Hardening resin composition

Abstract

To provide a curable resin composition which is firmly bonded to surfaces of various kinds of materials.SOLUTION: The curable resin composition contains a monomer A and a monomer B. The monomer A is one or more compounds represented by formula (I) [where R1 represents a hydrogen atom or methyl; L1 represents a single bond, -O- or the like; W1 represents a single bond or a C1-20 alkylene; and R2 represents hydroxyl or the like]. The monomer B is one or more compounds represented by formula (II) [where R3 represents a hydrogen atom or methyl; W2 represents a single bond or an optionally substituted C1-20 alkylene; L2 represents a single bond or the like; W3 represents a single bond or the like; and R4 and R5 each independently represent a hydrogen atom or hydroxyl].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 a (meth)acrylic acid derivative monomer as a structural unit, and a surface coating agent containing a polymer containing a (meth)acrylic acid derivative monomer 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 are being studied.

[0003] Patent Document 1 discloses a curable resin composition, an adhesive, and a surface coating agent that strongly bond to the surfaces of various types of materials, including 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, as constituent elements, 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, dopamine acrylamide, which is an adhesive monomer described in Patent Document 1, does not have high solubility in the base monomer, and there is room for improvement.

[0006] Therefore, an object of the present invention is to provide a further 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

[15] etc. are provided.

[0008] [1] A curable resin composition containing monomer A and monomer B, wherein monomer A is represented by formula (I):

Chemical formula

[0009] [2] The curable resin composition according to [1] above, wherein L 1 is a single bond or -O-.

[0010] [3] R 2 is (1) methyl, (2) hydroxyl, (3) optionally substituted C 1-6 alkoxy, (4) optionally substituted 3- to 8-membered saturated heterocyclic group, or (5) optionally substituted phenyl and is the curable resin composition according to [1] or [2] above.

[0011] [4] W 1 is a single bond or C 1-6 alkylene, and W 2 is optionally substituted with hydroxyl C 1-6The curable resin composition according to any one of the above [1] to [3], wherein the alkylene is as defined above.

[0012] 〔5〕L 2 The curable resin composition according to any one of the above [1] to [4], wherein L is -OC(O)-.

[0013] 〔6〕W 3 is a single bond or C 2-6 The curable resin composition according to any one of the above [1] to [5], wherein W is an alkenylene.

[0014] 〔7〕The curable resin composition according to any one of the above [1] to [6], wherein the monomer B contains a compound in which R 4 and R 5 are hydroxyl groups.

[0015] 〔8〕The curable resin composition according to any one of the above [1] to [7], wherein the content of the monomer B in the composition is more than 10.0% by mass and less than 50.0% by mass.

[0016] 〔9〕The curable resin composition according to any one of the above [1] to [8], further containing a crosslinkable monomer.

[0017] 〔10〕The curable resin composition according to [9] above, wherein the crosslinkable monomer is a polyfunctional (meth) acrylate and / or a polyfunctional isocyanate.

[0018] 〔11〕An adhesive containing a polymer containing monomer A and monomer B as constituent units, wherein monomer A has the formula (I):

Chemical formula

Chemical formula

[0019] 〔12〕The adhesive according to 〔11〕 above, wherein W 3 is a single bond or C 2-6 alkenylene.

[0020] A surface coating agent containing a polymer having monomer A and monomer B as constituent units, wherein monomer A is represented by formula (I):

Chemical formula

Chemical formula

[0021]

[14] W 3 is a single bond or C 2-6 alkenylene, and the surface coating agent according to

[13] above.

[0022]

[15] Formula (IIa): [Chemical formula] [wherein R 3a represents a hydrogen atom or methyl; W 2a is a single bond or optionally substituted C 3-20 alkylene; L 2a represents a single bond, -O-, -CH(OH)-, -C(O)O-, -OC(O)-, or -OC(O)O-; W 3a is C 2-6 alkenylene; R 4a and R 5a each independently represents a hydrogen atom or a hydroxyl group; wherein R 4a and R 5a are both not hydrogen atoms], and is a compound represented by the formula. [Advantages of the Invention]

[0023] According to the present disclosure, it is possible to provide a curable resin composition, an adhesive, and a surface coating agent that strongly bond to various types of materials. [Modes for Carrying Out the Invention]

[0024] As described above, the curable resin composition of the present disclosure contains monomer A and monomer B as monomer components. Among them, monomer B having a predetermined structure not only has excellent adhesiveness but also has improved solubility in the base monomer. The inventors have hitherto examined (meth)acrylamide derivatives having hydroxyl or B(OH)2 in a benzene ring as an adhesive monomer. For example, dopamine acrylamide (N-(3,4-dihydroxyphenethyl)acrylamide), which is a typical monomer thereof, does not have a very high solubility in the base monomer, and it has been difficult to increase its concentration in the composition. On the other hand, 2-(acryloyloxy)ethyl 3,4-dihydroxybenzoate (DHBA-HEA), which is an example of monomer B according to the present disclosure, has been found to generally have a higher solubility in various base monomers compared to dopamine acrylamide. Regarding this difference in solubility, X-ray crystal structure analysis of dopamine acrylamide and DHBA-HEA was performed and compared. In dopamine acrylamide, two types (1.71 Å) of hydrogen bonds were found between the hydrogen of catechol-OH and the oxygen of the amide group CO, two types (2.08 Å) of hydrogen bonds were found between the oxygen of catechol OH and the hydrogen of the amide group NH, and two types (2.08 Å) of hydrogen bonds were found between the two catechol groups, for a total of six types of hydrogen bonds. On the other hand, in DHBA-HEA, two types (1.88 Å) of hydrogen bonds were found between the hydrogen of catechol-OH and the oxygen of benzoic acid CO, and two types (2.04 Å) of hydrogen bonds were found between the two catechol groups, for a total of four types of hydrogen bonds. No hydrogen bond was confirmed for the carbonyl group in the acrylate moiety. Here, when comparing the shortest hydrogen bond distances between the two compounds, the distance was 1.71 Å for dopamine acrylamide and 1.88 Å for DHBA-HEA, and the distance of DHBA-HEA was slightly longer. Furthermore, the number of hydrogen bonds per molecule was also smaller for DHBA-HEA. From these facts, it is presumed that monomer B of the present disclosure does not have an acrylamide group and has a (meth)acrylate ester structure, thereby improving its solubility in the base monomer.

[0025] In this specification, when indicating the number of carbons in the definition of "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.

[0026] "C 1-20 alkylene" means a linear or branched divalent saturated hydrocarbon group having 1 to 20 carbon atoms. Preferably, it is "C 3-20 alkylene", more preferably "C 1-8 alkylene", still more preferably "C 1-6 alkylene", and most preferably "C 1-4 alkylene". Specific examples of "C 1-20 alkylene" include, for example, methylene, ethylene, trimethylene, tetramethylene, hexamethylene, octamethylene, 1-methylmethylene, 1-ethylmethylene, 1-propylmethylene, 1-methylethylene, 2-methylethylene, 1-ethylethylene, etc.

[0027] "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, ethenylenylene, propylenylene, butylenylene, pentalenylene, hexalenylene, 1-methylethinylenine, 2-methylethinylenine, 1-methylpropylenylene, etc.

[0028] "C 1-8 alkyl" means a linear or branched saturated hydrocarbon group having 1 to 8 carbon atoms. Preferably, it is "C 1-6 alkyl", more preferably "C 1-4 alkyl". "C 1-8Specific examples of "alkyl" include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl, hexyl, isohexyl, heptyl, octyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, and the like.

[0029] "C" 1-6 "alkoxy" means a substituent in which an alkyl is bonded to an oxygen atom and is bonded to the parent molecule through the oxygen atom. The "C" 1-6 "alkoxy" 1-6 The "C" 1-6 "alkyl" part of "alkoxy" is 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.

[0030] Examples of "5- or 6-membered heteroaryl" include, for example, 5- or 6-membered monocyclic aromatic heterocyclic groups and the like. The group contains one or more (for example, 1 to 4) identical or different heteroatoms selected from nitrogen atoms, sulfur atoms, and oxygen atoms as atoms constituting the ring. Specific examples of "5- or 6-membered heteroaryl" include pyridyl, pyrimidyl, pyrazyl, pyridazyl, triazyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, and the like.

[0031] Examples of "3- to 8-membered saturated or partially unsaturated hydrocarbon group" include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopentenyl, cyclohexenyl, cyclohexadienyl, and the like.

[0032] 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, oxygen, and sulfur atoms as ring-constituting atoms, and the like. 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 bonding site of the group may be any of the carbon and nitrogen atoms constituting the ring.

[0033] Examples of the "3- to 8-membered oxygen-containing saturated heterocyclic group" include monocyclic 3- to 8-membered saturated heterocyclic groups containing 1 to 2 oxygen atoms and optionally 1 to 2 identical or different atoms selected from nitrogen and sulfur atoms, and the like. The oxygen, nitrogen, and sulfur atoms are all ring-constituting atoms. 4- to 6-membered oxygen-containing saturated heterocyclic groups are preferred. Specifically, oxiranyl, oxetanyl, tetrahydrofuryl, tetrahydropyranyl, dioxanyl, dioxolanyl, oxazolidinyl, oxepanyl, oxecanyl, morpholinyl, and the like can be mentioned; oxetanyl, tetrahydrofuryl, tetrahydropyranyl, dioxanyl, and dioxolanyl are preferred; and oxetanyl and tetrahydrofuryl are more preferred.

[0034] "Optionally substituted C1-8 "alkyl", "optionally substituted C 1-6 "alkoxy", and "optionally substituted C 1-20 "alkylene" or "optionally substituted C 3-20 Examples of the substituent in "alkylene" include hydroxyl, halogen atom, C 1-6 alkoxy and the like.

[0035] Examples of the substituent 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 and the like.

[0036] Specific examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0037] In this specification, "(meth)acryloyloxy" is assumed to include a methacryloyloxy group and an acryloyloxy group.

[0038] In this specification, when indicating a numerical range using "~", it is assumed to include the numerical values at both ends.

[0039] <Monomer component> The curable resin composition according to one embodiment of the present disclosure is a composition that binds to a substrate by curing. The curable resin composition according to one embodiment of the present disclosure is characterized by containing a first monomer (monomer A) and a second monomer (monomer B).

[0040] (Monomer A) The curable resin composition according to one embodiment of the present disclosure uses, 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 6 (wherein R is an alkyl group having 1 to 6 carbon atoms), -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 6 represents optionally substituted C 1-8 alkyl], and contains one or more compounds represented by the formula.]

[0041] L 1 is preferably a single bond or -O-; more preferably -O-. The compound of formula (I) in which L 1 is -O- is preferred because it has good compatibility with the monomer B described below that the curable resin composition according to an embodiment of the present disclosure may contain.

[0042] W 1 is preferably a single bond or C 1-6 alkylene; more preferably a single bond or C 1-4 alkylene. Further, as another embodiment of W 1 , C 1-8 alkylene, C 1-6 alkylene, C 2-6 alkylene, C 1-4 alkylene, C 2-4 alkylene, etc. may be mentioned.

[0043] R 2 is preferably, (1) methyl, (2) hydroxyl, (3) Optionally substituted C 1-6 Alkoxy, for example, hydroxyl or C 1-6 Optionally substituted C with alkoxy 1-6 Alkoxy, (4) Optionally substituted 3- to 8-membered saturated heterocyclic group, for example a halogen atom, hydroxyl, C 1-6 Alkyl, and C 1-6 Optionally substituted 4- to 7-membered oxygen-containing saturated heterocyclic group selected from the group consisting of the same or different 1 to 4 groups selected from hydroxyl, C (5) Optionally substituted phenyl, or (6) (Meth)acryloyloxy; More preferably, (1) Methyl, (2) Hydroxyl, (3) C 1-4 Alkoxy, (4) 4- to 7-membered oxygen-containing saturated heterocyclic group optionally substituted with 1 to 4 C 1-6 Alkyl, or (5) Optionally substituted phenyl; Even more preferably, C 1-4 Alkoxy, 4- to 6-membered oxygen-containing saturated heterocyclic group optionally substituted with 1 to 4 C 1-6 Alkyl, or phenyl.

[0044] From the viewpoint of adhesion, it is also possible to select monomer A used according to the material of the target base material. For an organic base material, it is preferable to use monomer A which is a 3- to 8-membered oxygen-containing saturated heterocyclic group in which R 2 may be substituted. For an inorganic base material, by using monomer A in which R 2 is hydroxyl, the effect of adding monomer B is more likely to be obtained.

[0045] R 2Monomer A in which R is hydroxyl, and R 2 is optionally substituted C 1-6 When alkoxy or optionally substituted phenyl is used in combination with monomer A, R in monomer A 2 is hydroxyl in monomer A and R 2 is optionally substituted C 1-6 The mass ratio of monomer A in which alkoxy or optionally substituted phenyl is [R 2 is hydroxyl in monomer A: R 2 is optionally substituted C 1-6 alkoxy or optionally substituted phenyl monomer A] is preferably 0.5:99.5 to 20:80, more preferably 1:99 to 10:90, from the viewpoint that the properties of monomer A in which alkoxy or optionally substituted phenyl is expressed in adhesion, tackiness, and adhesiveness. 2 is optionally substituted C 1-6 From the viewpoint that the properties of monomer A in which alkoxy or optionally substituted phenyl are expressed in adhesion, tackiness, and adhesiveness, 0.5:99.5 to 20:80 is preferable, and 1:99 to 10:90 is more preferable.

[0046] From the viewpoint of good solubility of monomer B, in formula (I), L 1 is -O-, and R 2 is methyl, hydroxyl, optionally substituted C 1-6 alkoxy, optionally substituted 4- to 7-membered oxygen-containing saturated heterocyclic group, or optionally substituted phenyl monomer A is preferably used. Further, from the viewpoint of the effect of improving the solubility of the adhesive monomer by combining with monomer B as the adhesive monomer, L 1 is -O-, and R 2 is methyl, optionally substituted C 1-6 alkoxy, optionally substituted 3- to 8-membered saturated or partially unsaturated heterocyclic group, or optionally substituted phenyl monomer A is preferably used.

[0047] As another aspect of monomer A, L 1 and W 1 in formula (I) are single bonds, and R 2 is hydroxyl, or L 1is -O-, and W 1 is C 2-20 is alkylene, and R 2 is hydroxyl, optionally substituted C 1-6 is alkoxy, or L 1 is -O-, and W 1 is C 1-8 is 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-, and W 1 is a single bond, or C 1-6 is alkylene, and R 2 is preferably one or more compounds where R 1 is -O-, and W 1 is C 2-8 is alkylene, and R 2 is hydroxyl, optionally substituted C 1-4 is alkoxy, or L 1 is -O-, and W 1 is C 1-4 is alkylene, and R 2 is an optionally substituted 4- to 6-membered oxygen-containing saturated heterocyclic group, or optionally substituted phenyl, or L 1 is -O-, and W 1 is a single bond, or C 1-4 is alkylene, and R 2 is more preferably one or more compounds where R

[0048] Furthermore, as another aspect of monomer A, in formula (I), [R 1 represents a hydrogen atom or methyl; L 1 represents a single bond, -O-, -NH-, -NR 6 -, -NHC(O)O-, or -NHC(O)NH-; W 1 represents a single bond, or C 1-20 represents alkylene; R 2 is methyl, hydroxyl, optionally substituted C 1-6represents an alkoxy group, an optionally substituted phenyl group, an optionally substituted phenoxy group, an optionally substituted 5- or 6-membered heteroaryl group, an optionally substituted 3- to 8-membered saturated or partially unsaturated hydrocarbon ring group, or an optionally substituted 3- to 8-membered saturated or partially unsaturated heterocyclic group; R 6 represents an optionally substituted C 1-8 alkyl group; wherein when R 2 is methyl, W 1 is a single bond or C 1-8 alkylene] and includes a compound represented by

[0049] In another aspect, monomer A in formula (I) is [R 1 represents a hydrogen atom or methyl; L 1 represents a single bond, -O-, -NH-, -NR 6 -, -NHC(O)O-, or -NHC(O)NH-; W 1 represents a single bond or C 1-20 alkylene; R 2 represents methyl, hydroxyl, an optionally substituted C 1-6 alkoxy group, an optionally substituted phenyl group, an optionally substituted phenoxy group, an optionally substituted 5- or 6-membered heteroaryl group, an optionally substituted 3- to 8-membered saturated or partially unsaturated hydrocarbon ring group, or an optionally substituted 3- to 8-membered saturated or partially unsaturated heterocyclic group; R 6 represents an optionally substituted C 1-8 alkyl group; wherein when R 2 is hydroxyl, an optionally substituted C 1-6 alkoxy group, or an optionally substituted phenoxy group, W 1 is C 2-20 alkylene] and includes a compound represented by

[0050] The content of monomer A relative to the total amount of monomers is not particularly limited, and the balance excluding the following monomer B, crosslinkable monomer, and other monomers can be used as its 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 even 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 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, insulation, etc.

[0051] Monomer A is synthesized by a method combining a known compound and a known synthesis method. Also, a commercially available product may be used as monomer A.

[0052] (Monomer B) In the curable resin composition according to one embodiment of the present disclosure, as the second monomer (monomer B), formula (II):

Chemical formula

[0053] Monomer B has a hydroxyl substituent on the benzene ring as described above. In the curable resin composition which is one embodiment of the present disclosure and the adhesives and surface coating agents described later, it is considered that the hydroxyl substituent present on this benzene ring is oriented on the adhesion surface, which is one factor enabling stronger bonding to a wider variety of materials.

[0054] W 2 is preferably an optionally substituted C 1-8 alkylene; more preferably an optionally substituted C 1-6 alkylene; still more preferably an optionally substituted C 2-6 alkylene; most preferably an optionally substituted C 2-4 alkylene. Also, when W 2 is a C 1-20 alkylene substituted with a hydroxyl group, this hydroxyl substituent also tends to contribute to the improvement of adhesiveness and adhesivity, and is particularly preferable because the effect tends to be greater when monomer A having no hydroxyl group is used.

[0055] L 2 is preferably -O-, -C(O)O-, or -OC(O)-; more preferably -OC(O)-.

[0056] W 2 is preferably a single bond or C 2-6 alkenylene; more preferably a single bond or C 2-4 alkenylene.

[0057] R 4 and R 5 are both preferably hydroxyl groups.

[0058] As another embodiment of monomer B, in formula (II), W 2 is optionally substituted C 2-6 alkylene, L 2 is -OC(O)-, and W 3 is a single bond or C 2-4 alkenylene, and it preferably contains one or more compounds in which both R 4 and R 5 are hydroxyl, and more preferably contains one or more compounds represented by formula (IIa) described later.

[0059] Monomer B is synthesized by a method combining known compounds and known synthesis methods. Also, commercially available products may be used as monomer B.

[0060] Among monomers B, formula (IIa): [Chemical formula] [In the formula, R 3a represents a hydrogen atom or methyl; W 2a represents a single bond or optionally substituted C 3-20 alkylene; L 2a represents -C(O)O-, -OC(O)-, or -OC(O)O-; W 3a is C 2-6 alkenylene; R 4a and R 5a each independently represent a hydrogen atom or hydroxyl; wherein, R 4a and R 5a are not both hydrogen atoms] The represented compound is a novel compound and can be synthesized, for example, by the following method.

[0061] 1. Dehydration condensation reaction of catechol group-containing carboxylic acid compound and hydroxyalkyl (meth)acrylate This reaction is, for example, in formula (IIa), W 2aIt can be applied to cases where the alkylene is unsubstituted, and specifically, a method of synthesizing (E)-4-((3-(3,4-dihydroxyphenyl)acryloyl)oxy)butyl acrylate by a dehydration condensation reaction between (E)-((3-(3,4-dihydroxyphenyl)acrylic acid and 4-hydroxybutyl acrylate can be mentioned. Since the synthesis method by dehydration condensation can synthesize the target product under relatively mild conditions, the workability is good. The method of dehydration condensation is not particularly limited.

[0062] 2. Ring-opening reaction of glycidyl group-containing (meth)acrylate with catechol group-containing carboxylic acid compound This reaction can be applied, for example, to cases where in formula (IIa), W 2a is an alkylene substituted with a hydroxyl group, and specifically, a method of synthesizing (E)-3-((3-(3,4-dihydroxyphenyl)acryloyl)oxy)-2-hydroxypropyl methacrylate by a ring-opening reaction of glycidyl methacrylate with 3-(3,4-dihydroxyphenyl)acrylic acid can be mentioned. 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, but as long as the resulting 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. Since the synthesis method by ring-opening reaction can synthesize the target product at a relatively low cost compared to other methods, the productivity is good. The method of ring-opening reaction is not particularly limited.

[0063] 3. Condensation reaction of catechol group-containing aliphatic alcohol compound with carboxylic acid group-containing (meth)acrylate This reaction can be applied, for example, to cases where in formula (IIa), W 2aIt can be applied, for example, when it is an alkylene substituted with a carboxylic acid group. Specifically, a method of synthesizing 2-((3,4-dihydroxybenzyl)oxy)-2-oxyethyl methacrylate 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 can be mentioned.

[0064] 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.

[0065] In addition, when producing the monomer B represented by the formula (II) or (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 the by-products without purifying and isolating the monomer B.

[0066] 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 substituted with a hydroxyl group 3-4 alkylene.

[0067] L 2a is preferably -O-, -C(O)O-, or -OC(O)-; more preferably -OC(O)-.

[0068] W 2a is preferably C2-4 is an alkenylene; more preferably ethenyl.

[0069] R 3a and R 4a are both preferably hydroxyl.

[0070] The content of monomer B in the composition is not particularly limited, but is preferably more than 5.0% by mass and less than 70.0% by mass, and more preferably 10.0 to 50% 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. When the curable resin composition is used 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 0.1 to 10% by mass, more preferably 0.3 to 5% by mass. By setting the content of monomer B in the composition to 0.5% by mass or more, it is possible to obtain a curable resin composition, an adhesive, and a surface coating agent that strongly bond to various types of materials.

[0071] Furthermore, in another embodiment, the content of monomer B relative to the total amount of monomer A and monomer B is preferably more than 5.0% by mass and less than 50.0% by mass, and more preferably 6.5 to 45% by mass. Also, the total content of monomer A and monomer B relative to the total monomer amount is preferably more than 55.0% by mass and less than 95.0% by mass, and more preferably 65.0 to less than 90% by mass.

[0072] (Crosslinkable monomer) In the curable resin composition according to an embodiment of the present disclosure, a crosslinkable monomer may be blended within a range that does not inhibit the object of the present invention. 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 methylene bisacrylamide and methylene bismethacrylamide; 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, methylidine triphenylene triisocyanate; polyfunctional amines having two or more (preferably two or three) carbon-carbon double bonds such as diallylamine and triallylamine; 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 kinds.

[0073] 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, or 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, or 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.

[0074] (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, 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) and (II). However, alkyl (meth) acrylates having 10 or more carbon atoms, particularly 15 or more carbon atoms, may inhibit the object of the present invention, and thus it is preferable not to contain them. In the present specification, the "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 constituting the (meth) acrylic acid part is not included in the number of carbon atoms. The same applies to alkyl (meth) acrylates having 15 or more carbon atoms.

[0075] 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, and the crosslinkable monomer.

[0076] The above-mentioned monomer components (monomer A, monomer B, crosslinkable monomer, and other monomers) may be used alone or in combination of two or more.

[0077] The curable resin composition according to an embodiment of the present disclosure may contain, within a range that does not inhibit the object of the present disclosure, in addition to the above-mentioned monomer components (monomer A, monomer B, crosslinkable monomer, and other monomers), a solvent and additives generally added to an adhesive or an adhesive. 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.

[0078] <Adhesive and method for producing the same> 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 viewed 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 have to be completely cured. The certain range may be determined according to the location where the two substrates are arranged, the purpose of use, and the like. So to speak, the adhesive may be an adhesive having an adhesiveness 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 preferably used in applications where vibration resistance and the like are required.

[0079] 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 fillers, etc., which are generally added to adhesives or bonding agents.

[0080] The adhesive according to an 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 an 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 polyvinyl chloride (PVC), polycarbonate (PC), 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 an 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 an embodiment of the present disclosure may also be used to join substrates of the same material.

[0081] Furthermore, the adhesive according to an embodiment of the present disclosure is also intended for use in joining a surface coating agent such as a so-called undercoat paint, a midcoat paint, a primer, etc. to a substrate.

[0082] 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, the shape of one and the other can be any of the shapes selected from a plate shape, a sheet shape, a rod shape, and the like.

[0083] The polymer contained in the adhesive can be obtained by polymerizing monomer A, monomer B, and a crosslinkable monomer. The polymerization method is not particularly limited, and examples thereof include bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, and the like. In particular, from the viewpoints of productivity and handleability, bulk polymerization and solution polymerization are preferable, and bulk polymerization is more preferable.

[0084] As the solvent for polymerizing the monomer component by the solution polymerization method, a non-aqueous organic solvent is preferable from the viewpoints of productivity and handleability. 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, and the like. 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.

[0085] When polymerizing the monomer component, a polymerization initiator can be used. Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator. Among them, a photopolymerization initiator is preferable from the viewpoint of not leaving a thermal history in the adhesive.

[0086] 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.

[0087] Examples of the thermal polymerization initiator include azo-based polymerization initiators such as dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobisisobutyronitrile (AIBN), dimethyl 2,2'-azobisisobutyrate, and azobisdimethylvaleronitrile; peroxide-based 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.

[0088] 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.

[0089] The order of blending each monomer when producing an adhesive by polymerizing each monomer is not particularly limited. As an example, an adhesive can be produced by blending monomer A, monomer B, and a crosslinkable monomer and then polymerizing each monomer. As another example, monomer A and monomer B are blended and then 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.

[0090] <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 paint. In addition to the above-described materials, the substrate also includes an undercoat paint, a midcoat paint, a primer, and the like.

[0091] 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, similarly 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 on the base material side of this cured product is bonded to the base material, and the other surface (typically the opposite surface of the base material) is in an exposed state. 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 will be omitted.

[0092] The adhesive and the surface coating agent according to one embodiment of the present disclosure described above are considered to bind 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 test methods such as those listed in the examples described later, 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.

[0093] 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.

[0094] 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, when making an adhesive with excellent viscoelasticity and toughness while suppressing adhesion, a peelable adhesive tape or the like can be produced. Also, when improving the adhesion, viscoelasticity, and toughness of the adhesive, an adhesive tape or the like that can guarantee bonding for a relatively long period, for example, can be produced.

[0095] 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 breakage of the resin that is the adhesive in two base materials joined by an adhesive. Generally, when measuring adhesion, the bonding between the two base materials collapses by the adhesive breaking or the bond between the base material and the adhesive being severed. The difference between adhesion and adhesiveness is generally that adhesiveness is an index for easy adhesion and easy peeling, while adhesion is an index for 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 field and the automotive field 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 field and the automotive field.

[0096] Although the reason why the adhesive according to one embodiment of the present disclosure binds more strongly to more types of base materials is not necessarily clear, it is considered as follows. When one base material is joined to another base material by an adhesive, the adhesive is interposed between the base materials, and typically, a cured product of the adhesive is formed between the base materials. Similarly, the surface coating agent can be said to be a cured product in which a cured product of a curable resin composition is joined to a base material. Depending on the installation location and use of these base materials, etc., stress such as vibration and impact may be directly or indirectly applied to these cured products, resulting in the cured products being destroyed or the bond between the surface of the base material and the surface of the cured product being destroyed. That is, in the adhesive, there is a possibility that the joining of the base materials (so to speak, the relative positional relationship between the base materials) cannot be maintained, and in the surface coating agent, the joining of the surface coating agent and the base material 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 base material can be maintained even when stress is directly or indirectly applied to the cured product.

[0097] Moreover, monomer B constituting the adhesive and the surface coating agent according to one embodiment of the present disclosure has a hydroxyl group. It is considered that the orientation of this group on the surface side of the base material is one of the factors that enables the adhesive and the surface coating agent according to one embodiment of the present disclosure to strongly bond to various types of materials.

Examples

[0098] The present disclosure will be described more specifically 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.

[0099] The chemicals used in this example are shown below together with abbreviations. <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-Hydroxyethyl acrylate (trade name: HEA, manufactured by Osaka Organic Chemical Industry Co., Ltd.) Monomer A4: 2-Methoxyethyl acrylate (trade name: 2-MTA, manufactured by Osaka Organic Chemical Industry Co., Ltd.) Monomer A5: (2-Methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate (MEDOL-10) (trade name: MEDOL-10, manufactured by Osaka Organic Chemical Industry Co., Ltd.) Monomer A6: Methyl acrylate (MA) (manufactured by Tokyo Chemical Industry Co., Ltd.) Monomer A7: Benzyl acrylate (trade name: Biscote #160 (abbreviation BZA), manufactured by Osaka Organic Chemical Industry Co., Ltd.) <Monomer B> Monomer B1: 2-(Acryloyloxy)ethyl 3,4-dihydroxybenzoate (DHBA-HEA) (manufactured according to Synthesis Example 1 described below) Monomer B2: (E)-3-((3-(3,4-Dihydroxyphenyl)acryloyl)oxy)-2-hydroxypropyl methacrylate (DHCA-GMA) (manufactured according to Example 1 described below) Monomer B3: 2-Hydroxy-3-(methacryloyloxy)propyl 3,4-dihydroxybenzoate (DHBA-GMA) (manufactured according to Synthesis Example 2 described below) <Other adhesive monomers> Adhesive monomer (DA): N-(3,4-Dihydroxyphenethyl)acrylamide <Crosslinkable monomer> Crosslinkable monomer 1: Trimethylolpropane triacrylate (TMP3A) Crosslinkable monomer 2: Toluene diisocyanate (TDI) (trade name: Coronate T-80, manufactured by Tosoh Corporation (a mixture of 2,4-tolylene diisocyanate / 2,6-tolylene diisocyanate = 80:20)) <Polymerization initiator> TPO: 2,4,6-Trimethylbenzoyl diphenyl acylphosphine oxide (manufactured by Tokyo Chemical Industry Co., Ltd.) <Base material> PVC: Polyvinyl chloride PC: Polycarbonate PET: Polyethylene terephthalate PP: Polypropylene PE: Polyethylene ABS: Acrylonitrile-butadiene-styrene copolymer resin Cu: Copper Al: Aluminum ITO: Indium tin oxide (coated on glass)

[0100] Synthesis Example 1: Synthesis of DHBA-HEA (Monomer B1) 12.33 g (80.0 mmol) of 3,4-dihydroxybenzoic acid, 60.0 g (461.0 mmol) of 2-hydroxyethyl acrylate (HEA), 23.01 g (120 mmol) of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC·HCl), and 0.49 g (4.0 mmol) of N,N-dimethylaminopyridine (DMAP) were placed in a container and stirred in an ice water bath for 7 hours. Then, 20.0 g of ethyl acetate was further added for dilution, and the mixture was washed 3 times with 50.0 g of water. The oily substance obtained by concentrating the resulting organic layer under reduced pressure was purified by silica gel column chromatography (n-hexane:ethyl acetate = 3:1) and concentrated to obtain DHBA-HEA (12.0 g, yield 59%, HPLC purity 100% / UV254 nm).

[0101] 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 72.0 g of cyclopentanone in a container and stirred in a water bath maintained at 80 °C for 21 hours. Then, water was added to the container, ethyl acetate was added, and DMAP was removed by washing with 3N HCl. The resulting 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%).

[0102] Example 1: Synthesis of DHCA-GMA (Monomer B2) 8.0 g (44.4 mmol) of caffeic acid, 12.7 g (88.8 mmol) of glycidyl methacrylate (GMA), and 0.38 g (3.1 mmol) of 4-dimethylaminopyridine (DMAP) were dissolved in 160 g of cyclopentanone in a container and stirred in a water bath maintained at 80 °C for 15 hours. Then, water was added to the container, ethyl acetate was added, and DMAP was removed by washing with 3N HCl. The resulting organic layer was concentrated under reduced pressure to obtain DHCA-GMA as an oily substance (HPLC purity 89% / UV210 nm). By 1H-NMR measurement, it was confirmed that this oily substance contained a compound in which GMA had reacted with two hydroxyl groups of the catechol of caffeic acid together with the target DHCA-GMA, and it was used in the examples without further purification. 1 By 1H-NMR measurement, it was confirmed that this oily substance contained a compound in which GMA had reacted with two hydroxyl groups of the catechol of caffeic acid together with the target DHCA-GMA, and it was used in the examples without further purification.

[0103] Examples 2 to 6: Preparation of curable resin compositions According to the composition in Table 1, 10 parts by mass of 2,4,6-trimethylbenzoyl diphenyl acylphosphine oxide (TPO) as a polymerization initiator was added to a formulation containing monomer A, monomer B, and a crosslinkable monomer, and mixed well to prepare each curable resin composition (hereinafter also referred to as a monomer solution) with respect to 100 parts by mass of the total amount of monomers contained in each formulation.

[0104] Comparative Examples 1 and 3 According to the composition in Table 1, 10 parts by mass of 2,4,6-trimethylbenzoyldiphenylacylphosphine oxide (TPO) as a polymerization initiator was added to the formulation containing monomer A and the crosslinkable monomer, based on 100 parts by mass of the total amount of monomers contained in each formulation, and mixed well to prepare a curable resin composition (hereinafter also referred to as a monomer solution).

[0105] Comparative Examples 2 and 4 A monomer solution was prepared in the same manner as in Examples 2 and 5, respectively, except that an adhesive monomer (N-(3,4-dihydroxyphenethyl)acrylamide (DA)) was used instead of monomer B.

[0106] Test Example 1: Adhesion Test ≪Preparation of Test Specimens≫ Each monomer solution prepared in Examples 2 to 6 and Comparative Examples 1 to 4 was applied onto a test plate formed of each material described in Table 1 using a bar coater No. 10. 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 prepare each test specimen, which was then allowed to stand at room temperature for 24 hours (film thickness 22.90 μm).

[0107] ≪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 specimens, using a cutter knife, the coating film was cross-cut (25 squares) in a 2×2 mm grid pattern. Subsequently, a 24 mm wide cellophane tape manufactured by Nichiban Co., Ltd. was affixed 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 when it was peeled off in 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.

[0108] [Evaluation Criteria] 0: The cut lines are completely smooth, and there is no peeling in any of the grid squares. 1: Small peeling at the intersection of cuts. Less than 5% is affected in the cross-cut part. 2: The coating film is peeling along the edge of the cut and / or at the intersection. 5 - 15% is affected in the cross-cut part. 3: The coating film has partial or complete large peeling along the edge of the cut, and / or various parts are partially or completely peeled off. 15 - 35% is affected in the cross-cut part. 4: The coating film has partial or complete large peeling along the edge of the cut, and / or several parts are partially or completely peeled off. Less than 35% is affected in the cross-cut part. 5: Large peeling that cannot be classified in the above 4.

[0109] ≪Results≫ The results are shown in Table 1. Note that the smaller the numerical value, the better the adhesion to the substrate, and an evaluation of 3 or less indicates a higher possibility of being preferably used. Comparing Examples 2 - 4 with Comparative Example 1, it can be seen that including Monomer B increases the types of substrates that exhibit good adhesion. Also, comparing with Comparative Example 2 using DA instead of Monomer B, it can be seen that the adhesion is improved in glass and ITO. Furthermore, Example 6 using DHCA - GMA as Monomer B shows excellent adhesion for all the materials tested, and comparing with Comparative Examples 3 and 4, it can be seen that the adhesion is significantly improved in glass, copper, aluminum, and ITO.

[0110]

Table 1

[0111] Examples 7 - 12: Preparation of curable resin composition According to the composition of Table 2, 2,4,6-trimethylbenzoyldiphenylacylphosphine oxide (TPO) was added as a polymerization initiator to each formulation containing Monomer A and Monomer B in an amount of 10 parts by mass based on 100 parts by mass of the total amount of monomers contained in each formulation, and the mixture was thoroughly mixed to prepare the curable resin compositions of Examples 7 to 12 (hereinafter also referred to as monomer solutions).

[0112] Comparative Examples 5 and 7 According to the composition of Table 2, 2,4,6-trimethylbenzoyldiphenylacylphosphine oxide (TPO) was added as a polymerization initiator to Monomer A in an amount of 10 parts by mass based on 100 parts by mass of Monomer A, and the mixture was thoroughly mixed to prepare a curable resin composition (hereinafter also referred to as a monomer solution).

[0113] Comparative Examples 6 and 8 Monomer solutions were prepared in the same manner as in Examples 7 and 10, respectively, except that an adhesive monomer (N-(3,4-dihydroxyphenethyl)acrylamide (DA)) was used instead of Monomer B.

[0114] Test Example 2: Adhesion Test ≪Preparation of Samples≫ Each monomer solution prepared in Examples 7 to 12 and Comparative Examples 5 to 8 was applied onto a test plate formed of any one of Cu, glass, Al, and ITO using a bar coater No. 10. Next, a PET film cut to 300 mm × 24 mm was placed on the coating film and crimped, and the coating film was completely cured by irradiating UV light with an exposure amount of 3000 mJ / cm 2 to prepare each sample, which was allowed to stand at room temperature for 24 hours.

[0115] ≪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. For each of the above samples, after gripping the end of the film and folding it back at 180° and peeling it off 25 mm from the test plate, the test plate was fixed to the lower chuck of the 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 of room temperature and humidity of 45% to start the measurement, and the peel adhesion was measured by averaging the measured values of the adhesion at 50% of the length peeled off from the test plate.

[0116] <<Results>> The results are shown in Table 2. The peel adhesions between each substrate of Examples 7 to 9 and Comparative Examples 5 and 6 and PET are relatively shown with the peel adhesion of Comparative Example 5 as 100, and the peel adhesions between each substrate of Examples 10 to 12 and Comparative Examples 7 and 8 and PET are relatively shown with the peel adhesion of Comparative Example 7 as 100. It should be noted that for adhesiveness, the larger the numerical value, the higher the adhesive strength. It can be seen that in Examples 7 to 9, the adhesive strength of the PET film to the test plate (Cu) was significantly improved compared to Comparative Example 5. Also, it can be seen that in Example 9, the adhesive strength of the PET film to the test plates (glass and ITO) was significantly improved compared to Comparative Example 5. Furthermore, it can be seen that in Example 7, the adhesive strength of the PET film to the test plates (Cu and Al) was improved compared to Comparative Example 1. In Example 10, the adhesive strength of the PET film to all the test plates is small compared to Comparative Example 7, but considering that the adhesive strength of Comparative Example 7 is about 1.4 to 14 times that of Comparative Example 5, it can be said that it shows sufficiently good adhesiveness.

[0117]

Table 2

[0118] Examples 13 to 16 Monomer A and Monomer B were each mixed in the monomer composition described in Table 3 (the total amount of Monomer A, B, and DA in Table 3). To the 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 was added later, and the mixture was stirred at 85°C for 5 hours. Thereafter, crosslinkable monomer 2 was added to each mixture according to the composition in Table 3 to prepare each mixture.

[0119] Comparative Examples 9 and 11 According to the composition in Table 3, 2,2'-azobisisobutyronitrile (AIBN) was added as a polymerization initiator to Monomer A 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 was added later, and the mixture was stirred at 85°C for 5 hours. Thereafter, crosslinkable monomer 2 was added to each mixture according to Table 3 to prepare the mixture.

[0120] Comparative Examples 10 and 12 Mixtures were prepared in the same manner as in Examples 13 and 16, respectively, except that an adhesive monomer (N-(3,4-dihydroxyphenethyl)acrylamide (DA)) was used instead of Monomer B.

[0121] Test Example 3: Adhesion Test ≪Preparation of Test Specimens≫ On one of two test plates (length: 25 mm × width: 10 mm) each of the combinations of PP-Al and Al-Al, the respective mixtures of Examples 13 to 16 and Comparative Examples 9 to 12 were applied to the entire surface 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 the position 12 mm from one end of one test plate, so that the other test plate was brought 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 specimen.

[0122] ≪Test Method≫ In accordance with JIS K 6850:1999 "Adhesives - Test Method for Tensile Shear Adhesion Strength of Rigid Substrates", one of the test plates constituting the test piece was pulled in the longitudinal direction, while 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.

[0123] ≪Results≫ The results are shown in Table 3. The adhesive forces of Examples 13 to 15 and Comparative Examples 9 and 10 are relatively represented with the adhesive force of Comparative Example 9 as 100, and the adhesive forces of Example 16 and Comparative Examples 11 and 12 are relatively represented with the adhesive force of Comparative Example 11 as 100. The larger the numerical value, the higher the adhesive force. From Table 2, it can be seen that the adhesiveness of PP - Al and Al - Al is significantly improved by Monomers B1 to B3. Also, it can be seen that in Example 16 using Monomer B3, the adhesiveness of PP - Al and Al - Al is significantly improved compared to Comparative Example 12 using the adhesive monomer (DA).

[0124]

Table 3

[0125] Test Example 5: Solubility Test for Monomer A The solubility of the adhesive monomers (Monomer B1 (DHBA - HEA), Monomer B3 (DHBA - GMA), and DA) in the base monomer (Monomer A) at room temperature was determined by adding each base monomer to 0.20 g of each adhesive monomer in a 50°C water bath to dissolve a part (not completely dissolved), allowing it to stand overnight at room temperature, and quantifying the adhesive monomer dissolved in the supernatant by HPLC. When 50 wt% or more was dissolved, it was evaluated as ≧50 without quantification by HPLC. <HPLC Analysis Conditions> Equipment: Agilent 1260 Infinity LC [manufactured by Agilent Technologies, Inc.] Column: YMC - PacK ODS - AM AM - 302 150 mm × φ4.6 mm, S - 5μm·120A Temperature: 40°C Mobile phase: Acetonitrile / 0.5 wt% phosphoric acid = 1 / 1, flow rate 1 mL / min UV 254 nm

[0126] ≪Results≫ The results are shown in Table 4. In the table, "poor solubility" means a solubility of 1.5% or less, and "-" indicates that the test has not been conducted. It can be seen that monomer B1 has improved solubility compared to DA with respect to monomers A such as monomer A2 (THFA), monomer A4 (2-MTA), monomer A5 (MEDOL-10), and monomer A6 (AM). Monomer B3 shows a very high solubility of 50 wt% or more with respect to all monomers A (monomer A1 (4-HBA), monomer A2 (THFA), monomer A3 (HEA), monomer A7 (AZB)) tested, and it can be seen that the solubility is significantly improved compared to DA.

[0127]

Table 4

[0128] Test Example 6: Solubility test in solvents The solubility of the adhesive monomers (monomer B3 (DHBA-GMA) and DA) in solvents at room temperature was determined in the same manner as in Test Example 5. The results are shown in Table 5. In the table, "poor solubility" indicates a solubility of 1.5% or less. It can be seen that monomer B3 shows a very high solubility of 50 wt% or more with respect to all solvents tested, and the solubility is significantly improved compared to DA.

[0129]

Table 5

Claims

1. A curable resin composition containing monomer A and monomer B, 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, —O—, —NH—, or —NR 6 -, -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 6 is an optionally substituted C 1-8 represents alkyl], and monomer B is represented by formula (II): 【Chemistry 2】 [In the formula, R 3 represents a hydrogen atom or methyl; W 2 represents a single bond or an optionally substituted C 1-20 alkylene; L 2 represents a single bond, —O—, —CH(OH)—, —C(O)O—, —OC(O)—, or —OC(O)O—; W 3 represents a single bond, C 1-6 alkylene, C 2-6 alkenylene; R 4 and R 5 Each of which represents hydroxyl], and is a curable resin composition in which the content of monomer B in the composition is 0.5% by mass or more.

2. L 1 The curable resin composition according to claim 1, wherein L is a single bond or -O-.

3. R 2 but, (1) Methyl, (2) Hydroxyl, (3) optionally substituted C 1-6 Alkoxy, (4) An optionally substituted 3- to 8-membered saturated heterocyclic group, or (5) An optionally substituted phenyl The curable resin composition according to claim 1 or 2.

4. W 1 is a single bond or C 1-6 alkylene, and W 2 C optionally substituted with hydroxyl 1-6 The curable resin composition according to any one of claims 1 to 3, wherein the alkylene is alkylene.

5. L 2 The curable resin composition according to any one of claims 1 to 4, wherein L is -OC(O)-.

6. W 3 is a single bond or C 2-6 The curable resin composition according to any one of claims 1 to 5, which is alkenylene.

7. The curable resin composition according to any one of claims 1 to 6, wherein the content of monomer B in the composition is more than 10.0% by mass and less than 50.0% by mass.

8. The curable resin composition according to any one of claims 1 to 7, further containing a crosslinkable monomer.

9. The curable resin composition according to claim 8, wherein the crosslinkable monomer is a polyfunctional (meth)acrylate and / or a polyfunctional isocyanate.

10. An adhesive or a surface coating agent containing a polymer containing monomer A and monomer B as constituent units, wherein monomer A is represented by formula (I): 【Chemistry 3】 [wherein, R 1 represents a hydrogen atom or methyl; L 1 represents a single bond, -O-, -NH-, -NR 6 -, -NHCOO-, or -NHCONH-; W 1 is a single bond, or C 1-20 represents 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 6 is one or more compounds represented by [which may represent an optionally substituted C 1-8 alkyl], and and monomer B is represented by formula (II): [Chemical Formula 4] [In the formula, R 3 represents a hydrogen atom or methyl; W 2 is a hydroxyl-substituted C 1-20 represents alkylene; L 2 represents a single bond, —O—, —CH(OH)—, —C(O)O—, —OC(O)—, or —OC(O)O—; W 3 represents a single bond, C 1-6 alkylene, or C 2-6 alkenylene; R 4 and R 5 is one or more compounds represented by [wherein both represent hydroxyl], and an adhesive or a surface coating agent in which the content of monomer B is 1.0% by mass or more based on the total amount of monomer A and monomer B.

11. W 3 is a single bond or C 2-6 The adhesive or surface coating agent according to claim 10, wherein the adhesive or surface coating agent is alkenylene.

12. Formula (IIa): [Chemical Formula 5] [In the formula, R 3a represents a hydrogen atom or methyl; W 2a represents C alkylene substituted with hydroxyl; 3-20 ​ L 2a represents a single bond, -O-, -CH(OH)-, -C(O)O-, -OC(O)-, or -OC(O)O-; W 3a represents C 2-6 alkenylene; R 4a and R 5a each independently represents a hydrogen atom or a hydroxyl group; Here, R 4a and R 5a and neither of them is a hydrogen atom.

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