JP3226952B2 - Elastic elastomer and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition containing an elastic elastomer, particularly a polyurethane resin, a polyurea resin, a polyurethane / urea resin and / or a polyurea / amide resin, formed by a reaction injection molding method and containing a polyester condensate. The present invention relates to an elastic elastomer molded by a reaction injection molding method using a release agent and a method for producing the same.

[0002]

2. Description of the Related Art Methods for producing molded articles of polyurethane resin, polyurea resin and other synthetic resins by a reaction injection molding method (hereinafter referred to as RIM method) are known. R
The IM method is an injection molding method in which an active hydrogen component and a polyisocyanate component are sufficiently mixed, and then this mixture is rapidly cured and molded in a mold, which is a so-called "one-shot" molding method. . The active hydrogen component is a component having a functional group containing an active hydrogen capable of reacting with an isocyanate group. The functional group containing an active hydrogen includes a hydrogen group, an amino group, and an imino group (in the phase variability relationship with the imino group). The reaction of a hydrogen group with an isocyanate group is a urethane condensation, and the resulting resin is a polyurethane resin. In the following, a polyurea resin is used when the one reacting with the isocyanate group is an amino group, and a mixture of a hydroxyl group and an amino group is referred to as a polyurethane / urea resin.
It is called amide resin. In the RIM method, an elastic elastomer such as a polyurethane resin or a polyurea resin refers to a non-foamed elastomer or a microcellular elastomer, the density of which is about 0.8 g / cm ³ or more, and when no filler is contained, Its upper limit is 1.2 g / cm ³ . This elastic elastomer is used for, for example, external parts of an automobile body.

[0003] The feature of the RIM method is that the molding time from the injection of the raw material to the removal of the molded article is short, but the overall molding cycle time is not yet sufficiently short. The most problematic point in shortening the molding cycle time is that it takes a long time to clean the mold and apply a release agent. In order to solve this, it is important from the viewpoint of productivity that the molded product is easily released from the mold. Various internal release agents have been developed to achieve these objects. The internal release agent has excellent solubility stability in the raw materials used, does not inhibit the reactivity during thermosetting, and has excellent release properties from the mold. What does not happen is desired.

Japanese Patent Application Laid-Open No. 61-91216 discloses that
When producing a polyurethane elastomer having an average density of 1.4 g / cm ³ , as an internal mold release agent, an average molecular weight of 900 to 1000 formed from 3 to 15 mol of ricinoleic acid and 1 mol of a monohydric or polyhydric alcohol. 4500, acid value 5
Hereinafter, ester group-containing condensates having an OH value of 12.5 to 125 are mentioned. The ester group-containing condensate of ricinoleic acid is excellent in dissolution stability and applicability in raw materials used. However, the mold release performance is still insufficient, and it is very difficult to reduce the acid value to 2 or less from the viewpoint of synthesis. Therefore, when a large amount is added, the polyaddition reaction of the polyurethane is inhibited. Further, when the molded product is taken out from the mold, the rigidity of the polyurethane molded product is inferior, and the polyurethane product is liable to be deformed. Further, in terms of physical properties, there is a disadvantage that heat resistance is deteriorated.

[0005]

DISCLOSURE OF THE INVENTION The present inventors have made intensive studies to develop an elastic elastomer excellent in the above-mentioned problems, in particular, continuous mold release properties and coatability, and have already studied Japanese Patent Application No. Hei. Patent No. 214311 discloses that "condensate containing 12-hydroxystearic acid and alkanediol containing an ester group" does not decrease the rigidity and heat resistance in terms of physical properties of a molded article, and has filed a patent application. Also, a hydroxy fatty acid ester or a mixture of the ester and a polyether polyol is reacted with diisocyanate to form a prepolymer, and the prepolymer is further substituted with an organic polyamine component at its molecular terminal with an amino group as an internal release agent. It has been found that, when used, it is possible to produce an elastic elastomer having excellent continuous release properties and coating properties (hereinafter, referred to as “elastomer”).
Terminal amine modification technique), Japanese Patent Application No. 2-246282.
No. filed. As a result of further study after that, when an ester of a saturated fatty acid having a hydroxyl group and an alkanediol or a diol having an ether group were condensed by a transesterification method, the acid value was extremely low,
It has been found that an ester group-containing condensate having remarkably improved mold release performance can be obtained as compared with an ester group-containing condensate obtained by performing a dehydration reaction between a conventional fatty acid and an alkanediol (hereinafter, referred to as a transesterification technique). When this technology was further applied to the above-mentioned terminal amino modification technology, it was found that the performance was further improved, and the present invention was completed.

[0006]

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention provides a method of synthesizing a polyurethane resin, a polyurea resin, a polyurethane / urea resin and / or a polyurea / amide resin by a transesterification reaction. A polyester condensate of a saturated fatty acid having a hydroxy group and / or an unsaturated fatty acid having a hydroxy group,
And / or to provide an elastic elastomer molded by a reaction injection molding method using a composition containing a polyester condensate whose molecular terminal is substituted with an amino group or an imino group as an internal release agent. This polyester condensate of a saturated fatty acid having a hydroxy group is

Embedded image Or

Embedded image Can be Further, the polyester condensate of the saturated fatty acid having a hydroxy group is preferably

Embedded image Or

Embedded image Is a condensate of 12-hydroxystearic acid ester represented by the formula: Further, the polyester condensate of the saturated fatty acid having a hydroxy group,

Embedded image With saturated fatty acid esters

Embedded image Alkanediol or

Embedded image Having an average molecular weight of 1,000 to 8,000 and a hydroxyl value of 5 to 7
It can be zero. Further, the ester condensate of the unsaturated fatty acid having a hydroxyl group is

Embedded image Or

Embedded image Can be a condensate of ricinoleic acid ester.
The polyester condensate of the unsaturated fatty acid having a hydroxyl group is preferably

Embedded image And an alkane diol of formula 17 or a diol of formula 18, and has an average molecular weight of 1,000 to 8,000 and a hydroxyl value of 5 to 70.

[0007] The polyester condensate substituted with the amino terminal or imino group at the molecular terminal contains the above-mentioned polyester condensate of the saturated fatty acid having a hydroxy group and / or the unsaturated fatty acid having a hydroxy group with diisocyanate. It can be obtained by reacting a prepolymer obtained by the reaction with at least one selected from aromatic polyamines, polyether polyamines and polyether polyimines. This aromatic polyamine is, for example,

Embedded image At least one selected from the group consisting of: The above polyether polyamine is, for example, a polyol in which the molecular terminal is substituted with a primary or secondary amino group. The above-mentioned polyether polyimine is obtained, for example, by substituting the molecular terminal of a polyol with an imino group.

The elastic elastomer of the present invention comprises (a) an organic polyisocyanate, (b) a polyol having two or more active hydrogen groups and a molecular weight of 800 to 12000, or a primary amino group or a secondary Amino group, aromatic 1
A polyester condensate of a polyether polyamine or a polyether polyimine substituted with a secondary amino group or an imino group and (d) a saturated fatty acid having a hydroxy group and / or an unsaturated fatty acid having a hydroxy group synthesized by a transesterification reaction; And / or a mixture containing a polyester condensate whose molecular terminal is substituted with an amino group or an imino group and having an isocyanate index of 70 to 130. The reaction can be performed in a reaction injection molding method. In the above production method, preferably, a chain extender comprising 5 to 80 parts by weight of an aromatic diamine [component (c)] is used in combination with 100 parts by weight of the total amount of the component (b). Further, the polyester condensate in the internal release agent of the component (d) is preferably
It is used in an amount of 0.5 to 30 parts by weight based on 100 parts by weight of the total amount of the component (b).

The polyester condensate of the present invention is, for example,
It can be produced by the following transesterification reaction.
The polyester condensate of the present invention can be obtained by reacting a lower alcohol ester of a hydroxy-saturated or unsaturated fatty acid with glycol.

In the present invention, the hydroxy saturated fatty acid esters (Chemical Formula 16) used include 8-hydroxystearic acid, 9-hydroxystearic acid, and 10-hydroxystearic acid.
Hydroxystearic acid, 11-hydroxystearic acid, 12-hydroxystearic acid, 8-hydroxypalmitic acid, 9-hydroxypalmitic acid, 10-hydroxypalmitic acid, 11-hydroxypalmitic acid,
The methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester and the like of 12-hydroxypalmitic acid can be used. The hydroxy unsaturated fatty acid ester used in the present invention includes ricinoleic acid (12-oxy-
cis-9-octadecenoic acid), ricinoelaidic acid (1
Esters such as 2-oxy-trans-9-octadecenoic acid) and 16-oxy-Δ ^9,10 -hexadecenoic acid can be used. Industrially, it is difficult to use these high-purity products, and usually, a saturated or unsaturated fatty acid ester having no hydroxy group derived from the raw material (for example, 5 to 15
%), But has no effect on the reaction and the resulting polyester condensate.

The glycols used include:
As the compound represented by Chemical formula 17, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol , 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol and the like can be used. Chemical 1
As the compound represented by 8, 2,3-butanediol, diethylene glycol, triethylene glycol,
Tetraethylene glycol, dipropylene glycol,
Tripropylene glycol, tetrapropylene glycol and the like can be used.

The glycol used is 5 to 3 with respect to 100 equivalents of the hydroxy fatty acid ester used in the reaction.
0 equivalent parts are good. When a condensation reaction is performed with such a composition,
Finally, a polyester condensate having an average molecular weight of 1,000 to 8,000 and a hydroxyl value of 5 to 70 is obtained. If it is less than 5 equivalents, the releasability is poor, and if it exceeds 30 equivalents, the molecular weight does not increase. As a result, the viscosity is high and the fluidity is low. Bad
The viscosity of the raw material is increased, which impairs the formability.

The reaction temperature for the condensation is not particularly limited.
The temperature may be 100 to 250 ° C, preferably 170 to 210 ° C.
Although the reaction proceeds without a catalyst, the reaction time required for condensation can be reduced by adding a catalyst. As the catalyst, inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, etc., organic acids such as p-toluenesulfonic acid, methanesulfonic acid, etc., which are used as usual esterification catalysts, alkoxy titanium, acidic ion exchange resin, etc. Can be used.

Although the reaction proceeds even at normal pressure, it is desirable to carry out the reaction under reduced pressure because removing the lower alcohol produced by condensation from the system can shorten the condensation time. The pressure may be about 10 to 100 mmHg. Although the reaction time depends on the reaction temperature and the kind of the hydroxy fatty acid ester used, 20 to 50 hours is sufficient. The end point of the reaction can be determined by measuring the molecular weight by gel column chromatography and measuring the hydroxyl value. After completion of the reaction, the obtained ester condensate can be used as it is as a release agent. The above-mentioned polyester condensate thus synthesized is used as the polyurethane resin, polyurea resin, polyurethane / urea resin, polyurea / polyurea resin of the present invention.
An elastic elastomer can be manufactured by using an amide resin as an internal release agent when molding by a reaction injection molding method.

Furthermore, in the present invention, a polyester condensate of a saturated fatty acid having a hydroxy group and / or an unsaturated fatty acid having a hydroxy group synthesized by a transesterification reaction is substituted with an amino group or an imino group at the molecular terminal. The composition containing the polyester condensate can be used as an internal release agent. The amino-terminal or imino-substituted polyester condensate at the molecular terminal is a derivative of a polyester condensate of a saturated fatty acid having a hydroxy group and / or an unsaturated fatty acid having a hydroxy group synthesized by a transesterification reaction. The polyester condensate of a saturated or unsaturated fatty acid can be prepared directly or by amination or imino treatment of a derivative containing the polyester condensate as a main part. The polyester condensate in which the molecular terminal is substituted with an amino group or an imino group can be produced, for example, as follows. (A) reacting a diisocyanate with at least one selected from the group consisting of a polyester condensate of a saturated or unsaturated fatty acid having a hydroxy group, and a mixture of the polyester condensate and a polyol; (B) an aromatic polyamine, a polyether polyamine,
And a component selected from the group consisting of polyether polyimine (hereinafter referred to as polyamine polyimine component) and one selected from the group consisting of a mixture of the polyamine polyimine component and a polyol. The reaction is carried out with 2 equivalents or more of the component (B) with respect to the equivalent.

The diisocyanate which is a raw material of the component (A) includes fatty acid diisocyanates such as ethylene diisocyanate, tetramethylene-1,4-diisocyanate, and hexamethylene-1,6-diisocyanate. , Dodecane-1,12-diisocyanate, etc., alicyclic diisocyanates, for example, cyclobutane-1,3-
Diisocyanate, cyclobutane-1,4-diisocyanate, 1-isocyanate-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane, hexahydrotolylene-2,4-diisocyanate, hexahydro Tolylene-3,6-diisocyanate, hexahydrophenylene-1,3-diisocyanate, hexahydrophenylene-1,4-diisocyanate, perhydrodiphenylmethane-2,4'-diisocyanate, perhydro Aralkyl diisocyanates such as diphenylmethane-4,4'-diisocyanate, for example, α, α.
α ′, α′-tetramethyl-xylylene diisocyanate (ie, TMXDI), and aromatic diisocyanates such as phenylene-1,3-diisocyanate,
Phenylene-1,4-diisocyanate, tolylene-
2,4-diisocyanate, tolylene-2,6-diisocyanate, diphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, naphthylene-1,5-diisocyanate, etc. Can be mentioned. Diisocyanates which are liquid at room temperature are more preferred, especially tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate or mixtures of isomers thereof, α, α, α ', α'- Tetramethyl-xylylene diisocyanate and 1-isocyanate-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane are preferred.

The prepolymer of the component (A) of the present invention can be obtained by mixing the polyester condensate or the polyester condensate with a polyol in the diisocyanate and reacting the mixture. The NCO content in the prepolymer (A) is suitably 0.5 to 5%, particularly preferably 0.5 to 2%. This NCO content is 5%
The following is preferable from the viewpoint of preventing the reaction product from gelling in the reaction with the component (B). When the content is 0.5% or more, the viscosity of the reaction product with the component (B) does not increase.
preferable. The prepolymer is preferably reacted with diisocyanate in 1-2 equivalents, more preferably 1.3 equivalents, with respect to 1 equivalent of the polyester condensate or a mixture of the polyester condensate and the polyol.
React in -1.8 equivalents. If the diisocyanate exceeds 2 equivalents, free isocyanate is present in the prepolymer, and the reaction product is liable to gel during the reaction with the component (B).

The "polyamine polyimine component" used in the component (B) means one member selected from aromatic polyamines, polyether polyamines and polyether polyimines as described above. These may be used alone or in combination. As the aromatic polyamine, for example, 2,4- or 2,6-diaminotoluene, 2,2
4'- or 4,4'-diamino-diphenylmethane,
1,3- or 1,4-phenylenediamine, polyphenyl-polymethylene-polyamine obtained by condensation of aniline and formaldehyde, liquid or soluble fragrance described in JP-B-54-17359, which is incorporated herein by reference. Aromatic diamines, such as 1,3-diethyl-
2,4-diaminobenzene, 2,4-diaminomesitylene, 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'-diamino-diphenylmethane, 1,1-dimethyl-4,6-dimethyl-5,7-diaminoindan and the like. Particularly suitable aromatic polyamines are 1-methyl-3,5-diethyl-2,4-diaminobenzene,
There is a mixture of 1-methyl-3,5-diethyl-2,6-diaminobenzene (hereinafter abbreviated as DETDA).

Further, as the aromatic polyamine, for example, compounds represented by the following formulas may be used.
As the polyether polyamine, those obtained by substituting the molecular terminal of a polyol with a primary amino group or a secondary amino group can be used. Further, for example, a terminal aromatic polyether polyamine obtained by hydrolyzing a reaction product of a polyol and tolylene diisocyanate described in JP-B-63-56887, which is inserted here as a reference, with a large excess of water, Alternatively, primary aliphatic polyether polyamines obtained by reacting polypropylene glycol with ammonia can be mentioned. As the polyether polyimine, those obtained by substituting the molecular terminal of a polyol with an imino group can be used. Further, for example, Japanese Patent Application Laid-Open No. 63-2736, which is inserted here as a reference.
Polyether polyimine obtained by dehydrating primary terminal aliphatic polyether polyamine described in No. 23 with cyclohexanone is preferred. Examples of particularly preferred primary aliphatic polyether polyamines include Texaco's Je
ffamine D-230, D-400, D-2000 and the like. The amount of the polyamine polyimine component (B) or the mixture of the polyamine polyimine component and the polyol is preferably 2 equivalents or more, more preferably 5 equivalents, per equivalent of the prepolymer (A). Above, particularly preferably at least 10 equivalents are used. (A)
When the component (B) is used in an amount of 2 equivalents or more with respect to 1 equivalent of the prepolymer of the component, it is possible to sufficiently prevent the residual isocyanate from being mixed in the resin composition, and to maintain the activity of the resin well. Shows good release performance.

The aromatic polyamine, polyether polyamine or polyether polyimine as the component (B) is preferably liquid at room temperature.
The component can be used by previously dissolving it in a polyol by heating. The polyol used for the component (A) or the component (B) is preferably a polyol containing two or more molecular terminal OH groups. For example, an initiator having a reactive hydrogen atom such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin in the presence of BF ₃ , for example, water, alcohol, ethylene glycol, propylene glycol, trimethylol Propane, 4,4-dihydroxy-diphenylpropane,
It is obtained by chemically polymerizing aniline, ethanolamine, ethylenediamine and the like. Those obtained by transesterifying a hydroxyl group at the terminal of the polyol with castor oil may also be used. The molecular weight of the polyol is preferably between 800 and 12,000. In some cases, a polyol having a molecular weight of 800 to 12,000 can be used as a solvent and a viscosity reducing agent for the reaction between the components (A) and (B).
Although the prepolymer of the component (A) may be made of a polyester condensate and a diisocyanate, it is preferable to include a polyol to improve the compatibility in the resin and further improve the continuous release property. As the polyol used for the prepolymer of the component (A), all of the above-mentioned polyols can be used, and particularly preferably polypropylene diol having a molecular weight of 200 to 4000 is desirable.

The above-mentioned condensate of the amino-terminal or imino-substituted polyester at the molecular terminal can be produced, for example, by a two-step reaction. In the first step, the diisocyanate is reacted with a polyester condensate (or a mixture of a polyester condensate and a polyol) to obtain the component (A), a prepolymer. Next, the component (A), the prepolymer, the component (B), and the polyamine polyimine component (or a mixture of the polyamine polyimine component and the polyether polyol) as the second stage are added to 1 equivalent of the component (A). The reaction is carried out with 2 equivalents or more of the component (B) to obtain the condensate of the amino-terminal or imino-substituted polyester at the molecular terminal.

The production operation will be described below by taking as an example the case of using a hydroxy fatty acid ester obtained by using ricinoleic acid and 12-hydroxystearic acid. The isocyanate-reactive resin composition is produced by a two-step reaction. First, in the first stage, a self-condensate of ricinoleic acid or 12-hydroxystearic acid having an OH value of 12 to 125 and an acid value of 10 or less, or ricinoleic acid and / or 12-hydroxyester having an OH value of 12 to 125 and an acid value of 10 or less. An ester compound of hydroxystearic acid and an alkanediol (for example, Chemical formula 17) or a diol (for example, Chemical formula 18) is further synthesized by a similar transesterification reaction with an alkanediol (for example, Chemical formula 17) or a diol (for example, Chemical formula 18). Prepolymer (A) having a composition containing a polyester condensate and a diisocyanate having an NCO content of 0.5 to 5%
To manufacture. Next, as a second step, (A) is reacted by reacting 2 equivalents or more of the aromatic polyamine, polyol or polyether polyimine as the component (B) with 1 equivalent of the prepolymer of the component (A). An amino group or an imino group at each terminal of the prepolymer molecule of the component;
An isocyanate-reactive resin composition which contains a compound having at least one compound and is liquid at room temperature is obtained, and is used as an internal mold release agent of the present invention.

Hereinafter, the method for producing the elastic elastomer of the present invention will be described. As the organic polyisocyanate of the component (a), known aliphatic, alicyclic or aromatic polyisocyanates and the like are used. Specifically, for example, 4,4'-diphenylmethane diisocyanate, 2,4- And / or 2,6-tolylene diisocyanate, polymethylene polyphenyl polyisocyanate, xylene diisocyanate, polyisophorone diisocyanate, other aliphatic polyisocyanates or dimers of these isocyanates Monomer, modified carbodiimide, prepolymer and the like. In particular, an aromatic polyisocyanate containing a liquid at room temperature is preferable, and specific examples thereof include:
Preferred are 4,4'-diphenylmethane diisocyanate, a mixture of the substance and a homolog thereof, a modified isocyanate obtained by reacting these polyisocyanates with a compound having a polyfunctional hydroxyl group, or modifying the polyisocyanates by carbodiimidation.

Examples of the polyol as the component (b) include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, 1,3,6-hexanetriol, pentaerythritol and sorbitol. And polyether polyols obtained by subjecting these polyhydroxy compounds to addition polymerization of alkylene oxide. In addition, diethanolamine, alkanolamines such as triethanolamine, ethylenediamine, diethylenetriamine, ammonia, aniline, tolylenediamine,
A polyether polyol or polytetramethylene ether glycol obtained by subjecting an amine having two or more active hydrogens such as xylylenediamine and diaminodiphenylmethane to addition polymerization with ethylene oxide, propylene oxide, styrene oxide and the like can also be used. In addition to the above, a polyester polyol obtained by reacting a higher fatty acid ester polyol or polycarboxylic acid with a low molecular weight polyol, a polyester polyol or a polycarbonate polyol obtained by polymerizing caprolactone,
Higher fatty acid esters having a hydroxyl group such as castor oil or dehydrated castor oil can also be used. Furthermore, a polymer polyol obtained by grafting an ethylenically unsaturated compound such as styrene, acrylonitrile, and methyl methacrylate to the above-mentioned known polyol, 1,2- or 1,4-polybutadiene polyol or a hydrogenated product thereof can also be used. These can be used alone or in combination of two or more. The above-mentioned polyols can be used as the component (A) and component (B) polyols for producing a polyester condensate having an amino or imino group at the molecular terminal.

As examples of the polyether polyamine or polyether polyimine of the component (b), the terminal of the polyols of the component (b) may be a primary amino group, a secondary amino group or an aromatic primary amino group. Or those substituted with an imino group. Preferred examples include Texaco J described in U.S. Pat. No. 4,396,729.
effamine T-5000, D-2000, and hydroxyl number 2 described in JP-A-64-81816.
N- (polyoxyalkyl) -N- (alkyl) amine having a molecular weight of about 600 obtained by reacting 8 mg KOH / g of a polyoxyalkylene ether polyol with diisopropylamine using a catalyst under hydrogen pressure and a method disclosed in 4
No. 1857, obtained by hydrolyzing NCO-preadduct (NCO value: 3.4%) produced from tolylene-2,4-diisocyanate and polypropylene glycol ether (average molecular weight: 2,000) by the above method. NH value 44.3 [KOH (mg) / g], acid value 0.1
[KOH (mg) / g], molecular weight 2500, viscosity (mPa · s:
(75 ° C.) polyoxyalkylene ether polyol having an amino group at the terminal. Examples of the imine-terminated polyethers include polyetheramines obtained by a dehydration reaction of cyclohexanone with a polyetheramine commercially available under the name Jeffamine from Texaco described in Examples of JP-A-63-273623. Ether imines are mentioned.

The aromatic diamine of component (c) used as a chain extender includes aromatic diamines having one or more alkyl substituents ortho to the amino group, especially ortho diamine to the primary amino group. Preferred are aromatic primary diamines having two or more alkyl substituents each having 1 to 4 carbon atoms in the ortho position relative to the second amino group.

Examples of preferred aromatic diamines include:
2,4-diaminomesitylene, 1,3,5-triethyl-2,4-diaminobenzene, 1,3,5-triisopropyl-2,4-diaminobenzene, 1-methyl-3
5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 4,
6-dimethyl-2-ethyl-1,3-diaminobenzene, 3,5,3 ', 5'-tetraisopropyl-4-
4'-diaminodiphenylmethane, 3,5-diethyl-
3 ', 5-diisopropyl-4,4'-diaminodiphenylmethane, 1,3-dimethyl-5-tert-butyl, -4,6-diaminobenzene or 1,3 dimethyl-5-tert-butyl-2,6- Diaminobenzene,
1-methyl-5-tert-butyl-2,4-diaminobenzene or 1-methyl-3-tert-butyl-
2,6-diaminobenzene, 5,7-diamino-1,
Preference is given to 1,4,6-tetramethylindane or a mixture of such diamines. 1-methyl-3,5-diethyl-2,4-diaminobenzene and its mixture with 1-ethyl-3,5-diethyl-2,6-diaminobenzene and 5,7-diamino-1,1,4 , 6-Tetramethylindane is particularly preferred.

As described above, the amount of the aromatic diamine of the component (c) is preferably about 5 to 80 parts by weight based on 100 parts by weight of the polyol or the polyether polyamine or the polyether polyimine of the component (b). Particularly preferably, it is used in an amount of 8 to 30 parts by weight. As the component (c), a mixture of an aromatic diamine and a low-molecular alkanediol such as ethylene glycol, propylene glycol or 1,4 butanediol can also be used. In this case, the preferred amount of the aromatic diamine is the above amount with respect to 100 parts by weight of the total amount of the polyol and the like in the component (b) and the component (c).

Other additives that may be used in the present invention include catalysts that promote the polyaddition reaction between the isocyanate and the isocyanate-reactive group. Catalysts include in particular tin salts of carboxylic acids, dialkyltin salts of carboxylic acids, dialkyltin mercaptides, dialkyltin dithioesters and tertiary amines. Further, as an additive, a foam stabilizer such as polydimethylpolysiloxane, water and / or a volatile organic substance and / or a dissolved inert gas may be used.

[0030]

The production examples of the internal mold release agent and the present invention will be described in more detail with reference to the following examples. Parts are parts by weight unless otherwise indicated. Production Example-1 (Internal mold release agent-1) 2089 parts of ricinoleic acid, 118 parts of 1,6-dihydroxyhexane and 0.11 part of titanium tetrabutyrate (50 ppm)
Was condensed by the method of Example 1 of JP-A-61-91216. That is, the above components are charged into a reactor, heated to 180 ° C., and the produced water is withdrawn under atmospheric pressure for 4 hours. The pressure is then gradually reduced to 15 mmHg and more water of reaction is drawn off. All water, including small amounts of organic components, is then distilled off over a period of 7.5 hours. The mixture is maintained at 15 mm Hg for an additional hour before cooling. The resulting ester group-containing condensate has an acid value of 3.8 mg KOH / g, a hydroxyl value of 36.5 mg KOH / g, and a viscosity of 995 cps / 2.
5 ° C.

Production Example-2 (Internal mold release agent-2) Ricinoleic acid 60 was placed in a vessel equipped with a stirrer and a reflux condenser.
Then, 0 g, methanol 1.31 and p-toluenesulfonic acid 3 g were charged and refluxed for 3 hours. After completion of the reaction, excess methanol is distilled off, and the residue is heated with warm water (70 to 80 ° C).
Washing was performed four times with 700 ml and dehydration was performed to obtain a methyl ester. 33.9 g of 1,6 hexanediol and 0.05 ml of tetrabutoxytitanium were added thereto, and
The reaction was carried out at a normal pressure at a temperature of 10 ° C. for 10 hours and at a pressure of 10 to 20 mmHg for 30 hours to obtain a polyester condensate. Yield: 595 g Acid value: 0.2 Hydroxyl value: 36 mg KOH / g Average molecular weight: about 3000

Production Example-3 (Internal mold release agent-3) 2103 parts of 12-hydroxystearic acid, 118 parts of 1,6-dihydroxyhexane and 0.1 part of titanium tetrabutyrate
One part was condensed by the method of the above-mentioned internal release agent-1. Acid value =
2.7 mg KOH / g, hydroxyl value = 32.2 mg KOH / g
g, viscosity = 1320 cps / 25 ° C.

Production Example-4 (Internal mold release agent-4) In a vessel equipped with a stirrer and a reflux condenser, 600 g of 12-hydroxystearic acid (purity 87%, other main component is stearic acid), methanol 1. 31 and 3 g of p-toluenesulfonic acid were charged and refluxed for 3 hours. After completion of the reaction, excess methanol was distilled off, and the residue was washed with warm water (70 mL).
Washing was performed four times with 700 ml (７００80 ° C.), followed by dehydration to obtain a methyl ester. To this, 1,6-hexanediol 3
3.7 g, 0.05 ml of tetrabutoxy titanium were charged,
10 hours at normal pressure at 190 ° C to 200 ° C
The reaction was carried out at 20 mmHg for 30 hours to obtain a polyester condensate. Yield: 590 g Acid value: 0.4 Hydroxyl value: 10 mg KOH / g Average molecular weight: about 3000

Production Example-5 (Internal mold release agent-5) A vessel equipped with a stirrer and a reflux condenser was charged with 515 g of 9 (10) -hydroxystearic acid, 1.21 of methanol and 3 g of p-toluenesulfonic acid. And refluxed for 3 hours. After completion of the reaction, excess methanol was distilled off, and the residue was washed four times with 700 ml of warm water (70 to 80 ° C) and dehydrated to obtain a methyl ester. 33.7 g of 1,6-hexanediol and 0.05 ml of tetrabutoxy titanium
And reacted under normal pressure at a temperature of 190 ° C. to 200 ° C. for 10 hours and at 10 to 20 mmHg for 30 hours to obtain a polyester condensate. Yield: 490 g Acid value: 0.7 Hydroxyl value: 15 mg KOH / g Average molecular weight: about 3000

Production Example-6 (Internal mold release agent-6) Terminal amination from transesterification of ricinoleic acid 6 equivalents (522 g) of TDI-100 and 4 equivalents (622)
2 g) of the internal release agent-2 was reacted at 100 ° C. for 2 hours to synthesize a prepolymer having an NCO% of 1.30%.
25 parts (0.2451 equivalent parts) of 5,7-diamino-1,1,4,6-tetramethylindane and polyol A 1
9 parts (0.00279 equivalents) of the above-mentioned TDI prepolymer was added dropwise to the mixed solution with 00 parts (0.0606 equivalents) at room temperature, and the mixture was stirred for 1 hour. One day later, the absorption of NCO was measured by an infrared absorption spectrum, but no absorption of NCO was observed. Active hydrogen value (mg / KOH): 123 Viscosity (cps / 25 ° C): 1900

Production Example-7 (Internal mold release agent-7) Terminal amination by transesterification of 12-hydroxystearic acid Two equivalents (174 g) of TDI-100 and one equivalent (561)
0 g) of the internal release agent-4 was reacted at 100 ° C. for 2 hours to synthesize a prepolymer having an NCO% of 0.76%.
25 parts (0.2451 equivalent parts) of 5,7-diamino-1,1,4,6-tetramethylindane and polyol A 1
9 parts (0.00162 equivalent parts) of the above-mentioned TDI prepolymer was added dropwise to the mixed solution with 00 parts (0.0606 equivalent parts) at room temperature, followed by mixing and stirring for 1 hour. One day later, the absorption of NCO was measured by an infrared absorption spectrum, but no absorption of NCO was observed. Active hydrogen value (mg / KOH): 123 Viscosity (cps / 25 ° C.): 4000

Production Example-8 (Internal mold release agent-8) Terminal amination by transesterification of 12-hydroxystearic acid Two equivalents (220 g) of α, α, α ', α'-tetramethyl-xylylene diisocyanate (M-TM manufactured by Takeda Pharmaceutical Co., Ltd.
XDI) and one equivalent (5610 g) of the internal mold release agent-4
Was reacted at 100 ° C. for 2 hours to synthesize a prepolymer having an NCO% of 0.76%. Etacure 100 (Eth
To 39 parts (0.4380 equivalents) of yl-Corp, 9 parts (0.00162 equivalents) of the above prepolymer was added dropwise at room temperature, and the mixture was stirred for 1 hour. One day later, the absorption of NCO was measured by infrared absorption spectrum.
Was not observed. Active hydrogen value (mg / KOH): 507 Viscosity (cps / 25 ° C.): 4000

Production Example-9 (Internal mold release agent-9) Terminal amination of transesterification method of ricinoleic acid 6 equivalents (660 g) of α, α, α ', α'-tetramethyl-xylylene diisocyanate (Takeda Pharmaceutical m-TM
XDI) and 4 equivalents (6233 g) of said internal release agent-2
Was reacted at 100 ° C. for 2 hours to synthesize a prepolymer having an NCO% of 1.25%. Etacure 100 (Eth
yl-Corp) (11.8 parts (0.1325 equivalent parts), 9 parts of the above prepolymer (0.002 parts)
(67 equivalents) was added dropwise at room temperature, and the mixture was stirred for 1 hour. 1
NCO absorption was measured by infrared absorption spectrum after day,
No NCO absorption was observed. Active hydrogen value (mg / KOH): 350 Viscosity (cps / 25 ° C): 4000

Production Example-10 (Internal mold release agent-10) 12 Terminal amination of transesterification method of hydroxystearic acid Etacure 100 (manufactured by Ethyl-Corp) 1
Production Example-1.8 parts (0.1325 equivalent parts)
9 parts (0.00162 equivalent parts) of the prepolymer No. 8 were added dropwise at room temperature, and then mixed and stirred for 1 hour. One day later, the absorption of NCO was measured by an infrared absorption spectrum, but no absorption of NCO was observed. Active hydrogen value (mg / KOH): 353 Viscosity (cps / 25 ° C.): 10,000

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. The components used in the following Examples and Comparative Examples are as follows. 1) Internal release agent (1); Internal release agent-1 (6); Internal release agent-6 (2); Internal release agent-2 (7); Internal release agent-7 (3); the internal release agent-3 (8); the internal release agent-8 (4); the internal release agent-4 (9); the internal release agent-9 (5); Release agent-5 (10); The above-mentioned internal release agent-10 2) Polyol A; EP-33 manufactured by Mitsui Toatsu Chemicals, Inc.
A glycerin-initiated poly (oxyalkylene) polyether triol having a 0N hydroxyl number (OH number) of 34 and containing about 85% propylene oxide and having about 15% ethylene oxide at the end. 3) Polyether polyamine B having an amino group at a terminal; Jeffamine D-20 manufactured by Texaco
4) Chain extender C: Ethacure 100 manufactured by Ethy-Corp Co., Ltd. About 1-methyl-3,5-diethyl-2,4-diaminobenzene and 1-methyl-3,5-diethyl-2,6-diaminobenzene 80:20 mixture of isomers. 5) Chain extender D; 5,7-diamino-1,1,4,6
-Tetramethylindane 6) Compatibilizer E; Jeffamine manufactured by Texaco
e D-400 Polyetherdiamine having a terminal amino group and a molecular weight of about 400 7) Compatibilizer F; AE-3 manufactured by Mitsui Toatsu Chemicals, Inc.
00 O with propylene oxide added to ethylenediamine
8) Isocyanate G; tripropylene glycol and 4,4'-diphenylmethane diisocyanate (MD
Prepolymer reacted with I) NCO% = 22.5%, viscosity 800 CPS / 250 ° C. 9) Isocyanate H; Jeffamine D-2
Prepolymer reacted with 000 and 4,4'-diphenylmethane diisocyanate NCO% = 22.2%, viscosity 500 CPS / 25 ° C 10) Tin catalyst; Stan BL dibutyltin dilaurate manufactured by Sankyoki Co., Ltd. 11) Amine Catalyst: Air Product DA
BCO 33LV 12) Zinc stearate; Zinc stearate GF-200 13) manufactured by NOF CORPORATION Primer; Flexen-600 from Top-Chemical Co .; Primer Top coat; Flexen-105 from Bee-Chemical Co.

Examples 1 to 11 and Comparative Examples 1 to 6 Polyol A or polyether polyamine B, chain extenders C and D, compatibilizers E and F and internal release agent (1)
(10), zinc stearate, catalyst and polyisocyanates G and H were used as shown in Tables 1 to 3 to prepare a polyurethane elastomer under the following conditions. (Table-1
The numerical values of these materials in Table 3 are parts by weight. )
That is, an active hydrogen compound (Solution A) containing a polyol or polyether, a chain extender, an internal release agent and a catalyst as main components,
Isocyanate (liquid B) is supplied to a high-pressure foaming machine (Toho Kikai NR-
230), the solution A and the solution B were mixed by a high-pressure foaming machine and then injected into a simple bumper mold (U-shaped; about 500 cc capacity, wall thickness 3 mm). Before injection, the mold surface was washed with DMF, and then an external release agent, D-186 wax manufactured by Chukyo Yushi Co., Ltd., was spray applied. In the releasability test, it was actually examined how many times the mold can be continuously released from the lower mold by a single application of the external release agent from the simple bumper mold. The coating was performed under the following conditions. One hour after molding, post-curing was performed at 120 ° C. for 30 minutes. 1 hour after post cure
1,1-Trichloroethane (Central Glass) Va
Washing and degreasing were performed using por. Flexene-600 primer is applied to the washed and degreased sample.
It was left at 20 ° C. for 20 minutes. After leaving at room temperature for 30 minutes, Flexen-105 (white) topcoat was applied, and baking was left at 120 ° C. for 30 minutes. Evaluation Repelling; Visual adhesion test; JIS D0202 grid test

Tables 1 and 2 show the results of the example, and Table 3 shows the results of the comparative example.

[Table 1]

[Table 2]

[Table 3]

[0043]

According to the present invention, it is possible to obtain a molded article of an elastic elastomer which exhibits an excellent releasing effect from a mold, contributes to a great improvement in productivity and is excellent in coatability. The internal release agent used in the present invention has a low acid value that does not inhibit the polyaddition reaction of polyurethane, and provides an elastic elastomer having excellent coatability and excellent releasability by reaction injection molding.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Toshiaki Moriya 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Toatsu Chemical Co., Ltd. (56) References JP-A-61-91216 (JP, A) JP-A-5-5019 (JP, A)

Claims (13)

(57) [Claims] 1. A polyurethane resin, a polyurea resin, a polyurethane / urea resin and / or a polyurea / amide resin having a saturated fatty acid and / or a hydroxy group having a hydroxy group having an acid value of 1 or less synthesized by a transesterification reaction. Using a composition containing a polyester condensate of an unsaturated fatty acid and / or a polyester condensate in which the molecular terminal of the polyester condensate is substituted with an amino group or an imino group as an internal mold release agent, a reaction injection molding method is used. Molded elastic elastomer. 2. A polyester condensate of a saturated fatty acid having a hydroxy group is represented by the following formula: Or The elastic elastomer according to claim 1, wherein 3. A polyester condensate of a saturated fatty acid having a hydroxy group is represented by the following formula: Or The elastic elastomer according to claim 2, which is a condensate of 12-hydroxystearic acid ester represented by the following formula: 4. A polyester condensate of a saturated fatty acid having a hydroxy group is represented by the following formula: And a saturated aliphatic ester represented by the formula: An alkanediol represented by or The elastic elastomer according to claim 2, which is synthesized by a transesterification reaction with a diol represented by the following formula, and has an average molecular weight of 1,000 to 8,000 and a hydroxyl value of 5 to 70. 5. A polyester condensate of an unsaturated fatty acid having a hydroxy group is represented by the following formula: Or The elastic elastomer according to claim 1, which is a condensate of a ricinoleic acid ester represented by the formula: 6. A polyester condensate of an unsaturated fatty acid having a hydroxy group is represented by the following formula: The compound is synthesized by a transesterification reaction of an unsaturated aliphatic ester represented by the following formula with an alkanediol of the formula (6) or a diol of the formula (7), and has an average molecular weight of 1,000 to 8,000 and a hydroxyl value of 5 to 70. Elastic elastomer. 7. A composition in which the polyester condensate whose molecular terminal is substituted with an amino group or an imino group contains the above-mentioned unsaturated fatty acid having a hydroxy group and / or the polyester condensate of an unsaturated fatty acid having a hydroxy group. A prepolymer obtained by reacting with a diisocyanate and at least one selected from aromatic polyamines, polyether polyamines and polyether polyimines;
2. A composition obtained by reacting with a seed.
An elastic elastomer as described. 8. The method according to claim 1, wherein the aromatic polyamine is The elastic elastomer according to claim 7, which is at least one member selected from the group consisting of: 9. The elastic elastomer according to claim 7, wherein the polyether polyamine is obtained by substituting the molecular terminal of the polyol with a primary or secondary amino group. 10. The elastic elastomer according to claim 7, wherein the polyether polyimine is obtained by substituting a molecular terminal of a polyol with an imino group. (A) an organic polyisocyanate,
(B) having two or more active hydrogen groups and having a molecular weight of 800 to
12,000 polyols, or polyetherpolyamines or polyetherpolyimines in which the molecular terminals thereof have been substituted with primary amino groups, secondary amino groups, aromatic primary amino groups or imino groups, and (d) A method for producing an elastic elastomer, comprising reacting a mixture containing a release agent and having an isocyanate index of 70 to 130 in a closed mold, followed by molding by a reaction injection molding method. 12. An aromatic diamine (component (c)) in an amount of 5 to 80 parts by weight based on 100 parts by weight of the total amount of the component (b).
The method for producing an elastic elastomer according to claim 11, further comprising a chain extender comprising: 13. The polyester condensate of the component (d) in the internal release agent according to claim 1, wherein the total amount of the component (b) is 1
13. The method for producing an elastic elastomer according to claim 11, wherein the elastomer is used in an amount of 0.5 to 30 parts by weight based on 00 parts by weight.