WO2021029341A1

WO2021029341A1 - Firing paste resin composition and paste composition

Info

Publication number: WO2021029341A1
Application number: PCT/JP2020/030308
Authority: WO
Inventors: 聖司西岡
Original assignee: 住友精化株式会社
Priority date: 2019-08-09
Filing date: 2020-08-07
Publication date: 2021-02-18
Also published as: TW202112986A; JPWO2021029341A1

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

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

In the field of electronic members, electronic members having various circuit patterns are manufactured by using a paste material in which inorganic powders such as conductive particles, ceramics, glass and phosphors and a binder resin are dispersed in a solvent. Is being done. This paste material is fired after being coated on a base material or the like, and the binder resin contained in the paste material is burnt down by thermal decomposition during this firing.

As a binder resin, a polyalkylene carbonate resin produced by copolymerization of epoxide and carbon dioxide is known. Since the polyalkylene carbonate resin is excellent in thermal decomposition property, it is being studied as a binder resin for various paste materials. For example, Patent Document 1 proposes a polyalkylene carbonate-containing phosphor paste having excellent printability by using a solvent having a specific parameter. Further, Patent Document 2 proposes a polyalkylene carbonate having a specific molecular weight distribution.

Japanese Unexamined Patent Publication No. 2001-226669 Re-table No. 2016/167064

By the way, as a coating method of a paste material, a printing method such as screen printing, doctor blade printing, offset printing, gravure printing, flexo printing and inkjet printing, or a casting method for processing into a sheet shape is known. .. As a specific example, a circuit pattern of a predetermined shape is printed on a substrate by a screen printing method of a paste material in which conductive particles are dispersed, dried, and then fired to form a circuit pattern on the substrate. .. Since the printability of the paste material is easily affected by the characteristics of the paste material itself, it is important to select a paste material having characteristics suitable for printing. Therefore, of course, it can be said that the characteristics of the binder resin contained in the paste material cannot be ignored.

However, in the case of a paste material containing polyalkylene carbonate as a binder resin, the relationship between polyalkylene carbonate and printability has not been studied in great detail. Therefore, the conventional paste material using the polyalkylene carbonate as the binder resin has not always been able to preferably adopt the printing method. With the rapid development of miniaturization and complexity of electronic components in recent years, it is desired to develop a paste material more suitable for a printing method.

In this regard, the present inventor considered that the rheological properties of the binder resin, polyalkylene carbonate, are closely related to the printing performance in the paste material, and examined them in detail. As a result, in order to suitably adopt the screen printing method, it was found that the so-called pseudo-plasticity, which is an ology property that has a low viscosity when a shearing force is applied and a high viscosity when a shearing force is not applied, is important. It was. Therefore, in order to construct a paste material having good printing performance, it is important for the present inventors to develop a binder capable of imparting pseudoplasticity to the paste material while maintaining excellent thermal decomposability. I arrived at something.

The present invention has been made in view of the above, and is a resin composition for a baking paste and the baking paste, which has excellent thermal decomposition properties and can also impart pseudoplasticity, which is also important for printability. It is an object of the present invention to provide a paste composition containing a resin composition for use.

As a result of intensive studies to achieve the above object, the present inventor has found that the above object can be achieved by using a polyalkylene carbonate and an organic compound having a specific functional group and having 8 or more carbon atoms in combination. , The present invention has been completed.

That is, the present invention includes, for example, the subjects described in the following sections.
Item 1
A resin composition used as a baking paste.
Containing polyalkylene carbonate and an organic compound having 8 or more carbon atoms,
The organic compound has at least one functional group selected from the group consisting of a carboxy group, a hydroxy group and an amide group.
The organic compound is a resin composition for a baking paste, which is contained in an amount of 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 polyalkylene carbonate has the following general formula (1):

(In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or different, and may be substituted with a hydrogen atom or a substituent. A linear or branched alkyl group having 1 to 10 carbon atoms or a substituent. Indicates an aryl group having 6 to 20 carbon atoms which may be substituted with. ^{Two of} R ¹ , R ² , R ³ and R ⁴ are bonded to each other and may be substituted with a substituent. 3 to 10 aliphatic rings may be formed)
Item 2. The resin composition for a baking paste according to Item 1, which comprises a structural unit represented by.
Item 3
The organic compound includes an aliphatic carboxylic acid having 8 or more carbon atoms, an aliphatic hydroxycarboxylic acid having 8 or more carbon atoms, an aliphatic alcohol having 8 or more carbon atoms, and an aliphatic alcohol having 8 or more carbon atoms. Item 2. The resin composition for a calcined paste according to Item 1 or 2, which is at least one selected from the group consisting of amides.
Item 4
A paste composition containing the resin composition according to any one of Items 1 to 3, a solvent, and an inorganic powder.

The resin composition for a baking paste according to the present invention has excellent thermal decomposability, and can impart pseudoplasticity, which is also important for printability, to the baking paste.

It is the result of the viscoelasticity measurement of the resin composition obtained in Examples 1 and 13 and Comparative Example 1.

Hereinafter, embodiments of the present invention will be described in detail. In addition, in this specification, the expressions "contains" and "includes" include the concepts of "contains", "includes", "substantially consists" and "consists of only".

1. 1. Resin Binder Resin Composition for Calcination The resin composition for calcining paste of the present invention is a resin composition used as a calcining paste and contains a polyalkylene carbonate and an organic compound having 8 or more carbon atoms. Has at least one functional group selected from the group consisting of a carboxy group, a hydroxy group and an amide group. In the resin composition for a baking paste of the present invention, the organic compound is contained in an amount of 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 a baking paste of the present invention is simply abbreviated as "resin composition".

The resin composition of the present invention has excellent thermal decomposability, and can also impart pseudoplasticity, which is important for printability. The term "pseudoplasticity" as used herein can mean a property of having a low viscosity when a shearing force is applied and a high viscosity when a shearing force is not applied.

(Polyalkylene 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 adopted. Examples of the polyalkylene carbonate include a copolymer of cyclic ether and carbon dioxide, a polycondensate of diol and a carbonic acid derivative such as carbonic acid ester or phosgene, and a ring-opening polymer of cyclic carbonate. Among them, the polyalkylene carbonate is preferably a copolymer of epoxide, which is one kind of cyclic ether, and carbon dioxide from the viewpoint that a high molecular weight substance can be easily produced.

Such a 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 tends to have a desired pseudoplasticity.

Here, in the formula (1), R ¹ , R ² , R ³ and R ⁴ are the same or different, and may be substituted with a hydrogen atom or a substituent. A linear or branched alkyl having 1 to 10 carbon atoms. Indicates an aryl group having 6 to 20 carbon atoms which may be substituted with a group or a substituent. Further, ^{two of} R ¹ , R ² , R ³ and R ⁴ may be bonded to each other to form an aliphatic ring having 3 to 10 ring members which may be substituted with a substituent.

In the formula (1), the linear or branched alkyl group having 1 to 10 carbon atoms is a linear or branched chain having 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. Alkyl group in the form. The number of carbon atoms of this alkyl group is preferably 1 to 4, and particularly preferably 1 or 2. Specifically, the alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group and n-. Examples thereof include a heptyl group, an n-octyl group, an n-nonyl group and an n-decyl group.

In the 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 1 or 2 or more. Examples of the substituent in this case include a hydroxy group, an alkoxy group, an ester group, a silyl group, a sulfanyl group, a cyano group, a nitro group, a sulfo group, a formyl group, a carboxy group, an aryl group and a halogen atom (for example, a fluorine atom, Chlorine atom, bromine atom, iodine atom) and the like. Examples of the alkoxy group here include a methoxy group, an ethoxy group, an isopropoxy group, a tert-butoxy group and the like. Examples of the aryl group include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a naphthyl group and the like.

In the formula (1), the aryl group having 6 to 20 carbon atoms means that the aryl group has 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. It is an aryl group. The aryl group preferably has 6 to 14 carbon atoms. Examples of the aryl group include a phenyl group, a naphthyl group, a tetrahydronaphthyl group and the like.

In the formula (1), when an aryl group having 6 to 20 carbon atoms is substituted with a substituent, the number of substituents can be 1 or 2 or more. Examples of the substituent in this case include an alkyl group, a hydroxy group, an alkoxy group, an ester group, a silyl group, a sulfanyl group, a cyano group, a nitro group, a sulfo group, a formyl group, a carboxy group, an aryl group and a halogen atom (for example). Fluorine atom, chlorine atom, bromine atom, iodine atom) and the like. Examples of the alkyl group here include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and the like. Examples of the aryl group include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a naphthyl group and the like. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a tert-butoxy group and the like.

In formula (1), R ¹ , R ² , R ³ and R ⁴ can be the same, or part or all may be different. For example, in equation (1), R ¹ , R ² , R ³ and R ⁴ may all be the same, R ¹ , R ² and R ³ may be the same and R ⁴ may be different, and R ¹ , R ³ may be different. , R ⁴ may be the same and R ² may be different, and R ¹ , R ² , R ³ and R ⁴ may all be different.

In formula (1), ^{two of} R ¹ , R ² , R ³ and R ⁴ may be bonded to each other to form an aliphatic ring having 3 to 10 ring members which may be substituted with a substituent. it can. Specifically, ^{two of} R ¹ , R ² , R ³ , and R ⁴ are bonded to each other, and the number of substituted or unsaturated saturated or unsaturated ring members is 3 to 10 together with the carbon atom to which they are bonded. It can also form an aliphatic ring of. The aliphatic ring may be substituted with one or more substituents.

Examples of such an aliphatic ring include a 3- to 8-membered aliphatic ring which may be substituted with a substituent. More specific examples of the aliphatic ring include a cyclopentane ring, a cyclopentene ring, a cyclohexane ring, a cyclohexene ring, a cycloheptane ring and the like. When the aliphatic ring is substituted with a substituent, the substituents include, for example, an alkyl group, an aryl group, an alkoxy group, an acyloxy group, an alkoxycarbonyl group, a silyl group, a sulfanyl group, a cyano group and a nitro group. , Sulf 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 a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and the like. Examples of the aryl group include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a naphthyl group and the like. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a tert-butoxy group and the like. Examples of the acyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, a benzoyloxy group and the like. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, and a tert-butoxycarbonyl group.

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

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 polycyclohexene carbonate. When the polyalkylene carbonate contains polyethylene carbonate, R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms in the structural unit represented by the formula (1). When the polyalkylene carbonate contains a polypropylene carbonate, R ¹ , R ² and R ³ are hydrogen atoms and R ⁴ is a methyl group in the structural unit represented by the formula (1).

The polyalkylene carbonate may have a structural unit other than the formula (1), or the terminal group may be modified. Examples of the structural unit other than the formula (1) include structural units such as polyether, polyester, polyamide and polyacrylate, and structural units having a reactive group such as a carboxy group, a hydroxy group and an amino group. Modifications of the terminal groups include modifications with acid anhydrides, cyclic acid anhydrides, acid halides, isocyanate compounds and the like. When the polyalkylene carbonate has a structural unit other than the formula (1), its content is preferably 10 mol% or less, preferably 5 mol% or less, based on the total structural units of the polyalkylene carbonate. Is more preferable, and it is more preferably 3 mol% or less, and most preferably 1 mol% or less.

When the polyalkylene carbonate has a structural unit other than the formula (1), the structural unit may be randomly contained in the polyalkylene carbonate or contained in the form of a block polymer, in the form of a graft polymer. It may be included.

In the polyalkylene carbonate of the present invention, the structural unit represented by the formula (1) can be only one kind, or can be two or more kinds.

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

There is no particular limitation on the mass average molecular weight Mw or the molecular weight distribution (Mw / Mn) of the polyalkylene carbonate. For example, the mass average molecular weight Mw of the polyalkylene carbonate is preferably 5000 or more, more preferably 10000 or more, and further preferably 100,000 or more, in that the viscosity suitable for the printing process can be easily obtained. The mass average molecular weight Mw of the polyalkylene carbonate is preferably 1,000,000 or less, more preferably 750000 or less, still more preferably 500,000 or less, in that viscosity suitable for the printing process can be easily obtained. When the mass average molecular weight of the polyalkylene carbonate is in this range, the viscosity suitable for the printing process can be obtained. The mass average molecular weight referred to in the present specification is determined by using gel permeation chromatography (Waters2695 Separation Module manufactured by Japan Waters) in a solution of 5 mmol / L of polyalkylene carbonate in a lithium N, N-dimethylformiamide bromide. It is a value calculated by measuring at 40 ° C. (using standard polystyrene as a reference).

The molecular weight distribution (Mw / Mn) of the polyalkylene carbonate is preferably 1.0 to 15.0, preferably 2.0 to 10.0, in that viscosity suitable for the printing process can be easily obtained. Is particularly preferable.

The method for producing polyalkylene carbonate is not particularly limited, and for example, a known method for producing polyalkylene carbonate can be widely adopted. For example, a polyalkylene carbonate can be produced by a method of polymerizing epoxide and carbon dioxide. This method will be referred to as "manufacturing method P" below.

In the production method P, the epoxide may be a compound capable of forming a structural unit represented by the formula (1), and examples thereof include ethylene oxide, propylene oxide, 1,2-butylene oxide and 2,3-butylene. Oxide, isobutylene oxide, 1-pentene oxide, 2-pentene oxide, 1-hexene oxide, 1-octene oxide, 1-dodecene oxide, cyclopentene oxide, cyclohexene oxide, styrene oxide, vinyl cyclohexane oxide, 3-phenylpropylene oxide, Examples thereof include 3,3,3-trifluoropropylene oxide, 3-naphthylpropylene oxide, 2-phenoxypropylene oxide, 3-naphthoxypropylene oxide, butadienemonooxide, 3-vinyloxypropylene oxide and 3-trimethylsilyloxypropylene oxide. Be done. Among them, ethylene oxide, propylene oxide, cyclohexene oxide and 1,2-butylene oxide are preferable, and ethylene oxide, propylene oxide and cyclohexene oxide are more preferable from the viewpoint of having high reactivity. When the epoxide contains ethylene oxide, the resulting polyalkylene carbonate contains polyethylene carbonate, and when the epoxide contains propylene oxide, the resulting polyalkylene carbonate contains polypropylene carbonate. When the epoxide contains cyclohexene oxide, the obtained polyalkylene carbonate contains polycyclohexene oxide carbonate.

In the production method P, the polymerization reaction between 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, cobalt-based catalysts and the like. Among these, a zinc-based catalyst or a cobalt-based catalyst is preferable because it has high polymerization activity in the polymerization reaction between epoxide and carbon dioxide.

Examples of the zinc-based catalyst include diethylzinc-aqueous catalyst, diethylzinc-pyrogalol-based catalyst, bis ((2,6-diphenyl) phenoxy) zinc, and N- (2,6-diisopropylphenyl) -3,5-di. -Tert-Butylsalicylic aldoiminato zinc, 2-((2,6-diisopropylphenyl) amide) -4-((2,6-diisopropylphenyl) imino) -2-pentenzinc acetate, zinc adipate, glutaric acid Examples include zinc.

Examples of the cobalt-based catalyst include cobalt acetate-acetic acid-based catalyst, N, N'-bis (3,5-di-tert-butylsalicylidene) -1,2-cyclohexanediaminocobalt acetate, N, N'-bis (3,5-di-tert-butylsalicylidene). 3,5-di-tert-butylsalicylidene) -1,2-cyclohexanediaminocobalt pentafluorobenzoate, N, N'-bis (3,5-di-tert-butylsalicylidene) -1,2- Cyclohexanediaminocobalt chloride, N, N'-bis (3,5-di-tert-butylsalicylidene) -1,2-cyclohexanediaminocobalt nitride, N, N'-bis (3,5-di-tert) -Butylsalicylidene) -1,2-cyclohexanediaminocobalt 2,4-dinitrophenoxide, tetraphenylporphyrin cobalt chloride, tetraphenylporphyrin cobalt acetate, N, N'-bis [2- (ethoxycarbonyl) -3-oxobutylidene ] -1,2-Cyclohexanediaminatocobalt chloride, N, N'-bis [2- (ethoxycarbonyl) -3-oxobutylidene] -1,2-cyclohexanediaminatocobalt pentafluorobenzoate and the like.

When using a cobalt catalyst, it is preferable to use a co-catalyst. As co-catalysts, pyridine, N, N-4-dimethylaminopyridine, N-methylimidazole, tetrabutylammonium chloride, tetrabutylammonium acetate, triphenylphosphine, bis (triphenylphosphoranylidene) ammonium chloride, bis (tri). Examples thereof include phenylphosphoranylidene) ammonium acetate.

The amount of the metal catalyst (co-catalyst if necessary) used in the polymerization reaction is preferably 0.001 mol or more, more preferably 0.005 mol or more, based on 1 mol of the epoxide, from the viewpoint of promoting the progress of the polymerization reaction. More than a mole. The amount of the metal catalyst (co-catalyst if necessary) used in the polymerization reaction is preferably 0.2 mol or less, more preferably 0, with respect to 1 mol of the epoxide, from the viewpoint of obtaining an effect commensurate with the amount used. .1 mol or less.

A reaction solvent may be used for the polymerization reaction if necessary. The reaction solvent is not particularly limited, but various organic solvents can be used. Examples of the organic solvent include aliphatic hydrocarbon solvents such as pentane, hexane, octane, decane and cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene and xylene; methylene chloride, chloroform, 1,1-dichloroethane, and the like. Halogenated hydrocarbon solvents such as 1,2-dichloroethane, chlorobenzene and bromobenzene; ether solvents such as dimethoxyethane, tetrahydrofuran, 2-methyltetrahexyl, 1,4-dioxane, 1,3-dioxolane and anisole; ethyl acetate , Ester solvents such as n-propyl acetate and isopropyl acetate; amide solvents such as N, N-dimethylformiamide, N, N-dimethylacetamide; carbonate solvents such as dimethyl carbonate, diethyl carbonate and propylene carbonate. Can be mentioned.

The amount of the reaction solvent used is preferably 100 to 10000 parts by mass with respect to 100 parts by mass of the epoxide from the viewpoint of allowing the reaction to proceed smoothly.

The method for polymerizing epoxide and carbon dioxide in the presence of a metal catalyst is not particularly limited. For example, an epoxide, a catalyst, and if necessary, a co-catalyst, a reaction solvent, and the like are charged into an autoclave, mixed, and then dioxide. Examples thereof include a method of press-fitting carbon to cause a reaction.

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

In the polymerization reaction, the pressure of carbon dioxide is not particularly limited, but from the viewpoint of allowing the reaction to proceed smoothly, it is preferably 0.1 MPa or more, more preferably 0.2 MPa or more, still more preferably 0.5 MPa or more, and is used. From the viewpoint of obtaining an effect commensurate with the pressure, it is preferably 20 MPa or less, more preferably 10 MPa or less, still more preferably 5 MPa or less.

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

The reaction time cannot be unconditionally determined because it varies depending on the polymerization reaction conditions, but it is usually preferably about 1 to 40 hours.

(Organic compounds with 8 or more 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 carboxy group, a hydroxy 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 easily imparts pseudoplasticity, the upper limit of the carbon number is preferably 100, and more preferably 50.

The number of the functional groups contained in the organic compound A is preferably 1 to 5, more preferably 1 to 4, and 1 to 3 from the viewpoint that the resin composition easily exhibits pseudoplasticity. It is more preferable that the number is individual. When the number of the functional groups contained in the organic compound A is two or more, it is preferable that at least one functional group is a carboxy group. When the number of the functional groups contained in the organic compound A is two or more, all of them may be the same functional group, or some of them may be different functional groups.

The organic compound A is an aliphatic carboxylic acid having 8 or more carbon atoms, an aliphatic hydroxycarboxylic acid having 8 or more carbon atoms, an aliphatic alcohol having 8 or more carbon atoms, and an aliphatic alcohol having 8 or more carbon atoms. It is preferably one or more selected from the group consisting of amides. In this case, the resin composition tends to exhibit pseudoplasticity, and the thixotropic index described later can be easily adjusted to a desired range.

Examples of the aliphatic carboxylic acid include capric acid, pelargonic acid, capric acid, lauric acid, melissic acid, pentadecyl acid, palmitic acid, palmitreic acid, sapienic acid, margaric acid, stearic acid, oleic acid, eleostearic acid, and vaccenic acid. Gadoleic acid, linoleic acid, linolenic acid, eleostearic acid, tuberculostearic acid, arachidic acid, arachidonic acid, bechenic acid, erucic acid, lignoceric acid, nervonic acid, serotic acid, montanic acid, melissic acid, suberic acid, azeline Examples thereof include acid, sebacic acid, dimeric acid, Japanese acid, 2-dodecylsuccinic acid and the like. Among them, the preferred aliphatic carboxylic acid is caprylic acid, myristic acid, palmitic acid and stearic acid.

Examples of the aliphatic hydroxycarboxylic acid include 2-hydroxycaprylic acid, 3-hydroxycaprylic acid, 2-hydroxypelargonic acid, 3-hydroxypelargonic acid, 3-hydroxycapric acid, 10-hydroxycapric acid, and 2-hydroxylauric acid. , 12-Hydroxymyristic acid, 2-hydroxymyristic acid, 3-hydroxymyristic acid, 6-hydroxymyristic acid, 2-hydroxypalmitic acid, 2-hydroxystearic acid, 12-hydroxystearic acid, 2-hydroxyarachidic acid, Examples thereof include 2-hydroxybechenic acid, 10-hydroxy-3-hydroxyundecyleneic acid, and ricinoleic acid. Among them, the preferred aliphatic hydroxycarboxylic acid is 12-hydroxystearic acid.

Examples of the aliphatic alcohol include capryl alcohol, pelargone alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, ellaidyl alcohol, linoleyl alcohol, linolenoyl alcohol, 1,8-octanediol, 1, Examples thereof include 10-decanediol, 1,12-dodecanediol, castor oil, hydrogenated castor oil, polyoxyethylene hydrogenated castor oil and the like. Of these, the preferred aliphatic alcohols are 1,12-dodecanediol, hydrogenated castor oil, and polyoxyethylene cured castor oil.

Examples of the aliphatic amide include capric acid amide, pelargonic acid amide, lauric acid amide, myristic acid amide, stearic acid amide, oleic acid amide, ellagic acid amide, linoleic acid amide, erucic acid amide, methylene bisstearic acid amide and ethylene. Examples thereof include bislauric acid amide, ethylene bisstearic acid amide, and ethylene bisoleic acid amide. Among them, the preferred aliphatic amides are ethylene bisstearic acid amide (ethylene bisstearyl amide) and erucic acid amide.

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 always clear. One inference is that since the organic compound A has a functional group, the organic compound A acts like a cross-linking point between the polyalkylene carbonate molecules, whereby the polyalkylene carbonate chains form a weak cross-link. Can be. When such a polyalkylene carbonate chain is stressed, its cross-linking is easily eliminated, so that a significant difference in viscosity of the resin composition may occur before and after the stress is applied. As a result, it is inferred that the resin composition has pseudoplasticity.

(Resin composition)
In the resin composition, the organic compound A is contained in an amount of 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the polyalkylene carbonate. As a result, the resin composition can exhibit pseudoplasticity, and the thixotropic index described later is adjusted to a desired range. When the content of the organic compound A is less than 1 part by mass with respect to 100 parts by mass of the polyalkylene carbonate, the effect of the organic compound A is difficult to be exhibited, and when it exceeds 50 parts by mass, a thermal decomposition residue is generated. It becomes easy to increase.

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

The resin composition can contain various additives as long as the effects of the present invention are not impaired. Examples of the additive include a plasticizer, an antioxidant, an ultraviolet absorber, an antistatic agent and the like. When the resin composition contains an additive, 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, based on the total amount of the polyalkylene carbonate composition. .1% by mass or less.

The method for preparing the resin composition is not particularly limited. For example, the resin composition of the present invention can be prepared by mixing the polyalkylene carbonate and the organic compound A by an appropriate method. As a specific example, the resin composition of the present invention can be prepared by dissolving or dispersing a raw material containing a polyalkylene carbonate and an organic compound A in a solvent, mixing them, and then removing the solvent. Alternatively, a method of melt-kneading a raw material containing a polyalkylene carbonate and an organic compound A using a roll kneader, an extruder, a Banbury mixer, a plast mill, a lavender mixer or the like can be mentioned. Any raw material may contain the above-mentioned additives, if necessary.

When a raw material containing a polyalkylene carbonate and an organic compound A is dissolved or dispersed in a solvent and mixed, the type of solvent used is not particularly limited. For example, as the solvent, aromatic hydrocarbon solvents such as benzene, toluene, styrene and xylene; ketone solvents such as acetone, methyl ethyl ketone and isophorone; alcohol solvents such as tert-butyl alcohol, benzyl alcohol, phenoxyethanol and phenylpropylene glycol; Halogenized hydrocarbon solvents such as methylene chloride and chloroform; Ether solvents such as 1,2-dimethoxyethane, tetrahydrofuran, 1,4-dioxane and anisole; Ethyl acetate, propyl acetate, ethyl carbitol acetate, butyl carbitol Esther-based solvents such as acetate; amide-based solvents such as N, N-dimethylformiamide and N, N-dimethylacetamide; carbonate-based solvents such as dimethyl carbonate, diethyl carbonate and propylene carbonate can be mentioned.

The resin composition can be in various forms such as powder, granule, lump, pellet, strand, fibrous, liquid, dispersion, solution, molded body and the like. Usually, when the resin composition is applied to the paste composition, the paste composition can be prepared by using the powdery resin composition.

A solution (paste) in which the resin composition is dissolved in a solvent exhibits a viscosity suitable for printing. Specifically, when the paste is applied, the viscosity decreases due to the application of stress, so that the paste has an appropriate fluidity. On the other hand, since the stress is removed after coating, the viscosity becomes high and there is no sagging or bleeding. As described above, the solution in which the resin composition is dissolved in the solvent can have so-called pseudo-plasticity, that is, the resin composition of the present invention can bring about pseudo-plasticity to the paste. Moreover, since the resin composition contains a polyalkylene carbonate, there is little residue after thermal decomposition. Therefore, the resin composition can be suitably used as a baking paste.

The thixotropic index (TI) can be used as an index of whether or not the resin composition can exhibit the desired pseudoplasticity. The thixotropic index is defined by the ratio of the viscosities ηa and ηb at two different shear rates a, b (where a <b). Specifically, the pseudoplasticity is calculated by the following equation (2).
TI = ηa / ηb (2)
It can be evaluated from the TI defined in.

In the present invention, TI can be measured using a stress-controlled rotary viscoelasticity measuring device (AR-2000ex, manufactured by TA Instruments). A 1 ° cone plate can be used for the measurement of TI, and the measurement sample is measured at 25 ° C. for the respective viscosities (ηa and ηb) at shear rates of 0.3 / s and 3.0 / s. TI is calculated by applying to equation 2). In the present invention, as the measurement sample for measuring TI, a solution having a total concentration of polyalkylene carbonate and organic compound A of 20% by mass (hereinafter referred to as a 20% by mass solution) is used.

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

The measurement solvent for preparing the 20% by mass solution is not particularly limited as long as it is a solvent that dissolves the polyalkylene carbonate. Examples of the measurement solvent include toluene, xylene, ethylbenzene, tert-butylbenzene, ethyl acetate, propyl acetate, butyl acetate, cyclohexyl acetate, ethyl lactate, propyl lactate, butyl lactate, ethylene glycol diacetate, triacetin and propylene glycol diacetate. , Turt-butanol, tarpineol, tarpinyl acetate, dihydroterpineol, dihydroterpinyl acetate, mentanol, texanol, phenylethylene glycol, phenylpropylene glycol, benzyl alcohol, isophorone, γ-butyrolactone, ethylene glycol monoethyl ether acetate, diethylene glycol Examples thereof include monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethyl carbonate, ethylene carbonate, propylene carbonate, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and the like. These solvents can be used alone or in combination of two or more.

2. 2. Paste Composition The paste composition of the present invention contains the above-mentioned 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 a known paste composition, and in particular, a solvent having a boiling point and vapor pressure suitable for the printing process is preferable. From this point of view, examples of the solvent include the same types of solvents as the measurement solvents that can be used to prepare the above-mentioned 20% by mass solution.

The inorganic powder contained in the paste composition of the present invention can be, for example, an inorganic powder similar to a known paste composition. Specifically, as the inorganic powder, at least one selected from the group consisting of conductor particles, ceramic powder, glass powder, and phosphor powder is preferable.

Examples of the conductor particles include metal particles made of copper, iron, nickel, palladium, platinum, gold, silver, aluminum, tungsten, ruthenium and alloys thereof; carbon black, graphite carbon, fullerenes, carbon nanotubes, etc. Examples include carbon materials such as nanodiamond.

Examples of the glass powder include various silicon oxides such as CaO-Al ₂ O _3- SiO ₂ system, MgO-Al ₂ O _3- SiO ₂ system, LiO _2- Al ₂ O _3- SiO ₂ system; bismuth oxide glass. , Glass components such as silicate glass, lead glass, zinc glass, borate glass and the like.

Examples of the ceramic powder include alumina, zirconia, ferrite, titanium oxide, barium titanate, hydroxyapatite, aluminum nitride, silicon nitride, boron nitride, silicon carbide, ITO (tin-doped indium oxide), lead zirconate titanate, and steatite. Such as powder

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, the total amount of the polyalkylene carbonate and the organic compound A in the paste composition is 0 per 100 parts by mass of the inorganic powder in that the paste composition has appropriate dispersion stability and easily forms a dense sintered body. It can be 0.01 to 30 parts by mass, preferably 0.05 to 20 parts by mass, and more preferably 0.1 to 15 parts by mass.

Further, in the paste composition, the total amount of the solvent in the paste composition is 0.001 to 100 with respect to 100 parts by mass of the inorganic powder in that the paste composition tends to have appropriate dispersion stability and fluidity. It is preferably 0.01 to 80 parts by mass, and more preferably 0.1 to 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 accelerator include amine-based silane coupling agents and glycidyl-based silane coupling agents. Examples of the surfactant include polyoxyethylene-based surfactants and fatty acid ester-based surfactants. Examples of the plasticizer include polyether polyols, phthalates, adipates and the like. Examples of the storage stabilizer include amine compounds, carboxylic acid compounds, phosphorus compounds, sulfur compounds, and triazole compounds. Examples of the defoaming agent 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, more preferably 30 parts by mass or less, based on 100 parts by mass of the inorganic powder.

The method for preparing the paste composition of the present invention is not particularly limited, and for example, the resin composition of the present invention, a solvent, an inorganic powder, and if necessary, an additive may be mixed by an appropriate method. Can be done. This mixing method is also not particularly limited, and for example, a known mixing method can be widely adopted. Specific examples of the mixing method include a method of mixing using an apparatus such as a ball mill, a bead mill, a lavender mill, a three-roll mill, and a method of mixing using a mortar.

Since the paste composition of the present invention contains the above-mentioned resin composition of the present invention, it has excellent thermal decomposability, and also has excellent printability due to its pseudoplasticity. Therefore, by using the paste composition of the present invention, for example, it becomes possible to adopt an economical printing process, particularly a screen printing process, in the production of electronic members. Further, since the paste composition of the present invention has excellent thermal decomposability, the amount of residue after firing is small, which makes it easy to suppress a decrease in conductivity and a decrease in strength of the electronic member.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the aspects of these Examples.

[Measurement of mass average molecular weight (Mw) and molecular weight distribution (Mw / Mn)]
The mass average molecular weight (Mw) of the polyalkylene carbonate obtained in each production example was measured using gel permeation chromatography (Waters 2695 Separation Module manufactured by Japan Waters). Specifically, a sample was prepared by mixing polyalkylene carbonate with a 5 mmol / L solution of lithium N, N-dimethylformiamide bromide (concentration of polyalkylene carbonate was 0.3% by mass), and at 40 ° C. It was measured. The mass average molecular weight (Mw) was calculated based on standard polystyrene.

[Evaluation method of thermal decomposition characteristics]
The thermal decomposition characteristics of the binder resin composition for firing obtained in this example and the like were evaluated by the following method. A TG / DTA7220 manufactured by SII Nanotechnology Co., Ltd. was used as a measuring device, and the measurement was carried out under the condition of raising the temperature from room temperature (for example, 20 ° C.) to 500 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere. In this measurement, the pyrolysis initiation temperature was in accordance with the definition of JIS K7120: 1987. Specifically, in the decomposition curve obtained by the measurement, the intersection of the line parallel to the horizontal axis passing through the mass before the start of test heating and the tangent line drawn so as to maximize the gradient between the bending points in the decomposition curve. Was defined as the thermal decomposition start temperature. The residual amount (decomposition residue ratio) was calculated from the ratio of the sample mass before the start of test heating to the sample mass when the temperature reached 500 ° C.

[Evaluation method of thixotropic index (TI)]
The thixotropic index (TI) was measured using a stress-controlled rotary viscoelasticity measuring device (AR-2000ex, manufactured by TA Instruments). A 1 ° cone plate was used for the measurement. As a measurement sample, a solution having a total concentration of 20% by mass of the polyalkylene carbonate and the organic compound A in the resin compositions obtained in each Example and Comparative Example was prepared. The solvent (measurement solvent) used when preparing this solution was as shown in Tables 1 and 2 below. The viscoelasticity measurement was performed at 25 ° C., the viscosity was measured in the range of a shear rate of 0.1 / sec to 50.0 / sec, and the viscosities (ηa and ηb) at a shear rate of 0.3 / sec and 3.0 / sec were measured. Measured and the following formula TI = ηa / ηb (2)
The TI was calculated by applying it to.

(Production Example 1; Production of Organozinc Catalyst)
A 1 L volume four-necked flask equipped with a stirrer, a nitrogen gas introduction tube, a thermometer, a Dean Stark tube, and a reflux condenser was replaced with nitrogen to 77.3 g (0.95 mol) of zinc oxide, 123 g (1 mol) of glutaric acid, 1.14 g (0.02 mol) of acetic acid and 760.0 g of toluene were charged. Next, the temperature was raised to 60 ° C., and the mixture was stirred and reacted at the same temperature for 4 hours. Then, the temperature was raised to 110 ° C., the water generated by the reaction was azeotropically dehydrated, and then cooled to room temperature to obtain a slurry liquid containing an organozinc catalyst (zinc glutarate).

(Production Example 2; Production of polypropylene carbonate)
After replacing the inside of a 1 L autoclave system equipped with a stirrer, a gas introduction pipe, and a thermometer with a nitrogen atmosphere in advance, 50 g of a slurry liquid containing an organozinc catalyst obtained in Production Example 1 (0.05 mol of organozinc catalyst). Included), 700 g of 1,2-dichloroethane and 78.3 g (1.35 mol) of propylene oxide were charged. Next, carbon dioxide was added under stirring, and carbon dioxide was filled until the inside of the reaction system became 1.5 MPa. Then, the temperature was raised to 60 ° C., and the polymerization reaction was carried out for 8 hours while supplying carbon dioxide consumed by the reaction. After the reaction, the autoclave was cooled and decompressed, the obtained reaction solution was filtered, and then dried under reduced pressure to obtain 110 g of polypropylene carbonate. The obtained polypropylene carbonate had Mw = 210,000 and Mw / Mn = 10.4.

(Production Example 3; Production of polyethylene carbonate)
The same operation as in Production Example 2 was carried out except that 59.4 g of ethylene oxide was used instead of propylene oxide to obtain 108 g of polyethylene carbonate. The obtained polyethylene carbonate had Mw = 205,000 and Mw / Mn = 5.4.

(Production Example 4; Production of polycyclohexene carbonate)
The same procedure as in Production Example 2 was carried out except that 67.5 g of cyclohexene oxide was used instead of propylene oxide to obtain 53.5 g of polycyclohexene carbonate. The obtained polycyclohexene carbonate had Mw = 273,000 and Mw / Mn = 7.8.

(Example 1)
As shown in Table 1, 100 parts by mass of polypropylene carbonate obtained 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 a solvent were prepared. These were stirred and mixed while heating at 50 ° C. to prepare a solution. The solvent was dried from this solution to obtain a resin composition. A 20% by mass solution, which is a sample for TI measurement, was prepared by dissolving 100 parts by mass of the obtained resin composition in 400 parts by mass of propylene carbonate, which is a TI measurement solvent.

(Examples 2 to 11, Comparative Examples 1 to 6)
A resin composition was obtained in the same manner as in Example 1 except that the type and amount of the polyalkylene carbonate and the type and amount of the organic compound A were selected as shown in Table 1. For each of the obtained resin compositions, a 20% by mass solution, which is a sample for TI measurement, was prepared using the measurement solvent shown in Table 1. In Table 1, polypropylene carbonate used was obtained in Production Example 1, and polyethylene carbonate used was obtained in Production Example 2.

(Example 12)
As shown in Table 2, 100 parts by mass of polypropylene carbonate obtained in Production Example 1 and 1 part by mass of hydrogenated castor oil (Kao Wax 85P) were prepared as polyalkylene carbonate. These were kneaded at 120 ° C. for 10 minutes using a two-roll kneader (No. 191-TM-4 type manufactured by Yasuda Seiki Seisakusho) to obtain a resin composition. A 20% by mass solution, which is a sample for TI measurement, was prepared by dissolving 100 parts by mass of the obtained resin composition in 400 parts by mass of propylene carbonate, which is a TI measurement solvent.

(Examples 13 to 16)
A resin composition was obtained in the same manner as in Example 12 except that the type and amount of the organic compound A were selected as shown in Table 2. For each of the obtained resin compositions, a 20% by mass solution, which is a sample for TI measurement, was prepared in the same manner as in Example 12.

As can be seen from the TI values shown in Tables 1 and 2, the resin composition containing a specific amount of the organic compound A is pseudoplastic (that is, low viscosity when stressed and high viscosity when stress is not applied). It had the property of becoming). On the other hand, when a predetermined amount of organic compound A was not contained, no pseudoplasticity was exhibited.

FIG. 1 shows the results of viscoelasticity measurement of the resin compositions of Examples 1 and 13 and Comparative Example 1. In Examples 1 and 13, the viscosity decreased as stress (shear) was applied, whereas in Comparative Example 1, no change in viscosity was observed. From this, it was found that the resin composition containing a specific amount of the organic compound A has pseudoplasticity.

The resin composition of the present invention has excellent thermal decomposability, and moreover, pseudoplasticity is exhibited when a paste is used as a material. Therefore, the resin composition of the present invention can be suitably used as a paste material, and for example, a printing process excellent in economy, particularly a screen printing process, can be adopted in the production of electronic members.

Claims

A resin composition used as a baking paste.
It contains a polyalkylene carbonate and an organic compound having 8 or more carbon atoms.
The organic compound has at least one functional group selected from the group consisting of a carboxy group, a hydroxy group and an amide group.
The organic compound is a resin composition for a baking paste, which is contained in an amount of 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the polyalkylene carbonate.
The polyalkylene carbonate has the following general formula (1):

(In the formula, R 1 , R 2 , R 3 and R 4 are the same or different, and may be substituted with a hydrogen atom or a substituent. A linear or branched alkyl group having 1 to 10 carbon atoms or a substituent. Indicates an aryl group having 6 to 20 carbon atoms which may be substituted with. Two of R 1 , R 2 , R 3 and R 4 are bonded to each other and may be substituted with a substituent. 3 to 10 aliphatic rings may be formed)
The resin composition for a baking paste according to claim 1, which comprises a structural unit represented by.
The organic compound includes an aliphatic carboxylic acid having 8 or more carbon atoms, an aliphatic hydroxycarboxylic acid having 8 or more carbon atoms, an aliphatic alcohol having 8 or more carbon atoms, and an aliphatic alcohol having 8 or more carbon atoms. The resin composition for a calcined paste according to claim 1 or 2, which is at least one selected from the group consisting of amides.
A paste composition containing the resin composition according to any one of claims 1 to 3, a solvent, and an inorganic powder.