JPS6212658A - Ceramic binder - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a ceramic binder, and more specifically, for example, when manufacturing ceramic and wax products by injection molding, moldability, patternability, and degreasing are The present invention relates to a ceramic binder that makes it possible to eliminate cracking, expansion, etc. of molded products during molding.

[Prior art and its problems] Conventionally, as a manufacturing method for ceramic products, a powdered ceramic raw material and a binder are mixed to form a clay having plasticity, and this clay is shaped and then fired. can be mentioned.

Conventional binders are made from a mixture of a base agent made of a plastic resin and an auxiliary agent made of an organic compound such as naphthalene, anthracene, ginger, or phenanthrene. Become.

However, when such a binder is used for injection molding, it is difficult to mold the clay under relatively mild conditions, and molding properties are poor when molded under high temperature conditions. The degreasing properties of the product are poor. Due to this poor degreasing property, when the molded product is fired, cracks, voids, cracks, etc. occur on the surface of the ceramic molded product, and the molded product expands during firing, making accurate molding difficult.

This invention has been made based on the above problem.

That is, the purpose of the present invention is to reduce the amount of residual binder and thereby eliminate the occurrence of cracks, voids, fissures, expansion, etc., and to make injection molding durable under mild conditions when performing injection molding. Our goal is to provide a ceramic binder that can

[Means for solving the above problems] The outline of the present invention for solving the above problems is as follows: A cyclopentadiene monomer and a vinyl substituted yi aromatic hydrocarbon 1
copolymerization reaction product (A) with cyclopentadiene monomer and vinyl-substituted aromatic hydrocarbon (hydrogenated product (B) of polymerization reaction product, cyclopentadiene monomer and unsaturated dicarboxylic acid) or a copolymerization reaction product (C) with an anhydride thereof, and a hydrogenated product (D) of a copolymerization reaction product of a cyclopentadiene monomer and an unsaturated dicarboxylic acid or anhydride thereof. 14, and a ceramic substance.

Examples of the cyclopentadiene monomer include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, or divalent forms thereof, E1
Examples include body, two-stitch body, etc.

Examples of the vinyl-substituted aromatic hydrocarbon include styrene, α-methylstyrene, vinyltoluene, and impropenylbenzene.

Further, examples of the unsaturated dicarboxylic acid include maleic acid, citraconic acid, itaconic acid, etc., and examples of the unsaturated dicarboxylic acid anhydride include anhydrides of the various unsaturated dicarboxylic acids described above.

A copolymerization reaction product of a cyclopentadiene monomer and a vinyl-substituted aromatic hydrocarbon (hereinafter referred to as (A
) It? , sometimes abbreviated as minute. ) can be obtained by a copolymerization reaction of the cyclopentadiene monomer and the vinyl-substituted aromatic hydrocarbon.

An example of a preferred method for producing component (A) will be described below.

The cyclopentadiene-based 1,000-nomate and the vinyl-substituted aromatic hydrocarbon are mixed in an aromatic hydrocarbon solvent such as xylene, and heated at a temperature of 220 to 320°C, preferably 250 to 30°C.
Component (A) can be obtained by removing the solvent after 6 reactions of heating at 0° C. for 1 to 8 hours, preferably 1.5 to 5 hours. In addition, as the component (A), products produced by other methods than those described above can also be used. Note that the structure of component (A) obtained by such a production method is not yet established, and it is presumed to be a copolymer of a cyclopentadiene monomer and a vinyl-substituted aromatic 15-carboxylic acid. It may also contain homopolymers of cyclopentadiene monomers.

In any case, the preferred component (A) in the present invention has a median content of monomers derived from cyclopentadiene monomers of 80 to 30 @B%, preferably 60 to 40%. %
and has a softening point of 40 to 160°C, preferably 70-1
The temperature is 40℃, and the bromine number is 30 to l Og/100g.
, preferably 40-70g/long.

In addition, a preferred component (A) from the viewpoint of raw material components is a copolymerization reaction product obtained by copolymerizing cyclopentadiene and styrene.

Hydrogenated product of copolymerization reaction product of cyclopentadiene monomer and vinyl-substituted aromatic hydrocarbon (hereinafter referred to as (B))
Sometimes abbreviated as component. )teeth.

It can be produced by hydrogenating the Ili component (A).

A preferred method for producing component (B) is shown below.

Ni, Pd, Co in solvents such as hydrocarbons such as cyclohexane or without the use of solvents.

In the presence of pt, Rh, system catalyst, temperature 130-300℃
The component (A) is brought into contact with hydrogen while heating, preferably at 150 to 260° C., for 1 to 7 hours, preferably 2 to 5 hours. Since the structure of the component (A) itself is not established, the resulting component (B) contains cyclopentadiene monomers and vinyl-substituted aromatic hydrocarbons in addition to the hydrogenated product of the copolymerization reaction. May contain hydrogenated homopolymers of pentadiene monomers.

In any case, considering (B) which is preferable in this invention,
The content of seven units derived from cyclopentadiene is 80 to 30% by weight, preferably 60 to 40 Ti,'
6% Tear'J, Softening=:, <b<s o ~t 65
C, preferably 75 to 150 C, the odor value is more than 3 and 7 or more F, and the degree of hydrogenation of the aromatic ring is 0 to 60%.

In addition, from the viewpoint of raw material components, preferred (B) rR, is a hydrogenated product of a Jt-ff1 reaction product obtained by copolymerizing cyclopentadiene and styrene.

A copolymerization reaction product of a cyclopentadiene monomer and an unsaturated dicarboxylic acid or its anhydride (hereinafter sometimes abbreviated as component (C)).

It can be produced by copolymerizing the cyclopentadiene monomer and the unsaturated dicarboxylic acid or its anhydride.

A preferred method for producing this (C) rrt component is the same as the method for producing component (A) above, except that the unsaturated dicarboxylic acid or its anhydride is used instead of the vinyl-substituted aromatic hydrocarbon. Detailed explanation will be omitted.

Although this component (C) is presumed to be a copolymer of a cyclopentadiene monomer and an unsaturated dicarboxylic acid or its anhydride, similar to the It component (A) above, it is a homopolymer of the cyclopentadiene monomer. It has a summability that also includes merging.

In any case, the preferred (C) component in the present invention is that the content of monomer units derived from cyclopentadiene monomers is 90 to 30% by weight, preferably 80 to 40% by weight, and unsaturated dicarboxylic acid or the content of seven units derived from its anhydride is 10 to 70% by weight, preferably 2
0 to 60% by weight, a softening point of 60 to 200°C, preferably 90 to 180°C, and a bromine number of 10 to 200g
/100g, preferably 50-130g/100
g, and the acid value is Zoo to 500 mgKOH/g, preferably 200 to 450 mgKOH/g.

A preferred component (G) from the viewpoint of raw material components is a copolymerization reaction product obtained by copolymerizing cyclopentadiene and maleic anhydride.

The hydrogenated product of the Jt-m reaction product of a cyclopentadiene monomer and an unsaturated dicarboxylic acid or its anhydride (hereinafter sometimes abbreviated as component ([1)) is the component (C). It can be produced by hydrogenating.

A preferred method for producing this (D) ti is the above-mentioned (A)
The above (B) except that the above (C) component is used instead of the above component (B).
) The detailed explanation will be omitted since it is almost the same as the method for producing the component.

The obtained component (D) is the same as the dt component of (A) above.

In addition to hydrogenated products of copolymers of cyclopentadiene monomers and unsaturated dicarboxylic acids or their anhydrides, there is a possibility that hydrogenated products of homopolymers of cyclopentadiene monomers are included.

In any case, the preferred component (D) in this invention is one containing seven units derived from a cyclopentadiene monomer.
The rate is 90-30%, preferably 80-40% per 1J%.
, the content of one monomer unit derived from an unsaturated dicarboxylic acid or its anhydride is 10 to 70% by weight, preferably 20 to 60% by weight, and the softening point is 60 to 200°C,
Preferably, the temperature is Zoo-190°C, and the bromine number is 1O to Z
o.

g/100g, preferably 15-50 g/10
0 g, and the acid value is ioo to 500 gKOH/g, preferably 150 to 400 gKOH/g.

A preferred component (b) from the viewpoint of raw material components is a hydrogenated product of a copolymerization reaction product obtained by copolymerizing cyclopentadiene and maleic anhydride.

The ceramic binder according to the present invention includes the above (A)
~ (D) Any one of the components may be used,
Moreover, any two or more types may be used in combination.

Next, the ceramic binder according to the present invention includes at least one selected from the group consisting of components (^) to (D) above as a binder main material, and a binder auxiliary agent that is a sublimable substance. It is something that

Examples of the binder auxiliary include naphthalene, anthracene, phenanthrene, camphor, adamantane, trimethylene norbornane, and among these, naphthalene, allethracene, adamantane, endo-trimethylene norbornane, etc. are preferred.

Combination of the binder agent and the binder auxiliary agent; 1
In general, the amount of the binder auxiliary agent is 0.5 to 15 f[) parts, preferably 2 to 8 times darker parts, based on the ceramic raw material ioo@B part, although it differs depending on the type of ceramic raw material.

The ceramic binder according to the present invention may further contain additives such as a plasticizer and a lubricant in addition to the binder main agent and the binder auxiliary agent.

Examples of the plasticizer include diethyl phthalate, dibutyl phthalate, dioctyl phthalate, fatty acid ester, etc., and examples of the lubricant include aluminum stearate, magnesium stearate, diglycol stearate 2 crumbs, mineral oil, etc. It will be done.

However, in the case of injection molding, the clay in which the ceramic binder according to the present invention is blended with the raw material ceramics can be molded by both the binder r agent and the binder auxiliary agent without the need to specifically blend the plasticizer and the lubricant. but,
Its heat flow properties are good, and the surface appearance of the injection molded product obtained is good.

A ceramic binder obtained from the binder main agent and the binder auxiliary agent is blended with the ceramic raw material to form clay.

In this case, the ceramic raw materials include, for example, non-plastic raw materials such as silica, porcelain stone, pottery stone, lithium ore, sillimanite, alumina, zirconia, silicon carbide, silicon nitride, and kaolin, plastic viscosity, frog's eye clay, fire clay, etc. - Examples include plastic raw materials such as clay.

It goes without saying that these ceramic raw materials are subjected to treatments such as pulverization, wet mixing, sieving, and removal of impurities in the same manner as in the production of ordinary ceramic molded products before being blended with the ceramic binder according to the present invention. stomach.

The ceramic raw material and the ceramic binder according to the present invention can be blended by kneading, and the mixing conditions are, for example.

0.5 at 80-150℃, preferably 100-120℃
-3 hours, preferably 0.5-1 hour.

The cross-wire can be carried out using, for example, a ball mill, a plasto mill, a heating niegoo, a cross-wire machine that applies shearing force simultaneously with co-kneader heating, or the like. In addition, as a blending procedure, the binder base agent and the binder auxiliary agent may be mixed together to obtain a ceramic binder, and then this ceramic binder and the ceramic raw material may be blended.
Furthermore, the ceramic raw material, the binder main agent, and the binder auxiliary agent may be blended simultaneously or sequentially. However, if a good dispersion state of the ceramic binder in the clay is to be achieved, A compounding procedure that involves blending is preferred.

The resulting clay can be formed using conventional ceramic molding methods such as the soft mud method, semi-soft mud method, plastic pressure molding method, mechanical potter's wheel method, roller machine method, extrusion molding method, hard mixing method, isostatic pressing method, etc.
It can be molded into a predetermined shape by a rubber press method, a tamping method, a high temperature pressure molding method, an injection molding method, or the like. Among these various molding methods, the injection molding method is particularly preferable because the clay containing the ceramic binder according to the present invention can be injection molded well even at low injection molding pressures. This is because it is possible to improve degreasing properties after injection molding.

To further explain product production by injection molding, the ceramic raw material and the ceramic binder according to the present invention are usually heated and kneaded to obtain a clay, and the clay is granulated with a roll, pelletized with a pelletizer, or mixed with a mixer. Pellets or powder as a molding material are obtained by pulverization by cold pulverization with a roller or by pulverization by cold extrusion into a sheet shape with a roll. Then, this molding material is subjected to a plunger type, pre-plastic type, or screw-in-line type injection molding machine to obtain a primary molded body.

Injection molding is performed, for example, at 120-200°C and 300-80°C.
It can be carried out under 0Kg/crn'c7) conditions.

The ceramic/x binder is removed from the primary molded body by degreasing treatment. Degreasing treatment is usually carried out at 20 to 400°C.
This can be done by heating for 20 to 40 hours. It is noteworthy that in this degreasing process, the ceramic binder of the present invention is removed in a much shorter time than conventional ceramic binders, and the amount remaining is extremely small.

After the degreasing treatment, a ceramic molded product can be obtained by firing the next molded product.

[Effects of the Invention] The ceramic binder according to the present invention is made by blending a specific compound into a specific binder base material as a binder auxiliary agent. # Ceramic products with beautiful surfaces free of cracks and voids.
It can be molded with good properties, and the formability of the molded product from the mold is also good. Moreover, it is possible to produce a ceramic product with a reduced amount of residual ceramic binder.

In particular, when this ceramic binder is used in clay for injection molding, the injection molding pressure can be lowered, the degreasing time can be shortened, and the amount of ceramic binder remaining after degreasing can be reduced to a negligible level. can. therefore,
The surface of the ceramic molded product, which is degreased after injection molding and then fired, is very beautiful.

[Examples] Next, the present invention will be explained in more detail by showing examples and comparative examples of the present invention.

(Production of component (A)) Into a polymerization reaction vessel equipped with a stirrer and purged with nitrogen, xylene (solvent) lOOg, cyclopentadiene 100g, and styrene 100g were charged, heated to 260°C, and stirred. The copolymerization reaction was carried out for 2 hours.

After the reaction is completed, xylene is removed and 180g of cyclopentadiene-styrene is combined to form a reaction product of 1! ) 7',
The softening point of this cyclopentadiene-styrene copolymerization reaction product is 91"C, the content of styrene as a monomer unit is 50% by weight, and the bromine number is 56g/1.
00g, the acid value was 1 gKOH/g or less, and the Gardner hue was 8.

This cyclopentadiene-styrene copolymerization reaction product is indicated by ■ in Table 1.

(Preparation of component (B) 5a) The above (A) 1 was placed in a reaction vessel equipped with a stirrer and replaced with nitrogen.
Cyclopentadiene-styrene obtained in 5 minutes of production (100 g of polymerization reaction product and cyclohexane (solvent))
g and 5 g of Pd catalyst (supporting 0.5% by weight of Pd metal), hydrogen was injected under pressure to give 30 K g/c, and the mixture was heated to 200°C and hydrogenated for 4 hours with stirring. The reaction was carried out.

After the reaction was completed, the solvent, catalyst, etc. were removed to obtain 100 g of a hydrogenated cyclopentadiene-styrene copolymerization reaction product.

This hydrogenated product has a softening point of 109°C, a bromine number of 5.1 g/100 g, and a degree of aromatic ring hydrogenation of 3.
4%, and the Gardner hue was 1 or less. In addition,
The acid value was 1 mgKOH/g or less.

The hydrogenated product of this cyclopentadiene-styrene copolymerization reaction product is indicated by ■ in Table 1.

(Manufacture of component (C)) In a polymerization reaction vessel with a stirrer purged with nitrogen.

40g of xylene (soluble fi) and 100g of cyclopentadiene
g and 35 g of maleic anhydride.

The mixture was heated to 260° C. and co-permeation reaction was carried out for 3 hours while stirring.

After the reaction was completed, xylene was removed to obtain 127 g of a cyclopentadiene-maleic anhydride copolymerization reaction product. The softening point of this cyclopentadiene-maleic anhydride copolymerization reaction product is 142°C, the content of cyclopentadiene as a monomer unit is 75 tons, and the nominal price is 64 g and 7100 g. , acid value is 233mgKO
H/g, and the Gardner hue was 18 or higher.

In addition, this cyclopentadiene-maleic anhydride copolymerization reaction product is indicated by ■ in Table 1.

(Production of component (D)) In a reaction vessel equipped with a stirrer and replaced with nitrogen, 100 g of the cyclopentadiene-maleic anhydride copolymerization reaction product obtained in the production of component (C) and 1 liter of tetrahydrofuran (solvent) were added.
ong and 5 g of Pd catalyst (supporting 0.5i11:% of Pd metal), hydrogen was press-injected to give 30 kg/CG, and the mixture was heated to 200°C and hydrogenated for 3.5 hours with stirring. The reaction was carried out.

After the reaction is completed, the solvent, catalyst, etc. are removed to obtain hydrogenated product 10 of the cyclopentadiene-maleic anhydride copolymerization reaction product.
1g was obtained.

This hydrogenated product has a softening point of 158°C, an odor value of 16 g/100 g, and an acid value of 230 gKOH.
/g, and the Gardner hue was 16.

In Table 1, the hydrogenated product of this cyclopentadiene-maleic anhydride copolymerization reaction product is indicated by ■.

(Examples 1 to 7, Comparative Examples 1 to 4) Ceramic 2 having the types shown in Table 1 and the characteristics shown in Table 2
At the compounding site shown in Table 1, the sugar raw materials, the binder main ingredients and binder auxiliary agents of the types shown in Table 1 were kneaded at 100±10°C for 30 minutes using a Laboplast Mill (the torque at this time was 150 kg). @cm)l,ta.

Next, the kneaded material was pulverized using a single manual press, and then further ground into a lump having a diameter of 5 to 7 mm.

This lump was molded using an injection molding machine [manufactured by Yamaguchi Seiki Co., Ltd.].

A set of vertical plungers] was used to mold the piece shown in FIG. 1 under the molding conditions shown in Table 1.

This piece-shaped object was degreased under the degreasing conditions shown in Table 1, and then heated to 1620°C (+ft temperature at Zoo°C/hour).
It was fired to make ceramic products.

Table 1 shows the evaluation of the appearance of the ceramic product (based on 1 visual inspection).

[Brief explanation of drawings]

FIG. 1 is a perspective view showing a top-shaped article molded in an embodiment of the present invention. Patent applicant: Idemitsu Petrochemical Co., Ltd. Figure 1

Claims (3)

[Claims] (1) Copolymerization reaction product of a cyclopentadiene monomer and a vinyl-substituted aromatic hydrocarbon (A), hydrogenated product of a copolymerization reaction product of a cyclopentadiene monomer and a vinyl-substituted aromatic hydrocarbon (B) , a copolymerization reaction product (C) of a cyclopentadiene monomer and an unsaturated dicarboxylic acid or its anhydride, and a hydrogenated product (C) of a copolymerization reaction product of a cyclopentadiene monomer and an unsaturated dicarboxylic acid or anhydride thereof. A ceramic binder comprising at least one member selected from the group consisting of D) and a sublimable substance. (2) The ceramic binder according to claim 1, wherein the sublimable substance is at least one selected from the group consisting of anthracene, naphthalene, adamantane, and endo-trimethylenenorbornane. (3) The ceramic binder according to claim 1 or 2, which is used in clay for injection molding.