JPH0327586B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to an internal mold release agent composition used in the production of polyurethane and/or polyurea molded products (hereinafter referred to as polyurethane/polyurea molded products).

Depending on their physical properties, polyurethane/polyurea molded products are used for seat cushions, automobile parts, and parts for electronic and electrical equipment, and in recent years, their application to interior and exterior materials for automobile parts has progressed. There is. Polyurethane resin molded products having a foamed center portion and a non-foamed skin portion or a skin portion containing fine bubbles are used for automobile bumpers, armrests, steering wheels, etc. Polyurethane/polyurea molded products reinforced with fillers such as glass fibers are being developed for facias and car body skins.

BACKGROUND OF THE INVENTION Molded articles are produced by introducing into a sealable mold a reactive mixture consisting of a polyisocyanate, a compound containing at least two hydrogen atoms reactive with isocyanate groups, and additives.

Regarding the reaction injection molding method, JP-A-51-119796, JP-A-52-142797, JP-A-55-
It is described in Publication No. 27098, etc.

Examples of polyisocyanates include tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, isophorone diisocyanate, polymethylene poly(phenyl isocyanate), chemically modified versions of these polyisocyanates, and these isocyanate compounds and polyols. or mixtures of these polyisocyanates have been used.

As active hydrogen compounds, polyols, polyvalent amino compounds, amino alcohols, etc. are used. As high molecular weight polyols, those obtained by adding ethylene oxide and/or propylene oxide to propylene glycol, glycerin, trimethylolpropane, ethanolamine, etc. are used, and the molecular weight is about 1800 to about
It is 12000. Furthermore, polymer polyols in which vinyl monomers such as styrene and acrylonitrile are polymerized in the presence of these polyols are also used.

Low molecular weight polyols include ethylene glycol, propylene glycol, butanediol,
Polyhydric alcohols such as trimethylolpropane and bis(2-hydroxyethyl)hydroquinone, and polyols with a molecular weight of 500 or less, which are obtained by adding ethylene oxide or propylene oxide to these alcohols, ethanolamine, ethylenediamine, etc., are also used.

As the polyvalent amino compound, diaminodiethyltoluene, low molecular weight or high molecular weight terminally aminated polyether, etc. are used, and as the amino alcohol, methyldiethanolamine, triethanolamine, etc. are used.

Tertiary amines and organic tin compounds are used as catalysts.

Other auxiliary agents used include foaming agents, foam stabilizers, discoloration inhibitors, and coloring agents.

In addition, the rigidity of polyurethane/polyurea molded products,
Various fillers such as glass fiber, milled glass, mica, and rock wool are used to improve dimensional stability and the like.

The reactive mixture consisting of the polyisocyanate component and the active hydrogen compound component reacts and hardens in the mold,
It is extracted as a molded product. The mold is made of a highly thermally conductive material in order to control the reaction temperature, and generally iron or aluminum molds are used.

Usually, in order to prevent polyurethane/polyurea molded products from sticking to the mold surface, a method of applying a mold release agent such as wax, metal soap, or oil to the mold surface is adopted. On the other hand, a method of adding a compound having mold release properties to a polyurethane/polyurea resin raw material composition has also been developed. The mold release agent applied to the mold surface is called an external mold release agent, and the mold release agent added to the polyurethane/polyurea resin raw material composition is called an internal mold release agent.

When using an external mold release agent, a new mold release agent must be applied each time molding is performed, and old mold release agent remaining on the mold surface must be removed at regular intervals.

Organic silicon compounds, higher fatty acid esters, and the like have been used as internal mold release agents, but the mold release effect is insufficient.

Many higher fatty acid metal salts are solid at room temperature.
Insufficient compatibility with high molecular weight polyols.
Even if the higher fatty acid metal salt is added as a solid to the active hydrogen compound component, the mold releasability of the polyurethane/polyurea molded article will not be improved.

When using a higher fatty acid metal salt as an internal mold release agent, it is necessary to dissolve it in a dissolving agent.

JP-A-58-15593 describes epoxidized vegetable oil as a dissolving agent for metal salts.

Patent Publication No. 60500418 uses an active hydrogen-containing substance containing a primary amine group or a secondary amine group as a solubilizer, while JP 61-83215 uses an isocyanate-reactive compound containing nitrogen, such as ethylenediamine. In the patent publication No. 61-501575, reaction products of tertiary amine compounds having at least one tertiary nitrogen atom, such as ethylenediamine, and propylene oxide are described.

An internal mold release agent composition consisting of a higher fatty acid metal salt and a solubilizing agent is mixed with an active hydrogen compound component prior to the production of polyurethane/polyurea molded articles,
At room temperature or until the reaction with the isocyanate component.
It is stored in tanks at a temperature of around 50℃.

Even if the higher fatty acid metal salt is present in the solid state in the polyurethane/polyurea resin raw material, there is no mold release effect, so the dissolution stability of the higher fatty acid metal salt once dissolved is an important factor, and the above-mentioned dissolving agent is The internal mold release agent composition used still has insufficient storage stability as an active hydrogen compound-containing composition.

Means for Solving the Problems The present invention relates to internal mold release agent compositions used in the production of polyurethane/polyurea moldings.

The internal mold release agent composition of the present invention comprises a higher fatty acid metal salt and N,N,N'-tris(2-hydroxypropyl)ethylenediamine.

Zinc stearate is preferred as the higher fatty acid metal salt. N,N,N'-tris(2-hydroxypropyl)ethylenediamine is obtained by adding 4 moles or less of propylene oxide to 1 mole of ethylenediamine without using a catalyst such as caustic potash.

N,N,N'-tris(2-hydroxypropyl)ethylenediamine is obtained by adding 3 moles of propylene oxide to 1 mole of ethylenediamine.

The number of moles of propylene oxide added to 1 mole of ethylenediamine varies depending on the amount of propylene oxide present in the reaction system, but in the absence of a catalyst such as caustic potash, the maximum number of moles added is 4, and the hydrogen of the amino group is All are substituted with propylene oxide.

In order to increase the number of moles added to ethylenediamine to be greater than 4, the hydrogen of the hydroxyl group introduced by propylene oxide must be further replaced with propylene oxide, and for this purpose a catalyst such as caustic potash is required. JP-A-61-83215
The number of moles of the reaction product of ethylenediamine and propylene oxide shown in Japanese Patent Publication No. 61-501575 is 4 or more.

N suitable for dissolving higher fatty acid metal salts,
The amount of N,N'-tris(2-hydroxypropyl)ethylenediamine is 0.5 parts by weight or more per 1 part by weight of the higher fatty acid metal salt.

Other compounds can also be used in combination as solubilizers. Particularly suitable is an ethylenediamine/propylene oxide adduct in which 4 or more moles of propylene oxide are added to 1 mole of ethylenediamine. A compound in which the number of moles of propylene oxide added to ethylenediamine is 4 is a by-product when producing N,N,N'-tris(2-hydroxypropyl)ethylenediamine, so higher fatty acid metal salts can be prepared without separation from the reaction mixture. Can be used as a solubilizer.

A chelating agent such as acetylacetone or a nitrogen-containing compound such as aminated polyether may be used in combination to promote solubility of the higher fatty acid metal salt.

The amount of solubilizing agent must take into account not only the storage stability of the internal mold release agent composition but also the storage stability of the active hydrogen compound-containing composition. Furthermore, the ethylenediamine/propylene oxide adduct is a low molecular weight polyol having four functional groups, and it also affects the flowability and physical properties of polyurethane/polyurea molded products.

The amount of higher fatty acid metal salt is preferably 0.5 to 5 parts by weight based on 100 parts by weight of the active hydrogen compound-containing composition, and the amount of N,N,N'-tris(2-hydroxypropyl)ethylenediamine is also 0.5 to 5 parts by weight. A range of is preferred. The amount of ethylenediamine/propylene oxide adduct that can be used in combination is 0 to
It is 5 parts by weight.

Examples of the organic polyisocyanate used in the production of the polyurethane/polyurea molded product of the present invention include diphenylmethane diisocyanate, a mixture of diphenylmethane diisocyanate and its homolog,
Modified isocyanates obtained by reacting these polyisocyanates with polyfunctional hydroxyl group-containing compounds or by carbodiimidation are preferred.

As the high molecular weight polyol, a polyether polyol with a molecular weight of 3000 to 8000, which is obtained by adding ethylene oxide and propylene oxide to glycerin or the like, is preferable. Other active hydrogen compounds that can be used include ethylene glycol and diethyltoluenediamine.

The catalyst is generally triethylenediamine,
Tertiary amines such as dimethylethanolamine and metal compounds such as tin octoate, dibutyltin dilaurate, and dimethyltin dilaurate are used. As the blowing agent, water, halogenated hydrocarbons, nitrogen, etc. are used.

Examples, comparative examples and reference examples The details of the present invention will be explained by examples and the like.

Reference example 1 N,N,N'-tris(hydroxypropyl)
Ethylenediamine was prepared by the following method.
270 parts of a 93.5% ethylenediamine aqueous solution (parts by weight; the same applies hereinafter) was placed in an autoclave equipped with a stirrer, and the autoclave was purged with nitrogen. At 105℃, the temperature and pressure were increased to 2Kg/cm ² (G), and 730 parts of propylene oxide was added to 3 to 4 parts of propylene oxide.
The solution was added dropwise over a period of time and kept at 105°C for an additional 3 hours.
The reaction mixture was dehydrated at 110° C. and below 10 mmHg, dissolved in acetonitrile, and insoluble matter was filtered. After removing acetonitrile, it was dissolved in water and extracted with chloroform. After the aqueous layer was dehydrated, it was distilled at 150° C. and 3 mmHg to remove low-boiling substances. The product obtained is GLC
2 moles of propylene oxide added to 1 mole of ethylenediamine (EDA)
6% (abbreviated as -2PO), about 90% with 3 moles of propylene oxide added (EDA-3PO),
It was a mixture containing approximately 4% of propylene oxide (EDA-4PO) with 4 moles added thereto.

Reference example 2 For 270 parts of 93.5% ethylenediamine aqueous solution,
Using 730 parts of propylene oxide at 105℃, 2
The reaction was carried out at Kg/cm ² (G) for about 7 hours. 110℃, 10mmHg
The product obtained by dehydration with EDA−2PO is about 15
%, about 50% EDA-3PO, and about 35% EDA-4PO.

Reference example 3 For 220 parts of 93.5% ethylenediamine aqueous solution,
Using 780 parts of propylene oxide at 105℃, 2
The reaction was carried out at Kg/cm ² (G) for about 7 hours. After removing unreacted propylene oxide, it was dehydrated at 110°C and 10 mmHg. The obtained product has an EDA−4PO of approximately 95
%, EDA-2PO and EDA-3PO were below 0.5%.

Reference Example 4 4 parts of a 50% caustic potassium aqueous solution was added to 830 parts of the product obtained in Reference Example 3, and water was distilled off at 110°C.

170 parts of propylene oxide was added at 105° C. and 2 Kg/cm ² (G). After the product was neutralized with sulfuric acid and dehydrated, the generated potassium sulfate was filtered. The obtained products were EDA−4PO28%, EDA−5PO48%, EDA
-It is a mixture of 24% of substances with higher molecular weight than 6PO,
The hydroxyl value was 630 mg KOH/g.

Example 1 2 parts of zinc stearate and 3 parts of N,N,N'-tris(2-hydroxypropyl)ethylenediamine were heated to 90 to 100°C and uniformly dissolved.
Although it was left at room temperature and 45°C for one month, no turbidity or precipitate was observed.

Example 2 2 parts of zinc stearate and ethylenediamine/propylene oxide adduct 3 obtained in Reference Example 2
The mixture was heated and dissolved at 90 to 100°C, and insoluble matter was filtered.

Although it was left at room temperature for one month, no turbidity or precipitate was observed.

Example 3 2 parts of zinc stearate and 2 parts of N,N,N'-tris(2-hydroxypropyl)ethylenediamine
and ethylenediamine obtained in Reference Example 4.
Two parts of propylene oxide adduct were mixed and heated to 90-100°C to uniformly dissolve.

Although it was left at room temperature for one month, no turbidity or precipitate was observed.

Example 4 80 parts of branched polyoxyalkylene ether polyol (OHV 28) using alcohol as an initiator,
15 parts of diaminodiethyltoluene mixture, Example 1
5 parts of the internal mold release agent composition shown in 1., 0.1 part of triethylenediamine, and 0.1 part of dibutyltin dilaurate were uniformly mixed. Mix this mixture at room temperature and at 45°C.
Although the solution was left for one month, there was no turbidity and no precipitate was formed.

For the above compounded liquid, urethane-modified diphenylmethane diisocyanate (isocyanate content 23
%) is determined by the isocyanate index.
107, and a plate-shaped polyurethane/polyurea molded product was obtained by reaction injection molding.

The physical properties were as follows. Density 1.1g/
cc, bending modulus 2700Kg/cm ² , tensile strength 265
Kg/cm ² , elongation 230%.

A polyurethane/polyurea resin was molded using a U-shaped mold with the above raw material composition, but it was easily demolded.

Example 5 80 parts of branched polyoxyalkylene ether polyol (CHV 28) using alcohol as an initiator,
15 parts of diaminodiethyltoluene mixture, Example 2
5 parts of the internal mold release agent composition shown in 1., 0.1 part of triethylenediamine, and 0.1 part of dibutyltin dilaurate were uniformly mixed. Mix this mixture at room temperature and at 45°C.
Although the solution was left for one month, there was no turbidity and no precipitate was formed.

For the above compounded liquid, urethane-modified diphenylmethane diisocyanate (isocyanate content 23
%) is determined by the isocyanate index.
107, and a polyurethane/polyurea molded product was obtained using a U-shaped mold by reaction injection molding. The molded product could be easily demolded.

Example 6 78 parts of branched polyoxyalkylene ether polyol (OHV 28) using alcohol as an initiator,
2 parts of the ethylenediamine/propylene oxide adduct shown in Reference Example 4, 15 parts of the diaminoethyltoluene mixture, and 55 parts of the internal mold release agent composition shown in Example 1.
1 part, 0.1 part of triethylenediamine, and 0.1 part of dibutyltin dilaurate were uniformly mixed. This mixed solution was left at room temperature and 45℃ for one month,
There was no turbidity and no precipitate was formed.

For the above compounded liquid, urethane-modified diphenylmethane diisocyanate (isocyanate content 23
%) is determined by the isocyanate index.
107, and a polyurethane/polyurea molded product was obtained using a U-shaped mold by reaction injection molding. The molded product could be easily demolded.

Comparative Example 1 80 parts of branched polyoxyalkylene ether polyol (OHV 28) using alcohol as an initiator,
15 parts of a diaminodiethyltoluene mixture, 5 parts of an internal mold release agent composition consisting of 2 parts of zinc stearate and 3 parts of the ethylenediamine/propylene oxide adduct obtained in Reference Example 3, and triethylenediamine.
0.1 part and 0.1 part of dibutyltin dilaurate were uniformly mixed. When this liquid mixture is left at room temperature,
A precipitate was formed after 2 days, and the whole solution became cloudy after 3 weeks.

For the above compounded liquid, urethane-modified diphenylmethane diisocyanate (isocyanate content 23
%) is determined by the isocyanate index.
107 and molded the polyurethane/polyurea resin by reaction injection molding, but it was difficult to continuously demold the molded product.

Comparative Example 2 80 parts of branched polyoxyalkylene ether polyol (OHV 28) using alcohol as an initiator,
15 parts of a diaminodiethyltoluene mixture, 5 parts of an internal mold release agent composition consisting of 2 parts of zinc stearate and 3 parts of the ethylenediamine/propylene oxide adduct obtained in Reference Example 4, and triethylenediamine.
0.1 part and 0.1 part of dibutyltin dilaurate were uniformly mixed. When this liquid mixture is left at room temperature,
A precipitate was formed after 2 days, and the whole solution became cloudy after 4 weeks.

For the above compounded liquid, urethane-modified diphenylmethane diisocyanate (isocyanate content 23
%) is determined by the isocyanate index.
107 and molded the polyurethane/polyurea resin by reaction injection molding, but it was difficult to continuously demold the molded product.

Claims (1)

[Claims] 1. An internal mold release agent composition for producing polyurethane and/or polyurea molded products, comprising a higher fatty acid metal salt and N,N,N'-tris(2-hydroxypropyl)ethylenediamine. 2. The internal mold release agent composition for producing polyurethane and/or polyurea molded products according to claim 1, wherein the higher fatty acid metal salt is zinc stearate.