JPS6144604A - Mold release composition - 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 [Field of Industrial Application] The present invention relates to a mold release agent composition. More specifically, it is suitable for the production of inorganic molded products such as ceramic products, concrete products, and plaster products, and is capable of producing high-quality inorganic molded products even under harsh molding conditions, and exhibits excellent mold release effects. The present invention relates to a drug composition.

The demand for inorganic molded products has expanded with the development of industry, and the applications have also become more diverse.There is a need to manufacture precise and uniform products efficiently (and at low cost), and the conditions for molding processing are increasing. In order to meet these demands, the role of mold release agents is also increasing.

[Conventional technology]

Conventionally, in the production of inorganic molded products, mineral oil has been used as a mold release agent, or asphalt, petroleum pitch, Kajig+1-su, silicone oil/Lr.

Mineral oil and naphtha with phosphoric acid ester added are widely used. However, these conventional products
When applied to formwork, the strength of the coating is weak, and especially when forming concrete containing aggregate, when filling the material, large pressure is applied locally to the contact surface between the formwork and aggregate. The film of the mold release agent breaks and creates unevenness. In addition, for lightweight aerated concrete, cement slurry at 70 to 80°C
- After the filler is mainly filled in the mold, foaming starts from the bottom of the filler and progresses radially upward, so that the mold release agent film is further peeled off because it is carried out on the mold. Therefore, when the mold is removed from the molded product (demolding), part of the material on the mold is peeled off, making it impossible to obtain a product with a smooth surface. In addition, the mold release agent mixes into the surface or surface layer of the product, causing discoloration or deterioration of the surface of the product. In addition, there are disadvantages such as rust easily forming on the formwork, and the rust contaminating the surface of the product. Furthermore, in the case of a phosphoric acid ester mold release agent, the phosphoric acid ester is eluted into the waste water for washing the used mold, and special waste water treatment is required.

[Problem that the invention seeks to solve]

The inventors of the present invention have focused on these points and have conducted intensive studies to find a product that is suitable for the production of inorganic molded products and has an excellent mold release effect even for molded products with complex shapes and under harsh molding conditions. It has been found that a product with good performance and a good appearance can be obtained, and the above problems can be solved [Means for solving the problems] That is, the present invention provides at least one selected from rosin and rosin derivatives, 1 to 50% by weight of rosin ester obtained by esterifying part or all of its carboxylic acid with a monohydric or polyhydric alcohol, and a carbon number of 8 to 50% by weight.
Higher fatty acid ester obtained by esterifying 24 higher fatty acids with monohydric or polyhydric alcohol 50-99% by weight
This is a mold release agent composition made of a mixed ester consisting of the following, as it is, or mixed with mineral oil, an emulsifier, water, etc. as necessary.

The mold release agent composition of the present invention can be easily applied to a mold by spraying or brushing, and is effective even if the coating is thin. The amount of application is 1.
5 to 5 g/m2, but the mold release agent composition of the present invention exhibits a sufficient effect even at 1 g/m2 or less, and is economical since the amount of application is small.

Moreover, the mold release agent does not migrate to the surface or surface layer of the product, and a product having a smooth surface and the same quality as the interior can be obtained.

Furthermore, it prevents rust from forming on the formwork, and does not contaminate the wastewater used to wash the formwork.

The rosin and rosin derivatives used in the present invention include rosins such as gum rosin, tall oil rosin, and wood rosin, as well as their modified products such as disproportionated rosin, hydrogenated rosin, and rosin obtained by treating rosin in the presence of an acid catalyst. Polymerized rosin, aldehyde-modified rosin obtained by treating rosin with an aldehyde such as formaldehyde or crotonaldehyde in the presence of an acid catalyst, rosin and acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, anhydride Itaconic acid, ntraconic acid, anhydraconic acid, etc., reinforced rosins obtained by reaction with β-unsaturated carboxylic acids; rosin-based condensation resins obtained by adding 7-enol formaldehyde resin to rosin; Examples include rosin-based condensation resins that are polyesters with basic acids and have at least one carboxylic acid group in the molecule. A part or all of the alcohol is esterified with a monohydric or polyhydric alcohol.

Monohydric or polyhydric alcohols used in the present invention include methanol, ethanol, propatool, impropatol, butanol, t-butanol, n-nonyl alcohol, lauryl alcohol, oleyl alcohol, stearyl alcohol, rylyl alcohol, and eicosanol. ,
Monohydric alcohols such as pentadecyl alcohol and heptadecyl alcohol, dihydric alcohols such as ethylene glycol, flopylene glycol, butylene glycol, 1,4-butanediol, neopentyl glycol, glycerin, polyglycerin, pentaerythritol, dihydric alcohol, etc. Examples include polyhydric alcohols such as pentaerythritol and trimethylolpropane, and at least one of these is used.

Esters of rosin or/and rosin derivatives and monohydric or polyhydric alcohols are produced by carrying out an esterification reaction or transesterification reaction according to a conventional method. For example, when producing by an esterification reaction, rosin or/and a rosin derivative and a monohydric or polyhydric alcohol are heated at a temperature of 100 to 300°C in the presence of a dehydration catalyst such as p-toluenesulfonic acid, phosphoric acid, or sulfuric acid. React for ~10 hours. When produced by transesterification, rosin or 1
and rosin derivatives are pre-sterilized with a monohydric lower alcohol such as methyl alcohol or ethyl alcohol, and then esterified with other monovalent alcohols other than the above in the presence of a basic catalyst such as sodium methylate, sodium hydroxide, or quicklime. A transesterification reaction is carried out with a hydrohydric alcohol or a polyhydric alcohol. The rosin ester thus obtained has increased tackiness and enhances the strength of the coated film compared to rosin esters that are not esterified.

The higher fatty acids used in the present invention include capric acid, pelargonic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, arachidic acid, citronel acid, undecenoic acid, oleic acid, elaidic acid, Erucic acid, brassic acid, linoleic acid, linoleic acid, wasillic acid, pentacosonic acid, mixed fatty acids thereof, and fatty acids produced from animal and vegetable oils and fats,
and synthetic fatty acids having 8 to 24 carbon atoms produced by the oxo method, etc., and at least one selected from these higher fatty acids is subjected to an esterification reaction with a monohydric or multivalent alcohol in the same manner as in the production of the rosin ester. Alternatively, a higher fatty acid ester is obtained by performing a transesterification reaction.

In addition to the higher fatty acid esters obtained above, the higher fatty acid esters obtained in the present invention include yeast oil, palm oil,
Soybean oil, rapeseed oil, sunflower oil, safflower oil, beef tallow,
It includes animal and vegetable oils and fats such as lard and fish oil, as well as their hydrogenated fats and transesterified fats. When used, it has excellent affinity for molds, especially molds, and compatibility with rosin ester.

[For production]

The release agent composition of the present invention focuses on the adhesiveness and tackiness of rosin ester, which is conventionally used in adhesives and paints, and uses a higher fatty acid ester with good compatibility with the rosin ester to be used as a mold release agent. This product has achieved the intended purpose of 1 to 50% by weight of rosin ester and 5% by weight of higher fatty acid ester.
A composition containing 0 to 99% by weight of rosin ester is excellent in coating properties, film strength, and mold release properties as a mold release agent, and if the rosin ester content is less than 1% by weight, the strength of the film is insufficient;
If it exceeds % by weight, the adhesiveness of the rosin ester becomes strong and the mold release effect decreases.

The mold release agent composition of the present invention can be used in the same way as conventional mold release agents; for example, it can be directly applied to the mold by brushing, spraying, etc., or it can be applied by dissolving it in mineral oil such as spindle oil, machine oil, or naphtha. You may do so.

Furthermore, by using a surfactant, emulsifying it as it is in water, or forcefully emulsifying it with ultrasound etc., O/W or W
It can also be used as a type 10 emulsion.

The mold release agent composition of the present invention is used when molding an inorganic material or a composite material using a mold.

Products molded from inorganic materials include ceramic products such as firebricks, tiles, ceramics, insulators, casting molds, tiles, U-shaped grooves, flat plates, humid pipes, concrete piles, lightweight cellular concrete, and mock wood. Examples include concrete products such as , concrete stones, and blocks. Products molded from composite materials include cement products that use lightweight silicic aggregates such as perlite, vermiculite, and mica, cement products that use inorganic fiber materials such as rock wool and asbestos, and reinforcing materials. Reinforced plastics, reinforced ceramics, laminates, carbon, organic polymer-ceramic composites, etc. using fibers, asbestos, metal fibers, wood, etc.; fiber reinforcements such as pulp, hemp, cotton, etc.
Examples include cement products and plaster using reinforcing materials such as wool, silk, asbestos, glass, vinyl alcohol, polyvinyl, string, polyvinylidene chloride, and polyurethane.

The present invention will be explained in more detail below with reference to Examples and Comparative Examples. In the text, "%" means % by weight, and "part" means parts by weight.

〔Example〕

Example-1 A container equipped with a stirring device, a moisture meter, a thermometer, and a nitrogen gas blowing tube! 300 g of tall rosin (acid value: 171.0, saponification value: 173.4, iodine value: 177.6) was placed in a four-low flask and heated to 180°C to dissolve.

Add 2 g of p-toluenesulfonic acid while passing nitrogen gas, and gradually add 60 g of glycerin and heat to 250°C. The reaction was carried out at the same temperature for 4 hours, and rosin ester (a
) (acid value=40) was obtained. This rosin ester (a) 5
95 parts of soybean oil were mixed to obtain a mold release agent composition hole.

A rectangular iron plate with a smooth surface (50 x 200 mm dimensions) and a rectangular iron plate with mesh-like protrusions on the surface (50 x 200 mm)
200 mm size) Apply 1 g of the above mold release agent composition hole to each sheet.

Separately prepared 200 (horizontal) x 100 (vertical) x 100 mm
(depth), place these two iron plates face up on the bottom of a wooden box with a removable bottom plate, and pour a cement slurry consisting of 35 parts of ordinary Portland cement, 50 parts of sand, and 15 parts of water. do. Examples 2 to 8 which were left as they were for one week, and rosin esters (release side compositions with different blending ratios of Al and soybean oil (Examples 2 to 6, Comparative Examples 2 to 3), and rosin esters. A mold release agent composition (Examples 7 to 8) consisting of fa), soybean oil, and C-machine oil was prepared, and its performance was evaluated in the form of a rectangular mold having mesh-like protrusions on the surface similar to Example 1. Table 1 shows the results of the evaluation using the iron plate test method.
Shown below. Comparative Example-1 is C-machine oil 10096.

The mold release agent compositions of Examples 2 to 8 have excellent mold release performance,
150 g of gum rosin (acid value = 170) and methyl alcohol i were placed in the obtained electromagnetic stirring autoclave with a volume of flH1.
So g and 4 g of zinc chloride were added and the temperature was raised to 250°C.

Maintained at the same temperature for 5 hours, rosin ester (acid value: 35)
I got it. Fifty parts of this rosin ester and 50 parts of methyl stearate were mixed to obtain a mold release agent composition.

Using this mold release agent composition and using the method of Example 1, 400 g of wood rosin (dehydroabietic acid content = 7.1%) was charged into the reaction vessel of Example 10 and Example 1 and dissolved under a nitrogen atmosphere. let Add 0.73 g of ferrous iodide at 170 to 180°C, stop blowing nitrogen gas, and slowly raise the temperature to 215°C with stirring. The reaction was carried out at the same temperature for 2 hours to obtain a disproportionated rosin (dehydrobietic acid content: 30.196), and then an esterified product of the disproportionated rosin was obtained according to the method of Example-1. 10 parts of this disproportionated rosin ester and 90 parts of soybean oil were mixed to obtain a mold release agent composition.

Regarding this, performance was evaluated using the method of Example-1.
11-17 In the reaction container of Example-1, tall rosin (acid value = 17
1.0, saponification value = 173.4, iodine value = 177
．． 6) Prepare 400g and 80g of maleic anhydride,
React at 80°C for 2 hours. Using the obtained maleated rosin (acid value = 228.2, saponification value = 254.3, iodine value = 98.8), an esterified product of maleated rosin tb+ was obtained according to the method of Example-2. Mold release agent compositions (Examples 11 to 15) with different blending ratios of this maleated rosin ester (fb) and methyl stearate
, Comparative Example 5.6), and a mold release agent composition (Examples 16 and 17) consisting of an esterified product of maleated rosin fbl, methyl stearate, and spindle oil were manufactured.

200 x 100 made by combining iron plates in advance
1 g of the above mold release agent composition is applied to a mold having dimensions of xloo mm. A well-stirred cement slurry consisting of 36 parts of Portland cement, 24 parts of silica sand, 0.08 parts of aluminum powder, and 40 parts of water was placed in a room adjusted to 80% humidity and 30°C. Leave it for 4 hours. After cutting the cement body that protruded from the top of the formwork due to foaming with piano wire, the side frame was removed from the mold and heated at 180°C1I.
Q kg/cm2 (1) The mold release agent was cured in an autoclave for 8 hours in high-temperature, high-pressure steam, and the performance of the mold release agent was evaluated. The results are shown in Table 2. Comparative example-4 is C-machine oil 1
It is 00%.

Evaluation method (1) Mold releasability... ease of peeling between the iron plate and the molded product◎
...Extremely easy to peel O ... Easy to peel △ ... Slightly difficult to peel, even the surface is smooth O ... No adhesion to the iron plate surface, Measure hardness ◎・・・The surface is hard and does not scratch ○・・・・・・
・The surface is not easily scratched △...The surface is easily damaged ×...The surface is easily scratched and chipped Page 17 (4) Rust on iron plate...・Existence of rust on the iron plate, no coloring on the molded surface ○... There was almost no rust on the iron plate, so it was left at room temperature for one week after being colored. After drying, cross it with a cutter.
Make a cut, apply sellotape over it, then peel off the sellotape and observe whether there is a paint film on the adhesive side of the sellotape.

◎・・・・・・The painted surface does not peel off and has excellent coating suitability.
...The painted surface hardly peels off and has good paintability...
・・・・There is some peeling of the painted surface×・・・・・・
Painted surface peels off, poor coating suitability 6) Compressive strength...
...Measured in accordance with the method of JIS A1161.

Claims (1)

[Claims] 1. 1 to 50% by weight of rosin ester obtained by esterifying at least one kind selected from rosin and rosin derivatives with a monohydric or polyhydric alcohol, and a part or all of the carboxylic acid contained therein; A mixed ester consisting of 50 to 99% by weight of a higher fatty acid ester obtained by esterifying 24 higher fatty acids with a monohydric or polyhydric alcohol is used as it is, or it is mixed with mineral oil, an emulsifier, water, etc. as necessary. Characteristic mold release agent composition.