Adhesive resin composition, cured product and laminate

Abstract

To provide an adhesive resin composition which has high flexibility and excellent impact resistance and followability, is particularly suitable for the fields of a housing material, a marine vessel and the like, and is usable without a solvent.SOLUTION: An adhesive resin composition contains a curing agent containing a polyurethane urea resin (D) which is a reaction product of polyol (A), polyisocyanate (B) and polyamine (C) (excluding polyether polyamine (E)) and has an amino group at a terminal, and polyether polyamine (E), and a main agent containing a liquid epoxy resin (F), and satisfies all the following (i) to (iii). (i) In 100 mass% of the total of an organic component having a primary amino group, an organic component having a secondary amino group, and an organic component having an epoxy group, which are contained in the adhesive resin composition, 15 to 40 mass% of the polyurethane urea resin (D) is contained. (ii) The polyamine (C) has a number average molecular weight of less than 300. (iii) The total of the molar numbers of the primary amino group and the secondary amino group in the polyurethane urea resin (D) is 3 to 40 mol%, with respect to 100 mol% of the total of the molar numbers of the primary amino group and the secondary amino group in the polyether polyamine (E).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an adhesive resin composition, a cured product thereof, and a laminate including the cured product. [Background technology]

[0002] In recent years, in the fields of building materials and ships, there has been progress in improving reliability and functionality, and the proportion of light metals such as aluminum and magnesium, and fiber reinforced plastic materials (hereinafter referred to as FRP), etc., used is increasing. The use of adhesives as a joining method is increasing, and among them, two-part curing epoxy adhesives are widely used as structural joining agents because they have high adhesive strength and durability for various materials, and also have a gradual increase in viscosity after mixing and excellent workability.

[0003] However, when used to bond exterior walls, flooring, etc., if a strong impact is applied in the thickness direction of the adhesive layer, conventional epoxy adhesives have the problem that they are easily destroyed by the impact due to their hardness and brittleness.

[0004] In response to such problems, polymeric epoxies such as epoxy-terminated polybutadiene, polyurethane, and polyester, rubber-like polymer particles having epoxy groups, and polymeric amines such as amino-terminated polybutadiene and polyamidoamine have been investigated as components for increasing flexibility (Patent Documents 1 to 5).

[0005] However, in general, when using polymeric epoxy or polymeric amine, the balance of crosslinking state and compatibility with other components is lost, so simple mixing may result in a deterioration in flexibility and strength. In addition, when rubber-like polymer fine particle components are mixed, it is easier to adjust the crosslinking state and compatibility compared to polymeric epoxy or polymeric amine, but there is a problem that the viscosity increases significantly with the amount added, and workability decreases when flexibility is increased. For this reason, various combinations are currently being investigated to appropriately impart flexibility.

[0006] Here, Patent Document 5 discloses that high impact resistance can be obtained by using an amino-terminated urethane urea chain-extended with a diamine having an ether group as an impact resistance improver. However, although the impact resistance in the direction perpendicular to the thickness direction of the adhesive is increased, the impact resistance in the thickness direction of the adhesive is still insufficient, and the conformability is also insufficient, so there is also a problem that the adhesive deteriorates due to continuous impact. For this reason, an adhesive that is excellent in impact resistance and conformability in the thickness direction of the adhesive is desired. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2015-182248 A [Patent Document 2] JP 2015-063595 A [Patent Document 3] JP 2017-002130 A [Patent Document 4] JP 2018-002766 A [Patent Document 5] Special Publication No. 2013-521361 Summary of the Invention [Problem to be solved by the invention]

[0008] An object of the present invention is to provide an adhesive resin composition which has high adhesion, excellent impact resistance and conformability, and in which the difference in physical properties due to the curing temperature is small, and which is particularly suitable for fields such as building materials and ships, and which can be used without solvent. [Means for solving the problem]

[0009] As a result of intensive research into solving the above problems, the present inventors have found that the problems of the present invention can be solved in the following aspect, and have completed the present invention.

[0010] The present invention relates to an adhesive resin composition comprising a polyurethane urea resin (D) having an amino group at its terminal, a curing agent including a polyether polyamine (E), and a base material including a liquid epoxy resin (F), wherein the polyurethane urea resin (D) having an amino group at its terminal is a reaction product of a polyol (A), a polyisocyanate (B), and a polyamine (C) (excluding the polyether polyamine (E)), and wherein all of the following (i) to (iii) are satisfied: (i) The adhesive resin composition contains 15 to 40 mass% of a polyurethane urea resin (D) relative to a total of 100 mass% of an organic component having a primary amino group, an organic component having a secondary amino group, and an organic component having an epoxy group. (ii) The polyamine (C) has a number average molecular weight of less than 300. (iii) The total number of moles of primary amino groups and secondary amino groups in the polyurethane urea resin (D) is 3 to 40 mol %, relative to 100 mol % of the total number of moles of primary amino groups and secondary amino groups in the polyether polyamine (E).

[0011] The present invention also relates to the adhesive resin composition, wherein the polyether polyamine (E) has a number average molecular weight of 300 or more.

[0012] The present invention also relates to a cured product made from the adhesive resin composition.

[0013] The present invention also relates to a laminate having a layer formed from the above cured product on a substrate. Effect of the Invention

[0014] The present invention can provide an adhesive resin composition which has high adhesive strength, excellent impact resistance and conformability, and can be used without solvent, and is particularly suitable for use in fields such as building materials and ships. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] The present invention will be described in detail below. Other embodiments are also included in the scope of the present invention as long as they are consistent with the gist of the present invention. In addition, a numerical range specified using "~" in this specification includes the numerical values ​​written before and after "~" as the range of the lower and upper limits. In addition, various components appearing in this specification may be used independently alone or in combination of two or more types, unless otherwise noted.

[0016] The adhesive resin composition of the present invention contains a polyurethane urea resin (D) having an amino group at its terminal, a curing agent including a polyether polyamine (E), and a base agent including a liquid epoxy resin (F), wherein the polyurethane urea resin (D) having an amino group at its terminal is a reaction product of a polyol (A), a polyisocyanate (B), and a polyamine (C) (excluding the polyether polyamine (E)), and is characterized in that it satisfies all of the following (i) to (iii): (i) The adhesive resin composition contains 15 to 40 mass% of a polyurethane urea resin (D) relative to a total of 100 mass% of an organic component having a primary amino group, an organic component having a secondary amino group, and an organic component having an epoxy group. (ii) The polyamine (C) has a number average molecular weight of less than 300. (iii) The total number of moles of primary amino groups and secondary amino groups in the polyurethane urea resin (D) is 3 to 40 mol %, relative to 100 mol % of the total number of moles of primary amino groups and secondary amino groups in the polyether polyamine (E). By satisfying all of (i) to (iii), a suitable phase separation structure is formed when the curing agent undergoes a crosslinking reaction with the liquid epoxy resin (F), and the composition exhibits excellent flexibility while maintaining strength. The cured film thus obtained has extremely high impact resistance and conformability in the thickness direction of the adhesive. Therefore, the adhesive resin composition of the present invention is suitable for use as a structural adhesive in the fields of building materials, ships, etc. In addition, the adhesive resin composition of the present invention can be used as a liquid solvent-free adhesive, and is excellent in terms of safety and environmental friendliness.

[0017] <Polyurethane urea resin having amino groups at its terminals (D)> The polyurethane urea resin (D) having an amino group at its terminal of the present invention is a reaction product obtained by reacting a polyol (A), a polyisocyanate (B) and a polyamine (C) so that the amino group in the polyamine (C) remains. Although there are no limitations on the method for producing the polyurethane urea resin (D), it can be preferably produced by the following method. Step 1: A polyol (A) and a polyisocyanate (B) are subjected to a urethane reaction under conditions in which the isocyanate groups are in excess relative to the hydroxyl groups, to obtain a urethane prepolymer having an isocyanate group at the molecular terminal. Step 2: The urethane prepolymer and the polyamine (C) are reacted with each other to form an amine bond to the isocyanate group. A urea reaction is carried out under conditions in which the amino group is in excess to obtain a polyurethane urea resin (D) having an amino group at the terminal.

[0018] The reactions in steps 1 and 2 may be carried out using or without a solvent. When a solvent is used in steps 1 and 2, the solvent can be removed under reduced pressure or normal pressure during or after the reaction to obtain a solventless polyurethane urea resin (D).

[0019] The reaction in step 1 is carried out using a known urethane reaction, and a catalyst may be used for the purpose of adjusting the reactivity.

[0020] <Catalyst> As the catalyst, known metal catalysts, amine catalysts, etc. can be used. As the metal catalyst, dibutyltin dilaurate, tin octoate, dibutyltin di(2-ethylhexoate), 2-ethylhexoate lead, 2-ethylhexyl titanate, titanium ethyl acetate, 2-ethylhexoate iron, 2-ethylhexoate cobalt, zinc naphthenate, cobalt naphthenate, tetra-n-butyltin, etc. can be mentioned. As the amine catalyst, tertiary amines such as tetramethylbutanediamine, etc. can be mentioned. The amount of the catalyst used is preferably in the range of 0.01 to 0.05% by mass based on the total mass of the polyol (A) and the polyisocyanate (B).

[0021] The number average molecular weight of the polyurethane urea resin (D) is not particularly limited, but is preferably 2,000 to 15,000. If it is 2,000 or more, the cohesive force is good and the adhesive force is excellent, and if it is 15,000 or less, the viscosity is low and it is easy to adjust the viscosity in the absence of a solvent.

[0022] <Polyol (A)> The polyol (A) is a compound having two or more hydroxyl groups in the molecule, and representative examples thereof include polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, and plant-derived polyols.

[0023] Further, examples of the compound having two or more hydroxyl groups in the molecule include polyols obtained by adding alkylene oxides such as methylene oxide, ethylene oxide, propylene oxide, tetrahydrofuran, or polyoxytetramethylene oxide to a compound having at least two active hydroxyl groups, such as low molecular weight polyols, aliphatic amine compounds, aromatic amine compounds, alkanolamines, or bisphenols, as a starting material. Examples include ru.

[0024] Examples of the low molecular weight polyol include difunctional low molecular weight polyols and tri- or higher functional low molecular weight polyols.

[0025] The bifunctional low molecular weight polyol is not particularly limited, and examples thereof include 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, and the like. Examples of the monomer include diol, polyoxyethylene glycol (10 or less moles added), polyoxypropylene glycol (10 or less moles added), cyclohexanediol, cyclohexanedimethanol, tricyclodecane dimethanol, cyclopentadiene dimethanol, dimer diol, bisphenol A, N,N-bis(2-hydroxypropyl)aniline, dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolpentanoic acid, dihydroxysuccinic acid, dihydroxypropionic acid, and dihydroxybenzoic acid.

[0026] The trifunctional or higher low molecular weight polyol is not particularly limited, and examples thereof include trimethylolethane, trimethylolpropane, 1,1,1-trimethylolbutane, 1,2,3-butanetriol, 1,2,4-butanetriol, 1,2,6-butanetriol, trimethylolbutene, trimethylolpentene, trimethylolhexene, trimethylolheptene, trimethyloloctene, trimethylolnonene, trimethyloldecene, trimethylolundecene, trimethyloldodecene, and trimethyloltridecene. , trimethylol pentadecene, trimethylol hexadecene, trimetrol heptadecene, trimethylol octadecene, 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, trimethylol hexene, 1,2,3-octane triol, 1,3,7-octane triol, 3,7-dimethyl-1,2,3-octane triol, 1,1,1-, 1, 1,1-trimethylol decane, 1,2,10-decanetriol, 1,1,1-trimethylol isoheptadecane, 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 1,1,1-trimethylol-2-ethyl-hexane, 1,1,1-trimethylol-3-ethyl-hexane, 1,1,1-trimethylol isoheptadecane, 1,2,3,4-butanetetraol, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerin, triglycerin, polyglycerin, ditrimethylolethane, ditrimethylolpropane, tris(2-hydroxyethyl)isocyanurate, benzene-1,3,5-triol, benzene-1,2,3-triol, stilbene-3,Examples of such sugars include 4',5-triol, sucrose, inositol, sorbitan, sorbitol, mannitol, saccharose, cellulose, and xylitol.

[0027] Examples of the aliphatic amine compounds include ethylenediamine, triethylenetetramine, diethylenetriamine, and triaminopropane. Examples of the aromatic amine compounds include toluenediamine and diphenylmethane-4,4-diamine. Examples of alkanolamines include ethanolamine and diethanolamine. Examples of bisphenols include bisphenol A, bisphenol AP, bisphenol B, bisphenol C, bisphenol E, bisphenol F, etc.

[0028] Examples of polyether polyols include polymers or copolymers of methylene oxide, ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, etc., glycols such as polyethylene glycol, polypropylene glycol, poly(ethylene / propylene) glycol, etc. In addition, examples of polyether polyols include hexanediol, methylhexanediol, heptanediol, octanediol, or polyether polyols obtained by condensation of a mixture thereof.

[0029] The polyester polyol may be, for example, a polyester polyol obtained by condensation reaction between the above-mentioned low molecular weight polyol and a dibasic acid component.

[0030] Examples of the dibasic acid component include aliphatic or aromatic dibasic acids such as terephthalic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, hydrogenated dimer acid, phthalic anhydride, isophthalic acid, trimellitic acid, glutaric acid, pimelic acid, suberic acid, and sebacic acid, and their anhydrides. Further, polyester polyols obtained by ring-opening polymerization of cyclic ester compounds such as lactones, such as ε-caprolactone, poly(β-methyl-γ-valerolactone) and polyvalerolactone, can also be used.

[0031] Examples of the polycarbonate polyol include those obtained by reacting the above-mentioned low molecular weight polyol with a carbonate compound such as a dialkyl carbonate, an alkylene carbonate, or a diaryl carbonate. Examples of the dialkyl carbonate include dimethyl carbonate and diethyl carbonate, examples of the alkylene carbonate include ethylene carbonate, and examples of the diaryl carbonate include diphenyl carbonate.

[0032] Examples of polyolefin polyols include hydroxyl-containing polybutadiene, hydrogenated hydroxyl-containing polybutadiene, hydroxyl-containing polyisoprene, hydrogenated hydroxyl-containing polyisoprene, hydroxyl-containing chlorinated polypropylene, and hydroxyl-containing chlorinated polyethylene.

[0033] Examples of the vegetable oil-based polyol include polyols made from castor oil, dimer acid, or soybean oil, which are derived from plants.

[0034] Among these, polyether polyols and polycarbonate polyols are preferred due to their excellent flexibility.

[0035] The number average molecular weight of the polyol (A) is preferably 500 to 5,000, and more preferably 700 to 3500. When the number average molecular weight is 500 to 5,000, the resulting cured product has better adhesive strength and flexibility, which is preferable.

[0036] Furthermore, the polyol (A) may be used in combination with the above-mentioned low molecular weight polyols for the purpose of adjusting the urethane bond concentration and introducing various functional groups, within the scope of not impairing the effects of the present invention.

[0037] <Polyisocyanate (B)> The polyisocyanate (B) may be any compound having two or more isocyanate groups in the molecule, and examples thereof include aromatic, aliphatic, or alicyclic diisocyanates.

[0038] Examples of aromatic diisocyanates include 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, tolidine diisocyanate, xylylene diisocyanate, m-tetramethylxylene diisocyanate, p-tetramethylxylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, and 1,5-tetrahydronaphthalene diisocyanate.

[0039] Examples of the aliphatic diisocyanate include 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, pentamethylene diisocyanate, and trimethylhexamethylene diisocyanate.

[0040] Examples of alicyclic diisocyanates include 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(isocyanatemethyl)cyclohexane, hydrogenated xylylene diisocyanate, dimer acid diisocyanate, and norbornene diisocyanate.

[0041] <Polyamine (C)> The polyamine (C) is a compound having two or more amino groups in the molecule, excluding the polyether polyamine (E) described below, and may have a number average molecular weight of less than 300, such as aromatic, aliphatic, or alicyclic diamines. If the number average molecular weight is less than 300, the urea bonds are close to each other, which promotes the formation of a phase-separated structure, resulting in excellent impact resistance and conformability. The number average molecular weight is preferably less than 200.

[0042] Examples of the aromatic diamine include aromatic amines such as m-xylylenediamine, p-xylylenediamine, and m-phenylenediamine.

[0043] Examples of the aliphatic diamine include ethylenediamine, diaminopropane, diaminobutane, diaminohexane, 2,5-dimethylhexamethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, and iminobispropylamine.

[0044] Examples of the alicyclic diamine include alicyclic amines such as isophorone diamine and methacene diamine.

[0045] <Polyetherpolyamine (E)> Polyetherpolyamine (E) is a compound that has two or more amino groups in the molecule. There is no particular limitation on the polyamine as long as it has a repeating ether chain structure. Examples of the polyamine include 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 / ethylene glycol) diamine, and poly(propylene / ethylene glycol) triamine. In particular, the number average molecular weight is preferably 300 or more. Although there is no particular upper limit, it is preferably 3,000 or less. When the number average molecular weight is 300 to 3,000, it is preferable since it facilitates the formation of a phase separation structure described later and provides excellent flexibility.

[0046] The polyether polyamine (E) of the present invention is used in such a manner that the total molar number of the primary amino groups and the secondary amino groups in the polyurethane urea resin (D) is in the range of 3 to 40 mol %, relative to 100 mol %, the total molar number of the primary amino groups and the secondary amino groups in the polyether polyamine (E). When it is used in an amount less than 3 mol % or more than 40 mol %, the impact resistance is significantly reduced, whereas when it is used in the range of 8 to 30 mol %, the impact resistance is particularly excellent, which is preferable.

[0047] <Hardening agent> The adhesive resin composition of the present invention contains a polyurethane urea resin (D) having an amino group at the end and a polyether polyamine (E) as a curing agent. In this specification, the curing agent refers to a curing agent in a two-component curing adhesive, and includes not only the polyurethane urea resin (D) and the polyether polyamine (E) that contribute to the crosslinking reaction with the epoxy resin of the main component, but also amine curing agents other than the polyether polyamine (E), curing accelerators, and additives used as needed.

[0048] The content of the polyurethane urea resin (D) is 15 to 40% by mass in the total of 100% by mass of the organic component having a primary amino group, the organic component having a secondary amino group, and the organic component having an epoxy group contained in the adhesive resin composition. By setting it in this range, the formation of phase separation is promoted, and the impact resistance and followability are excellent. The organic component having a primary amino group and the organic component having a secondary amino group contained in the adhesive resin composition refer to the total of the organic component having a primary amino group and the organic component having a secondary amino group among the polyurethane urea resin (D) (organic component having a primary amino group) which is a curing agent, the polyether polyamine (E) (organic component having a primary amino group), and other amine curing agents and curing accelerators. In addition, the organic component having an epoxy group contained in the adhesive resin composition refers to the total of the liquid epoxy resin (F) which is the main agent and other epoxy compounds which are optional components.

[0049] As the amine curing agent other than the polyether polyamine (E), a known amine capable of curing an epoxy resin can be used within a range that does not impair flexibility. For example, an amine compound, an amide compound, etc. can be mentioned.

[0050] Examples of the amine compound include aliphatic amines such as ethylenediamine, diaminopropane, diaminobutane, diaminohexane, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, and dimer acid esters of tetra(hydroxyethyl)ethylenediamine polyethyleneimine; alicyclic amines such as isophorone diamine, methacenediamine, N-aminoethylpiperazine, bis(4-amino-3-methyldicyclohexyl)methane, bis(aminomethyl)cyclohexane, 3,9-bis(3-aminopropyl)2,4,8,10-tetraoxaspiro(5,5)undecane, norbornene diamine, bis(aminomethyl)norbornane, and bis(4-aminocyclohexyl)methane; Tetrachloro-p-xylylenediamine, m-xylylenediamine, p-xylylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-diaminoanisole, 2,4-toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4, Aromatic amines such as 4'-diaminodiphenyl sulfone, m-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2-dimethylaminomethyl)phenol, triethanolamine, methylbenzylamine, α-(m-aminophenyl)ethylamine, α-(p-aminophenyl)ethylamine, diaminodiethyldimethyldiphenylmethane, α,α'-bis(4-aminophenyl)-p-diisopropylbenzene, 3,3'-diisopropyl-4,4'-diaminodiphenylmethane, 3,3'-di-t-butyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-5,5'-dimethyl-4,4'-diaminodiphenylmethane, N,N-dimethylaniline, N,N-dimethylbenzylamine, and 2,4,6-tris(dimethylaminomethyl)phenol; 2-Phenyl-4,5-dihydroxymethylimidazole, 2-Phenyl-4-methylimidazole imidazole derivatives such as midazole, 2-ethyl-4-methylimidazole, 2,4-diethylimidazole, and 2-phenyl-4-methyl-5-hydroxyimidazole; Boron trifluoride-amine complexes such as boron trifluoride-monoethylamine, boron trifluoride-piperidine, boron trifluoride-triethylamine, and boron trifluoride-aniline complex; Examples of the compound include guanidine derivatives such as dicyandiamide, methyl guanidine, ethyl guanidine, propyl guanidine, butyl guanidine, dimethyl guanidine, trimethyl guanidine, phenyl guanidine, diphenyl guanidine, toluyl guanidine, 2,3-guanylurea, benzoyl dicyandiamide, 2,6-xylenyl biguanide, and phenyl biguanide; and polyolefin compounds having an amino group such as amine-modified polypropylene, amine-modified polyethylene, amine-modified polybutadiene, and amine-modified butadiene-acrylonitrile copolymer.

[0051] Examples of the amide compound include polyamidoamines having a primary amine and a secondary amine in the molecule, which are obtained by reacting a dimer (dimer acid) of linoleic acid or oleic acid with a polyamine such as diethylenetriamine or triethylenetetramine.

[0052] Examples of the curing accelerator include tertiary amines and their salts, imidazoles and their salts, urea compounds, phosphorus compounds, organic phosphine compounds and their salts, metal salts such as zinc octoate and tin octoate, compounds having a hydroxyl group such as phenols and alcohols, Lewis acids, and amine complex salts.

[0053] The amount of the curing accelerator added is preferably 0.01 to 20% by mass relative to 100% by mass of the total organic components of the curing agent, where the total organic components of the curing agent refer to organic components excluding inorganic fillers.

[0054] Additives that are used as needed include known additives such as silane coupling agents, leveling agents or defoamers, fillers, propellants, plasticizers, superplasticizers, wetting agents, flame retardants, viscosity modifiers, preservatives, stabilizers, and colorants. Such additives preferably include the following compounds, but are not limited thereto.

[0055] Examples of the silane coupling agent include trialkoxysilanes having a vinyl group, such as vinyltrimethoxysilane and vinyltriethoxysilane; trialkoxysilanes having an amino group, such as 3-aminopropyltriethoxysilane and N-(2-aminoethyl)3-aminopropyltrimethoxysilane; trialkoxysilanes having a glycidyl group, such as 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane; trialkoxysilanes having an isocyanate group, such as 3-isocyanatepropyltriethoxysilane; and trialkoxysilanes having a mercapto group, such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane. The amount of the silane coupling agent is preferably 0.05 to 10% by mass relative to 100% by mass of the total organic components of the curing agent.

[0056] Examples of the leveling agent include polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, aralkyl-modified polymethylalkylsiloxane, polyester-modified hydroxyl group-containing polydimethylsiloxane, polyetherester-modified hydroxyl group-containing polydimethylsiloxane, acrylic copolymers, methacrylic copolymers, polyether-modified polymethylalkylsiloxane, acrylic acid alkyl ester copolymers, methacrylic acid alkyl ester copolymers, and lecithin.

[0057] Examples of the defoaming agent include known ones such as silicone resin, silicone solution, copolymers of alkyl vinyl ether, alkyl acrylate, and alkyl methacrylate.

[0058] <Liquid epoxy resin (F)> The adhesive resin composition of the present invention contains an epoxy resin (F) as a main component. The liquid epoxy resin (F) is incorporated into a crosslinked structure during curing, thereby exerting excellent adhesive strength.

[0059] The liquid epoxy resin (F) is not particularly limited as long as it is a compound that is liquid at room temperature (23°C), but it is preferable that the liquid epoxy resin (F) has two or more epoxy groups in the molecule. In addition, the epoxy equivalent is preferably 200g / eq or less, more preferably 150 to 200g / eq. The epoxy equivalent of the liquid epoxy resin (F) can be determined by measuring in accordance with JIS K-7236.

[0060] Examples of the liquid epoxy resin (F) include 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 novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, glycidyl amine type epoxy resin, and epoxy resin having a butadiene structure, etc. Among these, bisphenol A type epoxy resin is more preferable because it is easily available and has good viscosity and adhesive strength.

[0061] The ratio of the total number of moles of all epoxy groups to the total number of moles of all primary and secondary amino groups (epoxy groups / active hydrogen groups of primary and secondary amino groups) contained in the adhesive resin composition is preferably in the range of 0.5 to 2.0, more preferably 0.6 to 1.5. When in the range of 0.5 to 2.0, no unreacted functional groups remain, and good crosslinking density is formed, thereby enabling excellent adhesive strength and flexibility to be exhibited.

[0062] <Other epoxy compounds> In addition to the liquid epoxy resin (F), any epoxy compound that can be cured by an amine curing agent as required can be used as the base resin, such as a solid epoxy resin.

[0063] <Adhesive resin composition> The adhesive resin composition of the present invention forms a highly flexible phase-separated structure and exhibits excellent impact resistance and bending resistance by mixing polyurethane urea resin (D), polyether polyamine (E), and liquid epoxy resin (F) in an appropriate range and crosslinking them. In particular, when these are mixed under conditions of no solvent or low volatile components, the formation of the phase-separated structure is promoted during the crosslinking reaction, and impact resistance and conformability are further improved, so it is preferable to use the composition under conditions of no solvent or low volatile components.

[0064] The adhesive resin composition of the present invention can be obtained by mixing the polyurethane urea resin (D), the polyether polyamine (E), and the liquid epoxy resin (F) by a known method.

[0065] ≪Cured product≫ The cured product of the present invention is obtained by curing the adhesive resin composition, and can be obtained by mixing the polyurethane urea resin (D), polyether polyamine (E), liquid epoxy resin (F), and other components by a known method and curing the mixture at a temperature of 5 to 150° C. Using the mixture at a temperature of 20 to 40° C., including the time of mixing, is preferred because it promotes the formation of a phase-separated structure and provides excellent impact resistance and conformability.

[0066] <Laminate> The laminate of the present invention has a layer made of the above-mentioned cured product on a substrate. The laminate can be formed by using a known lamination method. For example, an adhesive resin composition is applied to one side of a substrate to form an adhesive layer, and then another substrate is placed on the adhesive layer before curing treatment, and the adhesive layer is cured under a condition of 5 to 150°C, thereby obtaining a laminate having a substrate and a layer of a cured product made of the adhesive resin composition.

[0067] The substrate used in the laminate is not particularly limited. Suitable substrates include, for example, metals such as stainless steel, thermoplastic polymers such as polyethylene, polyurethane, polyacrylate, polycarbonate and copolymers thereof, thermosetting polymers such as vulcanized rubber, urea-formaldehyde foam, melamine resin, wood, carbon fiber reinforced plastic, glass fiber reinforced plastic and other fiber reinforced plastics.

[0068] The adhesive resin composition of the present invention can be used for bonding between various kinds of substrates. The substrates to be bonded may be the same or different. The thickness of the adhesive resin composition is preferably 0.1 μm to 30 mm.

[0069] The adhesive resin composition of the present invention has high adhesive strength and excellent impact resistance and conformability, and a laminate using the adhesive resin composition is useful as a building material, a structural member (floor material, exterior wall, etc.) for a ship, etc. EXAMPLES

[0070] The present invention will be described in more detail below with reference to examples, but the following examples are not intended to limit the scope of the invention. In the examples, "parts" means "parts by mass" and "%" means "% by mass" unless otherwise specified.

[0071] <Number average molecular weight (Mn)> The number average molecular weight of the polyurethane urea resin (D) was calculated by GPC (gel permeation chromatography) using standard polystyrene as a conversion value. The measurement was performed using ACQUITY UPLC (Waters Corporation), an N,N-dimethylformamide solution of 3 mM triethylamine and 10 mM LiBr as an eluent, three TSKgel SuperHM-M (Tosoh Corporation) columns connected in series, and conditions were: flow rate 0.6 mL / min, injection volume 10 μL, and column temperature 40°C.

[0072] <Amine value> The amine value was measured in accordance with JIS K-7237.

[0073] The abbreviations for compounds used in this specification are shown below. <Polyol (A)> P-2000: Bifunctional polypropylene glycol, number average molecular weight 2,000, manufactured by ADEKA Corporation C-1090: Bifunctional polycarbonate polyol, number average molecular weight 1,000, manufactured by Kuraray Co., Ltd. <Polyisocyanate (B)> IPDI: Isophorone diisocyanate ·MDI: Diphenylmethane diisocyanate ·TODI: 3,3'-Dimethyl-4,4'-biphenylene diisocyanate <Polyamine (C)> IPDA: Isophoronediamine, number average molecular weight 222, amine value 506 mgKOH / g PRIAMINE 1075: Dimer diamine, number average molecular weight 550, amine value 205 mgKOH / g, manufactured by Cargill <Polyether polyamine (E)> D-400: Polyoxypropylenediamine, number average molecular weight 430, amine value 520 mgKOH / g, manufactured by HUNTSMAN D-2000: Polyoxypropylenediamine, number average molecular weight 2000, amine value 110 mgKOH / g, manufactured by HUNTSMAN T-403: Polyoxypropylenediamine, number average molecular weight 440, amine value 765 mgKOH / g, manufactured by HUNTSMAN T-3000: Polyoxypropylenediamine, number average molecular weight 3000, amine value 445 mgKOH / g, manufactured by HUNTSMAN D-230: Polyoxypropylenediamine, number average molecular weight 230, amine value 490mgKOH / g, manufactured by HUNTSMAN <Amine hardener> P-1: Polyurethane urea resin produced in Comparative Production Example 1: an organic component having a primary amino group P-2: Polyurethane urea resin produced in Comparative Production Example 2: an organic component having a primary amino group P-3: Polyurethane urea resin produced in Comparative Production Example 3: an organic component having a primary amino group P-4: Polyurethane urea resin produced in Comparative Production Example 4: an organic component having a primary amino group Triethylenetetramine: an organic component containing primary and secondary amino groups <Curing accelerator> Bis(dimethylaminomethyl)phenol: an organic component with a tertiary amino group <Liquid epoxy resin (F)> jER828: Bisphenol A type epoxy resin, epoxy equivalent 190g / eq, manufactured by Mitsubishi Chemical Corporation: organic component with epoxy group jER806: Bisphenol F type epoxy resin, epoxy equivalent 170g / eq, manufactured by Mitsubishi Chemical Corporation: organic component with epoxy group

[0074] (Production Example 1) In a dropping vessel equipped with a nitrogen gas inlet tube, a stirrer, a thermometer, and a reflux condenser, 46.6 parts of P-2000 and 22.7 parts of C-1090 as polyol (A), 20.2 parts of IPDI as polyisocyanate (B), and 0.01% of dibutyltin dilaurate as a catalyst based on the total mass of polyol (A) and polyisocyanate (B) were charged and uniformly stirred, and the mixture was stirred for 4.5 hours at 90°C under a nitrogen atmosphere to synthesize an isocyanate-terminated prepolymer, and then 50 parts of ethyl acetate were added to obtain an isocyanate-terminated prepolymer solution. Next, 10.5 parts of hexamethylenediamine and 50 parts of ethyl acetate were charged in another vessel equipped with a nitrogen gas inlet tube, a stirrer, a thermometer, and a reflux condenser, and the isocyanate-terminated prepolymer solution was dropped over 30 minutes while stirring uniformly at 40°C under a nitrogen atmosphere, and then the mixture was stirred and reacted for 1 hour to obtain a polyurethane urea resin solution having an amino group at the end. The solvent in the obtained polyurethane urea resin solution was removed under reduced pressure to obtain polyurethane urea resin (D-1). The end point of the reaction was confirmed by FT-IR based on the disappearance of the peak (around 2270 cm-1) derived from the isocyanate group. The obtained polyurethane urea resin (D-1) was an organic component having a primary amino group, and had a number average molecular weight of 3900 and an amine value of 50.9 mg KOH / g.

[0075] (Production Examples 2-3, Comparative Production Examples 1-3) The polyurethane urea resins (D-2 to 3, P-1 to 3) of Production Examples 2 to 3 and Comparative Production Examples 1 to 3 were obtained by the same operation as in Production Example 1, except that the compounds and blending compositions were changed as shown in Table 1. The obtained polyurethane urea resins (D-2 to 3, P-1 to 3) are organic components having a primary amino group, and their number average molecular weights and amine values ​​are as shown in Table 1.

[0076] [Table 1]

[0077] (Comparative Manufacturing Example 4) In a reaction vessel equipped with a nitrogen gas inlet tube, a stirrer, a thermometer, and a moisture trap, 865 g of commercially available polymerized fatty acid, 600 g of soybean oil fatty acid, 945 g of tetraethylenepentamine, and 0.3 g of iron powder were added and reacted at 200°C for 1 hour under a nitrogen atmosphere to obtain polyamidoamine (P-3). The amine value of the obtained polyamidoamine (P-4) was 390 mgKOH / g.

[0078] <Preparation of adhesive resin composition> [Example 1] The adhesive resin composition of Example 1 was prepared by mixing and degassing 3.6 parts of the polyurethane urea resin (D-1) obtained in Production Example 1, 3.6 parts of D-400 as the polyether polyamine (E), 0.4 parts of triethylenetetramine, 0.4 parts of bis(dimethylaminomethyl)phenol, and 10 parts of a liquid epoxy resin (F) at room temperature.

[0079] [Examples 2 to 10 and Comparative Examples 1 to 8] The adhesive resin compositions of Examples 2 to 10 and Comparative Examples 1 to 8 were prepared in the same manner as in Example 1, except that the blending compositions were changed as shown in Tables 2 and 3.

[0080] [Table 2]

[0081] [Table 3]

[0082] In Tables 2 and 3, "amino groups in (D) / amino groups in (E)" means the ratio (mol %) of the total molar number of primary amino groups and secondary amino groups in the polyurethane urea resin (D) to the total molar number of primary amino groups and secondary amino groups in the polyether polyamine (E) (100 mol %).

[0083] <Evaluation of adhesive resin composition> The adhesive resin compositions prepared in the Examples and Comparative Examples were subjected to the following tests. The results are shown in Table 2.

[0084] [Shear adhesive strength] Each adhesive resin composition was applied to a carbon fiber reinforced plastic substrate (length 100 mm, width 25 mm, thickness 2 mm) to a length of 10 mm, width 25 mm, and thickness of 0.1 mm, and then bonded to the carbon fiber reinforced plastic substrate and cured at 25°C for 7 days while being pressed to maintain a thickness of 0.1 mm to obtain a test specimen. The shear adhesive strength of the obtained test specimen was measured using a tensile tester at a tensile speed of 1 mm / min under conditions of a temperature of 25°C and a relative humidity of 50%, and evaluated according to the following criteria. (Evaluation Criteria) ○: Shear adhesive strength is 15 MPa or more (good) △: Shear adhesive strength is 10MPa or more and less than 15MPa (usable) ×: Shear adhesive strength is less than 10 MPa (not suitable for use)

[0085] [Impact resistance] Each adhesive resin composition was applied to a stainless steel substrate (length 100 mm, width 25 mm, thickness 2 mm) to a length of 10 mm, width 25 mm, and thickness of 0.1 mm, and then laminated to the stainless steel substrate, and cured at 25°C for 7 days while being pressed to maintain a thickness of 0.1 mm to obtain a test piece. Under conditions of temperature 25°C and relative humidity 50%, a DuPont impact test was used to apply impact to the adhesive portion of the obtained test piece in the thickness direction, and the number of impacts until breakage was measured and evaluated according to the following criteria. The DuPont impact test was performed by fixing both ends of the test piece so that the thickness direction of the stainless steel substrate was perpendicular to the ground, and the tip of a shot mold with a 1 / 2 inch round tip was grounded vertically to the adhesive portion of the fixed test piece, and a weight of 500 g was allowed to fall freely from a height of 10 cm onto the grounded shot mold. (Evaluation Criteria) ○: No breakage even after 100 tests (good) △: Breaks after 20 to 99 uses (usable) ×: Broken after 19 uses or less (cannot be used)

[0086] [Following ability (bending resistance)] Each resin composition adhesive was filled into a sheet-like mold of 2 mm in thickness, the surface was smoothed, and after curing at 25°C for 7 days, it was punched out with a No. 3 dumbbell mold to prepare a dumbbell-shaped test piece for evaluation. The test piece was folded in half at the center in the long axis direction, and then inverted around the bent part to the other side and folded in half again. This operation was repeated 100 times, and the condition of the bent part was visually observed to evaluate the conformability. (Evaluation Criteria) ○: No breakage even after 100 tests, and no cracks in the bent parts (good) △: No breakage after 100 tests, but cracks are observed at the bent parts (usable). ×: Breaks within 100 times (cannot be used)

[0087] <Overall rating> The adhesive resin compositions prepared in the Examples and Comparative Examples were comprehensively evaluated according to the following criteria. The evaluation results are shown in Tables 2 and 3.

[0088] (Overall evaluation criteria) ◯: All evaluation items are judged to be ◯ (good). △: All evaluation items are judged to be △ or higher. (Usable) ×: Any evaluation item was judged as ×. (Not available)

[0089] The adhesive resin composition of the present invention exhibited good results in all of adhesion, conformability, and impact resistance, whereas the adhesive resin composition of the comparative example exhibited results inferior to those of the examples in some or all of adhesion, conformability, and impact resistance.

Claims

1. The composition comprises a curing agent including a polyurethane urea resin (D) having an amino group at its terminal and a polyether polyamine (E), and a base material including a liquid epoxy resin (F), The polyurethane urea resin (D) having an amino group at its terminal is a reaction product of a polyol (A), a polyisocyanate (B), and a polyamine (C) (excluding a polyether polyamine (E)); And, the adhesive resin composition satisfies all of the following (i) to (iii): (i) The adhesive resin composition contains 15 to 40 mass% of a polyurethane urea resin (D) relative to a total of 100 mass% of the organic component having a primary amino group, the organic component having a secondary amino group, and the organic component having an epoxy group. (ii) The polyamine (C) has a number average molecular weight of less than 300. (iii) The total number of moles of primary amino groups and secondary amino groups in the polyurethane urea resin (D) is 3 to 40 mol %, relative to 100 mol %, which is the total number of moles of primary amino groups and secondary amino groups in the polyether polyamine (E).

2. The adhesive resin composition according to claim 1 , wherein the polyether polyamine (E) has a number average molecular weight of 300 or more.

3. A cured product comprising the adhesive resin composition according to claim 1 or 2.

4. A laminate having a layer formed from the cured product according to claim 3 on a substrate.

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