JP3109061B2 - Method for producing polyurethane and / or polyurea molded article having excellent self-releasing property - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyurethane and / or polyurea molded product, and more particularly to a method for producing a polyurethane and / or polyurea molded product by reaction injection molding. It relates to a manufacturing method.

[0002]

2. Description of the Related Art Polyurethane and / or polyurea molded products have excellent mechanical properties such as tensile strength, heat resistance and impact resistance. Molded products obtained by reaction injection molding are used for automobile parts and electronic parts. It is used for furniture and furniture. However, urethane bonds and urea bonds have an adhesive property to metal, depending on the molecular structure of the resin skeleton, so that an external or internal release agent is required to release a molded product from a mold. is necessary. Polyurea resin is more reactive than polyurethane resin, so by using an external release agent, a certain degree of continuous demolding is possible,
As a method to make demolding of molded products easier,

For example, as an external release agent, (a) a method in which an organosilane is applied to a mold to form a polysiloxane (Japanese Patent Publication No. 3-11248), (b) a release mold comprising an isobutylene oligomer and wax Agent (Tokuhei 3-
No. 11604), and (c) use of a release agent containing a halogen-containing polyether as a main component (Japanese Patent Publication No. 3-9848).

[0004] These methods reduce the adhesive strength between the mold and the molded product interface in the production of polyurethane and / or polyurea molded products, and are effective to some extent in reaction injection molding. However, the external release agent is not always satisfactory in release properties, it takes time to mix the release agent to be used, and the surface of the molded product is rough due to the release agent adhered to the molded product, and the complex shape is complicated. There is a problem that skill is required to uniformly apply the release agent to the mold.

[0005] A method using zinc stearate as an internal mold release agent (JP-A-60-245622) is described. However, zinc stearate has poor solubility in polyol and sediments and separates when left at room temperature. In order to improve the compatibility with the polyol, it is mixed with an amine compound and added to the polyol. However, there is a drawback that the preparation of the raw material is troublesome, and improvement in the releasability has been required.

[0006]

In the production of a polyurethane and / or polyurea molded product, the stability, physical properties, release properties and coating properties of a polyol solution are excellent even if an internal release agent is added, and bleeding occurs over time. As a result of intensive studies on an internal mold release agent having a low content, the present inventors have found that the object can be achieved by using a metal salt of a specific higher fatty acid, and have reached the present invention.

[0007]

The present invention comprises (a) an organic polyisocyanate (b) a polyol and / or a polyamine (c) a chain extender (d) an internal mold release agent (e) foaming if necessary In the production of a polyurethane and / or polyurea molded product by reaction injection molding using an agent and an auxiliary , ( d ) an internal release agent represented by the following general formula (1) (R-COO) ₄ Zr (1) Represents an alkyl group having 8 to 25 carbon atoms.) The zirconium salt of a higher fatty acid represented by the formula (1) is added in an amount of 0.1 to 100 parts by weight of polyol and / or polyamine .
A method for producing a polyurethane and / or polyurea molded product having excellent self-releasing properties, characterized by using 5 to 5.0 parts by weight.

The organic polyisocyanate used in the present invention includes aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate and the like.
For example, diphenylmethane diisocyanate (MDI),
Polymethylene polyphenylene polyisocyanate, tolylene diisocyanate, naphthalene diisocyanate,
Xylylene diisocyanate, isophorone diisocyanate, methylene bis (cyclohexyl isocyanate), hexamethylene diisocyanate, and the like. Further, a polymeric polyisocyanate which is a polyisocyanate having an isocyanate group obtained by a reaction of the above-mentioned diisocyanate polymer or a bifunctional or more polyol with the diisocyanate compound and the polymer, a polyol adduct of isocyanate, uretdione, isocyanurate And carbodiimide modified products.

Known polyols can be used as the polyol of the present invention. A polyether polyol obtained by using water, a polyhydric alcohol, a polyhydric phenol, an alkanolamine, a mono- or polyamine as an initiator, and subjecting a cyclic ether to addition polymerization is preferable. The polyether polyol preferably has 2 to 8 functional groups, more preferably 2 to 3 functional groups.
Is preferred.

As polyhydric alcohols as initiators,
Ethylene glycol, propylene glycol, diethylene glycol, glycerin, trimethylolpropane,
Hexanetriol, diglycerin, pentaerythritol, methylglycoxide, dextrol, sorbitol, sucrose and the like. Examples of the polyhydric phenol as the initiator include a phenol-aldehyde precondensate, bisphenol A, bisphenol F and the like.

As the alkanolamine as the initiator, monoethanolamine, diethanolamine, triethanolamine, diisopropylamine, and as the mono or polyamine, aniline, diaminodiphenylmethane, tolylenediamine, ethylenediamine and the like can be mentioned. Examples of the cyclic ethers include ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, and halogen-substituted compounds thereof. Known polyamines can be used as the polyamine of the present invention. There are aminated polyether polyols, preferably having 2 or more functional groups and a molecular weight of 200 to 5000, but are not limited thereto.

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. Preferred chain extenders include
Among the above compounds, those having two or more active hydrogen groups and having a molecular weight of 500 or less. For example, polyhydric alcohols include ethylene glycol, 1,4-butanediol,
Propylene glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane alkanolamines include monoethanolamine, diethanolamine, triethanolamine, diisopropanolamine, N-alkyl-substituted diethanolamine, and aromatic polyamines such as 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.

The internal release agent used in the present invention includes:
General formula (R-COO) ₄ Zr (where R is a carbon number of 8 to 25
Represents an alkyl group containing ) Is a zirconium salt of a higher fatty acid. Examples of the higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, arginic acid, behenic acid, oleic acid, linoleic acid and the like. Preferably, stearic acid having 18 carbon atoms is used, and this internal release agent is used by dissolving it in a polyol. If it is difficult to dissolve in the polyol, a solubilizer may be used. As the solubilizer, as a phosphorus compound, for example, poly (dipropylene glycol) phenyl phosphite (DHOP), phenyl neopentylene glycol phosphite, heptakis (dipropylene glycol) triphosphite, tetraphenyl dipropylene glycol phosphite ( THOP).
Examples of the amine-based compound include N, NN-, N'-tetrakis (2-hydroxypropyl) ethylenediamine (EDA-p4). Preferred solubilizers are phosphorus compounds.

The blowing agent and auxiliary agent which can be used as required in the present invention include two types of blowing agents, namely, an inert low-boiling solvent and a reactive blowing agent. Methylene chloride, trichlorofluoromethane,
Examples thereof include dichlorodifluoromethane, acetone, and hexane, and further include nitrogen gas and air. The latter includes water, and includes azo compounds that decompose at a temperature higher than room temperature to generate gas.

[0015] Examples of the auxiliary agent include a foam stabilizer and a catalyst. Examples of the foam stabilizer include an organopolysiloxane and a catalyst.
Examples include silicone-based surfactants such as organopolysiloxane-polyoxyalkylene copolymers and polyalkenylsiloxanes having a polyoxyalkylene side chain, and cationic, anionic, and nonionic surfactants.

As the catalyst, for example, triethylamine,
Amines such as triethanolamine, diethanolamine, diethylmonoethanolamine, tetramethylethylenediamine, tetramethylpropanediamine, tetramethylhexanediamine, pentamethyldiethylenetriamine, for example, stannas octoate, dibutyltin dilaurate, dibutyltin diacetate, dimethyltin Conventional organic metal compounds such as methylcaptide, dibutyltin mercaptide, tetrabutyl-1,3-diacetoxydistannoxane, tetrabutyl-1,3-dilauroyloxydistannoxane, and carboxylate salts of tertiary amines Known materials can be used, and mixtures thereof are also included. Reaction injection molding is a method in which at least two components, a polyol component and an isocyanate component, are prepared, and they are made to collide at a high pressure to form a reaction mixture. The reaction mixture is filled in a mold to obtain a molded product. The polyol component comprises a polyol and / or polyamine, a chain extender, an internal mold release agent, and, if necessary, a foaming agent and an auxiliary.

[0017]

Industrial Applicability The polyurethane and / or polyurea molded products obtained by the present invention have excellent moldability by a reaction injection molding machine, show good releasability from a mold, and have physical properties of the obtained molded products. Good paintability.

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,
"Parts" means "parts by weight", and "%" means "% by weight". The samples used in the examples and comparative examples are as follows. Polyol B: a polyoxypropylene polyol having a hydroxyl value of 29.7. (FA-909; trade name of Sanyo Chemical Industries) Polyamine A: bifunctional amine-terminated polyoxypropylene having an amine value of 56. (D-2000; trade name of Texaco Chemical) DETDA: 8: 2 mixture of 3,5-diethyl-2,4-diaminotoluene and 3,5-diethyl-2,6-diaminotoluene. EDA-p4: N, N-N ', N'-tetrakis (2-
(Hydroxypropyl) ethylenediamine. DHOP: poly (dipropylene glycol) phenyl phosphite. THOP: tetraphenyldipropylene glycol diphosphite. Catalyst A: a mixture of triethylenediamine and dipropylene glycol of 1: 2. Catalyst B: dibutyltin dilaurate.

Isocyanate A: MDI-modified uretonimine-modified liquid isocyanate having an NCO content of 29.1% modified with a polyoxypropylene polyol having a hydroxyl value of 33 (trade name FA-703; manufactured by Sanyo Chemical Industries)
Liquid isocyanate with a CO content of 22.7%. Isocyanate B: MDI modified with ureton imine
A liquid isocyanate having an NCO content of 16.1% obtained by modifying a liquid isocyanate having an NCO content of 29.1% with a polyol A.

(Preparation of Polyol Mixture) Each polyol mixture is prepared by the following method, and its composition is shown in Table 1. Preparation of Polyol Mixture A In a four-necked flask, 100 parts of polyol B and DETDA
25 parts and 2 parts of zirconium stearate were charged and stirred and mixed at 100 ° C. for 10 minutes to dissolve zirconium stearate in the raw material polyol.
Parts and 0.15 parts of catalyst B were added and mixed to prepare a polyol mixture A. Preparation of Polyol Mixtures B to F The preparations were made in the same manner as for polyol mixture A with the tissues shown in Table 1.

Preparation of Polyol Mixtures G to I Using the composition shown in Table 1, zinc stearate was used as an internal mold release agent.
After stirring and mixing for 0 minutes, the catalyst shown in Table 1 was added. However, the polyol mixture I was the same amount of the solubilizing agent E as zinc stearate.
DA-p4 was used.

[0021]

[Table 1]

Example 1 A molded product (W250 × D180 × t3 mm) shown in FIG. 1 using a reaction injection molding machine (PU-50 RIM manufactured by Polyurethane Engineering) using isocyanate A as liquid A and polyol mixed liquid A as liquid B. Was performed at an NCO index of 105. Table 2 shows the results.

Example 2 Example 1 was repeated except that the polyol mixture B was used as the liquid B.
Molding was carried out in the same manner as in Table 2 shows the results.

Examples 3 to 6 Molded articles were obtained in the same manner as in Example 1 by using Liquid A and Liquid B shown in Table 2. Table 2 shows the results.

Comparative Examples 1 to 3 Molded articles were obtained in the same manner as in Example 1 by using Liquid A and Liquid B shown in Table 2. Table 2 shows the results.

[0026]

[Table 2]

Each of the molded articles obtained in Examples 1 to 6 exhibited excellent mold release properties and good physical properties and coating properties.

The evaluation of the resins shown in Examples and Comparative Examples was performed as follows. Number of continuous demolding: The number of times that D-186 (manufactured by Chukyo Yushi Co., Ltd.) as an external release agent is applied to the surface of the mold only for the first time and the molded product can be released without breaking. Flexural modulus: according to JIS K-6911. Elongation: According to JIS K-6301. Heat sag: 10.16 cm (4 inch) overhang,
120 ° C x 1 hr.

[Brief description of the drawings]

FIG. 1 is an external view of a product.

FIG. 2 is a side view of a product.

FIG. 3 is a sectional view of a product.

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI // B29K 75:00 Examiner Tomoya Kato (56) References JP-A-2-14226 (JP, A) JP-A-63-72757 (JP) , A) JP-A-2-20961 (JP, A) JP-A-63-207622 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B29C 45/00-45/84 B29C 33/00-33/76 C08G 18/65 C08K 5/09 C08L 75/04

Claims (2)

(57) [Claims] 1. A reaction injection using (a) an organic polyisocyanate (b) a polyol and / or a polyamine (c) a chain extender (d) an internal mold release agent (e) a foaming agent and an auxiliary as required. In the production of a polyurethane and / or polyurea molded product by molding, ( d ) an internal release agent represented by the following general formula (1) (R-COO) ₄ Zr (1) (wherein R contains 8 to 25 carbon atoms) A zirconium salt of a higher fatty acid represented by the formula ( 1): 0.1 to 100 parts by weight of polyol and / or polyamine .
A method for producing a polyurethane and / or polyurea molded product having excellent self-releasing properties, comprising using 5 to 5.0 parts by weight. 2. The method according to claim 1, wherein the zirconium salt of a higher fatty acid represented by the general formula (1) is zirconium stearate.