JPH0253818A - Production of polyurethane-polyurea composition - Google Patents

Abstract

PURPOSE:To economically obtain the subject composition suitable for car bumper, fender and door, etc., having excellent coating properties and self- releasability, etc., by mixing specific internal release agent having amino group, etc., on both terminals and subjecting to reaction injection molding. CONSTITUTION:(A) Polyisocyanate such as 4,4'-diphenylmethane diisocyanate is mixed with (B) active hydrogen-containing compound such as polyether polyol preferably having 1000-18000 molecular weight, (C) chain extender such as ethylene glycol and (D) catalyst (e.g., dibutyltin diacetate) and (E) internal release agent expressed by the formula (R is H or 1-10C alkylene, etc.; A is 2-10C alkylene; Y is alkyl, etc.; a+b is 0-270; b is 0-10) is added, then subjected to reaction injection molding to afford the aimed composition.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention is directed to reaction injection molding (hereinafter referred to as RIM) of a polyurethane/polyurea composition that uses an internal mold release agent and has excellent paintability and self-release properties. (abbreviated as "method").

Polyurethane/polyurea compositions produced by the RIM method have excellent physical properties, moldability, and appearance, and are widely used.

Specific examples include automobiles, sports and leisure goods, office equipment housings, furniture, agricultural equipment, etc.

Particularly for automotive applications, elastic elastomers can be used for fascias, bumpers, fenders, doors, sides, etc.
It is taken by i.

In this case, the mold must be completely covered with mold release agent,
In this method, it is necessary to apply a mold release agent each time molding is performed. In addition, the old mold release agent that remains and accumulates,
In order to impair the gloss and surface properties of the molded product, it is necessary to remove the mold release agent remaining on the mold surface at regular intervals and clean the surface. This takes a considerable amount of time.

On the other hand, a method of producing a polyurethane/polyurea composition having self-releasing properties by adding a compound having mold-releasing properties to a polyurethane-polyurea composition reaction mixture has also been studied. The agent is called an internal mold release agent.

As internal mold release agents, organic silicon compounds, higher fatty acid esters, higher fatty acid metal salts, etc. are known.

However, higher fatty acid esters have insufficient mold release effects, and higher fatty acid metal salts are often solid at room temperature and are often insoluble in high molecular weight polyols.

Compositions having a foamed center part and a dense skin part, such as molding, are used for armrests, steering wheels, air spoilers, and the like.

As described above, the present invention provides a method for producing polyurethane/polyurea compositions that have excellent paintability and self-releasing properties for material systems that have a very wide range of applications. productivity of composition manufacturing;
The purpose is to contribute to economic efficiency.

[Conventional technology]

Polyurethane/polyurea compositions are usually produced by charging a reaction mixture consisting of a polyisocyanate, an active hydrogen compound, a chain extender, a catalyst, and, if necessary, a blowing agent, auxiliaries, additives, and inorganic fillers, in a closed mold. It is manufactured by reaction molding.

The reaction mixture is cured in the mold and removed as a molded article. Polyurethane/polyurea compositions are extremely easy to adhere to metals, and to prevent this, wax or wax is applied to the surface of the mold.
Applying a mold release agent such as metal soapAlso, higher fatty acid metal salts remain solid and have no mold release effect even when added to the active hydrogen compound component.If used as an internal mold release agent, they must be dissolved in a dissolving agent. It is necessary to use the

Usually, active hydrogen compounds containing primary amines and secondary amines are used as solubilizing agents, but ethylene glycol,
Ordinary polyurethane compositions that use low-molecular-weight diols such as , 4-butanediol, etc. as chain extenders are insufficiently effective.

On the other hand, organic silicon compounds have extremely good mold releasability due to their characteristics, but they have fatal defects such as repellency of the paint during painting and poor adhesion of the paint film. Several improvements have been attempted to solve the problems of paint repellency and poor adhesion of paint films during painting.

Generally, compounds are known in which an organic group with or without an active hydrogen atom is added to the side chain of a dimethylsiloxane compound, as shown in the following general formula (1), with respect to isocyanate. These could not completely prevent paint repellency and poor adhesion of the paint film during painting.

General formula (1) (wherein Z is an organic group with or without an active hydrogen atom with respect to isocyanate) As a result of extensive studies, the present inventors have found that the following general formula (TI)
When an organosilicon compound having an amino group or an imino group at both ends, represented by They have discovered that the drawbacks of conventional organic silicon compounds, such as poor adhesion, can be completely eliminated, and have finally arrived at the present invention.

The present invention can omit the application of an external mold release agent and the cleaning of the mold surface, and completely eliminates the problems of paint repellency and poor adhesion of the paint film when painting a molded polyurethane/polyurea composition. Another object of the present invention is to provide a manufacturing method that contributes to improved productivity and economical efficiency when molding polyurethane/polyurea compositions.

An alkoxyalkyl group, an alkylcarbonyl group, an alkylcarbamoyl group, an aralkyl group or a phenylcarbamoyl group, and Y represents an alkyl chain or a polyalkylene oxide chain with or without an active hydrogen atom relative to the isocyanate.

Also, a and b are positive integers, a+b=o~270, b=
Represents 0 to 10. ) As the internal mold release agent used in the present invention, in the above formula (n), A is a linear or branched alkylene group having 2 to 10 carbon atoms, preferably a linear or branched alkylene group having 2 to 5 carbon atoms. It is a side alkylene group. R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms,
It is an alkoxyalkyl group, an alkylcarbonyl group, an alkylcarbamoyl group, an aralkyl group, or a phenylcarbamoyl group, preferably a hydrogen atom, with the following general formula (I
II) is an organic silicon compound having amino groups at both ends. Examples of substances in which R is other than a hydrogen atom include a derivative derived from a silicon compound having amino groups at both ends represented by the following formula (1); In a method for producing a polyurethane/polyurea composition from a chain extender, a catalyst, an internal mold release agent, and other auxiliary agents, an amino group at both ends represented by the following general formula (II) is used as an internal mold release agent. Alternatively, the present invention relates to a method for producing a polyurethane/polyurea composition having excellent paintability and self-releasing properties, which is characterized by using an organosilicon compound having an imino group.

General formula (II) (wherein, 8 is an alkylene group having 2 to 10 carbon atoms, R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a compound active against the amine compound of (I [[), for example, isocyanate) It is an organic silicon compound having imino groups at both ends, which is obtained by reacting compounds, carboxylic acid compounds, alcohols, chlorinated compounds, etc., and is an alkyl group, alkoxyalkyl group, alkylcarbonyl group, alkyl group having 1 to IO carbon atoms. These include a carbamoyl group, an aralkyl group, and a phenylcarbamoyl group.

General formula (Iff) (In the formula, A=Y or a, b represent the same group or the same meaning as in the above formula (II).) Furthermore, Y has an active hydrogen atom with respect to isocyanate, or an alkyl chain or a polyalkylene oxide chain, such as a methyl group, -CH2-CH(
CH3) -C6H5 α-methylstyrene modification, -Cf11□□, (r is an integer from 1 to 20) α-olefin modification, -c, H6o(c, n4o)g
(C: +H60)kR'(R' is a hydrogen atom or a methyl group, g0 is an integer of 1 to 5) modified with polyalkylene oxide, CJJI (CJIJ)12, or -C
Alkylamine modified, C31 (6S
There are modified alkyl mercaptans represented by H, etc.
Preferably it is a methyl group.

Also, a and b are positive integers, and a + b = 0 to 27
0b-represents 0 to 10, preferably a 10b = 0 to
130°b=o~3.

Among the above, the following general formula (IV
) is a compound represented by

General formula (IV) (n=0-270) Various organosilicon compounds having amino groups or imino groups at both ends of the above formula (II), (III), or (IV) are commercially available. , can be easily obtained. Such specific compounds and salts (preferably 70
Examples include urethane group-containing polyisocyanates obtained by reacting polypropylene glycol (having a molecular weight of less than 0), and 44'-diphenylmethane diisocyanate-based polyisocyanates having carbodiimide groups and/or urethane imine groups. Examples of preferred polyisocyanates include products obtained by modifying a mixture of 2,4' and 4,4'-diphenylmethane diisocyanates as described above, or 4'4' modified as described above. - A mixture of diphenylmethane diisocyanate and a small amount of diphenylmethane-based polyisocyanate having a higher functionality than difunctionality.

The high molecular weight active hydrogen-containing compound used in the present invention is an active hydrogen compound having a molecular weight of 1,000 to 18,000, such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerin, triethylene glycol, Methylolpropane, 1,3゜6-hexandriol, pentaerythritol, e.g. Silabrene FM-33 series manufactured by Chisso, X- manufactured by Shin-Etsu Chemical
22-161 series and the like.

The polyisocyanate used in the present invention is a commonly used known polyisocyanate, a modified product thereof, or a mixture thereof, such as 4.4°-diphenylmethane diisocyanate, 2.4°- and/or 2.4°-diphenylmethane diisocyanate. 6
-1-lylene diisocyanate, polymethylene polyphenyl polyisocyanate, xylylene diisocyanate, isophorone diisocyanate, other aliphatic polyisocyanates, and dimers, trimers, carbodiimide modified products, allophanate modified products of these isocyanates These include biuret modified products, prepolymers, etc.

A particularly preferred isocyanate compound is a modified form of 4,4'-diphenylmethane diisocyanate, which is liquid at room temperature. Specific examples of this compound include 4,4
゛-Polyether polyols obtained by addition polymerizing alkylene oxide to polyhydric alcohols such as diphenylmethane diisocyanate and low molecular weight diols or trio-sorbitol, and alkanolamines such as jetanolamine and triethanolamine, Addition polymerization of ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc. to amines containing two or more active hydrogens, such as ethylene diamine, diethylene triamine, ammonia, aniline, tolylene diamine, xylylene diamine, and diaminodiphenylmethane. and polytetramethylene ether glycol obtained by ring-opening polymerization of tetrahydrofuran.

Further, a polymer polyol obtained by grafting an ethylenically unsaturated compound such as styrene, acrylonitrile, or methyl methacrylate to the above polyol, and a 1,2- or 1.4 polybutadiene polyol,
Alternatively, hydrogenated products of these can also be used.

Furthermore, polyester polyols obtained by reacting polycarboxylic acids and low molecular weight polyols, and polyester polyols and polycarbonate polyols obtained by ring-opening polymerization of caprolactone can also be used.

In addition to the above high molecular weight active hydrogen-containing compounds, for example,
A primary or secondary amine obtained by aminating the OH group of the polyether polyol, specifically, a polyether polyol obtained by addition polymerizing propylene oxide to glycerin in the presence of a catalyst, There are also high molecular weight polyether polyamines obtained by reaction with ammonia or alkyl amines. Alternatively, a polyether polyamine obtained by reacting a polyether polyol with an isocyanate and hydrolyzing the obtained prepolymer may be used. Alternatively, a polyether polyamine obtained by chemically bonding a high molecular weight polyether and an aromatic amine may be used.

As a low molecular weight active hydrogen-containing compound (chain extender),
There are low molecular weight alkanediols and aromatic polyamines. Examples of the former include amine catalysts such as ethylene glycamine, 1,4-diazabicyclo(2,2,2)octane, and pentamethyldiethylenetriamine.

As a blowing agent, for example, trichlorofluoromethane, C
C.I. Examples include F -CClF2, methylene chloride, water, nitrogen gas, and carbon dioxide gas.

As the filler, glass fiber, flake glass, mica, talc, inorganic compound fisker, etc. are used.

〔Example〕

EXAMPLES Hereinafter, in order to explain the present invention more specifically, Examples and Comparative Examples will be given and explained, but the present invention is not limited to these Examples.

Examples 1 to 6 100 parts of a polyether polyol (polyol A) with an OH value of 28 KOH/g, which is obtained by adding ethylene oxide and propylene oxide to glycerin, 20 parts of ethylene glycol, 0.7 parts of triethylene diamine, 0 parts of dibutyltin dilaurate .05 parts and a predetermined amount of a double-terminated amine organosilicon compound, such as alcohol, propylene glycol, 1,4-butanediol, etc.; Amine and methylene-bis(
Dianiline L3,5-diethyl-2,4-diaminotoluene, 3,5-diethyl-2,6-diaminotoluene,
methylene-bis(2,6-diitupropylaniline),
There are aromatic polyamines such as methylene-bis(2-ethylaniline) and diaminoindan.

When carrying out the present invention, the equivalent ratio of the NGO group and the active hydrogen-containing compound contained in the polyisocyanate is 0.8
The amount of each raw material used is adjusted so that the amount becomes 1.3.

Auxiliary agents used in the present invention include catalysts, blowing agents, fillers, pigments, antioxidants, weathering stabilizers, and the like.

Catalysts include organometallic catalysts such as dibutyltin diacetate, dibutyltin dilaurate, silver oleate, silver octoate, and triethyleneamine, N, N, N', N''-
Tetramethylpropane shea polyol component and diphenylmethane diisocyanate derivative (mixture of urethane modified product and carbodiimide modified product (isocyanate) B) having an isocyanate group content of 26.0% were mixed with a Toho Kikai NR-230 high-pressure foaming machine. A U-shaped mold with a width of 20 cm+, a height of 20 cm, and a length of 40 cm was sprayed with a predetermined amount of wax-based mold release agent (Murikei B-712 manufactured by Chukyo Yushi Co., Ltd.) and set at a temperature of 75°C. injected inside.

After 50 seconds, the mold was opened to obtain a U-shaped molded product.

Thereafter, the above-described operation was repeated without applying an external mold release agent, and the number of times until demolding became impossible was determined.

In addition, the molded product was steam cleaned with I.Reclen for 30 seconds and then painted. (Paint: Branit made by Dainippon Toyo Co., Ltd.)
S, Baking temperature: 100° C. x 30 minutes) The coated products were examined for paint repellency by visual inspection and adhesion of the coating film by a goblin test.

The results are shown in Table-1.

Comparative Example 1 A test was carried out in exactly the same manner as in the example except that the internal mold release agent was not used, and the results are shown in Table 1.

Comparative Examples 2 to 4 Tests were conducted in exactly the same manner as in the example except that a conventional organic silicon compound was used instead of the internal mold release agent in the example, and the results are shown in Table 1.

In Table 1, the internal mold release agents used are as follows.

The amino acid used in the silicon is manufactured by Chisso ■, the product name is Silablane FM-
3321, and the molecular weight 5 represented by the general formula (V)
000 organic silicon compound.

General formula (V) Ⅰ is manufactured by Chisso ■, product name Silablane FM-
3311, and the molecular weight 1 represented by the general formula (Vl)
000 organic silicon compound.

Amine silicone-3 is a trade name X22-161E manufactured by Shin-Etsu Chemical Co., Ltd., and is an organic silicon compound having a molecular weight of 7000 and represented by the general formula (V).

Add amino acid to silicone ↓ is made by Chisso ■, product name Silablane FM-
3325, and the molecular weight 1 represented by the general formula (V)
000 organic silicon compound.

The above is an organic silicon compound in which the side chain (Z) of the general formula (Vl) is modified with a polyether polyol.

1-M"KoniZ2"-work is the side chain (Z) of the general formula (Vl)
is an organic silicon compound modified with higher fatty acids.

1'3L=J('-) represents the side chain (Z) of the general formula (Vl).
) is an alkylamine-modified organosilicon compound.

General formula (VI) Example 7 100 parts of polyol A, 22 parts of diethyltoluenediamine (hereinafter referred to as DETDA), dibutyltin dilaure)
0.085 part, both terminal amine organosilicon compound 0.
A polyol component mixed with 87 parts and isocyanate B
were molded in the same manner and the number of demolding cycles was investigated.

Demolding time: 90 seconds Comparative Example 5 The test was carried out in exactly the same manner as in Example 7, except that the internal mold release agent was not used.

〔Effect of the invention〕

As is clear from the Examples and Comparative Examples, when an organosilicon compound having amino groups at both ends is used as an internal mold release agent, the mold removability of the polyurethane/polyurea composition is improved, and the application of an external mold release agent is improved. The amount of work required has been significantly reduced, and defects during painting of molded products have been completely eliminated.

Claims (1)

[Claims] 1. Polyisocyanate, active hydrogen compound, chain extender,
In a method for producing a polyurethane/polyurea composition from a catalyst, internal mold release agent, and other auxiliary agents, an organic mold release agent having amino groups or imino groups at both ends represented by the following general formula (II) is used as the internal mold release agent. A method for producing a polyurethane/polyurea composition with excellent paintability and self-releasing properties, characterized by using a silicone compound. General formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (II) (In the formula, A is an alkylene group with 2 to 10 carbon atoms, R is a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, an alkoxyalkyl group , an alkylcarbonyl group, an alkylcarbamoyl group, an aralkyl group, or a phenylcarbamoyl group, and Y represents an alkyl chain or a polyalkylene oxide chain with or without an active hydrogen atom relative to the isocyanate. integer, a+b=0 to 270, b=
Represents 0 to 10. 2. The method for producing a polyurethane/polyurea composition according to claim 1, wherein the internal mold release agent is a compound represented by general formula (IV). General formula (IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV) 3. A claim characterized in that the internal mold release agent is used in an amount of 0.1 to 5% of the polyurethane/polyurea composition. 1. A method for producing a polyurethane/polyurea composition according to 1. 4. Polyurethane with excellent paintability and self-releasing properties.
The polyurethane composition according to claim 1, wherein the method for producing the polyurea composition is a RIM method.
A method for producing a polyurea composition.