JP4166642B2 - Resin having a bicontinuous structure, method for producing the same, and use - Google Patents

Description

  The present invention relates to a resin useful as, for example, a paint or primer for a resin molded article or the like, or as an adhesive.

  Polyolefin resins generally have many advantages such as high productivity, excellent various moldability, light weight, rust prevention and impact resistance. Therefore, it is used for a wide range of applications as interior and exterior of automobiles and ships, home appliances, furniture, sundries, building materials, and the like.

  Unlike a synthetic resin having a polarity typically represented by a polyurethane resin, a polyamide resin, an acrylic resin, a polyester resin, or the like, the polyolefin resin is nonpolar and crystalline. Therefore, it is very difficult to perform coating and adhesion on polyolefin resin moldings using general-purpose paints and adhesives. Therefore, when coating or adhering to such a molded product, the adhesion to the surface is improved by priming or activating the surface. For example, for automotive bumpers, the surface is etched with a halogen-based organic solvent such as trichloroethane to improve adhesion to the coating film, or after pretreatment such as corona discharge treatment, plasma treatment, ozone treatment, etc. And there is a method of bonding. However, in order to carry out these treatments, a large amount of equipment costs are required, the construction takes a long time, and the finish is not uniform and the surface treatment state tends to vary.

  On the other hand, as coating compositions with improved adhesion, for example, compositions in which maleic acid is introduced into polyolefin (Patent Document 1, etc.) and compositions containing chlorinated modified polyolefin as a main component (Patent Document 2, etc.) have been proposed. ing. However, they are inferior in weather resistance although they are excellent in adhesion to polyolefin-based resin moldings and the like. Therefore, it is usually limited to use as a primer or in places where weather resistance is not required. When painting these in places where weather resistance is required, it is usually a two-coat finish that is cumbersome to operate. Is required.

  In addition, the development of paints that can exhibit excellent adhesion without pretreatment and that have excellent weather resistance and can be subjected to a one-coat finishing treatment is also underway. For example, a resin composition obtained by copolymerizing an acrylic monomer and a chlorinated polyolefin (Patent Document 3, etc.), a coating composition comprising a hydroxyl group-containing acrylic-chlorinated polyolefin copolymer and an isocyanate compound (Patent Document 4) Has been proposed. However, since these contain chlorine, there is a concern about the environmental impact.

  In addition, a method of introducing an unsaturated bond into a polyolefin (Patent Document 5, Patent Document 6, etc.), a method of introducing an organic peroxide (Patent Document 7, etc.), a method of using a bifunctional organic peroxide (Patent Document 8) has also been proposed. These are all methods for improving the reactivity between the polyolefin and the radically polymerizable unsaturated monomer. However, in these methods, in many cases, the reaction must be carried out at a dilute concentration due to the problem of viscosity, and the graft copolymerization efficiency to polyolefin is low, and a homopolymer of a radical polymerizable unsaturated monomer is likely to be formed. Therefore, the obtained resin solution is very susceptible to separation, and usually has a drawback that it cannot be used as it is, and those coated with these also have a drawback of causing stickiness.

As for adhesion between polyolefin and metal such as aluminum, for example, a resin dispersion of modified polypropylene (Patent Document 9 etc.) has been proposed. However, in this resin dispersion, a raw material having a high melting point is used because it is necessary to reduce the stickiness of the coating film, and therefore there is a disadvantage that the heat seal temperature is high.
Japanese Patent Publication No. 62-21027 Japanese Patent Publication No. 50-10916 JP 58-71966 A JP 59-27968 JP-A-1-123812 JP-A-2-269109 JP-A-1-131220 JP-A 64-36614 JP-A 63-12651

  The present invention has been made to solve the problems of the conventional techniques described above. That is, the object of the present invention is to show excellent adhesion as a coating film to both the nonpolar material and the polar material, and also has excellent weather resistance, and the resin is difficult to separate in the state of the resin solution. Another object of the present invention is to provide a resin excellent in heat sealability at low temperatures, a method for producing the same, and a use thereof.

  As a result of intensive studies and studies to achieve the above object, the present inventors have found that a resin having a specific composition and structure is extremely effective for achieving the above object. It came to be completed.

That is, the resin having a co-continuous structure according to the present invention is [1] polymerizing two or more α-olefins.
( 2 ) A polymer obtained from a thermoplastic elastomer (A) which is an olefin polymer obtained in the above , and [2] a monomer (C) containing at least a monomer having an α, β-monoethylenically unsaturated group ( In the polymer alloy in which D) is mixed, both the parts [1] and [2] have a phase structure, and the phases of the parts [1] and [2] are both three-dimensionally continuous. It has a phase separation structure .

Further, the resin having a co-continuous structure of the present invention includes: [1] At least a part of the thermoplastic elastomer (A), which is an olefin polymer obtained by polymerizing two or more α-olefins, is modified with a functional group. and those, [2] α, in the polymer (D) and the polymer alloy to coexist derived from monomers containing at least a monomer having a β- monoethylenically unsaturated group (C), these Both portions [1] and [2] have a phase structure, respectively, and the phases of the portions [1] and [2] both have a three-dimensionally continuous phase separation structure .

Furthermore, in the method for producing a resin having a co-continuous structure according to the present invention, at least a part of the thermoplastic elastomer (A) which is an olefin polymer obtained by polymerizing two or more kinds of α-olefins in an organic solvent is used. After the modification with the functional group, the monomer (C) containing at least a monomer having an α, β-monoethylenically unsaturated group has a mass of (A) / (C) = 20/80 to 80/20. have a step of reacting at a ratio, [1] and in which at least a portion of two or more thermoplastic elastomer is an olefin-based polymer obtained by polymerizing an α- olefin (a) is modified with a functional group [2] In a polymer alloy in which a polymer (D) obtained from a monomer (C) containing at least a monomer having an α, β-monoethylenically unsaturated group is mixed, both these parts [1 ] And [2] each have a phase structure, and A resin having a phase separation structure in which the phases of the portions [1] and [2] are both three-dimensionally continuous is produced .

Furthermore, in the method for producing a resin having a co-continuous structure according to the present invention, at least a part of the thermoplastic elastomer (A) which is an olefin polymer obtained by polymerizing two or more kinds of α-olefins in an organic solvent is used. After modifying with a functional group and mixing the polyolefin (B), the monomer (C) containing at least a monomer having an α, β-monoethylenically unsaturated group is converted into [(A) + (B)]. / (C) = 20 / 80~80 / 20 mass ratio have a step of reacting, [1] more thermoplastic elastomer is an olefin-based polymer obtained by polymerizing an α- olefin (a ) At least partially modified with a functional group, and a polyolefin (B) and [2] a monomer (C) containing at least a monomer having an α, β-monoethylenically unsaturated group. Polymer (D) mixed with polymer (D) Roy manufactures a resin having a phase separation structure in which both the parts [1] and [2] each have a phase structure and the phases of the parts [1] and [2] are both three-dimensionally continuous. It is characterized by doing .

  Furthermore, the present invention is a paint or adhesive that forms a coating film comprising the resin of the present invention, and a coating film obtained by applying and curing them on a substrate.

  In the resin of the present invention, a thermoplastic elastomer (A) or a material in which at least a part of the thermoplastic elastomer (A) is modified with a functional group and a specific polymer (D) form a co-continuous structure. Therefore, it has both resin characteristics well, and exhibits excellent adhesion to both non-polar materials such as untreated polyolefin resin films, sheets, molded products, and polar materials such as metals and general-purpose paints. . Further, in a state dissolved by a solvent, the resin solution can be spray coated or the like in a high concentration state without causing a separation phenomenon. In addition, the surface of the obtained coating film has no stickiness and is excellent in heat sealability at low temperatures. Therefore, the resin of the present invention is, for example, a molded product of various resins composed of polyolefin, synthetic rubber, unsaturated polyester, epoxy resin, urethane resin, etc., and paints, primers, and adhesives used for metals such as steel plates and aluminum. It is very useful for applications such as agents.

  Furthermore, using a thermoplastic elastomer (A) modified with at least a part of the functional group, a specific amount of the monomer (C) is added in an organic solvent in the presence of the modified thermoplastic elastomer and reacted. Then, in the resin coating film obtained by applying and curing the resin solution, in particular, a very fine co-continuous structure as shown in FIG. 1 described later is formed, and better characteristics can be obtained.

In the present invention, “co-continuous structure” means
[1] A thermoplastic elastomer (A) or a thermoplastic elastomer (A) in which at least a part is modified with a functional group, and optionally a polyolefin (B),
[2] A polymer (D) obtained from a monomer (C) containing at least a monomer having an α, β-monoethylenically unsaturated group;
In a polymer alloy in which both of these parts [1] and [2] have phase structures, and the phases of the parts [1] and [2] are both three-dimensionally continuous. Means to take. That is, the phase separation form of the resin composite having such a phase separation structure basically takes a three-dimensional network structure, not a sea-island structure. However, the co-continuous structure means a structure having a network structure as a main structure. For example, there may be a part where the phases are partially interrupted, or a part of the sea island structure may exist. Absent. In the present invention, the mesh size in the co-continuous structure is preferably in the range of 0.0001 to 5 μm and more preferably in the range of 0.0005 to 2 μm in the thickness direction of the coating film.

  The bicontinuous structure can be confirmed, for example, by a transmission electron microscope. Specifically, for example, FIG. 1 is a transmission electron micrograph of the cross section of the coating film of the resin solution of Example 1 to be described later. From this photograph, each phase of both portions [1] and [2] It can be seen that both are continuous and a network structure is formed. In addition, the black part of the photograph of FIG. 1 corresponds to the part [1], and the white part corresponds to the part [2]. Further, FIG. 2 is a schematic view illustrating a typical phase separation structure. Among these, (a) and (c) schematically show the sea-island structure, and (b) schematically shows the co-continuous structure in the present invention. That is, in observation with a transmission electron microscope, if the phase separation structure is not a sea-island structure as shown in FIGS. 2A and 2C but a co-continuous structure as shown in FIG. Can be judged to be a resin having a co-continuous structure.

  Examples of the resin composite having a co-continuous structure include those proposed in Japanese Patent Application Laid-Open Nos. 2001-240718 and 2002-372607. As described in these publications, different resins (for example, cross-linked polymer and thermoplastic resin, or acrylic resin and styrene resin) are mixed to form a co-continuous structure, breaking strength, breaking elongation, impact resistance Techniques for improving mechanical properties such as sex or light diffusion properties are known. However, as in the present invention, [1] the thermoplastic elastomer (A) or at least a part of the thermoplastic elastomer (A) is modified with a functional group, and optionally a polyolefin (B), and [2] α, A resin having a co-continuous structure formed from a polymer (D) obtained from a monomer (C) containing at least a monomer having a β-monoethylenically unsaturated group is not known, This new resin also improves the properties required for applications such as paints, primers, adhesives, etc., such as adhesion to substrates, spray coating, non-stickiness, heat sealability, etc. It was not done. Furthermore, in an organic solvent, if a specific amount of the monomer (C) is added and reacted in the presence of at least a part of the thermoplastic elastomer (A) modified with a functional group, finer co-continuity is achieved. It was also not known that body structure was obtained and better properties were obtained. That is, the present invention is not only characterized in that a co-continuous structure is formed, but also in terms of the types of components used and the production method.

  Examples of the thermoplastic elastomer (A) used in the present invention include ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, and 1-heptene. , 1-hexene, 1-octene, 1-decene, 1-dodecene and other α-olefin homopolymers, or thermoplastic elastomers composed of copolymers of two or more of these. Typically, polyethylene, polypropylene, poly-1-butene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4-methyl-1-pentene, ethylene / propylene copolymer A thermoplastic elastomer composed of a polymer, an ethylene / 1-butene copolymer, a propylene / 1-butene copolymer, and other polymers can be used. In particular, one or more α-olefins selected from the group consisting of ethylene, propylene, and butene are used as the main component, and other α-olefins are used in combination as needed to polymerize two or more α-olefins. A thermoplastic elastomer made of the olefin copolymer thus obtained is preferred. Specifically, ethylene / butene copolymer, ethylene / propylene copolymer, ethylene / butene copolymer, ethylene / octene copolymer, ethylene / propylene / butene copolymer, propylene / butene copolymer, propylene -A thermoplastic elastomer made of octene copolymer or the like is particularly preferable.

  The α-olefin homopolymer or copolymer has a weight average molecular weight (hereinafter referred to as “Mw”) of preferably 5,000 to 200,000, more preferably 10,000 to 100,000, and particularly preferably 40,000 to 100,000.

  Further, as the thermoplastic elastomer (A), for example, a styrene thermoplastic elastomer composed of a hydrogenated styrene-conjugated diene block copolymer, a hydrogenated styrene-conjugated diene random copolymer, or the like may be used. it can. Specific examples of hydrogenated styrene-conjugated diene block copolymers include hydrogenated styrene-conjugated diene diblock copolymers and hydrogenated styrene-conjugated diene-styrene triblock copolymers. Etc. Examples of the conjugated diene include butadiene and isoprene.

  The styrene content of the styrenic thermoplastic elastomer is preferably 2 to 60% by mass, and more preferably 3 to 45% by mass. Further, in the case of a hydrogenated product of a styrene-butadiene copolymer, the styrene content is particularly preferably from 3 to 40% by mass, and in the case of a hydrogenated product of a styrene-isoprene-styrene copolymer, the styrene content. Is particularly preferably 5 to 45% by mass. The Mw of the styrenic thermoplastic elastomer is preferably 5,000 to 500,000. Further, in the case of a hydrogenated product of a styrene-butadiene copolymer, the Mw is more preferably from 30,000 to 500,000. In the case of a hydrogenated product of a styrene-isoprene-styrene copolymer, the Mw is from 5,000 to 300,000 is more preferable.

  The various thermoplastic elastomers mentioned above may be used alone or in combination of two or more.

  In the present invention, the thermoplastic elastomer (A) can be used without being modified, but it is preferable to use a material obtained by modifying at least a part of the thermoplastic elastomer (A) with a functional group. Such a modified resin is not particularly limited, but can be produced by, for example, a method described in JP-B-62-21027.

  The thermoplastic elastomer (A) in which at least a part is modified with a functional group is obtained by, for example, reacting the above-mentioned various thermoplastic elastomers or a mixture of two or more thereof with a monomer containing a functional group. Obtained. The monomer containing the functional group used here may contain a monomer that does not react partially. The functional group is preferably an acid and / or a hydroxyl group.

  Examples of monomers containing functional groups include hydroxyl group-containing vinyls such as 2-hydroxyethyl (meth) acrylate, lactone-modified hydroxyethyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl acrylate; acrylic acid, Carboxyl group-containing vinyls such as methacrylic acid, maleic acid, itaconic acid, ω-carboxy-polycaprolactone monoacrylate, monohydroxyethyl acrylate phthalate; nitrogen compounds such as acrylamide, methacrylamide, methylolacrylamide, methylolmethacrylamide; maleic anhydride Carboxylic anhydrides such as acid and citraconic anhydride; and the like. These may be used alone or in combination of two or more.

  0.5-20 mass parts is preferable with respect to 100 mass parts of thermoplastic elastomer (A), and, as for the addition amount of the monomer containing a functional group, 1-15 mass parts is more preferable.

  In the present invention, it is preferable to use the polyolefin (B) in combination with a thermoplastic elastomer (A) or a thermoplastic elastomer (A) that is at least partially modified with a functional group. Specifically, in an organic solvent, a thermoplastic elastomer (A) or a thermoplastic elastomer (A) at least partly modified with a functional group is mixed with a polyolefin (B) under heating. Can be used. That is, in the present invention, a resin further containing a polyolefin (B) is one of the preferred forms.

  Examples of the polyolefin (B) include homopolymers such as ethylene, propylene, 1-butene, 1-heptene, 1-octene, 1-hexene, 1-decene, 4-methyl-1-pentene, or two types thereof. The copolymer obtained by using above is mentioned. Further, two or more different types of polyolefins may be mixed and used. In particular, when producing a paint, primer, or adhesive used for a substrate made of polypropylene, it is preferable to introduce polyolefin (B). In this case, it is particularly preferable to use an ethylene-propylene-butene copolymer, a propylene-butene copolymer, an ethylene-propylene copolymer, or a mixture of two or more of these. Moreover, it is preferable that the propylene component of these copolymers is 50 mol% or more.

  The Mw of the polyolefin (B) is preferably 5,000 to 200,000, more preferably 10,000 to 100,000, and particularly preferably 30,000 to 100,000.

  In the present invention, the thermoplastic elastomer (A) or at least a part of the thermoplastic elastomer (A) is modified with a functional group (and optionally a polyolefin (B)) and an α, β-monoethylenically unsaturated group. The polymer (D) obtained from the monomer (C) containing at least a monomer having a group forms a co-continuous structure.

  In the monomer (C), examples of the monomer having an α, β-monoethylenically unsaturated group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl ( (Meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, lauroyl (meth) acrylate, cyclohexyl (meth) acrylate, (Meth) acrylic acid esters such as benzyl (meth) acrylate, phenyl (meth) acrylate, dimethylamonoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate; hydroxyethyl acrylate, 2-hydroxyethyl (meth) ) Hydroxyl group-containing vinyls such as acrylates and lactone-modified hydroxyethyl (meth) acrylates; Carboxyl group-containing vinyls such as acrylic acid, methacrylic acid, maleic acid and itaconic acid, and monoesterified products thereof; glycidyl (meth) acrylate, methyl Epoxy group-containing vinyls such as glycidyl (meth) acrylate; Isocyanate group-containing vinyls such as vinyl isocyanate and isopropenyl isocyanate; Aromatic vinyls such as styrene, α-methylstyrene, vinyltoluene, and t-butylstyrene Other acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, acrylamide, methacrylamide, methylol acrylamide, methylol methacrylamide, ethylene, propylene, C4-C20 α- Olefin, and the like. In the present specification, “(meth) acrylate” refers to methyl acrylate and methyl methacrylate. These monomers may be used independently and may use 2 or more types together. Moreover, the macromonomer etc. which have the homopolymer or polymer of these monomers in a segment, and have a vinyl group at the terminal can be used.

  The monomer (C) may be a monomer having a part or all of an α, β-monoethylenically unsaturated group. When a monomer having an α, β-monoethylenically unsaturated group is used as a part of the monomer (C), the remaining part of the monomer (C) is other copolymerizable monomer. You just have to be your body. Examples of the copolymerizable monomer include carboxylic anhydrides such as maleic anhydride and citraconic anhydride.

  As for the usage-amount of a monomer (C), 20-80 mass parts is preferable on the basis of a total of 100 mass parts of a thermoplastic elastomer (A) and a monomer (C). Moreover, when using polyolefin (B), the usage-amount of a monomer (C) is 20 on the basis of a total of 100 mass parts of a thermoplastic elastomer (A), polyolefin (B), and a monomer (C). -80 mass parts is preferable.

  In the present invention, when using a thermoplastic elastomer (A) having at least a part modified with a functional group, after modifying at least a part of the thermoplastic elastomer (A) with a functional group in an organic solvent, It is preferable to add the monomer (C) for reaction. Further, when the polyolefin (B) is also used, at least a part of the thermoplastic elastomer (A) is modified with a functional group in an organic solvent, and after mixing the polyolefin (B), the monomer (C) is added. In addition, it is preferable to react. In this case, a resin is obtained in which at least a part of the thermoplastic elastomer (A) modified with a functional group reacts with at least a part of the monomer (C).

  Examples of the organic solvent used in these reactions include aromatic hydrocarbons such as xylene, toluene, and ethylbenzene; aliphatic hydrocarbons such as hexane, heptane, octane, and decane; fats such as cyclohexane, cyclohexene, methylcyclohexane, and ethylcyclohexane. Cyclic hydrocarbons; ester solvents such as ethyl acetate, n-butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and 3-methoxybutyl acetate; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone And so on. These organic solvents may be used as a mixture of two or more. Among these, aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons are preferable, and aliphatic hydrocarbons and alicyclic hydrocarbons are more preferable. Among the aliphatic hydrocarbons, C6-C20 aliphatic hydrocarbons are particularly preferable, and among the alicyclic hydrocarbons, methylcyclohexane and ethylcyclohexane are particularly preferable.

  The amount of the organic solvent is such that at least a part of the thermoplastic elastomer (A), the thermoplastic elastomer (A) is modified with a functional group, or at least a part of the thermoplastic elastomer (A) is modified with a functional group. In a resin solution composed of a mixture of resin and polyolefin (B) and an organic solvent, an amount such that the nonvolatile content thereof is 2 to 50% by mass is preferable.

  A thermoplastic elastomer (A), a resin solution in which at least a part of the thermoplastic elastomer (A) is modified with a functional group, or a resin solution in which at least a part of the thermoplastic elastomer (A) is modified with a functional group and a polyolefin ( When adding and reacting the monomer (C) to the resin solution of the mixture of B), it is preferable to generate radicals in the resin solution for reaction. In order to generate radicals, known methods such as a method of irradiating light in the presence of a photopolymerization initiator and a method of adding an organic peroxide can be used.

  Examples of the photopolymerization initiator include benzoyl, benzoin methyl ether, benzoin isopropyl ether, benzyl, benzophenone, 2-hydroxy-2-methylpropiophenone, 2,2-diethoxyacetophenone, benzylmethyl ketal, anthraquinone, chloroanthraquinone. , Ethyl anthraquinone, butyl anthraquinone, diphenyl sulfide, dithiocarbamate, 2-chlorothioxanthone, α-chloromethylnaphthalene anthracene, 3,3′-4,4′-tetra-benzophenone, 2,4,6-trimethylbenzoyl diphenylphos Examples include fin oxide. These may be used alone or in combination of two or more. The photopolymerization initiator may be used in combination with amines such as Michler's ketone, trimethyleneamine and alkylmorpholine. The amount of the photopolymerization initiator used is such that at least a part of the thermoplastic elastomer (A) or the thermoplastic elastomer (A) is modified with a functional group, or at least a part of the thermoplastic elastomer (A) is a functional group. 0.01-10 mass parts is preferable and 0.1-5 mass parts is more preferable with respect to a total of 100 mass parts of the modified and polyolefin (B) mixture and the monomer (C). By making the usage-amount of a photoinitiator into this range, the big effect appears in reaction stability.

  Examples of the organic peroxide include di-tert-butyl peroxide, tert-butyl peroxy-2-ethylhexanoate, benzoyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, lauroyl peroxide, Examples include cumene hydroperoxide. These can be used alone or in admixture of two or more. Of these, di-tert-butyl peroxide and tert-butyl peroxy-2-ethylhexanoate are preferable. An organic peroxide having a tert-butyl group and / or a benzyl group in the molecule has a relatively high hydrogen abstraction ability and has an effect of improving the graft ratio with polyolefin. The amount of the organic peroxide used is such that at least a part of the thermoplastic elastomer (A) or the thermoplastic elastomer (A) is modified with a functional group, or at least a part of the thermoplastic elastomer (A) is a functional group. 2-50 mass parts is preferable with respect to a total of 100 mass parts of the modified and polyolefin (B) mixture and the monomer (C), more preferably 3-30 mass parts. By making the amount of the organic peroxide used within this range, a great effect appears in the stability of the reaction. Depending on the amount used, the organic peroxide can be added in a batch, but the reaction solution is relatively easy to gel. Therefore, it can be added in small portions over time or in small portions. preferable.

  Incidentally, initiators other than photopolymerization initiators and organic peroxides, such as azobisisobutyronitrile, 4,4′-azobis (4-cyanopentanoic acid), 2,2′-azobis (2-methyl-N—) An azo compound such as (2-hydroxyethyl) propioamide) can also be used.

  In order to react the monomer (C), for example, a thermoplastic elastomer (A), a resin solution in which at least a part of the thermoplastic elastomer (A) is modified with a functional group, or a thermoplastic elastomer (A) The monomer (C) is reacted with a photopolymerization initiator, an organic oxide or the like fed to a resin solution of a mixture of at least a part of which is modified with a functional group and a polyolefin (B). Also good. Further, for example, a thermoplastic elastomer (A), a resin solution in which at least a part of the thermoplastic elastomer (A) is modified with a functional group, or a resin solution in which at least a part of the thermoplastic elastomer (A) is modified with a functional group The monomer (C) may be mixed in advance in a resin solution of a mixture of olefin and polyolefin (B), and then reacted while feeding a photopolymerization initiator, an organic oxide or the like. This monomer (C) undergoes a polymerization reaction to produce a polymer (D).

  In addition to the components described above, the resin of the present invention may contain one or more components selected from the group consisting of fats and oils, derivatives of fats and oils, epoxy resins and polyester resins, for example, as the third component. Such a 3rd component can be added in the reaction process of a monomer (C), for example.

  Examples of fats and oils include linseed oil, soybean oil, castor oil, and purified products thereof. As the derivatives of fats and oils, for example, short oil alkyd resins in which polybasic acids such as phthalic anhydride and polyhydric alcohols such as glycerin, pentaerythritol, and ethylene glycol are modified with fats and oils (fatty acids), Medium oil alkyd resin, long oil alkyd resin, natural resin, synthetic resin and rosin modified alkyd resin modified with polymerizable monomer, phenol modified alkyd resin, epoxy modified alkyd resin, acrylated alkyd resin, urethane modified alkyd resin, etc. . Two or more of these oils and fats and derivatives thereof can be used in combination. The resin composition using the fats and oils and the derivatives of fats and oils as the third component has good stability, good compatibility with other resins, and markedly improved peel strength. Particularly, those containing castor oil, castor oil fatty acid, and refined castor oil are highly effective.

  Examples of the epoxy resin include an epoxy resin obtained by glycidyl etherification of bisphenol A, bisphenol F, novolac, and the like, an epoxy resin obtained by adding propylene oxide or ethylene oxide to bisphenol A, and the like. Moreover, you may use the amine modified epoxy resin etc. which added the polyfunctional amine to the epoxy group. Furthermore, aliphatic epoxy resins, alicyclic epoxy resins, polyether-based epoxy resins, and the like can also be used. Two or more of these epoxy resins can be used in combination.

  The polyester resin is obtained by condensation polymerization of a carboxylic acid component and an alcohol component. Examples of the carboxylic acid component include terephthalic acid, isophthalic acid, phthalic anhydride, naphthalenedicarboxylic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, 1,10-decanedicarboxylic acid, cyclohexanedicarboxylic acid, trimellitic acid. And polyhydric carboxylic acids such as maleic acid and fumaric acid and lower alcohol esters thereof; hydroxycarboxylic acids such as paraoxybenzoic acid; monovalent carboxylic acids such as benzoic acid; Two or more of these carboxylic acid components can be used in combination. Examples of the alcohol component include ethylene glycol, diethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,10. -Decanediol, 3-methyl-pentanediol, 2,2'-diethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, glycerin, Examples thereof include pentaerythritol, an ethylene oxide adduct of bisphenol A, a propylene oxide adduct of bisphenol A, an ethylene oxide adduct of hydrogenated bisphenol A, a propylene oxide adduct of hydrogenated bisphenol A, and the like. Two or more of these alcohol components can be used in combination. And only one type of polyester resin may be used, or two or more types may be used in combination.

  The third component may be added while being fed into the reactor, or may be initially charged into the reactor for use. The addition amount of the third component is usually 0.5 to 60 parts by mass, preferably 2 to 40 parts by mass with respect to 100 parts by mass of the resin component. Further, it may be added after the step of generating and reacting radicals.

  For the resin solution obtained by the reaction in the organic solvent as described above, for example, after removing the solvent at the time of the reaction, a method of adding a desired solvent to dissolve and disperse the resin, or a desired solvent After the addition, it can be changed to a resin solution having a desired solvent composition by a method of removing the solvent during the reaction or the like.

  This resin solution is particularly useful as a coating agent for paints, primers, adhesives and the like. In addition, when the resin contains, as a structural unit, hydroxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, acrylic acid, methacrylic acid, etc. and has active hydrogen and / or hydroxyl group, it reacts with the active hydrogen and / or hydroxyl group. Possible curing agents can also be used in the resin solution. For example, by mixing with a curing agent having an isocyanate group in the molecule, which is one of the curing agents capable of reacting with active hydrogen and / or hydroxyl groups, it is very useful as a paint, primer and adhesive having urethane bonds. is there. Specifically, a coating film or an adhesive containing a curing agent capable of reacting with active hydrogen and / or a hydroxyl group as a main component and a resin having active hydrogen and / or a hydroxyl group is, for example, chlorinated This is preferable because it shows better weather resistance than a coating film obtained from a polyolefin-based paint or the like.

  Examples of the curing agent having an isocyanate group in the molecule include aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate; hexamethylene diisocyanate, trimethyl. Aliphatic diisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; Alicyclic diisocyanates such as isophorone diisocyanate and dicyclohexylmethane diisocyanate; Other, one or more of the isocyanate compounds And polyhydric alcohols such as dihydric alcohols such as ethylene glycol, propylene glycol, xylylene glycol and butylene glycol, and trihydric alcohols such as glycerin, trimethylolpropane and trimethylolethane. Adducts, adducts with low molecular weight polyester resins having functional groups capable of reacting with isocyanate groups, adducts thereof with water or the like, or burettes, polymers of diisocyanates, and lower monovalents. Examples include those obtained by blocking isocyanate groups with known blocking agents such as alcohol and methyl ethyl ketoxime. Also in the case of using an isocyanate prepolymer, for example, an external catalyst such as dibutyltin dilaurate or triethylamine can be added.

  Further, it is a resin synthesized from at least one of melamine, urea, benzoguanamine, glycoluril, and formaldehyde and formaldehyde, for example, a part of methylol group by a lower alcohol such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol or the like. Amino resins which are all alkyl etherified can also be used as curing agents.

  The curing agent capable of reacting with the resin solution and active hydrogen and / or hydroxyl group can be used in an arbitrary ratio. For example, when a curing agent having an isocyanate group is used, the blending ratio is preferably 0.5: 1.0 to 1.0: 0.5 in terms of an equivalent ratio of active hydrogen and isocyanate group, and 0.8. It is more preferably 1.0 to 1.0: 0.8. Moreover, when using an amino resin as a hardening | curing agent, 95 / 5-20 / 80 are preferable by solid content mass ratio of resin / amino resin in a solution, and 90 / 10-60 / 40 is more preferable.

  If necessary, components such as various stabilizers such as antioxidants, weathering stabilizers, heat resistance inhibitors, colorants such as inorganic pigments and organic pigments, and conductivity imparting agents such as carbon black and ferrite may be included. You can also.

  When this resin solution is used as, for example, a coating agent such as a paint, a primer, or an adhesive, a method for applying the resin solution to a substrate surface such as a molded product is not particularly limited. In particular, spray application is suitable, and for example, it can be applied by spraying the surface of a molded article or the like with a spray gun. This application can usually be easily performed at room temperature. Moreover, the drying method after application | coating is also not specifically limited, It can dry suitably by natural drying, heat forced drying, etc. Such a dry / cured coating film is very useful as a coating film, but can also be applied to a wide range of uses as a primer. For example, other paints can be applied to the dried surface by electrostatic coating, spray coating, brush coating, or the like. Other paints are not particularly limited, and examples thereof include solvent-type thermoplastic acrylic resin paints, solvent-type thermosetting acrylic resin paints, acrylic-modified alkyd resin paints, epoxy resin paints, polyurethane resin paints, and melamine resin paints.

  When this resin solution is used particularly as a paint, for example, polyolefins such as polyethylene and polypropylene, ethylene-propylene copolymers, ethylene-butene copolymers, propylene-butene copolymers, ethylene-propylene-butene copolymers, etc. It can be suitably used as an overcoat on the surface of molded products made of olefin copolymers, molded products made of polypropylene and synthetic rubber, and the like. Furthermore, it can be used for polyamide resins, unsaturated polyester resins, polycarbonate resins, epoxy resins, polyurethane resins, steel plates, electrodeposition-treated steel plates, and the like.

  In particular, when this resin solution is used as a primer, it is useful as a primer for, for example, a paint or adhesive mainly composed of polyurethane resin, polyester resin, melamine resin, epoxy resin or the like. Further, it can be mixed with these paints or adhesives to improve the adhesion of paints and the like to the surface of various objects to be coated, and can also be used to form a coating film with better visibility.

  In particular, when this resin solution is used as an adhesive, the coating film has no stickiness as an adhesive or heat sealant between metals, between polyolefins, or between metal and polyolefin, and exhibits excellent adhesion performance and adhesion performance. In heat sealing, the performance is exhibited at a low temperature. These can also be used as an adhesive for PTP packaging and an adhesive for laminating.

  As described above, when the resin solution is used as a coating agent such as a paint, a primer, or an adhesive, the coating film obtained by applying the resin solution on a substrate and curing it by a technique such as curing reaction and / or drying is The coating film made of the resin of the present invention, that is, the coating film made of a resin having a co-continuous structure. Therefore, this coating film exhibits very excellent characteristics. For example, this coating film is a molded product made of polyolefin such as polypropylene, a molded product made of polypropylene and synthetic rubber, a molded product using unsaturated polyester, epoxy resin, polyurethane resin, etc., a steel plate or an electrodeposition-treated steel plate. Suitable for the material.

  Furthermore, it can be used in applications other than the above-described coating agents. For example, in order to improve the adhesion of the paint to the surface of these molded products, steel plates, electrodeposition-treated steel plates, etc., or as a primer for imparting the softness of the coating film after painting, as an additive, polyurethane resin, It can be suitably used by mixing with a paint or adhesive such as polyester resin, melamine resin, and epoxy resin. Moreover, it is also possible to manufacture a resin film, a resin sheet, etc. from the resin of this invention.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these. “Parts” and “%” are based on mass.

[Example 1]
In a four-necked flask equipped with a stirrer, a thermometer, a reflux cooling device, and a nitrogen introduction tube, 100 parts of a propylene-butene-ethylene copolymer (trade name Best Plast 750, manufactured by Degussa Huls Co., Ltd.) as a thermoplastic elastomer, 150 parts of an isoparaffin-based organic solvent (trade name Shellsol TG, manufactured by Shell Japan Co., Ltd.) was charged, and the temperature was raised to 130 ° C. while purging with nitrogen. Next, 5 parts of unsaturated fatty acid hydroxyalkyl ether-modified epsilon-caprolactone (trade name Plaxel FM-3, manufactured by Daicel Chemical Industries, Ltd.) as a monomer having a functional group was added and dispersed therein. Thereafter, 5 parts of tert-butyl peroxide (hereinafter abbreviated as PBD) is added and reacted for 2 hours, and an additional 200 parts of isoparaffinic organic solvent is added to partially modify the thermoplastic elastomer with functional groups. A solution of the soup was obtained.

  Next, while maintaining the inside of the reactor at 130 ° C., 50 parts of methyl methacrylate, 17 parts of isobutyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate, 20 parts of unsaturated fatty acid hydroxyalkyl ether-modified epsilon-caprolactone, 3 parts of methacrylic acid and PBD1 A mixture of parts was fed over 4 hours. 30 minutes after the end of the feed, the temperature was raised to 135 ° C., and another 30 minutes later, 100 parts of an isoparaffinic organic solvent and 0.5 part of PBD were added, and 0.5 part of PBD was further added after 1 hour. 30 minutes after the addition of PBD, the temperature was raised to 160 ° C., and the mixture was further allowed to react for 1 hour to obtain a resin solution.

  FIG. 1 is a transmission electron micrograph of a cross-section of a coating film formed by preparing the resin solution of this example as a paint by the method described below and coating and curing on a substrate. Here, the black part is a modified thermoplastic elastomer, and the white part is a polymer (D). From this photograph, it can be seen that both phases are continuously forming a three-dimensional network structure. That is, this electron microscope observation confirmed that the resin of this example had a co-continuous structure.

[Example 2]
A resin solution was obtained in the same manner as in Example 1 except that all the solvents used were changed to methylcyclohexane and the polymerization temperature in all steps was changed to 97 ° C.

[Example 3]
As a mixed solution fed over 4 hours, 40 parts of methyl methacrylate, 17 parts of isobutyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate, 20 parts of unsaturated fatty acid hydroxyalkyl ether-modified epsilon-caprolactone, 3 parts of methacrylic acid, oil-based polyol (product) A resin solution was obtained in the same manner as in Example 1 except that a mixed solution consisting of 10 parts of name olester C1000, manufactured by Mitsui Takeda Chemical Co., Ltd. and 0.9 parts of PBD was used.

[Example 4]
A resin solution was obtained in the same manner as in Example 1 except that methacrylic acid was used as the monomer having a functional group.

[Example 5]
A resin solution was obtained in the same manner as in Example 1 except that maleic anhydride was used as the monomer having a functional group.

[Example 6]
After changing the amount of the propylene-butene-ethylene copolymer to 70 parts and adding 200 parts of an isoparaffinic organic solvent, a propylene-butene copolymer (trade name Ube Tac UT2715, Ube Industries, Ltd.) is further added as polyolefin (B). A resin solution was obtained in the same manner as in Example 1 except that 30 parts of Co., Ltd. were added.

[Example 7]
The same method as in Example 1 except that at the end of the process, the temperature was raised to 160 ° C. 30 minutes after the addition of PBD, and then 3 parts of PBD was added 30 minutes later and allowed to react for 2 hours. A resin solution was obtained.

[Example 8]
At the end of the process, the same method as in Example 6 except that the temperature was raised to 160 ° C. 30 minutes after the addition of PBD, and then 3 parts of PBD was added 30 minutes later and left to react for 2 hours. A resin solution was obtained.

[Example 9]
A resin solution was obtained in the same manner as in Example 1 except that a hydrogenated styrene-butadiene copolymer (trade name Dynalon 1320P, manufactured by JSR Corporation) was used as the thermoplastic elastomer.

[Example 10]
A resin solution was obtained in the same manner as in Example 4 except that a hydrogenated styrene-butadiene copolymer (trade name Dynalon 1320P, manufactured by JSR Corporation) was used as the thermoplastic elastomer.

[Example 11]
A resin solution was obtained in the same manner as in Example 1 except that a hydrogenated styrene-isoprene copolymer (trade name: Septon 2002, manufactured by Kuraray Co., Ltd.) was used as the thermoplastic elastomer.

[Example 12]
A resin solution was obtained in the same manner as in Example 4 except that a hydrogenated styrene-isoprene copolymer (trade name Septon 2002, manufactured by Kuraray Co., Ltd.) was used as the thermoplastic elastomer.

[Example 13]
50 parts of propylene glycol monomethyl ether acetate was further added to the resin solution obtained in Example 2 (solid content: 100 parts) and heated under normal pressure to remove 50 parts of the solvent to obtain a resin solution.

[Examples 14 to 20]
To each resin solution obtained in Examples 1, 4, 6, 7, 9, 11, and 13, a curing agent (trade name D-170HN, manufactured by Mitsui Takeda Chemical Co., Ltd.) was added to OH / NCO = 1/1. (Molar ratio) to obtain a curing agent-containing resin solution.

[Examples 21 to 27]
30 parts of titanium oxide pigment (trade name Tipeq-CR93, manufactured by Ishihara Sangyo Co., Ltd.) is added to each resin solution (solid content: 100 parts) obtained in Examples 1, 4, 6, 7, 9, 11, and 13. Further, 40 parts of an organic solvent mixed at a ratio of xylene / toluene / ethyl acetate = 1/1/1 was added to obtain a titanium pigment-containing resin solution.

[Examples 28 to 34]
A curing agent (trade name D-170HN, manufactured by Mitsui Takeda Chemical Co., Ltd.) was mixed with each resin solution of Examples 21 to 27 so that OH / NCO = 1/1 (molar ratio), and cured. An agent and a titanium pigment-containing resin solution were obtained.

[Comparative Example 1]
A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube was charged with 30 parts of a propylene-butene-ethylene copolymer and 50 parts of an isoparaffinic organic solvent as a thermoplastic elastomer, while purging with nitrogen. The temperature was raised to 130 ° C. Next, 1.5 parts of unsaturated fatty acid hydroxyalkyl ether-modified epsilon-caprolactone was added and dispersed therein as a monomer having a functional group. Thereafter, 1.5 parts of PBD was added and reacted for 2 hours, and an additional 300 parts of an isoparaffinic organic solvent was added to obtain a solution in which a part of the thermoplastic elastomer was modified with a functional group.

  Next, while maintaining the inside of the reactor at 130 ° C., 85 parts of methyl methacrylate, 28.9 parts of isobutyl methacrylate, 17 parts of 2-hydroxyethyl methacrylate, 34 parts of unsaturated fatty acid hydroxyalkyl ether-modified epsilon-caprolactone, 5. A mixture consisting of 1 part and 1.7 parts of PBD was fed over 4 hours. 30 minutes after the end of the feed, the temperature was raised to 135 ° C., and after another 30 minutes, 100 parts of an isoparaffinic organic solvent and 0.8 parts of PBD were added, and another 1 hour later, 0.8 parts of PBD was added. 30 minutes after the addition of PBD, the temperature was raised to 160 ° C., and the mixture was further allowed to react for 1 hour to obtain a resin solution.

[Comparative Example 2]
A four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube was charged with 170 parts of a propylene-butene-ethylene copolymer as a thermoplastic elastomer and 250 parts of an isoparaffin-based organic solvent, while substituting nitrogen. The temperature was raised to 130 ° C. Next, 8 parts of unsaturated fatty acid hydroxyalkyl ether-modified epsilon-caprolactone was added and dispersed therein as a monomer having a functional group. Thereafter, 8 parts of PBD was added and reacted for 2 hours, and an additional 100 parts of isoparaffinic organic solvent was added to obtain a solution in which a part of the thermoplastic elastomer was modified with a functional group.

  Next, while maintaining the inside of the reactor at 130 ° C., 15 parts of methyl methacrylate, 5.1 parts of isobutyl methacrylate, 3 parts of 2-hydroxyethyl methacrylate, 6 parts of unsaturated fatty acid hydroxyalkyl ether-modified epsilon-caprolactone, and 0.7 parts of methacrylic acid. A mixture consisting of 9 parts and 0.3 parts of PBD was fed over 4 hours. 30 minutes after the end of the feed, the temperature was raised to 135 ° C., and further 30 minutes later, 100 parts of an isoparaffinic organic solvent and 0.15 part of PBD were added, and another 1 hour later, 0.15 part of PBD was added. 30 minutes after the addition of PBD, the temperature was raised to 160 ° C., and the mixture was further allowed to react for 1 hour to obtain a resin solution.

[Evaluation]
The following evaluation was performed on each of the above Examples and Comparative Examples. The results are shown in Tables 1 to 4.

<Stability of resin solution>
The obtained resin solution was allowed to stand at room temperature and 40 ° C. for 1 month, and the state of the solution was evaluated. After 1 month, “○” indicates that neither separation nor precipitation has been confirmed, “△” indicates that separation and / or precipitation is observed, and can be easily dispersed by stirring, “△” indicates separation and / or precipitation. Those that were not easily dispersible by the observed stirring were evaluated as “x”.

<Observation of coating film>
A cross-section of the coating film was observed using a transmission electron microscope (trade name H-7000, manufactured by Hitachi, Ltd.). Samples were made of ultrathin sections stained with ruthenium tetroxide, and those with a co-continuous structure were marked as “Yes” and those not taken as “None”.

<Sprayability>
Using a paint gun (trade name: Weider Spray Gun W-88-13H5G, manufactured by Iwata Co., Ltd.), atomizing pressure 4 kg / cm ² , opening the nozzle one time, each at a temperature of 30 ° C in the painting booth The resin solution was sprayed, and it was observed whether stringing occurred or not. “O” was not generated, and “X” was generated even when one was generated.

<Evaluation of coating film>
(1) Evaluation on polypropylene substrate:
The same solvent as that at the time of manufacture was further added to the obtained resin solution, and adjusted so that the number of seconds dropped at Ford Cup No. 4 was 15 ± 2 seconds at 25 ° C. Next, it was spray-coated on a square plate of polypropylene (trade name J700, manufactured by Sumitomo Mitsui Polyolefin Co., Ltd.) whose surface was wiped with isopropyl alcohol so that the film thickness after drying was 10 μm, and dried at 80 ° C. for 20 minutes. A coating film was obtained. With respect to this coating film, a cross-cut peel test was performed, and the stickiness of the coating film surface was evaluated by touch. Furthermore, a white top coat was applied to this coating film so that the film thickness after drying would be 20 μm, left at room temperature for 10 minutes, then placed in an oven at 80 ° C. and baked for 20 minutes to obtain a coating film. It was. A cross-cut peel test was performed on this coating film. In addition, a weather resistance test was performed, and the gloss retention after the test and evaluation of cross-cut peeling were performed. The peel strength test was performed using the above-mentioned coating film coated with a white top coat so that the film thickness after drying was 40 μm.

  Further, for the resin solutions obtained in Examples 21 to 34, a UV absorber (trade name TINUVIN 327) and an antioxidant (trade name IRGANOX 1330) were further added, and a weather resistance test was also conducted on the coating film without overcoating. The gloss retention after the test and the cross-cut peeling were evaluated. In addition, the addition amount of a ultraviolet absorber and antioxidant is 0.2% respectively with respect to the resin part of each resin composition.

(2) Evaluation on olefinic thermoplastic elastomer (tuffmer) substrate:
The same solvent as that at the time of manufacture was further added to the obtained resin solution, and adjusted so that the number of seconds dropped at Ford Cup No. 4 was 15 ± 2 seconds at 25 ° C. Next, spray coating was applied to a square plate of an olefin-based thermoplastic elastomer (trade name Toughmer A4070, manufactured by Mitsui Chemicals, Inc.) whose surface was wiped with isopropyl alcohol so that the film thickness after drying was 5 μm. It was dried for 20 minutes to obtain a coating film. A cross-cut peel test was performed on this coating film. Further, a white top coat was applied to this coating film so that the film thickness after drying would be 10 μm, left at room temperature for 10 minutes, then placed in an oven at 80 ° C. and baked for 20 minutes to obtain a coating film. It was. A cross-cut peel test was performed on this coating film.

(3) Evaluation on olefinic thermoplastic elastomer (miralastomer) substrate:
Evaluation was performed in the same manner as in the above (2) except that a square plate of an olefin-based thermoplastic elastomer (trade name Miralastomer 8030, manufactured by Mitsui Chemicals, Inc.) was used.

  In the above evaluation methods (1) to (3), as the top coating material, a thermoplastic polyurethane resin (trade name Olester Q186, manufactured by Mitsui Chemicals, Inc., nonvolatile content 50%, hydroxyl value 30 KOHmg / g) is absorbed by ultraviolet rays. Agent (trade name TINUVIN327) 0.2% with respect to resin content, antioxidant (trade name IRGANOX1330) 0.2% with respect to resin content, titanium oxide pigment (trade name Tippe-CR93, Ishihara Sangyo Co., Ltd.) )) And a curing agent containing NCO (trade name MT Orester NM89-50G, manufactured by Mitsui Takeda Chemical Co., Ltd., nonvolatile content 50%, NCO% = 6%) prepared by mixing so that OH / NCO = 0.95 was used.

  In addition, the cross-cut peel test is performed in accordance with the cross-cut peel test method of JIS-K-5400, and a test piece with a cross cut is prepared, and an adhesive tape (trade name cello tape, manufactured by Nichiban Co., Ltd.) is used on the cross cut. After being pasted, it was quickly pulled and peeled in the direction of 90 °, and evaluation was performed based on the number of grids that were not peeled out of 100 grids.

  The peel strength is measured by cutting the coating film with a width of 1 cm, peeling off the end portion, then measuring the peel strength by pulling the end portion in a 180 ° direction at a speed of 50 mm / min, and the peel strength is 1300 g. "O" is indicated by "/" or more than 500 g / cm, "△" is indicated by 500 g / cm or more and less than 1500 g / cm, and "X" is indicated by less than 500 g / cm.

  In addition, the weather resistance test is evaluated by a sunshine carbon arc lamp type according to the accelerated weather resistance test method of JIS-K-5400, and according to 60 degree specular gloss (JIS-K-5400) after 500 hours. Retention rate of measured value (%) = (Glossiness after test / Initial glossiness) × 100 was calculated, and “○” indicates that no change in color was observed when the gloss retention rate was 80% or more, and 60% or more and 80%. Less than% is indicated by “Δ”, and less than 60% is indicated by “X”.

<Heat seal test>
The same solvent as in the production was further added to the resin solutions obtained in Examples 1 to 20 and Comparative Examples 1 and 2, to prepare a solution having a nonvolatile content of 10%. Next, it was coated on an aluminum foil with a bar coater so that the film thickness after drying was 2 μm, air-dried, and then heated in an air oven set at 200 ° C. for 20 seconds to produce a uniform transparent coating foil. . This coated foil and a polypropylene sheet (trade name: East Cello # 500T-T) were heat sealed by applying a pressure of 0.098 MPa at 120 ° C. for 1 second by a method based on JISZ1707. The test piece thus obtained was cut into a strip having a width of 15 mm, and a 180 ° peel test was performed at room temperature. A peel strength of 1500 g / 15 mm or more was indicated as “◯”, a peel strength of 500 g / 15 mm or more and less than 1500 g / 15 mm as “Δ”, and a peel strength of less than 500 g / 15 mm as “X”.

2 is a transmission electron micrograph of the cross section of the coating film of the resin solution of Example 1. FIG. It is a schematic diagram which illustrates three types of typical phase-separation structures, (a) and (c) shows a sea-island structure typically, (b) shows the co-continuous structure in this invention typically.

Claims (14)

[1] A thermoplastic elastomer (A) that is an olefin polymer obtained by polymerizing two or more α-olefins ;
[2] alpha, in β- monoethylenically polymer (D) and a mixed polymer alloy obtained from monomer (C) containing at least a monomer having unsaturated groups,
Both of these parts [1] and [2] have a phase structure, and the phases of the parts [1] and [2] both have a three-dimensionally continuous phase separation structure.
A resin having a co-continuous structure characterized by the following . [1] A thermoplastic elastomer (A), which is an olefin polymer obtained by polymerizing two or more kinds of α-olefins, is modified with a functional group;
[2] alpha, in β- monoethylenically polymer (D) and a mixed polymer alloy obtained from monomer (C) containing at least a monomer having an unsaturated group,
Both of these parts [1] and [2] have a phase structure, and the phases of the parts [1] and [2] both have a three-dimensionally continuous phase separation structure.
A resin having a co-continuous structure characterized by the following .   The resin having a co-continuous structure according to claim 2, wherein the thermoplastic elastomer (A) at least partially modified with a functional group and at least a part of the monomer (C) are reacted. After modifying at least a part of the thermoplastic elastomer (A) with a functional group,
The resin having a co-continuous structure according to claim 2, wherein the monomer (C) containing at least a monomer having an α, β-monoethylenically unsaturated group is added and reacted. The resin having a co-continuous structure according to any one of claims 2 to 4 , wherein the functional group is an acid and / or a hydroxyl group. The resin having a co-continuous structure according to any one of claims 1 to 5, wherein the phase of the part [1] and / or [2] has a partly discontinuous portion. A part of phases of the portions [1] and [2] have a sea-island structure.
Resin which has a co-continuous body structure of any one of -6. Further resin having a co-continuous structure according to any one of claims 1 to 7 comprising a polyolefin (B). After modifying at least a part of the thermoplastic elastomer (A) with a functional group and mixing the polyolefin (B),
The resin having a co-continuous structure according to claim 8, wherein the monomer (C) containing at least a monomer having an α, β-monoethylenically unsaturated group is added and reacted. After at least a part of the thermoplastic elastomer (A), which is an olefin polymer obtained by polymerizing two or more kinds of α-olefins in an organic solvent , is modified with a functional group, α, β-monoethylenic unsaturated the monomer (C) containing at least a monomer having a group, have a step of reacting at a weight ratio of (a) / (C) = 20 / 80~80 / 20,
[1] A thermoplastic elastomer (A), which is an olefin polymer obtained by polymerizing two or more kinds of α-olefins, is modified with a functional group;
[2] In a polymer alloy in which a polymer (D) obtained from a monomer (C) containing at least a monomer having an α, β-monoethylenically unsaturated group is mixed,
Producing a resin having a phase separation structure in which both the parts [1] and [2] have a phase structure and the phases of the parts [1] and [2] are both three-dimensionally continuous.
A process for producing a resin having a co-continuous structure characterized by the following. At least a part of the thermoplastic elastomer (A), which is an olefin polymer obtained by polymerizing two or more α-olefins in an organic solvent , is modified with a functional group, and after mixing the polyolefin (B), α , A monomer containing at least a monomer having a β-monoethylenically unsaturated group (
The C), have a step of reacting with [(A) + (B) ] / (C) weight ratio = 20/80 to 80/20,
[1] A thermoplastic elastomer (A), which is an olefin polymer obtained by polymerizing two or more α-olefins, at least partly modified with a functional group, and a polyolefin (B),
[2] In a polymer alloy in which a polymer (D) obtained from a monomer (C) containing at least a monomer having an α, β-monoethylenically unsaturated group is mixed,
Producing a resin having a phase separation structure in which both the parts [1] and [2] have a phase structure and the phases of the parts [1] and [2] are both three-dimensionally continuous.
A process for producing a resin having a co-continuous structure characterized by the following. Coating composition forming a coating film made of a resin according to any one of claims 1-9. Adhesive forming a coating film made of a resin according to any one of claims 1-9. The coating film formed by apply | coating and hardening the coating material of Claim 12, or the adhesive agent of Claim 13 on a base material.