JPS6171151A - Peroxide composition for casting mold - Google Patents

Abstract

PURPOSE:To improve safety and to reduce cost by incorporating a dilution stabilizing agent adjusted to uniform quality by a solubilizing agent into a titled compsn. and specifying the ratios of ketone peroxide, dilution stabilizing agent, solubilizing agent and water at specific weight %. CONSTITUTION:At least one kind of alicyclic group ketone of 3-8C or alicyclic group ketone of 6-10C is oxidized by hydrogen peroxide water in the presence of an acid catalyst to prepare ketone peroxide. The keton peroxide is solubilized by the solubilizing agent without separating the water during or after the production thereof. A water soluble monocarboxylic acid or polyhydric carboxylic acid is used for the solubilizing agent. Oleic acid, dimethyl phthalate, etc. are used for the dilution stabilizing agent. The component ratios are specified to 35-60% ketone peroxide, 5-40% water, 10-40% dilution stabilizing agent and 5-40% solubilizing agent. The safety is improved and the cost is reduced by the above-mentioned method.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention is an oxidizing agent used when forming a mold by adding sulfur dioxide to a granular refractory aggregate mixture to which an acid-curable resin and an oxidizing agent have been added. This is related to drugs. More particularly, the present invention relates to certain aqueous organic peroxide compositions used as a heat treatment for the hardenable molds.

[Conventional technology]

Conventionally, for high-speed mold production applications such as automotive castings, the cloning method, in which novolac-type phenolic resin is used as a binder and heat-cured, or the hot-box method, in which liquid phenolic resin or furan-based resin is heat-cured, have been widely used. It has been used extensively. All of these are 200℃~5
Usually, glazes are fired and hardened at 00°C, which causes problems such as energy consumption, hardening time, distortion of molds, poor dimensions of castings due to deformation, and working environment.

In recent years, a molding method that has improved these drawbacks has been to inject gaseous or ecosol-like substances at room temperature to form H-shaped molds.
)r The MV4 cold box method is attracting attention and becoming popular.

As a cold box method, there is a urethane-based cold box method in which curing is performed using a polyol compound and a polyincyanate as a binder and a tertiary amine as a catalyst. However, in the urethane cold box method, even if the granular refractory mixture containing polyol and polyincyanate is left to stand, the curing reaction proceeds gradually, resulting in a short pot life of the mixture, or problems such as drop defects, gas defects, etc. There are drawbacks such as many casting defects. Another cold box method currently available is an acid curing cold box method in which an acid curing resin and an oxidizing agent are added to granular refractories, and then sulfur dioxide is blown into the refractory to form a mold.

[Problem that the invention seeks to solve]

In this method, the curing reaction does not proceed unless the granular refractory mixture and sulfur dioxide come into contact with each other, so the pot life of the mixture is long. Since it is used as a binder, it has advantages such as fewer defects in castings.

However, this acid-curing cold box method requires the use of an expensive organic peroxide as an oxidizing agent, and also has the drawback of concerns about the stability of the organic peroxide. Peroxide is being sought.

Hydrogen peroxide is also used as a cheap and highly safe peroxide, but hydrogen peroxide is decomposed by alkaline earth metal oxides and other impurities contained in granular fire-resistant aggregate. However, the usable time after mixing a mixture obtained by adding and kneading a resin and peroxide to a fire-resistant aggregate, the so-called pot life, is short, making it practically unusable.

[Means for solving problems]

Under such circumstances, as a result of intensive research, the present inventor has arrived at the invention of a peroxide composition for curable molds that is inexpensive, highly safe, and has excellent performance. A peroxide composition used as an oxidizing agent when manufacturing a mold by injecting gaseous or aerosolized sulfur dioxide into a granular refractory aggregate mixture to which a curable resin and an oxidizing agent have been added, The present invention relates to a peroxide composition for molds, which is a hydrous ketone peroxide composition containing a dilution stabilizer homogeneously solubilized with a solubilizer.

Normally, ketone peroxide compositions are made by using mineralized minerals such as sulfuric acid in hydrogen peroxide solution as a catalyst to produce aliphatic, alicyclic ketones and aliphatic,
A non-aqueous peroxide composition produced by dropping an aromatic dibasic acid diester as a carrier agent under cooling, separating the aqueous layer after the reaction, neutralizing, washing, drying and purifying the non-aqueous layer. It is. This product has a complicated manufacturing process and requires many man-hours.
Considering the amount of raw materials used, the yield is also significantly lower, it is expensive, and it is non-aqueous, so it is dangerous.

On the other hand, polyhydric alcohols such as glycerin, N-methyl-2-
There are hydrous homogenized ketone peroxide compositions that use nitrogen-containing water-soluble solvents such as pyrrolidone as carrier agents, but these carrier agents do not act as curing retarders for acid-curing resins, are cheap, and are not safe. Although it is expensive, when used as an oxidizing agent in acid-curable cold box, it causes poor curing of the mold and is practically unusable.

The peroxide composition of the present invention improves these drawbacks, contains a dilution stabilizer that eliminates the solvent that acts as a curing retarder during homogenization, and is water-containing, so it is acid-curing cold. As an oxidizing agent for boxes, it has excellent performance, does not require complicated manufacturing processes, is inexpensive, and is water-containing, so it is excellent in fire safety, so it provides practically satisfactory results. be.

As a preferred method for producing the hydrous ketone peroxide composition of the present invention, at least one of an aliphatic ketone having 3 to 8 carbon atoms or an alicyclic ketone having 6 to 10 carbon atoms is mixed with hydrogen peroxide under an acid catalyst. This is a method of solubilizing ketone peroxide, which is produced by oxidation in water, with a solubilizer without removing water during or after production.

The solubilizing agents used in the present invention include water-soluble monocarboxylic acids, water-soluble hydroxy mono- or polycarboxylic acids,
At least one selected from the group of acidic alkali metal salts of polyhydric carboxylic acids or hydroxy polycarboxylic acids, water-bathable monoalcohol compounds, water-soluble lactone compounds, water-soluble ketone compounds, and water-soluble ether ester compounds can be mentioned. The number of carbon atoms in the hydroxy polyhydric carboxylic acid is 2 to 6,
The acidic alkali metal salt of polycarboxylic acid or hydroxy polycarboxylic acid preferably has 2 to 6 carbon atoms, and the water-soluble monoalcohol preferably has 1 to 6 carbon atoms.

The dilution stabilizers used in the present invention are as follows (D~[
One or more of the compounds represented by [v] can be mentioned.

[■]O It is an alkyl group, an aryl group or an aralkyl group.

When n = 2, X is an alkylene group having 2 to 20 carbon atoms, an alkenylene group,
Alkynylene group, cycloalkylene group, phenylene group,
It is an aralkylene group or an alkyl substituted product thereof.

In the case of n = 3, for n = 1 to 3, R1 may be the same or different, and the total number of carbon atoms in R1 is an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, An aryl group, an aralkyl group, or a halogen, alkoxy, acyloxy, or alkoxycarbonyl substituted product thereof. ) [:II O II RlR2-0-0(-Y-0-).

(In the formula, m is a scale of 1 to 300.

Y is an alkylene group having 2 to 20 carbon atoms, an alkenylene group,
It is an alkynylene group, a phenylene group or an aralkylene group.

R and R may be the same or different, and the total number of carbon atoms is an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aryl group, or aralkyl group, and R3 is a hydrogen atom. , also includes acyl groups. ) [111) Glycerin esters 0) I2-0-CR.

(In the formula, R,, R, and R6 are hydrogen atoms, or alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, aryl groups, or aralkyl groups having a total number of carbon atoms of 1 to 60.

However, at least one of R11, R, and R6 is not a hydrogen atom. ) [■] Phosphorus esters (in the formula, R7, R,, R5 are hydrogen atoms or have 1 to 2 carbon atoms)
0 alkyl group, alkenyl group, alkynyl group,
A halogen, alkoxyacyloxy substituted product of an aralkyl group, an aralkyl group, or a cholera group. However, R7, R8, R
At least one of 1 is not a hydrogen atom. ) [■]
Saturated or unsaturated fatty acids having 12 to 24 carbon atoms, furfuryl alcohol, phenolic compounds, aliphatic or aromatic aldehyde compounds, furfuryl alcohol/formalin polycondensate, phenolic compound/formalin polycondensate, urea/formalin Polycondensates, melamine/formalin condensates.

The proportions of each component in the peroxide composition of the present invention are: ketone bar, 35 to 60% by weight of oxide, 5 to 40% by weight of water,
10 to 40% by weight of dilution stabilizer and 5 to 40% by weight of solubilizer are common.

Furthermore, the composition of the present invention may contain a nonionic or anionic surfactant in addition to the above-mentioned essential components.

Generally, when molding a mold, silica sand containing quartz as a main component, zircon sand, and chromite sand are used as the granular refractory aggregate, but the present invention is not limited to these. Furan resin and phenol resin are acid-curable resins.

Examples include urea resins, melamine resins, and cocondensates or mixtures thereof.
It is usually used in an amount of 5 to 20 parts by weight per 1,000 parts by weight.

The peroxide composition of the present invention is usually used in an amount of 3 to 10 parts by weight per 1000 parts by weight of aggregate.

〔Example〕

EXAMPLES Below, Examples will be described to explain the present invention in more detail, but the scope of the present invention is not limited by the Examples.

Examples 1 to 6 and Comparative Examples 1 to 3 Ketone peroxide 50% by weight, carrier agent (dilution stabilizer) 20% by weight, solubilizer 10% by weight, water 20%
To evaluate the performance of the hydrous ketone peroxide compositions of the present invention and comparative water-containing ketone peroxide compositions as acid-curable cold box oxidizers containing % by weight, molds were formed and the mechanical properties of the molds were examined.

A mixture of 1,000 parts by weight of Australian 7-lattery silica sand, 12 parts by weight of furan resin, and 5 parts by weight of peroxide composition was added and kneaded into a 25 x 25 x 250 m/In mold, gaseous sulfur dioxide was blown in, and then compressed air was added. The mold was molded after washing with water.

1. After forming the i-type, the bending strength of the mold was measured over time.

The results are shown in Table-1.

Procedural Ordinance (Procedural Ordinance Fusho 1) February 13, 1985 1, Indication of the case Patent Application No. 59-191367 2, Title of the invention: Peroxide composition for molds 3, Person making the amendment Relationship with the case Patent Applicant: Kao Quaker Co., Ltd. 4, Agent: Nakai Building, 1-3 Nihonbashi Yokoyama-cho, Chuo-ku, Tokyo The description is corrected as shown in the attached sheet. (1) Compound (1) on page 12, lines 11-12 of the specification is corrected as follows: (1) 0 A peroxide composition used as an oxidizing agent in the production of molds by injecting gaseous or aerosolized sulfur dioxide into a granular refractory aggregate mixture to which a curable resin and an oxidizing agent have been added; 1. A peroxide composition for molding, characterized in that it is a hydrous ketone peroxide composition containing a dilution stabilizer homogeneously prepared by solubilizing it with a dilution stabilizer.

2. The composition according to claim 1, wherein the ketone peroxide is at least one of a peroxide of an aliphatic ketone having 3 to 8 carbon atoms or a peroxide of an alicyclic ketone having 6 to 10 carbon atoms.

3 The solubilizer is a water-soluble monocarboxylic acid, a water-soluble hydroxy mono- or polycarboxylic acid, an acidic alkali metal salt of a polycarboxylic acid or a hydroxy-polycarboxylic acid, a water-soluble monoalcohol compound, a water-soluble lactone compound, a water-soluble The composition according to claim 1, which is at least one selected from the group of water-soluble ketone compounds and water-soluble ether ester compounds.

4. The composition according to claim 3, wherein the hydroxy polycarboxylic acid has 2 to 6 carbon atoms.

5. The composition according to claim 3, wherein the acidic alkali metal salt of polycarboxylic acid or hydroxy polycarboxylic acid has 2 to 6 carbon atoms.

6. The composition according to claim 3, wherein the water-soluble monoalcohol has 1 to 6 carbon atoms.

7. The composition according to claim 1, wherein the dilution stabilizer is one or more of the compounds represented by (1) to (V) below.

[Eng.] 0 :I X(-C-0-R1).

(In the formula, n is 1 to 3, and when n = 1, X is carbon number 1 to
20 alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, aryl groups, or aralkyl groups.

When n = 2, X is an alkylene group having 2 to 20 carbon atoms, an alkenylene group,
Alkynylene group, cycloalkylene group, phenylene group,
It is an aralkylene group or an alkyl substituted product thereof.

When n=3, CGHZ For n=1 to 3, R, may be the same or different, and is an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group in which the total number of carbon atoms in R1 is n=60. group, an aryl group, an aralkyl group, or a halogen, alkoxy, acyloxy, or alkoxycarbonyl substituted product thereof. ) [■]0 R, -C-0(~Y-'0-)ffiR.

(In the formula, m is an integer from 1 to 300.

Y is an alkylene group having 2 to 20 carbon atoms, an alkenylene group,
It is an alkynylene group, a phenylene group or an aralkylene group.

R2Jl may be the same or different and is an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aryl group or aralkyl group having a total number of carbon atoms of 1 to 20.

R3 further includes a hydrogen atom and an acyl group. ) (III) Glycerin esters CH2-0-C-R4 CH0-C-Rs CH2-0-C-R6 (In the formula, Rt, Rs, Rh are hydrogen atoms or They are an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, or an aralkyl group.

However, at least one of R4, Rs, and Rh is not a hydrogen atom. ) [It/) Phosphorus esters (in the formula, R?, Re, R9 are hydrogen atoms or have 1 to 2 carbon atoms
0 alkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group, or a halogen-, alkoxy-, or acyloxy-substituted product thereof. However, R? +R8
, R9 is not a hydrogen atom. )(
V) Saturated or unsaturated fatty acids having 12 to 24 carbon atoms, furfuryl alcohol, phenolic compounds, aliphatic or aromatic aldehyde compounds, furfuryl alcohol/formalin polycondensates, phenolic compounds/formalin polycondensates, urea/ Formalin polycondensate, melamine/formalin condensate.

8 The proportion of each component is: ketone peroxide 35-60% water by weight
5-40 Dilution stabilizer
The composition according to claim 1, wherein the solubilizing agent is 5 to 40.

Claims (1)

[Claims] 1. A peroxide used as an oxidizing agent when producing a mold by injecting gaseous or aerosolized sulfur dioxide into a granular refractory aggregate mixture to which an acid-curing resin and an oxidizing agent have been added. A peroxide composition for molding, characterized in that the composition is a hydrous ketone peroxide composition containing a dilution stabilizer solubilized with a solubilizer to be homogeneous. 2. The composition according to claim 1, wherein the ketone peroxide is at least one of a peroxide of an aliphatic ketone having 3 to 8 carbon atoms or a peroxide of an alicyclic ketone having 6 to 10 carbon atoms. 3 The solubilizer is a water-soluble monocarboxylic acid, a water-soluble hydroxy mono- or polycarboxylic acid, an acidic alkali metal salt of a polycarboxylic acid or a hydroxy-polycarboxylic acid, a water-soluble monoalcohol compound, a water-soluble lactone compound, a water-soluble The composition according to claim 1, which is at least one selected from the group of water-soluble ketone compounds and water-soluble ether ester compounds. 4. The composition according to claim 3, wherein the hydroxy polycarboxylic acid has 2 to 6 carbon atoms. 5. The composition according to claim 3, wherein the acidic alkali metal salt of polycarboxylic acid or hydroxy polycarboxylic acid has 2 to 6 carbon atoms. 6. The composition according to claim 3, wherein the water-soluble monoalcohol has 1 to 6 carbon atoms. 7. The composition according to claim 1, wherein the dilution stabilizer is one or more compounds represented by the following [I] to [V]. [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, n is 1 to 3, and when n = 1, X is an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, a cycloalkyl group, It is an aryl group or an aralkyl group. When n=2, X is an alkylene group having 2 to 20 carbon atoms, an alkenylene group, an alkynylene group, a cycloalkylene group, a phenylene group, an aralkylene group, or an alkyl substituted product thereof. When n=3, X is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. For n=1 to 3, R_1 may all be the same or different, and the total number of carbon atoms in R_1 is n to 60 alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, aryl groups, aralkyl groups, or halogens and alkoxy groups thereof. , acyloxy, and alkoxycarbonyl substituents.) [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (In the formula, m is an integer from 1 to 300. Y is an alkylene group or alkenylene group having 2 to 20 carbon atoms. , an alkynylene group, a phenylene group, or an aralkylene group. R_2 and R_3 may be the same or different, and the total number of carbon atoms is an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group. or an aralkyl group. R_3 further includes a hydrogen atom or an acyl group.) [m] Glycerin esters ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (In the formula, R_4, R_5, R_6 are hydrogen atoms or the number of carbon atoms is an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aryl group, or aralkyl group in which the sum of all of is 1 to 60. However, at least one of R_4, R_5, and R_6 is not a hydrogen atom.) IV] Phosphorous esters ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. or halogen, alkoxy, or acyloxy substituted products of these.However, R_7, R_8,
At least one of R_9 is not a hydrogen atom. ) [V] Saturated or unsaturated fatty acids having 12 to 24 carbon atoms, furfuryl alcohol, phenolic compounds, aliphatic or aromatic aldehyde compounds, furfuryl alcohol/formalin polycondensates, phenolic compounds/formalin polycondensates, Urea/formalin polycondensate, melamine/formalin condensate. 8. The composition according to claim 1, wherein the proportions of each component are: Ketone peroxide: 35-60% by weight Water: 5-40% Dilution stabilizer: 10-40% Solubilizer: 5-40%.