JPH06239954A - Production of molded article of polyurethane and/or polyurea - Google Patents

Abstract

PURPOSE:To obtain the subject molded article having excellent releasability from a mold, coating performance and physical properties by using a specific organic polyisocyanate prepolymer without utilizing an internal mold release agent. CONSTITUTION:(A) An organic p6lyisocyanate prepolymer obtained by reacting (i) an organic polyisocyanate with (ii) a compound of the formula [R<1> is 6-24C acyl; R<2> is (a)-functional polyol residue; R<3> is (halogen-substituted)2-4C alkylene; (a) is >=2. (b) is 0-400; (c) is >=1 and <=a-1] or its mixture, (B) a polyol and/or a polyamine, a chain extender and optionally (C) a blowing agent and an auxiliary are subjected to reaction injection molding. The compound of the formula is preferably obtained by esterifying a bi- or polyfunctional polyol such a ethylene glycol with a higher fatty acid such as capric acid and adding an alkylene oxide to the esterified substance.

Description

Detailed Description of the Invention

[0002]

BACKGROUND OF THE INVENTION The present invention is based on reaction injection molding.
The present invention relates to a method for producing a polyurethane and / or polyurea molded product having a self-releasing property.

[0003]

2. Description of the Related Art Organic polyisocyanates conventionally used for the production of polyurethane, polyurethane urea or polyurea molded products by reaction injection molding include those obtained by reacting an organic polyisocyanate with a polyether polyol, a polyester polyol or the like. Was known.

However, in the conventional method for producing a polyurethane, polyurethane urea or polyurea resin by reaction injection molding using an organic polyisocyanate, the adhesiveness between the molded product and the mold is strong and the molded product is difficult to remove from the mold. Or, there is a problem that the molded product adheres to the mold.

As a method of improving the releasing property, it is known to use an internal releasing agent such as a carboxylic acid metal salt (JP-A-1-92268) and polydimethylsiloxane (JP-A-60-108415). However, these internal release agents adversely affect the paintability, and since the carboxylic acid metal salt has a high melting point, the workability is poor and it is difficult to remove the release agent remaining in the molded article. It has not been possible to obtain satisfactory polyurethane, polyurethaneurea or polyurea resins.

[0006]

DISCLOSURE OF THE INVENTION The present invention does not use such an internal mold release agent, has a good releasability from a mold, and has excellent paintability and physical properties.
Another object is to provide a method for producing a polyurea resin.

[0007]

In order to solve the problems of the conventional polyurethane and / or polyurea resin, the present inventors have introduced a long-chain alkyl group into the skeleton of polyisocyanate to form a resin. The inventors have found that the overall self-releasing property is improved, and have completed the present invention.

That is, the present invention comprises: (a) an organic polyisocyanate prepolymer, (b) a polyol and / or a polyamine, a chain extender, and (c) a polyurethane by a reaction injection molding using a foaming agent and an auxiliary agent if necessary. And / or in a method for producing a polyurea molded article,
(A) As the organic polyisocyanate prepolymer, a general formula (1) derived from an organic polyisocyanate, a bifunctional or higher functional polyol, and an esterified product of a higher fatty acid.

(R ¹ O) _c R ² {(OR ³ ) _b OH} _(ac) (1) (wherein R ¹ is an acyl group having 6 to 40 carbon atoms, R ² is an a-functional polyol residue, R 2 ³ represents an alkylene group having 2 to 4 carbon atoms or a halogen-substituted compound thereof, a is an integer of 2 or more, b is an integer of 0 to 400, and c is an integer of 1 or more and a-1 or less.). Alternatively, it is a method for producing a polyurethane and / or polyurea molded product characterized by being an organic polyisocyanate prepolymer obtained by reacting a mixture thereof.

Next, the constituent components of the present invention will be described.
In the present invention, as an organic polyisocyanate for obtaining an organic polyisocyanate prepolymer by reacting with a bifunctional or higher functional polyol, there are aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate and the like. For example, there are diphenylmethane diisocyanate (hereinafter abbreviated as MDI), polymethylene polyphenylene polyisocyanate, tolylene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, methylene bis (cyclohexyl isocyanate), hexamethylene diisocyanate and the like. Further, these polyisocyanate compounds may be modified with various treatments or compounds. Examples thereof include carbodiimide, isocyanurate, uretdione, uretonimine, allophanate, uretonimine, and prepolymer-type modified isocyanates.

In the present invention, as a polyol for obtaining an organic polyisocyanate prepolymer by reacting with an organic polyisocyanate, at least one hydroxyl group of a bifunctional or higher-functional polyol is esterified with a higher fatty acid, and 1 mol of the remaining hydroxyl group is used. On the other hand, alkylene oxide is 0 to 400 mol (preferably 10 to 10).
(0 mol) added general formula (1)

(R ¹ O) _c R ² {(OR ³ ) _b OH} _(ac) (1) (wherein R ¹ is an acyl group having 6 to 40 carbon atoms, R ² is an a-functional polyol residue, R 2 ³ is an alkylene group having 2 to 4 carbon atoms or a halogen-substituted compound thereof, a is an integer of 2 or more, b is an integer of 0 to 400, and c is an integer of 1 or more and a-1 or less.) One of them or a mixture thereof is used, however, in order to esterify the bifunctional or higher functional polyol with the high fatty acid, the compound represented by the general formula (2)

(R ¹ O) _a R ² (2) (wherein R ¹ is an acyl group having 6 to 40 carbon atoms, R ² is an a-functional polyol residue, and a is an integer of 2 or more). The compounds shown may not contain active hydrogen, but these can be used as they are without removal.

Further, known polyether polyols,
It can also be used in combination with a polyester polyol or the like.

Representative examples of bifunctional or higher functional polyols, higher fatty acids and alkylene oxides are shown below, but the present invention is not limited thereto.

As the bifunctional or higher functional polyol, ethylene glycol, propylene glycol, diethylene glycol, glycerin, trimethylolpropane, hexanetriol, diglycerin, pentaerythritol,
Examples thereof include methyl glycoside, dextrol, sorbitol, sucrose, phenolaldehyde initial condensate, bisphenol A, bisphenol F, diethanolamine, triethanolamine, diisopropylamine, and alkylene oxide adducts thereof.

As the higher fatty acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, montanic acid, myristoleic acid, palmitoleic acid, oleic acid, linoleic acid, 2-
Ethyl hexanoic acid, 4,6-dimethyloctanoic acid, 2-
Methyl undecanoic acid, 2,3-dimethyldodecanoic acid, 2
-Ethyl tetradecanoic acid, 2-ethyl hexadecanoic acid, etc. are mentioned.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide and halogen-substituted compounds thereof.

The organic polyisocyanate prepolymer is
It can be obtained by reacting an organic polyisocyanate and a polyol at 50 to 80 ° C.

The polyol used in the present invention is preferably a polyether polyol obtained by addition-polymerizing a cyclic ether using water, polyhydric alcohol, polyhydric phenol, alkanolamine, mono- or polyamine as an initiator. 2-8 are preferable and, as for the average functionality of this polyether polyol, 2-3 are more preferable. The average molecular weight is preferably 200 to 12,000, more preferably 2000 to 8000. Typical examples of the initiator and the cyclic ethers are shown below, but the invention is not limited thereto.

As the polyhydric alcohol, ethylene glycol, propylene glycol, diethylene glycol,
Examples thereof include glycerin, trimethylolpropane, hexanetriol, diglycerin, pentaerythritol, methylglycoside, dextrol, sorbitol, sucrose and the like.

Examples of the polyphenols include phenol-aldehyde initial condensates, bisphenol A and bisphenol F.

Examples of the alkanolamine include monoethanolamine, diethanolamine, triethanolamine and diisopropylamine, and examples of the mono- or polyamine include aniline, diaminodiphenylmethane, tolylenediamine and ethylenediamine.

Examples of cyclic ethers include ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin and halogen-substituted compounds thereof.

The polyamine (b) used in the present invention includes those obtained by aminating the above polyether polyol, preferably having an average number of functional groups of 2 or more and an average molecular weight of 200 to 5,000. It is not limited.

The chain extender used in the present invention includes
There are active hydrogen compounds such as polyhydric alcohols, alkanolamines, polyether polyols, aromatic polyamines and aliphatic polyamines. As a preferred chain extender,
Among the above compounds, those having an average of 2 or more active hydrogen-containing groups and an average molecular weight of 500 or less. Typical examples of the chain length extender are shown below, but not limited to these.

As the polyhydric alcohol, ethylene glycol, 1,4-butanediol, propylene glycol,
Examples thereof include diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane and the like.

Examples of the alkanolamine include monoethanolamine, diethanolamine, triethanolamine, diisopropanolamine and N-alkyl-substituted diethanolamine.

As the aromatic polyamine, 1-methyl-
3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene,
1,3,5-triethyl-2,6-diaminobenzene,
3,5,3 ', 5'-tetraethyl-4,4'-diaminodiphenylmethane and the like can be mentioned.

The reaction injection molding is a method in which at least two components of the active hydrogen component and the isocyanate component are collided with each other under high pressure to form a reaction mixture, and the reaction mixture is filled in a mold to obtain a molded article. As a device for performing reaction injection molding, various commercially available devices can be used.

[0031]

The polyurethane and / or polyurea resin molded article obtained by the present invention has excellent moldability in reaction injection molding and exhibits good mold releasability from the mold. Further, the organic polyisocyanate prepolymer synthesized according to the present invention has a low viscosity and excellent storage stability, and the obtained molded product has good physical properties and coating properties.

[0032]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In Examples and Comparative Examples,
All "parts" mean "parts by weight" and all "%" mean "% by weight". The raw materials used in the examples and comparative examples are as follows.

Alkyl polyol A: Monoester, diester, and triester abundance ratios of 71: 26: 3, respectively, were obtained by adding ethylene oxide to an esterified product of glycerin and stearic acid to give a hydroxyl value of 93.8.
% Polyether polyol.

Alkyl polyol B: a polyether polyol in which the abundance ratios of monoester and diester each having a hydroxyl value of 42.4 by adding propylene oxide to an esterified product of dipropylene glycol and stearic acid are 96: 4%.

Polyol A: Hydroxyl value is 33 3
Functional polyoxypropylene polyol. Polyol B: Trifunctional polyoxypropylenepolyol having a hydroxyl value of 29.7 Polyamine A: Bifunctional amine-terminated polyoxypropylene having an amine value of 56. (D-2000; trade name of Texaco Chemical Campany)

DETDA: 3,5-diethyl-2,4-
An 8: 2 mixture of diaminotoluene and 3,5-diethyl-2,6-diaminotoluene. Catalyst A: a 1: 2 mixture of triethylenediamine and dipropylene glycol. Catalyst B: dibutyltin dilaurate.

Isocyanate A: Liquid isocyanate having an NCO content of 29.1% obtained by modifying MDI with uretone imine.

Composition A: Polyamine A 70 parts and DET
A mixed solution of 25 parts of DA. Composition B: Polyol B 100 parts, DETDA 25
Part, a mixed solution of 0.3 part of catalyst A and 0.15 part of catalyst B.

Prepolymer A: Isocyanate A 64
16.1% NCO isocyanate prepolymer obtained by reacting 16 parts with alkyl polyol A. Prepolymer B: NCO 16.1% isocyanate prepolymer obtained by reacting 62 parts of isocyanate A, 19 parts of alkyl polyol A and 19 parts of polyol A. Prepolymer C: Isocyanate A 59.2 parts, Alkyl Polyol B 20.4 parts and Polyol A 20.
NCO 16.1% obtained by reacting 4 parts
Isocyanate prepolymer.

Prepolymer D: Isocyanate A 59
16.1% NCO isocyanate prepolymer obtained by reacting 100 parts of Polyol A with 41 parts of Polyol A. Prepolymer E: Isocyanate prepolymer of 22.7% NCO obtained by reacting 82 parts of Isocyanate A with 18 parts of Alkyl Polyol A. Prepolymer F: NCO2 obtained by reacting 80 parts of isocyanate A and 20 parts of polyol A
2.7% isocyanate prepolymer.

The resins obtained in the examples and comparative examples were evaluated as follows. Number of continuous mold release: The number of times that D-186 (manufactured by Chukyo Yushi Co., Ltd.) as an external mold release agent is applied to the mold only for the first time and the mold can be released without breaking. Flexural modulus: JIS K-6911. Elongation rate: JIS K-3601. Heat Sag: 10.16 cm (4 inches) overhang, 120 ° C x 1 hr.

[0042]

Example 1 PU-50 manufactured by Polyurethane Engineering Co., Ltd. using prepolymer A as solution A and composition A as solution B
With a RIM machine, the molded product shown in Fig. 1 (approximately W250 x D
180 × H150 × t3 mm) was obtained by reaction injection molding with NCO index (% molar ratio of NCO groups to OH groups and / or NH ₂ groups) 105.
The results are shown in Table 1.

[0043]

Example 2 Molding was carried out in the same manner as in Example 1 except that Prepolymer B was used as Liquid A. The results are shown in Table 1.
Shown in.

[0044]

Example 3 Molding was carried out in the same manner as in Example 1 except that Prepolymer C was used as Liquid A. The results are shown in Table 1.
Shown in.

[0045]

Comparative Example 1 Molding was carried out in the same manner as in Example 1 except that Prepolymer D was used as the liquid A. The results are shown in Table 1.
Shown in.

[0046]

Example 4 Molding was carried out in the same manner as in Example 1 except that Prepolymer E was used as the A liquid and Composition B was used as the B liquid. The results are shown in Table 2.

[0047]

Comparative Example 2 Molding was carried out in the same manner as in Example 4 except that Prepolymer F was used as Liquid A. The results are shown in Table 2.

The molded articles obtained in Examples 1 to 4 all showed excellent releasability from the mold, and did not impair the physical properties and coating properties of conventional polyurethaneurea or polyurea resins.

[0049]

[Table 1]

[0050]

[Table 2]

Notes to Table 1) Prepolymer A 2) Prepolymer B 3) Prepolymer C 4) Prepolymer D 5) Prepolymer E 6) Prepolymer F

[0051]

[Brief description of drawings]

FIG. 1 is an external view of a product obtained by a mold used in the present invention.

FIG. 2 is a side view of FIG.

FIG. 3 is a sectional view of FIG.

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[Procedure amendment]

[Submission date] August 27, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0029

[Correction method] Change

[Correction content]

As the aromatic polyamine, 1-methyl 3,
5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 1,
3,5-triethyl-2,6-diaminobenzene, 3,
5,3 ', 5'-tetraethyl-4,4'-diaminodiphenylmethane and the like can be mentioned. There are two types of foaming agents and auxiliaries that can be used as necessary in the present invention: an inert low boiling point solvent as a foaming agent and a reactive foaming agent. The former include methylene chloride, methylene trichloride, Trichlorofluoromethane, dichlorodifluoromethane,
Acetone, hexane, etc. are mentioned, and also nitrogen gas, air, etc. are included. Examples of the latter include water, and include those that generate gas by decomposing at a high temperature, such as azo compounds. Examples of the auxiliaries include foam stabilizers and catalysts, and as the foam stabilizers, organopolysiloxanes, organopolysiloxane-polyoxyalkylene copolymers, and silicone-based silicones such as polyalkenylsiloxanes having polyoxyalkylene side chains. Surfactants and cationic, anionic and nonionic surfactants can also be used. As the catalyst, as amines, triethylamine, triethanolamine, diethanolamine, monoethanolamine, triethylenediamine, dimethylmonoethanolamine, diethylmonoethanolamine,
Examples thereof include tetramethylethylenediamine, tetramethylpropanediamine, tetramethylbutanediamine, tetramethylhexanediamine and pentamethyldiethylenetriamine. Examples of the organometallic compound include stannous octoate, dibutyltin dilaurate, dibutyltin diacetate, dimethyltin methylcaptite, dibutyltin mercaptite, tetrabutyl-1,3-diacetoxydistannoxane, tetrabutyl-1,3-dilauroyl. Oxidistanoxane etc. are mentioned. Further, conventionally known compounds such as carboxylic acid salts of tertiary amines can be used, and a mixture thereof can also be used.

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Claims (1)

[Claims] 1. An organic polyisocyanate prepolymer (a) a polyol and / or a polyamine, a chain extender (c) a polyurethane and / or a polyurea by reaction injection molding using a foaming agent and an auxiliary agent if necessary. In the method for producing a molded article,
(A) As the organic polyisocyanate prepolymer, a compound of the general formula (1) (R ¹ O) _c R ² {(OR ³ _B OH} _(ac) (1) (wherein R ¹ is an acyl group having 6 to 40 carbon atoms, R ² is an a-functional polyol residue, R ³ is an alkylene group having 2 to 4 carbon atoms or a halogen-substituted compound thereof. , A is an integer of 2 or more, b is an integer of 0 to 400, c is an integer of 1 or more and a-1 or less), or an organic polyisocyanate prepolymer obtained by reacting a mixture thereof. A method for producing a polyurethane and / or polyurea molding characterized by the following.