Hardened resin composition

Abstract

To provide a curable resin composition that firmly couples to surfaces of different types of materials.SOLUTION: A curable resin composition contains monomers represented by specific general formulas, namely, a base monomer A, a monomer B excellent in adhesiveness and pressure-sensitive adhesiveness, and a monomer C having a phosphate group. An adhesive or surface coating agent contains a polymer comprising the monomer A, the monomer B and the monomer C as constitutional units.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a curable resin composition containing a (meth)acrylic acid derivative as a monomer component, an adhesive containing a polymer containing the monomer component as a structural unit, and a surface coating agent containing a polymer containing the monomer component as a structural unit.

Background Art

[0002] Typified by weight reduction of vehicles, aircraft, etc., so-called multi-materialization, which combines materials of a plurality of different materials, is progressing. In multi-materialization, for example, by joining materials of different materials such as iron and aluminum alloy, metal and resin, metal and CFRP (Carbon Fiber Reinforced Plastics) (hereinafter referred to as joining of dissimilar materials), weight reduction and imparting functions that are difficult to achieve with a single material become possible. In the joining of dissimilar materials, since joining by welding may not be applicable in some cases, adhesive technologies capable of joining various types of materials have been studied.

[0003] Patent Document 1 discloses, as a curable resin composition, an adhesive, and a surface coating agent that strongly bond to the surfaces of various types of materials, a base monomer that is a (meth)acrylic acid derivative, a crosslinking agent, a polymerization initiator, and an adhesive monomer that is a (meth)acrylamide derivative having a hydroxyl group or B(OH)2 in a benzene ring, and an adhesive and a surface coating agent containing a polymer containing the base monomer and the adhesive monomer as structural units.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, the adhesive monomer described in Patent Document 1 still has room for improvement in adhesion to metals.

[0006] Therefore, an object of the present invention is to provide a curable resin composition, an adhesive, and a surface coating agent that strongly bond to various types of materials.

Means for Solving the Problems

[0007] That is, in the present invention, for example, the following [1] to

[17] etc. are provided.

[0008] [1] A curable resin composition containing monomer A, monomer B, and monomer C, wherein monomer A has the formula (I): [Chemical formula] [In the formula, R 1 represents a hydrogen atom or methyl; L 1 represents a single bond, -O-, -NH-, -NR 9 -, -NHC(O)O-, or -NHC(O)NH-; W 1 represents a single bond or C 1-20 alkylene; R 2 represents methyl, hydroxyl, optionally substituted C 1-6 alkoxy, optionally substituted phenyl, optionally substituted phenoxy, optionally substituted 5- or 6-membered heteroaryl, optionally substituted 3- to 8-membered saturated or partially unsaturated hydrocarbon ring group, optionally substituted 3- to 8-membered saturated or partially unsaturated heterocyclic group, or (meth)acryloyloxy; R 9 represents optionally substituted C 1-8 alkyl; Here, R 2 is optionally substituted C 1-6When it is alkoxy or optionally substituted phenoxy, W 1 is C 2-20 alkylene], and is one or more compounds represented by Monomer B is of formula (II):

Chemical formula

Chemical formula

[0009] [2] In formula (I), L 1 is -O-; in formula (II), L 2 is -O- or -NH-, and the curable resin composition according to [1] above.

[0010] [3] In formula (I), R 2 is methyl, optionally substituted C 1-6 alkoxy, optionally substituted 4- to 7-membered oxygen-containing saturated heterocyclic group, or optionally substituted phenyl, and the curable resin composition according to [1] or [2] above.

[0011] [4] In formula (II), L 2 is -NH-, W 2 is a single bond; L 3 is a single bond; W 3 is C 1-6 alkylene, and the curable resin composition according to any one of [1] to [3] above.

[0012] [5] In formula (II), L 2 is -O-, W 2 is optionally substituted C 1-20 alkylene, L 3 is -OC(O)-; W 3 is a single bond, and the curable resin composition according to any one of [1] to [3] above.

[0013] [6] The curable resin composition according to any one of [1] to [5] above, wherein monomer B contains a compound in which R 4 and / or R 5 is hydroxyl.

[0014] 〔7〕The curable resin composition according to any one of the above 〔1〕~〔6〕, wherein the content of monomer B in the composition is 0.1 to 10.0% by mass.

[0015] 〔8〕Monomer C is a compound represented by the formula (IIIa):

Chemical formula

[0016] 〔9〕The curable resin composition according to any one of the above 〔1〕~〔8〕, wherein monomer C contains a compound in which n is 1, a compound in which n is 2, and a compound in which n is 3 in the formula (IIIa).

[0017] 〔10〕The curable resin composition according to any one of the above 〔1〕~〔9〕, further containing a crosslinkable monomer.

[0018] 〔11〕The curable resin composition according to the above 〔10〕, wherein the crosslinkable monomer is a polyfunctional (meth) acrylate and / or a polyfunctional isocyanate.

[0019] 〔12〕An adhesive containing a polymer containing monomer A, monomer B, and monomer C as constituent units, Monomer A is a compound represented by the formula (I):

Chemical formula

Chemical formula

Chemical formula

[0020] 〔13〕Monomer C is of formula (IIIa):

Chemical formula

[0021] 〔14〕The adhesive according to the above 〔12〕 or 〔13〕, further containing a crosslinkable monomer.

[0022] 〔15〕A surface coating agent containing a polymer having monomer A, monomer B and monomer C as constituent units, wherein monomer A is of formula (I):

Chemical formula

Chemical formula

Chemical formula

[0023] 〔16〕Monomer C is of formula (IIIa):

Chemical formula

[0024] 〔17〕The surface coating agent according to the above 〔15〕 or 〔16〕, further containing a crosslinkable monomer.

Advantages of the Invention

[0025] According to the present disclosure, curable resin compositions, adhesives, and surface coating agents that strongly bond to various types of materials can be provided.

Embodiments for Carrying Out the Invention

[0026] In this specification, when indicating the number of carbons in the definition of a "substituent", it may be expressed as, for example, "C 1-6 ", etc. Specifically, the notation "C 1-6 alkyl" is synonymous with an alkyl group having 1 to 6 carbon atoms.

[0027] "C 1-20 alkylene" means a linear or branched divalent saturated hydrocarbon group having 1 to 20 carbon atoms. Preferably, it is "C 1-8 alkylene", more preferably, it is "C 1-6 alkylene", still more preferably, it is "C 1-4 alkylene". Specific examples of "C 1-20 alkylene" include, for example, methylene, ethylene, trimethylene, tetramethylene, hexamethylene, octamethylene, 1-methylmethylene, 1-ethylethylene, 1-propylethylene, 1-methylethylene, 2-methylethylene, 1-ethylethylene, etc.

[0028] "C 2-6 alkenylene" means a linear or branched divalent hydrocarbon group having 2 to 6 carbon atoms and having a double bond. Preferably, it is "C 2-4 alkylene". Specific examples of "C 2-6 alkenylene" include, for example, ethylenylene, propylenylene, butylenylene, pentalenylene, hexalenylene, 1-methylethynylenine, 2-methylethynylenine, 1-methylpropynylene, etc.

[0029] "C 1-8 alkyl" means a linear or branched saturated hydrocarbon group having 1 to 8 carbon atoms. Preferably, it is "C1-6 "alkyl", more preferably, "C 1-4 alkyl". "C 1-8 Specific examples of "C

[0030] "C 1-6 "alkoxy" means a substituent in which C 1-6 alkyl is bonded to an oxygen atom and is bonded to the parent molecule by the oxygen atom. The "C 1-6 alkyl" part of "alkoxy" is 1-6 synonymous with the above-mentioned "C 1-6 alkyl". Preferably, it is "C 1-4 alkoxy". Specific examples of "C 1-6 alkoxy" include, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy and the like.

[0031] Examples of "5- or 6-membered heteroaryl" include, for example, 5- or 6-membered monocyclic aromatic heterocyclic groups and the like. The group contains, as atoms constituting the ring, one or more (for example, 1 to 4) same or different heteroatoms selected from nitrogen atoms, sulfur atoms and oxygen atoms. Specific examples of "5- or 6-membered heteroaryl" include, for example, pyridyl, pyrimidyl, pyrazyl, pyridazyl, triazolyl, imidazolyl, pyrazolyl, triazoyl, tetrazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl and the like.

[0032] Examples of the "3- to 8-membered saturated or partially unsaturated hydrocarbon group" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopentenyl, cyclohexenyl, cyclohexadienyl, and the like.

[0033] Examples of the "3- to 8-membered saturated or partially unsaturated heterocyclic group" include monocyclic 3- to 8-membered saturated or partially unsaturated heterocyclic groups containing 1 to 3 identical or different heteroatoms selected from nitrogen atoms, oxygen atoms, and sulfur atoms as ring-constituting atoms. Preferred are 4- to 6-membered saturated or partially unsaturated heterocyclic groups, more preferably 4- to 6-membered saturated or partially unsaturated heterocyclic groups containing 1 to 2 oxygen atoms as ring-constituting atoms, and even more preferably 4- to 6-membered saturated heterocyclic groups containing 1 to 2 oxygen atoms as ring-constituting atoms. Specific examples of the "3- to 8-membered saturated or partially unsaturated heterocyclic group" include oxiranyl, oxetanyl, tetrahydrofuryl, dihydrofuryl, pyranyl, dihydropyranyl, tetrahydropyranyl, dioxanyl, dioxolanyl, oxazolidinyl, oxepanyl, oxecanyl, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, piperazinyl, azepanyl, azecanyl, morpholinyl, thiomorpholinyl, and the like. Oxetanyl, tetrahydrofuryl, tetrahydropyranyl, dioxanyl, and dioxolanyl are preferred, and tetrahydrofuryl and dioxolanyl are more preferred. The bond of the group may be to either a carbon atom or a nitrogen atom constituting the ring.

[0034] Examples of the "oxygen-containing saturated heterocyclic group having 3 to 8 members" include monocyclic saturated heterocyclic groups having 3 to 8 members containing 1 to 2 oxygen atoms and optionally 1 to 2 same or different atoms selected from nitrogen atoms and sulfur atoms. The oxygen atom, nitrogen atom, and sulfur atom are all atoms constituting the ring. An oxygen-containing saturated heterocyclic group having 4 to 6 members is preferred. Specifically, oxiranyl, oxetanyl, tetrahydrofuryl, tetrahydropyranyl, dioxanyl, dioxolanyl, oxazolidinyl, oxepanyl, oxecanyl, morpholinyl, etc. can be mentioned; oxetanyl, tetrahydrofuryl, tetrahydropyranyl, dioxanyl, and dioxolanyl are preferred; oxetanyl and tetrahydrofuryl are more preferred.

[0035] "Optionally substituted C 1-8 alkyl", "optionally substituted C 1-6 alkoxy", and "optionally substituted C 1-20 alkylene" or "optionally substituted C 3-20 alkylene" include substituents such as hydroxyl, halogen atom, C 1-6 alkoxy, etc.

[0036] Examples of the substituents in "optionally substituted phenyl", "optionally substituted phenoxy", "optionally substituted 5- or 6-membered heteroaryl", "optionally substituted 3- to 8-membered saturated or partially unsaturated hydrocarbon ring group", and "optionally substituted 3- to 8-membered saturated or partially unsaturated heterocyclic group" include, for example, hydroxyl, amino, halogen atom, C 1-6 alkyl, C 1-6 alkoxy, etc.

[0037] Specific examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0038] In this specification, "(meth)acryloyloxy" shall include a methacryloyloxy group and an acryloyloxy group.

[0039] In this specification, when a numerical range is indicated using "~", it is intended to include the numerical values at both ends thereof.

[0040] <Monomer component> The curable resin composition according to one embodiment of the present disclosure is a composition that cures to bond to a substrate. The curable resin composition according to one embodiment of the present disclosure is characterized by containing a first monomer (monomer A), a second monomer (monomer B), and a third monomer (monomer C).

[0041] (Monomer A) The curable resin composition according to one embodiment of the present disclosure contains, as the first monomer (monomer A), the following formula (I): [Chemical formula] [In the formula, R 1 represents a hydrogen atom or methyl; L 1 represents a single bond, -O-, -NH-, -NR 9 -, -NHC(O)O-, or -NHC(O)NH-; W 1 represents a single bond or C 1-20 alkylene; R 2 represents methyl, hydroxyl, optionally substituted C 1-6 alkoxy, optionally substituted phenyl, optionally substituted phenoxy, optionally substituted 5- or 6-membered heteroaryl, optionally substituted 3- to 8-membered saturated or partially unsaturated hydrocarbon ring group, optionally substituted 3- to 8-membered saturated or partially unsaturated heterocyclic group, or (meth)acryloyloxy; R 9 represents optionally substituted C 1-8 alkyl; wherein when R 2 is optionally substituted C 1-6 alkoxy or optionally substituted phenoxy, then W 1 is C 2-20 alkylene] and contains one or more compounds represented thereby.

[0042] L 1 is preferably a single bond or -O-; more preferably -O-. L 1 The compound of formula (I) in which L is -O- is preferred because it has good compatibility with monomer B described below, which may be included in the curable resin composition according to an embodiment of the present disclosure.

[0043] W 1 is preferably a single bond or C 1-6 alkylene; more preferably a single bond or C 1-4 alkylene. Further, W 1 in another embodiment, C 1-8 alkylene, C 1-6 alkylene, C 2-6 alkylene, C 1-4 alkylene, C 2-4 alkylene and the like can be mentioned.

[0044] R 2 is preferably (1) methyl, (2) hydroxyl, (3) optionally substituted C 1-6 alkoxy, for example, C alkoxy optionally substituted with hydroxyl or C 1-6 alkoxy, 1-6 alkoxy, (4) an optionally substituted 3- to 8-membered saturated heterocyclic group, for example, a 4- to 7-membered oxygen-containing saturated heterocyclic group optionally substituted with one or more identical or different groups selected from the group consisting of a halogen atom, hydroxyl, C 1-6 alkyl, and C 1-6 alkoxy (for example, oxetanyl, tetrahydrofuryl, tetrahydropyranyl, dioxanyl, dioxolanyl, oxazolidinyl, oxepanyl, morpholinyl, etc.), (5) optionally substituted phenyl, or (6) (meth)acryloyloxy; more preferably (1) methyl, (2) hydroxyl, (3) C1-4 alkoxy, (4) a 4- to 7-membered oxygen-containing saturated heterocyclic group optionally substituted with 1 to 4 C 1-6 alkyl groups, or (5) phenyl optionally substituted; More preferably, it is C 1-4 alkoxy, a 4- to 6-membered oxygen-containing saturated heterocyclic group optionally substituted with 1 to 4 C 1-6 alkyl groups, or phenyl.

[0045] From the viewpoint of adhesion, it is also possible to select monomer A used according to the material of the target substrate. For organic substrates, it is preferable to use monomer A which is a 3- to 8-membered oxygen-containing saturated heterocyclic group in which R 2 is optionally substituted. For inorganic substrates, by using monomer A in which R 2 is hydroxyl, the effect of adding monomer B tends to be more easily obtained. Further, from the viewpoint of adhesiveness, as monomer A, it is more preferable to use a combination of a compound in which R 2 is hydroxyl and a compound in which R 2 is optionally substituted C 1-6 alkoxy.

[0046] R 2 When using in combination monomer A in which is hydroxyl and monomer A in which R 2 is optionally substituted C 1-6 alkoxy or optionally substituted phenyl, the mass ratio of monomer A in which R 2 is hydroxyl to monomer A in which R 2 is optionally substituted C 1-6 alkoxy or optionally substituted phenyl [monomer A in which R 2 is hydroxyl: monomer A in which R 2 is optionally substituted C 1-6 alkoxy or optionally substituted phenyl] is R 2 is optionally substituted C 1-6From the viewpoint that the properties of monomer A, which is alkoxy or optionally substituted phenyl, are exhibited in adhesion, tackiness, and adhesiveness, 0.5:99.5 to 20:80 is preferable, and 1:99 to 10:90 is more preferable.

[0047] From the viewpoint of the good solubility of monomer B, in formula (I), L 1 is -O-, and R 2 is methyl, hydroxyl, optionally substituted C 1-6 It is preferable to use monomer A which is alkoxy, an optionally substituted 4- to 7-membered oxygen-containing saturated heterocyclic group, or optionally substituted phenyl. From the viewpoint that the addition effect of monomer C described later is easily obtained, in formula (I), L 1 is -O-, and R 2 is methyl, optionally substituted C 1-6 It is preferable to use monomer A which is alkoxy, an optionally substituted 4- to 7-membered oxygen-containing saturated heterocyclic group, or optionally substituted phenyl.

[0048] As another aspect of monomer A, in formula (I), L 1 and W 1 are single bonds, and R 2 is hydroxyl, or L 1 is -O-, W 1 is C 2-20 alkylene, and R 2 is hydroxyl, optionally substituted C 1-6 alkoxy, or L 1 is -O-, W 1 is C 1-8 alkylene, and R 2 is an optionally substituted 3- to 8-membered saturated or partially unsaturated heterocyclic group, or optionally substituted phenyl, or L 1 is -O-, W 1 is a single bond, or C 1-6 alkylene, and R 2 is preferably a compound containing one or more methyls; L 1 is -O-, W 1 is C2-8 is an alkylene, and R 2 is hydroxyl or an optionally substituted C 1-4 alkoxy, or L 1 is -O-, and W 1 is C 1-4 is an alkylene, and R 2 is an optionally substituted 4- to 6-membered oxygen-containing saturated heterocyclic group or an optionally substituted phenyl, or L 1 is -O-, and W 1 is a single bond or C 1-4 is an alkylene, and R 2 More preferably, it contains one or more compounds in which R is methyl.

[0049] The content of monomer A relative to the total amount of the monomers is not particularly limited, and the balance excluding the following monomer B, crosslinkable monomer, and other monomers can be used as the content, but 50% by mass or more is preferable, 60% by mass or more is more preferable, and 70% by mass or more is even more preferable. Further, when used as an adhesive or a surface coating agent without diluting the curable resin composition, the content of monomer A is preferably 75% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more. By setting the content of monomer A to 75% by mass or more, 80% by mass or more, 90% by mass or more, 93% by mass or more, the characteristics of monomer A can be exhibited. The upper limit of the content of monomer A relative to the total amount of the monomers is preferably less than 90% by mass, more preferably 80% or less, in order to ensure the content of monomer B. Further, when used as an adhesive or a surface coating agent without diluting the curable resin composition, it is preferably 99% by mass or less, more preferably 98% by mass or less, and even more preferably 97% by mass or less. Examples of the characteristics of monomer A include flexibility.

[0050] Monomer A is synthesized by a method combining known compounds and known synthesis methods. Further, a commercially available product may be used as monomer A.

[0051] (Monomer B) The curable resin composition according to one embodiment of the present disclosure contains, as a second monomer (monomer B), a compound represented by the formula (II): [Chemical formula] [In the formula, R 3 represents a hydrogen atom or methyl; L 2 represents -O-, -NH-, -NHC(O)O-, or -NHC(O)NH-; W 2 represents a single bond or an optionally substituted C 1-20 alkylene; L 3 represents a single bond, -O-, -CH(OH)-, -NH-, -NHC(O)-, -NHC(O)O-, -NHC(O)NH-, -C(O)O-, -C(O)NH-, -OC(O)-, -OC(O)NH-, or -OC(O)O-; W 3 represents a single bond, C 1-6 alkylene, or C 2-6 alkenylene; R 4 and R 5 each independently represent a hydrogen atom, a hydroxyl group, or B(OH)2; provided that R 4 and R 5 are not both hydrogen atoms] and contains one or more compounds represented by the formula.

[0052] As described above, monomer B has a hydroxyl group or B(OH)2 on the benzene ring. In the curable resin composition, the adhesive, and the surface coating agent, which are one embodiment of the present disclosure, it is considered that the orientation of these groups on the adhesive surface is one factor that enables stronger bonding to a wider variety of materials.

[0053] L 2 is preferably -O- or -NH-; more preferably -NH-. The compound of formula (II) in which L 2 is -NH- is preferred because it forms an adhesive or a surface coating agent that is less likely to hydrolyze after the curable resin composition has cured.

[0054] W 2is preferably a single bond or an optionally substituted C 1-8 alkylene; more preferably, a single bond or an optionally substituted C 1-4 alkylene; even more preferably, a single bond, C 1-2 alkylene, or C substituted with hydroxyl 2-4 alkylene. Also, when both R 4 and R 5 are hydroxyl, W 2 is preferably ethylene or trimethylene substituted with hydroxyl, and when R 4 or R 5 is B(OH)2, W 2 is preferably a single bond.

[0055] L 3 is preferably a single bond, -O-, -NHC(O)O-, -NHC(O)NH-, or -OC(O)-; more preferably a single bond or -OC(O)-.

[0056] W 3 is preferably a single bond.

[0057] R 4 and R 5 are both preferably hydroxyl. Also, in another aspect, it is preferable from the viewpoint of improving adhesiveness that R 4 is B(OH)2 and R 5 is a hydrogen atom, or R 4 is a hydrogen atom and R 5 is B(OH)2.

[0058] As one aspect of monomer B, it includes a compound in which R 4 and / or R 5 is B(OH)2. Also, in another aspect, it includes a compound in which R 4 and / or R 5 is hydroxyl. Among them, it is preferable that R 4 is B(OH)2 and R 5 is a hydrogen atom, or R 4is a hydrogen atom, and R 5 is B(OH)2, and the compound (monomer B-a), and R 4 as well as R 5 is a compound (monomer B-b) in which both are hydroxyl groups, which is a preferred embodiment.

[0059] The amounts of monomer B-a and monomer B-b can be appropriately changed according to the adhesiveness between the respective materials. Either only one of monomer B-a and monomer B-b may be used, or monomer B-a and monomer B-b may be used in combination. When monomer B-a and monomer B-b are used in combination, the mass ratio [monomer B-a / monomer B-b] of the content of monomer B-a to the content of monomer B-b can be, for example, in the range of 0.01 to 100, 0.05 to 20, 0.1 to 10, 0.2 to 5.0, 0.4 to 2.5, 0.5 to 2.0, 0.7 to 1.4.

[0060] From the viewpoint that monomer B tends to show adhesiveness to a wider variety of materials without inhibiting the adhesion characteristics of monomer C, it is more preferable to include monomer B-a and monomer B-b, and it is even more preferable to consist only of monomer B-a and monomer B-b.

[0061] Monomer B is synthesized by a method combining known compounds and known synthesis methods. Also, commercially available products may be used as monomer B.

[0062] Among monomers B, formula (IIa):

Chemical formula

[0063] 1. Dehydration condensation reaction between a catechol group-containing carboxylic acid compound and a hydroxyalkyl (meth) acrylate This reaction can be applied, for example, when W in formula (IIa) 2a is an unsubstituted alkylene. Specifically, (E)-4-((3-(3,4-dihydroxyphenyl)acryloyl)oxy)butyl acrylate can be synthesized by the dehydration condensation reaction of (E)-3-(3,4-dihydroxyphenyl)acrylic acid and 4-hydroxybutyl acrylate. The synthesis method by dehydration condensation can synthesize the target product under relatively mild conditions, so the workability is good. The method of dehydration condensation is not particularly limited.

[0064] 2. Ring-opening reaction of glycidyl group-containing (meth) acrylate with a catechol group-containing carboxylic acid compound This reaction can be applied, for example, when W in formula (IIa) 2a is an alkylene substituted with a hydroxyl group. Specifically, (E)-3-((3-(3,4-dihydroxyphenyl)acryloyl)oxy)-2-hydroxypropyl methacrylate can be synthesized by the ring-opening reaction of glycidyl methacrylate with 3-(3,4-dihydroxyphenyl)acrylic acid. In this ring-opening reaction, a plurality of by-products such as compounds obtained by the reaction of the glycidyl group with any hydroxyl group of the catechol group can be generated. As long as the obtained monomer B can be contained in an amount that can exhibit its characteristics, it can also be used in a state of a mixture with by-products without special purification or isolation. The synthesis method by ring-opening reaction can synthesize the target product at a relatively low cost compared to other methods, so the productivity is good. The method of ring-opening reaction is not particularly limited.

[0065] 3. Condensation reaction of a carboxylic acid group-containing (meth) acrylate with a catechol group-containing aliphatic alcohol compound This reaction can be applied, for example, when W in formula (IIa) 2a is an alkylene substituted with a carboxylic acid group. Specifically, 2 - ((3,4 - dihydroxybenzyl)oxy) - 2 - oxyethyl methacrylate can be synthesized by dehydration condensation of hydroxycarbonylmethyl methacrylate obtained by a substitution reaction of sodium methacrylate or the like with monochloroacetic acid and 3,4 - dihydroxybenzyl alcohol.

[0066] 4. Substitution reaction of a catechol group-containing carboxylic acid compound with an alkyl (meth) acrylate having a leaving group under basic conditions As yet another example, a method of synthesizing (E) - 4 - ((3 - (3,4 - dihydroxyphenyl)acryloyl)oxy)butyl acrylate by a substitution reaction of 3 - (3,4 - dihydroxyphenyl)acrylic acid and 4 - bromobutyl (meth) acrylate in the presence of triethylamine can be mentioned. The method of the substitution reaction is not particularly limited.

[0067] When producing the monomer B represented by formula (II) or formula (IIa), by-products may be generated as described above. However, as long as the monomer B can be contained in an amount that can exhibit the characteristics of the monomer B, it can also be used in a state of a mixture with by-products without purifying and isolating the monomer B.

[0068] W 2a is preferably an optionally substituted C 3-8 alkylene; more preferably an optionally substituted C 3-6 alkylene; still more preferably an unsubstituted C 3-4 alkylene or a C 3-4 alkylene substituted with a hydroxyl group.

[0069] L2a is preferably -O-, -C(O)O-, or -OC(O)-; more preferably -OC(O)-.

[0070] W 2a is preferably C 2-4 alkenylene; more preferably ethenyl.

[0071] R 3a and R 4a are both preferably hydroxyl.

[0072] The content of monomer B in the composition is not particularly limited, but is preferably more than 2.0% by mass and less than 50.0% by mass, more preferably 5.0 to 40.0% by mass, and even more preferably 10.0 to 30.0% by mass. By setting the content of monomer B in the composition to more than 10.0% by mass, a curable resin composition with a high content of monomer B can be circulated and can be diluted and used as appropriate according to the application. The upper limit of the content of monomer B in the composition is not particularly limited because it depends largely on the solubility of monomer B in monomer A, but is preferably less than 50.0% by mass, more preferably 40.0% by mass or less. Also, when using the curable resin composition without dilution, from the viewpoints of both the function exhibition of monomer B and cost, the content of monomer B in the composition is preferably 0.10 to 10.0% by mass, more preferably 0.50 to 5.0% by mass. By setting the content of monomer B in the composition to 0.10% by mass or more, it is possible to obtain a curable resin composition, an adhesive, and a surface coating agent that can strongly bond to various types of materials.

[0073] (Monomer C) The curable resin composition according to an embodiment of the present disclosure includes, as a third monomer (monomer C),

Chemical formula

[0074] As described above, monomer C has a phosphate group. The curable resin composition according to an embodiment of the present disclosure, and the adhesives and surface coating agents described later, by using monomer C, the adhesiveness to more materials is improved. Furthermore, monomer C also has the effect of improving the solubility of monomer B in the base monomer (monomer A). Thereby, the amount of monomer B excellent in adhesiveness and tackiness can be increased, and it can be made more useful as an adhesive and a surface coating agent. Furthermore, as the curable resin composition according to an embodiment of the present disclosure, the content of monomer B can be increased in the distribution stage, and it can be diluted and used with various diluents etc. according to the application at the time of use, and the distribution cost can be suppressed. Dopamine acrylamide (N-(3,4-dihydroxyphenethyl)acrylamide), which is a typical example of monomer B, does not have very high solubility in the base monomer, and it has been difficult to increase the concentration in the composition. On the other hand, by using monomer C according to the present disclosure in combination, it has been found that the solubility of monomer B in various base monomers (monomer A), particularly in a lipophilic monomer A, is improved. When X-ray crystal structure analysis was performed on dopamine acrylamide, it was found that the hydrogen bond between the hydrogen of catechol-OH and the oxygen of the amide group CO was strong. And dopamine acrylamide shows high solubility in alcohols such as methanol that can break such hydrogen bonds, N,N-dimethylformamide, dimethyl sulfoxide, etc. Monomer C, which is a phosphoric acid-based monomer, is also highly polar and can break the hydrogen bond between these hard dopamine acrylamide molecules in the same manner as the above solvents. Therefore, it is presumed that when monomer C is added, the solubility of monomer B in monomer A is improved.

[0075] W 4a is preferably C 2-16 alkylene, and W 4b is preferably C 1-8 alkylene, more preferably C 1-6 alkylene, still more preferably C 1-4 alkylene, particularly preferably C 2-4An alkylene, most preferably ethylene.

[0076] In the above formula (IIIb), in the formula, R 6b represents methyl; W 4b is C 2-8 represents alkylene; R 7b , R 8b both represent C 1-4 alkoxy compounds are preferred, R 6b represents methyl; W 4b is C 2-4 represents alkylene; R 7b , R 8b both represent C 1-2 alkoxy compounds are more preferred.

[0077] In the above formula (IIIc), in the formula, R 6c represents hydrogen; R 7c , R 8c both represent hydroxyl compounds are preferred, R 6b is hydrogen; R 7c , R 8c both represent C 1-2 alkoxy compounds are more preferred.

[0078] In one embodiment of the present disclosure, monomer C more preferably contains one or more compounds represented by the above formula (IIIa). The compound represented by formula (IIIa) can be obtained as a mixture of a compound with n = 1, a compound with n = 2, and a compound with n = 3 during synthesis, and this mixture can be used. For example, commercially available 2-(phosphonooxy)ethyl methacrylate (trade name: MR-200, manufactured by Daihachi Chemical Industry Co., Ltd.) and 10-(phosphonooxy)decyl methacrylate (trade name: 10-MDP, manufactured by Fujifilm Wako Pure Chemical Corporation) are also mixtures of a compound with n = 1, a compound with n = 2, and a compound with n = 3.

[0079] The content of monomer C relative to the total amount of monomers is not particularly limited, but is preferably 0.10 to 50.0% by mass, more preferably 0.10 to 40.0% by mass, and even more preferably 0.20 to 35.0% by mass. By setting the content of monomer C to 0.10% by mass or more relative to the total amount of monomers, the solubility of monomer B in monomer A can be improved, and with an amount of use similar to that of monomer B, a curable resin composition, an adhesive, and a surface coating agent that can firmly bond to a wider variety of materials while maintaining the adhesiveness and bonding properties of monomer B can be obtained. Also, when the curable resin composition is used without dilution, considering both the exertion of the function of the monomer C and cost, 、0 .10 to 10.0% by mass is preferred, and 0.50 to 5.0% by mass is more preferred. However, when the properties of monomer C are further required, monomer C can also be used in excess of monomer B .

[0080] Monomer C is synthesized by a method combining known compounds and known synthesis methods. Also, commercially available products may be used as monomer C.

[0081] (Crosslinkable monomer) In the curable resin composition according to one embodiment of the present disclosure, a crosslinkable monomer may be blended as long as it does not inhibit the object of the present disclosure. The crosslinkable monomer is a monomer having at least two polymerizable functional groups. Examples of the crosslinkable monomer include polyfunctional (meth)acrylamides having two or more (preferably two) (meth)acryloyl groups such as methylenebisacrylamide and methylenebismethacrylamide; ethylene di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, etc., polyfunctional (meth)acrylates having two or more (preferably two or three) (meth)acryloyl groups; polyfunctional isocyanates having two or more (preferably two or three) isocyanate groups such as hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane-4,4'-diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, lysine triisocyanate, and methylene triphenylene triisocyanate; polyfunctional amines having two or more (preferably two or three) carbon-carbon double bonds such as diallylamine and triallylamine; and polyfunctional monomers such as aromatic compounds having two or more (preferably two or three) carbon-carbon double bonds such as divinylbenzene and diallylbenzene. These crosslinkable monomers may be used alone or in combination of two or more.

[0082] The content of the crosslinkable monomer relative to the total amount of the monomers is preferably 0.10 to 20% by mass, more preferably 0.50 to 15% by mass, and even more preferably 1.0 to 10% by mass. By setting the content of the crosslinkable monomer relative to the total amount of the monomers to 0.10% by mass or more, 0.50% by mass or more, and 1.0% by mass or more, it is possible to obtain a curable resin composition, an adhesive, and a surface coating agent that bind more firmly to various types of materials. Further, by setting the content of the crosslinkable monomer relative to the total amount of the monomers to 20% by mass or less, 15% by mass or less, and 10% by mass or less, it is possible to obtain a curable resin composition, an adhesive, and a surface coating agent that bind firmly to various types of materials.

[0083] (Other monomers) In the curable resin composition according to one embodiment of the present disclosure, other monomers other than the above-described monomer A, monomer B, monomer C, and crosslinkable monomer may be blended within a range that does not inhibit the object of the present disclosure. Examples of other monomers include, but are not limited to, acrylates and methacrylates not included in the above formulas (I), (II), (IIIa), (IIIb), and (IIIc). However, as the monomer used in the curable resin composition according to one embodiment of the present disclosure, it is preferably free of alkyl-(meth)acrylate having 10 or more carbon atoms. In the present specification, "alkyl-(meth)acrylate having 10 or more carbon atoms" means an alkyl ester of (meth)acrylic acid, and the alkyl group constituting the alkyl ester part is a linear or branched alkyl group having 10 or more carbon atoms. That is, the carbon atoms constituting the (meth)acrylic acid part are not included in the above carbon number.

[0084] The content of other monomers relative to the total amount of the monomers is not particularly limited, and the content can be the remainder excluding monomer A, monomer B, monomer C, and the crosslinkable monomer.

[0085] The above monomer components (monomer A, monomer B, monomer C, crosslinkable monomer, and other monomers) may be used alone or in combination of two or more.

[0086] The curable resin composition according to an embodiment of the present disclosure may further contain a solvent and additives generally added to an adhesive or an adhesive, within a range that does not inhibit the object of the present disclosure, in addition to the above monomer components (monomer A, monomer B, monomer C, crosslinkable monomer, and other monomers). Examples of the additives include silane coupling agents, crosslinking agents, polymerization initiators, ultraviolet absorbers, tackifiers, adhesion promoters, anti-aging agents, plasticizers, softeners, dyes, pigments, and fillers. Among them, it is preferable to contain a polymerization initiator described later.

[0087] <Adhesive and its manufacturing method> The adhesive according to an embodiment of the present disclosure refers to a material that binds to both one substrate and the other substrate and prevents the one substrate from moving relative to the other substrate. Preventing the other substrate from moving relative to one substrate includes not only the case where the one substrate does not move at all as seen from the other substrate, but also fixing the one substrate so as to allow it to move within a certain range relative to the other substrate. In other words, the adhesive according to an embodiment of the present disclosure does not necessarily need to be completely cured. The certain range may be determined according to the location where the two substrates are arranged, the purpose of use, etc. So to speak, the adhesive may be an adhesive having an adhesive property that is difficult to peel off, or an adhesive having a softness similar to that of an adhesive. The adhesive may be used in place of joining methods such as fastening with bolts or welding from the viewpoints of weight reduction and simplification of work in joints where strength is not required. In addition, the adhesive having softness is suitably used for applications where vibration resistance is required.

[0088] The adhesive according to this embodiment contains a polymer (copolymer) having monomer A and monomer B as constituent units, and preferably further contains a crosslinkable monomer as a constituent unit. Further, if necessary, it may further contain a solvent, a silane coupling agent, a crosslinking agent, a polymerization initiator, an ultraviolet absorber, a tackifier, an adhesion promoter, an antioxidant, a plasticizer, a softening agent, a dye, a pigment, and an additive generally added to an adhesive or an adhesive, such as a filler.

[0089] The adhesive according to one embodiment of the present disclosure has strong adhesiveness to substrates of various materials. Examples of the materials of the substrates that can be joined by the adhesive according to one embodiment of the present disclosure include inorganic materials such as glass, hydroxyapatite, titanium oxide, zinc oxide, iron oxide, indium tin oxide (ITO), and a molybdenum-aluminum-molybdenum laminated structure (MAM); metal materials such as aluminum (Al), copper (Cu), iron (Fe), platinum (Pt), silver (Ag), zinc (Zn), tin (Sn), titanium (Ti), and alloys thereof; organic materials such as PVC: polyvinyl chloride, PC: polycarbonate, polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), acrylonitrile-butadiene-styrene copolymer resin (ABS), polytetrafluoroethylene (PTFE), polyimide (PI), and fiber-reinforced plastic (FRP). Further, since the adhesive according to one embodiment of the present disclosure has good adhesiveness to substrates of various materials, it is suitable as an adhesive for joining substrates of different materials. Of course, the adhesive according to one embodiment of the present disclosure may be used to join substrates of the same material.

[0090] Furthermore, the adhesive according to one embodiment of the present disclosure is also intended for use in joining a surface coating agent such as a so-called undercoat paint, a middle coat paint, a primer, etc. to a substrate.

[0091] The shapes of the substrates fixed by the adhesive according to an embodiment of the present disclosure are not particularly limited. As an example of the shape of the substrate, it can be mentioned that the shapes of one and the other are any of the shapes selected from a plate shape, a sheet shape, a rod shape, etc.

[0092] The polymer contained in the adhesive can be obtained by polymerizing monomer A, monomer B, monomer C, and a crosslinkable monomer. The polymerization method is not particularly limited, and examples thereof include bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, etc. In particular, from the viewpoints of productivity and handleability, etc., bulk polymerization and solution polymerization are preferred, and bulk polymerization is more preferred.

[0093] As the solvent for polymerizing the monomer component by the solution polymerization method, a non-aqueous organic solvent is preferred from the viewpoints of productivity and handleability, etc. Examples of the non-aqueous organic solvent include hydrocarbon-based organic solvents such as hexane, heptane, octane, isooctane, decane, and liquid paraffin; ether-based organic solvents such as dimethyl ether, diethyl ether, and tetrahydrofuran; ketone-based organic solvents such as acetone and methyl ethyl ketone; ester-based organic solvents such as methyl acetate, ethyl acetate, and butyl acetate; chloride-based organic solvents such as methylene chloride, chloroform, and carbon tetrachloride; dimethylformamide, diethylformamide, dimethyl sulfoxide, dioxane, etc. These organic solvents may be used alone or in combination of two or more. The amount of the solvent is usually about 100 to 1000 parts by mass per 100 parts by mass of the monomer component, but is not limited to this range.

[0094] When polymerizing the monomer component, a polymerization initiator can be used. Examples of the polymerization initiator include photoinitiators, thermal initiators, etc. Among them, a photoinitiator is preferred from the viewpoint of not leaving a thermal history in the adhesive.

[0095] Examples of the photoinitiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,1'-biimidazole, 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(p-methoxyphenylvinyl)-1,3,5-triazine, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphate, 4,4'-di-tert-butyldiphenyliodonium tetrafluoroborate, 4-diethylaminophenylbenzenediazonium hexafluorophosphate, benzoin, 2-hydroxy-2-methyl-1-phenylpropan-2-one, benzophenone, thioxanthone, 2,4,6-trimethylbenzoyldiphenylacylphosphine oxide (TPO), triphenylbutylborate tetraethylammonium, diphenyl-4-phenylthiophenylsulfonium hexafluorophosphate, 2,2-dimethoxy-1,2-diphenylethane-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 1,2-octanedione, 1-[4-(phenylthio)-2-(o-benzoyloxime)], bis(η5-2,4-cyclopentadien-1-yl)bis[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyltitanium] and other free radical photoinitiators; 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(p-methoxyphenylvinyl)-1,3,5-triazine, diphenyliodonium tetrafluoroborate, 4,4'-di-tert-butyldiphenyliodonium tetrafluoroborate, 4-diethylaminophenylbenzenediazonium hexafluorophosphate, diphenyl-4-phenylthiophenylsulfonium hexafluorophosphate and other cationic ring-opening photoinitiators. These photoinitiators may be used alone or in combination of two or more thereof.

[0096] Examples of the thermal polymerization initiator include azo polymerization initiators such as dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobisisobutyronitrile (AIBN), dimethyl 2,2'-azobisisobutyrate, and azobisdimethylvaleronitrile; peroxide polymerization initiators such as benzoyl peroxide, potassium persulfate, and ammonium persulfate. These thermal polymerization initiators may be used alone or in combination of two or more thereof.

[0097] The addition amount of the polymerization initiator is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and even more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the monomer component.

[0098] The order of blending each monomer when producing the adhesive by polymerizing each monomer is not particularly limited. As an example, it is possible to produce an adhesive by blending monomer A, monomer B, and a crosslinkable monomer and then polymerizing each monomer. As another example, after blending monomer A and monomer B, both monomers are polymerized to produce a first polymer, and then the first polymer and the crosslinkable monomer are blended to produce a second polymer (adhesive) in which the first polymer is crosslinked by the crosslinkable monomer.

[0099] <Surface coating agent> The surface coating agent according to an embodiment of the present disclosure refers to a material that binds to a substrate and cures to protect the surface of the substrate. An example of the surface coating agent is a paint. In addition to the above-described various materials, the substrate also includes an undercoat paint, a midcoat paint, a primer, and the like.

[0100] The surface coating agent according to one embodiment of the present disclosure contains a polymer (copolymer) having monomer A and monomer B as constituent units, similar to the adhesive according to one embodiment of the present disclosure described above, and preferably further contains a crosslinkable monomer as a constituent unit. So to speak, the curable resin composition which is one embodiment of the present disclosure is a cured product cured on the surface of a base material, and the surface of the cured product on the base material side is bonded to the base material, and the other surface (typically the opposite surface of the base material) is exposed. Therefore, since the basic configuration and manufacturing method are the same as those of the adhesive according to one embodiment of the above-described invention, the description thereof is omitted.

[0101] The adhesive and the surface coating agent according to one embodiment of the present disclosure described above are considered to bond more firmly to the base material by exhibiting at least one of adhesion, tackiness, and adhesiveness to various types of materials. Adhesion, tackiness, and adhesiveness can generally be evaluated for each performance by the test methods as listed in the examples described below according to the applications and purposes for which the adhesive is used. Therefore, any of these performances is a performance for evaluating the strength of the bond of the adhesive and the surface coating agent according to one embodiment of the present disclosure to the base material.

[0102] Adhesion (the magnitude of adhesive force) indicates the adhesive force between the base material and the interface of the adhesive or the cured surface coating agent (paint). Generally, intermolecular forces, ionic bonds, and hydrogen bonds are involved in the magnitude of the adhesive force between the base material and the adhesive. Also, the anchor effect between the irregularities of the base material and the adhesive resin contributes to the improvement of adhesion. Therefore, by improving adhesion, for example, peeling between the paint and the base material can be suppressed.

[0103] Adhesiveness (the magnitude of adhesive force) indicates, for example, the force required to peel two base materials adhered by an adhesive, and is the combined force of the adhesion between the base material and the adhesive, as well as the viscoelasticity and toughness of the adhesive itself. The magnitudes of the viscoelasticity and toughness of the resin that is the adhesive generally involve intermolecular forces, ionic bonds, and hydrogen bonds, along with the molecular weight and three-dimensional structure of the resin, similar to adhesion. As an example, if an adhesive with suppressed adhesion but excellent viscoelasticity and toughness is used, a peelable adhesive tape or the like can be produced. Also, if the adhesion, viscoelasticity, and toughness of the adhesive are improved, an adhesive tape or the like that can guarantee bonding for a relatively long period, for example, can be produced.

[0104] Adhesion (the magnitude of adhesive strength) is, for example, the combined force of the interfacial peeling (adhesion) between the adhesive and the base material and the force (toughness) required to cause the resin that is the adhesive to break in two base materials joined by an adhesive. Generally, when measuring adhesion, the bonding between the two base materials collapses when the adhesive breaks or the bond between the base material and the adhesive is severed. The difference between adhesion and adhesiveness is generally that adhesiveness is an index of easy adhesion and easy peeling, while adhesion is an index of the strength of the bond between two base materials. An adhesive capable of strong bonding can be used as an adhesive in fields where strength is required, such as the construction and automotive fields where durability and heat resistance are necessary. Also, an adhesive having viscoelasticity can be used for bonding between a base material and an interior material in the construction and automotive fields.

[0105] Although the reason why the adhesive according to one embodiment of the present disclosure binds more strongly to more types of substrates is not necessarily clear, it is considered as follows. When one substrate is joined to another substrate by an adhesive, the adhesive is interposed between the substrates, and typically, a cured product of the adhesive is formed between the substrates. Similarly, the surface coating agent can be said to be a cured product in which a cured product of the curable resin composition is joined to the substrate. Depending on the installation location and use of the substrate, etc., stress such as vibration and impact is directly or indirectly applied to these cured products, which may cause the cured products to break or the bond between the surface of the substrate and the surface of the cured product to break. That is, in the adhesive, there is a possibility that the joining of the substrates (so to speak, the relative positional relationship between the substrates) cannot be maintained, and in the surface coating agent, the joining of the surface coating agent and the substrate cannot be maintained. Since the adhesive and the surface coating agent according to the embodiment of the present disclosure are excellent in at least one of adhesion, tackiness, and adhesiveness, it is considered that the bond with the substrate can be maintained even when stress is directly or indirectly applied to the cured product.

[0106] Further, monomer B constituting the adhesive and the surface coating agent according to one embodiment of the present disclosure has a hydroxyl group or B(OH)2. It is considered that the orientation of these groups on the surface side of the substrate is one of the factors that enable the adhesive and the surface coating agent according to one embodiment of the present disclosure to strongly bond to various types of materials.

[0107] Furthermore, monomer C constituting the adhesive and the surface coating agent according to one embodiment of the present disclosure has a phosphate group. Due to the affinity with the material of the oxygen atom having a double bond with the phosphorus atom (P=O), the hydroxyl group having a single bond with the phosphorus atom (OH group), and the alkoxy group bonded to the phosphorus atom, which are different in characteristics from the catechol group and the phenylboronic acid group, it is considered that the adhesive and the surface coating agent according to one embodiment of the present disclosure are one of the factors that can strongly bond to various types of materials.

Examples

[0108] The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to the Examples. Note that the compound names shown in the following Examples and Comparative Examples do not necessarily follow the IUPAC nomenclature.

[0109] In this Example, the following abbreviations may be used. <Monomer A> Monomer A1: 4-hydroxybutyl acrylate (trade name: 4-HBA, manufactured by Osaka Organic Chemical Industry Co., Ltd.) Monomer A2: Tetrahydrofurfuryl acrylate (trade name: THFA, manufactured by Osaka Organic Chemical Industry Co., Ltd.) Monomer A3: 2-methoxyethyl acrylate (trade name: 2-MTA, manufactured by Osaka Organic Chemical Industry Co., Ltd.) Monomer A4: 2-hydroxyethyl acrylate (trade name: HEA, manufactured by Osaka Organic Chemical Industry Co., Ltd.) Monomer A5: Acrylic acid (trade name: 98% acrylic acid, manufactured by Osaka Organic Chemical Industry Co., Ltd.) Monomer A6: (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate (trade name: MEDOL-10, manufactured by Osaka Organic Chemical Industry Co., Ltd.) Monomer A7: Methyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) Monomer A8: Benzyl acrylate (trade name: Biscote #160 (abbreviation BZA), manufactured by Osaka Organic Chemical Industry Co., Ltd.) Monomer A9: 1,6-hexanediol diacrylate (trade name: Biscote #230 (abbreviation 1,6-HDDA), manufactured by Osaka Organic Chemical Industry Co., Ltd.) <Monomer B> Monomer B1: N-(3,4-dihydroxyphenethyl)acrylamide (trade name: DopAm, manufactured by Osaka Organic Chemical Industry Co., Ltd.) Monomer B2: 4-MAPB: 4-(methacrylamido)phenylboronic acid (trade name: 4-MAPB, manufactured by Osaka Organic Chemical Industry Co., Ltd.) Monomer B3: 2-hydroxy-3-(methacryloyloxy)propyl 3,4-dihydroxybenzoate (DHBA-GMA) (manufactured according to Synthesis Example 2 described below) <Monomer C> Monomer C1: 2-(Phosphonooxy)ethyl methacrylate (Trade name: MR-200, manufactured by Daihachi Chemical Industry Co., Ltd.) Monomer C2: 10-(Phosphonooxy)decyl methacrylate (Trade name: 10-MDP, manufactured by Fujifilm Wako Pure Chemical Corporation) Monomer C3: 2-(Dimethylphosphonate)ethyl methacrylate (manufactured according to Synthesis Example 1 described below) Monomer C4: Vinylphosphonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) Monomer C5: Dimethyl vinylphosphonate (manufactured by Tokyo Chemical Industry Co., Ltd.) <Crosslinkable Monomer> Crosslinkable Monomer 1: Trimethylolpropane triacrylate (Trade name: TMP3A, manufactured by Osaka Organic Chemical Industry Co., Ltd.) Crosslinkable Monomer 2: Toluene diisocyanate (Trade name: Coronate T-80, manufactured by Tosoh Corporation (mixture of 2,4-tolylene diisocyanate / 2,6-tolylene diisocyanate = 80:20)) <Polymerization Initiator> Polymerization Initiator: 2,4,6-Trimethylbenzoyl diphenylphosphine oxide (manufactured by Tokyo Chemical Industry Co., Ltd.) <Substrate> PVC: Polyvinyl chloride PC: Polycarbonate PET: Polyethylene terephthalate PP: Polypropylene PE: Polyethylene ABS: Acrylonitrile-butadiene-styrene copolymer resin FRP: Glass fiber-reinforced epoxy resin PEEK: Polyetheretherketone PPS: Polyphenylene sulfide EP: Epoxy resin Cu: Copper Al: Aluminum ITO: Indium tin oxide (coated on glass)

[0110] Synthesis Example 1: Synthesis of 2-(dimethylphosphonate)ethyl methacrylate (0.500 g, 3.25 mmol) of dimethyl (2-hydroxyethyl)phosphonate and (0.415 g, 4.10 mmol) of triethylamine were dissolved in (2.00 g) of tetrahydrofuran, and methacryloyl chloride (0.390 g, 3.73 mmol) was added dropwise in a water bath. Heat was generated during the addition, and after stirring for 5 hours, water (5.00 g) was added, and extraction was performed twice with toluene (5.00 g). The organic layer was washed with 3N hydrochloric acid (4.01 g), and then successively washed with a 5 wt% sodium hydrogen carbonate solution (4.00 g) and water (4.00 g). After washing, the organic layer was concentrated under reduced pressure in a hot water bath at about 40 °C to obtain 2-(dimethylphosphonate)ethyl methacrylate (0.350 g, yield 49%) as an oily substance.

[0111] Synthesis Example 2: Synthesis of DHBA-GMA (Monomer B3) 8.00 g (51.9 mmol) of 3,4-dihydroxybenzoic acid, 14.8 g (103.8 mmol) of glycidyl methacrylate (GMA), and 0.44 g (3.6 mmol) of 4-dimethylaminopyridine (DMAP) were dissolved in cyclopentanone (72.0 g) in a container and stirred in a hot water bath maintained at 80 °C for 21 hours. Thereafter, water was added to the container, ethyl acetate was added, and DMAP was removed by washing with 3N HCl. The obtained organic layer was concentrated under reduced pressure to obtain an oily substance, which was purified by silica gel column chromatography (n-hexane:ethyl acetate = 3:1) and concentrated to obtain DHBA-GMA (4.61 g, yield 30%).

[0112] <Adhesion Test> ≪Preparation of Test Specimens≫ According to the compositions in Table 1 and Table 2, 2,4,6-trimethylbenzoyldiphenylacylphosphine oxide (TPO) was added as a polymerization initiator to the formulation containing Monomer A, Monomer B, Monomer C, and the crosslinkable monomer in an amount of 10 parts by mass per 100 parts by mass of the total amount of monomers contained in each formulation, and thoroughly mixed to prepare each curable resin composition (hereinafter also referred to as monomer solution) according to each example and comparative example described in Table 1 and Table 2. Next, each adjusted monomer solution was applied onto a test plate formed of each material described in Table 1 and 2 using a bar coater No. 10 (manufactured by Daiichi Rika Co., Ltd., wet film thickness: approximately 22.90 μm). Next, using a UV exposure machine, UV with an exposure amount of 3000 mJ / cm 2 was irradiated to completely cure the coating film to produce each test piece, which was allowed to stand at room temperature for 24 hours (film thickness: approximately 20 μm).

[0113] ≪Test method≫ The adhesion test was carried out in accordance with JIS K 5600-5-6:1999 "General test methods for paints - Part 5: Mechanical properties of coating films - Section 6: Adhesion (cross-cut method)". For the above test pieces, using a cutter knife, the coating film was cross-cut (25 squares) in a grid pattern of 2×2 mm. Subsequently, a 24-mm-wide cellophane tape manufactured by Nichiban Co., Ltd. was attached onto this grid, and this cellophane tape was pressure-bonded for 2 minutes by pressing it with the tester's hand. Then, when the cellophane tape was peeled off at an angle of 45° with respect to the substrate within 0.5 seconds and within 2 seconds, the number of squares remaining on the substrate was counted respectively, and the average was taken and evaluated according to the following criteria.

[0114] [Evaluation criteria] 0: The cut lines are completely smooth, and there is no peeling in any grid. 1: Small peeling at the intersections of the cuts. Those affected in the cross-cut part are less than 5%. 2: The coating film is peeled off along the edges of the cuts and / or at the intersections. Those affected in the cross-cut part are 5 - 15%. 3: The coating film has partially or entirely peeled off along the edge of the cut, and / or various parts of the eyes have partially or entirely peeled off. Those affected in the cross-cut part are 15 - 35%. 4: The coating film has partially or entirely peeled off along the edge of the cut, and / or several eyes have partially or entirely peeled off. Those affected in the cross-cut part are less than 35%. 5: Large peeling that cannot be classified as in 4 above.

[0115] ≪Results≫ The results are shown in Table 1 and Table 2. Note that the smaller the numerical value, the better the adhesion to the substrate, and an evaluation of 3 or less indicates a preferable possibility for use. Comparing Example 1 and 4 with Comparative Example 1 and 2, it can be seen that the combined use of Monomer B and Monomer C increases the materials showing good adhesion, especially the adhesion to metal is improved. Comparing Example 2 and 5 with Comparative Example 1 and 3, it can be seen that the combined use of Monomer B and Monomer C increases the materials showing good adhesion, especially the adhesion to metal is improved. Comparing Example 3 and 6 with Comparative Example 1, 4, 6 and 7, it can be seen that by using Monomer B1 (Monomer B-b) and Monomer B2 (Monomer B-a) in combination as Monomer B and further using Monomer C, it is difficult to reduce the adhesion of Monomer C. Also, comparing Example 7 - 9 with Comparative Example 1 and 5, it can be seen that the combined use of Monomer B and Monomer C increases the materials showing good adhesion, especially the adhesion to metal is improved. Furthermore, it can be seen that these tendencies of the combined use of Monomer B and Monomer C increasing the materials showing good adhesion, especially the adhesion to metal being improved, are also observed when the type of Monomer A is changed (Table 2).

[0116]

Table 1

[0117]

Table 2

[0118] <Adhesion Test> ≪Preparation of Samples≫ After preparing each formulation by blending Monomer A, Monomer B, and Monomer C at the ratios described in Table 3 or Table 4, 2,4,6-trimethylbenzoyl diphenyl acylphosphine oxide (TPO) was added to each formulation in an amount of 10 parts by mass per 100 parts by mass of the total amount of monomers contained in each formulation, and thoroughly mixed to prepare monomer solutions according to each example and comparative example described in Table 3 and Table 4. Next, the prepared monomer solution was applied onto a test plate formed of Al using a bar coater No. 10. Next, a PET film cut into 300 mm × 24 mm was placed on the coating film and crimped, and using a UV exposure machine, UV with an exposure amount of 3000 mJ / cm 2 was irradiated to completely cure the coating film to prepare each sample, which was allowed to stand at room temperature for 24 hours.

[0119] ≪Test Method≫ The adhesion test was carried out in accordance with the "180° Peel Adhesion Test Method" described in the 17th Revised Japanese Pharmacopoeia 6.12. In each of the above samples, after gripping the end of the film and folding it back at 180° to peel it off from the test plate by 25 mm, the test plate was fixed to the lower chuck of a tensile testing machine, and the film was fixed to the upper chuck. The tensile testing machine was moved at a peeling rate of 300 mm / second in an environment at room temperature and a humidity of 45% to start the measurement, and the peel adhesion was measured by averaging the measured values of the adhesion force at 50% of the length peeled off from the test plate.

[0120] ≪Results≫ The results are shown in Table 3 and Table 4. The peel adhesions of Examples 17 to 22 and Comparative Examples 14 to 18 are represented relatively with the peel adhesion of Comparative Example 14 as 100, and the peel adhesions of Examples 23 to 30 and Comparative Examples 19 to 26 are represented relatively with the peel adhesion of Comparative Example 19 as 100. Note that for adhesiveness, the larger the numerical value, the higher the adhesive force. It can be seen that for Examples other than Example 18, the adhesive force of the PET film to the test plate (Al) has improved compared to the reference Comparative Example 14 or 19. Although the adhesive force of Example 18 is lower than that of Comparative Example 14, it can be seen that the adhesive force has improved compared to Comparative Example 16 using only the corresponding Monomer B. Among the Examples using Monomer C in combination, although there are some cases where the adhesive force is lower than that of Comparative Examples 15 to 17 and 20 to 23 using only Monomer B, considering the results of the adhesion tests in Tables 1 and 2 above, it can be said that all of Examples 17 to 30 exhibit sufficiently good adhesiveness.

[0121]

Table 3

[0122]

Table 4

[0123] <Adhesion Test> ≪Preparation of Test Specimens≫ Mixtures were prepared by mixing Monomer A, Monomer B, and Monomer C with the monomer compositions described in Table 5 (total amounts of Monomers A to C in Table 5), respectively. To each mixture, 2,2'-azobisisobutyronitrile (AIBN) was added as a polymerization initiator in an amount of 1 part by mass per 100 parts by mass of the total amount of the monomers to which the crosslinkable monomer to be added later was added, and the mixture was stirred at 85°C for 5 hours. Thereafter, the crosslinkable monomer 2 described in Table 5 was added to each mixture. Then, each mixture was applied to the entire surface of one of two test plates (length: 25 mm × width: 10 mm) of the PP-Al combination from one end side in the length direction to a position 12 mm. The other test plate was arranged such that one end in the length direction protruded from one end side of one test plate in the length direction and the other end was at a position 12 mm from one end of one test plate, thereby bringing the other test plate into contact with each mixture. Note that the two test plates were brought into contact such that one test plate did not protrude from the width direction of the other test plate. Thereafter, the two test plates were exposed in a hot air circulation type constant temperature bath under the conditions of 80°C for 3 hours to cure each mixture, and the cured product was used as a test piece.

[0124] ≪Test Method≫ In accordance with JIS K 6850:1999 "Adhesives - Test Method for Tensile Shear Adhesion Strength of Rigid Adherends", one test plate constituting the test piece was pulled in its longitudinal direction, and the other test piece was pulled in the direction opposite to the direction in which one test plate was pulled, and the adhesive force between the respective materials was measured. The pulling speed was 5.0 mm / second for all test pieces.

[0125] ≪Results≫ The results are shown in Table 5. The adhesive forces of Examples 31 to 36 and Comparative Examples 27 to 31 are represented relatively for each test piece with the adhesive force of Comparative Example 27 as 100, and the adhesive forces of Examples 37 to 40 and Comparative Examples 32 to 35 are represented relatively for each test piece with the adhesive force of Comparative Example 32 as 100. A larger numerical value indicates a higher adhesive force. From Table 5, it can be seen that the adhesiveness of PP-Al is improved by combining Monomer B and Monomer C.

[0126]

Table 5

[0127] <Solubility Test 1> ≪Solubility of Monomer B in Monomers A and C≫ In a hot water bath at 50 °C, each monomer described in Table 6 (Monomers A1 - A7, Monomers C1, C4, and C5) was added to 10.20 g of Monomer B, and a part of it was dissolved (not completely dissolved). It was left standing at room temperature overnight, and Monomer B1 dissolved in the supernatant was quantified by HPLC. The solubility of Monomer B1 in each monomer at room temperature was determined as the saturation concentration (mass %).

[0128] ≪Solubility of Monomer B in Monomer A in the Presence of Monomer C≫ Next, regarding the solubility of Monomer B1 in Monomer A in the presence of Monomer C, for a mixture of 10.20 g of Monomer B and 0.20 g of Monomer C described in Table 7 in a hot water bath at 50 °C, each type and amount of Monomer A described in Table 7 was added to partially dissolve it (not completely dissolved), left standing at room temperature overnight, and the amount (A) of Monomer B1 dissolved in the supernatant was quantified by HPLC.

[0129] Using the saturation concentration of Monomer B1 in each obtained monomer (Table 6), the theoretical amount (B) of Monomer B1 dissolved in the presence of Monomer C was determined, and the ratio of the measured amount (A) of Monomer B1 dissolved by adding Monomer C to this theoretical amount (B) was determined as (A) / (B).

[0130] ≪Results≫ As a result, the saturation concentration of Monomer B1 in each monomer is shown in Table 6, and the ratio of the measured amount of Monomer B1 dissolved when Monomer A and Monomer C are used in combination to the theoretical amount is shown in Table 7. From Table 6, it can be seen that Monomer B1 is easily soluble in Monomer A having a hydroxyl group. Also, from Table 7, in the above formula (I), when R 2 is methyl, optionally substituted C 1-6 alkoxy, or Monomer A which is an optionally substituted 4 - to 7 - membered oxygen - containing saturated heterocyclic group, it can be seen that the solubility of Monomer B1 is improved by the combined use of Monomer C.

[0131]

Table 6

[0132]

Table 7

[0133] <Solubility Test 2> The amounts of Monomers A1, A8, and A9 that can completely dissolve 10 g of a mixture obtained by mixing 5.0 g of Monomer B3 and 5.0 g of Monomer C1 were examined. Specifically, 10 g each of Monomers A1, A8, and A9 were added to 10 g of the mixture in a 50°C water bath, and the mixture dissolved in all of the Monomer A. On the other hand, when Monomer B1 was used instead of Monomer B3, 30 g of Monomer A1 and 240 g of Monomer A9 were required to dissolve the entire amount of the mixture. Also, even when 250 g of Monomer A8 was added, not all of the mixture dissolved, and undissolved residue was observed.

Claims

1. A curable resin composition containing monomer A, monomer B, and monomer C, wherein monomer A is represented by formula (I): 【Chemical 1】 [wherein, R 1 represents a hydrogen atom or methyl; L 1 represents a single bond or -O-; W 1 represents a single bond or C 1-20 alkylene; R 2 represents methyl, hydroxyl, C 1-6 alkoxy, optionally substituted phenyl, optionally substituted 3- to 8-membered saturated or partially unsaturated heterocyclic group, or (meth)acryloyloxy; wherein the substituents in the optionally substituted phenyl and the optionally substituted 3- to 8-membered saturated or partially unsaturated heterocyclic group are hydroxyl, amino, halogen atom, C1-6 alkyl, or C1-6 alkoxy; Here, R 2 is C 1-6 when it is alkoxy, W 1 is C 2-20 is one or more compounds represented by [is alkylene], monomer B is represented by formula (II): [Chemical 2] [wherein, R 3 represents a hydrogen atom or methyl; L 2 represents -O- or -NH-; W 2 represents a single bond or C 1-20 alkylene which may be substituted with a hydroxyl group; L 3 represents a single bond, -O-, -CH(OH)-, -NH-, -NHC(O)-, or -OC(O)-; W 3 represents a single bond or C 1-6 alkylene; R 4 and R 5 each independently represents a hydrogen atom, a hydroxyl group, or B(OH) 2 ; Here, R 4 and R 5 are not both hydrogen atoms], and is one or more compounds represented by monomer C is [Chemical Formula 3] [wherein, R 6a , R 6b , and R 6c each represent a hydrogen atom or methyl; W 4a and W 4b each represents C 1-20 alkylene; n represents an integer of 1 to 3; R 7b 、R 7c 、R 8b 、and R 8c are each one or more compounds represented by [representing hydroxyl or C 1-6 alkoxy], a curable resin composition in which, based on the total amount of monomers, the content of monomer A is 75% by mass or more, the content of monomer B is 0.25% by mass or more, and the content of monomer C is 0.10 to 10.0% by mass.

2. In formula (I), L 1 The curable resin composition according to claim 1, wherein 1 is -O-.

3. In formula (I), R 2 is methyl, C 1-6 alkoxy, an optionally substituted 4- to 7-membered oxygen-containing saturated heterocyclic group, or an optionally substituted phenyl. The curable resin composition according to claim 1 or 2.

4. In formula (II), L 2 is -NH-, W 2 is a single bond; L 3 is a single bond; W 3 is C 1-6 The curable resin composition according to any one of claims 1 to 3, wherein it is alkylene.

5. In formula (II), L 2 is -O-, and W 2 is C 1-20 alkylene which may be substituted with a hydroxyl group, and L 3 is -OC(O)-; W 3 The curable resin composition according to any one of claims 1 to 3, wherein is a single bond.

6. Monomer B is R 4 and / or R 5 The curable resin composition according to any one of claims 1 to 5, comprising a compound in which is hydroxyl.

7. Monomer C is represented by formula (IIIa): 【Chemical 4】 [wherein, R 6a represents a hydrogen atom or methyl; W 4a represents C 1-20 alkylene; n represents an integer of 1 to 3] The curable resin composition according to any one of claims 1 to 6, which is one or more compounds represented by

8. The curable resin composition according to any one of claims 1 to 7, wherein monomer C includes a compound in which n is 1, a compound in which n is 2, and a compound in which n is 3 in formula (IIIa).

9. The curable resin composition according to any one of claims 1 to 8, further containing a crosslinkable monomer.

10. The curable resin composition according to claim 9, wherein the crosslinkable monomer is a polyfunctional (meth)acrylate and / or a polyfunctional isocyanate.

11. An adhesive or a surface coating agent containing a polymer containing monomer A, monomer B, and monomer C as constituent units, wherein monomer A is represented by formula (I): [Chemical Formula 5] [wherein, R 1 represents a hydrogen atom or methyl; L 1 represents a single bond or -O-; W 1 represents a single bond or C 1-20 alkylene; R 2 represents methyl, hydroxyl, C 1-6 alkoxy, optionally substituted phenyl, optionally substituted 3- to 8-membered saturated or partially unsaturated heterocyclic group, or (meth)acryloyloxy; wherein the substituents in the optionally substituted phenyl and the optionally substituted 3- to 8-membered saturated or partially unsaturated heterocyclic group are hydroxyl, amino, halogen atom, C1-6 alkyl, or C1-6 alkoxy; Here, R 2 is C 1-6 when it is an alkoxy group, W 1 is C 2-20 is one or more compounds represented by [being alkylene], monomer B is represented by formula (II): [Chemical Formula 6] [wherein, R 3 represents a hydrogen atom or methyl; L 2 represents -O- or -NH-; W 2 represents a single bond or C alkylene which may be optionally substituted with a hydroxyl group; 1-20 ​ L 3 represents a single bond, -O-, -CH(OH)-, -NH-, -NHC(O)-, or -OC(O)-; W 3 represents a single bond or C 1-6 alkylene; R 4 and R 5 each independently represents a hydrogen atom, a hydroxyl group, or B(OH) 2 ; Here, R 4 and R 5 is not a hydrogen atom in any case], and is one or more compounds represented by monomer C is [Chemical Formula 7] [wherein, R 6a , R 6b , and R 6c each represents a hydrogen atom or a methyl group; W 4a and W 4b each represents C 1-20 alkylene; n represents an integer of 1 to 3; R 7b 、R 7c 、R 8b 、and R 8c is one or more compounds represented by [each representing hydroxyl or C 1-6 alkoxy], an adhesive or a surface coating agent in which, based on the total amount of monomers, the content of monomer A is 75% by mass or more, the content of monomer B is 0.25% by mass or more, and the content of monomer C is 0.10 to 10.0% by mass.

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