JPH02209961A - Production of molded article of polyurethane/polyurea - Google Patents

Abstract

PURPOSE:To efficiently produce molded articles of polyurethane/polyurea by using a composition comprising a metallic salt of higher fatty acid and N,N,N'- tris(2-hydroxypropyl)ethylenediamine as an inner mold release agent. CONSTITUTION:A reactive mixture comprising (A) a polyisocyanate, (B) an active hydrogen-containing compound (e.g. polyol, polyfunctional amine compound or amino-alcohol), (C) a catalyst (e.g. tertiary amine or organotin compound) and optionally, a blowing agent, foam stabilizer, etc., is blended with (D) a composition comprising D1: a metallic salt of higher fatty acid (preferably zinc stearate) and D2: N,N,N'-tris(2-hydroxypropyl)ethylenediamine prepared by adding <=4mol propylene oxide to ethylenediamine and is subjected to reaction injection molding to produce molded articles of polyurethane/polyurea.

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.In recent years, polyurethane/polyurea molded products have been applied to interior and exterior materials as automobile parts. is progressing.

Polyurethane/polyurea molded products with a foamed core and a non-foamed or fine-celled skin are used in automobile bumpers, armrests, steering wheels, etc.

Polyurethane reinforced with fillers such as glass fiber/
Polyurea molded products are being developed for fascias and car body skins.

[Prior art 1] Polyurethane/polyurea molded products are made of polyisocyanate, a compound containing at least two hydrogen atoms reactive with isocyanate groups (hereinafter referred to as active hydrogen compound)
A method in which a reactive mixture consisting of additives such as a catalyst and a catalyst is introduced into a sealable mold (hereinafter referred to as reaction injection molding method).

) is manufactured by.

Regarding the reaction injection molding method, see JP-A-51-119796.
Publication No. 52-142797, Special Public Rescript 55
It is described in, for example, Japanese Patent No.-27098.

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

As active hydrogen compounds, polyols, polyvalent amine 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 thereof is about 1,800 to about 12,000. It is.

Furthermore, polymer polyols in which vinyl monomers such as styrene and acrylonitrile are polymerized in the presence of these polyols are also used.

Examples of low molecular weight polyols include ethylene glycol,
Polyhydric alcohols such as propylene glycol, butanediol, trimethylolpropane, 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. It is used.

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

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

Other additives include foaming agents, foam stabilizers, discoloration inhibitors,
Colorants and the like are used as necessary.

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

A reactive mixture consisting of a polyisocyanate, an active hydrogen compound, etc. is reacted and cured in a mold, and then taken out as a molded product.

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

[Problem to be solved by the invention] Generally, 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 used. It is being 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 polyurethane/
The mold release agent added to the raw material for 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 a primary amino group or secondary amino group, and JP-A-61-83215 describes compounds containing nitrogen-containing isocyanate reactivity. A compound such as a propoxylated compound of ethylenediamine is disclosed in Japanese Patent Application Publication No. 1983-501575, a tertiary amine compound containing at least one tertiary nitrogen atom such as a reaction product of ethylenediamine and propylene oxide is Are listed.

The internal mold release agent consists of a higher fatty acid metal salt and a dissolving agent.
Prior to the production of polyurethane/polyurea molded articles, it is mixed with an active hydrogen compound and stored in a tank or the like at a temperature between room temperature and about 50° C. until reaction with polyisocyanate.

Even if higher fatty acid metal salts exist in a solid state in the raw materials for polyurethane/polyurea molded products, there is no release effect, so the dissolution stability of higher fatty acid metal salts once dissolved is an important factor. In the internal mold release agent using the above-mentioned dissolving agent,
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 products of the present invention includes a higher fatty acid metal salt and N,
N, N'-tris(2-hydroxypropyl)
It is a composition consisting of ethylenediamine.

Zinc stearate is suitable 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; 3 moles of propylene oxide are added to 1 mole.

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 of amino groups are converted by propylene oxide. has been replaced. In order to increase the number of moles of propylene oxide 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. . Unexamined Japanese Patent Publication No. 1983-83215 and Special Publication No. 1983-50
The number of moles of the reaction product of ethylenediamine and propylene oxide described in JP 1575 is 4 or more.

N, suitable for dissolving higher fatty acid metal salts.

The amount of N'-tris(2-hydroxypropyl)ethylenediamine is 0.0 parts by weight of higher fatty acid metal salt.
It is 5 parts by weight or more.

Other compounds can also be used in combination as solubilizers. In this case, an ethylenediamine/propylene oxide adduct in which 4 or more moles of propylene oxide is added to 1 mole of ethylenediamine is particularly suitable. Compounds in which the number of moles of propylene oxide added to ethylenediamine is 4 are N, N.

Since it is produced as a by-product when N'-tris(2-hydroxypropyl)ethylenediamine is produced, it can be used as a dissolving agent 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.

In addition, ethylenediamine propylene oxide adduct is a low molecular weight polyol having four functional groups,
It also affects the flowability and physical properties of polyurethane/polyurea molded products.

The amount of the higher fatty acid metal salt is preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the composition containing the active hydrogen compound, and N, N, N'-t-lis(2-hydroxypropyl)ethylenediamine The amount is also preferably 0.5 to 5 parts by weight. 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, mixtures of diphenylmethane diisocyanate and its homologs, and polyisocyanates modified by reacting with polyfunctional hydroxyl group-containing compounds or by carbodiimidation. Modified isocyanates and the like are preferred.

As the high molecular weight polyol, a polyether polyol having a molecular weight of 3,000 to aooo, which is obtained by adding ethylene oxide and propylene oxide to glycerin or the like, is preferable.As the other active hydrogen compound, ethylene glycol or diethyltoluenediamine is 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 I NIN, 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. to 2 g/c 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 below 11OsaH, 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. with 3 Hg to remove low boiling point substances.

From the GLC chart, the obtained products were approximately 6% with 2 moles of propylene oxide added to 1 mole of ethylenediamine (hereinafter referred to as EDA-2PO), and 3 moles with propylene oxide added (hereinafter referred to as EDA-2PO). 3
It's called PO. It was a mixture of about 90% (hereinafter referred to as EDA-4PO) and about 4% (hereinafter referred to as EDA-4PO) with 4 moles of propylene oxide added.

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

The product obtained by dehydration at 110°C and 110 mHg contains approximately 15% EDA-2PO, approximately 50% EDA-aPO,
It was a mixture of about 35% EDA-4PO.

Reference example 3 For 220 parts of 93.5% ethylenediamine aqueous solution,
Using 780 parts of propylene oxide, 105°C
The reaction was carried out at 12 Kg/c2 (G) for about 7 hours.

After removing unreacted propylene oxide, at 110°C,
It was dehydrated with 10 ml of Hg.

The resulting product contains 95% EDA-4PO and EDA-4PO.
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 7cs2 (G).

After the product was neutralized with sulfuric acid and dehydrated, the generated potassium sulfate was filtered.

The obtained products were EDA-4P028%, EDA-5
P048%, higher molecular weight than EDA-6PO 24%
The hydroxyl value (hereinafter referred to as OHV) was 630 gKOH/g.

Example 1 2 parts of zinc stearate and N,N,N'-tris(2-
3 parts of (hydroxypropyl) ethylene diamine 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 3 parts of the ethylenediamine/propylene oxide adduct obtained in Reference Example 2 were 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 the mixture was mixed with 90 to 100 parts of zinc stearate. °C
It was heated to dissolve uniformly.

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

Example 4 80 parts of a branched polyoxyalkylene ether polyol (OHV28) using an alcohol as an initiator, 15 parts of a diaminodiethyltoluene mixture, 5 parts of the internal mold release agent shown in Example 1, 0.1 part of triethylenediamine, and dibutyl 0.1 part of tinjilaurate was mixed uniformly.

This mixed solution was allowed to stand at room temperature and 45°C for one month, but it did not become cloudy and no precipitate was formed.

The amount of urethane-modified diphenylmethane diisocyanate (isocyanate content 23%) was adjusted to the above-mentioned liquid mixture so that the isocyanate index was 107, and a plate-shaped polyurethane/polyurea molded product was obtained by reaction injection molding.

Physical properties: density 1.1g/cc, bending modulus 2
．． 700g/c*2, tensile strength 265Kg/Cm2,
The elongation was 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 a branched polyoxyalkylene ether polyol (OHV 28 ) using an alcohol as an initiator, 15 parts of a diaminodiethyltoluene mixture, 5 parts of the internal mold release agent shown in Example 2, 0.1 part of triethylenediamine, and 0.1 part of dibutyltin dilaurate was mixed uniformly.

This mixed solution was left at room temperature and 45°C for one month,
There was no turbidity and no precipitate was formed.

The amount of urethane-modified diphenylmethane diisocyanate (isocyanate content 23%) was adjusted to the above mixture so that the isocyanate index was 107, and a polyurethane/polyurea molded product was produced using a U-shaped mold by reaction injection molding. However, the molded product could be easily demolded.

Example 6 78 parts of a branched polyoxyalkylene ether polyol (OHV 28 ) using an 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.
parts were mixed uniformly.

This mixed solution was allowed to stand at room temperature and 45°C for one month, but it did not become cloudy and no precipitate was formed.

The amount of urethane-modified diphenylmethane diisocyanate (isocyanate content 23%) was adjusted to the above mixture so that the isocyanate index was 107, and a polyurethane/polyurea molded product was produced using a U-shaped mold by reaction injection molding. However, the molded product could be easily demolded.

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

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.

The amount of urethane-modified diphenylmethane diisocyanate (isocyanate content 23%) was adjusted to the above compounded liquid so that the isocyanate index was 107, and a polyurethane/polyurea resin was molded by reaction injection molding. It was difficult to remove the mold.

Comparative Example 2 80 parts of a branched polyoxyalkylene ether polyol (○HV28) using an alcohol as an initiator, 15 parts of a diaminodiethyltoluene mixture, 2 parts of zinc stearate, and the ethylenediamine/propylene oxide adduct 3 obtained in Reference Example 4. 0.1 part of triethylenediamine and 0.1 part of dibutyltin dilaurate were uniformly mixed.

When this mixed solution was left at room temperature, a precipitate formed on the surface for 2 days, and after 4 weeks, the entire solution became cloudy.

The amount of urethane-modified diphenylmethane diisocyanate (isocyanate content 23%) was adjusted to the above compounded liquid so that the isocyanate index was 107, and a polyurethane/polyurea molded product was molded by reaction injection molding. It was difficult to demold continuously.

that's all

Claims (1)

[Claims] 1. A method for producing polyurethane/polyurea molded products by reaction injection molding using a polyisocyanate, an active hydrogen compound, a catalyst, and an internal mold release agent, in which a higher fatty acid metal is used as the internal mold release agent. Polyurethane and/or polyurethane characterized by using a composition consisting of a salt and N,N,N'-tris(2-hydroxypropyl)ethylenediamine
Or a method for manufacturing polyurea molded products. 2. The method for producing polyurethane and/or polyurea molded articles according to claim 1, wherein the higher fatty acid metal salt is zinc stearate. 3. Active hydrogen compound, catalyst, higher fatty acid metal salt and N
, N,N'-tris(2-hydroxypropyl)ethylenediamine. 4. The composition according to claim 3, wherein the higher fatty acid metal salt is zinc stearate.