JP2014080583A - Resin composition for paste, paste composition and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for paste excellent in leveling property and suppressing generation of stringing while having thixotropic nature without disturbing printing.SOLUTION: A resin composition for paste contains an organic solvent, (meth)acrylate resin A (resin A) having a SP value with an absolute value of difference from the SP value of the organic solvent of 0.5 (cal/cm)or less, and a (meth)acrylate resin B (resin B) having the absolute value of difference from the SP value of the organic solvent of 0.5 (cal/cm)or less and smaller than the absolute value of difference between the SP values of the organic solvent and the resin A, at least one of the resin A and the resin B contains a constitutional unit derived a hydroxyl group-containing monomer, and a percentage of the constitutional unit derived the hydrogen group-containing monomer in the resin A and the resin B is 3 mass% to 15 mass% based on the total amount of all constitutional units of the resin A and the resin B.

Description

  The present invention relates to a resin composition for paste in which a resin component is dispersed in an organic solvent, a paste composition, and a method for producing the paste composition.

  Inorganic pastes prepared by mixing inorganic materials such as inorganic fine particles such as glass powder and conductive powder and organic materials (binder resin dissolved in organic solvent) are used to obtain fired bodies of various shapes Widely used in

  In producing a fired body using an inorganic paste, it is processed into a predetermined shape by screen printing, a coating method using a doctor blade, a casting method for processing into a sheet shape, etc., and then dried and fired. Thus, a desired fired body can be obtained. Among these, the method by screen printing is a method particularly suitable for mass production, and is applied to the formation of various electronic parts and the like.

  For example, partition walls (ribs) provided on a rear glass substrate of a PDP (plasma display), PDP phosphors, dielectrics, solar cell electrodes, and the like can be formed using an inorganic paste. Among these, for example, in the case of inorganic pastes used for phosphors, dielectrics, and solar cell electrodes, after processing into a predetermined shape by screen printing or nozzle coating, etc., drying and firing are performed as desired. A fired body can be obtained.

  For example, when applying screen printing, in order to perform printing well, it is required to have a high non-volatile content (solid content) and a sufficiently low viscosity at the time of coating. On the contrary, after coating, it is required that the viscosity is high and does not flow. That is, for example, in applications where PDP partition walls (ribs) are formed, high thixotropy is required in order to obtain a desired shape by a single operation. On the other hand, the phosphor paste, the dielectric paste, and the inorganic paste used as the electrode paste of the solar cell do not require high thixotropy as required for the partition wall use. In the case of such an inorganic paste, while having a certain degree of thixotropy, the paste can be applied without interruption when the paste is discharged from the pump during nozzle coating (pressure responsiveness), and after coating It is required to have excellent leveling properties and to prevent stringing.

  As a related technology, a resin composition obtained by dissolving a binder resin for baking obtained by copolymerizing a predetermined monomer mixture such as alkyl (meth) acrylate in terpineol is disclosed, and leveling properties are disclosed. And excellent printability in screen printing (see, for example, Patent Document 1). Also disclosed is an inorganic fine particle-dispersed paste composition using swollen gel-like particles of a crosslinked (meth) acrylic resin having a particle diameter of 10 μm or less as a binder resin as an inorganic paste having high viscosity and suppressing stringing. (For example, refer to Patent Document 2).

  In addition, the inorganic paste is also required to have a property (baking property) that the binder has good thermal decomposability at a low temperature and no residue remains after baking. In a composition with poor flammability, an organic component (carbon) remains as an impurity, and it is necessary to heat at a higher temperature.

International Publication No. 2011/13861 Pamphlet JP 2011-122129 A

Conventionally, various studies have been made on the properties of inorganic pastes. Although phosphor pastes, dielectric pastes, and solar cell electrode pastes have been studied in the past, leveling effects after coating are expected while maintaining the thixotropy (printability) required for printing to some extent. In fact, no technology has yet been provided that enables the simultaneous creation of mutually contradictory properties that do not invite stringing.
In addition to the above properties, it is also desirable that the inorganic paste has a calcination property that generates little residue during calcination.

  The present invention has been made in view of the above. An object of the present invention is to provide a resin composition for paste, a paste composition, and a method for producing the same, which have thixotropy that does not hinder printing, have excellent leveling properties, and suppress the occurrence of stringing. It is in.

  In the present invention, a polymer component that is soluble and insoluble in an organic solvent to be used is selected within a predetermined solubility parameter range, and the total amount of hydroxyl groups present in these polymer components is not too large. The knowledge that by adjusting, while maintaining printability with a certain degree of thixotropy, it is possible to simultaneously establish mutually contradictory properties that make the film leveling and stringing properties effective. And have been achieved based on such findings.

Specific means for achieving the above object are as follows.
<1> (meth) acrylate-based resin A having a solubility parameter in which the absolute value of the difference between the organic solvent and the solubility parameter of the organic solvent is 0.5 (cal / cm ³ ) ^0.5 or less; The absolute value of the difference from the solubility parameter is 0.5 (cal / cm ³ ) ^0.5 or less and smaller than the absolute value of the difference in solubility parameter between the organic solvent and the (meth) acrylate resin A (Meth) acrylate resin B, and at least one of (meth) acrylate resin A and (meth) acrylate resin B includes a structural unit derived from a hydroxyl group-containing monomer, and (meth) acrylate resin A and The ratio of the structural unit derived from the hydroxyl group-containing monomer in the (meth) acrylate resin B is that of the (meth) acrylate resin A and (meth) acrylate resin B It is the resin composition for paste which is 3 mass% or more and 15 mass% or less with respect to the total amount of all the structural units.
<2> The (meth) acrylate-based resin A according to <1>, including a structural unit derived from an alkyl acrylate having an alkyl group having 1 to 3 carbon atoms in a range of 10% by mass to 50% by mass. It is a resin composition for pastes.
<3> The absolute value of the difference between the solubility parameter of the (meth) acrylate resin A and the solubility parameter of the (meth) acrylate resin B is 0.1 (cal / cm ³ ) ^0.5 or more and 1.0. (Cal / cm ³ ) The resin composition for paste according to <1> or <2>, which is ^0.5 or less.
<4> The (meth) acrylate-based resin A and the (meth) acrylate-based resin B are at least partially bonded to the polymer structure portion SA and the polymer structure portion SA in which the (meth) acrylate-based resin A is assembled. The resin for paste according to any one of <1> to <3>, which is contained as a dispersed resin that includes the adsorbed (meth) acrylate resin B and is dispersed in the organic solvent. It is a composition.

<5> The organic solvent is a resin composition for paste according to any one of <1> to <4>, which has a boiling point of 180 ° C. or higher and 280 ° C. or lower.
<6> The above organic solvent, wherein the solubility parameter is 8.0 (cal / cm ³ ) ^0.5 or more and 11.0 (cal / cm ³ ) ^0.5 or less It is the resin composition for pastes as described in any one.
<7> A paste composition containing the resin composition for paste according to any one of <1> to <6> and inorganic particles.
<8> A method for producing a paste composition comprising a step of preparing a paste composition by mixing the resin composition for paste according to any one of <1> to <6> and inorganic particles. is there.
<9> Furthermore, the paste as described in said <8> which has the process of synthesize | combining (meth) acrylate type resin A in presence of an organic solvent and (meth) acrylate type resin B, and preparing the resin composition for pastes. It is a manufacturing method of a composition.

According to the present invention, there are provided a resin composition for paste, a paste composition, and a method for producing the same, which have thixotropic properties that do not hinder printing, have excellent leveling properties, and suppress the occurrence of stringing. .
Moreover, the resin composition for pastes and the paste composition of the present invention can also exhibit sinterability with little generation of residue during firing.

  Hereinafter, the resin composition for paste of the present invention, the paste composition using the resin composition, and the production method thereof will be described in detail.

In the resin composition for paste of the present invention, the absolute value of the difference between the organic solvent and the solubility parameter of the organic solvent (hereinafter also referred to as “SP value”) is 0.5 (cal / cm ³ ) ^0.5 or less. The absolute value of the difference between the (meth) acrylate resin A having an SP value of 0.5 and the SP value of the organic solvent is 0.5 (cal / cm ³ ) ^0.5 or less, and the organic solvent and the (meta) And (meth) acrylate resin B smaller than the absolute value of the difference in SP value of acrylate resin A, and at least one of (meth) acrylate resin A and (meth) acrylate resin B is a hydroxyl group Containing structural units derived from the contained monomer. Moreover, the resin composition for pastes of this invention is the ratio of the structural unit derived from the hydroxyl-containing monomer in (meth) acrylate resin A and (meth) acrylate-type resin B, (meth) acrylate-type resin A and (meth) acrylate. It is comprised as 3 to 15 mass% with respect to the total amount of all the structural units of the resin B.
This paste resin composition can be constituted by using other components such as a polymerization initiator and other additives as required.

In general, when there are a plurality of polymer components, the SP value difference is increased to improve the thixotropy, but if the thixotropy is prioritized too much, the leveling property after coating is insufficient. In addition, the inorganic paste is required to have good calcination properties. However, if it is simply made of (meth) acrylic resin from the viewpoint of calcination properties, stringing at the coating nozzle tends to occur. In order to realize all of these properties, it is necessary to carefully adjust the composition balance of the polymer components constituting the paste. In the present invention, in particular, a polymer component that is soluble and insoluble in the organic solvent to be used is selected within a predetermined small SP value range in relation to the SP value (solubility parameter) of the organic solvent. , By making the total amount of hydroxyl groups present in these polymer components within a specific range, leveling properties are imparted to the coated film and stringing is improved while maintaining thixotropy necessary for printability. The Moreover, since it is comprised with (meth) acrylic-type resin, it is excellent also in baking property.
Thus, the resin composition for pastes of the present invention is suitable for uses of phosphor pastes, dielectric pastes, and solar cell electrode pastes.

  The thixotropy is a property in which, when an external stress such as a shearing force is applied, the bond is broken and the viscosity is lowered, the fluidity is developed, the fluidity is lowered and the viscosity is restored again when it is stationary.

In the present invention, the solubility parameter (SP value, unit: (cal / cm ³ ) ^0.5 ) of the organic solvent is a value represented by the square root of the molecular aggregation energy, and is calculated by the Hildebrand method. is there.
In the present invention, the solubility parameter (SP value, unit: (cal / cm ³ ) ^0.5 ) of the (meth) acrylate-based resin is calculated based on the molecular attractive constant G of the structural unit constituting the resin. It is what
When the (meth) acrylate resin is a homopolymer, it is calculated by the following formula. In the case of a copolymer, the SP value of each homopolymer of each structural unit constituting the resin is calculated. It is calculated by the following calculation formula, and is calculated by adding each of the SP values multiplied by the mole fraction of each structural unit.
SP value of homopolymer = dΣG / M
Here, d represents the density (g / l) of the homopolymer, ΣG represents the sum of molecular attractive constants in the molecules of the structural unit, and M represents the molecular weight (g / mol) of the structural unit. .

  In the present specification, (meth) acryl means both acrylic and methacrylic.

Hereinafter, each component which comprises the resin composition for pastes of this invention is explained in full detail.
(Organic solvent)
The resin composition for paste of the present invention contains at least one organic solvent. The organic solvent is selected in consideration of the degree of hydrophilicity / hydrophobicity of the resin component dispersed therein, thixotropy, volatility, leveling property when the resin component is dispersedly contained.

Specific examples of the organic solvent include, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, n-hexyl alcohol, n-octyl alcohol, i-octyl alcohol. Alcohol organic solvents such as 2-ethylhexyl alcohol, 2- (4-methylcyclohex-3-enyl) propan-2-ol (terpineol (also known as terpineol));
Methyl carbitol, ethyl carbitol, n-propyl carbitol, i-propyl carbitol, n-butyl carbitol, i-butyl carbitol, i-amyl carbitol, phenyl carbitol, benzyl carbitol diethyl carbitol, butyl Carbitol organic solvents such as carbitol acetate (BCA) and carbitol acetate;
Ester organic solvents such as propylene carbonate, 2-ethylhexyl acetate, 2-ethylhexanoic acid-ethylhexyl;
Ketone organic solvents such as acetone, methyl ethyl ketone, methyl-i-butyl ketone, methyl amyl ketone, cyclohexanone, diacetone alcohol;
Hydrocarbon organic solvents such as isoparaffin;
amine-based organic solvents such as n-methylpyrrolidone;
And so on.

The solubility parameter (SP value) of the organic solvent is determined from the relationship between the SP value of the (meth) acrylate resin A (insoluble polymer A) described later and the SP value of the (meth) acrylate resin B (soluble polymer B). However, it is preferably 8.0 (cal / cm ³ ) ^0.5 or more and 11.0 (cal / cm ³ ) ^0.5 or less. When the SP value is within the above range, the viscosity when prepared to a composition containing a non-volatile content at a high concentration is kept low, and thixotropic properties are also obtained. Among these, the SP value of the organic solvent is more preferably in the range of 8.5 (cal / cm ³ ) ^0.5 or more and 9.5 (cal / cm ³ ) ^0.5 or less for the same reason as described above.

Moreover, as an organic solvent, the organic solvent whose boiling point exists in the range of 180 to 280 degreeC is preferable. When the boiling point is 180 ° C. or higher, it is suitable for screen printing, and the coating workability during coating when used for screen printing is reduced. Moreover, it is advantageous at the leveling property that a boiling point is 280 degrees C or less.
Among these, for the same reason as described above, the boiling point is more preferably 200 ° C. or higher and 260 ° C. or lower.

  Among the organic solvents described above, the organic solvent in the present invention is preferably an alcohol organic solvent or a carbitol organic solvent from the viewpoint that it has a relatively high boiling point and does not easily volatilize in the atmosphere and can easily maintain thixotropic properties. Furthermore, terpineol, butyl carbitol acetate (BCA), and texanol are more preferable in that better thixotropy can be obtained. Among these, butyl carbitol acetate having a boiling point of 247 ° C. is particularly preferable.

  As content of the organic solvent in the resin composition for pastes of this invention, 30-60 mass% is preferable with respect to the total amount of the insoluble polymer A and the soluble polymer B mentioned later. When the content of the organic solvent is within the above range, a composition having a high nonvolatile content and a thixotropic property can be easily obtained, and a structure having a good height and shape can be formed when screen printing is performed.

-(Meth) acrylate resin A-
The resin composition for paste of the present invention is an SP in which the absolute value of the difference from the SP value (solubility parameter) of the organic solvent is 0.5 (cal / cm ³ ) ^0.5 or less as a polymer insoluble in the organic solvent. It contains at least one kind of (meth) acrylate resin A (hereinafter also referred to as “insoluble polymer A”) having a value. Insoluble in an organic solvent means that the insoluble polymer A is not dissolved in the organic solvent but is dispersed in the organic solvent because the polarity of the insoluble polymer A is different from that of the organic solvent.

Insoluble polymer A is a monomer having a relatively high SP value because the SP value of the homopolymer is separated from the SP value of the organic solvent in order to increase the SP value of the polymer itself and to have thixotropy. It is preferable that it is comprised. However, if the SP value becomes too high, the leveling property at the time of film formation deteriorates although it is advantageous in terms of thixotropy. Therefore, similarly to the (meth) acrylate resin B described later, the SP value is set to an absolute value of the difference from the SP value of the organic solvent in the range of 0.5 (cal / cm ³ ) ^0.5 or less.
As a result, the difference between the SP value of the (meth) acrylate resin B, which is a soluble polymer to be described later, is prevented from becoming too large, and the balance between thixotropic property and leveling property is achieved. Moreover, in this invention, a (meth) acrylate type monomer is used as a monomer which comprises the insoluble polymer A, baking property improves simultaneously, and the residue after baking as a paste is suppressed more.
Moreover, it has affinity between an organic solvent and the insoluble polymer A because the difference of SP value with an organic solvent is 0.5 (cal / cm < ³ >) ^0.5 or less small range. Insoluble polymer A is a polymer that has a low solubility in an organic solvent and does not completely dissolve but exists in a dispersed state. By giving affinity to the organic solvent, it gives a leveling effect when a paste is prepared. be able to.

The insoluble polymer A may be any form of resin as long as the polymer has a difference in SP value from that of an organic solvent of 0.5 (cal / cm ³ ) ^0.5 or less. In the present invention, the homopolymer or copolymer of monomers having an absolute value of the difference between the SP value of the homopolymer and the SP value of the organic solvent of 0.5 (cal / cm ³ ) ^0.5 or less. A monomer having an absolute value of 0.5 (cal / cm ³ ) ^0.5 or less and an absolute value of the difference of 0.5 (cal / cm ³ ) ^0.5 or more Any of a copolymer with a kind of monomer may be sufficient.

Examples of monomers that form insoluble polymers include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, and i-octyl. Alkyl or aryl ester of acrylic acid (preferably, alkyl moiety (including cycloalkyl) = 1 to 18, such as acrylate, 2-ethylhexyl acrylate, i-nonyl acrylate, stearyl acrylate, cyclohexyl acrylate, benzyl acrylate, etc. Carbon number of aryl moiety = 6-8);
Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, i-octyl methacrylate, 2-ethylhexyl methacrylate, i-nonyl methacrylate, n-dodecyl methacrylate , I-dodecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, etc., alkyl or aryl ester of methacrylic acid (preferably, carbon number of alkyl moiety (including cycloalkyl) = 1 to 18, carbon number of aryl moiety = 6-8);
Aromatic vinyl such as styrene, vinyl toluene, ethyl vinyl benzene;
And radical polymerizable unsaturated monomers.

Moreover, the following functional group monomer can be copolymerized with the radical polymerizable unsaturated monomer. That is, for example, a carboxyl group-containing monomer (preferably acrylic acid, methacrylic acid) such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, citraconic acid;
Amide group or substituted amide group-containing monomers such as acrylamide, methacrylamide, N, N-dimethylacrylamide, N-methylacrylamide, Nn-butoxymethylacrylamide (preferably acrylamide, methacrylamide);
Hydroxyl-containing monomers such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, allyl alcohol, methallyl alcohol (preferably 2-hydroxyethyl acrylate, 2-hydroxypropyl Hydroxy lower alkyl (meth) acrylates such as acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, etc. (preferably, lower alkyl having 1 to 4 carbon atoms);
Amino group or substituted amino group-containing monomer such as aminoethyl acrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate (Preferably, N, N-dilower alkylamino lower alkyl (meth) acrylate such as N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl methacrylate, etc. Carbon number = 1 to 4]);
Epoxy group-containing monomers such as glycidyl methacrylate, glycidyl acrylate, glycidyl allyl ether, glycidyl methallyl ether, glycidyl vinyl ether;
Mercapto group-containing monomers such as vinyl mercaptan and allyl mercaptan;
(Poly) ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, divinylbenzene Monomers having two or more radically polymerizable unsaturated groups in one molecule; and the like.

  The monomer forming the insoluble polymer A is selected in terms of the type and the proportion of the polymer in consideration of the solubility in an organic solvent, the viscosity of the composition, the thixotropy, and the baking property.

  Among them, as the insoluble polymer A, a polymer obtained by polymerizing a methacrylate monomer is preferable from the viewpoint of calcination, and in particular, a homopolymer of a methacrylate monomer, or a methacrylate monomer and other polymers. A copolymer with at least one monomer is preferred.

  Examples of the methacrylate monomer include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, i-octyl methacrylate, 2-ethylhexyl methacrylate ( 2-EHMA), i-nonyl methacrylate, n-dodecyl methacrylate, i-dodecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate (2-HEMA), 2-hydroxypropyl methacrylate, N, N-dimethylaminoethyl Methacrylate, N, N-diethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, methacrylamid , N- methyl acrylamide, and monomers such as benzyl methacrylate are preferably exemplified. As the methacrylate monomer constituting the insoluble polymer A, one kind or two or more kinds selected from the group (group X) containing these monomers can be used.

In addition, the insoluble polymer A in the present invention preferably has a structural unit derived from an alkyl acrylate having an alkyl group having 1 to 3 carbon atoms from the viewpoint of controlling whiteness and stabilizing particles. . Examples of the alkyl acrylate having an alkyl group having 1 to 3 carbon atoms include methyl acrylate, ethyl acrylate, and n-propyl acrylate.
The ratio of such structural units in the insoluble polymer A is preferably in the range of 10% by mass to 50% by mass with respect to the total mass of the insoluble polymer A. The ratio of the structural unit derived from the alkyl acrylate having an alkyl group having 1 to 3 carbon atoms is 10% by mass or more, so that it has an excellent thixotropic property, has excellent leveling properties, and has a long-term storage property. It can be set as the stable particle | grains which are hard to settle and isolate | separate. Moreover, calcination property can be improved because this ratio is 50 mass% or less. The proportion of the structural unit is more preferably 20% by mass or more and 40% by mass or less for the same reason as described above.

The absolute value of the difference between the SP value of the homopolymer of the monomer constituting the insoluble polymer A and the SP value of the organic solvent is 0.1 (cal / cm ^{3) in} terms of leveling properties when the film is formed. ) It is preferable that it is ^0.5 or more and 6.5 (cal / cm ³ ) ^0.5 or less.

The insoluble polymer A preferably contains a structural unit derived from a hydroxyl group-containing monomer. By having a hydroxyl group, dispersibility and leveling properties can be improved.
Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl acrylate (2-HEA), 2-hydroxyethyl methacrylate (2-HEMA), 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, allyl alcohol, methacryl alcohol, and the like. Is mentioned. Among them, hydroxy lower alkyl methacrylate (lower alkyl carbon number = 1 to 4) is preferable, and for example, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and the like are particularly preferable.

As the insoluble polymer A, the absolute value of the difference between the SP value of the homopolymer and the SP value of the organic solvent is 0.5 (cal / cm ³ ) ^0.5 or less, the methacrylate monomer, A copolymer with an aryl ester is preferable. Furthermore, the absolute value of the difference between the SP value of the homopolymer and the SP value of the organic solvent is 0.5 (cal / cm ³ ) ^0.5 or less, and an alkyl moiety. (Including cycloalkyl) methacrylate monomer having 1 to 18 carbon atoms, hydroxy lower alkyl methacrylate (lower alkyl carbon number = 1 to 4), and alkyl ester of acrylic acid (preferable alkyl moiety carbon number = 1) More preferably, it is a copolymer with ~ 3).
When the insoluble polymer A is a polymer containing an alkyl ester of acrylic acid, it becomes stable particles and is excellent in storage stability. In addition, since the insoluble polymer A is a polymer containing a methacrylate monomer, the firing property when a structure (baked body) is obtained by firing after screen printing is improved, and the firing residue can be reduced. This is more effective when the copolymer is a copolymer obtained by copolymerizing at least 2-methyethyl methacrylate, which is a methacrylate monomer, and an alkyl ester of acrylic acid (preferably alkyl having 1 to 3 carbon atoms). It is done.

  The average molecular weight of the insoluble polymer A is preferably 10,000 to 300,000, more preferably 100,000 to 250,000 in terms of weight average molecular weight.

  The SP value of the insoluble polymer A is preferably in the range where the difference from the SP value of the organic solvent is 0.1 or more and 0.5 or less in absolute value. Since the SP value of the resin component itself dispersed and contained in the composition is somewhat apart from the SP value of the organic solvent, it is possible to maintain the difference in SP value from the soluble polymer B described later, which is necessary for printability. Thixotropy can be obtained. From the viewpoint of improving pressure response in addition to thixotropy, the absolute value of the difference between the SP value of the insoluble polymer A and the SP value of the organic solvent is more preferably in the range of 0.1 to 0.2.

The solubility parameter of the insoluble polymer A (SP value, unit: (cal / cm ³ ) ^0.5 ; hereinafter sometimes abbreviated as SPA) is the SP value of the organic solvent or the SP value of the soluble polymer B. Although determined from the relationship and the like, from the above points, it is preferably 9.0 (cal / cm ³ ) ^0.5 or more, more preferably 9.2 (cal / cm ³ ) ^0.5 or more. 3 (cal / cm ³ ) ^0.5 or more is particularly preferable. The upper limit of the SP value is 11.0 (cal / cm ³ ) ^0.5 .
The method for obtaining the SP value is as described above.

  Among the monomers constituting the insoluble polymer A, the proportion of the structural unit derived from the monomer selected from the group X in the insoluble polymer A is based on the total amount of all the structural units in the insoluble polymer A. Thus, it is preferably 25% or more, more preferably 40% or more on a mass basis.

-(Meth) acrylate resin B-
The resin composition for paste of the present invention is a polymer soluble in an organic solvent, and the absolute value of the difference from the SP value (solubility parameter) of the organic solvent is 0.5 (cal / cm ³ ) ^0.5 or less. And this absolute value is smaller than the absolute value of the difference in solubility parameter between the organic solvent and the (meth) acrylate resin A described above (hereinafter also referred to as “soluble polymer B”). .)). The term “soluble in an organic solvent” means that the resin B is dissolved in the organic solvent because the polarity of the resin B is close to that of the organic solvent.

  In the soluble polymer B, the absolute value of the difference in SP value with the organic solvent is smaller than the absolute value of the difference in SP value (SPA) between the organic solvent and the aforementioned (meth) acrylate resin A (insoluble polymer A). Since it is a polymer, it is composed of at least a monomer having an SP value that is closer to the SP value of the organic solvent than the insoluble polymer A described above. As a result, the SP value of the soluble polymer B itself is lower than that of the insoluble polymer A, the difference from the SP value of the insoluble polymer A described above is maintained, and thixotropic properties necessary for printability are obtained. Moreover, by using a (meth) acrylate monomer as the monomer of the soluble polymer B, the calcination property is improved at the same time, and the generation of a residue after calcination as a paste can be suppressed.

The soluble polymer B has a high affinity for the organic solvent and better dispersibility because the absolute value of the difference in SP value from the organic solvent is 0.5 (cal / cm ³ ) ^0.5 or less. Can be maintained, and leveling is improved.

The soluble polymer B is a polymer in which the absolute value of the difference in SP value from an organic solvent is 0.5 (cal / cm ³ ) ^0.5 or less, like the insoluble polymer A described above. Any form of resin may be used. In the present invention, a monomer homopolymer or copolymer in which the absolute value of the difference between the SP value of the homopolymer and the SP value of the organic solvent is 0.5 (cal / cm ³ ) ^0.5 or less. Or an absolute value of the difference of 0.5 (cal / cm ³ ) ^0.5 or less and at least one other type of absolute value of the difference exceeding 0.5 (cal / cm ³ ) ^0.5 Any of the copolymer with the monomer may be used.

  When the insoluble polymer A and the soluble polymer B described above are dispersed and contained as a dispersion resin as described later by bonding or adsorbing to each other, the soluble polymer B is advantageous for bonding or adsorption with the insoluble polymer A. From the standpoint of achieving both excellent properties and solubility in an organic solvent, it is preferably a copolymer of two or more monomers.

Examples of the monomer forming the soluble polymer include the same monomers as those constituting the insoluble polymer A described above. The monomer that forms the soluble polymer B is selected in terms of the type and the ratio of the monomer to the polymer in consideration of solubility in an organic solvent, viscosity as a composition, thixotropy, and calcinability.
Examples of the monomer include radical polymerizable unsaturated monomers such as alkyl or aryl esters of acrylic acid, alkyl or aryl esters of methacrylic acid, and aromatic vinyl monomers, as well as carboxyl group-containing monomers and amide group-containing monomers. Preferred examples thereof include functional monomers such as a monomer, a hydroxyl group-containing monomer, and a substituted amino group-containing monomer. Details of these monomers are the same as those described in the insoluble polymer A described above, and preferred embodiments thereof are also the same.

Soluble polymer B is (meth) acrylate resin, monomer selected from alkyl or aryl ester of acrylic acid, and alkyl or aryl ester of methacrylic acid, carboxyl group-containing monomer, amide group-containing monomer More preferred is a polymer formed by copolymerization with a monomer selected from a hydroxyl group-containing monomer and a substituted amino group-containing monomer.
More preferably, the soluble polymer B is a C1-C18 (meth) acrylic acid alkyl ester having an alkyl moiety (including cycloalkyl), (meth) acrylic acid, (meth) acrylamide, and an alkyl moiety having a carbon number. It is preferably formed by copolymerization with a monomer selected from 1-4 hydroxyalkyl (meth) acrylate and N, N-di-alkylaminoalkyl (meth) acrylate having 1 to 4 carbon atoms in the alkyl moiety.
As described above, by using the (meth) acrylate-based resin, the baking property is improved as described above, and the baking residue can be reduced.

As the monomer having an absolute value of the difference between the SP value of the homopolymer and the SP value of the organic solvent of 0.5 (cal / cm ³ ) ^0.5 or less, a methacrylate monomer is particularly preferable. Preferred examples include 2-ethylhexyl methacrylate (2-EHMA), n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, methyl methacrylate, ethyl methacrylate, isobornyl methacrylate, propyl methacrylate, n- Stearyl methacrylate, lauryl methacrylate, isodecyl methacrylate, tridecyl methacrylate, glycidyl methacrylate and the like can be preferably mentioned.
The methacrylate monomer constituting the soluble polymer B is preferably one or more selected from the group (group Y) containing these monomers.

  The absolute value of the difference between the SP value of the homopolymer of the monomer constituting the soluble polymer B and the SP value of the organic solvent is 0 or more and 6.5 or less in terms of leveling properties when the film is formed. It is preferable that it is 0 or more and 3 or less.

Moreover, it is preferable that the soluble polymer B contains the structural unit derived from a hydroxyl-containing monomer. By having a hydroxyl group, dispersibility and leveling properties can be improved.
Examples of the hydroxyl group-containing monomer include the same ones as mentioned for the insoluble polymer A described above. Specific examples include 2-hydroxyethyl acrylate (2-HEA), 2-hydroxyethyl methacrylate (2-HEMA), 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, allyl alcohol, methacryl alcohol, and the like. . Among them, hydroxy lower alkyl methacrylate (lower alkyl carbon number = 1 to 4) is preferable, and for example, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate and the like are preferable.

In the present invention, in the aforementioned (meth) acrylate resin A (insoluble polymer A) and (meth) acrylate resin B (soluble polymer B), it is derived from a hydroxyl group-containing monomer in the insoluble polymer A and soluble polymer B. The ratio of the total of the structural units is in the range of 3% by mass to 15% by mass with respect to the total amount of all the structural units of the insoluble polymer A and the soluble polymer B.
As described above, the SP value difference between the insoluble polymer A and the soluble polymer B from the organic solvent is reduced to 0.5 (cal / cm ³ ) ^0.5 or less, and the content ratio of the structural unit derived from the hydroxyl group-containing monomer is as described above. By setting it as the range, when the paste is prepared, the inorganic particles are excellent in dispersibility while having an appropriate thixotropic property. In other words, when the proportion of the structural unit derived from the hydroxyl group-containing monomer is less than 3% by mass, the thixotropic property is poor, the dispersibility is lowered, and the leveling property at the time of coating is also poor. Moreover, when the ratio of the structural unit derived from a hydroxyl-containing monomer exceeds 15 mass%, it will become difficult to apply without interruption at the time of discharge at the time of coating, and the stringiness will also deteriorate.
The proportion of the structural unit derived from the hydroxyl group-containing monomer is preferably 5% by mass or more and 13% by mass or less, and more preferably 5% by mass or more and 10% by mass or less for the same reason as above.

  The hydroxyl group-containing monomer may be contained in at least one of the aforementioned (meth) acrylate resin A (insoluble polymer A) and (meth) acrylate resin B (soluble polymer B). However, from the viewpoint of stringiness, the hydroxyl group-containing monomer is preferably contained in the insoluble polymer A, and the hydroxyl group-containing monomer is more preferably contained only in the insoluble polymer A and not in the soluble polymer B. .

  For the insoluble polymer A and the soluble polymer B in the present invention, a (meth) acrylate-based resin is used from the viewpoint of enabling low-temperature firing at 600 ° C. or less and reducing the firing residue.

  The average molecular weight of the soluble polymer B is preferably 10,000 to 300,000 in terms of weight average molecular weight, more preferably 100,000 to 250,000.

  The SP value of the soluble polymer B is preferably in the range where the difference from the SP value of the organic solvent is 0 or more and less than 0.1 in absolute value. Since the SP value of the resin component itself dispersed and contained in the composition is somewhat apart from the SP value of the organic solvent, the difference in SP value from the insoluble polymer A described later can be maintained, which is necessary for printability. Thixotropic properties are obtained.

The solubility parameter of the soluble polymer B (SP value, unit: (cal / cm ³ ) ^0.5 ; hereinafter sometimes abbreviated as SPB) is the SP value of the organic solvent or the SP value of the insoluble polymer A. However, it is preferably 8.0 (cal / cm ³ ) ^0.5 or more and 9.5 (cal / cm ³ ) ^0.5 or less, and more preferably 8.5 (cal / cm ³ ). cm ³ ) ^0.5 or more and 9.0 (cal / cm ³ ) ^0.5 or less.
The method for obtaining the SP value is as described above.

  Of the monomers constituting the soluble polymer B, the proportion of the structural unit derived from the monomer selected from the group Y in the soluble polymer B is the sum of all the structural units in the soluble polymer B. The amount is preferably 25% or more, more preferably 40% or more, based on the mass.

In the present invention, the SP value (SPA) of the insoluble polymer A and the SP value (SPB) of the soluble polymer B preferably satisfy SPA> SPB. The fact that SPA is larger than SPB is advantageous in that a difference between the SPA and the SP value of the organic solvent can be obtained to some extent, and the dispersion stability in the organic solvent can be further enhanced. More preferably, SPA and SPB satisfy the following formula 1. “||” represents an absolute value.
0.1 ≦ | SPA-SPB | ≦ 1.0 (Formula 1)
The absolute value of the difference obtained by subtracting SPB from SPA is 0.1 or more means that at least an insoluble portion exists. In addition, the absolute value of the difference obtained by subtracting SPB from SPA being 1.0 (cal / cm ³ ) ^0.5 or less indicates that the values of SPA and SPB are relatively close. Therefore, the affinity between the insoluble polymer A and the soluble polymer B is high, and even when a part of the soluble polymer B is dissolved in the organic solvent, the polymer structure portion SA (hereinafter, referred to as “insoluble polymer A”) Since the state where the soluble polymer B is firmly connected to the “polymer structure portion SA”) is maintained, stable dispersibility and thixotropy are ensured, and a highly stable non-aqueous dispersion is obtained. .
Among these, the absolute value (| SPA-SPB |) of “SPA-SPB” is more preferably in the range of 0.1 to 0.6, and still more preferably in the range of 0.1 to 0.4.

The ratio (A / B; mass ratio) of the insoluble polymer A to the soluble polymer B in the organic solvent is preferably in the range of 0.5 / 1 to 5/1. If the ratio A / B is 0.5 / 1 or more, it is advantageous in terms of leveling properties, and if it is 5/1 or less, it is advantageous in terms of dispersion stability.
The ratio A / B is more preferably in a range from 1/1 to 3/1. Better thixotropy can be ensured because the ratio of the insoluble polymer A insoluble in the organic solvent to the soluble polymer B soluble in the organic solvent is large.

  In the present invention, a dispersion resin comprising an insoluble polymer A and a soluble polymer B comprising a polymer structure portion SA in which the insoluble polymer A is aggregated and a soluble polymer B at least partially bonded or adsorbed to the polymer structure portion SA. Can be dispersed and contained in an organic solvent. That is, the insoluble polymer A and the soluble polymer B are organic in a state in which the insoluble polymer A gathers to form a polymer structure portion SA, and at least a part of the soluble polymer B is bonded or adsorbed to the polymer structure portion SA. Dispersed in solvent.

  This dispersion resin has at least a polymer structure portion SA in which insoluble polymers A are aggregated and a soluble polymer B at least partially bonded or adsorbed to the polymer structure portion. The polymer structure portion SA is an organic solvent. The soluble polymer B which is not dissolved therein but is bonded or adsorbed thereto is dissolved in an organic solvent and can be kept in a dispersed state. That is, the polymer structure portion SA constituting the dispersion resin forms a particle-like nucleus formed by the insoluble polymer A being aggregated, and the soluble polymer B is bonded or adsorbed to the particle nucleus. Thus, part of the particle nucleus (insoluble polymer A) can be dissolved in an organic solvent, and dispersion stability can be maintained in the organic solvent.

  The resin composition for paste of the present invention contains a non-aqueous dispersion resin in which at least a part of the soluble polymer B is bonded or adsorbed to the polymer structure part SA, but may not be bonded or adsorbed to the polymer structure part SA. An embodiment in which the dissolved polymer B is present in a floating state in an organic solvent is more preferable. The presence of such a soluble polymer B in an organic solvent improves the miscibility between the non-aqueous dispersion resin and the inorganic material, and improves the dispersibility of the inorganic material, thereby obtaining a paste having excellent leveling properties. .

When the soluble polymer B and the insoluble polymer A are contained in the form of the dispersion resin, the dispersion resin is dispersed in an organic solvent to form a non-aqueous dispersion resin. This dispersion resin may be synthesized by previously forming a graft copolymer in an organic solvent and then performing polymerization for forming dispersed particle nuclei.
The non-aqueous dispersion resin is dispersed in an organic solvent to form a non-aqueous dispersion. This non-aqueous dispersion resin forms a polymer soluble in an organic solvent (soluble polymer B) in an organic solvent in advance, and forms a polymer insoluble in the organic solvent (insoluble polymer A) in the presence of this polymer. The polymer may be polymerized, or a polymer part in which a polymer part soluble in an organic solvent and a polymer part insoluble in an organic solvent are previously blocked or grafted is formed. A polymer obtained by polymerizing a monomer that forms a polymer insoluble in an organic solvent in the presence thereof may be used.
Among these polymerization methods, a method in which a polymer soluble in an organic solvent is previously formed in an organic solvent, and a monomer that forms a polymer insoluble in the organic solvent in the presence of this polymer is simply not known. This is preferable from the viewpoint of obtaining a water-dispersed resin.
In the method of obtaining a non-aqueous dispersion resin by polymerizing a monomer that forms a polymer insoluble in an organic solvent in the presence of a polymer soluble in the organic solvent, the polymer soluble in the organic solvent is solution-polymerized in the organic solvent. Can be synthesized. This soluble polymer is charged with a monomer and, if necessary, a polymerization initiator and a chain transfer agent in the same organic solvent as that constituting the resin composition for paste, and stirred in a nitrogen stream or at the reflux temperature of the organic solvent. However, it can be suitably synthesized by heating reaction for several hours. At this time, at least a part of the organic solvent, monomer, polymerization initiator and / or chain transfer agent may be sequentially added. The polymerization temperature is generally preferably 30 to 180 ° C (preferably 60 to 150 ° C).
Subsequently, in an organic solvent in which a polymer soluble in the organic solvent exists, a monomer that gives a polymer portion that is insoluble in the organic solvent, together with a polymerization initiator and, if necessary, a chain transfer agent in a nitrogen stream or reflux of the organic solvent By heating and polymerizing for several hours while stirring at temperature, an insoluble polymer insoluble in the organic solvent and a copolymer in which the insoluble polymer part is bonded to the soluble polymer part are formed. The generated polymer insoluble in the organic solvent forms a particle nucleus together with the insoluble polymer portion of the copolymer, and the polymer structure portion SA in which insoluble polymers insoluble in the organic solvent are assembled, and at least a part of the polymer structure portion SA. Dispersed resin particles having a soluble polymer B bonded or adsorbed to can be obtained.

Examples of the polymerization initiator used for the polymerization include benzoyl peroxide, lauroyl peroxide, caproyl peroxide, di-i-propyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and t-butylperoxydioxide. Organic peroxides such as valates and t-butylperoxy-2-ethylhexanate; 2,2′-azobis-i-butylnitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, 2,2′- Azo compounds such as azobis-4-methoxy-2,4-dimethylvaleronitrile and the like can be used alone or in combination.
Among the polymerization initiators, in the organic solvent in which a polymer soluble in the organic solvent is present, when polymerizing the monomer that gives the polymer structure portion SA insoluble in the organic solvent, an organic peroxide having a high hydrogen abstraction ability is used. It is preferable to use it. By using a polymerization initiator having a high hydrogen abstraction ability, an unstable hydrogen atom in the soluble polymer is efficiently extracted, and a monomer that gives an insoluble polymer portion A is added thereto. As a result, a graft or block copolymer in which the soluble polymer portion and the insoluble polymer portion are bonded to each other is formed, and the generated insoluble polymer in the organic solvent forms a particle nucleus together with the insoluble polymer portion of the graft or block copolymer. Can be formed.

  The usage-amount of a polymerization initiator is the range of 0.01-5 mass parts normally with respect to a total of 100 mass parts of monomers, Preferably it is 0.02-2 mass parts.

  Moreover, as an example of a chain transfer agent, the compound as described in the paragraph number [0051] of Unexamined-Japanese-Patent No. 2000-095917 can be used. When using a chain transfer agent, the usage-amount is preferable 0.005-3 mass parts with respect to a total of 100 mass parts of monomers.

In the resin composition for paste of the present invention, the proportion of the non-aqueous dispersion resin is preferably 30 parts by mass or more, and more preferably 30 to 60 parts by mass with respect to 100 parts by mass of the organic solvent. In other words, the nonvolatile content in the paste resin composition of the present invention is preferably 30% by mass or more, and more preferably 30 to 60% by mass.
When the ratio of the non-aqueous dispersion resin to the organic solvent is 30 parts by mass or more, that is, the non-aqueous dispersion resin is in a range that is not too small relative to the organic solvent, a composition having a high non-volatile content can be obtained, When done, heat shrinkage is suppressed. Further, when the ratio of the non-aqueous dispersion resin is 60 parts by mass or less, that is, the non-aqueous dispersion resin is not too much in the organic solvent, the low viscosity is maintained and good thixotropic properties are exhibited.

  The paste composition of this invention is comprised using the resin composition for pastes of the above-mentioned this invention, and inorganic particle | grains, and may contain the other component as needed. The details of the resin composition for paste are as described above, and the preferred embodiments are also the same. Since the paste resin composition of the present invention described above is used, the paste composition of the present invention is excellent in leveling properties when formed into a paste while maintaining thixotropy that does not hinder printing. Also, stringing is less likely to occur. Also, good sinterability is imparted.

  Examples of the inorganic particles contained in the paste composition include particles of metal, glass, silicon compounds (silica, silica sand, silicon dioxide, etc.), pigments such as carbon black, calcium carbonate, clay, and talc.

  The content of the inorganic particles in the paste composition is preferably 50 to 95% by mass with respect to the total mass of the paste composition.

  The manufacturing method of the paste composition of this invention is provided with the process of preparing a paste composition by mixing at least a resin composition for paste and inorganic particles. Furthermore, other steps may be provided. Specifically, it is preferably configured by further synthesizing (meth) acrylate resin A in the presence of an organic solvent and (meth) acrylate resin B, and preparing a paste resin composition. . In this case, as described above, the resin contains a polymer structure part SA in which the (meth) acrylate resin A is assembled and a (meth) acrylate resin B in which at least a part is bonded or adsorbed to the polymer structure part SA. A paste resin composition is prepared, and a paste composition in which the paste resin composition is mixed with inorganic particles is obtained. Thereby, the miscibility with the inorganic particles can be improved, the dispersibility of the inorganic particles can be increased, and the leveling property of the paste composition can be further improved.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.

<Preparation of copolymer (B) solution>
As shown below, a copolymer (B) was prepared as a (meth) acrylate resin B which is a soluble polymer.

(Production Example 1-1)
A reactor equipped with a stirrer, reflux condenser, sequential dripping device, and thermometer was charged with 630.0 parts by mass of butyl carbitol acetate (BCA; boiling point = 247 ° C.) and 70.0 parts by mass of methanol (MeOH). . Then, in another container, a monomer mixture 1531.3 consisting of 62.0% by mass of 2-ethylhexyl methacrylate (2EHMA), 18.0% by mass of methyl methacrylate (MMA) and 20.0% by mass of butyl acrylate (BA). A part by mass was prepared, 525 parts by mass of this was charged into a reactor, and 0.42 part by mass of 2,2′-azobis (2-methylbutyronitrile) (ABN-E) was added as a polymerization initiator. After the addition, it was heated and kept at reflux temperature for 30 minutes. Further, a mixture comprising 1006.3 parts by mass of the remaining monomer mixture, 236.3 parts by mass of BCA, 26.3 parts by mass of MeOH, and 1.30 parts by mass of ABN-E was successively added dropwise over 90 minutes. After maintaining at the same temperature for 60 minutes, 472.5 parts by mass of BCA, 52.5 parts by mass of MeOH, and 2.63 parts by mass of ABN-E were successively added dropwise over 30 minutes. The mixture was further maintained at the same temperature for 180 minutes, diluted with BCA and then cooled to obtain a polymer B1 solution (soluble polymer B solution).

Table 1 below shows the SP value of the homopolymer of each monomer, the SP value of the organic solvent, the nonvolatile content of the obtained polymer B1 solution, and the Tg, SP value, and weight average molecular weight (Mw) of the polymer B1. Show.
In addition, Mw is a value obtained by gel conversion chromatograph (GPC) and measuring TSK-GEL GMHXL (Tosoh styrene polymer filler) as a column and converting to polystyrene.

(Production Examples 1-2 to 1-17)
A copolymer B2-B17 solution was obtained in the same manner as in Production Example 1-1 except that the composition of the monomer in Production Example 1-1 was changed as shown in Table 1 below.

(Production Example 1-18)
In 100.0 parts by mass of butyl carbitol acetate (BCA), 20.0 parts by mass of ethyl cellulose was dissolved to obtain an EC solution.

(Example 1): Preparation of non-aqueous dispersion resin In a reactor equipped with a stirrer, a reflux condenser, a sequential dropping device, and a thermometer, 158.6 parts by mass of butyl carbitol acetate (BCA), methanol (MeOH) 99 .8 parts by mass and 1218.0 parts by mass of the “polymer B1 solution” obtained in Production Example 1-1 were charged, and the temperature was raised to the reflux temperature. After the temperature rise, this was a monomer mixture 974 consisting of 59.0% by mass of n-butyl methacrylate (nBMA), 36.0% by mass of ethyl acrylate (EA) and 5.0% by mass of 2-hydroxyethyl methacrylate (2HEMA). 4 parts by mass, 280.1 parts by mass of BCA, 136.1 parts by mass of MeOH, and 7.62 parts by mass of t-butylperoxy 2-ethylhexanate (PB-O) were successively added dropwise over 90 minutes. After completion of dropping, the temperature was maintained for 60 minutes. Thereafter, 203.1 parts by mass of BCA and 20.31 parts by mass of PB-O were successively added dropwise over 90 minutes and kept at the same temperature for 90 minutes. Thereafter, it was diluted with BCA, MeOH was extracted and cooled.
As described above, a non-aqueous dispersion resin solution in which the nBMA / 2HEMA / EA copolymer (insoluble polymer A) was dispersed in the polymer B1 (soluble polymer B) solution was obtained. A part of the polymer B1 of the dispersion resin solution is present by being bonded or adsorbed to the polymer structure part of the insoluble polymer A, and a part of the polymer B1 is present in a floating state.

  The composition of the monomer used here, the SP value of the monomer homopolymer, the nonvolatile content of the obtained resin dispersion, the SP value of the nBMA / 2HEMA / EA copolymer, Tg, and Mw are shown in the table below. It is shown in 1. Mw was measured by the same method as described above.

(Examples 2 to 15)
In Example 1, the polymer B1 solution was replaced with copolymers B2 to B15 having the monomer composition shown in Table 1 below, and the type of organic solvent and the monomer composition of insoluble polymer A were shown in Table 1 below. A resin dispersion solution (resin composition for paste) was obtained in the same manner as in Example 1 except that the changes were made as shown in FIG. The nonvolatile concentration of each resin dispersion is as shown in Table 1 below.

(Comparative Examples 1-2)
In Example 1, the polymer B1 solution was replaced with copolymers B16 to B17 having the monomer composition shown in Table 1 below, and the monomer composition of the insoluble polymer A was changed as shown in Table 1 below. Except that, a resin dispersion solution (resin composition for paste) was obtained in the same manner as in Example 1. The nonvolatile concentration of each resin dispersion is as shown in Table 1 below.

(Comparative Example 3)
The EC solution of Production Example 1-18 was used as a resin dispersion solution (resin composition for paste). Nonvolatile content concentrations are as shown in Table 1 below.

(Evaluation)
The following evaluation was performed about each of the resin dispersion solution (resin composition for paste) prepared in said Examples 1-15 and Comparative Examples 1-3. The evaluation results are shown in Table 1 below.

-1. Firing property
About 10 mg of the dried resin is placed on an aluminum pan, and the temperature is raised from room temperature to 600 ° C. at a temperature rising temperature of 10 ° C./min in a nitrogen atmosphere using a thermogravimetric / analytical apparatus (SSTA Nanotechnology, EXSTAR6000 TG / DTA6200). Warm up. Then, it cooled to room temperature, the ratio (residue rate) of the residue with respect to the amount of resin collection | recovery of resin was computed, and it evaluated according to the following evaluation criteria by using this residue rate as a parameter | index.
Residual rate (%) = (collected resin amount−resin decrease amount) / (collected resin amount) × 100
<Evaluation criteria>
A: Residue rate: less than 2% B: Residue rate: 2% or more and less than 7% C: Residue rate: 7% or more

-2. Thixotropic-
The prepared resin dispersion solution was evaluated using a dynamic viscoelasticity measuring device (Physica MCR301 manufactured by Anton Paar) at an evaluation temperature of 25 ° C., a cone of 25 mmφ, 2 °, a measurement gap of 103 μm, and a shear rate of 0.01 to 60 [1 / s. ] The shear viscosity in the shear rate region was measured. Shear rate 1 [1 / s] determined the ratio of the viscosity eta ¹ and shear rate 10 [1 / s] Viscosity eta ¹⁰ of (= η ¹ / η ¹⁰⁾ of was used as an index for evaluating thixotropic property (thixotropic property) . Evaluation was performed according to the following evaluation criteria. The higher the viscosity ratio, the higher the thixotropic property and the better the printability.
<Evaluation criteria>
A: The viscosity ratio was 1.5 or more, and excellent printability was exhibited.
B: Viscosity ratio was 1.2 or more and less than 1.5, indicating good printability.
C: The viscosity ratio was less than 1.2, and the printability was poor.

-3. Pressure response
Creep of the prepared resin dispersion solution using a dynamic viscoelasticity measuring device (Physica MCR301 manufactured by Anton Paar) at an evaluation temperature = 25 ° C., a cone used = 25 mmφ, 2 °, and a measurement gap = 103 μm under the following measurement conditions. Recovery was measured. From the results of creep recovery, (1) the amount of shear strain after measurement was r1, and (2) the amount of recovery after measurement was r2, and the recovery rate was calculated from r2 / r1. The recovery rate was used as an index for evaluating the pressure response to the pump during nozzle coating. Evaluation was performed according to the following evaluation criteria. In addition, it shows that it is excellent in pressure responsiveness, so that a recovery rate is low.
<Measurement conditions> Pressure 20Pa x 60sec → Pressure 0Pa x 120sec
<Evaluation criteria>
A: The recovery rate is less than 0.5, and the pump supply property at the time of nozzle coating is good.
B: The recovery rate is 0.5 or more and less than 1.0, and the pump supply property at the time of nozzle coating is slightly good.
C: The recovery rate is 1.0 or more, and the pump supply property at the time of nozzle coating is poor.

-4. Leveling properties
(1) Glass paste formation The resin dispersion solution prepared in Examples 1 to 15 and Comparative Examples 1 and 2 was added in an amount of 11.1 parts by mass with respect to 75 parts by mass of the glass powder, and the non-volatile content was adjusted to 80% by BCA. After the adjustment, a glass paste was prepared using a three roll mill (N-R42A manufactured by Noritake Company Limited) according to the following dispersion conditions. In addition, 25.0 parts by mass of the EC solution prepared in Comparative Example 3 was added to 75 parts by mass of the glass powder, and after adjusting the non-volatile content to 80% with BCA, the glass paste was adjusted in the same manner. did.
Dispersion condition: Roll gap: Between F / C = 50 μm
Between C / A = 50 μm
Roll speed: F / C / A = 50 rpm / 100 rpm / 200 rpm
Number of roll passes: 3 times (2) Leveling evaluation Using the dynamic viscoelasticity measuring device (Physica MCR301 manufactured by Anton Paar), the evaluation temperature: 25 ° C., cone used: 25 mmφ, 2 °, measurement gap : Shear viscosity in a shear rate region of 103 μm, shear rate: 0.01 to 60 [1 / s] was measured. The viscosity at a shear rate of 0.1 [1 / s] was used as an index for evaluating the leveling property of screen printability. Evaluation was performed according to the following evaluation criteria. In addition, it shows that leveling property is so high that the viscosity of shear rate 0.1 [1 / s] is low, and it is excellent in printability.
<Evaluation criteria>
A: Shear viscosity at a shear rate of 0.1 [1 / s]: less than 1000 Pa · s B: Shear viscosity at a shear rate of 0.1 [1 / s]: 1000 Pa · s to less than 2000 Pa · s C: Shear rate 0. 1 [1 / s] shear viscosity: 2000 Pa · s or more

-5. Stringing ability
The glass paste prepared in the above “4. Leveling property” is evaluated using a dynamic viscoelasticity measuring device (Physica MCR301 manufactured by Anton Paar) at an evaluation temperature of 25 ° C., a cone of 25 mmφ, 2 °, a measurement gap of 103 μm, and a shear rate of 1000. The shear viscosity and the first normal stress difference in the shear rate region of (1 / s) were measured. The first normal stress difference at a shear rate of 1000 (1 / s) was used as an index for evaluating the stringiness of screen printing. Evaluation was performed according to the following evaluation criteria. In addition, the lower the first normal stress difference, the lower the stringing property and the better the printability.
<Evaluation criteria>
A: The first normal stress difference at a shear rate of 1000 [1 / s] is less than 100 Pa, and there is almost no stringing during printing, which is good.
B: The first normal stress difference at a shear rate of 1000 [1 / s] is 100 Pa or more and less than 200 Pa, and the stringing property at the time of printing is small.
C: The first normal stress difference at a shear rate of 1000 [1 / s] is 200 Pa or more, and stringing is easy during printing.

Details of the monomers in Table 1 are as follows.
-2EHMA: 2-ethylhexyl methacrylate-MMA: methyl methacrylate-nBMA: normal butyl methacrylate-BA: butyl acrylate-2HEMA: 2-hydroxyethyl methacrylate-EA: ethyl acrylate

As shown in Table 1, in the examples, the obtained resin solution (resin composition for paste) is prepared to have a high non-volatile content, and maintains leveling properties and stringing while maintaining good thixotropy. It was excellent in nature. Moreover, the resin solution of the Example showed the favorable pressure responsiveness without a paste being interrupted at the time of coating. Therefore, the resin solutions of the examples have good printability and are suitable for screen printability. When screen printing is performed, it is possible to form a structure having a better shape as compared with the conventional case. In addition, the remaining carbon component after firing was significantly reduced.
On the other hand, in the comparative example, if thixotropy is prioritized, pressure response and stringiness are inferior, and when trying to increase pressure response, not only thixotropy is insufficient, but also leveling and stringiness are reduced. have done. In addition, it has been difficult to satisfy the sinterability with a composition using ethyl cellulose that has been conventionally used.

  The resin composition for paste of the present invention has a high non-volatile content, low viscosity and thixotropic properties, is suitable as a coating solution used for screen printing, and has few residues such as residual carbon after firing. Therefore, it is suitable for uses such as a paste for firing. For example, it is suitably used for forming PDP phosphors, dielectrics, solar cell electrodes, and the like.

Claims (9)

An organic solvent,
(Meth) acrylate resin A having a solubility parameter whose absolute value of the difference from the solubility parameter of the organic solvent is 0.5 (cal / cm ³ ) ^0.5 or less;
The absolute value of the difference from the solubility parameter of the organic solvent is 0.5 (cal / cm ³ ) ^0.5 or less, and the solubility parameter between the organic solvent and the (meth) acrylate resin A is (Meth) acrylate resin B smaller than the absolute value of the difference;
Containing
At least one of the (meth) acrylate resin A and the (meth) acrylate resin B includes a structural unit derived from a hydroxyl group-containing monomer,
The ratio of the structural unit derived from the hydroxyl group-containing monomer in the (meth) acrylate resin A and the (meth) acrylate resin B is the total amount of all the structural units of the (meth) acrylate resin A and (meth) acrylate resin B. The resin composition for paste which is 3 mass% or more and 15 mass% or less with respect to.   The resin composition for paste according to claim 1, wherein the (meth) acrylate-based resin A includes a structural unit derived from an alkyl acrylate having an alkyl group having 1 to 3 carbon atoms in a range of 10% by mass to 50% by mass. object. The absolute value of the difference between the solubility parameter of the (meth) acrylate resin A and the solubility parameter of the (meth) acrylate resin B is 0.1 (cal / cm ³ ) ^0.5 or more and 1.0 (cal / The resin composition for paste according to claim 1 or 2, wherein cm ³ ) is ^0.5 or less.   The (meth) acrylate-based resin A and the (meth) acrylate-based resin B are the polymer structure portion SA in which the (meth) acrylate-based resin A is aggregated and at least a part of which is bonded or adsorbed to the polymer structure portion SA. The resin composition for pastes according to any one of claims 1 to 3, wherein the resin composition is contained as a dispersed resin containing (meth) acrylate-based resin B and dispersed in the organic solvent.   The resin composition for paste according to any one of claims 1 to 4, wherein the organic solvent has a boiling point of 180 ° C or higher and 280 ° C or lower. The organic solvent has a solubility parameter 8.0 (cal ^/ cm ^{3) 0.5} or more 11.0 (cal ^/ cm ³⁾ is ^0.5 or less according to any one of claims 1 to 5 A resin composition for pastes.   The paste composition containing the resin composition for pastes of any one of Claims 1-6, and inorganic particle | grains.   The manufacturing method of the paste composition which has the process of preparing a paste composition by mixing the resin composition for pastes and inorganic particle of any one of Claims 1-6.   Furthermore, manufacture of the paste composition of Claim 8 which has the process of synthesize | combining the (meth) acrylate type resin A in presence of an organic solvent and the (meth) acrylate type resin B, and preparing the resin composition for pastes. Method.