Nonaqueous dispersion composition, adhesive composition, heat seal lacquer, and coating composition

Abstract

To provide a nonaqueous dispersion composition enabling compliance with halogen-free specifications and allowing superior adhesion to a polyolefin-based substrate and a metal-based substrate.SOLUTION: A nonaqueous dispersion composition comprising an acrylic resin (A), an olefin resin (B), and an organic solvent (E), wherein the acrylic resin (A) includes structural units derived from a (meth)acrylic monomer (a1) (excluding a carboxyl group-containing monomer (a2)) and structural units derived from the carboxyl group-containing monomer (a2), and wherein, in the acrylic resin (A), a content of structural units derived from a monomer (a1-1) having a glass transition temperature of 100°C or more is 18.5 mass% or less relative to a mass of the acrylic resin (A), and a content of a chlorine-containing compound is less than 25 mass% relative to a mass of the nonaqueous dispersion composition.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to non-aqueous dispersion compositions, adhesive compositions, heat seal lacquers, and coating compositions. [Background technology]

[0002] Polyolefin resins containing polymers of olefin monomers have excellent mechanical properties and chemical resistance, and are easy to mold and process at low cost, so they are widely used in a variety of applications. Furthermore, these resins are highly recyclable, and their applications are expanding further in light of recent global environmental issues. However, due to the low polarity of polyolefin resins, they are generally considered difficult to adhere to polyolefin substrates.

[0003] Known methods for improving adhesion to polyolefin substrates include chemically treating the surface of the polyolefin substrate with chemicals, etc., and oxidizing the surface by corona discharge treatment, plasma treatment, flame treatment, etc. However, these methods have the problem that they require special equipment and do not provide sufficient adhesive improvement effects.

[0004] On the other hand, a known method for improving adhesion between polyolefin-based substrates and metal-based substrates is to apply inks, paints, or adhesives containing chlorinated polyolefins to the surface of the polyolefin-based substrate. However, due to recent growing concern about environmental issues, the use of chlorine-containing compounds such as chlorinated polyolefins is being avoided. Furthermore, the fact that chlorinated polyolefins are not listed in the positive list (21 CFR 177.1520) for the use of olefin polymers as indirect food additives established by the U.S. Food and Drug Administration (FDA) indicates that the use of chlorinated polyolefins in food packaging materials is undesirable. For this reason, there has been an increasing demand in recent years for resin compositions composed of chlorine-free compounds.

[0005] Patent Document 1 describes a resin solution containing a graft copolymer obtained by graft polymerizing a specific monomer onto an olefin polymer, which is a chlorine-free resin that has high adhesion to polyolefin substrates and metal substrates. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent No. 4773041 Summary of the Invention [Problem to be solved by the invention]

[0007] However, while there has been a demand in recent years for compositions that do not use halogens, the resin described in Patent Document 1 uses a vinyl chloride-vinyl acetate copolymer resin, and is a composition that does not satisfy the halogen-free requirement. Furthermore, for example, non-aqueous dispersion compositions used as food packaging materials are required to be halogen-free and to have excellent adhesion to polyolefin-based substrates and metal-based substrates.

[0008] An object of the present invention is to provide a non-aqueous dispersion composition which is halogen-free and has excellent adhesion to polyolefin substrates and metal substrates. [Means for solving the problem]

[0009] The present invention is summarized as follows [1] to

[17] . [1] A non-aqueous dispersion composition comprising a resin composition (D) containing an acrylic resin (A) and an olefin resin (B), and an organic solvent (E), The acrylic resin (A) contains a structural unit derived from a (meth)acrylic monomer (a1) (excluding a carboxyl group-containing monomer (a2)) and a structural unit derived from a carboxyl group-containing monomer (a2), the content of structural units derived from the monomer (a1-1) having a glass transition temperature of 100°C or higher in the acrylic resin (A) is 18.5% by mass or less relative to the mass of the acrylic resin (A); A non-aqueous dispersion composition, wherein the content of a chlorine-containing compound is less than 25% by mass based on the mass of the non-aqueous dispersion composition. [2] The resin composition (D) The non-aqueous dispersion composition according to [1], which is obtained by polymerizing a (meth)acrylic monomer composition (a) containing a (meth)acrylic monomer (a1) (excluding a carboxyl group-containing monomer (a2)) and the carboxyl group-containing monomer (a2) in the presence of an olefin resin (B). [3] The nonaqueous dispersion composition according to [1] or [2], wherein the mass ratio of the acrylic resin (A) to the olefin resin (B) is 80 / 20 to 10 / 90. [4] The nonaqueous dispersion composition according to any one of [1] to [3], wherein the acrylic resin (A) has a glass transition temperature (Tg) of -50 to 50°C. [5] The acrylic resin (A) has a solubility parameter (SP value) calculated by the Fedors method of 18 to 21 (J / cm 3 ) 1 / 2 The nonaqueous dispersion composition according to any one of [1] to [4], wherein [6] The nonaqueous dispersion composition according to any one of [1] to [5], wherein the degree of acid modification of the olefin resin (B) is 0% by mass or more and 20% by mass or less, with the weight of the modified polyolefin resin (B1) being 100% by mass. [7] The nonaqueous dispersion composition according to any one of [1] to [6], wherein the olefin resin (B) has a heat of crystalline fusion of 5 to 50 J / g. [8] The nonaqueous dispersion composition according to any one of [1] to [7], wherein the olefin resin (B) has a melting point of 40 to 120°C. [9] The nonaqueous dispersion composition according to any one of [1] to [8], wherein the olefin resin (B) has a crystallization temperature of 10 to 60°C.

[10] The nonaqueous dispersion composition according to any one of [1] to [9], wherein the olefin resin (B) contains at least one of an ethylene-derived structural unit and a propylene-derived structural unit.

[11] The nonaqueous dispersion composition according to

[10] , wherein the ratio of the total mass of the ethylene-derived structural units and the propylene-derived structural units to the total mass of the olefin-based resin (B) is 50 mass% or more.

[12] The nonaqueous dispersion composition according to any one of [1] to

[11] , wherein the olefin resin (B) comprises an ethylene-propylene copolymer or polypropylene.

[13] The nonaqueous dispersion composition according to any one of [1] to

[12] , wherein the weight average molecular weight of the resin composition (D) containing the acrylic resin (A) and the olefin resin (B) is 5,000 to 500,000.

[14] The organic solvent (E) has a hydrogen bond term δh in the Hansen solubility parameter of 7 MPa. 0.5 The nonaqueous dispersion composition according to any one of [1] to

[13] , which contains the organic solvent (E1) described above.

[15] An adhesive composition comprising the nonaqueous dispersion composition according to any one of [1] to

[14] .

[16] A heat seal lacquer comprising the non-aqueous dispersion composition according to any one of [1] to

[14] .

[17] A coating composition comprising the non-aqueous dispersion composition according to any one of [1] to

[14] . [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a non-aqueous dispersion composition which is halogen-free and has excellent adhesion to polyolefin-based substrates and metal-based substrates. DETAILED DESCRIPTION OF THE INVENTION

[0011] In the present invention, "(meth)acrylic" is a general term for "acrylic" and "methacrylic". Furthermore, "(meth)acrylate" is a general term for "acrylate" and "methacrylate". Furthermore, "(meth)acryloyl" means "acryloyl" or "methacryloyl". Furthermore, "(meth)acryloyloxy" means "acryloyloxy" or "methacryloyloxy".

[0012] In the present invention, the term "resin" includes a polymer or copolymer obtained by polymerizing one or more monomers. That is, the "resin" of the present invention may be a single polymer or a single copolymer, or may include multiple polymers, multiple copolymers, or both polymers and copolymers.

[0013] In the present invention, a non-aqueous dispersion composition refers to a composition in which the main component of the medium is an organic solvent and which contains a resin stably dispersed in the medium. The main component of the organic solvent that is the medium of the non-aqueous dispersion composition must be an organic solvent with low olefin solubility. If the main component of the organic solvent is an organic solvent with high olefin solubility, such as an aromatic organic solvent such as toluene or xylene, the composition does not fall under the category of a non-aqueous dispersion composition. The main component of the organic solvent is preferably a component that accounts for 50% by mass or more of the organic solvent. "Non-aqueous" does not mean that the composition is completely free of water, but rather that it may contain water to the extent that the effects of the present invention are not impaired.

[0014] [Non-aqueous dispersion composition] A first embodiment of the nonaqueous dispersion composition of the present invention is a nonaqueous dispersion composition comprising a resin composition (D) containing an acrylic resin (A) and an olefin resin (B), and an organic solvent (E), wherein the acrylic resin (A) contains structural units derived from a (meth)acrylic monomer (a) and structural units derived from a carboxy group-containing monomer (a2), and the structural units of the acrylic resin (A) contain 18.5 mass% or less of structural units derived from a monomer (a1-1) having a glass transition temperature of 100°C or higher, and the content of chlorine-containing compounds in the nonaqueous dispersion composition is less than 25 mass% of the total composition. In the nonaqueous dispersion composition of the present invention, the resin composition (D) is obtained by polymerizing a (meth)acrylic monomer composition (a) containing a (meth)acrylic monomer (a1) (excluding a carboxy group-containing monomer (a2)) and the carboxy group-containing monomer (a2) in the presence of an olefin resin (B).

[0015] <Acrylic resin (A)> In the nonaqueous dispersion composition of the present invention, the acrylic resin (A) contains a structural unit derived from a (meth)acrylic monomer (a1) (sometimes referred to as a "structural unit derived from a (meth)acrylic monomer (a1)") and a structural unit derived from a carboxy group-containing monomer (a2). The acrylic resin (A) used in the present invention is obtained by polymerizing a (meth)acrylic monomer (a1), a carboxyl group-containing monomer (a2), and other copolymerizable monomers. However, the acrylic resin (A) does not have a structure derived from the olefin resin (B).

[0016] ((Meth)acrylic monomer (a1)) The (meth)acrylic monomer (a1) is a monomer having a (meth)acryloyl group in the molecule, excluding the carboxyl group-containing monomer (a2). The (meth)acrylic monomer (a1) is used to synthesize the acrylic resin (A). Non-limiting examples of the (meth)acrylic monomer (a) are listed below:

[0017] alkyl (meth)acrylates having a linear or branched hydrocarbon skeleton, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, and 4-tert-butylcyclohexyl (meth)acrylate;

[0018] Alkyl (meth)acrylates having an alicyclic skeleton, such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentadienyl (meth)acrylate, and dicyclopentanyl (meth)acrylate.

[0019] (meth)acrylic acid esters having a glycidyl group, such as glycidyl (meth)acrylate and hydroxybutyl (meth)acrylate glycidyl ether;

[0020] (meth)acrylic acid esters having an aromatic ring, such as phenoxy (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, nonylphenol EO adduct (meth)acrylate, and o-biphenyloxyethyl (meth)acrylate;

[0021] (meth)acrylates having a cyclic ether, such as tetrahydrofurfuryl (meth)acrylate;

[0022] (meth)acrylates having an amino group, such as N-dimethylaminoethyl (meth)acrylate and N-diethylaminoethyl (meth)acrylate;

[0023] (meth)acrylamide derivatives such as (meth)acrylamide, (meth)acrylamide diacetone acrylamide, N-methylol (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, and (meth)acryloylmorpholine;

[0024] Monomers having a phosphate group, such as 2-(meth)acryloyloxyethyl acid phosphate, 2-(meth)acryloyloxyethyl acid phosphate monoethanolamine salt, diphenyl((meth)acryloyloxyethyl)phosphate, (meth)acryloyloxypropyl acid phosphate, 3-chloro-2-acid phosphooxypropyl (meth)acrylate, acid phosphooxypolyoxyethylene glycol mono(meth)acrylate, and acid phosphooxypolyoxypropylene glycol (meth)acrylate;

[0025] hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 1,2-dihydroxyethyl (meth)acrylate, 1,2-dihydroxypropyl (meth)acrylate, 1,2-dihydroxybutyl (meth)acrylate, 1,2-dihydroxy-5-ethylhexyl (meth)acrylate, 1,1-dihydroxyethyl (meth)acrylate, 1,1-dihydroxypropyl (meth)acrylate, 1,1-dihydroxybutyl (meth)acrylate, 1,2,3-trihydroxypropyl (meth)acrylate, 1,2,3-trihydroxybutyl (meth)acrylate, 1,1,2-trihydroxypropyl (meth)acrylate, and 1,1,2-trihydroxybutyl (meth)acrylate;

[0026] Hydroxy(meth)acrylates having an aromatic ring, such as 2-hydroxy-3-phenoxypropyl(meth)acrylate;

[0027] Hydroxypolyalkylene oxide (meth)acrylates such as hydroxypolyethylene oxide mono(meth)acrylate, hydroxypolypropylene oxide mono(meth)acrylate, hydroxy(polyethylene oxide-polypropylene oxide) mono(meth)acrylate, hydroxy(polyethylene oxide-propylene oxide) mono(meth)acrylate, hydroxy(polyethylene oxide-polytetramethylene oxide) mono(meth)acrylate, hydroxy(polyethylene oxide-tetramethylene oxide) mono(meth)acrylate, hydroxy(polypropylene oxide-polytetramethylene oxide) mono(meth)acrylate, hydroxy(polypropylene oxide-polytetramethylene oxide) mono(meth)acrylate, 1,2-dihydroxypolyethyl oxide (meth)acrylate, 1,2-dihydroxypolypropylene oxide (meth)acrylate, polyhydroxyalkyl (meth)acrylates, 1,2,3-trihydroxypropylene glycol (meth)acrylate, and 1,1,2-trihydroxypropylene glycol (meth)acrylate.

[0028] The acrylic resin (A) may contain at least one type of structural unit derived from the (meth)acrylic monomer (a1), and may contain two or more types.

[0029] Among these, from the viewpoints of adhesion to polyolefin-based substrates and metal-based substrates and solubility in solvents, the (meth)acrylic monomer (a1) is preferably at least one selected from the group consisting of alkyl (meth)acrylates having a linear or branched hydrocarbon skeleton and alkyl (meth)acrylates having an alicyclic skeleton, more preferably at least one selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate, and even more preferably includes two of methyl (meth)acrylate and n-butyl (meth)acrylate.

[0030] The content of the structural units derived from the (meth)acrylic monomer (a1) is preferably 70 to 99.99 mass%, more preferably 90 to 99.9 mass%, and still more preferably 94 to 99.8 mass%, relative to the total mass of the structural units constituting the acrylic resin (A).

[0031] (Carboxy group-containing monomer (a2)) Examples of the carboxy group-containing monomer (a2) include (meth)acrylates having a carboxy group, such as acrylic acid, methacrylic acid, mono(2-(meth)acryloyloxyethyl) succinate, and ω-carboxy-polycaprolactone mono(meth)acrylate. Of these, (meth)acrylic acid is preferred.

[0032] The content of the structural units derived from the carboxy group-containing monomer (a2) is preferably 0.01 to 30 mass%, more preferably 0.1 to 10 mass%, and still more preferably 0.2 to 6 mass%, relative to the total mass of the structural units constituting the acrylic resin (A).

[0033] (Structural unit (a3) ​​derived from other monomers) The acrylic resin (A) may contain, in addition to the structural units derived from the (meth)acrylic monomer (a1) and the structural units derived from the carboxyl group-containing monomer (a2), structural units derived from monomers other than the (meth)acrylic monomer (a1) and the carboxyl group-containing monomer (a2) (hereinafter also referred to as "other monomers") (also referred to as "structural units derived from other monomers"). The other monomers are monomers copolymerizable with the (meth)acrylic monomer (a) or monomers graft polymerizable with the olefin resin (B). The structural units derived from the other monomers (a3) ​​contained in the acrylic resin (A) may be of one type or two or more types.

[0034] Examples of the other monomer (a3) ​​include the following:

[0035] aromatic vinyl monomers such as styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, and chlorostyrene;

[0036] vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, α-cyanoacrylate, dicyanovinylidene, and fumaronitrile;

[0037] Sulfonic acid group-containing monomers such as vinyl sulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid;

[0038] Multifunctional monomers such as divinylbenzene, divinylnaphthalene, and divinyl ether;

[0039] vinyl monomers such as vinyl acetate and vinyl propionate; and

[0040] Conjugated diene monomers such as 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene, and chloroprene.

[0041] When the acrylic resin (A) contains a structural unit derived from the other monomer (a3), the content of the structural unit derived from the other monomer (a3) ​​is preferably 20% by mass or less, more preferably 5% by mass or less, and still more preferably 1% by mass or less, relative to the total mass of the structural units constituting the acrylic resin (A).

[0042] [Monomer (a1-1) having a glass transition temperature of 100°C or higher when made into a homopolymer] The (meth)acrylic resin (A) used in the present invention may have a structural unit derived from a monomer (a1-1) that has a glass transition temperature of 100° C. or higher when made into a homopolymer. The monomer (a1-1) having a glass transition temperature of 100° C. or higher is a monomer that falls under the category of the (meth)acrylic monomer (a1), and does not fall under the category of the carboxy group-containing monomer (a2). Examples of the monomer (a1-1) having a glass transition temperature of 100° C. or higher include acryloylmorpholine, t-butyl methacrylate, methyl methacrylate, acrylonitrile, and isobornyl acrylate.

[0043] The content of structural units derived from the monomer (a1-1) having a glass transition temperature of 100°C or higher when made into a homopolymer is 18.5% by mass or less, preferably 15% by mass or less, and more preferably 10% by mass or less, based on the total mass of all structural units of the acrylic resin (A). When this content is within the above range, the viscosity after polymerization is good and the adhesion in low-temperature heat sealing is also excellent.

[0044] [Monomer (a1-2) having a glass transition temperature of less than 100°C when made into a homopolymer] The (meth)acrylic resin (A) used in the present invention preferably has a structural unit derived from a monomer (a1-2) that has a glass transition temperature of less than 100°C when made into a homopolymer. Examples of the monomer (a1-2) having a glass transition temperature of less than 100°C include methyl acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate. The content of structural units derived from monomer (a1-2) having a glass transition temperature of less than 100°C when made into a homopolymer is preferably more than 50% by mass, more preferably 80% by mass to 100% by mass, even more preferably 85% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass, based on the total mass of all structural units of the acrylic resin (A). When the content is within the above range, the viscosity after polymerization is good and the adhesion in low-temperature heat sealing is excellent.

[0045] [Acrylic resin (A)] The acrylic resin (A) used in the present invention can be produced by copolymerizing a copolymerization component (a) containing the above-mentioned (meth)acrylic monomer (a1) and the carboxyl group-containing monomer (a2) as essential components, and further containing the above-mentioned optional polymerization components (a3), (a1-1) and (a1-2), as necessary.

[0046] As the polymerization method for the acrylic resin (A), for example, a conventionally known polymerization method such as solution polymerization, suspension polymerization, bulk polymerization, emulsion polymerization, etc. can be used. In the present invention, however, production by solution polymerization is preferred in that the acrylic resin (A) can be produced safely and stably with any monomer composition.

[0047] As described above, the acrylic resin (A) used in the present invention can be produced, and the weight-average molecular weight of the acrylic resin (A) is preferably 5,000 to 1,000,000, more preferably 10,000 to 300,000, particularly preferably 20,000 to 200,000, and even more preferably 30,000 to 100,000. If the weight-average molecular weight is too large, the viscosity tends to be too high, which can reduce the coatability and handling properties, whereas if the weight-average molecular weight is too small, the cohesive force tends to decrease, which can reduce the adhesive properties. The weight average molecular weight of the acrylic resin (A) is the weight average molecular weight at the time of completion of production, that is, the weight average molecular weight of the acrylic resin (A) that has not been heated or otherwise subjected to any treatment after production.

[0048] The dispersity (weight average molecular weight / number average molecular weight) of the acrylic resin (A) is preferably 15 or less, more preferably 10 or less, particularly preferably 7 or less, and even more preferably 5 or less. If the dispersity is too high or too low, the handling property tends to decrease. The lower limit of the dispersity is usually 1.1 in view of production limitations.

[0049] The weight-average molecular weights are those calculated in terms of standard polystyrene molecular weights and are measured using a high-performance liquid chromatograph (Waters Japan, "Waters 2695 (main unit)" and "Waters 2414 (detector)") equipped with three Shodex GPC KF-806L columns (molecular weight exclusion limit: 2 × 107, separation range: 100 to 2 × 107, theoretical plate number: 10,000 plates / column, packing material: styrene-divinylbenzene copolymer, packing particle size: 10 μm) in series. The number-average molecular weight can also be measured using a similar method. The polydispersity can be calculated from the weight-average molecular weight and the number-average molecular weight.

[0050] The acrylic resin (A) used in the present invention has a glass transition temperature (Tg) of −50 to 50° C., preferably −30 to 40° C., more preferably 0 to 35° C., and particularly preferably 10 to 30° C. If the glass transition temperature is too high, the viscosity tends to increase. If the glass transition temperature is too low, the blocking property tends to decrease.

[0051] The glass transition temperature (Tg) is a value calculated by applying the glass transition temperature and mass fraction of each of the monomers constituting the acrylic resin (A) as a homopolymer to the following Fox's formula.

[0052]

number

[0053] Tg: Glass transition temperature (K) of acrylic resin (A) Tga: Glass transition temperature of the homopolymer of monomer A (K) Wa: Mass fraction of monomer A Tgb: Glass transition temperature of the homopolymer of monomer B (K) Wb: Mass fraction of monomer B Tgn: Glass transition temperature (K) of the homopolymer of monomer N Wn: mass fraction of monomer N (Wa+Wb+···+Wn=1)

[0054] The content of the acrylic resin (A) is preferably from 10 to 80 mass %, more preferably from 20 to 70 mass %, based on the total mass of the resin composition (D).

[0055] <Olefin resin (B)> In a first embodiment of the nonaqueous dispersion composition of the present invention, the olefin resin (B) contains a structural unit derived from an olefin monomer (b) (sometimes referred to as a "structural unit derived from an olefin monomer (b)"). That is, the olefin resin (B) is a polymer containing a structural unit derived from at least one type of olefin monomer (b).

[0056] The olefin resin (B) may have a reactive group such as a carboxy group, an epoxy group, an isocyanate group, a sulfonic acid group, a hydroxyl group, or an amino group. The reactive group may be an acid anhydride structure of a carboxy group, i.e., an acid anhydride group formed by dehydration condensation of two carboxy groups intermolecularly or intramolecularly.

[0057] Non-limiting examples of the olefinic monomer (b) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, cyclopentene, cyclohexene, and norbornene.

[0058] The olefin resin (B) may contain at least one type of structural unit derived from the olefin monomer (b), and may contain two or more types. The olefinic monomer (b) can be used alone or in combination of two or more when synthesizing the olefinic resin (B).

[0059] Non-limiting specific examples of the olefin resin (B) are listed below: a homopolymer of an olefin monomer (b); a copolymer of ethylene and propylene; a copolymer of at least one of ethylene and propylene with a monomer copolymerizable with ethylene and propylene (for example, an α-olefin having 4 or more carbon atoms, such as 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, cyclopentene, cyclohexene, or norbornene); a copolymer of two or more α-olefins selected from the group consisting of the monomers exemplified for the α-olefins having 4 or more carbon atoms; a copolymer of an α-olefin having 2 or more carbon atoms with a non-aromatic monomer other than an α-olefin, such as vinyl acetate, an acrylic acid ester, or a methacrylic acid ester; a copolymer of an α-olefin having 2 or more carbon atoms with an aromatic monomer, or a hydrogenated product thereof; and a conjugated diene block copolymer or a hydrogenated product thereof.

[0060] The mass proportion of the structural units derived from the olefin monomer (b) relative to the total mass of the structural units constituting the olefin resin (B) is preferably 50 mass% or more, more preferably 80 mass% or more, and even more preferably 90 mass% or more. The upper limit is preferably 100 mass% or less. The higher the mass proportion of the structural units derived from the olefin monomer (b), the more likely the nonaqueous dispersion composition of the present invention will have improved adhesion to polyolefin substrates.

[0061] The olefin resin (B) contains at least one of ethylene-derived structural units and propylene-derived structural units, and the ratio of the total mass of the ethylene-derived structural units and the propylene-derived structural units to the total mass of the structural units derived from all monomers constituting the olefin resin (B) is preferably 50% by mass or more, more preferably 65% ​​by mass or more, and even more preferably 75% by mass or more, and may even be 100% by mass. When the ratio is equal to or more than the lower limit, the nonaqueous dispersion composition of the present invention is likely to have excellent adhesion to polyolefin substrates.

[0062] From the viewpoint of adhesion to polyolefin substrates, the olefin resin (B) is preferably a propylene copolymer having a structural unit derived from propylene, more preferably at least one selected from the group consisting of polypropylene, ethylene-propylene copolymer, ethylene-propylene-butene copolymer, and propylene-butene copolymer, and even more preferably an ethylene-propylene copolymer or polypropylene. In terms of adhesion to polyolefin substrates, the mass ratio of propylene-derived structural units in the propylene polymer is preferably 50 mass% or more, more preferably 70 mass% or more, and even more preferably 90 mass% or more, relative to the mass of the propylene polymer, with the upper limit preferably being 100 mass% or less. The mass ratio represented by [ethylene-derived structural units] / [propylene-derived structural units] is preferably from 0 to 1, and more preferably from 0.01 to 0.25.

[0063] The polymer contained in the olefin resin (B) may have any structure such as a random copolymer, a graft copolymer, a block copolymer, a linear or branched structure, etc. However, this does not apply to the acrylic olefin composite resin (C) described later.

[0064] The weight average molecular weight Mw (hereinafter also referred to as "Mw") of the olefin resin (B) measured by gel permeation chromatography (GPC) is not particularly limited, but is preferably 20,000 to 150,000, more preferably 30,000 to 120,000, and even more preferably 40,000 to 90,000. When Mw is at least the lower limit of the above range, the adhesion to polyolefin-based substrates and metal-based substrates is better, and when it is at most the upper limit, the dispersion stability of the nonaqueous dispersion composition of the present invention is better, and separation is less likely to occur.

[0065] The heat of crystalline fusion of the olefin resin (B) is not particularly limited, but is preferably 5 to 50 J / g, more preferably 10 to 40 J / g, and even more preferably 12 to 30 J / g. A larger heat of crystalline fusion indicates a higher degree of crystallinity of the resin. When the heat of crystalline fusion is equal to or greater than the lower limit of the above range, the adhesion to the polyolefin substrate and the metal substrate is excellent, and when it is equal to or less than the upper limit, the dispersion stability of the nonaqueous dispersion composition of the present invention is excellent and separation is less likely to occur.

[0066] The melting point Tm (hereinafter also referred to as "Tm") of the olefin resin (B) is not particularly limited, but is preferably 40 to 120° C., more preferably 50 to 100° C., and even more preferably 60 to 90° C. When the melting point is at least the lower limit of the above range, the non-dispersion composition of the present invention has superior adhesion to polyolefin-based substrates and metal-based substrates, and when it is not more than the upper limit, the non-dispersion composition has superior liquid dispersion stability.

[0067] The crystallization temperature of the olefin resin (B) is not particularly limited, but is preferably 10 to 60° C., more preferably 15 to 55° C., and even more preferably 20 to 50° C. When the crystallization temperature is equal to or higher than the lower limit of the above range, the adhesion to the polyolefin substrate and the metal substrate is excellent, and when it is equal to or lower than the upper limit, the liquid dispersion stability is excellent.

[0068] In this specification, the heat of crystalline fusion, melting point Tm, and crystallization temperature all refer to values ​​measured by differential scanning calorimetry (DSC). The heat of crystalline fusion, the melting point Tm, and the crystallization temperature are determined, for example, by the following measurement method (I) using a differential scanning calorimeter DSC6200 manufactured by Seiko Instruments Inc. ·Measurement method (I) A sample (approximately 3-5 mg) is weighed out and placed in a special aluminum pan. After melting the sample at 200°C, the temperature is lowered to 0°C at a rate of 10°C / min, and then raised to 200°C at 10°C / min to obtain a melting curve. The melting point is determined as the peak-top temperature of the main endothermic peak in the final heating stage. The heat of crystalline fusion (joules / g) is calculated by dividing the heat quantity calculated from the area enclosed by the peak and the baseline by the weight of the sample. The peak-top temperatures of the main exothermic peak in the cooling stage and the final heating stage are determined as the crystallization temperature.

[0069] The method for producing the olefin resin (B) is not particularly limited, but it can be produced, for example, by polymerizing an olefin by a method such as radical polymerization, cationic polymerization, anionic polymerization, or coordination polymerization. Each of these polymerization methods may be living polymerization. The olefin resin (B) can be produced by a known production method. As the olefin resin (B), a commercially available product may be used.

[0070] When the olefin resin (B) has a reactive group, the content of the reactive group is not particularly limited, but is preferably 1 mmol / g or less, more preferably 0.5 mmol / g or less, and even more preferably 0.3 mmol / g or less, per 1 g of the olefin resin (B).

[0071] From the viewpoint of liquid dispersion stability, the olefin resin (B) preferably does not contain an acid-modified polyolefin. In this specification, the acid-modified polyolefin refers to a polyolefin having one or more reactive groups (including chlorinated groups) selected from a carboxy group, a sulfonic acid group, and an acid anhydride structure of a carboxy group, where the acid anhydride structure of a carboxy group refers to an acid anhydride group formed by dehydration condensation between or within two carboxy groups in a molecule.

[0072] The degree of acid modification of the olefin resin (B) is preferably 20% by weight or less, more preferably 10% by weight or less, and even more preferably 5% by weight or less, based on 100% by weight of the weight of the modified polyolefin resin (B1).

[0073] It is an essential requirement that the olefin resin (B) has a chlorine content of 25% or less, preferably 15% or less, more preferably 5% or less, and most preferably 0%.

[0074] The content of the olefin resin (B) is preferably from 20 to 90 mass %, more preferably from 30 to 80 mass %, and still more preferably from 40 to 70 mass %, based on the total mass of the resin composition (D). The mass ratio represented by [acrylic resin (A)] / [olefin resin (B)] is preferably from 0.2 to 2.3, more preferably from 0.4 to 1.3.

[0075] <Acryloolefin composite resin (C)> The first, second, and third embodiments of the nonaqueous dispersion composition of the present invention may further contain an acrylic olefin composite resin (C). The acrylic olefin composite resin (C) has a structure in which a polymer chain containing a structural unit derived from the (meth)acrylic monomer (a) is chemically bonded to the olefin resin (B). Here, "chemically bonded" means a covalent bond, an ionic bond, a metallic bond, etc., and does not include intermolecular forces such as a hydrogen bond or van der Waals force. The acrylic olefin composite resin (C) can be produced by radically polymerizing a monomer mixture containing the (meth)acrylic monomer (a) in the presence of the olefin resin (B). The acrylic olefin composite resin (C) preferably contains a graft copolymer having the olefin resin (B) as a trunk polymer structure and a polymer chain containing a structural unit derived from the (meth)acrylic monomer (a) as a branch polymer structure. As used herein, a "graft copolymer" refers to a graft copolymer composed of a main chain polymer structure and a side chain polymer structure (branch polymer structure) chemically bonded to the main chain polymer structure (backbone polymer structure). As used herein, a graft copolymer refers to a polymer having one or more types of blocks connected as side chain polymer structures to the main chain polymer structure. The structures of the main chain polymer and the side chain polymer may be different or the same. There are no particular limitations on the method for producing a graft copolymer. Examples include a method in which a macromonomer having a radically polymerizable double bond at its end is produced as a side chain polymer structure, followed by radical polymerization with a monomer that will become a structural unit of the main chain polymer; a method in which a main chain polymer having a reactive site and a macromonomer having a reactive site are produced in advance, followed by reaction of the main chain polymer and the macromonomer; and a method in which, after the main chain polymer is produced, a radical is generated on the main chain polymer using an initiator having hydrogen abstraction ability, and then the radical is reacted with a monomer that will become a structural unit of the side chain polymer to produce a side chain polymer structure. The monomer mixture may contain other monomers in addition to the (meth)acrylic monomer (a). According to this manufacturing method, a mixture of the acrylic resin (A), which is a product of polymerization of only the monomers in the monomer mixture, and the unreacted olefin resin (B) is obtained. Hereinafter, this mixture may be referred to as "resin composition (D)." The resin composition (D) will be described later.

[0076] Examples of the (meth)acrylic monomer (a) include the compounds exemplified as the (meth)acrylic monomer (a) used in the synthesis of the acrylic resin A.

[0077] The acrylic olefin composite resin (C) may have one or more structural units derived from a monomer other than the (meth)acrylic monomer (a). The other monomer is, for example, a monomer copolymerizable with the (meth)acrylic monomer (a) or a monomer graft-polymerizable with the olefin resin (B). Examples of the other monomer include the compounds exemplified as the other monomer used in the synthesis of the acrylic resin (A).

[0078] <Resin composition (D)> The resin composition (D) contains an acrylic resin (A) and an olefin resin (B), and may further contain an acrylic olefin composite resin (C) having structural units derived from the acrylic resin (A) and structural units derived from the olefin resin (B). In the resin composition (D), the mass ratio Wb / Wa of the total mass Wb of the structural units derived from all monomers constituting the olefin resin (B) to the total mass Wa of the structural units derived from the (meth)acrylic monomer (a) is preferably 20 / 80 to 90 / 10, more preferably 30 / 70 to 80 / 20, and even more preferably 40 / 60 to 75 / 25.

[0079] In the resin composition (D), the sum of the total mass Wa and the total mass Wb is preferably 60% by mass or more, more preferably 80% by mass or more, and may be 100% by mass, based on the total mass of the structural units derived from all monomers.

[0080] The resin composition (D) preferably has a weight-average molecular weight of 5,000 to 500,000, more preferably 10,000 to 300,000, particularly preferably 20,000 to 200,000, and even more preferably 30,000 to 100,000. If the weight-average molecular weight is too large, the viscosity will be too high, which tends to reduce the coatability and handling properties, whereas if it is too small, the cohesive force will decrease, which tends to reduce the adhesive properties. The weight average molecular weight of the resin composition (D) is the weight average molecular weight at the time of completion of production, that is, the weight average molecular weight of the resin composition (D) that has not been heated or otherwise subjected to any treatment after production.

[0081] The dispersity (weight average molecular weight / number average molecular weight) of the acrylic resin (A) is preferably 15 or less, more preferably 10 or less, particularly preferably 7 or less, and even more preferably 5 or less. If the dispersity is too high or too low, the handling property tends to decrease. The lower limit of the dispersity is usually 1.1 in view of production limitations.

[0082] The weight-average molecular weights are those calculated in terms of standard polystyrene molecular weights and are measured using a high-performance liquid chromatograph (Waters Japan, "Waters 2695 (main unit)" and "Waters 2414 (detector)") equipped with three Shodex GPC KF-806L columns (molecular weight exclusion limit: 2 × 107, separation range: 100 to 2 × 107, theoretical plate number: 10,000 plates / column, packing material: styrene-divinylbenzene copolymer, packing particle size: 10 μm) in series. The number-average molecular weight can also be measured using a similar method. The polydispersity can be calculated from the weight-average molecular weight and the number-average molecular weight.

[0083] <Organic solvent (E)> In the first embodiment of the nonaqueous dispersion composition of the present invention, the organic solvent (E) has a value of the hydrogen bond term Δh in the Hansen solubility parameters of 7.0 MPa. 0.5 It is preferable that the nonaqueous dispersion composition of the present invention contains an organic solvent (E1) having the above-mentioned properties. The organic solvent (E1) contributes to improving the liquid stability of the nonaqueous dispersion composition of the present invention. Non-limiting examples of the organic solvent (E1) include propylene glycol monomethyl ether acetate (Δh: 9.8 MPa 0.5 ), isobutyl alcohol (δh: 15.9 MPa 0.5 ), and ethyl acetate (δh: 7.2 MPa 0.5 )

[0084] The Δh of the organic solvent (E1) is 7.0 MPa. 0.5 There is no particular limitation as long as it is equal to or greater than 8.0 MPa. 0.5 Preferably, it is 9.0 MPa or more. 0.5 More preferably, it is 9.5 MPa or more. 0.5 The upper limit of Δh is not particularly limited, but from the viewpoint of liquid dispersion stability, it is preferably 20 MPa. 0.5 Preferably, it is 19 MPa or less. 0.5 More preferably, it is:

[0085] The dispersion force term Δd in the Hansen solubility parameter of the organic solvent (E1) is not particularly limited, but is preferably 10 to 20 MPa. 0.5 Preferably, the pressure is 13 to 18 MPa. 0.5 The polarity parameter Δp is more preferably, but not limited to, 0 to 15 MPa. 0.5 Preferably, the pressure is 3 to 10 MPa. 0.5 It is more preferable that:

[0086] The dispersion force term δd, polarity term δp, and hydrogen bond term δh in the above-mentioned Hansen solubility parameters can be calculated using the software package HSPiP 5th Edition 5.3.06 based on Hansen Solubility Parameters: A User's Handbook, CRC Press, (B)oca Raton FL, 2007.

[0087] The organic solvent (E) may contain an organic solvent other than the organic solvent (E1) (hereinafter also referred to as "organic solvent (E2)") within the range that does not impair the effects of the present invention. The organic solvent (E2) is not particularly limited as long as it does not impair the dispersion stability of the non-aqueous dispersion composition of the present invention. Non-limiting specific examples of the organic solvent (E2) include xylene (Δh: 3.1 MPa 0.5 ), methyl ethyl ketone (δh: 5.1 MPa 0.5 )

[0088] The content of the organic solvent (E) is preferably from 20 to 70% by mass, more preferably from 30 to 60% by mass, based on the mass of the nonaqueous dispersion composition.

[0089] The content of the organic solvent (E1) relative to the total mass of the organic solvent (E), i.e., the total mass of the organic solvent (E1) and the organic solvent (E2), is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more. The upper limit of the content of the organic solvent (E1) relative to the total mass of the organic solvent (E) may be 100% by mass or less.

[0090] <Viscosity of non-dispersion composition> The viscosity of the nonaqueous dispersion composition of the first embodiment of the present invention at 25°C after heat treatment at 70°C for 1 hour is 20,000 mPa·s or less, preferably 100 to 20,000 mPa·s, more preferably 300 to 10,000 mPa·s, and even more preferably 500 to 7,000 mPa·s. A viscosity within the above range provides good handleability. In this specification, the viscosity is a value measured by adjusting the temperature of the non-aqueous dispersion composition to 25°C (room temperature) and using a B-type viscometer at a rotational viscometer speed of 12 rpm. The solid content of the non-aqueous dispersion composition at the time of viscosity measurement is in the range of 45%±10%.

[0091] <Moisture content> In the first, second, and third embodiments of the non-dispersion composition of the present invention, the water content relative to the total mass of the non-aqueous dispersion composition is not particularly limited, but is preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.1% by mass or less.

[0092] [Method for producing non-aqueous dispersion composition] The nonaqueous dispersion composition of the present invention can be produced by a method in which a monomer mixture containing the (meth)acrylic monomer composition (a) is subjected to a radical polymerization reaction in a solution in which the olefin resin (B) is dissolved in an organic solvent (E) in the presence of a radical polymerization initiator. The reaction liquid after the radical polymerization reaction can be used as an adhesive composition, a heat seal lacquer, a coating composition, etc. as it is, or after adjusting the solid content as necessary. If the reaction liquid after the radical polymerization reaction becomes extremely viscous and solidifies, it may be liquefied by heat treatment at a temperature higher than 50° C. The nonaqueous dispersion composition liquefied by heat treatment can be used for various applications such as adhesive compositions as it is, or after adjusting the solid content as necessary.

[0093] The radical polymerization initiator may be an organic peroxide, an azo compound, or the like, with organic peroxides being particularly preferred. One type of radical polymerization initiator may be used alone, or two or more types may be used in combination.

[0094] Specific examples of the organic peroxide that is the radical polymerization initiator include o-methylbenzoyl peroxide, bis-3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, cyclohexanone peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, lauroyl peroxide, diisopropylbenzene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, tert-hexylperoxy-2-ethylhexanoate, tert-butylperoxypivalate, tert-butylperoxyneoheptanoate, tert-butylperoxyneodecanoate, and tert-butylperoxy-2-ethylhexanoate. peroxyhexanoate, tert-butyl peroxylaurate, tert-butyl peroxyacetate, tert-butyl peroxyisobutyrate, tert-butyl peroxyisononanoate, tert-butyl peroxybenzoate, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butyl peroxymaleic acid, tert-butylperoxyisopropyl monocarbonate, tert-butylperoxy-2-ethylhexyl monocarbonate, di-tert-butylperoxyhexahydroterephthalate, 1,6-di-(tert-butylperoxycarbonyloxy)hexane, tert-butyl peroxyisonanoate, tert-butylperoxyisopropyl carbonate, tert-butylperoxy-2-ethylhexyl carbonate, and the like. Specific examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile).

[0095] Among these, radical polymerization initiators with high hydrogen abstraction ability, such as dicumyl peroxide, di-tert-butyl peroxide, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxylaurate, tert-butylperoxyacetate, tert-butylperoxybenzoate, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxyisopropyl monocarbonate, and tert-butylperoxy-2-ethylhexyl monocarbonate, are preferred.

[0096] The amount of the radical polymerization initiator used is preferably 0.0001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, and even more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the total of the monomer mixture containing the (meth)acrylic monomer composition (a) and the olefin resin (B). The greater the amount of radical polymerization initiator used, the more improved the adhesion to the substrate. The smaller the amount of radical polymerization initiator used, the more improved the liquid dispersion stability.

[0097] The hydrogen abstraction ability referred to here is an index showing the likelihood of a hydrogen abstraction reaction, which is one of the reactions involving radical species generated from an organic peroxide. The hydrogen abstraction ability of an organic peroxide can be measured by methods described in various literature (e.g., Polymer Journal, 29, 366 (1997), Polymer Journal, 29, 940 (1997), and Polymer Journal, 29, 733 (1997)).

[0098] The solid content of the nonaqueous dispersion composition of the present invention is preferably 5 to 80 mass %, more preferably 10 to 70 mass %, and even more preferably 20 to 60 mass %, relative to the total mass of the composition. When the solid content is within the above range, the composition is easy to handle. In this specification, the solid content is a value calculated by the formula: solid content (mass%) = 100 - organic solvent (mass%). The organic solvent content is a value measured by heating and drying at normal pressure.

[0099] The nonaqueous dispersion composition of the present invention may contain other resins in addition to the resin D, as long as the adhesive strength to the substrate is not impaired. Examples of other resins include polyaromatic vinyl compounds such as polystyrene, polyester resins, polyurethane resins, alkyd resins, epoxy resins, cellulose-based resins such as nitrocellulose, cellulose acetate butyrate, cellulose acetate propionate, and cellulose acetate, and vinyl chloride-vinyl acetate copolymer-based resins such as vinyl chloride resins, vinyl chloride-vinyl acetate copolymer resins, and vinyl acetate resins. In order to comply with halogen-free standards, it is preferable that the resin does not contain vinyl chloride resin, vinyl chloride vinyl acetate copolymer resin such as vinyl acetate resin, or vinyl chloride vinyl acetate copolymer resin.

[0100] To the nonaqueous dispersion composition of the present invention, various additives can be added, as needed, by a general blending method, such as conductivity imparting agents such as carbon black and ferrite; inorganic fillers, lubricants, plasticizers, organic peroxides, aluminum paste, and mica as luminescent agents; antioxidants, ultraviolet absorbers, weather resistance imparting agents, radiation resistance imparting agents, thermal stability imparting agents, surface conditioners, crosslinking agents, curing catalysts, pigment sedimentation inhibitors, and silane coupling agents.

[0101] The non-aqueous dispersion composition of the present invention has excellent adhesion, particularly to the surface of a substrate made of a polyolefin resin, to which adhesion has been difficult using conventional techniques. For example, the adhesive strength obtained is such that the peel strength measured by the method described below is 7 to 40 N / 15 mm, preferably 9 to 30 N / 15 mm.

[0102] Examples of substrates made of polyolefin-based resins include polyethylene film (PE), unstretched polypropylene film (CPP), oriented polypropylene film (OPP), ethylene-vinyl acetate copolymer film (EVA), ethylene-vinyl alcohol copolymer film (EVOH), and polyvinyl chloride film (PVC); polyolefins such as high-pressure polyethylene, medium- and low-pressure polyethylene, polypropylene, and poly4-methyl-1-pentene, and polyolefin-based resins such as ethylene-propylene copolymer, ethylene-butene copolymer, and propylene-butene copolymer.

[0103] The nonaqueous dispersion composition of the present invention can also be used as an adhesive for substrates other than those made of polyolefin resins, such as plastic films such as polyethylene terephthalate film (PET), amorphous polyethylene terephthalate film (A-PET), polycarbonate film, polybutylene terephthalate (PBT) resin film, unstretched nylon film, biaxially oriented nylon film, polyvinylidene chloride film, polyvinyl alcohol film, and polystyrene film; polymer substrates such as acrylic resins such as polymethyl methacrylate and copolymers having structural units derived from methyl methacrylate, polyester resins, resin alloys made of polypropylene and synthetic rubber, polyamide resins, unsaturated polyester resins, polybutylene terephthalate resins, polycarbonate resins, and polystyrene resins; metal substrates such as untreated steel sheets and steel sheets plated with a zinc or aluminum oxide film; and non-ferrous metal substrates such as copper sheets, aluminum sheets, aluminum foil, aluminum alloy sheets, and titanium sheets.

[0104] The adhesive composition of the present invention includes the nonaqueous dispersion composition of the present invention. Specific applications of the adhesive composition include heat seal lacquers and hot melts.

[0105] Heat seal lacquers are lacquer-type adhesive compositions used to hermetically seal packaging containers for food, pharmaceuticals, industrial products, daily necessities, cosmetics, etc. with lids, and are used for packaging containers and lids on various plastic films, vapor-deposited films, aluminum foil, paper, nonwoven fabrics, glass, etc. The aluminum foil may be a single layer of aluminum foil, or a laminate containing aluminum foil and a sealant film (for example, a laminate having aluminum foil, an adhesive layer, and a sealant film in this order). When the laminate is used as a lid material, the adhesive composition of the present invention is preferably used as an adhesive layer interposed between the sealant film and the container.

[0106] Examples of methods for applying the adhesive composition of the present invention include bar coating, gravure coating, roll coating, knife coating, and kiss coating. After applying the adhesive composition to a substrate, it may be heated and dried. For example, when applying the adhesive composition to aluminum foil, drying conditions are preferably in the range of 100 to 200°C for 5 to 1000 seconds. The thickness of the adhesive composition after heat drying is appropriately set depending on the lid material and container to be adhered, and is preferably 0.1 to 40 μm, more preferably 1 to 20 μm, and even more preferably 3 to 15 μm.

[0107] The adhesive composition of the present invention may contain other resins in addition to the resin D, provided that the adhesive composition does not impair its adhesion to the substrate. Examples of other resins include polyaromatic vinyl compounds such as polystyrene, polyester resins, polyurethane resins, alkyd resins, epoxy resins, cellulose-based resins such as nitrocellulose, cellulose acetate butyrate, cellulose acetate propionate, and cellulose acetate, vinyl chloride resins, and vinyl acetate resins.

[0108] The content of the nonaqueous dispersion composition in the adhesive composition is preferably 10% by mass or more, more preferably 50% by mass or more, and even more preferably 70% by mass or more, based on the mass of the adhesive composition.

[0109] The content of the non-aqueous dispersion composition in the heat seal lacquer is preferably 10% by mass or more, more preferably 50% by mass or more, and even more preferably 70% by mass or more, based on the mass of the heat seal lacquer.

[0110] The coating composition of the present invention comprises the non-aqueous dispersion composition of the present invention. Specific examples of coating methods for applying the coating composition of the present invention include spray coating, brush coating, dip coating, roll coating, and flow coating. The temperature and time for drying the applied coating composition of the present invention can be appropriately selected depending on the type and content of the solvent in the composition. From the viewpoint of the heat resistance of the substrate, the temperature for drying the composition is preferably room temperature to 200°C. Furthermore, from the viewpoint of the heat resistance of the substrate, the temperature for drying the composition is preferably equal to or lower than the heat resistance temperature of the substrate. From the viewpoint of the drying property of the composition, the drying time for the composition is preferably 1 to 30 minutes or more, and can be set according to the purpose, taking into account the evaporation rate of the organic solvent used, drying conditions, etc.

[0111] The coating composition may contain, as other components, polyaromatic vinyl compounds such as polystyrene; polyester resins; polyurethane resins; alkyd resins; epoxy resins; cellulose-based resins such as nitrocellulose, cellulose acetate butyrate, cellulose acetate propionate, and cellulose acetate; vinyl chloride resins; and vinyl acetate resins.

[0112] The content of the nonaqueous dispersion composition in the coating composition is preferably 10% by mass or more, more preferably 50% by mass or more, and even more preferably 70% by mass or more, based on the mass of the coating composition. [Example]

[0113] The present invention will be explained in more detail below using examples, but the present invention is not limited to these examples. Examples 1 to 7 are working examples, and Examples 8 and 9 are comparative examples.

[0114] [Viscosity measurement method] The viscosity of the non-aqueous dispersion composition immediately after production was measured. The viscosity was measured by adjusting the temperature of the non-aqueous dispersion composition to 25°C and using a B-type viscometer at a rotational viscometer speed of 12 rpm. The results are shown in the table below. ○ 500 mPa·s or more and less than 7000 mPa·s △ 300 mPa·s or more and less than 500 mPa·s, or 7000 mPa·s or more and less than 10000 mPa·s × Less than 300 mPa·s or 10,000 mPa·s or more

[0115] [Method for measuring adhesion to polyolefin substrate] A resin solution adjusted to 25% with ethyl acetate was applied to a hard aluminum foil (Takeuchi Metal Foil Co., Ltd., A1N30H-H18) using a bar coater to a thickness of 5 μm after drying, and then dried at 180°C for 3 minutes. Next, a CPP film (Mitsubishi Chemical Corporation, Super Foil E0025NA) was placed on the coated surface, and the film was tested at 120°C and 2.1 kgf / cm using a heat seal tester (Tester Sangyo Co., Ltd., TP-701). 2 The sealed area was cut into a 15 mm wide piece and pulled in a 180° direction at a speed of 250 mm / min using a tensile tester (Shimadzu Corporation, small tabletop tester EZ) to measure the peel strength (unit: N / 15 mm). ○ 9N or more △ 7N or more and less than 9N × Less than 7N

[0116] [Raw materials] <(Meth)acrylic resin (A)> (Meth)acrylic monomer (a1) MMA: Methyl methacrylate (Mitsubishi Chemical Corporation, Acryester M) nBMA: n-butyl methacrylate (manufactured by Mitsubishi Chemical Corporation, Acryester B) Carboxy group-containing monomer (a2) MAA: methacrylic acid (Mitsubishi Chemical Corporation)

[0117] <Olefin resin> PP1602: Ethylene-propylene copolymer resin (Clariant, LICOCENE PP1602, Mw 61,532, heat of crystalline fusion 15.5 J / g, melting point 70.1°C, crystallization temperature 27.6°C)

[0118] (Example 1) In a polymerization vessel equipped with a stirrer, a condenser, a dropping funnel, and a thermometer, 60 parts by mass of olefin resin (B) was heated and dissolved in 35 parts by mass of iBuOH, 25.9 parts by mass of nBMA, and 0.1 parts by mass of MAA, which are organic solvents (E) shown in Table 2. The atmosphere inside the polymerization vessel was thoroughly purged with nitrogen, and while stirring, the liquid temperature in the polymerization vessel was maintained at the polymerization temperature of 85 ° C. 46 parts by mass of the solvent, 14 parts by mass of nBMA, and 0.7 parts by mass of Perbutyl D were added dropwise over 3 hours. After reacting for another hour, 1 part by mass of the solvent and 0.35 parts by mass of Perbutyl D were added, and the reaction was continued for 2.5 hours. 50 parts of MEK was added to terminate the reaction, and the mixture was cooled to room temperature to obtain a nonaqueous dispersion composition. The mass ratio Wb / Wa of the olefin resin (B) to the total mass of MAA and nBMA was 60 / 40. The composition of the (meth)acrylic monomer composition (a) is shown in Table 1. The solid content of the obtained non-aqueous dispersion composition is shown in Table 2.

[0119] (Example 2) In this example, 60 parts by mass of olefin resin (B) was dissolved by heating in 35 parts by mass of iBuOH, 25.5 parts by mass of nBMA, and 0.5 parts by mass of MAA, which were organic solvents (E) shown in Table 2. A nonaqueous dispersion composition was produced in the same manner as in Example 1 except for the above. The composition of the (meth)acrylic monomer composition (a) is shown in Table 1. The solid content of the obtained nonaqueous dispersion composition is shown in Table 2.

[0120] (Example 3) In this example, 60 parts by mass of olefin resin (B) was dissolved by heating in 35 parts by mass of iBuOH, 25.0 mass of nBMA, and 1.0 mass of MAA, which were organic solvents (E) shown in Table 2. A nonaqueous dispersion composition was produced in the same manner as in Example 1 except for the above. The composition of the (meth)acrylic monomer composition (a) is shown in Table 1. The solid content of the obtained nonaqueous dispersion composition is shown in Table 2.

[0121] (Example 4) In this example, 60 parts by mass of the olefin resin (B) was dissolved by heating in 35 parts by mass of iBuOH, 24.0 parts by mass of nBMA, and 2.0 parts by mass of MAA, which were organic solvents (E) shown in Table 2. A non-aqueous dispersion composition was produced in the same manner as in Example 1 except for the above. The composition of the (meth)acrylic monomer composition (a) is shown in Table 1. The solid content of the obtained non-aqueous dispersion composition is shown in Table 2.

[0122] (Example 5) In this example, 50 parts by mass of the olefin resin (B) was dissolved by heating in 35 parts by mass of iBuOH, 35 parts by mass of nBMA, and 1.0 parts by mass of MAA, which were organic solvents (E) shown in Table 2. A nonaqueous dispersion composition was produced in the same manner as in Example 1. The composition of the (meth)acrylic monomer composition (a) is shown in Table 1. The mass ratio Wb / Wa of the olefin resin (B) to the total mass of MAA and nBMA was 50 / 50. The solid content of the obtained non-aqueous dispersion composition is shown in Table 2.

[0123] (Example 6) In this example, 60 parts by mass of olefin resin (B) was dissolved by heating in 35 parts by mass of iBuOH, which was the organic solvent (E) shown in Table 2, 16.8 mass of nBMA, 7.2 mass of MMA, and 2.0 mass of MAA. Otherwise, a non-aqueous dispersion composition was produced in the same manner as in Example 1. The composition of the (meth)acrylic monomer composition (a) is shown in Table 1. The solid content of the obtained non-aqueous dispersion composition is shown in Table 2.

[0124] (Example 7) In this example, 35 parts by mass of the olefin resin (B) was dissolved by heating in 35 parts by mass of iBuOH, 50 parts by mass of nBMA, and 1.0 parts by mass of MAA, which was the organic solvent (E) shown in Table 2. A nonaqueous dispersion composition was produced in the same manner as in Example 1. The composition of the (meth)acrylic monomer composition (a) is shown in Table 1. The mass ratio Wb / Wa of the olefin resin (B) to the total mass of MAA and nBMA was 35 / 60. The solid content of the obtained non-aqueous dispersion composition is shown in Table 2.

[0125] (Example 8) In this example, 60 parts by mass of the olefin resin (B) was dissolved by heating in 35 parts by mass of iBuOH and 26.0 parts by mass of nBMA, which are the organic solvents (E) shown in Table 2. A non-aqueous dispersion composition was produced in the same manner as in Example 1 except for the above. The composition of the (meth)acrylic monomer composition (a) is shown in Table 1. The solid content of the obtained non-aqueous dispersion composition is shown in Table 2.

[0126] (Example 9) In this example, 60 parts by mass of olefin resin (B) was dissolved by heating in 35 parts by mass of iBuOH, which is the organic solvent (E) shown in Table 2, 15.2 mass of nBMA, 8.8 mass of MMA, and 2.0 mass of MMA. Otherwise, a non-aqueous dispersion composition was produced in the same manner as in Example 1. The composition of the (meth)acrylic monomer composition (a) is shown in Table 1. The solid content of the obtained non-aqueous dispersion composition is shown in Table 2.

[0127] [Table 1]

[0128] [Table 2]

[0129] The acrylic resin (A) contains structural units derived from a (meth)acrylic monomer (a1) (excluding the carboxyl group-containing monomer (a2)) and structural units derived from the carboxyl group-containing monomer (a2), and the structural units of the acrylic resin (A) contain 18.5 mass% or less of structural units derived from the monomer (a1-1) having a glass transition temperature of 100°C or higher. In Examples 1 to 7, the nonaqueous dispersion compositions had excellent adhesion to polyolefin substrates and metal substrates. On the other hand, Example 8, which did not contain any structural units derived from the carboxyl group-containing monomer (a2), and Example 9, in which the structural units of the acrylic resin (A) contained 18.5 mass % or more of structural units derived from the monomer (a1-1) having a glass transition temperature of 100°C or higher, resulted in low adhesion to polyolefin-based substrates and metal-based substrates.

Claims

1. A non-aqueous dispersion composition comprising a resin composition (D) containing an acrylic resin (A) and an olefin resin (B), and an organic solvent (E), The acrylic resin (A) contains a structural unit derived from a (meth)acrylic monomer (a1) (excluding a carboxy group-containing monomer (a2)) and a structural unit derived from a carboxy group-containing monomer (a2), the content of structural units derived from a monomer (a1-1) having a glass transition temperature of 100°C or higher in the acrylic resin (A) is 18.5% by mass or less, relative to the mass of the acrylic resin (A); A non-aqueous dispersion composition, wherein the content of a chlorine-containing compound is less than 25% by mass based on the mass of the non-aqueous dispersion composition.

2. The resin composition (D) 2. The nonaqueous dispersion composition according to claim 1, which is obtained by polymerizing a (meth)acrylic monomer composition (a) containing a (meth)acrylic monomer (a1) (excluding the carboxy group-containing monomer (a2)) and the carboxy group-containing monomer (a2) in the presence of an olefin resin (B).

3. 2. The nonaqueous dispersion composition according to claim 1, wherein the mass ratio of the acrylic resin (A) to the olefin resin (B) is 80 / 20 to 10 / 90.

4. 2. The nonaqueous dispersion composition according to claim 1, wherein the acrylic resin (A) has a glass transition temperature (Tg) of −50 to 50° C.

5. The acrylic resin (A) has a solubility parameter (SP value) calculated by the Fedors method of 18 to 21 (J / cm ３ ) １／２ 2. The non-aqueous dispersion composition according to claim 1, wherein

6. 2. The nonaqueous dispersion composition according to claim 1, wherein the degree of acid modification of the olefin resin (B) is 0% by mass or more and 20% by mass or less, with the weight of the modified polyolefin resin (B1) being 100% by mass.

7. 2. The nonaqueous dispersion composition according to claim 1, wherein the olefin resin (B) has a heat of crystalline fusion of 5 to 50 J / g.

8. 2. The nonaqueous dispersion composition according to claim 1, wherein the melting point of the olefin resin (B) is 40 to 120°C.

9. 2. The nonaqueous dispersion composition according to claim 1, wherein the crystallization temperature of the olefin resin (B) is 10 to 60°C.

10. 2. The nonaqueous dispersion composition according to claim 1, wherein the olefin resin (B) contains at least one of a structural unit derived from ethylene and a structural unit derived from propylene.

11. The nonaqueous dispersion composition according to claim 10, wherein a ratio of the total mass of the ethylene-derived structural units and the propylene-derived structural units to the total mass of the olefin-based resin (B) is 50 mass% or more.

12. The nonaqueous dispersion composition according to claim 1, wherein the olefin-based resin (B) comprises an ethylene-propylene copolymer or polypropylene.

13. 2. The nonaqueous dispersion composition according to claim 1, wherein the weight average molecular weight of the resin composition (D) containing the acrylic resin (A) and the olefin resin (B) is 5,000 to 500,000.

14. The organic solvent (E) has a hydrogen bond parameter δh of 8 MPa in the Hansen solubility parameter. ０．５ The nonaqueous dispersion composition according to claim 1, comprising an organic solvent (E1) of the above formula.

15. An adhesive composition comprising the nonaqueous dispersion composition according to any one of claims 1 to 14.

16. A heat seal lacquer comprising the non-aqueous dispersion composition according to any one of claims 1 to 14.

17. A coating composition comprising the non-aqueous dispersion composition according to any one of claims 1 to 14.

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