JPH07126521A - Method for producing molded polyurethane and / or polyurea having excellent self-releasing property - Google Patents

Abstract

(57) [Abstract] [Purpose] Polyurethane by reaction injection molding and /
Alternatively, in the method for producing a polyurea resin molded product, by using a specific internal release agent, a molded product having good releasability from the mold and excellent in coatability and physical properties is provided. [Structure] Using (a) an organic polyisocyanate and (b) a polyol and / or a polyamine, a chain extender (c) an internal mold release agent (d) a polyol mixed solution containing a foaming agent and an auxiliary agent as required. In the method for producing a polyurethane and / or polyurea molded product by reaction injection molding, a specific metal silicate compound having a long-chain aliphatic substituent is used as an internal mold release agent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an internal release agent.
More specifically, the present invention relates to a production method using a specific internal release agent in the production of a polyurethane and / or polyurea molded article having excellent self-release properties by reaction injection molding.

[0002]

2. Description of the Related Art Polyurethane and / or polyurea moldings are excellent in mechanical properties such as tensile strength, heat resistance and impact resistance, and moldings obtained by reaction injection molding are automobile parts, electronic parts. It is used in parts and furniture. However, since the urethane bond and the urea bond have adhesiveness to metal, depending on the molecular structure of the resin skeleton, an external or internal mold release agent is used for releasing the molded product from the mold. is necessary. Since polyurea resin has a higher reactivity than polyurethane resin, continuous demolding is possible to some extent by using an external mold release agent, but as a method for making it easier to demold a molded product,

For example, as an external release agent, (a) a method of coating an organosilane compound on a mold to form a polysiloxane compound (Japanese Patent Publication No. 3-11248),
(B) A mold release agent comprising an isobutylene oligomer and a wax (Japanese Patent Publication No. 3-11604), and (c) a mold release agent containing a halogen-containing polyether as a main component (Japanese Patent Publication No. 3-98).
No. 48) is used.

These methods reduce the adhesive force between the mold and the interface of the molded article in the production of polyurethane and / or polyurea molded articles, and are effective to some extent in reaction injection molding. However, these external mold release agents are not always satisfactory in mold releasability, it takes time and effort to mix the mold release agent to be used, and the mold release agent attached to the molded product causes the surface of the molded product to be rough or complicated. There is a problem that skill is required to uniformly apply the release agent to the shaped mold.

Further, a method of using zinc stearate as an internal mold release agent (JP-A-60-245622) is described. However, zinc stearate has poor solubility in polyols and will settle and separate if left at room temperature. In order to improve the compatibility with the polyol, it is added to the polyol after being mixed with the amine compound, but it has a drawback that preparation of the raw material is troublesome, and the release property is also required to be improved.

[0006]

In the production of polyurethane and / or polyurea moldings, the stability, physical properties, mold releasability and coatability of the polyol solution are excellent even when an internal mold release agent is added, and the bleeding phenomenon occurs over time. As a result of earnest studies on an internal mold release agent having a small amount, the present invention has been found to achieve the object by using a specific organosilicon compound, resulting in the present invention.

[0007]

[Means for Solving the Problems] That is, the present invention provides (a) an organic polyisocyanate and (b) a polyol and / or a polyamine, a chain extender (c) an internal mold release agent (d) an optional foaming agent. In the production of a polyurethane and / or polyurea molded product by reaction injection molding using a polyol mixed solution containing an auxiliary, (c) as an internal release agent, (c)
-1) Organosilicon obtained by reacting an organosilicon compound containing active hydrogen and a hydrolyzable group with a long-chain aliphatic monoisocyanate, and hydrolyzing the hydrolyzable group in a solvent containing a metal ion. A release agent that is a compound. (C-2) An organosilicon compound containing an isocyanate group or an epoxy group and a hydrolyzable group is reacted with a long-chain aliphatic monoamine or a long-chain aliphatic monoalcohol to cause the hydrolyzable group to exist in a solvent containing a metal ion. A release agent which is an organosilicon compound obtained by hydrolysis with an internal release agent (c-1) or (c-2) is used in an amount of 0.05 to 100 parts by weight based on 100 parts by weight of the polyol mixed solution. 10.0
It is a method for producing a polyurethane and / or polyurea molded article having excellent self-releasing properties, characterized by using 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,
Examples include xylylene diisocyanate, isophorone diisocyanate, methylene bis (cyclohexyl isocyanate), hexamethylene diisocyanate and the like. Further, polymeric polyisocyanates, which are polyisocyanates having an isocyanate group obtained by the reaction of the above-mentioned diisocyanate polymers, difunctional or higher-functional polyols, etc. with the above-mentioned diisocyanate compounds and the polymers thereof, isocyanate polyol adducts, uretdiones, isocyanurates. And carbodiimide modified products are also included.

Known polyols can be used as the polyol of the present invention. A polyether polyol obtained by addition polymerization of cyclic ethers using water, polyhydric alcohol, polyhydric phenol, alkanolamine, mono- or polyamine, etc. as an initiator is preferable. The number of functional groups of this polyether polyol is preferably 2 to 8, more preferably 2 to 3.

As the polyhydric alcohol as the initiator,
Ethylene glycol, propylene glycol, diethylene glycol, glycerin, trimethylolpropane,
Examples include hexanetriol, diglycerin, pentaerythritol, methylglycoxide, dextrol, sorbitol, sucrose and the like. Examples of the polyhydric phenol as an initiator include phenol-aldehyde initial condensate, bisphenol A, bisphenol F and the like.

Examples of the alkanolamine as the initiator 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. Known polyamines can be used as the polyamine of the present invention. Some of the above polyether polyols are aminated, preferably having 2 or more functional groups and a molecular weight of 2
However, the number is not limited to these.

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 two or more active hydrogen groups and having a molecular weight of 500 or less. For example, as the polyhydric alcohol, ethylene glycol, 1,4-butanediol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, and as the alkanolamine, monoethanolamine, diethanolamine, triethanolamine,
As diisopropanolamine, N-alkyl-substituted diethanolamine, and 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, 3,5-diethyl-2,4-diaminotoluene and 3,5-diethyl-2,6-diaminotoluene were 8: 2. A mixture (DETDA) etc. are mentioned.

The internal release agent used in the present invention includes:
An organosilicon compound or isocyanate obtained by reacting an organic silicon compound containing an active hydrogen and a hydrolyzable group with a long-chain aliphatic monoisocyanate, and hydrolyzing the hydrolyzable group in a solvent in which a metal ion is present. Obtained by reacting an organosilicon compound containing a group and a hydrolyzable group with a long-chain aliphatic monoamine or a long-chain aliphatic monoalcohol to hydrolyze the hydrolyzable group in a solvent containing a metal ion. It is an organosilicon compound. These can be derived from organosilicon compounds. Examples of the organosilicon compound include γ-aminopropyltriethoxysilane, γ-aminopropyldimethyltriethoxysilane, and N- (β-aminoethyl) γ.
-Aminopropyltrimethoxysilane, octadecyltrichlorosilane, dimethyloctadecylchlorosilane,
γ-mercaptopropyltrimethoxysilane, γ-isocyanatopropylmethoxysilane, γ-glycidoxypropyltrimethoxysilane and the like can be mentioned. As the compound containing a long-chain alkyl group which is reacted with the organosilicon compound, octadecyl isocyanate (ODI) having 18 carbon atoms, octadecyl alcohol, octadecylamine and the like are preferable. Preferable zinc octadecylureapropyldimethyl silicate derived from ODI and an organosilicon compound having a terminal amino group [C ₁₈ H ₃₇ NHCONHC ₃ H ₆ Si (CH ₃ ) ₂ O]
₂ Zn, octadecyl ureapropyl dimethyl magnesium silicate [C ₁₈ H ₃₇ NHCONHC ₃ H ₆ Si (CH ₃ ) ₂ O]
_Disodium Mg and octadecyl urea propyltrimethoxysilane silicate _{C 18 H 37 NHCONHC 3 H 6} Si (ONa) 3 and the like. Further, when the derivative is derived from an organosilicon compound having a terminal isocyanate group, octadecylamine can be used. The metal silicate compound can be easily obtained by hydrolyzing methoxysilane, ethoxysilane and chlorosilane using a solvent containing metal ions. These release agents can be used both as an external release agent and as an internal release agent, and when used as an internal release agent, the polyol mixed liquid 1
0.5 to 10.0 parts by weight is used with respect to 00 parts by weight.
In addition, known solubilizers can be used if necessary.

As the foaming agent and auxiliary agent that can be used as required in the present invention, there are two kinds of foaming agents, which are an inert low boiling point solvent and a reactive foaming agent. Methylene chloride, trichlorofluoromethane,
Examples thereof include dichlorodifluoromethane, acetone and hexane, and nitrogen gas, air and the like are also included. Examples of the latter include water, and include those that generate gas by decomposing at a temperature higher than room temperature, such as azo compounds.

Examples of auxiliaries include foam stabilizers and catalysts.
Examples of the foam stabilizer include silicone-based surfactants such as organopolysiloxanes, organopolysiloxane-polyoxyalkylene copolymers, polyalkenylsiloxanes having a polyoxyalkylene side chain, and cationic, anionic and nonionic surfactants. Examples include system surfactants.

Examples of the catalyst include amines such as triethylamine, triethanolamine, diethanolamine, diethylmonoethanolamine, tetramethylethylenediamine, tetramethylpropanediamine, tetramethylhexanediamine and pentamethyldiethylenetriamine, for example stannas octoate, Organometallic compounds such as dibutyltin dilaurate, dibutyltin diacetate, dimethyltin methylcaptide, dibutyltin mercaptide, tetrabutyl-1,3-diacetoxydistannoxane, tetrabutyl-1,3-dilauroyloxydistannoxane, etc. Conventionally known compounds such as carboxylic acid salts of tertiary amines can be used, and a mixture thereof can also be used. The reaction injection molding is a method in which at least two components of a polyol component and an isocyanate component are prepared, subjected to high pressure collision to form a reaction mixture, and the reaction mixture is filled in a mold to obtain a molded article. The polyol component comprises a polyol and / or a polyamine, a chain extender, an internal release agent, and if necessary, a foaming agent and an auxiliary agent.

[0017]

The polyurethane and / or polyurea molded articles obtained by the present invention have excellent moldability by a reaction injection molding machine and exhibit good mold releasability from the mold, and the physical properties of the obtained molded articles. The paintability is also good.

[0018]

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 "%" means "% by weight". The samples used in Examples and Comparative Examples are as follows. Polyol A: Polyoxypropylene polyol having a hydroxyl value of 28.0. (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) Internal mold release agent A: octadecyl ureapropyl dimethyl zinc silicate. Internal release agent B: octadecyl ureapropyl dimethyl magnesium silicate. Internal release agent C: sodium octadecyl ureapropyl trisilicate. Internal release agent D: zinc stearate. EDA-p4: N, NN ', N'-tetrakis (2-
Hydroxypropyl) ethylenediamine. Catalyst A: a 1: 2 mixture of triethylenediamine and dipropylene glycol. Catalyst B: dibutyltin dilaurate.

Isocyanate A: N is obtained by modifying uretonimine-modified MDI with a liquid isocyanate having an NCO content of 29.1% with a polyoxypropylene polyol having a hydroxyl value of 33 (trade name FA-703; manufactured by Sanyo Chemical Industry Co., Ltd.).
Liquid isocyanate having a CO content of 22.7%. Isocyanate B: MDI modified with uretone 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 was prepared by the following method, and its composition is shown in Table 1. Preparation of Polyol Mixture A 100 parts of Polyol A and DETDA were placed in a four-necked flask.
Charge 25 parts and 2 parts of internal mold release agent A to 10 at 80 ° C.
After stirring and mixing for minutes, the internal release agent A was dissolved in the raw material polyol, and then 0.3 parts of the catalyst A and 0.15 part of the catalyst B were added and mixed to prepare a polyol mixed solution A. Preparation of Polyol Mixtures B to E The structures shown in Table 1 were used to prepare polyol mixes A in the same manner.

Preparation of Polyol Mixtures F to H Using the composition shown in Table 1 and using zinc stearate as an internal mold release agent, the same procedure as in the preparation of Polyol Mixture A was performed at 80 ° C.
After stirring and mixing for minutes, the catalyst of Table 1 was added. However, the polyol mixed solution H contains the same amount of the solubilizer ED as zinc stearate.
A-p4 was used.

[0022]

[Table 1]

Example 1 Using a reaction injection molding machine (PU-50 RIM manufactured by Polyurethane Engineering) with isocyanate A as liquid A and polyol mixed liquid A as liquid B, a molded product (W250 × D180 × t3 mm) shown in FIG. Was molded with NCO index 105. The results are shown in Table 2.

Examples 2 to 5 Example 1 was repeated except that the polyol mixed solution B was used as the solution B.
Molding was carried out in the same manner as in. The results are shown in Table 2.

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

[0026]

[Table 2]

The molded articles obtained in Examples 1 to 5 all showed excellent mold releasability from the mold and had good physical properties and coating properties.

The resins shown in Examples and Comparative Examples were evaluated as follows. Number of continuous demolding: The number of times that D-186 (manufactured by Chukyo Yushi Co., Ltd.) as an external mold release agent is applied to the surface of the mold only for the first time, and the molded product can be demolded without breaking. Flexural modulus: According to JIS K 6911. Elongation: According to JIS K6301. Heat Sag: 10.16 cm (4 inches) overhang,
120 ° C x 1 hr

[Brief description of drawings]

FIG. 1 is an external view of a product obtained by the mold used in the present invention. FIG. 2 is a side view of FIG. FIG. 3 is a sectional view of FIG.

Claims (1)

[Claims] 1. An organic polyisocyanate (a) and (b)
Polyurethane and / or polyurea molded product by reaction injection molding using a polyol and / or polyamine, a chain extender (c) an internal mold release agent (d) a polyol mixed solution consisting of a foaming agent and an auxiliary if necessary. In manufacturing, (c)
As an internal mold release agent, (c-1) an organosilicon compound containing active hydrogen and a hydrolyzable group is reacted with a long-chain aliphatic monoisocyanate, and the hydrolyzable group is hydrolyzed in a solvent containing a metal ion. A release agent which is an organosilicon compound obtained by decomposition. (C-2) An organosilicon compound containing an isocyanate group or an epoxy group and a hydrolyzable group is reacted with a long-chain aliphatic monoamine or a long-chain aliphatic monoalcohol to cause the hydrolyzable group to exist in a solvent containing a metal ion. A release agent, which is an organosilicon compound obtained by hydrolysis in step 1, is used, and the internal release agent (c-1) or (c-2) is added in an amount of 0.05 to 100 parts by weight with respect to 100 parts by weight of the polyol mixed solution. A method for producing a polyurethane and / or polyurea molded article having excellent self-releasing properties, which comprises using 10.0 parts by weight.