TW202112986A - Firing paste resin composition and paste composition - Google Patents

Abstract

Provided are: a resin composition for firing paste, having excellent thermal decomposition properties and having the pseudo-plasticity that is important for printability; and a paste composition including said resin composition for firing paste. This resin composition is used as a firing paste and includes a polyalkylene carbonate and a C8 or higher organic compound. The organic compound has at least one type of functional group selected from the group consisting of a carboxy group, a hydroxy group, and an amide group. The organic compound is contained in the amount of 1-50 parts by mass relative to 100 parts by mass of the polyalkylene carbonate.

Description

Resin composition for baking paste and paste composition

Invention field The present invention relates to a resin composition for baking paste and a paste composition.

Background technique In the field of electronic components, it is currently used paste materials in which inorganic powders such as conductive particles, ceramics, glass, phosphors, and binder resins are dispersed in a solvent to produce electronic components with various circuit patterns. The paste material is fired after being applied to a substrate or the like, and the binder resin contained in the paste material is burned out due to thermal decomposition during the firing.

As the binder resin, a polyalkylene carbonate resin manufactured by copolymerization of epoxide and carbon dioxide is known. Polyalkylene carbonate resin has excellent thermal decomposition properties, so it is being explored as a binder resin for various paste materials. For example, Patent Document 1 proposes a phosphor paste containing polyalkylene carbonate, which uses a solvent with specific parameters, and therefore has excellent printability. In addition, Patent Document 2 proposes a polyalkylene carbonate having a specific molecular weight distribution.

Prior art literature Patent literature Patent Document 1: Japanese Patent Laid-Open No. 2001-226669 Patent Document 2: Japanese Relisted Publication No. 2016/167064

Summary of the invention The problem to be solved by the invention However, as the coating method of the paste material, printing methods such as screen printing, doctor blade printing, offset printing, gravure printing, flexographic printing, and inkjet printing, or casting methods for processing into a sheet are known. As a specific example, an existing screen printing method using a paste material in which conductive particles have been dispersed is used to print a circuit of a predetermined shape on a substrate, dry and fire it to form a circuit pattern on the substrate. The printability of the paste material is easily affected by the characteristics of the paste material itself. Therefore, it becomes important to select a paste material with characteristics suitable for printing. Therefore, of course, the characteristics of the binder resin contained in the paste material cannot be ignored.

However, in paste materials containing polyalkylene carbonate as a binder resin, the relationship between polyalkylene carbonate and printability has not been discussed in such detail. Therefore, in the past, the paste material using polyalkylene carbonate as the binder resin may not be able to appropriately adopt the printing method. In recent years, with the rapid development of miniaturization and complexity of electronic parts, it is desired to develop paste materials that are more suitable for printing methods.

Regarding this point, the inventor of the present case believes that the rheological properties of polyalkylene carbonate as the binder resin in the paste material have a close relationship with the printing performance, and they have discussed in detail. As a result, it has been investigated that in order to appropriately use the screen printing method, the rheological properties of low viscosity when a shear force is applied and high viscosity when no shear force is applied, that is, so-called pseudoplasticity is important. Therefore, the inventors of the present case finally discovered that in order to form a paste material with good printing performance, it is important to develop a binder that can maintain excellent thermal decomposition properties and impart pseudoplasticity to the paste material.

The present invention is made in view of the above, and its object is to provide a resin composition for a fired paste that has excellent thermal decomposition properties and can also impart pseudoplasticity that is also important for printability, and a paste containing the resin composition for fired paste Composition.

Means to solve the problem In order to achieve the above-mentioned object, the inventors of the present invention have repeatedly studied carefully and found that the above-mentioned object can be achieved by combining polyalkylene carbonate and an organic compound having a specific functional group with a carbon number of 8 or more, thus completing the present invention.

That is, the present invention includes, for example, the subjects described in the following items. Item 1 A resin composition for firing paste, which is used as a resin composition for firing paste, and contains polyalkylene carbonate and an organic compound with a carbon number of 8 or more. The organic compound is selected from the group consisting of carboxyl group, hydroxyl group and alcohol. At least one functional group in the group consisting of an amine group, and the aforementioned organic compound is contained at 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the polyalkylene carbonate. Item 2 The resin composition for baking paste according to item 1, wherein the aforementioned polyalkylene carbonate contains a structural unit represented by the following general formula (1):

(式中，R¹ 、R² 、R³ 及R⁴ 為相同或相異，表示氫原子、可經取代基取代之碳數1至10之直鏈或支鏈烷基、或可經取代基取代之碳數6至20之芳基；R¹ 、R² 、R³ 、R⁴ 中，2個可相互鍵結，形成可經取代基取代之3員環至10員環之脂肪族環)。 項3 如項1或2之燒成糊用樹脂組成物，其中前述有機化合物為選自於由碳數8以上的脂肪族羧酸、碳數8以上的脂肪族羥基羧酸、碳數8以上的脂肪族醇及碳數8以上的脂肪族醯胺所構成群組中之至少1種。 項4 一種糊組成物，含有如項1至3中任一項之樹脂組成物、溶劑及無機粉末。[Chemical formula 1]

(In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or different, and represent a hydrogen atom, a linear or branched alkyl group with 1 to 10 carbon atoms that may be substituted by a substituent, or a substituent that may be substituted Substituted aryl group with 6 to 20 carbon atoms; two of R ¹ , R ² , R ³ , and R ⁴ may be bonded to each other to form an aliphatic ring from a 3-membered ring to a 10-membered ring that may be substituted by a substituent) . Item 3 The resin composition for baking paste according to Item 1 or 2, wherein the aforementioned organic compound is selected from aliphatic carboxylic acids having 8 or more carbons, aliphatic hydroxycarboxylic acids having 8 or more carbons, and 8 or more carbons. At least one of the group consisting of aliphatic alcohols and aliphatic amines with a carbon number of 8 or more. Item 4 A paste composition containing the resin composition of any one of items 1 to 3, a solvent, and an inorganic powder.

Invention effect The resin composition for the fired paste of the present invention has excellent thermal decomposition properties and can impart the fired paste with pseudoplasticity which is also important for printability.

The form used to implement the invention Hereinafter, embodiments of the present invention will be described in detail. In addition, in this manual, the expressions of "contains" and "contains" include the concepts of "contains", "contains", "substantially constituted by", and "constituted only by".

1. Resin binder resin composition for firing The resin composition for baking paste of the present invention is used as a resin composition for baking paste, and contains polyalkylene carbonate and an organic compound having a carbon number of 8 or more. The aforementioned organic compound is selected from the group consisting of a carboxyl group, a hydroxyl group, and an organic compound having a carbon number of 8 or more. At least one functional group in the group formed by the amide group. In the resin composition for baking paste of the present invention, the organic compound is contained at 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the polyalkylene carbonate. Hereinafter, the resin composition for baking paste of the present invention is simply referred to as "resin composition".

The resin composition of the present invention has excellent thermal decomposition properties and can also impart pseudoplasticity which is also important for printability. The so-called "pseudoplasticity" in this specification can mean low viscosity when shearing force is applied, and high viscosity when no shearing force is applied.

(Polyethylene carbonate) In the resin composition of the present invention, the type of polyalkylene carbonate is not particularly limited, and for example, known polyalkylene carbonates can be widely used. Examples of polyalkylene carbonates include copolymers of cyclic ethers and carbon dioxide, polycondensates of diols and carbonates or carbonic acid derivatives such as carbonyl dichloride, and ring-opening polymers of cyclic carbonates. Among them, the polyalkylene carbonate is preferably a copolymer of epoxide and carbon dioxide, which is one of cyclic ethers, from the viewpoint of easy production of high molecular weight products.

Such polyalkylene carbonate preferably contains a structural unit represented by the following general formula (1). In this case, the resin composition of the present invention has more excellent thermal decomposability and is likely to have the desired pseudoplasticity.

[Chemical formula 2]

Here, in the formula (1), R ¹ , R ² , R ³ and R ⁴ are the same or different, and represent a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbons which may be substituted by a substituent, Or an aryl group having 6 to 20 carbons which may be substituted by a substituent. In addition, two of R ¹ , R ² , R ³ , and R ⁴ may be bonded to each other to form an aliphatic ring from a 3-membered ring to a 10-membered ring that may be substituted by a substituent.

In formula (1), the so-called linear or branched alkyl group with carbon number of 1 to 10 refers to linear or branched chain with carbon number of 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 alkyl. The number of carbon atoms in the alkyl group is preferably 1 to 4, more preferably 1 or 2. Specifically, the alkyl group can be enumerated such as: methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary butyl, tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n- Octyl, n-nonyl, n-decyl, etc.

In formula (1), when a linear or branched alkyl group having 1 to 10 carbon atoms is substituted with a substituent, the number of substituents can be set to 1 or 2 or more. Examples of the substituent at this time include: a hydroxyl group, an alkoxy group, an ester group, a silyl group, a sulfhydryl group, a cyano group, a nitro group, a sulfonic acid group, a methanoyl group, a carboxyl group, an aryl group, and a halogen atom (such as a fluorine atom). , Chlorine atom, bromine atom, iodine atom) and so on. The alkoxy group here includes, for example, a methoxy group, an ethoxy group, an isopropoxy group, and a tertiary butoxy group. In addition, examples of the aryl group include phenyl, o-tolyl, m-tolyl, p-tolyl, and naphthyl.

In formula (1), the so-called aryl group having 6 to 20 carbon atoms is an aryl group having 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. base. The carbon number of the aryl group is preferably 6-14. Examples of the aryl group include phenyl, naphthyl, and tetrahydronaphthyl.

In formula (1), when the aryl group having 6 to 20 carbon atoms is substituted with a substituent, the number of substituents can be set to 1 or 2 or more. Examples of the substituent at this time include: alkyl, hydroxyl, alkoxy, ester, silyl, sulfhydryl, cyano, nitro, sulfonic acid, methanoyl, carboxyl, aryl, halogen atom ( For example, fluorine atom, chlorine atom, bromine atom, iodine atom) and the like. Examples of the alkyl group here include methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary butyl, tertiary butyl, and the like. In addition, examples of the aryl group include phenyl, o-tolyl, m-tolyl, p-tolyl, and naphthyl. Moreover, the alkoxy group includes, for example, a methoxy group, an ethoxy group, an isopropoxy group, and a tertiary butoxy group.

In the formula (1), R ¹ , R ² , R ³ and R ⁴ may be the same, or may be partially or completely different. For example, in formula (1), R ¹ , R ² , R ³ and R ⁴ may all be the same, or R ¹ , R ² , R ³ may be the same and R ⁴ may be different, or R ¹ , R ³ , R ^{4 is the} same but R ^{2 is} different, and R ¹ , R ² , R ³ and R ^{4 may} all be different.

In the formula (1), two of R ¹ , R ² , R ³ and R ⁴ may be bonded to each other to form an aliphatic ring from a 3-membered ring to a 10-membered ring which may be substituted by a substituent. Specifically, two of R ¹ , R ² , R ³ , and R ⁴ can also be bonded to each other and form a substituted or unsubstituted saturated or unsaturated 3-membered ring together with the bonded carbon atoms to 10-membered aliphatic ring. The aliphatic ring may be substituted with 1 or 2 or more substituents.

Examples of such aliphatic rings include aliphatic rings of 3- to 8-membered rings which may be substituted with substituents. More specifically, examples of the aliphatic ring include a cyclopentane ring, a cyclopentene ring, a cyclohexane ring, a cyclohexene ring, and a cycloheptane ring. In addition, when the aliphatic ring is substituted with a substituent, the substituent includes, for example, an alkyl group, an aryl group, an alkoxy group, an acyloxy group, an alkoxycarbonyl group, a silyl group, a sulfhydryl group, a cyano group, a nitro group, Sulfonic acid group, formyl group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom) and the like. Examples of the alkyl group here include methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary butyl, tertiary butyl, and the like. In addition, examples of the aryl group include phenyl, o-tolyl, m-tolyl, p-tolyl, and naphthyl. Moreover, the alkoxy group includes, for example, a methoxy group, an ethoxy group, an isopropoxy group, and a tertiary butoxy group. In addition, examples of the acyloxy group include acetoxy, propionyloxy, butyroxy, isobutyroxy, trimethylacetoxy, and benzyloxy. In addition, examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, and a tertiary butoxycarbonyl group.

In formula (1), R ¹ , R ² , R ³ and R ^{4 are} preferably the same or different, and are a hydrogen atom or an alkyl group with 1 to 4 carbon atoms. It is particularly desirable that R ¹ , R ² and R ³ are hydrogen atoms, and R ⁴ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Alternatively, in formula (1), two of R ¹ , R ² , R ³ and R ⁴ are also preferably bonded to each other to form a cyclohexene ring. Among them, it is more desirable that R ¹ , R ² and R ³ are hydrogen atoms, and R ⁴ is a hydrogen atom, a methyl group or an ethyl group, and it is particularly desirable that R ¹ , R ² and R ³ are hydrogen atoms, and R ⁴ is methyl.

In the resin composition of the present invention, the polyalkylene carbonate is preferably one or more selected from the group consisting of polyethylene carbonate, polypropylene carbonate, and cyclohexene carbonate. When the polyalkylene carbonate contains polyethylene carbonate, in the structural unit represented by formula (1), R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms. When the polyalkylene carbonate contains polypropylene carbonate, in the structural unit represented by formula (1), R ¹ , R ² and R ³ are hydrogen atoms, and R ⁴ is a methyl group.

Polyalkylene carbonate may have other structural units other than formula (1), and the terminal group may be modified. Examples of structural units other than formula (1) include structural units such as polyether, polyester, polyamide, and polyacrylate, and structural units having reactive groups such as carboxyl groups, hydroxyl groups, or amino groups. The modification of the terminal group can be exemplified: modification using acid anhydrides, cyclic acid anhydrides, acid halides, isocyanate compounds, and the like. When polyalkylene carbonate has structural units other than formula (1), its content relative to the total structural units of polyalkylene carbonate is preferably 10 mol% or less, preferably 5 mol% or less, more preferably It is 3 mol% or less, preferably 1 mol% or less.

When the polyalkylene carbonate has a structural unit other than formula (1), the structural unit may be contained in the polyalkylene carbonate in a random manner, may be contained in the form of a block polymer, or may be graft polymerized Contains in the form of things.

In the polyalkylene carbonate of the present invention, the structural unit represented by the formula (1) may be only one type, or may be two or more types.

The content (content rate) of the structural unit represented by the formula (1) in the polyalkylene carbonate can be determined by, for example, nuclear magnetic resonance spectroscopy (NMR analysis).

The mass average molecular weight Mw or molecular weight distribution (Mw/Mn) of polyalkylene carbonate is not particularly limited. For example, from the viewpoint of easily obtaining viscosity suitable for the printing process, the mass average molecular weight Mw of the polyalkylene carbonate is preferably 5000 or more, preferably 10000 or more, and more preferably 100,000 or more. In addition, from the viewpoint of easily obtaining viscosity suitable for the printing process, the mass average molecular weight Mw of the polyalkylene carbonate is preferably 1,000,000 or less, preferably 750,000 or less, and more preferably 500,000 or less. If the mass average molecular weight of the polyalkylene carbonate is within this range, the viscosity suitable for the printing process can be obtained. In addition, the so-called mass average molecular weight in this specification refers to the use of gel permeation chromatography (Waters 2695 separation module manufactured by Waters, Japan), based on polyalkylene carbonate 5mmol/L N,N-dimethyl A value calculated by measuring in a formamide lithium bromide solution at 40°C (using standard polystyrene as a reference).

From the viewpoint of easy to obtain viscosity suitable for printing process, the molecular weight distribution (Mw/Mn) of polyalkylene carbonate is preferably 1.0~15.0, particularly preferably 2.0~10.0.

The production method of polyalkylene carbonate is not particularly limited, and for example, the production methods of known polyalkylene carbonates can be widely used. For example, by polymerizing epoxide and carbon dioxide, polyalkylene carbonate can be produced. Hereinafter, this method is referred to as "manufacturing method P".

In the production method P, epoxides can be exemplified: compounds capable of forming the structural unit represented by formula (1), for example: ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3- Butylene oxide, isobutane epoxy, 1-epoxypentane, 2-epoxypentane, 1-epoxyhexane, 1-epoxyoctane, 1-epoxydodecane, epoxy ring Pentane, cyclohexane oxide, phenyl ethylene oxide, vinyl cyclohexane oxide, 3-phenyl propylene oxide, 3,3,3-trifluoropropylene oxide, 3-naphthyl propylene oxide , 2-phenoxy propylene oxide, 3-naphthoxy propylene oxide, butylene oxide, 3-vinyloxy propylene oxide and 3-trimethylsiloxy propylene oxide, etc. Among them, from the viewpoint of high reactivity, ethylene oxide, propylene oxide, cyclohexane oxide, and 1,2-butylene oxide are preferable, and ethylene oxide, propylene oxide, Epoxy cyclohexane. When the epoxide contains ethylene oxide, the prepared polyalkylene carbonate contains polyethylene carbonate, and when the epoxide contains propylene oxide, the prepared polyalkylene carbonate contains polypropylene carbonate. . In addition, when the epoxide contains cyclohexane oxide, the obtained polyalkylene carbonate contains polycyclohexane oxide carbonate.

In the production method P, the polymerization reaction of the epoxide and carbon dioxide is preferably carried out in the presence of a metal catalyst. Examples of the metal catalyst include zinc-based catalysts, aluminum-based catalysts, chromium-based catalysts, and cobalt-based catalysts. Among these, from the viewpoint of high polymerization activity in the polymerization reaction of epoxide and carbon dioxide, a zinc-based catalyst or a cobalt-based catalyst is preferable.

Examples of zinc-based catalysts include: diethyl zinc-water-based catalysts, diethyl zinc-gallic phenol-based catalysts, bis((2,6-diphenyl)phenoxy)zinc, and N-(2,6-diisopropyl) Phenyl)-3,5-di-tertiary butyl salicylidene zinc, 2-((2,6-diisopropylphenyl) amide)-4-((2,6-diiso Propylphenyl)imino)-2-pentene zinc acetate, zinc adipate, zinc glutarate and the like.

Examples of cobalt-based catalysts include cobalt acetate-acetic acid-based catalysts, N,N'-bis(3,5-di-tertiary butylsalicylidene)-1,2-cyclohexanediaminocobalt acetate, and N ,N'-bis(3,5-di-tertiary butylsalicylidene)-1,2-cyclohexanediaminocobalt pentafluorobenzoate, N,N'-bis(3,5-bis- Tertiary butyl ylidene)-1,2-cyclohexanediamino cobalt chloride, N,N'-bis(3,5-di-tertiary butyl ylidene)-1,2-ring Hexane diamino cobalt nitrate, N,N'-bis(3,5-di-tertiary butyl sulfarylene)-1,2-cyclohexane diamino 2,4-dinitrophenoxy cobalt oxide , Tetraphenylporphyrin cobalt chloride, tetraphenylporphyrin cobalt acetate, N,N'-bis[2-(ethoxycarbonyl)-3-oxobutylene]-1,2-cyclohexanediamine Cobalt chloride, N,N'-bis[2-(ethoxycarbonyl)-3-oxobutylene]-1,2-cyclohexanediaminocobalt pentafluorobenzoate, etc.

When a cobalt catalyst is used, a co-catalyst is preferably used. Examples of co-catalysts include: pyridine, N,N-4-dimethylaminopyridine, N-methylimidazole, tetrabutylammonium chloride, tetrabutylammonium acetate, triphenylphosphine, bis(triphenylphosphine) En)ammonium chloride, bis(triphenylphosphene)ammonium acetate, etc.

From the viewpoint of promoting the progress of the polymerization reaction, the amount of the metal catalyst used in the polymerization reaction (optional co-catalyst) is preferably 0.001 mol or more relative to 1 mol of epoxide, more preferably 0.005 mol or more . In addition, from the viewpoint of obtaining the effect in accordance with the usage amount, the usage amount of the metal catalyst (optional co-catalyst) used in the polymerization reaction is preferably 0.2 mol or less relative to 1 mol of epoxide, more preferably 0.1 Mole or less.

In the polymerization reaction, a reaction solvent may be used as needed. The reaction solvent is not particularly limited, and various organic solvents can be used. Examples of organic solvents include: aliphatic hydrocarbon solvents such as pentane, hexane, octane, decane, and cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; dichloromethane, chloroform, 1,1 -Dichloroethane, 1,2-dichloroethane, chlorobenzene, bromobenzene and other halogenated hydrocarbon solvents; dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 1, Ether solvents such as 3-dioxolane and anisole; ester solvents such as ethyl acetate, n-propyl acetate and isopropyl acetate; N,N-dimethylformamide, N,N-dimethyl Amine-based solvents such as methyl acetamide; carbonate-based solvents such as dimethyl carbonate, diethyl carbonate, and propylene carbonate.

From the viewpoint of smoothly proceeding the reaction, the amount of the reaction solvent used is preferably 100 to 10,000 parts by mass relative to 100 parts by mass of the epoxide.

There are no special restrictions on the method of polymerization reaction between epoxide and carbon dioxide in the presence of a metal catalyst. For example, the following method may be mentioned: injecting epoxide, catalyst, and co-catalyst, reaction solvent, etc. as needed into the autoclave, and then mixing , Press in carbon dioxide to make it react.

The amount of carbon dioxide used in the polymerization reaction is preferably 0.5 to 10 mol, preferably 0.6 to 5 mol, and more preferably 0.7 to 3 mol relative to 1 mol of epoxide.

In the polymerization reaction, the pressure of carbon dioxide is not particularly limited. From the viewpoint of smoothly proceeding the reaction, it is preferably 0.1 MPa or more, preferably 0.2 MPa or more, and more preferably 0.5 MPa or more, in order to obtain an effect in accordance with the use pressure From a viewpoint, it is preferably 20 MPa or less, preferably 10 MPa or less, and more preferably 5 MPa or less.

The polymerization temperature in the polymerization reaction is not particularly limited. From the viewpoint of shortening the reaction time, it is preferably 0°C or higher, preferably 20°C or higher, more preferably 30°C or higher, from the viewpoint of suppressing side reactions and improving yield From a standpoint, it is preferably 100°C or lower, preferably 80°C or lower, and more preferably 60°C or lower.

The reaction time varies depending on the polymerization reaction conditions, so it cannot be determined uniformly, and it is usually 1 to 40 hours.

(Organic compounds with more than 8 carbon atoms) As described above, the organic compound having 8 or more carbon atoms (hereinafter, referred to as "organic compound A") has at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, and an amide group.

The upper limit of the carbon number of the organic compound A is not particularly limited. For example, from the viewpoint that the resin composition can easily impart pseudoplasticity, the upper limit of the carbon number is preferably 100, and more preferably 50.

From the viewpoint that the resin composition easily exhibits pseudoplasticity, the number of the above-mentioned functional groups possessed by the organic compound A is preferably 1 to 5, preferably 1 to 4, and more preferably 1 to 3. When the number of the aforementioned functional groups possessed by the organic compound A is 2 or more, at least one functional group is preferably a carboxyl group. When the number of the above-mentioned functional groups possessed by the organic compound A is two or more, all of them may be the same functional group, or several of them may be different functional groups.

The organic compound A is preferably selected from aliphatic carboxylic acids with 8 or more carbons, aliphatic hydroxycarboxylic acids with 8 or more carbons, aliphatic alcohols with 8 or more carbons, and aliphatic amines with 8 or more carbons. One or more types in the group. In this case, the resin composition is likely to exhibit pseudoplasticity, and it is easy to adjust the thixotropic index described below within a desired range.

Examples of the aforementioned aliphatic carboxylic acids include caprylic acid, nonanoic acid, capric acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, palmitic acid, cis-6-hexadecenoic acid (sapienic acid), Seventeen acid, stearic acid, oleic acid, elaidic acid, isoleic acid, codoleic acid, linoleic acid, hypolinoleic acid, oleostearic acid, tubercle stearic acid, arachidic acid, arachidic acid, oleic acid , Erucic acid, tetracosonic acid, arachidonic acid, cervic acid, octadecanoic acid, beeswalic acid, suppository acid, azelaic acid, sebacic acid, dimeric acid, Japanese ceric acid, 2- Dodecyl succinic acid and so on. Among them, the preferred aliphatic carboxylic acids are caprylic acid, myristic acid, palmitic acid, and stearic acid.

Examples of the aforementioned aliphatic hydroxycarboxylic acid include: 2-hydroxyoctanoic acid, 3-hydroxyoctanoic acid, 2-hydroxynonanoic acid, 3-hydroxynonanoic acid, 3-hydroxydecanoic acid, 10-hydroxydecanoic acid, 2-hydroxylauric acid, 12-hydroxylauric acid, 2-hydroxymyristic acid, 3-hydroxymyristic acid, 6-hydroxymyristic acid, 2-hydroxypalmitic acid, 2-hydroxystearic acid, 12-hydroxystearic acid, 2- Hydroxyarachidic acid, 2-hydroxylic acid, 10-hydroxy-3-hydroxyundecylenic acid, ricinoleic acid, etc. Among them, the preferred aliphatic hydroxycarboxylic acid is 12-hydroxystearic acid.

The aforementioned aliphatic alcohols include, for example, octanol, nonanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, trans-oleyl alcohol, linolenic alcohol, linolenic alcohol, 1,8-octanol , 1,10-decanediol, 1,12-dodecanediol, castor oil, hydrogenated castor oil, polyoxyethylene hardened castor oil, etc. Among them, desirable aliphatic alcohols are 1,12-dodecanediol, hydrogenated castor oil, and polyoxyethylene hardened castor oil.

The aforementioned aliphatic amides can be enumerated such as: amide caprate, pelargonate, laurate amide, myristic acid amide, stearic acid amide, oleic acid amide, linoleic acid amide, linoleic acid Diamide, erucamide, methylene distearate, ethylene distearate, ethylene distearate, ethylene distearate, etc. Among them, the ideal aliphatic amides are ethylene distearate (ethylene distearate) and erucamide.

In the resin composition, the organic compound A can be used alone or in combination of two or more.

The mechanism of action of the organic compound A in the resin composition is not necessarily clear. As one of the inferences, since the organic compound A has a functional group, the organic compound A acts like a cross-linking point between polyalkylene carbonate molecules, whereby the polyalkylene carbonate chains can form weak cross-links with each other. The state of the union. If stress is applied to the polyalkylene carbonate chain, the cross-linking can be easily eliminated. Therefore, the viscosity of the resin composition can be significantly different before and after the stress is applied. As a result, it is estimated that the resin composition has pseudoplasticity.

(Resin composition) In the resin composition, the organic compound A is contained at 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the polyalkylene carbonate. Thereby, the resin composition can exhibit pseudoplasticity, and the thixotropic index described later can be adjusted within a desired range. If the content of the organic compound A is less than 1 part by mass relative to 100 parts by mass of the polyalkylene carbonate, the effect of the organic compound A is not easily exerted, and if it is more than 50 parts by mass, the thermal decomposition residue is likely to increase.

From the viewpoint of easily imparting excellent printability to the paste material, the content of the organic compound A relative to 100 parts by mass of polyalkylene carbonate is preferably 2 parts by mass or more, and more preferably 5 parts by mass or more. From the same viewpoint, the content of the organic compound A relative to 100 parts by mass of polyalkylene carbonate is preferably 30 parts by mass or less, and more preferably 20 parts by mass or less. The polyalkylene carbonate contained in the resin composition may be one type or two or more types, and the organic compound A may be one type or two or more types. In addition, the types of polyalkylene carbonate and organic compound A contained in the resin composition may be any combination.

As long as the effect of the present invention is not hindered, the resin composition may contain various additives. Examples of additives include plasticizers, antioxidants, ultraviolet absorbers, and antistatic agents. When the resin composition contains additives, the content thereof is, for example, 10% by mass or less, preferably 5% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.1% by mass relative to the total amount of the polyalkylene carbonate composition. the following.

The method of preparing the resin composition is not particularly limited. For example, a suitable method can be used to mix polyalkylene carbonate and organic compound A to prepare the resin composition of the present invention. As a specific example, a raw material containing polyalkylene carbonate and organic compound A can be dissolved or dispersed in a solvent and mixed, and then the solvent is removed to prepare the resin composition of the present invention. Or the following methods can be exemplified: using a roll kneader, extruder, Banbury mixer, Plastomill, Brabender mixer, etc., will contain polyalkylene carbonate and The raw materials of the organic compound A are melt-kneaded. Any of the raw materials may optionally contain the aforementioned additives.

When dissolving or dispersing the raw materials containing polyalkylene carbonate and organic compound A in a solvent and mixing, there is no particular limitation on the type of solvent used. For example, the solvent may include: aromatic hydrocarbon solvents such as benzene, toluene, styrene, and xylene; ketone solvents such as acetone, methyl ethyl ketone, and isophorone; tertiary butanol, benzyl alcohol, benzene Alcohol solvents such as oxyethanol and phenylpropanediol; halogenated hydrocarbon solvents such as dichloromethane and chloroform; ether solvents such as 1,2-dimethoxyethane, tetrahydrofuran, 1,4-dioxane, and anisole; Ester solvents such as ethyl acetate, propyl acetate, ethyl carbitol acetate, butyl carbitol acetate, etc.; N,N-dimethylformamide, N,N-dimethylacetate Amine-based solvents such as amines; carbonate-based solvents such as dimethyl carbonate, diethyl carbonate, and propylene carbonate.

The resin composition can be in various forms such as powder, pellets, agglomerates, flakes, bundles, fibers, liquids, dispersions, solutions, and molded bodies. Generally, when a resin composition is applied to a paste composition, a powdered resin composition can be used to prepare the paste composition.

The solution (paste) in which the resin composition has been dissolved in the solvent exhibits viscosity suitable for printing. Specifically, when the paste is applied, the viscosity is reduced due to the application of stress, so it has moderate fluidity. On the other hand, the stress is removed after coating, so the viscosity is increased without sag or penetration. Accordingly, the solution in which the resin composition has been dissolved in the solvent can have so-called pseudoplasticity, that is, the resin composition of the present invention can impart paste pseudoplasticity. In addition, since the resin composition contains polyalkylene carbonate, there is little residue after thermal decomposition. Therefore, the resin composition can be suitably used as a fired paste.

The thixotropic index (TI) can be used as an indicator of whether the resin composition can exhibit the desired pseudoplasticity. The thixotropic index is defined by the ratio of the respective viscosities ηa and ηb at two different shear rates a and b (here a<b). Specifically, pseudoplasticity can be evaluated from TI defined by the following formula (2): TI=ηa/ηb (2).

In the present invention, TI can be measured using a stress-controlled rotary viscoelasticity measuring device (manufactured by TA Instruments, AR-2000ex). When measuring TI, use a 1° cone plate, and measure the viscosity (ηa and ηb) of the measured sample at a shear rate of 0.3 per second and 3.0 per second at 25°C, by applying it to the formula (2), TI can be calculated. In the present invention, the aforementioned measurement sample for measuring TI is a solution in which the total concentration of polyalkylene carbonate and organic compound A is 20% by mass (hereinafter referred to as 20% by mass solution).

From the viewpoint of easy formation of a viscous paste suitable for screen printing, the TI (thixotropic index) of the 20% by mass solution is preferably 1.2 or more, and preferably 5.0 or less. The TI (thixotropic index) of the 20% by mass solution is more preferably 1.4 or more, and more preferably 1.5 or more. In addition, the TI (thixotropic index) of the 20% by mass solution is more preferably 4.0 or less, more preferably 3.6 or less, and particularly preferably 3.0 or less.

The measurement solvent used to prepare the 20% by mass solution is not particularly limited as long as it is a solvent that dissolves polyalkylene carbonate. Examples of measurement solvents include: toluene, xylene, ethylbenzene, tertiary butylbenzene, ethyl acetate, propyl acetate, butyl acetate, cyclohexyl acetate, ethyl lactate, propyl lactate, butyl lactate, and ethylene diacetate. Alcohol diacetate, glycerol triacetate, propylene glycol diacetate, tertiary butanol, terpineol, terpineol acetate, dihydroterpineol, terpineol dihydroacetate, menthol, alcohol ester 12 (TEXANOL), phenyl glycol, phenyl propylene glycol, benzyl alcohol, isophorone, γ-butyrolactone, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate , Diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethyl carbonate, ethylene carbonate, propylene carbonate, N-methyl Pyrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc. These solvents can be used individually by 1 type or in combination of 2 or more types.

2. Paste composition The paste composition of the present invention contains the aforementioned resin composition (resin composition for baking paste), a solvent, and an inorganic powder.

The solvent contained in the paste composition of the present invention can be, for example, the same solvent as the known paste composition, and particularly preferably a solvent having a boiling point and vapor pressure suitable for a printing process. From this point of view, the solvent can be exemplified by the same type of solvent as the aforementioned measurement solvent that can be used to prepare a 20% by mass solution.

The inorganic powder contained in the paste composition of the present invention can be, for example, the same inorganic powder as the known paste composition. Specifically, the inorganic powder is preferably at least one selected from the group consisting of conductive particles, ceramic powder, glass powder, and phosphor powder.

The conductive particles include, for example, metal particles composed of copper, iron, nickel, palladium, platinum, gold, silver, aluminum, tungsten, ruthenium, and alloys thereof; carbon black, graphite carbon, fullerenes, carbon nano Carbon materials such as rice tubes, nano diamonds, etc.

Examples of the glass powder include _{various silicon oxides such as CaO-Al 2} O ₃ -SiO ₂ series, MgO-Al ₂ O ₃ -SiO ₂ series, LiO ₂ -Al ₂ O ₃ -SiO ₂ series; bismuth oxide glass, silicon Glass components such as salt glass, lead glass, zinc glass, boric acid glass, etc.

Examples of ceramic powder include: alumina, zirconia, ferrite, titanium oxide, barium titanate, hydroxyapatite, aluminum nitride, silicon nitride, boron nitride, silicon carbide, and ITO (tin-doped indium oxide) , Lead zirconate titanate, talc and other powders.

Examples of the phosphor powder include BaMgAl ₁₀ O ₁₇ : Eu, Zn ₂ SiO ₄ : Mn, (Y, Gd)BO ₃ : Eu, and the like.

In the paste composition of the present invention, the content ratio of the resin composition, the solvent, and the inorganic powder is not particularly limited. For example, from the viewpoint that the paste composition has moderate dispersion stability and is easy to form a dense sintered body, the total amount of polyalkylene carbonate and organic compound A in the paste composition can be set as the inorganic powder per 100 parts by mass 0.01-30 parts by mass, preferably 0.05-20 parts by mass, more preferably 0.1-15 parts by mass.

In addition, from the viewpoint that the paste composition easily has moderate dispersion stability and fluidity, the total amount of solvent in the paste composition in the paste composition is 0.001 to 100 parts by mass relative to 100 parts by mass of the inorganic powder, preferably 0.01 ~80 parts by mass, more preferably 0.1-50 parts by mass.

The paste composition of the present invention may contain other additives. Examples of such additives include adhesion promoters, surfactants, plasticizers, storage stabilizers, defoamers, and the like.

Examples of the adhesion promoter include amine-based silane coupling agents and epoxypropyl-based silane coupling agents. Examples of the surfactant include polyoxyethylene-based surfactants, fatty acid ester-based surfactants, and the like. Examples of plasticizers include polyether polyols, phthalates, and adipates. Examples of storage stabilizers include amine compounds, carboxylic acid compounds, phosphorus compounds, sulfur compounds, and triazole-based compounds. Examples of defoamers include hydrophobic silica, polyalkylene derivatives, polyether derivatives, and the like.

When the paste composition of the present invention contains the above-mentioned other additives, the content thereof is preferably 50 parts by mass or less, and more preferably 30 parts by mass or less relative to 100 parts by mass of the inorganic powder.

The method of preparing the paste composition of the present invention is not particularly limited. For example, it can be prepared by mixing the resin composition of the present invention, solvent, inorganic powder, and additives as needed in an appropriate method. The mixing method is also not particularly limited, and for example, a well-known mixing method can be widely used. Specific mixing methods include, for example, a method of mixing using a ball mill, a bead mill, a Brabender mill, or a three-roll mill; a method of mixing using a mortar, and the like.

The paste composition of the present invention contains the aforementioned resin composition of the present invention, and therefore has excellent thermal decomposition properties and pseudoplasticity, whereby the printability is also excellent. Therefore, if the paste composition of the present invention is used, for example, an economical printing process, especially a screen printing process, can be used in the manufacture of electronic components. In addition, the paste composition of the present invention has excellent thermal decomposability, so the amount of residue after firing is small, and thereby, it is easy to suppress the decrease in conductivity and strength of the electronic component.

Example Hereinafter, embodiments will be used to explain the present invention more specifically, but the present invention is not limited to the aspects of these embodiments.

[Determination of mass average molecular weight (Mw) and molecular weight distribution (Mw/Mn)] The mass average molecular weight (Mw) of the polyalkylene carbonate prepared in each production example was measured by gel permeation chromatography (Waters 2695 separation module manufactured by Waters, Japan). Specifically, polyalkylene carbonate was mixed with 5 mmol/L of N,N-dimethylformamide lithium bromide solution to prepare a sample (polyalkylene carbonate concentration of 0.3% by mass), and set at 40 Measure at ℃. The mass average molecular weight (Mw) is calculated based on standard polystyrene.

[Evaluation method of thermal decomposition characteristics] The thermal decomposition characteristics of the binder resin composition for firing prepared in this example and the like were evaluated by the following method. The measurement device uses TG/DTA7220 manufactured by SII Nanotechnology Co., Ltd., and the measurement is performed under conditions of heating from room temperature (for example, 20°C) to 500°C at a temperature increase rate of 10°C/min under nitrogen atmosphere. In this measurement, the thermal decomposition start temperature is based on the definition of JIS K7120:1987. Specifically, in the decomposition curve obtained by measurement, the temperature at the intersection of the following lines is set as the thermal decomposition start temperature, that is, the line parallel to the horizontal axis of the mass before heating through the start of the test, and the deflection curve in the decomposition curve The gradient between the points constitutes the maximum and drawn tangent. The amount of residue (decomposition residue rate) is calculated from the ratio of the mass of the sample before starting the test heating to the mass of the sample at the time point when the temperature reaches 500°C.

[Evaluation method of thixotropic index (TI)] The thixotropic index (TI) is measured using a stress-controlled rotary viscoelasticity measuring device (manufactured by TA Instruments, AR-2000ex). Use a 1° cone plate for the measurement. As a measurement sample, a solution in which the total concentration of the polyalkylene carbonate and the organic compound A in the resin composition prepared in each of the Examples and Comparative Examples constitutes 20% by mass was prepared. The solvent (solvent for measurement) used when preparing this solution is as shown in Table 1 and Table 2 mentioned later. The viscoelasticity measurement is performed at 25°C. The viscosity is measured at a shear rate of 0.1 per second to 50.0 per second, and the viscosity (ηa and ηb) at the shear rate of 0.3 per second and 3.0 per second (ηa and ηb) is measured. Apply it to the following formula to calculate TI: TI=ηa/ηb (2).

(Manufacturing Example 1; Manufacturing of organic zinc catalyst) A 1L four-necked flask equipped with a stirrer, a nitrogen introduction tube, a thermometer, a Dean-Stark tube, and a reflux cooling tube was replaced with nitrogen, and 77.3g (0.95mol) of zinc oxide, Diacid 123g (1mol), acetic acid 1.14g (0.02mol) and toluene 760.0g. Next, the temperature was raised to 60°C, and the mixture was stirred at the same temperature for 4 hours to allow it to react. Then, the temperature was raised to 110°C to azeotropically dehydrate the water generated by the reaction, and then cooled to room temperature to prepare a slurry containing an organozinc catalyst (zinc glutarate).

(Manufacturing Example 2; Manufacturing of Polypropylene Carbonate) After replacing the system with a 1L autoclave equipped with a stirrer, a gas introduction tube, and a thermometer with a nitrogen atmosphere in advance, inject 50g of the slurry containing the organozinc catalyst prepared in Production Example 1 (containing 0.05mol of the organozinc catalyst ), 700g of 1,2-dichloroethane, 78.3g (1.35mol) of propylene oxide. Next, under stirring, carbon dioxide is added, and the carbon dioxide is filled until the reaction system constitutes 1.5 MPa. Then, the temperature was raised to 60°C, and the polymerization reaction was performed for 8 hours while replenishing the carbon dioxide consumed by the reaction. After the reaction, the autoclave was cooled and depressurized, and the obtained reaction solution was filtered and dried under reduced pressure to obtain 110 g of polypropylene carbonate. The obtained polypropylene carbonate has Mw=210,000 and Mw/Mn=10.4.

(Manufacturing Example 3; Manufacturing of Polyethylene Carbonate) Except that 59.4 g of ethylene oxide was used instead of propylene oxide, the same operation as in Production Example 2 was performed to obtain 108 g of polyethylene carbonate. The obtained polyethylene carbonate has Mw=205,000 and Mw/Mn=5.4.

(Production Example 4; Production of Polycyclohexenyl Carbonate) Except that 67.5 g of cyclohexane oxide was used instead of propylene oxide, the same operation as in Production Example 2 was performed to obtain 53.5 g of polycyclohexene carbonate. The obtained polycyclohexene carbonate has Mw=273,000 and Mw/Mn=7.8.

(Example 1) As shown in Table 1, 100 parts by mass of polypropylene carbonate prepared in Production Example 1 as polyalkylene carbonate, 2 parts by mass of palmitic acid as organic compound A, and 400 parts by mass of acetone as solvent were prepared. These were stirred and mixed while heating at 50°C to prepare a solution. The resin composition is prepared by drying the solvent from the solution. 100 parts by mass of the prepared resin composition was dissolved in 400 parts by mass of propylene carbonate as the solvent for TI measurement, thereby preparing a 20% by mass solution of the sample for TI measurement.

(Examples 2 to 11, Comparative Examples 1 to 6) Except for selecting the type and usage amount of polyalkylene carbonate, and the type and usage amount of organic compound A as shown in Table 1, a resin composition was prepared by the same method as in Example 1. Each of the prepared resin compositions used the measurement solvents shown in Table 1 to prepare a 20% by mass solution of the TI measurement sample. In addition, in Table 1, the polypropylene carbonate was obtained in Production Example 1, and the polypropylene carbonate was obtained in Production Example 2.

(Example 12) As shown in Table 2, 100 parts by mass of polypropylene carbonate prepared in Production Example 1 of polyalkylene carbonate and 1 part by mass of hydrogenated castor oil (KAO WAX85P manufactured by Kao) were prepared. Using a two-roll kneader (No. 191-TM-4 model manufactured by Yasuda Seiki Seisakusho, Ltd.), these were kneaded at 120°C for 10 minutes to obtain a resin composition. 100 parts by mass of the prepared resin composition was dissolved in 400 parts by mass of propylene carbonate as the solvent for TI measurement, thereby preparing a 20% by mass solution of the sample for TI measurement.

(Examples 13~16) Except for selecting the type and usage amount of the organic compound A as shown in Table 2, the resin composition was prepared by the same method as in Example 12. Each of the prepared resin compositions was prepared by the same method as in Example 12 to prepare a 20% by mass solution of the TI measurement sample.

[Table 1]

[Table 2]

From the TI values shown in Tables 1 and 2, it can be seen that the resin composition containing a specific amount of organic compound A has pseudoplastic properties (that is, the properties of low viscosity when stress is applied, and high viscosity when no stress is applied). On the other hand, when the predetermined amount of organic compound A is not contained, pseudoplasticity is not exhibited.

Fig. 1 shows the viscoelasticity measurement results of the resin compositions of Examples 1, 13 and Comparative Example 1. In Examples 1 and 13, the higher the stress (shear), the lower the viscosity. In contrast, in Comparative Example 1, no change in viscosity was seen. It can also be seen from this that the resin composition containing a specific amount of the organic compound A has pseudoplasticity.

Industrial availability The resin composition of the present invention has excellent thermal decomposition properties, and can exhibit pseudoplasticity when a paste is used as a material. Accordingly, the resin composition of the present invention can be suitably used in paste materials, and, for example, a printing process with excellent economic efficiency in the manufacture of electronic components, especially a screen printing process, can be used.

FIG. 1 shows the results of the viscoelasticity measurement of the resin compositions prepared in Examples 1, 13 and Comparative Example 1.

(no)

Claims (4)

A resin composition for baking paste, which is used as a resin composition for baking paste, and contains polyalkylene carbonate and an organic compound with a carbon number of 8 or more. The organic compound is selected from the group consisting of a carboxyl group, a hydroxyl group, and an alcohol. At least one functional group in the group consisting of an amine group, and the organic compound is contained at least 1 part by mass and not more than 50 parts by mass with respect to 100 parts by mass of the polyalkylene carbonate. The resin composition for baking paste according to claim 1, wherein the aforementioned polyalkylene carbonate contains a structural unit represented by the following general formula (1): [Chemical formula 1]

(In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or different, and represent a hydrogen atom, a linear or branched alkyl group with 1 to 10 carbon atoms that may be substituted by a substituent, or a substituent that may be substituted Substituted aryl group with 6 to 20 carbon atoms; two of R ¹ , R ² , R ³ , and R ⁴ may be bonded to each other to form an aliphatic ring from a 3-membered ring to a 10-membered ring which may be substituted by a substituent) . The resin composition for baking paste according to claim 1 or 2, wherein the aforementioned organic compound is selected from aliphatic carboxylic acids having 8 or more carbons, aliphatic hydroxycarboxylic acids having 8 or more carbons, and those having 8 or more carbons. At least one of the group consisting of aliphatic alcohols and aliphatic amides having 8 or more carbon atoms. A paste composition containing the resin composition according to any one of claims 1 to 3, a solvent and an inorganic powder.

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