JP7264756B2 - Two-liquid type epoxy resin composition, watch parts and luminous capsule - Google Patents

Description

TECHNICAL FIELD The present invention relates to a two-part epoxy resin composition, watch parts and luminous capsules.

Patent Literature 1 describes a decorative member with a luminous paint. Specifically, the recessed characters provided on the outer surface of the watch case are coated with a highly reflective white paint, and then coated with a luminous paint to form the decorative member.

JP-A-7-48532

However, in the decorative member with luminous paint of Patent Document 1, the layer of white paint is too thick, so it is difficult to provide two layers, a layer of white paint and a layer of luminous paint, in the recessed characters.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a resin composition capable of forming a thin colored layer or luminous layer in the concave portion of a timepiece component.

The two-component epoxy resin composition of the present invention comprises a bisphenol type epoxy resin (A1) having an epoxy equivalent of 1500 or more and a softening point of 80°C or more, and an epoxy equivalent of 200 or less and being liquid at 25°C. a base composition (A) containing a bisphenol-type epoxy resin (A2), a coloring agent or a phosphorescent agent, and an organic solvent having a boiling point of 140° C. or higher; and N,N-diethyl-1,3-diaminopropane and a curing agent composition (B) containing an organic solvent having a boiling point of 140° C. or higher, and the coloring agent or the phosphorescent agent contained in the main composition (A) is the bisphenol epoxy resin ( A1), the bisphenol-type epoxy resin (A2), and the N,N-diethyl-1,3-diaminopropane are contained in an amount of 150 parts by mass or more and 300 parts by mass or less based on a total of 100 parts by mass, and the main agent The organic solvent contained in the composition (A) and the organic solvent contained in the curing agent composition (B) are, in total, the bisphenol-type epoxy resin (A1), the bisphenol-type epoxy resin (A2), the It is contained in an amount of 50 parts by mass or more and 100 parts by mass or less with respect to a total of 100 parts by mass of the coloring agent or the phosphorescent agent and the N,N-diethyl-1,3-diaminopropane.

According to the two-liquid type epoxy resin composition of the present invention, a thin colored layer or luminous layer can be formed in the concave portion of the timepiece component.

FIG. 1 is a diagram for explaining the timepiece component of the embodiment. FIG. 2 is a diagram for explaining the luminous capsule of the embodiment.

A form (embodiment) for carrying out the present invention will be described in detail. The present invention is not limited by the contents described in the following embodiments. In addition, the components described below include those that can be easily assumed by those skilled in the art and those that are substantially the same. Furthermore, the configurations described below can be combined as appropriate. In addition, various omissions, substitutions, or changes in configuration can be made without departing from the gist of the present invention.

<Two-component epoxy resin composition>
The two-component epoxy resin composition of the embodiment comprises a bisphenol type epoxy resin (A1) having an epoxy equivalent of 1500 or more and a softening point of 80°C or more, and an epoxy equivalent of 200 or less and being liquid at 25°C. a base composition (A) containing a bisphenol-type epoxy resin (A2), a coloring agent or a phosphorescent agent, and an organic solvent having a boiling point of 140° C. or higher; and N,N-diethyl-1,3-diaminopropane and a curing agent composition (B) containing an organic solvent having a boiling point of 140° C. or higher. The colorant or the phosphorescent agent contained in the main composition (A) includes the bisphenol-type epoxy resin (A1) and the bisphenol-type epoxy resin (A2), and the N,N-diethyl-1,3-diaminopropane. It is contained in an amount of 150 parts by mass or more and 300 parts by mass or less with respect to a total of 100 parts by mass. The organic solvent contained in the main agent composition (A) and the organic solvent contained in the curing agent composition (B) are, in total, the bisphenol-type epoxy resin (A1) and the bisphenol-type epoxy resin (A2). , 50 parts by mass or more and 100 parts by mass or less based on a total of 100 parts by mass of the colorant or the phosphorescent agent and the N,N-diethyl-1,3-diaminopropane.

Specifically, the two-component epoxy resin composition of the embodiment contains a white pigment as a coloring agent and usually does not contain a phosphorescent agent (Embodiment 1); and a two-liquid type epoxy resin composition (Embodiment 2) that usually does not contain a colorant. The two-component epoxy resin compositions of Embodiments 1 and 2 are described in detail below.

[Two-component epoxy resin composition of Embodiment 1]
The two-component epoxy resin composition of Embodiment 1 has a main agent composition (A) and a curing agent composition (B). The main component composition (A) consists of a bisphenol epoxy resin (A1) having an epoxy equivalent of 1500 or more and a softening point of 80°C or more, and a bisphenol epoxy resin (A1) having an epoxy equivalent of 200 or less and being liquid at 25°C. It contains a resin (A2), a white pigment as a coloring agent, and a base composition (A) containing an organic solvent having a boiling point of 140° C. or higher. Curing agent composition (B) contains N,N-diethyl-1,3-diaminopropane and an organic solvent having a boiling point of 140° C. or higher. The above white pigment is contained in the main composition (A) with respect to a total of 100 parts by mass of the bisphenol-type epoxy resin (A1), the bisphenol-type epoxy resin (A2), and N,N-diethyl-1,3-diaminopropane. , in an amount of 150 parts by mass or more and 300 parts by mass or less. The organic solvent contained in the main agent composition (A) and the organic solvent contained in the curing agent composition (B) are, in total, the bisphenol-type epoxy resin (A1), the bisphenol-type epoxy resin (A2), and the white pigment. and N,N-diethyl-1,3-diaminopropane in an amount of 50 parts by mass or more and 100 parts by mass or less with respect to a total of 100 parts by mass.

According to the two-liquid type epoxy resin composition of Embodiment 1, since it contains the white pigment, it is possible to form a thin white layer in the concave portion of the timepiece component. The white layer is suitably used as a base layer for forming a luminous layer or a colored layer thereon. In this specification, this white layer is also referred to as a base layer.

The two-pack type epoxy resin composition of Embodiment 1 usually has a main agent composition (A) and a curing agent composition (B) independently. Specifically, when forming the underlayer, the main composition (A) and the curing agent composition (B) are mixed to prepare an epoxy resin mixed composition before use. The epoxy resin mixed composition applied to the concave portion is cured to form the underlying layer made of the cured product. In the cured product, the organic solvent is evaporated and removed. Moreover, the two-liquid type epoxy resin composition of Embodiment 1 has a pot life that is preferable for the formation of the base layer.

The main agent composition (A) contains two types of epoxy resins, ie, a bisphenol-type epoxy resin (A1) and a bisphenol-type epoxy resin (A2), as main agents.

The bisphenol type epoxy resin (A1) has an epoxy equivalent of 1500 or more, preferably 1500 or more and 10000 or less. As used herein, epoxy equivalent weight means the number of grams (g/eq) of resin containing one gram equivalent of epoxy groups. The bisphenol type epoxy resin (A1) has a softening point of 80°C or higher, preferably 80°C or higher and 150°C or lower. Therefore, the bisphenol type epoxy resin (A1) is solid at 25°C. The softening point is determined by the ring and ball method described in JIS K 7234. The bisphenol-type epoxy resin (A1) may be used singly or in combination of two or more.

The bisphenol type epoxy resin (A2) has an epoxy equivalent of 200 or less, preferably 160 or more and 200 or less. The bisphenol type epoxy resin (A2) is liquid at 25°C. The bisphenol type epoxy resin (A2) may be used singly or in combination of two or more.

By using the bisphenol-type epoxy resin (A1) and the bisphenol-type epoxy resin (A2) in combination, it is possible to spread the white pigment evenly throughout the recess when forming the base layer in the recess of the watch part. can. Therefore, a uniform and thin underlayer can be formed in the concave portion of the timepiece component. By providing the base layer, the color of the colored layer formed thereon can be visually recognized as a clear color. Further, when the underlayer is provided, the luminous layer formed thereon becomes bright and visible due to the improvement in the reflectance of the underlayer. Since the underlayer can be formed thin, it is particularly suitable when the concave portion is thin.

In addition, since the epoxy equivalent of the bisphenol-type epoxy resin (A1) is within the above range, it is believed that the epoxy resin mixture composition can be prevented from protruding from the concave portions during curing when forming the underlayer.

Moreover, when two kinds of bisphenol-type epoxy resin (A1) and bisphenol-type epoxy resin (A2) are used, the crosslink density of the cured product is increased, and the underlayer having high reliability can be obtained.

Specifically, the bisphenol type epoxy resin (A1) and the bisphenol type epoxy resin (A2) may be a bisphenol A type epoxy resin or a bisphenol F type epoxy resin. When a bisphenol F type epoxy resin is used as the bisphenol type epoxy resin (A2), the white pigment can be evenly distributed to every corner of the concave portion when the base layer is formed. That is, a uniform and thin base layer can be formed in the recesses of the timepiece component.

The bisphenol type epoxy resin (A1) is preferably used in an amount of 300 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the bisphenol type epoxy resin (A2). When the bisphenol-type epoxy resin (A1) is used in the above amount, the white pigment can be evenly distributed to every corner of the concave portion when the underlayer is formed. That is, a uniform and thin base layer can be formed in the recesses of the timepiece component.

In addition, the main component composition (A) contains a white pigment. Specific examples of the white pigment include titanium oxide, barium sulfate, zinc oxide, alumina, magnesium oxide, antimony oxide, zirconium oxide, white lead, kaolin, calcium carbonate, and barium carbonate. The said white pigment may be used individually by 1 type, or may be used in combination of 2 or more type.

Among these, titanium oxide is preferably used because it has preferable whiteness, has good hiding power, and easily spreads evenly to every corner of the concave portion. When a colored layer is provided on the underlayer using titanium oxide, it becomes possible to visually recognize a clearer color. Further, when a luminous layer is provided on the underlayer using titanium oxide, it can be visually recognized more brightly.

The white pigment preferably has an average particle diameter D50 of 0.15 μm or more and 0.50 μm or less. The average particle diameter D50 refers to the median diameter D50 measured with a laser diffraction particle size distribution analyzer. Catalog values may be used for commercial products. When the average particle diameter D50 is within the above range, it becomes easier for the powder to spread evenly throughout the recesses of the timepiece component. Therefore, excellent hiding power can be exhibited even if the white pigment is not used so much.

Moreover, the main component composition (A) contains an organic solvent. The organic solvent has a boiling point of 140° C. or higher, preferably 140° C. or higher and 200° C. or lower. The above organic solvents may be used singly or in combination of two or more. When the boiling point is within the above range, it is easy to apply the epoxy resin mixture composition to the concave portions of timepiece components. In addition, when the epoxy resin mixture composition is cured, it evaporates at an appropriate speed, and a uniform and thin base layer can be formed. If the boiling point is too low, it may evaporate quickly and may not be applied uniformly. On the other hand, if the boiling point is too high, it may be difficult to evaporate and form the underlayer.

Specific examples of the organic solvent include propylene glycol 1-monomethyl ether 2-acetate and ethylene glycol.

Moreover, the main composition (A) may further contain other components such as a leveling agent and a surface modifier. Other components may be used individually by 1 type, or may be used in combination of 2 or more type.

Curing agent composition (B) contains N,N-diethyl-1,3-propanediamine as a curing agent. The use of N,N-diethyl-1,3-propanediamine can favorably cure the epoxy resin mixture composition.

Moreover, the curing agent composition (B) contains an organic solvent. The organic solvent is the same as the organic solvent contained in the main composition (A).

In addition, the curing agent composition (B) may further contain other components such as leveling agents and surface modifiers. Other components may be used individually by 1 type, or may be used in combination of 2 or more type.

In the two-component epoxy resin composition of Embodiment 1, the white pigment is contained in the main composition (A), the bisphenol-type epoxy resin (A1) and the bisphenol-type epoxy resin (A2), and N,N-diethyl-1 It is contained in an amount of 150 parts by mass or more and 300 parts by mass or less based on a total of 100 parts by mass of ,3-diaminopropane. When the white pigment is used in the above amount, the white pigment can be evenly distributed to every corner of the concave portion when the underlayer is formed. That is, a uniform and thin base layer can be formed in the recesses of the timepiece component.

Further, in the two-component epoxy resin composition of Embodiment 1, the organic solvent contained in the main composition (A) and the organic solvent contained in the curing agent composition (B) are combined to form a bisphenol epoxy resin. Contained in an amount of 50 parts by mass or more and 100 parts by mass or less with respect to a total of 100 parts by mass of (A1) and bisphenol type epoxy resin (A2), the white pigment and N,N-diethyl-1,3-diaminopropane ing. When the organic solvent is used in the above amount, the white pigment can be evenly distributed to every corner of the concave portion when the underlayer is formed.

The amount of the organic solvent contained in the main agent composition (A) and the amount of the organic solvent contained in the organic solvent and curing agent composition (B) are They can be appropriately set so that they are easy to handle. For example, if the amount of the organic solvent contained in the curing agent composition (B) is too small, the required amount of the curing agent composition (B) is It may become too small and difficult to weigh.

In the two-component epoxy resin composition of Embodiment 1, the active hydrogen equivalent of N,N-diethyl-1,3-diaminopropane with respect to the epoxy equivalent of the main composition (A) is 0.9 to 1.2 (molar ratio ), the bisphenol type epoxy resin (A1), the bisphenol type epoxy resin (A2) and N,N-diethyl-1,3-diaminopropane are preferably blended. Here, the epoxy equivalent of the main composition (A) is the epoxy equivalent of the mixture of the bisphenol-type epoxy resin (A1) and the bisphenol-type epoxy resin (A2) contained in the main composition (A). It is determined from the specific types and mixing ratios of the bisphenol-type epoxy resin (A1) and the bisphenol-type epoxy resin (A2) contained in the main component composition (A).

Further, in the two-component epoxy resin composition of Embodiment 1, when the other components are used, the other components contained in the main composition (A) and the other components contained in the curing agent composition (B) In total, for example, the bisphenol type epoxy resin (A1) and the bisphenol type epoxy resin (A2), the above white pigment and N,N-diethyl-1,3-diaminopropane, with respect to a total of 100 parts by mass, 0 It is contained in an amount exceeding 5 parts by mass and not more than 5 parts by mass.

The main component composition (A) is obtained by mixing the above components in the above amounts. Curing agent composition (B) can also be obtained in the same manner. It is preferable to filter the main composition (A) and the curing agent composition (B) after mixing the components described above. A nozzle is usually used to apply the epoxy resin mixture composition. This is to prevent the mixed composition from clogging the nozzle.

Although the two-liquid type epoxy resin composition of Embodiment 1 has been described above as containing a white pigment as a coloring agent, it may contain another coloring agent instead of the white pigment.

The other coloring agent may be either an inorganic pigment or an organic pigment. Examples of other coloring agents include phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, azo pigments such as azo yellow lake, azo lake red, and monoazo yellow, quinacridone pigments, perylene pigments, quinophthalone pigments, anthraquinone pigments, ultramarine blue, and cobalt. , red iron oxide, nickel titanium yellow, chrome titanium yellow, and carbon black. The other coloring agents may be used singly or in combination of two or more.

When other coloring agents are included, a thin colored layer having a color corresponding to the coloring agent can be formed in the concave portion of the timepiece component.

[Two-component epoxy resin composition of Embodiment 2]
The two-component epoxy resin composition of Embodiment 2 has a main agent composition (A) and a curing agent composition (B). The main component composition (A) consists of a bisphenol epoxy resin (A1) having an epoxy equivalent of 1500 or more and a softening point of 80°C or more, and a bisphenol epoxy resin (A1) having an epoxy equivalent of 200 or less and being liquid at 25°C. It contains a resin (A2), a phosphorescent agent, and an organic solvent having a boiling point of 140° C. or higher. Curing agent composition (B) contains N,N-diethyl-1,3-diaminopropane and an organic solvent having a boiling point of 140° C. or higher. The phosphorescent agent is contained in the main composition (A) with respect to a total of 100 parts by mass of the bisphenol-type epoxy resin (A1), the bisphenol-type epoxy resin (A2), and N,N-diethyl-1,3-diaminopropane. , in an amount of 150 parts by mass or more and 300 parts by mass or less. The organic solvent contained in the main agent composition (A) and the organic solvent contained in the curing agent composition (B) are, in total, the bisphenol-type epoxy resin (A1), the bisphenol-type epoxy resin (A2), and the phosphorescent agent. and N,N-diethyl-1,3-diaminopropane in an amount of 50 parts by mass or more and 100 parts by mass or less with respect to a total of 100 parts by mass.

According to the two-liquid type epoxy resin composition of Embodiment 2, since it contains the phosphorescent agent, it is possible to form a thin luminous layer in the concave portion of the timepiece component. In the noctilucent layer, energy is accumulated in the phosphorescent agent contained in the layer by light irradiation in a bright place. Then, during darkening, the energy is emitted as light. That is, even in a dark place, the luminous layer can be recognized by the luminescence of the phosphorescent agent. Regarding the two-liquid type epoxy resin composition of Embodiment 2, differences from Embodiment 1 will be described below, and description of the same points as Embodiment 1 will be omitted.

When irradiated with light such as ultraviolet rays and visible light contained in sunlight and artificial light, the phosphorescent agent absorbs and stores the light. After that, even if the light irradiation is stopped, that is, even in a dark place, it continues to emit light for a predetermined time. The phosphorescent agent is not particularly limited as long as it has the properties described above. Examples of the phosphorescent agent include a sulfide-based phosphorescent agent and an aluminate-based phosphorescent agent. Specific examples of sulfide-based phosphorescent agents include CaS:Bi, CaSrS:Bi, and ZnCdS:Cu. Specific examples of _the aluminate- _{based phosphorescent agent} include RMg2Al16O27:Eu, _RMg2Al16O27 :Eu, _{Mn , RMg2Al10O17} : _{Eu , RMg2Al10O17} :Eu _, Mn ( _R is Sr or _Ba , which _may be _combined ), _SrAl2O4 :Eu, _SrAl2O4 :Eu, _{Dy , Sr4Al14O25} :Eu, _Sr4Al14O25 :Eu, Dy, CaAl ₂ O ₄ :Eu, Nd and the like. Among these, from the viewpoint of afterglow brightness and afterglow time, the alumina acid-based phosphorescent agent is more preferably used. The phosphorescent agent may be used singly or in combination of two or more.

The phosphorescent agent preferably has an average particle size D50 of 5 μm or more and 30 μm or less. The average particle diameter D50 refers to the median diameter D50 measured with a laser diffraction particle size distribution analyzer. Catalog values may be used for commercial products. When the average particle diameter D50 is within the above range, it becomes easy to spread uniformly to every corner of the concave portion of the timepiece component. Therefore, the luminous layer can be easily recognized without using a large amount of the phosphorescent agent.

The phosphorescent agent is 180 parts by mass or more and 300 parts by mass or less with respect to a total of 100 parts by mass of the bisphenol-type epoxy resin (A1), the bisphenol-type epoxy resin (A2), and the N,N-diethyl-1,3-diaminopropane. is preferably contained in an amount of When the above phosphorescent agent is used in the above amount, the luminous layer becomes more recognizable.

[Two-liquid type epoxy resin composition of other embodiments]
A two-part epoxy resin composition of another embodiment comprises a bisphenol type epoxy resin (A1) having an epoxy equivalent of 1500 or more and a softening point of 80°C or more, and an epoxy equivalent of 200 or less and at 25°C A base composition (A) containing a liquid bisphenol-type epoxy resin (A2) and an organic solvent having a boiling point of 140°C or higher; N,N-diethyl-1,3-diaminopropane; and a boiling point of 140°C. and a curing agent composition (B) containing the above organic solvent. The organic solvent contained in the main agent composition (A) and the organic solvent contained in the curing agent composition (B) are, in total, the bisphenol-type epoxy resin (A1) and the bisphenol-type epoxy resin (A2). , and N,N-diethyl-1,3-diaminopropane in an amount of 60 parts by mass or more and 200 parts by mass or less based on a total of 100 parts by mass.

As described above, the two-component epoxy resin composition of other embodiments is different from the two-component epoxy resin composition of Embodiment 1 except that it does not contain a colorant and the amount of the organic solvent is different. It is the same.

According to the two-part epoxy resin composition of another embodiment, the base layer, the colored layer, or the luminous layer can be formed by further adding the above-described coloring agent or phosphorescent agent to the main composition (A). It can be used as a two-liquid type epoxy resin composition. The amount of coloring agent or phosphorescent agent to be added can be set appropriately. For example, the coloring agent or the phosphorescent agent is contained in the main composition (A), bisphenol type epoxy resin (A1) and bisphenol type epoxy resin (A2), and N,N-diethyl-1,3-diaminopropane, totaling 100 mass. It can be added in an amount of 150 parts by mass or more and 300 parts by mass or less. In the case of a phosphorescent agent, the main composition (A) preferably contains a total of 100 mass of bisphenol-type epoxy resin (A1), bisphenol-type epoxy resin (A2), and N,N-diethyl-1,3-diaminopropane. It can be added in an amount of 180 parts by mass or more and 300 parts by mass or less.

When a coloring agent or a luminous agent is further added to the two-component epoxy resin composition of the other embodiments, the concave portions of the timepiece parts are colored in the same manner as the two-component epoxy resin compositions of Embodiments 1 and 2. A thin layer or noctilucent layer can be formed.

<watch parts>
The watch component of the embodiment has a cured product obtained from the two-liquid type epoxy resin composition of the first embodiment as a display portion. The timepiece component of the embodiment will be described more specifically below.

FIG. 1 is a diagram for explaining the timepiece component of the embodiment. That is, it represents a cross section of the rotary bezel 10, which is a timepiece component of the embodiment. The rotary bezel 10 has a rotary bezel main body 11 and a concave portion 12 . A base layer 13 and a luminous layer 14 are formed in the concave portion 12 . The base layer 13 is made of a cured product obtained from the two-component epoxy resin composition of Embodiment 1 containing the white pigment as a coloring agent. Also, the luminous layer 14 is made of a cured product obtained from the two-liquid type epoxy resin composition of the second embodiment.

The rotating bezel main body 11 is normally made of metal. The concave portion 12 is formed in the shape of a desired letter, number, circle, triangle, or other mark when the rotating bezel 10 is viewed from above. By providing the base layer 13, the visibility of the luminous layer 14 can be improved. Further, by using the two-component epoxy resin composition of Embodiment 1 and the two-component epoxy resin composition of Embodiment 2, the base layer 13 and the luminous layer 14 can be formed thinly and uniformly. The size and shape of the bottom surface of the concave portion 12 can be appropriately set so as to obtain a desired display portion.

A known method can be adopted as a method for manufacturing the rotating bezel 10 . For example, an epoxy resin mixture composition prepared from the two-liquid type epoxy resin composition of Embodiment 1 is adhered to the concave portion 12 . Specifically, it is applied using a nozzle. Next, the base layer 13 is formed by heating at, for example, 70° C. or more and 100° C. or less for 1 hour or more and 6 hours or less to evaporate the organic solvent and advance the curing reaction. In addition, in order to completely evaporate the organic solvent, heating may be performed at 130° C. or more and 170° C. or less for 30 minutes or more and 1 hour or less. Next, an epoxy resin mixture composition prepared from the two-component epoxy resin composition of Embodiment 2 is adhered onto the underlayer 13 . Specifically, it is applied using a nozzle. Next, the substrate is heated, for example, at a temperature of 70° C. or more and 100° C. or less for 1 hour or more and 6 hours or less to evaporate the organic solvent and proceed with the curing reaction to form the luminous layer 14 . In addition, in order to completely evaporate the organic solvent, heating may be performed at 130° C. or more and 170° C. or less for 30 minutes or more and 1 hour or less. Thus, the rotating bezel 10 can be manufactured.

The above watch component is a rotating bezel, but other components having recesses may also be used. The watch part may be, for example, a watch case part (body, back cover, crown, etc.) other than the rotating bezel, or a band part (piece, clasp, etc.). . Furthermore, the timepiece parts may be dials and hands provided inside the glass instead of the parts forming the outer surface of the timepiece. Note that the timepiece component may be used for a wristwatch, table clock, or wall clock.

By using the two-component epoxy resin composition of Embodiment 1 and the two-component epoxy resin composition of Embodiment 2 in the timepiece component described above, the base layer 13 and the luminous layer 14 can be formed thinly and uniformly. Therefore, these layers can be formed even in particularly thin recesses, for example recesses with a thickness of 80 μm to 180 μm. The base layer 13 and the luminous layer 14 can each be formed with a thickness such that the two layers can be accommodated in a thin recess. When a conventional paint is applied to a thin concave portion, there are problems that the paint cannot be applied thinly and uniformly, and the paint protrudes during curing. By using the two-component epoxy resin composition of Embodiment 1 and the two-component epoxy resin composition of Embodiment 2, the above problems can be solved. Of course, these layers may also be formed in recesses of normal thickness, for example recesses with a thickness greater than 180 μm.

Note that the aforementioned timepiece component was provided with the base layer 13 and the luminous layer 14 described above. However, a cured product obtained from a material other than the two-component epoxy resin composition of Embodiment 2 is placed on an underlayer which is a cured product obtained from the two-component epoxy resin composition of Embodiment 1 containing the white pigment. A noctilucent layer may be provided. Further, from the two-component epoxy resin composition of Embodiment 1 containing the other colorant on the underlayer which is a cured product obtained from the two-component epoxy resin composition of Embodiment 1 containing the white pigment A colored layer, which is a cured product obtained, may be provided. In addition, on the base layer which is a cured product obtained from the two-component epoxy resin composition of Embodiment 1 containing the white pigment, other than the two-component epoxy resin composition of Embodiment 1 containing the other colorant A colored layer that is a cured product obtained from may be provided.

Further, a cured product obtained from the two-component epoxy resin composition of Embodiment 2 is placed on an underlayer which is a cured product obtained from a material other than the two-component epoxy resin composition of Embodiment 1 containing the white pigment. A noctilucent layer may be provided. Further, the two-component epoxy resin composition of Embodiment 1 containing the other colorant is placed on a base layer which is a cured product obtained from a material other than the two-component epoxy resin composition of Embodiment 1 containing the white pigment. A colored layer that is a cured product obtained from may be provided.

Further, a luminous layer, which is a cured product obtained from the two-component epoxy resin composition of Embodiment 2, may be provided without providing the underlayer. Alternatively, a colored layer, which is a cured product obtained from the two-liquid type epoxy resin composition of Embodiment 1 containing the other coloring agent, may be provided without providing the underlayer. In either case, these layers can be suitably formed even in thin recesses.

<Luminous Capsule>
The luminous capsule of the embodiment contains a cured product obtained from the two-component epoxy resin composition of the first embodiment in the cylindrical body. The luminous capsule of the embodiment will be described more specifically below.

FIG. 2 is a diagram for explaining the luminous capsule of the embodiment. That is, it is a perspective view of the luminous capsule 20. FIG. The luminous capsule 20 has a base layer 22 and a luminous layer 23 formed in a cylindrical body 21 having openings at both ends. The base layer 22 is made of a cured product obtained from the two-component epoxy resin composition of Embodiment 1 containing the white pigment as a coloring agent. The luminous layer 23 is made of a cured product obtained from the two-liquid type epoxy resin composition of the second embodiment.

A luminous capsule 20 is glued to be embedded in the watch part and used to represent the desired mark. The barrel 21 is typically made of metal or plastic. The cylindrical body 21 may be a cylinder, an elliptical cylinder, or a hollow polygonal prism (such as a triangular prism). In other words, the shape of the opening of the cylinder 21 may be circular, elliptical, or polygonal (triangular, etc.). In this way, any shape may be used as long as a desired mark can be obtained. The size of the luminous capsule can be appropriately set according to the embedded watch component.

The method for producing the luminous capsule 20 includes, for example, the steps of putting an epoxy resin mixture composition prepared from the two-liquid type epoxy resin composition of Embodiment 1 into the cylinder 21; and curing the epoxy resin mixture composition. Specifically, first, the cylindrical body 21 is fixed on a supporting member such as double-sided tape. The epoxy resin mixture composition is put from above into the hollow portion of the cylindrical body 21 whose lower side is fixed. Next, the base layer 22 is formed by heating at, for example, 70° C. or more and 100° C. or less for 1 hour or more and 6 hours or less to evaporate the organic solvent and advance the curing reaction. In addition, in order to completely evaporate the organic solvent, heating may be performed at 130° C. or more and 170° C. or less for 30 minutes or more and 1 hour or less. Next, an epoxy resin mixture composition prepared from the two-liquid type epoxy resin composition of Embodiment 2 is put on the base layer 22 to fill the hollow portion. Next, the substrate is heated at, for example, 70° C. or more and 100° C. or less for 1 hour or more and 6 hours or less to evaporate the organic solvent and promote a curing reaction to form the luminous layer 23 . In addition, in order to completely evaporate the organic solvent, heating may be performed at 130° C. or more and 170° C. or less for 30 minutes or more and 1 hour or less. Thus, the luminous capsule 20 can be manufactured.

By the way, in the production of conventional luminous capsules, an ultraviolet curable resin composition containing a phosphorescent agent is used. In the production of conventional luminous capsules, first, the UV-curable resin composition is placed in a cup-shaped container whose bottom is made of glass. Next, ultraviolet rays are irradiated from the glass side of the bottom surface to cure the composition, thereby obtaining a cured product. In this case, since ultraviolet rays are irradiated from the glass side of the bottom surface, even the ultraviolet-curable resin composition present in the upper part of the container may not be cured uniformly. Moreover, the cured product obtained from the UV-curable resin composition is weak against water and inferior in durability. On the other hand, since the luminous capsule 20 uses the two-component epoxy resin composition of Embodiment 1 and the two-component epoxy resin composition of Embodiment 2, it is cured evenly microscopically. . The resulting cured product is resistant to water and has excellent durability. Furthermore, it is excellent also in productivity.

In the luminous capsule described above, by using the two-component epoxy resin composition of Embodiment 1 and the two-component epoxy resin composition of Embodiment 2, the base layer 22 and the luminous layer 23 can be formed thinly and uniformly. Therefore, these layers can be formed even on cylinders of particularly low height. The base layer 22 and the luminous layer 23 can each be formed with a thickness such that the two layers can be accommodated in a low cylinder. When conventional paint is applied to a thin, low-height cylindrical body, there are problems that the paint cannot be applied thinly and evenly, and that the paint protrudes during curing. By using the two-component epoxy resin composition of Embodiment 1 and the two-component epoxy resin composition of Embodiment 2, the above problems can be solved. Of course, these layers may be formed on a cylinder of normal height.

In addition, in the luminous capsule described above, the base layer 22 and the luminous layer 23 described above were provided. However, a cured product obtained from a material other than the two-component epoxy resin composition of Embodiment 2 is placed on an underlayer which is a cured product obtained from the two-component epoxy resin composition of Embodiment 1 containing the white pigment. A noctilucent layer may be provided. In addition, a thermosetting resin composition of the two-component epoxy resin composition of Embodiment 2 is applied on a base layer which is a cured product obtained from a material other than the two-component epoxy resin composition of Embodiment 1 containing the white pigment. A luminous layer that is a cured product obtained from may be provided. Further, a luminous layer, which is a cured product obtained from the two-component epoxy resin composition of Embodiment 2, may be provided without providing the underlayer. In any case, these layers can be suitably formed even in a cylinder having a particularly low height.

As described above, the present invention relates to the following.
[1] A bisphenol-type epoxy resin (A1) having an epoxy equivalent of 1500 or more and a softening point of 80°C or more, and a bisphenol-type epoxy resin (A2) having an epoxy equivalent of 200 or less and being liquid at 25°C. , a coloring agent or a phosphorescent agent, and an organic solvent having a boiling point of 140° C. or higher; and a curing agent composition (B) containing a solvent, and the coloring agent or the phosphorescent agent contained in the main composition (A) comprises the bisphenol epoxy resin (A1) and the bisphenol epoxy resin ( A2) and the N,N-diethyl-1,3-diaminopropane in an amount of 150 parts by mass or more and 300 parts by mass or less based on a total of 100 parts by mass, and the above contained in the main component composition (A) The organic solvent and the organic solvent contained in the curing agent composition (B) are, in total, the bisphenol-type epoxy resin (A1) and the bisphenol-type epoxy resin (A2), the colorant or the phosphorescent agent, and the N ,N-diethyl-1,3-diaminopropane in an amount of 50 parts by mass or more and 100 parts by mass or less based on a total of 100 parts by mass of N-diethyl-1,3-diaminopropane.

[2] The two-component epoxy resin composition according to [1] above, wherein the main composition (A) contains the colorant.

[3] The main composition (A) contains the phosphorescent agent, and the phosphorescent agent contained in the main agent composition (A) is the bisphenol epoxy resin (A1) and the bisphenol epoxy resin (A2). and the two-component epoxy according to [1] above, which is contained in an amount of 180 parts by mass or more and 300 parts by mass or less with respect to a total of 100 parts by mass of the N,N-diethyl-1,3-diaminopropane Resin composition.

According to the two-liquid type epoxy resin compositions [1] to [3] above, it is possible to form a thin colored layer or luminous layer in the recesses of timepiece parts.

[4] The coloring agent is at least one white pigment selected from titanium oxide, barium sulfate, zinc oxide, alumina, magnesium oxide, antimony oxide, zirconium oxide, white lead, kaolin, calcium carbonate and barium carbonate. The two-component epoxy resin composition according to [1] or [2] above.

[5] The two-component epoxy resin composition according to [4] above, wherein the white pigment is titanium oxide.

According to the two-liquid type epoxy resin composition of [4] and [5] above, a thin white undercoating can be formed in the recesses of watch parts.

[6] A timepiece component comprising a cured product obtained from the two-component epoxy resin composition according to any one of [1] to [5] above.

[7] The timepiece component according to [6] above, wherein the timepiece component is a case portion component or a band portion component.

In the timepiece parts [6] and [7], a thin colored layer or luminous layer is formed in the concave portion of the timepiece part.

[8] A luminous capsule comprising a cylindrical body having openings at both ends, and a cured product obtained from the two-component epoxy resin composition according to any one of [1] to [5] in the cylindrical body. .

In the luminous capsule of [8] above, the base layer or the luminous layer is formed thin.

[9] A bisphenol-type epoxy resin (A1) having an epoxy equivalent of 1500 or more and a softening point of 80°C or more, and a bisphenol-type epoxy resin (A2) having an epoxy equivalent of 200 or less and being liquid at 25°C. , a base composition (A) containing an organic solvent having a boiling point of 140° C. or higher, and a curing agent composition containing N,N-diethyl-1,3-diaminopropane and an organic solvent having a boiling point of 140° C. or higher. (B), and the organic solvent contained in the main composition (A) and the organic solvent contained in the curing agent composition (B) are the total of the bisphenol type epoxy resin (A1) and the bisphenol-type epoxy resin (A2) and the N,N-diethyl-1,3-diaminopropane in an amount of 60 parts by mass or more and 200 parts by mass or less, based on a total of 100 parts by mass, 2 A liquid epoxy resin composition.

According to the two-liquid type epoxy resin composition of [9] above, a thin colored layer or luminous layer can be formed in the concave portion of the timepiece component.

EXAMPLES The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[Example]
[Example 1-1]
[Preparation of two-component epoxy resin composition (two-component epoxy resin composition for forming base layer)]
The following components were used for the preparation of the main ingredient composition (A).
Main agent: Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name 1009, epoxy equivalent 2,400 to 3,300, softening point 128° C.) as bisphenol type epoxy resin (A1)
As the bisphenol type epoxy resin (A2), a bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name 807, epoxy equivalent 160 to 175, liquid at 25°C)
Colorant: Titanium oxide (average particle size 0.29 μm)
Organic solvent: Propylene glycol 1-monomethyl ether 2-acetate Bisphenol epoxy resin (A1) 57.0 parts by mass, bisphenol epoxy resin (A2) 12.84 parts by mass, colorant 152.4 parts by mass, organic solvent 124.2 parts by mass were mixed, and the resulting mixture was filtered to prepare a liquid base composition (A).
Moreover, the following components were used for the preparation of the curing agent composition (B).
Curing agent: N,N-diethyl-1,3-diaminopropane Organic solvent: propylene glycol 1-monomethyl ether 2-acetate 6.36 parts by mass of curing agent and 28.27 parts by mass of organic solvent were mixed to obtain The mixture was filtered to prepare a liquid curing agent composition (B).
In this manner, a two-liquid type epoxy resin composition for forming a base layer containing the main composition (A) and the curing agent composition (B) was obtained.
[Formation of underlayer]
A base layer 13 was formed in the concave portion 12 of the rotary bezel 10 as shown in FIG.
First, 346.4 parts by mass of the main component composition (A) of the two-component epoxy resin composition for forming an underlayer and 34.63 parts by mass of the curing agent composition (B) are mixed to obtain an epoxy resin mixture composition. got Here, the active hydrogen equivalent of N,N-diethyl-1,3-diaminopropane with respect to the epoxy equivalent of the main component composition (A) was 1.0 (molar ratio).
Next, the epoxy resin mixed composition was applied to the concave portion 12 (thickness: 80 μm) with a dispenser. Next, the applied epoxy resin mixture composition was heated at 80° C. for 1 hour to cure while evaporating the organic solvent, thereby forming the underlying layer 13 .
Further, in the case where the thickness of the concave portion 12 was 120 μm and 180 μm, the underlying layer 13 was formed in the same manner as described above using the above epoxy resin mixed composition.

[Example 1-2]
[Preparation of two-component epoxy resin composition (two-component epoxy resin composition for forming base layer)]
The following components were used for the preparation of the main ingredient composition (A).
Main agent: bisphenol A type/bisphenol F type mixed type as bisphenol type epoxy resin (A1) (manufactured by Mitsubishi Chemical Corporation, trade name 4250, epoxy equivalent 7,500 to 8,900, softening point 140°C or higher)
As the bisphenol type epoxy resin (A2), a bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name 828, epoxy equivalent 184 to 194, liquid at 25°C)
Colorant: Titanium oxide (average particle size 0.29 μm)
Organic solvent: propylene glycol 1-monomethyl ether 2-acetate 85.0 parts by mass of bisphenol type epoxy resin (A1), 23.1 parts by mass of bisphenol type epoxy resin (A2), 237.0 parts by mass of colorant, and organic solvent 190.5 parts by mass were mixed, and the resulting mixture was filtered to prepare a liquid base composition (A).
Moreover, the following components were used for the preparation of the curing agent composition (B).
Curing agent: N,N-diethyl-1,3-diaminopropane Organic solvent: propylene glycol 1-monomethyl ether 2-acetate 10.4 parts by mass of the curing agent and 43.16 parts by mass of the organic solvent were mixed to obtain The mixture was filtered to prepare a liquid curing agent composition (B).
In this manner, a two-liquid type epoxy resin composition for forming a base layer containing the main composition (A) and the curing agent composition (B) was obtained.
[Formation of underlayer]
A base layer 13 was formed in the concave portion 12 of the rotary bezel 10 as shown in FIG.
First, 535.6 parts by mass of the main component composition (A) of the two-component epoxy resin composition for forming the base layer and 53.56 parts by mass of the curing agent composition (B) are mixed to obtain an epoxy resin mixed composition. got Here, the active hydrogen equivalent of N,N-diethyl-1,3-diaminopropane with respect to the epoxy equivalent of the main component composition (A) was 1.0 (molar ratio).
Next, the epoxy resin mixed composition was applied to the concave portion 12 (thickness: 80 μm) with a dispenser. Next, the applied epoxy resin mixture composition was heated at 80° C. for 1 hour to cure while evaporating the organic solvent, thereby forming the underlying layer 13 .
Further, in the case where the thickness of the concave portion 12 was 120 μm and 180 μm, the underlying layer 13 was formed in the same manner as described above using the above epoxy resin mixed composition.

[Example 1-3]
[Preparation of two-component epoxy resin composition (two-component epoxy resin composition for forming base layer)]
The following components were used for the preparation of the main ingredient composition (A).
Main agent: Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name 1009, epoxy equivalent 2,400 to 3,300, softening point 128° C.) as bisphenol type epoxy resin (A1)
As the bisphenol type epoxy resin (A2), a bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name 828, epoxy equivalent 184 to 194, liquid at 25°C)
Colorant: Titanium oxide (average particle size 0.29 μm)
Organic solvent: propylene glycol 1-monomethyl ether 2-acetate 57.0 parts by mass of bisphenol type epoxy resin (A1), 14.49 parts by mass of bisphenol type epoxy resin (A2), 152.4 parts by mass of colorant, and organic solvent 95.11 parts by mass were mixed, and the resulting mixture was filtered to prepare a liquid base composition (A).
Moreover, the following components were used for the preparation of the curing agent composition (B).
Curing agent: N,N-diethyl-1,3-diaminopropane Organic solvent: Propylene glycol 1-monomethyl ether 2-acetate 6.36 parts by mass of the curing agent and 25.54 parts by mass of the organic solvent were mixed to obtain The mixture was filtered to prepare a liquid curing agent composition (B).
In this manner, a two-liquid type epoxy resin composition for forming a base layer containing the main composition (A) and the curing agent composition (B) was obtained.
[Formation of underlayer]
A base layer 13 was formed in the concave portion 12 of the rotary bezel 10 as shown in FIG.
First, 319.0 parts by mass of the main component composition (A) of the two-component epoxy resin composition for forming an underlayer and 31.9 parts by mass of the curing agent composition (B) are mixed to obtain an epoxy resin mixed composition. got Here, the active hydrogen equivalent of N,N-diethyl-1,3-diaminopropane with respect to the epoxy equivalent of the main component composition (A) was 1.0 (molar ratio).
Next, the epoxy resin mixed composition was applied to the concave portion 12 (thickness: 80 μm) with a dispenser. Next, the applied epoxy resin mixture composition was heated at 80° C. for 1 hour to cure while evaporating the organic solvent, thereby forming the underlying layer 13 .
Further, in the case where the thickness of the concave portion 12 was 120 μm and 180 μm, the underlying layer 13 was formed in the same manner as described above using the above epoxy resin mixed composition.

[Example 1-4]
[Preparation of two-component epoxy resin composition (two-component epoxy resin composition for forming base layer)]
The following components were used for the preparation of the main ingredient composition (A).
Main agent: Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name 1009, epoxy equivalent 2,400 to 3,300, softening point 128° C.) as bisphenol type epoxy resin (A1)
As the bisphenol type epoxy resin (A2), a bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name 807, epoxy equivalent 160 to 175, liquid at 25°C)
Colorant: Titanium oxide (average particle size 0.29 μm)
Organic solvent: propylene glycol 1-monomethyl ether 2-acetate 57.0 parts by mass of bisphenol type epoxy resin (A1), 12.84 parts by mass of bisphenol type epoxy resin (A2), 120.0 parts by mass of colorant, organic solvent 124.2 parts by mass were mixed, and the resulting mixture was filtered to prepare a liquid base composition (A).
Moreover, the following components were used for the preparation of the curing agent composition (B).
Curing agent: N,N-diethyl-1,3-diaminopropane Organic solvent: propylene glycol 1-monomethyl ether 2-acetate 6.36 parts by mass of curing agent and 28.27 parts by mass of organic solvent were mixed to obtain The mixture was filtered to prepare a liquid curing agent composition (B).
In this manner, a two-liquid type epoxy resin composition for forming a base layer containing the main composition (A) and the curing agent composition (B) was obtained.
[Formation of underlayer]
A base layer 13 was formed in the concave portion 12 of the rotary bezel 10 as shown in FIG.
First, 314.04 parts by mass of the main component composition (A) of the two-component epoxy resin composition for forming the base layer and 34.63 parts by mass of the curing agent composition (B) are mixed to obtain an epoxy resin mixed composition. got Here, the active hydrogen equivalent of N,N-diethyl-1,3-diaminopropane with respect to the epoxy equivalent of the main component composition (A) was 1.0 (molar ratio).
Next, the epoxy resin mixed composition was applied to the concave portion 12 (thickness: 80 μm) with a dispenser. Next, the applied epoxy resin mixture composition was heated at 80° C. for 1 hour to cure while evaporating the organic solvent, thereby forming the underlying layer 13 .
Further, in the case where the thickness of the concave portion 12 was 120 μm and 180 μm, the underlying layer 13 was formed in the same manner as described above using the above epoxy resin mixed composition.

[Example 1-5]
[Preparation of two-component epoxy resin composition (two-component epoxy resin composition for forming base layer)]
The following components were used for the preparation of the main ingredient composition (A).
Main agent: Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name 1009, epoxy equivalent 2,400 to 3,300, softening point 128° C.) as bisphenol type epoxy resin (A1)
As the bisphenol type epoxy resin (A2), a bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name 807, epoxy equivalent 160 to 175, liquid at 25°C)
Colorant: Titanium oxide (average particle size 0.29 μm)
Organic solvent: propylene glycol 1-monomethyl ether 2-acetate 57.0 parts by mass of bisphenol type epoxy resin (A1), 12.84 parts by mass of bisphenol type epoxy resin (A2), 220.0 parts by mass of colorant, and organic solvent 124.2 parts by mass were mixed, and the resulting mixture was filtered to prepare a liquid base composition (A).
Moreover, the following components were used for the preparation of the curing agent composition (B).
Curing agent: N,N-diethyl-1,3-diaminopropane Organic solvent: propylene glycol 1-monomethyl ether 2-acetate 6.36 parts by mass of curing agent and 28.27 parts by mass of organic solvent were mixed to obtain The mixture was filtered to prepare a liquid curing agent composition (B).
In this manner, a two-liquid type epoxy resin composition for forming a base layer containing the main composition (A) and the curing agent composition (B) was obtained.
[Formation of underlayer]
A base layer 13 was formed in the concave portion 12 of the rotary bezel 10 as shown in FIG.
First, 414.04 parts by mass of the main component composition (A) of the two-component epoxy resin composition for forming an underlayer and 34.63 parts by mass of the curing agent composition (B) are mixed to obtain an epoxy resin mixture composition. got Here, the active hydrogen equivalent of N,N-diethyl-1,3-diaminopropane with respect to the epoxy equivalent of the main component composition (A) was 1.0 (molar ratio).
Next, the epoxy resin mixed composition was applied to the concave portion 12 (thickness: 80 μm) with a dispenser. Next, the applied epoxy resin mixture composition was heated at 80° C. for 1 hour to cure while evaporating the organic solvent, thereby forming the underlying layer 13 .
Further, in the case where the thickness of the concave portion 12 was 120 μm and 180 μm, the underlying layer 13 was formed in the same manner as described above using the above epoxy resin mixed composition.

[Example 2-1]
[Preparation of two-component epoxy resin composition (two-component epoxy resin composition for forming luminous layer)]
The following components were used for the preparation of the main ingredient composition (A).
Main agent: Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name 1009, epoxy equivalent 2,400 to 3,300, softening point 128° C.) as bisphenol type epoxy resin (A1)
As the bisphenol type epoxy resin (A2), a bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name 807, epoxy equivalent 160 to 175, liquid at 25°C)
Phosphorescent agent: Nemoto Special Chemical Co., Ltd., N Luminous G-300M, average particle size 25 μm, SrAl ₂ O ₄ : Eu, Dy
Organic solvent: Propylene glycol 1-monomethyl ether 2-acetate Bisphenol epoxy resin (A1) 57.0 parts by mass, bisphenol epoxy resin (A2) 12.84 parts by mass, phosphorescent agent 200.0 parts by mass, organic solvent 124.2 parts by mass were mixed, and the resulting mixture was filtered to prepare a liquid base composition (A).
Moreover, the following components were used for the preparation of the curing agent composition (B).
Curing agent: N,N-diethyl-1,3-diaminopropane Organic solvent: propylene glycol 1-monomethyl ether 2-acetate 6.36 parts by mass of curing agent and 28.27 parts by mass of organic solvent were mixed to obtain The mixture was filtered to prepare a liquid curing agent composition (B).
Thus, a two-liquid type epoxy resin composition for forming a luminous layer comprising the main composition (A) and the curing agent composition (B) was obtained.
[Formation of luminous layer]
A luminous layer 14 was formed on the underlayer 13 obtained in Example 1-1.
First, 394.04 parts by mass of the main component composition (A) of the two-component epoxy resin composition for forming a luminous layer and 34.63 parts by mass of the curing agent composition (B) are mixed to obtain an epoxy resin mixed composition. got Here, the active hydrogen equivalent of N,N-diethyl-1,3-diaminopropane to the epoxy equivalent of the main component composition (A) was 1.0 (molar ratio).
Next, the epoxy resin mixed composition was applied onto the base layer 13 with a dispenser. Next, the applied epoxy resin mixed composition was heated at 80° C. for 1 hour to cure while evaporating the organic solvent, thereby forming the luminous layer 14 .
The luminous layer 14 was formed on the underlying layer 13 for the cases where the thickness of the concave portion 12 was 80 μm, 120 μm, and 180 μm.
[Examples 2-2 to 2-5]
In Examples 2-2 to 2-5, the underlayer 13 was formed in the same manner as in Example 2-1 except that the underlayer 13 obtained in Examples 1-2 to 1-5 was used. A luminous layer 14 was formed thereon.

[Comparative Example 1]
A two-component epoxy resin (main agent/curing agent set) (manufactured by ThreeBond Co., Ltd., trade name TB2086M) was used as a composition for forming a base layer. First, titanium oxide (average particle size: 0.29 μm) was added to this agent. Next, this agent and a curing agent were mixed to obtain a composition for forming an underlayer.
Using this base layer forming composition, the base layer 13 was formed in the concave portion 12 of the rotating bezel 10 . Specifically, the base layer-forming resin composition was applied to the concave portions 12 with a dispenser. Next, the applied base layer forming resin composition was heated at 150° C. for 30 minutes to be cured, and the base layer 13 was formed.

In Examples 1-1 to 1-5, the underlying layer 13 could be formed inside the recess 12 . Furthermore, in Examples 2-1 to 2-5, the underlying layer 13 and the luminous layer 14 could be formed so as to fit within the recess 12 . On the other hand, in Comparative Example 1, the underlying layer 13 was formed to be thicker than the recesses 12 and was raised.

REFERENCE SIGNS LIST 10 Rotating bezel 11 Rotating bezel body 12 Concave part 13 Underlying layer 14 Noctilucent layer 20 Noctilucent capsule 21 Cylinder 22 Underlying layer 23 Noctilucent layer

Claims (8)

A bisphenol-type epoxy resin (A1) having an epoxy equivalent of 1500 or more and a softening point of 80°C or more, a bisphenol-type epoxy resin (A2) having an epoxy equivalent of 200 or less and being liquid at 25°C, and a coloring agent. or a main composition (A) containing a phosphorescent agent and an organic solvent having a boiling point of 140° C. or higher;
a curing agent composition (B) containing N,N-diethyl-1,3-diaminopropane and an organic solvent having a boiling point of 140° C. or higher;
The colorant or the phosphorescent agent contained in the main composition (A) includes the bisphenol-type epoxy resin (A1) and the bisphenol-type epoxy resin (A2) and the N,N-diethyl-1,3-diaminopropane. Contained in an amount of 150 parts by mass or more and 300 parts by mass or less with respect to the total 100 parts by mass of
The organic solvent contained in the main agent composition (A) and the organic solvent contained in the curing agent composition (B) are, in total, the bisphenol-type epoxy resin (A1) and the bisphenol-type epoxy resin (A2). , contained in an amount of 50 parts by mass or more and 100 parts by mass or less with respect to a total of 100 parts by mass of the colorant or the phosphorescent agent and the N,N-diethyl-1,3-diaminopropane;
A two-component epoxy resin composition. The main composition (A) contains the colorant,
The two-component epoxy resin composition according to claim 1. The main composition (A) contains the phosphorescent agent,
The phosphorescent agent contained in the main ingredient composition (A) comprises the bisphenol-type epoxy resin (A1), the bisphenol-type epoxy resin (A2), and the N,N-diethyl-1,3-diaminopropane, totaling 100 mass. contained in an amount of 180 parts by mass or more and 300 parts by mass or less,
The two-component epoxy resin composition according to claim 1. The coloring agent is at least one white pigment selected from titanium oxide, barium sulfate, zinc oxide, alumina, magnesium oxide, antimony oxide, zirconium oxide, white lead, kaolin, calcium carbonate and barium carbonate.
The two-component epoxy resin composition according to claim 1 or 2. The white pigment is titanium oxide,
The two-component epoxy resin composition according to claim 4. Having a cured product obtained from the two-component epoxy resin composition according to any one of claims 1 to 5,
watch parts. The watch component is a component of the case portion or a component of the band portion,
A watch component according to claim 6 . a cylindrical body having openings at both ends;
The cylindrical body contains a cured product obtained from the two-component epoxy resin composition according to any one of claims 1 to 5,
Noctilucent capsule.

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