JP2008214152A - Glass paste composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a glass paste which is inhibited in the sedimentation and separation of frit glass and filler particles and thus forms a good sealing. <P>SOLUTION: The glass paste has a vehicle containing a solvent and a dispersant, and a frit glass and a filler powder that are dispersed in the vehicle, wherein the value S of each of the frit glass and the filler powder calculated according to the formula:S=D<SP>2</SP>×ρ(wherein D exhibits an average particle diameter [μm], and ρ exhibits a density [g/cm<SP>3</SP>]) is 3,000 or less, or the density of the filler powder is smaller than that of the frit glass. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a glass paste composition used for sealing / bonding members / parts composed of glass, metal, ceramics, etc., and in particular, displays such as plasma display panels (PDP) and field emission displays (FED). The present invention relates to a glass paste composition that can be used as a sealing material for sealing and adhering components in the manufacture of devices, IC packages, electrical / electronic devices, and the like.

In the manufacture of thin flat displays such as PDP and FED, the sealing process for sealing and adhering the front plate and the back plate to form a discharge space is performed at a sealing temperature of 400 to 500 ° C. and a thermal expansion coefficient. It is carried out using a sealing / adhesive material (sealing material) of about 70 to 80 × 10 ⁻⁷ / ° C.

Conventionally, this type of sealing material, a mixture of PbO · B ₂ O ₃ based glass or Bi ₂ O ₃ based glass powder (frit glass) and low filler powder thermal expansion coefficient which melts at the sealing working temperature (See Patent Documents 1 and 2 below). The filler with a low thermal expansion coefficient is added for the purpose of reducing the difference in thermal expansion coefficient between the front plate or the back plate and the sealing material and suppressing the generation of cracks due to thermal stress. Ceramics are common.

Such a sealing material is prepared as a paste by using a solvent in which a resin is dissolved as a vehicle and mixing a frit glass that melts at a sealing operation temperature and a filler for adjusting thermal expansion. As an actual usage, for example, a sealing material is applied to the peripheral edge of the front plate to a width of 3 to 5 mm and a thickness of about 10 to 500 μm using a dispenser, and pre-baked at 400 to 500 ° C. After that, it is generally used in accordance with a procedure such as baking together at 400 to 450 ° C. and pasting together with the back plate.
JP 2002-348144 A JP 2005-314136 A

  However, the frit glass and filler used in the above-mentioned sealing material are likely to cause sedimentation during storage, and it takes time and labor to disperse the sediment once settled and return to the original paste state. The workability is bad.

  In order to suppress sedimentation of the components contained in the paste, there is a measure to increase the dispersibility by making the inclusion particles fine. However, since the surface of glass becomes active when it is made into fine particles, there is a concern that crystallization occurs or that the adsorbed gas tends to become bubbles on the surface during firing. Moreover, it is not preferable industrially and economically to make the frit glass fine.

  Another method to prevent sedimentation of paste-containing materials is to increase the paste viscosity by increasing the amount of resin dissolved in the solvent. However, since organic substances such as resin become sources of gas during firing, the amount increased. Is not preferred. In addition, in order to form a coating film by a general dispensing method or screen printing, it is necessary to make the viscosity range 35 to 60 Pa · s, preferably 40 to 55 Pa · s. There is a limit from the viewpoint.

  It is an object of the present invention to suppress the settling and separation of solid particles such as frit glass and filler particles dispersed in the paste, so that handling in use is easy, and a good seal is formed without causing problems even during firing. The object is to provide a glass paste composition.

  Another object of the present invention is to provide a glass paste composition in which sedimentation and separation in a paste is suppressed and a good sealing is formed without causing any problems even during firing using a glass having a low softening point. It is in.

In order to solve the above problems, according to one aspect of the present invention, a glass paste composition includes a vehicle containing a solvent and a dispersant, a frit glass and a filler powder dispersed in the vehicle, and the frit For each of the glass and the filler powder, a numerical value S calculated according to the formula: S = D ² × ρ (where D is the average particle diameter [μm] and ρ is the density [g / cm ³ ]) Or the density of the filler powder is smaller than the density of the frit glass.

In the above glass paste composition, the frit glass has a density of 2.5 to 4.4 g / cm ³ , and the filler powder has a density of 2 to 4.5 g / cm ³ and a thermal expansion coefficient of 80 × 10 6. ^-7 / ° C or less is preferable.

  The frit glass preferably has an average particle size of 1.5 to 35 μm, and the filler powder preferably has an average particle size of 1 to 40 μm.

  The dispersant is an organic resin, the solvent is an organic solvent that dissolves the dispersant, the frit glass is particles of low-melting glass having a softening point of 350 to 550 ° C., and the filler powder is Ceramics and / or a high melting point glass powder having a strain point of 450 ° C. or higher is preferable.

The frit glass is a glass containing vanadium in a proportion of 45 to 65% by mass in terms of V ₂ O ₅ , and the filler powder includes silica, alumina, aluminum titanate, and CaO—B ₂ O ₃ —Al ₂ O. preferably when at least one of the material of the particles ₃ is selected from the group consisting of low-alkali glass -SiO ₂ composition, relative to the frit glass 100 parts by weight, containing the filler powder in a proportion of 5 to 100 parts by weight can do.

According to another aspect of the present invention, a glass paste composition has a vehicle containing a solvent and a dispersant, and a frit glass dispersed in the vehicle, and the frit glass has the formula: S = D ² × The gist is that the numerical value S calculated according to ρ (wherein D represents an average particle diameter [μm] and ρ represents a density [g / cm ³ ]) is 3000 or less.

  Note that the present invention is not limited to the technical contents described in the above-described configuration and the embodiments described later, and various modifications can be made without departing from the technical idea of the present invention.

  According to the present invention, since the paste is prepared by adjusting the physical properties of the frit glass and the filler powder with an appropriate balance by selecting the material constituting the paste composition, the sedimentation of particles in the paste is suppressed. Therefore, it is possible to easily provide a glass paste composition capable of forming a good sealing and bonding while preventing problems during firing.

Since the lead component (PbO) contained in the conventional paste has a density of about 9 g / cm ³ , when the paste is formed using a general solvent (a density of about 1 g / cm ³ ), Since the density difference is large, the frit glass tends to settle and separate from the paste. The same can be said for the filler powder. In order to prevent sedimentation, it is conceivable that the density of the frit glass and filler powder is close to the density of the vehicle, but considering that the density of the vehicle is about 1 g / cm ³ , this method is practically difficult. I can say that.

  However, if the particles in the glass paste do not form a hard deposit by sedimentation during a certain storage period, it is easy to re-disperse and homogenize by applying a light vibration or rotational load. In consideration of suppressing the sedimentation to such a degree, the relationship between the density and particle diameter of the frit glass and filler powder and the sedimentation state was examined.

In general, it is known that the sedimentation rate (U _m ) of particles is expressed by the following formula 1, and based on this, the solvent density (ρ _s ) of a general organic solvent used in the paste is approximately 1 g / Considering that it is about cm ³ , the sedimentation rate of the particles contained in the glass paste composition is proportional to each of the square value of the particle diameter (D _P ) and the density of the particles (ρ _p ), and the paste viscosity (μ Is inversely proportional to

U _m = KD _P ² (ρ _p −ρ _s ) / μ (Formula 1)
For the particles constituting the paste, the numerical value S represented by the formula: S = D ² × ρ (D is the particle diameter [μm], ρ is the density [g / cm ³ ]) is calculated, When the numerical value S is 3000 or less, it was found that the sedimentation of particles is clearly suppressed, the formation of hard deposits is prevented, and redispersion is facilitated. Therefore, if a glass paste is prepared using a frit glass and a filler powder having a particle size and density satisfying the above numerical value S ≦ 3000, sedimentation separation during storage is suppressed, and a uniform glass paste can be easily redispersed and dispersed. Can be supplied. The same applies to pastes that do not use filler powder.

  Further, when observing hard deposits that make redispersion difficult, many deposits in a form in which the filler powder is mainly compacted are recognized. That is, when the filler powder is more likely to settle than the frit glass, such a deposit is easily formed. When the density of the filler powder is smaller than the frit glass, it is difficult for the filler powder to be positioned below the frit glass. it is conceivable that. Therefore, when a filler powder that is lighter than frit glass is used, it is difficult for the settled particles to form a hard deposit, and a glass paste that can be easily redispersed even when the above numerical value S requirement is not satisfied. Is possible.

  Therefore, the requirements of the frit glass and the filler powder constituting the glass paste that suppresses sedimentation separation and is easily redispersed satisfy either of the following requirements a) or b).

Requirement a) In each of the frit glass and the filler powder, the particle diameter D [μm] and the density ρ [g / cm ³ ] satisfy 3000 ≧ S = D ² × ρ.

      Requirement b) Density of filler powder ≦ density of frit glass.

According to the above requirement a), it is preferable to use particles having a particle size of about 27 μm or less when the density is 4 g / cm ³ and particles having a particle size of about 32 μm or less when the density is 3 g / cm ^3. Paste is prepared.

  Below, the glass paste composition of this invention is demonstrated in detail.

In the glass paste composition of the present invention, frit glass and filler particles having a density about half that of lead-based glass can be suitably used. Specifically, as the glass material of the frit glass, a glass having a density of about 4.4 g / cm ³ or less, preferably about 4.2 g / cm ³ or less may be used.

The composition of the glass material is based on the glass raw material and preparation, and the density of the glass varies depending on the composition. Glass raw materials include B ₂ O ₃ , SiO ₂ , Al ₂ O ₃ , P ₂ O ₅ , V ₂ O ₅ , Sb ₂ O ₅ , ZrO ₂ , ZnO, SnO, BaO, Bi ₂ O ₃ , TeO ₂ , _{GeO 2, MgO, CaO, SrO} , TiO 2, MnO, Sb 2 O 3, CaO, NiO, Y 2 O 3, MoO, Rh 2 O 3, PdO, Ag 2 O, in 2 O 3, WO 3 , etc. There are inorganic oxides, and glass is prepared by appropriately selecting and blending from such oxide components, heating and melting and cooling and solidifying. For the preparation of the low-melting glass, an oxide component having a low softening point is used as a raw material, and as an oxide component capable of constituting a low-melting glass having a softening point of about 400 to 500 ° C., B ₂ O ₃ , SiO ₂ , _{al 2 O 3, P 2 O} 5, V 2 O 5, Sb 2 O 5, ZrO 2, ZnO, SnO, BaO, Bi 2 O 3, TeO 2 , and the like. Oxides other than these can also be used within an allowable range in terms of sealing temperature.

At this time, the density of the glass can be brought close to the value set based on the requirement a) by preparing the glass by determining the ratio of the raw material oxide based on the additivity of the glass. An oxide having a low density tends to have a high softening point. Examples of the oxide having a relatively low softening point and a low density include V ₂ O ₅ and SnO ₂ , and V ₂ O ₅ is optimal. A glass composition mainly composed of vanadium (vanadium oxide) is preferable as the low-density glass material of the present invention, and is most suitable for the preparation of a paste composition using a low-melting glass frit. As the glass composition in this case, a composition in which vanadium is about 45 to 65% by mass in terms of V ₂ O ₅ is preferable. By mixing the raw material oxide so as to have such a composition, the density is 2.5. A glass material of about 4.4 g / cm ³ can be suitably prepared. As a component other than V ₂ O ₅ , an oxide capable of constituting the above low-melting glass may be used. From the viewpoint of density, P ₂ O ₅ , Sb ₂ O ₅ , BaO, SrO, ZnO, Al _{2 are used.} O ₃ , Na ₂ O and the like are preferable, and P ₂ O ₅ , BaO, and Sb ₂ O ₅ are particularly preferable. Although oxides such as WO ₃ and TeO ₂ have a large density, they are useful in terms of lowering the softening point, and can be used limited to a ratio in which the density falls within the above range. Using such components, a glass having a softening point of 300 to 400 ° C. can be prepared.

The glass material as described above is crushed into a frit and used for preparing the paste composition. The pulverization may be performed according to a general method. The frit in the paste tends to settle when the particle size increases, and the fired coating film tends to become non-homogeneous. Conversely, extremely small particles have poor pulverization efficiency during production, resulting in low economic efficiency and surface activation. As a result, chemical stability is also lowered. For this reason, it is convenient to use a frit glass having an average particle diameter of 1.5 to 35 μm, preferably 2 to 15 μm. In order to satisfy the requirement a) with respect to the particle diameter, a glass material having a density of 7.5 g / cm ³ or less may be employed. Any shape of the frit in the range obtained by a general pulverization method can be used, but a substantially spherical particle tends to be preferable in terms of suppression of sedimentation.

In the glass paste composition as the sealing material, the filler powder is not an essential component, the thermal expansion difference with the adherend (front plate, back plate, etc.) is reduced, the strength of the formed sealing part is increased, and the paste It is an extremely useful component for improving fluidity. Therefore, you may comprise a glass paste composition, without using a filler. When filler powder is used as a component for reducing the difference in thermal expansion, a heat-resistant material having a smaller thermal expansion coefficient than that of the frit glass is appropriately selected as the filler material in accordance with the thermal expansion coefficient of the frit glass and the adherend, and the blending ratio is the heat It is adjusted according to the degree of relaxation of the expansion difference. Preferably, a refractory material having a thermal expansion coefficient of 80 × 10 ⁻⁷ / ° C. or less is used. By changing the filler material, the use of the glass paste composition of the present invention can also be changed and applied to various uses other than the sealing material. As the filler material, a refractory material [specifically ceramics, high melting point glass, etc.] is preferably used. For example, cordierite, zircon, zirconia, barium titanate, aluminum titanate, titania, silica, alumina, tin oxide, niobium oxide, zirconium phosphate, willemite, mullite, NbZr (PO ₄ ), β-euclibutite, β- Examples include inorganic substances such as spodumene, sialon, silicon nitride, and β-quartz solid solution, ceramics, quartz glass, and other high melting point glass (glass having a strain point of 450 ° C. or higher that does not soften at the sealing temperature). One or more of these materials can be used in combination.

In the paste composition as a sealing material, excessively fine particles are not suitable for the filler powder to suitably exhibit functions such as thermal expansion relaxation, and the average particle diameter is generally 1 to 40 μm, preferably 2 to 2 μm. A powder of about 30 μm is used. In consideration of the suppression of sedimentation separation, a powder prepared by preparing a filler material having a density of about 2 to 4.5 g / cm ³ into particles of about 10 to 30 μm, preferably about ³ to 25 μm may be used. If the difference in thermal expansion coefficient from the frit glass is excessive, there is a risk of peeling due to thermal stress after firing, so the difference in thermal expansion coefficient from the frit glass is preferably 15 × 10 ⁻⁷ or less. Considering the above comprehensively, as the filler material, silica, alumina, aluminum titanate, cordierite, CaO—B ₂ O ₃ —Al ₂ O ₃ —SiO ₂ based low alkali glass, etc. are suitable, and these It is preferable to select one or more of these.

  When the difference between the density of the frit glass and the density of the filler powder is large, the glass and the filler are separated at the time of firing the paste composition, and the filler may concentrate on the surface of the glass composition to form a layer. This is usually not a problem. However, when the filler material is lighter than frit glass and the particle size of the filler powder is very small, the layer formed by the floatation and concentration of the filler on the surface of the glass during firing becomes dense and the glass and adherend It may be difficult to seal with the material. In such a case, the average particle size of the filler powder is preferably about 20 μm or more.

  Ceramic powder or high melting point frit glass obtained by pulverizing the filler material as described above is used for preparing the paste composition. The shape of the filler powder may be any shape such as a substantially spherical shape or an irregular crushed powder, but a substantially spherical shape is excellent. The particle size of the filler powder is preferably in the range of 1 to 40 μm, and such filler powder is industrially mass-produced and is stably available. Desirably, it is made to be about the same as the particle size of the frit glass.

  The glass paste composition contains an organic resin as a dispersant for stabilizing the dispersion of frit glass and filler powder in a solvent and imparting shape retention (plasticity), and a resin having low reactivity with frit glass is used. Is done. From the viewpoints of chemical stability, cost and safety, cellulose derivatives such as nitrocellulose, methylcellulose, ethylcellulose, carboxymethylcellulose, vinyl resins such as polyvinyl alcohol, polyvinyl butyral, polyethylene glycol, carbonate resins, urethane resins, acrylic resins Melamine resin and the like are preferable.

  As the solvent constituting the vehicle of the paste composition, an organic solvent that dissolves the dispersant and has low reactivity with the frit glass is used, taking into consideration chemical stability, cost, safety, compatibility with the resin, etc. As appropriate. Specifically, alcohols, ketones, esters such as aliphatic carboxylic acid esters and hydroxycarboxylic acid esters, ethers such as ethylene glycol alkyl ether, amides, carbonates and the like can be used, for example, isohexyl. Alcohol, isodecyl alcohol, isododecyl alcohol, terpineol, butyl acetate, isoamyl acetate, ethyl hydroxyacetate, ethyl 2-hydroxypropionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, butyl carbitol acetate, ethyl acetoacetate , Ethylene glycol monomethyl ether, N-methylpyrrolidone, N, N-dimethylformamide and the like. You may use the said solvent individually or in combination of 2 or more types.

  A glass paste composition is obtained by dissolving the above-mentioned resin in the above-mentioned solvent, using this as a vehicle, blending frit glass and filler powder, and mixing and dispersing in a paste. The mixing and homogenizing operation may be performed using a general stirring / kneading means such as a ball mill or a roll mill. The blending amount of the filler powder is preferably about 5 to 40 parts by mass with respect to 100 parts by mass of the frit glass, and if it is excessive, sufficient sealing cannot be obtained. The amount of the resin used is preferably about 0.5 to 5 parts by mass with respect to 100 parts by mass of the frit glass, and if it is excessive, it cannot be sufficiently removed at the time of firing, and a bad effect due to the residue tends to occur. The amount of the solvent used is an amount capable of dissolving the resin, and is preferably about 10 to 30 parts by mass with respect to 100 parts by mass of the total mass of the frit glass and filler powder. It becomes a suitable paste state of about ~ 55 Pa · s.

  The glass paste composition may contain additives such as surfactants, development accelerators, adhesion assistants, antihalation agents, storage stabilizers, antifoaming agents, ultraviolet absorbers, pigments, and dyes as necessary. May be appropriately blended.

  The glass paste composition prepared as described above can be used as an adhesive for joining and adhering members in the manufacture of electronic / electrical equipment and as a sealing material for sealing between members. Moreover, you may apply to the coating material for manufacturing a glass film and a glass covering structure member. When used as a sealing material, for example, a paste composition is applied to one adherend using a dispenser, a screen printing device, or the like and dried, and then the resin is incinerated and removed by heating and pre-baking. At the same time, the frit glass is softened. Once this is cooled and solidified, the other adherend is brought into contact and heated to the sealing temperature while being appropriately pressed to seal and adhere the adherend. Usually, the heating temperature for pre-baking is set to a temperature slightly higher than the sealing temperature.

  In this way, a low melting point frit glass is used to prepare a glass paste composition that is less susceptible to sedimentation separation than conventional lead-based frit glass sealing pastes, which are used for suitable sealing and film formation. Can be implemented.

  The use of the glass frit paste composition of the present invention is not limited to a low melting point glass paste for sealing / adhesion of thin flat displays, but for adhesion of glass structural members for electronic devices such as magnetic disk substrates and coating coating materials. Is also applicable.

  Hereinafter, the present invention will be specifically described with reference to examples.

(Example 1)
<Preparation of glass>
According to Table 1, V ₂ O _5: 35 wt%, TeO _2: 30 wt%, WO _3: 6 wt%, ZnO: 4 wt%, BaO: 18 wt%, Sb ₂ O _{3: 3} wt%, SrO: The raw material oxide was blended so as to have a composition ratio of 4% by mass, and the total blending amount was set to 100 g, put into a platinum crucible, held at 900 ° C. for 30 minutes in the atmosphere to dissolve the raw material, and then cooled. To obtain glass A.

V ₂ O ₅ : 60% by mass, P ₂ O ₅ : 22% by mass, TeO ₂ : 6% by mass, BaO: 5% by mass, Sb ₂ O ₃ : 7% by mass After mixing, the total blending amount was set to 100 g, and put into a Pt crucible. The raw material was dissolved in the atmosphere at 900 ° C. for 30 minutes, and then cooled and vitrified to obtain glass B.

V ₂ O _5: 65% by weight, P ₂ O _5: The crude oxide were blended so that the composition ratio of 35 wt%, was charged into Pt crucible the whole amount as 100 g, the 900 ° C. in air The raw material was dissolved by holding for 30 minutes and then cooled, but it did not vitrify.

(Table 1)
Glass V ₂ O ₅ P ₂ O ₅ TeO ₂ BaO Sb ₂ O ₃ ZnO WO ₃ SrO
A 35 0 30 18 3 4 6 4
B 60 22 6 5 7 0 0 0
C 65 35 0 0 0 0 0 0 0

For each of the prepared glasses A and B, after coarsely pulverizing with a mortar and further pulverizing with a ball mill, adjusting the pulverization time with the ball mill to 60 minutes, 30 minutes or 15 minutes, the average particle diameter is 2 μm, 10 μm or 30 μm frit glass was prepared, respectively. The average particle diameter was measured using a laser optical particle size distribution analyzer SALD-2000 (manufactured by Shimadzu Corporation). Further, the density of the glass block after melting was measured by the Archimedes method, whereby the density of the glass A was 4.2 g / cm ³ and the density of the glass B was 3.2 g / cm ³ .

<Preparation of glass paste>
For each of the three types of frit glass having a particle size prepared from glass A, 15 g of a vehicle (ethyl cellulose content: 15% by mass) composed of ethyl cellulose and an organic solvent (butyl carbitol) was blended with 50 g of frit glass, and a mortar After mixing, the glass paste samples A1 to A3 were prepared by kneading with a three-roll mill.

<Evaluation of sedimentation of glass paste>
For each of the glass paste samples A1 to A3, the viscosity of the paste was adjusted to 50 Pa · s using a small amount of vehicle or organic solvent.

  100 g of the paste sample with adjusted viscosity is put into a container and sealed in a state where the depth of the paste is 50 mm, and then centrifuged at 1000 rpm for 30 minutes using a centrifugal separator (manufactured by Kokusan Co., Ltd.). Attempted forced sedimentation. Thereafter, the portion other than the portion settled at the bottom of the paste was extracted from the container, and the amount (depth) of the sediment remaining in the container was confirmed.

  Moreover, after putting the paste sample 100g which adjusted the viscosity into the container similar to the above, and sealing and standing for one month at normal temperature, when the state of the paste was observed, a little amount of supernatant was produced in any sample. It was. The sample was passed through a planetary rotary defoamer while the vessel was sealed, and the vessel was subjected to a homogenization treatment for 10 minutes with a rotational load of 2000 rpm, and the degree of dispersion of the sample in the vessel was visually observed. The results are shown in Table 2.

  According to Table 2, for sample A3, a hard deposit was formed after forced sedimentation, and the deposit remained not uniform even in the homogenization treatment after standing, but the other samples About became a uniform paste easily.

(Table 2)
Evaluation of glass paste
Sample frit glass sedimentation evaluation
Glass density Particle size Numerical value S Sedimentation amount Uniform
[g / cm ³ ] [μm] [mm]
A1 A 4.2 2 16.8 0 Good A2 A 4.2 10 420 2 Good
A3 A 4.2 30 3780 10 (hard) Defective B1 B 3.2 2 12.8 0 Good B2 B 3.2 10 320 0 Good
B3 B 3.2 30 2880 5 Good

(Example 2)
<Filler specifications>
Filler powders shown in Table 3 were prepared. The particle size was adjusted by the pulverization time in a ball mill as in the case of the glass frit, and the average particle size was measured using a particle size distribution measuring device.

(Table 3)
Filler powder
Filler material Density [g / cm ³ ] Average particle size
S: Silica (SiO ₂ ) 2.2 10 μm, 20 μm, 30 μm
Z: Zircon 4.6 10 μm, 20 μm, 30 μm
T: Lead titanate 8.0 10 μm, 20 μm, 30 μm

<Preparation of glass paste>
Using frit glasses A and B having an average particle diameter of 10 μm and the filler powder of Table 3, paste samples were prepared as follows.

  According to the combination of frit glass and filler powder described in Table 4, 50 g of frit glass and 10 g of filler powder were mixed with 15 g of a vehicle (ethyl cellulose content: 15% by mass) in which ethyl cellulose was dissolved in an organic solvent (butyl carbitol). After mixing using a mortar, the glass paste samples AS1 to AS3, BZ1 to BZ3, and BT1 to BT3 were prepared by kneading with a three-roll mill.

<Evaluation of sedimentation of glass paste>
For each of the glass paste samples AS1 to AS3, BZ1 to BZ3, BT1 to BT3, the viscosity of the paste is adjusted to 50 Pa · s using a small amount of vehicle or organic solvent, and in the same manner as in the evaluation method described above, by forced sedimentation The amount (depth) of the sediment and the degree of dispersion after the homogenization treatment were evaluated. The results are shown in Table 4.

<Evaluation of sealing properties>
Using a dispenser, the glass paste sample that has been subjected to the homogenization treatment after standing in the above-mentioned manner is 3 mm wide and thick at the periphery of a glass plate (product number PD200, manufactured by Asahi Glass Co., Ltd.) having a length of 50 mm × width 50 mm × thickness 2 mm. It was applied to a thickness of 1 mm. This was heated to 150 ° C. for 10 minutes to volatilize the organic solvent in the paste coating film to some extent, and then heated to 455 ° C. for 30 minutes to perform preliminary firing to remove organic substances and bubbles.

  A glass plate of the same size was superposed on the glass plate after pre-baking and pressure-bonded with a clip. The glass plate was heated to 435 ° C. at a heating rate of 10 ° C./min, held at 435 ° C. for 15 minutes, and then cooled to room temperature. Then, the glass plate was adhered without a gap, and the sealing state was visually evaluated. The results are shown in Table 4.

<Analysis of sample evaluation results>
According to Table 4, in the samples AS1 to AS3, sedimentation is suppressed and redispersion is easy. The reason why the sealing state of the sample AS1 is not good is that the light filler powder floats on the glass surface and forms a dense layer, thereby inhibiting the adhesion of the coating film.

  In the samples AZ1, AT1, BZ1 to BZ3, and BT1 to BT3, the settling property of the paste differs depending on the numerical value S of the filler powder. When the numerical value S exceeds 3000, the redispersion of particles is difficult and the glass paste cannot be made uniform. Even if the glass paste molecules are easy to settle and separate, it seems that the sealing property is not lowered, but if separated, it is difficult to redisperse and cannot be used.

(Table 4)
Evaluation of glass paste
Frit glass filler powder sedimentation evaluation
Sample Glass Density Value Type Density Particle size Value Sedimentation amount Uniform sealing
[g / cm ³ ] S [g / cm ³ ] [μm] S [mm] State AS1 A 4.2 420 S 2.2 10 220 0 Good Defect AS2 A 4.2 420 S 2.2 20 20 80 0 Good Good
AS3 A 4.2 420 S 2.2 30 1980 10 Good Good AZ1 A 4.2 420 Z 4.6 30 4 140 10 Bad Good
(Hard)
AT1 A 3.2 420 T 8.0 20 3200 20 Defect Good
(Hard)
BZ1 B 3.2 320 Z 4.6 10 460 2 Good Good BZ2 B 3.2 320 Z 4.6 20 1840 5 Good Good BZ3 B 3.2 320 Z 4.6 30 4 140 15 Bad Good
(Hard)
BT1 B 3.2 320 T 8.0 10 800 15 Good Good BT2 B 3.2 320 T 8.0 20 3200 15 Bad Good
BT3 B 3.2 320 T 8.0 30 7200 20 Defect Good

(Example 3)
Glass A prepared in Example 1 (density 4.2 g / cm ³ ) was pulverized to an average particle size of 15 μm or 20 μm to prepare a frit glass.

  According to the combination of frit glass and filler powder described in Table 5, 50 g of frit glass and 10 g of filler powder were blended in 15 g of a vehicle (ethyl cellulose content: 15% by mass) in which ethyl cellulose was dissolved in an organic solvent (butyl carbitol). After mixing using a mortar, the mixture was kneaded with a three roll mill to prepare glass paste samples AV1, AW, AX, A0. Symbol V in the filler type in the table indicates cordierite (spherical particles), W indicates low alkali glass (spherical particles), and X indicates alumina (spherical particles).

  The prepared glass paste sample was subjected to sedimentation evaluation by homogenization after standing in the same manner as in Example 2.

  According to Table 5, it can be seen that the precipitate in the paste can be easily redispersed by preparing the glass paste in a particle state where the numerical value S is 3000 or less.

(Table 5)
Evaluation of glass paste
Frit glass filler powder sedimentation evaluation <br/> Sample glass Particle size Numerical value Type Density Particle size Numerical value Uniform
[μm] S [g / cm ³ ] [μm] S
AV A 15 945 V 2.5 20 1000 Good
AW A 15 945 W 2.6 20 1040 Good
AX A 15 945 X 3.9 20 1560 Good
A0 A 20 1680---1680 Good
(Glass)

Claims (7)

A vehicle containing a solvent and a dispersant, and a frit glass and a filler powder dispersed in the vehicle, each of the frit glass and the filler powder,
The numerical value S calculated according to the formula: S = D ² × ρ (where D represents the average particle diameter [μm] and ρ represents the density [g / cm ³ ]) is 3000 or less, or A glass paste composition, wherein the density of the filler powder is smaller than the density of the frit glass. The frit glass has a density of 2.5 to 4.4 g / cm ³ , the filler powder has a density of 2 to 4.5 g / cm ³ and a thermal expansion coefficient of 80 × 10 ⁻⁷ / ° C. or less. The glass paste composition according to claim 1.   The glass paste composition according to claim 1 or 2, wherein the frit glass has an average particle size of 1.5 to 35 µm, and the filler powder has an average particle size of 1 to 40 µm.   The dispersant is an organic resin, the solvent is an organic solvent that dissolves the dispersant, the frit glass is particles of low-melting glass having a softening point of 350 to 550 ° C., and the filler powder is The glass paste composition according to claim 1, wherein the glass paste composition is a high melting point glass powder having a ceramic and / or strain point of 450 ° C. or higher. The frit glass is a glass containing vanadium in a proportion of 45 to 65% by mass in terms of V ₂ O ₅ , and the filler powder includes silica, alumina, aluminum titanate, and CaO—B ₂ O ₃ —Al ₂ O. ₃ -SiO ₂ glass paste composition according to claim 1 comprising at least one material particle selected from the group consisting of low-alkali glass composition.   The glass paste composition according to claim 1, wherein the filler powder is contained at a ratio of 5 to 100 parts by mass with respect to 100 parts by mass of the frit glass. A vehicle containing a solvent and a dispersant, and a frit glass dispersed in the vehicle. The frit glass has the formula: S = D ² × ρ (where D is an average particle diameter [μm], The glass paste composition is characterized in that the numerical value S calculated according to ρ indicates density [g / cm ³ ] is 3000 or less.