JPH02184559A - Liquid composition for ceramics - Google Patents

Abstract

PURPOSE:To enable to form a ceramic molded product having improved surface smoothness, green density and green strength and containing inorganic compound particles having good dispersibility by preparing a liquid composition containing the inorganic compound particles and a polymer obtained from an addition- oxazoline as a binder. CONSTITUTION:The liquid composition for ceramics contains (A) a polymer obtained by polymerizing monomer components containing (a) an addition- polymerizable oxazoline of formula I (R1, R2, R3 and R4 are independently H, halogen, alkyl, aralkyl, phenyl or substituted phenyl; R5 is a non-cyclic organic group) and (B) inorganic compound particles. The components A and B are compounded in a ratio of approximately 1-30 pts.wt. of the component A per 100 pts.wt. of the component B. The addition-polymerizable oxazoline (a) in the monomer components is preferably used in an 0.5-100wt.%.

Description

[Detailed Description of the Invention] (Field of Industrial Application) The present invention relates to a liquid composition for ceramics using particles of inorganic compounds such as alumina, silica, zirconia, titania, barium titanate, silicon carbide, and silicon nitride. be.

t's (wherein, R1, f?2, Rs, Rh are each independently hydrogen, halogen, alkyl, aralkyl, phenyl or substituted phenyl group, and R5 is an acyclic organic compound having an addition-polymerizable unsaturated bond. A liquid composition for ceramics comprising a polymer (A) obtained by polymerizing a monomer component comprising an addition-polymerizable oxazoline (a) represented by .

2. The composition according to claim 1, wherein the polymer (A) is used in an amount of 1 to 30 parts by weight (in terms of non-volatile content) per 100 parts by weight of the inorganic compound particles (B).

<Prior art and problems to be improved by the invention] Conventionally, in order to produce ceramic molded products, a liquid composition containing inorganic compound particles and a binder is processed by dry press molding, sheet molding, extrusion molding, etc. Generally, it is molded into various shapes using the following molding method. However, the various binders used in the liquid compositions in these methods have many drawbacks.

In the sheet forming method, inorganic compound particles are dispersed in a solution containing a binder plasticizer to create a slurry, and this is coated onto a carrier film in a layer using a doctor blade, etc., and dried, resulting in a sheet (called a green sheet). .

) is rolled up and stored, taken out as needed and punched out with a mold, and then fired to decompose the binder and sinter the inorganic compound particles to form ceramics. In this method, conventional binders include butyral resins such as polyvinyl butyral, cellulose resins such as ethyl cellulose, and (meth)acrylic resins.

However, when these binders are used, the dispersibility of the S machine compound particles is insufficient, and the particles enter a secondary agglomerated state, resulting in large gaps between the particles, causing holes in the sheet and poor surface smoothness. become inferior. There is also a desire for improvement in the low green density and green strength of the resulting molded products. In liquid compositions used in dry press molding and extrusion molding, binders similar to those used in sheet molding have traditionally been used, and the dispersibility of inorganic compound particles has also been affected. As a result, the resulting molded products had problems in that they had low green density and green strength. In recent years, many proposals have been made to eliminate such drawbacks (Japanese Patent Application Laid-Open Nos. 58-167471, 1983).
-182265, JP-A No. 59-182266, and JP-A No. 60-46964) have not yet achieved sufficient results.

(Means and effects for solving the problem) In view of the current situation, the inventors of the present invention have conducted extensive research and have found that a liquid composition using a polymer obtained using addition-polymerizable oxazoline as a binder is It was discovered that a ceramic molded article with good dispersion of inorganic compound particles and improved surface smoothness, green density, and green strength could be obtained, and this led to the completion of the present invention.

That is, the present invention is directed to the general formula (I) (wherein R1, R2, R3, and R4 are each independently hydrogen, halogen, alkyl, phenyl, or substituted phenyl group, and R5 has an addition-polymerizable unsaturated bond).

It is an acyclic organic group. ) A liquid composition for ceramics comprising a polymer (A) obtained by polymerizing a monomer component comprising an addition-polymerizable oxazoline (a) represented by (A) and inorganic compound particles (B). .

Addition-polymerizable oxazoline (a
) is represented by the general formula (I), and specific examples include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-2-oxazoline, and 2-vinyl-2-oxazoline.
Vinyl-5-methyl-2-oxazoline, 2-impropenyl-2-oxacillin, 2-impropenyl-4-
Methyl-2-oxacillin, 2-isopropenyl-5-
Examples include ethyl-2-oxazoline, and one type or a mixture of two or more types selected from these groups can be used. Among them, 2-isopropenyl-2-
Oxazoline is preferred because it is industrially available. The amount of addition polymerizable oxazoline (a) used is not particularly limited.

In the monomer component, the amount is preferably 0.5 to 100% by weight, and if the amount is 0.5% by weight, the dispersibility of the inorganic compound particles (B) tends to be impaired.

The monomer component may contain other monomers (b) as necessary.Other monomers (b) used in the present invention include addition-polymerizable oxazolines (a) and copolymerizable As long as it is possible, there is no particular restriction.1 For example, (meth)acrylic acid esters such as butyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate; (meth)acrylic acid. unsaturated carboxylic acids such as itaconic acid and maleic acid; unsaturated nitriles such as (meth)acrylonitrile; (meth)acrylamide;
Unsaturated amides such as N-methylol (meth)acrylamide; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; α- such as ethylene and propylene
Olefins; halogen-containing α, β-unsaturated motumers such as vinyl chloride, vinylidene chloride, and vinyl fluoride; α, β-unsaturated aromatic heptamers such as styrene and α-methylstyrene; One type or a mixture of two or more types can be used. Among these, (meth)acrylic acid esters that do not leave any residual liquid upon firing and are completely decomposed at relatively low temperatures are preferred.

Polymer (A) is prepared by polymerizing monomer components containing addition-polymerizable oxazoline (a) and, if necessary, at least one other monomer (b) using conventionally known polymerization methods such as suspension polymerization and solution polymerization. , emulsion polymerization, etc. The polymer (A) produced by these polymerization methods is usually obtained as a liquid substance dissolved or dispersed in a solvent, but the liquid substance can also be used as it is without separating and removing the solvent.

The inorganic compound particles (B) used in the present invention may be those conventionally used in the production of ceramics.

Although not particularly limited, alumina, silica, magnesia, zirconia, titania, barium titanate, titanium-ugly lead zirconate, silicon carbide and silicon nitride, copper-based ferroskite, cordierite, mullite, festerite, spinel, aluminum nitride, Crystallized glass, borosilicate glass, and quartz glass have particularly excellent compatibility with the polymer (A), and a liquid composition using at least one selected from these has further improved surface smoothness. This method is preferable because a ceramic molded article with high quality can be obtained.

The liquid composition for ceramics of the present invention comprises the polymer (A
) and inorganic compound particles CB). Polymer (A) and inorganic compound particles C in liquid composition
The blending ratio of B) may be within a range conventionally known to those skilled in the art, but in consideration of the surface smoothness of the resulting ceramic molded product, it is usually 1 polymer to too many parts by weight of the inorganic compound particles (B). (A) 1 to 30 parts by weight, preferably 3 to 2 parts by weight
It is preferable that the amount is 0 parts by weight (in terms of non-volatile content).

To prepare the liquid composition for ceramics of the present invention, a solvent that can stably disperse or dissolve the polymer (A) is usually used. Examples of the solvent include water and various organic solvents. However, if the polymer (A) is obtained as a liquid substance dissolved or dispersed in a sufficient amount of solvent to prepare a liquid composition for ceramics, the liquid composition for ceramics may be prepared at the stage of preparing the liquid composition for ceramics. It is not necessarily necessary to separately add a solvent.

The liquid composition for ceramics of the present invention may contain additives in addition to the above-mentioned components. Examples of additives used as necessary include butyral resin, cellulose resin, (meth)acrylic resin, etc. Known binder components such as resins; plasticizers such as dibutyl phthalate and butyl benzyl phthalate; wetting agents such as alkylaryl polyether alcohol and polyethylene glycol ethyl ether; dispersants such as polyhydric alcohol ester polyethers such as glycerin and sorbitan. etc. can be mentioned.

The liquid composition for ceramics of the present invention can be formed into a desired shape by a molding method such as a sheet molding method, a dry press molding method, or an extrusion molding method, and then fired to produce ceramic molded products of various shapes. It can be done as follows.

<Effects of the Invention> The liquid composition for ceramics of the present invention has good surface smoothness because the inorganic compound particles (B) are extremely well dispersed by using the polymer (A). It is possible to produce ceramic molded products with high density and green strength. Therefore, various ceramic molded products obtained using the liquid composition for ceramics of the present invention, such as IC
It can be suitably used as a substrate, an IC package, or a dielectric.

(Examples) Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

In addition, unless otherwise specified in the examples, % indicates weight %, and parts indicate parts by weight.

Reference Example 1 782.4 parts of deionized water and 15% of Hytenol N-08 (manufactured by Daiichi Kogyo Seiyaku ■) were placed in a flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel.
Prepare 128 parts of aqueous solution and add appropriate amount of ammonia water (28%
) to adjust the pH to 9, and heated to 70° C. while slowly flowing nitrogen gas. 64 parts of aqueous solution of potassium persulfate was poured into the solution, followed by 139.5 parts of ethyl acrylate, 436.5 parts of methyl acrylate and 64 parts of 2-impropenyl-2-oxazoline, which had been prepared in advance. The monomer mixture was added dropwise over a period of 3 hours.

During the reaction, nitrogen gas was blown into the reactor to keep the internal temperature at 1°C for 70 parts.After the dropwise addition was completed, the temperature was kept at the same temperature for 2 hours, and then the internal temperature was raised to 80°C and stirring was continued for 1 hour to react. completed. Thereafter, it was cooled to obtain an aqueous polymer dispersion [1] with a nonvolatile content of 39.8%.

Reference examples 2-3. Comparative Reference Example 1 The same operations as in Reference Example 1 were repeated except that the composition of the monomer mixture was changed as shown in Table 1 to prepare aqueous polymer dispersions [2] to [3]. An aqueous dispersion [1'] of a comparative polymer was obtained.

Table 1 Examples 1-3. Comparative Example 1 Alumina (manufactured by Showa Light Metal ■, trade name AL-1603G)
100 parts of water, 40 parts of water, and 20 parts of an aqueous dispersion of the polymer shown in Table 2 were mixed in a ball mill for 24 hours to obtain a liquid composition for ceramics.

After drying this liquid composition at 80 ° C. until the moisture content becomes 0.2% or less, it is filled into a mold, and
, Ot/c/(7) Perform press forming at each press pressure,
A ceramic molded product with a thickness of 3 rall, a width of 10 mm, and a length of 30 mm was obtained. Table 2 shows the measurement results of green density and green bending strength (flexural strength), which is one of the green strengths, of these ceramic molded products.

The measurement method is as follows.

Calculated using the green density quadratic formula.

Weight of molded product Jl (g) Green density (g/cei') = Volume of molded product (Q/) Green bending strength (flexural strength): Using an Instron testing machine,
Measurements were made with a span width of 20 mm and a head speed of 0.5 cts for 1 minute.

Table 2 Reference Example 4 100 parts of ethyl acetate was charged into a four-bottle flask similar to Reference Example 1, and the temperature was raised to 80°C. While blowing nitrogen gas therein, a mixture consisting of 50 parts of ethyl acrylate, 10 parts of butyl acrylate, 20 parts of methyl methacrylate, 20 parts of 2-impropenyl-2-oxazoline, and 1.5 parts of azobisisobutyronitrile was added. was added dropwise from the dropping funnel over 2 hours, and after further holding at 80°C for 6 hours,
It was cooled to room temperature to obtain a polymer solution [4] in an organic solvent with a nonvolatile content of 50.0%.

Reference examples 5-6. Comparative Example 2 The same operations as in Reference Example 4 were repeated except that the composition of the polymerizable monomer mixture in Reference Example 4 was changed as shown in Table 3 to prepare polymer organic solvent solutions [5] to [6]. ] and an organic solvent solution (2') of a comparative polymer were obtained.

Table 1: Ceramic green sheets were obtained by heat drying. The measurement results of the smoothness and green density of these ceramic green sheets are shown in Table 4.

The measurement method is as follows.

Green density: same as Example 1 Smoothness: Measured according to JISBO601.

(Displayed at river m) Table 4 Examples 4 to 6. Comparative Example 2 100 parts of alumina (same as Example 1), 60 parts of a mixed solvent of ethyl alcohol/ethyl acetate/toluene = 1, /2/2, and 20 parts of an organic solvent solution of the polymer shown in Table 4 were added, and the mixture was milled in a ball mill. The mixture was mixed for 24 hours and defoamed using an evaporator to prepare a liquid composition for ceramics. This liquid composition was cast onto a polyester film to a thickness of 2 mm using an applicator. Then, delayed addition at 50'0 for 1 hour, 80°C for 3 hours, and 105°C for 2 hours.

Claims (2)

[Claims] 1. General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1, R_2, R_3, R_4 are each independently hydrogen, halogen, alkyl, aralkyl, phenyl or substituted phenyl group, is an acyclic organic group having an addition-polymerizable unsaturated bond.) A polymer (A) and an inorganic compound obtained by polymerizing a monomer component containing an addition-polymerizable oxazoline (a) represented by A liquid composition for ceramics comprising particles (B). 2. 2. The composition according to claim 1, wherein the polymer (A) is used in an amount of 1 to 30 parts by weight (in terms of non-volatile content) based on 100 parts by weight of the inorganic compound particles (B).