TW202113020A - Binder resin composition for burning use, and paste composition - Google Patents

Abstract

Provided are: a binder resin composition for burning use, which has excellent thermal decomposition properties and also has excellent stringiness when used as a paste material; and a paste composition. The binder resin composition for burning use according to the present invention is a composition that can be used as a binder resin for burning use, and comprises a polyalkylene carbonate and a cellulose-type resin. The paste composition of according to the present invention comprises the binder resin composition for burning use, a solvent and an inorganic powder. The binder resin composition for burning use according to the present invention has excellent thermal decomposition properties and also has excellent stringiness when used as a paste material.

Description

Binder resin composition and paste composition for firing

Invention field The present invention relates to a binder resin composition for firing and a paste composition containing the composition.

Background technique With the development of the industry, a large amount of carbon dioxide is emitted as a problem. Therefore, research on technologies for suppressing carbon dioxide emissions, or technologies for immobilizing carbon dioxide by physical or chemical methods is popular. Among them, the manufacturing technology of polyalkylene carbonate that utilizes the copolymerization reaction of carbon dioxide and epoxide is not only from the viewpoint of the chemical fixation of carbon dioxide, but also from the viewpoint of the effective use of carbon dioxide as a carbon resource. By the attention.

Although polyalkylene carbonate differs according to the type of epoxide used for its manufacture, it is generally a soft rubber-like resin, and it is known that it can be used in combination with various fillers. Recently, in order to make use of the speciality of polyalkylene carbonate as an environmental protection material using carbon dioxide as a raw material, researches on blending polyalkylene carbonate with polysaccharides and other natural ingredients have also been actively conducted. For example, Patent Document 1 discloses that by blending polypropylene carbonate and thermoplastic starch, a biodegradable resin with excellent mechanical properties can be obtained. Patent Documents 2 and 3 disclose that by blending polypropylene carbonate and cellulose fibers, a resin composition with improved blocking resistance or tensile strength can be obtained.

In addition, in recent years, the use of polyalkylene carbonate as a binder resin for firing has also been studied. The binder resin for firing is, for example, a binder component added to a paste material, and is a component that substantially disappears after firing the paste material. For example, Patent Document 4 discloses a glass paste containing polyalkylene carbonate as a binder resin, and Patent Document 5 discloses a ceramic paste containing polyalkylene carbonate as a binder resin. Patent Document 6 discloses a technique that uses a binder of a specific range of molecular weight composed of aliphatic polycarbonate to control silk viscosity to form a good printing pattern. Generally speaking, when cellulose resin, acrylic resin, wax-based binder, starch, gelatin, etc. are used as the binder for firing, polyalkylene carbonate has excellent thermal decomposition properties for these materials, so firing can be expected Step of energy saving.

Prior art literature Patent literature Patent Document 1: Japanese Special Form No. 2013-503921 Patent Document 2: Japanese Patent Application Publication No. 2014-001262 Patent Document 3: Japanese Patent Application Laid-Open No. 2014-001263 Patent Document 4: Japanese Patent Laid-Open No. 1-108128 Patent Document 5: Japanese Patent Laid-Open No. 6-334282 Patent Document 6: International Publication No. 2016/098423

Summary of the invention The problem to be solved by the invention However, the paste material using the conventional binder resin for firing does not have the performance that satisfies both the silk viscosity and the thermal decomposability, and there is still room for improvement. Especially in recent years, the miniaturization and precision of components have rapidly expanded. In order to cope with this, it is expected that the development of binder resin for firing can further improve the performance of both silk viscosity and thermal decomposition, resulting in excellent printing. Paste material of sexual characteristics.

The present invention is made in view of the above, and its object is to provide a binder resin composition for firing and a paste composition that have excellent thermal decomposition properties and also excellent silk viscosity when used as a paste material.

Means to solve the problem The inventors of the present case have repeatedly studied to achieve the above-mentioned object, and as a result, found that the above-mentioned object can be achieved by using polyalkylene carbonate and cellulose resin in combination, and completed the present invention.

That is, the present invention includes, for example, the subjects described in the following items. Item 1 A binder resin composition for firing is a composition used as a binder resin for firing, and contains polyalkylene carbonate and cellulose resin. Item 2 The binder resin composition for firing according to item 1, wherein the cellulose resin is one or more selected from the group consisting of alkyl cellulose, hydroxyalkyl cellulose, and esterified cellulose. Item 3 The binder resin composition for firing according to item 1 or 2, 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 及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4 如項1至3中任一項之燒成用黏結劑樹脂組成物，其中前述聚碳酸伸烷酯為選自於由聚碳酸伸乙酯、聚碳酸伸丙酯、聚碳酸伸丁酯及聚碳酸環己烯酯所構成群組中之1種以上。 項5 如項1至4中任一項之燒成用黏結劑樹脂組成物，其中相對於前述聚碳酸伸烷酯100質量份，含有前述纖維素系樹脂10質量份以上、100質量份以下。 項5-1 一種如項1至4中任一項之組成物作為燒成用黏結劑樹脂的用途。 項6 一種糊組成物，含有如項1至5中任一項之燒成用黏結劑樹脂組成物、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 which may be substituted by a substituent) . Item 4 The binder resin composition for firing according to any one of items 1 to 3, wherein the aforementioned polyalkylene carbonate is selected from the group consisting of poly(ethylene carbonate), poly(propylene carbonate), and poly(butylene carbonate). And one or more of the group consisting of polycyclohexenyl carbonate. Item 5 The binder resin composition for firing according to any one of items 1 to 4, which contains 10 parts by mass or more and 100 parts by mass of the cellulose resin with respect to 100 parts by mass of the polyalkylene carbonate. Item 5-1 A use of the composition according to any one of items 1 to 4 as a binder resin for firing. Item 6 A paste composition containing the binder resin composition for firing according to any one of items 1 to 5, a solvent, and an inorganic powder.

Invention effect The binder resin composition for firing of the present invention has excellent thermal decomposability and also excellent silk viscosity when used as a paste material.

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. Binder resin composition for firing The binder resin composition for firing of the present invention is used as a binder for firing, and contains polyalkylene carbonate and cellulose resin. Thereby, the binder resin composition for firing of the present invention has excellent thermal decomposability and also excellent silk viscosity when used as a paste material. Hereinafter, the binder resin composition for firing of the present invention is simply referred to as "resin composition". The term “excellent thermal decomposability” means that, for example, there are few residues due to thermal decomposition, and the term “excellent silk viscosity” means that the resin composition solution of a predetermined concentration is less likely to cause stickiness of the resin composition solution.

(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 better thermal decomposability, and is less likely to cause stickiness when used as a paste material.

[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 which 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 selected from the group consisting of polyethylene carbonate, polypropylene carbonate, polybutylene carbonate and polycyclohexene carbonate. More than species. 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. When the polyalkylene carbonate contains polybutylene carbonate, in the structural unit represented by formula (1), R ¹ , R ² and R ³ are hydrogen atoms, and R ⁴ is an ethyl group. When polyalkylene carbonate contains polycyclohexene carbonate, in the structural unit represented by formula (1), R ¹ and R ³ are hydrogen atoms, and R ² and R ⁴ are bonded to each other to form unsubstituted 6 members ring.

For the purpose of improving the compatibility with the cellulose resin, the polyalkylene carbonate may have other structural units other than formula (1), and the terminal group may also 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 mass average molecular weight in this specification refers to a 5mmol/L N,N-dimethylformamide lithium bromide solution using gel permeation chromatography (Waters 2695 separation module manufactured by Waters, Japan) In, the value calculated by measuring 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, and more preferably 1.0~10.0.

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 polycyclohexenyl 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.

(Cellulose resin) In the resin composition of the present invention, the type of cellulose resin is not particularly limited, and for example, known cellulose resins can be widely used. Specifically, cellulosic resins include methyl cellulose, ethyl cellulose, methyl ethyl cellulose, n-propyl cellulose, isopropyl cellulose, n-butyl cellulose, tertiary cellulose, etc. Alkyl cellulose such as cellulose and n-hexyl cellulose; Hydroxyalkyl cellulose such as hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and hydroxybutyl cellulose; cellulose acetate, diacetic acid Esterified cellulose such as cellulose, cellulose triacetate, cellulose acetate propionate, and cellulose acetate butyrate; carboxyalkyl cellulose such as carboxymethyl cellulose, carboxyethyl cellulose, carboxypropyl cellulose; others Cellulose derivatives or cellulose such as nitrocellulose, aldehyde-based cellulose, dialdehyde-based cellulose, and sulfonated cellulose. Among them, the cellulose resin is preferably one or more selected from the group consisting of alkyl cellulose, hydroxyalkyl cellulose, and esterified cellulose from the viewpoint of excellent thermal decomposability. From the viewpoint of particularly excellent silk viscosity, the cellulose resin is more preferably at least one selected from the group consisting of ethyl cellulose, hydroxypropyl cellulose and cellulose acetate butyrate, and Ethyl cellulose is particularly preferred.

The degree of substitution of the cellulose resin is not particularly limited, and is preferably 0.1 to 3.0, preferably 1.0 to 2.9, more preferably 1.5 to 2.7 from the viewpoint of showing good solubility in solvents. In addition, the degree of substitution in this specification means the total degree of substitution when there are plural kinds of substituents.

The mass average molecular weight of the cellulose resin is also not particularly limited. For example, from the viewpoint of easily obtaining viscosity suitable for the printing process, the mass average molecular weight of the cellulose resin is preferably 5000 or higher, preferably 10000 or higher, and more preferably 100000 or higher. In addition, the mass average molecular weight of the cellulose resin is preferably 1,000,000 or less, preferably 750,000 or less, and more preferably 500,000 or less. In addition, the mass average molecular weight of the cellulose resin can be measured by the same method as that of polyalkylene carbonate.

The cellulose resin contained in the composition of the present invention may be only one type or two or more types.

The manufacturing method of cellulose resin is not specifically limited, For example, it can manufacture by a well-known method. Alternatively, the cellulose resin used in the present invention may be obtained from a commercially available product or the like.

(Resin composition) In the resin composition of the present invention, the content ratio of polyalkylene carbonate to cellulose resin is not particularly limited. For example, in the resin composition of the present invention, relative to 100 parts by mass of polyalkylene carbonate, the cellulose resin preferably contains 5 parts by mass or more and 100 parts by mass or less, and more preferably contains 10 parts by mass or more and 100 parts by mass. the following. In this case, the resin composition of the present invention has excellent thermal decomposability and is less likely to cause stickiness, especially with regard to the thermal decomposability of the resin composition, even if the thermal decomposition characteristics of polyalkylene carbonate and cellulose are added Due to the unique thermal decomposition characteristics of the resin, the thermal decomposition properties of the resin composition can also be additively improved.

In the resin composition of the present invention, relative to 100 parts by mass of polyalkylene carbonate, the content of cellulose resin is more preferably 20 parts by mass or more, particularly preferably 30 parts by mass or more, and more preferably 80 parts by mass or less , Particularly preferably 50 parts by mass or less.

The resin composition of the present invention may contain various additives in addition to polyalkylene carbonate and cellulose resin. Examples of additives include plasticizers, antioxidants, ultraviolet absorbers, and antistatic agents.

When the resin composition of the present invention contains additives, the content thereof is, for example, 10% by mass or less relative to the total amount of the polyalkylene carbonate composition, preferably 5% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.1% by mass or less.

The method of preparing the resin composition of the present invention is not particularly limited. For example, a suitable method can be used to mix polyalkylene carbonate and cellulose resin to prepare the resin composition of the present invention. As a specific example, a raw material containing polyalkylene carbonate and a cellulose resin can be dissolved or dispersed in a solvent and mixed, and then the solvent can be 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 cellulose resin are melted and kneaded. Any of the raw materials may optionally contain the aforementioned additives.

When dissolving or dispersing the raw materials containing polyalkylene carbonate and cellulose resin in a solvent and mixing, the kind of solvent used is not particularly limited. For example, the solvent may include hydrocarbon solvents such as benzene, toluene, and xylene; ketone solvents such as acetone, methyl ethyl ketone, and isophorone; tertiary butanol, benzyl alcohol, phenoxyethanol, phenyl Alcohol solvents such as propylene glycol; halogenated hydrocarbon solvents such as dichloromethane and chloroform; ether solvents such as 1,2-dimethoxyethane, tetrahydrofuran, 1,4-dioxane, and anisole; ethyl acetate, acetic acid Ester solvents such as propyl ester, ethyl carbitol acetate, and butyl carbitol acetate; N,N-dimethylformamide, N,N-dimethylacetamide and other amine-based solvents Solvents: carbonate-based solvents such as dimethyl carbonate, diethyl carbonate, and propylene carbonate.

The resin composition of the present invention can be in various forms such as powder, pellets, agglomerates, flakes, bundles, fibers, liquids, dispersions, solutions, and molded bodies.

The resin composition of the present invention has excellent thermal decomposition properties and also excellent silk viscosity when used as a paste material. Specifically, the paste composition prepared by using the resin composition of the present invention shows solution characteristics suitable for printing, that is, the silk viscosity is low, and the release amount after coating is also good. Accordingly, by applying the resin composition of the present invention to a paste material (especially a binder resin for firing), it is possible to use, for example, an economical printing process in the manufacture of electronic components, especially a screen printing process. .

2. Paste composition The paste composition of the present invention contains the aforementioned resin composition (binder resin composition for firing), 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. Specifically, the solvent may include: toluene, ethyl acetate, butyl acetate, ethanol, isopropanol, methyl isobutyl ketone, methyl ethyl ketone, N-methyl-2-pyrrolidone, ethyl acetate Glycol ethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoisobutyl Base ether, trimethylpentanediol monoisobutyrate, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, butyl carbitol acetate, terpineol, terpene Pinitol acetate, dihydroterpineol, dihydroterpineol acetate, alcohol ester 12 (TEXANOL), isophorone, butyl lactate, benzyl alcohol, phenylpropanediol, cresol, N,N- Dimethylformamide, N,N-dimethylacetamide and propylene carbonate, etc.

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, inorganic powders include metal particles composed of gold, silver, copper, iron, nickel, palladium, platinum, aluminum, tungsten, and alloys thereof; 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 and other silicon oxides; bismuth oxide glass, silicate glass, lead glass, zinc glass, boron glass and other glass powders; Sn-Pb Alloys, Sn-Pb alloys with silver, bismuth, indium and other alloys added, Sn-Ag series alloys, Sn-Cu series alloys, Sn-Ag-Cu series alloys and other solder alloy powders; aluminum oxide, zirconium oxide, cerium oxide , Titanium oxide, zinc oxide, barium titanate, aluminum nitride, silicon nitride, boron nitride, silicon carbide and other ceramic powders; carbon black, graphite carbon, fullerenes, carbon nanotubes, nanodiamonds, etc. Carbon materials, etc.

The paste composition of the present invention may contain other additives. Examples of such additives include decomposition accelerators such as organic peroxides and organic azo compounds; adhesion promoters such as amine-based silane coupling agents and epoxypropyl-based silane coupling agents; polyoxyethylene-based surfactants, fats Surfactants such as acid ester surfactants; plasticizers such as polyether polyols, phthalates, and adipates; storage stabilizers such as amine compounds, carboxylic acid compounds, phosphorus compounds, sulfur compounds, and triazole compounds ; Antifoaming agents such as hydrophobic silica, polyalkylene derivatives, polyether derivatives, etc.

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, for every 100 parts by mass of the resin composition, the content of the solvent can be set to 100 to 5000 parts by mass, preferably 400 to 2000 parts by mass. In addition, per 100 parts by mass of the resin composition, the content of the inorganic powder may be 100 to 5000 parts by mass, preferably 500 to 1000 parts by mass. When the paste composition of the present invention contains the aforementioned 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 binder resin composition for firing, and therefore has excellent thermal decomposability and silk viscosity. 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 obtained decomposition curve, the temperature at the intersection of the following lines is set as the thermal decomposition start temperature, namely: the line parallel to the horizontal axis of the mass before heating through the start of the test, and the gradient between the inflection points in the decomposition curve Make up the largest tangent line drawn. The 50% by mass decomposition temperature is the temperature at which half of the mass composition of the sample (resin composition) is read before the test heating starts. 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 silk stickiness] The silk viscosity of the binder resin composition for firing prepared in this example and the like was evaluated by the following method. The solution of the binder resin composition for firing is placed in the container, and a cylindrical rod with a diameter of 2.9 mm made of polytetrafluoroethylene is immersed in the solution at room temperature (23°C), and the cylindrical rod is 5 mm in diameter. The speed per second is pulled up in the vertical direction with respect to the solution surface. At this time, among the silk sticks generated between the cylindrical rod and the surface of the solution, the maximum length is measured with a vernier to evaluate the silk stickiness. The solution used in this evaluation was an ethyl carbitol acetate solution using the binder resin composition for firing, and the concentration was set to 20% by mass.

(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 122.8g (0.93mol), 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 of a 1L autoclave equipped with a stirrer, a gas introduction tube, and a thermometer with a nitrogen atmosphere in advance, inject 117.3g of the slurry containing the organozinc catalyst prepared in Production Example 1 (containing 135mmol of the organozinc catalyst ), toluene 530.0g, propylene oxide 78.3g (1.35mol). Next, under stirring, carbon dioxide is added, and the carbon dioxide is filled until the reaction system constitutes 1 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 completion of the reaction, the autoclave was cooled and depressurized, and the reaction solution was filtered and dried under reduced pressure to obtain 100.3 g of polypropylene carbonate. The Mw of the obtained polypropylene carbonate was 236000.

(Manufacturing Example 3; Manufacturing of Polyethylene Carbonate) Except that 59.0 g of ethylene oxide was used instead of propylene oxide, the same operation as in Production Example 2 was performed to obtain polyethylene carbonate 102.1. The Mw of the obtained polyethylene carbonate was 210,000.

(Production Example 4; Production of Polycyclohexenyl Carbonate) Except that 130.0 g of cyclohexene oxide was used instead of propylene oxide, the same operation as in Production Example 2 was performed to obtain 75.3 g of polycyclohexene carbonate. The Mw of the obtained polycyclohexenyl carbonate was 258,000.

(Example 1) 100 parts by mass of polypropylene carbonate prepared in Production Example 2 and 11 parts by mass of ethyl cellulose (Nacalai Tesque manufacturing reagent, Mw=180000, degree of substitution 2.6) were dissolved in 1000 parts by mass of chloroform, After uniformly mixing at room temperature, the solution is dried, thereby preparing a resin composition.

(Examples 2 to 6, Comparative Examples 1 to 2) Except that the blending amounts of polypropylene carbonate (PPC) and ethyl cellulose (EC) were changed as shown in Table 1 to be disclosed later, the resin composition was prepared by the same method as in Example 1.

[Table 1]

A resin composition containing a specific amount of polyalkylene carbonate and cellulose resin will have the following result: Compared with the polyalkylene carbonate alone, the length of the silk is reduced by at least half. Compared with the cellulose resin alone, the decomposition start temperature is greatly reduced, and the residue is also greatly reduced. Therefore, the resin composition of the examples also exhibits excellent thermal decomposition.

In Example 5 in which the polyalkylene carbonate and the cellulose resin were mixed in equal weight, the amount of residue was reduced more than half of the cellulose resin alone. It is believed that this is because the thermal decomposition reaction of polyalkylene carbonate acts on the thermal decomposition reaction of the cellulose resin, and the entire resin composition becomes easier to thermally decompose (that is, the thermal decomposition characteristic of the resin composition is increased reason).

(Example 7) Except for changing ethyl cellulose to hydroxypropyl cellulose (Fuji Film Wako Pure Chemical Industries, Ltd. Reagent, Mw=380000, degree of substitution 2.9), a resin composition was prepared by the same method as in Example 1.

(Example 8, Comparative Example 3) Except that the blending amount of polypropylene carbonate (PPC) and hydroxypropyl cellulose (HPC) was changed as shown in Table 2 below, the same method as in Example 7 was used to obtain a resin composition .

(Example 9) Except for changing ethyl cellulose to cellulose acetate butyrate (Aldrich manufacturing reagent, Mw=140000, degree of substitution 2.5), a resin composition was prepared by the same method as in Example 1.

(Example 10, Comparative Example 4) Except that the blending amounts of polypropylene carbonate (PPC) and cellulose acetate butyrate (CAB) were changed as shown in Table 2 below, the same method as in Example 9 was used to prepare a resin composition .

[Table 2]

(Example 11) The resin composition was prepared by the same method as in Example 1, except that the polypropylene carbonate obtained in Production Example 2 was changed to the polypropylene carbonate obtained in Production Example 3.

(Example 12, Comparative Example 5) Except that the blending amounts of polyethylene carbonate (PEC) and ethyl cellulose (EC) were changed as shown in Table 3 to be disclosed later, a resin composition was prepared by the same method as in Example 11.

(Example 13) Except that the polypropylene carbonate obtained in Production Example 2 was changed to the polycyclohexenyl carbonate produced in Production Example 4, a resin composition was produced by the same method as in Example 1.

(Example 14, Comparative Example 6) Except that the blending amount of polycyclohexenyl carbonate (PCHC) and ethyl cellulose (EC) was changed as shown in Table 3 below, the resin composition was obtained by the same method as in Example 13 .

[table 3]

From Table 2 and Table 3, it can be understood that regardless of the type of cellulose resin and the type of polyalkylene carbonate, the resin composition is not easy to cause stickiness, and the thermal decomposition property can be additively improved.

Industrial availability The resin composition of the present invention has excellent thermal decomposition properties and also excellent silk viscosity when used as a paste 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.

(no)

Claims (6)

A binder resin composition for firing is a composition used as a binder resin for firing, and contains polyalkylene carbonate and cellulose resin. The binder resin composition for firing according to claim 1, wherein the cellulose resin is one or more selected from the group consisting of alkyl cellulose, hydroxyalkyl cellulose, and esterified cellulose. The binder resin composition for firing according to claim 1 or 2, 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 binder resin composition for firing according to any one of claims 1 to 3, wherein the aforementioned polyalkylene carbonate is selected from the group consisting of polyethylene carbonate, polypropylene carbonate, polybutylene carbonate and One or more of the group consisting of polycyclohexenyl carbonate. The binder resin composition for firing according to any one of claims 1 to 4, which contains 10 parts by mass or more and 100 parts by mass or less of the cellulose resin with respect to 100 parts by mass of the polyalkylene carbonate. A paste composition containing the binder resin composition for firing according to any one of claims 1 to 5, a solvent, and an inorganic powder.