably 130°C or above.
- the softening point of the polypropylene wax (C) may be 220°C or lower, 210°C or lower, 190°C or lower, 180°C or lower, 170°C or lower, 160°C or lower, or 150°C or lower, preferably 190°C or lower, e.g.
- the temperature is 160°C or less.
- the content be within the above range from the viewpoint of better achieving the effects of the present disclosure.
- the softening point can be measured by the ring and ball method. It is preferable that the softening point of the polypropylene wax (C) is below the above upper limit because the melting temperature can be set low and the working time can be shortened.
- the weight average molecular weight of the polypropylene wax (C) may be 3,000 or more, 5,000 or more, or 7,000 or more, preferably 3,000 or more.
- the weight average molecular weight of the polypropylene wax (C) may be less than 40,000, 35,000 or less, 30,000 or less, 20,000 or less, or 10,000 or less, preferably 20,000 or less. It is preferable that the weight average molecular weight is within the above range from the viewpoint of better achieving the effects of the present disclosure.
- the polypropylene wax (C) may have repeating units other than repeating units derived from propylene, such as repeating units derived from ⁇ -olefin.
- the polypropylene wax (C) may be a low molecular weight polyolefin, particularly a low molecular weight ⁇ -olefin polymer.
- the polypropylene wax (C) may be a homopolymer, a copolymer, or a mixture thereof.
- the form of the copolymer may be random copolymerization, block copolymerization, graft copolymerization, or the like.
- repeating units contained in the polypropylene wax (C) other than repeating units derived from propylene include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1- Putene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, and repeating units derived from 1-eicosene and the like, which may be used alone or in combination of two or more.
- the repeating units derived from propylene are 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, or 70 mol%. % or more, preferably 30 mol% or more.
- Examples of typical commercial products of polypropylene wax (C) include the product names "Viscol 660-P”, “Viscol 550-P”, “Viscol 440-P”, and “Viscol 330-P” manufactured by Sanyo Chemical Industries, Ltd. Viscole series such as ⁇ Hiwax 100P'', ⁇ Hiwax 200P'', ⁇ Hiwax 400P'', ⁇ Hiwax 800P'', ⁇ Hiwax 410P'', ⁇ Hiwax 420P'', etc. manufactured by Mitsui Chemicals.
- the hot melt adhesive composition of the present disclosure may also include a tackifier (D).
- the tackifier (D) can improve tackiness when melted.
- the softening point of the tackifier (D) is 90°C or higher, 100°C or higher, 110°C or higher, 120°C or higher, 130°C or higher, 140°C or higher, or 150°C or higher, preferably 110°C or higher, more preferably 120°C.
- the temperature is above, more preferably 130°C or above.
- the softening point of the tackifier (D) may be 220°C or lower, 210°C or lower, 190°C or lower, 180°C or lower, 170°C or lower, 160°C or lower, or 150°C or lower, preferably 190°C or lower, e.g.
- the temperature is 160°C or less.
- the content be within the above range from the viewpoint of better achieving the effects of the present disclosure.
- the softening point can be measured by the ring and ball method. It is preferable that the softening point of the tackifier (D) is below the above upper limit, since the melting temperature can be set low and the working time can be shortened.
- tackifier (D) examples include rosin resin, rosin ester, disproportionated rosin ester, hydrogenated rosin ester, polymerized rosin, aliphatic hydrocarbon resin, aliphatic aromatic copolymer resin, and aromatic petroleum.
- tackifier (D) is distinguished from other components such as polyolefin in terms of the presence or absence of intramolecular double bonds, intramolecular polar groups, intramolecular hydrocarbon groups, etc.
- Examples of typical commercially available tackifiers (D) include the product names "Alcon P-90”, “Alcon P-100”, “Alcon P-115”, and “Alcon P-140” manufactured by Arakawa Chemical Co., Ltd. , “Alcon M-90”, “Alcon M-100”, “Alcon M-115”, “Alcon M-135” and other Alcon series; product names manufactured by Idemitsu Kosan Co., Ltd.
- YS resin series such as “TO115”, “YS Resin TO105”, “YS Polyster T160”, “YS Polyster T145”, “YS Polyster T130”, “YS Polyster T115”, “YS Polyster T100”, “YS Polyster UH115”, etc.
- YS polyster series examples include FTR series such as “FTR6100”, “FTR6110", and “FTR6125” manufactured by Mitsui Chemicals.
- the tackifier (D) may be used alone or in combination of two or more. Furthermore, a tackifier having a softening point of less than 90° C. can be blended within a range that does not impair the desired physical properties.
- the hot melt adhesive composition of the present disclosure may also include an antioxidant (E).
- an antioxidant (E) improves thermal stability and may be suitable from the viewpoint of favorably achieving the effects of the present disclosure.
- antioxidant (E) examples include hindered phenols, polyphenols, bisphenols, phosphates, thioethers, hydrosarites, benzimidazoles, aromatic secondary amines, and the like.
- antioxidants examples include BASF's product names "Irganox 1010,” “Irganox 1035,” “Irganox 1076,” “Irganox 1098,” and “Irganox 1330.” “, “Irganox 245", “Irganox 259”, “Irganox 3114”, “Irganox 565", “Irganox 168”, etc.
- ADEKA product name "ADEKA STAB AO-20", " ADEKA STAB AO-30'', ⁇ ADEKA STAB AO-40'', ⁇ ADEKA STAB AO-50'', ⁇ ADEKA STAB AO-60'', ⁇ ADEKA STAB AO-80'', ⁇ ADEKA STAB AO-330'', ⁇ ADEKA STAB PEP-8'', ⁇ ADEKA STAB Examples include the “ADK STAB” series such as "PEP-36", “ADK STAB HP-10", “ADK STAB 2112", “ADK STAB AO-412S", etc.
- the antioxidant (E) may be used alone or in combination of two or more kinds.
- the hot melt adhesive composition of the present disclosure may also include an inorganic filler (F).
- an inorganic filler (F) By adding the inorganic filler (F), it is possible to adjust adhesiveness, sagging properties, specific gravity, etc.
- inorganic fillers (F) include calcium carbonate (ground calcium carbonate, surface-untreated calcium carbonate, surface-treated calcium carbonate (e.g. fatty acid-treated calcium carbonate, etc.), acicular crystalline calcium carbonate), silica (fume silica), , hydrophobic silica, precipitated silica, etc.), talc, mica (mica), clay, chrysotile, wollastonite, carbon black, graphite, balloons (shirasu balloon, glass balloon, silica balloon, etc.), inorganic fiber (glass fiber) , metal fibers, etc.), titanium oxide, aluminum oxide, aluminum borate, silicon carbide, silicon nitride, potassium titanate, magnesium borate, titanium diboride, aluminum flakes, aluminum powder, iron powder, and the like.
- the inorganic filler (F) may be used alone or in combination of two or more kinds.
- the hot melt adhesive composition of the present disclosure may include an elastomer (G).
- Elastomer (G) is a polymer that exhibits elasticity.
- the elastomer (G) may be thermoset or thermoplastic, preferably thermoplastic.
- Elastomer (G) is distinguished from the other components described herein in terms of crystallinity, Shore A hardness, and/or molecular weight.
- the elastomer (G) is not amorphous.
- the elastomer (G) has a Shore A hardness of less than 80.
- the elastomer (G) has a weight average molecular weight of 40,000 or more.
- the Shore A hardness of the elastomer (G) may be 20 or more, 30 or more, 40 or more, 50 or more, 60 or more, or 70 or more, preferably 40 or more.
- the Shore A hardness of the elastomer (G) may be less than 80, 75 or less, 70 or less, 65 or less, or 60 or less. It is preferable that the Shore A hardness of the elastomer (G) is within the above range from the viewpoint of better achieving the effects of the present disclosure.
- the MFR of the elastomer (G) may be 3 g/10 minutes or more, 5 g/10 minutes or more, 7 g/10 minutes or more, 10 g/10 minutes or more, 12 g/10 minutes or more, or 15 g/10 minutes or more, preferably It is 5 g/10 minutes or more, more preferably 7 g/10 minutes or more.
- the MFR of the elastomer (G) may be 40 g/10 minutes or less, 30 g/10 minutes or less, 20 g/10 minutes or less, 15 g/10 minutes or less, or 10 g/10 minutes or less. It is preferable that the MFR is in a range equal to or higher than the above lower limit from the viewpoint of low melt viscosity and coating stability. MFR can be measured based on JIS K7210.
- the weight average molecular weight of the elastomer (G) may be 40,000 or more, 50,000 or more, 75,000 or more, 100,000 or more, 200,000 or more, 300,000 or more, or 500,000 or more; ,000 or more is preferable.
- the weight average molecular weight of the elastomer (G) is 5,000,000 or less, 2,000,000 or less, 1,500,000 or less, 1,200,000 or less, 1,000,000 or less, 800,000 or less, 600 ,000 or less, 400,000 or less, or 200,000 or less, preferably 1,000,000 or less, such as 600,000 or less. It is preferable that the weight average molecular weight is within the above range from the viewpoint of better achieving the effects of the present disclosure.
- elastomer (G) examples include rubber elastomer, olefin elastomer, styrene elastomer (for example, hydrogenated or non-hydrogenated styrene elastomer), vinyl chloride elastomer, urethane elastomer, ester elastomer, and amide elastomer. etc. From the viewpoint of compatibility, olefin elastomers are preferred.
- the olefinic elastomer may be an olefinic elastomer having repeating units derived from propylene.
- elastomer (G) examples include the Tafmer PN series, such as Mitsui Chemicals' product name “Tafmer PN-2070” and “Tafmer PN-3560”; the Dow Chemical Company's product name “INFUSE9807”; ”, “INFUSE9817”, “INFUSE9990”, and the Vistamaxx series, such as “Vistamaxx6502” and “Vistamaxx6202” manufactured by ExxonMobil.
- the elastomer (G) may be used alone or in combination of two or more.
- the hot melt adhesive composition of the present disclosure may also include a plasticizer (H).
- the plasticizer (H) is an oily substance such as a low molecular weight compound containing a chain alkyl group or an olefin oligomer.
- the plasticizer (H) can improve the applicability and wettability to adherends by lowering the viscosity of the hot melt adhesive.
- the weight average molecular weight of the plasticizer (H) may be 100 or more, 300 or more, or 500 or more.
- the weight average molecular weight of the plasticizer (H) may be less than 3000, 2500 or less, 20000 or less, 1500 or less, or 1000 or less, preferably 2000 or less. It is preferable that the weight average molecular weight is within the above range from the viewpoint of better achieving the effects of the present disclosure.
- plasticizer (H) examples include liquid paraffin, process oil, phthalic acid plasticizer, butene oligomer, butadiene oligomer, liquid ethylene/propylene oligomer, liquid rubber, etc. From the viewpoint of compatibility, Butene oligomers or liquid ethylene/propylene oligomers are preferred.
- plasticizers (H) examples include “NOF Polybutene 0N”, “NOF Polybutene 015N”, “NOF Polybutene 3N”, “NOF Polybutene 10N”, and “NOF Polybutene 10N” manufactured by NOF Corporation.
- Polybutene series such as “Oil Polybutene 30N” and “NOF Polybutene 200N”; "Lucant LX004", “Lucant LX010", “Lucant LX020”, “Lucant LX100”, “Lucant LX200”, “Lucant LX400” manufactured by Mitsui Chemicals , Lucant series such as “Lucant LX900Z”, etc.
- the plasticizer (H) may be used alone or in combination of two or more kinds.
- Adhesives silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, aminosilane, mercaptosilane, epoxysilane, etc., glycidyl having a polyoxyalkylene skeleton
- Vulcanization accelerators guanidines, aldehyde-amines, aldehyde-ammonias, thiazoles, sulfenamides, thioureas, thiurams, dithiocarbamates, xanthates, etc.
- Vulcanization aids long-chain fatty acids with 12 or more carbon atoms such as stearic acid, oleic acid, and palmitic acid; metal oxides such as zinc oxide, magnesium oxide, and lead oxide); anti-aging agents (hindered phenols, mercaptans, sulfides,
- the hot melt adhesive composition of the present disclosure may be solvent-free and may not contain a solvent.
- the hot melt adhesive composition of the present disclosure may be non-reactive and may not contain reactive additives.
- the amount of crystalline polyolefin (A) is 2.5% by weight or more, 5% by weight or more, 7.5% by weight or more, 10% by weight or more, 12.5% by weight or more, 15% by weight or more in the hot melt adhesive composition. It may be at least 17.5% by weight, at least 20% by weight, at least 22.5% by weight, or at least 25% by weight, preferably at least 10% by weight, more preferably at least 15% by weight.
- the amount of crystalline polyolefin (A) is 40% by weight or less, 35% by weight or less, 30% by weight or less, 25% by weight or less, 20% by weight or less, or 15% by weight or less in the hot melt adhesive composition. The amount may be 30% by weight or less, preferably 30% by weight or less.
- the amount of amorphous polyolefin (B) in the hot melt adhesive composition is 2.5% by weight or more, 5% by weight or more, 7.5% by weight or more, 10% by weight or more, 12.5% by weight or more, It may be 15% by weight or more, 17.5% by weight or more, 20% by weight or more, 22.5% by weight or more, or 25% by weight or more, preferably 10% by weight or more, more preferably 15% by weight or more. .
- the amount of amorphous polyolefin (B) is 40% by weight or less, 35% by weight or less, 30% by weight or less, 25% by weight or less, 20% by weight or less, or 15% by weight or less in the hot melt adhesive composition. It may be present, preferably 30% by weight or less.
- the amount of polypropylene wax (C) is 10% by weight or more, 15% by weight or more, 20% by weight or more, 25% by weight or more, 30% by weight or more, 35% by weight or more, 40% by weight in the hot melt adhesive composition. % or more, 45 weight % or more, or 50 weight % or more, preferably 20 weight % or more, more preferably 30 weight % or more.
- the amount of polypropylene wax (C) is 75% by weight or less, 70% by weight or less, 65% by weight or less, 60% by weight or less, 55% by weight or less, 50% by weight or less, or 45% by weight or less in the hot melt adhesive composition. It may be up to 65% by weight, more preferably up to 50% by weight.
- the amount of the tackifier (D) is 2.5% by weight or more, 5% by weight or more, 7.5% by weight or more, 10% by weight or more, 12.5% by weight or more, 15% by weight or more in the hot melt adhesive composition. It may be at least 17.5% by weight, at least 20% by weight, at least 22.5% by weight, or at least 25% by weight, preferably at least 10% by weight, more preferably at least 15% by weight.
- the amount of tackifier (D) is 40% by weight or less, 35% by weight or less, 30% by weight or less, 25% by weight or less, 20% by weight or less, or 15% by weight or less in the hot melt adhesive composition. The amount may be 30% by weight or less, preferably 30% by weight or less.
- the amount of the inorganic filler (F) is 1% by weight or more, 2.5% by weight or more, 5% by weight or more, 7.5% by weight or more, 10% by weight or more, 12.5% by weight or more in the hot melt adhesive composition. It may be at least 15% by weight, preferably at least 2.5% by weight, more preferably at least 5% by weight.
- the amount of the inorganic filler (F) is 30% by weight or less, 25% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, or 5% by weight or less in the hot melt adhesive composition. It's fine.
- the amount of elastomer (G) is 0.5% by weight or more, 1% by weight or more, 2% by weight or more, 3% by weight or more, 4% by weight or more, 5% by weight or more, 6% by weight in the hot melt adhesive composition. % or more, 7 weight % or more, 8 weight % or more, 9 weight % or more, or 10 weight % or more, preferably 1 weight % or more, more preferably 3 weight % or more.
- the amount of elastomer (G) in the hot melt adhesive composition is 25% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, 7.5% by weight or less, 5% by weight or less, or 2% by weight or less. It may be up to .5% by weight, preferably up to 15% by weight, more preferably up to 10% by weight.
- the amount of the other component (I) in the hot melt adhesive composition of the present disclosure may be appropriately selected depending on each component.
- the total amount of other components (I) in the hot melt adhesive composition is 0.1% by weight or more, 0.2% by weight or more, 0.5% by weight or more, 1% by weight or more, 2.5% by weight or more, Or it may be 5% by weight or more.
- the total amount of other components (I) in the hot melt adhesive composition is 30% by weight or less, 25% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, 7.5% by weight or less, or It may be 5% by weight or less, 2.5% by weight or less, or 1% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less.
- the respective amounts of other components (I) are 0.01% by weight or more, 0.05% by weight or more, 0.1% by weight or more, 0.3% by weight or more, and 0.5% by weight in the hot melt adhesive composition. % or more, 0.75% or more, 1% or more by weight, or 2.5% or more by weight. Further, the amount of each of the other components (I) in the hot melt adhesive composition is 10% by weight or less, 7.5% by weight or less, 5% by weight or less, 2.5% by weight or less, or 1% by weight or less. It's good to be there.
- the amount of plasticizer (H) may be based on the amount of other component (I).
- the total amount of crystalline polyolefin (A) and amorphous polyolefin (B) is 5% by weight or more, 10% by weight or more, 15% by weight or more, 20% by weight or more, 25% by weight in the hot melt adhesive composition. % or more, 30 wt.% or more, 35 wt.% or more, 40 wt.% or more, 45 wt.% or more, or 50 wt.% or more, preferably 20 wt.% or more, more preferably 30 wt.% or more.
- the total amount of crystalline polyolefin (A) and amorphous polyolefin (B) is 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight in the hot melt adhesive composition. % or less, or 30% by weight or less, preferably 60% by weight or less. Being within the above range is preferable from the viewpoint of achieving the effects of the present disclosure favorably.
- the amount of crystalline polyolefin (A) is 15 parts by weight or more, 25 parts by weight or more, more than 50 parts by weight, 75 parts by weight or more, 100 parts by weight or more with respect to 100 parts by weight of the amorphous polyolefin (B). , 125 parts by weight or more, 150 parts by weight or more, preferably 25 parts by weight or more, more preferably 60 parts by weight or more, still more preferably 75 parts by weight or more.
- the amount of crystalline polyolefin (A) is 500 parts by weight or less, 450 parts by weight or less, 400 parts by weight or less, 350 parts by weight or less, 300 parts by weight or less, based on 100 parts by weight of the amorphous polyolefin (B).
- 200 parts by weight or less 150 parts by weight or less, 100 parts by weight or less, 75 parts by weight or less, or 50 parts by weight or less, preferably 400 parts by weight or less, more preferably 300 parts by weight or less, still more preferably 200 parts by weight or less. Parts by weight or less. Being within the above range is preferable from the viewpoint of achieving the effects of the present disclosure favorably.
- the amount of polypropylene wax (C) is more than 50 parts by weight, 60 parts by weight or more, 70 parts by weight or more, based on 100 parts by weight of the total amount of crystalline polyolefin (A) and amorphous polyolefin (B).
- the amount may be 80 parts by weight or more, 90 parts by weight or more, 100 parts by weight or more, 110 parts by weight or more, or 120 parts by weight or more, preferably 60 parts by weight or more, more preferably 80 parts by weight or more, and even more preferably It is 90 parts by weight or more.
- the amount of polypropylene wax (C) is 350 parts by weight or less, 300 parts by weight or less, 250 parts by weight or less, based on 100 parts by weight of the total amount of crystalline polyolefin (A) and amorphous polyolefin (B).
- the amount may be 200 parts by weight or less, 150 parts by weight or less, or 100 parts by weight or less, preferably 300 parts by weight or less, more preferably 250 parts by weight or less, still more preferably 200 parts by weight or less.
- Being within the above range is preferable from the viewpoint of achieving the effects of the present disclosure favorably.
- the crystallization promoting effect can be improved and the mold releasability can be improved.
- adhesiveness can be improved.
- the amount of the tackifier (D) is 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, based on 100 parts by weight of the total amount of the crystalline polyolefin (A) and the amorphous polyolefin (B).
- the amount may be 40 parts by weight or more, 50 parts by weight or more, or 60 parts by weight or more, preferably 20 parts by weight or more, and more preferably 40 parts by weight or more.
- the amount of the tackifier (D) is 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, based on 100 parts by weight of the total amount of the crystalline polyolefin (A) and the amorphous polyolefin (B).
- the amount may be 75 parts by weight or less, 50 parts by weight or less, or 30 parts by weight or less, preferably 100 parts by weight or less, more preferably 75 parts by weight or less. It is preferable that the content be within the above range from the viewpoint of achieving the effects of the present disclosure favorably.
- the amount of the inorganic filler (F) is 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, based on 100 parts by weight of the total amount of the crystalline polyolefin (A) and the amorphous polyolefin (B).
- the amount may be 20 parts by weight or more, 25 parts by weight or more, or 30 parts by weight or more, preferably 10 parts by weight or more, more preferably 20 parts by weight or more.
- the amount of the inorganic filler (F) is 75 parts by weight or less, 60 parts by weight or less, 50 parts by weight or less, based on 100 parts by weight of the total amount of the crystalline polyolefin (A) and the amorphous polyolefin (B).
- the amount may be 40 parts by weight or less, 30 parts by weight or less, or 20 parts by weight or less, preferably 60 parts by weight or less, more preferably 40 parts by weight or less. Being within the above range is preferable from the viewpoint of achieving the effects of the present disclosure favorably.
- the amount of the elastomer (G) is 0.5 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, based on 100 parts by weight of the total amount of the crystalline polyolefin (A) and the amorphous polyolefin (B).
- the amount may be 5 parts by weight or more, 7 parts by weight or more, 10 parts by weight or more, 12 parts by weight or more, or 15 parts by weight or more, preferably 3 parts by weight or more, and more preferably 10 parts by weight or more.
- the amount of elastomer (G) is 60 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight based on 100 parts by weight of the total amount of crystalline polyolefin (A) and amorphous polyolefin (B). parts by weight or less, 20 parts by weight or less, 15 parts by weight or less, or 10 parts by weight or less, preferably 40 parts by weight or less, more preferably 20 parts by weight or less. Being within the above range is preferable from the viewpoint of achieving the effects of the present disclosure favorably.
- the hot melt adhesive composition of the present disclosure has a melt viscosity of 5,000 mPa ⁇ s or more, 7,500 mPa ⁇ s or more, or 10,000 mPa ⁇ s or more at 180° C., which is a common coating temperature for hot melt adhesives. , 12,000 mPa ⁇ s or more, 15,000 mPa ⁇ s or more, 20,000 mPa ⁇ s or more, or 25,000 mPa ⁇ s or more, preferably 10,000 mPa ⁇ s or more, more preferably 15,000 mPa or more It is.
- the hot melt adhesive composition of the present disclosure has a melt viscosity of 200,000 mPa ⁇ s or less, 150,000 mPa ⁇ s or less, or 100,000 mPa ⁇ s or less at 180° C., which is a common coating temperature for hot melt adhesives. , 50,000 mPa ⁇ s or less, 30,000 mPa ⁇ s or less, or 20,000 mPa ⁇ s or less, preferably 150,000 mPa ⁇ s or less, more preferably 100,000 mPa ⁇ s or less. It is preferable that the melt viscosity is within the above range because dripping, uneven coating, etc. will not occur when applying to an adherend.
- the above melt viscosity is a value measured using a parallel plate type rheometer at a shear rate of 4.3 sec -1 .
- the storage modulus at 60°C is 1 ⁇ 10 4 Pa or more, 5 ⁇ 10 4 Pa or more, 1 ⁇ It may be 10 5 Pa or more, 5 ⁇ 10 5 Pa or more, 1 ⁇ 10 6 Pa or more, 2 ⁇ 10 6 Pa or more, or 3 ⁇ 10 6 Pa or more, preferably 1 ⁇ 10 5 Pa or more, more preferably It is 1 ⁇ 10 6 Pa or more.
- the storage modulus at 60°C is 1 ⁇ 10 8 Pa or less, 5 ⁇ 10 7 Pa or less, 1 ⁇ It may be 10 7 Pa or less, 5 ⁇ 10 6 Pa or less, 3 ⁇ 10 6 Pa or less, or 1 ⁇ 10 6 Pa or less.
- the above storage modulus is a value measured using a parallel plate rheometer at a shear rate of 4.3 sec -1 .
- the temperature at which tan ⁇ becomes 1 or less is 30°C or higher, 40°C or higher, 50°C or higher, or 60°C or higher. , or 70°C or higher, preferably 40°C or higher, more preferably 60°C or higher.
- the temperature at which tan ⁇ becomes 1 or less is 100°C or lower, 90°C or lower, 80°C or lower, or 70°C.
- the temperature may be below, preferably 80°C or below.
- tan ⁇ is a loss tangent, and is the ratio of the storage shear modulus (G') to the loss shear modulus (G''), G''/G'.
- tan ⁇ is a value measured using a parallel plate rheometer at a shear rate of 4.3 sec ⁇ 1 .
- the hot melt adhesive composition of the present disclosure can be produced by mixing (A) to (C).
- the hot melt adhesive composition can be produced by mixing (A) to (C) together with other components as necessary using a heating mixer.
- the adhesive body of the present disclosure has a first base material and a second base material adhered to the first base material via a hot melt adhesive layer formed from a hot melt adhesive composition.
- the base materials used as the first base material and the second base material are not particularly limited, and include, for example, wood materials; plastic materials such as polyolefin, polyvinyl chloride, polyurethane, polyester, and epoxy resin; foamed materials of the above plastic materials; Materials include: rubber materials such as natural rubber and synthetic rubber; metal materials such as aluminum, iron, and stainless steel; and inorganic materials such as ceramics.
- the shape of each base material is also not particularly limited, and may be, for example, sheet-like, foil-like, plate-like, or molded. Further, each base material may be made of only one kind of material, or may be made of two or more kinds of materials.
- the material of the surface of the base material on which the adhesive layer is provided is preferably a non-metal, more preferably a resin as described above, and still more preferably a polyolefin including polypropylene.
- various hot melt applicators can be used as a method for coating the substrate, and examples include methods using a spray gun, comma coater, die coater, roll coater, and the like.
- a spray gun When applying to a substrate, it is usually heated at a temperature of 140° C. to 200° C. to melt it, and it can be applied in a molten state.
- After applying it to a release film or paper it may be used by thermally transferring it to another base material.
- the hot melt adhesive layer may be solidified on the substrate by cooling.
- the precoated base material (adhesive layer-containing base material) obtained after the coating process may be used as is for the next molding process, or it can be stored and then used for the next process.
- the hot melt adhesive layer may be heated and activated to melt it again.
- means for thermal activation include methods using heating, ultrasound, high frequency, microwave, etc., but there are no particular limitations.
- the reactivation is performed immediately before the pre-coated base material and the second base material are pressed together.
- the pre-coated base material and the second base material are pressed together before the surface of the hot melt adhesive composition layer is solidified.
- the second base material may or may not be heated. Further, as long as the hot-melt adhesive composition layer is in a reactivated state, it is not necessary to heat it at the time of pressure bonding, but it may be heated at the same time as the pressure is applied, if necessary.
- the temperature for heat activation is preferably 100 to 200°C, for example 100 to 180°C, more preferably 120 to 160°C, based on the surface temperature of the hot melt adhesive layer.
- the pressure during pressure bonding for adhesion between the first base material and the second base material may be 0.01 to 0.5 MPa, preferably 0.01 to 0.20 MPa, and more preferably 0.01 to 0.10 MPa. preferable.
- the time for pressure bonding may be, for example, 1 to 300 seconds, preferably 1 to 60 seconds, and more preferably 10 to 30 seconds.
- the method for manufacturing an adhesive body of the present disclosure includes a step in which a mold and a hot melt adhesive composition are brought into contact with each other.
- the mold and the hot melt adhesive composition may be in contact with each other during the coating process or the bonding process.
- the method for producing an adhesive body of the present disclosure can be suitably used in a vacuum forming method that includes a step in which a mold and a hot melt adhesive composition are brought into contact.
- the material of the mold is not limited, but may be made of metal, ceramic, etc., and is preferably made of metal (for example, various alloys such as aluminum, iron, stainless steel, etc.).
- the method for producing an adhesive body of the present disclosure may further include the step of peeling off the hot melt adhesive layer formed from the hot melt adhesive composition from the mold.
- the hot melt adhesive layer may be peeled off from the mold after cooling.
- the automobile interior material of the present disclosure includes an automobile interior molded article and an automobile interior adhered to the automobile interior molded article through a hot melt adhesive layer formed from the hot melt adhesive composition of the present disclosure. (hereinafter also referred to as "skin material").
- the skin material may be a skin material derived from a hot melt adhesive layer-containing skin material (pre-coated skin material). Examples of automobile interior materials include door trims, instrument panels, ceiling materials, rear trays, pillars, and the like.
- molded products for automobile interiors there are no particular restrictions on the material for molded products for automobile interiors, as long as they are used for automobile interior materials, such as wood materials such as paper and wood; polyolefins (polypropylene, polyethylene, ethylene-propylene copolymer, etc.), Plastic materials such as polyvinyl chloride, polyurethane, polyester, epoxy resin, nylon, polyester, polycarbonate, polyurethane, acrylic, ABS, and PCABS; Rubber materials such as natural rubber and synthetic rubber; Metal materials such as aluminum, iron, and stainless steel; Examples include inorganic materials such as ceramics. Molded products for automobile interiors may be made of only one kind of material, or may be made of two or more kinds of materials.
- the material of the surface of the molded article for automobile interiors on which the adhesive layer is provided is preferably the above-mentioned molded article material for automobile interiors that is non-metallic, and more preferably the above-mentioned molded article material for automobile interiors that is made of resin.
- Polyolefins such as polypropylene are more preferred.
- the skin material is not particularly limited as long as it is a material used for automobile interior materials, such as plastic sheets such as polyolefin, soft polyvinyl chloride, and polyurethane; foams of the above plastics; rubbers such as natural rubber and synthetic rubber. Sheets; fabric materials such as woven fabrics and non-woven fabrics; metal foils such as aluminum, and the like.
- the skin material may consist of only one layer, or may include two or more layers of the same kind of material or different materials.
- a skin material containing two or more types of layers includes, for example, one or more layers of the above-mentioned plastic sheet, rubber sheet, fabric material, metal foil, etc., and one or more types of the above-mentioned plastic foam. Examples include sheet materials with laminated layers.
- laminated sheet materials include flexible polyvinyl chloride with polyolefin foam, olefinic thermoplastic elastomer with polyolefin foam, fabric with polyurethane foam, and the like.
- the material of the surface on which the adhesive layer of the skin material is provided is preferably the skin material mentioned above which is non-metallic, more preferably the skin material mentioned above which is made of resin, and still more preferably polypropylene or the like. It is a polyolefin.
- the method for producing an automobile interior material of the present disclosure includes the method for producing an adhesive body described above, wherein the adhesive body is an automobile interior material, the first base material is a skin material, and the second base material is an automobile interior material. It may be a molded article for use. Conversely, the adhesive body may be an automobile interior material, the first base material may be a molded article for automobile interiors, and the second base material may be a skin material.
- An example of a method for manufacturing an automobile interior material is to apply the hot melt adhesive composition of the present disclosure to the back surface of a skin material (for example, the foamed layer surface of the skin material), and prepare a hot melt adhesive layer-containing skin material (pre-coated skin material).
- Step of obtaining After reactivating the obtained pre-coated skin material with a far-infrared heater etc. and melting the hot melt adhesive layer, the skin material and the molded article for automobile interior are crimped together via the hot melt adhesive layer.
- the process may include a step of causing Furthermore, a curing step for crystallizing the hot melt adhesive layer may be included.
- the back surface of the skin material means the surface that faces the molded product for automotive interior when the skin material and the molded product for automotive interior are bonded together.
- Component A ⁇ A-1: VERSIFY4200 manufactured by Dow Chemical Company (melting point 84°C, Shore A hardness 94, propylene/ethylene copolymer)
- ⁇ A-2 VERSIFY3000 manufactured by Dow Chemical Company (melting point 108°C, Shore A hardness 96, propylene/ethylene copolymer)
- Component B ⁇ B-1: VESTOPLAST792 manufactured by Evonik (softening point 108°C, propylene-ethylene-butene copolymer)
- ⁇ B-2 RT2585 manufactured by REXTAC (softening point 132°C, propylene/ethylene copolymer)
- Component C ⁇ C-1: Viscol 660-P manufactured by Sanyo Chemical Industries, Ltd.
- YS resin PN1150 softening point 115°C, terpene type
- ⁇ D-4 YS Polyster T145 manufactured by Yasuhara Chemical Co., Ltd. (softening point 145°C, terpene phenol type)
- Component E ⁇ E-1: BASF Irganox 1010 (melting point 110°C, hindered phenol type)
- E-2 Irgafos 168 manufactured by BASF (melting point 183°C, phosphorus type)
- Component F ⁇ F-1: Calcium carbonate 300 mesh product manufactured by Shiraishi Calcium Co., Ltd.
- sample 1 for adhesion test The above adhesive was applied to the surface of the skin material (TPO/PPF, total thickness 4 mm) at 180° C. using a roll coater so that the adhesive layer was 100 g/m2. Next, within one day after applying the adhesive, this skin material was heated with a far-infrared heater to a temperature of 160°C or higher, then immediately stacked on an aluminum plate (1 mm thick) and pressed under 0.1 MPa for 15 seconds. A laminate (sample 1 for adhesion test) was obtained.
- sample 2 for adhesion test The above adhesive was applied to the surface of the skin material (TPO/PPF, total thickness 4 mm) at 180° C. using a roll coater so that the adhesive layer was 100 g/m2. Next, within one day after applying the adhesive, this skin material was heated with a far-infrared heater to a temperature of 160°C or higher, then immediately stacked on a PP board (thickness 2 mm) and pressed under 0.1 MPa and 15 seconds. A laminate (sample 2 for adhesion test) was obtained.
- the hot melt adhesive composition of the present disclosure can be used, for example, as a solvent-free adhesive without VOC emissions, and has excellent adhesion and heat resistance to resin base materials, especially olefin base materials.
- the workability allows for easy peeling from the mold (for example, when bonded using a vacuum forming method), it can be suitably used as an adhesive for automobile interiors.
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Abstract
Description
[項1]
ショアA硬度が80以上である結晶性ポリオレフィン(A)、
非晶性ポリオレフィン(B)及び
ポリプロピレン系ワックス(C)
を含み、
前記結晶性ポリオレフィン(A)と前記非晶性ポリオレフィン(B)との合計量100重量部に対し、前記ポリプロピレン系ワックス(C)の量が60重量部以上300重量部以下である、ホットメルト接着剤組成物。
[項2]
前記結晶性ポリオレフィン(A)の融点が80℃以上である、項1に記載のホットメルト接着剤組成物。
[項3]
前記結晶性ポリオレフィン(A)が、エチレン-プロピレン共重合体を含む、項1又は2に記載のホットメルト接着剤組成物。
[項4]
前記非晶性ポリオレフィン(B)の軟化点が100℃以上である、項1~3のいずれか一項に記載のホットメルト接着剤組成物。
[項5]
前記非晶性ポリオレフィン(B)がエチレン-プロピレンの二元共重合体及びエチレン-プロピレン-ブテンの三元共重合体からなる群から選択される少なくとも一種を含む、項1~4のいずれか一項に記載のホットメルト接着剤組成物。
[項6]
前記ポリプロピレン系ワックス(C)の軟化点が130℃以上である、項1~5のいずれか一項に記載のホットメルト接着剤組成物。
[項7]
粘着付与剤(D)を含む、項1~6のいずれか一項に記載のホットメルト接着剤組成物。
[項8]
前記粘着付与剤(D)の軟化点が90℃以上である、項7に記載のホットメルト接着剤組成物。
[項9]
前記粘着付与剤(D)が、水添石油樹脂、テルペン樹脂、及びテルペンフェノール樹脂からなる群から選択される少なくとも一種を含む、項7に記載のホットメルト接着剤組成物。
[項10]
酸化防止剤(E)を含む、項1~9のいずれか一項に記載のホットメルト接着剤組成物。
[項11]
無機充填剤(F)を含む、項1~10のいずれか一項に記載のホットメルト接着剤組成物。
[項12]
エラストマー(G)を含む、項1~11のいずれか一項に記載のホットメルト接着剤組成物。
[項13]
180℃における溶融粘度が15,000mPa・s以上100,000mPa・s以下である、項1~12のいずれか一項に記載のホットメルト接着剤組成物。
[項14]
自動車内装材用である、項1~13のいずれか一項に記載のホットメルト接着剤組成物。
[項15]
自動車内装用表皮材、及び、前記自動車内装用表皮材の裏面に項1~14のいずれか一項に記載のホットメルト接着剤組成物から形成されるホットメルト接着剤層を含む、自動車内装用プレコート表皮材。
[項16]
自動車内装用成形品、及び、前記ホットメルト接着剤層を介して前記自動車用成形品に接着する項15に記載の前記自動車内装用プレコート表皮材を含む、自動車内装材。
[項17]
接着体の製造方法であって、
前記接着体は、第一基材、及び、項1~14のいずれか一項に記載のホットメルト接着剤組成物から形成されるホットメルト接着剤層を介して前記第一基材に接着している第二基材を有し、
金型と前記ホットメルト接着剤組成物とが接触する工程を有する、接着体の製造方法。
本開示のホットメルト接着剤組成物は、結晶性ポリオレフィン(A)、非晶性ポリオレフィン(B)、およびポリプロピレン系ワックス(C)を含む。本開示のホットメルト接着剤組成物は、(A)~(C)に加えて、必要に応じて、粘着付与剤(D)、酸化防止剤(E)、無機充填剤(F)、エラストマー(G)、可塑剤(H)、その他添加剤(I)等から選択された一以上をさらに含むことができる。
本開示のホットメルト接着剤組成物は結晶性ポリオレフィン(A)を含む。結晶性ポリオレフィン(A)は高い結晶性を有するポリオレフィンである。結晶性ポリオレフィン(A)は、結晶化度、ショアA硬度、及び/又は分子量等の観点から本明細書にて説明される他の成分とは区別されるものである。典型的には結晶性ポリオレフィン(A)の結晶化度は20%以上である。典型的には結晶性ポリオレフィン(A)のショアA硬度は80以上である。典型的には結晶性ポリオレフィン(A)は重量平均分子量40,000以上である。
本開示のホットメルト接着剤組成物は非晶性ポリオレフィン(B)を含む。非晶性ポリオレフィン(B)は結晶性を有しない、又は少量の結晶性を有するポリオレフィンであり、柔軟性を付与することができる。非晶性ポリオレフィン(B)は、結晶化度、及び/又は分子量等の観点から本明細書にて説明される他の成分とは区別されるものである。典型的には非晶性ポリオレフィン(B)の結晶化度は20%未満である。典型的には非晶性ポリオレフィン(B)は重量平均分子量40,000以上である。
本開示のホットメルト接着剤組成物はポリプロピレン系ワックス(C)を含む。ポリプロピレン系ワックス(C)は、プロピレンから誘導された繰り返し単位を有するワックスのことである。ポリプロピレン系ワックス(C)は一般に低分子量(40,000未満)であり、ホットメルト接着剤を低粘度化することで塗布性や被着体への濡れ性を付与することができる。また、ポリプロピレン系ワックス(C)は結晶性ポリオレフィン(A)の結晶化および固化を促進し、ホットメルト接着剤の固化速度を向上させ、金型剥離性を向上し得る。
本開示のホットメルト接着剤組成物は粘着付与剤(D)を含んでもよい。粘着付与剤(D)は、溶融時タック性を向上し得る。
本開示のホットメルト接着剤組成物は酸化防止剤(E)を含んでもよい。酸化防止剤(E)を含むことにより、熱安定性が向上し、本開示の効果を良好に奏する観点から好適となり得る。
本開示のホットメルト接着剤組成物は無機充填剤(F)を含んでもよい。無機充填剤(F)の添加により、接着性、たれ性、及び比重等の調整が可能である。
本開示のホットメルト接着剤組成物はエラストマー(G)を含んでもよい。エラストマー(G)は弾性を示す高分子である。エラストマー(G)は熱硬化性又は熱可塑性であってよく、好ましくは熱可塑性である。エラストマー(G)は、結晶化度、ショアA硬度、及び/又は分子量等の観点から本明細書にて説明される他の成分とは区別されるものである。典型的にはエラストマー(G)は非晶性ではない。典型的にはエラストマー(G)はショアA硬度80未満である。典型的にはエラストマー(G)は重量平均分子量40,000以上である。
本開示のホットメルト接着剤組成物は可塑剤(H)を含んでもよい。可塑剤(H)は鎖状アルキル基含有低分子化合物やオレフィンオリゴマー等のオイル状物質である。可塑剤(H)はホットメルト接着剤を低粘度化することで塗布性や被着体への濡れ性を向上し得る。
本開示のホットメルト接着剤組成物は上記以外に、必要に応じて、その他成分(I)を含んでもよい。その他成分(I)の例としては、着色剤(例えばベンガラ、酸化チタン、他の着色顔料、染料等);有機溶剤(メタノール、エタノール、イソプロピルアルコール、ブタノール、アセトン、メチルエチルケトン、リグロイン、酢酸エチル、テトラヒドロフラン、n-ヘキサン、ヘプタンや、イソパラフィン系高沸点溶剤等);密着剤(ビニルトリメトキシシラン、ビニルトリエトキシシラン、アミノシラン、メルカプトシラン、エポキシシラン等のシランカップリング剤、ポリオキシアルキレン骨格を有するグリシジルエーテル等のエポキシ化合物等);加硫促進剤(グアニジン類、アルデヒド-アミン類、アルデヒド-アンモニア類、チアゾール類、スルフェンアミド類、チオ尿素類、チウラム類、ジチオカルバメート類、ザンテート類等);加硫助剤(ステアリン酸、オレイン酸、およびパルミチン酸等の炭素数12以上の長鎖脂肪酸、酸化亜鉛、酸化マグネシウム、および酸化鉛等の金属酸化物);老化防止剤(ヒンダードフェノール類、メルカプタン類、スルフィド類、ジチオカルボン酸塩類、チオウレア類、チオホスフェイト類、チオアルデヒド類等);紫外線吸収剤・光安定剤(ベンゾトリアゾール類、ヒンダードアミン類等);揺変剤(コロイダルシリカ、有機ベントナイト、脂肪酸アマイド、水添ひまし油等);上記以外の樹脂・ポリマー成分(熱硬化性樹脂、熱可塑性樹脂等)が挙げられる。これらは単独で用いてもよいし、又は二種類以上を併用してもよい。
結晶性ポリオレフィン(A)の量は、ホットメルト接着剤組成物において、2.5重量%以上、5重量%以上、7.5重量%以上、10重量%以上、12.5重量%以上、15重量%以上、17.5重量%以上、20重量%以上、22.5重量%以上、又は25重量%以上であってよく、好ましくは10重量%以上、より好ましくは15重量%以上である。結晶性ポリオレフィン(A)の量は、ホットメルト接着剤組成物において、40重量%以下、35重量%以下、30重量%以下、25重量%以下、20重量%以下、又は15重量%以下であってよく、好ましくは30重量%以下である。
本開示のホットメルト接着剤組成物は、ホットメルト接着剤の一般的な塗工温度である180℃における溶融粘度が5,000mPa・s以上、7,500mPa・s以上、10,000mPa・s以上、12,000mPa・s以上、15,000mPa・s以上、20,000mPa・s以上、又は25,000mPa・s以上であってよく、好ましくは10,000mPa・s以上、より好ましくは15,000mPa以上である。本開示のホットメルト接着剤組成物は、ホットメルト接着剤の一般的な塗工温度である180℃における溶融粘度が200,000mPa・s以下、150,000mPa・s以下、100,000mPa・s以下、50,000mPa・s以下、30,000mPa・s以下、又は20,000mPa・s以下であってよく、好ましくは150,000mPa・s以下、より好ましくは100,000mPa・s以下である。溶融粘度が上記範囲内であれば、被着体に塗布する際に液垂れや塗りムラ等が生じることがないため好ましい。上記溶融粘度は、パラレルプレート型のレオメーターを用いて、せん断速度4.3sec-1の条件で測定した値である。
本開示のホットメルト接着剤組成物は、(A)~(C)を混合することにより製造することができる。例えば、ホットメルト接着剤組成物は、(A)~(C)を必要に応じてその他成分と共に、加熱混合撹拌機を用いて一括混合することにより製造することができる。
本開示の接着体は、第一基材、及び、ホットメルト接着剤組成物から形成されるホットメルト接着剤層を介して前記第一基材に接着している第二基材を有する。
第一基材及び第二基材として使用される基材には、特に制限はなく、例えば、木質材;ポリオレフィン、ポリ塩化ビニル、ポリウレタン、ポリエステル、エポキシ樹脂等のプラスチック材;前記プラスチック材の発泡体;天然ゴム、合成ゴム等のゴム材;アルミニウム、鉄、ステンレス鋼等の金属材;セラミックス等の無機質材等を材質とするものが挙げられる。各基材の形状も特に制限はなく、例えば、シート状、箔状、板状又は成形体等でもよい。また、各基材は、一種の材質のみからなるものであってもよいし、二種以上から構成されるものであってもよい。基材の接着剤層が設けられる表面の材質は非金属であることが好ましく、より好ましくは上述したような樹脂であり、さらに好ましくは特にポリプロピレンをはじめとするポリオレフィンである。
塗布工程における、基材への塗布方法としては、各種ホットメルトアプリケーターを用いることができ、例えば、スプレーガン、コンマコーター、ダイコーター、ロールコーター等を用いる方法が挙げられる。基材への塗布の際は、通常、140℃~200℃の温度で加熱して溶融させ、溶融状態で塗布することができる。離型フィルムや離型紙に塗布した後、別の基材へ熱転写して使用しても構わない。塗布後、冷却することにより、基材にホットメルト接着剤層を固化させてもよい。塗布工程後に得られるプレコート基材(接着剤層含有基材)は、そのまま、次の成形工程に供してもよく、あるいは保管してから次の工程に供することもできる。
接着工程においては、必要により、ホットメルト接着剤層を加熱活性化して再度溶融させてもよい。加熱活性化の手段としては、例えば、加熱、超音波、高周波、マイクロ波による方法等があるが、特に制限はない。再活性化は、プレコート基材と第二基材との圧着直前に行うことが好ましい。プレコート基材と第二基材との圧着は、ホットメルト接着剤組成物層面が固化する前に行う。圧着方法としては特に制限はなく、例えば、プレス圧着工法、真空成形工法等が挙げられる。第二基材は、加熱されていてもよいし、加熱されていなくてもよい。また、ホットメルト接着剤組成物層が再活性化された状態であれば、圧着時には加熱しなくてもよいが、必要に応じて加圧と同時に加熱してもよい。
本開示の接着体の製造方法は、金型とホットメルト接着剤組成物とが接触する工程を有することが好ましい。本開示のホットメルト接着剤組成物は、塗布工程又は接着工程において金型とホットメルト接着剤組成物とが接触していてよい。例えば、本開示の接着体の製造方法は金型とホットメルト接着剤組成物とが接触する工程を含む真空成型工法に好適に用いることができる。
[自動車内装材]
本開示の自動車内装材は、自動車内装用成形品、及び、本開示のホットメルト接着剤組成物から形成されるホットメルト接着剤層を介して前記自動車内装用成形品に接着されている自動車内装用表皮材(以下、「表皮材」ともいう。)を含む。表皮材はホットメルト接着剤層含有表皮材(プレコート表皮材)由来の表皮材であってよい。自動車内装材の例としては、ドアトリム、インストルメントパネル、天井材、リアトレイ、ピラー等が挙げられる。
本開示の自動車内装材の製造方法は、上記の接着体の製造方法において、接着体が自動車内装材であって、第一基材が表皮材であって、かつ、第二基材が自動車内装用成形品であってよい。逆に、接着体が自動車内装材であって、第一基材が自動車内装用成形品であって、かつ、第二基材が表皮材である場合であってよい。
以下の表1に示す組成にて、下記に示す各成分を、混合撹拌機(森山製作所製双腕式ニーダーSV-1-1)を用いて、180℃で混合することにより、ホットメルト接着剤組成物を得た。
・A-1:ダウケミカル社製VERSIFY4200(融点84℃、ショアA硬度94、プロピレン・エチレン共重合体)
・A-2:ダウケミカル社製VERSIFY3000(融点108℃、ショアA硬度96、プロピレン・エチレン共重合体)
[成分B]
・B-1:エボニック社製VESTOPLAST792(軟化点108℃、プロピレン・エチレン・ブテン共重合体)
・B-2:REXTAC社製RT2585(軟化点132℃、プロピレン・エチレン共重合体)
[成分C]
・C-1:三洋化成工業社製ビスコール660-P(軟化点145℃、重量平均分子量8000、ポリプロピレンワックス)
・C-2:三洋化成工業社製サンワックス171-P(軟化点107℃、重量平均分子量9500、ポリエチレンワックス)
[成分D]
・D-1:荒川化学社製アルコンP140(軟化点140℃、水添石油系)
・D-2:荒川化学社製アルコンP90(軟化点90℃、水添石油系)
・D-3:ヤスハラケミカル社製YSレジンPN1150(軟化点115℃、テルペン系)
・D-4:ヤスハラケミカル社製YSポリスターT145(軟化点145℃、テルペンフェノール系)
[成分E]
・E-1:BASF社製イルガノックス1010(融点110℃、ヒンダードフェノール系)
・E-2:BASF社製イルガフォス168(融点183℃、リン系)
[成分F]
・F-1:白石カルシウム社製炭酸カルシウム300メッシュ品
[成分G]
・G-1:三井化学社製タフマーPN-2070(融点140℃、ショアA硬度75、プロピレン系エラストマー)
・G-2:エクソンモービル社製VISTAMAXX6202(ビカット軟化点48℃、ショアA硬度61、プロピレン系エラストマー)
パラレルプレート型のレオメーターを用いて、温度180℃、せん断速度4.3sec-1の条件で測定した。結果を表1に示す。
パラレルプレート型のレオメーターを用いて、160℃から33℃毎分で急冷した際の粘弾性挙動をせん断速度4.3sec-1の条件で測定した。60℃における貯蔵弾性率を記録した。また、tanδが1以下になる温度を記録した。結果を表1に示す。tanδが1以下になる温度は金型離型性の指標として用いることができる。測定初期において、ホットメルト接着剤は溶融状態にあるため、弾性より粘性が優位に働くため、tanδは1以上を示すが、急冷することでホットメルト接着剤が固化するため、粘性より弾性が優位に働くようになる。tanδが1以下になる温度はホットメルト接着剤が固化する温度と考えることができる。
上記接着剤を180℃にて、表皮材(TPO/PPF、総厚4mm)の表面に、ロールコーターを用いて、接着層が100g/平米になるように塗布した。次に、接着剤塗布後1日以内に本表皮材を160℃以上になるまで遠赤外線ヒーターで加熱した直後、アルミ板(厚み1mm)に重ね合わせ、0.1MPa、15秒の条件で圧締し、積層体(接着試験用試料1)を得た。
積層体(接着試験用試料1)を得てから一分以内に、プッシュプルゲージを用いて、90度剥離での剥離強度(N/25mm)を測定した。
〇:10N/25mm以上
×:10N/25mm未満
上記接着剤を180℃にて、表皮材(TPO/PPF、総厚4mm)の表面に、ロールコーターを用いて、接着層が100g/平米になるように塗布した。次に、接着剤塗布後1日以内に本表皮材を160℃以上になるまで遠赤外線ヒーターで加熱した直後、PPボード(厚み2mm)に重ね合わせ、0.1MPa、15秒の条件で圧締し、積層体(接着試験用試料2)を得た。
積層体(接着試験用試料2)を得た後、60℃雰囲気中において200g/25mmの荷重を90度角方向に加え、5分後の剥離長さ(mm)を測定した。結果を表1に示す。
BA:基材側での界面破壊
FB:表皮材の材料破壊
CF:接着剤の凝集破壊
破壊状態の後の数字は破壊状態の割合を示す。
積層体(接着試験用試料2)を25℃24時間養生後、180度剥離での剥離強度(N/25mm)を測定した。PPボードを治具で固定し、表皮材を引っ張る形で剥離した。剥離速度は200mm毎分で測定した。結果を表1に示す。
積層体(接着試験用試料2)を25℃24時間養生後、80℃雰囲気中において100g又は200g/25mmの荷重を90度角方向に加え、24時間後の剥離長さ(mm)を測定した。結果を表1に示す。
実施例1~13の試料では、良好な金型離型性、接着特性が得られた。比較例1及び2では、結晶性ポリオレフィン(A)が配合されていないため、金型離型性および/または耐熱クリープが低下した。比較例3および4では、ポリプロピレン系ワックスの配合量が本開示の範囲外であるため、金型離型性が低下した。比較例5では、ポリエチレン系ワックスを使用したため、金型離型性および耐熱クリープが低下した。
Claims (17)
- ショアA硬度が80以上である結晶性ポリオレフィン(A)、
非晶性ポリオレフィン(B)及び
ポリプロピレン系ワックス(C)
を含み、
前記結晶性ポリオレフィン(A)と前記非晶性ポリオレフィン(B)との合計量100重量部に対し、前記ポリプロピレン系ワックス(C)の量が60重量部以上300重量部以下である、ホットメルト接着剤組成物。 - 前記結晶性ポリオレフィン(A)の融点が80℃以上である、請求項1に記載のホットメルト接着剤組成物。
- 前記結晶性ポリオレフィン(A)が、エチレン-プロピレン共重合体を含む、請求項1又は2に記載のホットメルト接着剤組成物。
- 前記非晶性ポリオレフィン(B)の軟化点が100℃以上である、請求項1~3のいずれか一項に記載のホットメルト接着剤組成物。
- 前記非晶性ポリオレフィン(B)がエチレン-プロピレンの二元共重合体及びエチレン-プロピレン-ブテンの三元共重合体からなる群から選択される少なくとも一種を含む、請求項1~4のいずれか一項に記載のホットメルト接着剤組成物。
- 前記ポリプロピレン系ワックス(C)の軟化点が130℃以上である、請求項1~5のいずれか一項に記載のホットメルト接着剤組成物。
- 粘着付与剤(D)を含む、請求項1~6のいずれか一項に記載のホットメルト接着剤組成物。
- 前記粘着付与剤(D)の軟化点が90℃以上である、請求項7に記載のホットメルト接着剤組成物。
- 前記粘着付与剤(D)が、水添石油樹脂、テルペン樹脂、及びテルペンフェノール樹脂からなる群から選択される少なくとも一種を含む、請求項7又は8に記載のホットメルト接着剤組成物。
- 酸化防止剤(E)を含む、請求項1~9のいずれか一項に記載のホットメルト接着剤組成物。
- 無機充填剤(F)を含む、請求項1~10のいずれか一項に記載のホットメルト接着剤組成物。
- エラストマー(G)を含む、請求項1~11のいずれか一項に記載のホットメルト接着剤組成物。
- 180℃における溶融粘度が15,000mPa・s以上100,000mPa・s以下である、請求項1~12のいずれか一項に記載のホットメルト接着剤組成物。
- 自動車内装材用である、請求項1~13のいずれか一項に記載のホットメルト接着剤組成物。
- 自動車内装用表皮材、及び、前記自動車内装用表皮材の裏面に請求項1~14のいずれか一項に記載のホットメルト接着剤組成物から形成されるホットメルト接着剤層を含む、自動車内装用プレコート表皮材。
- 自動車内装用成形品、及び、前記ホットメルト接着剤層を介して前記自動車用成形品に接着する請求項15に記載の前記自動車内装用プレコート表皮材を含む、自動車内装材。
- 接着体の製造方法であって、
前記接着体は、第一基材、及び、請求項1~14のいずれか一項に記載のホットメルト接着剤組成物から形成されるホットメルト接着剤層を介して前記第一基材に接着している第二基材を有し、
金型と前記ホットメルト接着剤組成物とが接触する工程を有する、接着体の製造方法。
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| US18/875,198 US20250388787A1 (en) | 2022-06-29 | 2023-06-15 | Hot-melt adhesive composition, precoated surface material for automobile interior, automobile interior material, and method for producing bonded object |
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| CN120988574A (zh) * | 2025-10-24 | 2025-11-21 | 中国建筑科学研究院有限公司 | 一种具备制冷性能的超疏建筑防水涂料及其制备方法 |
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| WO2020050225A1 (ja) * | 2018-09-04 | 2020-03-12 | 出光興産株式会社 | 熱可塑性樹脂組成物及びホットメルト接着剤 |
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2023
- 2023-06-15 US US18/875,198 patent/US20250388787A1/en active Pending
- 2023-06-15 WO PCT/JP2023/022213 patent/WO2024004673A1/ja not_active Ceased
- 2023-06-15 CN CN202380046702.0A patent/CN119384477A/zh active Pending
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| JP2009057397A (ja) * | 2007-08-29 | 2009-03-19 | Sanyo Chem Ind Ltd | 難接着基材用ホットメルト接着剤 |
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| CN120988574A (zh) * | 2025-10-24 | 2025-11-21 | 中国建筑科学研究院有限公司 | 一种具备制冷性能的超疏建筑防水涂料及其制备方法 |
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| US20250388787A1 (en) | 2025-12-25 |
| CN119384477A (zh) | 2025-01-28 |
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