JPH02232216A - Production of polyurethane - Google Patents

Abstract

PURPOSE:To produce a polyurethane being good in dispersion stability of an internal mold release and free from its adverse effect on the properties by reacting a starting material in the presence of a specified amount of a metal salt of a fatty acid and a specified amount of a solubilizer of this salt. CONSTITUTION:A process for producing a polyurethane by reacting an organic polyisocyanate with a high-molecular active hydrogen compound and a low- molecular active hydrogen compound in the presence of optionally a catalyst, a blowing agent, a foam stabilizer and other adjuvants, wherein 0.5-8.0 pts.wt. metal salt (A) of a fatty acid and 0.5-10 pts.wt. solubilizer (B) of component A of formula I [wherein R1 is a 2-4C alkylene; and R2 is a 1-28C alkyl, a phenyl or a group of formula II (wherein R2 is a phenyl or a 1-28C alkyl); and n1 is 2-6] are used per 100 pts.wt. high-molecular active hydrogen compound, and A/B ratio is 0.5-2.0 by weight. A polyurethane resin having excellent moldability, being good in dispersion stability of the internal mold release and free from its adverse affect on the properties can be obtained.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing polyurethane, specifically, a Reaxine injection molding method (hereinafter abbreviated as RIM method).
The present invention relates to a method for producing polyurethane suitable for molding.

[Prior Art] Conventionally, the RIM method has been put to practical use as a means of manufacturing urethane molded products for applications such as automobile exterior and interior materials such as hampers, fascias, instrument panels, and control handles. In the RIM method, a carboxylic acid metal salt is used as an internal mold release agent and a tertiary amine compound is used as its solubilizer (Japanese Patent Publication No. 1986-501).
It is known to use primary amine groups and secondary amine groups as solubilizers (Japanese Patent Application Publication No. 500418/1983).

[Problem to be solved by the invention] The use of an internal mold release agent is effective for shortening the production cycle time, but because the dispersion stability of the internal mold release agent in the raw material premix is poor, There are problems such as separation, resulting in a decrease in self-release performance, and the solubilizing agent of the internal mold release agent having a negative effect on the physical properties of the molded product. There is a need for a method for producing polyurethane using a molding agent system.

[Means for Solving the Problems] The present inventors conducted studies to find raw materials and polyurethane manufacturing methods that would satisfy these requirements, and as a result, they arrived at the present invention.

That is, the present invention produces polyurethane by reacting an organic polyincyanate with a high-molecular active hydrogen-containing compound and a low-molecular active hydrogen-containing compound in the presence of a catalyst, a blowing agent, a foam stabilizer, and other auxiliary agents if necessary. In the manufacturing method, 0.0% of the fatty acid metal salt (A) is added per 100 parts by weight of the polymeric active hydrogen-containing compound. 5 to 8 parts by weight and general formula C=O C=0 (1)
[In the ceremony. -Rl is a 02-C4 alkylene group, R2 is C
+ ” C
I is an alkyl group. )n+ is an integer from 2 to 6.

] Solubilizer (B) of (A) shown in 0.5 to 10
Use parts by weight and (A) / (B) = 0. 5～
2. This is a method for producing polyurethane, which is characterized in that it is used at a weight ratio of:

In general formula (1), examples of the C2-C4 alkylene group of R include ethylene, propylene, and butylene groups. Preferred are propylene and butylene groups. Examples of C, to C2-alkyl groups of R2 and R3 include methyl, ethyl, probyl, isobrobyl, n-butyl, isobutyl, n-butyl, n-hexynole, n-
Heptinole. Examples include n-octyl and n-nonyl groups. Preferred are methyl, ethyl, probyl, and isoprobyl groups, and more preferred are methyl and ethyl groups.

n+ is usually 2 to 6, preferably 2 to 3, and particularly preferably 2.

Examples of the compound represented by general formula (1) include the following.

These compounds are produced by adding 2 moles of alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) to 1 mole of alkylene diamine (ethylene diamine, propylene diamine, butylene diamine, bentamethylene diamine, hexamethylene diamine, etc.), and then adding fatty acids. It can be obtained by amidating a secondary amine with or by ureating it with a monoisocyanate (phenylisocyanate, etc.). It can also be obtained by reacting 1 mole of the alkylene diamine with 2 moles of fatty acid to form a bisamidation, or by reacting 2 moles of monoisocyanate to form bisurea, followed by addition of alkylene oxide.

The fatty acid metal salt (A) used in the present invention includes zinc stearate, zinc oleate, zinc palmitate, zinc laurate, calcium stearate, calcium oleate, calcium palmitate, lucium laurate, and stearic acid. Magnesium,
Magnesium oleate, magnesium laurate, magnesium balmitate, zinc stearoyl sarcosine, zinc oleyl sarcosine, zinc palmitoyl sarcosine, zinc lauroyl sarcosine, calcium stearoyl sarcosine, calcium oleyl sarcosine, calcium palmitoyl sarcosine. lauroyl sarcosine, threayl sarcosine, stearoyl sarcosine magnesium, oleyl sarcosine magnesium, palmitoyl sarcosine magnesium, lauroyl sarcosine magnesium, threadaroyl sarcosine magnesium, stearoyl sarcosine nickel, oleyl Examples include sarcosine nickel, palmitoyl sarcosine nickel, lauroyl sarcosine nickel, stearoyl sarcosine copper, oleyl sarcosine copper, palmitoinolezanolecosine steel, lauroyl sarcosine steel, and mixtures thereof. Among these, preferred are zinc stearate, zinc oleate, and zinc palmitate, and particularly preferred is zinc stearate.

The polymeric active hydrogen-containing compounds used in the present invention include compounds containing at least two active hydrogens in the molecule and having a molecular weight of 2,000 or more (e.g., polyhydric alcohols, polyhydric phenols, amines), ethylene oxide, propylene, etc. Compounds with a structure in which oxide and other alkylene oxides are added (polyether polyols), compounds with a structure in which the hydroxyl group at the terminal of the polyether polyol molecule is replaced with an amino group (polyether polyamines), and these A mixture of

The polyhydric alcohol mentioned above is ethylene glycol. Diethylene glycol, propylene glycol. l,3-
and 1,4-butanedione. Alkylene glycols such as 1,6-hexanediol and neobentyl glycol, and diols having a cyclic group (for example, those described in Japanese Patent Publication No. 1474/1982), etc.
Alcohol; glycerin, trimethylolpropane, trimethylolethane, hexanetriol,
Trihydric alcohols such as triethanololeamine; tetrahydric alcohols such as bentaerythritol, methyl glycoside, diglycerin; and alcohols with higher functional groups such as pentitol, sorbitol, mannitol, iditol, etc., such as adonitol, arabitol, xylitol, etc. Hexitol; Sugars, such as monosaccharides such as glucose, mannose, fructose, and sorbose; Minor S-saccharides such as sea sugar, crehalose, lactose, and raffinose; Glucosides, such as polyols (e.g., glycols such as ethylene glycol and propylene glycol; glucosides of alkane polyols such as trimethylolpropane, hexanetriol, and pentaerythritol;
Examples include polyglycerols such as triglycerin and tetraglycerin, polybentaerythritols such as diventaerythritol and tribentaerythritol; and cycloalkane polyols such as tetrakis(hydroxymethyl)cyclohexanol. Examples of polyhydric phenols include monocyclic polyhydric phenols such as birogallol, hydroquinone, and phloroglucin; bisphenols such as bisphenol A and bisphenol sulfone; condensates of phenol and formaldehyde (novolak); Examples include the polyphenols listed above.

Examples of amines include ammonia; alkanolamines such as mono-, di-, and triethanolamine, isopropanolamine, and aminoethylethanolamine; C, ~Cps alkylamines; Aliphatic amines such as methylene diamine and polyalkylene polyamines such as diethylene triamine and triethylene tetramine; Aniline, phenylene diamine, diaminotoluene, xylylene diamine, methylene dianiline, diphenylene diamine and other aromatic amines; Isophorone Diamines: Alicyclic amines such as cyclohexylene diamine and dicyclohexylmethane diamine; examples include aminoethylpiverazine and other heterocyclic amines described in Japanese Patent Publication No. 55-21044.These active hydrogen atom-containing compounds Two or more of these may be used in combination. Among these, preferred are polyhydric alcohols, particularly sorbitol and sucrose.

Examples of the alkylene oxide to be added to the active hydrogen atom-containing compound include ethylene oxide (hereinafter abbreviated as EO). Propylene oxide (hereinafter abbreviated as PO),
Examples include 1.2-, 2.3-butylene oxide, inbutylene oxide, styrene oxide, etc., and combinations (block and/or random addition) of 2N or more of these.

Among the polyols (C) used in the present invention, preferred are those having a polyoxyethylene chain, that is, as alkylene oxides, EO and other alkylene oxides (hereinafter abbreviated as AO) [PO] are used as alkylene oxides. and PO in combination with a small amount (for example, 5% or less) of other AO (butylene oxide, styrene oxide).

The polyoxyethylene chain content (abbreviated as EO amount) is usually 5% (weight%, the same applies hereinafter) or more, preferably 7 to 50%.
%. More preferably, it is 10 to 40%. EO amount is 5
If it is less than %, the reactivity is low, the curing property and initial physical properties are low, and the compatibility with incyanate, the reaction partner, is poor, making it impossible to react in a homogeneous system, and particularly when molding by the RIM method, a satisfactory effect cannot be obtained. I can't do it. Furthermore, if the amount of EO exceeds 509A, the curing properties will be improved, but the viscosity will be high and the workability will be poor, and the temperature characteristics and water absorption properties will be deteriorated in terms of physical properties. In addition. Even if EOffi is less than 5%, the EO amount is 5
% or more, or those having an EOfl of more than 50% can be combined with those having an EO fl of less than 50% so that the overall (average) amount of EO falls within the above range.

The above-mentioned polyol having a polyoxyethylene chain includes EO and AO in addition to the above-mentioned active hydrogen atom-containing compound. (
1) Added in the order of AO-EO (chipped). (
2) Added in the order of AO-EO-AO-EO (balanced) + (3) Added in the order of EO-AO-EO, (4) A O - E O - A O
Block adducts such as those added in the order of (active secondary); (5) Random adducts in which EO and AO are added in a mixed manner; and (6) JP-A-57-209
(7) Random/block additions such as those added in the order described in JP-A-53-13700 and the like are mentioned.

Among these, preferred are those having terminal polyoxyethylene chains, especially (1) and (2). The amount of terminal EO is usually 5%, preferably 7% or more, and more preferably 7 to 30%. The internal EO amount is usually 50% or less, preferably 10 to 40%.

The primary hydroxyl group content of polyol (C) is usually 206
A or more, preferably 30% or more, more preferably 50V
& or more, most preferably 70% or more.

The molecular weight of the polyoxyalkylene polyol (C) is 13,000 to 25,000 or more, preferably 13,000 to 20,000. If the molecular weight is lower than 13,000, the resulting polyurethane has poor moldability and physical properties such as elongation.
The equivalent weight of (C) is usually 1,820 to 4. IIliO is preferably 1,620 to 3,340.

In implementing the polyurethane manufacturing method of the present invention,
The polyoxyalkylene polyol (C) can be used in combination with other polymeric polyols if necessary. Other polyether polyols, polyester polyols, and polymer polyols can be used as other polymer polyols that may be used in combination. Polyether polyols include those with a molecular weight of less than 13,000 and having a polyoxyethylene chain, which are obtained by adding alkylene oxide to the above-mentioned active hydrogen-containing compounds (polyhydric alcohols, etc.), and those with a molecular weight of 13,000 and less. or more or 13
,000 does not grow polyoxyethylene chains in the groove (EO
Examples of polyester polyols (such as PO adducts) include the above-mentioned polyhydric alcohols (ethylene glycol, diethylene glycol, propylene glycol, 1,3- or 1,4-butane diol, 1. tohexane diol) , neoventinole glycol, etc.
alcohol or a mixture thereof with a 3M or higher alcohol such as glycerin or trimethylolpropane) and/or polyether polyol (the above-mentioned EO content of 5% or more and/or 5% ungrooved polyether polyol) In addition, polycarboxylic acids or their anhydrides, ester-forming derivatives such as lower esters (e.g. adivic acid, sebacic acid, maleic anhydride, phthalic anhydride, dimethyl terephthalate, etc.), or their anhydrides and alyleon oxides. React (EO, PO, etc.) (
condensation) or by ring-opening polymerization of lactones (epsilon-cabrolactone, etc.). Polymer polyols include polyols obtained by polymerizing these polyols (polyether polyols and/or polyester polyols, etc.) and ethylenically unsaturated monomers (for example, JP-A-54-1018).
No. 99, and those described in JP-A-54-1223H).

Also, polybutadiene boriol, hydroxyl group-containing vinyl polymer (acrylic polyol), for example, JP-A-58-5
Natural oil-based polyols such as those described in No. 7413 and No. 57414, castor oil, and modified polyols can also be used.

Among polymeric polyols, polyether polyols [especially those having polyoxyethylene chains (E
O content of 5% by weight or more)] and its polymer polyol. (C) in the total amount of polymeric active hydrogen-containing compounds
The amount is usually 30% or more, preferably 40% or more, and more preferably 50% or more.

If 30% (C) is ungrooved, a polyurethane with excellent moldability and good initial physical properties cannot be obtained.

The low-molecular active hydrogen-containing compounds used in the present invention include aliphatic polyamines (Ce to C+-), alicyclic or heterocyclic polyamines (CCa to C1), aromatic polyamines (Ca to C2s), Mention may be made of molecular polyols. Among these, aromatic polyamines,
Low molecular weight polyols or mixtures thereof.

Examples of the aromatic polyamines (C● to CI) include unsubstituted aromatic polyamines described in JP-A-61-171720, aromatic polyamines that grow nuclear-substituted alkyl groups, and aromatic polyamines that have nuclear-substituted electron-withdrawing groups. Specifically: Phenylenediamine. TDA (tolylene diamine). Crude TDA. Dithiomethyltolylene diamine, MDA (methylene diamine), Knorade MDA, diaminodiphenynolesulfone, benzidine, 4. 4
'-bis(o-tonoresin). Thiodianiline, dianisidine, methylenebis(0-chloroaniline), bis(3,4-diaminophenyl)sulfone, diaminoditolylsulfone, 2,6-diaminobiridine, 4-chloro10-phenylenediamine, 11-aminobenzylamine, 4,4ξdiaminodiphenylmethane, etc.:
Alkyltoluenediamines in which the 01-C4 alkyl group is ortho to the amine group, such as diethyltolylenediamine, tert-butyl TDA. Examples include 4-methoxymonomethylenyl-phenylenediamine, 4,4'-diamino-3,3'-dimethyldiphenylmethane, and mixtures of two or more of these. Among these, preferred are TDA and jetyltolylene diamine. tsrt-butyl TDA. These are dithiomethinoretolylene diamine, 4,4'-diamino-3,3'-dichlorodiphenylmethane, and mixtures of these with a size of 2 m or more.

The low molecular weight polyols used in the present invention include:
It is a compound having a molecular weight of 500 or less (preferably 60 to 400) and having at least 2 (preferably 2 to 3, particularly preferably 2) hydroxyl groups.

For example, ethylene glycol, diethylene glycol, propylene glycol, dibrobylene glycol. ! , 4-butanediol, neoventinole glycol. Dihydric alcohols such as hexanediol: chrycerin, trimethylonolepropane, pentaerythritol, diglycerin, α-methylglucoside. Trihydric or higher polyhydric alcohols such as sorbitol, Kinlift, mannitol, diventaerythritol, gnorecose, funolectose, and silosaccharide; low molecular weight (e.g. molecular weight 200-40G) polyhydric alcohol AO adducts (polyethylene glycol, polyhydric alcohol) (probylene glycol, etc.)
; Low-molecular-weight diols having a cyclic group [e.g.
-1474 (brobylene oxide adduct of bisphenol A, etc.)]; tertiary or quaternary nitrogen atom-containing low-molecular polyols [for example, JP-A No. 54-130
Those described in G99 (toalkyldialkanolamines such as tomethyldiethanolamine, N-butyldiethanolamine, etc. and their quaternized products); trialkanolamines (triethanolamine, tribropanolamine, etc.); thiodiethylene glycol, etc. can be mentioned. Examples of the amino alcohol include mono- or di-alkanolamines (eg, monoethanolone, diethanolone, monopropanolamine, etc.). Among these, preferred are low molecular weight polyols (especially diols), specifically ethylene glycol, 1,4-butanediol, neopentylene glycol, 1,6-hexanediol, and two or more thereof. It is a mixture of

The aromatic polyamine is generally used in an amount of 50% or less, preferably 5 to 40%, based on the weight of the polymeric active hydrogen-containing compound. If the amount is more than 40%, the activity of the active hydrogen-containing compound component (the entire mixture of the polymeric active hydrogen-containing compound, the low-molecular active hydrogen-containing compound, and other auxiliary agents) is very high, and when poured into the mold, it will not meet the purpose. The reaction liquid does not fill up to the corners of the shape, resulting in poor flowability. When aromatic polyamine and low molecular weight polyol are used together, the weight ratio of polyamine to polyol is from too:o to 20:80, preferably from 100:0 to 30:70. The above weight ratio is 80
If the reaction liquid exceeds 100%, the liquid will flow well when reacting with incyanate, but the initial thickening time will be long, and when the reaction liquid flows in the mold, air will be easily drawn in and voids will easily occur in the molded product. In addition, in this case, the exothermic temperature during the reaction becomes high, and for a short period of time (
For example, if the mold is released for less than 20 seconds, flow marks (wavy phenomenon) and blisters will occur near the injection port of the molded product. Ethylene glycol, which is used as a low-molecular polyol, is easy to handle, has a good balance of various physical properties in molded products, and is inexpensive; ), and molding defects are likely to occur. Aromatic polyamines, low molecular weight polyols, etc. are usually used in an amount of 2 to 50% based on the weight of the polymeric active hydrogen-containing compound. The molar ratio of the polymeric active hydrogen-containing compound and the low-molecular active hydrogen-containing compound is usually 1.
:0.3-230, preferably 1:0.4-150.

As the organic polyisocyanate used in the present invention, those conventionally used in the production of polyurethane can be used. Such polyisocyanates include aromatic polyisocyanates having 20 carbon atoms (excluding carbon in the κCO group), aliphatic polyisocyanates having 2 to 18 carbon atoms, and 4 to 18 carbon atoms! 5 ring type polyisocyanate, carbon number 8~! Aromatic polyinyanate of No. 5 and modified products of these polyisocyanates (modified products containing urethane group, carposiimide group, allophate group, urea group, beureft group, uretdione group, uretonimine group, incyanurate group, oxazolidone group) etc.) are included. Specific examples of such polyisocyanates include 1,3- and 1,4-phenylene diisocyanates}
, 2.4-and/or 2l totolylene diisocyanate (TDI), crude TDI, diphenylmethane-2.4- and/or 4. diisocyanate (MD I ) + crude 15 MDI [crude diaminophenylmethane [condensation product of formaldehyde and aromatic amine (aniline) or mixtures thereof; diaminodiphenylmethane and a small amount (e.g. 5-20% by weight)
Phosgenated product of [Mixture with trifunctional or higher functional polyamine]; Polyallylborisocyanate (PAPI): 1.
Naphthylene! ,5-diisocyanate. Aromatic polyisocyanates such as liphenylmethane-4.4-, 4" monotriisocyanate, ■ mono- and p-isocyanatophenylsulfonyl isocyanate; ethylene diisocyanate 1, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate , 1,8.11-undodecane triisocyanate, 2,2.4- }limethylhexane diisocyanate, lysine diisocyanate}, 2.6
- Aliphatic polyisocyanates such as diisocyanate methyl caproate, bis(2-incyanate ethyl) fumarate, bis(2-incyanate ethyl) carbonate, 2-inocyanate ethyl-2,8-diisocyanate hexanoate; isophorone diisocyanate , dicyclohexylmethane diisocyanate (hydrogenated MD
I), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI),
Alicyclic polyinsyanates such as bis(2-inocyanate ethyl) 4-cyclohexene-1,2-dicarboxylate; Aroaliphatic polyisocyanates such as xylylene diisocyanate and diethylbenzene diisocyanate Monomodified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate modified MDI, etc.). Modified polyisocyanates such as urethane-modified TDI and mixtures of two or more thereof [.
For example, a combination of modified MDI and urethane-modified TDI (incyanate-containing prevolimer) can be mentioned. Urethane-modified polyisocyanate [The polyol used in the production of the free incyanate-containing prebolymer co obtained by reacting excess polyisocyanate (TDI, MDI, etc.) with a polyol is a polyol having an equivalent weight of 30 to 200, such as ethylene glycol, propylene glycol. , diethylene glycol, and diprobylene glycol; triols such as trimethylonolepropane and glycerin; high-functional polyols such as bentaerythritol and sorbitol; and their alkylene oxides (ethylene oxide and/or
or propylene oxide) adducts. Among these, those having 2 to 3 functional groups are preferred. The incyanate equivalent of the above-mentioned modified polyisocyanate and prebolimer is usually 130 to 230, preferably 1
45-230, particularly preferably 180-210. Among these, aromatic diisocyanates are preferred, and 2,4- and 2,4-diisocyanates are particularly preferred.
G-T D I and mixtures of these isomers, crude! M
TDI, t,4'- and 2,4'-M D I and mixtures of these isomers, PAPI, also called crude MDI, and urethane groups derived from these polyisocyanates. Modified polyisocyanates containing a carbodiimide group, an allophonate group, a urea group, a beureft group, and an incyanurate group, and the most preferred is modified MDI, especially those having an NGO equivalent of 156 to 2.
20 and preferably has a functional group number of 2.1 to 2.5. When the NGO equivalent is larger than the above range, heat sag becomes worse, and when it is smaller, the mixing ratio of the active hydrogen-containing compound component and the incyanate component becomes wide, which is unfavorable for molding.

In the present invention, the incyanate index [NGO/active hydrogen atom-containing base equivalent ratio
It is.

{Total of active hydrogen-containing groups (hydroxyl groups, amino groups) other than zero carboxyl groups} Also, if the isocyanate index is significantly higher than the above range (for example, 130 to 1,00G or more), polyisocyanate is added to the polyurethane. It can also be introduced.

The amount of solubilizer (B) used per 100 weight meters of the polymeric active hydrogen-containing compound is 0.5 to 10. ．．・Parts by weight,
Preferably 1.0-5. It is 0 parts by weight. (B)
The amount used is 0. If it is less than 5 parts by weight, the dispersion stability in the active hydrogen-containing compound (A) will be insufficient and the mold release performance will deteriorate. When the amount of (B) used is more than 10.C parts by weight, the physical properties of the molded product (elongation, heat sag, impact strength, etc.)
decreases, which is not desirable.

The amount of fatty acid metal salt (A) used per 100 parts by weight of the polymeric active hydrogen-containing compound is 0. 5-8. parts by weight, preferably 1.0-3. ,,0 parts by weight. The amount of fatty acid gold group salt (A) used is 0. If it is less than 5 parts by weight, the self-releasing performance will be insufficient, and if it exceeds 8 parts by weight, the adhesion between the molded product and the coating will deteriorate, which is not preferable.

According to the present invention, when producing polyurethane using a polymeric active hydrogen-containing compound, a low-molecular active hydrogen-containing compound, a fatty acid gold salt, and a solubilizer, the polyurethane foam may be produced by foaming. Polyurethane resin (elastomer sheet) may also be manufactured without using a polyurethane resin. In the former case, the total density of the resulting polyurethane (foam) is usually 0.3 g/am" or more, preferably 0.5 g
It is preferable to carry out the foaming so that the foaming temperature is greater than /am", particularly preferably O.llg/c+a" or greater.

Foaming can be carried out using water and/or a volatile foaming agent, or by introducing a gas such as air during molding (air loading).

As the volatile blowing agent, a halogen-substituted aliphatic hydrocarbon blowing agent (fluorocarbons such as triclomonofluoromethane) can be used. The amount of water used is usually 0.4% or less, preferably 0.2% or less, based on the polymeric active hydrogen-containing compound. If the amount of water used exceeds 0.4%, carbon dioxide gas generated by the reaction will be exposed to the surface as bubbles, impairing the appearance of the molded product. Also,
In terms of physical properties, the increased number of low-molecular-weight urea bonds increases hardness, which increases brittleness especially at low temperatures, making it difficult to use.

If water is not used, the amount of halogen-substituted hydrocarbon blowing agent used is the total amount of resin raw materials (organic polyisocyanate, polymeric active hydrogen-containing compound, low-molecular active hydrogen-containing compound, fatty acid metal salt, and solubilizer) Usually 30% based on weight
(preferably 2 to 20%), and when 0.4% water is used in conjunction with the polymer polyol, it is usually 20% or less (especially l)-1.5%) based on the weight of the resin raw material. . When air loading is performed using equipment capable of increasing the amount of gas loading, it is desirable to introduce the gas in an amount of 5 to 40% of the specific gravity of the resin raw material. Among these, it is preferable to introduce the gas so that the air loading amount is 20 to 40%.

In the present invention, in order to accelerate the reaction, catalysts commonly used in polyurethane reactions [for example, amine catalysts (tertiary amines such as triethylenediamine and N-ethylmorpholine), tin catalysts (stannous octylate, dibutyltin dilaurate, etc.), and other metals. A catalyst (such as lead octylate) can be used. Amounts of catalyst are used in small amounts, for example from about 0.001 to about 5%, based on the weight of the reaction mixture.

Other additives that can be used as necessary in the present invention include surfactants as emulsifiers and foam stabilizers, and silicone surfactants (polysiloxane-bolioxyalkylene copolymers) are particularly important.

Other additives that can be used in the present invention include known additives such as flame retardants, reaction retarders, colorants, anti-aging agents, antioxidants, plasticizers, fungicides, carbon black, and other fillers. .

The polyurethane manufacturing method may be the same as conventional methods, and either the one-shot method or the prebolymer method (quasi-prepolymer method) can be applied. A one-shot method is preferred.

The polyurethane manufacturing method of the present invention is particularly suitable for molding by the RuM method, but it can also be applied to other methods such as the spray method.

In the present invention, the method of manufacturing polyurethane molded products by molding using the RIM method can be carried out by a normal method, but fatty acid metal salts are generally solid at room temperature, and have a high melting point and can be mixed uniformly with other raw materials at room temperature. Since it is difficult to mix, it is mixed in advance with a predetermined amount of solubilizer at 80 to 110°C and used as a uniform solution. For example, a high-molecular active hydrogen-containing compound, a low-molecular active hydrogen-containing compound, an internal mold release agent (a mixture of a fatty acid metal salt and a solubilizer), a catalyst, a pigment,
A foam stabilizer and a flame retardant are added and mixed uniformly, and if necessary, a foaming agent (water and/or fluorocarbons) or air loaded is used as liquid A. Organic incyanate is prepared in advance as liquid B. Fill the A and B liquid tanks of the high-pressure foaming machine. Connect the injection nozzle of the high-pressure foaming machine to the injection port of the mold in advance, and pour liquid A into the mixing head. Mix B liquid, inject into a closed mold, harden and remove from the mold.

For example, raw materials whose temperature is usually controlled at 25 to 90°C (2 to 4
components) at a pressure of 100 to 2 GO kg/am 2 G, and preheated at 30 to 150°C (preferably 60 to
This can be carried out by pouring into a mold whose temperature is controlled to 90° C. and then removing the mold within 0.1 to 5 minutes.

[Example] The present invention will be explained below with reference to Examples, but the present invention is not limited thereto. The parts shown in the examples represent parts by weight.

The components used in the Examples and Comparative Examples are as follows.

(+) Polymer active hydrogen-containing compound polyol: 342 parts of Japanese sugar and 15.65 parts of PO
A polyether polyol having a hydroxyl value of 22.3 to which 8 parts and then 4,000 parts of EO were added.

Polyol ■: A polyether polyol with a hydroxyl value of 28.0, made by adding 4,785 parts of PO and then 123 parts of EOI to 92 parts of glycerin.

Polyol ■: Po 3 in propylene glycol 7B part
A polyether polyol with a hydroxyl value of 28.0 to which 920 parts of E 2 O was added.

(2) Low-molecular active hydrogen-containing compound TBTD A: tert-butyltolylene diamine (2.4-diamino-5-1-butyltoluene/2.diamino-3-butyltoluene = 80/20 weight ratio) DETDA: diethyltolylenediamine (3.
5 diethyl-2.4 tolylene diamine 73.5 diethyl-2,6 tolylene diamine = 80/
(20 weight ratio) (3) Polyisocyanate Incyanate I: Modified MDI (NGO content 25%) Incyanate ■: Modified MDI (NGO content 23%) (4) Fatty acid metal restoration: Zinc stearate (5) Solubilizer Solubilizer ~■: Compound solubilizer M with the above composition
■: Tertiary amine polyol prepared by adding 32 parts of P0 to 60 parts of ethylenediamine.

(8) Catalyst DABCO33LV: Ecozy-bro 5f'yy amine catalyst.

DBTDL: Dibutyltin dilaurate (7) External mold release agent: D-188 Chukyo Yushi Co., Ltd. External mold release agent [Molding conditions: High pressure foaming machine: MC-102R [Manufactured by Neuriurethane Engineering Co., Ltd.] Discharge rate: 280 g/sec Discharge pressure: 150 ~ 17 (l kg/cm') Injection time: Approx. 1.6 seconds Raw material temperature: Both A and B liquids approx. 40°C Air rotor ink amount = 30% Mold temperature: Approx. 60 ~ 70℃ Mold release time: 30 seconds to 15 seconds Mold: 1 hole for lamp installation, thickness 3
．． The mold is a 400g urethane molded product in the form of a hm mini bumper.

The dispersion stability of the internal mold release agent was evaluated by the following method.

A high-molecular active hydrogen-containing compound, a low-molecular active hydrogen-containing compound, a Uchiro mold release agent (a mixture of a fatty acid metal salt and a solubilizing agent), and a catalyst are mixed, and the mixture is left at 40°C to release the fatty acid metal salt over time. Sedimentation was evaluated visually.

Furthermore, moldability was evaluated using the following method.

■ Product paris adhesion rate: (amount of paris attached to the product) of (
Percentage of the total amount of paris attached to the product and mold.

■Number of self-releases: After applying external mold release agent once to the mold,
During continuous molding, the number of times the polyurethane resin must be released from the mold until a portion of it adheres to the mold and becomes difficult to mold.

■Evaluation of physical properties: After cutting out the sample for measurement, evaluate the physical properties at 20°C x 85% R. ll. It was measured after being left for more than a week.

Density (g/am): JIS K-71!2
Tensile strength (Kg/cl/): J Is K-
11i301 elongation rate (%): JIS
K-s3o+tear strength (Kg/am): JIS
K-[i301 bending modulus (Kg/c+/): JIS K-11t301 sample 25++mX 70 error X 3. Omm(t
) Span 40ml Punch diameter 5R Pressure speed 10mm/win Heat sag Cm): Sample 25mmX 125mmX 3. Omm(t
) After leaving the sample sample above at 120°C for 1 hour with 100% overhang of fat, the sample was cooled at room temperature for 30 minutes and the distance it sank was measured.

Examples 1 to 12 and Comparative Examples 1 to 4 Table 1.2 shows the test results of the dispersion stability of the internal mold release agent. In addition, Tables 3 and 4 show that under the above molding conditions, components (A liquid) whose main components are a polymeric active hydrogen-containing compound, a low molecular active hydrogen-containing compound, an internal mold release agent, and a catalyst, an incyanate component (B liquid) ) were respectively charged into the raw material tank of a high-pressure foaming machine, mixed with the high-pressure foaming machine, and then poured into a temperature-adjustable sealed mold to produce polyurethane molded products. Examples and comparative examples will be described.

[Effects of the Invention] According to the polyurethane production method of the present invention, a polyurethane resin having excellent moldability, good dispersion stability of an internal mold release agent, and no adverse effect on physical properties can be obtained. The present invention, in which the Yoiki polyisocyanate according to the present invention, a high-molecular active hydrogen-containing compound, and a low-molecular active hydrogen-containing compound are molded by the RIM method in the presence of the fatty acid metal salt and a solubilizing agent, is superior to conventional methods. It is clearly superior in the following points.

(1) Due to its high reactivity, the cycle time from injection to molding can be shortened, and the original characteristics of the RIM method can be fully demonstrated. In particular, the resin has high strength during demolding in a short period of time, and there is little paris left on the mold, resulting in excellent productivity.

(2) The dispersion stability of the internal mold release agent in the active hydrogen-containing compound is good, and self-mold release performance does not deteriorate over time, allowing stable continuous production.

(3) Since there is no deterioration in physical properties due to internal mold release agents, molded products having excellent mechanical strength, heat resistance, and low-temperature impact resistance can be obtained.

Because of the above-mentioned effects, the polyurethane manufacturing method of the present invention has remarkable flexibility in improving the productivity of exterior materials such as automobile bumper fascias and general polyurethane molded products that are molded in molds. Demonstrate.

Claims (1)

[Claims] 1. An organic polyisocyanate and a polymeric active hydrogen-containing compound and a low-molecular active hydrogen-containing compound are reacted in the presence of a catalyst, a blowing agent, a foam stabilizer, and other auxiliary agents, if necessary. In the method for producing polyurethane, fatty acid metal salt (A) per 100 parts by weight of polymeric active hydrogen-containing compound
0.5 to 8. Parts by weight and general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (1) [In the formula, R_1 is an alkylene group of C_2 to C_4, R_
2 is an alkyl group of C_1 to C_2_0, a phenyl group, or -NHR_3 (however, R_3 is a phenyl group or an alkyl group of C_1 to C_2_0.) n_1 is 2
It is an integer of ~6. ] It is characterized by using 0.5 to 10 parts by weight of the solubilizing agent (B) of (A) shown in (A) at a weight ratio of (A)/(B) = 0.5 to 2. Polyurethane manufacturing method. 2. The method according to claim 1, wherein the fatty acid metal salt (A) is zinc stearate. 3. The production method according to claim 1 or 2, wherein a polyoxyalkylene polyol (C) containing a polyoxyethylene chain having a molecular weight of 13,000 or more is used as at least a part of the polymeric active hydrogen-containing compound. 4. The method according to claim 3, wherein the polyol (C) is used in an amount of 30% or more based on the weight of the polymeric active hydrogen-containing compound. 5. The method according to claim 3 or 4, wherein the polyoxyethylene chain content of the polyol (C) is 5% by weight or more. 6. The production method according to any one of claims 1 to 5, wherein an alkyltoluenediamine (D) in which the alkyl groups of C_1 to C_4 are in the ortho position with respect to the amino group is used as the low-molecular active hydrogen-containing compound. 7. Using water, volatile blowing agent and/or forced gas as blowing agent, total density 0.3 g/cm
The manufacturing method according to any one of claims 1 to 6, wherein a polyurethane having a polyurethane of ^3 or more is produced. 8. The manufacturing method according to any one of claims 1 to 7, characterized in that the molding is performed by a reaction injection molding method.