Block urethane material, composition, cured product, method for producing cured product, and block urethane compound contained therein

Abstract

The present disclosure provides: a block urethane compound which is formed with a polyisocyanate compound, a polyhydroxy compound, and a blocking agent, wherein the polyhydroxy compound contains one or more compounds selected from the group consisting of unsaturated polyol derivatives, unsaturated polyols, and acrylic polyols; a block urethane material containing the block urethane compound; a composition containing the block urethane compound; a cured product formed from the composition; and a method for producing the cured product.

Description

Block urethane material, composition, cured product, method for producing the cured product, and block urethane compound used therein

[0001] The present disclosure relates to block urethane materials.

[0002] A blocked urethane compound is a compound in which an isocyanate group is reacted with an active hydrogen group-containing compound (blocking agent) to inactivate (block) the reactivity of the isocyanate group. When this compound is heated, the blocking agent dissociates and the isocyanate group is regenerated.

[0003] Examples of uses of block urethane compounds include adhesion promoters for thermoplastic resin compositions (see, for example, Patent Documents 1 and 2), and also include the use of block urethane compounds as a curable component of a curable composition containing an epoxy resin (see, for example, Patent Document 3).

[0004] JP 2021-011525 A JP 2014-210900 A International Publication No. 2022 / 050005

[0005] After the block urethane material is applied to a substrate, and before the deblocking step in which the blocking agent is dissociated, the block urethane material may be stored in an environment in which it comes into contact with moisture in the surrounding air (storage step), or a step in which it comes into contact with water, such as a water-washing step, may be carried out. In other words, the block urethane material may be intentionally or unintentionally placed in an environment in which it comes into contact with water before the deblocking step. In such cases, there is a problem in that the adhesive strength exhibited by the block urethane material decreases. In this specification, the form in which the block urethane material is intentionally or unintentionally placed in an environment in which it comes into contact with water (including moisture in the air) before the deblocking step is referred to as the "water contact step before deblocking."

[0006] The present disclosure has been made in consideration of the above-mentioned problems, and aims to provide a block urethane material that has excellent adhesion even when a water contact step is performed before the deblocking step.

[0007] As a result of intensive investigations into solving the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using a block urethane compound having a specific structure, specifically, by making the polyhydroxy compound that constitutes the block urethane compound a compound having a specific structure.

[0008] Specifically, the present disclosure provides a block urethane material comprising a block urethane compound formed using a polyisocyanate compound, a polyhydroxy compound, and a blocking agent, wherein the polyhydroxy compound comprises one or more compounds selected from an unsaturated polyol derivative, an unsaturated polyol, and an acrylic polyol. According to the present disclosure, the block urethane material exhibits excellent adhesion even when contacted with water before deblocking.

[0009] The block urethane material of the present disclosure is preferably one that passes through a contact step before deblocking, because the block urethane material of the present disclosure can maintain excellent adhesion even when contacted with water before deblocking. In addition, the block urethane material of the present disclosure has moisture resistance.

[0010] In the present disclosure, the polyhydroxy compound preferably includes one or more compounds selected from the group consisting of unsaturated polyol derivatives and unsaturated polyols, because this allows the block urethane material to provide better adhesion.

[0011] In the present disclosure, the unsaturated polyol derivative is preferably an epoxidized or hydrogenated product of the unsaturated polyol, since this allows the block urethane material to provide better adhesion.

[0012] In the present disclosure, the unsaturated polyol is preferably one or more compounds selected from the group consisting of unsaturated hydroxy fatty acid glycerides, dimer acid polyols, polybutadiene polyols, and unsaturated aliphatic group-containing phenolic compounds, because this allows the block urethane material to provide better adhesion.

[0013] In the present disclosure, the unsaturated polyol is preferably one or more compounds selected from the group consisting of unsaturated hydroxy fatty acid glycerides and unsaturated aliphatic group-containing phenolic compounds, because this allows the block urethane material to provide better adhesion.

[0014] In the present disclosure, the polyisocyanate compound is preferably an alicyclic isocyanate compound, because the block urethane material can provide better adhesion.

[0015] In the present disclosure, the blocking agent is preferably a monophenol, since the blocked urethane material can provide better adhesion.

[0016] In the present disclosure, the block urethane compound is preferably formed further using a branching agent. The branching agent is one or more compounds having at least three groups reactive with an isocyanate group, and is a compound other than an unsaturated polyol, an unsaturated polyol derivative, or an acrylic polyol. This is because the block urethane material can provide better adhesion.

[0017] The present disclosure provides a composition comprising an epoxy compound, a curing agent, and a blocked urethane compound, the blocked urethane compound being formed using a polyisocyanate compound, a polyhydroxy compound, and a blocking agent, the polyhydroxy compound comprising one or more compounds selected from the group consisting of an unsaturated polyol derivative, an unsaturated polyol, and an acrylic polyol. According to the present disclosure, the composition can easily form a cured product with excellent adhesion even when the blocked urethane compound comes into contact with water before being deblocked.

[0018] The present disclosure provides a cured product formed using the above-described composition. According to the present disclosure, the cured product has excellent adhesion even when contacted with water before the blocked urethane compound is deblocked.

[0019] The present disclosure provides a method for producing a cured product, the method comprising: a water contacting step of contacting a composition with water; and a deblocking step of deblocking a blocking agent for a blocked urethane compound contained in the composition after the water contacting step, the composition comprising an epoxy compound, a curing agent, and a blocked urethane compound, the blocked urethane compound being a compound formed using a polyisocyanate compound, a polyhydroxy compound, and a blocking agent, the polyhydroxy compound comprising one or more compounds selected from the group consisting of an unsaturated polyol derivative, an unsaturated polyol, and an acrylic polyol. According to the present disclosure, a cured product with excellent adhesion can be easily formed even if the blocked urethane compound in the composition comes into contact with water before being deblocked.

[0020] The present disclosure provides a block urethane compound formed using a polyisocyanate compound, a polyhydroxy compound, and a blocking agent, wherein the polyhydroxy compound includes one or more compounds selected from the group consisting of an unsaturated polyol derivative, an unsaturated polyol, and an acrylic polyol. According to the present disclosure, the block urethane compound has excellent adhesion.

[0021] In the present disclosure, it is preferable to satisfy at least one condition selected from the following conditions 1, 2, and 3. This is because a block urethane compound having superior adhesion can be provided.

[0022] (Condition 1) The polyhydroxy compound includes an unsaturated polyol derivative, and the unsaturated polyol derivative includes an epoxidized product of an unsaturated polyol.

[0023] (Condition 2) The polyhydroxy compound contains an unsaturated hydroxy fatty acid glyceride as an unsaturated polyol, the block urethane compound is formed further using a branching agent, the branching agent being one or more compounds having at least three groups reactive with an isocyanate group, and being a compound other than an unsaturated polyol, an unsaturated polyol derivative, or an acrylic polyol, and the branching agent ratio of the block urethane compound is within the range of 1% or more and 60% or less.

[0024] (Condition 3) The polyhydroxy compound contains a derivative of an unsaturated aliphatic group-containing phenol as an unsaturated polyol, and the unsaturated aliphatic group of the unsaturated aliphatic group-containing phenol has 1 to 30 carbon atoms.

[0025] The present disclosure can provide a block urethane material with excellent adhesion.

[0026] The present disclosure relates to a block urethane material, a composition, a cured product, a method for producing the cured product, and a block urethane compound.

[0027] A. Block Urethane Material First, the block urethane material of the present disclosure will be described. The block urethane material of the present disclosure includes a block urethane compound formed using a polyisocyanate compound, a polyhydroxy compound, and a blocking agent, and the polyhydroxy compound includes one or more compounds selected from the group consisting of unsaturated polyol derivatives, unsaturated polyols, and acrylic polyols. In particular, the block urethane material exhibits excellent adhesion even when used after passing through a water contact step before deblocking.

[0028] Here, the reason why the polyhydroxy compound constituting the block urethane compound is a compound with a specific structure results in excellent adhesion even when subjected to a water contact step before deblocking is not clear, but is presumed as follows.

[0029] That is, by using a compound having a specific structure as the polyhydroxy compound, the amount of moisture adsorbed by the block urethane compound when it passes through a water contact step before deblocking can be reduced. Therefore, when it is heated or the like in the deblocking step, the formation of a non-adhesion surface such as a void at the interface between the layer containing the block urethane material and the substrate due to foaming of the moisture adsorbed in the block urethane compound can be suppressed, resulting in excellent adhesion. In other words, stable adhesion can be exhibited regardless of whether or not a water contact step before deblocking is performed.

[0030] The block urethane material according to the present disclosure is moisture resistant. Here, "moisture resistant" refers to an adhesive strength retention rate of at least 50%, preferably at least 60%, more preferably at least 70%, even more preferably at least 80%, and even more preferably at least 90%, where the adhesive strength retention rate is defined as the adhesive strength after the water bonding step relative to the adhesive strength before the water bonding step, as measured using an evaluation composition in the Examples described below by an evaluation method specified in the Examples.

[0031] The block urethane material of the present disclosure includes a block urethane compound. The block urethane material of the present disclosure is preferably one that passes through a water contact step before deblocking. Hereinafter, embodiments and components of the block urethane material of the present disclosure will be described in detail.

[0032] 1. Embodiments The block urethane material of the present disclosure can be used in an embodiment in which a water contacting step before deblocking is performed. The water contacting step before deblocking can include an embodiment in which a block urethane compound is contacted with water before the deblocking step in which the block urethane compound is deblocked, and an embodiment in which the block urethane compound is contacted with water. Note that "contacting a block urethane compound with water" also includes an embodiment in which a composition containing the block urethane compound and other components is contacted with water. Furthermore, "contacting a block urethane compound with water" refers not only to contact with water as a liquid, but also to an embodiment in which the block urethane compound or a composition containing the block urethane compound and other components is contacted with water as a gas, such as moisture contained in air.

[0033] The details of the water contact step and deblocking step used as the water contact step before deblocking can be the same as the details of "1. Water contact step" and "2. Deblocking step" described in the section "D. Method for producing a cured product" described below. Furthermore, other steps that are preferably carried out together with such water contact step and deblocking step can also be the same as the details described in the section "D. Method for producing a cured product" described below.

[0034] The embodiment of the block urethane material of the present disclosure is not particularly limited as long as it is in a form that requires adhesion, but it is preferably in a form in which a water contact step is carried out before deblocking. Examples include paints and adhesives, but adhesives are preferred because the effects of the present disclosure can be more effectively exhibited.

[0035] Substrates to which the block urethane material is applied as a coating material, adhesive, etc. include metal substrates, inorganic material substrates, and polymer material substrates, but preferably include metal substrates. Substrates to which the block urethane material is applied as a coating material, adhesive, etc. preferably include substrates on which a coating layer is formed, and particularly preferably substrates on which a cationic electrodeposition coating film is formed between the substrate and the coating layer. Among these, substrates that are particularly preferred are substrates that are degreased before the formation of the cationic electrodeposition coating film. Among these, substrates to which the block urethane material is applied before the formation of the coating layer are particularly preferred. Among these, substrates to which the block urethane material is applied before the formation of the electrodeposition coating film are particularly preferred. Among these, substrates to which the block urethane material is applied before the degreasing treatment are particularly preferred. Among these, substrates that are particularly preferred are substrates that are stored in an environment in which the block urethane material comes into contact with air after application. This is because the storage process, degreasing treatment, water washing processes before and after the degreasing treatment, etc., include the timing when the pre-deblocking water contact process is performed, thereby enabling the effects of the present disclosure to be effectively exhibited.

[0036] Examples of substrates to which the block urethane material can be applied include transportation equipment such as automobiles, ships, and aircraft, electrical materials, and building materials, and among these, transportation equipment is preferred, and automobiles are particularly preferred, as this allows the effects of the present disclosure to be more effectively exhibited.

[0037] Furthermore, in the manufacture of automobile bodies, a body forming process and a painting process may be performed in this order. Examples of body forming processes include press molding, an adhesion process in which press-molded substrates are bonded together using an adhesive containing a block urethane compound, and a welding process in which the substrates are joined by welding or the like, performed in this order. Examples of the painting process include a degreasing process, a cationic electrodeposition process, and a paint layer formation process, performed in this order. Furthermore, the adhesive used in the adhesion process must be subjected to a curing process in which the block urethane compound is deblocked and the adhesive is cured.

[0038] In recent years, environmental conservation has led to a demand for a reduction in the number of heat treatments required for the curing process, and the curing process may be carried out during the painting process, or even later in the painting process. Furthermore, when the body building process and the painting process are carried out in separate factories, the block urethane compound applied in the bonding process within the body building process is exposed to moisture in the air for a long period of time during the storage process. For these reasons, the block urethane material of the present disclosure can more effectively demonstrate the effects of the present disclosure, particularly in the manufacture of automobile bodies.

[0039] Among the substrates used in automobiles, examples of the components on which a paint layer is formed on the above-mentioned metal substrate include the lower structural parts of the automobile body, i.e., the underside of the floor, the wheel house (tire house), the rocker panel, the side sill, the front apron, the front and rear fenders, the lower parts of the doors, etc.

[0040] The block urethane material can be used as an additive to a thermoplastic resin composition or as a curing component of a curable compound. In the present disclosure, the block urethane material is preferably used as a curing component of a curable compound, and more preferably as a curing component of a curable compound containing an epoxy compound. This is because the effects of the present disclosure can be more effectively exhibited.

[0041] 2. Blocked Urethane Compound The blocked urethane compound is formed using a polyisocyanate compound, a polyhydroxy compound, and a blocking agent. More specifically, the blocked urethane compound can be a compound obtained by reacting an isocyanate group contained in a urethane polyisocyanate compound, which is a reaction product of a polyisocyanate compound and a polyhydroxy compound, with a blocking agent. The blocked urethane compound can also be a compound obtained by reacting an isocyanate group contained in a branched urethane polyisocyanate compound, which is a reaction product of a urethane polyisocyanate compound and a branching agent, with a blocking agent.

[0042] (1) Polyhydroxy Compound In the present disclosure, the polyhydroxy compound includes one or more compounds selected from the group consisting of unsaturated polyols, unsaturated polyol derivatives, and acrylic polyols (hereinafter, these may be collectively referred to as polyhydroxy compound A). In the present disclosure, the polyhydroxy compound preferably includes one or more compounds selected from the group consisting of unsaturated polyols and unsaturated polyol derivatives, and particularly preferably includes an unsaturated polyol derivative. This is because the block urethane material can provide better adhesion. Also, this is because it is easy to make the block urethane material have excellent adhesion.

[0043] The hydroxyl value of the polyhydroxy compound is preferably in the range of 10 mgKOH / g to 400 mgKOH / g, more preferably in the range of 30 mgKOH / g to 200 mgKOH / g, and particularly preferably in the range of 40 mgKOH / g to 120 mgKOH / g, because this allows the block urethane material to have better adhesion. Also, this makes it easier to provide the block urethane material with excellent adhesion.

[0044] The number average molecular weight of the polyhydroxy compound is preferably in the range of 500 to 10,000, more preferably in the range of 800 to 5,000, and particularly preferably in the range of 1,000 to 3,000, because this allows the block urethane material to have better adhesion. Also, this makes it easier to make the block urethane material have excellent adhesion.

[0045] In the present disclosure, the number average molecular weight (Mn) and weight average molecular weight (Mw) can be measured by GPC (gel permeation chromatography) and calculated using a calibration curve based on standard polystyrene. Specifically, the GPC conditions are as follows: column: "TSKgel G4000HXL + TSKgel G3000HXL + TSKgel G2000HXL + TSKgel G1000HXL + TSKgel G1000HXL" manufactured by Tosoh Corporation, mobile phase: THF (tetrahydrofuran), mobile phase flow rate: 1.0 mL / min, column temperature: 40°C, sample injection amount: 50 μL, and sample concentration: 0.2% by mass.

[0046] (1-1) Unsaturated Polyol The unsaturated polyol may be any polyol containing an unsaturated group in the molecule, such as a carbon-carbon double bond or a carbon-carbon triple bond.

[0047] Examples of such unsaturated polyols include unsaturated hydroxy fatty acid glycerides, dimer acid polyols, polydiene polyols, and unsaturated aliphatic group-containing phenolic compounds. In the present disclosure, it is preferable to include a polydiene polyol or an unsaturated hydroxy fatty acid glyceride, and it is particularly preferable to include an unsaturated hydroxy fatty acid glyceride. This is because the block urethane material can provide better adhesion. Also, it is easy to make the block urethane material have excellent adhesion.

[0048] The number-average molecular weight of the unsaturated polyol is preferably in the range of 1,000 to 3,000, more preferably in the range of 1,000 to 2,000, and particularly preferably in the range of 1,000 to 1,500, because this allows the block urethane material to have better adhesion. Also, this makes it easier to make the block urethane material have excellent adhesion.

[0049] The hydroxyl value of the unsaturated polyol is preferably in the range of 40 mgKOH / g to 120 mgKOH / g, more preferably in the range of 80 mgKOH / g to 115 mgKOH / g, and particularly preferably in the range of 100 mgKOH / g to 110 mgKOH / g, because this allows the block urethane material to have better adhesion. Also, this makes it easier to provide the block urethane material with excellent adhesion.

[0050] (1-1-1) Unsaturated Hydroxy Fatty Acid Glycerides The unsaturated hydroxy fatty acid glycerides are esters of glycerol and fatty acids, and the fatty acids include unsaturated hydroxy fatty acids. Examples of the unsaturated hydroxy fatty acids include fatty acids having one or more hydroxyl groups and one or more ethylenically unsaturated groups, such as 10-hydroxy-2-decenoic acid, 2-hydroxy-15-tetracosenoic acid, ricinoleic acid, lesquerolic acid, cerebronic acid, densiporic acid, and auricolic acid, which are compounds having 8 to 30 carbon atoms. In the present disclosure, 2-hydroxy-15-tetracosenoic acid, ricinoleic acid, lesquerolic acid, cerebronic acid, densiporic acid, and auricolic acid are preferred, with ricinoleic acid being particularly preferred.

[0051] In the present disclosure, the unsaturated hydroxy fatty acid preferably contains a compound having 12 to 25 carbon atoms, more preferably a compound having 14 to 22 carbon atoms, and particularly preferably a compound having 16 to 20 carbon atoms. This is because the block urethane material can provide better adhesion. Also, it is easy to make the block urethane material have excellent adhesion.

[0052] The content of the unsaturated hydroxy fatty acid per 100 parts by mass of fatty acid is preferably 50 parts by mass or more, more preferably in the range of 70 parts by mass to 95 parts by mass, and particularly preferably in the range of 80 parts by mass to 90 parts by mass, because this allows the block urethane material to provide better adhesion. Also, this makes it easy to make the block urethane material have excellent adhesion.

[0053] The unsaturated hydroxy fatty acid glyceride may contain unsaturated fatty acids and saturated fatty acids in addition to unsaturated hydroxy fatty acids as the fatty acids. In the present disclosure, it is preferable that the unsaturated hydroxy fatty acid glyceride contains both unsaturated fatty acids and saturated fatty acids.

[0054] The unsaturated fatty acid may be one that does not contain a hydroxyl group, and examples thereof include compounds having 10 to 30 carbon atoms, such as oleic acid, linoleic acid, and linolenic acid. In the present disclosure, the unsaturated fatty acid preferably contains a compound having 12 to 25 carbon atoms, more preferably a compound having 14 to 22 carbon atoms, and particularly preferably a compound having 16 to 20 carbon atoms.

[0055] Examples of saturated fatty acids include compounds having 10 to 30 carbon atoms and no hydroxyl group, such as lauric acid, myristic acid, palmitic acid, and stearic acid. In the present disclosure, the saturated fatty acids preferably include compounds having 12 to 25 carbon atoms, more preferably compounds having 14 to 22 carbon atoms, and particularly preferably compounds having 16 to 20 carbon atoms.

[0056] The unsaturated hydroxy fatty acid glyceride may use castor oil as the fatty acid. Here, castor oils containing unsaturated hydroxy fatty acids as the main component are known, and examples thereof include those containing unsaturated hydroxy fatty acids (87% ricinoleic acid), unsaturated fatty acids (7% oleic acid, 3% linoleic acid), and small amounts of saturated fatty acids (3% palmitic acid, stearic acid, etc.). When the unsaturated hydroxy fatty acid glyceride is a glyceride of castor oil, the unsaturated hydroxy fatty acid contained in the fatty acid may contain ricinoleic acid. Commercially available unsaturated hydroxy fatty acid glycerides include castor oil polyols such as H-1890 and HF-2009 manufactured by Ito Oil Mills, Ltd.

[0057] (1-1-2) Unsaturated aliphatic group-containing phenolic compound As the unsaturated aliphatic group-containing phenolic compound, an unsaturated aliphatic group-containing phenol or a derivative thereof can be used. In the present disclosure, it is particularly preferable to include a derivative of an unsaturated aliphatic group-containing phenol. This is because the block urethane material can provide better adhesion. Also, it is easy to make the block urethane material have excellent adhesion.

[0058] The unsaturated aliphatic group-containing phenol may include an unsaturated aliphatic group-containing phenolic compound or a polymer thereof in which one or more hydrogen atoms in the benzene ring constituting the phenol are substituted with an unsaturated aliphatic group. Examples of the unsaturated aliphatic group-containing phenolic compound include monounsaturated aliphatic group-containing phenolic compounds having one phenolic hydroxyl group, such as vinylphenol, allylphenol, eugenol, isopropenylphenol, diisopropenylphenol, butenylphenol, isobutenylphenol, cyclohexenylphenol, and cardanol, and polyfunctional unsaturated aliphatic group-containing phenolic compounds having two or more phenolic hydroxyl groups, such as urushiol, thitsiol, and laccol. In the present disclosure, the unsaturated aliphatic group-containing phenol preferably includes a monounsaturated aliphatic group-containing phenolic compound. This is because the block urethane material can provide better adhesion. Furthermore, it is easy to make the block urethane material have excellent adhesion.

[0059] In the present disclosure, the number of carbon atoms in the unsaturated aliphatic group is preferably in the range of 1 to 30, more preferably in the range of 5 to 25, particularly preferably in the range of 10 to 20, and most preferably in the range of 12 to 18. This is because the block urethane material can provide better adhesion. Also, it is easy to make the block urethane material have excellent adhesion.

[0060] Examples of the polymer include those obtained by addition condensation of an unsaturated aliphatic group-containing phenol compound and an aldehyde compound.

[0061] Examples of the derivatives of the unsaturated aliphatic group-containing phenols include unsaturated aliphatic group-containing alcohols in which the phenolic hydroxyl group in the unsaturated aliphatic group-containing phenol is converted into a group having an alcoholic hydroxyl group.

[0062] Examples of the unsaturated aliphatic group-containing alcohol include alkylene oxide adducts of unsaturated aliphatic group-containing phenols, in which an alkylene oxide such as ethylene oxide is added to the phenolic hydroxyl group of an unsaturated aliphatic group-containing phenol, and polyol adducts of unsaturated aliphatic group-containing phenols, in which a polyol compound is added directly or indirectly to the phenolic hydroxyl group of an unsaturated aliphatic group-containing phenol. Examples of the method for indirectly adding the polyol compound include a method in which the phenolic hydroxyl group of the unsaturated aliphatic group-containing phenol is converted to an epoxy group-containing group, and then a polyol compound is added. Examples of the method for converting to an epoxy group-containing group include a method in which epichlorohydrin or the like is reacted with the phenolic hydroxyl group of the unsaturated aliphatic group-containing phenolic compound.

[0063] In the present disclosure, the unsaturated aliphatic group-containing alcohol is preferably a polyol adduct of an unsaturated aliphatic group-containing phenol, in which a polyol compound is added directly or indirectly to the phenolic hydroxyl group of the unsaturated aliphatic group-containing phenol. Among these, a polyol adduct of an epoxidized unsaturated aliphatic group-containing phenol, in which a polyol compound is added to a compound in which the phenolic hydroxyl group of the unsaturated aliphatic group-containing phenol has been converted to an epoxy group-containing group, is preferred. This is because the block urethane material can provide better adhesion. Furthermore, it is easy to make the block urethane material have excellent adhesion.

[0064] Examples of the polyol compound include polyether polyol, polyester polyol, polycarbonate polyol, polyesteramide polyol, acrylic polyol, and polyurethane polyol. In the present disclosure, the polyol compound preferably includes polyester polyol or polycarbonate polyol, and more preferably includes polycarbonate polyol. This is because the block urethane material can provide better adhesion. Also, it is easy to make the block urethane material have excellent adhesion. Examples of polyether polyol, polyester polyol, polycarbonate polyol, polyesteramide polyol, acrylic polyol, and polyurethane polyol are exemplified in, for example, JP 2023-032555 A.

[0065] In the present disclosure, examples of polycarbonate polyols include those obtained by reacting a carbonate ester and / or phosgene with a low-molecular-weight polyol. Examples of the carbonate ester include dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, diphenyl carbonate, dinaphthyl carbonate, and phenyl naphthyl carbonate. The polycarbonate polyol preferably contains a carbonate ester such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, or propylene carbonate. Among these, a cyclic carbonate ester such as ethylene carbonate or propylene carbonate is preferred, and ethylene carbonate is particularly preferred. This is because the block urethane material can provide superior adhesion. Furthermore, it is easy to make the block urethane material have excellent adhesion.

[0066] In the present disclosure, when the unsaturated aliphatic group-containing alcohol is a polycarbonate polyol adduct of an epoxidized saturated aliphatic group-containing phenol, the polycarbonate polyol is preferably one obtained by reacting the epoxy group with the cyclic carbonate ester.

[0067] Commercially available products of the unsaturated aliphatic group-containing phenolic compound include NX-5285, NX-9001, NX-9005, NX-90065, NX-9007, NX-9008, NX-9201, NX-9201LP, NX-9203, and NX-9203LP manufactured by Cardrite Japan Co., Ltd.

[0068] (1-1-3) Polydiene-Based Polyol As the polydiene-based polyol, a polydiene into which a hydroxyl group has been introduced can be used. Examples of the polydiene-based polyol include polybutadiene polyol, polyisoprene polyol, and polypentadiene polyols such as 1,3-polypentadiene polyol. In the present disclosure, the polydiene-based polyol preferably includes polybutadiene polyol or polyisoprene polyol, and more preferably includes polybutadiene polyol. This is because the block urethane material can provide better adhesion.

[0069] The polybutadiene polyol may contain a 1,2-vinyl structure, a 1,4-vinyl structure, or both structures in the molecule. The content of the 1,2-vinyl structure in the polybutadiene polyol is preferably 50% by mass or less, and more preferably 10% by mass or more and 30% by mass or less. The content of the 1,4-vinyl structure in the polybutadiene polyol is preferably 50% by mass or more, and more preferably 60% by mass or more and 90% by mass or less. This is because the block urethane material can provide better adhesion. Furthermore, it is easy to make the block urethane material have excellent adhesion.

[0070] Commercially available polydiene polyols include G-1000, G-2000, and G-3000 (manufactured by Nippon Soda Co., Ltd.), Poly bd R-15HT and Poly bd R-45HT (manufactured by Idemitsu Kosan Co., Ltd.), and Krasol LBH-P3000 (manufactured by Cray Valley Chemical Industries, Ltd.).

[0071] (1-1-4) Dimer Acid Polyol The dimer acid polyol may be any compound having a structure derived from a dimer acid and having two or more hydroxyl groups. Examples of such dimer acid polyols include a reaction product of a dimer acid and a polyhydric alcohol, and a dimer acid diol obtained by reducing a dimer acid. In the present disclosure, the dimer acid polyol is preferably a reaction product of a dimer acid and a polyhydric alcohol. This is because the block urethane material can provide better adhesion. In addition, it is easy to make the block urethane material have excellent adhesion.

[0072] The dimer acid may be a dicarboxylic acid that is a dimer of an unsaturated fatty acid, and the unsaturated fatty acid may be the unsaturated fatty acid having 10 to 25 carbon atoms and no hydroxyl group described in the above section "(1-1-1) Unsaturated hydroxy fatty acid glyceride."

[0073] In the present disclosure, the number of carbon atoms in the unsaturated fatty acid constituting the dimer acid is preferably in the range of 12 to 25, more preferably in the range of 14 to 22, particularly preferably in the range of 16 to 20, and particularly preferably 18, i.e., the number of carbon atoms in the dimer acid is 36. This is because the block urethane material can provide better adhesion. Also, it is easy to make the block urethane material have excellent adhesion.

[0074] Examples of the polyhydric alcohol that reacts with the dimer acid include aliphatic or alicyclic polyhydric alcohols having 2 to 40 carbon atoms. Specific examples include linear polyhydric alcohols having 2 to 20 carbon atoms, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, 1,18-octadecanediol, and 1,20-eicosanediol; Examples of suitable branched chain polyhydric alcohols having 4 to 40 carbon atoms include 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 2-methyl-1,4-butanediol, 2-ethyl-1,6-hexanediol, 2,4-diethyl-1,5-pentanediol, neopentyl glycol, 2-ethyl-2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, and dimer diol; polyhydric alcohols having 4 to 20 carbon atoms and a cyclic structure in the molecule, such as 1,3-cyclohexanediol, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol; diethylene glycol, triethylene glycol, polytetramethylene ether glycol, and dimer acid diol.

[0075] Commercially available products of the dimer acid polyol include Priplast (registered trademark) 1837, 1838, 3187, 3196, 3197, 3199, or 3238, PRIPOL (registered trademark) 2033 (average hydroxyl value: 202 to 212 mg KOH / g, average functionality: 2), 2043, Hitachi Chemical Polymer Co., Ltd.'s TA22-558 (hydroxyl value: 70 to 75 mg KOH / g, average functionality: 3), TA22-559 (hydroxyl value: 78 to 82 mg KOH / g, average functionality: 3), Kao Corporation's Ediform E-404 (hydroxyl value: 120 mg KOH / g, average functionality: 3), and the like.

[0076] (1-2) Unsaturated Polyol Derivative The unsaturated polyol derivative can be one in which the unsaturated groups in the unsaturated polyol are modified. Examples of the modification method include epoxidation and hydrogenation. In the present disclosure, it is preferable that the modification method is epoxidation, i.e., the unsaturated polyol derivative is an epoxidized product of an unsaturated polyol. This is because the block urethane material can provide better adhesion. Furthermore, it is easy to make the block urethane material have excellent adhesion.

[0077] The hydroxyl value of the unsaturated polyol is preferably in the range of 40 mgKOH / g to 120 mgKOH / g, more preferably in the range of 40 mgKOH / g to 80 mgKOH / g, and particularly preferably in the range of 40 mgKOH / g to 50 mgKOH / g. This is because the block urethane material can provide better adhesion. Also, it is easy to make the block urethane material have excellent adhesion.

[0078] The number-average molecular weight of the unsaturated polyol is preferably in the range of 1,000 to 5,000, more preferably in the range of 1,500 to 4,000, particularly preferably in the range of 2,000 to 3,500, and particularly preferably in the range of 2,500 to 3,300. This is because the block urethane material can provide better adhesion. Also, it is easy to make the block urethane material have excellent adhesion.

[0079] Such unsaturated polyol derivatives may be those in which the unsaturated groups in the unsaturated polyols described in the above section "(1-1) Unsaturated Polyol" have been modified, but epoxy products of polydiene polyols and hydrogenated polydiene polyols are preferred, and epoxy products of polydiene polyols are particularly preferred. This is because the block urethane material can provide better adhesion. Also, it is easy to make the block urethane material have excellent adhesion.

[0080] Furthermore, the polydiene polyol used in the unsaturated polyol derivative preferably includes polybutadiene polyol or polyisoprene polyol, and particularly preferably includes polybutadiene polyol. This is because the block urethane material can provide better adhesion. Also, it is easy to make the block urethane material have excellent adhesion. In the present disclosure, the unsaturated polyol derivative is preferably an epoxidized product of polybutadiene polyol. This is because the block urethane material can provide better adhesion. Also, it is easy to make the block urethane material have excellent adhesion.

[0081] Commercially available unsaturated polyol derivatives include hydrogenated polydiene polyols GI-1000, GI-2000, and GI-3000 manufactured by Nippon Soda Co., Ltd., and epoxidized polybutadiene Poly bd 700 manufactured by Cray Valley.

[0082] (1-3) Acrylic Polyol The acrylic polyol may be a (co)polymer of a (meth)acrylic monomer having a hydroxyl group and any other (meth)acrylic monomer, etc. Examples of such an acrylic polyol include those described as acrylic polyols in JP-A-2023-073657.

[0083] Commercially available acrylic polyols include, for example, ARUFON UH-2000, UH-2032, UH-2041, and UH-2190 manufactured by Toagosei Co., Ltd.

[0084] (1-4) Diol Compound The polyhydroxy compound preferably contains a diol compound (hereinafter, sometimes referred to as polyhydroxy compound B) as a polyhydroxy compound other than polyhydroxy compound A. This is because the block urethane material can provide better adhesion. In addition, it is easy to make the block urethane material have excellent adhesion. The polyhydroxy compound B may be any diol compound other than the polyhydroxy compound A described above, and examples thereof include low-molecular-weight diol compounds and high-molecular-weight diol compounds. In the present disclosure, it is preferable that the polyhydroxy compound B contains a low-molecular-weight diol compound. This is because the block urethane material can provide better adhesion. In addition, it is easy to make the block urethane material have excellent adhesion.

[0085] The low molecular weight diol compound may have a molecular weight of 500 or less. In the present disclosure, the molecular weight of the low molecular weight diol compound is preferably 50 or more and 300 or less, more preferably 70 or more and 200 or less, and particularly preferably 80 or more and 150 or less. This is because the block urethane material can provide better adhesion. Also, it is easy to make the block urethane material have excellent adhesion.

[0086] Examples of the low molecular weight diol compound include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2, aliphatic diols such as 4-diethyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, diethylene glycol, and triethylene glycol; and alicyclic diols such as cyclohexanedimethanol and cyclohexanediol.

[0087] The polymer diol compound may have a molecular weight of more than 500. Examples of such polymer diol compounds include polyether polyols, polyester polyols, polycarbonate polyols, polyesteramide polyols, and polyurethane polyols. Examples of these polymer diol compounds are described in, for example, JP 2023-032555 A.

[0088] The content of the polyhydroxy compound B is preferably 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, particularly preferably 3 parts by mass or more and 15 parts by mass or less, and particularly preferably 5 parts by mass or more and 10 parts by mass or less, per 100 parts by mass of the total of polyhydroxy compound A and polyhydroxy compound B. This is because the block urethane material can provide better adhesion. Also, this is because it is easy to make the block urethane material have excellent adhesion.

[0089] (1-5) Others The content of the polyhydroxy compound A is preferably 10 parts by mass or more per 100 parts by mass of the block urethane compound, more preferably 20 parts by mass or more and 80 parts by mass or less, and particularly preferably 30 parts by mass or more and 70 parts by mass or less. This is because the block urethane material can provide better adhesion. Also, this is because it is easy to make the block urethane material have excellent adhesion. The content of the polyhydroxy compound in the block urethane compound refers to the content of the polyhydroxy compound-derived moiety that constitutes the block urethane compound.

[0090] The content of the polyhydroxy compound is preferably 10 parts by mass or more, more preferably 20 parts by mass or more and 80 parts by mass or less, and particularly preferably 30 parts by mass or more and 70 parts by mass or less, per 100 parts by mass of the block urethane compound. This is because the block urethane material can provide better adhesion. Also, it is easy to make the block urethane material have excellent adhesion.

[0091] (2) Polyisocyanate Compounds Examples of the polyisocyanate compound include compounds having two or more isocyanate groups, such as aromatic diisocyanate compounds such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate; chain aliphatic diisocyanate compounds such as hexamethylene diisocyanate and lysine diisocyanate; and alicyclic structure-containing diisocyanate compounds such as cyclohexane diisocyanate, isophorone diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate. Furthermore, isocyanurate compounds obtained by trimerizing diisocyanate compounds such as the aromatic diisocyanate compounds, the chain aliphatic diisocyanate compounds, and alicyclic structure-containing diisocyanate compounds can also be used.

[0092] In the present disclosure, the polyisocyanate compound preferably contains a chain aliphatic diisocyanate compound or an alicyclic structure-containing diisocyanate compound, and more preferably contains an alicyclic structure-containing diisocyanate compound, particularly preferably contains isophorone diisocyanate. This is because the block urethane material can provide better adhesion. Also, it is easy to make the block urethane material have excellent adhesion.

[0093] In the present disclosure, a known method can be used as a method for synthesizing an isocyanurate compound by trimerizing a diisocyanate compound.

[0094] The content of the polyisocyanate compound is preferably 5 to 40 parts by mass, more preferably 10 to 38 parts by mass, particularly preferably 15 to 36 parts by mass, and particularly preferably 20 to 34 parts by mass, per 100 parts by mass of the block urethane compound. This is because the block urethane material can provide better adhesion. Also, it is easy to make the block urethane material have excellent adhesion.

[0095] (3) Blocking Agent Examples of the blocking agent include active methylene compounds such as malonic acid diesters (diethyl malonate, etc.), acetylacetone, and acetoacetic acid esters (ethyl acetoacetate, etc.); oxime compounds such as acetoxime, methyl ethyl ketoxime (MEK oxime), and methyl isobutyl ketoxime (MIBK oxime); monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, heptyl alcohol, hexyl alcohol, octyl alcohol, 2-ethylhexyl alcohol, isononyl alcohol, and stearyl alcohol, and isomers thereof; glycol derivatives such as methyl glycol, ethyl glycol, ethyl diglycol, ethyl triglycol, butyl glycol, and butyl diglycol; amine compounds such as dicyclohexylamine; phenols; ε-caprolactone, and ε-caprolactam.

[0096] Examples of the phenols include monophenols and diphenols. Examples of the monophenols include phenol and substituted monophenols. Examples of the phenols include diphenols such as resorcinol, catechol, hydroquinone, bisphenol A, bisphenol S, bisphenol F, and naphthol. The substituted monophenols may be compounds having only one phenolic hydroxyl group, such as the monounsaturated aliphatic group-containing phenols (e.g., cardanol), saturated aliphatic group-containing monophenols, aromatic group-containing monophenols, and halogen-substituted monophenols.

[0097] Examples of the saturated aliphatic group-containing phenols include compounds in which one or more hydrogen atoms in the aromatic ring of phenol, such as methylphenol (cresol), ethylphenol, n-propylphenol, isopropylphenol, butylphenol, tertiary butylphenol, octylphenol, nonylphenol, dodecylphenol, and cyclohexylphenol, have been substituted with saturated aliphatic groups. Examples of the aromatic group-containing phenols include compounds in which one or more hydrogen atoms in the aromatic ring of phenol, such as paracumylphenol, have been substituted with a substituent containing an aromatic group. Examples of the halogen-substituted phenols include chlorophenol and bromophenol.

[0098] In the present disclosure, the blocking agent is preferably a phenol, and more preferably a monophenol, and particularly preferably phenol or a substituted monophenol, and particularly preferably a substituted monophenol, and particularly preferably a monounsaturated aliphatic group-containing phenol, a saturated aliphatic group-containing monophenol, or an aromatic group-containing monophenol. This is because the blocked urethane material can provide better adhesion. In the present disclosure, from the viewpoint of reducing viscosity, the blocking agent is preferably a monounsaturated aliphatic group-containing phenol.

[0099] In the present disclosure, the monounsaturated aliphatic group-containing phenolic compound used in the blocking agent preferably has an unsaturated aliphatic group constituting the monounsaturated aliphatic group-containing phenolic compound with a carbon atom number in the range of 1 to 30, more preferably in the range of 5 to 25, particularly preferably in the range of 10 to 20, and particularly preferably in the range of 12 to 18. This is because the block urethane material can provide better adhesion. Also, it is easy to make the block urethane material have excellent adhesion.

[0100] The content of the blocking agent is preferably 5 to 30 parts by mass, more preferably 10 to 25 parts by mass, and particularly preferably 12 to 22 parts by mass, per 100 parts by mass of the block urethane compound. This is because the block urethane material can provide better adhesion. This is also because it is easy to make the block urethane material have excellent adhesion.

[0101] (4) Branching Agent The block urethane compound contains a polyisocyanate compound, a polyhydroxy compound, and a blocking agent as constituent materials, but preferably contains a compound having at least three groups reactive with an isocyanate group (hereinafter, sometimes referred to as a branching agent), because this allows the block urethane material to provide better adhesion.

[0102] In the present disclosure, when the constituent components of the polyisocyanate compound include an unsaturated polyol or an unsaturated polyol derivative, especially when the constituent component includes an unsaturated polyol, and particularly when the constituent component includes an unsaturated hydroxy fatty acid glyceride, it is preferable to use a branching agent as a constituent component in combination. This is because the block urethane material can provide better adhesion. Also, this is because it is easy to make the block urethane material have excellent adhesion.

[0103] Here, the branching agent is a compound having at least three groups reactive with an isocyanate group. Examples of the group reactive with an isocyanate group include a hydroxyl group, an amino group, a mercapto group, and a carboxyl group. In the present disclosure, the group reactive with an isocyanate group is preferably a hydroxyl group or an amino group, and among these, a hydroxyl group is particularly preferred. This is because the block urethane material can provide better adhesion. Also, this is because it is easy to make the block urethane material have excellent adhesion. Note that when the branching agent contains two or more hydroxyl groups, it is included in the polyhydroxy compound, but the branching agent is a compound different from any of the polyhydroxy compounds, namely, the unsaturated polyol, the unsaturated polyol derivative, and the acrylic polyol.

[0104] The number of groups reactive with the isocyanate group may be three or more, preferably three to six, more preferably three to five, and particularly preferably three to four, because the block urethane material can provide better adhesion. Also, it is easy to make the block urethane material have excellent adhesion.

[0105] The number average molecular weight of the branching agent is preferably in the range of 50 to 2,000, more preferably in the range of 80 to 1,000, even more preferably in the range of 100 to 500, and even more preferably in the range of 120 to 300. This is because the block urethane material can provide better adhesion. Also, it is easy to make the block urethane material have excellent adhesion.

[0106] As the compound having at least three hydroxyl groups, for example, as described above, compounds other than the compounds listed as the polyhydroxy compounds can be used, such as aliphatic compounds and alkylene oxide adducts of aliphatic compounds. In the present disclosure, it is preferable that the compound having at least three hydroxyl groups is an aliphatic compound. This is because the block urethane material can provide better adhesion. In addition, it is easy to make the block urethane material have excellent adhesion.

[0107] The aliphatic compound may be any compound that does not have an aromatic ring, such as a chain aliphatic compound, a cyclic aliphatic compound, or a chain aliphatic amine compound. In the present disclosure, the aliphatic compound preferably includes a chain aliphatic compound, a cyclic aliphatic compound, or the like, and more preferably includes a chain aliphatic compound. This is because the block urethane material can provide better adhesion. Also, it is easy to make the block urethane material have excellent adhesion.

[0108] Examples of the chain aliphatic compounds include compounds that do not contain nitrogen atoms, such as trimethylolethane, trimethylolpropane, ditrimethylolpropane, tritrimethylolpropane, 1,2,6-hexanetriol, pentaerythritol, and dipentaerythritol. Examples of the cyclic aliphatic compounds include compounds that do not contain nitrogen atoms, such as sorbitol and sucrose. Examples of the chain aliphatic amine compounds include triethanolamine and triisopropanolamine.

[0109] As the alkylene oxide adduct of the aliphatic compound, commercially available products may be used, and examples thereof include the Adeka Polyether series manufactured by ADEKA Corporation, such as AM-302, AM-502, AM-702, GM-30, GR-2505, GR-3308, G-300, G-400, G-700, G-1500, G-3000B, G-4000, and T-400.

[0110] Examples of compounds having at least three amino groups include melamine, polyether polyamine, etc. Commercially available polyether polyamines include T-403, T-3000, and T-5000, which are part of the Jeffamine series manufactured by Huntsman. These may be used alone or in combination of two or more.

[0111] The branching agent may be used by reacting the branching agent with isocyanate groups contained in a urethane polyisocyanate compound, which is a reaction product of a polyisocyanate compound and a polyhydroxy compound, to form a branched urethane polyisocyanate compound. In this case, the blocked urethane compound may be a compound obtained by reacting the isocyanate groups of the branched urethane polyisocyanate compound with a blocking agent.

[0112] The NCO INDEX of the block urethane compound is preferably 1.1 or more and 2.0 or less, more preferably 1.20 or more and 1.80 or less, particularly preferably 1.40 or more and 1.72 or less, particularly preferably 1.50 or more and 1.70 or less, particularly preferably 1.55 or more and 1.68 or less, because the block urethane material can provide better adhesion. Also, it is easy to make the block urethane material have excellent adhesion.

[0113] The NCO INDEX is defined as the ratio (number of NCO groups / number of NCO reactive groups) of the number of moles of isocyanate groups in the polyisocyanate compound to the total number of moles of hydroxyl groups in the polyhydroxy compound and groups reactive with isocyanate groups in the branching agent (number of NCO reactive groups).

[0114] The branching agent ratio (%) of the block urethane compound is preferably in the range of 1% to 60%, more preferably in the range of 5% to 50%, and particularly preferably in the range of 10% to 40%, and particularly preferably in the range of 15% to 30%, and particularly preferably in the range of 16% to 25%. This is because the block urethane material can provide better adhesion. Also, it is easy to make the block urethane material have excellent adhesion.

[0115] The branching agent ratio is defined as the ratio of the number of moles of groups reactive with isocyanate groups in the branching agent (number of NCO reactive groups in the branching agent) to the total number of moles of hydroxyl groups in the polyhydroxy compound and groups reactive with isocyanate groups in the branching agent (number of NCO reactive groups in the branching agent) (number of NCO reactive groups in the branching agent / number of NCO reactive groups × 100 (%)).

[0116] 3. Other The block urethane material includes a block urethane compound. The block urethane compound is included as a main component of the block urethane material. In one embodiment of the block urethane material, the block urethane material consists of the block urethane compound. In another embodiment, the block urethane material may be a mixture with other components, such as by-products generated during the synthesis of the block urethane compound.

[0117] The content of the block urethane compound is preferably 50 parts by mass or more, more preferably 80 parts by mass or more, particularly preferably 90 parts by mass or more, and particularly preferably 95 parts by mass or more, per 100 parts by mass of the block urethane material. This is because the block urethane material can provide better adhesion. Also, this is because it is easy to make the block urethane material have excellent adhesion.

[0118] The block urethane material may contain components other than the block urethane compound. Examples of such components include the curing agent, curing accelerator, and filler described in the section "B. Composition" below, as well as the components described in the section "4. Other." However, the block urethane material does not contain the epoxy compound described in the section "2. Epoxy Compound."

[0119] B. Composition Next, the composition of the present disclosure will be described. The composition of the present disclosure comprises an epoxy compound, a curing agent, and a blocked urethane compound. The blocked urethane compound is a compound formed using a polyisocyanate compound, a polyhydroxy compound, and a blocking agent, and the polyhydroxy compound is one or more compounds selected from the group consisting of unsaturated polyol derivatives, unsaturated polyols, and acrylic polyols. In particular, it is preferable that the composition be used in the water-contacting step before deblocking.

[0120] According to the present disclosure, the composition can form a cured product that exhibits superior adhesion. In addition, it is easy to make the cured product have excellent adhesion.

[0121] The composition of the present disclosure contains an epoxy compound, a curing agent, and a block urethane compound. Each component of the composition of the present disclosure will be described in detail below. Note that, since the embodiment of the composition of the present disclosure can be the same as that described in the above section "A. Block urethane material," a description thereof will be omitted here.

[0122] 1. Block Urethane Compound The block urethane compound used in the present disclosure can be the same as that described in the above section "A. Block Urethane Material," and therefore, description thereof will be omitted here.

[0123] The content of the block urethane compound is preferably in the range of 1 part by mass to 60 parts by mass inclusive, more preferably in the range of 3 parts by mass to 40 parts by mass inclusive, particularly preferably in the range of 5 parts by mass to 30 parts by mass inclusive, and particularly preferably in the range of 10 parts by mass to 20 parts by mass inclusive, per 100 parts by mass of the composition. This is because the composition can form a cured product exhibiting superior adhesion. In addition, it is easy to make the cured product have excellent adhesion.

[0124] The content of the block urethane compound is preferably in the range of 5 to 70 parts by mass, more preferably in the range of 10 to 50 parts by mass, particularly preferably in the range of 15 to 40 parts by mass, and particularly preferably in the range of 20 to 30 parts by mass, per 100 parts by mass of the epoxy compound. This is because the composition can form a cured product exhibiting superior adhesion. In addition, it is easy to make the cured product have excellent adhesion.

[0125] The content of the block urethane compound is preferably in the range of 3 to 60 parts by mass, more preferably in the range of 5 to 40 parts by mass, particularly preferably in the range of 10 to 30 parts by mass, and most preferably in the range of 15 to 25 parts by mass, per 100 parts by mass of the total of the block urethane compound, epoxy compound, and curing agent. This is because the composition can form a cured product exhibiting superior adhesion. Furthermore, it is easy to make the cured product have excellent adhesion.

[0126] 2. Epoxy Compounds Examples of the epoxy compounds include polyglycidyl ethers of mononuclear polyhydric phenol compounds such as hydroquinone, resorcinol, pyrocatechol, and phloroglucinol; polyglycidyl ethers of polynuclear polyhydric phenol compounds such as dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis(ortho-cresol), ethylidenebisphenol, isopropylidenebisphenol (bisphenol A), isopropylidenebis(ortho-cresol), tetrabromobisphenol A, 1,3-bis(4-hydroxycumylbenzene), 1,4-bis(4-hydroxycumylbenzene), 1,1,3-tris(4-hydroxyphenyl)butane, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolac, orthocresol novolac, ethylphenol novolac, butylphenol novolac, octylphenol novolac, resorcinol novolac, and terpene phenols; Polyglycidyl ethers of polyhydric alcohol compounds such as ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyethylene glycol, polypropylene glycol, thioglycol, dicyclopentadiene dimethanol, 2,2-bis(4-hydroxycyclohexyl)propane (hydrogenated bisphenol A), glycerin, trimethylolpropane, pentaerythritol, sorbitol, and bisphenol A-alkylene oxide adducts; glycidyl esters of aliphatic, aromatic, or alicyclic polybasic acids such as maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, and endomethylenetetrahydrophthalic acid, and homopolymers or copolymers of glycidyl methacrylate;Epoxy compounds having a glycidylamino group such as N,N-diglycidylaniline, bis(4-(N-methyl-N-glycidylamino)phenyl)methane, diglycidyl orthotoluidine, N,N-bis(2,3-epoxypropyl)-4-(2,3-epoxypropoxy)-2-methylaniline, N,N-bis(2,3-epoxypropyl)-4-(2,3-epoxypropoxy)aniline and N,N,N',N'-tetra(2,3-epoxypropyl)-4,4-diaminodiphenylmethane; epoxidized products of cyclic olefin compounds such as vinylcyclohexene diepoxide, cyclopentadiene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate and bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate; Epoxidized conjugated diene polymers such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymers; heterocyclic compounds such as triglycidyl isocyanurate;

[0127] These epoxy compounds can also be used in a form in which they are internally crosslinked with a prepolymer of a terminal isocyanate, or in a form in which they are polymerized with a polyvalent active hydrogen compound (such as a polyhydric phenol, a polyamine, a carbonyl group-containing compound, or a polyphosphate ester).

[0128] The epoxy compound may be used alone or in combination of two or more. In the present disclosure, the epoxy compound preferably contains a polyglycidyl ether of a polynuclear polyhydric phenol compound, and among them, the polynuclear polyhydric phenol compound is preferably a compound having a bisphenol structure in which two hydroxyphenyl groups are bonded by one atom, and particularly preferably a compound having a bisphenol A structure. This is because the composition can form a cured product exhibiting superior adhesion. In addition, it is easy to make the cured product have excellent adhesion.

[0129] The content of the epoxy compound is preferably in the range of 10 to 80 parts by mass per 100 parts by mass of the composition, more preferably in the range of 30 to 75 parts by mass, particularly preferably in the range of 40 to 70 parts by mass, and particularly preferably in the range of 50 to 65 parts by mass. This is because the composition can form a cured product exhibiting superior adhesion. In addition, it is easy to make the cured product have excellent adhesion.

[0130] The content of the epoxy compound is preferably in the range of 10 to 95 parts by mass, more preferably in the range of 40 to 90 parts by mass, particularly preferably in the range of 60 to 85 parts by mass, and particularly preferably in the range of 70 to 80 parts by mass, per 100 parts by mass of the total of the block urethane compound, epoxy compound, and curing agent. This is because the composition can form a cured product exhibiting superior adhesion. In addition, it is easy to make the cured product have excellent adhesion.

[0131] 3. Curing Agent The curing agent may be any curing agent used to cure the epoxy compound. Examples of such curing agents include acid anhydride curing agents, phenolic curing agents, amine curing agents, polythiol curing agents, and imidazole curing agents. In the present disclosure, the curing agent preferably includes an amine curing agent or an imidazole curing agent, and more preferably includes an amine curing agent. This is because the composition can form a cured product exhibiting superior adhesion. For example, those described as curing agents in International Publication No. 2022 / 168665 can be used as such curing agents.

[0132] The amine-based curing agent includes amines and modified amines obtained by modifying amines. In the present disclosure, the amine-based curing agent preferably contains amines, because the composition can form a cured product exhibiting superior adhesion.

[0133] Methods for modifying amines include dehydration condensation with carboxylic acid, addition reaction with epoxy resin, addition reaction with isocyanate, Michael addition reaction, Mannich reaction, condensation reaction with urea, and condensation reaction with ketone, etc. Examples of epoxy resins that can be used for modifying amines include the epoxy compounds exemplified in "2. Epoxy compounds" above.

[0134] Examples of the amines include alkylenediamines such as ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,3-diaminobutane, 1,4-diaminobutane, hexamethylenediamine, and metaxylenediamine; polyalkylpolyamines such as diethylenetriamine, triethylenetriamine, and tetraethylenepentamine; alicyclic polyamines such as 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 1,3-diaminomethylcyclohexane, 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, 4,4'-diaminodicyclohexylmethane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 4,4'-diaminodicyclohexylpropane, bis(4-aminocyclohexyl)sulfone, 4,4'-diaminodicyclohexyl ether, 2,2'-dimethyl-4,4'-diaminodicyclohexylmethane, isophoronediamine, and norbornenediamine; aromatic polyamines such as diaminodiphenylmethane, diaminodiphenyl sulfone, diethyltoluenediamine, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 1,3,5-triethyl-2,6-diaminobenzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, and 3,5,3',5'-tetramethyl-4,4'-diaminodiphenylmethane;N,N-dimethylaminoethylamine, N,N-diethylaminoethylamine, N,N-diisopropylaminoethylamine, N,N-diallylaminoethylamine, N,N-benzylmethylaminoethylamine, N,N-dibenzylaminoethylamine, N,N-cyclohexylmethylaminoethylamine, N,N-dicyclohexylaminoethylamine, N-(2-aminoethyl)pyrrolidine, N-(2-aminoethyl)piperidine, N-(2-aminoethyl)morpholine, N-(2-aminoethyl)piperazine, N-(2-aminoethyl)-N'-methylpiperazine, N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, N,N-diisopropylaminopropylamine, N,N-diallylaminopropylamine, N,N-benzylmethylaminopropylamine, N,N-dibenzylaminopropylamine, N,N-cyclohexylmethylaminopropylamine, N,N-dicyclohexylaminopropylamine, N-(3-aminopropyl)pyrrolidine, N-(3-aminopropyl)piperidine, N-(3-aminopropyl)morpholine, N-(3-aminopropyl)piperazine, N-(3-aminopropyl)-N'-methylpiperidine, 4-(N,N-dimethylamino)benzylamine, 4-(N,N-diethylamino)benzylamine, 4-(N,N-diisopropylamino)benzylamine, N,N,-dimethylisophoronediamine, N,N-dimethylbisaminocyclohexane, N,N,N'-trimethylethylenediamine, N'-ethyl-N,N-dimethylethylenediamine, N,N,N'-triethylethylenediamine, N'-ethyl-N,N-dimethylpropanediamine, N'-ethyl-N,N-dibenzylaminopropylamine;N,N-(bisaminopropyl)-N-methylamine, N,N-bisaminopropylethylamine, N,N-bisaminopropylpropylamine, N,N-bisaminopropylbutylamine, N,N-bisaminopropylpentylamine, N,N-bisaminopropylhexylamine, N,N-bisaminopropyl-2-ethylhexylamine, N,N-bisaminopropylcyclohexylamine, N,N-bisaminopropylbenzylamine, N,N-bisaminopropylallylamine, bis[3-(N,N-dimethylaminopropyl)]amine, bis[3-(N,N-diethylaminopropyl)]amine, bis[3-(N,N-diisopropylaminopropyl)]amine, bis[3-(N,N-dibutylaminopropyl)]amine; Dibasic acid dihydrazides such as oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, and phthalic acid dihydrazide; guanidine compounds such as dicyandiamide, benzoguanamine, and acetoguanamine; melamine, etc.;

[0135] In the present disclosure, the amines preferably include a guanidine compound, and in particular, dicyandiamide. This is because the composition can form a cured product exhibiting superior adhesion. Commercially available guanidine compounds include Omicure DDA-5 manufactured by PTI Japan Co., Ltd., DICY7, DICY15, DICY50, ADEKA HARDNER EH-3636AS, and ADEKA HARDNER EH-4351S manufactured by Mitsubishi Chemical Corporation.

[0136] The content of the curing agent is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 15 parts by mass or less, and particularly preferably 3 parts by mass or more and 10 parts by mass or less, per 100 parts by mass of the composition. This is because the composition can form a cured product exhibiting superior adhesion. In addition, it is easy to make the cured product have excellent adhesion.

[0137] The content of the curing agent is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 3 parts by mass or more and 20 parts by mass or less, and particularly preferably 5 parts by mass or more and 15 parts by mass or less, relative to 100 parts by mass of the epoxy compound. This is because the composition can form a cured product exhibiting superior adhesion. In addition, it is easy to make the cured product have excellent adhesion.

[0138] The content of the curing agent is preferably 1 part by mass or more and 20 parts by mass or less, more preferably 2 parts by mass or more and 15 parts by mass or less, and particularly preferably 3 parts by mass or more and 10 parts by mass or less, per 100 parts by mass of the total of the block urethane compound, epoxy compound, and curing agent. This is because the composition can form a cured product exhibiting superior adhesion. In addition, it is easy to make the cured product have excellent adhesion.

[0139] 4. Curing Accelerator The composition preferably contains a curing accelerator. This is because the composition can form a cured product exhibiting superior adhesion. The curing accelerator may be any one that can lower the curing temperature of the epoxy compound and improve the curing rate, and examples of the curing accelerator include phosphines such as triphenylphosphine; phosphonium salts such as tetraphenylphosphonium bromide; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, and 1-cyanoethyl-2-methylimidazole; and mixtures of the above imidazoles with trimellitic acid, isocyanuric acid, boric acid, and the like. imidazole salts which are salts with amines such as benzyldimethylamine and 2,4,6-tris(dimethylaminomethyl)phenol; quaternary ammonium salts such as trimethylammonium chloride; and ureas such as 3-(p-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-phenyl-1,1-dimethylurea, isophorone diisocyanate-dimethylurea, and tolylene diisocyanate-dimethylurea.

[0140] 5. Filler A filler can be used to, for example, adjust the viscosity characteristics of the composition, improve the physical strength of a cured product of the composition, etc. As such a filler, either an inorganic filler or an organic filler can be used.

[0141] Examples of the inorganic filler include silicas such as fused silica, fused spherical silica, crystalline silica, colloidal silica, fumed silica, and silica gel; metal oxides such as alumina, iron oxide, and antimony trioxide; ceramics such as silicon nitride, aluminum nitride, boron nitride, and silicon carbide; minerals such as mica and montmorillonite; metal hydroxides such as aluminum hydroxide and magnesium hydroxide, or those modified by organic modification treatment; metal carbonates such as calcium carbonate, calcium silicate, magnesium carbonate, and barium carbonate, or those modified by organic modification treatment; pigments such as metal borates and carbon black; carbon fiber, graphite, whiskers, kaolin, talc, glass fiber, glass beads, glass microspheres, silica glass, layered clay minerals, clay, silicon carbide, quartz, aluminum, and zinc. Examples of the organic filler include acrylic beads, polymer microparticles, transparent resin beads, wood flour, pulp, and cotton chips.

[0142] In the present disclosure, the filler preferably contains an inorganic filler, and more preferably contains silicas or metal carbonates, and more preferably contains both silicas and metal carbonates. This is because the composition can form a cured product that exhibits superior adhesion. In addition, it is easy to make the cured product have excellent adhesion.

[0143] The content of the filler is preferably 0.1 parts by mass or more and 50 parts by mass or less, more preferably 5 parts by mass or more and 40 parts by mass or less, and particularly preferably 10 parts by mass or more and 30 parts by mass or less, per 100 parts by mass of the composition. This is because the composition can form a cured product exhibiting superior adhesiveness. In addition, it is easy to make the cured product have excellent adhesive strength.

[0144] The compositions according to the present disclosure are moisture resistant, and the term "moisture resistant" refers to compositions that include the moisture resistant block urethane material described above.

[0145] 6. Others The composition may contain other components in addition to the block urethane compound, epoxy compound, curing agent, curing accelerator, and filler. Examples of such other components include known additives such as an isocyanate curing catalyst, plasticizer, colorant, antioxidant, foaming agent, diluent, and ultraviolet absorber.

[0146] C. Cured Product Next, the cured product of the present disclosure will be described. The cured product of the present disclosure is formed using the above-described composition. According to the present disclosure, the cured product exhibits superior adhesion. The contents of the composition can be the same as those described in the above section "B. Composition," and therefore, description thereof will be omitted here.

[0147] The method for producing the cured product may be any method that can form a cured product with excellent adhesion, and may be similar to the method described in the section "D. Method for producing cured product" below, and therefore, further explanation will be omitted here.

[0148] The embodiment of the cured product can be the same as that described in the section "A. Block urethane material" above, and therefore a description thereof will be omitted here.

[0149] D. Manufacturing Method of Cured Product Next, a manufacturing method of a cured product of the present disclosure will be described. The manufacturing method of a cured product of the present disclosure includes a water contacting step in which a composition is brought into contact with water, and a deblocking step in which, after the water contacting step, a blocking agent for a blocked urethane compound contained in the composition is unblocked. The composition includes an epoxy compound, a curing agent, and a blocked urethane compound. The blocked urethane compound is a compound formed using a polyisocyanate compound, a polyhydroxy compound, and a blocking agent, and the polyhydroxy compound is one or more compounds selected from an unsaturated polyol derivative, an unsaturated polyol, and an acrylic polyol. According to the present disclosure, a cured product exhibiting superior adhesion can be easily formed.

[0150] The method for producing a cured product according to the present disclosure includes a water contact step and a deblocking step. Each step of the method for producing a cured product according to the present disclosure will be described in detail below.

[0151] 1. Water Contact Step In the present disclosure, the water contact step refers to a step in which the composition is brought into contact with water. Specific examples of this step include immersing the composition in a water tank, applying water to the composition, and storing the composition in an environment in contact with air. A combination of these steps may also be used.

[0152] In this step, the temperature of the water to be contacted can be set to 10°C or higher and 70°C or lower, and is preferably 20°C or higher and 60°C or lower, because this allows the effects of the present disclosure to be more effectively exhibited.

[0153] The composition used in this step can be the same as that described in the section "B. Composition" above, and therefore a description thereof will be omitted here.

[0154] The timing of carrying out this step is not particularly limited as long as it is before the above-mentioned deblocking step, but when this step is carried out together with a coating step of forming a coating layer on the substrate, it is preferably before the above-mentioned coating step, and particularly preferably before the cationic electrodeposition step of forming an electrodeposition coating film on the substrate, because this allows the effects of the present disclosure to be exerted more effectively.

[0155] In the present disclosure, when this step is carried out together with a coating step of forming a coating layer on the substrate, it is preferable that this step be carried out as a water rinsing step (hereinafter sometimes referred to as a second water rinsing step) after a chemical conversion treatment step of forming a chemical conversion coating on the substrate before the cationic electrodeposition step, a degreasing step of degreasing the surface of the substrate before the chemical conversion treatment step, a water rinsing step (hereinafter sometimes referred to as a first water rinsing step), a storage step before the first water rinsing step, or the like, because this allows the effects of the present disclosure to be exerted more effectively.

[0156] The washing method used in the first and second washing steps can be the same as the known washing method carried out before the formation of the coating layer. Such a washing method can be the same as the washing step described in JP 2022-156466 A, for example, and includes a method of spraying or immersing the coating layer once or multiple times within a range that does not affect the adhesion of the coating layer.

[0157] The degreasing method in the degreasing step can be the same as a known degreasing method carried out before the formation of a coating layer. Such a degreasing method can be, for example, the same as the alkaline degreasing step described in JP 2022-156466 A, and includes a method in which the substrate on which the coating layer is to be formed is immersed in a degreasing agent such as a phosphorus-free, nitrogen-free degreasing cleaning solution at a temperature of 30°C to 55°C for several minutes, within a range that does not affect the adhesion of the coating layer.

[0158] A specific example of the storage step is to store the composition in a state where it can come into contact with the air in the surrounding environment (for example, by storing the composition as is after applying it to a substrate). The storage period may be any period that allows the effects of the present disclosure to be exhibited.

[0159] 2. Deblocking Step The deblocking step is a step of deblocking the blocking agent of the blocked urethane compound contained in the composition. A specific example of deblocking is heating the composition. The heating temperature is preferably in the range of 70°C or higher and 200°C or lower, and more preferably in the range of 100°C or higher and 150°C or lower. This is because the effects of the present disclosure can be more effectively exhibited. The heating time is preferably in the range of 1 minute or higher and 60 minutes or lower, and more preferably in the range of 5 minutes or higher and 30 minutes or lower, and particularly preferably in the range of 10 minutes or higher and 20 minutes or lower. This is because the effects of the present disclosure can be more effectively exhibited.

[0160] When this step is performed together with a coating step of forming a coating layer on the substrate, it is preferably performed after the degreasing step, more preferably after the first water-washing step, and particularly preferably after the chemical conversion treatment step, more preferably after the second water-washing step, more preferably after the cationic electrodeposition step, and most preferably before the coating step. This is because the effects of the present disclosure can be more effectively exhibited. Also, this makes it easier to form the coating layer.

[0161] 3. Other Steps The manufacturing method of the present disclosure includes the water contact step and the deblocking step, but may also include other steps. When the manufacturing method of the present disclosure is used in a form in which a coating film is formed on a substrate, such other steps include a coating step of applying the composition to the substrate before the water contact step, a curing step of curing the composition after the coating step, a coating step of forming a coating layer on the substrate, a cationic electrodeposition step of forming an electrodeposition coating on the substrate before the coating step, a baking step performed after the cationic electrodeposition step of curing the electrodeposition coating, a chemical conversion treatment step of forming a chemical conversion coating on the substrate before the cationic electrodeposition step, a degreasing step of degreasing the substrate surface before the chemical conversion treatment step, a second water washing step performed between the cationic electrodeposition step and the chemical conversion treatment step, and a first water washing step performed between the chemical conversion treatment step and the degreasing step. The details of the degreasing step, the first water washing step, and the second water washing step may be the same as those described in the above section "1. Water Contact Step."

[0162] (1) Coating Step The coating step is a step of coating the composition onto a substrate. Specific examples of this step include known coating methods such as brush coating, roller coating, air spray coating, and airless spray coating.

[0163] Examples of the substrate include metal substrates, inorganic material substrates, polymer material substrates, etc. Examples of the metal substrates include iron, zinc, aluminum, titanium, stainless steel, mild steel, plated steel, etc. Examples of the inorganic material substrates include glass substrates such as quartz glass substrates, Pyrex (registered trademark) glass substrates, and synthetic quartz substrates.

[0164] Examples of the polymer material substrate include cellulose esters such as diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetylpropionyl cellulose, and nitrocellulose; polyamide; polyimide; polyurethane; epoxy resin; polycarbonate; polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4'-dicarboxylate, and polybutylene terephthalate; polystyrene; polyolefins such as polyethylene, polypropylene, and polymethylpentene; vinyl compounds such as polyvinyl acetate, polyvinyl chloride, and polyvinyl fluoride; acrylic resins such as polymethyl methacrylate and polyacrylate; polycarbonate; polysulfone; polyethersulfone; polyetherketone; polyetherimide; polyoxyethylene, norbornene resin, and cycloolefin polymer (COP).

[0165] When this step is carried out together with a coating step of forming a coating layer on a substrate, the timing of carrying out this step is preferably before the coating step, more preferably before the cationic electrodeposition step, particularly preferably before the second water-washing step, particularly preferably before the degreasing step, particularly preferably before the first water-washing step, and particularly preferably before the storage step before the first water-washing step, because this allows the effects of the present disclosure to be exerted more effectively.

[0166] (2) Curing Step The curing step is a step of curing the composition, and can be a step of polymerizing epoxy compounds using a curing agent contained in the composition. A specific form of this step is heating the composition. The heating temperature is preferably in the range of 70°C or higher and 200°C or lower, and more preferably in the range of 100°C or higher and 150°C or lower. This is because the effects of the present disclosure can be more effectively exhibited.

[0167] The timing for carrying out this step may be any timing as long as it is after the coating step, and may be before the deblocking step, after the deblocking step, or simultaneously with the deblocking step. In this step, it is preferable that the step be carried out simultaneously with the deblocking step, because this allows the effects of the present disclosure to be exerted more effectively.

[0168] (3) Chemical Conversion Treatment Step The chemical conversion treatment step is a step of forming a chemical conversion coating on the substrate before the cationic electrodeposition step. Examples of the chemical conversion treatment method include a method of contacting a chemical conversion treatment agent with the substrate surface. The contact method is not particularly limited, and examples include immersion, spraying, and roll coating. The treatment temperature during the chemical conversion treatment can be within a range of 20°C to 70°C, and preferably within a range of 30°C to 50°C. The treatment time during the chemical conversion treatment can be within a range of 5 seconds to 1200 seconds, and preferably within a range of 30 seconds to 120 seconds. This is because the chemical conversion coating can be formed efficiently.

[0169] The timing for carrying out this step may be any time after the degreasing step, preferably after the coating step, and more preferably before both the curing step and the deblocking step, because this allows the effects of the present disclosure to be exerted more effectively.

[0170] (4) Cationic Electrodeposition Step The cationic electrodeposition step is a step of forming an electrodeposition coating film on the substrate before the coating step. Specific embodiments of this step include the use of a cationic electrodeposition paint. The cationic electrodeposition paint is not particularly limited, and conventionally known cationic electrodeposition paints made of aminated epoxy resins, aminated acrylic resins, sulfonated epoxy resins, etc. can be used. The specific embodiment of forming the electrodeposition coating film using the cationic electrodeposition paint is not particularly limited, and known cationic electrodeposition coating methods can be applied.

[0171] The timing for carrying out this step may be any timing as long as it is before the painting step, preferably after the application step, and particularly preferably before both the curing step and the deblocking step, because this allows the effects of the present disclosure to be exhibited more effectively.

[0172] (5) Baking Step The baking step is carried out after the cationic electrodeposition step and includes a step of curing the electrodeposition coating film. One method for curing the electrodeposition coating film is to heat the electrodeposition coating film. The heating temperature may be any temperature that can cure the electrodeposition coating film and is set appropriately depending on the type of cationic electrodeposition paint, etc. For the main body, the heating temperature is preferably in the range of 70°C or higher and 200°C or lower, and more preferably in the range of 100°C or higher and 150°C or lower. This is because the effects of the present disclosure can be more effectively exhibited.

[0173] The timing for carrying out this step may be any time after the cationic electrodeposition step, and may be before the deblocking step, after the deblocking step, or simultaneously with the deblocking step. In this step, it is preferable that the step be carried out simultaneously with the deblocking step and the curing step, because this allows the effects of the present disclosure to be exerted more effectively.

[0174] (6) Painting Step The painting step is a step of forming a paint layer on the substrate. Such a paint layer can be, for example, the same as that used as an intermediate coat layer or a top coat layer formed on an automobile component. The specific form of this step is not particularly limited as long as it is a means for applying a paint that can form a paint layer of the desired thickness, and known painting methods shown as specific forms in the painting step above can be used. The means for forming the paint layer in this step may also include a baking treatment in which the paint film is baked. Such a baking treatment can be performed in the same manner as the baking step above.

[0175] E. Block Urethane Compound Next, the block urethane compound of the present disclosure will be described. The block urethane compound of the present disclosure is formed using a polyisocyanate compound, a polyhydroxy compound, and a blocking agent, and the polyhydroxy compound contains one or more compounds selected from the group consisting of unsaturated polyol derivatives, unsaturated polyols, and acrylic polyols. According to the present disclosure, the block urethane compound can provide superior adhesion.

[0176] Hereinafter, the block urethane compound of the present disclosure is a compound formed using a polyisocyanate compound, a polyhydroxy compound, and a blocking agent. The constituent materials of such a block urethane compound can be the same as those described in the above section "A. Block urethane material," and therefore, a description thereof will be omitted here.

[0177] The polyhydroxy compound used in the present disclosure includes one or more compounds selected from the group consisting of unsaturated polyol derivatives, unsaturated polyols, and acrylic polyols. In the present disclosure, it is preferable that the polyhydroxy compound A is one or more compounds selected from the group consisting of unsaturated polyol derivatives and unsaturated polyols. This is because the effects of the present disclosure can be more effectively exhibited.

[0178] In the present disclosure, the unsaturated polyol preferably contains one or more compounds selected from the group consisting of unsaturated hydroxy fatty acid glycerides and unsaturated aliphatic group-containing phenolic compounds, because this allows the effects of the present disclosure to be exhibited more effectively.

[0179] In the present disclosure, when the unsaturated polyol contains an unsaturated hydroxy fatty acid glyceride, the block urethane compound is further formed using a branching agent, the branching agent being one or more compounds having at least three groups reactive with an isocyanate group, other than an unsaturated polyol, an unsaturated polyol derivative, and an acrylic polyol, and the branching agent ratio of the block urethane compound is preferably within the range of 1% to 60%, because this allows the effects of the present disclosure to be more effectively exhibited.

[0180] In the present disclosure, when the unsaturated polyol contains an unsaturated aliphatic group-containing phenolic compound, the number of carbon atoms in the unsaturated aliphatic group contained in the unsaturated aliphatic group-containing phenol is preferably within the range of 1 to 30. This is because the effects of the present disclosure can be more effectively exhibited.

[0181] In the present disclosure, when the polyhydroxy compound includes an unsaturated polyol derivative, the unsaturated polyol derivative preferably includes an epoxidized product of an unsaturated polyol, because the effects of the present disclosure can be more effectively exhibited.

[0182] Other details regarding the block urethane compound can be the same as those described in the section "A. Block urethane material" above, and therefore a description thereof will be omitted here.

[0183] F. Other The present disclosure includes the following aspects. [1] A block urethane material comprising a block urethane compound formed using a polyisocyanate compound, a polyhydroxy compound, and a blocking agent, wherein the polyhydroxy compound comprises one or more compounds selected from the group consisting of unsaturated polyol derivatives, unsaturated polyols, and acrylic polyols. [2] The block urethane material according to [1], which is intended to be passed through a water contact step before deblocking. [3] The block urethane material according to [1] or [2], which has moisture resistance. [4] The block urethane material according to any one of [1] to [3], wherein the polyhydroxy compound comprises one or more compounds selected from the group consisting of unsaturated polyol derivatives and unsaturated polyols. [5] The block urethane material according to any one of [1] to [4], wherein the unsaturated polyol derivative is an epoxidized product or a hydrogenated product of the unsaturated polyol. [6] The block urethane material according to any one of [1] to [5], wherein the unsaturated polyol is one or more compounds selected from the group consisting of unsaturated hydroxy fatty acid glycerides, dimer acid polyols, polybutadiene polyols, and unsaturated aliphatic group-containing phenolic compounds. [7] The block urethane material according to any one of [1] to [6], wherein the unsaturated polyol is one or more compounds selected from the group consisting of unsaturated hydroxy fatty acid glycerides and unsaturated aliphatic group-containing phenolic compounds. [8] The block urethane material according to any one of [1] to [7], wherein the polyisocyanate compound is an alicyclic isocyanate compound. [9] The block urethane material according to any one of [1] to [8], wherein the blocking agent is a monophenol.

[10] The block urethane material according to any one of [1] to [9], wherein the block urethane compound is further formed using a branching agent, and the branching agent is one or more compounds having at least three groups reactive with an isocyanate group, and is a compound other than an unsaturated polyol, an unsaturated polyol derivative, or an acrylic polyol.

[11] A composition comprising an epoxy compound, a curing agent, and a blocked urethane compound, wherein the blocked urethane compound is formed using a polyisocyanate compound, a polyhydroxy compound, and a blocking agent, and the polyhydroxy compound comprises one or more compounds selected from the group consisting of unsaturated polyol derivatives, unsaturated polyols, and acrylic polyols.

[12] The composition according to

[11] , which is intended to be passed through a water contact step before deblocking.

[13] The composition according to

[11] or

[12] , which has moisture resistance.

[14] A cured product formed using the composition according to

[11] or

[12] .

[15] A method for producing a cured product, comprising: a water contacting step of contacting a composition with water; and a deblocking step of deblocking a blocking agent for a blocked urethane compound contained in the composition after the water contacting step, wherein the composition comprises an epoxy compound, a curing agent, and a blocked urethane compound, wherein the blocked urethane compound is a compound formed using a polyisocyanate compound, a polyhydroxy compound, and a blocking agent, and the polyhydroxy compound comprises one or more compounds selected from the group consisting of unsaturated polyols, unsaturated polyol derivatives, and acrylic polyols.

[16] A block urethane compound formed using a polyisocyanate compound, a polyhydroxy compound, and a blocking agent, wherein the polyhydroxy compound comprises one or more compounds selected from the group consisting of unsaturated polyol derivatives, unsaturated polyols, and acrylic polyols.

[17] The block urethane compound according to

[16] , which satisfies at least one condition selected from the following conditions 1, 2, and 3: (Condition 1) The polyhydroxy compound includes the unsaturated polyol derivative, and the unsaturated polyol derivative includes an epoxidized product of an unsaturated polyol.(Condition 2) The polyhydroxy compound contains an unsaturated hydroxy fatty acid glyceride as the unsaturated polyol, the block urethane compound is further formed using a branching agent, the branching agent being one or more compounds having at least three groups reactive with an isocyanate group and being a compound other than an unsaturated polyol, an unsaturated polyol derivative, or an acrylic polyol, and the branching agent ratio of the block urethane compound is in the range of 1% to 60%. (Condition 3) The polyhydroxy compound contains a derivative of an unsaturated aliphatic group-containing phenol as the unsaturated polyol, and the number of carbon atoms in the unsaturated aliphatic group of the unsaturated aliphatic group-containing phenol is in the range of 1 to 30.

[0184] The present disclosure is not limited to the above-described embodiments. The above-described embodiments are merely examples, and any embodiment that has substantially the same configuration as the technical idea described in the claims of the present disclosure and exhibits similar effects is included within the technical scope of the present disclosure.

[0185] [Examples 1 to 13, 20 to 35 and Comparative Examples 1 to 5] Polyhydroxy compound A and polyhydroxy compound B (total number of moles of hydroxyl groups: 0.30 moles) and polyisocyanate compound C (number of moles of isocyanate groups: 0.61 moles) were added to a 1 L five-neck separable round-bottom flask equipped with a Dimroth stirrer, a stirring blade, and a nitrogen line according to the formulation (parts by mass) shown in Table 1 below, and the mixture was allowed to react for 3 hours at 100 to 110°C. Next, blocking agent D (number of moles of hydroxyl groups: 0.33 moles) was added, and the mixture was allowed to react for an additional 3 hours at 90 to 100°C. The reaction was terminated when it was confirmed that the NCO absorption had disappeared in the IR absorption spectrum, yielding a blocked urethane compound.

[0186] Examples 14 to 19 Block urethane compounds were obtained in the same manner as in Example 1, except that polyhydroxy compound A, polyhydroxy compound B, and polyisocyanate compound C were reacted according to the formulation (parts by mass) shown in Table 1 below, and then branching agent E1 was added in amounts of 0.05 mol (branching agent ratio: 14%), 0.07 mol (branching agent ratio: 20%), 0.11 mol (branching agent ratio: 26.0%), and 0.14 mol (branching agent ratio: 32%) so as to achieve the branching agent ratios (%) shown in the table.

[0187] [Polyhydroxy Compound A] A1: Unsaturated polyol (dimer acid polyol, PRIPLAST 3197 manufactured by CRODA, polyester polyol formed from dimer acid and dimer diol, number average molecular weight Mn: 2,000, bifunctional, hydroxyl value 56.0 mg KOH / g) A2: Unsaturated polyol (dimer acid polyol, PRIPLAST 1838 manufactured by CRODA, polyester polyol formed from dimer acid and petroleum alcohol, number average molecular weight Mn: 2,000, bifunctional, hydroxyl value 56.0 mg KOH / g) A3: Unsaturated polyol (polydiene polyol, G-2000 manufactured by Nippon Soda Co., Ltd., 1,2-butadiene polyol, number average molecular weight Mn: 1900, bifunctional, hydroxyl value 53.0 mg KOH / g) A4: Unsaturated polyol (polydiene polyol, Idemitsu Kosan Co., Ltd. R-15HT, 1,4-butadiene polyol, number average molecular weight Mn: 1200, 2.3 functionality, hydroxyl value 101.1 mgKOH / g) A5: Unsaturated polyol (polydiene polyol, Idemitsu Kosan Co., Ltd. R-45HT, 1,4-butadiene polyol, number average molecular weight Mn: 2800, 2.3 functionality, hydroxyl value 44.9 mgKOH / g) A6: Unsaturated polyol (unsaturated hydroxy fatty acid glyceride, Ito Oil Mills Co., Ltd. H-1890, castor oil polyol, number average molecular weight Mn: 1200, 2.2 functionality, hydroxyl value 105.0 mgKOH / g) A7: Unsaturated polyol (unsaturated hydroxy fatty acid glyceride, HF-2009 manufactured by Ito Oil Mills, castor oil polyol, number average molecular weight Mn: 2550, bifunctional, hydroxyl value 44.0 mg KOH / g) A8: Unsaturated polyol (alkylene phenol derivative, NX-9201 manufactured by Cardrite, cardanol polyol, number average molecular weight Mn: 1600, bifunctional, hydroxyl value 69.0 mg KOH / g) A9: Unsaturated polyol derivative (hydrogenated polydiene polyol, GI-2000 manufactured by Nippon Soda, hydrogenated butadiene polyol, number average molecular weight Mn: 2000, bifunctional, hydroxyl value 46.1 mg KOH / g) A10: Unsaturated polyol derivative (epoxidized polydiene polyol, Polybd700 manufactured by Cray Valley, epoxidized 1,A11: 4-butadiene polyol, number average molecular weight Mn: 2950, ​​2.3 functionality, hydroxyl value 44.3 mg KOH / g), A12: Acrylic polyol (Toagosei UH-2041, number average molecular weight Mn: 1500, 3.3 functionality, hydroxyl value 120.0 mg KOH / g),

[0188] [Polyhydroxy Compound B] B1: Polyol (low molecular weight alcohol, 2-EHD (2-ethyl-1,3-hexanediol) manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight Mn: 146, bifunctional) B2: Aliphatic polyol (low molecular weight alcohol, ND-15 manufactured by Kuraray Co., Ltd. (mixture of 1,9-nonanediol and 2-methyl-1,8-octanediol in a mass ratio of 15:85), molecular weight Mn: 160, bifunctional) B3: Aliphatic polyol (low molecular weight alcohol, 3-methyl-1,5-pentanediol (MPD) manufactured by Kuraray Co., Ltd., molecular weight Mn: 118, bifunctional) B4: Polyol (low molecular weight alcohol, CHDM (1,4-cyclohexanedimethanol) manufactured by Eastman Chemical Co., molecular weight Mn: 144, bifunctional) B5: Polyether polyol (polymer polyol G-3000 manufactured by Nippon Soda Co., Ltd., number average molecular weight Mn: 3000, bifunctional) B6: Polyether polyol (polymer polyol H-2000 manufactured by SK Chemicals, number average molecular weight Mn: 2000, bifunctional) B7: Polyester polyol (polymer polyol P-2050 manufactured by Kuraray, number average molecular weight Mn: 2000, bifunctional) B8: Polycarbonate polyol (polymer polyol NT-2006 manufactured by Mitsubishi Chemical Corporation, number average molecular weight Mn: 2000, bifunctional) B9: Polycarbonate polyol (polymer polyol T5652 manufactured by Asahi Kasei Corporation, number average molecular weight Mn: 2000, bifunctional)

[0189] [Polyisocyanate Compound C] C1: VESTANAT IPDI (isophorone diisocyanate, manufactured by EVONIC Corporation, molecular weight 223, bifunctional)

[0190] [Blocking Agent D] D1: para-cumylphenol (manufactured by SASOL, molecular weight 212, monofunctional) D2: para-tert-butylphenol (manufactured by DIC, molecular weight 150, monofunctional) D3: Cardanol (manufactured by Cardrite, molecular weight 305, monofunctional)

[0191] [Branching Agent E] E1: Trimethylolpropane

[0192] [Evaluation] The resulting block urethane compounds were evaluated for adhesion strength before and after water contact, and viscosity according to the following procedures. The results are shown in Tables 1 and 2.

[0193] 1. Adhesion strength before water contact step The block urethane compounds obtained in the examples and comparative examples were blended according to the formulation (parts by mass) shown below to obtain a composition for evaluation. The numerical values ​​for the formulation below represent parts by mass.

[0194] <Composition for evaluation> The above block urethane compound: 20 parts by mass Epoxy compound (EP-4100E manufactured by ADEKA Corporation, structure (bisphenol A type epoxy compound, epoxy equivalent 190 g / eq): 80 parts by mass Calcium carbonate (Whiten SB manufactured by Shiraishi Calcium Co., Ltd.): 25 parts by mass Dicyandiamide (EH-3636AS manufactured by ADEKA Corporation): 7 parts by mass Urea compound (UR-300 manufactured by AlzChem, 1,1-dimethyl-3-phenylurea, curing accelerator): 1 part by mass Silica (RY-200S manufactured by Nippon Aerosil Co., Ltd., hydrophobic fumed silica): 1 part by mass

[0195] <Evaluation Method> Evaluation was performed using the evaluation composition in accordance with JIS K6854-3. The surfaces of two SPCC plates (200 mm long x 25 mm wide x 0.3 mm thick) were degreased with acetone. Next, the evaluation composition was used to bond the two SPCC plates together, overlapping them to form a bonded area of ​​150 mm x 25 mm, as described in JIS K6854-3, and then secured with clips. The excess evaluation composition was removed to obtain an evaluation sample. The prepared evaluation sample was heated at 180°C for 30 minutes, and the clips were then removed to obtain Measurement Sample 1. The resulting Measurement Sample 1 was pulled at a pulling rate of 100 mm / min. The average peel adhesion strength (unit: N) was read from the curve recording the T-peel adhesion strength (unit: N) excluding the first 25 mm and the last 25 mm. The obtained average peel adhesion strength was divided by 25 mm to obtain the T-peel adhesion strength (unit: kN / m), which was then used as the adhesion strength before the water contact step. The results are shown in Tables 1 and 2 below.

[0196] 2. Adhesion strength after water contact process The evaluation sample was left to stand for 5 days in an environment of 40°C and relative humidity 85% to perform a wet heat test, and then heated at 180°C for 30 minutes, after which the clips were removed to obtain measurement sample 2. The peel strength was measured in the same manner as in "1. Adhesion strength before water contact process," and the adhesion strength after water contact process was obtained. The results are shown in Tables 1 and 2 below.

[0197] 3. Adhesion The ratio of the adhesion strength before water contact process obtained in "1. Adhesion strength before water contact process" to the adhesion strength after water contact process obtained in "2. Adhesion strength after water contact process" (adhesion strength after water contact process / adhesion strength before water contact process x 100 (%), hereinafter sometimes referred to as adhesion strength retention rate) was calculated, and the adhesion was evaluated according to the following criteria. The results are shown in Tables 1 and 2 below.

[0198] <Adhesion> 〇〇: 90% or more 〇: 70% or more but less than 90% △: 50% or more but less than 70% ×: Less than 50% The higher the adhesion strength retention rate, that is, the smaller the decrease in adhesion strength after the water contact step compared to the adhesion strength before the water contact step, the better the adhesion can be determined to be.

[0199] The viscosity of the block urethane materials obtained in Examples 6, 12, 13, 18, and 19 at 50°C was measured for 1 minute at 50 rpm and 200 rpm using a Brookfield CAP2000+, and the viscosity was evaluated according to the following criteria. The results are shown in Tables 1 and 2.

[0200] <Viscosity> 〇〇: 200,000 mPa·s or less 〇: More than 200,000 mPa·s to 500,000 mPa·s The lower the viscosity, the better the coatability, and it can be determined that the material is more suitable for use as, for example, a paint, adhesive, etc. It was also confirmed that a low viscosity of the block urethane material not only facilitates production of the block urethane material, but also makes it easier to mix with curable compounds such as epoxy compounds.

[0201]

[0202]

[0203] [Summary] From the results in Tables 1 and 2, it was confirmed that excellent adhesion could be achieved by using the block urethane materials of the examples.

Claims

1. A block urethane material comprising a block urethane compound formed using a polyisocyanate compound, a polyhydroxy compound and a blocking agent, the polyhydroxy compound comprising one or more compounds selected from the group consisting of an unsaturated polyol derivative, an unsaturated polyol, and an acrylic polyol.

2. The block urethane material according to claim 1, which is intended to pass through a water contact step before deblocking.

3. The block urethane material of claim 1, which is moisture resistant.

4. The block urethane material of claim 1, wherein the polyhydroxy compound comprises one or more compounds selected from the group consisting of unsaturated polyol derivatives and unsaturated polyols.

5. The block urethane material according to claim 1, wherein the unsaturated polyol derivative is an epoxidized or hydrogenated product of the unsaturated polyol.

6. The block urethane material according to claim 1, wherein the unsaturated polyol is one or more compounds selected from the group consisting of unsaturated hydroxy fatty acid glycerides, dimer acid polyols, polybutadiene polyols, and unsaturated aliphatic group-containing phenolic compounds.

7. The block urethane material according to claim 6, wherein the unsaturated polyol is one or more compounds selected from the group consisting of unsaturated hydroxy fatty acid glycerides and unsaturated aliphatic group-containing phenolic compounds.

8. The block urethane material according to claim 1, wherein the polyisocyanate compound is an alicyclic isocyanate compound.

9. The blocked urethane material of claim 1, wherein said blocking agent is a monophenol.

10. The block urethane material according to claim 1, wherein the block urethane compound is further formed using a branching agent, the branching agent being one or more compounds having at least three groups reactive with an isocyanate group, and being a compound other than an unsaturated polyol, an unsaturated polyol derivative, or an acrylic polyol.

11. A composition comprising an epoxy compound, a curing agent, and a blocked urethane compound, wherein the blocked urethane compound is formed using a polyisocyanate compound, a polyhydroxy compound, and a blocking agent, and the polyhydroxy compound comprises one or more compounds selected from the group consisting of an unsaturated polyol derivative, an unsaturated polyol, and an acrylic polyol.

12. A cured product formed using the composition according to claim 11.

13. A method for producing a cured product, comprising: a water contacting step of contacting a composition with water; and a deblocking step of deblocking a blocking agent of a blocked urethane compound contained in the composition after the water contacting step, wherein the composition comprises an epoxy compound, a curing agent, and a blocked urethane compound, the blocked urethane compound is a compound formed using a polyisocyanate compound, a polyhydroxy compound, and a blocking agent, and the polyhydroxy compound comprises one or more compounds selected from the group consisting of an unsaturated polyol derivative, an unsaturated polyol, and an acrylic polyol.

14. A blocked urethane compound formed using a polyisocyanate compound, a polyhydroxy compound and a blocking agent, wherein the polyhydroxy compound contains one or more compounds selected from the group consisting of unsaturated polyol derivatives, unsaturated polyols and acrylic polyols.

15. The block urethane compound according to claim 14, which satisfies at least one of the following conditions 1, 2, and 3. (Condition 1) The polyhydroxy compound contains the unsaturated polyol derivative, and the unsaturated polyol derivative contains an epoxidized product of an unsaturated polyol. (Condition 2) The polyhydroxy compound contains an unsaturated hydroxy fatty acid glyceride as an unsaturated polyol, and the block urethane compound is further formed using a branching agent, and the branching agent is one or more compounds having at least three groups that react with an isocyanate group, and is a compound other than an unsaturated polyol, an unsaturated polyol derivative, and an acrylic polyol, and the branching agent ratio of the block urethane compound is within the range of 1% to 60%. (Condition 3) The polyhydroxy compound contains a derivative of an unsaturated aliphatic group-containing phenol as the unsaturated polyol, and the number of carbon atoms of the unsaturated aliphatic group of the unsaturated aliphatic group-containing phenol is within the range of 1 to 30.

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