JPH01278558A - Composition for injection molding production thereof and usage thereof - Google Patents

Abstract

PURPOSE:To obtain the title composition capable of reducing the degreasing temperature and shortening the degreasing time in degreasing the resultant forms by incorporating ceramic powder and/or metallic powder with a polyether. CONSTITUTION:A blend comprising (A) 50-99.9 (pref. 70-99.9) wt.% of ceramic powder (e.g., aluminum oxide, silicon carbide) and/or metallic powder (e.g, iron powder, nickel powder), 0.1-100 (pref. 0.1-50) mum in particle size and (B) 0.1-50 (pref. 0.1-30) wt.% of a polyether of the formula (R1 is residue of active hydrogen atom-contg. compound; R2 is H, alkyl, etc.; A is 1-4C alkylene group; n is >=2; m is 1-8), 150-10,000,000 in molecular weight (e.g., polyethylene oxide) is heated and kneaded, and then the resultant composition is put to injection molding and the component B is heated and removed.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to injection molding compositions, methods of manufacture, and methods of use. More specifically, the present invention relates to compositions for injection molding of ceramic powders and metal powders, and methods for producing and using them.

[Prior Art] Conventionally, a methacrylic ester copolymer and an ethylene-vinyl acetate copolymer or a methacrylic ester copolymer and a low-density polyethylene have been used as an injection molding composition, for example, a metal powder injection molding composition. Some are used as binders (for example, JP-A-59-229403).

[Problems to be Solved by the Invention] However, this method requires high temperature and a long time to remove organic matter from the molded article (hereinafter abbreviated as degreasing).

[Means for Solving the Problems] The present inventors have conducted intensive studies to obtain an injection molding composition that lowers the temperature at which molded articles are degreased and shortens the degreasing time, and as a result, they have arrived at the present invention. Na.

That is, the present invention comprises: ceramic powder and/or metal powder (a) and polyether as binder (
An injection molding composition characterized by comprising b); heating and kneading ceramic powder and/or metal powder (a) and polyether (1)! 1Og; and ceramic powder and/or metal powder (a) and polyether (]]
) is a method of using an injection molding composition, which is characterized by injection molding a composition and removing the molded material by heating.

In the present invention, the general formula % formula % (
1) (In the formula, R□ is a residue of a compound containing an active hydrogen atom; R2 is a hydrogen atom, an alkyl group, an aromatic hydrocarbon group or an acyl group; A is an alkylene group having 1 to 4 carbon atoms or an aryl group; It is an alkylene group having 2 to 4 carbon atoms and having a group in its side chain.

n is an integer greater than or equal to 2.

Ill is 1.~8. ).

In the general formula (1), the active hydrogen atom-containing compound of R1 (active hydrogen atom-containing compound constituting the residue of the phonon) is
Water, alcohols such as low molecular weight polyols (ethylene glycol, propylene glycol, 1,3- or 1-
．． 4-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexylene glycol,
chrycerin, trimethylolbutan, pentaesosuri, sucrose) and -hydric alcohols [fats 11/j group (carbon number 1 to 20)
or aromatic-hydric alcohols], phenols such as phenols [such as bisphenol such as bisphenol A] and -hydric phenols [phenol naphthol; alkyl groups (1 to 12 carbon atoms) or Phenols having an aryl group such as ophthylphenol, nonylphenol, dodecylfuconol and phenylphenol/'Kotoeha alkanolamines: aliphatic or aromatic polyamines (ethylene diamine, diethylene hI noamine, etc.) and aliphatic monoamines [monoyo/ Q is a dialkyl (carbon number 1-20) amine].

Among the active hydrogen atom-containing compounds, water and low molecular weight polyols are preferred, and ethylene glycol and propylene glycol are more preferred.

In the general formula (1), the alkyl group in R2 is an alkyl group having 1 to 20 carbon atoms, such as a methyl group, an ethyl group,
Examples include 1-copyl group, butyl group, hexyl group, octyl group and tesyl group. Aromatic degree (e 7J (as a base group, aryl group (phenyl group, naphthyl group, etc.); arylarchel group (benzylno 1!, phenethyl group, etc.); alkylaryl group (otanafuconyl group, nonylphenyl group) ) is ()-. Examples of the ph'yl group include acyl groups derived from carboxylic acids having 2 to 20 carbon atoms.

Among F-techniques 2, preferred are hydrogen atoms and carbon atoms of 1 to 2.
4, more preferably a hydrogen atom, a methyl group, or an ethyl group.

Examples of the alkylene group having 1 to 4 carbon atoms in A include methylene group, ethylene group, propylene group, butylene-Jl (and the like; examples of the alkylene group having 2 to 11 carbon atoms having an aryl group in the side chain include: Examples include phenylethylene group. n A's may be the same or different.

Among them, preferred are ethylene group, propylene group, butylene group, and a group for 01 of ethylene group and propylene group, and more preferred is ethylene group.

11 is preferably 40,000 to 100,000.

111 is preferably 1-3.

-The number of molecular legs of polyether indicated by (1) is usually 1
5() to i,ooo million, preferably 200 to
:i million.

Specific examples of the polyether represented by the general formula (1) include alkylene oxide A-side (carbon numbers 2 to 4) adducts or alkylene oxides (carbon numbers 2 to 4) adducts of the active hydrogen atom-containing compound. Ring polymers [polyethylene oxide (molecular weight usually 1.5 to 10 million), polyethylene oxide (molecular weight usually 200 to 5,000)
, Volite 1 to ramethylene glycol (molecular weight is usually 20
0 to 3,000>, ethylene oxide-propylene oxide copolymers (molecular weight usually 200 to 20,000)] and ring-opening polymers of cyclic polymers [polyoxymethylene (molecular weight usually 3000 to 100,000), etc. ) and mixtures of two or more of these.

, Of the two spatulas, preferably polyethylene oxide,
These are polypropylene oxide→noyl and ethylene oxide do-propylene oxide copolymers, and polyethylene oxide is more preferable.

Ceramic powders include oxides (aluminum oxide,
Silicon oxide, zirconium oxide, titanium oxide, Murai 1, Coop Yerai 1~, beryllium oxide, magnesium oxide, barium titanate, etc.), carbides (silicon carbide, boron carbide, aluminum carbide, tungsten carbide, titanium carbide, zirconium carbide, carbide) hafnium,
chromium carbide, vanadium carbide, carbon, etc.), nitrides (silicon nitride, aluminum nitride, boron nitride, titanium nitride, etc.), silicides (molybdenum disilicide, etc.), sulfides (
cadmium sulfide, zinc sulfide, etc.) and mixtures of two or more of these.

The particle size of the ceramic powder is usually 0.01 μm to 100 μm, preferably 0.1 μm to 50 μm.

Metal powders include iron powder (carbonyl iron powder, atomized iron powder, reduced iron powder, etc.), nickel powder (carbonyl nickel powder, etc.), aluminum powder, copper powder, titanium powder, zirconium powder, zinc powder, chromium powder, molybdenum powder. powder, tungsten powder, beryllium powder, germanium powder, etc., and alloy powders (iron-butyl alloy powder, stainless steel copper powder, iron-
Metal powders such as silicon alloy powder, iron-boron alloy powder, etc.) and these 2'M! Examples include mixtures of the above. In addition to these, non-metallic powders such as silicon powder and boron powder can also be included.

The particle size of the metal powder is usually 0.1 μm to 100 μm, preferably 0.1 μm to 50 μm.

Mixtures of ceramic and metal powders (tungsten carbide-cobalt, aluminum oxide-aluminum oxide, etc.) can also be used. This mixture includes a mixture of ceramic powder and metal powder and an alloy of ceramic powder and metal powder.

The grain size of this alloy is usually 0.1 μm to 100 μm,
Preferably it is 0.1 μrn to 50 μm.

A plasticizer, a lubricant, a surfactant, etc. can be added to the composition of the present invention, if necessary.

As a plasticizer, Nisder phthalate (dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-n-octyl phthalate, di-2 phthalate)
-ethylhexyl, diinnonyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, butylbenzyl phthalate, etc.), aliphatic-basic acid esters (butyl oleate, glycerin monooleate, etc.), aliphatic dibasic acids Esters (dibutyl adipate, di-n-hexyl adipate, dioctyl adipate, di-2-ethylhexyl adipate, di, isodecyl adipate, dialkyl adipate (dihexyl, dioctyl, didecyl, etc.), dibutyl diglycol adipate, azelain) di-2-ethylbutyl acid, di-2-ethylhexyl azelaate, dibutyl sebacate, di-2-ethylhexyl sebacate, dioctyl sebacate, etc.), dihydric alcohol ester (diethylene glycol dibenzoate I, l-diethylene glycol) Di-2-ethylbutylar 1~, etc.), oxyacid esters (methyl acetyl ricinoleate, butyl acetyl ricinoleate, butylphthalyl butyl glycolate, acetyltriedyl citrate, acedel I helibutyl citrate, etc.), phosphoric acid esters (phosphoric acid 1) ~liezyl, tributyl phosphate, trioctyl phosphate, 1-lichloroethyl phosphate, helicresyl phosphate, 1-libutoxyedyl phosphate, 1-helidic 1-cob Y-copyl phosphate, 1-lis-(β-chloropropyl phosphate) ), triphenyl phosphate, ocdyldiphenyl phosphate, trisisopropylphenyl phosphate), maleic acid esters (dibutyl maleate, di-2-ethylhexyl maleate, etc.), dibdel fumarate, 1-realkyl trimellitate ( The number of carbon atoms in alkyl is usually 4 to 11), 1 helimeric acid, 1 helic acid, 2-ethylhexyl, polyoxyalkylene benzoate (polyoxyethylene benzoate, etc.), polyester plasticizer (polyadipate propylene glycol) ), epoxy plasticizer (epoxy fatty acid ester), stearic acid plasticizer,
Chlorinated paraffin and a mixture of these two divine tools -1-'Nakaaa (Surareru).

Among these, preferred are fucuric acid esters, aliphatic dibasic acid esters, and polyoxyalkylene benzoic acid esters.

As lubricants, aliphatic hydrocarbons (liquid paraffin, microcrystalline wax, natural paraffin wax, synthetic paraffin, polyolefin wax and their partial oxides, fluorides, chlorides, etc.), higher aliphatic alcohols ( lauryl alcohol, stearyl alcohol, oleyl alcohol, mixed fatty alcohols, etc.), higher fatty acids [lauric acid, stearic acid, mixed fatty acids (fatty acids from beef tallow, fish oil, coconut oil, soybean oil, rapeseed oil, rice bran oil, etc.) ], fatty acid amides (oleic acid amide, stearic acid amide, medilene-bis-stearamide, ethylene-bis-stear 1 coamide, etc.), metal soaps (barium stearate, calcium stearate, zinc stearate, aluminum stearate) , magnesium stearate), fatty acid Nisdel [-higher fatty acid esters of alcohols (butyl oleate, etc.), higher fatty acids of polyalcohols [
parts] esters (such as glyceryl monooleate), montan wax, etc.], aliphatic amines [primary amines such as C5-3o alkyl amines (stearylamine, etc.),
Secondary and/or tertiary amines, e.g. Japanese Patent Application No. 63=1
-2- those described in the specification of No. 136380], and mixtures of two or more of these. Among these, preferred are aliphatic hydrocarbons, higher fatty acids, fatty acid esters, montan wax, and aliphatic secondary and/or tertiary amines.

In addition, as a surfactant, for example, US Pat. No. 113
Anionic surfactant (dodecylbenzenesulfonate, polyoxyethylene (4) described in No. 314/17)
nonylphenyl ether sulfate, etc.).

Nonionic surfactants (polyoxyethylene (4) stearylamine, stearic acid mono- and/or jetanolamine 1~, etc.), cationic surfactants (lauryl 1~limethylammonium chloride 1~) 4 amphoteric Examples include surfactants (stearyldimethylcarbo-A-dimethylbetaine, etc.), and mixtures of two or more thereof.

In the composition of the present invention, the content of each component (a) is usually 50 to 99.9%, preferably 70 to 999%, based on the weight of the composition. If (a) is less than 50%, the strength of the molded body and the degreased body after degreasing will decrease, and the strength will be 99.
If it exceeds 9%, the moldability of the molding composition decreases.

(1)) is usually o, i~50%, preferably 0.1~3
It is 0%. If (1)) is less than 0.1%, the moldability of the molding composition decreases. If it exceeds 50%, the strength of the degreasing ability after degreasing will decrease.

In the present invention, in addition to (a) and page b), if necessary, a small proportion of a solvent-soluble thermoplastic resin (C) [(b)
Less than 30% based on the combined weight of and (C).

It can be used preferably at less than 20%, especially at most 18%. (C) is patent application No. 61-266482.
Examples include those described in the specification of the No.

The remainder (plasticizer, lubricant, surfactant, etc.) is usually O~40
%.

The composition of the present invention comprises (a) and (b) optionally (C)
and the remainder are mixed and dried if necessary, then heated, kneaded, cooled and pulverized (crushed), and if necessary formed into pellets.

In -1-, mixing is done using a V-type mixer, Henschelmi A
- In the case of laser, the mixing temperature is usually O~100°C1I
Preferably at 0-50°C, mixing time is usually 10 minutes.
It is carried out for 6 hours, preferably 30 minutes to 2 hours. In the case of a ball mill, the dry method is a wet method, and the mixing temperature is usually O ~
The mixing time is usually 6 hours to 72 hours, preferably 6 hours to 36 hours.

Dry soot is carried out in air or in an inert gas atmosphere, under normal pressure or reduced pressure, and under heating and/or hot air.

For mixing, use a normal kneading machine such as a Pamberimi type mixer, plus 1~mil, Nigu, pressurized Nigu, roll mill, or screw extruder, and the mixing temperature is usually JJO~300.
'C1 is preferably 50 to 200'C, and temperature control is carried out by constant temperature, temperature increase, temperature decrease, etc. Kneading time is usually 1
It is carried out for 0 minutes to 10 hours, preferably 10 minutes to 3 hours.

The kneading method is to mix everything at once,
A method of mixing by kneading a part and then adding the rest [(1
)), (c), etc. are added and kneaded, and then (il) is added and kneaded. Prepare (a), then (b),
(C) etc. and kneading], etc.

Using the composition of the present invention, a sheet 1 or a complex-shaped object is formed by injection molding, extrusion molding, press molding, etc., degreased, sintered, and processed as necessary to form a molded product.

For molding, a normal molding machine such as an injection molding machine, an extrusion molding machine, or a press molding machine is used, and the molding pressure is usually 10 to 20,000.
kK/Iτ, preferably 20-10.000kK/
a (, the molding temperature is usually 20 to 300'C2, preferably 5
Perform at 0-200°C.

11 (A fat is usually heated at 1 to 500° under reduced pressure, normal pressure, or increased pressure in an oxidizing, reducing, or inert gas atmosphere.
C/l+r, preferably 1 to 200' C/llr heating rate to 200 to 500 °C, 200 to 50
This is carried out by holding at 0'C for usually 10 hours or less, preferably 5 hours or less.

Sintering is usually performed using an oxidizing, reducing or inert gas mixture;
600℃~2.50 under reduced pressure, normal pressure or increased pressure under ambient atmosphere
Perform at 0°C.

[Examples] The present invention will be further described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In Examples and Comparative Examples, parts are parts by weight, and the average particle size of European alumina powder is 1 μm or less, and the average particle size of stainless steel powder is 10 μrTl.

Example 1 Using a mill to Labo Plus 1, 80°C, rotor rotation 1
Polyethylene oxide (molecular weight 10
Alumina powder was charged and kneaded for 30 minutes at 80°C and a concave rotor speed of 501 to 11. This kneaded material was pulverized to obtain a composition for injection molding (1). The blending ratio is shown below.

Alumina powder 100 parts Polyethylene oxide (molecular weight 100,000) 20.0 parts Example 2 Kneading and pulverization were carried out in the same manner as in Example 1, and the following t1
A single injection molding composition (2) of the present invention was obtained.

Stainless steel powder 100 parts Polyethylene oxide (molecular weight 20,000) 10.0 parts Example 3 Using Labo Plus H Mill, 130°C, rotor speed 81
After charging and melting phthyl remethacrylate and polyethylene oxide (molecular weight 200,000), gradually add alumina powder and montan wax, and after adding the entire amount, heat at 130°C in a rotor concave. The mixture was kneaded for 30 minutes at a rotation speed of 5 rpm. This kneaded material was pulverized to obtain a composition for injection molding (3). The blending ratio is shown below.

Polybutyl methacrylate 3.2 parts Polyethylene oquinide (molecular weight 200,000) 15.0 parts Monkun wax 1.6 parts Alumina powder 100 parts Example 4 and Comparative Example 1.2 Kneaded in the same manner as Example 3 The injection molding composition (4) of the present invention having the following composition and #r of Comparative Example were prepared by pulverization.
1 compound acid Jul and (b) obtained.

Example t1 Stainless steel powder Ioo part Polybutyl methacrylate 1.6 parts Boliena
To A-Zai 1 (molecular weight: 200,000) 7.5 parts Monkun wax 1.0 parts Comparative example 1 Alumina powder 100 parts Polybutyl methacrylate 6.5 parts Enalene-vinyl acetate copolymerization (4 < 5.5 parts Phthalate) Dibutyl acid 2.5 parts Monkun wax 2.9 parts jL comparative example 2 Sudenless powder 100 parts Polybutyl methacrylate 3.2 parts Ethylene-vinyl acetate copolymer 2.8 parts wax
1.3 parts Examples 5-8, ratio 1 bite Examples 3-6 Examples]. ~4 compositions (1) to (4) of the present invention and compositions (a) and (b) of Example 1.2 were molded at an injection pressure of 1,500 using an injection molding machine (screw type).
kg/αK and injection molding at a molding temperature of 150'C to obtain an injection molded article.

-Kei 9- This injection molded body is degreased and sintered to obtain a molded product.

The occurrence of microcracks (MC>), bulk specific gravity, and relative density (%) of this molded article were investigated.The results are not shown in Table 1-.

Table 1, Note) *Degreasing conditions ■: Maximum degreasing temperature 300'C Degreasing time 32 hours; ■: Maximum degreasing temperature 400'C Degreasing time 52 hours.

Citrus sintering A. In the air, 1. GOO'CX 2 hours; oral, under reduced pressure, 1,250'CX 2 hours.

Micro crack occurrence status in April ○: No occurrence; ×: Occurrence.

[Effect of the invention] The composition of the present invention has the following effects.

(2) The composition of the present invention can lower the degreasing temperature during moldability degreasing and shorten the degreasing time.

■ Almost no impurities such as carbon remain in the fired product.

■ A molded body with high density can be obtained by injection molding. Hyakuhyo is given the title.

(■ Molded articles produced by applying the composition of the present invention have a high relative density and high strength.

(2) In addition to the effects described in item 1, when using a saw with the composition of (a) and (1)), deformation during degreasing and direct application of force can be reduced.

I; (-Nowadays, degreasing complex-shaped injection molded bodies made of ceramic powder or metal powder requires high temperatures and a long time.) This is because organic substances such as binders rapidly decompose and emit gas. This was an unavoidable measure to prevent cracking of the molded product caused by this.The composition of the present invention can be degreased at a relatively low temperature, so the degreasing time can be shortened.

Claims (1)

[Claims] 1. An injection molding composition comprising ceramic powder and/or metal powder (a) and polyether (b) as a binder. 2. The composition according to claim 1, wherein the molecular weight of (b) is 1.5 to 10 million. 3. (b) is a general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) (In the formula, R_1 is the residue of a compound containing an active hydrogen atom; R_
2 is a hydrogen atom, an alkyl group, an aromatic hydrocarbon group, or an acyl group; A is an alkylene group having 1 to 4 carbon atoms or an alkylene group having 2 to 4 carbon atoms having an aryl group as a side chain. n is an integer of 2 or more. m is 1-8. ) Claim 1 is a compound represented by
Or the composition according to 2. 4. A method for producing an injection molding composition, which comprises heating and kneading ceramic powder and/or metal powder (a) and polyether (b). 5. Injection molding a composition consisting of ceramic powder and/or metal powder (a) and polyether (b)
) is removed by heating.