JPH0337216A - Internal mold release and production of polyurethane - Google Patents

Abstract

PURPOSE:To obtain a molding excellent in coatability when a polyurethane is produced by the RIM process by using a metal complex of a dicarbonyl compound as an internal mold release. CONSTITUTION:A metal complex salt of a dicarbonyl compound of formula I (wherein R1 is a 2-31C aliphatic residue; R2 is a 1-9C aliphatic ketone residue; and R3 is H or a 1-8C aliphatic ketone residue), e.g. a compound of any one of formulas II-V (wherein M is a metal of group I or II, Al, Cr, Mo, Fe, Co, Ni, Sn, Pb, or Bi; and X is a halogen atom or OH), optionally mixed with a compatibilizer (an active hydrogen compound having an NCO-reactive nitrogen atom, e.g. ethylenediamine-propylene oxide/polyol adduct) is used as an internal mold release for polyurethane molded by the reaction injection molding process.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Application on M Beams The present invention relates to an internal mold release agent and a method for producing polyurethane.

[Conventional technology] Conventionally, bumper fascia - instrument panel.

The reactor injection molding method (RIM method) has been put into practical use as a means of manufacturing urethane molded products for applications such as automotive exterior and interior materials such as steering wheels. The use of a metal salt of carboxylic acid and an active hydrogen compound containing a primary amine group and a secondary amine group as a mold release agent (for example, Japanese Patent Publication No. 63-52058), and a metal salt of carboxylic acid and a third compound as a solubilizer thereof It is known to use grade amine compounds (for example, Japanese Patent Publication No. Sho E31-501575).

[Problems to be Solved by the Invention] However, these techniques have the problem of having an adverse effect of repelling paint when painting molded products, and there is a need for an internal mold release agent with good paintability.

[Means for Solving the Problems] The present inventors conducted studies to find an internal mold release agent composition that satisfies these requirements, and as a result, they arrived at the present invention.

That is, the present invention includes an internal mold release agent consisting of a metal complex of a dicarbonyl compound having 8 or more carbon atoms and, if necessary, a compatibilizer, as well as an organic polyisocyanate, a polymeric active hydrogen-containing compound, and, if necessary, a low-molecular active hydrogen-containing compound. , a method for producing a polyurethane and/or polyurea resin, which is reacted in the presence of the mold release agent according to any one of claims 1 to 6, and optionally a catalyst, a blowing agent, a foam stabilizer, an inorganic filler, and other auxiliary agents. be.

In the present invention, metal complexes of dicarbonyl compounds having 6 or more carbon atoms include general formulas (2) to (9) (4) (5) : (6) (7) (wherein, fatty acids of RI41C1 to c!+ residue, Rajt
C+ to C・ aliphatic ketone residue, Rs is H or c1
~Ce aliphatic ketone residue, M is a metal, and X is a halogen or OH. ) can be mentioned.

In general formulas (1) to (9), the fatty acids forming the fatty acid residues of 01 to cal of RI (groups obtained by removing C0OH from fatty acids) include acetic acid, propionic acid, butyric acid, valeric acid,
caproic acid, dinandoic acid, caprylic acid, pelargonic acid,
Capric acid, undecylic acid, lauric acid, tridecylic acid, mystylic acid, pentadecylic acid, valmitic acid,
Saturated fatty acids such as heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, heptacosanoic acid, montanic acid, melisic acid, lafcelic acid, oleic acid, elaidic acid, cetoleic acid, erucic acid, brasidine Examples include unsaturated fatty acids such as acids, and those containing amides such as oleoyl sarcosinate, lauroyl sarcosinate, and stearoyl sarcosinate. Preferably, it is a C. to C2s saturated fatty acid,
Especially stearic acid.

-・In Monana (1) to (9), the aliphatic ketone forming an aliphatic ketone residue (a group obtained by removing C0CHa from an aliphatic ketone) with Ra=Rs has the general formula % formula %). The compounds shown include aliphatic ketones (acetone,
Methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, binacolon, diethyl ketone, dipropyl ketone, butylone, diisopropyl ketone, 3-methyl-5-heptanone, diisobutyl ketone, methyl nonyl ketone, dinonyl ketone, etc.), alicyclic ketone (cyclobutanone) , cyclopentanone, cyclohexanone, methylcyclohexanone and 3.3
．． 5-) Rontylcyclohexanone, etc.). Preference is given to aliphatic ketones containing 2 to 19 carbon atoms, especially acetone and methyl ethyl ketone.

The metals M in general formulas (2) to (9) include Group 1 of the periodic table of elements (lithium, sodium, potassium, copper, etc.), Group 2 (magnesium, calcium, barium, zinc, cadmium, etc.), These include aluminum, chromium, molybdenum, iron, cobalt, nickel, tin, lead, antimony, bismuth, and combinations thereof. Preferably zinc, iron, copper, nickel, sodium,
Potassium and combinations thereof, particularly preferred are zinc and iron.

Examples of the halogen for X in general formulas (2) to (9) include chlorine, bromine, iodine, fluorine, and combinations thereof. Preferably it is chlorine.

The metal complex of the dicarbonyl compound in the present invention has 6 or more carbon atoms, preferably 12 to 51 carbon atoms.

When the number of carbon atoms is 5 or less, the mold releasability becomes low.

Examples of the metal complex of the dicarbonyl compound in the present invention include those having the following groups.

Ha”b-J! -L LL JL X -NL■
C a H * C H s H Zinc - C6) ■ C? HIII CH3 H
Zinc Chlorine (q)■ C++H2t CHa
H Zinc − (0■ C+tH*s
CHz H Zinc Chlorine (WA■ C**
Has CHz H Zinc Chlorine (￥)
■ C ItH3s CHI
H Zinc - Do6no■
C+yHs* CHs H Zinc −
(S■ CIte Has CHI CHs
Zinc Chlorine (ψ■ C+vH□ C * H ls
C * H + t Zinc Chlorine @ CI7H
36 CHt H Iron Chlorine■ C+v
Hss CHs H yA Chlorine @
C+vH*s CHI H
Nickel Chlorine @ C+tHss C
HI H Sodium ■ C+
tHss CHt H Zinc Iodine It is preferably a metal complex of a dicarboni compound in which R+ is stearyl, R is methyl, and M is zinc.

In the present invention, the metal complex of the dicarbonyl compound is a fatty acid alkyl ester (alkyl ester having 1 to 4 carbon atoms of the fatty acid, such as methyl, ethyl, butyl).
, can be obtained by reacting ketones (acetone, methyl ethyl ketone, etc.) and alkoxides (methylates such as sodium methylate, potassium methylate, etc.) (metal complex A1), and can also be obtained by reacting A+ with salts of other metals (zinc chloride, iron chloride, etc.). etc.) can be obtained by exchanging metals with (
metal complex A m ). Alternatively, the above reaction may be performed in one step.

The molar ratio of the dicarbonyl compound to the metal in the metal complex (A+) of the dicarbonyl compound (As) is usually O15:
The ratio is 1 to 3:1, preferably 1:1 to 2:1.

The dicarbonyl metal complex obtained by the above reaction is -
By-products other than the metal complexes shown in Patterns (2) to (9) may be included, but this does not pose a problem for the purpose of the present invention.

Compatibilizers used as necessary in the present invention include incyanate-reactive nitrogen-containing active hydrogen compounds, such as compounds having a structure in which ethylene oxide, propylene oxide, and other alkylene oxides are added to amines (
Amine-initiated polyether polyols), polyether polyols (for example, those with structures in which ethylene oxide, propylene oxide, and other alkylene oxides are added to polyhydric alcohols, amines, and polyhydric phenols) convert the hydroxyl group at the molecular terminal into an amino group. Examples include compounds with substituted structures (polyether polyamines), aliphatic amines, alicyclic amines, heterocyclic amines, aromatic amines, and mixtures of two or more of these.

Among the amine-initiated polyether polyols, the amines include ammonia; alkanolamines such as mono-, di-, and triethanolamine, monocodi- and tri-isopropanolamine, aminoethylethanolamine, etc.; C+"Ca.alkylamines; Aliphatic amines such as C2-C@alkylene diamines (ethylene diamine, propylene diamine, hexamethylene diamine, etc.), polyalkylene polyamines (diethylene triamine, triethylene tetramine, etc.): Aromatic amines such as aniline, phenylene diamine, diaminotoluene, xylylene diamine, etc. Amines, methylene dianiline, diphenyl ether diamine, etc.; alicyclic amines such as inphorone diamine, cyclohexylene diamine, dicyclohexylmethane diamine, etc. Niaminoethyl piperazine and other Japanese Patent Publication No. 55-210
Examples include the heterocyclic amines described in Publication No. 44.

Examples of the alkylene oxide to be added include ethylene oxide (hereinafter abbreviated as EO), propylene oxide (
(hereinafter abbreviated as PO), I, 2-, 2,3-butylene oxide, inbutylene oxide, styrene oxide, etc., and combinations of two or more of these (block and/or random addition). Preferred are propylene oxide and 1,21 butylene oxide adducts of ammonia, ethylenediamine, and aminoethylpiperazine.

In the polyether polyamines, the above-mentioned polyhydric alkals include ethylene glycol, diethylene glycol,
Propylene glycol, 1.3- and 1.4-"i methanol, 1.8-hexanediol.

alkylene glycols such as neopentyl glycol,
and diols having a cyclic group (for example, Japanese Patent Publication No. 45
dihydric alcohols such as those described in Publication No. 1474; trihydric alcohols such as glycerin, trimethylolpropane, trimethylolethane, hexanetriol, and triethanolamine; tetrahydric alcohols such as pentaerythritol, methyl glycoside, diglycerin, etc. alcohols; and alcohols with higher functional groups such as pentitol such as adonitol, arabitol, xylitol, hexitols such as sorbitol, mannitol, isotol; sugars such as glucose,
monosaccharides such as mannose, fructose, and sorbose;
Oligosaccharides such as sucrose, crehalose, lactose, and raffinose; Glucosides For example, glucosides of polyols (e.g. glycols such as ethylene glycol and propylene glycol, and alkane polyols such as glycerin, trimethylolpropane, hexanetriol, and pentaerythritol): Poly( alkane polyol)
Examples include polyglycerols such as triglycerin and tetraglycerin, polypentaerythritols such as dipentaerythritol and tripentaerythritol; and cycloalkane polyols such as tetrakis(hydroxymethyl)cyclohexanol.
Polyhydric phenols include monocyclic polyhydric phenols such as pyrogallol, hydroquinone, and phloroglucin; bisphenol A;

Bisphenols such as bisphenol sulfone; condensates of phenol and formaldehyde (novolac); and polyphenols described in US Pat. No. 32Ei5G41, for example. Terminal amination of polyether polyols is performed by direct amination under reducing conditions,
Obtained by methods such as cyanoethyl translocation reduction. Preferably, it is a terminally aminated polypropylene glycol.

Examples of aliphatic amines include CI'' C group alkylamines; C to C6 alkylene diamines such as ethylene diamine, propylene diamine, hexamethylene diamine,
Examples of polyalkylene polyamines include diethylenetriamine and triethylenetetramine.
As aromatic amines, for example, JP-A-81-171
Unsubstituted aromatic polyamines, aromatic polyamines having a nuclear-substituted alkyl, and aromatic polyamines having a nuclear-substituted electron-withdrawing group described in No. 720, specifically, nearaniline, phenylenediamine, diaminotoluene (TDA), crude TDA, diethyl Tolylene diamine, tert-butyl TDA, dithiomethyltolylene diamine, xylylene diamine, methylene dianiline (MDA), crude MDA, diphenyl ether diamine, diaminodiphenylsulfone, benzidine, 4. v-bis(0-toluidine), thiodianiline, dianidine, methylenebis(0-chloroaniline), bis(3,4-diaminophenyl)sulfone, diaminoditolylsulfone, 2. G-
Diaminopyridine, 4-chloro-0-phenylenediamine, 4-methoxy-6-methyl-phenylenediamine.

1-aminobenzylamine, 4,4'-diamino-3,3
Examples include '-dimethyldiphenylmethane and 4,4'-diaminodichlorodiphenylmethane. Examples of the alicyclic amines include inphorone diamine, cyclohexylene diamine, and dicyclohexylmethane diamine. Examples of the heterocyclic amines include aminoethylpiperazine and others described in Japanese Patent Publication No. 55-21044. Preferably propylene diamine, diethyltolylene diamine, tert-butyl TD
A. Dithiomethyltolylenediamine.

The weight ratio of the metal complex of the dicarbonyl compound having 6 or more carbon atoms and the compatibilizer is usually 1:0 to 1:100, preferably 1:0 to 1:10.

When producing an internal mold release agent using a metal complex of a dicarbonyl compound and a compatibilizer together, the two may be mixed in advance, or both may be added when producing a polyurethane and/or polyurea resin. Internal mold release agents may be formed within the active hydrogen-containing composition. The former is preferred.

When producing polyurethane and/or polyurea resin using the internal mold release agent of the present invention, the polymeric active hydrogen-containing compound used is a compound having at least two active hydrogens in the molecule and having a molecular weight of 2000 or more ( For example, compounds with a structure in which alkylene oxides such as ethylene oxide, propylene oxide, and other alkylene oxides are added to polyhydric alcohols, polyhydric phenols, and amines (polyether polyols) and hydroxyl groups at the terminals of polyether polyol molecules. Compounds with a structure substituted with 7 amino groups (polyether polyamines)
and mixtures thereof.

Examples of the polyhydric alcohol, polyhydric phenol, and amines include those mentioned above. Two or more of these active hydrogen atom-containing compounds may be used in combination.

Among these, polyhydric alcohols are preferred.

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),
, 2-, 2.3-butylene oxide.

Examples include inbutylene oxide, styrene oxide, etc., and combinations (block and/or random addition) of two or more thereof.

Preferably, the adduct has a polyoxyethylene chain, that is, the alkylene oxide includes EO and other alkylene oxides (hereinafter abbreviated as AO) [especially PO9
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 10040%. 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 the reaction partner incyanate is poor, resulting in uniformity.
No reaction can take place in the system, and a satisfactory effect cannot be obtained, especially in the case of molding by the RIM method. Moreover, when the amount of EO exceeds 50%, the curing properties are improved, but the viscosity becomes high and the workability deteriorates.

Moreover, in terms of physical properties, temperature characteristics and water absorption become worse. In addition, E
Even if the O amount is less than 5%, it can be combined with an EO amount of 5% or more, or if the EO amount is more than 50%, it can be combined with something that is 50% or less, so that the overall (average) EO amount is above the above. They can be mixed and used within a certain range.

As the polyol having a polyoxyethylene chain, EO and AO are added to the 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) Added in the order of A O-E O-A O Block adducts such as adducts (active secondary); (5) Random adducts in which EO and AO are added in a mixed manner; 7) Japanese Patent Publication No. 53-137
Examples include random/block additions such as those added in the order described in No. 00.

Among these, preferred are those having terminal polyoxyethylene chains, especially (get) 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 is usually 20% or more, preferably 3
It is 0% or more, more preferably 50% or more, most preferably 70% or more.

In producing polyurethane and/or polyurea resins according to the present invention, polyester polyols and polymer polyols can be used in addition to poly1-tyl polyols and polyether polyamines.

The polyester polyols include the above-mentioned polyhydric alcohols (dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, 1,3-*riharil, 4-butanediol, 1, tohexanediol, neopentyl glycol, or these together with glycerin). ,
Polycarboxylic acid or its anhydride (mixture with trihydric or higher alcohol such as trimethylolpropane) and/or polyether polyol (polyether polyol with an EO content of 5% or more and/or less than 5% as described above) , lower esters and other ester-forming derivatives (e.g. adipic acid, sepacic acid, maleic anhydride, phthalic anhydride, dimethyl terephthalate, etc.).

or its anhydrides and alkyleonoxides (EO,
react (condensate) lactones (PO) or lactones (
Examples include those obtained by ring-opening polymerization of ε-caprolactone, etc.).

Polymer polyols include polyols obtained by polymerizing these polyols (polyether polyols and/or polyester polyols, etc.) and ethylenically unsaturated monomers (styrene, acrylonitrile, etc.) (for example, JP-A-54-101839). , Japanese Unexamined Patent Publication No. 54-12
2398)). Additionally, polybutadiene polyols, hydroxyl group-containing vinyl polymers (acrylic polyols) such as those described in JP-A-58-57413 and 57414, natural oil-based polyols such as castor oil, and modified polyols can also be used. .

The molecular weight of the polymeric active hydrogen-containing compound used in the present invention is 2,000 to 25,000. The equivalent weight is from 800 to 4,500, preferably from 1,000 to 3,500.

Preferred among the polymeric active hydrogen-containing compounds are polyether polyols [especially those having a polyoxyethylene chain (EO content 5 to 30%)], polyether polyamines, and polymer polyols.

Among polyether polyols, polyether polyols whose polyhydric alcohol is sorbitol or sucrose and whose molecular weight is 13,000 or more are preferable because they have excellent moldability (curing properties, hardness upon demolding) and physical properties.

The amount of this polyether polyol having a molecular weight of 13,000 or more in the total amount of polymeric active hydrogen-containing compounds is usually 30% or more, preferably 40% or more, and more preferably 5% or more.
It is 0% or more. If it is less than 30%, it is difficult to obtain a polyurethane with excellent moldability and good initial physical properties.

In the present invention, the low-molecular active hydrogen-containing compounds used for resin production include aromatic polyamines (06-211);
Examples include low-molecular polyols, low-molecular terminal aminopolyethers, aliphatic polyamines (C2-01.), and alicyclic or heterocyclic polyamines (04-C+s).

Preferred among these are aromatic polyamines, low-molecular polyols, low-molecular terminal amino polyethers, or mixtures thereof.

Examples of aromatic polyamines (Co-C1a) include unsubstituted aromatic polyamines described in JP-A-61-171720, aromatic polyamines having a nuclear substituted alkyl, and aromatic polyamines having a nuclear substituted electron-withdrawing group. For: phenylenediamine, TDA.

crude TDA, diethyltolylenediamine, tert
-Butyl TDA, dithiomethyltolylenediamine, MD
A, crude MDA, diaminodiphenylsulfone, benzidine, 4,4'-bis(0-)luidine), thiodianiline, dianisidine, methylenebis(0-chloroaniline), bis(3,←diaminophenyl)sulfone,
Diaminoditolylsulfonelysine, 4-chloro-O-phenylenediamine, 4-methoxy-6-methyl-phenylenediamine, 11-
Aminobenzylamine, 4,4'-diamino3.
Examples include 3'-dimethyldiphenylmethane, 4,v-diaminodichlorodiphenylmethane, etc., and mixtures of two or more thereof. Among these, T is preferable.
DA, diethyltolylene diamine, tert-butyl T
DA, dithiomethyltolylene diamine, 4,4'-diamino-3,3'-dichlorodiphenylmethane, and mixtures of two or more thereof.

The low molecular weight polyols used in the present invention include:
It is a compound having a molecular weight of 500 or less (preferably 80 to 400) and having at least 2 (preferably 2 to 3, particularly preferably 2) hydroxyl groups.

For example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, l
, 241 alcohols such as 4-butanediol, neopentyl glycol, hexanediol; glycerin,
Trimethylolpropane, pentaerythritol, diglycerin, α-methylglufuside, nrubitol,
Trihydric or higher polyhydric alcohols such as xylitol, mannitol, dipentaerythritol, glucose, fructose, and SiB sugar: Low molecular weight (e.g., molecular weight 200-40
0) polyhydric alcohol AO adduct (polyethylene glycol.

polypropylene glycol, etc.); low-molecular-weight diols having a cyclic group [for example, those described in Japanese Patent Publication No. 45-1474 (propylene oxide adduct of bisphenol A, etc.)]: tertiary or quaternary nitrogen atom-containing low-molecular polyols [ For example, the one described in JP-A-54-130H9 (N-methyljetanolamine).

N-alkyl dialkanolamines such as N-butyljetanolamine and their quaternized products); trialkanolamines (triethanolamine, tripropanolamine, etc.); thiodiethylene glycol, and the like. Amino alcohols include mono- or di-alkanolamines such as monoethanolamine, jetanolamine, monopropanolamine, etc.). Preferred among these are low-molecular polyols (especially diols), specifically ethylene glycol, 1,4-butanediol, neopentyl glycol, I,6-hexanediol, and mixtures of two or more of these. It is.

As the low-molecular terminal aminopolyether, the molecule fi2
Examples include terminal aminated products of AO adducts of the above-mentioned polyhydric alcohols having a molecular weight of 0 0 or less.

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. When 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 stimulants) is very high, and when poured into the mold, the desired The reaction liquid does not fill up to the corners of the shape, resulting in poor flowability. When using an aromatic polyamine and a low-molecular-weight polyol in combination, if the amount of the low-molecular-weight polyol increases, the liquid flow will be good when reacting with the isocyanate, but the initial thickening time will be longer and air will not be allowed to pass through the reaction liquid as it flows through the mold. It is easy to get caught and voids are likely to occur in the molded product. Further, in this case, the exothermic temperature during the reaction becomes high, and if the mold is released in a short time (for example, 20 seconds or less), flow marks (wavy phenomenon) and blisters are likely to 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 physical properties in molded products, and is inexpensive, but compared to aromatic polyamines,
Effect of temperature during reaction with incyanate (mold temperature, liquid temperature, etc.)
It is easy to receive, and molding defects are likely to occur. Low-molecular terminal aminopolyethers have higher reactivity than aromatic polyamines, and when used in large quantities, the reaction balance with the polymeric active hydrogen-containing compound is disrupted and molding defects are likely to occur.

Aromatic polyamines, low-molecular polyols, low-molecular terminal aminopolyethers, etc. are each 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 1:0.4-230.
It is 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 8 to 20 carbon atoms (excluding the carbon in the NGO group), aliphatic polyisocyanates having 2 to 18 carbon atoms, and alicyclic carbon atoms having 4 to 15 carbon atoms. Formula polyisocyanates, aromatic polyisocyanates having 8 to 15 carbon atoms, and modified products of these polyisocyanates (urethane groups, carbodiimide groups).

Allophanate group, urea group, biuret group.

uretdione group, uretonimine group, isocyanurate group, oxazolidone group-containing modified products, etc.). Specific examples of such polyisocyanates include 1,3-
and 1,4-phenylene diisocyanate 2,4- and/or 2. Todolylene diisodicyanate (TD
IL crude TDI, diphenylmethane-2,
4- and/or 4,4-diisocyanate (MD
I)t Crude MDI [crude diaminophenylmethane] condensation product of formaldehyde and aromatic amine (aniline) or a mixture thereof; mixture of diaminodiphenylmethane and a small amount (e.g. 5-20% by weight) of a trifunctional or higher functional polyamine ] Phosgenated product: polyallyl polyisocyanate (PAP1)], ]naphthylene-1
．． 5-diisocyanate triphenylmethane-4,4
, 4″-triisocyanate.

- Aromatic polyisocyanates such as mono- and p-isocyanatophenylsulfonyl isocyanate; ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate.

dodecamethylene diisocyanate), 1. B,ll-
land decane triisocyanate, 2,2,4-trimethylhexane diisocyanate, lysine diisocyanate), 2,8-diisocyanate methyl caproate.

Bis(2-isocyanatoethyl) fumarate, bis(
Aliphatic polyisocyanates such as 2-indianate ethyl) carbonate, 2-indianate ethyl-2,8-diisocyanate hexanoate; isophorone diisocyanate, dicyclohexylmethane diisocyanate (water ffiMD I), cyclohexylene diisocyanate, methylcyclohexanoate Cycloaliphatic polyisocyanates such as silane diisocyanate (hydrogenated TDI), 'bis(2-isocyanatoethyl) 4-cyclohexene-1,2-dicarboxylate; Aroaliphatic polyisocyanates such as xylylene diisocyanate and diethylbenzene diisocyanate; Modified MDI (urethane modified MDI.

Carbodiimide modified MD1. ), polyisocyanate modified products such as urethane-modified TDI, and mixtures of two or more thereof [e.g., modified MDI and urethane-modified TDI (
inocyanate-containing prepolymer)]. Urethane-modified polyisocyanate [polyol used in the production of a prepolymer co containing free incyanate obtained by reacting excess polyisocyanate (TDl, MDI, etc.) with a polyol, having an equivalent weight of 30 to
200 polyols such as ethylene glycol.

Propylene glycol, diethylene glycol.

Glycols such as dipropylene glycol; triols such as trimethylolpropane and glycerin; high-functional polyols such as pentaerythritol and sorbitol; and alkylene oxide (ethylene oxide and/or propylene oxide) adducts thereof. Among these, the preferable one has a functional group number of 2
~3. The isocyanate equivalent of the above-mentioned modified polyisocyanate and prepolymer is usually 130 to 28
0, preferably 145 to 230. Preferred among these are aromatic diisocyanates, particularly preferred are 2,4- and 2,8-TDI and mixtures of these isomers, crude TDI, 4.4
``- and 2,4'-MD I and mixtures of these isomers, PAPI, also referred to as crude MDI, and urethane groups derived from these polyisocyanates.

Carbodiimide group, allophanate group, urea group.

Modified polyisocyanates containing biuret groups and incyanurate groups, most preferably modified MD
It is I.

NGO equivalent is usually 130-280, preferably 145-2
It is 30. 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, in the production of polyurethane molded articles, the incyanate index [NCO/basic equivalent ratio X1001 containing active hydrogen atoms] is usually 80 to 120. Preferably 8
5-115. Particularly preferably 100-113.

(*The total number of active hydrogen-containing groups (hydroxyl group, amino group) includes the active hydrogen-containing group of the compatibilizer) Also, the isocyanate index is significantly higher than the above range (for example, !30-1.
000 or more) polyinsyanurates can also be incorporated into the polyurethane.

In the present invention, the internal mold release agent is usually 0.00 parts by weight per 100 parts by weight of the polymeric active hydrogen-containing compound. 1 to 30 parts by weight,
Preferably 0. Use 5 to 10 parts by weight. 0. 1
If the amount is less than 30 parts by weight, the mold release performance will be insufficient, and if it exceeds 30 parts by weight, the adhesion between the molded product and the coating will decrease.

According to the present invention, an organic polyisocyanate, a high-molecular active hydrogen-containing compound, and optionally a low-molecular active hydrogen-containing compound are combined with an internal mold release agent consisting of a metal complex of a dicarbonyl compound and an optional compatibilizing agent, and optionally a catalyst and foaming. In producing polyurethane and/or polyurea resins by reacting in the presence of foam stabilizers, inorganic fillers and other auxiliaries, polyurethane foams and/or polyurea foams may be produced by foaming, or without foaming. Polyurethane and polyurea resins (elastomers, sheets) may be produced. In the former case, the total density of the polyurethane (foam) produced is usually 0.3 g/a.
It is preferable to carry out foaming so that the foaming capacity is at least 0.5 g/cm1, particularly preferably at least 0.8 g/cm1.

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 trichloromonofluoromethane) 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 increase in low molecular weight urea bonds increases hardness, which is undesirable as it increases brittleness especially at low temperatures. If water is not used, the amount of the substituted hydrocarbon blowing agent used is the same as that of the resin raw material (organic polyisocyanate, polymeric active hydrogen-containing compound, low-molecular active hydrogen-containing compound,
Total weight of metal complex of dicarbonyl compound and compatibilizer)
It is usually 30% or less, preferably 2 to 20% based on the polymer polyol, and when O and 4% water are used together with the polymer polyol, it is usually 20% or less (especially 0% or less) based on the weight of the resin raw material.
~1.5%) is preferred.

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. Of these, the air loading amount is 20
It is preferable to introduce the gas so that the content is 409A.

In the present invention, in order to accelerate the reaction, catalysts commonly used in polyurethane and/or polyurea reactions [for example, amine catalysts (tertiary amines such as triethylenediamine and N-ethylmorpholine), tin catalysts (stannous octylate, etc.), and , dibutyltin dilaurate, etc.), other metal catalysts (such as lead octylate)] can be used.

Amounts of catalyst are used in small amounts, for example from about 0,000 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-polyoxyalkylene copolymers) are particularly important.

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

The method for producing polyurethane and/or polyurea may be the same as conventional methods, and either the one-shot method or the prepolymer method (quasi-prepolymer method) can be applied.

A one-sheet method is preferred.

The method for producing polyurethane and/or polyurea of the present invention is particularly useful for molding by the RIM method, but it can also be applied to other methods such as the spray method.

In the present invention, the method for producing polyurethane molded articles by molding by the RIM method can be carried out by a normal method, but the metal complex of the dicarbonyl compound is solid at room temperature,
In addition, if the melting point is high and it is difficult to mix uniformly with other raw materials at room temperature, it is heated and mixed with a predetermined amount of a compatibilizer in advance and used as a uniform solution. For example, a polymeric active hydrogen-containing compound, a low-molecular active hydrogen-containing compound, an internal mold release agent (a mixture of a dicarbonyl metal complex and a compatibilizing agent), a catalyst, a pigment, a foam stabilizer, and a flame retardant are added and mixed uniformly. If necessary, a blowing agent (water and/or fluorocarbons) or air loaded is used as liquid A, and liquid B is an organic isocyanate prepared in advance and filled into the tanks of liquids A and B of the high-pressure foaming machine. The injection nozzle of the high-pressure foaming machine is connected in advance to the injection port of the mold, and liquids A and B are mixed using a mixing head, and the mixture is injected into a sealed mold and demolded using a hardening machine.

For example, raw materials whose temperature is usually controlled at 25 to 90"C (2 to 90"C)
4 components) at a pressure of 100 to 200 kg/am"G, and preheated at 30 to 150°C (preferably 80
This can be carried out by pouring into a mold whose temperature is controlled to 0° C.) and then removing the mold within 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.

D) Polymer active hydrogen-containing compound polyol 1: 15,858 P O to 342 parts of sugar
Part 1 A polyether polyol having a hydroxyl value of 22.3 to which 4,000 parts of EO was added.

Polyol 2: PO4,785 in 32 parts of glycerin
Department.

Then 123 parts of EOI was added. Polyether polyester with a hydroxyl value of 28.0 Riolu.

Polyamine 1: A polyether polyamine with an amine equivalent weight of 1880, which is obtained by aminating the terminals of a polyether polyol obtained by adding 92 parts of glycerin to 918 parts of P04.

(2) Low-molecular active hydrogen-containing compound TBTDA: tertiary-butyltolylenediamine (2
, 4-diamino-5-tert-butyltoluene/2-diamino-3-tert-butyltoluene = = 80/20 weight ratio) DETDA: diethyltolylenediamine (3,
5 diethyl-2,4 tolylene diamine/3,5 diethyl-2,8 tolylene diamine: 80/
(20 weight ratio) (3) Polyisocyanate Isocyanate 1: Modified MDI (NCO content 1i23%
) Isocyanate 2: Modified MDI (including NGO! 12G%)
) (4) Catalyst DABCO33LV: An amine catalyst manufactured by Sankyo 17-Brotacts.

DBTDL: Dibutyltin dilaurate (5) Black toner: Carbon black, anti-aging agent (mixture of ultraviolet absorber, antioxidant, heat resistance improver, etc.) dispersed in polyether polyol.

(G) Inorganic filler: FESS-005 (Milled glass manufactured by Fuji Fiber Glass.) (7) External mold release agent: D-188 External mold release agent manufactured by Chukyo Yushi [Molding conditions High pressure foaming machine: MC-102R [N] Manufactured by Near Link Co., Ltd.] Discharge fl: 2 GOg/sec Discharge pressure: 150-170 kg/cm2・Injection time: Approx. 1.6 seconds Raw material temperature HA and B liquids both approx. 40°C Air rotor: 30%
Mold temperature: Approximately 60-70°C Mold release time: 30 seconds to 15 seconds Mold: The lamp is installed at the dose hole I location.

Thickness 3. (Mold of Im- mini bumper type, 400g urethane molded product.

Furthermore, moldability was evaluated using the following method.

■Green strength : The molded product released from the mold for 15 seconds was heated to 180 Cracks appear in folded parts. Time to disappear. (seconds) Apply external mold release agent once to the mold. On the right rear, continuous molding is performed and polyurethane is applied. Part of the rethane resin adheres to the mold and release until it becomes difficult to demold. Type count.

Physical properties were evaluated after cutting out a sample for measurement and leaving it at 20°C x 65% R, I1 for over a week before measurement.

Density (g/c+s”): JISK
-7112 tensile strength (Kg/c/): J I
S K-Ei301 elongation rate (%): J
IS K-E+301 tear strength (Kg/cm):
J I S K-6301 bending modulus (Kg
/c/ ): JIS K-Ei301 Sample 25 Layers (+sm): Sample 25mm x 125+mm x 3. Omm(
t) After leaving the above sample at 120°C for Ihr with an overhang of 100 mm, the sample was cooled at room temperature for 30 minutes and the overlapping distance was measured.

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, an internal mold release agent (a mixture of a dicarbonyl metal complex and a compatibilizing agent), and a catalyst are mixed, and the mixture is allowed to stand at 40°C for 30 days before precipitation of the dicarbonyl metal complex. was evaluated based on appearance.

Paintability was evaluated using the following method.

After steam cleaning the molded product with trichloroethane, a commercially available paint (Flexene) was applied to it and the repellency of the paint was examined.

O: No repelling.

Δ: Some cracks can be seen.

×: The repellency is terrible.

Example 1 Internal mold release agent 1 was obtained by the following method.

54g of sodium methylate and 116g of acetone
Methyl stearate 2 F38 g 200 g of ethyl ether was added, and stirring and reflux was performed at about 40 to 50° C. for about 2 hours. Gradual precipitation of solid was observed. Next, filtration is performed, and hot water at about 70 to 80°C is poured into the filtrate for 60 minutes.
0 g was added and stirred to dissolve the filtrate. Next, the above solution was added dropwise to a mixed solution of 136 g of zinc chloride and 250 g of methanol. Rapid precipitation of solid matter was observed. After about 30% mixing, the mixture was cooled and filtered. The product obtained by filtration was washed with hot water, further washed with acetone, filtered, and then dried. 300 g of internal mold release agent 1 as a white powder was obtained.

Examples 2 to 18 Internal mold release agents 2 to 16 (
Examples 2 to 16) were obtained.

Internal mold release agent 2: Sodium methyla) 54g, 7
t) The reaction was carried out using 118 g of zinc chloride and 138 g of 270 g% methyl halumitate.

Internal mold release agent 3: Sodium methyla) 54g, 7t)
, Furohi.

The reaction was carried out using 102 g of ethyl onate and 136 g of zinc chloride.

Internal mold release agent 4: Potassium methylate 70g, 7t
The reaction was carried out using 118 g of sodium chloride, 200 g of ethyl purinate, and 138 g of zinc chloride.

Sodium methylate 54g, acetone 116g,
Methyl laurate was reacted with 138 g of zinc chloride.

Sodium methylate 54g 1 atton 116g,
The reaction was carried out using 298 g of JF stearate and 1118 g of zinc chloride.

Sodium methylate 54g, acetone 116g,
The reaction was carried out using 298 g of methyl stearate and 91 g of zinc chloride.

The reaction was carried out using 54 g of sodium methylate, 8 g of 7t), 354 g of henic acid JF#, and 136 g of zinc chloride.

Sodium methylate 54g, 7t) 11gg,
Internal mold release agent 7: Internal mold release agent 8: Internal mold release agent 5: Internal mold release agent 6: Internal mold release agent 9: were reacted using 310 g of oleic acid Xfll and 118 g of zinc chloride.

Internal mold release agent 10: Sodium methyla) 54g
, 118 g of acetone, 352 g of methoxy 168 acid*, and 1:16 g of zinc chloride.

1: Sodium methylate 54g, acetone 11
8g, methi-k stearate 298g, zinc chloride 13
8g was used for the reaction.

Internal mold release agent 12: Sodium methylate 54g,
Methyl nonyl ketone 340g, Methyl stearate #
The reaction was carried out using 298 g of zinc chloride and 138 g of zinc chloride.

Internal mold release agent 13: Sodium methyler) 54g
, acetone lleg, methyl stearate 298g,
The reaction was carried out using 127 g of iron(II) chloride.

Internal mold release agent 14: Sodium methylate 54g,
The reaction was carried out using 11 gg of 7t) and 298 g of medicinal stearate.

Internal mold release agent 15: Sodium methyla) 54g
, 7t) 11gg, Methyl stearate 29gg
The reaction was carried out using 134 g of chlorinated steel (II).

Internal mold release agent 18: Sodium methylate 54g,
Acetone 8g, stair internal mold release agent 1 Methyl phosphate 298g, difluoride(II) chloride 1
The reaction was carried out using 30 g.

Example 17 50 g of internal mold release agent 1 was mixed with 50 g of compatibilizer 1 (a polyol prepared by adding 232 parts of PO to 60 parts of ethylenediamine).
g, compatibilizer 2 (diisopropanolamine) 50
g and mixed with heat to obtain 150 g of internal mold release agent 17.

Example 18.19 and Comparative Example 1.2 Table 1 shows the components whose main components were an internal mold release agent, a compatibilizer, a polymeric active hydrogen-containing compound, a low-molecular active hydrogen-containing compound, and a catalyst under the above molding conditions. (Liquid A).

Examples and comparative examples will be described in which polyurethane molded products were produced by charging the isocyanate component (liquid B) into the raw material tanks of a high-pressure foaming machine, mixing them in the high-pressure foaming machine, and then injecting them into a temperature-adjustable sealed mold.

Table-1 1 Riolu! BTDA DABCO33LY BTDL Internal mold release agent 1 Internal mold release agent 2 Zinc stearate compatibilizer 1 Compatibilizer 2 00 4 0.3 0.03 2.7 1.3 1.3 00 4 0.3 603 2.7 1.3 1.3 00 4 0.3 0.03 2.7 1.3 1.3 Isocyanate! NCOINDEX 88.3 05 68.3 05 11i8.3 [+8.3 105 105 Lean strength demolding number dispersion stability 30> 5 3G> 3 30>30> 1 Δ-"Shish" L-m- m Compare "-" (-Density 50 550 8 6.2 Paint film repellency 0 ○ ◎ Δ Examples 20 to 33 Internal mold release agents 3 to 16 were molded using the following molding recipe in the same manner as in Example 18 to produce polyurethane molded products.The results are shown in Table 1. -2.

Polyol 1 BTDA 0 4 DABCO331J Oo BTDL Internal mold release agent Compatibilizer l Compatibilizer 2 3 Isocyphnate 1 88°NCOIIfDEl 06 Table-2! uuJW! ] 20 3 io
30>21 4 +7
30>22 5 33
30>23 8 41
30>24 7 4
0 30>25 8
48 30>28 9
19 30>27 10
23 30>28 11
44 30>29 12
49 30>30 13
29 3G>31 14
11 30>32 15
25 30>33 1 e
23 30> Examples 34 to 41 Using internal mold release agent 1 and compatibilizer 3 (a polyol prepared by adding 290 parts of 1.2 butylene oxide to 80 parts of ethylene diamine), a polymeric active hydrogen-containing compound, a low-molecular active hydrogen-containing compound Polyurethane molded products were obtained by changing the types of compounds, polyisocyanate, and other moving agents. The results are shown in Table 3.
4.

Table-3 Molding recipe Neo #l BTDA DABCO33LV BTDL Internal mold release agent 1 Compatibilizer 3 111 111t Main 1 100 100 10028
24 20 0.3 0.3 0.3 G, 05 0. Q3 0.051.0
5.0 10.02.0 5.0
5.0 Incyanate 1 NCOINDEX 72.9 70.8 212 05 05 05 Re-lean strength Mold release number 30>30>30> 5 8 8 Table-4 Molding recipe 1 Group 1 1 Riolu 1 Neo 112 Ne Su7min I BTDA ETDA DABCO33LV BTDL Kuroto 1- Inorganic filler internal mold release agent 1 Compatibilizer 3 Isocyanate I Isocyanate 2 11 COINDEX 11 Ebon Toyu 40. 70 100 0 26 2B 0.3 0.3 0.3 0.3 0
．． 30.05 0.05 0.03 0.05
(1,Q30 3.5 5.0 75.1 3.5 3.5 3.0 82.1 1 3.5 4.0 60.6 1.5 65.6 05 05 53.0 05 Lean Number of times of strength mold release 30>30>30>30>30> 48 41 8 [Effects of the invention] The internal mold release agent and the method for producing polyurethane and/or polyurea resin of the present invention have the following advantages compared to conventional methods and methods. It is clearly superior in this respect.

(1) Molded products with excellent paintability can be obtained because there is no repellency of the coating film due to the internal mold release agent.

(2) Since it is highly reactive, the cycle time from injection to demolding 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.

(3) 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.

(4) 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.

(5) It has good slip properties and is stable, and can be widely applied to resin fields that require internal mold release performance.

Because of the above-mentioned effects, the method for producing polyurethane and/or polyurea resin using the internal mold release agent of the present invention is widely used in exterior materials such as automobile bumper fascia and polyurethane resin molded in molds. It is extremely useful in improving the productivity of molded products in general.

Claims (1)

[Claims] 1. An internal mold release agent comprising a metal complex of a dicarbonyl compound having 6 or more carbon atoms and, if necessary, a compatibilizer. 2. The dicarbonyl compound has the general formula (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) (In the formula, R_1 is the fatty acid residue of C_2 to C_3_1, R
2. The internal mold release agent according to claim 1, wherein _2 is an aliphatic ketone residue of C_1 to C, and R is H or an aliphatic ketone residue of c'' to C_3. 3. The metal complex of the dicarbonyl compound has the general formula (2) ~
(9) ▲There are mathematical formulas, chemical formulas, tables, etc.▼▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲Mathematical formulas, chemical formulas, tables, etc. There are ▼▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 is a fatty acid residue of C_2 to C_3_1, R
_2 is an aliphatic ketone residue of C_1 to C_2, R_3 is H or an aliphatic ketone residue of C_1 to C_3, M is a metal, and X is a halogen or OH. 3. The internal mold release agent according to claim 1 or 2, which is at least one metal complex represented by: 4. The metal is selected from the group consisting of Group I and Group II of the Periodic Table of Elements, aluminum, chromium, molybdenum, iron, cobalt, nickel, tin, lead, antimony, and bismuth. internal mold release agent. 5. Dicarbonyl metal complex (A_1) obtained by reacting a metal complex of a dicarbonyl compound with a fatty acid alkyl ester, a ketone, and an alkoxide, or a metal-exchanged dicarbonyl metal complex obtained from (A_1) and a salt of another metal. The internal mold release agent according to any one of claims 1 to 4, which is (A_2). 6. The internal mold release agent according to any one of claims 1 to 5, wherein the compatibilizing agent is an isocyanate-reactive nitrogen-containing active hydrogen compound. 7. An active hydrogen-containing composition comprising the internal mold release agent according to any one of claims 1 to 6, a polymeric active hydrogen-containing compound, and optionally a low-molecular active hydrogen-containing compound. 8. The active hydrogen-containing composition according to claim 7, wherein a polyoxyalkylene polyol having 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. 9. The active hydrogen-containing composition according to claim 7 or 8, wherein the low-molecular active hydrogen-containing compound is an alkyltoluenediamine in which the alkyl groups of C_1 to C_4 are in the ortho position with respect to the amino group. 10. An organic polyisocyanate, a high-molecular active hydrogen-containing compound, and optionally a low-molecular active hydrogen-containing compound, the mold release agent according to any one of claims 1 to 6, and optionally a catalyst, a blowing agent, a foam stabilizer, and an inorganic filler. and other auxiliary agents. 11. The production method according to claim 10, wherein the metal complex of the dicarbonyl compound is used in an amount of 0.5 to 10 parts by weight per 100 parts by weight of the polymeric active hydrogen-containing compound. 12. Using water, volatile blowing agent and/or forced gas as blowing agent, total density 0.3 g/cm^3
The manufacturing method according to claim 10 or 11, wherein the above polyurethane and/or polyurea is manufactured. 13. The manufacturing method according to any one of claims 10 to 12, which is molded by a reaction injection molding method.