JP4937411B2 - Inorganic fine particle dispersed paste composition - Google Patents

Description

The present invention relates to an inorganic fine particle-dispersed paste composition that can be degreased at a low temperature and has excellent dispersibility and storage stability.

In recent years, an inorganic fine particle-dispersed paste composition in which inorganic fine particles such as conductive powder and ceramic powder are dispersed in a binder resin has been used to obtain fired bodies having various shapes. In particular, a phosphor paste composition in which a phosphor is dispersed in a binder resin as inorganic fine particles and a glass paste in which a low melting point glass is dispersed are used for plasma displays and the like, and the demand is increasing in recent years.

As the binder resin used in the inorganic fine particle dispersed paste composition, it is common to use a cellulose resin such as ethyl cellulose having thixotropy. However, considering the process of dispersing inorganic fine particles, printing a pattern by screen printing, degreasing and baking, and obtaining an inorganic fine particle layer, cellulosic resin has poor thermal decomposability, so it degreases at higher temperatures. There is a problem that a large amount of energy is required in the production process.

For such problems, a method using an acrylic resin that has good thermal decomposability and can be degreased at a low temperature has been studied. For example, Patent Document 1 discloses an inorganic fine particle dispersed paste using an acrylic resin. A composition is disclosed. When comparing inorganic fine particle dispersion paste composition using ethyl cellulose and inorganic fine particle dispersion paste composition using acrylic resin that can be degreased at low temperature, inorganic fine particle dispersion paste composition using ethyl cellulose is more inorganic fine particles Sedimentation is difficult to occur. This is because the hydroxyl group in the cellulose molecule affects the dispersion stability. Therefore, the introduction of a polar group such as a hydroxyl group to the ester substituent of the monomer in the acrylic resin is expected to improve the dispersibility. There was no difference.

Therefore, in Patent Document 2, a method for improving the storage stability of the paste composition by adding a small amount of a dispersant to the paste composition without introducing a polar group into the ester substituent of the acrylic resin is studied. ing. In this case, glass powder, ceramic powder, phosphor, etc. tend to improve dispersion stability by adding a dispersant having an amino group, but the dispersant used is far more thermally decomposable than ethyl cellulose. However, even a small amount was likely to be a residue after sintering.

On the other hand, a method of introducing an amino group into an ester substituent in an acrylic resin has also been attempted, but even when a very small amount of an amino group is introduced, the thermal decomposability of the acrylic resin is greatly deteriorated. When a Michael addition reaction occurs between the acryl monomer and the acrylic monomer, the polymer tends to become a large molecule, and it has been difficult to adjust the molecular weight of the acrylic resin to be small.

JP 2004-002164 A Japanese Patent No. 3832177

An object of the present invention is to provide an inorganic fine particle-dispersed paste composition that can be degreased at a low temperature and has excellent dispersibility and storage stability.

The present invention is an inorganic fine particle-dispersed paste composition containing a (meth) acrylic resin, inorganic fine particles, and an organic solvent, wherein the (meth) acrylic resin has an amino group or an amide group at the molecular end, and The inorganic fine particle-dispersed paste composition having a weight average molecular weight of 5,000 to 100,000 in terms of polystyrene.
The present invention is described in detail below.

As a result of intensive studies, the present inventors introduced an amino group or an amide group without degrading the thermal decomposability of the acrylic resin by introducing an amino group or an amide group at the molecular end of the (meth) acrylic resin. It was found that the dispersibility and storage stability can be greatly improved as compared with the case of not doing so. Further, it was found that by introducing an amino group or an amide group at the molecular end of the (meth) acrylic resin, the weight average molecular weight can be adjusted to a range suitable for printability, and the present invention has been completed.

The inorganic fine particle-dispersed paste composition of the present invention contains a (meth) acrylic resin as a binder resin.

The (meth) acrylic resin is not particularly limited as long as it decomposes at a low temperature of about 350 to 400 ° C., for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (Meth) acrylate, tert-butyl (meth) acrylate, isobutyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxy Selected from the group consisting of butyl (meth) acrylate, isobornyl (meth) acrylate, n-stearyl (meth) acrylate, benzyl (meth) acrylate and (meth) acrylic monomers having a polyoxyalkylene structure. At least consisting of one polymer is are preferably used. Here, for example, (meth) acrylate means acrylate or methacrylate.
Among them, since a high viscosity can be obtained with a small amount of resin, polymethyl methacrylate (Tg 105 ° C.), which is a polymer of methyl methacrylate having a high glass transition temperature (Tg) and excellent low-temperature degreasing properties, is suitable. is there.
In the inorganic fine particle-dispersed paste composition of the present invention, when fluorescent fine particles are used as the inorganic fine particles, the (meth) acrylic resin is preferably a polymer made of methyl methacrylate. By using the polymer composed of methyl methacrylate, the organic residue after sintering can be reduced, and the luminance characteristics of the phosphor fine particles can be improved.

The (meth) acrylic resin has an amino group or an amide group at the molecular end.
When a highly interactive functional group such as an amino group or an amide group is introduced into the ester substituent of the (meth) acrylic monomer, depolymerization of the (meth) acrylic resin is inhibited in the firing step, The thermal decomposition end temperature becomes high, and the thermal decomposition is extremely deteriorated.
For example, the raw material for carbon fibers used in fishing rods and golf clubs is a product obtained by firing an aminoacrylate polymer, and the presence of amino groups promotes carbonization during firing.
However, when an amino group or an amide group is introduced at the molecular end, depolymerization is not inhibited and the thermal decomposition end temperature is hardly affected.
In addition, glass powder, ceramic powder, phosphor, etc. have high interaction with amino groups or amide groups, and when pasted together with the (meth) acrylic resin, one molecular terminal is the surface of fine particles such as ceramics. Since the other adsorbs to the organic solvent and extends to the organic solvent side, reaggregation of the fine particles can be prevented and the dispersion stability can be improved. In the inorganic fine particle dispersed paste composition, the dispersibility of the inorganic fine particles depends on the number of molecular chain terminals.
In addition, the presence of an amino group or an amide group at the molecular end causes the (meth) acrylic resin and the organic solvent to be incompatible with each other, thereby producing appropriate phase separation (microphase separation) and sufficient viscosity (thixotropic properties). ), The adhesive strength is reduced, so that the yarn is not generated and the screen printability is improved. In addition, by appropriately reducing the weight average molecular weight of (meth) acrylic resins having amino or amide groups at the molecular terminals, the microphase separation is suppressed and only dispersibility is improved, creating a paste showing Newtonian viscosity. can do.

The (meth) acrylic resin has an amino group or an amide group at the molecular end, but has an imidazoline group or a pyrrolidino group which is a kind of the amino group or amide group as long as the effects of the present invention are not impaired. You may do it. Thereby, affinity with glass powder, ceramic powder, phosphor, etc. becomes high.

The lower limit of the weight average molecular weight in terms of polystyrene of the (meth) acrylic resin is 5000, and the upper limit is 100,000. When the weight average molecular weight is less than 5000, sufficient viscosity cannot be expressed, so it is not suitable for a printing paste, and when it exceeds 100,000, the adhesive strength of the inorganic fine particle-dispersed paste composition of the present invention increases. As a result, it becomes difficult to use for screen printing and the like. The upper limit with the said preferable weight average molecular weight is 50000, and a more preferable upper limit is 40000. In particular, a weight average molecular weight of 10,000 to 20,000 is preferable because a clear image can be obtained during screen printing.
In addition, the measurement of the weight average molecular weight by polystyrene conversion can be obtained by performing GPC measurement using column LF-804 (made by Showa Denko KK) as a column, for example.

When the reaction solution after the (meth) acrylic resin polymerization reaction is used as it is as the binder resin used in the inorganic fine particle dispersed paste composition of the present invention, the polymerization solution contains low molecular weight components such as monomers and oligomers. Preferably not.

The molecular weight distribution (weight average molecular weight / number average molecular weight = Mw / Mn) of the (meth) acrylic resin is preferably 3 or less, more preferably 2.5 or less.
When the molecular weight distribution exceeds 3, a low molecular weight component such as an oligomer in the polymerization solution becomes a plasticizer, a sufficient viscosity cannot be obtained in the inorganic fine particle dispersed paste composition, and screen printability may be deteriorated. Molecular weight components may worsen the stringiness.

Although it does not specifically limit as content of the (meth) acrylic resin in the inorganic fine particle dispersion paste composition of this invention, A preferable minimum is 5 weight% and a preferable upper limit is 25 weight%. When the content of the (meth) acrylic resin is less than 5% by weight, sufficient viscosity may not be obtained in the inorganic fine particle dispersed paste composition, and screen printability may be deteriorated. The viscosity and adhesive strength of the inorganic fine particle-dispersed paste composition may become too high, resulting in poor screen printability.

As a method for producing the (meth) acrylic resin, for example, the above-described (meth) acrylic monomer is used in a free radical polymerization method, a living radical polymerization method, an inidium under a polymerization initiator having an amino group or an amide group. Freely use the (meth) acrylic monomers described above under copolymerization by conventional methods such as furter polymerization, anion polymerization, and living anion polymerization, and chain transfer agents having amino groups or amide groups Examples thereof include a copolymerization method by a conventionally known method such as a radical polymerization method, a living radical polymerization method, an iniferter polymerization method, an anionic polymerization method, and a living anion polymerization method. These methods may be used in combination.
However, in order to introduce amino groups or amide groups at more molecular ends, it is preferable to use a polymerization initiator having an amino group or an amide group as a radical polymerization initiator.
Moreover, it can be confirmed by, for example, ¹³ C-NMR that an amino group or an amide group is introduced only at the molecular end of the (meth) acrylic resin.

Of the methods for producing the (meth) acrylic resin, the case of using radical polymerization will be described.
General radical polymerization consists of elementary reactions shown in the following (1) to (4). In the formula, I is a radical (polymerization) initiator, M is a monomer, and P is a polymer obtained by polymerizing the monomer.
As shown in the following formulas (1) to (4), a radical initiator is added to the molecular ends of the polymer prepared by radical polymerization. Therefore, by selecting a radical initiator having an amino group or amide group to be introduced at the molecular end of the (meth) acrylic resin, a desired amino group or amide group can be introduced at the molecular end of the (meth) acrylic resin. it can.

I ₂ → 2I · (1); radical generation reaction I · + M → IM · (assumed P ·) (2); initiation reaction P · + M → PM · (assumed Pn ·) (3 ); Growth reaction Pn · + Pn · → Pn-Pn (4); Stop reaction

Of the methods for producing the (meth) acrylic resin, a case where radical polymerization is performed under a chain transfer agent will be described.
For example, when a chain transfer agent having a mercapto group is introduced into the reaction system, a chain transfer reaction represented by the following formula (5) occurs. Such a chain transfer reaction can extend the polymer from the chain transfer agent. Therefore, by selecting an amino group or amide group to be introduced into the molecular end of the (meth) acrylic resin and a chain transfer agent having a mercapto group, the desired amino group or amide group is added to the molecular end of the (meth) acrylic resin. Can be introduced.
When the chain transfer agent is used, there are polymers grown from the radical initiator in the reaction system, so the number of functional groups that can be introduced as compared with the case of using radical polymerization using the radical initiator described above. Will be less. Therefore, a method using a radical polymerization initiator having an amino group or an amide group is more preferable.

    P ・ + SH → P + S ・ (5); Chain transfer reaction

The (meth) acrylic resin is preferably one that is polymerized using an azo polymerization initiator and a terpene solvent that do not have a cyano group.
An azo polymerization initiator having a cyano group has no problem in the safety of the compound itself, but is highly toxic when a decomposition radical generated by thermal decomposition extracts and stabilizes a hydrogen atom from another substance. Become a chemical substance. Such a problem does not occur when polymerization is carried out using an azo polymerization initiator having no cyano group.

In addition, in order to polymerize a (meth) acrylic resin having a weight average molecular weight of 5,000 to 100,000 using an azo polymerization initiator, the molecular weight is adjusted by adjusting the addition amount of the azo polymerization initiator in a solvent such as toluene. In order to polymerize a (meth) acrylic resin having a lower molecular weight, it is necessary to add a larger amount of an azo polymerization initiator. However, since the azo polymerization initiator having an amino group or an amide group does not dissolve in a solvent suitable for dissolving a (meth) acrylic resin such as toluene, the radicals of the azo polymerization initiator are recombined. A reaction that becomes a stable impurity (caustic effect of the solvent) is likely to occur, and the amino group or amide group causes a Michael addition reaction with the double bond of the (meth) acrylic monomer. Even when a system polymerization initiator is added, it may be difficult to polymerize a low molecular weight resin.
On the other hand, it discovered that the polymerization which suppressed Michael addition reaction could be performed by using a terpene-type solvent. Although the azo polymerization initiator does not dissolve in the terpene solvent, the azo polymerization initiator is quickly dispersed in the reaction system by dispersing the azo polymerization initiator in the terpene solvent in advance and adding it to the polymerization system. In order to disperse the unsaturated double bond contained in the terpene solvent, the Michael addition reaction is inhibited, and the radical polymerization reaction caused by the azo polymerization initiator is gently suppressed. It is possible to polymerize a low molecular weight (meth) acrylic resin without generating it.

The azo polymerization initiator having no cyano group is not particularly limited as long as it has the amino group or amide group. For example, 2,2′-azobis [2- (2-imidazolin-2-yl] ) Propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate, 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2 , 2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate, 2,2′-azobis {2- [1- (2-droxyethyl) -2-imidazolin-2-yl] Propane} dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis (1-imino 1-pyrrolidino-2-methylpropane) dihydrochloride, 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′- And azo polymerization initiators such as azobis [2-methyl-N- (2-hydroxyethyl) propionamide].

The chain transfer agent is not particularly limited as long as it has the amino group or amide group. For example, mercaptoethanethiol having amino group, ammonium thioglycolate, ethanolamine thioglycolate, diammonium dithioglycolate Etc.

As the solvent that inhibits the Michael addition reaction and moderately suppresses the radical polymerization reaction, it is preferable to use a terpene solvent having an unsaturated double bond and an appropriate viscosity in the polymerization solvent. Examples of the terpene solvent having an unsaturated double bond include α-terpineol, β-terpineol, γ-terpineol, limonene, terpinolene, γ-terpinene, α-terpinene, d-limonene, α-terpineol acetate and the like. It is done.

In the paste composition according to the present invention, the organic solvent may be the same as or different from the polymerization solvent for the (meth) acrylic resin.
As the organic solvent, the terpene solvent is preferable. In the inorganic fine particle paste composition of the present invention, a solvent other than the terpene-based solvent may be used in combination.
Examples of organic solvents that can be used in combination with the terpene solvent include ethylene glycol ethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoisobutyl ether, trimethylpentanediol mono Examples include isobutyrate, butyl carbitol, butyl carbitol acetate, texanol, isophorone, butyl lactate, dioctyl phthalate, dioctyl adipate, benzyl alcohol, phenylpropylene glycol, cresol and the like. Of these, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoisobutyl ether, butyl carbitol, butyl carbitol acetate, and texanol are preferred because they easily develop moderate phase separation with (meth) acrylic resin. These organic solvents may be used alone or in combination of two or more.
In order to keep the temperature during the polymerization reaction constant, an organic solvent having a low boiling point may be added.
Although it does not specifically limit as said low boiling-point organic solvent, For example, ethyl acetate, propyl acetate, butyl acetate, methanol, ethanol, isopropanol, toluene, methyl ethyl ketone, acetone etc. are mentioned. The low-boiling organic solvent is added with a high-boiling organic solvent used for the inorganic fine particle-dispersed paste composition at the end of the polymerization, and then subjected to vacuum treatment to remove the monomer and low-boiling organic solvent that have not been incorporated into the polymer.
When these residual monomers and low boiling point organic solvents remain in the resin solution composition, the residual amount in the resin solution should be 100 ppm or less because it causes a decrease in viscosity and a deterioration in viscosity stability during printing. Is preferred.

When the inorganic fine particle-dispersed paste composition of the present invention is used as the phosphor fine particle-dispersed paste composition, it is preferable to use a material containing two or more kinds of solvents having different molecular weights as the organic solvent.
When (meth) acrylic resin is used as the binder resin of the phosphor fine particle dispersed paste composition, a skinning phenomenon occurs when the solvent is dried. May occur. Therefore, when the phosphor fine particle dispersed paste composition is filled in the partition walls of the plasma display and dried to form a phosphor layer along the side partition walls, it is preferable to use a highly volatile solvent, By using solvents with different vapor pressures, low molecular weight solvents improve the drying speed of the phosphor fine particle dispersed paste composition when dried, and high molecular weight solvents can control the solubility of (meth) acrylic resins. The phosphor fine particle dispersed paste composition can be attached to the upper part of the side wall of the partition wall, and the phosphor surface shape can be optimized.

Moreover, it is preferable that the said organic solvent contains the solvent whose vapor pressure in normal temperature is 0.1 mmHg or more.
Furthermore, it is preferable to contain a solvent having a vapor pressure of 0.1 mmHg or more at room temperature and a solvent having a vapor pressure of less than 0.01 mmHg at room temperature. Thus, by containing two kinds of solvents having different vapor pressures, a solvent having a vapor pressure of 0.1 mmHg or more improves the drying speed of the phosphor fine particle dispersed paste composition when dried, and the vapor pressure at room temperature is increased. Since the solvent of less than 0.01 mmHg can control the solubility of the (meth) acrylic resin, the phosphor fine particle dispersed paste composition can be attached to the upper part of the side wall of the partition wall, and the phosphor surface shape is optimized. be able to.

Examples of the solvent having a vapor pressure of 0.1 mmHg or higher at normal temperature include terpineol, terpineol acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, benzyl alcohol, carbitol acetate, ethylene glycol monohexyl ether, diethylene glycol monoethyl ether, Examples include butyl lactate, 2-butoxyethyl acetate, ethylene glycol diacetate, octanol, and isophorone.

Examples of the solvent having a vapor pressure of less than 0.01 mmHg at normal temperature include diethylene glycol monobutyl ether acetate, trimethylpentanediol monoisobutyrate, diethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, phenyl glycol, and phenylpropylene glycol. .

The organic solvent plays a very important role in screen printing. There are three main roles required for such an organic solvent. The first role is to dissolve the binder resin, the second role is to ensure the dispersibility of the phosphor fine particles, and the third role. The role is to have excellent screen printability. Therefore, in order to effectively achieve these three roles, it is preferable to use an appropriate organic solvent in combination.

In the present invention, when polymethyl methacrylate is used as the (meth) acrylic resin, if a polymethyl methacrylate having a relatively high weight average molecular weight is used, a highly polar solvent such as terpineol or butyl carbitol is basically used. Does not dissolve. However, the highly polar solvent is an indispensable solvent for the phosphor fine particle dispersed paste composition, and it is necessary to combine a solvent having a high vapor pressure and a high evaporation property in order to adhere the phosphor on the upper part of the PDP barrier rib. . Therefore, in order to achieve the first role, it is preferable to add a small amount of a solvent that does not have a hydroxyl group and dissolves polymethyl methacrylate well, such as terpineol or butyl carbitol.

Moreover, since the solvent consisting of a compound having a large number of hydroxyl groups in the molecule has good dispersibility of the phosphor fine particles, 2-ethyl-1,3-hexanediol is used for the purpose of achieving the second role. As described above, by adding a solvent composed of a compound having two hydroxyl groups in the molecule, the dispersibility of the phosphor fine particles is improved. Other examples of such a solvent include 3-methyl-1,5-pentanediol and 2-ethyl-1,3-hexanediol.
However, in this case, since the evaporability of the organic solvent is deteriorated and the solubility of polymethyl methacrylate is lowered, a solvent such as terpinyl acetate having no hydroxyl group is used as a solvent having a high vapor pressure at room temperature. It is preferably used in combination with a solvent comprising a compound having two hydroxyl groups therein.

In addition, the process of filling the phosphor fine particle dispersion paste into the partition walls of the PDP back plate is usually performed by screen printing or a dispenser. Particularly, in screen printing, a fine stainless steel mesh is used for the screen plate. A high solvent has a high applicability to the stainless steel member of the printing press, and is likely to deteriorate the plate release property, resulting in an insufficient filling amount of the phosphor fine particle dispersed paste. Therefore, it is preferable to add a solvent having no hydroxyl group and having a low polarity such as butyl carbitol acetate. In addition, about the magnitude | size of polarity, the number of the hydroxyl groups with respect to carbon number (carbon / hydroxyl group) in the chemical composition of a solvent, the solubility with respect to water, etc. become a standard. However, it is preferable to use a high molecular weight. For example, the solubility in water of butyl carbitol (carbon / hydroxyl group: 4) having a molecular weight of 162 is ∞, whereas texanol (carbon / hydroxyl group: 12) having a molecular weight of 216 has a hydroxyl group but is soluble in water. Is less than 0.9%, and by adjusting the molecular weight of the compound constituting the solvent, the above first to third roles can be made compatible.

In the above description, the solvent capable of optimizing the structure in the rib of the phosphor has been described. On the other hand, in the present invention, in addition to the (meth) acrylic resin, a small amount of solvent-drying resin is contained. May be. In particular, a cellulose resin does not have molecular chain entanglement and develops a thickening action by an interaction due to hydrogen bonding. Therefore, it does not cause skinning like a (meth) acrylic resin during solvent drying, and has a high drying speed. In addition, when it contains a cellulose resin, it is desirable to adjust the Tg of the (meth) acrylic resin to less than 80 ° C. and introduce a composition having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate into the polymer.
In addition to the (meth) acrylic resin, ethylcellulose is preferable as the cellulose resin to be contained. Although it does not specifically limit as a grade of the said ethyl cellulose, STD4-20 is preferable for reasons, such as being excellent in viscosity stability.

The minimum with the preferable addition amount of the said cellulose resin is 0.5 weight part with respect to 100 weight part of (meth) acrylic resins, and a preferable upper limit is 100 weight part.
When the addition amount of the cellulose-based resin is less than 0.5 parts by weight, the effect on the drying property may not be exhibited, and when it exceeds 100 parts by weight, the sinterability may be deteriorated. The more preferable lower limit of the addition amount is 10 parts by weight, and the more preferable upper limit is 70 parts by weight.

The inorganic fine particle-dispersed paste composition of the present invention contains inorganic fine particles.
The inorganic fine particles are not particularly limited, and examples thereof include glass powder, ceramic powder, phosphor fine particles, and silicon oxide.
The glass powder is not particularly limited, for example, bismuth oxide glass, silicate glass, lead glass, zinc glass, and glass frit such as boron _{glass, CaO-Al 2 O 3 -SiO} 2 system, _MgO-Al 2 O ₃ -SiO ₂ based _glass frit or the like of the LiO ₂ -Al ₂ O 3 -SiO ₂ system such as various silicon oxide and the like. In addition to these, PbO—B ₂ O ₃ —SiO ₂ mixture, BaO—ZnO—B ₂ O ₃ —SiO ₂ mixture, ZnO—Bi ₂ O ₃ —B ₂ O ₃ —SiO ₂ mixture, Bi ₂ O ₃ -B ₂ O ₃ -BaO-CuO _{mixture, Bi 2 O 3 -ZnO-B} 2 O 3 -Al 2 O 3 -SrO _{mixture, ZnO-Bi 2 O 3 -B} 2 O 3 mixture, _Bi 2 _{O 3} - SiO ₂ mixture, P ₂ O ₅ —Na ₂ O—CaO—BaO—Al ₂ O ₃ —B ₂ O ₃ mixture, P ₂ O ₅ —SnO mixture, P ₂ O ₅ —SnO—B ₂ O ₃ mixture, P ₂ O ₅ —SnO—SiO ₂ mixture, CuO—P ₂ O ₅ —RO mixture, SiO ₂ —B ₂ O ₃ —ZnO—Na ₂ O—Li ₂ O—NaF—V ₂ O ₅ mixture, P ₂ O ₅ —ZnO—SnO—R ₂ O— RO _mixture, B ₂ O ₃ -SiO ₂ -ZnO _{mixture, B 2 O 3 -SiO 2 -Al} 2 O 3 -ZrO 2 _{mixture, SiO 2 -B 2 O 3 -ZnO} -R 2 O-RO mixture, SiO _{2 -B 2 O 3 -Al 2 O 3} -RO-R 2 O _{mixture, SrO-ZnO-P 2 O} 5 _{mixtures, SrO-ZnO-P 2 O} 5 _{mixtures, BaO-ZnO-B 2 O} 3 -SiO 2 mixture (Wherein R is an element selected from the group consisting of Zn, Ba, Ca, Mg, Sr, Sn, Ni, Fe, and Mn).
Moreover, you may use the low melting glass powder whose melting | fusing point is 600 degrees C or less. Examples of the ceramic powder include alumina, zirconia, titanium oxide, barium titanate, alumina nitride, silicon nitride, and boron nitride. Examples of the phosphor fine particles include BaMgAl ₁₀ O ₁₇ : Eu, Zn ₂ SiO ₄ : Mn, (Y, Gd) BO ₃ : Eu, and the like.
In addition to the above-mentioned inorganic fine particles, it can be suitably used for metals such as copper and iron that have good adsorption characteristics and easily oxidize with amino groups or amide groups.

In addition, the inorganic fine particle dispersed paste composition of the present invention preferably contains a nonionic surfactant having an HLB value of 10 or more in order to stabilize an appropriate phase separation (microphase separation). Here, the HLB value is used as an index representing the hydrophilicity and lipophilicity of a surfactant, and several calculation methods have been proposed. For example, for a nonionic surfactant, the saponification value is S When the acid value of the fatty acid constituting the surfactant is A, the HLB value is defined as 20 (1-S / A).
The nonionic surfactant having an HLB value of 10 or more is not particularly limited, but those obtained by adding an alkylene ether to a fatty chain are preferred. Specifically, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl Ether and the like are preferred. The nonionic surfactant has good thermal decomposability, but if added in a large amount, the thermal decomposability of the inorganic fine particle-dispersed paste composition may be lowered. Therefore, the preferable upper limit of the content is 5% by weight. .

The inorganic fine particle-dispersed paste composition of the present invention preferably further contains an organic compound having a glass transition temperature of 0 ° C. or lower and a weight average molecular weight of 1000 to 30000.
The inorganic fine particle-dispersed paste composition of the present invention is usually applied by using a process such as die coating, roll coating, screen printing, dispenser, offset, etc., but the air bubbles entrained at the time of coating or releasing the plate are after firing. There was a problem with pinholes.
In particular, in the phosphor printing process of the plasma display, since the paste is printed in a narrow space in the glass rib, bubbles may be involved with high probability. Therefore, the phosphor paste has been desired to have a property that bubbles can be quickly removed during printing and drying.
In this invention, since the said organic compound has a defoaming effect, the malfunction at the time of a bubble mixing at the time of coating or the plate separation can be effectively prevented by containing the said organic compound.

The organic compound is desirably a low polarity compound. The (meth) acrylic resin used in the inorganic fine particle-dispersed paste composition of the present invention has a relatively high polarity derived from the polar group at the end, but it is polar by adding a low polarity compound as an organic compound. Due to the difference, the surface tension of the air bubble surface can be lowered, and as a result, the entrained air bubbles can be broken.

Examples of the organic compound include compounds such as polyolefin and polyether. Specifically, for example, polypropylene-polyethylene copolymer, polybutene, polypropylene glycol, polytetramethylene glycol, polypropylene glycol-polytetramethylene glycol copolymer. A polymer etc. are mentioned.

The glass transition temperature (Tg) of the organic compound is preferably 0 ° C. or lower. Since the Tg is 0 ° C. or less, it is incompatible with the vehicle contained in the inorganic fine particle dispersed paste composition of the present invention and can move around freely in the vehicle to some extent. It can work effectively as a starting point for bubble breaking. When Tg exceeds 0 ° C., the compatibility with the (meth) acrylic resin becomes too good, and the defoaming effect may not be obtained.

The minimum with a preferable weight average molecular weight of the said organic compound is 1000, and a preferable upper limit is 30000. If the weight average molecular weight of the organic compound is less than 1000, the compatibility with the (meth) acrylic resin may be too good, and the defoaming effect may be insufficient. May not be able to move, and the defoaming effect may be reduced.

The minimum with preferable content of the said organic compound is 0.1 weight part with respect to 100 weight part of (meth) acrylic resins, and a preferable upper limit is 10 weight part. When the content of the organic compound is less than 0.1 parts by weight, a sufficient defoaming effect may not be exhibited, and when it exceeds 10 parts by weight, the sinterability may be adversely affected.

The inorganic fine particle-dispersed paste composition of the present invention preferably contains an organic material having a surface conditioning effect (hereinafter also referred to as a surface conditioning agent). The surface conditioner is preferably a highly polar organic compound having a hydroxyl group in the molecule.
By using a highly polar organic compound as the surface conditioner, compatibility with inorganic fine particles can be increased, and bubbles can be prevented from being involved in the paste.
Furthermore, the high polar organic compound as described above can further increase the polarity of the inorganic fine particle dispersed paste composition. As a result, the difference in polarity from the organic compound can be further increased, and the bubble breaking effect can be further enhanced.

Examples of the surface conditioner include diol compounds and triol compounds, and specific examples include propylene glycol, trimethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, and 1,4-butylene. Glycol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethylpropanediol, 2-ethylhexanediol, 2,4-diethyl- Examples include 1,5-pentanediol, 2-methyl-2,4-pentanediol, glycerin, glycerin monoesters, and acetylene hydroxyl group-imparting products.

The boiling point of the surface conditioner is preferably 300 ° C. or lower. When the boiling point of the surface conditioner exceeds 300 ° C., it may have an adverse effect during sintering.

The preferable lower limit of the content of the surface conditioner is 1% by weight with respect to the content of the (meth) acrylic resin, and the preferable upper limit is 100% by weight. If the content of the surface conditioner is less than 1% by weight, the expected effect may not be obtained. If the content exceeds 100% by weight, the compatibility with the (meth) acrylic resin may be too poor. .

The method for producing the inorganic fine particle-dispersed paste composition of the present invention is not particularly limited, and includes conventionally known stirring methods, specifically, for example, a method of stirring each substance with a three roll or the like.

The inorganic fine particle dispersed paste composition of the present invention uses a glass paste composition particularly when glass powder is used as the inorganic fine particles, a ceramic paste composition when ceramic powder is used as the inorganic fine particles, and a phosphor powder as the inorganic fine particles. It is suitable as a phosphor paste composition when used, a conductive paste composition when conductive powder is used as inorganic fine particles, and a green sheet when glass powder or ceramic powder is used as inorganic fine particles.

The printing method for printing the inorganic fine particle-dispersed paste composition of the present invention is not particularly limited, but can be suitably used for various methods such as screen printing, dispenser, die coating, roll coating, and offset printing.
When printing the inorganic fine particle dispersed paste composition of the present invention using a die coat or a dispenser, it is preferable that the viscosity measured with a low shear rate is low. Specifically, the inorganic fine particle-dispersed paste composition of the present invention preferably has a viscosity of 50 (Pa · s) or less when measured with a shear rate of 2 (1 / s). When the viscosity exceeds 50 (Pa · s), a high pressure is required when extruding the inorganic fine particle dispersed paste composition from the metal spout, and the inorganic fine particle dispersed paste composition may be scattered or the coating amount may be uneven. There are things to do.

Since the inorganic fine particle dispersed paste composition of the present invention uses an organic solvent that evaporates at 280 ° C. or lower and a (meth) acrylic resin that depolymerizes and decomposes at 400 ° C. or lower, low-temperature degreasing is possible. Here, low temperature degreasing means that the degreasing temperature at which 99.5% by weight of the initial weight of the binder resin is lost is low temperature, and in the present specification, under a normal air atmosphere without nitrogen substitution, A case where the degreasing temperature is 250 to 400 ° C. is defined as low temperature degreasing.

According to the present invention, an inorganic fine particle-dispersed paste composition that can be degreased at a low temperature and has excellent dispersibility and storage stability can be provided.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

Example 1
Mixing 100 parts by weight of methyl methacrylate (MMA) and 100 parts by weight of terpineol as an organic solvent into a 2 L separatory flask equipped with a stirrer, a cooler, a thermometer, a hot water bath and a nitrogen gas inlet, a monomer mixture is obtained. It was.

The obtained monomer mixture was bubbled with nitrogen gas for 20 minutes to remove dissolved oxygen, and then the temperature inside the separable flask system was replaced with nitrogen gas and heated up until the oil bath reached 130 ° C. while stirring. . As a polymerization initiator, a solution obtained by diluting 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] with terpineol was added. Further, a terpineol solution containing a polymerization initiator was added several times during the polymerization, and 1.5 parts by weight of the polymerization initiator was added to 100 parts by weight of the monomer in total.

Seven hours after the start of polymerization, the polymerization was terminated by cooling to room temperature. Thereby, a terpineol solution of a (meth) acrylic resin having an amide group at the molecular end was obtained. The obtained polymer was analyzed by gel permeation chromatography using column LF-804 (manufactured by Showa Denko KK) as the column, and the weight average molecular weight in terms of polystyrene was as shown in Table 1.
To the solution of the (meth) acrylic resin thus obtained, terpineol was further added so as to have the composition ratio shown in Table 1, and dispersed with a high-speed disperser to prepare a vehicle composition.

With respect to the obtained vehicle composition, BL-9EX (manufactured by Nikko Chemicals) as a nonionic surfactant, glass fine particles (SiO ₂ 32.5%, B ₂ O with an average particle size of 2.0 μm as inorganic fine particles) ₃ ) 20.5%, ZnO 18%, Al ₂ O ₃ 10%, BaO 3.5%, Li ₂ O 9%, Na ₂ O 6%, SnO ₂ 0.5%) Was added so as to have the composition ratio shown in Table 1, and then sufficiently kneaded using a high-speed stirrer and processed until smooth by a three-roll mill to prepare an inorganic fine particle-dispersed paste composition.

(Example 2)
Mixing 100 parts by weight of methyl methacrylate (MMA) and 100 parts by weight of toluene as an organic solvent in a 2 L separatory flask equipped with a stirrer, cooler, thermometer, hot water bath and nitrogen gas inlet, a monomer mixture is obtained. It was.

The obtained monomer mixture was bubbled with nitrogen gas for 20 minutes to remove dissolved oxygen, and then the temperature inside the separable flask system was replaced with nitrogen gas and heated up until the oil bath reached 130 ° C. while stirring. . As a polymerization initiator, a solution obtained by diluting 2,2′-azobis [2- (2-imidazolin-2-yl) propane] with terpineol was added. Further, a terpineol solution containing a polymerization initiator was added several times during the polymerization, and 1.5 parts by weight of the polymerization initiator was added to 100 parts by weight of the monomer in total.

Seven hours after the start of polymerization, the polymerization was terminated by cooling to room temperature. Thereby, a toluene / terpineol solution of a (meth) acrylic resin having an amino group at the molecular end was obtained. The obtained polymer was analyzed by gel permeation chromatography using column LF-804 (manufactured by Showa Denko KK) as the column, and the weight average molecular weight in terms of polystyrene was as shown in Table 1.
Terpineol was further added to the solution of the (meth) acrylic resin thus obtained, and toluene was removed under reduced pressure by an evaporator to obtain a terpineol solution of a (meth) acrylic binder having an amino group at the molecular end. After confirming the resin solid content by a solvent drying method, terpineol was further added so as to have the composition ratio shown in Table 1, and dispersed with a high-speed disperser to prepare a vehicle composition.

With respect to the obtained vehicle composition, BL-9EX (manufactured by Nikko Chemicals) as a nonionic surfactant, glass fine particles (SiO ₂ 32.5%, B ₂ O with an average particle size of 2.0 μm as inorganic fine particles) ₃ ) 20.5%, ZnO 18%, Al ₂ O ₃ 10%, BaO 3.5%, Li ₂ O 9%, Na ₂ O 6%, SnO ₂ 0.5%) Was added to the composition ratio shown in Table 1, and then sufficiently kneaded using a high-speed stirrer and processed until smooth by a three roll mill to prepare an inorganic fine particle dispersed paste composition. .

(Example 3)
Mixing 100 parts by weight of methyl methacrylate (MMA) and 200 parts by weight of terpineol as an organic solvent into a 2 L separatory flask equipped with a stirrer, cooler, thermometer, hot water bath and nitrogen gas inlet, a monomer mixture is obtained. It was.

The obtained monomer mixture was bubbled with nitrogen gas for 20 minutes to remove dissolved oxygen, and then the temperature inside the separable flask system was replaced with nitrogen gas and heated up until the oil bath reached 130 ° C. while stirring. . As a polymerization initiator, a solution obtained by diluting 2,2′-azobis [2- (2-imidazolin-2-yl) propane] with terpineol was added. Further, a terpineol solution containing a polymerization initiator was added several times during the polymerization, and 10 parts by weight of the polymerization initiator was added to 100 parts by weight of the monomer in total.

Seven hours after the start of polymerization, the polymerization was terminated by cooling to room temperature. Thereby, a terpineol solution of a (meth) acrylic resin having an amino group at the molecular end was obtained. The obtained polymer was analyzed by gel permeation chromatography using column LF-804 (manufactured by Showa Denko KK) as the column, and the weight average molecular weight in terms of polystyrene was as shown in Table 1.
A part of terpineol was removed under reduced pressure from the solution of the (meth) acrylic resin thus obtained by an evaporator to adjust the resin solid content. After confirming the resin solid content by a solvent drying method, terpineol was further added so as to have the composition ratio shown in Table 1, and dispersed with a high-speed disperser to prepare a vehicle composition.

With respect to the obtained vehicle composition, BL-9EX (manufactured by Nikko Chemicals) as a nonionic surfactant, glass fine particles (SiO ₂ 32.5%, B ₂ O with an average particle size of 2.0 μm as inorganic fine particles) ₃ ) 20.5%, ZnO 18%, Al ₂ O ₃ 10%, BaO 3.5%, Li ₂ O 9%, Na ₂ O 6%, SnO ₂ 0.5%) Was added to the composition ratio shown in Table 1, and then sufficiently kneaded using a high-speed stirrer and processed until smooth by a three roll mill to prepare an inorganic fine particle dispersed paste composition. .

Example 4
Terpineol was further added to the terpineol solution having an amide group at the molecular end prepared in Example 1 so as to have the composition ratio described in Table 1, and dispersed with a high-speed disperser to prepare a vehicle composition.

With respect to the obtained vehicle composition, BL-9EX (manufactured by Nikko Chemicals) as a nonionic surfactant, and a red phosphor (manufactured by Nichia Corporation, (Y, Gd) BO ₃ : Eu) as inorganic fine particles. Was added to the composition ratio shown in Table 1, and then sufficiently kneaded using a high-speed stirrer and processed until smooth by a three roll mill to prepare an inorganic fine particle dispersed paste composition. .

(Example 5)
In a 2 L separatory flask equipped with a stirrer, cooler, thermometer, hot water bath and nitrogen gas inlet, 100 parts by weight of methyl methacrylate (MMA) and 100 parts by weight of terpineol as an organic solvent are mixed, and amino as a chain transfer agent. 0.8 part by weight of ethanethiol was added to obtain a monomer mixture.

The obtained monomer mixture was bubbled with nitrogen gas for 20 minutes to remove dissolved oxygen, and then the temperature inside the separable flask system was replaced with nitrogen gas and heated up until the oil bath reached 130 ° C. while stirring. . As a polymerization initiator, a solution obtained by diluting 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] with terpineol was added. Further, a terpineol solution containing a polymerization initiator was added several times during the polymerization, and 2.5 parts by weight of the polymerization initiator was added to 100 parts by weight of the monomer in total.

Seven hours after the start of polymerization, the polymerization was terminated by cooling to room temperature. Thereby, a terpineol solution of a (meth) acrylic resin having an amide group at the molecular end was obtained. The obtained polymer was analyzed by gel permeation chromatography using column LF-804 (manufactured by Showa Denko KK) as the column, and the weight average molecular weight in terms of polystyrene was as shown in Table 1.
To the solution of the (meth) acrylic resin thus obtained, terpineol was further added so as to have the composition ratio shown in Table 1, and dispersed with a high-speed disperser to prepare a vehicle composition.

With respect to the obtained vehicle composition, BL-9EX (manufactured by Nikko Chemicals) as a nonionic surfactant, and a red phosphor (manufactured by Nichia Corporation, (Y, Gd) BO ₃ : Eu) as inorganic fine particles. Was added so as to have the composition ratio shown in Table 1, and then sufficiently kneaded using a high-speed stirrer and processed until smooth by a three-roll mill to prepare an inorganic fine particle-dispersed paste composition.

(Comparative Example 1)
Chain transfer is performed by mixing 100 parts by weight of methyl methacrylate (MMA) and 100 parts by weight of butyl carbitol acetate as an organic solvent into a 2 L separate flask equipped with a stirrer, cooler, thermometer, hot water bath and nitrogen gas inlet. As an agent, 0.8 part by weight of aminoethanethiol was added to obtain a monomer mixture.

The obtained monomer mixture was bubbled with nitrogen gas for 20 minutes to remove dissolved oxygen, and then the temperature inside the separable flask system was replaced with nitrogen gas and heated up until the oil bath reached 130 ° C. while stirring. . As a polymerization initiator, a solution obtained by diluting perhexaTMH (manufactured by NOF Corporation), which is peroxyketal, with butyl carbitol acetate was added. Further, a butyl carbitol acetate solution containing a polymerization initiator was added several times during the polymerization, and 1.5 parts by weight of the polymerization initiator was added to 100 parts by weight of the monomer in total.

Seven hours after the start of polymerization, the polymerization was terminated by cooling to room temperature. Thereby, a butyl carbitol acetate solution of a (meth) acrylic resin having an amide group at the molecular end was obtained. When the obtained polymer was analyzed by gel permeation chromatography using column LF-804 (manufactured by Showa Denko KK) as a column, it became a polymer having a molecular weight of 3 times or more with respect to the original expected molecular weight. It was. Table 1 shows the weight average molecular weight in terms of polystyrene.
To the solution of the (meth) acrylic resin thus obtained, butyl carbitol acetate was further added so as to have the composition ratio shown in Table 1, and dispersed with a high-speed disperser to prepare a vehicle composition. .

With respect to the obtained vehicle composition, BL-9EX (manufactured by Nikko Chemicals) as a nonionic surfactant, glass fine particles (SiO ₂ 32.5%, B ₂ O with an average particle size of 2.0 μm as inorganic fine particles) ₃ ) 20.5%, ZnO 18%, Al ₂ O ₃ 10%, BaO 3.5%, Li ₂ O 9%, Na ₂ O 6%, SnO ₂ 0.5%) Was added so as to have the composition ratio shown in Table 1, and then sufficiently kneaded using a high-speed stirrer and processed until smooth by a three-roll mill to prepare an inorganic fine particle-dispersed paste composition.

(Comparative Example 2)
In a 2 L separable flask equipped with a stirrer, cooler, thermometer, hot water bath and nitrogen gas inlet, 90 parts by weight of methyl methacrylate (MMA), 10 parts by weight of methacrylamide (MAA), butyl carbitol acetate as an organic solvent 100 parts by weight were mixed, and 1.2 parts by weight of dodecyl mercaptan was added as a chain transfer agent to obtain a monomer mixture.

The obtained monomer mixture was bubbled with nitrogen gas for 20 minutes to remove dissolved oxygen, and then the temperature inside the separable flask system was replaced with nitrogen gas and heated up until the oil bath reached 130 ° C. while stirring. . As a polymerization initiator, a solution obtained by diluting perhexa TMH (manufactured by NOF Corporation) with butyl carbitol acetate was added. Further, a butyl carbitol acetate solution containing a polymerization initiator was added several times during the polymerization, and 1.5 parts by weight of the polymerization initiator was added to 100 parts by weight of the monomer in total.

Three hours after the start of polymerization, the methacrylic resin having an amide group in the molecular side chain gelled and could not be used for pasting.

(Comparative Example 3)
In a 2 L separate flask equipped with a stirrer, cooler, thermometer, hot water bath and nitrogen gas inlet, 90 parts by weight of methyl methacrylate (MMA), 10 parts by weight of n-isopropylamide methacrylate (NIPAM), and butyl as an organic solvent 100 parts by weight of carbitol acetate was mixed, and 1.2 parts by weight of dodecyl mercaptan was added as a chain transfer agent to obtain a monomer mixture.

The obtained monomer mixture was bubbled with nitrogen gas for 20 minutes to remove dissolved oxygen, and then the temperature inside the separable flask system was replaced with nitrogen gas and heated up until the oil bath reached 130 ° C. while stirring. . As a polymerization initiator, a solution obtained by diluting perhexa TMH (manufactured by NOF Corporation) with butyl carbitol acetate was added. Further, a butyl carbitol acetate solution containing a polymerization initiator was added several times during the polymerization, and 1.5 parts by weight of the polymerization initiator was added to 100 parts by weight of the monomer in total.

Seven hours after the start of polymerization, the polymerization was terminated by cooling to room temperature. This obtained the butyl carbitol acetate solution of the (meth) acrylic resin which has an amide group in a molecular side chain. When the obtained polymer was analyzed by gel permeation chromatography using column LF-804 (manufactured by Showa Denko KK) as a column, it became a polymer having a molecular weight of 2 times or more with respect to the original expected molecular weight. It was. Table 1 shows the weight average molecular weight in terms of polystyrene.
To the solution of the (meth) acrylic resin thus obtained, butyl carbitol acetate was further added so as to have the composition ratio shown in Table 1, and dispersed with a high-speed disperser to prepare a vehicle composition. .

With respect to the obtained vehicle composition, BL-9EX (manufactured by Nikko Chemicals) as a nonionic surfactant, glass fine particles (SiO ₂ 32.5%, B ₂ O with an average particle size of 2.0 μm as inorganic fine particles) ₃ ) 20.5%, ZnO 18%, Al ₂ O ₃ 10%, BaO 3.5%, Li ₂ O 9%, Na ₂ O 6%, SnO ₂ 0.5%) Was added to the composition ratio shown in Table 1, and then sufficiently kneaded using a high-speed stirrer and processed until smooth by a three roll mill to prepare an inorganic fine particle dispersed paste composition. .

(Comparative Example 4)
Mix the monomer by mixing 100 parts by weight of methyl methacrylate (MMA) and 100 parts by weight of butyl carbitol acetate as an organic solvent in a 2 L separate flask equipped with a stirrer, cooler, thermometer, hot water bath and nitrogen gas inlet. A liquid was obtained.

The obtained monomer mixture was bubbled with nitrogen gas for 20 minutes to remove dissolved oxygen, and then the temperature inside the separable flask system was replaced with nitrogen gas and heated up until the oil bath reached 130 ° C. while stirring. . A solution obtained by diluting azobisisobutyronitrile (AIBN) with butyl carbitol acetate as a polymerization initiator was added. Further, a butyl carbitol acetate solution containing a polymerization initiator was added several times during the polymerization, and 3 parts by weight of the polymerization initiator was added to 100 parts by weight of the monomer in total.

Seven hours after the start of polymerization, the polymerization was terminated by cooling to room temperature. As a result, a butyl carbitol acetate solution of a (meth) acrylic resin having isobutyronitrile at the molecular end was obtained. The obtained polymer was analyzed by gel permeation chromatography using column LF-804 (manufactured by Showa Denko KK) as the column, and the weight average molecular weight in terms of polystyrene was as shown in Table 1.
To the solution of the (meth) acrylic resin thus obtained, butyl carbitol acetate was further added so as to have the composition ratio shown in Table 1, and dispersed with a high-speed disperser to prepare a vehicle composition. .

With respect to the obtained vehicle composition, BL-9EX (manufactured by Nikko Chemicals) as a nonionic surfactant, and a red phosphor (manufactured by Nichia Corporation, (Y, Gd) BO ₃ : Eu) as inorganic fine particles. Was added to the composition ratio shown in Table 1, and then sufficiently kneaded using a high-speed stirrer and processed until smooth by a three roll mill to prepare an inorganic fine particle dispersed paste composition. .

<Evaluation>
The following evaluation was performed about the inorganic fine particle dispersion | distribution paste composition obtained in Examples 1-5 and Comparative Examples 1-4. The results are shown in Table 2.

(1) Transparency of binder resin composition (impurity generation)
The vehicle compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 4 were diluted 50 times with ethyl acetate, and the transparency was confirmed. When a large amount of impurities are generated due to the cage effect of the polymerization initiator, turbidity is observed. Therefore, the case where turbidity is observed is indicated as x, and the case where turbidity is not observed is indicated as ◯.

(2) Using an applicator set to sinterability of 5 mils, the inorganic fine particle dispersion paste was coated on a glass substrate, dried in a 150 ° C. blowing oven for 30 minutes, and then in an electric furnace at 500 ° C. for 30 minutes. Baked. Residual carbon (ppm) was measured by a carbon sulfur analyzer manufactured by Horiba. Moreover, the baked color was confirmed visually and evaluated as follows.
○: Residual carbon was 150 ppm or less.
X: Residual carbon was 150 ppm or more.

(3) Storage stability (presence or absence of precipitate)
The paste compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 4 were put in a 250 ml polyethylene container, and it was visually observed whether or not a precipitate was present at the bottom of the container. Thereafter, the phosphor paste composition placed in a polyethylene container was stored for one month in an environment of a temperature of 23 ° C. and a humidity of 50%, and then it was visually observed again whether a precipitate was present at the bottom of the container.
The following criteria were used to evaluate whether sediment was present at the bottom of the container.
○: No precipitate was observed at the bottom of the container.
X: A precipitate was observed at the bottom of the container.

(Example 6)
Mixing 100 parts by weight of methyl methacrylate (MMA) and 100 parts by weight of terpineol as an organic solvent into a 2 L separatory flask equipped with a stirrer, a cooler, a thermometer, a hot water bath and a nitrogen gas inlet, a monomer mixture is obtained. It was.

The obtained monomer mixture was bubbled with nitrogen gas for 20 minutes to remove dissolved oxygen, and then the temperature inside the separable flask system was replaced with nitrogen gas and heated up until the oil bath reached 130 ° C. while stirring. . As a polymerization initiator, a solution obtained by diluting 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] with terpineol was added. Further, a terpineol solution containing a polymerization initiator was added several times during the polymerization, and 1.5 parts by weight of the polymerization initiator was added to 100 parts by weight of the monomer in total.

Seven hours after the start of polymerization, the polymerization was terminated by cooling to room temperature. Thereby, a terpineol solution of a (meth) acrylic resin having an amide group at the molecular end was obtained. The obtained polymer was analyzed by gel permeation chromatography using column LF-804 (manufactured by Showa Denko KK) as a column, and the weight average molecular weight in terms of polystyrene was as shown in Table 3.
To the (meth) acrylic resin solution thus obtained, terpinyl acetate was further added so as to have the composition ratio shown in Table 3, and dispersed with a high-speed disperser to prepare a vehicle composition. .

For the obtained vehicle composition, BC-30 (manufactured by Nikko Chemicals) as a nonionic surfactant and phosphor inorganic fine particles for PDP (manufactured by Nichia Corporation, red phosphor (Y, Gd) as inorganic fine particles ) BO ₃ : Eu) was added so that the composition ratio shown in Table 3 was obtained, and then kneaded sufficiently using a high-speed stirrer and processed until it became smooth with a three-roll mill, and an inorganic fine particle dispersed paste composition A product was made.

(Example 7)
In the polymerization step, the same as Example 6 except that 2,2′-azobis [2- (2-imidazolin-2-yl) propane] was used as the polymerization initiator, and the organic solvent was blended as shown in Table 3. In this way, an inorganic fine particle dispersed paste composition was prepared.

(Example 8)
The polymerization step was carried out except that terpinyl acetate was used as a polymerization solvent and 2,2′-azobis [2- (2-imidazolin-2-yl) propane] was used as a polymerization initiator, and the formulation shown in Table 3 was used. In the same manner as in Example 6, an inorganic fine particle dispersed paste composition was prepared.

Example 9
In the polymerization step, an inorganic fine particle-dispersed paste composition was prepared in the same manner as in Example 6 except that the addition amount of the polymerization initiator was reduced and the formulation shown in Table 3 was used.

(Example 10)
Inorganic fine particle-dispersed paste composition in the same manner as in Example 6 except that the terpineol solution of (meth) acrylic resin having an amide group at the molecular end obtained in Example 5 was used and the formulation shown in Table 3 was used. Was made.

(Comparative Example 5)
A 2 L separate flask equipped with a stirrer, cooler, thermometer, hot water bath and nitrogen gas inlet is mixed with 100 parts by weight of methyl methacrylate (MMA) and 30 parts by weight of ethyl acetate as an organic solvent, Obtained.

The obtained monomer mixture was bubbled with nitrogen gas for 20 minutes to remove dissolved oxygen, and then the temperature inside the separable flask system was replaced with nitrogen gas and the temperature was raised until the mixed solution reached reflux with stirring. . A solution obtained by diluting perhexaTMH (manufactured by NOF Corporation) with ethyl acetate as a peroxyketal was added as a polymerization initiator. Further, an ethyl acetate solution containing a polymerization initiator was added several times during the polymerization, and 0.5 parts by weight of the polymerization initiator was added to 100 parts by weight of the monomer in total.

Seven hours after the start of polymerization, the polymerization was terminated by cooling to room temperature. Thereby, an ethyl acetate solution of polymethyl methacrylate was obtained. The obtained polymer was analyzed by gel permeation chromatography using column LF-804 (manufactured by Showa Denko KK) as a column, and the weight average molecular weight in terms of polystyrene was as shown in Table 3. Ethyl acetate was dried and redissolved with terpineol.
However, the high molecular weight polymethylmethacrylate resin did not dissolve in terpineol even at high temperatures, resulting in a resin solution with a texture like gelation, and subsequent evaluation was not possible.

(Comparative Example 6)
The ethyl acetate solution of polymethyl methacrylate obtained by the same method as in Comparative Example 5 was dried and redissolved in butyl carbitol acetate.
To the butyl carbitol acetate solution of polymethyl methacrylate thus obtained, butyl carbitol acetate was further added so as to have the composition ratio shown in Table 3, and dispersed with a high-speed disperser to obtain a vehicle composition. Produced.

For the obtained vehicle composition, BC-30 (manufactured by Nikko Chemicals) as a nonionic surfactant and phosphor inorganic fine particles for PDP (manufactured by Nichia Corporation, red phosphor (Y, Gd) as inorganic fine particles ) BO ₃ : Eu) was added so that the composition ratio shown in Table 3 was obtained, and then kneaded sufficiently using a high-speed stirrer and processed until it became smooth with a three-roll mill, thereby dispersing inorganic fine particles. A paste composition was prepared.

<Evaluation>
In addition to the evaluations (1) to (3) above, the following evaluations (4) to (5) were performed on the inorganic fine particle dispersed paste compositions obtained in Examples 6 to 10 and Comparative Examples 5 and 6. It was. The results are shown in Table 4.

(Production of evaluation substrate)
Ethyl cellulose (Sigma Aldrich, STD100) was dissolved in a terpineol solution to prepare a vehicle composition. Next, a glass frit having a softening point of about 550 ° C. and an ethylcellulose-containing vehicle composition were mixed so that the glass frit was 50% by weight and the vehicle composition was 50% by weight, then kneaded with a high-speed stirrer, and a three-roll mill was performed. The glass paste composition was produced by processing until it became smooth using. The obtained glass paste composition was applied to a 15 cm × 15 cm soda glass substrate using an applicator, dried in a 120 ° C. oven for 30 minutes, and then sintered at 550 ° C. for 20 minutes. A substrate A on which a glass layer was formed was produced.

Glass fine particles having an average particle size of 2.0 μm (SiO ₂ 35%, B ₂ O ₃ 20%, ZnO 18%, Al ₂ O ₃ 12%, BaO 5%, Li ₂ O 7%, Na the _{2 O} 2.5%, the a SnO ₂ 0.5% containing), was mixed with terpineol solution prepared by dissolving ethyl cellulose, and sufficiently kneaded by using a high speed stirrer, the process until smooth in a three-roll mill To obtain a glass paste composition. This glass paste composition was coated on the substrate A using an applicator at a setting of 5 mils, and dried in an oven at 150 ° C. for 60 minutes to obtain a substrate B.

A partition wall was formed on the glass layer of the obtained substrate B by sand blasting using a sand blasting machine (manufactured by Fuji Seisakusho, pneumatic blaster SMC-1ADE-401). Note that PDP sandblast media (S9 # 1200, manufactured by Fuji Seisakusho Co., Ltd.) was used as the abrasive, and the pressure in the sandblast treatment was 0.04 MPa and the injection amount was 200 g / min. Next, the substrate on which the barrier ribs were formed was baked at a maximum temperature of 550 ° C. for 10 minutes to produce an evaluation substrate having barrier ribs.

(4) Viscosity Evaluation Using a rheometer VAR100 (manufactured by REOLOGICA), the viscosity of the inorganic fine particle dispersed paste composition at a shear rate of 2 (1 / s) was measured. In the measurement, a parallel plate having a diameter of 10 mm was used and the gap was set to 0.5 mm.
The case where it was 50 (Pa · s) or less was rated as ◯, and the case where it exceeded 50 (Pa · s) was marked as x.

(5) Using the phosphor shape evaluation dispenser, the obtained inorganic fine particle dispersed paste composition was filled in the partition walls of the evaluation substrate, and then dried at 150 ° C. for 10 minutes in a blowing oven. Then, the shape of the fluorescent substance layer was confirmed by baking at 500 degreeC for 10 minute (s) in the muffle furnace, and observing the cross section of the obtained board | substrate with a stereomicroscope. The case where the phosphor layer adhered evenly to the upper part of the partition wall was marked with ◯, and the case where the phosphor layer was submerged at the bottom of the partition wall or was partially biased in the partition wall was marked with ×.

(Example 11)
In a 2 L separatory flask equipped with a stirrer, cooler, thermometer, hot water bath and nitrogen gas inlet, 100 parts by weight of methyl methacrylate (MMA), 0.8 part by weight of ammonium thioglycolate as a chain transfer agent, organic solvent As a result, 50 parts by weight of terpineol was mixed to obtain a monomer mixture.

The obtained monomer mixture was bubbled with nitrogen gas for 20 minutes to remove dissolved oxygen, and then the temperature inside the separable flask system was replaced with nitrogen gas and heated until the hot water bath boiled with stirring. A solution obtained by diluting perhexaTMH (manufactured by NOF Corporation) with ethyl acetate as a peroxyketal was added as a polymerization initiator. Further, an ethyl acetate solution containing a polymerization initiator was added several times during the polymerization, and 1.5 parts by weight of the polymerization initiator was added to 100 parts by weight of the monomer in total.

Seven hours after the start of polymerization, the polymerization was terminated by cooling to room temperature. Thereby, a terpineol solution of polymethyl methacrylate was obtained. When the obtained polymer was analyzed by gel permeation chromatography using column LF-804 (manufactured by Showa Denko KK) as a column, the weight average molecular weight in terms of polystyrene was as shown in Table 5.
A solvent and a surfactant were further added to the obtained terpineol solution of polymethylmethacrylate according to Table 5 to prepare a vehicle composition. After stirring with a high-speed stirrer, phosphor inorganic fine particles for PDP (manufactured by Nichia Corporation, red phosphor (Y, Gd) BO3: Eu) are added as inorganic fine particles and treated until smooth by a three-roll mill. Thus, an inorganic fine particle dispersed paste composition was prepared.

(Example 12)
A polymer was produced in the same manner as in Example 11 except that 1 part by weight of monoethanolamine thioglycolate was used instead of ammonium thioglycolate. Thereafter, using the obtained polymer, an inorganic fine particle paste composition was produced in the same manner as in Example 11 with the composition shown in Table 5.

(Example 13)
A polymer was produced in the same manner as in Example 11 except that 0.7 parts by weight of diammonium dithioglycolate was used instead of ammonium thioglycolate. Thereafter, using the obtained polymer, an inorganic fine particle paste composition was produced in the same manner as in Example 11 with the composition shown in Table 5.

(Example 14)
A polymer was produced in the same manner as in Example 11 except that 0.8 parts by weight of ammonium thiopropionate was used instead of ammonium thioglycolate. Thereafter, using the obtained polymer, an inorganic fine particle paste composition was produced in the same manner as in Example 11 with the composition shown in Table 5.

(Example 15)
A polymer was produced in the same manner as in Example 11 except that 1.1 parts by weight of monoethanolamine thiopropionate was used instead of ammonium thioglycolate. Thereafter, using the obtained polymer, an inorganic fine particle paste composition was produced in the same manner as in Example 11 with the composition shown in Table 5.

(Comparative Example 7)
In a 2 L separatory flask equipped with a stirrer, cooler, thermometer, hot water bath and nitrogen gas inlet, 100 parts by weight of methyl methacrylate (MMA), 0.8 part by weight of ammonium thioglycolate as a chain transfer agent, organic solvent As a mixture, 50 parts by weight of butyl carbitol acetate was mixed to obtain a monomer mixture.

The obtained monomer mixture was bubbled with nitrogen gas for 20 minutes to remove dissolved oxygen, and then the temperature inside the separable flask system was replaced with nitrogen gas and heated until the hot water bath boiled with stirring. A solution obtained by diluting perhexaTMH (manufactured by NOF Corporation) with ethyl acetate as a peroxyketal was added as a polymerization initiator. Further, an ethyl acetate solution containing a polymerization initiator was added several times during the polymerization, and 1.5 parts by weight of the polymerization initiator was added to 100 parts by weight of the monomer in total.

Seven hours after the start of polymerization, the polymerization was terminated by cooling to room temperature. Thus, a butyl carbitol acetate solution of polymethyl methacrylate was obtained. When the obtained polymer was analyzed by gel permeation chromatography using column LF-804 (manufactured by Showa Denko KK) as a column, the weight average molecular weight in terms of polystyrene was as shown in Table 5.
A solvent and a surfactant were further added to the obtained terpineol solution of polymethylmethacrylate according to Table 5 to prepare a vehicle composition. After stirring with a high-speed stirrer, phosphor inorganic fine particles for PDP (manufactured by Nichia Corporation, red phosphor (Y, Gd) BO3: Eu) are added as inorganic fine particles and treated until smooth by a three-roll mill. Thus, an inorganic fine particle dispersed paste composition was prepared.

(Comparative Example 8)
An inorganic fine particle paste composition was prepared in the same manner as in Comparative Example 7 except that 0.8 parts by weight of ammonium thiopropionate was used instead of ammonium thioglycolate.

(Example 16)
Mixing 100 parts by weight of terpineol as an organic solvent with 50 parts by weight of methyl methacrylate (MMA) and 50 parts by weight of butyl methacrylate (BMA) in a 2 L separatory flask equipped with a stirrer, cooler, thermometer, hot water bath and nitrogen gas inlet As a result, a monomer mixture was obtained.

The obtained monomer mixture was bubbled with nitrogen gas for 20 minutes to remove dissolved oxygen, and then the temperature inside the separable flask system was replaced with nitrogen gas and heated up until the oil bath reached 130 ° C. while stirring. . As a polymerization initiator, a solution obtained by diluting 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] with terpineol was added. Further, a terpineol solution containing a polymerization initiator was added several times during the polymerization, and 1.5 parts by weight of the polymerization initiator was added to 100 parts by weight of the monomer in total.

Seven hours after the start of polymerization, the polymerization was terminated by cooling to room temperature. Thereby, a terpineol solution of a (meth) acrylic resin having an amide group at the molecular end was obtained. When the obtained polymer was analyzed by gel permeation chromatography using column LF-804 (manufactured by Showa Denko KK) as a column, the weight average molecular weight in terms of polystyrene was as shown in Table 7.
The composition ratio described in Table 7 is ethylcellulose (Wako Pure Chemical Industries, STD10, weight average molecular weight: 65000) previously dissolved in texanol with respect to the solution of the (meth) acrylic resin thus obtained. Then, terpineol and texanol were further added and dispersed with a high-speed disperser to prepare a vehicle composition.

With respect to the obtained vehicle composition, BL-9EX (manufactured by Nikko Chemicals) as a nonionic surfactant and red phosphor fine particles (manufactured by Nichia Corporation, red phosphor (Y, Gd) as inorganic fine particles BO ₃ : Eu) was added so that the composition ratio shown in Table 7 was obtained, and then kneaded sufficiently using a high-speed stirrer and processed until it became smooth with a three-roll mill, and an inorganic fine particle-dispersed paste composition Was made.

(Example 17)
Mixing 50 parts by weight of methyl methacrylate (MMA) and 50 parts by weight of isobutyl methacrylate (IBMA) in 100 parts by weight of terpineol as an organic solvent in a 2 L separatory flask equipped with a stirrer, cooler, thermometer, hot water bath and nitrogen gas inlet As a result, a monomer mixture was obtained.

The obtained monomer mixture was bubbled with nitrogen gas for 20 minutes to remove dissolved oxygen, and then the temperature inside the separable flask system was replaced with nitrogen gas and heated up until the oil bath reached 130 ° C. while stirring. . As a polymerization initiator, a solution obtained by diluting 2,2′-azobis [2- (2-imidazolin-2-yl) propane] with terpineol was added. Further, a terpineol solution containing a polymerization initiator was added several times during the polymerization, and 1.5 parts by weight of the polymerization initiator was added to 100 parts by weight of the monomer in total.

Seven hours after the start of polymerization, the polymerization was terminated by cooling to room temperature. Thereby, a terpineol solution of a (meth) acrylic resin having an amide group at the molecular end was obtained. When the obtained polymer was analyzed by gel permeation chromatography using column LF-804 (manufactured by Showa Denko KK) as a column, the weight average molecular weight in terms of polystyrene was as shown in Table 7.
The composition ratio described in Table 7 is ethylcellulose (STD4, weight average molecular weight: 50000) previously dissolved in texanol with respect to the solution of the (meth) acrylic resin thus obtained. Then, terpineol and texanol were further added and dispersed with a high-speed disperser to prepare a vehicle composition.

With respect to the obtained vehicle composition, BL-9EX (manufactured by Nikko Chemicals) as a nonionic surfactant and red phosphor fine particles (manufactured by Nichia Corporation, red phosphor (Y, Gd) as inorganic fine particles BO ₃ : Eu) was added so that the composition ratio shown in Table 7 was obtained, and then kneaded sufficiently using a high-speed stirrer and processed until it became smooth with a three-roll mill, and an inorganic fine particle-dispersed paste composition Was made.

(Comparative Example 9)
Ethyl cellulose (STD4, manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight: 60000) is dissolved in terpineol, terpineol and texanol are further added to achieve the composition ratio shown in Table 7, and dispersed with a high-speed disperser to form a vehicle composition. A product was made.

With respect to the obtained vehicle composition, BL-9EX (manufactured by Nikko Chemicals) as a nonionic surfactant and red phosphor fine particles (manufactured by Nichia Corporation, red phosphor (Y, Gd) as inorganic fine particles BO ₃ : Eu) was added so that the composition ratio shown in Table 7 was obtained, and then kneaded sufficiently using a high-speed stirrer and processed until it became smooth with a three-roll mill, and an inorganic fine particle-dispersed paste composition Was made.

<Evaluation>
In addition to the evaluations (1) to (3) above, the following evaluations (4) to (5) were performed on the inorganic fine particle dispersed paste compositions obtained in Examples 11 to 17 and Comparative Examples 7 to 9. It was. The results are shown in Tables 6 and 8.

(Production of evaluation substrate)
Ethyl cellulose (Sigma Aldrich, STD100) was dissolved in a terpineol solution to prepare a vehicle composition. Next, a glass frit having a softening point of about 550 ° C. and an ethylcellulose-containing vehicle composition were mixed so that the glass frit was 50% by weight and the vehicle composition was 50% by weight, then kneaded with a high-speed stirrer, and a three-roll mill was performed. The glass paste composition was produced by processing until it became smooth using. The obtained glass paste composition was applied to a 15 cm × 15 cm soda glass substrate using an applicator, dried in a 120 ° C. oven for 30 minutes, and then sintered at 550 ° C. for 20 minutes. A substrate A on which a glass layer was formed was produced.

Glass fine particles having an average particle size of 2.0 μm (SiO ₂ 35%, B ₂ O ₃ 20%, ZnO 18%, Al ₂ O ₃ 12%, BaO 5%, Li ₂ O 7%, Na the _{2 O} 2.5%, a 0.5% content) SnO2 were mixed with terpineol solution prepared by dissolving ethyl cellulose, and sufficiently kneaded by using a high speed stirrer, the process until smooth in a three-roll mill A glass paste composition was obtained. This glass paste composition was coated on the substrate A using an applicator at a setting of 5 mils, and dried in an oven at 150 ° C. for 60 minutes to obtain a substrate B.

A partition wall was formed on the glass layer of the obtained substrate B by sand blasting using a sand blasting machine (manufactured by Fuji Seisakusho, pneumatic blaster SMC-1ADE-401). Note that PDP sandblast media (S9 # 1200, manufactured by Fuji Seisakusho Co., Ltd.) was used as the abrasive, and the pressure in the sandblast treatment was 0.04 MPa and the injection amount was 200 g / min. Next, the substrate on which the barrier ribs were formed was baked at a maximum temperature of 550 ° C. for 10 minutes to produce an evaluation substrate having barrier ribs.

(4) Viscosity Evaluation Using a rheometer VAR100 (manufactured by REOLOGICA), the viscosity of the inorganic fine particle dispersed paste composition at a shear rate of 2 (1 / s) was measured. In the measurement, a parallel plate having a diameter of 10 mm was used and the gap was set to 0.5 mm.
The case where it was 50 (Pa · s) or less was rated as ◯, and the case where it exceeded 50 (Pa · s) was marked as x.

(5) Using the phosphor shape evaluation dispenser, the obtained inorganic fine particle dispersed paste composition was filled in the partition walls of the evaluation substrate, and then dried at 150 ° C. for 10 minutes in a blowing oven. Then, the shape of the fluorescent substance layer was confirmed by baking at 500 degreeC for 10 minute (s) in the muffle furnace, and observing the cross section of the obtained board | substrate with a stereomicroscope. The case where the phosphor layer adhered evenly to the upper part of the partition wall was marked with ◯, and the case where the phosphor layer was submerged at the bottom of the partition wall or was partially biased in the partition wall was marked with ×.

(Example 18)
Mixing 100 parts by weight of methyl methacrylate (MMA) and 100 parts by weight of terpineol as an organic solvent into a 2 L separatory flask equipped with a stirrer, a cooler, a thermometer, a hot water bath and a nitrogen gas inlet, a monomer mixture is obtained. It was.

The obtained monomer mixture was bubbled with nitrogen gas for 20 minutes to remove dissolved oxygen, and then the temperature inside the separable flask system was replaced with nitrogen gas and heated up until the oil bath reached 130 ° C. while stirring. . As a polymerization initiator, a solution obtained by diluting 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] with terpineol was added. Further, a terpineol solution containing a polymerization initiator was added several times during the polymerization, and 1.5 parts by weight of the polymerization initiator was added to 100 parts by weight of the monomer in total.

Seven hours after the start of polymerization, the polymerization was terminated by cooling to room temperature. Thereby, a terpineol solution of a (meth) acrylic resin having an amide group at the molecular end was obtained. When the obtained polymer was analyzed by gel permeation chromatography using column LF-804 (manufactured by Showa Denko KK) as a column, the weight average molecular weight in terms of polystyrene was as shown in Table 9.
To the solution of the (meth) acrylic resin thus obtained, terpineol, an organic compound, and a surface conditioner were further added so as to have the composition ratio shown in Table 9, and dispersed with a high-speed disperser to obtain a vehicle composition. A product was made.

With respect to the obtained vehicle composition, BL-9EX (manufactured by Nikko Chemicals) as a nonionic surfactant, and a red phosphor (manufactured by Nichia Corporation, (Y, Gd) BO ₃ : Eu) as inorganic fine particles. Was added so as to have the composition ratio shown in Table 9, and then sufficiently kneaded using a high-speed stirrer and processed until it became smooth with a three-roll mill to prepare an inorganic fine particle-dispersed paste composition.
As the organic compound, Nissan polybutene (grade 200N, manufactured by NOF Corporation, glass transition temperature −24 ° C., weight average molecular weight 5500) was used.

(Example 19)
In a 2 L separate flask equipped with a stirrer, cooler, thermometer, hot water bath and nitrogen gas inlet, 50 parts by weight of methyl methacrylate (MMA), 50 parts by weight of isobutyl methacrylate (IBMA), and 100 parts by weight of terpineol as an organic solvent Were mixed to obtain a monomer mixture.

The obtained monomer mixture was bubbled with nitrogen gas for 20 minutes to remove dissolved oxygen, and then the temperature inside the separable flask system was replaced with nitrogen gas and heated up until the oil bath reached 130 ° C. while stirring. . As a polymerization initiator, a solution prepared by diluting 2,2′-azobis [2- (2-imidazolin-2-yl) propane] with terpineol was added. Further, a terpineol solution containing a polymerization initiator was added several times during the polymerization, and 1.5 parts by weight of the polymerization initiator was added to 100 parts by weight of the monomer in total.

Seven hours after the start of polymerization, the polymerization was terminated by cooling to room temperature. Thereby, a terpineol solution of a (meth) acrylic resin having an amide group at the molecular end was obtained. When the obtained polymer was analyzed by gel permeation chromatography using column LF-804 (manufactured by Showa Denko KK) as a column, the weight average molecular weight in terms of polystyrene was as shown in Table 9.
To the solution of the (meth) acrylic resin thus obtained, terpineol and an organic compound were further added so as to have the composition ratio shown in Table 9, and dispersed with a high-speed disperser to prepare a vehicle composition. .

With respect to the obtained vehicle composition, BL-9EX (manufactured by Nikko Chemicals) as a nonionic surfactant, and a red phosphor (manufactured by Nichia Corporation, (Y, Gd) BO ₃ : Eu) as inorganic fine particles. Was added so as to have the composition ratio shown in Table 9, and then sufficiently kneaded using a high-speed stirrer and processed until it became smooth with a three-roll mill to prepare an inorganic fine particle-dispersed paste composition.

(Example 20)
In a 2 L separate flask equipped with a stirrer, cooler, thermometer, hot water bath and nitrogen gas inlet, 50 parts by weight of methyl methacrylate (MMA), 50 parts by weight of isobutyl methacrylate (IBMA), and 100 parts by weight of terpineol as an organic solvent Were mixed to obtain a monomer mixture.

The obtained monomer mixture was bubbled with nitrogen gas for 20 minutes to remove dissolved oxygen, and then the temperature inside the separable flask system was replaced with nitrogen gas and heated up until the oil bath reached 130 ° C. while stirring. . As a polymerization initiator, a solution obtained by diluting 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] with terpineol was added. Further, a terpineol solution containing a polymerization initiator was added several times during the polymerization, and 1.5 parts by weight of the polymerization initiator was added to 100 parts by weight of the monomer in total.

Seven hours after the start of polymerization, the polymerization was terminated by cooling to room temperature. Thereby, a terpineol solution of a (meth) acrylic resin having an amide group at the molecular end was obtained. When the obtained polymer was analyzed by gel permeation chromatography using column LF-804 (manufactured by Showa Denko KK) as a column, the weight average molecular weight in terms of polystyrene was as shown in Table 9.
To the solution of the (meth) acrylic resin thus obtained, terpineol and a surface conditioner were further added so as to have the composition ratio shown in Table 9, and dispersed with a high-speed disperser to produce a vehicle composition. did.

With respect to the obtained vehicle composition, BL-9EX (manufactured by Nikko Chemicals) as a nonionic surfactant, and a red phosphor (manufactured by Nichia Corporation, (Y, Gd) BO ₃ : Eu) as inorganic fine particles. Was added so as to have the composition ratio shown in Table 9, and then sufficiently kneaded using a high-speed stirrer and processed until it became smooth with a three-roll mill to prepare an inorganic fine particle-dispersed paste composition.

(Comparative Example 10)
In a 2 L separatory flask equipped with a stirrer, cooler, thermometer, hot water bath, and nitrogen gas inlet, 100 parts by weight of methyl methacrylate (MMA), 1 part by weight of dodecyl mercaptan as a chain transfer agent, and terpineol as an organic solvent 100 parts by weight was added to obtain a monomer mixture.
The obtained monomer mixture was bubbled with nitrogen gas for 20 minutes to remove dissolved oxygen, and then the temperature inside the separable flask system was replaced with nitrogen gas and heated until the hot water bath boiled with stirring. A solution obtained by diluting perhexaTMH (manufactured by NOF Corporation) with ethyl acetate as a peroxyketal was added as a polymerization initiator. During the polymerization, an ethyl acetate solution containing a polymerization initiator was added several times. Seven hours after the start of polymerization, the polymerization was terminated by cooling to room temperature. Thereby, the terpineol solution of the polymethylmethacrylate polymer which has a methyl group at the terminal was obtained.
When the obtained polymer was analyzed by gel permeation chromatography using column LF-804 (manufactured by Showa Denko KK) as a column, the weight average molecular weight in terms of polystyrene was as shown in Table 9.

To the solution of the (meth) acrylic resin thus obtained, terpineol was further added so as to have the composition ratio shown in Table 9, and dispersed with a high-speed disperser to prepare a vehicle composition.

With respect to the obtained vehicle composition, BL-9EX (manufactured by Nikko Chemicals) as a nonionic surfactant, and a red phosphor (manufactured by Nichia Corporation, (Y, Gd) BO ₃ : Eu) as inorganic fine particles. Was added so as to have the composition ratio shown in Table 9, and then sufficiently kneaded using a high-speed stirrer and processed until it became smooth with a three-roll mill to prepare an inorganic fine particle-dispersed paste composition.

<Evaluation>
In addition to the evaluations (1) to (5) above, the evaluations (6) and (7) described below were performed on the inorganic fine particle dispersed paste compositions obtained in Examples 18 to 20 and Comparative Example 10. . The results are shown in Table 10.

(6) Antifoaming property The obtained vehicle composition was vigorously stirred for 30 seconds with a spatula and then allowed to stand. Those that broke off within 30 minutes were marked with ◎, those that broke within 1 hour were marked with ○, and those that did not break even after standing still were marked with x.

(7) Antifoaming property (after coating)
Using a screen printer, the obtained inorganic fine particle dispersed paste composition was filled into the partition walls of the evaluation substrate, and then allowed to stand at room temperature, and the cracking condition of the bubbles was observed visually. The case in which bubbles were broken within 10 minutes and the surface was in a smooth state was rated as “◯”, and the case in which bubbles were not broken or the surface was uneven even when left still was marked as “X”.

According to the present invention, an inorganic fine particle-dispersed paste composition that can be degreased at a low temperature and has excellent dispersibility and storage stability can be provided.

Claims (7)

An inorganic fine particle-dispersed paste composition containing a (meth) acrylic resin, inorganic fine particles, and an organic solvent, wherein the (meth) acrylic resin has an amino group or an amide group at a molecular end and is based on polystyrene conversion a weight average molecular weight of 5,000 to 100,000, wherein (meth) acrylic resin state, and are not formed by polymerization using a radical polymerization initiator having an amino group or an amide group, wherein the organic solvent is a vapor at room temperature pressure A terpene-based solvent having a water content of 0.1 mmHg or more . The inorganic fine particle-dispersed paste composition according to claim 1, wherein the organic solvent further contains a solvent having a vapor pressure of less than 0.01 mmHg at room temperature. 3. The inorganic fine particle dispersed paste composition according to claim 1, wherein the (meth) acrylic resin is polymerized using an azo polymerization initiator having no cyano group. The inorganic fine particle-dispersed paste composition according to claim 1, 2 or 3 , further comprising a cellulose resin. (Meth) acrylic resin, according to claim 1, 2, 3 or 4 inorganic fine particle-dispersed paste composition according to, characterized in that the formed by polymerization with a solvent containing a terpene solvent. Inorganic fine particles, glass powder, ceramic powder, according to claim 1, 2, 3, 4 or 5 inorganic fine particle-dispersed paste composition, wherein a is a fluorescent microparticles or silicon oxide. Further, the glass transition temperature of 0 ℃ or less, the inorganic fine particle-dispersed paste composition according to claim 2, 3, 4, 5 or 6, wherein the weight average molecular weight is characterized by containing an organic compound is 1000 to 30000 .