Resin composition, surface treatment method, and method for producing cured coating film-containing material

Abstract

To provide a resin composition which dissolves defects of a conventional art, and is excellent in low odor property, crack resistance in a cold heat cycle test, chemical resistance and air dryness, without using a copolymerizable monomer such as styrene with many regulations.SOLUTION: A resin composition contains a component (a) and a component (b). The component (a) has a structure derived from one or more compounds (DA) selected from the group consisting of a dimer acid which is a dimer of an unsaturated aliphatic acid having 18 carbon atoms and a trimer acid which is a trimer of an unsaturated aliphatic acid having 18 carbon atoms, a structure derived from a bisphenol a type epoxy resin (BP), a (meth)acryloyloxy group, and a terminal structure (T1) of a formula (1). The component (b) is a reactive diluent having a (meth)acryloyloxy group and viscosity at 25°C of 2 to 500 mPa s. In the formula, R1=H / CH3, and R2=H / (meth)acryloyl group.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin composition, a surface treatment method, and a method for manufacturing a cured coating film-containing material.

Background Art

[0002] For resins required for applications such as rooftop waterproofing, lining of concrete and mortar for sewers, verandas, corridors, pools, roads, water receiving tanks, etc., paints, putties, adhesives, etc., they should maintain high elongation against vibrations of buildings, cracks in the underlying concrete or mortar, and impacts of falling objects, and the waterproof layer should sufficiently follow the underlying concrete. In addition to this, the waterproof layer should have alkali resistance against Ca(OH)2 oozing out from the underlying concrete in contact with the waterproof layer, and further have high adhesiveness to the substrate. If the waterproof layer cannot sufficiently follow the stress of the elongation of the underlying concrete, cracks will occur in the waterproof layer, causing peeling from the underlying concrete or water infiltration. When water contacts the concrete, Ca(OH)2 oozes out and further deteriorates the waterproof layer.

[0003] Particularly, in the case of sewers, in the gas phase part of the concrete structures of sewer treatment facilities, hydrogen sulfide by sulfur-oxidizing bacteria is sulfated, and with long-term use, the surface becomes vulnerable, affecting the structural strength of the facilities.

[0004] For the repair method of aging sewer treatment facilities, a method is usually used in which a cross-sectional repair material is applied to the deteriorated layer thickness of the wall surface of the existing deteriorated concrete structure, hardened, then a primer is applied, and then a base adjustment material is applied for the purpose of unevenness adjustment, and subsequently a coating-type resin lining material is applied. Also, in the case of constructing new structures, a method is used in which a primer is applied to the concrete base, and then a base adjustment material is applied for the purpose of unevenness adjustment, and then an anticorrosive coating resin lining material is applied.

[0005] As the curable resin composition used for the coating-type resin lining material as described above, an unsaturated polyester resin composition has conventionally been used. Recently, a resin composition containing epoxy (meth)acrylate obtained by reacting an epoxy resin with an unsaturated monobasic acid, particularly acrylic acid or methacrylic acid (generally referred to as a "vinyl ester resin composition") has also been used.

[0006] In known unsaturated polyester resin compositions and vinyl ester resin compositions used for coating-type lining materials, styrene monomer is generally used as a reactive diluent (monomer). However, the mixture of this ester and styrene has a peculiar odor, and this odor diffuses into the surrounding environment during construction, causing problems. Therefore, a method of adsorbing volatile styrene with an activated carbon adsorption device has been introduced. In addition, for styrene, the emission quantity and transfer quantity publication system is applicable due to its designation as a Class I Specified Chemical Substance under the PRTR Act (Act on Promotion of Chemical Substances Discharge Control). Moreover, styrene was designated as a Specified Chemical Substance as of November 1, 2014 (Ministry of Health, Labour and Welfare), and its management is necessary. In addition, the regulation of the styrene concentration in styrene-containing unsaturated polyester resins and vinyl ester resins has become stricter, and countermeasures are urgently required.

[0007] Furthermore, unsaturated polyester resins generally have good rigidity and heat resistance, but are poor in elongation, water resistance, and alkali resistance. In addition, vinyl ester resins, which are excellent in water resistance and alkali resistance, have a low elongation rate. Therefore, improvement of these properties is desired.

[0008] As a method for imparting elongation to these unsaturated polyester resins and vinyl ester resins, there is a method of adding a flexibility-imparting agent to the resin, such as a flexible resin, a plasticizer, etc. Specifically, it is a method of dispersing and modifying a liquid polybutadiene copolymer such as a terminal carboxy group-modified butadiene-acrylonitrile copolymer, a terminal vinyl group-modified polybutadiene-acrylonitrile copolymer, etc. in the resin, or a method of dissolving and curing a compatible rubber component. Furthermore, a method of obtaining an elastic polymer by defining the mol% of the unsaturated acids in the main chain and at the terminals of the molecular structure of the unsaturated polyester as disclosed in Patent Document 1 is known as a known technique.

[0009] However, in these conventional techniques, for example, in the method of adding a flexible resin or a plasticizer, it is difficult to obtain a resin with a low water absorption rate. Furthermore, in the method of dispersing a liquid polybutadiene copolymer, the compatibility of the two components often becomes a problem, and in that case, it is likely to become a brittle resin. Also, the solution in which the liquid polybutadiene copolymer is dispersed has extremely poor workability due to its high viscosity. The method of obtaining an elastic polymer by defining the mol% of the unsaturated acids in the main chain and at the terminals in the molecular structure of the unsaturated polyester is effective for imparting elongation and impact resistance at room temperature, but in order to lower the crosslink density of the cured product, it will further increase the water absorption rate.

[0010] For the purpose of solving these problems, it has been proposed in Patent Document 2 to use a vinyl ester resin having a dimer acid or a dimer acid derivative in its molecular structure, but even when this method is used, the water absorption at high temperatures is still not sufficient.

[0011] On the other hand, regarding the response to the regulation of styrene, a resin composition comprising a so-called epoxy acrylate or epoxy methacrylate (i.e., a vinyl ester resin) obtained by reacting an epoxy resin with an unsaturated monobasic acid, particularly acrylic acid or methacrylic acid, and a mixture of monomers copolymerizable with this vinyl ester resin is known.

[0012] Regarding the technology of low-odor resin compositions, technologies related to low odor are disclosed in Patent Document 3, Patent Document 4, etc. Further, as a lining material using a photopolymerizable resin composition in which a photoinitiator is added to a curable resin composition and cured by ultraviolet irradiation, for example, Patent Document 5 describes a photocurable material containing an unsaturated polyester and / or a vinyl ester resin and a bisacylphosphine oxide compound. However, such resin compositions are not yet sufficient in terms of performance such as low odor, water resistance, chemical resistance, durability, adhesion, and air-dryability.

[0013] Furthermore, regarding the technology of aqueous resin compositions, for example, technologies related to aqueous systems are disclosed in Patent Document 6, Patent Document 7, etc. All of them have active hydrogen-containing compounds, polyisocyanate compounds, hydraulic cement, water, and cement water reducers as basic components. However, none of these materials had sufficient various properties such as the strength, waterproofness, and adhesiveness of the cured product, nor sufficient curing properties.

[0014] In addition, as other aqueous lining materials, emulsion-type aqueous lining materials such as those in Patent Document 8 and Patent Document 9 have been proposed. However, the technology described in Patent Document 8 utilizes the reaction between the carboxy group in the acrylic resin emulsion and a crosslinking agent having a carboximide group, and the reaction between the alcoholic hydroxyl group in the acrylic resin emulsion and a compound containing a plurality of isocyanato groups. Essentially, like Patent Document 6 and Patent Document 7, various properties such as the strength, waterproofness, and adhesiveness of the cured product, and the curing properties were not sufficient.

[0015] Regarding the technology described in Patent Document 9, it is an aqueous lining material using a radical-curable resin composition obtained by emulsifying a mixture of a vinyl ester resin, a polymerizable unsaturated monomer, water, a hardening accelerator, a reactive surfactant, and fibers, and using an organic peroxide as a curing agent as needed. Although this aqueous lining material exhibits resistance to repeated cold and heat tests by borrowing the strength of the fibers, the resistance of the resin cured product itself to repeated cold and heat tests was not satisfactory.

Prior Art Documents

Patent Document

[0016]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Patent Document 8

Patent Document 9

Summary of the Invention

Problems to be Solved by the Invention

[0017] An object of the present invention is to provide a non-styrene type vinyl ester resin-based polymerizable resin composition having low odor, crack resistance during a thermal cycle test, chemical resistance, and good workability. That is, an object is to provide a polymerizable resin composition that has an elongation rate of a resin cured product capable of withstanding a thermal cycle test, is resistant to a chemical resistance test (acid resistance test), has an appropriate resin viscosity, and has good workability.

[0018] Furthermore, the present invention also aims to provide a surface treatment material applied to the surfaces of metals, plastics, concrete, mortar, wood, glass, etc., which uses a resin composition containing the resin composition having the above characteristics as an essential component, and a surface treatment method using the surface treatment material. In addition, the present invention also aims to provide a method for manufacturing a resin-treated surface formed by applying a resin composition containing the resin composition having the above characteristics as an essential component to the surfaces of metals, plastics, concrete, mortar, wood, glass, etc.

Means for Solving the Problems

[0019] As a result of intensive studies, the present inventors have found that the above problems can be solved by using a resin composition containing the following components (a) and (b), and thus have arrived at the present invention. In this specification, when "~" is used for a numerical range, the numerical values at both ends are the upper limit value and the lower limit value, respectively, and are included in the numerical range. When a plurality of upper limit values or lower limit values are described, a numerical range can be formed from all combinations of the upper limit value and the lower limit value. Similarly, when a plurality of numerical ranges are described, separate numerical ranges can be formed by individually selecting and combining the upper limit value and the lower limit value from those numerical ranges. That is, the present invention is as follows. [1] A resin composition containing component (a) and component (b), wherein Component (a) has, in the molecule, a structure derived from at least one compound (DA) selected from the group consisting of dimer acid which is a dimer of an unsaturated fatty acid having 18 carbon atoms and trimer acid which is a trimer of an unsaturated fatty acid having 18 carbon atoms, a structure derived from bisphenol A type epoxy resin (BP), a (meth)acryloyloxy group derived from (meth)acrylic anhydride, and a terminal structure (T1) represented by the following formula (1), Component (b) is at least one reactive diluent having at least one (meth)acryloyloxy group in the molecule and having a viscosity of 2 to 500 mPa·s at 25°C, and is a resin composition.

Chemical formula

[10] The resin composition according to any one of [1] to [9], wherein the content of the component (a) is 60 to 80% by mass and the content of the component (b) is 20 to 40% by mass with respect to the total amount of all the polymerizable components including the component (a) and the component (b).

[11] The resin composition according to any one of [1] to

[10] , further comprising a polymerization accelerator as the component (c).

[12] The resin composition according to any one of [1] to

[11] , further comprising a polymerization initiator as the component (d).

[13] The resin composition according to

[12] , wherein the component (d) is at least one organic peroxide.

[14] The polymer of the resin composition according to

[12] .

[15] A surface treatment material applied to at least one surface selected from the group consisting of metal, plastic, concrete, mortar, wood and glass, the surface treatment material comprising the resin composition according to

[12] .

[16] A method for surface treatment of a material selected from the group consisting of metal, plastic, concrete, mortar, wood, and glass, comprising: A first step of preparing a coating solution by adding a polymerization initiator as component (d) to the resin composition according to any one of [1] to

[11] ; A second step of applying the coating solution prepared in the first step to the surface of the material and then curing it at 0 to 50°C to form a cured coating film on the surface of the material; A surface treatment method comprising the above steps.

[17] A method for producing a cured coating film-containing material, comprising a step of forming the cured coating film on the surface of the material using the surface treatment method of

[16] . [Advantages of the Invention]

[0020] According to the present invention, even without using a copolymerizable monomer with many regulations such as styrene, it is possible to eliminate the disadvantages of the prior art and provide a polymerizable resin composition excellent in low odor, crack resistance during a thermal cycle test, chemical resistance, and workability. [Embodiments for Carrying out the Invention]

[0021] (Resin Composition) The resin composition according to an embodiment of the present invention (hereinafter sometimes referred to as the resin composition of the present embodiment) contains component (a) and component (b). The component (a) has a structure derived from one or more compounds (DA) selected from the group consisting of dimer acid which is a dimer of an unsaturated fatty acid having 18 carbon atoms and trimer acid which is a trimer of an unsaturated fatty acid having 18 carbon atoms in the molecule, a structure derived from bisphenol A type epoxy resin (BP), a (meth)acryloyloxy group, and a terminal structure (T1) of the following formula (1) in the molecule. The component (b) is at least one reactive diluent having at least one (meth)acryloyloxy group in the molecule and having a viscosity at 25°C of 2 to 500 mPa·s. [Chemical Formula]

[0022] In the above formula (1), R1 represents H or CH3. The dashed line represents the bonding site. R 2 represents H or a (meth)acryloyl group.

[0023] Hereinafter, each component used in the resin composition of the present embodiment will be described in detail, but the present invention is not limited thereto.

[0024] <Component (a)> Component (a) contained in the resin composition of the present embodiment has a structure derived from one or more compounds (DA) selected from the group consisting of dimer acid which is a dimer of an unsaturated fatty acid having 18 carbon atoms and trimer acid which is a trimer of an unsaturated fatty acid having 18 carbon atoms in the molecule, a structure derived from bisphenol A type epoxy resin (BP), a (meth)acryloyloxy group, and the terminal structure (T1) of the above formula (1). In addition, the (meth)acryloyloxy group contained in the terminal structure of the formula (1) is also counted in the number of moles of the (meth)acryloyloxy group.

[0025] The structure derived from (BP) derived from the above bisphenol A type epoxy resin is an organic residue derived from bisphenol A type epoxy resin. When the bisphenol A type epoxy resin is an n-mer of bisphenol A, it is an organic residue derived from bisphenol A type epoxy resin including the n-mer. The structure derived from (DA) derived from one or more compounds selected from the group consisting of dimer acid which is a dimer of an unsaturated fatty acid having 18 carbon atoms and trimer acid which is a trimer of an unsaturated fatty acid having 18 carbon atoms is an organic residue derived from one or more compounds selected from the group consisting of dimer acid which is a dimer of an unsaturated fatty acid having 18 carbon atoms and trimer acid which is a trimer of an unsaturated fatty acid having 18 carbon atoms.

[0026] The "dimer acid which is a dimer of an unsaturated fatty acid having 18 carbon atoms" referred to here is a dicarboxylic acid having 36 carbon atoms produced by dimerization of an unsaturated fatty acid having 18 carbon atoms using vegetable oils such as linoleic acid as a raw material, and is, for example, as described in Non-Patent Document 1 (Akira Misono, Yasuzo Uchida, Journal of the Oil Chemical Society, 15, 363-368 (1966)).

[0027] The "trimer acid which is a trimer of an unsaturated fatty acid having 18 carbon atoms" referred to herein is a tricarboxylic acid having 54 carbon atoms produced by trimerization of an unsaturated fatty acid having 18 carbon atoms using vegetable oils and fats such as linoleic acid as a raw material.

[0028] The terminal structure (T1) of the formula (1) can generally be obtained by an addition reaction of acrylic acid or methacrylic acid and a compound having a glycidyl group. Further, the terminal structure (T1) of the formula (1) can generally be obtained by an addition reaction of glycidyl acrylate or glycidyl methacrylate and a compound having a carboxy group.

[0029] In addition, R in the formula (1) 1 represents H or CH3. However, when importance is attached to the hydrolysis resistance of the polymer of the resin composition of the present embodiment described later, R in the formula (1) 1 is preferably CH3.

[0030] The component (a) contained in the resin composition of the present embodiment is a compound having a structure derived from a bisphenol A type epoxy resin, and preferably a compound having at least one of the structures of the following formula (2) and the following formula (3).

[0031] One of the preferable factors that the resin composition of the present embodiment contains a compound having at least one of the structures of the formula (2) and the formula (3) is that when the polymer of the resin composition of the present embodiment is produced, the polymer is less likely to become opaque and is likely to form a uniform transparent film. As a result, the physical properties of the polymer film are stabilized. In addition, it can be mentioned that the water resistance is improved by containing a compound having at least one of the structures of the formula (2) and the formula (3).

[0032]

Chemical formula

[0033] In formula (2), R 11 and R 3 each independently represents H or CH3, and X represents a hydrocarbon group obtained by removing a carboxy group from the dimer acid. The dashed line represents the bonding site. R 21 represents H or a (meth)acryloyl group. R 6 represents H or a (meth)acryloyl group. n = 1 to 10. n is preferably n = 1 to 5, and more preferably n = 1. If n is within that range or value, the viscosity does not become too high and the workability is good.

[0034]

Chemical formula

[0035] In formula (3), R 12 and R 5 each independently represents H or CH3, and Y represents a hydrocarbon group obtained by removing a carboxy group from the trimer acid. The dashed line represents the bonding site. R 22 represents H or a (meth)acryloyl group. R 7 represents H or a (meth)acryloyl group. p = 1 to 10.

[0036] When emphasizing the hydrolysis resistance of the polymer according to this embodiment, R 11 in formula (2) is preferably CH3.

[0037] Also, when emphasizing the hydrolysis resistance of the polymer according to this embodiment, R 12 in formula (3) is preferably CH3.

[0038] In the component (a), when importance is attached to the flexibility, thermal stability, and light stability of the polymer according to the present embodiment, the proportion of the total amount of hydrocarbon groups derived from dimer acid, which is a dimer of an unsaturated fatty acid having 18 carbon atoms containing the hydrocarbon group X and the hydrocarbon group Y, and trimer acid, which is a trimer of an unsaturated fatty acid having 18 carbon atoms, in the total amount of the component (a) is preferably 10% by mass or more, more preferably 15% by mass or more.

[0039] Also, as described above, in the component (a), when importance is attached to the curing rate at the air contact surface of the resin composition in contact with air during the polymerization of the resin composition of the present embodiment, the proportion of the total amount of hydrocarbon groups derived from dimer acid, which is a dimer of an unsaturated fatty acid having 18 carbon atoms containing the hydrocarbon group X and the hydrocarbon group Y, and trimer acid, which is a trimer of an unsaturated fatty acid having 18 carbon atoms, in the total amount of the component (a) is preferably 40% by mass or more, more preferably 60% by mass or more. However, when importance is attached to thermal stability and light stability, it may also be solved by using an antioxidant or an ultraviolet absorber in some cases.

[0040] As an example of the component (a), when it contains the structure of the formula (2), a compound having the structure described in the following formula (4) can be mentioned.

[0041]

Chemical formula

[0042] (In the formula, R 13 , R 13a , R 3 , R 3a each independently represents H or CH3, R 6 , R 6a represents H or a (meth)acryloyl group, X represents a hydrocarbon group obtained by removing a carboxy group from the dimer acid. L represents an integer from 1 to 10. R 23 , R 23a represents H or a (meth)acryloyl group. n and o represent integers from 1 to 10. R 6 , R6a At least one of them is a (meth)acryloyl group.)

[0043] As other examples of the component (a), when it contains the structure of the above formula (3), compounds having the structure described in the following formula (5) can be mentioned.)

[0044] [Chemical formula]

[0045] (In the formula, R 14 , R 14a , R 5 , R 5a each independently represents H or CH3, R 7 , R 7a represents H or a (meth)acryloyl group, Y represents a hydrocarbon group obtained by removing a carboxy group from the above trimer acid. m represents an integer of 1 to 10. R 24 , R 24a represents H or a (meth)acryloyl group. p and q represent integers of 1 to 10. R 7 , R 7a At least one of them is a (meth)acryloyl group.)

[0046] When the mol ratio of the structure derived from the above (DA) in the component (a) is represented by the following formula (A), the mol ratio of the structure derived from the above (DA) is preferably 0.07 to 0.3, and more preferably 0.07 to 0.25.)

[0047] Mol ratio of the structure derived from (DA)=[(mol number of the structure derived from (DA))] / [(mol number of the structure derived from (DA))+(mol number of the structure derived from (BP))+(mol number of the (meth)acryloyloxy group)] (A) Note that the "number of moles of the structure derived from (DA)" is the total number of moles of the structures of formula (10) and formula (11), and the "number of moles of the structure derived from (BP)" is the number of moles of the structure of formula (12). The "number of moles of (meth)acryloyloxy group" is the total number of moles of all (meth)acryloyloxy groups bonded as the terminal structure (T1) or side chains.

[0048]

Chemical formula

[0049]

Chemical formula

[0050]

Chemical formula

[0051] When the mol ratio of the (meth)acryloyloxy group other than the terminal structure (T1) in the component (a) is represented by the following formula (B), the mol ratio of the (meth)acryloyloxy group other than the terminal structure (T1) is preferably 0.25 to 0.52, more preferably 0.30 to 0.47, and still more preferably 0.35 to 0.42.

[0052] Mol ratio of (meth)acryloyloxy group other than terminal structure (T1) = [Number of moles of (meth)acryloyloxy group other than terminal structure (T1)] / [(Number of moles of structure derived from (DA)) + (Number of moles of structure derived from (BP)) + (Number of moles of (meth)acryloyloxy group)] (B)

[0053] In the component (a), the mol ratio of the structure derived from (DA) represented by the formula (A) is 0.07 to 0.3, and the mol ratio of the (meth)acryloyloxy group other than the terminal structure (T1) represented by the formula (B) of the terminal structure (T1) is preferably 0.25 to 0.52. It is more preferable that the mol ratio of the structure derived from (DA) is 0.07 to 0.25, and the mol ratio of the (meth)acryloyloxy group other than the terminal structure (T1) is 0.30 to 0.47. Further, it is more preferable that the mol ratio of the structure derived from (DA) is 0.07 to 0.25, and the mol ratio of the (meth)acryloyloxy group other than the terminal structure (T1) is 0.35 to 0.42.

[0054] The component (a) contained in the resin composition of the present embodiment is preferably obtained by reacting a bisphenol A type epoxy resin (BP) with one or more compounds (DA) selected from the group consisting of dimer acid which is a dimer of an unsaturated fatty acid having 18 carbon atoms and trimer acid which is a trimer of an unsaturated fatty acid having 18 carbon atoms, and then reacting with maleic anhydride (meth)acrylate. With respect to 1 mol of the bisphenol A type epoxy resin (BP), the amount of one or more compounds (DA) selected from the group consisting of dimer acid which is a dimer of an unsaturated fatty acid having 18 carbon atoms and trimer acid which is a trimer of an unsaturated fatty acid having 18 carbon atoms to be reacted is preferably 0.1 to 0.6 mol, more preferably 0.2 to 0.5 mol, and still more preferably 0.3 to 0.4 mol.

[0055] It is more preferable that the component (a) is obtained by reacting a bisphenol A type epoxy resin (BP) with one or more compounds (DA) selected from the group consisting of dimer acid which is a dimer of an unsaturated fatty acid having 18 carbon atoms and trimer acid which is a trimer of an unsaturated fatty acid having 18 carbon atoms, and then reacting with maleic anhydride (meth)acrylate and (meth)acrylate. Preferably, the amount of the (meth)acrylic acid is 0.25 to 1.70 mol, more preferably 0.4 to 1.4 mol, and even more preferably 0.5 to 1.1 mol, per 1 mol of the anhydrous (meth)acrylic acid.

[0056] Specifically, as a method for obtaining component (a), for example, bisphenol A diglycidyl ether and dimer acid are used such that the number of moles of the glycidyl group of bisphenol A diglycidyl ether is larger than the number of moles of the carboxyl group of dimer acid, and they are heated and reacted in the presence of a catalyst. Then, the glycidyl group not used in the reaction of bisphenol A diglycidyl ether and dimer acid is reacted with (meth)acrylic acid, and further reacted with anhydrous (meth)acrylic acid to obtain it (Method 1). Also, in the above Method 1, instead of "reacting the glycidyl group with (meth)acrylic acid and further reacting with anhydrous (meth)acrylic acid", the glycidyl group may be reacted with (meth)acrylic acid and anhydrous (meth)acrylic acid simultaneously by adding (meth)acrylic acid and anhydrous (meth)acrylic acid at the same time. Alternatively, instead of "reacting the glycidyl group with (meth)acrylic acid and further reacting with anhydrous (meth)acrylic acid", the glycidyl group may be reacted only with anhydrous (meth)acrylic acid. Similarly, when using trimeric acid instead of dimeric acid, for example, 3 mol of bisphenol A diglycidyl ether (i.e., 6 mol of glycidyl groups in bisphenol A diglycidyl ether) and 1 mol of trimeric acid (i.e., 3 mol of carboxyl groups of trimeric acid) are heated and reacted in the presence of a catalyst. Then, the glycidyl groups not used in the reaction of bisphenol A diglycidyl ether and trimeric acid (in the case of 100% reaction rate, 3 mol of glycidyl groups will remain unused) are reacted with (meth)acrylic acid, and further reacted with anhydrous (meth)acrylic acid to obtain the product (Method 1'). In the above Method 1', instead of "reacting the glycidyl groups with (meth)acrylic acid and further reacting with anhydrous (meth)acrylic acid", the glycidyl groups may be reacted with (meth)acrylic acid and anhydrous (meth)acrylic acid simultaneously by adding (meth)acrylic acid and anhydrous (meth)acrylic acid at the same time. Alternatively, instead of "reacting the glycidyl groups with (meth)acrylic acid and further reacting with anhydrous (meth)acrylic acid", the glycidyl groups may be reacted only with anhydrous (meth)acrylic acid.

[0057] As another method, for example, bisphenol A diglycidyl ether and dimeric acid are used in such a way that the number of moles of glycidyl groups in bisphenol A diglycidyl ether is less than the number of moles of carboxyl groups in dimeric acid, heated and reacted in the presence of a catalyst. Then, the carboxyl groups not used in the reaction of bisphenol A diglycidyl ether and dimeric acid are reacted with glycidyl methacrylate, and further reacted with anhydrous (meth)acrylic acid to also obtain the product (Method 2). Similarly, when using trimeric acid instead of dimeric acid, for example, 2 mol of bisphenol A diglycidyl ether (i.e., 4 mol of glycidyl groups in bisphenol A diglycidyl ether) and 3 mol of trimeric acid (i.e., 9 mol of carboxyl groups of trimeric acid) are heated and reacted in the presence of a catalyst. Then, the carboxyl groups not used in the reaction of bisphenol A diglycidyl ether and trimeric acid (in the case of 100% reaction rate, 5 mol of carboxyl groups will remain unused) are reacted with glycidyl methacrylate, and further reacted with (meth)acrylic anhydride to obtain the product (Method 2').

[0058] Furthermore, as another method, for example, dimeric acid diglycidyl ester and bisphenol A are used such that the number of moles of phenolic hydroxyl groups of bisphenol A is less than the number of moles of glycidyl groups of dimeric acid diglycidyl ester, and they are reacted in the presence of a catalyst. Then, the glycidyl groups derived from dimeric acid diglycidyl ester not used in the reaction of dimeric acid diglycidyl ester and bisphenol A are reacted with (meth)acrylic acid, and further reacted with (meth)acrylic anhydride to also obtain the product (Method 3). Similarly, when using trimeric acid triglycidyl ester instead of dimeric acid diglycidyl ester, for example, 3 mol of bisphenol A (i.e., 6 mol of phenolic hydroxyl groups of bisphenol A) and 5 mol of trimeric acid triglycidyl ester (i.e., 15 mol of glycidyl groups of trimeric acid triglycidyl ester) are heated and reacted in the presence of a catalyst. Then, the glycidyl groups not used in the reaction of bisphenol A and trimeric acid triglycidyl ester (in the case of 100% reaction rate, 9 mol of glycidyl groups will remain unused) are reacted with (meth)acrylic acid, and further reacted with (meth)acrylic anhydride to obtain the product (Method 3').

[0059] Furthermore, as another method, for example, diglycidyl ester of dimer acid and bisphenol A are used with the moles of phenolic hydroxyl groups of bisphenol A being more than the moles of ester structure of diglycidyl dimer acid, heated in the presence of a catalyst, reacted, and then the phenolic hydroxyl groups not used in the reaction of bisphenol A and diglycidyl dimer acid are reacted with glycidyl methacrylate, and further reacted with (meth)acrylic anhydride, whereby it can also be obtained (Method 4). Similarly, when using triglycidyl ester of trimer acid instead of diglycidyl ester of dimer acid, for example, 3 moles of bisphenol A (i.e., 6 moles of phenolic hydroxyl groups of bisphenol A) and 1 mole of triglycidyl ester of trimer acid (i.e., 3 moles of glycidyl groups of triglycidyl ester of trimer acid) are heated in the presence of a catalyst and reacted, and then the phenolic hydroxyl groups not used in the reaction of bisphenol A and triglycidyl ester of trimer acid (when the reaction rate is 100%, 3 moles of phenolic hydroxyl groups will remain unused) are reacted with glycidyl (meth)acrylate, and further reacted with (meth)acrylic anhydride, whereby it can be obtained (Method 4').

[0060] When emphasizing the flexibility, thermal stability, and light stability of the polymer of the resin composition of the present embodiment described later (simply referred to as "the polymer according to the present embodiment"), the proportion of hydrocarbon groups derived from dimer acid, which is a dimer of unsaturated fatty acids having 18 carbon atoms, and trimer acid, which is a trimer of unsaturated fatty acids having 18 carbon atoms, in the total amount of component (a) is preferably 10% by mass or more, and more preferably 15% by mass or more. However, when emphasizing thermal stability and light stability, it is also possible to solve the problem by using an antioxidant or an ultraviolet absorber.

[0061] Regarding the mol ratio of the structure derived from (DA) represented by the above formula (A), as shown in the examples, a value calculated using the blending amount of the raw materials used may be used. For example, for the mol ratio of the structure derived from the above (DA), the calculated value of the mol ratio of compound (DA) represented by the following formula (A-1) may be used. Mol ratio of compound (DA) = mol number of compound (DA) / [mol number of bisphenol A type epoxy resin + mol number of compound (DA) + mol number of methacrylic acid + mol number of methacrylic anhydride] (A-1) Here, for the mol number of compound (DA), the mol number of methacrylic acid, and the mol number of methacrylic anhydride, they are the "mol numbers based on -COOH group" that react with epoxy groups. Also, for the mol number of bisphenol A type epoxy resin, it is the "mol number based on epoxy group".

[0062] Regarding the mol ratio of the (meth)acryloyloxy group other than the terminal structure (T1) represented by the above formula (B), as shown in the examples, the value calculated using the compounding amounts of the raw materials used may be used. For example, for the mol ratio of the (meth)acryloyloxy group other than the terminal structure (T1), the calculated value of the mol ratio of methacrylic anhydride represented by the following formula (B-1) may be used. Mol ratio of methacrylic anhydride = mol number of methacrylic anhydride / [mol number of bisphenol A type epoxy resin + mol number of dimer acid + mol number of methacrylic acid + mol number of methacrylic anhydride] (B-1) Here, for the mol number of compound (DA), the mol number of methacrylic acid, and the mol number of methacrylic anhydride, they are the "mol numbers based on -COOH group" that react with epoxy groups. Also, for the mol number of bisphenol A type epoxy resin, it is the "mol number based on epoxy group".

[0063] Next, component (b), which is an essential component of this embodiment, will be described. <Component (b)> Component (b) is at least one kind of reactive diluent. The reactive diluent has at least one (meth)acryloyloxy group in the molecule and has a viscosity at 25 °C of 2 to 500 mPa·s.

[0064] Component (b) is not particularly limited as long as it is a compound having at least one (meth)acryloyloxy group in the molecule and having a viscosity of 2 to 500 mPa·s at 25°C. Among them, component (b) preferably has 1 to 4 (meth)acryloyloxy groups in the molecule.

[0065] Note that the "viscosity at 25°C" regarding the compound belonging to component (b) described in this specification is the viscosity at 25°C when measured using a BL type viscometer (manufactured by Toki Sangyo Co., Ltd., model: RB80L type, rotor model number: No. 1 rotor). Specific examples of component (b) include, for example, the following.

[0066] Reactive diluents having one acryloyloxy group which is a polymerizable unsaturated group, such as methacrylic acid, lauryl acrylate (viscosity at 25°C: 4 to 5 mPa·s), ethoxy-diethylene glycol acrylate (viscosity at 25°C: 5 to 6 mPa·s), 2-ethylhexyloxyethyloxyethyl acrylate (viscosity at 25°C: 4 to 10 mPa·s), methoxypolyethylene glycol (average number of added ethylene oxide units: 9 mol) acrylate (viscosity at 25°C: 20 to 30 mPa·s), methoxydipropylene glycol acrylate (viscosity at 25°C: 2 to 3 mPa·s), phenoxyethyl acrylate (viscosity at 25°C: 10 to 15 mPa·s), phenoxyethoxyethyl acrylate (viscosity at 25°C: 10 to 12 mPa·s), tetrahydrofurfuryl acrylate (viscosity at 25°C: 4 to 5 mPa·s), isobornyl acrylate (viscosity at 25°C: 5 to 10 mPa·s), 2-hydroxy-3-phenoxypropyl acrylate (viscosity at 25°C: 150 to 200 mPa·s), 2-hydroxyethyl acrylate (viscosity at 25°C: 6 mPa·s), 2-hydroxypropyl acrylate (viscosity at 25°C: 4 mPa·s), 2-hydroxybutyl acrylate (viscosity at 25°C: 6 mPa·s), n-octyl acrylate (viscosity at 25°C: 2 mPa·s), isostearyl acrylate (viscosity at 25°C: 10 to 20 mPa·s), dicyclopentenyl acrylate (viscosity at 25°C: 8 to 18 mPa·s), dicyclopentenyl oxyethyl acrylate (viscosity at 25°C: 15 to 20 mPa·s), dicyclopentanyl acrylate (viscosity at 25°C: 7 to 17 mPa·s), benzyl acrylate (viscosity at 25°C: 3 to 8 mPa·s), nonylphenoxypolyethylene glycol (average number of added ethylene oxide units: 4) acrylate (viscosity at 25°C: 70 to 130 mPa·s), nonylphenoxypolyethylene glycol (average number of added ethylene oxide units: 8) acrylate (viscosity at 25°C: 120 to 180 mPa·s).

[0067] Reactive diluents having two acryloyloxy groups, which are polymerizable unsaturated groups, such as diethylene glycol dimethacrylate (viscosity at 25°C: 3 to 8 mPa·s), 1,4-butanediol diacrylate (viscosity at 25°C: 5 mPa·s), 1,6-hexanediol diacrylate (viscosity at 25°C: 7 mPa·s), 1,9-nonanediol diacrylate (viscosity at 25°C: 8 mPa·s), 1,10-decanediol diacrylate (viscosity at 25°C: 9 mPa·s), 1,12-dodecanediol diacrylate (viscosity at 25°C: 11 mPa·s), neopentyl glycol diacrylate (viscosity at 25°C: 5 mPa·s), 3-methyl-1,5-pentanediol diacrylate (viscosity at 25°C: 8 mPa·s), tricyclo[5.2.1.0(2,6)]decane dimethanol diacrylate (viscosity at 25°C: 130 to 170 mPa·s), diethylene glycol diacrylate (viscosity at 25°C: 3 to 9 mPa·s), triethylene glycol diacrylate (viscosity at 25°C: 9 to 11 mPa·s), tetraethylene glycol diacrylate (viscosity at 25°C: 10 to 15 mPa·s), polyethylene glycol (Mn = 400) diacrylate (viscosity at 25°C: 22 to 25 mPa·s), polyethylene glycol (Mn = 600) diacrylate (viscosity at 25°C: 50 to 70 mPa·s), polytetramethylene glycol (Mn = 250) diacrylate (viscosity at 25°C: 15 to 20 mPa·s), polytetramethylene glycol (Mn = 650) diacrylate (viscosity at 25°C: 120 to 160 mPa·s), tripropylene glycol diacrylate (viscosity at 25°C: 9 to 19 mPa·s), polypropylene glycol (Mn = 400) diacrylate (viscosity at 25°C: 32 to 37 mPa·s), polypropylene glycol (Mn = 700) diacrylate (viscosity at 25°C: 65 to 75 mPa·s), 3-(acryloyloxy)-2,2-dimethylpropyl-3-(acryloyloxy)-2,2-dimethylpropanoate (viscosity at 25°C: 40 to 80 mPa·s), etc.

[0068] Trimethylolpropane triacrylate (viscosity at 25°C: 70 to 110 mPa·s), trimethylolpropane ethylene oxide adduct (average addition number: 9 mol) triacrylate (viscosity at 25°C: 90 to 110 mPa·s), trimethylolpropane ethylene oxide adduct (average addition number: 20 mol) triacrylate (viscosity at 25°C: 210 to 230 mPa·s), glycerin ethylene oxide adduct (average addition number: 3 mol) triacrylate (viscosity at 25°C: 90 to 110 mPa·s), glycerin ethylene oxide adduct (average addition number: 9 mol) triacrylate (viscosity at 25°C: 90 to 110 mPa·s), glycerin ethylene oxide adduct (average addition number: 20 mol) triacrylate (viscosity at 25°C: 180 to 210 mPa·s), and other reactive diluents having three acryloyloxy groups which are polymerizable unsaturated groups.

[0069] Reactive diluents having a methacryloyloxy group, which is a polymerizable unsaturated group, such as dicyclopentenyl oxyethyl methacrylate (viscosity at 25 °C: 15 to 20 mPa·s), dicyclopentanyl methacrylate (viscosity at 25 °C: 7 to 17 mPa·s), pentamethylpiperidyl methacrylate (viscosity at 25 °C: 11 to 14 mPa·s), tetramethylpiperidyl methacrylate (viscosity at 25 °C: 3 to 6 mPa·s), methoxypolyethylene glycol (average number of added ethylene oxide units: 9 mol) methacrylate (viscosity at 25 °C: 20 to 30 mPa·s), benzyl methacrylate (viscosity at 25 °C: 2 to 4 mPa·s), 2-ethylhexyl methacrylate (viscosity at 25 °C: 2 mPa·s), lauryl methacrylate (viscosity at 25 °C: 5 mPa·s), cyclohexyl methacrylate (viscosity at 25 °C: 3 mPa·s), phenyl methacrylate (viscosity at 25 °C: 3 mPa·s), benenzyll methacrylate (viscosity at 25 °C: 3 mPa·s), isobornyl methacrylate (viscosity at 25 °C: 13 mPa·s), tetrahydrofurfuryl methacrylate (viscosity at 25 °C: 3 mPa·s), 2-hydroxyethyl methacrylate (viscosity at 25 °C: 7 mPa·s), 2-hydroxypropyl methacrylate (viscosity at 25 °C: 8 to 10 mPa·s), 2-methoxyethyl methacrylate (viscosity at 25 °C: 3 to 4 mPa·s).

[0070] Reactive diluents having two methacryloyloxy groups, which are polymerizable unsaturated groups, such as ethylene glycol dimethacrylate (viscosity at 25°C: 2 to 5 mPa·s), diethylene glycol dimethacrylate (viscosity at 25°C: 3 to 8 mPa·s), triethylene glycol dimethacrylate (viscosity at 25°C: 7 to 12 mPa·s), polyethylene glycol dimethacrylate (viscosity at 25°C: 12 to 17 mPa·s), polyethylene glycol (Mn = 600) dimethacrylate (viscosity at 25°C: 60 to 70 mPa·s), polypropylene glycol (average addition mole number: 7 mol) dimethacrylate (viscosity at 25°C: 100 mPa·s or less), 1,4-butylene glycol dimethacrylate (viscosity at 25°C: 3 to 5 mPa·s), 1,6-hexanediol dimethacrylate (viscosity at 25°C: 4 to 6 mPa·s), 1,9-nonanediol dimethacrylate (viscosity at 25°C: 5 to 10 mPa·s), 1,10-decanediol dimethacrylate (viscosity at 25°C: 7 to 12 mPa·s), 1,12-dodecanediol dimethacrylate (viscosity at 25°C: 11 to 15 mPa·s), neopentyl glycol dimethacrylate (viscosity at 25°C: 3 to 8 mPa·s), tricyclo[5.2.1.0(2,6)]decane dimethanol dimethacrylate (viscosity at 25°C: 100 to 120 mPa·s), (viscosity at 25°C: 40 to 80 mPa·s), 2-hydroxy-3-methacryloyloxypropyl methacrylate (viscosity at 25°C: 100 mPa·s or less), Reactive diluents having one acryloyloxy group and one methacryloyloxy group, which are polymerizable unsaturated groups, such as 2-hydroxy-3-acryloyloxypropyl methacrylate, Reactive diluents having three methacryloyloxy groups, which are polymerizable unsaturated groups, such as trimethylolpropane trimethacrylate (viscosity at 25°C: 45 mPa·s).

[0071] In component (b), from the viewpoint of dilution efficiency with respect to component (a) and component (b), it is desirable to contain 50% by mass or more of a reactive diluent having a viscosity at 25°C of 100 mPa·s or less with respect to the total amount of the compounds belonging to component (b). In addition, component (b) affects the curability, particularly the surface curability, during polymerization.

[0072] Also, when using a reactive diluent having one polymerizable unsaturated group, it is preferable to use one with good surface curability or one that does not adversely affect surface curability. Examples of such preferable reactive diluents having one polymerizable unsaturated group include dicyclopentenyl oxyethyl methacrylate (viscosity at 25°C: 15 - 20 mPa·s) and benzyl methacrylate (viscosity at 25°C: 2 - 4 mPa·s), and more preferably dicyclopentenyl oxyethyl methacrylate.

[0073] <Resin component that does not belong to either component (a) or component (b)> In the resin composition of this embodiment, a resin component that does not belong to either component (a) or component (b) may be used as long as the physical properties are not impaired.

[0074] Examples of these components include, for example, the following. A compound with a viscosity at 25°C higher than 500 mPa·s of urethane (meth)acrylate, a compound with a viscosity at 25°C higher than 500 mPa·s of polyester (meth)acrylate, a compound with a viscosity at 25°C higher than 500 mPa·s of polycarbonate (meth)acrylate, bisphenol A ethylene oxide adduct (average addition number: 3 mol) diacrylate (viscosity at 25°C: 1400 - 1500 mPa·s), bisphenol A ethylene oxide adduct (average addition number: 4 mol) diacrylate (viscosity at 25°C: 1000 - 1300 mPa·s), bisphenol A ethylene oxide adduct (average addition number: 10 mol) diacrylate (viscosity at 25°C: 550 - 700 mPa·s), bisphenol A ethylene oxide adduct (average addition number: 10 mol) diacrylate (viscosity at 25°C: 550 - 750 mPa·s), bisphenol A ethylene oxide adduct (average addition number: 2.3 mol) dimethacrylate (viscosity at 25°C: 1100 - 1500 mPa·s), bisphenol A ethylene oxide adduct (average addition number: 2.6 mol) dimethacrylate (viscosity at 25°C: 900 - 1450 mPa·s), bisphenol A ethylene oxide adduct (average addition number: 4 mol) dimethacrylate (viscosity at 25°C: 600 - 700 mPa·s), a compound of bisphenol A ethylene oxide adduct di(meth)acrylate with a viscosity at 25°C higher than 500 mPa·s.

[0075] A polymerizable component that does not belong to either component (a) or component (b), which are essential components of the resin composition of this embodiment. The ranges of the preferred amounts of use of component (a), component (b), and component (b) with respect to the total amount of all polymerizable components are 20 - 60% by mass, 15 - 60% by mass, and 10 - 50% by mass, respectively. The more preferred ranges of the amounts of use of component (a), component (b), and component (b) are 25 - 50% by mass, 18 - 55% by mass, and 10 - 40% by mass, respectively. The even more preferred ranges of the amounts of use of component (a), component (b), and component (b) are 30 - 50% by mass, 20 - 50% by mass, and 12 - 40% by mass, respectively.

[0076] If the amount of component (a) is 20 to 60% by mass based on the total amount of all polymerizable components including component (a), component (b), and polymerizable components that belong to neither component (a) nor component (b), it becomes possible to hardly generate cracks during the thermal cycle test and to keep the water absorption low. If the amount of component (b) is 15 to 60% by mass based on the total amount of all polymerizable components including component (a), component (b), and polymerizable components that belong to neither component (a) nor component (b), there is no lack of surface curing performance, cracks are hardly generated during the thermal cycle test, and defects such as swelling are hardly generated even when immersed in water at a temperature higher than room temperature. If the amount of component (b) is 10 to 50% by mass based on the total amount of all polymerizable components including component (a), component (b), and polymerizable components that belong to neither component (a) nor component (b), component (a) and component (b) can be dissolved to lower the viscosity, cracks are hardly generated during the thermal cycle test, the water absorption can be kept low, and defects such as swelling are hardly generated even when immersed in water at a temperature higher than room temperature.

[0077] Moreover, the acid value of the total polymerizable resin composition containing component (a) and component (b), which are essential components of the resin composition of the present embodiment, is preferably 10 mgKOH / g or less. If the acid value of the total polymerizable resin composition is 10 mgKOH / g or less, an improvement in the water resistance and resistance to an alkaline aqueous solution of the polymer of the resin composition of the present embodiment can be expected.

[0078] <Component (c)> Furthermore, the resin composition of the present embodiment may contain a polymerization accelerator (component (c)). It is preferable to use a polymerization accelerator when the storage stability is good even when containing a polymerization accelerator, or in applications where the polymerization accelerator can be added immediately before polymerizing the resin composition.

[0079] The polymerization accelerator used in the resin composition of the present embodiment is one having a reducing action with respect to the polymerization initiator when polymerizing the resin composition of the present embodiment at room temperature, specifically an organic peroxide.

[0080] As the coincidence accelerator (component (c)), specifically, the following can be mentioned. Metal acetylacetonate-based polymerization accelerators such as copper acetylacetonate, vanadium acetylacetonate, cobalt acetylacetonate, manganese acetylacetonate, and iron acetylacetonate, Aromatic amine-based polymerization accelerators such as N,N-dimethylaniline, N,N-diethylaniline, and N,N-dimethyl-p-toluidine, Polyvalent metal salt-based polymerization accelerators such as calcium naphthenate, copper naphthenate, manganese naphthenate, cobalt naphthenate, vanadium naphthenate, calcium octylate, copper octylate, manganese octylate, cobalt octylate, and vanadium octylate.

[0081] These polymerization accelerators may be used alone or in combination of two or more.

[0082] Preferred ones of these polymerization accelerators are cobalt acetylacetonate, cobalt naphthenate, and cobalt octylate, and more preferred ones are cobalt naphthenate and cobalt octylate.

[0083] The amount of these polymerization accelerators used is usually 0.1 to 10 parts by mass, preferably 0.15 to 8 parts by mass, and particularly preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the total amount of all polymerizable components including component (a), component (b), and polymerizable components not belonging to either component (a) or component (b). When the amount of these polymerization accelerators used is in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of all polymerizable components including component (a), component (b), and polymerizable components not belonging to either component (a) or component (b), it has an appropriate polymerization rate, can maintain the pot life after adding the polymerization initiator (organic peroxide described later) and the polymerization accelerator to the polymerizable resin composition when polymerizing the polymerizable components at room temperature, and can also sufficiently improve the surface curability.

[0084] <Component (d)> When polymerizing the resin composition of this embodiment, it is possible and preferable to add a polymerization initiator (component (d)) before starting the polymerization and then perform the polymerization.

[0085] As the polymerization initiator, an azo-based polymerization initiator, an organic peroxide-based polymerization initiator, a photoinitiator, etc. can be used. However, in applications where it is preferable to proceed with polymerization at room temperature, such as the lining material applications described later, it is preferable to use an organic peroxide-based polymerization initiator that can exhibit excellent polymerizability at room temperature by being used in combination with the above-mentioned component (c) (i.e., the polymerization accelerator).

[0086] As the organic peroxide-based polymerization initiator, one or more can be selected and used from the following known ones. Ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, and methylcyclohexanone peroxide, Hydroperoxides such as t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, and 2,5-dimethylhexanone-2,5-hydroperoxide, Peroxy esters such as t-butyl peroxy octoate, t-butyl peroxy benzoate, and t-butyl peroxy laurate, Diacyl peroxides such as lauroyl peroxide and benzoyl peroxide.

[0087] Among these organic peroxide-based polymerization initiators, it is preferable to use at least one selected from ketone peroxides, hydroperoxides, and peroxy esters. In addition, as the organic peroxide-based polymerization initiator, those having a 10-hour half-life temperature of 30 to 170°C are preferable. Note that component (d) may be used alone or in combination of two or more.

[0088] The amount of component (d) used is preferably in the range of 0.1 to 20 parts by mass, more preferably 0.3 to 17 parts by mass, and particularly preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable components in the resin composition of the present embodiment. If the amount of component (d) used is in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass of all the polymerizable components, it is possible to obtain a sufficient polymerization rate and sufficient hardness, and it is possible to have a sufficient pot life after adding component (d), and the ease of forming a coating film will not decrease. In addition, the resin composition of the present embodiment is characterized by excellent surface curability. However, if necessary, paraffin and / or waxes may be used in combination for the purpose of improving the drying property of the contact surface with air.

[0089] As the above-mentioned paraffin and / or waxes, one or more selected from waxes such as paraffin wax and polyethylene wax, and higher fatty acids such as stearic acid and 1,2-hydroxystearic acid can be used, but paraffin wax is preferably used. Paraffin and / or waxes are added not only for the purpose of blocking air during the curing reaction on the coating film surface but also for the purpose of improving stain resistance. When paraffin and / or waxes are used, the addition rate is 0.1 to 5 parts by mass, preferably 0.2 to 2 parts by mass with respect to 100 parts by mass of the total amount of all the polymerizable components.

[0090] <Particulate inorganic material> To the resin composition of the present embodiment, particulate inorganic materials or short fibrous organic and / or inorganic fillers can be further added. As such inorganic materials, sand, silica powder, crushed rock, calcium carbonate, alumina powder, fly ash, clay, silica flour, talc, glass powder, silica powder, glass powder, mica, aluminum hydroxide, silica sand, aluminum silicate, magnesium silicate, cement, marble, etc. can be used.

[0091] The average particle size of the fine particles is preferably about 0.5 μm to 20 μm. The addition rate of the particulate inorganic material is preferably added in an amount of 100 parts by mass or less as needed with respect to 100 parts by mass of all the polymerizable components. Further, the particulate inorganic material may be used alone or in combination of two or more kinds.

[0092] <Short fiber-like filler> The average fiber length of the short fiber-like organic and / or inorganic compound is preferably 1.0 mm or less, and the fiber diameter is preferably 80 μm or less on average. Specific examples of the short fiber-like organic and / or inorganic compound include, for example, cut fiber (registered trademark) "Product name: SS 05C-404" (average fiber length of about 0.1 mm, average fiber diameter of about 10 μm), "Product name: SS 05C-420" (average fiber length of about 0.3 mm, average fiber diameter of about 10 μm), "Product name: PF 301" (average fiber length of about 0.03 mm, average fiber diameter of about 10 μm), etc. of short fiber-like glass fibers, wollastonite (registered trademark) "Product name: NYGLOS-G" (average fiber length of about 0.825 mm, average fiber diameter of about 55 μm), "Product name: NYGLOS 8" (average fiber length of about 0.156 mm, average fiber diameter of about 12 μm), "Product name: NYGLOS 4W" (average fiber length of about 0.063 mm, average fiber diameter of about 7 μm), etc. of fillers manufactured by Balaguer Industries, glass flakes (registered trademark) "Product name: RCF-140" (average fiber length of about 0.15 mm, average fiber diameter of about 5 μm), etc. manufactured by Nippon Sheet Glass Co., Ltd., and "Product name: RCF-015" (average fiber length of about 0.045 mm, average fiber diameter of about 5 μm), Chemibest (registered trademark), a polyolefin-based fine fiber manufactured by Mitsui Chemicals Fine Products Co., Ltd., "Product name: FDSS-5" (average fiber length of 0.1 mm or less, average fiber diameter of about 10 μm), "Product name: FDSS-2" (average fiber length of 0.6 mm or less, average fiber diameter of about 10 μm), etc. The short fiber-like organic and / or inorganic compound may be used alone or in combination of two or more kinds.

[0093] Further, when the resin composition of the present embodiment contains particulate inorganic materials or short fibrous organic and / or inorganic fillers, the total amount of components (a) to (d) is preferably 60% by mass or more, more preferably 80% by mass or more, and particularly preferably 95% by mass or more with respect to the total amount of the resin composition.

[0094] <Polymer of Resin Composition> Next, the polymer obtained using the resin composition of the present embodiment (the polymer of the resin composition of the present embodiment) will be described. The polymer of the resin composition of the present embodiment is obtained by mixing the resin composition of the present embodiment and, if necessary, other components to form a mixed solution, and polymerizing the mixed solution using component (d). When a photopolymerization initiator is used as component (d), it is obtained by irradiating ultraviolet rays or visible light. When an azo-based polymerization initiator is used as component (d), it is obtained by heating. Similarly, when an organic peroxide-based polymerization initiator is used, it is also obtained by heating. In addition, when there is a case of polymerizing at room temperature, such as the surface treatment material described later, the polymer of the resin composition of the present embodiment can be obtained even at room temperature by using an organic peroxide and component (d) in combination.

[0095] <Surface Treatment Material and Surface Treatment Method> Next, an example of a surface treatment material containing the resin composition of the present embodiment and a surface treatment method using the treatment material will be described. The resin composition of the present embodiment containing component (d) and a composition obtained by adding known anti-sagging additives to these are used as surface treatment materials, and by performing surface treatment on various materials such as metal, plastic, concrete, wood, and glass, it is possible to impart an improvement effect on the water resistance, acid resistance, and base resistance of various materials.

[0096] Examples of the known anti-sagging additives used as described above include fumed silica such as Aerosil (registered trademark), and celluloses such as methyl cellulose, hydroxypropyl cellulose, and ethyl cellulose.

[0097] Specifically, a first step of preparing a coating solution by adding component (d) to the resin composition of the present embodiment containing components other than component (d), and a second step of forming a cured coating film on the surface of the material by curing at 0 to 50°C after applying the coating solution to the surface of the material can preferably be used.

[0098] As component (d), generally, an organic peroxide-based polymerization initiator is preferably used. Specific examples of the organic peroxide-based polymerization initiator are as described above, and for example, the following can be mentioned, but are not particularly limited thereto.

[0099] Ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, and methylcyclohexanone peroxide;

[0100] Hydroperoxides such as t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, and 2,5-dimethylhexanone-2,5-hydroperoxide; Peroxy esters such as t-butyl peroxybenzoate and t-butyl peroxylaurate.

[0101] As the organic peroxide, those having a 10-hour half-life temperature of 30 to 170°C are preferred. The curing agent may be used alone or in combination of two or more. Further, as the organic peroxide-based polymerization initiator, those having a 10-hour half-life temperature of 30 to 170°C are preferred. Note that component (d) may be used alone or in combination of two or more.

[0102] The amount of component (d) used is preferably in the range of 0.1 to 20 parts by mass, more preferably 0.3 to 17 parts by mass, and particularly preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the total amount of all polymerizable components in the resin composition of the present embodiment. If the amount of component (d) used is in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass of all polymerizable components, it is possible to obtain a sufficient polymerization rate and sufficient hardness, and it is possible to have a sufficient pot life after adding component (d), and the ease of forming a coating film will not decrease.

[0103] From the viewpoint of surface treatment, the film thickness of the formed cured coating film is preferably 0.1 to 2 mm, more preferably 0.3 to 2 mm, still more preferably 0.5 to 2 mm, and particularly preferably 0.5 to 1.5 mm from the viewpoint of achieving both the requirement that the film thickness is generally not too large and the requirement that the surface treatment effect can be maintained for a long time. Note that the film thickness of the cured coating film can be adjusted to the above range by adjusting the film thickness of the swollen coating film during coating to approximately these ranges.

[0104] The surface treatment material of the present embodiment can be used for materials such as metal, plastic, concrete, mortar, wood, and glass, which are materials that can be used under conditions of contact with rainwater, industrial wastewater, etc., and are materials for which surface treatment using the resin composition of the present embodiment is desired.

[0105] As the metal, those containing at least one selected from iron and aluminum are preferred. These are components contained in metals that are particularly often used under conditions of contact with rainwater, industrial wastewater, etc. As the metal containing iron, iron may be substantially 100% by mass, or it may contain metals other than iron (for example, chromium, etc.) such as stainless steel. There is no particular limitation on the material of the wood.

[0106] The glass is not particularly limited as long as it becomes an amorphous solid that exhibits a glass transition phenomenon upon heating. It may be a glass mainly composed of silicate, or a glass mainly composed of components other than silicate, such as acrylic glass, chalcogen glass, metallic glass, organic glass, etc. The surface of the glass to be surface-treated may be smooth or may have irregularities.

[0107] Typical shapes of these resin compositions are paste-like. However, for example, when the emulsified resin composition of the present embodiment is used as a surface treatment material and is applied using spray coating or the like, the amount of component (g) can be increased to increase fluidity. Also, within a range that does not impair the effects of the present invention, long fibrous compounds, and additives such as titanium oxide and carbon black may be added.

[0108] The surface treatment material of the present embodiment and the corrosion prevention method of the concrete structure using the same are suitable for corrosion prevention lining of kitchen drainage-related water tanks such as commercial buildings and hotels, building pit-related facilities such as sewage and miscellaneous wastewater, and sewer facilities.

[0109] Note that as a corrosion prevention method of a concrete structure using the surface treatment material of the present embodiment, it can be carried out, for example, by the method described in Japanese Patent Application Laid-Open No. 2019-38972.

[0110] <Method for manufacturing a cured film-containing material> The method for manufacturing a cured film-containing material of the present embodiment is a method for forming a cured film on the surface of a material selected from metals, plastics, concrete, mortar, wood, and glass. The method for manufacturing a cured film-containing material of the present embodiment includes a step of forming the cured film on the surface of the material using the surface treatment method of the above-described present embodiment.

[0111] In the method for manufacturing a cured film-containing material of the present embodiment, the surface treatment material and the formation conditions used are the same as those of the surface treatment method of the above-described present embodiment.

Examples

[0112] Next, examples of the present invention will be described, but the present invention is not limited thereto. In the examples, "parts" means "parts by mass" unless otherwise specified.

[0113] (Raw materials) Details of some of the raw materials used in the following production examples or examples are shown below. The epoxy equivalent is a value measured in accordance with JIS K7236:2001. · Bisphenol A type epoxy resin: "Epomic (registered trademark) EX-212", manufactured by Mitsui Chemicals, Inc., epoxy equivalent 188 · Dimer acid: "Haridimer (registered trademark) 200", manufactured by Harima Chemicals, Inc. ※ Monomer acid / Dimer acid / Trimer acid (mass%) Haridimer 200: 7.0 / 76.0 / 17 (carboxylic acid equivalent = 290.725) · Methacrylic acid: "MAA (methacrylic acid)", Mitsubishi Gas Chemical Company · Methacrylic anhydride: "VISIOMER (registered trademark) MAAH", Evonik Japan Co., Ltd. · Triphenylphosphine: "TPP", manufactured by Kitakyo Chemical Industry Co., Ltd.; Esterification catalyst · 2,4,6-Tris (dimethylaminomethyl) phenol: "Seikol (registered trademark) TDMP", manufactured by Seiko Chemical Co., Ltd.; Esterification catalyst

[0114] · Diethylene glycol dimethacrylate: "Light Ester (registered trademark) 2EG", manufactured by Kyoeisha Chemical Co., Ltd.; Radical polymerizable unsaturated monomer

[0115] (Evaluation method) (Evaluation of acid value of acid component (a)) In accordance with JIS K6901:2021 "Partial acid value (indicator titration method)", the mass of potassium hydroxide required to neutralize the acid component contained in the vinyl ester resin synthesized in each example and comparative example was measured to determine the acid value. Note that an "Auto Burette UCB-2000 (trade name, manufactured by Hiranuma Sangyo Co., Ltd.)" was used as the acid value measuring device, and a mixed indicator of bromothymol blue and phenol red was used as the indicator.

[0116] <Acid resistance test (chemical resistance)> The resin composition was applied onto a PET film supported by a glass plate so that the thickness after curing would be approximately 3.5 mm. It was cured in an environment of 23°C and 50% relative humidity for 3 days. Then, the PET film was peeled off to obtain a self-standing film. After leaving this film for one week, test pieces with a width of 15 mm, a length of 100 mm, and a thickness of 7 mm obtained by cutting the cured coating film were each immersed in 10% by volume acetic acid at 40°C for 2 months, and then taken out. The test pieces were washed with ion-exchanged water. By measuring the weight change, the swelling rate (unit: mass%) was obtained from the following calculation formula and used as an index of acid resistance. The smaller the value, the higher the acid resistance.

[0117] [Calculation formula] Swelling rate (mass%) = (mass of test piece after immersion - mass of test piece before immersion) / mass of test piece before immersion × 100 [Judgment method] Less than 2.0% is good (judgment ○). 2.0 - 2.5% is fairly good (judgment △). 2.5% or more indicates that chemical erosion has occurred (judgment ×).

[0118] <Viscosity measurement (workability)> Using an RE-85 type viscometer manufactured by Toki Sangyo Co., Ltd., of the cone plate type, with a predetermined rotor, The viscosity at 25°C was measured at a rotational speed of 50 rpm.

[0119] [Judgment method] Up to 15000 mPa·s is good, and 10000 mPa·s or less is even better. If it is 15000 mPa·s or more, there will be difficulties in workability and a uniform film cannot be formed.

[0120] <Tensile elongation rate measurement (crack resistance during thermal cycle test)> At 23°C, 1.0 part of 8% cobalt octylate was added to and mixed with 100 parts of the resin composition. Then, 1.5 parts of curing agent 328EM (manufactured by Chemical Nuon Co., Ltd.) was added and mixed to prepare a cast product. After 24 hours, post-curing was carried out at 120°C for 2 hours to obtain test pieces. For the measurement of the casting physical properties, in accordance with Japanese Industrial Standard (JIS K 7113:1995), using an Instron 5583 type (5590R) (Instron Japan Co., Ltd.), the tensile elongation rate was measured.

[0121] [Judgment Method] An elongation of 1.5% or more is good. An elongation of 2.0% or more is even better. An elongation of 1.5% or less is bad. When made into a coating film, it will crack during drying.

[0122] (Example 1) In a 1L four-neck separable flask equipped with a stirrer, thermometer, gas inlet tube, and reflux condenser, 356.18 g of bisphenol A type epoxy resin, 110.16 g of dimer acid, 0.70 g of methylhydroquinone, and 0.70 g of triphenylphosphine were placed. Under a nitrogen gas atmosphere, the temperature was raised to 125°C while mixing and stirring, and the reaction was carried out for about 2 hours. Then, 233.66 g (1.05 mol) of methacrylic anhydride, 0.00 g of methacrylic acid, and 0.70 g of triphenylphosphine were added, and the temperature was raised to 125°C and the reaction was carried out for about 3 hours to synthesize a vinyl ester resin (acid value 12 mgKOH / g) as component (a). The acid value of component (a) is shown in Table 1.

[0123] To the above vinyl ester resin as component (a), 300.0 g of diethylene glycol dimethacrylate was added as component (b) to obtain a vinyl ester resin composition (VE-1) as the resin composition of the present invention.

[0124] The weight blending amounts (unit: g) of the respective raw materials for synthesizing component (a) and the weight blending amount (unit: g) of component (b) are shown in Table 3.

[0125] In addition, the molar compounding amounts (unit: mol), the mol ratio of dimer acid, and the mol ratio of methacrylic anhydride calculated from the above weight compounding amounts are shown in Table 6.

[0126] Note that the mol ratio of dimer acid is represented by the following formula. Mol ratio of dimer acid = Molar compounding amount of dimer acid / Total molar compounding amount of [bisphenol A type epoxy resin + dimer acid + methacrylic acid + methacrylic anhydride] The mol ratio of methacrylic anhydride is represented by the following formula. Mol ratio of methacrylic anhydride = Molar compounding amount of methacrylic anhydride / Total molar compounding amount of [bisphenol A type epoxy resin + dimer acid + methacrylic acid + methacrylic anhydride]

[0127] The vinyl ester resin composition (VE-1) obtained was evaluated by the above evaluation methods, and the evaluation results are shown in Table 6.

[0128] (Examples 2 to 20, Comparative Examples 1 to 11) Except for using the raw materials and compounding amounts of each of the examples and comparative examples shown in Tables 3 to 5, a vinyl ester resin was synthesized as component (a) in the same manner as in Example 1. The acid values of component (a) are shown in Tables 1 and 2. Except for using the compounding amounts of component (b) of each of the examples and comparative examples shown in Tables 3 to 5, vinyl ester resin compositions (VE-1) to (VE-20) were obtained as the resin compositions of the present invention, and vinyl ester resin compositions (cVE-1) to (cVE-11) were obtained as the comparative resin compositions in the same manner as in Example 1.

[0129] In addition, in the same manner as in Example 1, the molar compounding amounts (unit: mol), the mol ratio of dimer acid, and the mol ratio of methacrylic anhydride calculated from the weight compounding amounts of each of the examples and comparative examples are shown in Tables 6 to 8. In addition, the evaluation was performed by the same evaluation method as in Example 1, and the obtained evaluation results are shown in Tables 6 to 8.

[0130]

Table 1

[0131]

Table 2

[0132]

Table 3

[0133]

Table 4

[0134]

Table 5

[0135]

Table 6

[0136]

Table 7

[0137]

Table 8

[0138] In Tables 6 to 8, regarding the number of moles of the raw material of component (a), in the case of bisphenol A type epoxy resin (*1), it is the number of moles based on the epoxy group, and in the case of dimer acid (*2) and methacrylic anhydride (*3), it is the number of moles based on the -COOH group.

[0139] From the results of Tables 6 to 8, it can be seen that when the resin composition or the emulsified resin composition of the present embodiment is used, it is easy to form a cured coating film at room temperature, and the cured coating film is excellent in hot water resistance, acid resistance and base resistance.

Industrial Applicability

[0140] The resin composition and the emulsified resin composition of the present invention can be used in the fields of coating agents, paints, inks, adhesives, food protection materials, fiber treatment materials, and the like. The resin composition and the emulsified resin composition of the present invention can be used particularly in the fields of lining materials for surface coating of concrete in sewage treatment facilities, lining materials for repair of manhole inner surfaces, etc., repair lining materials for concrete facilities in food factories, pharmaceutical factories, and electronic material-related factories, paints, putties, adhesives, and the like.

Claims

Claim 1 A resin composition comprising component (a) and component (b), wherein component (a) has, in the molecule, a structure derived from at least one compound (DA) selected from the group consisting of dimer acid which is a dimer of an unsaturated fatty acid having 18 carbon atoms and trimer acid which is a trimer of an unsaturated fatty acid having 18 carbon atoms, a structure derived from bisphenol A type epoxy resin (BP), a (meth)acryloyloxy group derived from (meth)acrylic anhydride, and a terminal structure (T1) represented by the following formula (1); Component (b) is at least one reactive diluent having at least one (meth)acryloyloxy group in the molecule and having a viscosity of 2 to 500 mPa·s at 25°C, and the resin composition. 【Chemical 1】 (wherein, R １ represents H or CH ３ . The dashed line represents the bonding site. R ２ represents H or a (meth)acryloyl group.) Claim 2 When the mol ratio of the structure derived from (DA) in component (a) is represented by the following formula (A), the resin composition according to claim 1, wherein the mol ratio of the structure derived from (DA) is 0.07 to 0.

3. Mol ratio of the structure derived from (DA) = [(mol number of the structure derived from (DA))] / [(mol number of the structure derived from (DA)) + (mol number of the structure derived from (BP)) + (mol number of (meth)acryloyloxy groups)] (A) Claim 3 When the mol ratio of the (meth)acryloyloxy group other than the terminal structure (T1) in component (a) is represented by the following formula (B), the resin composition according to claim 1, wherein the mol ratio of the (meth)acryloyloxy group other than the terminal structure (T1) is 0.25 to 0.

52. Mol ratio of the (meth)acryloyloxy group other than the terminal structure (T1) = [(mol number of the (meth)acryloyloxy group other than the terminal structure (T1))] / [(mol number of the structure derived from (DA)) + (mol number of the structure derived from (BP)) + (mol number of (meth)acryloyloxy groups)] (B) Claim 4 When the mol ratio of the structure derived from (DA) in component (a) is represented by the formula (A), the mol ratio of the structure derived from (DA) is 0.07 to 0.3, When the mol ratio of the (meth)acryloyloxy group other than the terminal structure (T1) in component (a) is represented by the formula (B), the resin composition according to claim 1, wherein the mol ratio of the (meth)acryloyloxy group other than the terminal structure (T1) is 0.25 to 0.

52. Claim 5 The resin composition according to claim 1, wherein the component (a) is obtained by reacting one or more compounds (DA) selected from the group consisting of bisphenol A type epoxy resin (BP), dimer acid which is a dimer of unsaturated fatty acid having 18 carbon atoms, and trimer acid which is a trimer of unsaturated fatty acid having 18 carbon atoms, and then reacting with (meth)acrylic anhydride.

6. The resin composition according to claim 5, wherein the total amount of one or more compounds (DA) selected from the group consisting of dimer acid which is a dimer of unsaturated fatty acid having 18 carbon atoms and trimer acid which is a trimer of unsaturated fatty acid having 18 carbon atoms to be reacted is 0.1 to 0.6 mol with respect to 1 mol of the bisphenol A type epoxy resin (BP).

7. The resin composition according to claim 5 or 6, wherein the component (a) is obtained by reacting one or more compounds (DA) selected from the group consisting of bisphenol A type epoxy resin (BP), dimer acid which is a dimer of unsaturated fatty acid having 18 carbon atoms, and trimer acid which is a trimer of unsaturated fatty acid having 18 carbon atoms, and then reacting with (meth)acrylic anhydride and (meth)acrylic acid.

8. The resin composition according to claim 7, wherein the (meth)acrylic acid is 0.25 to 1.70 mol with respect to 1 mol of the (meth)acrylic anhydride.

9. The resin composition according to claim 1 or 2, wherein the component (b) contains 50% by mass or more of a reactive diluent having a viscosity of 100 mPa·s or less at 25°C.

10. The resin composition according to any one of claims 1 to 3, wherein the content of the component (a) is 60 to 80% by mass and the content of the component (b) is 20 to 40% by mass with respect to the total amount of all polymerizable components including the component (a) and the component (b).

11. The resin composition according to any one of claims 1 to 3, further comprising a polymerization accelerator as the component (c).

12. The resin composition according to any one of claims 1 to 3, further comprising a polymerization initiator as the component (d).

13. The resin composition according to claim 12, wherein the component (d) is at least one organic peroxide.

14. The polymer of the resin composition according to claim 12.

15. A surface treatment material applied to at least one surface selected from the group consisting of metal, plastic, concrete, mortar, wood, and glass, the surface treatment material comprising the resin composition according to claim 12.

16. A method for surface treatment of a material selected from the group consisting of metal, plastic, concrete, mortar, wood, and glass, comprising: a first step of preparing a coating solution by adding a polymerization initiator as component (d) to the resin composition according to claim 1 or claim 2; a second step of applying the coating solution prepared in the first step to the surface of the material and then curing it at 0 to 50°C to form a cured coating film on the surface of the material; A surface treatment method comprising the above steps.

17. A method for manufacturing a cured coating film-containing material, comprising the step of forming the cured coating film on the surface of the material using the surface treatment method of claim 16.

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