JP6987091B2 - Resin composition and adhesive structure - Google Patents

Description

The present invention relates to a resin composition and an adhesive structure using the same as an adhesive.

Polyurethane resin is useful as an adhesive or a binder because of its large cohesive force and flexibility. For this reason, polyurethane resins are widely applied to various materials such as metals, wood, rubber, and plastics constituting paints, packaging, clothing, electric appliances, automobiles, building materials, and the like. Further, the polyurethane resin can be designed in various ways by selecting the type of the polyol, the extender, the isocyanate or the like used as the raw material thereof.

On the other hand, the base material (molded body) made of a polyolefin resin is widely applied to various materials such as automobiles, electric appliances, and building materials. In particular, as automobile interior parts, those in which various skin materials are adhered and laminated on various base materials are used for the purpose of upgrading. Recently, from the viewpoint of reducing the environmental load and protecting the environment, recycling of automobile parts is desired. In particular, as the study of component materials is required so that the recycling rate is 95% or more, polyolefin-based resin materials are being used for both the base material and the skin material.

Among the polyolefin resins, polypropylene (PP) resin is generally excellent in low cost, light weight, mechanical strength, heat resistance, chemical resistance, recyclability, etc., but on the other hand, it is suitable for adhesives and adhesion. There is almost no agent and the expansion coefficient is large. In recent years, PP resin has been increased in strength due to technological progress, and is expected to be used in various applications as a substitute for ABS (acrylonitrile / butadiene / styrene) resin, PC (polycarbonate) resin, ABS / PC resin, and the like. ..

Surface free energy (polarity) has a large effect on the adhesiveness between the base material and the adhesive, and a base material made of a polyolefin resin such as PP resin or polyethylene (PE) resin, which has low surface free energy, undergoes some kind of surface treatment. Without it, sufficient adhesive strength cannot be obtained. As one of the countermeasures, a primer treatment using a chlorinated polyolefin resin, an acid-modified polyolefin resin, or the like is generally used. For example, Patent Document 1 and Patent Document 2 propose that an acid-modified polyolefin resin is used as an adhesive layer as a method for producing a decorative molded product using a base material of a polyolefin resin.

Japanese Unexamined Patent Publication No. 2014-128922 Japanese Unexamined Patent Publication No. 2014-141807

However, as described above, the adhesive layer using the acid-modified polyolefin resin itself has poor durability, and in particular, the heat resistance is low due to the thermoplastic resin constituting the adhesive layer. When blending other resins or the like in order to improve the durability of the adhesive layer, it is often difficult for ordinary acid-modified polyolefin resins to be compatible with other resins, and blending is difficult.

Therefore, the present invention is intended to provide a resin composition useful as an adhesive or a binder which exhibits good adhesiveness and has excellent durability even with a non-polar substrate such as a polyolefin resin. be.

The present invention contains a polyurethane-based resin containing at least one of a structural unit (A) derived from a polyolefin polyol and a structural unit (B) derived from a dimer polyol, and a chemically modified acid-modified polyolefin resin. Provided is a resin composition in which the content of the chemically modified acid-modified polyolefin resin is in the range of 10 to 1000 parts by mass with respect to 100 parts by mass of the polyurethane resin.

According to the present invention, it is possible to provide a resin composition useful as an adhesive or a binder which exhibits good adhesiveness and has excellent durability even with a non-polar substrate such as a polyolefin resin.

It is sectional drawing which shows typically the adhesive structure of one Embodiment of this invention.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments.

<Resin composition>
The resin composition of one embodiment of the present invention comprises a polyurethane resin containing at least one of a structural unit (A) derived from a polyolefin polyol and a structural unit (B) derived from a dimer polyol, and a chemically modified acid. Contains a modified polyolefin resin. The content of the chemically modified acid-modified polyolefin resin is in the range of 10 to 1000 parts by mass with respect to 100 parts by mass of the polyurethane resin.

[Polyurethane resin]
The polyurethane-based resin contains at least one of a structural unit (A) derived from a polyolefin polyol and a structural unit (B) derived from a dimer polyol. The polyolefin polyol and the dimer polyol have a structure having a low polarity, and the polyurethane resin containing the structural unit (A) and / or the structural unit (B) has good compatibility with the chemically modified acid-modified polyolefin resin. it is conceivable that.

A polyolefin polyol is a polymer of a polyolefin skeleton having a plurality of hydroxy groups. Specific examples of such a polyolefin polyol include polyethylene butylene diol (polyethylene butylene polyol), polybutadiene diol (polybutadiene polyol), hydrogenated polybutadiene diol (hydrogenated polybutadiene polyol) and the like. The polyolefin polyol may be used alone or in combination of two or more. Commercially available polyethylene butylene diols include the trade name "Polytail" (manufactured by Mitsubishi Chemical Corporation). Further, as a commercially available product of polybutadiene diol, there is a trade name "KRASOL" (manufactured by Cray Valley Co., Ltd.) and the like. Further, as a commercially available product of hydrogenated polybutadiene diol, there is a trade name "NISSO-PB" (manufactured by Nippon Soda Co., Ltd.) and the like.

A dimer polyol is a polyol derived from dimer acid or derived from a mixture containing dimer acid and trimer acid. Dimeric acid is a dicarboxylic acid having 36 carbon atoms obtained by dimerizing unsaturated fatty acids having 18 carbon atoms such as oleic acid and linoleic acid, and is a plant-derived fatty acid. The typical structure of dimer acid is represented by the following formula (1). The trimeric acid is a tricarboxylic acid having 54 carbon atoms obtained by trimerizing the unsaturated fatty acid having 18 carbon atoms, and is by-produced during the production of dimer acid. For this reason, commercially available dimer acids are usually mixtures containing dimer acids and trimer acids.

Dimerdiol, which is a polyol derived from dimer acid, is a polyol having 36 carbon atoms obtained by reducing the carboxy group of dimer acid to a hydroxyl group, and may or may not have an unsaturated bond in its molecule. May be good. Similar to dimer diol, trimer triol is also a polyol having 54 carbon atoms obtained by reducing trimer acid, and may or may not have an unsaturated bond in its molecule. Commercially available dimer diols are usually mixtures containing dimer diols and trimer triols.

The polyurethane resin containing the structural unit (A) derived from the polyolefin polyol can be obtained by using the polyolefin polyol as a polymerization component, and the structural unit (A) can be contained in the main skeleton. That is, this polyurethane resin can contain a highly flexible hydrocarbon moiety derived from a polyolefin polyol as a soft segment in its molecular structure. Therefore, the resin composition containing this polyurethane resin exhibits good adhesiveness and adhesion to a substrate such as a film or sheet made of a polyolefin resin or a metal, which is generally difficult to adhere. Can be done.

The polyurethane resin containing the structural unit (B) derived from the dimer polyol can be obtained by using the dimer polyol as a polymerization component, and the structural unit (B) derived from the dimer polyol can be contained in the main skeleton. .. That is, the above polyurethane resin can contain a highly flexible hydrocarbon moiety derived from a dimer polyol as a soft segment in its molecular structure. Therefore, the resin composition containing this polyurethane resin exhibits good adhesiveness and adhesion to a substrate such as a film or sheet made of a polyolefin resin or a metal, which is generally difficult to adhere. Can be done.

The resin composition of one embodiment of the present invention contains a polyurethane resin having a highly polar urethane bond as a main component (preferably the total content of the polyurethane resin and the acid-modified polyolefin resin) together with the acid-modified polyolefin resin described later. It is contained as 50 to 100% by mass in the resin composition). Therefore, the resin composition can exhibit good adhesiveness and adhesion to various base materials made of materials such as polyester and metal, and is flexible enough to follow the deformation and thermal expansion of the base material. It is possible to form an adhesive layer or a binder layer showing properties.

Further, the polyurethane-based resin can have a structure having no degradable bond in its main skeleton. Since the polyurethane-based resin does not have a decomposable bond in its main skeleton, the resin composition containing this polyurethane-based resin is excellent in solvent resistance, hydrolysis resistance, chemical resistance, and heat resistance. It is possible to form an adhesive layer or a binder layer. Further, since the hydrocarbon portion in the polyurethane-based resin is highly hydrophobic, the resin composition containing the polyurethane-based resin can form an adhesive layer or a binder layer having excellent water vapor barrier properties.

The polyurethane resin can be produced, for example, by polymerizing at least one of a polyolefin polyol and a dimer polyol with a polyisocyanate. Further, if necessary, other polyols other than the polyolefin polyol and the dimer polyol may be further reacted as long as the effect of the present invention is not impaired. Specific examples of other polyols include both-ended polyols (polypolypolyols) having a carbonate bond in the polymer main chain, aromatic polyester polyols, aliphatic polyester polyols, alicyclic polyester polyols, polyether polyols, acrylic polyols, and epoxys. Examples thereof include polyols.

Further, in order to adjust the viscosity and strength of the polyurethane resin, a short chain diol having 2 to 10 carbon atoms may be further reacted, if necessary. Specific examples of the short chain diol include ethylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-hexanediol, 1,6-hexanediol and the like. be able to. The amount of the structural unit derived from the short-chain diol in the polyurethane resin is not limited, but if the amount introduced is too large, the effect of using the polyolefin polyol and / or the dimer polyol will be small, so adjust appropriately. Is preferable.

Further, in order to improve the adhesion of the resin composition to various substrates and to impart a cross-linking point to the resin composition, a short chain diol having a carboxy group may be further reacted, if necessary. Specific examples of the short chain diol having a carboxy group include dimethylolpropaneic acid and trimethylolbutanoic acid. The amount of the structural unit derived from the short chain diol having a carboxy group in the polyurethane resin is not limited, but if the amount introduced is too large, the effect of using the polyolefin polyol and / or the dimer polyol becomes small. , It is preferable to adjust as appropriate.

Further, for the purpose of improving the physical properties of the adhesive layer and the binder layer formed from the resin composition, polyamines may be further reacted, if necessary. That is, the polyurethane-based resin preferably further contains a structural unit (C) derived from polyamine, and is preferably a polyurethane urea resin having a urea bond in its molecular structure by containing the structural unit (C). In addition, in this specification, the concept of "polyurethane resin" includes not only "polyurethane resin" but also "polyurethane urea resin".

Specific examples of polyamines include aliphatic diamines such as ethylenediamine, N-hydroxyethylethylenediamine, tetramethylenediamine, hexamethylenediamine, and diethylenetriamine; 4,4-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 1,3-. Alicyclic diamines such as bis (aminomethyl) cyclohexane, isophoronediamine, and dimerdiamine; hydrazines such as hydrazine, carbodihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, and phthalic acid dihydrazide; unsaturated groups such as diallylamine compounds. Polyamines included; as well as N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dibutylethanolamine, N- (β-aminoethyl) ethanolamine, N-methylethanolamine, N-methyldiethanolamine , N-ethylethanolamine, N-ethyldiethanolamine, and aminoalcohols such as N- (β-aminoethyl) isopropanolamine. One of these polyamines can be used alone or in combination of two or more.

The type of polyisocyanate used in the polymerization reaction for obtaining a polyurethane resin is not particularly limited, and known polyisocyanates can be used. Specific examples of the polyisocyanate include aromatic polyisocyanates such as 4,4'-methylenebis (phenylene isocyanate) (MDI), tolylene diisocyanate (TDI), and xylylene diisocyanate (XDI); hexamethylene diisocyanate (HDI). , Trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, pentamethylene diisocyanate, and aliphatic polyisocyanates such as lysine diisocyanate; isophorone diisocyanate (IPDI), and 4,4'-methylenebis (cyclohexylisocyanate) (H12MDI). Examples thereof include alicyclic polyisocyanates. Among these, aromatic polyisocyanates are preferable from the viewpoint of improving durability.

The conditions of the polymerization reaction (urethanization reaction) for obtaining the polyurethane resin are not particularly limited, and known conditions for the urethanization reaction can be applied. For example, a polyurethane resin can be obtained by reacting a polyolefin polyol and / or a dimer polyol, a polyisocyanate, and the above-mentioned polyamine used as necessary in the presence or absence of a solvent containing no active hydrogen. Can be done. Further, the reaction may be carried out by either a one-shot method or a multi-step method.

The total content ratio of the structural unit (A) derived from the polyolefin polyol and the structural unit (B) derived from the dimer polyol in the polyurethane resin shall be 50 to 98% by mass based on the total mass of the polyurethane resin. Is preferable. The total content ratio of the constituent unit (A) and the constituent unit (B) means the content ratio of either one of the constituent units (A) and (B) when the polyurethane resin contains either of the constituent units (A) and (B). When both the constituent units (A) and (B) are included, it means the total content ratio of both. It is more preferable that the polyurethane resin contains both the structural unit (A) and the structural unit (B) from the viewpoint of enhancing the compatibility with the chemically modified acid-modified polyolefin resin. The presence or absence of the structural unit (A) and the structural unit (B) in the polyurethane resin and their content ratio can be confirmed by using various structural analysis methods such as analysis by pyrolysis gas chromatography. be.

The content ratio of the constituent unit (C) derived from polyamine in the polyurethane resin is preferably 0 to 10% by mass, more preferably 0.5 to 10% by mass, based on the total mass of the polyurethane resin. More preferably, it is 0.5 to 5% by mass in consideration of the balance between durability and adhesiveness.

The molecular weight of the polyurethane resin can be appropriately adjusted by changing the amount ratio of the hydroxy group of the polyol and the isocyanate group of the polyisocyanate. The weight average molecular weight (Mw) of the polyurethane resin is preferably 2,000 to 200,000, more preferably 4,000 to 100,000. Polyurethane-based resins having an Mw in the range of 2,000 to 200,000 can be suitably used as a material for an adhesive or a binder. Mw of the polyurethane resin is a polystyrene-equivalent value measured by gel permeation chromatography (GPC).

If an isocyanate group remains at the terminal of the polymer obtained after the polymerization reaction, a termination reaction at the isocyanate terminal may be carried out. Specifically, a monofunctional compound such as a monoalcohol or a monoamine; a compound having two kinds of functional groups having different reactivity with isocyanate may be used. Specific examples of such compounds include monoalcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol; monoethylamine, n-propylamine, diethylamine. , Monoamines such as di-n-propylamine and di-n-butylamine; alkanolamines such as monoethanolamine, diethanolamine and dimethylpyrazole can be mentioned. Of these, alkanolamine is preferable because it is easy to control the reaction. The temperature of the polymerization reaction is usually 20 to 150 ° C, preferably 50 to 110 ° C.

The polyurethane resin may be synthesized without a solvent or in the presence of an organic solvent. Suitable organic solvents include those that are inert to the isocyanate group or that are less active than the reaction component. Specific examples of such organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; aromatic hydrocarbon solvents such as toluene and xylene; and aliphatic hydrocarbon solvents such as n-hexane; Ethereal solvents such as dioxane and tetrahydrofuran; ester solvents such as ethyl acetate, butyl acetate and isobutyl acetate; ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl-3-ethoxy Glycol ether ester solvents such as propionate; amide solvents such as dimethylformamide and dimethylacetamide; lactam solvents such as N-methyl-2-pyrrolidone and the like can be mentioned. One of these organic solvents can be used alone or in combination of two or more.

When synthesizing the polyurethane resin, a catalyst can be used if necessary. Specific examples of the catalyst include salts of metals such as dibutyltin laurate, dioctyltin laurate, stanas octoate, zinc octylate, tetra n-butyl titanate and organic or inorganic acids; organic metal derivatives; triethylamine and the like. Organic amines; diazabicycloundecene-based catalysts and the like can be mentioned.

[Acid-modified polyolefin resin]
The resin composition of one embodiment of the present invention contains a chemically modified acid-modified polyolefin resin. By containing the acid-modified polyolefin resin in the resin composition, the adhesiveness with the polyolefin-based resin base material can be further improved.

Specific examples of the acid-modified polyolefin resin include maleic anhydride-modified polypropylene and the like. The acid-modified polyolefin resin is preferably soluble in a solvent. The melting point of the acid-modified polyolefin resin is preferably 60 to 160 ° C. in consideration of heat resistance, ease of lamination processing, and the like. Examples of commercially available products of such acid-modified polyolefin resins include the trade name "Aurolen" (manufactured by Nippon Paper Industries Co., Ltd.) and the trade name "Hardlen" (manufactured by Toyobo Co., Ltd.).

The acid-modified polyolefin resin used in the resin composition of one embodiment of the present invention is one derived by chemical modification (chemically modified acid-modified polyolefin resin). Ordinary (non-chemically modified) acid-modified polyolefin resins have poor durability in their own right, and in particular, have low heat resistance due to the thermoplastic resin constituting the adhesive layer. When an acid-modified polyolefin resin and another resin are blended in order to improve durability or the like, it is often difficult for them to be compatible with each other, and therefore it is difficult to blend them. On the other hand, by chemically modifying the acid-modified polyolefin resin, the compatibility with the above-mentioned polyurethane-based resin can be further enhanced. As described above, the chemically modified acid-modified polyolefin resin has a good affinity with the above-mentioned polyurethane resin, so that phase separation is less likely to occur, and as a result, good adhesive strength can be obtained. Conceivable.

Further, by using the chemically modified acid-modified polyolefin resin, it becomes possible to carry out a cross-linking reaction between the above-mentioned polyurethane resin and the chemically modified functional group in the acid-modified polyolefin resin. Thereby, it is possible to further improve the solvent resistance, chemical resistance, heat resistance, etc. of the adhesive layer and the binder layer formed from the resin composition, as well as the initial adhesion to the substrate and under high temperature. It is possible to improve the adhesive strength of.

The modification method is not particularly limited, and examples thereof include a method of reacting an acid-modified polyolefin resin with a chemical modification agent. Examples of the chemical modifier include an amine compound, a carbodiimide compound, an epoxy compound and the like, and one of these can be used alone or in combination of two or more. When the resin composition is used as an adhesive, it is preferable to use a monofunctional compound because if a compound having two or more functionalities is used as a chemical modifier, a three-dimensional reaction may occur and it may be difficult to use the resin composition as an adhesive. .. The chemically modified acid-modified polyolefin resin preferably contains a modifying group derived from at least one compound selected from the group consisting of amine compounds, carbodiimide compounds, and epoxy compounds.

Specific examples of amine compounds include methylamine, dimethylamine, triethylamine, monomethanolamine, monoethanolamine, N-methylethanolamine, propanolamine, diethanolamine, and N-2- (aminoethyl) -3-aminopropylmethyldimethoxy. Examples thereof include silane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and morpholin.

Specific examples of the carbodiimide compound include N, N'-dicyclohexylcarbodiimide, N, N'-diisopropylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and the like.

Specific examples of the epoxy compound include 2-[(dodecane-1-yloxy) methyl] oxylan, 2-[(tetradecyloxy) methyl] oxylan, 2-{[(1-methylheptyl) oxy] methyl} oxylan, and the like. Hexadecyloxymethyloxylan, octadecyloxylan, glycidyl acrylate, glycidyl methacrylate and the like can be mentioned.

The content of the chemically modified acid-modified polyolefin resin in the resin composition of one embodiment of the present invention is in the range of 10 to 1000 parts by mass with respect to 100 parts by mass of the above-mentioned polyurethane-based resin. When the content ratio of the chemically modified acid-modified polyolefin resin exceeds 1000 parts by mass with respect to 100 parts by mass of the polyurethane resin, the flexibility of the film formed from the resin composition is lowered, and the durability is further improved. It tends to be scarce. In particular, the heat resistance tends to decrease due to the thermoplastic resin constituting the film such as the adhesive layer. On the other hand, if the content ratio of the chemically modified acid-modified polyolefin resin is less than 10 parts by mass with respect to 100 parts by mass of the polyurethane resin, it may be difficult to obtain the effect of the chemically modified acid-modified polyolefin resin. , It may be difficult to adhere to the base material. The content of the chemically modified polyolefin resin is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, and further preferably 50 parts by mass or more with respect to 100 parts by mass of the polyurethane resin.

[Crosslinking agent]
The resin composition of one embodiment of the present invention preferably further contains a cross-linking agent. By containing a cross-linking agent in the resin composition, it is possible to further improve the solvent resistance, chemical resistance, and heat resistance of the adhesive layer and the binder layer formed from the resin composition, and also at the initial stage. Adhesion and adhesive strength at high temperature can be improved. As the cross-linking agent, known ones can be used. Examples of the cross-linking agent include an isocyanate cross-linking agent, a blocked isocyanate cross-linking agent, a carbodiimide cross-linking agent, an oxazoline cross-linking agent, an epoxy cross-linking agent, an aziridine cross-linking agent, a silane coupling agent, and a titanium coupling agent. One of these cross-linking agents can be used alone or in combination of two or more.

Specific examples of the isocyanate cross-linking agent include MDI, TDI, HDI, IPDI, and trimethylolpropane adducts, biuret-modified and nurate-modified; polypeptide MDI, terminal isocyanate prepolymers and the like. Specific examples of the blocked isocyanate cross-linking agent include a blocked body made of a blocking agent for the isocyanate cross-linking agent (for example, an alcohol-based compound, a phenol-based compound, an oxime-based compound, a lactam-based compound, a pyrazole-based compound, an active methylene compound, etc.). be able to. Examples of commercially available carbodiimide cross-linking agents include the trade name "carbodilite" (manufactured by Nisshinbo Chemical Co., Ltd.). Examples of commercially available oxazoline cross-linking agents include the trade name “Epocross” (manufactured by Nippon Shokubai Co., Ltd.). Examples of commercially available epoxy cross-linking agents include the trade name “jER” (manufactured by Mitsubishi Chemical Corporation). Examples of commercially available aziridine cross-linking agents include the trade name "Chemitite" (manufactured by Nippon Shokubai Co., Ltd.). Specific examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane. Specific examples of the titanium coupling agent include titanium di2-ethylhexoxybis (2-ethyl-3-hydroxyhexoxide) and the like.

The amount of the cross-linking agent with respect to 100 parts by mass of the polyurethane resin is preferably 0.1 to 50 parts by mass. When the amount of the cross-linking agent with respect to 100 parts by mass of the polyurethane resin exceeds 50 parts by mass, the formed adhesive layer or binder layer may become brittle, or the functional groups of the cross-linking agent tend to remain.

The resin composition of one embodiment of the present invention may contain a tackifier such as a terpene-based resin and a rosin-based resin.

The resin composition of one embodiment of the present invention can be used, for example, as a coating material, an ink, an adhesive, an adhesive, a binder, a packaging material, a molding material for molding products in various fields, and the like. Of these, the resin composition is more preferably used as an adhesive or a binder. When the resin composition is used as an adhesive or a binder, the material of the base material to be adhered to the resin composition is not particularly limited. Examples of the material of the base material include polyolefin resins such as PP resin and PE resin, nylon, polyester, and metal. The form of the base material is not particularly limited, and examples thereof include a film, a sheet, and a molded body.

Since the resin composition of one embodiment of the present invention can form an adhesive layer or a binder layer having good adhesiveness to a non-polar substrate and having excellent durability, it is a polyolefin-based material. It is preferably used for bonding resin substrates to each other. Examples of applications for adhering such polyolefin-based resin base materials to each other include interior parts for automobiles. As a more specific example, an automobile interior part in which a skin material made of a polyolefin resin is attached to a base material (molded body) made of a polyolefin resin such as PP resin can be mentioned.

The form of the resin composition may be solid or liquid. In the case of a solid form, for example, it can be in the form of particles, powder, pellets, film, sheet or the like. In the case of a liquid state, the above-mentioned solvent can be used in the form of a solution containing a solvent, a dispersed liquid state, or the like. Since the resin composition of one embodiment of the present invention is more preferably used as an adhesive or a binder, it is preferably in a liquid state. The liquid resin composition can contain the above-mentioned solvent and can take the form of a polymer solution containing the above-mentioned polyurethane resin and chemically modified acid-modified polyolefin resin.

The resin composition of one embodiment of the present invention described in detail above is chemically modified with a polyurethane resin containing a structural unit (A) derived from a polyolefin polyol and / or a structural unit (B) derived from a dimer polyol. Contains a specific proportion of the acid-modified polyolefin resin. Therefore, it is useful as an adhesive or a binder which exhibits good adhesiveness and has excellent durability even with a non-polar substrate such as a polyolefin resin. Further, the resin composition exhibits good adhesiveness to substrates of various materials such as polyolefin, metal, nylon, and polyester, and also has solvent resistance, hydrolysis resistance, chemical resistance, and heat resistance. It is also possible to form an adhesive layer or a binder layer having excellent properties.

As described above, the resin composition of one embodiment of the present invention can also have the following constitution.
[1] A polyurethane-based resin containing at least one of a structural unit (A) derived from a polyolefin polyol and a structural unit (B) derived from a dimer polyol, and a chemically modified acid-modified polyolefin resin are contained. A resin composition in which the content of the chemically modified acid-modified polyolefin resin is in the range of 10 to 1000 parts by mass with respect to 100 parts by mass of the polyurethane resin.
[2] The total content ratio of the structural unit (A) and the structural unit (B) in the polyurethane resin is 50 to 98% by mass based on the total mass of the polyurethane resin [1]. The resin composition according to.
[3] The resin composition according to the above [1] or [2], wherein the polyurethane-based resin has a weight average molecular weight of 2,000 to 200,000.
[4] The resin composition according to any one of the above [1] to [3], wherein the polyurethane-based resin contains both the structural unit (A) and the structural unit (B).
[5] The resin composition according to any one of the above [1] to [4], wherein the polyurethane resin further contains a structural unit (C) derived from a polyamine.
[6] The chemically modified acid-modified polyolefin resin contains a modifying group derived from at least one compound selected from the group consisting of an amine compound, a carbodiimide compound, and an epoxy compound [1] to [5]. The resin composition according to any one of.
[7] At least one cross-linking agent selected from the group consisting of an isocyanate cross-linking agent, a blocked isocyanate cross-linking agent, a carbodiimide cross-linking agent, an oxazoline cross-linking agent, an epoxy cross-linking agent, an aziridine cross-linking agent, a silane coupling agent, and a titanium coupling agent. The resin composition according to any one of the above [1] to [6], which further contains.
[8] The resin composition according to any one of the above [1] to [7], which is used as an adhesive or a binder.

<Adhesive structure>
Next, the adhesive structure of one embodiment of the present invention will be described. The adhesive structure includes an adhesive layer for adhering substrates made of polyolefin-based resin to each other, and the adhesive layer is formed by using the above-mentioned resin composition. Hereinafter, the configuration of the adhesive structure of the present embodiment will be described in detail with reference to FIG. FIG. 1 is a cross-sectional view schematically showing an example of an adhesive structure of the present embodiment, and is a diagram for explaining an example of a laminated structure of the adhesive structure.

As shown in FIG. 1, the adhesive structure 10 includes a first polyolefin-based resin base material 11, a second polyolefin-based resin base material 12, and an adhesive layer 13 for adhering them. The adhesive layer 13 is formed by using the above-mentioned resin composition.

The first polyolefin-based resin base material 11 is a polyolefin-based resin composition containing, for example, a polyolefin such as a PE resin, a PP resin, and an olefin-based thermoplastic elastomer as a main component (content of 50% by mass or more). Molded body is preferable. The molded body of the polyolefin-based resin composition can be obtained by, for example, injection molding, extrusion molding, compression molding, or the like.

As the second polyolefin-based resin base material 12, it is preferable to use a skin material made of a polyolefin-based resin. The skin material is used as a decorative material for imparting a good tactile sensation and design to the object to which the skin material is attached (here, the first polyolefin resin base material 11). Can be used. As the second polyolefin resin base material 12, the same material as the first polyolefin resin base material 11 can be used.

The method for forming the adhesive layer 13 by using the above-mentioned resin composition as an adhesive is not particularly limited. The adhesive may be provided on the first polyolefin-based resin base material 11, the second polyolefin-based resin base material 12, or both of them. Examples of the method for applying the adhesive include roll coat, gravure coat, comma coat, knife coat, die coat, and spray coat.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples. In the following description, those described as "part" and "%" are based on mass unless otherwise specified.

<Synthesis of polyurethane resin>
(Synthesis example 1: PU1 synthesis)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen blow tube, and a manhole was prepared. While replacing the inside of the reaction vessel with nitrogen gas, polybutadiene polyol (trade name "G-1000", manufactured by Nippon Soda Co., Ltd., hydroxyl value (OHv) = 70.7 mgKOH / g, 1,2-vinyl = 90.8% , Trans-1,4 = 9.2%) 100.0 g, dimerdiol (trade name "Pripol2033", manufactured by Claude Japan, OHv = 207 mgKOH / g) 34.2 g, methyl ethyl ketone (MEK) 33.1 g, and methyl. 8.3 g of cyclohexane (MCH) was charged. After starting heating and stirring to make the inside of the system uniform, 31.5 g of 4,4'-methylenebis (phenylene isocyanate) (MDI) was added at 50 ° C., and then the temperature was raised to 80 ° C. for reaction. .. The reaction was allowed to proceed until the absorption ^{of 2,270 cm-1} by the free isocyanate group measured by infrared absorption spectrum analysis disappeared. Then, 99.4 g of MEK and 24.9 g of MCH were added to obtain a solution of polyurethane resin PU1 (solid content 50%).

(Synthesis example 2: PU2 synthesis)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen blow tube, and a manhole was prepared. While replacing the inside of the reaction vessel with nitrogen gas, polybutadiene polyol (trade name "G-3000", manufactured by Nippon Soda, OHv = 31.1 mgKOH / g, 1,2-vinyl = 90.6%, trans-1 , 4 = 9.4%) 100.0 g, dimerdiol (trade name "Pripol2033", manufactured by Claude Japan, OHv = 207 mgKOH / g) 15.0 g, MEK 25.8 g, and MCH 6.4 g were charged. After starting heating and stirring to make the inside of the system uniform, 13.9 g of MDI was added at 50 ° C., and then the temperature was raised to 80 ° C. for reaction. The reaction was allowed to proceed until the absorption ^{of 2,270 cm-1} by the free isocyanate group measured by infrared absorption spectrum analysis disappeared. Then, 77.4 g of MEK and 19.3 g of MCH were added to obtain a solution of polyurethane resin PU2 (solid content 50%).

(Synthesis example 3: PU3 synthesis)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen blow tube, and a manhole was prepared. While replacing the inside of the reaction vessel with nitrogen gas, hydrogenated polybutadiene polyol (trade name "GI-1000", manufactured by Nippon Soda Co., Ltd., OHv = 66 mgKOH / g) 100.0 g, dimerdiol (trade name "Pripol 2033", clogder Japan, OHv = 207 mgKOH / g) 50.0 g, MEK 39.9 g, and toluene 39.9 g were charged. After starting heating and stirring, 36.2 g of MDI was added at 50 ° C., and then the temperature was raised to 80 ° C. for reaction. The reaction was allowed to proceed until the absorption ^{of 2,270 cm-1} by the free isocyanate group measured by infrared absorption spectrum analysis disappeared. Then, 53.6 g of MEK and 53.6 g of toluene were added to obtain a solution of polyurethane resin PU3 (solid content 50%).

(Synthesis example 4: PU4 synthesis)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen blow tube, and a manhole was prepared. While replacing the inside of the reaction vessel with nitrogen gas, polybutadiene polyol (trade name "G-1000", manufactured by Nippon Soda, OHv = 70.7 mgKOH / g, 1,2-vinyl = 90.8%, trans-1 , 4 = 9.2%) 100.0 g, Dimerdiol (trade name "Pripol2033", manufactured by Claude Japan, OHv = 207 mgKOH / g) 34.2 g, Dimethylol propanoic acid (DMPA) 5.0 g, MEK36.0 g , And 9.0 g of MCH were charged. After starting heating and stirring to make the inside of the system uniform, 40.8 g of MDI was added at 50 ° C., and then the temperature was raised to 80 ° C. for reaction. The reaction was allowed to proceed until the absorption ^{of 2,270 cm-1} by the free isocyanate group measured by infrared absorption spectrum analysis disappeared. Then, 108.0 g of MEK and 27.0 g of MCH were added to obtain a solution (solid content 50%) of the polyurethane resin PU4 having an acid value (Av) = 11.6 mgKOH / g.

(Synthesis Example 5: Synthesis of PU5)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen blow tube, and a manhole was prepared. While replacing the inside of the reaction vessel with nitrogen gas, polybutadiene polyol (trade name "G-1000", manufactured by Nippon Soda, OHv = 70.7 mgKOH / g, 1,2-vinyl = 90.8%, trans-1 , 4 = 9.2%) 100.0 g, MEK 23.2 g, and MCH 5.8 g were charged. After starting heating and stirring to make the inside of the system uniform, 15.8 g of MDI was added at 50 ° C., and then the temperature was raised to 80 ° C. for reaction. The reaction was allowed to proceed until the absorption ^{of 2,270 cm-1} by the free isocyanate group measured by infrared absorption spectrum analysis disappeared. Then, 69.4 g of MEK and 17.4 g of MCH were added to obtain a solution of polyurethane resin PU5 (solid content 50%).

(Synthesis example 6: PU6 synthesis)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen blow tube, and a manhole was prepared. While replacing the inside of the reaction vessel with nitrogen gas, 100.0 g of dimerdiol (trade name "Pripol2033", manufactured by Croda Japan, OHv = 207 mgKOH / g) and 36.5 g of MEK were charged. After starting heating and stirring to make the inside of the system uniform, 46.1 g of MDI was added at 50 ° C., and then the temperature was raised to 80 ° C. for reaction. The reaction was allowed to proceed until the absorption ^{of 2,270 cm-1} by the free isocyanate group measured by infrared absorption spectrum analysis disappeared. Then, 109.6 g of MEK was added to obtain a solution of polyurethane resin PU6 (solid content 50%).

(Synthesis Example 7: Synthesis of PU7)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen blow tube, and a manhole was prepared. While replacing the inside of the reaction vessel with nitrogen gas, polybutadiene polyol (trade name "G-1000", manufactured by Nippon Soda, OHv = 70.7 mgKOH / g, 1,2-vinyl = 90.8%, trans-1 , 4 = 9.2%) 100.0 g, dimethyl carbonate (DMC) 12.2 g, and MCH 17.8 g were charged. After starting heating and stirring to make the inside of the system uniform, 19.8 g of hydrogenated MDI was added at 50 ° C., the temperature was raised to 80 ° C., and the reaction was allowed to proceed until the NCO% reached the theoretical value. .. Then, the mixture was cooled to 30 ° C., a solution prepared by dissolving 2.1 g of isophorone diamine (IPDA) in 24.4 g of isopropyl alcohol (IPA) was added, the temperature was raised to 60 ° C., and the measurement was performed by infrared absorption spectrum analysis. The reaction was allowed to proceed until the absorption ^{of 2,270 cm-1} by the free isocyanate group was eliminated. Then, 67.5 g of MCH was added to obtain a solution of polyurethane urea resin PU7 (solid content 50%).

(Synthesis Example 8: Synthesis of PU8)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen blow tube, and a manhole was prepared. While replacing the inside of the reaction vessel with nitrogen gas, polybutadiene polyol (trade name "G-1000", manufactured by Nippon Soda, OHv = 70.7 mgKOH / g, 1,2-vinyl = 90.8%, trans-1 , 4 = 9.2%) 100.0 g, DMC 12.2 g, and MCH 17.8 g were charged. After starting heating and stirring to make the inside of the system uniform, 19.8 g of hydrogenated MDI was added at 50 ° C., the temperature was raised to 80 ° C., and the reaction was allowed to proceed until the NCO% reached the theoretical value. Then, the mixture was cooled to 30 ° C., a solution containing 6.9 g of dimerdiamine (trade name "Priamine 1074", manufactured by Croda Japan, AHEW = 136 g / eq) was added, and the temperature was raised to 60 ° C. to red. The reaction was allowed to proceed until the absorption ^{of 2,270 cm-1} by the free isocyanate group measured by external absorption spectrum analysis disappeared. Then, 72.3 g of MCH was added to obtain a solution of polyurethane urea resin PU8 (solid content 50%).

(Synthesis Example 9: Synthesis of PU9)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen blow tube, and a manhole was prepared. While replacing the inside of the reaction vessel with nitrogen gas, polybutadiene polyol (trade name "G-1000", manufactured by Nippon Soda, OHv = 70.7 mgKOH / g, 1,2-vinyl = 90.8%, trans-1 , 4 = 9.2%) 100.0 g, DMC 12.2 g, and MCH 17.8 g were charged. After starting heating and stirring to make the inside of the system uniform, 19.8 g of hydrogenated MDI was added at 50 ° C., the temperature was raised to 80 ° C., and the reaction was allowed to proceed until the NCO% reached the theoretical value. Then, the mixture is cooled to 30 ° C., a solution in which 1.3 g of N- (β-aminoethyl) ethanolamine is dissolved is added, the temperature is raised to 60 ° C., and the free isocyanate measured by infrared absorption spectrum analysis is added. The reaction was allowed to proceed until the absorption of 2,270 cm- ^{1 by the group disappeared.} Then, 66.2 g of MCH was added to obtain a solution of polyurethane urea resin PU9 (solid content 50%).

(Comparative synthesis example 1: PU10 synthesis)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen blow tube, and a manhole was prepared. While substituting the inside of the reaction vessel with nitrogen gas, polyester polyol (condensate of adipic acid and 1,4-butanediol, OHv = 112 mgKOH / g, Av = 0.1 mgKOH / g) 100.0 g, MEK 26.8 g, And 26.8 g of toluene were charged. After starting heating and stirring to make the inside of the system uniform, 25.0 g of MDI was added at 50 ° C., and then the temperature was raised to 80 ° C. for reaction. The reaction was allowed to proceed until the absorption ^{of 2,270 cm-1} by the free isocyanate group measured by infrared absorption spectrum analysis disappeared. Then, 35.7 g of MEK and 35.7 g of toluene were added to obtain a solution of polyurethane resin PU10 (solid content 50%).

<Chemical modification of acid-modified polyolefin resin>
(Synthesis Example 10: Synthesis of PO1)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen blow tube, and a manhole was prepared. While replacing the inside of the reaction vessel with nitrogen gas, 100.0 g of acid-modified polyolefin (trade name "Aurolen 500S", manufactured by Nippon Paper Industries, Ltd.) and 300.0 g of MCH were charged. After starting heating and stirring to make the inside of the system uniform, the temperature was raised to 90 ° C. to confirm that the acid-modified polyolefin was completely dissolved, and then the mixture was cooled to 30 ° C. to add 2.0 g of monoethanolamine. was added a solution prepared by dissolving in IPA50.0G, 1,780 cm by cyclic anhydride groups as measured by infrared absorption spectrum analysis ^-1, a reaction was progressed until the absorption of 1,860Cm ^-1 disappeared. Then, 50.0 g of MCH was added to obtain a solution (solid content 20%) of the acid-modified polyolefin resin PO1 chemically modified with the amine compound.

(Synthesis Example 11: Synthesis of PO2)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen blow tube, and a manhole was prepared. While replacing the inside of the reaction vessel with nitrogen gas, 100.0 g of acid-modified polyolefin (trade name "Aurolen 500S", manufactured by Nippon Paper Industries, Ltd.), 100.0 g of MCH, and 2.0 g of N, N'-dicyclohexylcarbodiimide were charged. .. After a uniform in the system to start the heating and stirring, the temperature was raised to 100 ° C., 1,780 cm by cyclic anhydride groups as measured by infrared absorption spectrum analysis ^-1, absorption of 1,860Cm ^-1 The reaction was allowed to proceed until it disappeared. Then, 300.0 g of MCH was added to obtain a solution (solid content 20%) of the acid-modified polyolefin resin PO2 chemically modified with the carbodiimide compound.

(Synthesis Example 12: Synthesis of PO3)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen blow tube, and a manhole was prepared. While replacing the inside of the reaction vessel with nitrogen gas, 100.0 g of acid-modified polyolefin (trade name "Aurolen 500S", manufactured by Nippon Paper Industries, Ltd.), 100.0 g of MCH, and 2.0 g of glycidyl methacrylate were charged. After a uniform in the system to start the heating and stirring, the temperature was raised to 100 ° C., 1,780 cm by cyclic anhydride groups as measured by infrared absorption spectrum analysis ^-1, absorption of 1,860Cm ^-1 The reaction was allowed to proceed until it disappeared. Then, 300.0 g of MCH was added to obtain a solution (solid content 20%) of the acid-modified polyolefin resin PO3 chemically modified with the epoxy compound.

(Comparative synthesis example 2: Preparation of PO4)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen blow tube, and a manhole was prepared. While replacing the inside of the reaction vessel with nitrogen gas, 100.0 g of acid-modified polyolefin (trade name "Aurolen 500S", manufactured by Nippon Paper Industries, Ltd.) and 400.0 g of MCH were charged. After starting heating and stirring to make the inside of the system uniform, the temperature was raised to 90 ° C. to confirm that the acid-modified polyolefin was completely dissolved, and then the mixture was cooled to 30 ° C. to obtain a solution of the acid-modified polyolefin resin PO4. (Solid content 20%) was obtained.

<Preparation of resin composition>
Using the solution of the polyurethane resin (PU1 to 10) and the solution of the polyolefin resin (PO1 to 4) obtained in the above synthetic examples, Tables 1-1 and Tables are shown as Examples 1 to 11 and Comparative Examples 1 to 5. Each component was blended according to the formulation shown in 1-2 to prepare resin compositions 1 to 16. The blending amounts (units: parts) in Table 1-1 and Table 1-2 are converted into solid content.

<Preparation of adhesive>
As Examples 12 to 26 and Comparative Examples 6 to 10, each component was blended according to the formulations shown in Tables 2-1 and 2-2 below to prepare adhesives 1 to 20. The blending amounts (units: parts) in Table 2-1 and Table 2-2 are in terms of solid content. The following cross-linking agents were used in the table.
-Isocyanate cross-linking agent: Product name "7960" manufactured by Baxenden (dimethylpyrazole block type, hexamethylene diisocyanate biuret, NV: 70%, effective NCO%: 10.2%)
-Carbodiimide cross-linking agent: trade name "carbodilite V-05" manufactured by Nisshinbo Chemical Co., Ltd. (NV: 100%, carbodiimide equivalent: 260)
-Epoxy cross-linking agent: Product name "jER 1001" manufactured by Mitsubishi Chemical Corporation (epoxy equivalent: 470)
-Oxazoline cross-linking agent: Trade name "Epocross RPS-1005" manufactured by Nippon Shokubai Co., Ltd. (oxazoline group-containing resin)
-Aziridine cross-linking agent: Trade name "Chemitite PZ-33" manufactured by Nippon Shokubai Co., Ltd. (Aziridine content: 6.3 meq / g)

<Making an adhesive structure>
In Examples 12 to 26 and Comparative Examples 6 to 10, the adhesive prepared as described above is applied to a skin material made of an olefin-based thermoplastic elastomer (TPO) so as to have a dry film thickness of 40 μm, and at 100 ° C. The mixture was dried for 1 minute to obtain a precoated skin material (TPO / adhesive). A bar coater was used to apply the adhesive. While heating the dried pre-coated skin material at 180 ° C. for 3 minutes, the PP substrates are overlapped and crimped with a load of 0.05 MPa for 30 seconds to form an adhesive structure (TPO skin material / adhesive layer /. PP substrate) was obtained. In order to use the adhesive structure for the "initial adhesion" and "heat resistant creep" tests described later, the dimensions of the TPO skin material and PP substrate are 50 mm wide x 100 mm long, and the adhesive layer is the TPO skin material. And, it was provided in a region of width 50 mm × length 90 mm from one end of the PP substrate. Then, this is cut into a test piece having a width of 25 mm and a length of 100 mm (the adhesive layer has a width of 25 mm and a length of 90 mm), and is tested in the "initial adhesion" and "heat resistant creep" tests described later. A test was conducted to peel off from a region (a region having a width of 25 mm and a length of 10 mm) in which the adhesive layer on the other end side of the piece was not provided.

<Evaluation>
(Adhesive condition)
Visually observe the condition of the prepared adhesives 1 to 20, and if there is fluidity, evaluate it as good condition and indicate "○" in the table, and if there is no fluidity due to gelation etc., evaluate it as poor condition. Indicated as "x" in the table.

(Initial adhesion)
After placing the test piece of the prepared adhesive structure at room temperature (25 ° C) for 10 minutes, a test was conducted in which the precoated skin material was peeled off from the PP substrate in the 90 ° direction with bare hands, and the initial adhesion (initial adhesion) was performed according to the following criteria. Adhesiveness) was evaluated. The evaluation results are shown in Table 2-1 and Table 2-2.
A: Since the pre-coated skin material was broken, it had excellent adhesion.
B: Since the pre-coated skin material was partially destroyed, it adhered well.
C: The pre-coated skin material was not destroyed, but was adhered.
D: The pre-coated skin material was easily peeled off from the PP substrate, so that it was hardly adhered.

(Heat-resistant creep)
In the evaluation of the initial adhesion, a heat-resistant creep test in the 90 ° direction according to JIS K6859 was performed on the test pieces of the adhesive structure whose evaluation result was other than "D". Specifically, after the test piece of the adhesive structure was cured at 40 ° C. for one day, a load of 100 g / 25 mm was applied in the 90 ° direction in an environment of 80 ° C., and the peeling distance length after 24 hours was determined. The measurement was performed and the heat-resistant creep was evaluated according to the following criteria. The evaluation results are shown in Table 2-1 and Table 2-2. In Table 2-2, "*" indicates that the measurement was impossible.
A: The peeling distance was less than 5 mm.
B: The peeling distance was 5 mm or more and less than 10 mm.
C: The peeling distance was 10 mm or more.
D: The skin material has peeled off.

Based on the above results, adhesives 1 to 15 using the resin compositions 1 to 11 containing the polyurethane resin of any of PU1 to 9 and the chemically modified acid-modified polyolefin resin of any of PO1 to 3 It was confirmed that an adhesive structure having good initial adhesion and heat-resistant creep could be produced by using the above. Therefore, the resin composition containing a polyurethane-based resin containing a structural unit derived from a polyolefin polyol and / or a structural unit derived from a dimer polyol and a chemically modified acid-modified polyolefin resin in a specific ratio is a polyolefin-based resin. It was confirmed that it is useful as an adhesive or a binder that exhibits good adhesiveness to a resin base material and has excellent durability.

10: Adhesive structure 11: First polyolefin-based resin base material 12: Second polyolefin-based resin base material 13: Adhesive layer

Claims (9)

A polyurethane resin containing at least one of a structural unit (A) derived from a polyolefin polyol and a structural unit (B) derived from a dimer polyol.
Contains chemically modified acid-modified polyolefin resin,
The content of the acid-modified polyolefin resin which is the chemical modification, to the polyurethane-based resin 100 parts by mass, Ri range der of 10 to 1000 parts by weight,
The chemically modified acid-modified polyolefin resin is a reaction product of at least one compound selected from the group consisting of an amine compound, a carbodiimide compound, and an epoxy compound as a chemical modifier and an acid-modified polyolefin resin. , An acid-modified polyolefin resin containing a modifying group derived from the compound by being chemically modified with the compound.
The amine compounds include methylamine, dimethylamine, triethylamine, monomethanolamine, monoethanolamine, N-methylethanolamine, propanolamine, diethanolamine, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N. -2- (Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and at least one selected from the group consisting of morpholin.
The carbodiimide compound is at least one selected from the group consisting of N, N'-dicyclohexylcarbodiimide, N, N'-diisopropylcarbodiimide, and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride.
The epoxy compounds include 2-[(dodecane-1-yloxy) methyl] oxylan, 2-[(tetradecyloxy) methyl] oxylan, 2-{[(1-methylheptyl) oxy] methyl} oxylan, and hexadecyloxy. A resin composition which is at least one selected from the group consisting of methyloxylan, octadecyloxylan, glycidyl acrylate, and glycidyl methacrylate. The resin according to claim 1, wherein the total content ratio of the structural unit (A) and the structural unit (B) in the polyurethane resin is 50 to 98% by mass based on the total mass of the polyurethane resin. Composition. The resin composition according to claim 1 or 2, wherein the polyurethane-based resin has a weight average molecular weight of 2,000 to 200,000. The resin composition according to any one of claims 1 to 3, wherein the polyurethane-based resin contains both the structural unit (A) and the structural unit (B). The resin composition according to any one of claims 1 to 4, wherein the polyurethane-based resin further contains a structural unit (C) derived from polyamine. The resin composition according to any one of claims 1 to 5, wherein the compound comprises at least one selected from the group consisting of the monoethanolamine, the N, N'-dicyclohexylcarbodiimide, and the glycidylmethacrylate. Further contains at least one cross-linking agent selected from the group consisting of an isocyanate cross-linking agent, a blocked isocyanate cross-linking agent, a carbodiimide cross-linking agent, an oxazoline cross-linking agent, an epoxy cross-linking agent, an aziridine cross-linking agent, a silane coupling agent, and a titanium coupling agent. The resin composition according to any one of claims 1 to 6. The resin composition according to any one of claims 1 to 7, which is used as an adhesive or a binder. An adhesive structure comprising an adhesive layer formed by using the resin composition according to any one of claims 1 to 8, which adheres a base material made of a polyolefin resin to each other.

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