JP2017082184A - (meth)acrylic resin composition - Google Patents

Abstract

An object of the present invention is to provide a new paste composition in which both coatability and thermal decomposability during firing are compatible, and a new binder resin composition suitably used for realizing the paste composition. SOLUTION: 100 parts by mass of a (meth) acrylic polymer (A) having a hydroxy group and a tertiary amino group in a side chain and having a weight average molecular weight of 5,000 to 300,000, and N-lauroyl-L-glutamic acid (Meth) acrylic resin composition containing 0.1 to 20 parts by mass of a mixture (B) composed of dibutylamide and N-2-ethylhexanoyl-L-glutamic acid dibutylamide, and an organic solvent (C), and inorganic A (meth) acrylic resin composition further comprising a filler (D) is provided. [Selection diagram] None

Description

  The present invention relates to a (meth) acrylic resin composition, and more particularly to a (meth) acrylic binder resin composition and a paste composition containing the same.

  A method of forming a layer or pattern of an inorganic filler by coating a base material with a paste composition in which an inorganic filler is dispersed in a binder resin composition containing a binder resin and an organic solvent, and then thermally decomposing the binder resin by firing. It has been known. For example, a fine pattern of a circuit included in various electronic components may be formed by this method. Since the coating property to the substrate and the dispersibility of the inorganic filler are relatively good, ethyl cellulose, butyral resin and the like have been conventionally used as the binder resin. In general, the binder resin is required to have good thermal decomposability (combustibility) and good coating properties when used as a paste composition.

  On the other hand, the range of applications (uses) of the paste composition used in the above method has been increasing in recent years, and the binder resin contained in the paste composition can be thermally decomposed at a lower temperature (hereinafter, this property is referred to in this specification). It is also called “low-temperature thermal decomposability”). However, conventional binder resins such as ethyl cellulose and butyral resin are not sufficiently heat decomposable (especially low temperature heat decomposability), and the paste composition using this tends to generate a residue composed of carbon components after firing. was there. This residue can degrade the properties of products such as electronic components.

  In order to solve the above problem, it is known that a (meth) acrylic resin having better thermal decomposability is used as a binder resin instead of ethyl cellulose or butyral resin (for example, Patent Documents 1 to 4).

Japanese Patent Laid-Open No. 10-167836 JP 2002-020570 A JP 2006-249248 A Japanese Patent Laying-Open No. 2015-059196

  Although the paste composition using a (meth) acrylic resin as a binder resin can exhibit good thermal decomposability, increasing the molecular weight of the (meth) acrylic resin in order to obtain a viscosity suitable for coating causes stringing. As a result, for example, the coating property when applied to the substrate by screen printing, dip coating or the like tends to be lowered. This problem of stringing is also discussed in Patent Documents 2 and 4 above.

  An object of the present invention is to provide a new paste composition having both coating properties and thermal decomposability at the time of firing, and a new binder resin composition suitably used for realizing the paste composition. There is to do.

  The present invention provides the following (meth) acrylic resin compositions [(meth) acrylic binder resin composition and (meth) acrylic paste composition].

[1] 100 parts by mass of a (meth) acrylic polymer (A) having a hydroxy group and a tertiary amino group in a side chain and having a weight average molecular weight of 5000 to 300,000,
0.1 to 20 parts by mass of a mixture (B) composed of N-lauroyl-L-glutamic acid dibutylamide and N-2-ethylhexanoyl-L-glutamic acid dibutylamide;
An organic solvent (C),
A (meth) acrylic resin composition.

[2] The (meth) acrylic polymer (A)
50-94.9 mol% of monomer units (a-1) of hydroxy methacrylate and N, N-dialkylamino group-free alkyl methacrylate,
5-49.9 mol% of the monomer unit (a-2) of hydroxyalkyl methacrylate;
0.1 to 5 mol% of monomer unit (a-3) of N, N-dialkylaminoalkyl methacrylate;
The (meth) acrylic resin composition according to [1], comprising:

  [3] The hydroxy group and the N, N-dialkylamino group-free alkyl methacrylate include at least one selected from the group consisting of isobutyl methacrylate, 2-ethylhexyl methacrylate, and lauryl methacrylate. (Meth) acrylic resin composition.

  [4] The N, N-dialkylaminoalkyl methacrylate includes at least one selected from the group consisting of N, N-dimethylaminoethyl methacrylate and N, N-diethylaminoethyl methacrylate [2] or [3] (Meth) acrylic resin composition described in 1.

  [5] The ratio of N-lauroyl-L-glutamic acid dibutylamide and N-2-ethylhexanoyl-L-glutamic acid dibutylamide contained in the mixture (B) is in the range of 1: 9 to 9: 1. The (meth) acrylic resin composition according to any one of [1] to [4].

  [6] The content of the organic solvent (C) is 40 to 500 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer (A). The (meth) acrylic resin composition as described.

  [7] The (meth) acrylic resin composition according to any one of [1] to [6], wherein the organic solvent (C) is composed of one or more organic solvents having a boiling point of 150 ° C. or higher. .

  [8] The (meth) acrylic material according to any one of [1] to [7], wherein the organic solvent (C) is at least one selected from the group consisting of butyl carbitol acetate and butyl carbitol. Resin composition.

[9] An inorganic filler (D) is further included,
The (meth) acrylic resin according to any one of [1] to [8], wherein the content of the inorganic filler (D) in 100 parts by mass of the (meth) acrylic resin composition is 70 to 97 parts by mass. Composition.

  [10] The (meth) acrylic resin composition according to [9], wherein the inorganic filler (D) includes a conductive powder.

  According to the present invention, there are provided a new paste composition having both coating properties and thermal decomposability upon firing, and a new binder resin composition suitably used for realizing the paste composition. can do.

  In this specification, “(meth) acrylic resin composition” means (meth) acrylic binder resin composition (hereinafter also referred to as “binder resin composition”) and (meth) acrylic paste composition ( Hereinafter, it is also referred to as “paste resin composition”). The binder resin composition is a resin composition contained in the paste composition and is used as at least a binder component thereof. The binder resin composition according to the present invention includes a (meth) acrylic polymer (A), a mixture (B), and an organic solvent (C), and the paste composition according to the present invention comprises (meth) acrylic. In addition to the system polymer (A), the mixture (B) and the organic solvent (C), an inorganic filler (D) is further included. Hereinafter, the binder resin composition and paste composition according to the present invention will be described in detail. In the present specification, “(meth) acryl” means acryl and / or methacryl, and “(meth)” such as (meth) acrylate, (meth) acryloyl, etc. has the same meaning.

<(Meth) acrylic binder resin composition>
[1] (Meth) acrylic polymer (A)
The (meth) acrylic polymer (A) which is a binder resin is a (meth) acrylic polymer having a hydroxy group and a tertiary amino group in the side chain. In the present specification, the “(meth) acrylic polymer” refers to a polymer obtained by (co) polymerizing a monomer composition containing a (meth) acrylic monomer, for example, including a methacrylic monomer, Polymer of monomer composition not containing acrylic monomer, polymer of monomer composition containing acrylic monomer and not containing methacrylic monomer, polymer of monomer composition containing methacrylic monomer and acrylic monomer obtain.

  In the (meth) acrylic polymer (A) according to the present invention, the content of the methacrylic monomer in the monomer composition is usually 50 mol% or more, and preferably 70 mol%, more preferably from the viewpoint of thermal decomposability. Is 90 mol% or more, more preferably 95 mol% or more, and most preferably 100 mol%. The (meth) acrylic polymer (A) may contain a monomer unit of an acrylic monomer as necessary. The content of the monomer unit of the acrylic monomer in the (meth) acrylic polymer (A) is usually 30 mol% or less.

  In the present specification, the “methacrylic monomer” means a polymerizable monomer having a methacryloyl group (more typically, a methacryloyloxy group). The “acrylic monomer” means a polymerizable monomer having an acryloyl group (more typically, an acryloyloxy group).

  As described above, the (meth) acrylic polymer (A) preferably contains a methacrylic monomer as a main component. This is because it is more advantageous in terms of thermal decomposability than the case of using an acrylic polymer mainly composed of an acrylic monomer.

  When the (meth) acrylic polymer (A) has a hydroxy group in the side chain, the dispersibility of the inorganic filler (D) in the paste composition can be improved. Moreover, the coating property of a paste composition can be improved because a (meth) acrylic-type polymer (A) has a tertiary amino group in a side chain. This point will be described in detail later.

  The (meth) acrylic polymer (A) having a hydroxy group and a tertiary amino group in the side chain includes a methacrylic monomer containing a hydroxy group and a methacrylic monomer containing a tertiary amino group as the monomer composition. It can be prepared by using a monomer containing a monomer and copolymerizing it. In consideration of the coating property and thermal decomposability of the paste composition, and the high viscosity at the time of coating required for coating by screen printing or the like, the monomer composition contains the above two types of functional group-containing methacrylic compounds In addition to the monomer, it is preferable to further contain a methacrylic monomer not containing a hydroxy group and a tertiary amino group. Any of the methacrylic monomers contained in the monomer composition is preferably alkyl methacrylate. The monomer composition may contain another monomer, for example, an acrylic monomer such as an acrylate, if necessary.

  Suitable examples of the (meth) acrylic polymer (A) include a monomer unit (a-1) of a hydroxy group and an N, N-dialkylamino group-free alkyl methacrylate and a monomer unit (a-2) of a hydroxyalkyl methacrylate. And a monomer unit (a-3) of N, N-dialkylaminoalkyl methacrylate. The monomer unit (a-1) is represented by the following formula (a-1):

Indicated by In the formula, R ¹ represents an alkyl group that does not contain a hydroxy group and an N, N-dialkylamino group. The monomer unit (a-2) has the following formula (a-2):

Indicated by In the formula, R ² represents a hydroxyalkyl group. The monomer unit (a-3) has the following formula (a-3):

Indicated by In the formula, R ³ represents an N, N-dialkylaminoalkyl group. A binder resin composition comprising a (meth) acrylic polymer (A) containing the monomer units (a-1) to (a-3), a predetermined mixture (B) described later, and an organic solvent (C). According to the product, it is possible to provide a paste composition in which the problem of stringing is suppressed, the coating property is good, and the thermal decomposability (particularly, low temperature thermal decomposability) is excellent.

The alkyl group R ¹ which does not contain a hydroxy group and an N, N-dialkylamino group, which the monomer unit (a-1) of the hydroxy methacrylate and N, N-dialkylamino group-free alkyl methacrylate has, for example, has 1 carbon atom. The linear, branched or cyclic unsubstituted alkyl group which is -24 can be mentioned. From the viewpoints of thermal decomposability, solubility in an organic solvent (C), and / or viscosity at the time of application of the paste composition, the carbon number of R ¹ is preferably 3-18, more preferably 4 ~ 12. Specific examples of R ¹ which is an unsubstituted alkyl group having 4 to 12 carbon atoms include n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n- Hexyl group, cyclohexyl group, n-heptyl group, cycloheptyl group, n-octyl group, 2-ethylhexyl group, isooctyl group, cyclooctyl group, n-decyl group, lauryl group (n-dodecyl group), isobornyl Groups, adamantyl groups, dicyclopentanyl and the like. Among them, R ¹ is composed of an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclohexyl group, an n-octyl group, a 2-ethylhexyl group, an isooctyl group, an n-decyl group, and a lauryl group from the above viewpoint. It is preferably at least one selected from the group, more preferably at least one selected from the group consisting of an isobutyl group, a 2-ethylhexyl group and a lauryl group. The (meth) acrylic polymer (A) may contain only one type of monomer unit (a-1) or two or more types of monomer units (a-1) different in R ^1. Also good.

  The content of the monomer unit (a-1) is preferably 50 mol% or more, more preferably 60 mol%, when the total amount of all monomers constituting the (meth) acrylic polymer (A) is 100 mol%. More preferably, it is 70 mol% or more (for example, 75 mol% or more). By setting the content of the monomer unit (a-1) in the above range, the thermal decomposability and low-temperature thermal decomposability of the paste composition, the solubility in the organic solvent (C), and the like can be improved. The viscosity at the time of application of a paste composition can be raised moderately. The content rate of a monomer unit (a-1) is 94.9 mol% or less normally, Preferably it is 90 mol% or less (for example, 85 mol% or less).

Examples of the hydroxyalkyl group R ² that the monomer unit (a-2) of hydroxyalkyl methacrylate has include a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms that is substituted with a hydroxy group. R ² may have two or more hydroxy groups, but preferably has one hydroxy group from the viewpoint of thermal decomposability. From the viewpoint of the thermal decomposability of the paste composition and the dispersibility of the inorganic filler (D), the carbon number of R ² is preferably 2 to 6, and more preferably 2 to 4. Specific examples of R ² are 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxy-n-propyl group, 2-hydroxy-n-propyl group, 3-hydroxy-n-propyl group, 1- (hydroxy Methyl) ethyl group, 1-hydroxy-n-butyl group, 2-hydroxy-n-butyl group, 3-hydroxy-n-butyl group, 4-hydroxy-n-butyl group, 2- (hydroxymethyl) -n- Including propyl group, 1-hydroxy-isobutyl group, 2-hydroxy-isobutyl group, hydroxy-tert-butyl group and the like. Among them, R ² is 2-hydroxyethyl group, 2-hydroxy-n-propyl group, 3-hydroxy-n-propyl group, 2-hydroxy-n-butyl group, 3-hydroxy-n-butyl from the above viewpoint. It is preferably at least one selected from the group consisting of a group and 4-hydroxy-n-butyl group, and at least one selected from the group consisting of 2-hydroxyethyl group and 2-hydroxy-n-propyl group It is more preferable that The (meth) acrylic polymer (A) may contain only one type of monomer unit (a-2) or two or more types of monomer units (a-2) different in R ^2. Also good.

  The content of the monomer unit (a-2) is preferably 5 to 49.9 mol%, more preferably 100 mol% when the total amount of all monomers constituting the (meth) acrylic polymer (A) is 100 mol%. Is 5 to 40 mol%, more preferably 10 to 35 mol%, and particularly preferably 12 to 30 mol% (for example, 15 to 25 mol%). By making the content rate of a monomer unit (a-2) into the said range, the thermal decomposability and low temperature thermal decomposability of a paste composition, the dispersibility of the inorganic filler (D) in a paste composition, etc. can be improved. . When the content of the monomer unit (a-2) is less than 5 mol%, the dispersibility of the inorganic filler (D) tends to deteriorate. When the content rate of a monomer unit (a-2) exceeds 49.9 mol%, the thermal decomposition property and low-temperature thermal decomposition property of a paste composition will become inadequate.

As the N, N-dialkylaminoalkyl group R ³ of the monomer unit (a-3) of N, N-dialkylaminoalkyl methacrylate, each of the alkyl groups constituting the N, N-dialkyl moiety independently has 1 carbon atom. A linear or branched alkyl group having 3 to 3, and the alkyl group to which the N, N-dialkylamino group is bonded is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms. Some can be mentioned. From the viewpoint of coating properties of the paste composition, the number of carbon atoms of the alkyl group constituting the N, N-dialkyl moiety is preferably 1 or 2, and an N, N-dialkylamino group is bonded. The number of carbon atoms of the alkyl group is more preferably 2 or 3.

Specific examples of R ³ are N, N-dimethylaminomethyl group, N, N-diethylaminomethyl group, N, N-di-n-propylaminomethyl group, N, N-di-isopropylaminomethyl group, N, N-dimethylaminoethyl group, N, N-diethylaminoethyl group, N, N-di-n-propylaminoethyl group, N, N-di-isopropylaminoethyl group, N, N-dimethylaminopropyl group, N, N-diethylaminopropyl group, N, N-di-n-propylaminopropyl group, N, N-di-isopropylaminopropyl group, N, N-dimethylaminobutyl group, N, N-diethylaminobutyl group, N, N -Di-n-propylaminobutyl group, N, N-di-isopropylaminobutyl group and the like are included. Among these, R ³ is at least one selected from the group consisting of an N, N-dimethylaminoethyl group and an N, N-diethylaminoethyl group from the viewpoint of the coating property and availability of the paste composition. Is preferred. The (meth) acrylic polymer (A) may contain only one type of monomer unit (a-3) or two or more types of monomer units (a-3) different in R ^3. Also good.

  The content of the monomer unit (a-3) is preferably 0.1 to 5 mol%, more preferably 100 mol% when the total amount of all monomers constituting the (meth) acrylic polymer (A) is 100 mol%. Is 0.5-4 mol% (for example, 1-3 mol%). By making the content rate of a monomer unit (a-3) into the said range, the thermal decomposability and low-temperature thermal decomposability of a paste composition, the applicability | paintability of a paste composition, etc. can be improved.

  The (meth) acrylic polymer (A) can contain one or more monomer units (a-4) other than the monomer units (a-1) to (a-3). By containing other monomer units (a-4), the solubility of the (meth) acrylic polymer (A) in the organic solvent (C) and the dispersibility of the inorganic filler (D) in the paste composition are adjusted. May be easier.

  Specific examples of the monomer constituting the other monomer unit (a-4) include those containing two or more methacrylate monomers (methacryloyl groups) other than the monomer units (a-1) to (a-3). ); Acrylate monomers such as acrylates (for example, alkyl acrylate) which may have a functional group such as hydroxy group and N, N-dialkylamino group (including those containing two or more acryloyl groups); Aromatic vinyl monomers such as styrene, vinyl toluene, α-methyl styrene and p-methyl styrene; Olefin monomers such as ethylene and propylene; (Meth) acrylamides such as (meth) acrylamide and (meth) acryloylmorpholine; (Meth) acrylic acid, crotonic acid, cinnamic acid, maleic acid, maleic anhydride, fumaric acid Mention may be made of N- vinylpyrrolidone, vinyl chloride, vinyl acetate: itaconic acid, itaconic anhydride, citraconic acid, acids such as citraconic anhydride. Especially, it is preferable that the monomer which comprises another monomer unit (a-4) is acrylates, such as alkyl acrylate. When the total amount of all monomers constituting the (meth) acrylic polymer (A) is 100 mol%, the content of the acrylate monomer units is usually 30 mol% or less.

  However, the content of other monomer units (a-4) is preferably as small as possible so that a desired effect can be obtained. Specifically, the content of the other monomer unit (a-4) is preferably 20 mol% or less when the total amount of all monomers constituting the (meth) acrylic polymer (A) is 100 mol%. More preferably 10 mol% or less, still more preferably 5 mol% or less, still more preferably 1 mol% or less, and most preferably 0 mol%.

  The weight average molecular weight of the (meth) acrylic polymer (A) is preferably 5,000 to 300,000, more preferably 6,000 to 200,000, and more preferably 6,000 to 150,000 in order to improve the coating property of the paste composition. More preferably. When the weight average molecular weight of the (meth) acrylic polymer (A) is in the above range, the paste composition can be imparted with a viscosity suitable for coating, and the problem of stringing is suppressed and good coating is achieved. Workability is obtained. The measuring method of a weight average molecular weight follows description of the term of the Example mentioned later.

  The (meth) acrylic polymer (A) can be prepared by radical polymerization of a monomer composition containing a monomer that forms the monomer unit described above using a known method such as a solution polymerization method.

[2] Mixture (B)
The binder resin composition concerning this invention contains a mixture (B) with the said (meth) acrylic-type polymer (A) which is binder resin. The mixture (B) has the following formula (B-1) and formula (B-2):

N-lauroyl-L-glutamic acid dibutyramide (B-1) and N-2-ethylhexanoyl-L-glutamic acid dibutylamide (B-2) represented by formula (1).

  By including the mixture (B) in the (meth) acrylic binder resin composition, the problem of stringing that tends to occur when a conventional (meth) acrylic polymer is used as a binder resin can be suppressed. Thus, it is possible to provide a paste composition that has high thermal decomposability and low temperature thermal decomposability and excellent coating properties. It is considered that the paste composition according to the present invention exhibits excellent coating properties due to the following action by the mixture (B).

  The paste composition for forming a layer or pattern with an inorganic filler after being applied to a substrate has an appropriate viscosity suitable for maintaining the shape of the coating film, while being rubbed or stirred during application. A thixotropic property that exhibits appropriate fluidity is required by applying a stress such as the above. For example, when the paste composition is applied to a substrate by screen printing, it is necessary to pass the paste composition through the fine mesh of the screen mesh for pattern formation by moving the squeegee. Required. However, in a conventional paste composition using a (meth) acrylic polymer as a binder resin, the (meth) acrylic polymer exists in a state where the molecular chains and the molecular chains are intertwined in a complicated manner. The product had a problem of stringing at the time of coating. The problem of stringing is that, for example, when a pattern is formed on a substrate by screen printing or dip coating, the desired thin line width pattern cannot be formed accurately or the pattern is disconnected. Was lowering.

  On the other hand, according to the paste composition using the (meth) acrylic binder resin composition containing the (meth) acrylic polymer (A) and the mixture (B) according to the present invention, there is a problem of stringing. It is suppressed and the coatability can be improved. This is considered to result from an interaction due to a hydrogen bond between the tertiary amino group introduced into the (meth) acrylic polymer (A) and the amide group of the mixture (B). That is, the above-mentioned interaction makes it difficult to cause the entanglement between the molecular chains and in the molecular chains, particularly in the (meth) acrylic polymer (A), thereby suppressing the stringing and maintaining the shape of the coating film. The paste composition is given a suitable viscosity suitable for the above. In addition, since the interaction is relatively easily cut by stress such as rubbing or stirring during coating, the paste composition can exhibit appropriate fluidity during coating. Thus, it is thought that the paste composition which concerns on this invention shows the outstanding coating property by the thixotropic property being improved while the stringing of binder resin is suppressed by the said interaction.

  The content of the mixture (B) in the methacrylic resin composition [(meth) acrylic binder resin composition and (meth) acrylic paste composition] is 100 parts by mass of the (meth) acrylic polymer (A). 0.1 to 20 parts by mass. By making content of a mixture (B) into 0.1 mass part or more, the applicability | paintability of a paste composition can be improved significantly. From the viewpoint of improving the coatability, the content of the mixture (B) is preferably 0.25 parts by mass or more, more preferably 0.000 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer (A). 5 parts by mass or more, more preferably 1 part by mass or more, and most preferably 2 parts by mass or more.

  On the other hand, by setting the content of the mixture (B) to 20 parts by mass or less with respect to 100 parts by mass of the (meth) acrylic polymer (A), the compatibility of the mixture (B) and the dispersion of the inorganic filler (D) (Meth) acrylic resin composition having good properties and excellent uniformity can be obtained. From the viewpoint of compatibility of the mixture (B), dispersibility of the inorganic filler (D), storage stability of the paste composition, and the like, the content of the mixture (B) is (meth) acrylic polymer (A) 100 Preferably it is 15 mass parts or less with respect to a mass part, More preferably, it is 12 mass parts or less, More preferably, it is 10 mass parts or less, Most preferably, it is 5 mass parts or less.

  The ratio of N-lauroyl-L-glutamic acid dibutylamide to N-2-ethylhexanoyl-L-glutamic acid dibutylamide in the mixture (B) is preferably in the range of 1: 9 to 9: 1, more preferably The range is from 1: 5 to 5: 1, more preferably from 1: 3 to 3: 1, and most preferably from 1: 2 to 2: 1. In addition, when N-lauroyl-L-glutamic acid dibutylamide or N-2-ethylhexanoyl-L-glutamic acid dibutylamide is used alone, the compatibility between the acrylic polymer (A) and the organic solvent (C). It has been clarified that (solubility) deteriorates (Comparative Examples 2 and 3 described later).

  It is also possible to control the viscosity and thixotropy of the paste composition by adjusting the content of the mixture (B).

  In addition, N-lauroyl-L-glutamic acid dibutylamide and N-2-ethylhexanoyl-L-glutamic acid dibutylamide contained in the mixture (B) are compounds known as gelling agents per se. However, it is the present invention that a paste composition having both thermal decomposability and coating property can be obtained by using the mixture (B) and the (meth) acrylic polymer (A) having a predetermined functional group. This is a new finding. In addition, the paste composition for forming a layer or pattern by an inorganic filler after being applied to a substrate is formed from the viewpoint of ensuring the homogeneity of the layer or pattern. When N-lauroyl-L-glutamic acid dibutylamide is used alone, N-2-ethylhexanoyl-L-glutamic acid dibutylamide is used alone, and other than the mixture (B) When other gelling agents are used, it has been clarified that the compatibility of the gelling agents, the dispersibility of the inorganic filler (D) and the storage stability are not satisfied (Comparative Examples 2 and 3 described later). And 4).

[3] Organic solvent (C)
It is preferable that the organic solvent (C) contained in the binder resin composition according to the present invention does not leave a residue after firing and can dissolve the (meth) acrylic polymer (A) and the mixture (B). . The organic solvent (C) preferably has a boiling point of 150 ° C. or higher. By using the organic solvent (C) having a boiling point of 150 ° C. or higher, the coating workability at the time of coating such as screen printing or dip coating can be enhanced. When the boiling point is less than 150 ° C., the volatilization rate is too high, and for example, the screen mesh used in screen printing may be clogged. The boiling point of the organic solvent (C) is preferably 180 ° C. or higher, more preferably 200 ° C. or higher, and further preferably 220 ° C. or higher.

  In addition, from the viewpoint of work efficiency when forming a layer or pattern with the inorganic filler (D), the boiling point of the organic solvent (C) is preferably not extremely high. Specifically, the boiling point of the organic solvent (C) The boiling point is preferably 300 ° C. or lower, and more preferably 290 ° C. or lower.

  The binder resin composition can contain one or more organic solvents (C). When 2 or more types of organic solvents (C) are included, it is preferable that each organic solvent has the boiling point of the said range.

  Specific examples of the organic solvent (C) include butyl carbitol acetate, butyl carbitol, terpineol, dihydroterpineol, dihydroterpinyl acetate, dipropylene glycol, dipropylene glycol monomethyl ether, diethylene glycol alkyl ether acetate (an example of alkyl is n-butyl, propyl, ethyl, etc. The same shall apply hereinafter), ethylene glycol alkyl ether acetate, ethylene glycol diacetate, diethylene glycol alkyl ether, ethylene glycol alkyl ether, dipropylene glycol alkyl ether, propylene glycol alkyl ether acetate, 2, 2,4-trimethylpentane-1,3-diol monoisobutyrate, 2,2,4-trimethylpentane 1,3-diol diisobutyrate, including 2,2,4-trimethylpentane-1,3-diol diisobutyrate, and the like.

  Among them, the organic solvent (C) includes butyl carbitol acetate and butyl carbitol in view of the compatibility (solubility) of the mixture (B), the dispersibility of the inorganic filler (D), the storage stability of the paste composition, and the like. It is preferable to include at least one selected from the group consisting of, and more preferable to include at least one selected from the group.

  The content of the organic solvent (C) in the (meth) acrylic resin composition [(meth) acrylic binder resin composition and (meth) acrylic paste composition] is the compatibility (solubility) of the mixture (B). In consideration of the dispersibility of the inorganic filler (D) and the viscosity of the paste composition, the amount is preferably 40 to 500 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer (A). It is more preferable to set it to -400 mass parts.

[4] Other components The binder resin composition according to the present invention comprises one or more components other than the (meth) acrylic polymer (A), the mixture (B) and the organic solvent (C). Can be included as needed. Specific examples of other components include dispersants (cationic dispersants, anionic dispersants, nonionic dispersants, amphoteric surfactants, polymer dispersants, etc.), plasticizers, wetting agents, antifoaming agents, and leveling. Contains agents. Moreover, the binder resin composition according to the present invention can contain other resins other than the (meth) acrylic polymer (A). Specific examples of other resins include (meth) acrylic polymers other than the (meth) acrylic polymer (A), ethyl cellulose resins, butyral resins, and the like.

<(Meth) acrylic paste composition>
The (meth) acrylic paste composition contains the above-mentioned (meth) acrylic binder resin composition and the inorganic filler (D). A paste composition can be prepared by kneading the binder resin composition and the inorganic filler (D). The paste composition can contain one or more inorganic fillers (D).

  Examples of the inorganic filler (D) include powders made of various materials. Specific examples of the powder include conductive powder, glass powder, pigment powder, phosphor powder, and ceramic powder. Examples of the conductive powder include copper, silver, gold, platinum, iron, nickel, palladium, aluminum, tungsten, and metal powder made of an alloy containing any of these; metal oxide powder made of ITO or the like; carbon A powder etc. are mentioned. Examples of the ceramic powder include those made of alumina, zirconia, titanium oxide, barium titanate, alumina nitride, silicon nitride, boron nitride, and the like.

  The content of the inorganic filler (D) in the paste composition is usually 100 to 5000 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer (A), and the viscosity of the paste composition and the inorganic filler (D ) Is preferably from 500 to 1500 parts by mass. For the same reason, the content of the inorganic filler (D) in 100 parts by mass of the (meth) acrylic resin composition (paste composition) may be, for example, 70 to 97 parts by mass. The content of the (meth) acrylic polymer (A) in 100 parts by mass of the paste composition may be, for example, 3 to 30 parts by mass.

  After the paste composition is applied to the base material, the organic solvent (C) is volatilized by subsequent baking, and the (meth) acrylic polymer (A) and the mixture (B) are thermally decomposed to produce an inorganic filler. A layer or pattern according to (D) can be formed. Examples of the coating method of the paste composition include screen printing, die coating printing, doctor blade printing, roll coating printing, offset printing, gravure printing, flexographic printing, inkjet printing, dispensing printing, casting method, dip coating, and the like. Screen printing and dip coating are suitable. The layer or pattern obtained by firing usually consists of a sintered body of inorganic filler (D).

  The paste composition according to the present invention is excellent in thermal decomposability, particularly low temperature pyrolysis, and can be fired without residue even at temperatures of 550 ° C. or lower, more preferably 500 ° C. or lower, and even 450 ° C. or lower. . Moreover, since stringing during coating is suppressed and thixotropy is excellent, according to the paste composition according to the present invention, a fine pattern made of a sintered body of the inorganic filler (D) is accurately produced. be able to. Furthermore, the paste composition according to the present invention has excellent compatibility with the (meth) acrylic polymer (A), the mixture (B), and the organic solvent (C), and the dispersibility of the inorganic filler (D) is also good. It can be excellent in storage stability without causing phase separation over time. The homogeneity of such a paste composition improves the homogeneity of layers and patterns formed by the firing.

  The paste composition according to the present invention can be suitably used as a paste for forming circuits, electrode patterns, dielectric layers, phosphor layers and the like of various electronic components.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated further more concretely, this invention is not limited by these examples.

<Example 1>
[1] Preparation of (meth) acrylic polymer In a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, the monomers shown in Table 1 were mixed in the proportions shown in Table 1 (Table 1 The numerical value shown is the mixing ratio of each monomer in mol%.) And the organic solvent (C) shown in Table 1 is charged and stirred for 30 minutes while introducing nitrogen gas into the flask. Then, after carrying out nitrogen substitution, the contents of the flask were heated to 80 ° C. Next, azobisisobutyronitrile was added as a radical polymerization initiator while maintaining the contents in the flask at 80 ° C., and the mixture was stirred at 80 ° C. for 6 hours and then at 105 ° C. for 1 hour. Thereafter, the organic solvent (C) shown in Table 1 is added so that the amount with respect to the (meth) acrylic polymer (A) becomes the amount shown in Table 1, and the solution is cooled to room temperature. A resin liquid of the system polymer (A) was obtained.

[2] Preparation of (meth) acrylic binder resin composition The mixture shown in Table 1 with respect to 100 parts by mass of the (meth) acrylic polymer (A) in the resin liquid obtained in [1] above ( B) was mixed in the amount shown in Table 1 to obtain a (meth) acrylic binder resin composition. In this example, “amino acid oil gelator GP-1” (manufactured by Ajinomoto Healthy Supply Co., Ltd.) was used as N-lauroyl-L-glutamic acid dibutylamide, and N-2-ethylhexanoyl-L-glutamic acid was used. “Amino acid oil gelling agent EB-21” (manufactured by Ajinomoto Healthy Supply Co., Ltd.) was used as dibutylamide.

[3] Preparation of (meth) acrylic paste composition With respect to 100 parts by mass of the (meth) acrylic binder resin composition obtained in [2] above, silver powder ("AG-3 manufactured by DOWA Electronics Co., Ltd." -8F ") 560 parts by mass, dispersant (" Span 85 "manufactured by Tokyo Chemical Industry Co., Ltd.) 3.2 parts by mass, and three rolls (" S-2x6 "manufactured by Inoue Seisakusho Co., Ltd.) By kneading, a (meth) acrylic paste composition (silver paste) was obtained.

[4] Measurement and Evaluation Regarding the (meth) acrylic polymer (A), the (meth) acrylic binder resin composition, and the (meth) acrylic paste composition, the following items were measured or evaluated. The results are shown in Table 1.

[4-1] Measurement of weight average molecular weight of (meth) acrylic polymer (A) The gel permeation chromatography was analyzed under the following conditions, and was calculated in terms of polystyrene. The weight average molecular weight of the ethyl cellulose resin and butyral resin used in Comparative Examples 6 and 7 was also measured by the same method.

(Measurement conditions for weight average molecular weight)
Apparatus: Pump [Product name: Pump PU-2080plus (manufactured by JASCO)], Detector [Product name: RI-2030plus (manufactured by JASCO)], Degasser [Product name: DG-2080-53 (manufactured by JASCO)], constant temperature bath SEC (Size Exclusion Chromatography) measuring device composed of [Product name: CO-2065plus (manufactured by JASCO)]
Column: Shodex KF-805L x 1,
Medium: tetrahydrofuran,
Flow rate: 1.0 mL / min,
Sample concentration: 1.5 mg / ml,
Injection volume: 300 μL,
Column temperature: 40 ° C.

[4-2] Measurement of solid content of (meth) acrylic binder resin composition About 0.3 g of (meth) acrylic binder resin composition is accurately weighed, and then heated at 150 ° C. for 5 hours before and after heat treatment. The solid content was calculated. The solid content is the following formula:
Solid content (mass%) = {(mass after heat treatment) / (mass before heat treatment)} × 100
Is calculated by

[4-3] Compatibility Evaluation of (Meth) Acrylic Binder Resin Composition The composition after the (meth) acrylic binder resin composition was heated and stirred at 80 ° C. for 3 hours and then allowed to stand at 25 ° C. for 8 hours. The appearance of the product was visually confirmed, and the compatibility was evaluated based on the following evaluation criteria.

(Compatibility evaluation criteria)
A: The composition is transparent or does not cause precipitation,
B: Almost no dissolution or precipitation occurred during heating and stirring.

[4-4] Evaluation of thermal decomposability of (meth) acrylic binder resin composition Using a differential thermal-thermogravimetric simultaneous measurement device, the thermogravimetric decrease was measured according to the following conditions. The thermal decomposability was evaluated based on the evaluation criteria.

(Measurement conditions for thermal decomposability)
Apparatus: TG-DTA (“EXSTAR TG / DTA6200” manufactured by Seiko Instruments Inc.),
Sample weight: 10 mg,
Temperature rising condition: 30 → 500 ° C. (temperature rising rate: 10 ° C./min),
Atmosphere: Nitrogen atmosphere.

(Evaluation criteria for thermal decomposability)
A: The sample residue mass after heating is less than 1.0 mass% with respect to the mass before heating.
B: The sample residue mass after heating is 1.0 mass% or more and less than 2.5 mass% with respect to the mass before heating.
C: The sample residue mass after heating is 2.5 mass% or more with respect to the mass before heating.

[4-5] Coating property of (meth) acrylic paste composition (screen printability)
A screen printing plate made of SUS304, with a wire diameter of 20 μm, plain weave calendering, with black dyeing, and a 500 μm mesh coated with a 12 μm thick resin was prepared. Using this screen printing plate, a squeegee width of 170 mm, a squeegee speed of 30 mm / s, a squeegee angle of 70 °, a printing pressure of 0.15 MPa, and a back pressure by a screen printing machine (“LS-150” manufactured by Neurong Seimitsu Kogyo Co., Ltd.) By applying the (meth) acrylic paste composition under squeegee conditions of 0.1 MPa and a clearance of 1.5 mm, a pattern made of the paste composition having a line width of about 165 μm was printed. Observe the printed pattern using a microscope (manufactured by Keyence Corporation), and randomly select 5 locations where the line width is widened and 5 locations where the line width is narrow (total of 10 locations). The line width of was measured. The maximum line width and the minimum line width were selected from these 10 line widths, the difference between them was determined, and the coatability was evaluated based on the following evaluation criteria.

(Evaluation criteria for coatability)
A: The difference between the maximum line width and the minimum line width is less than 20 μm.
B: The difference between the maximum line width and the minimum line width is 20 μm or more and less than 40 μm.
C: The difference between the maximum line width and the minimum line width is 40 μm or more, or the pattern is disconnected.

[4-6] Evaluation of dispersibility of inorganic filler in (meth) acrylic paste composition A pattern made of the paste composition formed in [4-5] above was observed using a microscope (manufactured by Keyence Corporation). The dispersibility of the inorganic filler was evaluated based on the following evaluation criteria.

(Evaluation criteria for dispersibility of inorganic filler)
A: Aggregates are not observed on the surface of the pattern,
B: Aggregates are observed on the surface of the pattern.

<Examples 2 to 11 and Comparative Examples 1 to 4>
Monomer composition, weight average molecular weight of (meth) acrylic polymer (A), and in Comparative Examples 2 and 3, N-lauroyl-L-glutamic acid dibutylamide or N-2-ethylhexanoyl instead of mixture (B) Table 1 or Table 2 shows that L-glutamic acid dibutylamide was used alone, and in Comparative Example 4, gelol D as a gelling agent was used instead of mixture (B), and the type of organic solvent (C). A resin solution of (meth) acrylic polymer (A) was prepared in the same manner as [1] of Example 1 except that it was as described above. Using the resin solution of the obtained (meth) acrylic polymer (A), a (meth) acrylic binder resin composition was prepared in the same manner as [2] of Example 1. In addition, a (meth) acrylic paste composition (silver paste) was prepared in the same manner as in [3] of Example 1 using the obtained (meth) acrylic binder resin composition. The obtained (meth) acrylic polymer (A), (meth) acrylic binder resin composition and (meth) acrylic paste composition were measured and evaluated in the same manner as in [4] of Example 1. It was. The results are shown in Tables 1 and 2. In Example 10 and Example 11, the compatibility of the mixture (B) was insufficient, and due to this, the dispersibility of the inorganic filler was insufficient. Further, in Comparative Examples 2, 3 and Comparative Example 4, the compatibility of the gelling agent was insufficient, and due to this, the dispersibility of the inorganic filler was insufficient.

<Comparative Examples 6 and 7>
An ethyl cellulose resin (Comparative Example 6) and a butyral resin (Comparative Example 7) were prepared as binder resins. Using this binder resin, a binder resin composition was prepared in the same manner as in [2] of Example 1. In addition, a paste composition (silver paste) was prepared in the same manner as [3] of Example 1 using the obtained binder resin composition. However, the mixing amount of the silver powder and the dispersant was 194 parts by mass and 1.1 parts by mass, respectively, with respect to 100 parts by mass of the binder resin composition. The binder resin, the binder resin composition, and the paste composition were measured and evaluated in the same manner as [4] of Example 1. The results are shown in Table 2.

Details of the abbreviations shown in Table 1 and Table 2 are as follows.
iBMA: isobutyl methacrylate,
2EHMA: 2-ethylhexyl methacrylate,
LMA: lauryl methacrylate,
2HEMA: 2-hydroxyethyl methacrylate,
DMAEMA: dimethylaminoethyl methacrylate,
DEAEMA: diethylaminoethyl methacrylate,
GP-1 (manufactured by Ajinomoto Healthy Supply): N-lauroyl-L-glutamic acid dibutyramide,
EB-21 (manufactured by Ajinomoto Healthy Supply): N-2-ethylhexanoyl-L-glutamic acid dibutylamide,
Gerol D: 1,3: 2,4-bis-O-benzylidene-D-glucitol (dibenzylidene sorbitol).

Claims (10)

100 parts by weight of a (meth) acrylic polymer (A) having a hydroxy group and a tertiary amino group in the side chain and having a weight average molecular weight of 5000 to 300,000,
0.1 to 20 parts by mass of a mixture (B) composed of N-lauroyl-L-glutamic acid dibutylamide and N-2-ethylhexanoyl-L-glutamic acid dibutylamide;
An organic solvent (C),
A (meth) acrylic resin composition. The (meth) acrylic polymer (A) is
50-94.9 mol% of monomer units (a-1) of hydroxy methacrylate and N, N-dialkylamino group-free alkyl methacrylate,
5-49.9 mol% of the monomer unit (a-2) of hydroxyalkyl methacrylate;
0.1 to 5 mol% of monomer unit (a-3) of N, N-dialkylaminoalkyl methacrylate;
The (meth) acrylic resin composition according to claim 1, comprising:   The (meth) acryl according to claim 2, wherein the hydroxy methacrylate and N, N-dialkylamino group-free alkyl methacrylate include at least one selected from the group consisting of isobutyl methacrylate, 2-ethylhexyl methacrylate and lauryl methacrylate. -Based resin composition.   4. The (meta) of claim 2, wherein the N, N-dialkylaminoalkyl methacrylate comprises at least one selected from the group consisting of N, N-dimethylaminoethyl methacrylate and N, N-diethylaminoethyl methacrylate. ) Acrylic resin composition.   The ratio of N-lauroyl-L-glutamic acid dibutylamide and N-2-ethylhexanoyl-L-glutamic acid dibutylamide contained in the mixture (B) is in the range of 1: 9 to 9: 1. The (meth) acrylic resin composition according to any one of 1 to 4.   Content of the said organic solvent (C) is 40-500 mass parts with respect to 100 mass parts of said (meth) acrylic-type polymers (A), (1) of any one of Claims 1-5. (Meth) acrylic resin composition.   The (meth) acrylic resin composition according to any one of claims 1 to 6, wherein the organic solvent (C) is composed of one or more organic solvents having a boiling point of 150 ° C or higher.   The (meth) acrylic resin composition according to any one of claims 1 to 7, wherein the organic solvent (C) is at least one selected from the group consisting of butyl carbitol acetate and butyl carbitol. . Further including an inorganic filler (D),
The (meth) acrylic resin according to any one of claims 1 to 8, wherein the content of the inorganic filler (D) in 100 parts by mass of the (meth) acrylic resin composition is 70 to 97 parts by mass. Composition.   The (meth) acrylic resin composition according to claim 9, wherein the inorganic filler (D) includes a conductive powder.