Adhesive resin composition, hardened product, and laminate

Abstract

To provide an adhesive resin composition, a hardened product, and a laminate, which have high flexibility, impact resistance, and adhesive force, and have small differences in physical properties caused by hardening temperature, are particularly suitable for use in the fields of automobiles, building materials, ships, aircraft, and the like, and can be used without solvents. The object of the present invention is achieved by an adhesive resin composition containing a comb-type urethane-acrylic composite resin (D) having residues derived from an acrylic polyol (A) having an epoxy group within the molecule and a hydroxyl group at a single terminal, a polyol (B) other than the acrylic polyol (A), and a diisocyanate (C), a liquid epoxy resin (E), and a hardening agent (F).

Description

[0001] This application claims priority to Japanese Patent Application No. 2022-130011, filed August 17, 2022, and Japanese Patent Application No. 2023-026828, filed February 24, 2023, the disclosures of which are incorporated herein in their entireties. TECHNICAL FIELD

[0002] The present application relates to an adhesive resin composition, a hardened product thereof, and a laminate including the hardened product. BACKGROUND

[0003] In recent years, in the fields of automobiles or aircraft, etc., in order to improve fuel efficiency, the use of lightweight materials such as aluminum, magnesium, or fiber-reinforced plastic materials (hereinafter, referred to as FRP) is increasing. In addition, in the assembly thereof, the use of adhesives is increasing instead of joining based on welding. Among them, two-part hardened epoxy adhesives have high adhesion to various members, high durability, and slow viscosity increase after mixing, and are excellent in workability, and thus are widely used as structural adhesives.

[0004] However, for example, in the case of bonding materials having different linear expansion coefficients such as metals such as aluminum and FRP, high stress is applied to the adhesive layer due to the difference in expansion rate between the materials due to temperature changes in the manufacturing process or the use temperature environment. The conventional epoxy adhesives have a problem that they are easily damaged by impact due to their hardness and brittleness.

[0005] In order to solve the problem, for example, in Patent Literature 1, softness is imparted by dispersing rubber-like polymer fine particles in a hardened resin composition in which an epoxy resin is a main component. In addition, in Patent Literatures 2 to 4, a high molecular epoxy resin or a modified epoxy resin is used in a relatively large amount to solve the problem.

[0006] PRIOR ART DOCUMENTS

[0007] PATENT LITERATURE

[0008] Patent Literature 1: Japanese Patent Application Publication No. 2015-182248

[0009] Patent Literature 2: Japanese Patent Application Publication No. 2015-063595

[0010] Patent Literature 3: Japanese Patent Application Publication No. 2017-002130

[0011] Patent Literature 4: Japanese Patent Application Publication No. 2018-002766 SUMMARY

[0012] Problem to be solved by the invention

[0013] However, if the rubbery polymer fine particles or the high molecular epoxy resin component is increased in order to improve the softness of the epoxy resin composition, the workability is reduced due to the increase in viscosity, and thus the amount of addition is limited, or a solvent needs to be added. That is, in the method of adding a soft component, sufficient softness cannot be imparted, and the material remains hard and fragile, and is not resistant to impact. In addition, the addition of a solvent increases the environmental load. Therefore, improvement is required in the market. In addition, in the case where softness skeleton is introduced by modifying the epoxy resin, as disadvantages, the compatibility with other materials is deteriorated, the physical properties are greatly changed due to the hardening temperature, or the handling becomes difficult.

[0014] The present invention was made in view of the background described above, and aims to provide an adhesive resin composition which has high softness, impact resistance, and adhesive force, and has small differences in physical properties caused by hardening temperature, is particularly suitable for the fields of automobiles, building materials, ships, aircraft, and the like, and can be used without a solvent.

[0015] Technical means to solve the problem

[0016] The present inventors repeatedly made research in order to solve the problem described above, and as a result, found that the problem of the present invention can be solved in the following manner, and thus completed the present invention.

[0017] [1] An adhesive resin composition comprising: a comb-type urethane-acrylic composite resin (D) having a residue derived from an acrylic polyol (A) having an epoxy group within the molecule and a hydroxyl group at a single terminal end, a polyol (B) other than the acrylic polyol (A), and a diisocyanate (C); a liquid epoxy resin (E); and a hardening agent (F).

[0018] [2] The adhesive resin composition according to [1], wherein the liquid epoxy resin (E) has two or more epoxy groups within the molecule.

[0019] [3] The adhesive resin composition according to [1] or [2], wherein the comb-type urethane-acrylic composite resin (D) contains 5 to 80 mass% of the acrylic polyol (A) in 100 mass%.

[0020] [4] The adhesive resin composition according to any one of [1] to [3], wherein the acrylic polyol (A) contains 5 mass% or more and less than 100 mass% of an ethylenically unsaturated monomer (a-1) having one or more epoxy groups within the molecule in 100 mass%.

[0021] [5] The adhesive resin composition according to any one of [1] to [4], wherein the total 100 mass% of the comb-type urethane-acrylic composite resin (D) and the liquid epoxy resin (E) contains 20 mass% to 80 mass% of the liquid epoxy resin (E).

[0022] [6] A hardened product comprising the adhesive resin composition according to any one of [1] to [5].

[0023] [7] A laminate having a layer comprising the hardened product according to [6] on a substrate.

[0024] Effects of the Invention

[0025] According to the present application, it is possible to provide an adhesive resin composition which has high softness, impact resistance, and adhesive force, and has small differences in physical properties caused by hardening temperature, and is particularly suitable for use in the fields of automobiles, building materials, ships, aircraft, and the like, and can be used without a solvent. DETAILED DESCRIPTION

[0026] Hereinafter, the present application will be described in detail. Furthermore, other embodiments are also included in the scope of the present application as long as they are in accordance with the spirit of the present application. In addition, in the present specification, a numerical range designated by "to" is set to include the numerical values recited before and after "to" as lower limit values and upper limit values. In addition, each of the various components recited in the present specification can be used independently of one another, or two or more of them can be used in combination, unless otherwise specifically noted.

[0027] In the present specification, the acrylic polyol (A) having an epoxy group within the molecule and a hydroxyl group at a single terminal is simply referred to as the acrylic polyol (A), and the polyol (B) (excluding the acrylic polyol (A)) is simply referred to as the polyol (B).

[0028] The adhesive resin composition of the present application contains: a comb-type urethane-acrylic composite resin (D) having residues derived from an acrylic polyol (A) having an epoxy group within the molecule and a hydroxyl group at a single terminal, a polyol (B), and a diisocyanate (C); a liquid epoxy resin (E); and a hardener (F).

[0029] By incorporating the acrylic polyol (A) having an epoxy group in the molecule and having a hydroxyl group at a single terminal into a urethane resin in a comb form, crosslinking of the epoxy group is formed away from the soft urethane main chain. Therefore, the comb urethane-acrylic hybrid resin (D) exhibits excellent softness while maintaining strength, as compared with a block structure of a straight chain type. In addition, the backbone is low in molecular weight and soft as compared with a rubber particle, and thus the viscosity is low, and workability can be improved. Furthermore, by hybridization of the acrylic resin and the urethane resin, compatibility with other materials becomes good, and thus a difference in properties caused by a difference in hardening temperature can be reduced.

[0030] Therefore, the adhesive resin composition of the present application is suitably used as a structural adhesive in the fields of automobiles, building materials, ships, aircraft, and the like. In addition, the adhesive resin composition of the present application can be used as a liquid solventless adhesive, and is excellent in terms of safety or environmental response.

[0031] Comb urethane-acrylic hybrid resin (D)

[0032] The comb urethane-acrylic hybrid resin (D) of the present application is not limited in the manufacturing method as long as it has a (meth)acrylic unit including the acrylic polyol (A) in the side chain, and a urethane unit including the polyol (B) and the diisocyanate (C) is provided as a main chain. It is preferable to be manufactured by the following method.

[0033] Step 1: The acrylic polyol (A) having an epoxy group in the molecule and having a hydroxyl group at a single terminal is synthesized by polymerization of an ethylenically unsaturated monomer (a-1) having one or more epoxy groups in the molecule with a chain transfer agent having two hydroxyl groups and a mercapto group in the molecule as a starting point, and an other ethylenically unsaturated monomer (a-2).

[0034] Step 2: The hydroxyl group in the acrylic polyol (A) and the hydroxyl group in the polyol (B) are reacted with the isocyanate group in the diisocyanate (C), and thereby the (meth)acrylic unit and the urethane unit are linked in a comb form.

[0035] Either of the reactions of Step 1 and Step 2 can be performed using a solvent, or can be performed without using a solvent. In addition, a part or all of the solvent can be replaced with the liquid epoxy resin (E). In this case, the liquid epoxy resin (E) functions as a reactive diluent.

[0036] In the case where a solvent is used in Step 1 and Step 2, the solvent is removed under reduced pressure or under normal pressure at an intermediate stage of the reaction or after the reaction, and thereby a solventless comb urethane-acrylic hybrid resin (D) can be obtained.

[0037] The reactive diluent in the present application is defined as a substance for diluting the concentration of substances in the reaction system and the viscosity of the reaction solution to an appropriate range, and a substance that participates in the hardening reaction without evaporating during the process of producing the adhesive resin composition and hardening it into a hardened product. On the other hand, the solvent is defined as a substance that, although it assumes the function of diluting the concentration of substances in the reaction system and the viscosity of the reaction solution to an appropriate range, evaporates and is removed by distillation or drying during either of the processes of producing the adhesive resin composition and hardening it into a hardened product.

[0038] The reaction of Step 2 is performed using an existing urethane reaction, and a catalyst can also be used for the purpose of adjusting the reactivity.

[0039] < Catalyst >

[0040] As the catalyst, an existing metal-based catalyst, an amine-based catalyst, or the like can be used. As the metal-based catalyst, dibutyltin dilaurate, tin octoate, dibutyltin di(2-ethylhexanoate), lead 2-ethylhexanoate, titanium 2-ethylhexylate, titanium ethylacetate, iron 2-ethylhexanoate, cobalt 2-ethylhexanoate, zinc naphthenate, cobalt naphthenate, tetra-n-butyltin, or the like can be exemplified. As the amine-based catalyst, a tertiary amine such as tetramethylbutanediamine, or the like can be exemplified. The amount of the catalyst used is preferably in the range of 0.01 parts by mass to 0.05 parts by mass, based on the total mass of the polyol (A) and the polyol (B).

[0041] The number average molecular weight of the comb-type urethane-acrylic composite resin (D) is not particularly limited, and is preferably in the range of 5,000 to 100,000. When it is 5,000 or more, the cohesion becomes good, and thus the adhesive force is excellent, and when it is 100,000 or less, it is low in viscosity, and thus the adjustment of the viscosity under the solventless condition is easy.

[0042] < Acrylic Polyol (A) >

[0043] The acrylic polyol (A) contains an epoxy group in the molecule, and has a hydroxyl group at a single terminal to be linked in a comb type with the urethane unit including the polyol (B) and the diisocyanate (C).

[0044] The method for producing the acrylic polyol (A) is not particularly limited as long as a hydroxyl group can be introduced at a single terminal, and an existing polymerization method using a radical polymerization initiator having a hydroxyl group, an active radical polymerization initiator, a chain transfer agent, or the like can be used, for example.

[0045] The method of producing the acrylic polyol (A) can use an existing method, but a method of polymerizing an ethylenically unsaturated monomer (a-1) having one or more epoxy groups in the molecule in the presence of a chain transfer agent having two hydroxyl groups and one mercapto group in the molecule is simple and preferred. In addition, for the purpose of adjusting compatibility and coagulation, in addition to the ethylenically unsaturated monomer (a-1) having one or more epoxy groups in the molecule, other ethylenically unsaturated monomers (a-2) can also be included.

[0046] <ETHYLENICALLY UNSATURATED MONOMER (a-1) HAVING ONE OR MORE EPOXY GROUPS IN THE MOLECULE>

[0047] As the ethylenically unsaturated monomer (a-1) having one or more epoxy groups in the molecule, without being limited to the following examples, a compound having one polymerizable unsaturated double bond and one or more epoxy groups in the molecule can be used. For example, (meth)acrylic acid glycidyl ester, (meth)acrylic acid-3,4-epoxybutyl ester, (meth)acrylic acid-4,5-epoxypentyl ester, (meth)acrylic acid-6,7-epoxypentyl ester, (meth)acrylic acid-3,4-epoxycyclohexyl ester, 4-hydroxybutyl acrylate glycidyl ether, lactone-modified (meth)acrylic acid-3,4-epoxycyclohexyl ester, vinyl cyclohexene oxide, and the like can be listed.

[0048] <OTHER ETHYLENICALLY UNSATURATED MONOMER (a-2)>

[0049] As the other ethylenically unsaturated monomer (a-2), without being limited to the following examples, for example, straight-chain or branched alkyl ethylenically unsaturated monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, isoamyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cetyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, and the like;

[0050] cyclic alkyl (meth)acrylates such as cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentanoxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, and the like;

[0051] fluoroalkyl vinyl unsaturated monomers such as trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluoro-octyl ethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, and the like;

[0052] tetrahydrofurfuryl (meth)acrylate, 3-methyl-3-oxetanyl (meth)acrylate, and the like having a heterocycle;

[0053] benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, p-cumylphenoxyethyl (meth)acrylate, p-cumylphenoxy polyethylene glycol (meth)acrylate, or nonylphenoxy polyethylene glycol (meth)acrylate, and the like having an aromatic ring; methoxy polyethylene glycol mono(meth)acrylate, octyloxy polyethylene glycol polypropylene glycol mono(meth)acrylate, lauryloxy polyethylene glycol mono(meth)acrylate, stearyloxy polyethylene glycol mono(meth)acrylate, phenoxy polyethylene glycol mono(meth)acrylate, phenoxy polyethylene glycol polypropylene glycol mono(meth)acrylate, polyethylene glycol monomethyl ether (meth)acrylate, lauryloxy polyethylene glycol mono(meth)acrylate, nonylphenoxy polyethylene glycol mono(meth)acrylate, nonylphenoxy polypropylene glycol mono(meth)acrylate, nonylphenoxy polyethylene glycol polypropylene glycol mono(meth)acrylate, phenoxy polyethylene glycol mono(meth)acrylate, methoxy polyethylene glycol (meth)acrylate, n-butoxyethyl (meth)acrylate, n-butoxy diethylene glycol (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and the like having an alkyl ether group;

[0054] 3-(acryloyloxymethyl) 3-methyloxetane, 3-(methacryloyloxymethyl) 3-methyloxetane, 3-(acryloyloxymethyl) 3-ethyloxetane, 3-(methacryloyloxymethyl) 3-ethyloxetane, 3-(acryloyloxymethyl) 3-butyloxetane, 3-(methacryloyloxymethyl) 3-butyloxetane, 3-(acryloyloxymethyl) 3-hexyloxetane, and 3-(methacryloyloxymethyl) 3-hexyloxetane, and the like having an oxetanyl group;

[0055] styrene, α-methylstyrene, vinyl acetate, vinyl (meth)acrylate, or allyl (meth)acrylate, and the like having a vinyl group;

[0056] ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, and the like having an ether group;

[0057] (meth)acrylonitrile, cyano styrene, cyano acrylate, and the like cyano-containing ethylenically unsaturated monomers;

[0058] propenal, methylpropenal, dipropyl ketone acrylamide, dipropyl ketone methacrylamide, vinyl methyl ketone, vinyl ethyl ketone, formyl styrol, and the like ketone group-containing ethylenically unsaturated monomers.

[0059] The content of the ethylenically unsaturated monomer (a-1) having one or more epoxy groups in the molecule is preferably 5% by mass or more and less than 100% by mass in 100% by mass of the total of the ethylenically unsaturated monomers constituting the acrylic polyol (A).

[0060] Further, in the case where the acrylic polyol (A) is produced by a method in which ethylenically unsaturated monomers including the ethylenically unsaturated monomer (a-1) having one or more epoxy groups in the molecule are polymerized in the presence of a chain transfer agent having two hydroxyl groups and one mercapto group in the molecule, the content of the monomer (a-1) is preferably 5% by mass or more and less than 100% by mass, and more preferably 10% by mass or more and 70% by mass or less. When the content of the ethylenically unsaturated monomer (a-1) having one or more epoxy groups in the molecule is 5% by mass or more and less than 100% by mass, it is sufficiently incorporated into a firm crosslinked structure including a liquid epoxy resin (E) and a hardener (F) by hardening, and thus a crosslinked structure excellent in adhesion and softness can be formed.

[0061] <Chain transfer agent>

[0062] There is no particular limitation on the chain transfer agent as long as it is a compound having a functional group reactive with an isocyanate group and a mercapto group in the molecule, and a compound having two hydroxyl groups and one mercapto group in the molecule is preferred. By making the mercapto group a chain transfer agent, an acrylic polyol (A) having a hydroxyl group at a single terminal can be efficiently synthesized.

[0063] There is no particular limitation on the compound having two hydroxyl groups and one mercapto group in the molecule, and 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin or thioglycerol), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, or 2-mercaptoethyl-2-ethyl-1,3-propanediol, for example, can be mentioned. Among these, 3-mercapto-1,2-propanediol is preferred because of its good reactivity and ease of synthesis.

[0064] <Polymerization initiator>

[0065] As the polymerization initiator, an existing azo-based compound or organic peroxide can be used, and as the azo-based compound, there is no limitation to the following examples, and for example, 2,2'-azobis isobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane 1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl 1,1'-azobis(1-cyclohexanecarboxylate), dimethyl 2,2'-azobis(2-methylpropanoate), 4,4'-azobis(4-cyanopentanoic acid), 2,2'-azobis(2-hydroxymethylpropionitrile), or 2,2'-azobis[2-(2-imidazolin-2-yl)propane] can be listed. As the organic peroxide, there is no limitation to the following examples, and for example, benzoyl peroxide, t-butyl peroxy-2-ethylhexanoate, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl) peroxydicarbonate, t-butyl peroxyneodecanoate, t-butyl trimethylperoxyacetate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide can be listed.

[0066] The polymerization initiator is preferably used in the range of 0.001 to 15 mass% with respect to the total mass of the acrylic polyol (A). When it is in the range of 0.001 to 15 mass%, chain transfer polymerization is effectively performed, and thus it is more preferable.

[0067] The comb-type urethane-acrylic hybrid resin (D) preferably contains 5 to 80 mass% of the acrylic polyol (A) in the total mass (100 mass%) thereof, and more preferably 15 to 60 mass%. When it contains 5 to 80 mass%, a sufficient crosslinking structure can be formed at a site away from the urethane main chain which is excellent in softness, and thus the softness and the breaking strength are excellent, and in addition, the compatibility becomes good, and thus phase separation at the time of hardening can be inhibited.

[0068] The number average molecular weight of the acrylic polyol (A) is not particularly limited, but is preferably 1,000 to 10,000.

[0069] <Polyol (B)>

[0070] The polyol (B) is a compound having two or more hydroxyl groups in the molecule other than the acrylic polyol (A), and as a representative polyol, polyether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol, vegetable oil-based polyol, and the like can be listed.

[0071] Further, as the compound having two or more hydroxyl groups in the molecule, for example, polyols such as a compound having at least two active hydroxyl groups such as a low molecular polyol, an aliphatic amine compound, an aromatic amine compound, an alkanolamine, or a bisphenol, to which a methylene oxide, an ethylene oxide, a propylene oxide, a tetrahydrofuran, or a polyoxytetramethylene oxide, or the like is added can be exemplified.

[0072] As the low molecular polyol, for example, a difunctional low molecular polyol or a low molecular polyol having a functionality of three or more can be exemplified.

[0073] As the difunctional low molecular polyol, there is no particular limitation, and for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, hexanediol, octanediol, nonanediol, dipropylene glycol, diethylene glycol, triethylene glycol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, polyoxyethylene glycol (addition mole number: 10 or less), polyoxypropylene glycol (addition mole number: 10 or less), cyclohexanediol, cyclohexanedimethanol, tricyclodecanedimethanol, cyclopentadienedimethanol, dimer diol, bisphenol A, N,N-bis(2-hydroxypropyl)aniline, dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutyric acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, dihydroxysuccinic acid, dihydroxypropionic acid, dihydroxybenzoic acid can be exemplified.

[0074] As the low-molecular polyol of three or more functions, there is no particular limitation, and for example, trimethylolethane, trimethylolpropane, 1,1,1-trimethylolbutane, 1,2,3-butanetriol, 1,2,4-butanetriol, 1,2,6-butanetriol, trimethylolbutene, trimethylolpentine, trimethylolhexene, trimethylolheptene, trimethylolloctene, trimethylolnonene, trimethyloldecene, trimethylolundecene, trimethyloldodecene, trimethyloltridecene, trimethylolpentadecene, trimethylohexadecene, trimethylolheptadecene, trimethylloctadecene, 1,1,1-trimethylol-2-methyl-hexane, 1,1,1-trimethylol-3-methyl-hexane, 1,1,1-trimethylol-2-ethyl-hexane, 1,1,1-trimethylol-3-ethyl-hexane, 1,2,3-octanetriol, 1,3,7-octanetriol, 3,7-dimethyl-1,2,3-octanetriol, 1,1,1-trimethyloldecane, 1,2,10-decanetriol, 1,1,1-trimethylol-sec-butane, 1,1,1-trimethylol-tert-pentane, 1,1,1-trimethylol-tert-nonane, 1,1,1-trimethylol-tert-tridecane, 1,1,1-trimethylol-tert-heptadecane, 1,1,1-trimethylol-2-methyl-hexane, 1,1,1-trimethylol-3-methyl-hexane, 1,1,1-trimethylol-2-ethyl-hexane, 1,1,1-trimethylol-3-ethyl-hexane, 1,1,1-trimethylol-sec-heptadecane, 1,2,3,4-butanetetrol, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerol, diglycerol, triglycerol, polyglycerol, di-trimethylolethane, di-trimethylolpropane, tris(2-hydroxyethyl)isocyanurate, benzene-1,3,5-triol, benzene-1,2,3-triol, diphenylstyrene-3,4',5-triol, sucrose, inositol, sorbitan, sorbitol, mannitol, saccharose, cellulose, xylitol.

[0075] As the aliphatic amine compound, for example, ethylenediamine, triethylenediamine, diethylenetriamine, triaminopropane can be exemplified. As the aromatic amine compound, for example, toluenediamine, diphenylmethane-4,4-diamine can be exemplified. As the alkanolamine, for example, ethanolamine and diethanolamine can be exemplified. As the bisphenol, for example, bisphenol A, bisphenol AP, bisphenol B, bisphenol C, bisphenol E, bisphenol F can be exemplified.

[0076] As the polyether polyol, for example, there can be mentioned: diols such as polyethylene glycol, polypropylene glycol, poly(ethylene / propylene) glycol, and the like which are polymers or copolymers of methylene oxide, ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, and the like. In addition, there can be mentioned: polyether polyols obtained by condensation of hexanediol, methylhexanediol, heptanediol, octanediol, or a mixture of these, and the like.

[0077] As the polyester polyol, for example, there can be mentioned: polyester polyols obtained by condensation reaction of the above-mentioned low-molecular polyol with a diacid component, and the like.

[0078] As the diacid component, there can be mentioned: aliphatic or aromatic diacids such as terephthalic acid, adipic acid, azelaic acid, dimer acid, hydrogenated dimer acid, phthalic anhydride, isophthalic acid, trimellitic acid, glutaric acid, pimelic acid, suberic acid, sebacic acid, and the like, and anhydrides of these, and the like.

[0079] In addition, there can be mentioned: polyester polyols obtained by ring-opening polymerization of cyclic ester compounds such as epsilon-caprolactone, poly(beta-methyl-gamma-valerolactone), polyvalerolactone, and the like, and the like.

[0080] As the polycarbonate polyol, for example, there can be mentioned: reaction products obtained by reaction of the above-mentioned low-molecular polyol with a carbonate compound such as dialkyl carbonate, alkylene carbonate, diaryl carbonate, and the like.

[0081] In addition, as the dialkyl carbonate, there can be mentioned: dimethyl carbonate, diethyl carbonate, and the like, as the alkylene carbonate, there can be mentioned: ethylene carbonate, and the like, and as the diaryl carbonate, there can be mentioned: diphenyl carbonate, and the like.

[0082] As the polyolefin-based polyol, there can be mentioned: hydroxyl group-containing polybutadiene, hydrogenated hydroxyl group-containing polybutadiene, hydroxyl group-containing polyisoprene, hydrogenated hydroxyl group-containing polyisoprene, hydroxyl group-containing chlorinated polypropylene, hydroxyl group-containing chlorinated polyethylene, and the like.

[0083] As the plant oil-based polyol, there can be mentioned: polyols obtained using castor oil, dimer acid, or soybean oil of plant origin as a raw material, and the like.

[0084] Of these, polyether polyols, polyester polyols, polycarbonate polyols are preferred, and polyether polyols, polycarbonate polyols, and the like are more preferred because of their excellent softness.

[0085] The number average molecular weight of the polyester polyol, polycarbonate polyol, polyolefin polyol, and vegetable oil-based polyol is preferably 500 to 5,000, and more preferably 700 to 3,500. When the number average molecular weight is 500 to 5,000, the adhesion and softness of the obtained hardened product are more excellent, and thus are preferred.

[0086] Further, the polyol (B) can also be used in combination with the low molecular polyol for the purpose of adjusting the urethane bond concentration or introducing various functional groups, within a range not impairing the effects of the present application.

[0087] <DIISOCYANATE (C)>

[0088] The diisocyanate (C) constituting the urethane unit is a compound having two isocyanate groups in the molecule, and examples thereof include aromatic, aliphatic, or alicyclic diisocyanates.

[0089] As the aromatic diisocyanate, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, toluidine diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, p-tetramethylxylylene diisocyanate, 3,3'-dimethyl-4,4'-diphenyl diisocyanate, 3,3'-dimethoxy-4,4'-diphenyl diisocyanate, 3,3'-dichloro-4,4'-diphenyl diisocyanate, 1,5-tetrahydronaphthalene diisocyanate can be mentioned.

[0090] As the aliphatic diisocyanate, for example, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,2- propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine ester triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate tetramethylene diisocyanate, trimethylhexamethylene diisocyanate can be mentioned.

[0091] As the alicyclic diisocyanate, for example, isophorone diisocyanate, 1,3- cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 1,4-bis(isocyanatomethyl)cyclohexane, hydrogenated xylene diisocyanate, dimer acid diisocyanate, norbornene diisocyanate can be exemplified.

[0092] Liquid epoxy resin (E)

[0093] The liquid epoxy resin (E) of the present application exhibits excellent adhesion by incorporating a crosslinked structure at the time of hardening. When the liquid epoxy resin (E) is used as the reactive diluent in the manufacturing process 1 and the manufacturing process 2 of the comb-type urethane-acrylic composite resin (D), synthesis under no solvent can be performed. In addition, the adhesive resin composition becomes a reaction component after being manufactured.

[0094] As the liquid epoxy resin (E), there is no particular limitation as long as it is a compound that is liquid at normal temperature, and it is preferable to have two or more epoxy groups in the molecule. In addition, the epoxy equivalent is preferably 200 g / eq or less, and more preferably 150 g / eq to 200 g / eq. The epoxy equivalent of the liquid epoxy resin (E) can be found by measuring in accordance with Japanese Industrial Standards (JIS) K-7236.

[0095] As the liquid epoxy resin (E), for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolak type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, and epoxy resin having a butadiene structure can be exemplified. Among these, bisphenol A type epoxy resin is more preferable in terms of easiness of obtaining, viscosity, and adhesion.

[0096] In the adhesive resin composition of the present application, the total of 100 mass% of the comb-type urethane-acrylic composite resin (D) and the liquid epoxy resin (E) is preferably composed of 20 mass% to 80 mass% of the liquid epoxy resin (E), and more preferably 30 mass% to 70 mass%. When the liquid epoxy resin (E) is contained in an amount of 20 mass% or more, the hardened product of the adhesive resin composition forms a firm crosslinked structure, thereby improving the breaking strength, and in addition, high adhesiveness with high cohesiveness can be exhibited. Further, since the liquid epoxy resin (E) has low viscosity, adjustment of the viscosity is easy. On the other hand, when the content of the liquid epoxy resin (E) is 80 mass% or less, the comb-type urethane-acrylic composite resin (D) is present in a high proportion in the adhesive resin composition, and high softness due to the comb-type urethane-acrylic composite resin (D) can be exhibited.

[0097]

[0098] The hardener (F) is not particularly limited, and an existing hardener for hardening an epoxy resin can be used. For example, amine compounds, amide compounds, urea compounds, acid anhydrides, and phenol resins can be mentioned. Two or more kinds can also be used in combination in order to adjust the hardening speed or the amine value.

[0099] As the amine compounds, aliphatic amines such as ethylenediamine, diaminopropane, diaminobutane, diaminohexane, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethyl ethylenediamine, tetra(hydroxyethyl)ethylenediamine, and dimer acid esters of polyethyleneimine;

[0100] Alicyclic amines such as isophorone diamine, metacendiamine, N-aminoethylpiperazine, bis(4-amino-3-methyl dicyclohexyl)methane, bis(aminomethyl)cyclohexane, 3,9-bis(3-aminopropyl)2,4,8,10-tetraoxaspiro(5,5)undecane, norbornenediamine, bis(aminomethyl)norbornane, and bis(4-aminocyclohexyl)methane;

[0101] ​tetra-chloro-p-xylenediamine, m-xylenediamine, p-xylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-diaminomethyl anisole, 2,4-toluenediamine, 2,4-diaminodiphenyl methane, 4,4'-diaminodiphenyl methane, 4,4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, m-aminophenol, m-aminobenzylamine, benzyl dimethyl amine, 2-(dimethylaminomethyl)phenol, triethanolamine, methylbenzylamine, α-(m-aminophenyl)ethylamine, α-(p-aminophenyl)ethylamine, diaminodiethyl dimethyl diphenyl methane, α,α'-bis(4-aminophenyl) p-diisopropyl benzene, 3,3'-diisopropyl-4,4'-diaminodiphenyl methane, 3,3'-di-t-butyl-4,4'-diaminodiphenyl methane, 3,3'-diethyl-5,5'-dimethyl-4,4'-diaminodiphenyl methane, N,N-dimethylaniline, N,N-dimethylbenzylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and the like aromatic amines;

[0102] 2-phenyl-4,5-dihydroxymethyl imidazole, 2-phenyl-4-methyl imidazole, 2-ethyl-4-methyl imidazole, 2,4-diethyl imidazole, 2-phenyl-4-methyl-5-hydroxy imidazole, and the like imidazole derivatives;

[0103] boron trifluoride-monoethyl amine, boron trifluoride-piperidine, boron trifluoride-triethyl amine, boron trifluoride-aniline complex, and the like boron trifluoride-amine complexes;

[0104] dicyandiamide, methyl guanidine, ethyl guanidine, propyl guanidine, butyl guanidine, dimethyl guanidine, trimethyl guanidine, phenyl guanidine, diphenyl guanidine, toluyl guanidine, 2,3-amidinourea, benzoyl dicyandiamide, 2,6-xylyl biguanide, phenyl biguanide, and the like guanidine derivatives;

[0105] triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis(propyl amine), poly(propylene glycol) diamine, poly(propylene glycol) triamine, poly(ethylene glycol) diamine, poly(ethylene glycol) triamine, poly(tetramethylene ether glycol) diamine, poly(tetramethylene ether glycol) triamine, poly(propylene glycol / ethylene glycol) diamine, poly(propylene glycol / ethylene glycol) triamine, and the like polyether polyamines;

[0106] amine-modified polypropylene, amine-modified polyethylene, amine-modified polybutadiene, amine-modified butadiene acrylonitrile copolymer, and the like polyolefin compounds having an amino group, and the like.

[0107] As the amide compound, polyamide amine having a primary amine and a secondary amine in the molecule, which is obtained by reacting a dimer of linolenic acid or oleic acid (dimer acid) with a polyamine such as diethylene triamine or triethylene tetramine, and the like can be exemplified.

[0108] As the urea compound, there is no particular limitation as long as it has an amino group and a urea group in the molecular structure, and it can be obtained, for example, by reacting the amine compound with a diisocyanate or an isocyanate-terminated prepolymer under an amino group-excess condition. The isocyanate-terminated prepolymer can be obtained, for example, by reacting the polyol with a diisocyanate under an isocyanate group-excess condition with respect to the hydroxyl group of the polyol.

[0109] As the acid anhydride, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride can be exemplified.

[0110] As the phenol resin, for example, phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol addition-type resin, phenol aralkyl resin (Zylock resin), polyphenol novolak resin represented by a polyhydroxy compound and formaldehyde, naphthol aralkyl resin, trimethylolmethane resin, tetraphenyl ethane resin, naphthol novolak resin, naphthol-phenol co-condensation novolak resin, naphthol-cresol co-condensation novolak resin, biphenyl-modified phenol resin (polyphenol compound in which a phenol nucleus is linked by a bis methylene group), biphenyl-modified naphthol resin (polyphenol compound in which a phenol nucleus is linked by a bis methylene group), aminotriazine-modified phenol resin (polyphenol compound in which a phenol nucleus is linked by melamine, benzoguanamine, or the like), alkoxyl group-containing aromatic ring-modified novolak resin (polyphenol compound in which a phenol nucleus and an alkoxyl group-containing aromatic ring are linked by formaldehyde), and the like can be exemplified.

[0111] Among these, from the viewpoint of ease of adjustment of the usable time and the hardening speed, an amine compound, an amide compound, and a urea compound are preferable. As the amine compound, a polyether polyamine is preferable in terms of adhesion, and when a polyether polyamine is used in combination with a urea compound or a polyolefin compound having an amino group, the impact resistance is excellent, and thus it is further preferable. The amine value of the hardening agent (F) is preferably 20 mgKOH / g to 800 mgKOH / g, and more preferably 180 mgKOH / g to 600 mgKOH / g. When the amine value is in the range of 20 mgKOH / g to 800 mgKOH / g, the hardening reaction sufficiently proceeds, and a good crosslinking density is formed, and thus excellent adhesion and softness can be exhibited. Furthermore, the amine value can be found by measurement in accordance with JIS K-7237.

[0112] The ratio of the total number of moles of all the epoxy groups contained in the adhesive resin composition to the total number of moles of active hydrogen groups in the hardener (F) involved in the reaction with the epoxy groups (epoxy groups / active hydrogen groups in hardener) is preferably in the range of 0.5 to 2.0, more preferably 0.6 to 1.5. When it is in the range of 0.5 to 2.0, no unreacted functional groups remain, a good crosslinking density is formed, and thus excellent adhesion and flexibility can be exhibited.

[0113] Adhesive resin composition

[0114] The adhesive resin composition in the present application is obtained by mixing the comb-type urethane-acrylic composite resin (D), the liquid epoxy resin (E), and the hardener (F) using existing methods. In addition to this, existing additives such as hardening accelerators, silane coupling agents, leveling agents or defoaming agents, fillers, blowing agents, plasticizers, superplasticizers, wetting agents, flame retardants, viscosity adjusting agents, preservatives, stabilizers, and colorants can be used. Such additives are preferably compounds that can be exemplified below, but are not limited to these compounds.

[0115] As the hardening accelerator, tertiary amines and their salts, imidazoles and their salts, urea-based compounds, phosphorus compounds, organic phosphine compounds and their salts, zinc octoate, tin octoate, and the like can be exemplified. In addition, compounds having a hydroxyl group such as phenols or alcohols, Lewis acids, amine complexes, and the like can be exemplified.

[0116] The amount of the hardening accelerator to be added is preferably 0.01 to 10 mass% with respect to the total mass of the comb-type urethane-acrylic composite resin (D) in the adhesive resin composition.

[0117] As the silane coupling agent, for example, vinyltrimethoxysilane, vinyltriethoxysilane, and the like can be exemplified. In addition, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)3-aminopropyltrimethoxysilane, and the like can be exemplified. In addition, 3-glycidyloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, and the like can be exemplified. In addition, 3-isocyanatepropyltriethoxysilane, and the like can be exemplified. In addition, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and the like can be exemplified.

[0118] The amount of the silane coupling agent to be blended is preferably 0.05 to 10 mass% with respect to the total mass of the comb-type urethane-acrylic composite resin (D).

[0119] As the leveling agent, for example, polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, aralkyl-modified polymethylalkylsiloxane, polyester-modified hydroxyl-containing polydimethylsiloxane, polyether ester-modified hydroxyl-containing polydimethylsiloxane, acrylic copolymer, methacrylic copolymer, polyether-modified polymethylalkylsiloxane, acrylic alkyl ester copolymer, methacrylic alkyl ester copolymer, lecithin can be exemplified.

[0120] As the defoaming agent, existing defoaming agents such as silicone resin, silicone solution, copolymer of alkyl vinyl ether and alkyl acrylate and alkyl methacrylate can be exemplified.

[0121] "HARDENED PRODUCT"

[0122] The hardened product of the present application is obtained by hardening the adhesive resin composition, and can be obtained by mixing the comb-type urethane-acrylic composite resin (D), liquid epoxy resin (E), hardening agent (F), and other components using existing methods, and hardening at 20°C to 200°C.

[0123] "LAMINATE"

[0124] The laminate of the present application has a layer containing the hardened product on a substrate. The laminate can be formed using existing laminating methods. For example, an adhesive layer is formed by applying the adhesive composition on one of the faces of the substrate, and next, the other substrate is overlapped on the adhesive layer before the hardening treatment, and the adhesive layer is hardened at 20°C to 200°C, whereby a laminate having a substrate, and a layer containing the hardened product of the adhesive resin composition can be obtained.

[0125] The substrate for the laminate is not particularly limited. As the suitable substrate, for example, metal such as stainless steel, thermoplastic polymers such as polyethylene, polypropylene, polyurethane, polyacrylate, and polycarbonate and copolymers of these, thermohardening polymers such as vulcanized rubber, urea-formaldehyde foam, melamine resin, wood, carbon fiber reinforced plastic, glass fiber reinforced plastic, and other fiber reinforced plastic can be exemplified.

[0126] The adhesive resin composition of the present application can be used for the adhesion between various substrates. The substrates to be adhered can be the same or different. The film thickness of the adhesive resin composition is desirably 0.1 μm to 300 mm.

[0127] The adhesive resin composition of the present application has excellent softness and adhesion, and the laminate using the adhesive resin composition is effectively used as a structural member (panel part, skeleton part, axle part, etc.) of a transportation equipment such as an automobile, building material, ship, aircraft, etc.

[0128] EXAMPLE

[0129] Hereinafter, the present application is more specifically described by way of examples, but the following examples do not limit the scope of the present application in any way. Furthermore, in the examples, "parts" means "mass parts" and "%" means "mass %" unless otherwise specified.

[0130] <Number average molecular weight>

[0131] The number average molecular weight of the acrylic polyol (A) and the urethane-acrylic hybrid resin (D) was calculated by gel permeation chromatography (GPC) as a value converted based on a standard polystyrene. The measurement was performed using GPC-8020 (manufactured by Tosoh Corporation) as a GPC device, tetrahydrofuran as an eluent, and three TSKgel Super HM-Ms (manufactured by Tosoh Corporation) connected in series as a column, under conditions of a flow rate of 0.6 mL / min, an injection amount of 10 μL, and a column temperature of 40°C. In addition, the number average molecular weight of the urea compound and the polyolefin compound was calculated in the same manner using an ACQUITY UPLC (Ultra Performance Liquid Chromatography) (manufactured by Waters Corporation), an N,N-dimethylformamide solution of 3 mM triethylamine and 10 mM LiBr as an eluent, and three TSKgel Super HM-Ms (manufactured by Tosoh Corporation) connected in series as a column, under conditions of a flow rate of 0.6 mL / min, an injection amount of 10 μL, and a column temperature of 40°C.

[0132] Hereinafter, the present application is more specifically described by way of examples, but the following examples do not limit the scope of the present application in any way. Furthermore, in the examples, "parts" means "mass parts" and "%" means "mass %" unless otherwise specified.

[0133] <Monomer having one or more ethylenically unsaturated groups and one or more epoxy groups (a-1)>

[0134] • GMA: glycidyl methacrylate

[0135] <Other ethylenically unsaturated monomer (a-2)>

[0136] • BMA: n-butyl methacrylate

[0137] • MMA: (Meth)acrylic acid methyl ester

[0138] <Polyol (B)>

[0139] • P-2000: difunctional polypropylene glycol, number average molecular weight 2,000, manufactured by ADEKA Corporation

[0140] • C-1090: difunctional polycarbonate polyol, number average molecular weight 1,000, manufactured by Kuraray Co., Ltd.

[0141] <Diisocyanate (C)>

[0142] • IPDI: isophorone diisocyanate

[0143] • MDI: diphenylmethane diisocyanate

[0144] <Liquid epoxy resin (E)>

[0145] • jER828: bisphenol A type epoxy resin, epoxy equivalent 190 g / eq, manufactured by Mitsubishi Chemical Corporation

[0146] • EX-141: phenyl glycidyl ether, epoxy equivalent 151 g / eq, manufactured by Nagase Chemtex Corporation

[0147] <Hardeners (F)>

[0148] • D-400: polyoxypropylenediamine, weight average molecular weight 430, amine value 520 mgKOH / g, manufactured by HUNTSMAN

[0149] • EH-4024W: polyamidoamine resin, amine value 200 mgKOH / g, manufactured by ADEKA

[0150] • D-2000: polyoxypropylenediamine, weight average molecular weight 2000, amine value 56.1 mgKOH / g, manufactured by HUNTSMAN

[0151] • Krasol LBH-P3000: liquid polybutadiene modified with terminal hydroxyl groups, weight average molecular weight 3000, manufactured by CRAY VALLEY

[0152] (Production Example 1)

[0153] In a reaction vessel including a nitrogen gas introduction tube, a stirring device, a thermometer, a refluxer, 1-thioglycerol 1.15 parts as a chain transfer agent having a mercapto group, glycidyl methacrylate 1.6 parts as an ethylenically unsaturated monomer (a-1) having one or more epoxy groups in a molecule, n-butyl methacrylate 29.0 parts as another ethylenically unsaturated monomer (a-2), methyl ethyl ketone at 50% relative to the total mass of the ethylenically unsaturated monomers were first added, and the temperature was raised to 75°C under a nitrogen atmosphere, and 2,2'-azobis(2,4-dimethylvaleronitrile) at 0.7% relative to the total mass of the chain transfer agent and the ethylenically unsaturated monomers as a polymerization initiator was added in seven portions every 1 hour, and after the addition of the polymerization initiator, the reaction was further carried out for 2 hours to obtain an acrylic polyol (A-1). Subsequently, 5.1 parts of P-2000 as a polyol (B), 2.9 parts of isophorone diisocyanate as a diisocyanate (C), and dibutyltin dilaurate at 0.01% relative to the total mass of the acrylic polyol (A-1), the polyol (B), and the diisocyanate (C) as a catalyst were charged, and after uniform stirring, the reaction was carried out at 90°C for 4 hours under a nitrogen atmosphere. Then, 60 parts of jER828 as a liquid epoxy resin (E) was added, and after uniform stirring, methyl ethyl ketone was removed under reduced pressure to obtain a composition (DE-1) containing a comb-type urethane-acrylic hybrid resin (D-1) and the liquid epoxy resin (E-1). The end point of the reaction was confirmed by the disappearance of a peak (2270 cm -1 nearby) derived from an isocyanate group according to FT-IR (Fourier Transform infrared spectroscopy). The number average molecular weight of the acrylic polyol (A-1) and the comb-type urethane-acrylic hybrid resin (D-1), the proportion (%) of the acrylic site in the comb-type urethane-acrylic hybrid resin (D-1), the proportion (%) of the monomer having an epoxy group in the acrylic polyol (A-1), and the proportion (%) of the liquid epoxy resin (E-1) relative to the total mass of the comb-type urethane-acrylic hybrid resin (D-1) and the liquid epoxy resin (E-1) are shown in Table 1.

[0154] (Production Examples 2 to 26)

[0155] The same operation as in Production Example 1 was performed except that the compound and the formulation composition shown in Tables 1 to 3 were changed, to obtain the compositions (DE-2 to DE-26) containing the comb-type urethane-acrylic hybrid resin (D) and the liquid epoxy resin (E) of Production Examples 2 to 26. The number average molecular weight of the acrylic polyol (A) and the comb-type urethane-acrylic hybrid resin (D) obtained, the proportion (%) of the acrylic site in the comb-type urethane-acrylic hybrid resin (D), the proportion (%) of the monomer having an epoxy group in the acrylic polyol (A), and the proportion (%) of the liquid epoxy resin (E) with respect to the total mass of the comb-type urethane-acrylic hybrid resin (D) and the liquid epoxy resin (E) are shown in Tables 1 to 3.

[0156]

[0157]

[0158]

[0159] (Comparative Production Example 1)

[0160] The same operation as in Production Example 1 was performed except that the compound and the formulation composition shown in Table 4 were changed, to obtain the composition (U-1) containing the comb-type urethane-acrylic hybrid resin and the liquid epoxy resin. The number average molecular weight of the acrylic polyol and the comb-type urethane-acrylic hybrid resin obtained, the proportion (%) of the acrylic site in the comb-type urethane-acrylic hybrid resin, the proportion (%) of the monomer having an epoxy group in the acrylic polyol, and the proportion (%) of the liquid epoxy resin with respect to the total mass of the comb-type urethane-acrylic hybrid resin and the liquid epoxy resin are shown in Table 3.

[0161] (Comparative Production Example 2)

[0162] In a reaction vessel including a nitrogen introduction tube, a stirring device, a thermometer, a refluxer, 1-thioglycerol 1.4 parts as a chain transfer agent having a mercapto group, glycidyl methacrylate 4.0 parts as an ethylenically unsaturated monomer having one or more epoxy groups in a molecule, n-butyl methacrylate 34.3 parts as another ethylenically unsaturated monomer, methyl ethyl ketone at 50% relative to the total mass of the chain transfer agent and the ethylenically unsaturated monomers were first added, and the temperature was raised to 75°C under a nitrogen atmosphere, and 2,2'-azobis(2,4-dimethylvaleronitrile) at 0.7% relative to the total mass of the ethylenically unsaturated monomers as a polymerization initiator was added thereto in seven portions every 1 hour, and after the addition of the polymerization initiator, the reaction was further continued for 2 hours to obtain an acrylic polyol. Subsequently, 60 parts of jER828 as a liquid epoxy resin was added, and after uniform stirring, methyl ethyl ketone was removed under reduced pressure to obtain a composition (U-2) containing the acrylic polyol and the liquid epoxy resin. The number average molecular weight of the obtained acrylic polyol, the proportion (%) of the acrylic polyol in the acrylic resin, the proportion (%) of the monomer having an epoxy group in the acrylic polyol, and the proportion (%) of the liquid epoxy resin relative to the total mass of the acrylic polyol and the liquid epoxy resin are shown in Table 3.

[0163] (Comparative Production Example 3)

[0164] In a reaction vessel including a nitrogen introduction tube, a stirring device, a thermometer, a refluxer, 36.8 parts of P-2000 as a polyol, 3.2 parts of isophorone diisocyanate as a diisocyanate, dibutyltin dilaurate at 0.01% relative to the total mass of the polyol and the diisocyanate as a catalyst, and methyl ethyl ketone at 50% relative to the total mass of the monomers were first charged, and after uniform stirring, the reaction was carried out at 90°C for 4 hours under a nitrogen atmosphere, 60 parts of jER828 as a liquid epoxy resin was added, and after uniform stirring, methyl ethyl ketone was removed under reduced pressure to obtain a composition (U-3) containing a urethane resin and the liquid epoxy resin. The end point of the reaction was confirmed by the disappearance of a peak (2270 cm -1 near) derived from an isocyanate group according to FT-IR. The number average molecular weight of the obtained urethane resin and the proportion (%) of the liquid epoxy resin relative to the total mass of the urethane resin and the liquid epoxy resin are shown in Table 3.

[0165] (Comparative Production Example 4)

[0166] A composition containing only the liquid epoxy resin described in Table 3 was set as a composition (U-4).

[0167] (Comparative Production Example 5)

[0168] In a reaction vessel including a nitrogen introduction tube, a stirring device, a thermometer, a refluxer, 0.7 parts of 1-thioglycerol as a chain transfer agent having a mercapto group, 2.0 parts of glycidyl methacrylate as an ethylenically unsaturated monomer having one or more epoxy groups in a molecule, 17.1 parts of n-butyl methacrylate as another ethylenically unsaturated monomer, and methyl ethyl ketone at 50% relative to the total mass of the monomers were first added, warmed to 75°C under a nitrogen atmosphere, and 0.7% relative to the total mass of the chain transfer agent and the ethylenically unsaturated monomers of 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator was added thereto in seven portions every 1 hour, and after the addition of the polymerization initiator, the reaction was further continued for 2 hours to obtain a polyol acrylate. Subsequently, in a reaction vessel different from the previous one including a nitrogen introduction tube, a stirring device, a thermometer, a refluxer, 18.4 parts of P-2000 as a polyol, 1.6 parts of isophorone diisocyanate as a diisocyanate, 0.01% relative to the total mass of the polyol and the diisocyanate of dibutyltin dilaurate as a catalyst, and methyl ethyl ketone at 50% relative to the total mass of the monomers were charged, and after uniform stirring, the reaction was carried out at 90°C for 4 hours under a nitrogen atmosphere to obtain a urethane resin. The end point of the reaction was confirmed by the disappearance of a peak (2270 cm -1 nearby) derived from an isocyanate group according to FT-IR. The previous polyol acrylate and the urethane resin were mixed, 60 parts of jER828 as a liquid epoxy resin was added, and after uniform stirring, methyl ethyl ketone was removed under reduced pressure to obtain a mixture (U-5) of the polyol acrylate, the urethane resin, and the liquid epoxy resin. The number average molecular weight of the obtained polyol acrylate and urethane resin, the proportion (%) of the monomer having an epoxy group in the polyol acrylate, and the proportion (%) of the liquid epoxy resin relative to the total mass of the polyol acrylate, the urethane resin, and the liquid epoxy resin are shown in Table 3.

[0169] (Comparative Production Example 6)

[0170] Comparative Production Example 6 was based on the production method of a polyurethane-modified epoxy resin described in Japanese Patent Publication No. 2017-2130, and the synthesis was performed as follows.

[0171] In a reaction vessel including a nitrogen introduction tube, a stirring device, a thermometer, a refluxer, 87 parts by mass of polycaprolactone diol ["Placcel 230" manufactured by Daicel Corporation, weight average molecular weight (Mw) 3,000] and 13 parts by mass of isophorone diisocyanate were mixed, and 0.1 part by mass of dioctyltin catalyst ["Neostann U-820" manufactured by Nitto Electric Industrial Co., Ltd.], as a catalyst, was added, and the mixture was allowed to react at 70°C for 3 hours, to obtain an isocyanate group-containing urethane resin. The isocyanate group content of the isocyanate group-containing urethane resin was 2.4% by mass. Subsequently, in another reaction vessel including a nitrogen introduction tube, a stirring device, a thermometer, a refluxer, 30 parts by mass of the isocyanate group-containing urethane resin and 70 parts by mass of a bisphenol A type epoxy resin ["EPICLON 850" manufactured by DIC Corporation, epoxy equivalent 188 g / eq, hydroxyl value 20 mgKOH / g] were mixed, and the temperature was raised to 70°C, to obtain a polyurethane-modified epoxy resin (U-6). The end point of the reaction was confirmed by disappearance of a peak (2270 cm -1 near) derived from an isocyanate group according to FT-IR. The epoxy equivalent of the obtained polyurethane-modified epoxy resin (U-6) was 255 g / eq.

[0172] [Table 4]

[0173] Table 4

[0174]

[0175] <Manufacturing Example of Hardener>

[0176] (Manufacturing Example I)

[0177] In a reaction vessel including a nitrogen introduction tube, a stirring device, a thermometer, a refluxer, 15.8 parts of D-400, 73.4 parts of D-2000, and 208 parts of isopropyl alcohol were charged, and under a nitrogen atmosphere, uniform stirring was performed at 40°C, and a mixed solution including 10.9 parts of isophorone diisocyanate and 35.2 parts of ethyl acetate was added dropwise over 30 minutes, and the mixture was allowed to react for 1 hour with stirring, to obtain a urea compound solution. The obtained urea compound solution was desolvated under reduced pressure, to obtain a urea compound (UR-1). The end point of the reaction was confirmed by disappearance of a peak (2270 cm -1 near) derived from an isocyanate group according to FT-IR. The number average molecular weight of the obtained urea compound (UR-1) was 3100, and the amine value was 27.4 mgKOH / g.

[0178] (Manufacturing Example II)

[0179] In a dropping vessel including a nitrogen introduction tube, a stirring device, a thermometer, a refluxer, 46.6 parts of P-2000, 22.7 parts of C-1090, 20.2 parts of isophorone diisocyanate, 0.01% of dibutyltin dilaurate as a catalyst with respect to the total mass of the polyol and the diisocyanate were charged, and after uniform stirring, reaction was performed at 90°C for 4 hours under a nitrogen atmosphere, and after synthesis of an isocyanate group-terminated prepolymer, 51.1 parts of ethyl acetate was added to prepare an isocyanate group-terminated prepolymer solution. Subsequently, 10.5 parts of hexamethylene diamine, 48.9 parts of isopropyl alcohol were charged, and after uniform stirring at 40°C under a nitrogen atmosphere, the isocyanate group-terminated prepolymer solution was added dropwise over 30 minutes, and after stirring, reaction was performed for 1 hour to obtain a urea compound solution. The obtained urea compound solution was desolvated under reduced pressure to obtain a urea compound (UR-2). The end point of the reaction was confirmed according to FT-IR by disappearance of a peak (2270 cm -1 The number average molecular weight of the obtained urea compound (UR-2) was 3900, and the amine value was 50.9 mgKOH / g.

[0180] (Manufacture Example III)

[0181] The polyolefin having an amino group was synthesized based on the well-known Gabriel reaction as follows. In a reaction vessel including a nitrogen introduction tube, a stirring device, a thermometer, a refluxer, 77.3 parts of Krasol LBH-P3000, 14.9 parts of p-toluenesulfonyl chloride, 7.9 parts of pyridine, 100 parts of chloroform were charged, and after stirring at room temperature under a nitrogen atmosphere, reaction was performed for 6 hours. After the reaction, after making acidic by adding 200 mL of 1M hydrochloric acid aqueous solution, extraction was performed using chloroform, the organic layer was separated, and dried to thereby obtain a tosylated polybutadiene. Subsequently, in a reaction vessel, the obtained tosylated polybutadiene 81.3 parts, potassium phthalimide 21.7 parts, N,N-dimethylformamide 80 parts were charged, and after refluxing at 140°C under a nitrogen atmosphere for 8 hours. After neutralization by adding an ammonium chloride aqueous solution to the reaction solution, extraction was performed using hexane, the organic layer was separated, and dried to thereby obtain a phthalimidized polybutadiene. Subsequently, in a reaction vessel, the obtained phthalimidized polybutadiene 42.0 parts, hydrazine monohydrate 6.75 parts, ethanol 50 parts were charged, and after stirring at room temperature under a nitrogen atmosphere, reaction was performed for 2 hours. After the reaction, after making alkaline using a sodium hydroxide aqueous solution, extraction was performed using hexane, the organic layer was separated, and dried to thereby obtain a polyolefin compound having an amino group (UR-3). The number average molecular weight of the obtained polyolefin compound (UR-3) was 3000, and the amine value was 34.0 mgKOH / g.

[0182] [Table 5]

[0183] Table 5

[0184]

[0185] Preparation of Adhesive Resin Composition

[0186] [Example 1]

[0187] A composition (DE-1) containing the comb-type urethane-acrylic composite resin (D-1) and the liquid epoxy resin (E) obtained in Production Example 1, 3.1 parts of D-400 as a hardener (F), and 0.1 part of triethylene tetramine were mixed by stirring at room temperature to prepare the adhesive resin composition of Example 1.

[0188] [Examples 2 to 32 and Comparative Examples 1 to 6]

[0189] The same operation as in Example 1 was performed except that the formulation composition shown in Tables 6 to 9 was changed to prepare the adhesive resin compositions of Examples 2 to 32 and Comparative Examples 1 to 6.

[0190] Evaluation 1 of Adhesive Resin Composition

[0191] The following tests were performed for the adhesive resin compositions prepared in the examples and comparative examples. The results of the evaluation are shown in Tables 6 to 9.

[0192]

[0193]

[0194]

[0195] [Table 9]

[0196] Table 9

[0197]

[0198] [Appearance]

[0199] Each of the adhesive resin compositions was filled in a sheet-shaped mold frame having a thickness of 2 mm, the surface was smoothed, and the obtained sheet was allowed to harden at 25°C for 7 days to obtain a test sheet. The obtained test sheet was evaluated according to the following evaluation criteria under the conditions of a temperature of 25°C and a relative humidity of 50%.

[0200] (Evaluation Criteria)

[0201] ++: transparent and no phase separation by visual observation. (Good)

[0202] +: Slight opacity or slight phase separation is visually confirmed. (Usable)

[0203] NG: Obvious opacity or obvious phase separation is visually confirmed. (Not usable)

[0204] [Shear adhesion]

[0205] Each of the adhesive resin compositions was applied to a carbon fiber reinforced plastic substrate (length 100 mm, width 25 mm, thickness 2 mm) in a manner to become 10 mm in length, 25 mm in width, and 0.1 mm in thickness, and was bonded to the carbon fiber reinforced plastic substrate, and was allowed to harden at 25°C for 7 days in a state where the thickness was maintained at 0.1 mm, to obtain a test piece. The shear adhesion of the obtained test piece was measured using a tensile testing machine at a tensile speed of 1 mm / min under conditions of a temperature of 25°C and a relative humidity of 50%, and was judged according to the following evaluation criteria.

[0206] (Evaluation criteria)

[0207] +++: The shear adhesion was 20 MPa or more. (Very good)

[0208] ++: The shear adhesion was 15 MPa or more and less than 20 MPa. (Good)

[0209] +: The shear adhesion was 10 MPa or more and less than 15 MPa. (Usable)

[0210] NG: The shear adhesion was less than 10 MPa. (Not usable)

[0211] [Breaking stress, breaking elongation]

[0212] Each of the resin composition adhesives was filled in a sheet-shaped mold frame having a thickness of 2 mm, the surface was flattened, and after allowing it to harden at 25°C for 7 days, a dumbbell-shaped test piece for evaluation was produced by punching using a No. 3 dumbbell mold. Using the dumbbell-shaped test piece, a tensile test was performed at a tensile speed of 50 mm / min under conditions of a temperature of 25°C and a relative humidity of 50%, and the breaking stress (MPa) and the breaking elongation (%) were measured, and were judged according to the following criteria.

[0213] (Evaluation criteria for breaking stress)

[0214] +++: The breaking stress was 20 MPa or more. (Very good)

[0215] ++: The breaking stress was 15 MPa or more and less than 20 MPa. (Good)

[0216] +: The breaking stress was 10 MPa or more and less than 15 MPa. (Usable)

[0217] NG: less than 10 MPa (unusable)

[0218] (Evaluation criteria for elongation at break)

[0219] +++ : 100% or more (excellent)

[0220] ++ : 80% or more and less than 100% (good)

[0221] + : 60% or more and less than 80% (usable)

[0222] NG: less than 60% (unusable)

[0223] [Impact resistance]

[0224] Each of the adhesive resin compositions was applied to a stainless steel substrate (length 100 mm, width 25 mm, thickness 2 mm) in a manner to become 10 mm in length, 25 mm in width, and 0.1 mm in thickness, and was bonded to the stainless steel substrate, and was hardened at 25°C for 7 days in a state where pressure bonding was performed to maintain a thickness of 0.1 mm, to obtain a test piece. The number of times until the obtained test piece was broken by a DuPont type impact test was measured under conditions of a temperature of 25°C and a relative humidity of 50%, and was judged according to the following criteria. The DuPont type impact test was performed using an impact mold having a 1 / 2 inch roundness at the front end, and a 500 g weight was dropped freely from a height of 5 cm.

[0225] (Evaluation criteria)

[0226] +++ : not broken even if tested 10 times (excellent)

[0227] ++ : broken at 5th to 9th times (good)

[0228] + : broken at 2nd to 4th times (usable)

[0229] NG: broken at the first time (unusable)

[0230] < Evaluation 2 of the adhesive resin composition>

[0231] The same test as in Evaluation 1 was performed on the adhesive resin compositions prepared in the examples and comparative examples, except that the hardening conditions were changed to 80°C for 1 day. The results of the judgment are shown in Tables 5 to 7.

[0232] < Comprehensive evaluation>

[0233] The adhesive resin compositions prepared in the examples and comparative examples were comprehensively evaluated according to the following judgment criteria. The results of the judgment are shown in Tables 6 to 9.

[0234] (Comprehensive evaluation criteria)

[0235] ++: In all test items of Evaluation 1 and Evaluation 2, it was determined to be ++ or more and there was no difference in the evaluation results. (Good)

[0236] +: In all test items of Evaluation 1 and Evaluation 2, it was determined to be ++ or more, but there was a difference in the evaluation results, or in either of Evaluation 1 and Evaluation 2, there was no NG determination regardless of the difference in the evaluation results, but there was a + determination.

[0237] (Usable)

[0238] NG: In either of Evaluation 1 and Evaluation 2, there was a determination of NG or less. (Not usable)

[0239] The adhesive resin composition of the present application achieved good results in adhesion, impact resistance, breaking stress, and elongation at break. On the other hand, the adhesion, breaking stress, and elongation at break of some or all of the adhesive resin compositions of the comparative examples were worse than the examples.

Claims

1. An adhesive resin composition, comprising: a comb-type urethane-acrylic hybrid resin (D) having residues of an acrylic polyol (A) having an epoxy group within a molecule and a hydroxyl group at a single terminal end, a polyol (B) other than the acrylic polyol (A), and a diisocyanate (C); a liquid epoxy resin (E); and a hardener (F), the hardener (F) is an amine compound, a ratio of a total number of moles of the epoxy groups contained in the adhesive resin composition to a total number of moles of active hydrogen groups in the hardener (F), that is, [epoxy groups] / [active hydrogen groups in the hardener] is 0.5 to 2.

0.

2. The adhesive resin composition according to claim 1, characterized by the liquid epoxy resin (E) has two or more epoxy groups within a molecule.

3. The adhesive resin composition according to claim 1, characterized by 5 to 80 mass% of the acrylic polyol (A) is contained in 100 mass% of the comb-type urethane-acrylic hybrid resin (D).

4. The adhesive resin composition according to claim 1, characterized by 5 mass% or more and less than 100 mass% of an ethylenically unsaturated monomer (a-1) having one or more epoxy groups within a molecule is contained in 100 mass% of the acrylic polyol (A).

5. The adhesive resin composition according to claim 1, characterized by 20 to 80 mass% of the liquid epoxy resin (E) is contained in 100 mass% of the total of the comb-type urethane-acrylic hybrid resin (D) and the liquid epoxy resin (E).

6. The adhesive resin composition according to claim 1, characterized by a ratio of a total number of moles of the epoxy groups contained in the adhesive resin composition to a total number of moles of active hydrogen groups in the hardener (F), that is, [epoxy groups] / [active hydrogen groups in the hardener] is 0.6 to 1.

5.

7. A hardened product comprising the adhesive resin composition according to any one of claims 1 to 6.

8. A laminate having a layer comprising the hardened product according to claim 7 on a substrate.

Images