JPH0739456B2 - Amine catalyst composition for producing polyurethane and method for producing polyurethane - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to amine catalysts for the production of polyurethanes such as soft, semi-rigid, hard or elastomers. More specifically, it relates to an amine catalyst composition for producing polyurethane which is non-migrating in a polyurethane resin and is excellent in moldability, and a method for producing polyurethane using the same.

[0002]

Polyurethane foams are usually produced by instantly stirring and foaming a polyol containing a catalyst, a blowing agent (halogenated hydrocarbon and / or water), and optionally other auxiliaries, and a polyisocyanate to foam. To be done.

Polyurethane foam is lightweight and has excellent cushioning properties, impact resistance, vibration damping properties and the like, and is used in various products. Conventionally, amine catalysts such as triethylamine, N-ethylmorpholine, triethylenediamine, and tetramethylhexamethylenediamine have been used as catalysts for producing these polyurethane foams, and they have been produced with good moldability. However, polyurethane foam and other materials, for example, vinyl chloride resin, ABS resin, polycarbonate resin, etc., in the form of foil, coating or edging material, and products manufactured by combination or integral molding, such as automobiles. It is known that various problems are newly caused when these amine catalysts are used for an instrument panel, a seat, a headrest, an armrest and the like as an interior material for automobiles. For example, the amine catalyst remaining in the polyurethane foam migrates to other materials with which it comes into contact, causing deterioration and discoloration, resulting in a decrease in commercial value. In particular, the instrument panel is likely to receive direct sunlight and is exposed to high temperature for a long time, so that deterioration and discoloration of the skin material are more serious.

Conventionally, as a method for solving this problem, a method of using an amine catalyst having a reactive primary amino group or secondary amino group in the molecule (Japanese Patent Laid-Open Nos. 46-4846 and 59-59). No. 191743, Japanese Patent Publication No. 61-3
1727) and a method using an amine catalyst having a reactive primary hydroxyl group in the molecule (Japanese Patent Publication No. Sho 5).
7-14762) and the like have been proposed. These amine catalysts accelerate the polyurethane foam formation reaction and, at the same time, have a reactive group in the molecule and thus react with the raw material polyisocyanate and are trapped in the polyurethane resin. Therefore, the problem of deterioration of physical properties and discoloration of the composite is avoided without transfer to other materials that come into contact. However, the amine catalyst having these reactive groups is trapped in the polyurethane resin, so that the catalytic activity is decreased during the reaction, resulting in insufficient formation of the polyurethane resin. For this reason, it has been pointed out that the moldability is deteriorated, and voids (voids) are generated in the polyurethane foam to increase the defective rate of the product.

That is, in a product manufactured by combining or integrally molding these polyurethane foams and other materials, deterioration and discoloration of other materials that come into contact with the product are prevented.
Further, an amine catalyst having excellent moldability is desired. The present inventors have previously filed a patent (Japanese Patent Application No. 2-199268).
Found that an amine catalyst having a secondary hydroxy group in the molecule can solve these problems. However, it has been found that these catalysts are difficult to deteriorate and discolor other materials that come into contact with them at a high temperature for a short time, but deteriorate and discolor for a long time.

[0006]

In view of the above circumstances, the present invention is a non-migration type polyurethane resin,
It is intended to provide an amine catalyst composition for producing a polyurethane, which has excellent aging resistance for a long time and excellent moldability, and a method for producing a polyurethane using the same.

[0007]

The present inventors have conducted extensive studies on amine catalysts for producing polyurethanes and methods for producing the same.

As a result, when an amine catalyst having a secondary hydroxyl group in the molecule and triethylenediamine are used together as a catalyst, in a product produced by combining or integrally molding polyurethane foam and other materials, The present invention has been completed by discovering a new fact that other materials that come into contact with each other are not deteriorated or discolored for a long time and are excellent in moldability.

That is, the present invention provides an amine catalyst composition for producing a polyurethane comprising a compound represented by the following general formula (I) and triethylenediamine (II), and a production method using the same.

[0010]

[Chemical 3]

[0011]

[Chemical 4] (In the formula, n is an integer of 0 to 3, and R ₁ , R ₂ and R ₃ independently represent an alkyl group having 1 to 3 carbon atoms)

[0012]

Next, the present invention will be described in detail.

The amine catalyst composition of the present invention comprises a tertiary amine compound represented by the general formula (I) and having a secondary hydroxyl group in the molecule, and triethylenediamine (I).
I). Weight ratio of (I) and (II) ((I) / (I
I)) is 0.75 or more and 12 or less, and when triethylenediamine is used in this range in combination, the good moldability of the tertiary amine represented by the general formula (I) is not impaired, while
The deterioration and discoloration property over a long period of time are greatly improved.
If the weight ratio of (I) / (II) is less than 0.75, the moldability is deteriorated, and if it exceeds 12, deterioration for a long time and discoloration are deteriorated.

Examples of the compound represented by the general formula (I) include N,
N-dimethyl-N- (2-hydroxypropyl) amine, N, N, N'-trimethyl-N '-(2-hydroxypropyl) ethylenediamine, N, N, N', N ''
-Tetramethyl-N "-(2-hydroxypropyl)
Diethylenetriamine, N, N, N ', N ", N"
Examples include ′ -pentamethyl-N ″ ″-(2-hydroxypropyl) triethylenetetraamine, and among these, N, N-dimethyl-N-2-hydroxypropyl) amine, N, N, N ′ -Trimethyl-N'-
(2-hydroxypropyl) ethylenediamine, N,
N, N ', N "-tetramethyl-N"-(2-hydroxypropyl) diethylenetriamine is more preferred.

These amine catalysts can be prepared by methods known in the art, for example, the corresponding alkanolamines can be prepared by the Leukart-Wallach reaction described in US Pat. No. 4,026,840 or West German Patent 261858.
It can be prepared using the reductive alkylation reaction described in No. 0. On the other hand, since triethylenediamine is a general-purpose catalyst for polyurethane production and is a crystalline product, it is preferable to use a liquid product dissolved in a solvent. As a solvent,
The amount of the amine catalyst composition of the present invention, such as a difunctional alcohol, particularly ethylene glycol, dipropylene glycol, 1.4 butanediol, etc., used for polyurethane production is usually 0.1 when the polyol is 100 parts by weight. It is from 02 to 10 parts by weight. Further, known tertiary amine catalysts and organic carboxylates or organic tin compounds thereof which are commonly used as a cocatalyst can be appropriately used as a cocatalyst as long as the catalytic function of the present invention is not lost.

In the method for producing a polyurethane using the amine catalyst composition of the present invention, conventionally known polyols, polyisocyanates and, if necessary, a foaming agent, a foam stabilizer and other auxiliaries can be used.

Examples of the polyol include polyether polyol, polymer polyol and polyester polyol having two or more reactive hydroxyl groups. Examples of the polyether polyol include glycol, glycerin,
Polyhydric alcohols such as pentaerythritol and sucrose, ammonia, aliphatic amine compounds such as ethyleneamine, toluenediamine, diphenylmethane-4,
An aromatic amine compound such as 4′-diamine and / or a polyether polyol obtained by adding ethylene oxide or propylene oxide to a mixture thereof may be used. Examples of the polymer polyol include those obtained by reacting the polyether polyol with an ethylenically unsaturated monomer such as butadiene, acrylonitrile and styrene in the presence of a radical polymerization catalyst. Examples of the polyester polyol include those produced from a dibasic acid and a polyhydric alcohol, such as polyethylene adipate and polyethylene terephthalate type, and these may be those regenerated from wastes.

As the polyisocyanate, known organic polyisocyanates may be used, for example, aromatic polyisocyanates such as toluene diisocyanate, diphenylmethane-4,4'-diisocyanate and their polymerized isocyanates; aliphatic polyisocyanates such as hexamethylene diisocyanate. An alicyclic polyisocyanate such as isophorone diisocyanate; or an isocyanate terminated prepolymer such as a toluene diisocyanate prepolymer or diphenylmethane-4,4'-diisocyanate prepolymer obtained by reacting them with a polyol; a modified isocyanate such as carbodiimide modification; Examples thereof include mixed polyisocyanates thereof.

The blowing agent is a low boiling point halogenated hydrocarbon and / or water. Well-known halogenated methane and halogenated ethane can be used as the halogenated hydrocarbon. Of these, trichloromonofluoromethane (R
-11), and dichlorotrifluoroethane (R-12
Freon compounds such as 3) and dichloromonofluoroethane (R-141b) are preferable. The amount used is not particularly limited, but the amount of fluorocarbon used is usually 35 parts by weight or less, preferably 0 to 30 parts by weight, and the amount of water used is 2.0 parts by weight per 100 parts by weight of the polyol. The above is preferably 3.0 to 10.0 parts by weight.

Examples of the foam stabilizer include organopolysiloxane-polyoxyalkylene copolymer and silicone-
A nonionic surfactant such as a glycol copolymer, or a mixture thereof, etc. The amount thereof is not particularly specified, but is usually 0 to 100 parts by weight of the polyol.
2.5 parts by weight.

In the present invention, other auxiliaries can be added, if necessary, and conventionally known flame retardants, colorants, extenders, antioxidants, UV inhibitors and the like can be mentioned.

The polyurethane produced using the amine catalyst composition of the present invention is a flexible foam, HR foam, semi-rigid foam, rigid foam or microcellular produced by the conventionally known one-shot method, prepolymer method or the like. Foams, elastomers, etc. Of these, a polyurethane foam that is foamed using a foaming agent,
Particularly preferred is a method for producing polyurethane foam in which the already-formed polyurethane foam is combined with another material in the form of foil, coating or edging or integrally molded. Other materials include vinyl chloride resin, ABS resin,
Resins such as polycarbonate resin, metals, glasses and the like. Examples of products include instrument panels, seats, headrests, armrests, door panels and packaging materials as interior materials for automobiles.

[0023]

INDUSTRIAL APPLICABILITY The amine catalyst composition of the present invention has a low defective rate when used in a product produced by combining polyurethane foam and another material or by integrally molding.
It is possible to manufacture a product without deterioration and discoloration of other materials with which it comes into contact with the material for a long time.

[0024]

EXAMPLES The present invention will be described below based on examples, but the present invention is not limited to these examples.

Examples 1 to 4 and Comparative Examples 1 to 7 In semi-rigid foam formulations in which the mixing ratios (formulations) of the raw materials are as shown below, the results are shown in Table 1 in Examples and Comparative Examples, respectively. A foaming test was conducted using a catalyst under predetermined foaming conditions. The moldability evaluation of the generated polyurethane foam and the discoloration test of the vinyl chloride resin were conducted by the following methods. The results are shown in Table 1.

A. Formulation (parts by weight) Polyol 1) 100 Water 2.8 Crosslinker 2) 3.0 Catalyst 3) Change Isocyanate 4) (NCO / OH = 1.05) 1) Polyether polyol, OHV = 33 mgKOH / g (FA-70 manufactured by Sanyo Kasei Co., Ltd.)
3) 2) Triethanolamine (manufactured by Mitsui Toatsu Chemicals, Inc.) 3) Explanation of catalyst used and catalyst abbreviation in the table DMPA; N, N-dimethyl-N-2-hydroxypropyl) amine TMAEPA; N, N, N'-trimethyl-N '-(2
-Hydroxypropyl) ethylenediamine TMAEEA; N, N, N'-trimethylaminoethylethanolamine TEDA; Triethylenediamine (Tosoh Corporation)
Manufactured by TEDA) 4) Crude MDI, NCO concentration = 31.0% (manufactured by Nippon Polyurethane Industry Co., Ltd., MR-200) b. Foaming conditions Raw material liquid temperature 25 ± 1 ° C Stirring speed 6000 rpm (7 seconds)

C. Measurement item At room temperature (20 to 25 ° C.), a polyurethane raw material was poured into a 2 liter polyethylene cup to cause foaming, and reactivity, foam density, and moldability were measured.

Reactivity Cream time; Foam rise time (seconds) Gel time; Resin (stringing) time (seconds) Rise time; Foam rise stop time (seconds) Foam density 6 × 6 in the center of foam Density is measured with a test piece cut into a size of 6 cm.

Moldability Voids generated at the bottom of the generated foam
Was evaluated according to the following three grades.

Large void ... Small void… △ No void… ○ ・ Discoloration test Mold made of aluminum whose temperature was adjusted to 40 ° C (dimension: 12
Vinyl chloride resin sheet (GA
-20; manufactured by Plastech Co., Ltd.) was set, and a polyurethane raw material was poured onto the foam and foamed to obtain a test piece for discoloration test. Place this in the oven and heat to 120 ° C for 20
The rate of discoloration after 0 hours, 400 hours, and 600 hours was measured with a chromaticity meter (manufactured by Nippon Denshoku Co., Ltd.) and expressed as a color difference value (ΔE; difference from blank value).

[0031]

[Table 1] As is clear from Table 1, the amine catalyst composition of the present invention has 6
It can be said that the color change value after 00 hours is small and the long-term color change property is good, and further the moldability is good. On the other hand, in the amine catalysts of Comparative Examples 1 and 2, the color change value after 200 hours is small, but the color change value after 600 hours is large, and it can be said that the long-term color change property is poor. The amine catalyst of Comparative Example 3 has poor moldability. The amine catalyst of Comparative Example 4 has poor moldability, and the catalysts of Comparative Examples 5 and 6 have poor long-term discoloration properties. The reactive catalyst having a primary hydroxyl group of Comparative Example 7 has poor moldability and long-term discoloration.

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area C08G 101: 00) B29K 75:00 105: 00 C08L 75:04

Claims (4)

[Claims] 1. A weight ratio ((I) / (I) of a compound represented by the following general formula (I) and triethylenediamine (II).
The amine catalyst composition for polyurethane production whose I)) is 0.75 or more and 12 or less. [Chemical 1] (In the formula, n is an integer of 0 to 3, and R ₁ , R ₂ and R ₃ independently represent an alkyl group having 1 to 3 carbon atoms). 2. A catalyst of polyol and polyisocyanate,
Reacting in the presence of a blowing agent and optionally other auxiliaries,
A method for producing a polyurethane foam, which comprises using the amine catalyst composition according to claim 1 as a catalyst in the method for producing polyurethane. 3. A method for producing polyurethane, wherein the polyurethane foam produced by the method according to claim 2 is combined with another material or processed integrally. 4. Other materials such as vinyl chloride resin and ABS
The method according to claim 3, wherein one or more kinds selected from resins and polycarbonate resins are used.