Classifications

• • 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
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
  • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
• • 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
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • 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
  • C09J123/26—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 modified by chemical after-treatment

Definitions

• the present invention relates to an adhesive composition and a laminate.
• Polyolefin-based resins such as polypropylene and polyethylene are inexpensive and have many excellent properties such as moldability, chemical resistance, water resistance, and electrical properties, and therefore have been widely adopted in recent years as sheets, films, molded products, and the like.
• polar substrates such as polyurethane resins, polyamide resins, acrylic resins, and polyester resins
• the substrates made of these polyolefin resins are non-polar and crystalline. , Has the drawback of being difficult to paint and bond.
• the number of olefin resin parts in automobile exteriors including bumpers is increasing, and due to the movement to reduce VOC and CO 2 , it is being considered to replace the paint with a paint substitute film.
• an adhesive layer having the same degree of adhesiveness is required for both steel plate parts and olefin resin parts, and further, performance such as chipping resistance is also required.
• the chipping resistance is durability against the fact that the coating film is locally destroyed or peeled off when a stone or the like that is flipped up while the automobile is running collides with it.
• adhesive compositions showing adhesiveness between polypropylene resin / polyethylene resin adhesive compositions showing adhesiveness between olefins (Patent Documents 1 to 3), and Adhesive compositions (Patent Documents 4 to 6) that exhibit adhesiveness even when an olefin resin and a non-olefin resin are bonded together have been proposed.
• the present invention provides an adhesive composition that exhibits good adhesiveness and chipping resistance between a polyolefin resin base material and a polar plastic base material or a metal base material other than the polyolefin resin base material, and can be bonded at a low temperature. It is to provide.
• the present inventors have studied diligently, found that a combination of a specific modified polyolefin, a stress relaxation agent and a tackifier is effective, and have proposed the following inventions. That is, the present invention has the following configuration.
• An adhesive composition which is at least one kind of resin selected from the group consisting of a based resin, a urethane based resin, and an amide based resin and a styrene based resin.
• the adhesive composition according to (1) above, wherein the stress relaxation agent (B) is an olefin resin (B1) and a hydrogenated styrene resin (B2). (3) The adhesive composition according to any one of (1) to (2) above, further comprising a solvent (D). (4) The adhesive composition according to any one of (1) to (3) above, wherein the solvent (D) contains an alicyclic hydrocarbon solvent (D1) and an ester solvent or a ketone solvent (D2). .. (5) The mass ratio of the alicyclic hydrocarbon solvent (D1) to the ester solvent or the ketone solvent (D2) is (D1) / (D2) 95/5 to 50/50, the above (1). The adhesive composition according to any one of (4).
• the adhesive composition according to any one of (1) to (5) above which comprises a curing agent (E).
• the adhesive composition according to any one of (1) to (6) above which is used for adhering a polyolefin resin base material 1 and a base material 2 different from the base material 1.
• the adhesive composition of the present invention contains an acid-modified polyolefin, a stress relieving agent and a tackifier, and has excellent adhesiveness to a poorly adhesive substrate such as a polyolefin. Further, since the coating can be performed by dry laminating, the equipment cost can be reduced and the film thickness can be reduced. Further, excellent adhesiveness is exhibited even when heat-bonding is performed at a low temperature such as 90 ° C. or lower, which has a small effect of heat shrinkage of the polyolefin base material.
• the adhesive composition of the present invention is useful as an adhesive for an automobile exterior coating substitute film because it exhibits not only adhesiveness to a difficult-to-adhere substrate such as polyolefin but also high chipping resistance.
• the acid-modified polyolefin (A) used in the present invention is not limited, but is preferably obtained by grafting at least one of ⁇ , ⁇ -unsaturated carboxylic acid and an acid anhydride thereof on the polyolefin.
• a propylene-based resin containing propylene as a constituent component is preferable, and homopolypropylene can be particularly preferably used, but a propylene / ⁇ -olefin copolymer can also be used.
• the propylene / ⁇ -olefin copolymer is obtained by copolymerizing propylene as a main component with ⁇ -olefin.
• the ⁇ -olefin for example, one or several kinds of ethylene, 1-butene, 1-heptene, 1-octene, 4-methyl-1-pentene, vinyl acetate and the like can be used. Among these ⁇ -olefins, ethylene and 1-butene are preferable, and 1-butene is particularly preferable.
• the acid-modified polyolefin (A) preferably contains 60 mol% or more of propylene as an olefin component. It is more preferably 70 mol% or more, still more preferably 80 mol% or more. More preferably, it is 90 mol% or more. The higher the propylene content, the better the adhesion to the polypropylene substrate.
• the molar ratio of propylene is 60% or more, excellent adhesion to the polyolefin substrate can be exhibited.
• Examples of at least one of ⁇ , ⁇ -unsaturated carboxylic acid and its acid anhydride include maleic acid, itaconic acid, citraconic acid and their acid anhydrides. Among these, acid anhydride is preferable, and maleic anhydride is more preferable.
• Specific examples of the acid-modified polyolefin (A) include maleic anhydride-modified homopolypropylene, maleic anhydride-modified propylene / ethylene copolymer, maleic anhydride-modified propylene / 1-butene copolymer, and maleic anhydride-modified propylene.
• Examples include ethylene / 1-butene copolymers, and these acid-modified polyolefins can be used alone or in combination of two or more. Of these, maleic anhydride-modified homopolypropylene is preferable.
• the acid value of the acid-modified polyolefin (A) is preferably in the range of 2 to 50 mgKOH / g. It is more preferably in the range of 3 to 40 mgKOH / g, further preferably 5 to 30 mgKOH / g, and particularly preferably in the range of 10 to 20 mgKOH / g.
• the acid value is 2 mgKOH / g or more, the molecular weight is high and the extensibility of the adhesive layer is satisfactorily exhibited.
• the acid value is 50 mgK. Below OH / g, the molecular weight is low and the solution stability at low temperatures tends to be good.
• the crystallinity of the acid-modified polyolefin (A) is preferably in the range of 12 to 70%. It is more preferably in the range of 15 to 60, and most preferably in the range of 18 to 50%. When the crystallinity is 12% or more, the cohesive force derived from the crystals becomes strong and the adhesiveness to the substrate is excellent. On the other hand, when it is 70% or less, the cohesive force derived from the crystal is moderate and the adhesiveness is good.
• the amount of heat of fusion of the modified polyolefin (A) is preferably in the range of 25 to 80 J / g. It is more preferably in the range of 28 to 75 J / g, and most preferably in the range of 30 to 70 J / g. When it is 25 J / g or more, the cohesive force derived from the crystal becomes strong and the adhesiveness is excellent. On the other hand, at 80 J / g or less, the cohesive force derived from crystals is moderate and the adhesiveness is good.
• the acid-modified polyolefin (A) may be chlorinated.
• the melting point (Tm) of the acid-modified polyolefin (A) is preferably 50 ° C. or higher and 130 ° C. or lower. It is more preferably 55 ° C. or higher, and even more preferably 60 ° C. or higher. Further, it is more preferably 125 ° C. or lower, further preferably less than 120 ° C., more preferably 115 ° C. or lower, and most preferably 110 ° C. or lower.
• the cohesive force derived from the crystals becomes strong and the adhesiveness is good.
• the weight average molecular weight (Mw) of the acid-modified polyolefin (A) is preferably in the range of 10,000 to 200,000. It is more preferably in the range of 20,000 to 180,000, still more preferably in the range of 30,000 to 160,000, particularly preferably in the range of 35,000 to 140,000, and most preferably in the range of 40. It ranges from 000 to 120,000. When it is 10,000 or more, the cohesive force becomes strong and the adhesiveness is good. On the other hand, when it is 200,000 or less, the fluidity is high, the operability at the time of adhesion is good, and the solution stability at a low temperature is good.
• the method for producing the acid-modified polyolefin (A) is not particularly limited, and for example, a radical graft reaction (that is, a radical species is generated for a polymer as a main chain, and the radical species is used as a polymerization initiation point to form an unsaturated carboxylic acid and (Reaction of graft polymerization of acid anhydride), and the like.
• a radical graft reaction that is, a radical species is generated for a polymer as a main chain, and the radical species is used as a polymerization initiation point to form an unsaturated carboxylic acid and (Reaction of graft polymerization of acid anhydride), and the like.
• the radical generator is not particularly limited, but it is preferable to use an organic peroxide.
• the organic peroxide is not particularly limited, but is not particularly limited, but is di-tert-butylperoxyphthalate, tert-butylhydroperoxide, dicumyl peroxide, benzoyl peroxide, tert-butylperoxybenzoate, tert-butylperoxy-.
• Peroxides such as 2-ethylhexanoate, tert-butylperoxypivalate, methylethylketone peroxide, di-tert-butyl peroxide, lauroyl peroxide, etc .; azobisisobutyronitrile, azobisisopropionitrile, etc. Examples include azonitriles.
• These acid-modified polyolefins (A) may be used alone or in combination of two or more.
• the adhesive composition of the present invention contains a stress relaxation agent (B).
• a stress relaxation agent (B) By containing the stress relaxation agent (B), the internal stress after the adhesive is formed can be reduced, the adhesiveness with the substrate can be improved, and the chipping resistance can be improved.
• the content of the stress relaxation agent (B) used in the present invention is preferably 1 part by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the acid-modified polyolefin (A). More preferably, 5 parts by mass or more and 200 parts by mass or less, further preferably 10 parts by mass or more and 100 parts by mass or less, particularly preferably 15 or more and 85 parts by mass or less, and more preferably 20 parts by mass or more and 70 parts by mass or less, most. It is preferably 25 parts by mass or more and 60 parts by mass or less. Further, when the amount is 1 part by mass or more, the compatibility is moderate, a stress relaxation effect is generated, and the chipping resistance is good. On the other hand, when it is 100 parts by mass or less, the compatibility is moderate, the adhesiveness is good, and the chipping resistance is good.
• the stress relieving agent (B) is at least one resin and a styrene resin selected from the group consisting of an olefin resin, a vinyl chloride resin, a urethane resin, and an amide resin containing a diene monomer as a constituent unit. Is.
• Olefin-based resin containing diene-based monomer as a constituent unit of ethylene- ⁇ -olefin-diene rubber vinyl chloride-based resin such as polyvinyl chloride elastomer, urethane-based resin such as polyurethane, amide-based resin such as polyamide elastomer, styrene-based
• vinyl chloride-based resin such as polyvinyl chloride elastomer
• urethane-based resin such as polyurethane
• amide-based resin such as polyamide elastomer
• styrene-based resin include styrene-based resins such as styrene-ethylene-butylene-styrene resin or hydrogen additives thereof, and these may be modified.
• an olefin resin containing a diene monomer As a constituent unit, it is preferable to use one or more of the group consisting of an olefin resin containing a diene monomer, a vinyl chloride resin, a urethane resin, and an amide resin.
• the stress relaxation agent (B) it is preferable to use two or more kinds including a styrene resin and an olefin resin containing a diene monomer, and it is particularly preferable to use a hydrogenated styrene resin and an olefin resin.
• the styrene resin is preferably a hydrogenated styrene resin which is a hydrogenated additive.
• the olefin-based resin (B1) is preferably an olefin resin containing a diene-based monomer as a constituent unit, and is preferably an amorphous resin.
• a diene-based monomer as a constituent unit
• the olefin resin may be an acid-modified product.
• the weight average molecular weight (Mw) of the olefin resin (B1) is preferably 20,000 or more and 200,000 or less. It is more preferably 25,000 or more and 160,000 or less, further preferably 30,000 or more and 140,000 or less, particularly preferably 35,000 or more and 120,000, 0 or less, and more preferably 37,000 or more and 100. It is 000 or less, most preferably 40,000 or more and 80,000 or less.
• Mw weight average molecular weight
• the hydrogenated styrene resin (B2) is a resin containing styrene in its skeleton, and is not particularly limited, and examples thereof include styrene-ethylene-butylene-styrene resin and styrene-ethylene-propylene-styrene resin. In particular, a styrene-ethylene-butylene-styrene resin is preferable.
• the MFR value of the hydrogenated styrene resin (B2) is preferably 0.1 g / 10 min or more and 50 g / 10 min or less under the condition of extruding at 230 ° C. with a load of 2.16 kgf (ISO1133). More preferably, it is 0.3 g / 10 min or more and 45 g / 10 min or less, more preferably 0.5 g / 10 min or more and 40 g / 10 min or less, particularly preferably 1 g / 10 min or more and 35 g / 10 min or less, and more preferably 1.
• it is 0.1 g / 10 min or more the compatibility with the acid-modified polyolefin (A) is moderate, and the stress relaxation effect tends to be easily exhibited. Further, when it is 50 g / 10 min or less, the compatibility with the acid-modified polyolefin (A) is remarkably improved.
• the stress relaxation agent (B) is preferably acid-modified, and the acid value is preferably 0.01 mgKOH / g or more and 50 mgKOH / g or less. More preferably 0.05 mgKOH / g or more and 45 mgKOH / g or less, further preferably 0.1 mgKOH / g or more and 40 mgKOH / g or less, particularly preferably 0.5 mgKOH / g or more and 35 mgKOH / g or less, and more preferably 1 mgKOH or less. It is / g or more and 30 mgKOH / g or less, and most preferably 1.5 mgKOH / g or more and 25 mgKOH / g or less. When it is 0.01 mgKOH / g or more and 50 mgKOH / g or less, the compatibility with the acid-modified polyolefin (A) is moderate and the adhesiveness is good.
• (B1) is preferably 1% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 48% by mass or less, and further preferably 10% by mass or more and 46% by mass or less. be. When it is 1% by mass or more and 50% by mass or less, the adhesiveness is good.
• (B2) is preferably 50% by mass or more and 99% by mass or less, more preferably 52% by mass or more and 95% by mass or less, and further preferably 55% by mass or more and 90% by mass or less. be. When it is 50% by mass or more and 99 parts by mass or less, both adhesiveness and chipping resistance can be achieved.
• the mass ratio of (B1) and (B2) is preferably 1/99 to 50/50. More preferably 5/95 to 49/51, even more preferably 10/90 to 48/52, particularly preferably 15/85 to 47/53, even more preferably 20/80 to 46/54, most preferably 25. It is / 75 to 45/55. When it is in the range of 1/99 to 50/50, both adhesiveness and chipping resistance are good.
• the total of (B1) and (B2) is preferably 50% by mass or more with respect to 100 parts by mass of the stress relaxation agent (B). 60% by mass or more is more preferable, and 70% by mass or more is most preferable. When it is 50% by mass or more, the adhesiveness and the chipping resistance are good.
• Adhesive imparting agent (C)> The adhesive composition of the present invention contains a tackifier (C). By containing the tackifier, the adhesiveness of the surface can be maintained after the adhesive is formed, and the adhesiveness with the substrate can be improved.
• the content of the tackifier (C) used in the present invention is preferably 1 part by mass or more and 500 parts by mass or less with respect to 100 parts by weight of the acid-modified polyolefin (A). More preferably, 5 parts by mass or more and 300 parts by mass or less, further preferably 10 parts by mass or more and 100 parts by mass or less, particularly preferably 15 parts by mass or more and 90 parts by mass or less, and more preferably 20 parts by mass or more and 85 parts by mass or less. Most preferably, it is 30 parts by mass or more and 65 parts by mass or less. Further, when it is 1 part by mass or more, the viscosity of the solution is moderate and the stability of the solution is good. On the other hand, when it is 500 parts by mass or less, the adhesiveness of the surface is moderate, the adhesiveness is exhibited well, and the chipping resistance is also good accordingly.
• the softening point of the tackifier (C) used in the present invention is preferably 60 ° C. or higher. It is more preferably 62 ° C. or higher, still more preferably 65 ° C. or higher, particularly preferably 70 ° C. or higher, more preferably 75 ° C. or higher, and most preferably 80 ° C. or higher. Further, it is preferably 150 ° C. or lower, more preferably 138 ° C. or lower, particularly preferably 135 ° C. or lower, more preferably 130 ° C. or lower, and most preferably 128 ° C. or lower. When the softening point is 60 ° C.
• the tackifier at room temperature does not easily bleed out to the surface, resulting in a smooth surface and good adhesiveness. Further, when the temperature is 140 ° C. or lower, tackiness occurs at room temperature and the adhesiveness is good. These may be used alone or in combination of two or more.
• the tackifier (C) of the present invention can improve compatibility and storage stability while maintaining good adhesiveness by using a tackifier having different softening points in an appropriate blending ratio.
• a tackifier (C1) having a softening point of 110 ° C. or higher and 150 ° C. or lower and a tackifier (C2) having a softening point of 75 ° C. or higher and lower than 110 ° C. can be combined.
• the tackifier (C1) is particularly preferably 115 ° C. or higher and 140 ° C. or lower, and most preferably 120 ° C. or higher and 130 ° C. or lower.
• the pressure-sensitive adhesive (C2) is particularly preferably 75 ° C.
• the tackifier (C) used in the present invention includes various types, and for example, petroleum resin (aliphatic, alicyclic, aromatic, etc.) and terpene resin ( ⁇ -pinene, ⁇ -). Polymers such as pinen and limonene), aromatic hydrocarbon-modified terpene resin, rosin-based resin (gamrosin, tall oil rosin, wood rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, maleated rosin, rosin ester, etc.), Examples thereof include terpene phenol resin, and rosin-based resin is particularly preferable. These may be used alone or in combination of two or more.
• the tackifier (C) used in the present invention may have a hydroxyl group.
• the adhesive composition of the present invention can contain a solvent (D).
• the solvent (D) is not particularly limited as long as it can dissolve or disperse the acid-modified polyolefin (A), the stress relieving agent (B) and the tackifier (C), but the alicyclic hydrocarbon solvent (D1), An ester solvent or a ketone solvent (D2) is preferable.
• examples of the alicyclic hydrocarbon solvent (D1) include cyclohexane, methylcyclohexane, and ethylcyclohexane.
• ester solvent or the ketone solvent (D2) examples include ethyl acetate, propyl acetate, butyl acetate, and methyl ethyl ketone. Of these, cyclohexane and butyl acetate are preferable. These may be used alone, or two or more kinds may be used in any combination.
• a mixed solvent containing an alicyclic hydrocarbon solvent (D1) and an ester solvent or a ketone solvent (D2) can be used.
• a mixed solvent of an alicyclic hydrocarbon solvent and an ester solvent or a ketone solvent By using a mixed solvent of an alicyclic hydrocarbon solvent and an ester solvent or a ketone solvent, the solubility of the adhesive composition can be improved.
• the solvent (D) can be contained in the range of 10 to 2000 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin (A). It is preferably 25 parts by mass or more and 1500 parts by mass or less, more preferably 50 parts by mass or more and 1000 parts by mass or less, further preferably 100 parts by mass or more and 900 parts by mass or less, and more preferably 100 parts by mass or more and 800 parts by mass or less. Is. Within the above range, it is advantageous in terms of manufacturing cost and transportation cost.
• the curing agent (E) used in the present invention is not particularly limited, but an epoxy compound, an isocyanate compound, a compound containing an oxazolin group or a carbodiimide group, a silane coupling agent, or the like can be appropriately used, which is good for a resin substrate.
• An isocyanate compound is preferable in terms of adhesiveness.
• the isocyanate compound used in the present invention is not particularly limited, and diisocyanate, triisocyanate and compounds derived from these can be preferably used.
• diisocyanate, triisocyanate and compounds derived from these can be preferably used.
• diisocyanates such as conjugated diphenylmethane diisocyanate.
• a compound derived from the diisocyanate that is, an isocyanurate form of the diisocyanate, an adduct form, a biuret type, a uretdione form, an allophanate form, a prepolymer having an isocyanate residue (a low polymer obtained from a diisocyanate and a polyol), and a tri.
• Glycidyl isocyanurate, or a complex thereof and the like can be mentioned. These may be used alone, or two or more kinds may be used in any combination.
• isocyanate compounds used in the present invention those having an isocyanurate form of the diisocyanate compound are preferable because they have excellent adhesiveness to a resin substrate.
• the epoxy compound used in the present invention is not particularly limited, and an epoxy resin and a compound derived from these can be preferably used, and a bifunctional epoxy is more preferable.
• Specific examples include glycidylamine type epoxy resin, glycidyl ether type epoxy resin such as bisphenol A, phenol novolac type epoxy resin, and cresol novolac type epoxy resin, glycidyl ester type such as hexahydrophthalic acid glycidyl ester, and dimer acid glycidyl ester, or glycidyl ester type.
• Examples thereof include alicyclic or aliphatic epoxisides such as 3,4-epoxycyclohexylmethylcarboxylate, epoxidized polybutadiene, and epoxidized soybean oil, and one type may be used alone or two or more types may be used in combination.
• alicyclic or aliphatic epoxisides such as 3,4-epoxycyclohexylmethylcarboxylate, epoxidized polybutadiene, and epoxidized soybean oil, and one type may be used alone or two or more types may be used in combination.
• the blending amount of the curing agent (E) used in the present invention is 100 parts by mass of the total solid content of the adhesive such as the acid-modified polyolefin (A), the stress relaxation agent (B) and the tackifier (C). It is preferably 10 parts by mass or less. In particular, the range is preferably 8 parts by mass or less, more preferably 6 parts by mass or less, further preferably 4 parts by mass or less, and particularly preferably 3 parts by mass or less. Further, 0.01 parts by mass or more is preferable. In particular, the range is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, further preferably 0.3 parts by mass or more, and particularly preferably 0.5 parts by mass or more.
• a curing agent When a curing agent is added, a sufficient crosslinked structure is obtained, and the heat resistance becomes better. When it is 10 parts by mass or less, the pot life is extended and the coating stability is improved. In addition, the curing shrinkage is reduced, and the adhesiveness to the substrate is improved.
• the adhesive composition according to the present invention contains, in addition to the acid-modified polyolefin (A), the stress relieving agent (B), and the tackifier (C), various plasticizers and curing as long as the performance of the present invention is not impaired. Additives such as accelerators, flame retardants, pigments and anti-blocking agents can be blended and used.
• the adhesive composition of the present invention contains a solvent (D), the total amount of the acid-modified polyolefin (A), the stress relieving agent (B) and the tackifier (C) in the adhesive composition / solvent (D).
• the amount is preferably 5/95 to 100/0. It is more preferably 7/93 to 40/60, still more preferably 10/90 to 35/65, and particularly preferably 12/88 to 30/70. Within the above range, the storage stability is good and the coatability tends to be good.
• the laminate of the present invention is a laminate of a polyolefin resin base material 1 and a polyolefin base material 1 or a dissimilar base material 2 with the adhesive composition according to the present invention.
• the dissimilar base material 2 is a base material different from the polyolefin base material 1.
• the polyolefin base material 1 is polypropylene
• the dissimilar base material 2 is an ABS resin other than polypropylene, polycarbonate, a galvanized steel plate, or the like.
• the laminate of the present invention described above includes, for example, automobile parts such as bumpers, instrument panels, trims, and garnishes, vehicle parts such as Shinkansen interior materials, televisions, washing machine tanks, refrigerator parts, air conditioner parts, and vacuum cleaner parts. It is useful for home appliance parts such as, mobile devices such as mobile phone terminals and notebook computers, communication devices, touch panels of various devices, and daily necessities.
• the adhesive composition is applied to the surface of the base material using an appropriate coating means such as an applicator or a bar coater, and dried. After drying, while the layer of the adhesive composition (adhesive layer) formed on the surface of the base material is in a molten state, the other base material is laminated and adhered (laminate adhesion, heat seal adhesion) to the coated surface. Can be obtained as a laminated body. Sufficient adhesiveness can be ensured by either method of laminating or heat-sealing bonding.
• the thickness of the adhesive layer formed by the adhesive composition is not particularly limited, but is preferably 0.5 to 60 ⁇ m, more preferably 1 to 50 ⁇ m, and further preferably 2 to 40 ⁇ m. preferable.
• the polyolefin resin base material may be appropriately selected from conventionally known polyolefin resins.
• polyethylene, polypropylene, ethylene-propylene copolymer and the like can be used.
• CPP polypropylene non-stretched film
• the thickness is not particularly limited, but is preferably 20 to 100 ⁇ m, more preferably 25 to 95 ⁇ m, and even more preferably 30 to 90 ⁇ m.
• the polyolefin resin base material may be blended with a pigment or various additives, or may be surface-treated.
• the polyolefin resin base material may be appropriately selected from conventionally known polyolefin resins.
• polyethylene, polypropylene, ethylene-propylene copolymer and the like can be used.
• the use of a polypropylene resin base material is preferable.
• the thickness is not particularly limited, but is preferably 0.1 to 100 mm, more preferably 0.5 to 90 mm, and even more preferably 1 to 80 mm. If necessary, the polyolefin resin base material may be blended with a pigment or various additives, or may be surface-treated.
• ⁇ Other dissimilar base materials (molded body)>
• ABS resin, polycarbonate, polyvinyl chloride, acrylic resin, urethane resin, zinc-plated steel plate, ED steel plate, Al and the like can be used as the dissimilar base material.
• the thickness thereof is not particularly limited, but is preferably 0.1 to 100 mm, more preferably 0.5 to 90 mm, still more preferably 1 to 80 mm. It may be surface-treated or may remain untreated. In either case, the same effect can be achieved.
• maleic anhydride-modified polypropylene (A-1, acid value 12 mgKOH / g-resin, weight average molecular weight 60,000, Tm80 ° C., heat of fusion 31J / g) which is an acid-modified polyolefin).
• Manufacturing example 2 By making the same as Production Example 1 except that the polypropylene used in Production Example 1 was changed to another polypropylene (Tm: 80 ° C., weight average molecular weight 45,000), the acid-modified polyolefin, maleic anhydride-modified polypropylene (Tm: 80 ° C., weight average molecular weight 45,000) was changed.
• Tm 80 ° C., weight average molecular weight 45,000
• A-2 acid value 12 mgKOH / g-resin, weight average molecular weight 45,000, Tm80 ° C., heat of fusion 34 J / g) were obtained.
• Production example 3 The polypropylene used in Production Example 1 is an acid-modified polyolefin in the same manner as in Production Example 1 except that the polypropylene is changed to a propylene-butene copolymer (Tm: 83 ° C., 80 mol% propylene, 20 mol% butene).
• a maleic anhydride-modified propylene-butene copolymer (A-3, acid value 12 mgKOH / g-resin, weight average molecular weight 90,000, Tm80 ° C., melting heat 48J / g) was obtained.
• Production example 4 Production Example 1 except that the polypropylene used in Production Example 1 was changed to a propylene-butene copolymer (Tm: 98 ° C., 85 mol% propylene, 15 mol% butene) and the maleic anhydride was changed to 20 parts by mass.
• Tm 98 ° C., 85 mol% propylene, 15 mol% butene
• maleic anhydride was changed to 20 parts by mass.
• maleic anhydride-modified propylene-butene copolymer (A-4, acid value 25 mgKOH / g-resin, weight average molecular weight 60,000, Tm95 ° C., heat of fusion 61J / g) which is an acid-modified polyolefin. ) was obtained.
• Example 1 In a 500 ml four-necked flask equipped with a water-cooled reflux condenser and a stirrer, 100 parts by mass of the maleic anhydride-modified polypropylene (A-1) obtained in Production Example 1 and 20 parts of a stress relieving agent (B1-1) were added. By mass, 25 parts by mass of stress relieving agent (B2-1), 35 parts by mass of tackifier (C-1), 15 parts by mass of (C-2), curing agent (E-1), cyclohexane (D1) ) To 432 parts by mass and 48 parts by mass of butyl acetate (D2), the temperature was raised to 70 ° C. with stirring, stirring was continued for 1 hour, and then cooled to obtain the adhesive composition 1. Using this adhesive composition 1, a laminate was prepared by the following method.
• a laminate was obtained by laminating at a temperature of 90 ° C. (55 ° C. on the test plate side) at 0.3 MPa for 15 seconds and curing at room temperature for 1 day. The adhesiveness of the obtained laminate was evaluated. The results are shown in Table 1.
• Examples 2 to 19, Comparative Examples 1 to 6) The acid-modified polyolefin (A), stress relaxation agent (B), tackifier (C) and curing agent (E) were changed as shown in Table 1, and the adhesive compositions 2 to 2 were modified in the same manner as in Example 1. 25 was made. Using the obtained adhesive compositions 2 to 25, a laminate was prepared in the same manner as in Example 1, and the adhesiveness was evaluated. The evaluation results are shown in Table 1.
• the stress relaxation agent (B) used in Table 1 is as follows.
• B1-1 and B1-2 are olefin resins containing a diene monomer as a constituent unit
• B2-1, B-2-2, and B2-3 are hydrogenated styrene resins
• B3 is hydrogenated. There is no styrene resin.
• B1-1 Trilene (registered trademark) 65 (Mw: 47,000) manufactured by LION ELASTOMERS B1-2: Trilene (registered trademark) 77 (Mw: 27,000) manufactured by LION ELASTOMERS B2-1: Asahi Kasei Corporation Tough Tech (registered trademark) M1911 (MFR: 4.5 g / 10 min, acid value: 2.1 mg KOH / g) B2-2: Asahi Kasei Corporation Tough Tech (registered trademark) M1913 (MFR: 4g / 10min, acid value: 10.4mgKOH / g) B2-3: Asahi Kasei Corporation Tough Tech (registered trademark) M1943 (MFR: 8g / 10min, acid value: 10.4mgKOH / g) B3-1: Asahi Kasei Tough Plane (registered trademark) A (MFR: 1.3g / 10min)
• the tackifier (C) used in Table 1 is as follows.
• C-1 Harima Chemicals, Inc.
• Haritac (registered trademark) FK125 Rosin ester adhesive, softening temperature 125 ° C)
• C-2 Harima Chemicals, Inc.
• Haritac (registered trademark) F85 rosin ester adhesive, softening temperature 85 ° C)
• C-3 Pine Crystal (registered trademark) KE-311 manufactured by Arakawa Chemical Co., Ltd. (rosin-based adhesive, softening temperature 95 ° C)
• C-4 Pine Crystal (registered trademark) KE-359 manufactured by Arakawa Chemical Co., Ltd.
• the curing agent (E) used in Table 1 is as follows.
• E-1 Tosoh Corporation (registered trademark) Coronate HX
• the acid-modified polyolefins, stress relaxation agents, tackifiers, adhesive compositions and laminates obtained as described above were analyzed, measured and evaluated based on the following methods.
• the acid value (mgKOH / g) in the present invention is the amount of KOH required to neutralize 1 g of the acid-modified polyolefin (A) and the hydrogenated styrene resin (B2), and is JIS K0070 (1992). ) was measured according to the test method.
• the melting point and the amount of heat of melting in the present invention are determined by holding at ⁇ 50 ° C. for 5 minutes using a differential scanning calorimeter (hereinafter, DSC, manufactured by TA Instruments Japan, Q-2000) and then holding at 10 ° C./min. It heats up and melts at a rate, and after melting at 230 ° C, it is held at 230 ° C for 2 minutes, cooled to -50 ° C at a rate of 10 ° C / min, and then heated again at a rate of 10 ° C / min. It was measured from the top temperature and area of the melting peak when melting.
• DSC differential scanning calorimeter
• MFR value in the present invention was measured according to the test method of ISO1133. Specifically, it is a measured value when extruded by applying a load of 2.16 kgf at 230 ° C. using MELT INDEXER X416 manufactured by Takara Kogyo Co., Ltd.
• the laminate was cut into strips of 15 mm, and the adhesiveness was evaluated by the 180 ° peeling test according to the following criteria.
• the 180 ° peeling test was based on the test method of ASTM-D1876-61, and the peeling strength was measured at a tensile speed of 50 mm / min in a 25 ° C environment using Tensilon RTM-100 manufactured by Orientec Corporation.
• the peel strength (N / 15 mm) between the dissimilar substrate / polyolefin resin substrate was taken as the average value of the two test values.
• ⁇ Chipping resistance test> It was carried out using a stepping stone tester (trade name "JA400" manufactured by Suga Test Instruments Co., Ltd.). A test coating plate was installed on the specimen holding table, and 100 g of granite crushed stone having a particle size of No. 6 was made to collide with the test plate at an angle of 90 degrees with compressed air of 480 to 520 kPa from a place 30 cm away from the test plate at room temperature. Then, the obtained test plate was flushed with water, dried, and an adhesive tape was attached to the coated surface. Then, the adhesive tape was peeled off, and the peeled area where PP, ABS, the PC base material, and the galvanized steel plate were exposed was evaluated according to the following criteria. ⁇ : The ratio of the peeled area to the original area is less than 6% ⁇ : The ratio of the peeled area to the original area is 6% or more and less than 10% ⁇ : The ratio of the peeled area to the original area is 10% or more
• the extensibility of the coating film in the present invention was measured by preparing a cast film having a thickness of 50 ⁇ m and using Tensilon RTM-100 manufactured by Orientec Corporation under the condition of a tensile speed of 50 mm / min in an environment of 25 ° C. .. The coating film was cut to 60 ⁇ 15 mm, and the elongation was calculated from the following formula. ⁇ (Length when the coating film breaks-Length of the first coating film) / Length of the first coating film ⁇ x 100 (%)
• the adhesive composition of the present invention contains an acid-modified polyolefin, a stress relieving agent and a tackifier, and adheres not only to non-polar substrates such as polyolefins but also to other dissimilar substrates such as polar substrates and metals. And has excellent chipping resistance. Further, since the coating can be performed by dry laminating, the equipment cost can be reduced and the film thickness can be reduced. Further, excellent adhesiveness is exhibited even by heat-bonding at a low temperature such as 90 ° C. or lower, which has a small effect of heat shrinkage of the polyolefin base material, and the extensibility is also good. Therefore, the adhesive composition of the present invention can be widely used as an adhesive for various purposes such as for a coating substitute film for bonding various types of substrates to each other.

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• 2021
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