JPWO2008140059A1 - Glass filler, photocurable coating composition and photocurable resin composition using the same, and photocurable adhesive - Google Patents

Abstract

The flaky glass of the present invention has a light transmittance at a wavelength of 360 nm of 80% or more when formed into a 1 mm thick glass plate, and a refractive index at a wavelength of 360 nm in the range of 1.55 to 1.61. It consists of a certain glass composition. Furthermore, it is preferable that the glass composition used for the flaky glass of the present invention has a refractive index in the range of 1.53 to 1.57 at a wavelength of 1300 nm.

Description

  The present invention relates to a glass filler, a photocurable coating composition and a photocurable resin composition using the glass filler, and a photocurable adhesive.

  In recent years, environmental issues and the importance of energy saving have increased. Since the photo-curing resin and paint are cured in a short time by irradiation with light such as ultraviolet rays, labor saving and automation can be achieved. Therefore, photocurable resins and paints are attracting attention because they save energy compared to thermosetting resins and paints. Typical examples of the photocurable resin include acrylic resins and epoxy resins.

  On the other hand, in order to improve the heat resistance, dimensional stability, linear expansion coefficient and rigidity of various thermoplastic resins, many resin compositions to which various inorganic fillers are added have been proposed (for example, JP-A-6-157896). JP-A-6-157898 and JP-A-8-104775). For example, Japanese Patent Application Laid-Open No. 62-109855 discloses a technique for improving the strength and dimensional stability of flaky glass blended with a thermoplastic resin. Japanese Patent Application Laid-Open No. 3-86753 describes blending a granular flaky glass granulated with a fibrous reinforcing material and a binder into a thermoplastic resin.

For these flaky glasses, so-called non-alkali silicate glasses such as E glass and alkali-containing silicate glasses such as C glass are used. Examples of the alkali-containing silicate glass mainly include, for example, 60 to 75% of SiO ₂ and 8 to 20% of R ₂ O (alkali metal oxides such as Na ₂ O and K ₂ O) by weight%. (However, SiO ₂ + R ₂ O is 75 to 90%). In addition, for example, one or more oxides such as CaO, MgO, B ₂ O ₃ , Al ₂ O ₃ , ZnO, and Fe ₂ O ₃ are used. The glass containing is mentioned.

  However, the flaky glass having the above composition absorbs ultraviolet rays, so when added to a photocurable resin, it does not cure sufficiently to the inside of the resin and cannot be used as a filler for the photocurable resin. It was.

  Even if it is added to a photocurable resin, the present invention does not prevent the resin from being cured by light irradiation and stabilizes a cured product of a thick film resin / glass composite (photocurable resin containing a glass filler). An object of the present invention is to provide a glass filler that can be produced automatically. The present invention also provides a photocurable resin composition in which a glass filler is added to a photocurable resin (or photocurable paint) for the purpose of improving characteristics such as heat resistance, dimensional stability and / or rigidity (or An object of the present invention is to achieve stable photocuring and high transparency in a photocurable coating composition). Another object of the present invention is to provide a photocurable adhesive using the photocurable resin composition.

  The glass filler of the present invention has a light transmittance of 80% or more (80% / mm or more) at a wavelength of 360 nm when molded into a 1 mm thick glass plate, and a refractive index of 1.55 to 1 at a wavelength of 360 nm. .61 of the glass composition.

  When the glass filler of the present invention is added to, for example, a photocurable resin (for example, an epoxy resin) having a refractive index of 1.55 to 1.61 at a wavelength of 360 nm in a state after curing, a sufficient amount Therefore, even if it is a thick film, the resin / glass composite can be stably cured.

  Moreover, this invention provides the photocurable coating composition containing the glass filler of said this invention, and the photocurable coating material whose refractive index in wavelength 360nm is in the range of 1.48-1.65. The present invention also provides a photocurable resin composition comprising the glass filler of the present invention described above and a photocurable resin having a refractive index in the range of 1.48 to 1.65 at a wavelength of 360 nm.

  Since the photocurable resin composition and the photocurable coating composition of the present invention contain the glass filler of the present invention as described above, light can reach the inside even if it is a thick film, A cured product can be obtained stably. Accordingly, it is possible to realize a resin molded product, a coating film or the like with improved heat resistance, dimensional stability, rigidity, and the like.

  Furthermore, this invention provides the photocurable adhesive agent containing the photocurable resin composition of said invention.

  Since the photo-curable adhesive of the present invention contains the photo-curable resin composition of the present invention as described above, stable and strong adhesion can be obtained by the same action by the glass filler, and heat resistance An adhesive having excellent properties, dimensional stability, rigidity and the like can be provided.

  Embodiments of the present invention will be described below.

(Glass filler)
The glass filler of this Embodiment is formed with the glass composition whose transmittance | permeability in wavelength 360nm is 80% / mm or more. A filler made of a material having a transmittance of less than 80% / mm at a wavelength of 360 nm cannot transmit sufficient ultraviolet rays. Therefore, when added to a photocurable resin, the filler has a depth of 1 mm or more ( It becomes difficult to stably cure the resin / glass composite). In order to cure more stably when added to the photocurable resin, the transmittance of the glass filler at a wavelength of 360 nm is more preferably 90% / mm or more.

A composition examples of glass compositions used in glass filler of the present invention (Composition Examples 1 to 3), for example, SiO ₂ is 60 to 70 wt%, Al ₂ O ₃ is 5 to 10 wt%, CaO is 20-30 % By mass, MgO 0-6% by mass, R ₂ O (R ₂ O = Li ₂ O + Na ₂ O + K ₂ O) 0-2% by mass, TiO ₂ 0-2% by mass (Composition Example 1), or SiO ₂ is 52 to 56 wt%, Al ₂ O ₃ is 12 to 20 mass%, CaO is 16-25 wt%, MgO 0 to 6 wt%, B ₂ O ₃ is 5 to 13 wt%, R ₂ O There 0-2 wt% (composition example 2), or, SiO ₂ is 63 to 72 wt%, Al ₂ O ₃ is 1-7 wt%, CaO 4 to 11 wt%, MgO from 0 to 5 wt%, B ₂ O ₃ is 0 to 8% by mass, R ₂ O is 9 to 19% by mass, ZnO is 0 to 6% by mass (Composition Example 3), and the like.

Iron oxide in the glass composition exists in the state of Fe ₂ O ₃ and FeO in the glass. The total iron oxide converted to Fe ₂ O ₃ is preferably less than 0.05% by mass, and more preferably 0.01% by mass or less. This is because ultraviolet absorption becomes large at 0.05 mass% or more, and it becomes difficult to make the transmittance at a wavelength of 360 nm less than 80% / mm.

  Moreover, the glass composition used for the glass filler of this Embodiment is the range whose refractive index in wavelength 360nm is 1.55-1.61. In general, an epoxy resin often used as a photocurable resin has a refractive index of 1.55 to 1.61 at a wavelength of 360 nm after curing. For this reason, when the glass filler of the present embodiment is added to these photocurable resins, the reflection at the resin / glass interface becomes so small that it can be ignored, and ultraviolet rays are absorbed inside the resin / glass composite (back, (Deep part), and the inside of the resin / glass composite can be completely solidified.

  Moreover, it is preferable that the glass composition used for the glass filler of this Embodiment has the refractive index in wavelength 1300nm in the range of 1.53-1.57. Thus, when the refractive index at a wavelength of 1300 nm is in the range of 1.53 to 1.57, the glass filler of the present embodiment has high transparency with respect to light having a wavelength in the vicinity. On the other hand, wavelengths generally used for optical communication are 1300 nm and 1550 nm. Therefore, when a resin composition containing such a glass filler is used in a portion where light from an optical communication device is transmitted, loss or scattering of the light amount can be prevented.

  The shape of the glass filler varies depending on the application and is not particularly limited, and examples thereof include glass fiber, glass powder, flaky glass, milled fiber, and glass beads. These may be used alone or in combination. When producing a resin molding etc., using in combination with glass fiber and flake shaped glass can be illustrated. Even when added to an adhesive or paint, the shape is not particularly limited. However, when the surface hardness and physical characteristics are improved or the surface smoothness is improved because the thickness of the coating film or the like is reduced, the glass filler is preferably flaky glass.

  Moreover, since the magnitude | size of a glass filler changes with usages, it is not specifically limited. However, since the surface becomes uneven when the average particle size of the glass filler is too large, it is desirable to reduce the average particle size of the glass filler when improvement in surface smoothness or the like is required.

  In general, when flaky glass is used as a filler for an adhesive such as a printed circuit board or a display element, it is preferable that the average thickness is 0.1 to 10.0 μm and the average particle size is 5 to 1,000 μm. If the average thickness exceeds 10.0 μm, irregularities may be formed on the surface of the adhesive or protrusions may be formed, which may cause problems on the adhesive surface. If the average particle diameter exceeds 1,000 μm, problems may occur for the same reason. Moreover, when average thickness is less than 0.1 micrometer, productivity of glass material may worsen extremely, and it is not realistic. Furthermore, when the average particle size is less than 5 μm, mechanical properties such as dimensional stability and strength may not be imparted. In the present specification, the average thickness of the flaky glass means that at least 100 pieces of flaky glass are extracted, and the thickness of the flaky glass is measured using a scanning electron microscope (SEM). This is the value obtained by dividing the total by the number of sheets to be measured. In the present specification, the average particle size of the flaky glass is a particle size (D50) corresponding to a cumulative mass percentage of 50% in the particle size distribution measured based on the laser diffraction scattering method.

  Moreover, the glass filler of this Embodiment may be coat | covered with the coupling agent, in order to improve affinity with these, when added to photocurable resin or a photocurable coating material. A typical example of the coupling agent is a silane coupling agent. Although the silane coupling agent varies depending on the resin used, vinyl silane, epoxy silane, methacryloxy silane, and amino silane are preferable. These silane coupling agents may be used alone or in combination.

  Examples of vinyl silane include vinyl trichlorosilane, vinyl trimethoxy silane, vinyl triethoxy silane and the like. Examples of the epoxy silane include 2- (3,4 epoxy cyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane. Can be illustrated. Examples of methacryloxysilane include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane. As aminosilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, Examples include 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine and N-phenyl-3-aminopropyltrimethoxysilane.

  It is preferable that the content rate of a silane coupling agent is 0.01 mass%-5.0 mass% with respect to the whole mass. If the content of the silane coupling agent is less than 0.01% by mass, it may be difficult to obtain sufficient affinity between the glass filler and the photocurable resin or photocurable paint. On the other hand, when the content of the silane coupling agent exceeds 5.0% by mass, the reaction between the coupling agents easily occurs, and the reaction impairs the affinity between the glass filler and the paint or resin, and the cost is low. Get higher.

  Moreover, since the thickness of the layer formed by these coupling agents is about the thickness of the molecular layer formed on the glass surface, it does not affect the refraction and reflection of light in the glass filler.

(Photo-curable coating composition, photo-curable resin composition, photo-curable adhesive, optical communication device)
The photocurable resin composition of the present embodiment includes the glass filler and the photocurable resin of the present embodiment described above. As the photocurable resin, for example, an epoxy resin, an acrylic resin, or the like can be used. The refractive index at a wavelength of 360 nm of the photocurable resin used in the present embodiment is 1.48 to 1.65, preferably in the range of 1.53 to 1.63, more preferably 1.55 to 1.61. Range. By including the photocurable resin having a refractive index in such a range and the glass filler of the present embodiment, the photocurable resin composition of the present embodiment is sufficient even in the case of a thick film. Can be made to reach the light, and a cured product can be obtained more stably. Accordingly, it is possible to realize a resin molded product having improved heat resistance, dimensional stability, rigidity, and the like.

  The photocurable coating composition of the present embodiment includes the glass filler and the photocurable coating composition of the present embodiment described above. The refractive index at a wavelength of 360 nm of the photocurable coating used in the present embodiment is 1.48 to 1.65, preferably in the range of 1.53 to 1.63, more preferably 1.55 to 1.61. Range. As the photocurable paint, for example, an epoxy paint, a urethane paint, a polyester paint, or the like can be used.

  The content ratio of the flaky glass in the photocurable resin composition and the photocurable coating composition of the present embodiment is not particularly limited, but is preferably 10 to 90% by mass, and 30 to 80% by mass. More preferably. If the content of the flaky glass is less than 10% by mass, it becomes difficult to improve the heat resistance, dimensional stability, rigidity, etc. of the resin, and if it exceeds 90% by mass, the function as a resin cannot be achieved. is there.

  The photocurable adhesive of the present embodiment includes the above-described photocurable resin composition of the present embodiment, and a plasticizer, a sensitizer, an organic peroxide, Other components necessary as an adhesive such as a polymerization initiator and a polymerization stabilizer can be appropriately contained.

  Moreover, it is also possible to provide an optical communication apparatus, for example, using the photocurable resin composition of this Embodiment demonstrated above. Such an optical communication device is excellent in heat resistance, dimensional stability, rigidity, and the like.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.

(Examples 1-8, Comparative Examples 1-4)
In order to obtain the composition shown in Table 1, ordinary glass raw materials such as silica sand were prepared to prepare Examples, Comparative Examples, and respective batches. These batches were heated to 1400 ° C. to 1600 ° C. using an electric furnace, melted, and maintained for about 4 hours until the composition became uniform. Then, the molten glass was poured out on the iron plate, and the plate-shaped glass sample was obtained by cooling to normal temperature. This was polished to a thickness of 1 mm to obtain a sample for measuring optical characteristics. In addition, Table 2 shows the transmittance at a wavelength of 360 nm and the refractive index at a wavelength of 360 nm measured for the plate-like glass samples of Examples 1 to 8 and Comparative Examples 1 to 4.

  The transmittance used in this example was measured using an ultraviolet-visible-near infrared spectrophotometer UV-3600 manufactured by Shimadzu Corporation. The refractive index is a value obtained by calculation from the reflectance measured by a spectrophotometer.

In the glass samples of Examples 1 to 8, a transmittance of 80% / mm or more at a wavelength of 360 nm could be obtained. In contrast, in the glass materials of Comparative Examples 1 to 3, the transmittance was less than 80% / mm. Moreover, since the refractive index is 1.55-1.58 in the glass sample of Examples 1-8, when it adds to an epoxy resin with a refractive index of about 1.56, for example, when the said resin is photocured, it is glass material. The reflection at the resin interface is so small that it can be ignored, so that it is assumed that the ultraviolet rays are transmitted through the entire surface and uniform curing can be realized. Next, after melting the glass of these examples and comparative examples, it was blown into a hollow shape with a blow gas to form a thin film, and the obtained glass thin film was crushed with a pressing roll into a flake shape (flaking process), A flaky glass was obtained. These flaky glasses were added to an ultraviolet curable resin (refractive index adjusted product (high Tg) type [epoxy]) manufactured by NTTAT. The ultraviolet curable resin used had a refractive index of 1.55 at a wavelength of 360 nm. Glass filler (flaked glass): UV curable resin is mixed and stirred so as to have a mass ratio of 80:20, put into a mold having a size of 50 mm × 50 mm × 2 mm, 30 mW / cm ² , 10 min. It was cured by irradiating a light amount of ultraviolet rays. Table 3 shows the results of visual observation of the cured state.

  From Examples 1 to 8 and Comparative Examples 1 to 3, when the refractive index of the glass filler is about the same as the refractive index of the resin, the flakes of Examples 1 to 8 having a transmittance at a wavelength of 360 nm of 80% / mm or more In the resin to which glassy glass is added, the entire resin is cured by transmitting ultraviolet rays to the inside of the resin, whereas in Comparative Examples 1 to 3 in which the transmittance at a wavelength of 360 nm is less than 80% / mm, ultraviolet rays are transmitted. It turns out that it did not harden by not doing. Further, from Examples 1 to 8 and Comparative Example 4, even if the transmittance at a wavelength of 360 nm is 80% / mm or more, the flakes of Comparative Example 4 in which the refractive index of the glass filler at a wavelength of 360 nm is significantly different from the refractive index of the resin. In the glass-like glass, it can be seen that due to the interface reflection at the glass material and the resin interface, ultraviolet rays did not pass through to the inside even if the outermost surface was cured, and the whole could not be cured.

  As is apparent from the above results, a glass filler made of a glass composition having a transmittance at a wavelength of 360 nm of 80% / mm or more and a refractive index at a wavelength of 360 nm of 1.55 to 1.61 is light. When filled into a curable resin, even if the glass filler content is large, it transmits sufficient ultraviolet rays. Especially when a glass filler having a refractive index matching that of the photocurable resin is added, reflection at the glass-resin interface is not possible. Therefore, ultraviolet rays are transmitted through the entire surface and uniform curing can be realized. Furthermore, according to such a glass filler, since a photocurable resin composition that can contain a large amount of glass filler relative to the resin can be produced, a resin molded product with improved heat resistance, dimensional stability, rigidity, etc., light Curable adhesives and paints can be provided.

  Even when the glass filler of the present invention is added to a photocurable resin, a sufficient amount of ultraviolet rays can reach the inside of the resin, and even if it is a thick film, the resin / glass composite is stably cured. Therefore, it can be applied to various applications such as a photocurable coating composition, a photocurable resin composition, a photocurable adhesive, and an optical communication device.

Claims (10)

  A glass filler comprising a glass composition having a light transmittance of 80% or more at a wavelength of 360 nm when formed into a 1 mm thick glass plate and a refractive index of 1.55 to 1.61 at a wavelength of 360 nm. . The content of Fe ₂ O ₃ is less than 0.05 wt% in the glass composition, the glass filler according to claim 1. The glass composition as a composition component,
SiO ₂ : 60 to 70% by mass,
Al ₂ O ₃ : 5 to 10% by mass,
CaO: 20 to 30% by mass,
MgO: 0 to 6% by mass,
R ₂ O (R ₂ O = Li ₂ O + Na ₂ O + K ₂ O): 0 to 2% by mass,
TiO ₂ : 0 to 2% by mass,
The glass filler according to claim 1, comprising: The glass composition as a composition component,
SiO _2: 52~56% by weight,
Al ₂ O ₃ : 12 to 20% by mass,
CaO: 16 to 25% by mass,
MgO: 0 to 6% by mass,
B ₂ O ₃ : 5 to 13% by mass,
R ₂ O (R ₂ O = Li ₂ O + Na ₂ O + K ₂ O): 0 to 2% by mass,
The glass filler according to claim 1, comprising: The glass composition as a composition component,
SiO _2: 63~72% by weight,
Al ₂ O ₃ : 1 to 7% by mass,
CaO: 4 to 11% by mass,
MgO: 0 to 5% by mass,
B ₂ O ₃ : 0 to 8% by mass,
R ₂ O (R ₂ O = Li ₂ O + Na ₂ O + K ₂ O): 9 to 19% by mass,
ZnO: 0 to 6% by mass,
The glass filler according to claim 1, comprising:   The glass filler according to claim 1, wherein the glass filler is at least one selected from flaky glass, glass powder, milled fiber, glass beads, and glass fiber.   The glass filler of Claim 1 whose refractive index of the said glass composition in wavelength 1300nm exists in the range of 1.53-1.57.   A photocurable coating composition comprising the glass filler according to claim 1 and a photocurable coating having a refractive index in the range of 1.48 to 1.65 at a wavelength of 360 nm.   A photocurable resin composition comprising the glass filler according to claim 1 and a photocurable resin having a refractive index in the range of 1.48 to 1.65 at a wavelength of 360 nm.   A photocurable adhesive comprising the photocurable resin composition according to claim 9.