JP4498702B2 - Adhesive composition and method for fixing ornament stone using the same, decorative article, and repair agent for decorative article - Google Patents

Description

  The present invention relates to an adhesive composition for fixing an ornamental stone to a decorative article base, a method for fixing an ornamental stone using the composition, an ornamental article to which the ornamental stone is fixed, and a repairing agent for the ornamental article.

  A watch is originally a precision machine for notifying the time, but a high-quality watch also has a value as a decorative item, and the proportion of such a watch is higher. Such a watch having a value as a decoration is often decorated with ornamental stones such as jewelry and glass.

  Such decoration with ornamental stones is applied not only to watches but also to various decorative items such as bracelets and metal fittings for bags. A decorative object using a gemstone such as diamond as a decoration stone has good shine and a beautiful appearance, but if the entire decorative object is decorated with a gemstone, it becomes very expensive.

  Therefore, a decorative article using glass as a decoration stone and having a high-class feeling is known. Although this uses glass instead of the jewels to make the ornaments inexpensive, there is a problem that the brightness of the ornamental stones is inferior to that of jewels such as diamonds.

  For this reason, conventionally, a decorative piece having a beautiful shine has been manufactured by fixing a glass decorative stone by the following method. First, a metal film such as aluminum is formed on the lower surface of glass cut like a jewel, and a glass decorative stone having the metal film is produced. Next, the decorative stone made of glass is fixed to the decorative article base using an adhesive. At this time, the surface on which the metal film of glass is formed is adhered to the substrate, so that light incident from the upper surface and side surfaces of the glass is reflected by the metal film. As a result, the ornamental stone appears to shine like a diamond, a beautiful appearance is obtained, and a high-quality feeling is given to the ornaments such as watches.

  However, such a fixing method has a problem in that, since the surface on which the metal film of glass is formed is bonded to the substrate, the ornamental stone is detached from the substrate when the metal film is peeled off from the glass.

Incidentally, metallic paints are known as glossy resin compositions (for example, Patent Documents 1 and 2). However, these paints coat the surface of the substrate and are not suitable as an adhesive because of insufficient adhesion.
JP 2003-213216 A JP 11-343431 A

  The present invention is intended to solve the problems associated with the prior art as described above, and is an adhesive composition capable of firmly fixing an ornamental stone to a substrate and making the ornamental stone shine beautifully, and its adhesion It is an object to provide a decorative article in which a decorative stone is fixed to a substrate using an agent composition. Furthermore, this invention makes it the subject to provide the fixing method of the ornamental stone using the said adhesive composition.

The present inventor has eagerly studied to solve the above problems, and by using an adhesive composition containing glossy aluminum fine particles and a specific binder, the ornamental stone is fixed to the substrate, Has a beautiful shine and is firmly fixed to the substrate, and has completed the invention.

  That is, the adhesive composition according to the present invention contains a binder having a cure shrinkage rate of less than 10% and aluminum fine particles having a particle size of 100 μm or less, and the aluminum fine particles are 100 parts by weight with respect to 100 parts by weight of the binder. -500 weight part is contained, It is characterized by the above-mentioned. The binder is preferably composed of an epoxy resin and a curing agent.

  In the decorative article according to the present invention, the ornamental stone is fixed to the substrate through the cured product of the adhesive composition.

  The timepiece according to the present invention has a timepiece exterior part to which a decorative stone is fixed through a cured product of the adhesive composition of the adhesive composition.

  The decorative stone fixing method according to the present invention is characterized in that the decorative stone is fixed to a decorative article base using the adhesive composition.

  The decorative article repair agent according to the present invention contains a binder having a curing shrinkage of less than 10% and aluminum fine particles having a particle size of 100 μm or less, and the aluminum fine particles are 100 to 100 parts by weight with respect to 100 parts by weight of the binder. 500 parts by weight is included. The binder is preferably composed of an epoxy resin and a curing agent.

  According to the present invention, the ornamental stone can be firmly fixed to the ornamental base, and the ornamental stone can be shined beautifully. In addition, the metal film forming process conventionally applied to the ornamental stone is not required, and it is possible to easily manufacture a decorative article base to which the ornamental stone having a beautiful shine is fixed, while greatly reducing the cost. Furthermore, the adhesive is not easily deteriorated, and the ornament can be used without the ornamental stone being detached from the base for a long period of time.

  The adhesive composition and the repairing agent according to the present invention contain aluminum fine particles and a binder. First, the raw material used for this invention is demonstrated.

(A) Aluminum fine particles:
The aluminum fine particles used in the present invention have a particle size of 100 μm or less, preferably 50 μm or less, more preferably 2 to 10 μm. When the particle size of the aluminum fine particle exceeds the above range, the glossiness of the aluminum fine particle is lowered, and the adhesive composition containing the fine particle having a large particle size is easy to separate the fine particle and the binder, and the cured product has an uneven brightness. It becomes.

  Examples of such aluminum fine particles include so-called leafing aluminum powder. Specifically, 0900M (average particle size 26 μm), 0670TS (average particle size 4.9 μm), 5207N (average particle size 6.0 μm), 5205 (average particle size 12 μm), 1200M (average particle size) manufactured by Toyo Aluminum Co., Ltd. Commercial products such as 10 μm), 8880 YF (average particle size 12 μm), MG1000 (average particle size 28 μm), 1950 M (average particle size 52 μm), 1109 M (average particle size 30 μm).

(B) Binder:
The binder used in the present invention is a resin composition having a cure shrinkage of less than 10%, preferably 5% or less, more preferably 3% or less, and has visible light transparency. Examples of such a binder include a normal epoxy resin adhesive composition comprising an epoxy resin and a curing agent, and a liquid epoxy resin adhesive composition having transparency. Such an epoxy resin adhesive composition may be either a thermosetting epoxy resin or a photocurable epoxy resin composition.

  Specific examples of the epoxy resin include Epicoat 828 (manufactured by Japan Epoxy Resin Co., Ltd.), DER331 (manufactured by Dow Chemical Co., Ltd.), AER-260 (manufactured by Asahi Ciba Co., Ltd.) YD128, YD-8125 (above, Toto Kasei Co., Ltd.) Bisphenol A type epoxy resin such as Epicoat 806, 807 (above, manufactured by Japan Epoxy Resin Co., Ltd.), Bisphenol F type epoxy resin such as YD8170C (manufactured by Tohto Kasei Co., Ltd.); Biphenyl such as YX4000 (manufactured by Japan Epoxy Resin Co., Ltd.) Type epoxy resin; naphthalene type epoxy resin such as NC7000 (manufactured by Nippon Kayaku Co., Ltd.), HP-4032 (manufactured by Dainippon Ink & Chemicals, Inc.); ESX-221 (manufactured by Sumitomo Chemical Co., Ltd.), VG3101 (manufactured by Mitsui Chemicals, Inc.), Polyfunctional epoxy resin such as EPPN-502 (manufactured by Nippon Kayaku Co., Ltd.); CC206,221,249,1234 (manufactured by Union Carbide Corporation), CY175, CY179 (manufactured by Ciba Geigy), Celloxide 2021 (Daicel Chemical Industries, Ltd.) include alicyclic epoxy resins such as.

  In addition, as the curing agent, phthalic anhydrides such as methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendomethylene phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylene phthalic anhydride; Methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2 -Imidazole such as 1-cyanoethyl-2-ethyl-4-methylimidazolium trimellitate, 2,4-diamino-6- (2'-methylimidazolyl- (1 '))-ethyl-s-triazine Etc.

  The mixing ratio of the epoxy resin and the curing agent (curing agent / epoxy resin) is 1.0 or more, preferably 1.0 to 1.5, more preferably 1.0, as the chemical equivalent ratio of the epoxy resin and the curing agent. ~ 1.3 is desirable.

<Adhesive composition and repair agent>
The adhesive composition according to the present invention can be produced by mixing the aluminum fine particles and a binder. The aluminum fine particles are included in an amount of 100 to 500 parts by weight with respect to 100 parts by weight of the binder. When the content of the aluminum fine particles is less than the lower limit, the amount of reflected light decreases, and the decoration stones become dull. When the content of the aluminum fine particles exceeds the above upper limit, the fluidity of the adhesive composition is lowered, and it becomes difficult to apply or inject the adhesive to the adhesion site.

  The adhesive composition according to the present invention can also be used as a repair agent for exterior parts of decorative items such as watches. For example, the adhesive composition is applied or injected to a wound made on the exterior part and cured to repair the exterior part. The repaired portion has a brightness comparable to that of the surroundings, and the cured product has high adhesion to the exterior part, so that the repaired portion is not peeled off or detached.

<Adhering method of decorative stone>
The method for adhering ornamental stones according to the present invention is a method for adhering ornamental stones to a decorative article substrate using the adhesive composition.

The ornamental stone used in the present invention is usually an ornamental stone used for ornaments, and does not have a metal film such as aluminum. Specifically, a glass decorative stone is raised. Further, the decorative article base body used in the present invention is not particularly limited as long as it is used for a decorative article, and examples thereof include a watch exterior part, a bracelet, a metal fitting such as a bag, and the like.

  First, a hole having a diameter of 1 to 1.5 mm is usually formed in a portion to which the ornamental stone of the decorative article base is fixed. Next, the adhesive composition is injected into the hole using a dispenser or the like, and then a decorative stone is inserted into the hole from the front side of the base. Thereafter, when a thermosetting epoxy resin adhesive is used, the adhesive composition is cured by heating at 80 to 120 ° C. for 30 minutes to 2 hours, and the ornamental stone is fixed to the substrate. Moreover, when a photocurable epoxy resin adhesive is used, the adhesive composition may be cured by irradiating ultraviolet rays or the like, and the ornamental stone may be fixed to the substrate.

  The ornamental stone fixed in this way is firmly fixed to the decorative article base. In particular, when the decorative article is a watch, the adhesive force between the ornamental stone and the watch exterior part is 3 kgf or more, preferably 3.5 to 4.0 kgf.

<Decoration>
The decorative article according to the present invention is one in which an ornamental stone is fixed to a decorative article base using the adhesive composition. Examples of such ornaments include watches, bracelets, and amber fittings.

<Example>
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by this Example. First, materials used in Examples and Comparative Examples are shown.

<Binder>
Epoxy resin binder A:
50 parts by weight of bisphenol A type epoxy resin (trade name: Epicoat 828, manufactured by Japan Epoxy Resin Co., Ltd.) and the following formula

50 parts by weight of an epoxy resin represented by the following formula: 47 parts by weight of methylendomethylenetetrahydrophthalic anhydride, 50 parts by weight of endomethylenetetrahydrophthalic anhydride, and 3 parts by weight of 2-ethyl-4-methylimidazole Binder A was prepared.

Acrylic binder B:
50 parts by weight of pentaerythritol triacrylate and the following formula

An acrylic adhesive was prepared by mixing 50 parts by weight of an ethylene oxide adduct diacrylate of bisphenol A and 5 parts by weight of t-butylperoxybenzoate as a radical generator.

<Example 1>
100 parts by weight of the epoxy resin binder A and 100 parts by weight of aluminum fine particles (particle size: 2 to 5 μm) obtained by sieving aluminum fine particles (trade name: 0670TS) manufactured by Toyo Aluminum Co., Ltd. Stirring and mixing for minutes, an epoxy resin adhesive composition 1 was prepared.

  Epoxy resin adhesive composition 1 was injected into a hole (1 mm diameter) of a watch exterior part (manufactured by SUS304 and SUS316L), and a glass decorative stone was inserted into this hole from the front side of the exterior part. Thereafter, the adhesive composition 1 was cured by heating at 100 ° C. for 1 hour, and the glass decorative stone was fixed to the watch exterior part.

  About this exterior component, the following method measured the adhesive force of an ornamental stone and an exterior component, the drop test, and observation of the brightness of the ornamental stone.

(Adhesive strength)
Using a push-pull gauge (manufactured by Aiko Engineering Co., Ltd., model number: 9500), the adhesion force when the decorative stone was detached from the exterior component was measured by pressing the fixed ornament stone through the hole on the back side of the exterior component.

(Drop test)
The exterior part to which the ornamental stone was fixed was freely dropped from a height of 1 m, and it was confirmed whether the ornamental stone was detached from the exterior part.

(Luminance)
Light was irradiated from the side of the ornamental stone fixed to the exterior part using a penlight (manufactured by Streamlight, trade name: stylus), and the brightness of the ornamental stone at this time was visually observed from the upper surface of the ornamental stone. In comparison with the diamond for watch decoration, it was evaluated based on the following criteria.

Evaluation A: Shine comparable to diamond
B: The brightness is inferior to diamond.

  Moreover, the cure shrinkage rate of the epoxy resin adhesive composition 1 was measured by the following method.

(Curing shrinkage)
First, the specific gravity of the adhesive composition before curing was measured. Next, this adhesive composition was heated at 100 ° C. for 1 hour to prepare a cured product. The specific gravity of the cured product was measured to calculate the curing shrinkage rate.

  These results are shown in Table 1.

<Comparative Example 1>
Example 1 except that 100 parts by weight of silver fine particles (particle diameter: 2 to 5 μm) obtained by sieving silver powder (trade name: Silcote AgC-B) manufactured by Fukuda Metal Co., Ltd. were mixed in place of the aluminum fine particles. In the same manner as above, an epoxy resin adhesive composition a was prepared, and a glass decorative stone was fixed to a watch exterior part. In the same manner as in Example 1, each physical property was measured and evaluated. The results are shown in Table 1.

<Comparative example 2>
Example 1 except that 100 parts by weight of copper fine particles (particle size: 2 to 5 μm) obtained by sieving copper powder (trade name: EFC-3000) manufactured by Fukuda Metal Co., Ltd. were mixed in place of the aluminum fine particles. In the same manner as above, an epoxy resin adhesive composition b was prepared, and a glass decorative stone was fixed to a watch exterior part. In the same manner as in Example 1, each physical property was measured and evaluated. The results are shown in Table 1.

<Comparative Example 3>
Each physical property was measured and evaluated in the same manner as in Example 1 except that 100 parts by weight of the acrylic adhesive B was used in place of the epoxy resin binder A. The results are shown in Table 1.

<Comparative example 4>
EVA hot melt adhesive and aluminum in the same manner as in Example 1 except that 100 parts by weight of EVA hot melt adhesive (trade name: DA574B, manufactured by Nogawa Chemical Co., Ltd.) was used instead of the epoxy resin adhesive. Although the fine particles were mixed, the viscosity increased during stirring, and it was difficult to prepare an adhesive composition.

<Comparative Example 5>
EVA hot melt adhesive and aluminum fine particles were used in the same manner as in Example 1 except that 100 parts by weight of chloroprene rubber (trade name: DW246, manufactured by Nogawa Chemical Co., Ltd.) was used instead of the epoxy resin adhesive. Although mixed, the viscosity increased during stirring, and the preparation of the adhesive composition was difficult.

<Example 2>
Except for using 100 parts by weight of aluminum fine particles (particle size 2 to 10 μm) obtained by sieving aluminum fine particles (trade name: 5207N) manufactured by Toyo Aluminum Co., Ltd. instead of aluminum fine particles having a particle size of 2 to 5 μm. In the same manner as in Example 1, an epoxy resin adhesive composition 2 was prepared, and a glass decorative stone was fixed to a watch exterior part. In the same manner as in Example 1, each physical property was measured and evaluated. The results are shown in Table 2.

< Reference Example 3>
Except for using 100 parts by weight of aluminum fine particles (particle size 20-30 μm) obtained by sieving aluminum fine particles (trade name: MG1000) manufactured by Toyo Aluminum Co., Ltd. instead of aluminum fine particles having a particle size of 2-5 μm. In the same manner as in Example 1, an epoxy resin adhesive composition 3 was prepared, and a glass decorative stone was fixed to an exterior part for a watch. In the same manner as in Example 1, each physical property was measured and evaluated. The results are shown in Table 2.

< Reference Example 4>
Except for using 100 parts by weight of aluminum fine particles (particle size 50 to 80 μm) obtained by sieving aluminum fine particles (trade name: 1950 M) manufactured by Toyo Aluminum Co., Ltd. instead of aluminum fine particles having a particle size of 2 to 5 μm. In the same manner as in Example 1, an epoxy resin adhesive composition 4 was prepared, and a glass decorative stone was fixed to a watch exterior part. In the same manner as in Example 1, each physical property was measured and evaluated. The results are shown in Table 2.

< Reference Example 5>
Except for using 100 parts by weight of aluminum fine particles (particle size 80-100 μm) obtained by sieving aluminum fine particles (trade name: 1950M) manufactured by Toyo Aluminum Co., Ltd. instead of aluminum fine particles having a particle size of 2-5 μm. In the same manner as in Example 1, an epoxy resin adhesive composition 5 was prepared, and a glass decorative stone was fixed to a watch exterior part. In the same manner as in Example 1, each physical property was measured and evaluated. The results are shown in Table 2.

<Comparative Example 6>
Example except that 100 parts by weight of aluminum fine particles (particle size 130 to 150 μm) obtained by cutting metal aluminum and sieving the obtained chips were used in place of the aluminum fine particles having a particle size of 2 to 5 μm. In the same manner as in No. 1, an epoxy resin adhesive composition 2 was prepared, and a glass decorative stone was fixed to a watch exterior part. In the same manner as in Example 1, each physical property was measured and evaluated. The results are shown in Table 2.

<Examples 6 to 10>
Epoxy resin adhesive compositions 6 to 10 were prepared in the same manner as in Example 1 except that the amount of aluminum fine particles shown in Table 3 was used instead of 100 parts by weight of the aluminum fine particles. Fixed to the exterior part. In the same manner as in Example 1, each physical property was measured and evaluated. The results are shown in Table 3.

<Comparative Examples 7-8>
Epoxy resin adhesive compositions cd were prepared in the same manner as in Example 1 except that the amount of aluminum fine particles shown in Table 3 was used instead of 100 parts by weight of the aluminum fine particles. Fixed to the exterior part. In the same manner as in Example 1, each physical property was measured and evaluated. The results are shown in Table 3.

<Comparative Example 9>
An aluminum thin film was deposited on the back side of the glass ornamental stone. Next, in the same manner as in Example 1, the epoxy resin binder A was injected into the hole of the watch exterior part. A glass decorative stone having an aluminum thin film on the back surface was inserted into the hole from the front side of the exterior part. Thereafter, the binder A was cured by heating at 100 ° C. for 1 hour, and the glass decorative stone was fixed to the watch exterior part.

  In the same manner as in Example 1, each physical property was measured and evaluated. The results are shown in Table 3.

<Example 11>
The watch exterior parts, to which the glass ornament stones were fixed, prepared in Examples 1 to 10 were stored at 90 ° C. for 1500 hours, and the watch exterior parts after storage were checked for the presence or absence of the ornament stones. As a result, the ornamental stones were not detached from any of the exterior parts. Moreover, when the adhesive force was measured, the adhesive force did not change before and after storage.

<Comparative Example 10>
The watch exterior part, to which the glass ornamental stone having the aluminum thin film prepared in Comparative Example 9 was fixed, was stored at 90 ° C. for 1500 hours, and the watch exterior part after storage was checked for the presence or absence of the ornamental stone, The adhesive force was measured. As a result, although the detachment of the ornamental stone was not observed, the adhesive strength after storage was lower than that before storage.

  According to the present invention, even if the ornamental stone is an inexpensive decorative product made of glass, it can give a high-class feeling. Further, the metal film forming process conventionally applied to the ornamental stone is not required, and the cost can be greatly reduced, and a decorative article base to which the ornamental stone having a beautiful shine is fixed can be easily manufactured. . Furthermore, since the ornamental stone fixed in this way does not detach from the base body for a long period of time, the decorative article can be used for a long period of time without repair.

Claims (5)

Cure shrinkage comprising a epoxy resin and the curing agent is contained and less than 10% binder, and aluminum fine particles of a particle size of 2 to 10 mu m,
The adhesive composition for decorative articles , wherein the aluminum fine particles are contained in an amount of 100 to 500 parts by weight with respect to 100 parts by weight of the binder. A decorative article in which ornamental stones are fixed to a substrate through a cured product of the adhesive composition for decorative articles according to claim 1. A timepiece having a watch exterior part to which a decorative stone is fixed via a cured product of the adhesive composition for decorative articles according to claim 1. A method for adhering ornamental stone, comprising adhering ornamental stone to a decorative article base using the ornamental adhesive composition according to claim 1. The repair agent for decorative articles which consists of the adhesive composition for decorative articles of Claim 1 .