JP2023135619A - Curable composition, cured product, laminate and method for producing them - Google Patents

Abstract

To provide: a curable composition capable of obtaining a coating film having excellent hot water adhesion resistance; a cured product of the curable composition; a laminate using the curable composition; and a method for producing them.SOLUTION: There is provided a curable composition comprising the following compound A and the following compound B. Compound A: a compound in which the following Ra(T) is 1.377 to 3.000 MPa0.5 (provided that the following compound B is excluded). Compound B: a polyfunctional (meth)acrylate monomer having three or more (meth)acryloyl groups. Ra(T)=[4×(δd-δdT)2+(δp-δpT)2+(δh-δhT)2]0.5, δd: the van der Waals dispersion power in the Hansen solubility parameter of the compound A alone, δp: the effect due to the dipole force in the same parameter of the compound A alone, δh: the effect due to the hydrogen bond force in the same parameter of the compound A alone. δdT:16.58, δpT:5.00, δhT:5.77.SELECTED DRAWING: Figure 1

Description

The present invention relates to a curable composition, a cured product, a laminate, and a method for producing these.

Resin molded products made from polymethyl methacrylate resin, polymethacrylimide resin, polycarbonate resin, polystyrene resin, acrylonitrile styrene resin, etc. are lightweight and have excellent impact resistance and transparency. Resin molded products are used as members such as various lamp lenses for automobiles, glazing, covers for instruments, and the like. In particular, resin molded products are often used for headlamp lenses for automobiles in order to respond to the demands for lighter weight and more diverse designs of automobiles.
However, since resin molded products lack wear resistance, their surfaces are easily damaged by contact with hard objects, friction, scratches, and the like. Damage to the surface of a resin molded product reduces its commercial value. In addition, weather resistance is also important in automotive components.

For example, polycarbonate resin is widely used as an engineering plastic with excellent transparency, easy moldability, heat resistance, and impact resistance. In automobile applications, polycarbonate resin is used as a material for headlamp lenses, tail lamps, side cover lamps, glazing, etc.
However, polycarbonate resin lacks abrasion resistance, so the surface is easily scratched. In addition, because it has lower weather resistance than other engineering plastics, it may cause significant yellowing and surface cracks due to ultraviolet rays.

Abrasion resistance and weather resistance may be imparted by forming a coating film of a coating agent on the surface of a resin molded product. Such coating agents often contain additives to improve adhesion to the substrate. The fact that the coating agent exhibits excellent adhesion to the substrate even after undergoing various long-term durability tests contributes to extending the life of the abrasion resistance, weather resistance, etc. imparted to the substrate.
For example, Patent Documents 1 to 3 discuss coating compositions aimed at improving adhesion. Patent Document 1 proposes the use of dimethylformamide. Furthermore, Patent Document 2 proposes the use of dimethylformamide, N-methylpyrrolidone, cyclohexanone, and methyl cellosolve acetate. Patent Document 3 proposes the use of (meth)acrylate having a cyclic ether structure.

Japanese Patent Application Publication No. 9-302268 Japanese Patent Application Publication No. 10-7939 JP 2017-8200 Publication

However, the coating films obtained by curing the compositions of Patent Documents 1 to 3 have insufficient adhesion to the substrate when immersed in hot water, that is, hot water resistance.
The present invention provides a curable composition from which a coating film with excellent hot water resistance adhesion can be obtained; a cured product of the curable composition; a laminate using the curable composition; and methods for producing these.

The present invention has the following aspects.
[1] A curable composition containing the following compound A and the following compound B.
Compound A: A compound whose Ra (T) calculated from the following formula (L) is 1.377 to 3.000 MPa ^0.5 . (However, the following compound B is excluded.)
Compound B: A polyfunctional (meth)acrylate monomer having three or more (meth)acryloyl groups.
Ra (T) = [4×(δd-δd _T ) ² + (δp-δp _T ) ² + (δh-δh _T ) ² ] ^0.5 ...Formula (L)
In formula (L),
Ra(T) is a Hansen solubility parameter distance indicating the vector distance between the compound A alone and point T in a three-dimensional space represented by δd, δp, and δh in the Hansen solubility parameter;
δd is the effect of van der Waals dispersion force on the Hansen solubility parameter of Compound A alone;
δp is the effect of dipole-dipole force on the Hansen solubility parameter of compound A alone;
δh is the effect of hydrogen bonding force on the Hansen solubility parameter of Compound A alone;
δd _T , δp _T , and δh _T are the coordinates of point T, which are the values of the following formulas (M), (N), and (O).
δd _T =16.58...Formula (M)
δp _T =5.00...Formula (N)
δh _T =5.77...Formula (O)
[2] The curable composition according to [1], further containing the following compound B-1.
Compound B-1: (meth)acrylate having at least one selected from the group consisting of a dendrimer structure and a hyperbranched structure (excluding the above compound B).
[3] The curable composition according to [1] or [2], wherein the curable composition has a viscosity at 25° C. of 250 mPa·s or less.
[4] A cured product of the curable composition according to any one of [1] to [3].
[5] A laminate comprising a base material and a layer made of the cured product according to [4].
[6] The laminate according to [5], wherein the base material is a polycarbonate resin.
[7] Mix compound A (excluding compound B below) whose Ra (T) calculated from the following formula (L) is 1.377 to 3.000 MPa ^0.5 and compound B below. A method for producing a curable composition, comprising:
Compound B: A polyfunctional (meth)acrylate monomer having three or more (meth)acryloyl groups.
Ra (T) = [4×(δd-δd _T ) ² + (δp-δp _T ) ² + (δh-δh _T ) ² ] ^0.5 ...Formula (L)
In formula (L),
Ra(T) is a Hansen solubility parameter distance indicating the vector distance between the compound A alone and point T in a three-dimensional space represented by δd, δp, and δh in the Hansen solubility parameter;
δd is the effect of van der Waals dispersion force on the Hansen solubility parameter of Compound A alone;
δp is the effect of dipole-dipole force on the Hansen solubility parameter of compound A alone;
δh is the effect of hydrogen bonding force on the Hansen solubility parameter of Compound A alone;
δd _T , δp _T , and δh _T are the coordinates of point T, which are the values of the following formulas (M), (N), and (O).
δd _T =16.58...Formula (M)
δp _T =5.00...Formula (N)
δh _T =5.77...Formula (O)
[8] The production method according to [7], further comprising mixing the following compound B-1.
Compound B-1: (meth)acrylate having at least one selected from the group consisting of a dendrimer structure and a hyperbranched structure (excluding the above compound B).
[9] A method for producing a cured product, comprising curing the curable composition obtained by the production method according to [7] or [8].
[10] A method for producing a laminate having a base material and a layer made of a cured product, comprising:
A method for producing a laminate, the method comprising curing the curable composition obtained by the production method according to [7] or [8] to obtain the cured product.
[11] The manufacturing method according to [10], wherein the base material is a polycarbonate resin.

According to the curable composition of the present invention, a coating film having excellent hot water resistant adhesion and moist heat resistant adhesion can be obtained.
The cured product of the present invention has excellent hot water resistant adhesion and moist heat resistant adhesion.
The laminate of the present invention has a layer made of a cured product that has excellent hot water resistant adhesion and moist heat resistant adhesion.
According to the method for producing a curable composition of the present invention, a curable composition having excellent hot water-resistant adhesion and moist heat-resistant adhesion when formed into a coating film can be obtained.
According to the method for producing a cured product of the present invention, a cured product having excellent hot water resistant adhesion and moist heat resistant adhesion can be obtained.
According to the method for manufacturing a laminate of the present invention, a laminate having a layer made of a cured product having excellent hot water resistant adhesion and moist heat resistant adhesion can be obtained.

The surface of the polycarbonate resin after the test piece dissolution experiment is observed using a scanning electron microscope (SEM) at magnifications of 500x, 2000x, and 5000x, respectively.

The meanings of the following terms in this specification are as follows.
"(Meth)acrylic" is a general term for "acrylic" and "methacrylic".
“(Meth)acryloyl” is a general term for “acryloyl” and “methacryloyl”.
"(Meth)acrylate" is a general term for "acrylate" and "methacrylate."
"Number of (meth)acryloyl functional groups" means the number of (meth)acryloyl groups contained in one molecule of (meth)acrylate.
"~" indicating a numerical range means that the numerical values written before and after it are included as the lower limit and upper limit. The numerical range disclosed in this specification can be set as a new numerical range by arbitrarily combining the lower limit value and the upper limit value.

<Curable composition>
The curable composition of the present invention contains the following compound A and the following compound B.
Compound A: A compound whose Ra (T) calculated from the following formula (L) is 1.377 to 3.000 MPa ^0.5 (excluding Compound B below).
Compound B: A polyfunctional (meth)acrylate monomer having three or more (meth)acryloyl groups.
Ra (T) = [4×(δd-δd _T ) ² + (δp-δp _T ) ² + (δh-δh _T ) ² ] ^0.5 ...Formula (L)
In formula (L),
Ra(T) is a Hansen solubility parameter distance indicating the vector distance between the compound A alone and point T in a three-dimensional space represented by δd, δp, and δh in the Hansen solubility parameter;
δd is the effect of van der Waals dispersion force on the Hansen solubility parameter of Compound A alone;
δp is the effect of dipole-dipole force on the Hansen solubility parameter of compound A alone;
δh is the effect of hydrogen bonding force on the Hansen solubility parameter of Compound A alone;
δd _T , δp _T , and δh _T are the coordinates of point T, which are the values of the following formulas (M), (N), and (O).
δd _T =16.58...Formula (M)
δp _T =5.00...Formula (N)
δh _T =5.77...Formula (O)

Hereinafter, regarding a curable composition according to one embodiment, Compound A and Compound B will be explained in order. Thereafter, components that can constitute the curable composition other than these, the composition and properties of the curable composition will be explained.

(Compound A)
Compound A is a compound whose Ra (T) calculated from the following formula (L) is 1.377 to 3.000 MPa ^0.5 .
Ra (T) = [4×(δd-δd _T ) ² + (δp-δp _T ) ² + (δh-δh _T ) ² ] ^0.5 ...Formula (L)
In formula (L),
Ra(T) is a Hansen solubility parameter distance indicating the vector distance between the compound A alone and point T in a three-dimensional space represented by δd, δp, and δh in the Hansen solubility parameter;
δd is the effect of van der Waals dispersion force on the Hansen solubility parameter of Compound A alone;
δp is the effect of dipole-dipole force on the Hansen solubility parameter of compound A alone;
δh is the effect of hydrogen bonding force on the Hansen solubility parameter of compound A alone;
δd _T , δp _T , and δh _T are the coordinates of point T, which are the values of the following formulas (M), (N), and (O).
δd _T =16.58...Formula (M)
δp _T =5.00...Formula (N)
δh _T =5.77...Formula (O)

Here, the Hansen solubility parameter is a solubility parameter introduced by Hildebrand divided into three components, δd, δp, and δh, and expressed in a three-dimensional space. δd represents the effect due to van der Waals dispersion force, δp represents the effect due to dipole-dipole force, and δh represents the effect due to hydrogen bond force. Hansen solubility parameter values for various compounds can be found, for example, in Charles M. Hansen, "Hansen Solubility Parameters: A Users Handbook (CRC Press, 2007)" and the like. δd, δp, and δh of a compound can be easily estimated from its chemical structure using, for example, computer software (Hansen Solubility Parameters in Practice (HSPiP). In the present invention, computer software (Hansen Solubility Parameters in Practice (HSPiP)) ractice For compounds registered in the database of (HSPiP) Ver. 5.3.02), use that value, and for compounds not in the database, use the value estimated by HSPiP Ver. 5.3.02. .

One type of compound A may be used alone, or two or more types may be used in combination. When two or more types of compounds A are mixed, the Hansen solubility parameter of the mixture is the sum of the values of δd, δp, and δh of each compound A alone multiplied by their mixing ratio, but in the following explanation, means δd, δp, and δh of compound A alone blended in the composition.

The point T according to one embodiment is the coordinates shown by the values of the following formulas (M), (N), and (O) in the three-dimensional space represented by δd, δp, and δh in the Hansen solubility parameter. .
δd _T =16.58...Formula (M)
δp _T =5.00...Formula (N)
δh _T =5.77...Formula (O)
When calculating the Hansen solubility parameter distance Ra (T) between compound A alone and the center of point T according to one embodiment, the above formula ( It is possible to calculate based on the values of M), (N), and (O).
Point T shown by the above formulas (M), (N), and (O) is when a test piece dissolution experiment using polycarbonate resin is performed, and the test piece does not completely dissolve after the test and swells and becomes white. These are the center coordinates of a sphere t with a radius of 2.00 MPa ^0.5 obtained by Hansen molten sphere analysis of the distribution state of a compound group in a three-dimensional space represented by δd, δp, and δh.
The above point T is the Hansen's distribution state in the three-dimensional space represented by δd, δp, and δh of the compound group completely dissolved in the test piece when performing a test piece dissolution experiment using polycarbonate resin. It is significantly different from the center coordinate U of the polycarbonate resin melt sphere u obtained by melt sphere analysis (δd _u =18.80, δp _u =7.50, δh _u =5.60, sphere radius 5.60 ). We speculate as follows. The compound located near the sphere u can dissolve the polycarbonate resin by exhibiting high compatibility with the entire main chain skeleton of the polycarbonate resin. On the other hand, the compound located near the sphere t exhibits compatibility with the partial skeleton of the polycarbonate resin, thereby forming a bond between the coating film and the substrate without dissolving and dispersing the polycarbonate resin into the cured coating film. By swelling, it becomes possible to form an interface with an increased contact area.
The δd, δp, δh of the compound, the δd, δp, δh of each sphere, and the radius of the sphere were estimated using computer software (Hansen Solubility Parameters in Practice (HSPiP) Ver. 5.3.02).

The test piece dissolution experiment according to one embodiment is specifically carried out according to the following procedure.
(1) Add 4 g of liquid sample to 0.02 g of polycarbonate resin at room temperature.
(2) Perform ultrasonic stirring for 5 minutes.
(3) Immediately leave the sample in a constant temperature bath set at 25°C for 24 hours.
(4) Observe the state of the resin after 24 hours and judge whether it has dissolved, swelled, or changed.
(5) Based on the molecular structural formula and appearance determination results of the liquid sample, analysis is performed using computer software (Hansen Solubility Parameters in Practice (HSPiP) Ver. 5.3.02).

As an example, in Figure 1, the surface of the polycarbonate resin after the test piece dissolution experiment was observed using a scanning electron microscope (SEM) at magnifications of 500x, 2000x, and 5000x using methoxy-triethylene glycol acrylate and polycarbonate resin. This shows how it was done. It can be seen that fine particles with a rough surface and a grain size of 0.5 to 50 μm are formed on the resin surface layer. From this, by including Compound A alone having a Hansen solubility parameter distance Ra (T) of 1.377 to 3.000 MPa ^0.5 with point T in the curable composition according to one embodiment, it is possible to By forming micron-order fine particles at the contact interface between the coating film and the polycarbonate resin, it becomes possible to significantly increase the surface area of the contact interface.

In the curable composition according to one embodiment, the Hansen solubility parameter distance Ra (T) between Compound A alone and point T is 1.377 to 3.000 MPa ^0.5 . Since the Hansen solubility parameter distance Ra (T) between compound A alone and point T is within the above numerical range, it is thought that the hot water resistant adhesion and moist heat resistant adhesion of the coating film obtained from the curable composition are improved. Although the detailed mechanism is unknown, it is assumed as follows.
Since the Hansen solubility parameter distance Ra (T) between compound A alone and point T is 1.377 to 3.000 MPa ^0.5 , compound A moderately swells the components constituting the polycarbonate resin. Compound A with such a molecular skeleton shows a moderate affinity for polycarbonate resin, and by penetrating into the resin, Compound A softens the surface of the base material, creating a composite in which the coating film and polycarbonate resin are mixed. It becomes possible to form particles. Furthermore, since Compound A is a molecule that is difficult to dissolve or elute from polycarbonate resin, it is possible to suppress the formed composite particles from diffusing into the coating film, and to prevent the formation of particles between the coating film and the base material. It becomes possible to hold composite particles with a large surface area. Therefore, it is thought that the contact surface area between the cured coating film and the substrate interface increases significantly. As a result of the increase in the contact surface area, it becomes easier to obtain an anchor effect, and the adsorption force based on van der Waals force, hydrogen bond force, etc. increases. Therefore, it is presumed that the hot water resistant adhesion and moist heat resistant adhesion of the coating film obtained from the curable composition are improved.
As explained above, according to compound A having a Hansen solubility parameter distance Ra (T) of 1.377 to 3.000 MPa ^0.5 with respect to point T, when it is made into a coating film of a cured product, it is difficult to coat the base material component. It is thought that it is easy to suppress excessive elution into the membrane and form an interface with increased contact area due to the particles, which provides a high anchoring effect. Therefore, the hot water resistant adhesion and moist heat resistant adhesion of the coating film are improved, and the functional coating on the surface of the base material can be maintained in a good appearance state for a long period of time.

When the Hansen solubility parameter distance Ra (T) between compound A alone and point T is greater than 1.377 MPa ^0.5 , the molecular skeleton has an affinity for the partial structure of the polycarbonate resin, and the polycarbonate resin swells appropriately. be able to. Therefore, the swelling and penetration behavior of the polycarbonate resin by Compound A occurs quickly. Thereby, after the curable composition contacts the polycarbonate resin, the rate at which swollen particulates are formed between the coating film and the substrate is faster than the rate at which erosion and diffusion of the polycarbonate resin occurs due to simultaneous dissolution or elution. exceeds. As a result, while forming an interface that exhibits good adhesion, it is possible to suppress poor appearance of the coating film due to excessive erosion of the base material.
When the Hansen solubility parameter distance Ra (T) between compound A alone and point T is smaller than 3.000 MPa ^0.5 , the molecular skeleton of compound A has a high affinity for the partial structure of the polycarbonate resin. Therefore, swelling particles can be formed at the interface between the cured coating film and the substrate while suppressing elution of the polycarbonate resin. This increases the contact area between the coating film and the base material interface, making it possible to create an interface that easily exhibits adsorption force based on van der Waals force, hydrogen bond force, etc. As a result, it is thought that the anchoring effect of the coating film on the surface of the base material is likely to occur.
From the above viewpoint, the Hansen solubility parameter distance Ra (T) between compound A alone and point T is preferably 1.379 to 2.900, more preferably 1.380 to 2.700, and 1.382 to 2.500. is more preferred, 1.384 to 2.000 is even more preferred, 1.386 to 1.800 is even more preferred, and 1.400 to 1.750 is most preferred.
One type of compound A may be used alone, or two or more types having different Hansen solubility parameter distances Ra (T) from point T may be used in combination.

In the curable composition according to one embodiment, the Hansen solubility parameter δd of Compound A alone is not particularly limited, but is 16.00 to 16.72 MPa ^0.5 . Since δd in the Hansen solubility parameter of Compound A is within the above numerical range, it is considered that the hot water resistant adhesion and moist heat resistant adhesion of the coating film obtained from the curable composition are improved. Although the detailed mechanism is unknown, it is assumed as follows.
δd in the Hansen solubility parameter represents van der Waals dispersion interaction, which is the most important interaction for hydrocarbons, and is higher for cyclic compounds than for linear compounds, and even higher for aromatics. A similar effect appears for ester compounds. It is also likely that chlorine, bromine, sulfur, etc., which are larger than carbon atoms, are included.
Since the Hansen solubility parameter δd of Compound A alone is 16.00 to 16.72 MPa ^0.5 , the molecular skeleton of Compound A is appropriately elongated and not bulky. Compound A having such a molecular skeleton exhibits a suitable affinity for the base material, and although Compound A easily penetrates into the interior of the base material and swells, it is difficult to cause the base material to dissolve. Therefore, it is thought that it is possible to suppress the elution and diffusion of the interface formed by the mixing of the cured coating film and the base material into the coating film. As a result of the interface remaining between the coating film and the base material, the anchoring effect of the contact interface is easily obtained, and the adsorption force based on van der Waals force, hydrogen bond force, etc. increases. Therefore, it is presumed that the hot water resistant adhesion and moist heat resistant adhesion of the coating film obtained from the curable composition are improved.
As explained above, according to Compound A whose Hansen solubility parameter δd is 16.00 to 16.72 MPa ^0.5 , when it is made into a cured coating, the adhesive interface with a large surface area is placed at the interface with the base material. It is thought that it is easy to form. Therefore, the hot water resistant adhesion and moist heat resistant adhesion of the coating film are improved, and the functional coating on the surface of the substrate can be maintained for a long period of time.

When δd in the Hansen solubility parameter of Compound A is larger than 16.00 MPa ^0.5 , the van der Waals interaction with the base material of the molecular skeleton becomes large. Therefore, it is thought that the affinity of Compound A to the substrate due to van der Waals force tends to increase, and as a result, the adhesion of the cured coating film to the substrate tends to increase.
When δd in the Hansen solubility parameter of Compound A is smaller than 16.72 MPa ^0.5 , the molecular skeleton will not be excessively similar to the base material. Therefore, it is thought that the dissolution or elution behavior of the base material by Compound A is moderately suppressed, and the components mixed with the coating film and base material are retained at the contact interface, improving adhesion due to the anchor effect. It will be done.
From the above viewpoint, δd in the Hansen solubility parameter of Compound A is preferably 16.10 to 16.52, more preferably 16.15 to 16.32, even more preferably 16.16 to 16.30, and even more preferably 16.18 to 16.32. 16.28 is even more preferred, 16.19 to 16.25 is even more preferred, and 16.20 to 16.23 is most preferred.

In the curable composition according to one embodiment, δp in the Hansen solubility parameter of Compound A alone is not particularly limited, but is 2.85 to 5.89 MPa ^0.5 . Since δp in the Hansen solubility parameter of Compound A is within the above numerical range, it is considered that the hot water resistant adhesion and moist heat resistant adhesion of the coating film obtained from the curable composition are improved. Although the detailed mechanism is unknown, it is assumed as follows.
Since δp in the Hansen solubility parameter of Compound A alone is 2.85 to 5.89 MPa ^0.5 , the molecular skeleton of Compound A has appropriate polarity. Compound A having such a molecular skeleton exhibits a suitable affinity for the polar functional groups on the surface of the substrate, and tends to increase the adsorption force between the surface of the substrate and the van der Waals force. As a result, it becomes easier to obtain an anchor effect and the adsorption power increases. Therefore, it is presumed that the hot water resistant adhesion and moist heat resistant adhesion of the coating film obtained from the curable composition are improved.
As explained above, Compound A with a Hansen solubility parameter δp of 2.85 to 5.89 MPa ^0.5 exhibits adsorption based on van der Waals forces with the surface of the substrate when formed into a cured coating. It is thought that it is easy to increase the force. Therefore, the hot water resistant adhesion and moist heat resistant adhesion of the coating film are improved, and the functional coating on the surface of the substrate can be maintained for a long period of time.

When δp in the Hansen solubility parameter of Compound A is larger than 2.85 MPa ^0.5 , the polarity of the molecular skeleton does not decrease too much. Therefore, it is thought that the adsorption force due to van der Waals force with the surface of the base material is unlikely to become excessively small, and the adhesion to the base material is improved.
When δp in the Hansen solubility parameter of Compound A is smaller than 5.89 MPa ^0.5 , the polarizability of the molecular skeleton is unlikely to become excessively large. Therefore, it becomes possible to suppress swelling and erosion of the cured coating film due to highly polar organic solvents such as water, alcohol, and ester. As a result, it is thought that the durability of the coating film against water and solvents can be easily improved.
From the above viewpoint, δp in the Hansen solubility parameter of Compound A is preferably 3.10 to 5.10, more preferably 3.30 to 4.90, even more preferably 3.60 to 4.70, and still more preferably 3.90 to 5.10. 4.50 is even more preferred, and 3.99 to 4.32 is most preferred.

In the curable composition according to one embodiment, the Hansen solubility parameter δh of Compound A alone is not particularly limited, but is 4.02 to 10.75 MPa ^0.5 . Since δh in the Hansen solubility parameter of Compound A is within the above numerical range, it is considered that the hot water resistant adhesion and moist heat resistant adhesion of the coating film obtained from the curable composition are improved. Although the detailed mechanism is unknown, it is assumed as follows.
Since the Hansen solubility parameter δh of Compound A alone is 4.02 to 10.75 MPa ^0.5 , the molecular skeleton of Compound A has appropriate water resistance. Compound A having such a molecular skeleton exhibits a suitable affinity for the polar functional groups on the surface of the substrate and easily forms hydrogen bonds with the surface of the substrate. Therefore, it is thought that the adhesion between the cured coating film and the substrate interface increases significantly. As a result, it becomes easier to obtain an anchor effect and the adsorption power increases. Furthermore, the molecular skeleton of Compound A exhibits appropriate water resistance, and the coating film does not swell even in an environment where it is exposed to water for a long time, and it is thought that the mechanical strength of the coating film is maintained. As a result, the water resistance of the coating film is improved. Therefore, it is presumed that the hot water resistant adhesion and moist heat resistant adhesion of the coating film obtained from the curable composition are improved.
As explained above, Compound A with a Hansen solubility parameter δh of 4.02 to 10.75 MPa ^0.5 has high water resistance and high adhesion to the substrate surface when formed into a cured coating. It is thought that it is easy to achieve both. Therefore, the hot water resistant adhesion and moist heat resistant adhesion of the coating film are improved, and the functional coating on the surface of the substrate can be maintained for a long period of time.

If δh in the Hansen solubility parameter of Compound A is larger than 4.02 MPa ^0.5 , the hydrogen bonding ability of the molecular skeleton will not be excessively reduced. Therefore, it is thought that it becomes possible to have an affinity with the polar functional groups on the surface of the substrate, making it easier for the coating film to adhere to the surface of the substrate.
When δh in the Hansen solubility parameter of Compound A is smaller than 10.75 MPa ^0.5 , the hydrophilicity of the molecular skeleton is unlikely to become excessively large. Therefore, swelling and erosion of the cured coating film due to water can be suppressed, and water resistance is likely to be improved. As a result, it is thought that the hot water resistant adhesion and moist heat resistant adhesion of the coating film are improved.
From the above viewpoint, δh in the Hansen solubility parameter of Compound A is preferably 4.20 to 8.50, more preferably 4.50 to 7.50, even more preferably 5.00 to 6.50, and even more preferably 5.20 to 8.50. 6.00 is even more preferred, and 5.40 to 5.70 is most preferred.

The present inventors further conducted various studies and found preferable molecular weight conditions for Compound A. The molecular weight of compound A is preferably 160 to 305, more preferably 170 to 275, even more preferably 175 to 250, particularly preferably 190 to 240, and most preferably 205 to 230.
Although the reason why these numerical ranges are preferable is speculation, it is thought to be as follows.
When the molecular weight is within the above numerical range, it is considered that the balance between the dissolution or elution behavior of the base material and the permeability into the interior of the base material is improved. It is presumed that when the molecular weight is 160 or more, the behavior of dissolution or elution of the base material due to diffusion is unlikely to occur, and an interface is likely to be formed between the cured product having a large surface area and the base material. On the other hand, when the molecular weight is 305 or less, the molecular size is not excessively large, and it is presumed that it is easy to maintain permeability into the inside of the base material.

Compound A may have various heteroatoms such as oxygen, nitrogen, sulfur, phosphorus, boron, silicon, and halogen atoms.

Examples of the compound A having an oxygen atom include ethers, ketones, carboxylic acids, esters including (meth)acrylate monomers and acetates, and carbonates.
Examples of the compound A having a nitrogen atom include amino, amides containing acrylamide monomers, amines, and semipolar compounds containing amine oxides.
Examples of the compound A having a sulfur atom include amphoteric compounds including thiol, thioester, sulfonic acid, and sulfobetaine.
Examples of the compound A having a phosphorus atom include phosphoric acid, phosphoric acid ester, and amphoteric compounds containing phosphobetaine.
Examples of the compound A having a boron atom include borane, boronic acid, and boronic acid ester.
Examples of the compound A having a silicon atom include silane, siloxane, and silanol.
Examples of the compound A having a halogen atom include halogenated alkanes, halogenated alkenes, and halogenated alkynes.

Compound A may be a chain compound consisting of a linear or branched chain structure, a cyclic compound consisting of a cyclic structure, or a compound consisting of both a chain structure and a cyclic structure. . Among these, from the viewpoint of swelling properties for the base material, Compound A preferably has a linear structure with a small molecular cross-sectional area. Further, some of the bonds constituting compound A may be unsaturated bonds, or all the bonds may be saturated bonds.

The cyclic structure may be an aliphatic ring, an aromatic ring, a non-aromatic heterocycle, or an aromatic heterocycle. Further, the cyclic structure may be a monocyclic structure or a polycyclic structure having two or more rings. Among these, from the viewpoint of weather resistance, aliphatic rings and non-aromatic heterocycles are preferred, and aliphatic rings are more preferred.

The aliphatic ring is a monocyclic ring or a polycyclic ring having two or more rings. Some of the bonds constituting the aliphatic ring may be unsaturated bonds. A part of the bicyclic aliphatic ring may have aromaticity. Examples of the aliphatic ring include cycloalkane, cycloalkene, cycloalkyne, bicycloalkane, and tricycloalkane.
The aromatic ring is a monocyclic ring or a polycyclic ring having two or more rings having aromatic properties. Examples of the aromatic ring include a benzene ring and a naphthalene ring.

A non-aromatic heterocycle is a monocyclic ring or a polycyclic ring having two or more rings having 1 to 4 identical or different heteroatoms selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms. Some of the bonds constituting the non-aromatic heterocycle may be unsaturated bonds. A part of the bicyclic non-aromatic heterocycle may have aromaticity. Examples of the non-aromatic heterocyclic group include aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, dihydropyridyl, oxetanyl, tetrahydrofuryl, dihydrofuryl, tetrahydropyranyl, dihydropyranyl, tetrahydrothienyl, tetrahydrothiopyranyl, dihydrothiopyranyl. , piperazinyl, dihydropyrazyl, morpholinyl, thiomorpholinyl, dihydroindolyl, dihydroisoindolyl, dihydrobenzofuryl, dihydroisobenzofuryl, tetrahydrobenzooxazolyl, dihydrofuropyridyl, dihydropyrazolomorpholinyl, pyridinodioxa and dihydroazaibenzofuryl, dihydroazaiisobenzofuryl, and dihydroazaindolyl.
The non-aromatic heterocycle may be a cyclic amino. "Cyclic amino" has a bond on the nitrogen atom that forms the ring structure of a non-aromatic heterocycle. Examples of the cyclic amino include azetidin-1-yl, pyrrolidin-1-yl, piperidin-1-yl, morpholin-4-yl, thiomorpholin-4-yl, and piperazin-1-yl.

Aromatic heterocycle refers to a monocyclic or bicyclic or more polycyclic ring that has aromatic properties and has 1 to 4 identical or different heteroatoms selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms. It is a ring. Examples of aromatic heterocyclic groups include pyrrolyl, furyl, thienyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazyl, indolyl, isoindolyl, benzofuryl, benzothienyl, indazolyl, benzimidazolyl, benzoxazolyl, Examples include benzothiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalyl, pyrrolopyridyl, and imidazolopyridyl.

As compound A, acetate and (meth)acrylate monomers are preferred.
Examples of the acetate include methyl carbitol acetate, ethyl carbitol acetate, propyl carbitol acetate, butyl carbitol acetate, pentyl carbitol acetate, hexyl carbitol acetate, heptyl carbitol acetate, and octyl carbitol acetate. However, acetate is not limited to these examples.
Examples of (meth)acrylate monomers include methoxyethoxyethyl acrylate, ethoxyethoxyethyl acrylate, propioxyethoxyethyl acrylate, butoxyethoxyethyl acrylate, pentoxyethoxyethyl acrylate, hexoxyethoxyethyl acrylate, heptoxyethoxyethyl acrylate, octoxyethoxyethyl acrylate, Xyethoxyethyl acrylate, caprolactone modified (1 mol) ethyl acrylate, caprolactone modified (2 mol) ethyl acrylate, methoxy-triethylene glycol acrylate, ethoxy-triethylene glycol acrylate, propoxy-triethylene glycol acrylate, butoxy-triethylene glycol acrylate, pentoxy -triethylene glycol acrylate, hexyloxy-triethylene glycol acrylate, heptoxy-triethylene glycol acrylate, octoxy-triethylene glycol acrylate, and 1,9-nonanediol diacrylate. However, the (meth)acrylate monomer is not limited to these examples.

Among them, from the viewpoint of durability of the coating film after curing, it is preferable that the compound A contains at most two substituents having polymerization activity. Since the crosslinking density of the curable composition can be further increased and the hardness can be increased, it is more preferable that the compound A contains one to two substituents having polymerization activity. Further, since the viscosity of the curable composition can be further lowered, it is most preferable that the compound A contains one substituent having polymerization activity.
For example, hexyloxyethoxyethyl acrylate, methoxy-triethylene glycol acrylate, and 1,9-nonanediol diacrylate are preferred, hexyloxyethoxyethyl acrylate and methoxy-triethylene glycol acrylate are more preferred, and methoxy-triethylene glycol acrylate is the most preferred. preferable.

(Compound B)
Compound B is a polyfunctional (meth)acrylate monomer having three or more (meth)acryloyl groups.
In relation to Compound A, if the compound falls under "a polyfunctional (meth)acrylate monomer having three or more (meth)acryloyl groups", the Hansen solubility parameter distance Ra(T) from point T is 1. 377 to 3.000 MPa Even if the pressure is ^0.5 , the compound is classified as Compound B.

The curable composition according to one embodiment contains compound B as one of the radically polymerizable compounds. Since the curable composition contains compound B, the curable composition exhibits good polymerization activity upon irradiation with active energy rays. As a result, the crosslinking density increases and the scratch resistance of the coating film improves.

As the compound B, from the viewpoint of scratch resistance and weather resistance, conventionally known compounds can be used as long as they contain at least three or more polymerizable functional groups in one molecule. For example, poly(meth) ) acrylate, polyester poly(meth)acrylate, epoxy poly(meth)acrylate, and poly[(meth)acryloyloxyalkyl](iso)cyanurate.

Compound B has a (meth)acryloyl functional group number of 3 to 20. From the viewpoint of curability and scratch resistance, the number of (meth)acryloyl functional groups in compound B is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more. Further, from the viewpoint of weather resistance and curing shrinkage, the number of (meth)acryloyl functional groups in compound B is preferably 18 or less, more preferably 16 or less, and even more preferably 14 or less.

Compound B includes, for example, poly[(meth)acryloyloxyalkyl](iso)cyanurate, isocyanuric acid EO-modified tri(meth)acrylate, polyester poly(meth)acrylate, polyester tri(meth)acrylate, polyester tetra( meth)acrylate, polyester penta(meth)acrylate, polyester hexa(meth)acrylate, as poly(meth)acrylate, glycerin tri(meth)acrylate, glycerin EO modified tri(meth)acrylate, glycerin PO modified tri(meth)acrylate, Glycerin caprolactone modified tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO modified trimethylolpropane tri(meth)acrylate, PO modified trimethylolpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate , pentaerythritol tri(meth)acrylate, EO-modified pentaerythritol tri(meth)acrylate, PO-modified pentaerythritol tri(meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, EO-modified pentaerythritol tri(meth)acrylate Erythritol tetra(meth)acrylate, PO-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, EO-modified dipentaerythritol penta(meth)acrylate, PO-modified dipentaerythritol penta(meth)acrylate Pentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, EO-modified dipentaerythritol hexa(meth)acrylate, PO-modified dipentaerythritol hexa(meth)acrylate, Examples include caprolactone-modified dipentaerythritol hexa(meth)acrylate.
Here, "EO" means ethylene oxide, and "PO" means propylene oxide.
One type of compound B may be used alone or two or more types may be used in combination.

Among them, from the viewpoint of the balance between scratch resistance and weather resistance (yellowing resistance, crack resistance), Compound B includes isocyanuric acid EO-modified tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, caprolactone-modified A polyfunctional (meth)acrylate having a dipentaerythritol skeleton is preferred, and a polyfunctional (meth)acrylate having a caprolactone-modified dipentaerythritol skeleton is more preferred. Namely, dipentaerythritol penta(meth)acrylate, EO-modified dipentaerythritol penta(meth)acrylate, PO-modified dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate. ) acrylate, EO-modified dipentaerythritol hexa(meth)acrylate, PO-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate are preferred, caprolactone-modified dipentaerythritol penta(meth)acrylate, caprolactone More preferred is modified dipentaerythritol hexa(meth)acrylate.

(Compound C)
The curable composition according to one embodiment preferably further contains the following compound C in addition to compound A and compound B. Compound C is a (meth)acrylate having a (meth)acryloyl group and a urethane bond.
In relation to compound A, if the compound corresponds to "(meth)acrylate having a (meth)acryloyl group and a urethane bond", the Hansen solubility parameter distance Ra(T) from point T is 1.377 ~ Even if the pressure is 3.000MPa ^0.5 , the compound is classified as compound C.

The curable composition according to one embodiment contains compound C as one of the radically polymerizable compounds. Since Compound C has a urethane bond, the toughness of the coating film is improved. Moreover, the weather resistance of the cured product of the curable composition and the adhesion after the durability test are improved.

As compound C, urethane (meth)acrylate having two or more urethane bonds and two or more (meth)acryloyloxy groups in one molecule is preferable.
For example, the following urethane (meth)acrylate (C1) is preferred.
Urethane (meth)acrylate (C1): A reaction product of a hydroxy group-containing (meth)acrylate (c1), a polyisocyanate (c2), and a polyol (c3) having two or more hydroxy groups in one molecule.

The hydroxy group-containing (meth)acrylate (c1) is not particularly limited as long as it is a (meth)acrylate having a hydroxy group and a (meth)acryloyloxy group. For example, 2-hydroxyethyl acrylate (HEA), 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl acrylate (HPA), 2-hydroxypropyl methacrylate (HPMA), 2-hydroxybutyl acrylate (HBA), 4-hydroxy Butyl acrylate (4-HBA), 2-hydroxybutyl methacrylate (HBMA), caprolactone 1 mol adduct of HEA (Daicel Plaxel (registered trademark) FA1), HEA caprolactone 2 mol adduct (Plaxel FA2D), HEA caprolactone 5 mol Examples include an adduct (Plaxel FA5), an adduct of HEA with 10 mol of caprolactone (Plaxel FA10L), and a compound whose skeleton is mono- or polypentaerythritol.
Examples of "compounds whose skeleton is mono- or polypentaerythritol" include pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate. Examples include acrylate.
One type of hydroxy group-containing (meth)acrylate (c1) may be used alone, or two or more types may be used in combination.

Among hydroxy group-containing (meth)acrylates (c1), 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 2-hydroxybutyl acrylate are selected from the viewpoints of ease of availability, reactivity, solubility in curable compositions, etc. , 4-hydroxybutyl acrylate, pentaerythritol triacrylate, 1 mol caprolactone adduct of HEA manufactured by Daicel (Plaxel FA1), 2 mol caprolactone adduct of HEA (Plaxel FA2D) are preferable, 2-hydroxyethyl acrylate, 2-hydroxypropyl Acrylate and 2-hydroxybutyl acrylate are more preferred, and 2-hydroxyethyl acrylate is even more preferred.

The polyisocyanate (c2) is not particularly limited as long as it is a polyisocyanate having two or more isocyanate groups in one molecule. for example,
Aliphatic polyisocyanates such as hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate;
Alicyclic polyisocyanates such as norbornane diisocyanate (NBDI), transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), bis(isocyanatemethyl)cyclohexane (hydrogenated XDI), dicyclohexylmethane diisocyanate (hydrogenated MDI);
2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4' -Diphenylmethane diisocyanate (2,4'-MDI), 1,4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), toridine diisocyanate (TODI), 1,5 - Aromatic polyisocyanates such as naphthalene diisocyanate (NDI) and triphenylmethane triisocyanate;
These isocyanurate bodies, adduct bodies, biuret bodies;
can be mentioned.
One type of polyisocyanate (c2) may be used alone, or two or more types may be used in combination.

Among them, from the viewpoint of weather resistance, as the polyisocyanate (c2), aliphatic polyisocyanates and alicyclic polyisocyanates are preferable, and hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), bis(isocyanate methyl)cyclohexane (water Added XDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), isocyanurate of hexamethylene diisocyanate manufactured by Asahi Kasei Corporation (product name: Duranate TPA-100), adduct of hexamethylene diisocyanate (product name: Duranate P301-75E) , a biuret form of hexamethylene diisocyanate (product name: Duranate 24A-100), and a bifunctional form of hexamethylene diisocyanate (product name: Duranate A-201H) are more preferred.
Among these, alicyclic polyisocyanates are particularly preferred from the viewpoint of scratch resistance, and dicyclohexylmethane diisocyanate (hydrogenated MDI) is even more preferred.

The polyol (c3) is not particularly limited as long as it is a polyol having two or more hydroxy groups in one molecule. For example, ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane, polyoxyethylene glycol, Oxypropylene glycol, polyoxybutylene glycol, polycaprolactone polyol (polycaprolactone diol, etc.), polytetramethylene ether glycol (PTMG), polycarbonate polyol (polycarbonate diol, etc.), lactone polyol (γ-butyrolactone and N-methylethanolamine) 4-hydroxy-N-(2-hydroxyethyl)-N-methylbutanamide, etc., obtained by reacting
Among them, from the viewpoint of weather resistance, polycaprolactone polyols, polycarbonate polyols, and lactone polyols are preferred, and polycarbonate polyols are more preferred. Further, from the viewpoint of improving the flexibility of the coating film and making it difficult for cracks to occur, polyoxyethylene glycol, polyoxybutylene glycol, and polytetramethylene ether glycol (PTMG) are preferred, and polytetramethylene ether glycol is more preferred.
One type of polyol (c3) may be used alone, or two or more types may be used in combination.

A commercially available product may be used as the polyol (c3).
Commercially available polycarbonate polyols include, for example,
Kuraray Polyol C-590, Kuraray Polyol C-770, Kuraray Polyol C-1050, Kuraray Polyol C-1090, Kuraray Polyol C1065N, Kuraray Polyol C-1015N, Kuraray Polyol C-2090, Kuraray Polyol C-3090 manufactured by Kuraray Co., Ltd. ;
Asahi Kasei Corporation Duranol T-5650E, Duranol T-5650J, Duranol T-5651, Duranol T-5652, Duranol G-4671, Duranol G-4672, Duranol G3450J, Duranol G3452;
Mitsubishi Chemical Co., Ltd. Benevol NL1010DB, Veneevol NL2010DB, Benevol NL3010DB, Benevol NL1005B, Benevior NL2005B, Venebiol1030B, Benevior HS0830B, Benevil HS08 40B, Veneevol HS0840h, Veneevol HS0850H;
can be mentioned.

Commercially available polytetramethylene ether glycols include, for example,
PTMG250, PTMG650, PTMG1000, PTMG2000, PTMG3000 manufactured by Mitsubishi Chemical Corporation;
PTMEG #220, PTMEG #650, PTMEG #1000, PTMEG #1400, PTMEG #2000 manufactured by Mihama Co., Ltd.;
PTG-650, PTG-850SN, PTG-3000 manufactured by Hodogaya Chemical Industry Co., Ltd.;
can be mentioned.

Urethane (meth)acrylate (C1) is obtained by reacting hydroxy group-containing (meth)acrylate (c1), polyisocyanate (c2), and polyol (c3).
As the reaction conditions, conditions under heating are preferred. For example, conditions include a reaction temperature of 70° C. and a reaction time of 8 hours.

As the urethane (meth)acrylate (C1), for example,
A reaction product of a polycarbonate polyol, a diisocyanate compound having an alicyclic structure, and a mono(meth)(meth)acrylate monomer having a hydroxy group;
Polytetramethylene ether glycol, 4-hydroxy-N-(2-hydroxyethyl)-N-methylbutanamide, a diisocyanate compound having an alicyclic structure, and a mono(meth)(meth)acrylate monomer having a hydroxy group. reactant;
is preferred.

From the viewpoint of improving spray coating properties by lowering the viscosity of the curable composition, the mass average molecular weight (Mw) of compound C is preferably 8,000 or less, more preferably 6,000 or less. Moreover, from the viewpoint of the bending resistance of the cured product, the mass average molecular weight (Mw) of the compound C is preferably 500 or more, and more preferably 1000 or more.
Therefore, the mass average molecular weight (Mw) of compound C is preferably from 500 to 8,000, more preferably from 1,000 to 6,000.
The mass average molecular weight (Mw) of Compound C is a value measured by gel permeation chromatography (GPC method) in terms of standard polystyrene.

The number of (meth)acryloyl functional groups in compound C is preferably 2 to 15, more preferably 2 to 10, even more preferably 2 to 6, particularly preferably 2 to 4, and most preferably 2. When the number of (meth)acryloyl functional groups of compound C is within the above numerical range, it is easy to achieve both scratch resistance and weather resistance.

(Compound B-1)
The curable composition according to one embodiment preferably further contains the following compound B-1 in addition to compound A, compound B, and compound C.
Compound B-1: A (meth)acrylate having at least one type selected from the group consisting of a dendrimer structure and a hyperbranched structure (excluding the aforementioned compound B and the aforementioned compound C).
In relation to compound A, if the compound falls under "(meth)acrylate having at least one type selected from the group consisting of a dendrimer structure and a hyperbranched structure," the Hansen solubility parameter distance Ra (T ) is 1.377 to 3.000 MPa ^0.5 , the compound is still classified as Compound B-1.

Compound B-1 contributes to improving the bending resistance of the cured product of the curable composition according to one embodiment. Compound B-1 also contributes to lowering the viscosity of the curable composition according to one embodiment. Therefore, when applying the present curable composition to a substrate using air spray, a good appearance can be obtained after coating even if the amount of diluting organic solvent used is small. Therefore, volatile organic compound (VOC) components can be reduced, and environmental load can be reduced.

The dendrimer structure means a structure in which a branched structure further branches to form a multi-branched structure, and the branched structures spread radially.
The term "hyperbranch structure" refers to a structure in which the multiple branch structures extend not radially but in a branched manner in one or more predetermined directions.

Compound B-1 is a polyfunctional (meth)acrylate having (meth)acryloyl groups at a plurality of tip portions of the multi-branched structure.
From the viewpoint of curability, the number of (meth)acryloyl functional groups in Compound B-1 is preferably 4 or more, more preferably 6 or more. Further, from the viewpoint of curing shrinkage, the number of (meth)acryloyl functional groups in compound B-1 is preferably 20 or less, more preferably 18 or less.

As compound B-1, compounds synthesized by various methods may be used, or commercially available products may be used. Examples of the method for synthesizing compound B-1 include the method described in JP-A-2016-190998.

Examples of the (meth)acrylate having a dendrimer structure include Viscoat (registered trademark) #1000, SIRIUS-501, and SUBARU-501 manufactured by Osaka Organic Chemical Industry Co., Ltd.
Examples of the (meth)acrylate having a hyperbranched structure include CN2302, CN2303, and CN2304 manufactured by SARTOMER.

Compound B-1 includes Viscoat #1000 manufactured by Osaka Organic Chemical Industry Co., Ltd., and CN2302, CN2303, and CN2304 manufactured by SARTOMER, from the viewpoint of improving spray coating properties by lowering the viscosity of the curable composition. is preferred.

From the viewpoint of spray coating properties, the viscosity (25°C) of Compound B-1 at 25°C is preferably 10,000 mPa·s or less, more preferably 7,000 mPa·s or less, even more preferably 4,000 mPa·s or less, and 2,000 mPa·s or less. Even more preferable. In addition, from the viewpoint of curability, the viscosity (25° C.) of compound B-1 is preferably 10 mPa·s or more, more preferably 20 mPa·s or more, more preferably 40 mPa·s or more, and even more preferably 60 mPa·s or more. .
The viscosity (25°C) of Compound B-1 is a value measured at 25°C using an E-type viscometer.

(other monomers)
The curable composition according to one embodiment of the present invention may further contain a compound having a (meth)acryloyl group other than Compound A, Compound B, Compound C, and Compound B-1 as another monomer.
Other monomers are not particularly limited. Examples include linear aliphatic hydrocarbon (meth)acrylates, aliphatic hydrocarbon (meth)acrylates with a branched structure, aliphatic hydrocarbon (meth)acrylates with a cyclic structure, and hydroxyl group-containing (meth)acrylates. . It is preferable that the other monomer has at least one polymerization active group in its molecular skeleton.
One type of other monomers may be used alone, or two or more types may be used in combination.

From the viewpoint of improving spray coating properties by lowering the viscosity of the curable composition, other monomers include linear aliphatic hydrocarbon (meth)acrylate, aliphatic hydrocarbon having a branched structure ( Preferred are meth)acrylates and aliphatic hydrocarbon (meth)acrylates having a cyclic structure. Examples include isobutyl acrylate, t-butyl acrylate, isononyl acrylate, isodecyl acrylate, 2-ethylhexyl acrylate, isostearyl acrylate, and isobornyl acrylate. Among them, 2-ethylhexyl acrylate and isostearyl acrylate are preferred from the viewpoint of viscosity-reducing effect.

(other ingredients)
The curable composition according to one embodiment of the present invention may further contain components other than Compound A, Compound B, Compound C, Compound B-1, and other monomers.
Examples of other components include ultraviolet absorbers, photopolymerization initiators, organic solvents, and additives. However, other components are not limited to these examples.

The ultraviolet absorber will be explained.
The ultraviolet absorber can impart the effect of absorbing ultraviolet rays contained in sunlight to the cured product of the curable composition. When the curable composition contains an ultraviolet absorber, the weather resistance of the cured product of the curable composition is further improved.

The ultraviolet absorber is not particularly limited as long as it can absorb ultraviolet rays. It is preferable to use one that can be uniformly dissolved in the curable composition and has a high ultraviolet absorption ability.

Examples of ultraviolet absorbers include:
2-Hydroxybenzophenone, 5-chloro-2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2 - Benzophenone-based ultraviolet absorbers such as hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone;
2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2- Benzotriazole-based UV absorbers such as hydroxy-5-(2-methacryloyloxyethyl)phenyl)-2H-benzotriazole;
2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2 -[4-[(2-hydroxy-3-tridesiloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[ 4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2 , 4-bis(2-hydroxy-4-butyroxyphenyl)-6-(2,4-bis-butyroxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-[1- Hydroxyphenyltriazine-based UV absorbers such as octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine;
Examples include phenyl salicylate, p-tert-butylphenyl salicylate, p-(1,1,3,3-tetramethylbutyl) phenyl salicylate, 3-hydroxyphenylbenzoate, and phenylene-1,3-dibenzoate.
One type of ultraviolet absorber may be used alone, or two or more types may be used in combination.

Among them, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl is used as an ultraviolet absorber from the viewpoint of long-lasting ultraviolet absorbing ability in the cured product. ]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-(2-ethyl)hexyl)oxy]-2-hydroxy phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyroxyphenyl)-6-(2,4-bis -butyroxyphenyl)-1,3,5-triazine and 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3, At least one selected from the group consisting of 5-triazine is preferred.

Furthermore, from the viewpoint of preventing ultraviolet deterioration of the base material, a hydroxyphenyltriazine-based ultraviolet absorber having an absorbance of 1.0 or more at 350 nm is preferable. For example, 2-[4-[(2-hydroxy-3-(2-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5 -triazine, 2,4-bis(2-hydroxy-4-butyroxyphenyl)-6-(2,4-bis-butyroxyphenyl)-1,3,5-triazine and 2-(2-hydroxy-4-triazine) At least one selected from the group consisting of -[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine is more preferred.
The absorbance is measured using a U-1900 spectrophotometer manufactured by Hitachi.

As the ultraviolet absorber, from the viewpoint of solubility in the curable composition and weather resistance, a compound derived from at least one selected from the group consisting of benzophenone, benzotriazole, hydroxyphenyltriazine, phenyl salicylate, and phenyl benzoate. Among these compounds, compounds having a maximum absorption wavelength within the range of 240 to 380 nm are more preferable.

From the viewpoint of being able to be contained in a large amount in the curable composition, as the ultraviolet absorber, benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, and hydroxyphenyltriazine-based ultraviolet absorbers are more preferable.
From the viewpoint that bleed-out from the cured product is less likely to occur, as the ultraviolet absorber, benzotriazole-based ultraviolet absorbers and hydroxyphenyltriazine-based ultraviolet absorbers are more preferable. Bleed-out is a phenomenon in which an ultraviolet absorber precipitates on the surface of a cured product and the surface of the cured product becomes white.
From the viewpoint of preventing yellowing of a base material such as a polycarbonate resin, a hydroxyphenyltriazine-based ultraviolet absorber is more preferable as the ultraviolet absorber.

The photopolymerization initiator will be explained.
In one embodiment, when ultraviolet rays are used for the curing reaction of the curable composition, it is preferable that the curable composition further contains a photopolymerization initiator. When the curable composition contains a photopolymerization initiator, the curable composition can be sufficiently cured by ultraviolet rays even in the presence of an ultraviolet absorber. However, in one embodiment, the photopolymerization initiator is not necessarily required when the curable composition is cured with active energy rays (such as electron beams) other than ultraviolet rays.
The photopolymerization initiator is not particularly limited as long as it has good solubility in the curable composition and can initiate polymerization of the acrylic monomer or oligomer upon irradiation with ultraviolet rays.

As the photopolymerization initiator, for example,
Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, acetoin, butyroin, toluoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2, 2-dimethoxy-1,2-diphenylethan-1-one, methylphenylglyoxylate, ethylphenylglyoxylate, 4,4-bis(dimethylaminobenzophenone), 2-hydroxy-2-methyl-1-phenylpropane Carbonyl compounds such as -1-one, 1-hydroxycyclohexylphenyl ketone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one;
Sulfur compounds such as tetramethylthiuram disulfide;
Azo compounds such as azobisisobutyronitrile and azobis-2,4-dimethylvaleronitrile;
Peroxide compounds such as benzoyl peroxide and ditertiary butyl peroxide;
Acyl phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide;
can be mentioned.

Among them, from the viewpoint of polymerization, photopolymerization initiators include benzophenone, methylphenylglyoxylate, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2,2 -dimethoxy-1,2-diphenylethan-1-one and 2,4,6-trimethylbenzoyldiphenylphosphine oxide are preferred.
One type of photopolymerization initiator may be used alone, or two or more types may be used in combination.

As the photopolymerization initiator, a photopolymerization initiator having an absorption maximum at a wavelength of 360 to 400 nm is preferable. When such a photopolymerization initiator is used, radicals are generated by ultraviolet rays when the curable composition is cured with ultraviolet rays, so that polymerizable compounds (polymerizable monomers, polymerizable oligomers, etc.) can be efficiently removed even deep into the coating film. Can be polymerized. As a result, it is easy to obtain a cured product that has excellent adhesion to the base material.

Organic solvents will be explained.
The curable composition of the present invention may contain an organic solvent as another component. When the curable composition contains an organic solvent, the uniform solubility and dispersion stability of the components of the curable composition tend to improve. Furthermore, the adhesion of the cured product to the base material, the smoothness and uniformity of the cured product, etc. are likely to be improved.

The type of organic solvent is not particularly limited. Examples include alcohols, hydrocarbons, halogenated hydrocarbons, ethers, ketones, esters, and polyhydric alcohol derivatives.
One type of organic solvent may be used alone, or two or more types may be used in combination.

Additives will be explained.
The curable composition of the present invention may further contain additives as necessary. Examples of additives include light stabilizers, antioxidants, anti-yellowing agents, bluing agents, pigments, leveling agents, antifoaming agents, thickeners, antisettling agents, antistatic agents, and antifogging agents. It will be done. However, the additives are not limited to these examples.

(solid content concentration)
The solid content concentration of the curable composition of the present invention is preferably 50 to 100% by mass, more preferably 60 to 95% by mass, and even more preferably 70 to 90% by mass, from the viewpoint of environmental impact and spray coating properties.

The solid content concentration is the mass ratio of the remainder (solid content) after removing volatile components from the curable composition to the total mass of the curable composition. The solid content concentration is measured by the method specified in GB/T 34675-2017 Nonvolatile Content Measurement Method. More specifically, the solid content concentration is determined by the following procedure.
(1) Place the aluminum plate in a dryer heated to 110° C. for 30 minutes, cool it in a desiccator, and then record the weight: W.
(2) Weigh 0.2±0.1 g of the curable composition and record the weight: W1.
(3) Immediately place the sample in a dryer heated to 50°C for 30 minutes to dry.
(4) After heating, the curable composition is cured using a curing device while being placed on the aluminum plate.
(5) Place the cured product in a dryer heated to 110° C. for 60 minutes to dry.
(6) After cooling in the desiccator, record the remaining weight: W2.
(7) Calculate solid content concentration: NV according to the following formula (α).
NV (mass%) = ((W2-W)/(W1-W)) x 100...Formula (α)

(Viscosity (25℃))
The viscosity (25° C.) of the curable composition according to one embodiment is preferably 250 mPa·s or less, more preferably 150 mPa·s or less, and even more preferably 100 mPa·s or less. When the viscosity (25° C.) of the curable composition is 250 mPa·s or less, even when the solid content concentration of the curable composition according to one embodiment is relatively high, such as 60% by mass or more, spray coating properties are maintained. Get better.
Further, from the viewpoint of preventing liquid dripping after coating, the viscosity (25° C.) of the curable composition is preferably 20 mPa·s or more.
The viscosity (25°C) of the curable composition is a value measured at 25°C using an E-type viscometer.

The components and amounts of the curable composition can be analyzed by nuclear magnetic resonance (NMR), infrared spectroscopy (IR), or the like. In addition, the components in the cured product can be analyzed by time-of-flight mass spectrometry (TOF-SIMS), X-ray photoelectron spectroscopy (ESCA), X-ray fluorescence, infrared spectroscopy (IR), etc. .

(composition)
The proportion of Compound A is preferably 1 to 50% by mass of the total mass of Compound A, Compound B, Compound C, Compound B-1 and other monomers. When the proportion of Compound A is within the above numerical range, the adhesion of the coating film to the substrate is further improved even after the durability test. From the viewpoint of adhesion after the durability test, the proportion of Compound A is preferably 3 to 35% by mass of the total mass of Compound A, Compound B, Compound C, Compound B-1 and other monomers, and 5 to 30% by mass. %, more preferably 6 to 25% by weight, particularly preferably 7 to 25% by weight.

The proportion of compound B is preferably 5 to 80% by mass of the total mass of compound A, compound B, compound C, compound B-1 and other monomers. When the proportion of compound B is within the above numerical range, the scratch resistance of the cured film is further improved. From the viewpoint of weather resistance (crack resistance) and heat resistance of the cured film, the proportion of compound B is 10 to 70% by mass of the total mass of compound A, compound B, compound C, compound B-1 and other monomers. It is more preferably 20 to 65% by weight, even more preferably 25 to 60% by weight, most preferably 30 to 50% by weight.

The proportion of compound C is preferably 0 to 70% by mass of the total mass of compound A, compound B, compound C, compound B-1, and other monomers. When the proportion of compound C is within the above numerical range, the weather resistance of the cured product and the adhesion after the durability test are further improved. Further, the viscosity of the curable composition is easily reduced, and spray coating properties are further improved. From the viewpoint of suppressing bleed-out of the ultraviolet absorber, the proportion of compound C is more preferably 5 to 50% by mass of the total mass of compound A, compound B, compound C, compound B-1 and other monomers, and 10 to 40% by mass. More preferably % by weight, particularly preferably 13-35% by weight, most preferably 15-30% by weight.

The proportion of compound B-1 is preferably 0 to 70% by weight based on the total weight of compound A, compound B, compound C, compound B-1, and other monomers. When the proportion of compound B-1 is within the above numerical range, the viscosity of the curable composition tends to decrease, and the spray coating properties tend to improve. From the viewpoint of spray coating properties, the proportion of Compound B-1 is more preferably 1 to 50% by mass, and 5 to 40% by mass of the total mass of Compound A, Compound B, Compound C, Compound B-1 and other monomers. is more preferable, 10 to 35% by weight is particularly preferable, and 15 to 30% by weight is most preferable.

When the curable composition according to one embodiment contains an ultraviolet absorber, the proportion of the ultraviolet absorber is from 0.05 to 0.05 of the total mass of Compound A, Compound B, Compound C, Compound B-1, and other monomers. It is preferably 20% by weight, more preferably 1 to 17% by weight, even more preferably 5 to 16% by weight.
If the proportion of the ultraviolet absorber is at least the above lower limit, the weather resistance of the cured product of the curable composition will further improve. If the proportion of the ultraviolet absorber is below the above upper limit, the curability will further improve.

When the curable composition according to one embodiment contains a photopolymerization initiator, the proportion of the photopolymerization initiator is determined from the viewpoint of obtaining a sufficient degree of polymerization: compound A, compound B, compound C, compound B-1 and It is preferably 0.05 to 25% by weight, more preferably 0.1 to 20% by weight of the total weight of other monomers. From the viewpoint of curability, it is more preferably 0.3 to 15% by mass or less.

(Production method)
In the method for producing a curable composition of the present invention, a compound A selected as a compound having a Hansen solubility parameter distance Ra (T) from point T of 1.377 to 3.000 MPa ^0.5 , and a compound B. Mix. Various types of stirrers can be used during mixing. Moreover, it is preferable to uniformly mix compound A and compound B.
At the time of mixing, compound C, compound B-1, other monomers, and other components may be further mixed as necessary.
Details and preferred embodiments of Compound A, Compound B, Compound C, Compound B-1, other monomers, and other components are as described above.
When selecting Compound A, it is preferable to use software to calculate the Hansen solubility parameter. The Hansen solubility parameter is as described in detail for Compound A.

(Application)
The curable composition of the present invention has excellent hot water resistance and adhesion. Further, the curable composition according to one embodiment has excellent spray coating properties, and excellent moisture and heat resistant adhesion. Therefore, the curable composition according to one embodiment can be suitably used for various automotive lamp lens hard coats, instrument hard coats, grill hard coats, exterior hard coats, and the like.

<Cured product>
The cured product of the present invention is a cured product obtained by curing the curable composition.
The cured product of the present invention can be obtained by curing the curable composition of the present invention by irradiating it with active energy rays such as ultraviolet rays. Examples of active energy rays include ultraviolet rays, electron beams, X-rays, infrared rays, and visible rays.

In one embodiment, when the curable composition is cured by ultraviolet irradiation, various ultraviolet irradiation devices can be used. As the light source of the ultraviolet irradiation device, a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, an LED-UV lamp, etc. can be used. The amount of ultraviolet ray irradiation is usually 10 to 10,000 mJ/cm ² , preferably 100 to 5,000 mJ/cm ² , and more preferably 150 to 3,000 mJ/cm ² .

When curing the curable composition by electron beam irradiation in one embodiment, various electron beam irradiation devices can be used. The amount of electron beam irradiation is usually 0.5 to 20 Mrad, preferably 1 to 15 Mrad.

In one embodiment, the temperature at which the curable composition is cured (the temperature at which active energy rays are irradiated) may be appropriately set in consideration of the heat resistance, thermal deformability, etc. of the base material. For example, the temperature is preferably 20 to 200°C, more preferably 60 to 150°C. The curing time is preferably, for example, 30 seconds to 1 hour, more preferably 1 minute to 15 minutes.

In one embodiment, when the curable composition contains an organic solvent, the organic solvent may be volatilized by drying the curable composition before irradiation with active energy rays.
The drying temperature may be appropriately set in consideration of the heat resistance and thermal deformability of the base material, the boiling point of the organic solvent, and the like. For example, the temperature is preferably 20 to 200°C, more preferably 60 to 150°C. The drying time is preferably, for example, 1 minute to 1 hour, more preferably 2 minutes to 15 minutes.

<Laminated body>
The laminate of the present invention includes a base material and a layer made of the cured product of the present invention (hereinafter also referred to as "cured product layer"). The cured material layer is laminated or composited with the base material. In one embodiment, the cured material layer may be provided on a part of the surface of the base material or may be provided on the entire surface.

(Base material)
The shape of the base material is not particularly limited. For example, the shape may be a film shape, a plate shape, or a geometric shape, but any shape may be used.
Examples of the material of the base material include:
Metals such as galvanized steel, zinc alloy plated steel, stainless steel, tin-plated steel;
Plastics such as polymethyl methacrylate resin, polycarbonate resin, polyester resin, polystyrene resin, ABS resin, AS resin, polyamide resin, polyarylate resin, polymethacrylimide resin, polyallyl diglycol carbonate resin;
can be mentioned.
As materials for these base materials, one type of metal or plastic may be used alone, or two or more types may be used in combination.

As the base material, a plastic base material is preferable since the provision of a cured material layer is highly useful (improvement in weather resistance, etc.). Examples of the plastic base material include a plastic base material containing at least one selected from the group consisting of polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, and polymethacrylimide resin.
Among these, polymethyl methacrylate resin and polycarbonate resin are preferred from the viewpoint of transparency and easy moldability. Furthermore, polycarbonate resin is more preferable from the viewpoint of heat resistance and impact resistance.

The thickness of the cured material layer is preferably 3 to 50 μm from the viewpoint of weather resistance and crack reduction. The thickness of the cured product layer can be adjusted by adjusting the thickness of the coating film of the curable composition applied to the substrate.

In one embodiment, the laminate may have a plurality of base materials. Moreover, in one embodiment, the laminate may have a plurality of cured material layers.
For example, multiple types of cured material layers may be laminated on the base material. Further, a plurality of base materials and a plurality of cured material layers may be laminated. When the base material is in the form of a film or a plate, a cured material layer may be laminated on one surface of the base material, or a cured material layer may be laminated on both surfaces of the base material.

The laminate can be manufactured by coating the surface of a base material with a curable composition and then curing the curable composition to form a cured product.
In one embodiment, the laminate can be produced by, for example, coating a substrate with the curable composition of the present invention to form a coating film, and then irradiating the coating film with active energy rays to cure it.

The coating method is not particularly limited. Various methods can be used. Examples include methods such as brush coating, bar coating, spray coating, dip coating, spin coating, and curtain coating, but are not limited to these examples.
Since the curable composition of the present invention tends to have a viscosity suitable for spray coating, a spray coating method is preferred as the coating method.
The coating film can be cured in the same manner as the curable composition described above.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following description. "Parts" in the examples represent "parts by mass."

<Raw materials and abbreviations>
The raw materials used and their abbreviations are as follows.

(Compound A)
- MTG-A: Methoxy-triethylene glycol acrylate (Ra(T): 1.407, δd: 16.32, δp: 5.14, δh: 7.07, Mw: 218.2).
- HE-EA: Hexyloxyethoxyethyl acrylate (Ra(T): 1.387, δd: 16.15, δp: 3.82, δh: 5.39, Mw: 244.3).
- C9DA: 1.9-nonanediol diacrylate (Ra(T): 2.446, δd: 16.20, δp: 3.25, δh: 4.24, Mw: 268.3).

(Compound B)
- TMPTA: Trimethylolpropane triacrylate (trade name Viscoat #295, manufactured by Osaka Organic Chemical Industry Co., Ltd.).
- M-315: A mixture of isocyanuric acid EO-modified diacrylate and isocyanuric acid EO-modified triacrylate (trade name: Aronix M-315, manufactured by Toagosei Co., Ltd.).
- DPCA-20: Dipentaerythritol caprolactone acrylic ester (trade name KAYARAD DPCA-20, manufactured by Nippon Kayaku Co., Ltd.).

(Compound C)
- C1-1: Polyfunctional urethane acrylate having an acryloyl group, number of (meth)acryloyl functional groups: 2, mass average molecular weight (Mw): 4100, obtained in Synthesis Example 1 below.
- C1-2: Polyfunctional urethane acrylate having an acryloyl group, number of (meth)acryloyl functional groups: 2, mass average molecular weight (Mw): 3600, obtained in Synthesis Example 2 below.

(Synthesis Example 1: Synthesis of C1-1)
530 parts of dicyclohexylmethane diisocyanate and 300 ppm of di-n-butyltin dilaurate were placed in a flask equipped with a dropping funnel with a heat-retaining function, a reflux condenser, a stirrer, and a thermometer, and the mixture was heated to 50°C. Then, as a polyol compound, 700 parts (1 mol) of Kuraray Polyol C-770, manufactured by Kuraray Co., Ltd., which is a polycarbonate diol, was added dropwise over 2 hours. After stirring at 50°C for 2 hours, the temperature was raised to 70°C over 1 hour. Thereafter, 239 parts of 2-hydroxyethyl acrylate was added dropwise over 2 hours, and the mixture was further stirred for 2 hours to obtain urethane acrylate C1-1.

(Synthesis Example 2: Synthesis of C1-2)
A flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer was charged with 530 parts of dicyclohexylmethane diisocyanate and 300 ppm of di-n-butyltin dilaurate, and heated to 50°C. Thereafter, 441 parts of PTG-850SN manufactured by Hodogaya Chemical Industry Co., Ltd. and 69 parts of 4-hydroxy-N-(2-hydroxyethyl)-N-methylbutanamide as polyol compounds were added dropwise over 2 hours. After stirring at 50°C for 2 hours, the temperature was raised to 70°C over 1 hour. Thereafter, 262 parts of 2-hydroxyethyl acrylate was added dropwise over 2 hours, and the mixture was further stirred for 2 hours to obtain urethane acrylate C1-2.

(Compound B-1)
- CN2303: Acrylate having a hyperbranched structure (manufactured by Sartomer), number of (meth)acryloyl functional groups: 6, viscosity (25°C): 375 mPa·s.
- CN2304: Acrylate having a hyperbranched structure (manufactured by Sartomer), number of (meth)acryloyl functional groups: 18, viscosity (25°C): 750 mPa·s.

(other monomers)
- C6DA: 1,6-hexanediol diacrylate (Ra(T): 1.376, δd: 16.33, δp: 3.92, δh: 5.08, Mw: 226.3).
-4-HBA: 4-hydroxybutyl acrylate (Ra(T): 5.246, δd: 16.73, δp: 6.59, δh: 10.76, Mw: 144.2).
- ISTA: Isostearyl acrylate (Ra(T): 5.058, δd: 15.80, δp: 1.78, δh: 2.17, Mw: 324.5).
-2-EHA: 2-ethylhexyl acrylate (Ra(T): 3.044, δd: 15.95, δp: 2.86, δh: 4.01, Mw: 184.3).

(other ingredients)
・Tinuvin 400 (ultraviolet absorber): 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis-(2,4-dimethylphenyl) -1,3,5-triazine and 2-[4-[(2-hydroxy-3-tridesiloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis-(2,4-dimethylphenyl)- A mixture of 1,3,5-triazine and 1-methoxy-2-propanol (manufactured by BASF).
・Tinuvin 405 (ultraviolet absorber): 2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis-(2,4- dimethylphenyl)-1,3,5-triazine (manufactured by BASF).
- Tinuvin 479 (ultraviolet absorber): Structure not disclosed (manufactured by BASF).

- Omnirad TPO (photoinitiator): 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
- Omnirad 184 (photoinitiator): 1-hydroxycyclohexyl-phenyl ketone.

(others)
・Tinuvin 123 (light stabilizer): reaction of decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) ester, 1,1-dimethylethyl hydroperoxide and octane Product (manufactured by BASF).
・BYK-333 (silicon leveling agent): Polyether modified polydimethylsiloxane (manufactured by BYK).

- PGM (organic solvent): Propylene glycol monomethyl ether.

<Measurement method>
The evaluation method for physical property values is as follows.
δd, δp, and δh: The effect of van der Waals dispersion force δd, the effect of dipole-dipole force δp, and the effect of hydrogen bond force δh on the Hansen solubility parameter of each compound were determined using computer software (Hansen Solubility Parameters in Practice (HSPiP) Ver. Estimation was made from the molecular structure of each compound using 5.3.02.
Ra(T): The Hansen solubility parameter distance between each compound and point T is δd, δp, and δh of each compound alone, and δd _T , δp of the polycarbonate resin shown in the following formulas (M), (N), and (O). _T and δh _T were calculated using the following formula (L). δd, δp, and δh of each compound alone were estimated using computer software (Hansen Solubility Parameters in Practice (HSPiP) Ver. 5.3.02. The coordinates of point T, δd _T , δp _T , and δh _T , are as follows: When performing the above-mentioned test piece dissolution experiment, the sphere radius 2 obtained by Hansen dissolution sphere analysis of the distribution state in the three-dimensional space represented by δd, δp, and δh of the compound group in which the test piece swelled. The center coordinates of the sphere t are .00 MPa ^0.5 , and were estimated using HSPiP Ver. 5.3.02. The test piece dissolution experiment related to one embodiment was performed according to the above-mentioned procedure.
Ra(S)=[4×(δd−δd _T ) ² +(δp−δp _T ) ² +(δh−δh _T ) ² ] ^0.5 ...Formula (L);
δd _T =16.58...Formula (M)
δp _T =5.00...Formula (N)
δh _T =5.77...Formula (O)

(Viscosity of compound B-1 (25°C))
The viscosity (25° C.) of Compound B-1 was measured using an E-type viscometer TVE-20H (manufactured by Toki Sangyo Co., Ltd.).

(Viscosity of curable composition (25°C))
After diluting the curable composition with PGM so that the solid content concentration of the curable composition becomes the concentration listed in Table 3, the viscosity ( 25°C) was measured.

(Mass average molecular weight (Mw))
The mass average molecular weight (Mw) of the polymer (compound C, etc.) is the molecular weight measured in terms of standard polystyrene by gel permeation chromatography (GPC method) under the following conditions.
Equipment: High-speed GPC device HLC-8320GPC type manufactured by Tosoh Corporation UV (ultraviolet) detector: UV-8320 type manufactured by Tosoh Corporation Flow rate: 0.35mL/min
Inlet temperature: 40℃
Oven temperature: 40℃
RI (differential refractometer) temperature: 40°C
UV wavelength: 254nm
Sample injection volume: 10μL
Column: Three columns were connected in the following order (1), (2), and (3).
(1) TSKgel superHZM-M manufactured by Tosoh Corporation (4.6mm ID x 15cmL)
(2) TSKgel superHZM-M manufactured by Tosoh Corporation (4.6mm ID x 15cmL)
(3) TSKgel HZ2000 manufactured by Tosoh Corporation (4.6mm ID x 15cmL)
Guard column: TSKguardcolumn SuperHZ-L (4.6mm ID x 3.5cmL) manufactured by Tosoh Corporation
Solvent: THF (stabilizer BHT)
The sample concentration was adjusted so that the resin content was 0.2% by mass.

<Evaluation method>
(Preparation of evaluation sample)
The curable composition was applied to a polycarbonate resin injection molded plate (Panlite L-1225Z-100 (trade name), manufactured by Teijin Ltd., 3 mm thick) by spraying or using a bar coater (#14). It was heated and dried in an IR (far infrared) drying oven at 70° C. for 240 seconds to form a coating film. Next, the formed coating film was exposed to an irradiation amount of 2000 mJ/cm ² (wavelength 340 to 380 nm) using a high-pressure mercury lamp in an air atmosphere using an ultraviolet light meter UV-351 manufactured by Oak Seisakusho Co., Ltd. The coating film was cured by irradiation with ultraviolet rays to form a cured layer. The thickness of the cured material layer was 9 μm. Thereby, a laminate having a polycarbonate resin injection molded plate and a cured material layer was obtained. The following evaluations were performed using the obtained laminate as an evaluation sample.

(Hot water adhesion)
The evaluation sample was immersed in warm water at 80° C. using a constant temperature water bath, and changes in the appearance of the evaluation sample after 8 hours were visually confirmed. Thereafter, 100 crosscuts of 1 mm ² were made in the cured coating film on the sample, reaching the base material at 1 mm intervals. Cellophane tape (manufactured by Nichiban Co., Ltd.) was applied to the surface of the cured coating film with cross cuts, and then rapidly peeled off, and the peeled off grid was counted. The criteria for determining hot water adhesion are as follows.
・Judgment criteria (checkerboard adhesion test)
5B (best): No peeling.
4B (Good): Fine peeling is seen at the cut portion, etc., but there is no peeling in the squares.
3B (Acceptable): Less than half of the squares are peeled off.
2B (Poor): Half or more of the squares peel off.
1B (unacceptable): All the coating films in the squares peeled off.

(Moisture heat resistant adhesion)
The evaluation sample was placed in an environment of 70° C. and 95% RH using a constant temperature and humidity machine, and changes in the appearance of the evaluation sample after 240 hours were visually confirmed. Moisture and heat resistant adhesion was evaluated by the same method as the hot water resistant adhesion. The criteria for determining moisture and heat resistant adhesion are as follows.
・Judgment criteria (checkerboard adhesion test)
5B (best): No peeling.
4B (Good): Fine peeling is seen at the cut portion, etc., but there is no peeling in the squares.
3B (Acceptable): Less than half of the squares are peeled off.
2B (Poor): Half or more of the squares peel off.
1B (unacceptable): All the coating films in the squares peeled off.

(Pencil hardness)
Pencil hardness evaluation is performed according to JIS K5600-5-4. Pencils of various hardnesses are placed on the surface of the evaluation sample at a 45° angle, a load is applied, and a scratch test is performed to find the hardest pencil that will not cause scratches. The hardness was defined as pencil hardness.

(Spray paintability)
The appearance of the evaluation samples was visually confirmed, and the spray coating properties at 25° C. and 50% RH were evaluated. The criteria for determining spray paintability are as follows.
- Judgment criteria A (good): There are no wrinkles or whitening on the surface of the evaluation sample.
B (Acceptable): Wrinkles and whitened areas are observed on the surface of the evaluation sample.
C (unacceptable): The curable composition had too high a viscosity to be spray coated, so bar coater coating was performed.

<Example 1>
15.6 parts of MTG-A, 3.4 parts of 2-EHA, 34.4 parts of DPCA-20, 21.9 parts of CN2303, 14.1 parts of C1-1, 10.6 parts of C1-2. 9.4 parts of Tinuvin 405, 5.0 parts of Omnirad TPO, 5.0 parts of Omnirad 184, 0.9 parts of Tinuvin 123, and 0.1 part of BYK-333 were uniformly mixed. Thereafter, using PGM as a diluting solvent, the mixture was diluted to have a solid content concentration shown in Table 3 to obtain a curable composition. The obtained curable composition was sprayed onto a polycarbonate resin injection molded plate (Panlite L-1225Z-100 (trade name), manufactured by Teijin Ltd., 3 mm thick). It was heated and dried in an IR (far infrared) drying oven at 70° C. for 240 seconds to form a coating film. Next, the formed coating film was exposed to an irradiation amount of 2000 mJ/cm ² (wavelength 340 to 380 nm) using a high-pressure mercury lamp in an air atmosphere using an ultraviolet light meter UV-351 manufactured by Oak Seisakusho Co., Ltd. The coating film was cured by irradiation with ultraviolet rays to form a cured layer. The thickness of the cured material layer was 9 μm. In this way, an evaluation sample having a polycarbonate resin injection molded plate and a cured material layer was produced. Table 3 shows the evaluation results of the obtained curable composition and evaluation samples.

<Examples 2 to 5, Comparative Examples 1 to 5>
A curable composition was prepared by the same method as in Example 1, except that the composition of the curable composition was changed as shown in Tables 1 and 2, and an evaluation sample was also produced. Table 3 shows the evaluation results of the obtained curable composition and evaluation samples. The numerical values of the compositions of the curable compositions shown in Tables 1 and 2 are expressed in grams (g).

As shown in Table 3, in Examples 1 to 5, cured coatings with excellent hot water adhesion and spray coating properties were obtained. Furthermore, in Examples 1 to 4, cured coatings were obtained that were excellent in not only hot water resistant adhesion but also moist heat resistant adhesion.
On the other hand, in Comparative Examples 1 to 4, which did not contain Compound A, the cured coatings had poor hot water resistant adhesion and moist heat resistant adhesion, as well as poor spray paintability.
Furthermore, in Comparative Example 5, which did not contain Compound B, the cured film had poor hot water resistant adhesion, moist heat resistant adhesion, and pencil hardness.

According to the curable composition of the present invention, a coating film having excellent hot water resistant adhesion and moist heat resistant adhesion can be obtained.
The cured product of the present invention has excellent hot water resistant adhesion and moist heat resistant adhesion.
The laminate of the present invention has a layer made of a cured product that has excellent hot water resistant adhesion and moist heat resistant adhesion.
According to the method for producing a curable composition of the present invention, a curable composition that is excellent in hot water resistant adhesion and moist heat resistant adhesion when formed into a coating film is obtained.
According to the method for producing a cured product of the present invention, a cured product having excellent hot water resistant adhesion and moist heat resistant adhesion can be obtained.
According to the method for manufacturing a laminate of the present invention, a laminate having a layer made of a cured product having excellent hot water resistant adhesion and moist heat resistant adhesion can be obtained.
By using the cured product and laminate obtained using the curable composition of the present invention, a functional coating with excellent scratch resistance and weather resistance can be applied to the polycarbonate resin surface for a long period of time in a wet state. It becomes possible to maintain adhesion. This makes it possible to suppress deterioration such as scratches and yellowing of the polycarbonate resin used outdoors or in humid environments, and to improve the durability of the member.

Claims (11)

A curable composition containing the following compound A and the following compound B.
Compound A: A compound whose Ra (T) calculated from the following formula (L) is 1.377 to 3.000 MPa ^0.5 . (However, the following compound B is excluded.)
Compound B: A polyfunctional (meth)acrylate monomer having three or more (meth)acryloyl groups.
Ra (T) = [4×(δd-δd _T ) ² + (δp-δp _T ) ² + (δh-δh _T ) ² ] ^0.5 ...Formula (L)
In formula (L),
Ra(T) is a Hansen solubility parameter distance indicating the vector distance between the compound A alone and point T in a three-dimensional space represented by δd, δp, and δh in the Hansen solubility parameter;
δd is the effect of van der Waals dispersion force on the Hansen solubility parameter of Compound A alone;
δp is the effect of dipole-dipole force on the Hansen solubility parameter of compound A alone;
δh is the effect of hydrogen bonding force on the Hansen solubility parameter of Compound A alone;
δd _T , δp _T , and δh _T are the coordinates of point T, which are the values of the following formulas (M), (N), and (O).
δd _T =16.58...Formula (M)
δp _T =5.00...Formula (N)
δh _T =5.77...Formula (O) The curable composition according to claim 1, further comprising the following compound B-1.
Compound B-1: A (meth)acrylate having at least one type selected from the group consisting of a dendrimer structure and a hyperbranched structure (excluding the above compound B). The curable composition according to claim 1, wherein the curable composition has a viscosity at 25°C of 250 mPa·s or less. A cured product of the curable composition according to any one of claims 1 to 3. A laminate comprising a base material and a layer made of the cured product according to claim 4. The laminate according to claim 5, wherein the base material is a polycarbonate resin. Includes mixing a compound A (excluding the following compound B) whose Ra (T) calculated from the following formula (L) is 1.377 to 3.000 MPa ^0.5 and the following compound B , a method for producing a curable composition.
Compound B: A polyfunctional (meth)acrylate monomer having three or more (meth)acryloyl groups.
Ra (T) = [4×(δd-δd _T ) ² + (δp-δp _T ) ² + (δh-δh _T ) ² ] ^0.5 ...Formula (L)
In formula (L),
Ra(T) is a Hansen solubility parameter distance indicating the vector distance between the compound A alone and point T in a three-dimensional space represented by δd, δp, and δh in the Hansen solubility parameter;
δd is the effect of van der Waals dispersion force on the Hansen solubility parameter of Compound A alone;
δp is the effect of dipole-dipole force on the Hansen solubility parameter of compound A alone;
δh is the effect of hydrogen bonding force on the Hansen solubility parameter of compound A alone;
δd _T , δp _T , and δh _T are the coordinates of point T, which are the values of the following formulas (M), (N), and (O).
δd _T =16.58...Formula (M)
δp _T =5.00...Formula (N)
δh _T =5.77...Formula (O) The manufacturing method according to claim 7, further comprising mixing the following compound B-1.
Compound B-1: (meth)acrylate having at least one selected from the group consisting of a dendrimer structure and a hyperbranched structure (excluding the above compound B). A method for producing a cured product, comprising curing the curable composition obtained by the production method according to claim 7 or 8. A method for producing a laminate having a base material and a layer made of a cured product, the method comprising:
A method for producing a laminate, the method comprising curing the curable composition obtained by the production method according to claim 7 or claim 8 to obtain the cured product. The manufacturing method according to claim 10, wherein the base material is a polycarbonate resin.