JPH03106920A - Production of polyurethane - Google Patents

Abstract

PURPOSE:To improve the cleanability of a mold and the surface appearance and coatability of the produced polyurethane by reacting an organic polyisocyanate with a polymeric active hydrogen compound and a specified internal release agent. CONSTITUTION:An internal release agent comprising a substituted urea is obtained by reacting an organic isocyanate (e.g. hexamethylene diisocyanate) with a prim. or sec. amine having a 12-22C alkyl or alkenyl (e.g. laurylamine) in an equivalent ratio of the isocyanate to the amino of 0.3-1. An organic polyisocyanate (e.g. 1,3-phenylene diisocyanate) is reacted with a polymeric active hydrogen compound at least partially consisting of a polyalkylenepolyol having a polyoxyethylene chain of a mol.wt. >=13000 and the above release agent in the presence of optionally a blowing agent, a catalyst and other assistants to obtain a polyurethane and/or a polyurea of a density >=0.3g/cm<3>.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing polyurethane and/or polyurea.

[Prior Art] Conventionally, the Reaxilon injection molding method (RIM) has been used as a means of manufacturing urethane molded products for use in automobile exterior and interior materials such as bumper fascias, instrument halls, and control handles. In this RIM method, a metal salt of carboxylic acid and an active hydrogen compound containing a primary amine group and a secondary amine group are used as an internal mold release agent (for example, Japanese Patent Publication No. 52058/1983). It is known to use a metal salt of carboxylic acid and a tertiary amine compound as its solubilizer (for example, Japanese Patent Publication No. 81-501575).

[Problems to be Solved by the Invention] However, in these techniques, the carboxylic acid metal salt precipitated from the molded product is deposited on the mold surface and deteriorates the surface appearance of the molded product. In addition, since there are no good solvents for carboxylic acid metal salts,
There are problems such as difficulty in cleaning the mold and insufficient cleaning of the mold release agent before painting, which tends to cause paint to repel.

[Means for Solving the Problems] The present inventors have developed a polyurethane resin which provides a molded product with a good surface appearance, the mold is easy to clean, and has excellent coating performance. The present invention was achieved through extensive research to find a method for producing tan and/or polyurea.

That is, the present invention produces polyurethane and/or This is a method for producing polyurethane and/or polyurea, characterized in that a substituted urea (A) obtained by reacting at a quantitative ratio of 0.9 to 1 is used.

Specific examples of the organic isocyanate (also referred to as incyanate) used to obtain the substituted urea (A) used in the present invention are as follows! ,3-and! , 4-phenylene diisocyanate 2,4- and/or 2, totolylene diisocyanate (TDI), crude TDI,
diphenylmethane-2,v- and/or 4.4
'-') isoshi7*-} (MDI), crude MDI
[crude diaminodiphenylmethane] condensation product of formaldehyde with an aromatic amine (aniline) or a mixture thereof; diaminodiphenylmethane with a small amount (e.g.
~20% by weight) of trifunctional or higher functional polyamine]
phosgenide co; polyaryl polyisocyanate (
Aromatic polyisocyanates such as m- and p-incyanatophenylsulfonyl incyanate; Methylene diisocyanate, hexamethylene diisocyanate (HM
D I ), dodecamethylene diisocyanate,
1,s,tt-undecane triisocyanate,
2,2,4-trimethylhexane diisocyanate,
Lysine diisocyanate, 2. Aliphatic polyisocyanates such as diisocyanate methyl caproate, bis(2-incyanate ethyl) fumarate, bis(2-incyanate ethyl) carbonate, 2-incyanate ethyl-2,8-diisocyanate hexanoate; isophorone diisocyanate (IPDI). Dicyclohexylmethane diisocyanate (hydrogenated MD I
), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI). Screw (2
-incyanate ethyl)4-cyclohexene-1.2
- Alicyclic polyisocyanates such as dicarboxylate; Aroaliphatic polyisocyanates such as xylylene diisocyanate and diethylbenzene diisocyanate;
lauryl isocyanate, stearyl isocyanate}
Examples include long-chain alkyl (alkyl usually has 10 to 22 carbon atoms) monoisocyanates such as (SI), and mixtures of two or more thereof. Among these, preferred are TD1, crude TDI, MDI, crude MDI, hexamethylene diisocyanate, isophorone diisocyanate, cyclohexyl diisocyanate, and stearyl isocyanate, and more preferred are TDI,
TDI, hexamethylene diisocyanate, inphorone diisocyanate and stearyl isocyanate. Substituted urea (A
) The primary or secondary amine substituted with an alkyl group or alkenyl group (also referred to as substituted amine) used to obtain For example, laurylamine, myristylamine, valmitylamine, stearylamine.・Primary amines such as luamine, aralkylamine, behenylamine, myristreylamine, palmitoylamine, oleinoleamine (OA); dilaurylamine (DLA), dimyristylamine, dipalmitylamine, distearylamine (DSA) ，
Examples include secondary amines such as dialkylamine, dibehenylamine, dimyristoleylamine, dipalmitoylamine, and dioleylamine (DOA). Among these, preferred are stearylamine, behenylamine, oleylamine, dilaurylamine, distearylamine, and dioleylamine, and more preferred are oleylamine and dilaurylamine. Distearylamine and dioleylamine.

The equivalent ratio of the organic isocyanate and the above substituted amine is usually O
．． S~I1 Preferably it is 0.95~I. 0.9
If it is less than 1, the amount of unreacted substituted amine increases and the compatibility with polymeric and low-molecular active hydrogen-containing compounds becomes poor. , it is not preferable because it has no effect.

Specific examples of the substituted urea (A) used as the internal mold release agent in the present invention include the reaction products of isocyanates and substituted amines shown in Table 1.

Table 1 These compounds are usually obtained by dropping an isocyanate onto a substituted amine and causing the reaction, but they can also be obtained by dropping a substituted amine onto an isocyanate and causing the reaction. Moreover, substituted urea (A) can also be obtained using two or more types of isocyanates or two or more types of substituted amines.

The polymer active hydrogen-containing compounds used in the present invention include compounds with at least two active hydrogens in the molecule and a molecular weight of 2,000 or more, such as polyhydric alcohols, polyhydric phenols, ayones, ethylene oxide, propylene, etc. Examples include 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 mixtures thereof. It will be done.

Examples of the polyhydric alcohols include alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, l,3- and 1,4-butanediol, l,tohexanediol, neobentyl glycol, and diols having a cyclic group (e.g. Tokuko Showa 4
dihydric alcohols such as those described in Publication No. 5-1474; trihydric alcohols such as glycerin, trimethylolpropane, trimethylolethane, hexanetriol, and triethanolamine; 44
1i anoleconoles: and alcohols with higher functional groups, such as pentitol, nrubitol, mannitol, iditol, etc., such as adonitol, arabitol, xylitol; hexitols, such as sugars, such as glucose, mannose, fructose, sonolebose; oligosaccharides such as sugars, cre/)ose, lactose, and raffinose; Gnorecosides; poly(anolecane polyols) such as triglycerin, polyglycerols such as tetraglycerine, polypentaerythritones such as dipentaerythritone, tripentaerythritone ν; and cycloanolecane polyols such as tetrakis(hydroxymethinole) Examples include cyclohexanol.

Polyhydric phenols include monocyclic polyi7 enols such as birogallol, hydroquinone, and phloroglucin; bisphenols such as bisphenol A and bisphenol sulfone; condensates of phenol and formaldehyde (
Novolac) Examples include polyphenols described in US Pat. No. 32G5641.

Examples of amines include ammonia; alkanolamines such as mono- and tri-ethanolamine, mono- and tri-isoprobanolamine, and aminoethylethanolamine; C1 to C. Alkylamines; C2-C6 anolekylene diamines such as ethylene diamine, propylene diamine, hexamethylene diamine, polyanolekylene polyamines; aliphatic amines such as diethylene triamine, triethylene tetramine; aniline, phenylene diamine, diaminotoluene, xylylene diamine; , methylene dianiline, diphenyl ether diamine and other aromatic amines; alicyclic amines such as isophorone diamine, cyclohexylene diamine, dicyclohexynolemethane diamine; aminoethyl piperazine and other Japanese Patent Publication No. 55-21044
Examples include the heterocyclic amines described in the above publication. 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), t
Examples include 1,2-, 2,3-butylene oxide, imbutylene oxide, styrene oxide, etc., and combinations (block and/or random addition) of two or more of these.

Preferred are those having a polyoxyethylene chain, that is, alkylene oxides such as EO and other alkylene oxides (hereinafter abbreviated as AO) [especially PO, and P
This is a mixture of O and a small amount (for example, 5% or less) of other AO (butylene oxide, styrene oxide). The polyoxyethylene chain content (abbreviated as EOflt) is usually 5% (weight %, the same applies hereinafter) or more, preferably 7 to 50%, and more preferably 10 to 40%.

When EOffi is less than 5%, reactivity is low and curing property is low.
The initial physical properties are low and the compatibility with the reaction partner incyanate is poor, making it impossible to react in a homogeneous system, and particularly when molding by the RIM method, satisfactory effects cannot be obtained.

Moreover, if the amount of EO exceeds 50%, the curing properties will be improved, but the viscosity will increase, resulting in poor workability, and in terms of physical properties, temperature characteristics and water absorption properties will deteriorate. In addition, even if the EO amount is less than 5%, it may be combined with one whose EO amount is 5% or more, or if the EOfl exceeds 50%, it may be combined with one whose EOfl is less than 50%, so that the overall (average) EO amount They can be mixed and used within the above range.

The above-mentioned polyoxyethylene chain-containing polyol includes EO and AO added 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) EO - AO - EO
Added in the order of (4) A O − E O
- block adducts such as those added in the order of AO (active secondary); (5) EO and AO;
Random adduct obtained by mixing and adding; and (6) JP-A-5
Added in the order listed in Publication No. 7-209920, (
7) Random/block adducts such as those added in the order described in JP-A-53-13700 can be 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 is usually 20% or more, preferably 3
It is 0% or more, more preferably 50% or more, and most preferably 70% or more.

In producing polyurethane and/or polyurea resin according to the present invention, polyether polyols,
In addition to polyether polyatones, polyester polyols and polymer polyols can be used.

As the polyester polyol, the above-mentioned polyhydric alcohols (dihydric alcohols such as ethylene glycol, diethylenecributanediol, 1,8-hexanediol, neopentyl glycol, or this together with glycerin,
mixtures with trihydric or higher alcohols such as trimethylolpropane) and/or polyether polyols (e.g. EOffi 5% or more and/or 5%
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 alkyleonoxide (EO.P
react (condensate) lactones (ε
Examples include those obtained by ring-opening polymerization (such as monocabrolactone).

Polymer polyols include polyols obtained by polymerizing these polyols (polyether polyols and/or polyester polyols, etc.) and ethylenically unsaturated monomers (for example, JP-A-54-101899,
(described in JP-A-54-1223911i). Furthermore, polyptadiene polyols, vinyl polymers containing hydroxyl groups (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 from 2000 to 250001, and the equivalent is 8
00 to 4500, preferably 1000 to 3500.

In the polyether polyol, polyoxyethylene chain-containing polyalkylene polyols in which the polyhydric alcohol is sorbitol or sucrose and have a molecular weight of 13,000 or more are preferred because they have excellent moldability (curing properties, hardness when molded) and physical properties. The amount of 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 50% or more. Excellent formability at 30% fullness,
Polyurethane with good initial physical properties cannot be obtained.

The low-molecular active hydrogen-containing compounds used in the present invention include aliphatic polyamines (c2 to C), alicyclic or heterocyclic polyamines (Ca to C+s), aromatic polyamines (Cs=*s), Examples include low molecular weight polyols and low molecular weight terminal aminopolyethers.

Examples of the aromatic polyamines (C● to C*@) include unsubstituted aromatic polyamines, aromatic polyamines having a nuclear substituted alkyl, and nuclear substituted electron-withdrawing groups described in JP-A-81-171720. Specifically, aromatic polyamines having: phenylenediamine, TDA, crude TDA, jetyltolylenediamine+tert-butyl TDA. Dithiomethyltolylenediamine, MDA. Crude MDA, diaminodiphenylsulfone, benzidine, 4,4'-bis(0-toluidine), thiodianiline, dianisidine, methylenebis(0-chloroaniline)
, bis(3,4-diaminophenyl)sulfone, diaminoditolylsulfone, 2,6-diaminopyridine, 4-
Chloro-0-phenylenediamine, 4-methoxy-6-
Methynole ■-phenylenediamine, m-aminobenzylamine, 4. 4'-Diamino-3,3'-dimethyldiphenylmethane, 4. Examples include 4'-diaminodichlorodiphenylmethane and mixtures of two or more thereof. The preferred among these is TDA,
Diethynoletolylene diamine, tert-butyl TD
A, dithiomethyltolylenediamine. 4.4'-diamino-3.3! Particularly preferred among dichlorodiphenylmethane is diethyltoluenediamine, ta, in which the alkyl group of 01 to C4 is in the ortho position to the aryono group.
rt-butyl TDA, dithiomethyltolylenediamine, and mixtures of 281 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 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, dipropylene glycol, l
, 4-butanediol, neopentylglycol, hexanediol, etc.; chrycerin, trimethylonolepropane, pentaerythritol, diglycerin, α-methynoleglucoside, sorbitol, xylitol, mannitol, cypentaerythritol, glucose, fructose , Shi I! 3 such as sugar
Polyhydric alcohol of 4 fJ or more; low molecular weight (e.g. molecular weight 200-400) polyhydric alcohol AO adduct (polyethylene glycol, polypropylene glycol, etc.)
; Low-molecular-weight diols having a cyclic group [e.g.
-1474 (propylene oxide adduct of bisphenol A, etc.)]; tertiary or quaternary nitrogen atom-containing low-molecular polyols [e.g., JP-A-54-130
[Things described in Publication i99 (Tolkyl dialkanolamines such as N-methyldiethanolamine, N-butyldiethanolamine, etc., and their quaternized products); Trialkanolamines (triearthanolamine, triprobanolamine, etc.) ]; Examples include thiodiethylene glycol. Examples of amino alcohols include mono- or di-alkanolamines (eg, monoethanolamine, diethanolamine, monopropanolamine, etc.). Preferred among these are low molecular weight polyols (especially diols), specifically ethylene glycol, 1,4-butanediol,
Neopentyl glycol, 1,6-hexanediol, and mixtures of two or more thereof.

Examples of the low-molecular terminal polyether polyamine include terminal aminated products of AO adducts of the above-mentioned polyhydric alcohols.

Among these low-molecular active hydrogen-containing compounds, aromatic polyamines, low-molecular polyols, or mixtures thereof are preferred, and aromatic polyamines are particularly preferred.

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, the desired 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 usually too:t~20:80,
Preferably the ratio is 100:1 to 30:70.

If the weight ratio exceeds 80, the liquid will flow well when reacted with isocyanate, but the initial thickening time will be long, and when the reaction liquid flows in the mold, it will easily entrain air and cause voids 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; etc.) and molding defects are likely to occur. Low-molecular-terminal polyether polyamines 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.

Low-molecular active hydrogen-containing compounds such as aromatic polyamines, low-molecular polyols, and low-molecular terminal polyether polyamines are
Usually 2 to 5 based on the weight of the polymeric active hydrogen-containing compound
0% used. The molar ratio of the polymeric active hydrogen-containing compound and the low-molecular active hydrogen-containing compound is usually 1:0.3 to 230, preferably 1:0. 4 to 150.

As the organic polyisocyanate used in the present invention, those conventionally used in the production of polyurethane can be used. Examples of such polyisocyanates include aromatic polyisocyanates having 6 to 20 carbon atoms (excluding carbon in the NCO group), aliphatic polyisocyanates having 2 to 18 carbon atoms, and alicyclic polyisocyanates having 4 to 15 carbon atoms. isocyanate,
Aromatic polyisocyanates having 8 to 15 carbon atoms and modified products of these polyisocyanates (containing urethane groups, carposiimide groups, allophanate groups, urea groups, puret groups, uretdione groups, uretonimine groups, incyanurate groups, oxazolidone groups) modified substances, etc.). Specific examples of such polyisocyanates include 1,3- and 1,4-phenylene diisocyanate, 2,4- and/or 2,8-}lylene diisocyanate (TD I L crude TDI, diphenylmethane-2,4 '1- and/or 4,4'-diisocyanes} (MDI). Crude MDI [: Crude diaminodiphenylmethane [formaldehyde and aromatic amines]
aniline) or mixtures thereof; diaminodiphenylmethane and small amounts (e.g. 5-20% by weight)
mixture with trifunctional or more functional polyamine]; polyarylboriincyane-}CPAPI)],
Naphthylene-1,5-diisocyanate, triphenylmethane-4,4'. 4″-triisocyanate, l
Aromatic polyisocyanates such as - and p-isocyanatophenylsulfonyl isocyanate; ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, P decamethylene diisocyanate, 1,8.11-undecane triisocyanate, 2,2.4- Trimethylhexane diisocyanate, lysine diisocyanate, 2,B-diisocyanate methylcabroate, bis(2-incyanateethyl) fumarate, bis(2-incyanateethyl) carbonate, 2-incyanateethyl-2.
Aliphatic polyisocyanates such as 8-diisocyanate hexanoate; isophorone diisocyanate, dicyclohexylmethane diincyanate (hydrogenated MD I L
Cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis(2
-ethyl isocyanate)4-cyclohexene-1,2
-Alicyclic polyisocyanates such as dicarboxylate; Aroaliphatic polyisocyanates such as xylylene diisocyanate and diethylbenzene diisocyanate; Modified MDI (urethane modified MDI, carbodiimide modified MDI, }lihydrocarbyl phosphate modified MDI)
etc.), urethane modification. - Modified polyisocyanates such as TDI and mixtures of two or more thereof [for example, combinations of modified MDI and urethane-modified TDI (isocyanate-containing prepolymers). Polyisocyanate with an excess of urethane-modified polyisocyanate C (T
DI, MDI, etc.) and a polyol], polyols having an equivalent weight of 30 to 200, such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, etc. Glycols such as Nore; 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, those having 2 to 3 functional groups are preferred.

The incyanate equivalent of the above-mentioned modified polyisocyanate and prepolymer is usually 130 to 280, preferably 145.
~230. If the NCO equivalent is larger than the above range, heat sag will worsen, and if it is smaller, the mixing ratio of the active hydrogen-containing compound component and the incyanate component will be wide, which will have an unfavorable effect on molding.

Among these, aromatic diisocyanates are preferred, and 2,4- and 2.8-T are particularly preferred.
DI and mixtures of these isomers, crude TDI,
PAPI, also called crude MDI
and modified polyisocyanates containing urethane groups, carbodiimide groups, allophanate groups, urea groups, puret groups, and isocyanurate groups derived from these polyisocyanates, and the most preferred is modified MDI.

In the present invention, the isocyanate index [NCO/active hydrogen atom-containing base equivalent ratio X 1001] in the production of polyurethane molded articles is usually 80 to 120, preferably 85 to 115, and particularly preferably 100 to 113. {Total of active hydrogen-containing groups (hydroxyl groups, amino groups) other than zero carboxyl groups} Also, the incyanate index is significantly higher than the above range (for example, 130 to 1,000
(or higher) It is also possible to incorporate polyisocyanurates 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.
If it is less than 5 parts by weight, the mold release performance is insufficient;
If the amount exceeds 0 parts by weight, the adhesion between the molded product and the coating film will decrease.

According to the present invention, an organic polyisocyanate, a polymeric active hydrogen-containing compound, a low-molecular active hydrogen-containing compound, and an internal mold release agent are reacted, optionally in the presence of a catalyst, a blowing agent, and other auxiliaries, to produce a polyurethane and/or In producing polyurea molded articles, polyurethane foam and/or polyurea foam may be produced by foaming, or polyurethane and polyurea resins (elastomers, sheets) may be produced without foaming.

In the former case, the total density of the resulting polyurethane (foam) is usually 0.3 g/cI or more, preferably 0.5 g/cI
It is preferable to carry out foaming so that the weight is 13 or more, particularly preferably 0.8 g/c+*' or more.

Foaming can be carried out by using water, a volatile foaming agent, or by forcibly introducing a gas such as air during molding (gas 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. When not using water, the amount of halogen-substituted hydrocarbon blowing agent used should be The amount is usually 30% or less (preferably 2 to 20%) based on the total weight of the polymer polyol, and when 0.4% water is used in combination with the polymer polyol, it is usually 20% or less (especially O
-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 ~40%.

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.), , dibutyl dilaurate, dilaurate, etc.), and other metal catalysts (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 known auxiliary agents that can be used in the present invention include foam stabilizers, inorganic fillers, flame retardants, reaction retarders, colorants, anti-aging agents, antioxidants, plasticizers, bactericides, carbon black, and other fillers. Additives include:

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

The one-shot 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, a polyurethane molded article can be produced by a conventional method by molding using the RIM method.

For example, a polymeric active hydrogen-containing compound, a low-molecular active hydrogen-containing compound, an internal mold release agent (substituted urea), a catalyst, an inorganic filler, a pigment, a foam stabilizer, and a flame retardant are uniformly mixed, and if necessary, a blowing agent (water and/or fluorocarbons) or gas loaded as the A liquid, and as the B liquid, prepare an organic isocyanate in advance.
．． Fill the liquid and B liquid tanks. Connect the injection nozzle of the high-pressure foaming machine to the injection port of the mold in advance, mix liquids A and B with a mixing head, inject into a sealed mold that has been previously treated with an external mold release agent, and mold after curing. .

For example, raw materials whose temperature is usually controlled at 25 to 90°C (2 to 4
components) are impingement-mixed at a pressure of too~200kg/cs''G, and preheated at 30~150℃ (preferably 60℃
After pouring into a mold whose temperature is controlled at ~90℃),
This can be done by demolding within 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.

(1) Polymer active hydrogen-containing compound polyol l: 342 parts of sucrose and 15,858 parts of P O
%, and then a polyether polyol with a hydroxyl value of 22.3 to which 4,000 parts of EO was added.

Boliol 2: 4.785 P O in 92 parts of glycerin
polyether polyol with 41 [i28.0] hydroxyl groups to which 123 parts of EOI were added.

Polyamine 1: P 0 4918 in 92 parts of glycerin
A polyether polyamine with an amine equivalent weight of 1,700, which is obtained by aminating the terminals of a polyether polyol to which a portion has been added.

Polyamine 2: P O in 76 parts of brobylene glycol
Polyether polyamine with an amine equivalent of 1780, obtained by aminating the terminals of a polyether polyol to which 3480 parts have been added (2) Low-molecular active hydrogen-containing compound TBTDA: 3-butinoletolylene diamine (
2,4-diamino-5-tert-butyltoluene/2,6
-Diamino-3-tert-butyltoluene = 80/2
0 weight ratio) DETDA: diethyltolylenediamine (3,
5 diethyl-2,4 tolylene diamine/3,5 diethyl-2,B tolylene diamine = 80/2
0° weight ratio) Polyol 3: Polyether polyol with a hydroxyl value of 750, which is obtained by adding 4G parts of PO2 to 60 parts of ethylene diamine (3) Polyisocyanate Incyanate 1: Modified MDI (NGO-containing ffi23
%) (4) Catalyst DABCO33LV: Amine catalyst manufactured by Sankyo Air Products Co., Ltd.

D. BTDL: Dibutynoretin dilaurate (5) Inorganic filler FESS-005 (Milled glass manufactured by Fuji Fiber Glass.

(6) External mold release agent: D-18E3 External mold release agent manufactured by Chukyo Yushi [Molding conditions High pressure foaming machine: MC-102R [manufactured by Polyurethane Engineering Co., Ltd.] Discharge rate: 2 [i0 g/sec Discharge pressure: 15G ~170 kg/am' Injection time: Approximately 1. G seconds Raw material temperature: Both A and B liquids approx. 40''C Process 7-0-Te ink amount: 30% Mold temperature: Approx. 60~70''C Mold release time: 30 seconds~15 seconds Mold: For lamp installation Open hole summer location, thickness 3
．． MONORED is a 400g urethane molded product with a 0mm mini-bumper type.

Furthermore, moldability was evaluated using the following method.

■Number of times of self-release: After applying an external mold release agent to the mold, continuous molding is performed, and the number of times the mold is released until a part of the polyurethane resin adheres to the mold and becomes difficult to release.

■Mold surface volume of internal mold release agent: Pour the mold surface at the 20th continuous mold release. Line drawing with a plastic spatula and check the amount of internal mold release agent deposited. Judging visually.

(Comment 4I: ○ Small amount, × Large amount) ■Product pari adhesion ffi: Ratio of (amount of pari attached to the product) to (total amount of pari attached to the product and mold).

■ Physical property evaluation i: After cutting out the sample for measurement, evaluate the physical properties at 20°C x 85% R. 11. It was measured after being left for more than a week.

Density (g/cm3): JIS K-
7112 tensile strength (Kg/c/): JIS
K-8301 elongation rate (%): JIS
K-s3ot tear strength (Kg/cm): J
IS K-8301 bending modulus (Kg/cd): JIS K-8301 sump/L/ 25mmX 70+aiX 3. Om
m(t) span 40mm Punch diameter 5R Pressure speed 10mm/min Heat sag (am): Sunf 7L/ 25mmX 125mmX 3. O
ms+(t) After leaving the above sample at 120°C for 1hr with an overhang of 100 mm, the sample was cooled at room temperature for 30 minutes and the distance it sank was measured.

Paintability was evaluated using the following method.

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

○: No repelling.

Δ: Some cracks can be seen.

×: The repellency is terrible.

Examples-1 to I4 and Comparative Example-1.2 Table-2, Table-3
Under the above molding conditions, a component (liquid A) containing a polymeric active hydrogen-containing compound, a low-molecular active hydrogen-containing compound, an internal mold release agent, and a catalyst as main components (liquid A), and an incyanate component (liquid B) are added as raw materials in a high-pressure foaming machine. Pour each into a tank, mix in a high-pressure foamer, and then adjust the temperature. Examples and comparative examples in which polyurethane molded articles were produced by injecting into closed molds are described.

Table-2 Molding recipe NERIOL L NERIOL 2 TBTDA DABCO33LV DBTDL Internal mold release agent Isocyanate I NCO INDEX Mold release number Product high adhesion amount 30 seconds Cu 7-15 seconds Cure Internal mold release agent Mold surface deposition density Tensile strength Formability and physical property values Example 123 50 100 100 50 24 24 24 0.3 0.3 0.3 0.03 0.03 0.03 III 4 4 4 [i0.8 59.9 59.9105 1
05 105 28 25 28 4 100 100 100 100100 95 35 97 8B O 1 . 06 235 O 1.07 241 ○ 1.05 240 O 1. 08 230 Elongation rate 320 310 33G bending modulus 3200 3310
3300 tear strength 78 80 82
Heat↑ku 7.3 8.0
7.8 Paint film repellency ○ 0 0 Table 3 Molding properties and physical property values Examples Molding recipe 5 6 7 1 Liol 1 100 100
100TBTD▲ 24 24 24
DABCO33LV O. 3 0.3 0
．． 3DBTDL O. 03 0.03 G.
03 Internal mold release agent I/If I/II [ I/IV
2/2 2/2 2/2 Isocyanate 1 59.9 59.9
59.9NGO INDEX 105
105 105 Number of demolding 35 33
31 product adhesive amount 30 seconds cure 100 100
100315 3180 83 7.5 0 8 100 24 0.3 0.03 ■ 4 59.9 105 33 100 l5 seconds Cure Internal release agent Mold surface Deposition Density Tensile strength Elongation Bending Mosilius Tear strength Heat No. ke Coating film Table 4 Molding recipe Newlyol TBTDA DETDA DABCO33LY DBTDL Inorganic filler 94 9B o O 1.0? 1.08 234 228 320 315 3200 3150 83 81 ? ,7 8.1 0 0 9B 97 O l. 06 230 32G 3180 81 8.0 0 O l. 07 240 320 3200 83 7.8 0 Formability and physical properties Example 9 10 11 100 100 10G 24 0.3 0.03 20 24 24 240.3
G. 3 Q. 3 0.03 G. 03 0.03 Internal mold release agent ■ 4 Isocyanate 1 59.9 NCiO INDEX 105 Number of mold release
28 Product adhesive amount 30 seconds cue - 100 15 seconds cue - 95 Internal mold release agent deposited on mold surface ○ Density 1.07 Tensile strength 240 Elongation rate 285 Bending modulus 3950 Tear strength 80 Heat ↑ Ku 3.5 The coating film is -Soon ○ 100 37 O l. 07 235 320 2950 82 6.2 0 l00 9B O t . oe 233 330 2310 80 B. 5 0 100 95 ○ l. 06 230 340 2850 79 6.0 0 Table-5 Molding properties and physical property values Example Comparative example molding recipe 13 14 1 2 NERIOR II 50 -
100 100 Nelior 3
− − −
3Neuriamine 1 50 5
0゜Liamine 2 50
− −TBTD▲
24 24 24
24DABCO33LV O. 1
- 0.3 0.3DBT
DL O. 02-
0.03 0.03 Internal mold release agent II-- 4 4 4 Zinc stearate 1 1-3 Isocyanate I B1.5 B2.3
59.9 8? ．． [iNCO INDE
X 105 105 105
105 Number of times of mold release 41 49
4 38 product high adhesion amount 30 seconds cure 100 100
100 100!5 seconds cuy-9
9 100 97 9
1i Internal mold release agent deposited on mold surface 0 0 × density
1.08 1.09 1.0B +. 0
7 Tensile strength 243 244 240
235 Growth rate 330 340 320
245 bending mossillus 3050
3+00 3150 3200 Tear strength 77 80 81 82
Heat No.ke S,0 3.2
B. 8 7.1 Paint film repellency
O O ○ ∆High and little residual material on the mold (excellent productivity).

Because of the above-mentioned effects, the polyurethane production method of the present invention is extremely useful for improving the productivity of exterior materials such as automobile bumper fascias and general polyurethane molded products that are molded in molds. do.

[Effects of the Invention] The method according to the present invention is clearly superior to the conventional method in the following points.

(1) Because the amount of internal mold release agent deposited on the mold surface is small,
No appearance defects occur on the surface of the molded product.

(2) Molded products with excellent paintability can be obtained because the coating film is not repelled by the internal mold release agent.

Claims (1)

[Claims] 1. An organic polyisocyanate, a polymeric active hydrogen-containing compound, a low-molecular active hydrogen-containing compound, and an internal mold release agent are reacted in the presence of a catalyst, a blowing agent, and other auxiliary agents if necessary. In a method for producing polyurethane and/or polyurea, an organic isocyanate and a primary or secondary amine having an alkyl group or alkenyl group are used as internal mold release agents in an equivalent ratio of isocyanate groups to amino groups of 0.
A method for producing polyurethane and/or polyurea, characterized in that a substituted urea (A) obtained by the reaction in 9-1 is used. 2. Substituted urea (A) as a polymeric active hydrogen-containing compound 100
2. The method according to claim 1, wherein 0.5 to 30 parts by weight are used per part by weight. 3. The manufacturing method according to claim 1 or 2, wherein the primary or secondary amine has a C_1_2 to C_2_2 alkyl group or alkenyl group. 4. Claims 1 to 3 wherein the organic isocyanate in the substituted urea (A) is an organic isocyanate selected from the group consisting of tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene isocyanate, isophorone diisocyanate and stearyl isocyanate.
The manufacturing method described in any of the above. 5. Claims 1 to 4 in which a polyoxyethylene chain-containing polyalkylene polyol (B) having a molecular weight of 13,000 or more is used as at least a part of the polymeric active hydrogen-containing compound.
The manufacturing method described in any of the above. 6. The manufacturing method according to any one of claims 1 to 5, wherein an alkyltoluenediamine in which the alkyl group of C_1 to C_4 is ortho to the amino group is used as the low-molecular active hydrogen-containing compound. 7. Using at least one of water, a volatile blowing agent, and a forcibly mixed gas as a blowing agent to achieve a total density of 0.
The manufacturing method according to any one of claims 1 to 6, wherein polyurethane and/or polyurea having a weight of 3 g/cm^3 or more is manufactured. 8. The manufacturing method according to any one of claims 1 to 7, which is molded by a reaction injection molding method.