JP7369671B2 - Coating agents and laminates - Google Patents

Description

The present invention relates to a coating agent applied to the surface of a building material or the like to impart matte properties, and a laminate using the coating agent.

In order to maintain the beautiful appearance of building materials used for the interior of buildings, such as baseboards, decorative boards, waist walls, flooring materials, etc., coating agents have traditionally been used to form a film on the surface to provide stain resistance. things are being done. In addition, in order to suppress the so-called "shininess" and create a calm atmosphere in these building materials, coating agents are also used to impart matte properties.

As coating agents that can impart such matting properties and antifouling properties, Patent Document 1 describes active energy ray-polymerizable acrylate monomers with bifunctionality or more, active energy ray-polymerizable acrylate oligomers with trifunctionality or more, Active energy ray-curable coating compositions for building material top coats containing a polymerization initiator, wax and/or resin bead components have been proposed.

Japanese Patent Application Publication No. 2005-047952

However, all of the coating compositions disclosed in Patent Document 1 had gloss values of 17 or more, and did not have sufficient matte properties.

The present invention has been made in view of these problems, and aims to provide a coating agent that can form a film with excellent matte properties, and a laminate using this coating agent.

As a result of various studies, the present inventors have found that the above object can be achieved by the following invention.

A coating agent according to one aspect of the present invention is a coating agent containing urethane acrylate having a functional group number of 3 or less, 2-hydroxyethyl acrylate, fluorine-based acrylate, matte particles, and a photopolymerization initiator. The coating agent has a gloss value of 15 or less after curing.

Further, a laminate according to another aspect of the present invention is a laminate including a base material and a film provided on the surface of the base material, and the film is a cured product of the coating agent.

According to the present invention, it is possible to provide a coating agent capable of forming a film with excellent matte properties, and a laminate having a film with excellent matte properties.

The coating agent according to the present embodiment is applied to the surface of a base material and cured to form a film, thereby suppressing gloss on the surface of the base material.

The coating agent according to the present embodiment is a coating agent containing urethane acrylate having a functional group number of 3 or less, 2-hydroxyethyl acrylate, fluorine-based acrylate, matte particles, and a photopolymerization initiator, The gloss value after curing of the coating agent is 15 or less. Therefore, the coating agent according to the present embodiment can form a film with excellent matte properties, and by applying the coating agent according to the present embodiment on the surface of the base material and curing it, the coating agent can be applied to the surface of the base material. Can reduce surface gloss.

Urethane acrylate and 2-hydroxyethyl acrylate having a functional group number of 3 or less are the main components of the coating agent and function as a binder.

Urethane acrylate having a functional group number of 3 or less has appropriate flexibility and is less prone to cracking, that is, it is a resin with good crack resistance. Therefore, the coating agent according to this embodiment has good crack resistance in the state of a film formed on a soft resin base material.

The flexibility of urethane acrylate varies depending on the number of functional groups, and the greater the number of functional groups, the harder and brittle the coating agent becomes after curing, and the lower the crack resistance. In this embodiment, the number of functional groups in the urethane acrylate is set to 3 or less in order to impart appropriate flexibility to the cured resin and improve crack resistance. From the viewpoint of maintaining a constant film strength, the number of functional groups in the urethane acrylate is preferably 2 or more.

In the coating agent according to the present embodiment, the urethane acrylate having a functional group number of 3 or less may be a mixture of urethane acrylate and an acrylate monomer such that the average functional group number is 3 or less, for example, the functional group number is 3 to 3. 0 to 50 parts by weight of an acrylate monomer having 1 to 2 functional groups can be mixed with 50 to 100 parts by weight of the urethane acrylate No. 5. By mixing the urethane acrylate and the acrylate monomer, the handling properties of the coating agent are improved, and the productivity of the laminate described below is improved. Furthermore, in the coating agent according to the present embodiment, it is preferable to mix 20 to 50 parts by mass of an acrylate monomer having 1 to 2 functional groups to 50 to 80 parts by mass of urethane acrylate having 3 to 5 functional groups.

2-Hydroxyethyl acrylate is an acrylate monomer having one functional group, and is a resin that imparts matte properties to the coating agent after curing.

The mass ratio of urethane acrylate with a functional group number of 3 or less and 2-hydroxyethyl acrylate is preferably 45:55 to 70:30 (the ratio of the mass of urethane acrylate with a functional group number of 3 or less to the mass of 2-hydroxyethyl acrylate) The value is preferably 45/55 to 70/30). By setting the mass ratio within this range, the adhesion of the coating agent to the base material can be improved, and the coating agent after curing can be made more difficult to stain. The mass ratio of urethane acrylate having a functional group number of 3 or less and 2-hydroxyethyl acrylate is more preferably 50:50 or more, and more preferably 65:35 or less.

Fluorine-based acrylate is a resin that imparts stain resistance and water repellency to the coating agent after hardening. As the fluorine-based acrylate, for example, a fluorine-modified urethane acrylate, an acrylate having a fluoroalkyl structure, or a perfluoropolyether structure can be used. The coating agent according to the present embodiment preferably contains 1 to 10 parts by mass of fluorine-based acrylate based on a total of 100 parts by mass of urethane acrylate having a functional group number of 3 or less and 2-hydroxyethyl acrylate. By setting the content of fluorine-based acrylate within this range, the coating agent after curing can be made more difficult to stain. The content of the fluorine-based acrylate is more preferably 3 parts by mass or more, and more preferably 8 parts by mass or less.

The matte particles are particles for imparting matte properties to the coating agent after hardening. The coating agent according to the present embodiment preferably contains 5 to 15 parts by mass of matte particles based on a total of 100 parts by mass of urethane acrylate having a functional group number of 3 or less and 2-hydroxyethyl acrylate. By setting the content of the matting particles within this range, sufficient matting properties can be obtained. The content of the matte particles is more preferably 7 parts by mass or more, and more preferably 12 parts by mass or less.

For the matting particles, for example, a particulate matting material can be used alone, or a combination of a matting material and a particulate wax can also be used.

For example, inorganic particles such as silica particles, aluminum oxide particles, and titanium oxide particles can be used as the matte material. Among these oriented particles, silica particles are preferable in consideration of the ability to develop matte properties and transparency. Furthermore, particles that have been surface-treated, such as polyether-modified silicone-treated silica, can also be used. The average particle size of the matte material is preferably 1 to 5 μm. In this embodiment, the average particle size of the matte material refers to the value of the median diameter (d50).

As the wax, for example, polyolefin wax, paraffin wax, microcrystalline wax, aliphatic wax, etc. can be used, and as the polyolefin wax, ordinary polyethylene wax, PTFE-modified polyethylene wax, etc. can be used. The average particle size of the wax is preferably 1 to 10 μm. In this embodiment, the average particle size of wax refers to the value of the median diameter (d50).

When the matte particles include a matte material and wax, it is preferable that the matte material is silica particles and the wax is polyethylene wax, and the mass of the matte material and wax contained in the matte particles is The ratio is preferably 3:7 to 7:3 (the ratio of the mass of silica particles to the mass of polyethylene wax is preferably 3/7 to 7/3). The polyethylene wax may be a normal polyethylene wax or a PTFE-modified polyethylene wax. By setting the mass ratio of the matting material to the wax within this range, high matting properties and stain resistance can be obtained. The mass ratio of the matte material and wax contained in the matte particles is more preferably 4:6 or more, and more preferably 6:4 or less.

The photopolymerization initiator has the effect of starting the curing of the urethane acrylate by irradiating the uncured coating agent with ultraviolet rays. Furthermore, the photopolymerization initiator can improve the antifouling properties of the coating agent after curing.

The coating agent according to the present embodiment preferably contains 2.5 to 3.5 parts by mass of a photopolymerization initiator based on a total of 100 parts by mass of urethane acrylate having a functional group number of 3 or less and 2-hydroxyethyl acrylate. . By setting the content of the photopolymerization initiator within this range, it is possible to sufficiently obtain the effect of initiating curing of the urethane acrylate by irradiation with ultraviolet rays, and it is also possible to make the coating agent after curing more difficult to stain.

Examples of the photopolymerization initiator include benzophenone, benzoin ethyl ether, 2,2-dimethoxy-2-phenylacetophenone, acetophenone, xanthone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybezophenone, N,N,N',N'-tetramethyl-4,4'-diaminobenzophenone, benzoinpropyl ether, benzyl dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one , 1-hydroxycyclohexylphenyl ketone, one or more of them can be used.

In addition to the above components, the coating agent according to the present embodiment may optionally contain other components such as antibacterial agents, antiviral agents, deodorants, etc. as additives. As the antibacterial agent, for example, inorganic antibacterial agents such as silver ion type or copper ion type, organic antibacterial agents such as organic synthetic antibacterial agents and organic natural antibacterial agents, photocatalysts, etc. can be used. As the antiviral agent, for example, an inorganic antiviral agent such as a silver ion type or a copper ion type, an organic antiviral agent such as a quaternary ammonium salt or an ionic group-containing polymer type, a photocatalyst, etc. can be used.

The coating agent according to this embodiment has a gloss value of 15 or less after curing. The gloss value is a value indicating the degree of matteness, and the smaller the gloss value, the higher the matteness. The gloss value can be measured as 60 degree specular gloss according to JIS Z 8741-1997.

Next, the laminate according to this embodiment will be explained. The laminate according to this embodiment includes a base material and a film provided on the surface of the base material, and the film is a cured product of the coating agent according to the above-described embodiment. Therefore, the laminate according to this embodiment has a film with excellent matte properties, and the surface gloss is suppressed.

The base material can be in the form of a sheet, for example. In this case, by applying a coating agent to one side of a sheet-like base material and irradiating it with ultraviolet rays, the urethane acrylate can be cured by a photopolymerization initiator to form a film. This completes the laminate.

The thickness of the film is preferably 5 μm or more. Further, the thickness is preferably 30 μm or less, and more preferably 15 μm or less. This makes it possible to obtain a film that is not only matte but also has excellent crack resistance. When the thickness of the film is less than 5 μm, the smoothness of the film surface decreases due to the influence of the matte particles, making it easy to stain. When the thickness of the film is greater than 30 μm, the brittleness of the film increases and crack resistance decreases.

The laminate is bonded, for example, to the surface of a floor base using an adhesive, thereby forming a matte flooring material. Moreover, the laminate can be applied not only to flooring materials but also to building materials such as baseboards, decorative boards, and waist walls. In this case as well, the laminate may be adhered to the surface of the base material of each building material.

The base material is preferably an extrusion molded body of resin. Further, the base material is preferably made of a soft resin such as soft PVC.

This specification discloses various techniques as described above, and the main techniques are summarized below.

As described above, the coating agent according to one aspect of the present invention includes a urethane acrylate having a functional group number of 3 or less, 2-hydroxyethyl acrylate, a fluorine-based acrylate, matte particles, and a photopolymerization initiator. The coating agent contains a gloss value of 15 or less after curing.

According to this configuration, a coating agent capable of forming a film with excellent matte properties can be obtained.

In the coating agent having the above configuration, the mass ratio of the urethane acrylate and the 2-hydroxyethyl acrylate is 45:55 to 70:30, and based on a total of 100 parts by mass of the urethane acrylate and the 2-hydroxyethyl acrylate, The composition may contain 1 to 10 parts by mass of the fluorine-based acrylate, 5 to 15 parts by mass of the matte particles, and 2.5 to 3.5 parts by mass of the photopolymerization initiator.

This makes it possible to more reliably obtain a coating agent capable of forming a film with excellent matte properties.

In the coating agent having the above configuration, the matte particles may include silica particles. Further, in the coating agent having the above configuration, the matte particles include silica particles and polyethylene wax, and the mass ratio of the silica particles and the polyethylene wax contained in the matte particles is 3:7 to 7:3. There may be.

Thereby, a coating agent capable of forming a film with excellent antifouling properties can be obtained.

The coating agent having the above structure may contain 0.1 to 5 parts by mass of at least one of an antibacterial agent and an antiviral agent based on a total of 100 parts by mass of the urethane acrylate and the 2-hydroxyethyl acrylate.

Thereby, a coating agent capable of forming a film with excellent antibacterial and/or antiviral properties can be obtained.

Further, a laminate according to another aspect of the present invention is a laminate including a base material and a film provided on the surface of the base material, and the film is a cured product of the coating agent.

According to this configuration, a laminate having a film with excellent matte properties can be obtained.

In the laminate having the above structure, the base material may be an extrusion molded body.

According to this configuration, a long laminate can be obtained more easily.

Hereinafter, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples, and can be practiced with modifications within the scope that fits the spirit of the preceding and following examples. All of them are included within the technical scope of the present invention.

[Test Example 1]
A coating agent was prepared by mixing each raw material at the component ratios shown in Tables 1 and 2 (the units of numerical values for components in the tables are parts by mass). The base material used was a sheet-shaped soft PVC extrusion molded body with a length of 100 mm, a width of 100 mm, and a thickness of 2 mm. The prepared coating agent was applied to the surface of the base material and cured by irradiation with ultraviolet rays to form a film with a thickness of 10 μm, which was used as a sample.

The raw materials for the coating agent used are as follows.
Urethane acrylate with a functional group number of 3 or less: Urethane acrylate EBECRYL8800 with a functional group number of 2.5 manufactured by Daicel Allnex Corporation (in Tables 1 and 2, it is simply referred to as "urethane acrylate").
2-Hydroxyethyl acrylate: Light ester HOA (N) manufactured by Kyoeisha Chemical Co., Ltd. (described as "HEA" in Tables 1 and 2).
Antifouling agent: Fluorine-modified urethane acrylate EBECRYL8110 manufactured by Daicel Allnex Corporation
Matte particles (silica particles): Evonik polyether-modified silicone-treated silica ACEMATT3600
Matte particles (wax): BYK-Chemie's polyethylene wax CERAFLOUR925 (described as "wax 1" in Tables 1 and 2), or PTFE-modified polyethylene wax CERAFLOUR996 manufactured by BYK-Chemie (described as "wax 1" in Tables 1 and 2); 2”.)
Photopolymerization initiator: Alkylphenone photopolymerization initiator omnirad184 manufactured by IGM Resins

The samples of Examples 1 to 9 and Comparative Examples 1 to 8 obtained as described above were subjected to an evaluation test for matteness (60° gloss value).

According to JIS Z 8741-1997, the 60 degree specular gloss (60 degree gloss value) of the film formed on the sample was measured using a gloss meter. A 60° gloss value of 15 or less defined in the present invention was considered to be a pass, and a value greater than 15 was considered a fail.

The measured 60° gloss values are shown in Tables 1 and 2 above, together with the component proportions of each sample.

As can be seen from Tables 1 and 2, the samples of Examples 1 to 14 had a 60° gloss value of 15 or less and had excellent matte properties. On the other hand, in Comparative Examples 1 and 2, the 60° gloss value was as large as 25, and the matte properties were poor.

The reason why the 60° gloss value was large in Comparative Example 1 and Comparative Example 2 is that the mass ratio of urethane acrylate with a functional group number of 3 or less and 2-hydroxyethyl acrylate (HEA) was in the preferable range of 80:20 (45:55). 70:30), which may have had an effect.

[Test Example 2]
For Examples 1 to 14 in which the gloss value was 15 or less, the following tests were conducted.

[Heel mark resistance (stain resistance)]
According to JIS K 3920, the heel mark resistance of the film formed on the sample was tested using a heel mark tester. Heel mark resistance (stain resistance) was evaluated based on the ratio of heel marks attached to the film after the test based on the following criteria.
◎: Less than 5% ○: 5% or more and less than 10% △: 10% or more and less than 20% ▲: 20% or more and less than 50% ×: 50% or more

[Adhesion]
In order to evaluate the adhesion of the film formed on the sample, a checkerboard peeling test was conducted in which cuts were made in the film with a total of 100 squares, 10 squares vertically and 10 squares, and a tape was attached to the film and then peeled off. Based on the ratio of the number of peeled squares to the total number of squares, the adhesion of the film was evaluated according to the following criteria.
○: Peeling less than 10% ×: Peeling 10% or more

The evaluation results for the above items are shown in Tables 3 and 4.

As can be seen from Tables 3 and 4, regarding the heel mark resistance (stain resistance) of the coating, Examples 1 to 5, 8, 9, 11, and 13 (ratings ◎, ○, △) were compared to Example 6. , 7, 10, 12, and 14 (ratings ▲, ×). Regarding adhesion, Examples 1 to 5, 8 to 11, 13, and 14 (rating ○) were better than Examples 6, 7, and 12 (rating ×).

Note that the heel mark resistance of the base material without a film formed on its surface was also evaluated, and the evaluation was poor.

In Examples 6, 7, and 12, the adhesion was evaluated as ×, and the heel mark resistance was evaluated as ▲ or ×. This is thought to be due to the fact that the mass ratio of urethane acrylate with a functional group number of 3 or less and 2-hydroxyethyl acrylate (HEA) was 40:60, which was smaller than the preferred range (45:55 to 70:30). Conceivable.

In Example 10, the evaluation of heel mark resistance was ▲. This is because the content of the photopolymerization initiator was higher than the preferred range (2.5 to 3.5 parts by mass), so the curing of the film progressed rapidly, and the unevenness caused by shrinkage of the film was caused by the photopolymerization initiator. This is thought to be due to the fact that the content of was larger than in Examples 8 and 9, which were within a preferable range.

In Example 14, the heel mark resistance was evaluated as poor. This is thought to be due to the fact that the matte particles were only the PTFE-modified polyethylene wax CERAFLOUR 996 (wax 2) and did not contain silica particles.

[Test Example 3]
A coating agent was prepared by mixing each raw material in the component proportions shown in Table 5 (the units of component values in the table are parts by mass). The coating agents of Example 15 and Example 16 are obtained by adding an antibacterial agent or an antiviral agent to the coating agent of Example 2, and the sample preparation conditions differ in that they contain an antibacterial agent or an antiviral agent. The rest was the same as in Example 2. The antibacterial agents and antivirals used are as follows.
Antibacterial agent: Bactekiller, a silver-based antibacterial agent manufactured by Fuji Chemical Co., Ltd. Antiviral agent: Willtaker, an ionic group-containing polymer antiviral agent manufactured by Sekisui Material Solutions Co., Ltd.

The films formed on the samples of Examples 15 and 16 were subjected to an evaluation test for matteness (60° gloss value) and an evaluation test for antibacterial or antiviral properties, respectively. The antibacterial evaluation test was conducted in accordance with the film adhesion method of JIS Z 2801, and the antiviral evaluation test was conducted with respect to influenza A virus and feline calicivirus in accordance with ISO21702.

When the antibacterial activity value was 2.0 or more or the antiviral activity value was 2.0 or more, the antibacterial or antiviral property was evaluated as ○. The evaluation results for these items are shown in Table 5 together with the component ratios.

As a result, in Example 15, the 60° gloss value was 6, indicating excellent matting properties, and the antibacterial property was evaluated as ○, confirming that the film had antibacterial properties.

In Example 16, the 60° gloss value was 6, and it had excellent matting properties, and the antiviral properties were evaluated as ○ for both influenza A virus and feline calicivirus, and the film showed no resistance. It was confirmed that it was viral.

It was confirmed that both the samples of Examples 15 and 16 had heel mark resistance and adhesion comparable to those of Example 2.

Claims (6)

A coating agent comprising urethane acrylate having a functional group number of 3 or less, 2-hydroxyethyl acrylate, fluorine-based acrylate, matte particles, and a photopolymerization initiator,
The coating agent has a gloss value of 15 or less after curing,
The mass ratio of the urethane acrylate and the 2-hydroxyethyl acrylate is 45:55 to 70:30,
For a total of 100 parts by mass of the urethane acrylate and 2-hydroxyethyl acrylate, 1 to 10 parts by mass of the fluorine-based acrylate, 5 to 15 parts by mass of the matte particles, and 2.5 parts of the photopolymerization initiator. ~3.5 parts by mass of each coating agent. The coating agent according to claim 1 , wherein the matte particles include silica particles. The matte particles include silica particles and polyethylene wax,
The coating agent according to claim 1 or 2 , wherein the mass ratio of the silica particles and the polyethylene wax contained in the matte particles is 3:7 to 7:3. Any one of claims 1 to 3, comprising 0.1 to 5 parts by mass of at least one of an antibacterial agent and an antiviral agent, based on a total of 100 parts by mass of the urethane acrylate and the 2 -hydroxyethyl acrylate. Coating agent described in section. A laminate comprising a base material and a film provided on the surface of the base material,
A laminate, wherein the film is a cured product of the coating agent according to any one of claims 1 to 4 . The laminate according to claim 5 , wherein the base material is an extrusion molded body of resin.