JPH0338305B2 - - Google Patents

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing polyurethane and/or polyurea molded products (hereinafter referred to as polyurethane/polyurea molded products) using an internal mold release agent. be.

Depending on their physical properties, polyurethane/polyurea molded products are used for seat cushions, automobile parts, electronic and electrical equipment parts, etc., and in recent years, they have been applied to interior and exterior materials as automobile parts. is progressing.

Polyurethane/polyurea molded products having a foamed center portion and a non-foamed or fine-celled skin portion 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.

[Prior Art] A polyurethane/polyurea molded product is a reactive mixture consisting of a polyisocyanate, a compound containing at least two hydrogen atoms reactive with an isocyanate group (hereinafter referred to as an active hydrogen compound), and additives such as a catalyst. It is manufactured by a method in which the liquid is introduced into a sealable mold (hereinafter referred to as reaction injection molding method).

For the reaction injection molding method, see Japanese Patent Application Laid-Open No. 51-119796.
Publication No. 52-142797, Special Publication No. 142797-
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 polyisocyanates and polyols. or mixtures of these polyisocyanates have been used.

As active hydrogen compounds, polyols, polyvalent amine compounds, amino alcohols, etc. are used.

As the high molecular weight polyol, those obtained by adding ethylene oxide and/or propylene oxide to propylene glycol, glycerin, trimethylolpropane, ethanolamine, etc. are used, and the molecular weight thereof is about 1,800 to about 12,000. 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 polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, trimethylolpropane, and bis(2-hydroxyethyl)hydroquinone, and ethylene oxide or propylene oxide added to these alcohols, ethanolamine, ethylenediamine, etc. The molecular weight
Polyols with a molecular weight of 500 or less are also used.

As polyvalent amine compounds, diaminodiethyltoluene and low or high molecular weight terminally aminated polyethers are used, and as amino alcohols, methyldiethanolamine,
Triethanolamine etc. are used.

Tertiary amines, organic tin compounds, and the like are used as catalysts.

As other additives, a foaming agent, a foam stabilizer, a discoloration inhibitor, a coloring agent, etc. are used as necessary.

Fillers such as glass fiber, milled glass, mica, and rock wool are sometimes used to improve the rigidity, dimensional stability, etc. of polyurethane/polyurea molded articles.

A reactive mixture consisting of polyisocyanate and an active hydrogen compound is reacted and cured in a mold.
It is extracted as a molded product.

The mold is made of a material with high thermal conductivity in order to control the reaction temperature, and is generally made of iron or aluminum.

[Problems to be Solved by the Invention] Normally, in order to prevent polyurethane/polyurea molded products from sticking to the mold surface, a method is used to apply a mold release agent such as wax, metallic soap, or oil to the mold surface. ing. On the other hand, a method has also been developed in which a compound having mold releasability is added to the raw material for polyurethane/polyurea molded products. The mold release agent applied to the mold surface is called an external mold release agent, and the mold release agent added to the raw material for polyurethane/polyurea molded products is called an internal mold release agent.

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

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

Many higher fatty acid metal salts are solid at room temperature and have insufficient compatibility with high molecular weight polyols. Even if a higher fatty acid metal salt is added as a solid to an active hydrogen compound, the mold release properties of polyurethane/polyurea molded products will not be improved, so when using it as an internal mold release agent, it must be dissolved in a dissolving agent. .

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

Japanese Patent Publication No. 60-500418 describes active hydrogen-containing compounds containing primary or secondary amino groups, and JP-A-61-83215 describes compounds containing nitrogen-containing isocyanate reactivity. Compounds such as propoxylated ethylene diamine are
JP-A-501575 describes tertiary amine compounds containing at least one tertiary nitrogen atom, such as reaction products of ethylenediamine and propylene oxide.

An internal mold release agent consisting of a higher fatty acid metal salt and a solubilizer is mixed with an active hydrogen compound prior to the production of polyurethane/polyurea moldings and kept at room temperature to 50°C until reaction with the polyisocyanate.
It is stored in tanks etc. at a certain temperature.

In the raw materials for polyurethane/polyurea molded products,
Even if higher fatty acid metal salts exist in a solid state, there is no mold release effect, so the dissolution stability of higher fatty acid metal salts once dissolved is an important factor. However, the storage stability as a composition containing an active hydrogen compound is still insufficient.

[Means for Solving the Problems] The present invention relates to a method for producing a polyurethane/polyurea molded article.

The internal mold release agent used in the method for producing polyurethane/polyurea molded articles of the present invention is a composition consisting of a higher fatty acid metal salt and N,N,N'-tris(2-hydroxypropyl)ethylenediamine.

Zinc stearate is suitable as the higher fatty acid metal salt.

N,N,N'-tris(2-hydroxypropyl)ethylenediamine can be added to 1 mole of ethylenediamine without using a catalyst such as caustic potash.
It is obtained by adding less than a mole of propylene oxide, which is 3 moles of propylene oxide added 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 is 4, and all hydrogens in the amino groups are converted into propylene oxide. Substituted by oxide. In order to increase the number of moles of propylene oxide added to ethylenediamine to more 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. It is. The number of moles of the reaction product of ethylenediamine and propylene oxide described in Japanese Patent Application Laid-Open No. 61-83215 and Japanese Patent Application 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 based on 1 part by weight of the higher fatty acid metal salt.

Other compounds can also be used in combination as solubilizers. In this case, 1 mole of ethylenediamine contains 4
Particularly suitable is an ethylenediamine/propylene oxide adduct to which more than one mole of propylene oxide is added. A compound in which the number of moles of propylene oxide added to ethylenediamine is 4 is N,
It is a by-product when producing N,N'-tris(2-hydroxypropyl)ethylenediamine, so
It can be used as a solubilizer for higher fatty acid metal salts without being separated from the reaction mixture.

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

The amount of solubilizer must take into account not only the storage stability of the internal mold release agent, but also the storage stability of the composition containing the active hydrogen compound.

Further, 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.

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

The polyisocyanates used in the production of the polyurethane/polyurea molded articles of the present invention include diphenylmethane diisocyanate, a mixture of diphenylmethane diisocyanate and its homologues,
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 having a molecular weight of 3,000 to 8,000, which is obtained by adding ethylene oxide and propylene oxide to glycerin or the like, is preferable. As other active hydrogen compounds, ethylene glycol or diethyltoluenediamine may be used.

As the catalyst, generally used are tertiary amines such as triethylenediamine and dimethylethanolamine, and organometallic compounds such as tin octoate, dibutyltin dilaurate, and dimethyltin dilaurate.

As the blowing agent, water, halogenated hydrocarbon, nitrogen, etc. are used.

[Example] The details of the present invention will be explained by reference examples, examples, and comparative examples.

Reference Example 1 N,N,N'-tris(2-hydroxypropyl)ethylenediamine was prepared by the following method.

270 parts by weight (hereinafter referred to as parts) of a 93.5% aqueous ethylenediamine solution was placed in an autoclave equipped with a stirrer, and the autoclave was purged with nitrogen.

The temperature and pressure were increased to 105° C. and 2 Kg/cm ² (G), 730 parts of propylene oxide was added dropwise over 3 to 4 hours, and the temperature was maintained at 105° C. for an additional 3 hours.

The reaction mixture was dehydrated at 110°C and below 10 mmHg, then dissolved in acetonitrile, and insoluble matter was filtered.

After removing acetonitrile, it was dissolved in water and extracted with chloroform. After dehydrating the water layer 150℃ 3mm
Low boilers were removed by distillation with Hg.

The obtained products were obtained by adding 2 moles of propylene oxide to 1 mole of ethylenediamine (hereinafter referred to as EDA-2PO) at a rate of about 6%, and products having 3 moles of propylene oxide added to 1 mole of ethylenediamine (hereinafter referred to as EDA-2PO) from the GLC chart. (referred to as 3PO) approximately 90%,
It was a mixture containing approximately 4% of propylene oxide (hereinafter referred to as EDA-4PO) with 4 moles added thereto.

Reference example 2 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.

The product obtained by dehydration at 110℃ and 10mmHg is
EDA−2PO approx. 15%, EDA−3PO approx. 50%, EDA−
It was a mixture of about 35% 4PO.

Reference example 3 Using 780 parts of propylene oxide to 220 parts of 93.5% ethylenediamine aqueous solution, 105°C, 2 kg/
The reaction was carried out at cm ² (G) for about 7 hours.

After removing unreacted propylene oxide,
Dehydration was performed at 110°C and 10mmHg.

The resulting product is 95% EDA−4PO and 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-24% with higher molecular weight than 6PO
The hydroxyl value (hereinafter referred to as OHV) 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 to uniformly dissolve them.

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, 2 parts of N,N,N'-tris(2-hydroxypropyl)ethylenediamine, and 2 parts of the ethylenediamine-propylene oxide adduct obtained in Reference Example 4 were mixed, and 90%
It was heated to 100°C to 100°C to uniformly dissolve it.

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 (OHV28) using alcohol as an initiator,
15 parts of diaminodiethyltoluene mixture, Example 1
5 parts of internal mold release agent shown in , triethylenediamine
0.1 part and 0.1 part of dibutyltin dilaurate were uniformly mixed.

This mixed solution was left at room temperature and 45° C. for one month, but it did not become cloudy 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 density 1.1 g/cc, bending modulus 2700 Kg/cm ² , tensile strength 265 Kg/cm ² and elongation 230%.

A polyurethane/polyurea molded product was molded using a U-shaped mold using the above raw material composition, and was easily demolded.

Example 5 80 parts of branched polyoxyalkylene ether polyol (OHV28) using alcohol as an initiator,
15 parts of diaminodiethyltoluene mixture, Example 2
5 parts of internal mold release agent shown in , triethylenediamine
0.1 part of dibutyltin dilaurate and 0.1 part of dibutyltin dilaurate were uniformly mixed.

This mixed solution was left at room temperature and 45° C. for one month, but it did not become cloudy 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, but the molded product could be easily demolded.

Example 6 78 parts of branched polyoxyalkylene ether polyol (OHV28) using alcohol as an initiator,
2 parts of the ethylenediamine/propylene oxide adduct shown in Reference Example 4, 15 parts of the diaminodiethyltoluene mixture, 5 parts of the internal mold release agent shown in Example 1,
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° C. for one month, but it did not become cloudy 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, but the molded product could be easily demolded.

Comparative Example 1 80 parts of branched polyoxyalkylene ether polyol (OHV28) using alcohol as an initiator,
15 parts of a diaminodiethyltoluene mixture, 5 parts of an internal mold release agent consisting of 2 parts of zinc stearate and 3 parts of the ethylenediamine/propylene oxide adduct obtained in Reference Example 3, 0.1 part of triethylenediamine, and 0.1 part of dibutyltin dilaurate were uniformly mixed. mixed with.

When this liquid mixture was left to stand at room temperature, a precipitate formed after two days, and the mixture became cloudy as a whole after three 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 (OHV28) using alcohol as an initiator,
15 parts of a diaminodiethyltoluene mixture, 5 parts of an internal mold release agent consisting of 2 parts of zinc stearate and 3 parts of the ethylenediamine/propylene oxide adduct obtained in Reference Example 4, 0.1 part of triethylenediamine, and 0.1 part of dibutyltin dilaurate were uniformly mixed. mixed with.

When this liquid mixture was left to stand at room temperature, a precipitate formed after two days, and the mixture became cloudy as a whole after four weeks.

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

Claims (1)

[Scope of Claims] 1. A method for producing polyurethane and/or polyurea molded articles by reaction injection molding using a polyisocyanate, an active hydrogen compound, a catalyst, and an internal mold release agent, as the internal mold release agent,
Higher fatty acid metal salt and N,N,N'-tris(2-
1. A method for producing polyurethane and/or polyurea molded articles, the method comprising using a composition comprising (hydroxypropyl) ethylene diamine. 2. The method for producing a polyurethane and/or polyurea molded article according to claim 1, wherein the higher fatty acid metal salt is zinc stearate.