WO2025047655A1 - Block urethane material, composition, cured product, method for producing cured product, and block urethane compound contained therein - Google Patents

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

This disclosure relates to block urethane materials.

Blocked urethane compounds are compounds in which isocyanate groups are reacted with active hydrogen group-containing compounds (blocking agents) to inactivate (block) the reactivity of the isocyanate groups; when they are heated, the blocking agent dissociates and the isocyanate groups are regenerated.

The block urethane compound can be used as an adhesion promoter for thermoplastic resin compositions (for example, Patent Documents 1 and 2).
Further, examples of applications of the block urethane compound include a curable component of a curable composition containing an epoxy resin (for example, Patent Document 3, etc.).

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

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

The present disclosure has been made in consideration of the above problems, and aims to provide a block urethane material that has excellent adhesion even when a water contact process is carried out before the deblocking process.

The inventors conducted extensive research to solve the above problems and discovered that the above problems can be solved by using a block urethane compound with a specific structure, specifically, by making the polyhydroxy compound that constitutes the block urethane compound a compound with a specific structure.

That is, 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 above-mentioned blocked urethane material has excellent adhesion even when in contact with water before being deblocked.

The blocked urethane material of the present disclosure is preferably one that is suitable for passing through a contact step before deblocking, because the blocked urethane material of the present disclosure can maintain excellent adhesion even when contacted with water before deblocking.
Additionally, the block urethane materials of the present disclosure are moisture resistant.

In the present disclosure, it is preferable that the polyhydroxy compound contains one or more compounds selected from the group consisting of unsaturated polyol derivatives and unsaturated polyols. This is because the block urethane material can provide better adhesion.

In the present disclosure, the unsaturated polyol derivative is preferably an epoxidized or hydrogenated product of the unsaturated polyol. This is because the block urethane material can provide better adhesion.

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. This is because the block urethane material can provide better adhesion.

In the present disclosure, it is preferable that 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. This is because the block urethane material can provide better adhesion.

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

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

In the present disclosure, it is preferable that the block urethane compound is further formed using a branching agent. 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, or an acrylic polyol. This is because the block urethane material can provide better adhesion.

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 having excellent adhesion even when the blocked urethane compound comes into contact with water before being deblocked.

The present disclosure provides a cured product formed using the above-mentioned composition. According to the present disclosure, the cured product has excellent adhesion even when the blocked urethane compound comes into contact with water before being deblocked.

The present disclosure provides 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.
According to the present disclosure, even if a blocked urethane compound in a composition comes into contact with water before being deblocked, a cured product having excellent adhesion can be easily formed.

The present disclosure provides a blocked 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.

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 with better adhesion can be provided.

(Condition 1)
The polyhydroxy compound includes an 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 an unsaturated polyol, the block urethane compound is further formed 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, and 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.

(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.

This disclosure can provide a block urethane material with excellent adhesion.

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.
The present disclosure will be described in detail below.

A. Block Urethane Material First, the block urethane material of the present disclosure will be described.
The blocked urethane material of the present disclosure includes a blocked 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 an unsaturated polyol derivative, an unsaturated polyol, and an acrylic polyol. In particular, the blocked urethane material exhibits excellent adhesion even when used after passing through a water contact step before deblocking.

The reason why the polyhydroxy compound that constitutes the block urethane compound has a specific structure results in excellent adhesion even after undergoing a water contact process before deblocking is not clear, but is presumed to be as follows.

That is, by using a compound having a specific structure as the polyhydroxy compound, it is possible to reduce the amount of water adsorbed by the blocked urethane compound when it passes through the water contact step before deblocking.
Therefore, when the layer is heated or the like in the deblocking step, the formation of non-adhesive surfaces such as voids 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, the adhesiveness can be stably exhibited regardless of the presence or absence of a water contact step before deblocking.

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%, defined as the adhesive strength retention rate after the water bonding process relative to the adhesive strength before the water bonding process, measured using an evaluation composition in the examples described below by an evaluation method specified in the examples.

The block urethane materials of the present disclosure include block urethane compounds.
In addition, the blocked urethane material of the present disclosure is preferably one that is passed through a water contact step before deblocking.
Hereinafter, the embodiment and each component of the block urethane material of the present disclosure will be described in detail.

1. Embodiments The blocked urethane material of the present disclosure can be used in an embodiment in which a water contact step is carried out before deblocking.
The water contact step before deblocking may include a form in which the blocked urethane compound is contacted with water before the deblocking step of deblocking the blocked urethane compound, and a form in which the blocked urethane compound is contacted with water.
The phrase "contacting the block urethane compound with water" also encompasses the form of contacting a composition containing the block urethane compound and other components with water.
Furthermore, "the block urethane compound comes into contact with water" means not only contact with water as a liquid, but also contact between the block urethane compound and water as a gas, such as moisture contained in air, or between the block urethane compound and a composition containing the block urethane compound and other components.

The contents of the water contact step and the deblocking step used as the water contact step before deblocking can be the same as the contents of "1. Water contact step" and "2. Deblocking step" described in the section "D. Production method of cured product" described later, respectively.
Furthermore, other steps that are preferably carried out together with the water contact step and the deblocking step can be similar to the contents described in the section "D. Method for producing a cured product" below.

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 preferable that the block urethane material be in a form in which a water contact step is carried out before deblocking. Examples include paints and adhesives, but it is preferable that the block urethane material be in an adhesive form, because this allows the effects of the present disclosure to be exerted more effectively.

Substrates to which the block urethane material is applied as a coating material, adhesive, etc. include metal substrates, inorganic material substrates, polymeric material substrates, etc., and metal substrates are preferred.
The substrate to which the block urethane material is applied as a paint, adhesive, etc. preferably includes a substrate on which a paint layer is formed, and among these, a substrate on which a cationic electrodeposition coating film is formed between the substrate and the paint layer is preferably used, and among these, a substrate on which a degreasing treatment is performed before the formation of the cationic electrodeposition coating film is particularly preferred, and among these, a substrate on which a block urethane material is applied before the formation of the paint layer is particularly preferred, and among these, a substrate on which a block urethane material is applied before the formation of the electrodeposition coating film is particularly preferred, and among these, a substrate on which a block urethane material is applied before the degreasing treatment is particularly preferred, and among these, a substrate on which the block urethane material is applied and then stored in an environment in which the block urethane material comes into contact with air is particularly preferred. This is because the storage step, degreasing treatment, water washing steps before and after the degreasing treatment, etc. include the timing at which the pre-deblocking water contact step is performed, and therefore the effects of the present disclosure can be effectively exhibited.

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

In the manufacture of automobile bodies, a body forming process and a painting process may be performed in this order. The body forming process may include a press molding process, a bonding process in which press-molded substrates are bonded to each other using an adhesive containing a block urethane compound, and a welding process in which the substrates are joined by welding or the like, in this order.
The coating process may include a process of degreasing, a process of cationic electrodeposition, and a process of forming a coating layer in this order.
In addition, the adhesive used in the bonding step must be subjected to a curing step of deblocking the blocked urethane compound and curing the adhesive.

Here, from the viewpoint of environmental conservation in recent years, there is a demand to reduce the number of times of heating treatment for the curing process, and the curing process may be carried out during the painting process, or even in the latter part of the painting process.
Furthermore, when the body manufacturing process and the painting process are carried out in different factories, the block urethane compound applied in the bonding process in the body manufacturing 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 exhibit the effects of the present disclosure, particularly in the manufacture of automobile bodies and the like.

Among the substrates used in automobiles, examples of components on which a paint layer is formed on the above-mentioned metal substrate include the lower structure 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.

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 used as a curing component of a curable compound containing an epoxy compound, because the effects of the present disclosure can be more effectively exhibited.

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.

(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 contains one or more compounds selected from the group consisting of unsaturated polyols and unsaturated polyol derivatives, and more preferably contains an unsaturated polyol derivative, because the block urethane material can provide better adhesion, and because it is easy to make the block urethane material have excellent adhesion.

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. This is because the block urethane material can provide better adhesion. Also, it is easy to make the block urethane material have excellent adhesion.

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. 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 number average molecular weight (Mn) and weight average molecular weight (Mw) can be values measured by GPC (gel permeation chromatography) and calculated using a calibration curve of standard polystyrene. In detail, 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, sample concentration: 0.2 mass%.

(1-1) Unsaturated Polyol The unsaturated polyol may be any polyol containing an unsaturated group in the molecule.
The unsaturated group includes a carbon-carbon double bond and a carbon-carbon triple bond.

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 and an unsaturated hydroxy fatty acid glyceride, and it is particularly preferable to include an unsaturated hydroxy fatty acid glyceride, because the block urethane material can provide better adhesion. Also, it is easy to make the block urethane material have excellent adhesion.

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. This is because the block urethane material can provide better adhesion. Also, it is easy to make the block urethane material have excellent adhesion.

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. This is because the block urethane material can provide better adhesion. Also, it is easy to make the block urethane material have excellent adhesion.

(1-1-1) Unsaturated Hydroxy Fatty Acid Glyceride The unsaturated hydroxy fatty acid glyceride is an ester of glycerol and a fatty acid, and the fatty acid contains an unsaturated hydroxy fatty acid.
As the unsaturated hydroxy fatty acid, a fatty acid having one or more hydroxyl groups and one or more ethylenically unsaturated groups can be used, and examples thereof include compounds having 8 to 30 carbon atoms such as 10-hydroxy-2-decenoic acid, 2-hydroxy-15-tetracosenoic acid, ricinoleic acid, lesquerolic acid, cerebronic acid, densiporic acid, and auricolic acid.
In the present disclosure, it is preferable to include 2-hydroxy-15-tetracosenoic acid, ricinoleic acid, lesquerolic acid, cerebronic acid, densiporic acid, and auricolic acid, and among these, it is preferable to include ricinoleic acid, lesquerolic acid, densiporic acid, and auricolic acid, and it is particularly preferable to include ricinoleic acid.

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.

The content of the unsaturated hydroxy fatty acid in 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 or more and 95 parts by mass or less, and particularly preferably in the range of 80 parts by mass or more and 90 parts by mass 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.

The unsaturated hydroxy fatty acid glyceride may contain unsaturated fatty acids and saturated fatty acids as the fatty acids other than the unsaturated hydroxy fatty acids.
In the present disclosure, it is preferred that the fatty acid comprises both unsaturated and saturated fatty acids.

As the unsaturated fatty acid, those containing no hydroxyl group can be used, 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 contains a compound having 14 to 22 carbon atoms, and particularly preferably contains a compound having 16 to 20 carbon atoms.

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 acid preferably contains a compound having 12 to 25 carbon atoms, more preferably contains a compound having 14 to 22 carbon atoms, and particularly preferably contains a compound having 16 to 20 carbon atoms.

The unsaturated hydroxy fatty acid glyceride may use castor oil as the fatty acid.
Here, castor oil is known to contain unsaturated hydroxy fatty acids as the main component, such as castor oil 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 include ricinoleic acid.
Commercially available unsaturated hydroxy fatty acid glycerides include castor oil polyols such as H-1890 and HF-2009 manufactured by Ito Oil Co., Ltd.

(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, because the block urethane material can provide better adhesion and because it is easy to make the block urethane material have excellent adhesion.

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

In the present disclosure, the number of carbon atoms in the unsaturated aliphatic group is preferably within the range of 1 to 30, more preferably within the range of 5 to 25, particularly preferably within the range of 10 to 20, and particularly preferably within 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.

The above polymer can be, for example, an addition condensation product of an unsaturated aliphatic group-containing phenol compound and an aldehyde compound.

An example of a derivative of the above-mentioned unsaturated aliphatic group-containing phenol is an unsaturated aliphatic group-containing alcohol in which the phenolic hydroxyl group in the unsaturated aliphatic group-containing phenol is converted to a group having an alcoholic hydroxyl group.

Examples of the unsaturated aliphatic group-containing alcohol include an alkylene oxide adduct of an unsaturated aliphatic group-containing phenol in which an alkylene oxide such as ethylene oxide is added to the phenolic hydroxyl group of an unsaturated aliphatic group-containing phenol, and 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 an unsaturated aliphatic group-containing phenol.
Examples of the method for indirectly adding the polyol compound include a method in which a phenolic hydroxyl group of an unsaturated aliphatic group-containing phenol is converted into an epoxy group-containing group, and then a polyol compound is added.
Examples of a method for converting the phenolic hydroxyl group of an unsaturated aliphatic group-containing phenol compound into 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 phenol compound.

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, and more preferably 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 is converted to an epoxy group-containing group. 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 the polyol compound include polyether polyol, polyester polyol, polycarbonate polyol, polyester amide polyol, acrylic polyol, and polyurethane polyol.
In the present disclosure, the polyol compound preferably contains a polyester polyol or a polycarbonate polyol, and more preferably contains a polycarbonate polyol, because the block urethane material can provide better adhesion, and because it is easy to make the block urethane material have excellent adhesion.
Polyether polyols, polyester polyols, polycarbonate polyols, polyesteramide polyols, acrylic polyols, polyurethane polyols, and the like are exemplified in, for example, JP-A-2023-032555.

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, and more preferably contains a cyclic carbonate ester such as ethylene carbonate or propylene carbonate, and particularly preferably contains ethylene carbonate, 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, 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 in which the epoxy group is reacted with the cyclic carbonate ester.

Commercially available products of the above unsaturated aliphatic group-containing phenolic compounds 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.

(1-1-3) Polydiene-Based Polyol As the polydiene-based polyol, a polydiene having a hydroxyl group introduced therein can be used.
Examples of the polydiene polyol include polybutadiene polyol, polyisoprene polyol, and polypentadiene polyols such as 1,3-polypentadiene polyol.
In the present disclosure, the polydiene polyol preferably contains polybutadiene polyol or polyisoprene polyol, and more preferably contains polybutadiene polyol, because the block urethane material can provide better adhesion.

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, and it is easy to make the block urethane material have excellent adhesion.

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.).

(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 reaction products of dimer acids with polyhydric alcohols, and dimer acid diols obtained by reducing dimer acids.
In the present disclosure, the dimer acid polyol is preferably a reaction product of a dimer acid and a polyhydric alcohol, because the block urethane material can provide better adhesion, and because it is easy to make the block urethane material have excellent adhesion.

The dimer acid includes dicarboxylic acids which are dimers of unsaturated fatty acids.
Examples of the unsaturated fatty acid include unsaturated fatty acids having 10 to 25 carbon atoms and no hydroxyl group, as described in the above section "(1-1-1) Unsaturated hydroxy fatty acid glycerides."

In the present disclosure, the number of carbon atoms in the unsaturated fatty acid constituting the dimer acid is preferably within the range of 12 to 25, more preferably within the range of 14 to 22, particularly preferably within 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.

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;
Polyhydric alcohols having a branched chain having 4 to 40 carbon atoms, such as 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 having a cyclic structure in the molecule, such as 1,3-cyclohexanediol, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol;
Examples of the glycol include diethylene glycol, triethylene glycol, polytetramethylene ether glycol, and dimer acid diol.

Commercially available products of the above dimer acid polyols include Priplast (registered trademark) 1837, 1838, 3187, 3196, 3197, 3199, or 3238, PRIPOL (registered trademark) 2033 (average hydroxyl value: 202-212 mg KOH/g, average functionality: 2), and 2043 manufactured by CRODA, TA22-558 (hydroxyl value: 70-75 mg KOH/g, average functionality: 3), TA22-559 (hydroxyl value: 78-82 mg KOH/g, average functionality: 3) manufactured by Hitachi Chemical Polymers, and Eddyform E-404 (hydroxyl value: 120 mg KOH/g, average functionality: 3) manufactured by Kao Corporation.

(1-2) Unsaturated Polyol Derivative The above unsaturated polyol derivative may be one in which the unsaturated groups in the above unsaturated polyol are modified.
The modification method includes epoxidation, hydrogenation, and the like.
In the present disclosure, it is preferable that the modification method is epoxidation, that is, the unsaturated polyol derivative is an epoxidized product of an unsaturated polyol, because the block urethane material can provide better adhesion, and it is also easy to make the block urethane material have excellent adhesion.

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.

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 most 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.

Such unsaturated polyol derivatives may be those in which the unsaturated groups in the unsaturated polyols described in the above section "(1-1) Unsaturated polyols" have been modified, but epoxy products of polydiene-based polyols and hydrogenated polydiene-based polyols are preferred, and epoxy products of polydiene-based 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.

In addition, the polydiene polyol used in the unsaturated polyol derivative preferably contains polybutadiene polyol and polyisoprene polyol, and more preferably contains polybutadiene polyol, because the block urethane material can provide better adhesion, and because it is easy to make the block urethane material have excellent adhesion.
In the present disclosure, the unsaturated polyol derivative is preferably an epoxidized polybutadiene polyol, because the block urethane material can provide better adhesion, and because it is easy to make the block urethane material have excellent adhesion.

Commercially available products of the above 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.

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

Commercially available products of the above acrylic polyols include, for example, ARUFON UH-2000, UH-2032, UH-2041, and UH-2190 manufactured by Toagosei Co., Ltd.

(1-4) Diol Compound The polyhydroxy compound preferably contains a diol compound (hereinafter, may be 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, because the block urethane material can provide better adhesion, and it is also easy to make the block urethane material have excellent adhesion.

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.

Examples of the low molecular weight diol compounds 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; alicyclic diols such as cyclohexanedimethanol and cyclohexanediol; etc.

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

The content of the polyhydroxy compound B is preferably 30 parts by mass or less in a total of 100 parts by mass of the polyhydroxy compound A and the polyhydroxy compound B, and 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. This is because the block urethane material can provide better adhesion. Also, it is easy to make the block urethane material have excellent adhesion.

(1-5) Others The content of the polyhydroxy compound A is preferably 10 parts by mass or more in 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, 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 moiety derived from the polyhydroxy compound constituting the block urethane compound.

The content of the polyhydroxy compound 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, it is easy to make the block urethane material have excellent adhesion.

(2) Polyisocyanate Compounds As the polyisocyanate compounds, for example, compounds having two or more isocyanate groups can be used, and examples thereof include 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.

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, and 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.

In the present disclosure, a known method can be used to synthesize an isocyanurate compound by trimerizing a diisocyanate compound.

The content of the polyisocyanate compound is preferably 5 parts by mass or more and 40 parts by mass or less, more preferably 10 parts by mass or more and 38 parts by mass or less, particularly preferably 15 parts by mass or more and 36 parts by mass or less, and particularly preferably 20 parts by mass or more and 34 parts by mass or less, in 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.

(3) Blocking Agent Examples of the blocking agent include active methylene compounds such as malonic acid diesters (diethyl malonate, etc.), acetylacetone, and acetoacetate 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, ε-caprolactam, and the like.

The phenols include monophenols and diphenols.
The monophenols include phenol and substituted monophenols.
Examples of the phenols include resorcin, catechol, hydroquinone, bisphenol A, bisphenol S, bisphenol F, and diphenols such as naphthol.
The substituted monophenol may be any compound having only one phenolic hydroxyl group, and examples thereof include the monounsaturated aliphatic group-containing phenols (e.g., cardanol), saturated aliphatic group-containing monophenols, aromatic group-containing monophenols, and halogen-substituted monophenols.

Examples of the above-mentioned saturated aliphatic group-containing phenol 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, are substituted with saturated aliphatic groups.
The aromatic group-containing phenol may be a compound 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 phenol include chlorophenol and bromophenol.

In the present disclosure, the blocking agent is preferably a phenol, more preferably a monophenol, particularly preferably phenol or a substituted monophenol, particularly preferably a substituted monophenol, particularly preferably a monounsaturated aliphatic group-containing phenol, a saturated aliphatic group-containing monophenol, or an aromatic group-containing monophenol, 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.

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.

The content of the blocking agent is preferably 5 parts by mass or more and 30 parts by mass or less, more preferably 10 parts by mass or more and 25 parts by mass or less, and particularly preferably 12 parts by mass or more and 22 parts by mass or less, in 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.

(4) Branching Agent The above-mentioned 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 that react with an isocyanate group (hereinafter, sometimes referred to as a branching agent), because this allows the above-mentioned block urethane material to provide better adhesion.

In the present disclosure, when the constituent components of the polyisocyanate compound include an unsaturated polyol or an unsaturated polyol derivative, particularly when the polyisocyanate compound includes an unsaturated polyol, and particularly when the polyisocyanate compound includes an unsaturated hydroxy fatty acid glyceride, it is preferable to use a branching agent as a constituent component. 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.

Here, the branching agent is a compound having at least three groups which react with an isocyanate group.
Examples of the group that reacts with the isocyanate group include a hydroxyl group, an amino group, a mercapto group, and a carboxyl group.
In the present disclosure, the group reactive with the isocyanate group is preferably a hydroxyl group or an amino group, and among them, a hydroxyl group is particularly preferable, because the block urethane material can provide better adhesion, and because it is easy to make the block urethane material have excellent adhesion.
In addition, 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.

The number of groups that react with the isocyanate group may be three or more, but is preferably between three and six, more preferably between three and five, and especially preferably between three and four. This is because the block urethane material can provide better adhesion. Also, it is easy to make the block urethane material have excellent adhesion.

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, more preferably in the range of 100 to 500, and 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.

As the compound having at least three hydroxyl groups, for example, as described above, compounds other than the compounds exemplified as the polyhydroxy compounds can be used, and examples thereof include aliphatic compounds and alkylene oxide adducts of aliphatic compounds.
In the present disclosure, the compound having at least three hydroxyl groups is preferably an aliphatic compound, because the block urethane material can provide better adhesion and because it is easy to make the block urethane material have good adhesion.

The aliphatic compound may be any compound that does not have an aromatic ring, and examples of the aliphatic compound include chain aliphatic compounds, cyclic aliphatic compounds, and chain aliphatic amine compounds.
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, because the block urethane material can provide better adhesion, and because it is easy to make the block urethane material have excellent adhesion.

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

　Commercially available products may be used as the alkylene oxide adducts of the above aliphatic compounds, such as the Adeka Polyether series manufactured by ADEKA CORPORATION, including 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.

Examples of compounds having at least three amino groups include melamine and polyether polyamines. Commercially available polyether polyamines include Huntsman's Jeffamine series, such as T-403, T-3000, and T-5000. These may be used alone or in combination of two or more.

An example of a method for using the branching agent is a method in which the branching agent is reacted with an isocyanate group 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 can be a compound obtained by reacting the isocyanate group of the branched urethane polyisocyanate compound with a blocking agent.

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. This is because the block urethane material can provide better adhesion. Also, it is easy to make the block urethane material have excellent adhesion.

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 a polyisocyanate compound (number of NCO groups) to the total number of moles of hydroxyl groups in a polyhydroxy compound and groups that react with isocyanate groups in a branching agent (number of NCO reactive groups).

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%, more 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.

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

3. Others 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 is made 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 synthesis of the block urethane compound.

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

The block urethane material may contain other components in addition to the block urethane compound.
Such other components include the curing agent, curing accelerator, filler, and components described in the section "B. Composition" below, as well as the components described in the section "4. Others." However, the block urethane material does not include the epoxy compound described in the section "2. Epoxy compound."

B. Composition Next, the composition of the present disclosure will be described.
The composition of the present disclosure includes 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, and the polyhydroxy compound being one or more compounds selected from the group consisting of an unsaturated polyol derivative, an unsaturated polyol, and an acrylic polyol. In particular, it is preferable to use the blocked urethane compound in the water contact step before deblocking.

According to the present disclosure, the above composition can form a cured product that exhibits superior adhesion. It is also easy to make the cured product have excellent adhesion.

The composition of the present disclosure includes 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.
In addition, the embodiment of the composition of the present disclosure can be the same as that described in the above section "A. Block urethane material," so the description here will be omitted.

1. Block Urethane Compound The block urethane compound used in the present disclosure may be similar to that described in the above section "A. Block Urethane Material," and therefore description thereof will be omitted here.

The content of the block urethane compound is preferably in the range of 1 to 60 parts by mass in 100 parts by mass of the composition, more preferably in the range of 3 to 40 parts by mass, particularly preferably in the range of 5 to 30 parts by mass, and especially preferably in the range of 10 to 20 parts by mass. This is because the composition can form a cured product that exhibits superior adhesion. It is also easy to make the cured product have excellent adhesion.

The content of the block urethane compound is preferably within a range of 5 parts by mass to 70 parts by mass, more preferably within a range of 10 parts by mass to 50 parts by mass, particularly preferably within a range of 15 parts by mass to 40 parts by mass, and most preferably within a range of 20 parts by mass to 30 parts by mass, relative to 100 parts by mass of the epoxy compound. This is because the composition can form a cured product that exhibits superior adhesion. It is also easy to make the cured product have excellent adhesion.

The content of the block urethane compound is preferably within the range of 3 to 60 parts by mass, more preferably within the range of 5 to 40 parts by mass, particularly preferably within the range of 10 to 30 parts by mass, and most preferably within the range of 15 to 25 parts by mass, per 100 parts by mass of the block urethane compound, epoxy compound, and curing agent combined. This is because the composition can form a cured product that exhibits superior adhesion. It is also easy to make the cured product have excellent adhesion.

2. Epoxy compound The epoxy compound includes:
Polyglycidyl ethers of mononuclear polyphenol compounds, such as hydroquinone, resorcinol, pyrocatechol, and phloroglucinol;
polyglycidyl ethers of polynuclear polyhydric phenol compounds such as dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis(ortho-cresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis(ortho-cresol), tetrabromo bisphenol 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, ortho-cresol novolac, ethylphenol novolac, butylphenol novolac, octylphenol novolac, resorcinol novolac, and terpene phenol;
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;
Homopolymers or copolymers of 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 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;
Examples of the epoxy resin include epoxidized conjugated diene polymers such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymers; and heterocyclic compounds such as triglycidyl isocyanurate.

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

The epoxy compounds may be used alone or in combination of two or more kinds.
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 that exhibits better adhesion. In addition, it is easy to make the cured product have excellent adhesion.

The content of the epoxy compound is preferably in the range of 10 to 80 parts by mass in 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 most preferably in the range of 50 to 65 parts by mass. This is because the composition can form a cured product that exhibits superior adhesion. It is also easy to make the cured product have excellent adhesion.

The content of the epoxy compound is preferably within the range of 10 to 95 parts by mass, more preferably within the range of 40 to 90 parts by mass, particularly preferably within the range of 60 to 85 parts by mass, and most preferably within 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 that exhibits superior adhesion. It is also easy to make the cured product have excellent adhesion.

3. Curing Agent The curing agent may be any agent that can be used to cure the epoxy compound.
Examples of such curing agents include acid anhydride-based curing agents, phenol-based curing agents, amine-based curing agents, polythiol-based curing agents, and imidazole-based curing agents.
In the present disclosure, the curing agent preferably contains an amine-based curing agent or an imidazole-based curing agent, and more preferably contains an amine-based curing agent, because the composition can form a cured product exhibiting superior adhesion.
As such a curing agent, for example, those described as curing agents in WO 2022/168665 can be used.

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.

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.
Examples of epoxy resins that can be used for modifying amines include the epoxy compounds exemplified in "2. Epoxy compounds" above.

Examples of the amines include alkylene diamines such as ethylene diamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,3-diaminobutane, 1,4-diaminobutane, hexamethylene diamine, and metaxylene diamine;
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-dimethylaminopropyl amidopropylamine, 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-bisaminopropyl Propylamine, 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;
Examples thereof include dicyandiamide, guanidine compounds such as benzoguanamine and acetoguanamine; melamine, and the like.

In the present disclosure, the amines preferably include a guanidine compound, and more preferably include dicyandiamide, 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 HARDENER EH-3636AS, ADEKA HARDENER EH-4351S, and the like manufactured by Mitsubishi Chemical Corporation.

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 that exhibits superior adhesion. It is also easy to make the cured product have excellent adhesion.

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 more 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 that exhibits superior adhesion. It is also easy to make the cured product have excellent adhesion.

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 even more 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 that exhibits superior adhesion. It is also easy to make the cured product have excellent adhesion.

4. Curing Accelerator The composition preferably contains a curing accelerator, because this enables the composition to form a cured product that exhibits superior adhesion.
The curing accelerator may be any one that can lower the curing temperature of the epoxy compound and improve the curing speed, and examples of such accelerators 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 the above-mentioned imidazoles together 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.

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

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 or the like;
Metal carbonates such as calcium carbonate, calcium silicate, magnesium carbonate, barium carbonate, etc., or those modified by organic modification treatment or the like;
Pigments such as metal borates and carbon black;
Examples of the material include carbon fiber, graphite, whisker, 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 fine particles, transparent resin beads, wood flour, pulp, and cotton chips.

In the present disclosure, the filler preferably contains an inorganic filler, and more preferably contains silicas and metal carbonates, and more preferably contains both silicas and metal carbonates. This is because the composition can form a cured product that exhibits better adhesion. It is also easy to make the cured product have excellent adhesion.

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 that exhibits superior adhesion. It is also easy to make the cured product have excellent adhesion.

The composition according to the present disclosure has moisture resistance. Here, "having moisture resistance" refers to a composition that contains the above-mentioned moisture-resistant block urethane material.

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

C. Cured Product Next, the cured product of the present disclosure will be described.
The cured products of the present disclosure are formed using the compositions described above.
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 a description thereof will be omitted here.

The method for producing the cured product may be any method capable of forming a cured product with excellent adhesion, and may be the same as that described in the section "D. Method for producing the cured product" below, so a detailed description is omitted here.

The manner in which the cured product is embodied can be the same as that described in the above section "A. Block urethane material," so a detailed description is omitted here.

D. Method for Producing the Cured Product Next, a method for producing the cured product of the present disclosure will be described.
The method for producing a cured product of the present disclosure includes 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 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, it is possible to easily form a cured product that exhibits superior adhesion.

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.

1. Water Contact Step In the present disclosure, the water contact step is a step in which the composition is brought into contact with water.
Specific examples of the form of this step include immersing the composition in a water tank, applying water to the composition, storing the composition in an environment in contact with air, etc. A combination of two or more forms may also be used.

The temperature of the water in contact in this process can be from 10°C to 70°C, but is preferably from 20°C to 60°C. This is because the effects of the present disclosure can be more effectively achieved.

The composition used in this step can be the same as that described in the "B. Composition" section above, so a detailed description is omitted here.

The timing of carrying out this process is not particularly limited as long as it is before the above-mentioned deblocking process, but if this process is carried out together with a painting process in which a coating layer is formed on the substrate, it is preferable to carry out this process before the above-mentioned painting process, and in particular, it is preferable to carry out this process before the cationic electrodeposition process in which an electrodeposition coating film is formed on the substrate. This is because the effects of the present disclosure can be exerted more effectively.

In the present disclosure, when this process is carried out together with a painting process for forming a paint layer on the substrate, it is preferable that this process be carried out as a water rinsing process (hereinafter sometimes referred to as a second water rinsing process) after a chemical conversion treatment process for forming a chemical conversion coating on the substrate before the cationic electrodeposition process, a degreasing process for degreasing the substrate surface before the chemical conversion treatment process, a water rinsing process after the degreasing process (hereinafter sometimes referred to as a first water rinsing process), a storage process before the first water rinsing process, or the like. This is because the effects of the present disclosure can be more effectively exhibited.

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

The degreasing method in the above degreasing step can be the same as a known degreasing method carried out before the formation of a paint 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 paint layer is to be formed is immersed in a degreasing agent such as a phosphorus-free, nitrogen-free degreasing cleaning solution for a few minutes at a temperature of 30°C to 55°C, within a range that does not affect the adhesion of the paint layer, etc.

A specific embodiment of the storage step includes storing the composition under conditions in which the composition can come into contact with the air of the surrounding environment (for example, storing the composition as is after application to a substrate).
The storage period may be any period during which the effects of the present disclosure can be exhibited.

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 the deblocking method is heating the composition.
The heating temperature is preferably in the range of 70° C. or more and 200° C. or less, and more preferably in the range of 100° C. or more and 150° C. or less, because the effects of the present disclosure can be more effectively exhibited.
The heating time is preferably within a range of 1 minute to 60 minutes, more preferably within a range of 5 minutes to 30 minutes, and particularly preferably within a range of 10 minutes to 20 minutes, because the effects of the present disclosure can be more effectively exhibited.

When this process is carried out together with a painting process for forming a paint layer on the substrate, it is preferably carried out after the above-mentioned degreasing process, more preferably after the above-mentioned first water washing process, and especially preferably after the above-mentioned chemical conversion treatment process, more preferably after the above-mentioned second water washing process, more preferably after the above-mentioned cationic electrodeposition process, and especially preferably before the above-mentioned painting process. This is because the effects of the present disclosure can be more effectively exerted. Also, this makes it easier to form the above-mentioned paint layer.

3. Other Steps The production method of the present disclosure includes the water contact step and the deblocking step described above, but may also include other steps.
When the method for producing a cured product 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 coating the composition on a 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 and 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 contents 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."

(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.

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

The above-mentioned polymeric material substrates 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).

When this process is carried out together with a coating process for forming a coating layer on the substrate, it is preferable to carry out this process before the coating process, and among these, it is preferable to carry out this process before the cationic electrodeposition process, and especially before the second water washing process, and among these, it is preferable to carry out this process before the degreasing process, and among these, it is preferable to carry out this process before the first water washing process, and among these, it is preferable to carry out this process before the storage process before the first water washing process. This is because the effects of the present disclosure can be exerted more effectively.

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

The timing of carrying out this step may be any time 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 above-mentioned timing is simultaneous with the above-mentioned deblocking step, because this allows the effects of the present disclosure to be exhibited more effectively.

(3) Chemical Conversion Treatment Step The chemical conversion treatment step is a step of forming a chemical conversion coating on the substrate prior to the cationic electrodeposition step.
The chemical conversion treatment method includes a method in which a chemical conversion treatment agent is brought into contact with the surface of the substrate.
The contact method is not particularly limited, and examples thereof 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 is 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 to 1200 seconds, and is preferably within a range of 30 to 120 seconds.
This is because the chemical conversion coating can be formed efficiently.

This step may be carried out after the degreasing step, preferably after the coating step, and more preferably before both the curing step and the deblocking step. This is because the effects of the present disclosure can be more effectively achieved.

(4) Cationic Electrodeposition Step The cationic electrodeposition step is a step of forming an electrodeposition coating film on the substrate before the painting step.
A specific embodiment of this step is to use a cationic electrodeposition paint.
The cationic electrodeposition paint is not particularly limited, and any of the conventionally known cationic electrodeposition paints made of aminated epoxy resins, aminated acrylic resins, sulfonated epoxy resins, etc. can be used.
The specific form of forming the electrodeposition coating film using the above cationic electrodeposition paint is not particularly limited, and any known cationic electrodeposition coating method can be applied.

This step may be carried out before the painting step, preferably after the application step, and more preferably before both the curing step and the deblocking step. This is because the effects of the present disclosure can be more effectively achieved.

(5) Baking Step The baking step is carried out after the cationic electrodeposition step, and includes a form in which the electrodeposition coating film is cured.
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 appropriately set depending on the type of cationic electrodeposition paint, etc.
In the main body, the heating temperature is preferably in the range of 70° C. or more and 200° C. or less, and more preferably in the range of 100° C. or more and 150° C. or less, because the effects of the present disclosure can be more effectively exhibited.

The timing of 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 above-mentioned timing is simultaneous with the above-mentioned deblocking step and curing step, because this allows the effects of the present disclosure to be exhibited more effectively.

(6) Painting Step The painting step is a step of forming a paint layer on the substrate.
Such a coating layer may be, for example, the same as those used as intermediate coating layers and top coating layers formed on automobile parts.
The specific form of this process is not particularly limited as long as it is a means for applying a paint that can form a coating layer of the desired thickness, but any of the known coating methods shown as specific forms of the above coating process can be used.
The method for forming the coating layer in this step may include a baking treatment for baking the coating film of the paint. Such a baking treatment can be carried out in the same manner as in the baking step.

E. Block Urethane Compound Next, the block urethane compound of the present disclosure will be described.
The blocked urethane compound of the present disclosure is formed using a polyisocyanate compound, a polyhydroxy compound, and a blocking agent,
The polyhydroxy compound includes 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 better adhesion.

Hereinafter, the blocked 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 block urethane compounds can be the same as those described in the above section "A. Block urethane materials," and therefore a description thereof will be omitted here.

The polyhydroxy compounds used in the present disclosure include one or more compounds selected from the group consisting of unsaturated polyol derivatives, unsaturated polyols, and acrylic polyols.
In the present disclosure, the polyhydroxy compound A is preferably one or more compounds selected from the group consisting of unsaturated polyol derivatives and unsaturated polyols, because the effects of the present disclosure can be more effectively exhibited.

In the present disclosure, it is preferable that the unsaturated polyol contains one or more compounds selected from the group consisting of unsaturated hydroxy fatty acid glycerides and unsaturated aliphatic group-containing phenolic compounds. This is because the effects of the present disclosure can be more effectively exhibited.

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, 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 it is preferable that the branching agent ratio of the block urethane compound is within the range of 1% to 60%. This is because the effects of the present disclosure can be more effectively exhibited.

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

In the present disclosure, when the polyhydroxy compound contains an unsaturated polyol derivative, it is preferable that the unsaturated polyol derivative contains an epoxidized product of an unsaturated polyol. This is because the effects of the present disclosure can be more effectively achieved.

Other details about the block urethane compound can be the same as those described in the "A. Block urethane materials" section above, so a detailed description will be omitted here.

F. Others The present disclosure includes the following aspects.
[1]
The present invention includes a blocked urethane compound formed by using a polyisocyanate compound, a polyhydroxy compound, and a blocking agent,
The polyhydroxy compound is
A block urethane material comprising one or more compounds selected from the group consisting of unsaturated polyol derivatives, unsaturated polyols, and acrylic polyols.
[2]
The blocked urethane material according to [1], which is for passing 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, 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, and an acrylic polyol.
[11]
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.
[12]
The composition according to [11], which is for passing 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 water contacting step in which the composition is contacted with water;
a deblocking step of deblocking a blocking agent of a blocked urethane compound contained in the composition after the water contacting step,
The composition includes an epoxy compound, a curing agent, and a block urethane compound,
The blocked urethane compound is a compound formed using a polyisocyanate compound, a polyhydroxy compound, and a blocking agent,
A method for producing a cured product, wherein 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 contains one or more compounds selected from the group consisting of an unsaturated polyol derivative, an unsaturated polyol and an acrylic polyol.
[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 an unsaturated polyol, the block urethane compound is further formed 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, and 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.
(Condition 3)
The polyhydroxy compound contains a derivative of an unsaturated aliphatic group-containing phenol as the unsaturated polyol, and the unsaturated aliphatic group of the unsaturated aliphatic group-containing phenol has 1 to 30 carbon atoms.

This disclosure is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical ideas described in the claims of this disclosure and provides similar effects is included within the technical scope of this disclosure.

[Examples 1 to 13, 20 to 35 and Comparative Examples 1 to 5]
According to the formulation (parts by mass) shown in Table 1 below, 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, stirring blade, and nitrogen line, and reacted at 100 to 110° C. for 3 hours. Next, blocking agent D (number of moles of hydroxyl groups: 0.33 moles) was added, and the reaction was further carried out at 90 to 100° C. for 3 hours. The reaction was terminated when it was confirmed that the absorption of NCO had disappeared in the IR absorption spectrum, and a blocked urethane compound was obtained.

[Examples 14 to 19]
A block urethane compound was 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 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%) of branching agent E1 were added so as to obtain the branching agent ratios (%) shown in the table.

[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 mgKOH/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 mgKOH/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 mgKOH/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, R-45HT manufactured by Idemitsu Kosan Co., Ltd., 1,4-butadiene polyol, number average molecular weight Mn: 2800, 2.3 functionality, hydroxyl value 44.9 mg KOH/g)
A6: Unsaturated polyol (unsaturated hydroxy fatty acid glyceride, H-1890 manufactured by Ito Oil Mills, castor oil polyol, number average molecular weight Mn: 1200, 2.2 functionality, hydroxyl value 105.0 mg KOH/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 (alkylenephenol derivative, NX-9201 manufactured by Cardlight Co., Ltd., cardanol polyol, number average molecular weight Mn: 1600, bifunctional, hydroxyl value 69.0 mgKOH/g)
A9: Unsaturated polyol derivative (hydrogenated polydiene polyol, GI-2000 manufactured by Nippon Soda Co., Ltd., hydrogenated butadiene polyol, number average molecular weight Mn: 2000, bifunctional, hydroxyl value 46.1 mgKOH/g)
A10: Unsaturated polyol derivative (epoxidized polydiene polyol, Polybd700 manufactured by Cray Valley, epoxidized 1,4-butadiene polyol, number average molecular weight Mn: 2950, 2.3 functionality, hydroxyl value 44.3 mgKOH/g)
A11: Acrylic polyol (Toagosei UH-2041, number average molecular weight Mn: 1500, 3.3 functionality, hydroxyl value 120.0 mg KOH/g)

[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, Kuraray ND-15: (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, Eastman Chemical Company's CHDM (1,4-cyclohexanedimethanol), 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 Co., Ltd., number average molecular weight Mn: 2000, bifunctional)
B8: Polycarbonate polyol (polymer polyol, Mitsubishi Chemical Corporation's NT-2006, 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)

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

[Blocking Agent D]
D1: Paracumylphenol (manufactured by SASOL, molecular weight 212, monofunctional)
D2: para-tertiary butylphenol (manufactured by DIC Corporation, molecular weight 150, monofunctional)
D3: Cardanol (Cardlight, molecular weight 305, monofunctional)

[Branching agent E]
E1: Trimethylolpropane

[evaluation]
The block urethane compound thus obtained was evaluated for adhesion strength before and after the water contact step, and viscosity according to the following procedures. The results are shown in Tables 1 and 2.

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

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

<Evaluation method>
The evaluation composition was used and evaluated in accordance with ISK6854-3.
The surfaces of two SPCC plates (length 200 mm x width 25 mm x thickness 0.3 mm) were degreased with acetone.
Next, using the composition for evaluation, two SPCC plates were laminated together so that the adhesion area was 150 mm × 25 mm, as described in JIS K6854-3, and fixed with clips. The protruding composition for evaluation was removed to obtain a sample for evaluation.
The prepared evaluation sample was heated at 180° C. for 30 minutes, and then the clips were removed to obtain measurement sample 1.
The obtained measurement sample 1 was pulled at a pulling speed of 100 mm/min, and the average peel adhesion strength was read from the curve showing the T-type peel adhesion strength (unit: N) excluding the first 25 mm and the last 25 mm, and the obtained average peel adhesion strength was divided by 25 mm to obtain the T-type peel adhesion strength (unit: kN/m), which was defined as the adhesion strength before the water contact step. The results are shown in Tables 1 and 2 below.

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

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×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.

<Adhesion>
○ ○: 90% or more ○: 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 less 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.

4. Viscosity 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 evaluated according to the following criteria. The results are shown in Tables 1 and 2.

<Viscosity>
〇〇: 200,000 mPa·s or less 〇: More than 200,000 mPa·s to 500,000 mPa·s or less The lower the viscosity, the better the coatability, and it can be determined that it is suitable for use as, for example, a paint, adhesive, etc. It was also confirmed that the low viscosity of the block urethane material makes it easy to manufacture the block urethane material and also makes it easy to mix with curable compounds such as epoxy compounds.

[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 (15)

The present invention includes a blocked urethane compound formed by using a polyisocyanate compound, a polyhydroxy compound, and a blocking agent,
The block urethane material, wherein 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. The blocked urethane material according to claim 1, which is intended to pass through a water contact process before deblocking. The block urethane material according to claim 1, which is moisture resistant. The block urethane material according to claim 1, wherein the polyhydroxy compound includes one or more compounds selected from the group consisting of unsaturated polyol derivatives and unsaturated polyols. The block urethane material according to claim 1, wherein the unsaturated polyol derivative is an epoxidized or hydrogenated product of the unsaturated polyol. 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. 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. The block urethane material according to claim 1, wherein the polyisocyanate compound is an alicyclic isocyanate compound. The blocked urethane material according to claim 1, wherein the blocking agent is a monophenol. 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 that react with an isocyanate group, and being a compound other than an unsaturated polyol, an unsaturated polyol derivative, or an acrylic polyol. The composition includes an epoxy compound, a curing agent, and a block urethane compound,
The blocked urethane compound is formed using a polyisocyanate compound, a polyhydroxy compound, and a blocking agent,
The composition, wherein 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. A cured product formed using the composition described in claim 11. a water contacting step in which the composition is contacted with water;
a deblocking step of deblocking a blocking agent of a blocked urethane compound contained in the composition after the water contacting step,
The composition includes an epoxy compound, a curing agent, and a block urethane compound,
The blocked urethane compound is a compound formed using a polyisocyanate compound, a polyhydroxy compound, and a blocking agent,
The method for producing a cured product, wherein 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. A block urethane compound formed using a polyisocyanate compound, a polyhydroxy compound, and a blocking agent, the polyhydroxy compound containing one or more compounds selected from the group consisting of unsaturated polyol derivatives, unsaturated polyols, and acrylic polyols. The block urethane compound according to claim 14, 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 an unsaturated polyol, the block urethane compound is further formed 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, and 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.
(Condition 3)
The polyhydroxy compound contains a derivative of an unsaturated aliphatic group-containing phenol as the unsaturated polyol, and the unsaturated aliphatic group of the unsaturated aliphatic group-containing phenol has 1 to 30 carbon atoms.