JPH01170611A - Production of polyurethane - Google Patents

Abstract

PURPOSE:To provide the title product having good physical properties without the sedimentary coagulation of a metal soap, by using a modified polyol produced by polymerizing an ethylenic unsaturated monomer in a polyether polyol in the presence of the metal soap as an inner mold release agent. CONSTITUTION:(C) An ethylenic unsaturated monomer is first polymerized in the coexistence of (B) a metal soap (preferably zinc stearate, etc.) in (A) a polyether polyol to provide a modified polyol. The produced modified polyol as at least part of active hydrogen atom-containing compounds is subsequently reacted with a polyisocyanate, as necessary, in the presence of a catalyst, foaming agent and other additives to provide a polyurethane. The component A is preferably one having a terminal polyoxyethylene chain. The component C is preferably hydroxyethyl methacrylate, etc.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a method for producing polyurethane molded articles.

[Prior art] Conventionally, as a method for manufacturing polyurethane, when molding a polyisocyanate and a compound containing an active hydrogen atom using a reaction injection molding method (hereinafter abbreviated as RIM method), active hydrogen was added using a metal soap as an internal mold release agent. A method of adding it to an atom-containing compound is known. In this method, a compatibilizer (e.g., epoxidized vegetable oil, nitrogen atom-containing polymer) is used in combination to prevent deterioration of workability and trouble in the molding machine due to precipitation and agglomeration of the metal soap in the active hydrogen atom-containing compound. , a method for preventing precipitation and agglomeration of metal soaps has been proposed (Japanese Patent Application Laid-open No. 15593/1983).
(Japanese Patent Application Laid-Open No. 61-83215, etc.).

[Problems to be Solved by the Invention] However, in this method for producing polyurethane molded products, there is a problem in that the compatibilizer has an adverse effect on the physical properties of the polyurethane molded products produced by the reaction, such as heat sag and elongation at break. be.

[Means for Solving the Problems] The present inventors have developed a polyurethane that can stably disperse metal soap in an active hydrogen-containing compound without sedimentation and agglomeration, and that does not adversely affect the physical properties of molded products. As a result of extensive research to find a manufacturing method, the present invention was achieved.

That is, the present invention provides a method for producing polyurethane by reacting a polyisocyanate and an active hydrogen atom-containing compound in the presence of a catalyst, a blowing agent, and other additives if necessary, in which at least one of the active hydrogen atom-containing compounds is reacted. As a part, ethylenically unsaturated monomer (iii) is coexisted with metal soap (ii) in polyether polyol (i).
) is produced by polymerizing modified polyol (
A patented method for producing rethane (first invention) characterized by using a), by reacting a polyisocyanate and an active hydrogen atom-containing compound in the presence of a catalyst, a blowing agent, and other additives (if necessary), In the method for producing polyurethane, as at least a part of the active hydrogen atom-containing compound,
Metal soap (ii) in polyether polyol (i)
Modified polyol (a) produced by polymerizing ethylenically unsaturated monomer (iii) in the coexistence of low molecular polyamine (b) and optionally low molecular polyol (c) and/or amino alcohol (d ) A method for producing polyurethane (second invention), which produces polyurethane by reacting a polyisocyanate and an active hydrogen atom-containing compound in the presence of a catalyst, a blowing agent, and other additives as necessary. In the method, an ethylenically unsaturated monomer (iii) is produced by polymerizing an ethylenically unsaturated monomer (iii) in the coexistence of a metal soap (ii) in a polyether polyol (i) as at least a part of the active hydrogen atom-containing compound. A method for producing polyurethane (third invention) characterized by using a modified polyol (a), a low molecular weight polyol (c) and/or an amino alcohol (d), and a polyisocyanate and an active hydrogen atom-containing compound, if necessary. A method for producing polyurethane by reacting in the presence of a catalyst, a blowing agent, and other additives, in which a metal soap (ii) is used in a polyether polyol (i) as at least a part of an active hydrogen atom-containing compound. This is a method for producing a polyurethane (fourth invention) characterized by using a modified polyol (a) produced by polymerizing an ethylenically unsaturated monomer (iii) in the coexistence of the polyol.

Examples of the metal soap used in the present invention include salts of fatty acids and metals, and mixtures of two or more thereof.

The above-mentioned fatty acids include monocarboxylic acids having usually 8 to 22 carbon atoms, preferably 10 to 20 carbon atoms, such as saturated fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, valmitic acid, stearic acid, aragidic acid, and behenic acid; Examples include unsaturated fatty acids such as myristoleic acid, palmitoleic acid, oleic acid, vaccenic acid, eicosenoic acid, and erucic acid, and mixtures of two or more thereof. Among these, preferred are lauric acid, myristic acid, valmitic acid, stearic acid, palmitoleic acid,
Oleic acid and mixtures of two or more thereof, most preferably myristic acid, valmitic acid, stearic acid and mixtures of two or more thereof.

The above metals include alkaline earth metals, VIa in the periodic table.
Examples include atoms belonging to the groups ①a, ③, Ib, and nb, aluminum, tin, lead, and mixtures of two or more thereof. Among these, calcium, magnesium, chromium, manganese, nickel, copper, zinc, cadmium, aluminum, lead, and mixtures of two or more of these are preferred, and calcium, zinc, cadmium, aluminum, lead, and mixtures of two or more of these are preferred. mixture of two or more types,
Most preferred is zinc. That is, the most preferred salts are zinc stearate, zinc balmitate, zinc myristate, and mixtures of two or more thereof.

The ethylenically unsaturated monomer (iii) used in the production of the modified polyol (a) in the present invention has the following formula [wherein R1 is hydrogen or a methyl group, Z is alkylene group, ml, m2゜m3. m4
is an integer of 0 or more, p is an integer of 2 to 6, and q is an integer of 0 or more: R2, -R3, --Ra, and Rs are hydrogen, an alkyl group having 1 to 3 carbon atoms, or a glycidyl group. ] Monomers containing monomer (iv) can be used.

A in the above formula (1) includes an ethylene group, a propylene group, a 1,2-butylene group, a 1,3-butylene group, 1.
Examples include 4-butylene group and 2,3-butylene group,
Preferably it is an ethylene group or a propylene group. mL
m2. m3. ml is preferably an integer of 0 to 100. nl, n2. n3. Preferably n4 is 0. , is preferably 2 or 3. q is preferably an integer of 1 to 6, more preferably 1 to 3. R2, R3, R4, R5 are hydrogen, methyl group, ethyl group, n-propyl group,
Examples include 1so-propyl group, preferably hydrogen and methyl group.

Specific examples of the monomer represented by general formula (1) include glycidyl ether and the like.

In the above, EO is CR2CR20, PO is CH2C
l (cH3)0.

- The monomer represented by formula (1) can be obtained by an esterification reaction between (meth)acrylic acid and a polyol having the corresponding structure, or an amidation reaction between an alkanolamine having the corresponding structure.

As (iii), the monomer represented by formula (1) is preferred, but other monomers may be used in place of or together with the monomer represented by formula (1). As this monomer, those commonly used in the production of polymer polyols can be used.
Examples include those described in the specification of No. 36. Specific examples include ethylenically unsaturated nitrile [(meth)acrylonitrile, etc.], ethylenically unsaturated carboxylic acid and its derivatives [(meth)acrylic acid, (meth)acrylate, etc.]
Aliphatic hydrocarbon monomers (ethylene, propylene, α-olefins having 4 to 20 carbon atoms, etc.), aromatic hydrocarbon monomers (styrene, methylstyrene, etc.), other vinyl monomers such as trostyrene, vinyl acetate etc.) etc. can be raised. Among these, acrylonitrile styrene and mixtures thereof are preferred.

- The content of the monomer of formula (1) is preferably at least 10%, particularly preferably at least 20%, based on the weight of all monomers.

The polyether polyol (i) used in the production of the modified polyol (a) used in the present invention is a compound having at least 2 (preferably 2 to 8) active hydrogen atoms (such as polyhydric alcohol, polyhydric phenol, etc.). ,
Compounds having a structure in which alkylene oxide is added to amines, polycarboxylic acids, phosphoric acid, etc.) and mixtures thereof can be mentioned.

Examples of the polyhydric alcohols include alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, 1,3- and 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol, and diols having a cyclic group (e.g. dihydric alcohols such as those described in Japanese Patent Publication No. 45-1474); trihydric alcohols such as glycerin, trimethylolpropane, trimethylolethane, hexanetriol, triethanolamine; pentaerythritol, methyl glycoside, diglycerin, etc. and sugar alcohols with higher functional groups such as pentitol such as adonitol, arabitol, xylitol, hexitol such as sorbitol, mannitol, isotol, talitol, dulcitol;
Sugars e.g. monosaccharides such as glucose, mannose, fructose, sorbose; oligosaccharides such as sucrose, crehalose, lactose, raffinose; glycosides e.g. polyols (e.g. glycols such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, hexane) Glucosides of poly(alkane polyols) such as triols; polyglycerols such as triglycerin and tetraglycerin. Polypentaerythritols such as dipentaerythritol and tripentaerythritol; and cycloalkane polyols such as tetrakis(hydroxymethyl)cyclohexanol.

The polyhydric phenols mentioned above include monocyclic polyhydric phenols such as pyrogallol, hydroquinone, and phloroglucin; bisphenols such as bisphenol A1 and bisphenolsulfon; condensates of phenol and formaldehyde (
(Novolak) Examples include polyphenols described in US Pat. No. 3,265,641.

Also, examples of amines include ammonia; mono-, di-, and triethanolamine, isopropanolamine,
Alkanolamines such as aminoethylethanolamine; C1-C2theta alkylamines; C2-C6 alkylene diamines such as ethylene diamine, pro-diamine, hexamethylene diamine, polyalkylene polyamines such as diethylene triamine, triethylene tetramine, etc.; Aniline, phenylenediamine, diaminotoluene, xylylenediamine,
Methylene dianiline, diphenyl ether diamine, and other aromatic amines listed as examples of (ii) above; alicyclic amines such as isophorone diamine, cyclohexylene diamine, and dicyclohexylmethane diamine; aminoethyl piperazine and other Japanese Patent Publication No. 1983 −
Examples include heterocyclic amines described in JP-A No. 21044. Two or more of these active hydrogen atom-containing compounds may be used in combination.

Among these, preferred are polyhydric alcohols.

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), 1
．． Examples include 2-11, 3-11, 4-12, 3-butylene oxide, styrene oxide, etc., and combinations of two or more of these (block and/or random addition).

Among the polyether polyols (i), preferred are those having a polyoxyethylene chain, that is, as alkylene oxides, EO and other alkylene oxides (hereinafter abbreviated as AO) [especially Po, and Po and other A
A small amount (for example, 5% or less) of O (butylene oxide, styrene oxide) is used in combination. Its polyoxyethylene chain content (abbreviated as EO amount) is usually 5% (
% by weight (hereinafter the same) or more, preferably 7 to 50%, more preferably 10 to 40%. If the amount of EO is less than 5%, the reactivity is low, the curing property and initial physical properties are low, and the compatibility with the reaction partner isocyanate is poor, making it impossible to react in a homogeneous system, which is particularly unsatisfactory in the case of molding by the RIM method. No effect will be obtained. Furthermore, when the amount of EO exceeds 50%, the curing properties are improved, but the viscosity becomes high and the workability deteriorates, and the temperature characteristics and water absorption properties deteriorate physically. In addition,
Even if the EO 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% or less, the overall (average) EO amount is above the above. They can be mixed and used within a certain range.

The above-mentioned polyether polyol having a polyoxyethylene chain includes those obtained by adding EO and AO to the above-mentioned active hydrogen atom-containing compound in the order of (1) AO-EO (under Nisso), (2) AO-EO-AO -EO order (balanced), (3) EO-AO-EO order, (4) 0-EO-AO order (active secondary), etc. block adducts; (5) random adducts obtained by mixing and adding EO and AO; and (6) those added in the order described in JP-A-57-209920, (7) JP-A-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 (1) and (2). The amount of terminal EO is usually 5% or more, preferably 7% or more, and more preferably 7 to 30%. Internal EO amount is usually 50
% or less, preferably 10 to 40%.

The primary hydroxyl group content of the polyether polyol (i) is usually 20% or more, preferably 30% or more, more preferably 50% or more, and most preferably 70% or more.

The hydroxyl value (average) of the polyether polyol (i) is usually 200 or less, preferably 15 to 100. 200
The rigidity of the polyurethane obtained is high when it exceeds
Becomes brittle.

As the polyether polyol (i), polyether polyols (i) having different hydroxyl values (for example, those having 70 or less (usually 50% by weight or more) and those having 80 to 500) may be used in combination, and in addition to these, polyether polyols (i) having higher hydroxyl values (for example, hydroxyl groups or less) may be used. A small amount (for example, 20% by weight or less, particularly 5% by weight or less) of a low-molecular-weight polyol having a value of 700 or more can also be used in combination. [Low-molecular polyols used in combination include the above polyhydric alcohols [listed as raw materials in (i)], and low molar AO adducts of the above polyhydric alcohols and amines. ] The molecular weight of polyether polyol (i) is usually 2.00
0-30,000 or more, preferably 3.00
0 to 25,000. If the molecular weight is lower than 2,000, the resulting polyurethane will have poor moldability and will be a molded product with poor elasticity.

Modified polyol (a
) is usually 20% by weight or more, preferably 50% by weight or more. If (a) is less than 20%, a sufficient mold release effect will not be exhibited.

In the present invention, the amount of ethylenically unsaturated monomer (iii) used in the production of modified polyol (a) is the total amount of polyether polyols (i), (ii), and (iii) of 1
The amount is usually 3 to 50 parts, preferably 5 to 25 parts per 00 parts (by weight, hereinafter the same). When (iii) exceeds 50 parts, separation of the polyether layer and polymer layer occurs. If the amount is less than 3 parts, (ii) will sediment and separate.

The modified polyol (a) can be produced by a conventional method for producing a polymer polyol. For example, ethylenically unsaturated monomer (iii) in polyether polyol (i)
A method of polymerizing in the presence of a polymerization initiator (radical generator, etc.) (U.S. Patent No. 3,383,351, Japanese Patent Publication No. 39-24737, Japanese Patent Publication No. 47-47999, Japanese Patent Application Laid-Open No. 15894-1989, etc.) There is a method of graft polymerizing a polymer obtained by prepolymerizing or (iii)' and (i) in the presence of a radical generator, and the former method is preferred.

A polymerization initiator is usually used in these polymerizations.

The polymerization initiator is one that generates free radicals to initiate polymerization, such as 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis-(
Azo compounds such as 2゜4-dimethylvaleronitrile (AVN); dibenzoyl peroxide, dicumyl peroxide, and peroxides other than those described in Japanese Patent Application No. 199160/1983; Although borates, persuccinic acids, etc. can be used, azo compounds, particularly AIBNSAVN, are preferred from a practical standpoint. The amount of polymerization initiator to be used is usually 0.00% based on the weight of the ethylenically unsaturated monomer.
It is 1 to 10%, preferably 0.2 to 5%.

The above polymerization reaction can be carried out without a solvent, but it can also be carried out in the presence of an organic solvent (especially when the polymer concentration is high). Examples of organic solvents include benzene, toluene, xylene, acetonitrile, ethyl acetate, hexane, heptane, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, isopropyl alcohol, n-butanol, and mixtures of two or more of these. can be mentioned.

Furthermore, if necessary, polymerization can be carried out in the presence of a known chain transfer agent other than alkyl mercaptans (carbon tetrachloride, carbon tetrabromide, chloroform, enol ethers described in JP-A-55-31880, etc.). .

Polymerization can be carried out either batchwise or continuously. The polymerization reaction is carried out at a temperature higher than the decomposition temperature of the polymerization initiator, usually 60 to 180°C.
Preferably 90-160°C, particularly preferably 100-1
It can be carried out at 50°C, and it can also be carried out under atmospheric pressure, increased pressure, or even reduced pressure.

After the polymerization reaction is complete, the resulting modified polyol can be used as it is to produce polyurethane without any post-treatment; however, after the reaction is complete, impurities such as organic solvents, decomposition products of the polymerization initiator, and unreacted monomers are commonly used. It is desirable to remove it by other means.

The hydroxyl value of the modified polyol (a) is usually 15-100, preferably 20-70.

In the polyurethane manufacturing method of the present invention, the modified polyol (a) can be used in combination with other active hydrogen atom-containing compounds if necessary. In addition to (a), other active hydrogen atom-containing compounds that may be used if necessary include polyether polyols, polyester polyols, and polymer polyols. Examples of the polyether polyol include those mentioned above as the raw material polyether polyol (i) in (a). The polyester polyols include the above polyhydric alcohols (ethylene glycol,
Diethylene glycol, propylene glycol, 1,3
- or a dihydric alcohol such as 1,4-butanediol, 1,6-hexanediol, neopentyl glycol or a mixture thereof with a trihydric or higher alcohol such as glycerin or trimethylolpropane) and/or polyether Polyol (the above-mentioned EO amount 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. adipic acid, sebacic acid, maleic anhydride, phthalic anhydride, dimethyl terephthalate, etc.), or their anhydrides and alkyleonoxides ( react (condense) EO, PO, etc.
Alternatively, examples include those obtained by ring-opening polymerization of lactones (epsilon-caprolactone, etc.). Polymer polyols include these polyols, polyether polyols and/or polyester polyols, etc.) and ethylenically unsaturated monomers [raw materials (ii) of (a) above].
Polyols (for example, those described in JP-A-54-101899 and JP-A-54-122396) obtained by polymerizing the compounds mentioned as i): acrylonitrile, styrene, etc.) are mentioned. Also, polybutadiene polyols, hydroxyl group-containing vinyl polymers (acrylic polyols), such as JP-A Nos. 58-57413 and 574
Natural oil-based polyols such as those described in Publication No. 14, castor oil, and modified polyols can also be used.

These polyols usually have 2 to 8 hydroxyl groups and 200 to
It has an OH equivalent of 4,000, preferably 2 to 4 hydroxyl groups and an OH equivalent of 400 to 3,000.

Among these, polyether polyols are preferred, and more preferred are polyether polyols containing EO chains (having 0 to 50% by weight of EO chains arbitrarily distributed in the molecule, and 0 to 30% by weight). The EO chain is tipped at the end of the molecule).

Low molecular weight polyamine (b) used in the second invention
(1) Aliphatic polyamines (c2 to C15)
, for example; C2-C6 alkylene diamine [ethylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, etc. copolyalkylene (
c2-Cs) Polyamines [diethylenetriamine, iminobispropylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.], their alkyls (01-Ca) or hydroxylalkyls (c2
~Ca) Substituted product [dialkyl (01-C3) aminopropylamine, aminoethylethanolamine, methyliminobispropylamine, etc.]: Alicyclic or heterocycle-containing aliphatic polyamine [3,9-bis(3-aminopropyl- 2,4,8,10-tetraoxaspiro[5,5]
Undecane, etc.]: Aromatic ring-containing aliphatic amines (c2~
C15) [Xylylene diamine, tetrachlor-p
-xylene diamine, etc.: (2) Alicyclic or heterocyclic polyamines (c4-C1
5) For example: menthanediamine, piperazine.

N-aminoethylpiperazine, 1,3-diaminocyclohexane, isophoronediamine, hydrogenated methylene dianiline, etc.: (3) Aromatic polyamines (cs-Ce), for example, unsubstituted aromatics described in JP-A-61-171720 group polyamines, aromatic polyamines having nuclear-substituted alkyl groups, and aromatic polyamines having nuclear-substituted electron-withdrawing groups, specifically: phenylenediamine, TDA, crude TDA,
diethyltolylene diamine, tert-butyl TDA,
Dithiomethyltolylene diamine, MDA, crude MD
A, diaminodiphenylsulfone, benzidine, 4,4
'-bis(0-toluidine), thiodianiline, dianisidine, methylenebis(0-chloroaniline), bis(
3,4-diaminophenyl) sulfone, diaminoditolylsulfone, 2,6-diamitubiridine.

4-chloro-〇-phenylenediamine, 4-methoxy-
6-methyl-m-phenylenediamine, m-aminobenzylamine, 4,4'-diamino-3,3ξdimethyldiphenylmethane, 4,4ξdiaminodichlorodiphenylmethane, etc.: and mixtures of two or more of these. It will be done. Among these, preferred are TDA, diethyltolylenediamine, tert-butylTDA, dithiomethyltolylenediamine, 4,4ζdiamino-3,3'-dichlorodiphenylmethane, and mixtures of two or more of these. The amount of (b) in the active hydrogen atom-containing compound is usually 3 to 30% by weight, preferably 5 to 25% by weight.

The low molecular weight polyol (c) and/or amino alcohol (d) used in the second and third inventions have at least two (preferably 2 to 3, particularly preferably 2) active hydrogen atoms (hydroxyl groups). , mercapto group, etc., preferably hydroxyl group) with a molecular weight of 500 or less (
Preferably 60 to 400) compounds, such as low molecular polyols (c) and/or amino alcohols (d)
can be used.

Examples of low-molecular polyols include dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, neopentyl glycol, and hexanediol;
Trivalent or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, diglycerin, α-methylglucoside, sorbitol, xylit, mannitol, dipentaerythritol, glucose, fructose, sucrose; low molecular weight (e.g. molecular weight 200
~400) polyhydric alcohol AO adducts (polyethylene glycol, polypropylene glycol, etc.); low molecular weight diols having a cyclic group [e.g.
Items described in No. 4 (propylene oxide adducts of bisphenol A, etc.); tertiary or quaternary nitrogen atom-containing low-molecular polyols (e.g., those described in JP-A-54-130699 (N-methyljetanolamine); , N-
N-alkyl dialkanolamines such as butylgetanolamine and their quaternized products); trialkanolamines (triethanolamine, tripropaturamine, etc.); thiodiethylene glycol, and the like.

Amino alcohols include mono- or di-alkanolamines such as monoethanolamine, jetanolamine, monopropanolamine, etc.). Among these, preferred are low molecular polyols (
In particular, they are ethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, and mixtures of two or more of these.

The amount of (, c ) and/or (d) in the entire active hydrogen atom-containing compound is usually 46% by weight or less, preferably 30%
It is more preferably 25% or less.

Part or all of (b), (c) and/or (d) are made to coexist in the polyether polyol (i) during the production of the modified polyol (a), and (iii) is polymerized, It is also possible to produce polyols modified with them.

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 6 to 20 carbon atoms (excluding the carbon in the NCO group) (for example, 2.4- and/or 2-,
6-Dylene diisocyanate) (TDI), crude T
DI, 2,4ζ and/or 4,49-diphenylmethane diisocyanate (MDI), crude MDl [crude diaminophenylmethane (condensation product of formaldehyde and aromatic amines (anilines) or mixtures thereof, diamino diphenylmethane and small amounts (e.g. 5-20
% by weight) of a mixture with a trifunctional or higher functional polyamine): polyallyl polyisocyanate (PAPI)
etc.; Aliphatic polyisocyanates having 2 to 18 carbon atoms (e.g. hexamethylene diisocyanate, lysine diisocyanate, etc.); Cycloaliphatic polyisocyanates having 4 to 15 carbon atoms (e.g. isophorone diisocyanate, dicyclohexylmethane diisocyanate); 8 to 18 carbon atoms
15 araliphatic polyisocyanates (for example, xylylene diisocyanate, etc.); and modified products of these polyisocyanates (urethane group, carbodiimide group, allophanate group, urea group, biuret group, uretdione group, uretonimine group, isocyanurate group) ,
oxazolidone group-containing modified products, etc.); and patent application filed in 1983.
Examples include polyisocyanates other than those described in JP-A-199160; and mixtures of two or more thereof.

Among these, commercially readily available polyisocyanates such as 2,4- and 2,6-TDI,
and mixtures of these isomers, crude TDI, 4,4ξ
and 2゜4'-MDI, and mixtures of these isomers, PAPI, also called crude MDI, and urethane groups, carbodiimide groups, allophanate groups, urea groups, biuret groups, and isocyanurates derived from these polyisocyanates. They are modified polyisocyanates containing groups.

In the present invention, the isocyanate index [NGO/active water active hydrogen atom-containing group weight ratio X100] during the production of polyurethane molded articles is usually 80 to 120, preferably 8
5 to 110, particularly preferably 95 to 108 (total of active hydrogen-containing groups (hydroxyl group, amino group) other than wood carboxyl groups). It is also possible to incorporate polyisocyanurates into polyurethanes with isocyanate indices significantly higher than the above ranges (eg, 300 to 1.000 or more).

In the present invention, in order to accelerate the reaction, catalysts commonly used in polyurethane reactions [for example, amine catalysts (tertiary amines such as triethylene amine and N-ethylmorpholine), tin catalysts (stannous octylate, dibutyl Other metal catalysts (such as lead octylate) can be used. The amount of catalyst may be, for example, from about 0.001 to about 5%, based on the weight of the reaction mixture.
used in small amounts.

Further, in the present invention, a blowing agent (for example, methylene chloride, monofluorotrichloromethane, water, etc.) can be used if necessary during the production of polyurethane. The amount of blowing agent used depends on the desired density of the polyurethane (
For example, it can be changed by 0.01 to 1.4 g/cT+13).

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

Additives that can be used in the pond water invention include flame retardants, reaction retarders, colorants, internal mold release agents, anti-aging agents, antioxidants, plasticizers, fungicides, carbon black and other fillers. Examples include additives.

A polyurethane molded article can be produced by a conventional method, and can be carried out by a known method such as a one-shot method, a semi-prepolymer method, or a prepolymer method. Manufacturing equipment commonly used can be used for producing polyurethane. In the case of no solvent, a device such as a kneader or an extruder can be used. Various types of unfoamed or foamed polyurethanes can be produced in closed or open molds. Polyurethane is usually produced by mixing and reacting raw materials using low or high pressure mechanical equipment. Furthermore,
Polyurethane can also be produced by removing gas such as dissolved air in the raw materials or air mixed during mixing by a vacuum method before and after mixing the raw materials (especially before mixing the raw materials).

The method of the invention is particularly useful for the production of polyurethanes by the RIM (reaction injection molding) process. Molding by the RIM method can be carried out under the same conditions as conventional methods.

For example, raw materials whose temperature is usually controlled at 25 to 90°C (2 parts, 4
components) at a pressure of 100 to 200 kg/cyn2G and preheated at 30 to 150°C (preferably 60 to 9°C).
This can be carried out by pouring into a mold whose temperature is controlled to 0° C. and then removing the mold within 0.1 to 5 minutes.

[Examples] The present invention will be specifically explained below using Examples, but the present invention is not limited to these Examples. Note that parts and % represent parts by weight and % by weight, respectively.

The composition of the raw materials used in the Examples and Comparative Examples is as follows.

(1) Polio-non-A: PO4,78 to 9292 parts of glycerin
Hydroxyl value 2 to which 5 parts and then EOI, 123 parts were added.
8 trifunctional polyol.

(2) Polyol B: P in 76 parts of propylene glycol
A bifunctional polyol with a hydroxyl value of 28 to which 3,004 parts of O and then 920 parts of EO were added.

(3) Polyol C: AIB in 90 parts of polyol A
A modified polyol having a hydroxyl value of 46.8, obtained by polymerizing 5 parts of acrylonitrile and 5 parts of hydroxyethyl methacrylate at a temperature of about 130°C using 0 parts of Nl as an initiator.

(4) Modified polyol I: by polymerizing 5 parts of acrylonitrile and 5 parts of hydroxyethyl methacrylate using 0 parts of AIBNl as an initiator in a mixture of 90 parts of polyol A and 5 parts of zinc stearate at a temperature of about 130°C. The obtained modified polyol had a hydroxyl value of 44.6.

(5) Modified polyol ■: In a mixture of 90 parts of polyol A and 5 parts of zinc stearate, using 0 parts of AIBN1 as an initiator, 5 parts of acrylonitrile and P of ethylenediamine.
5 parts of a condensate of O3 molar adduct and methacrylic acid was added to about 1
A modified polyol with a hydroxyl value of 52.4 obtained by polymerization at a temperature of 30°C.

(6) Low-molecular polyamine: DE-TDA diethyltolylene diamine (7) Low-molecular polyol: EG: Ethylene glycol (8) Polyisocyanate I CE-365: Modified liquid MDI (NCO=23°
I, ) [Co(9) Polyisocyanate 2 C-1059 manufactured by Nippon Boliutotashi Co., Ltd.: Modified liquid MDI (NGO=26%
) [Manufactured by Nippon Horiutan Co., Ltd.] (10) Catalyst DABCO33LV: ) 33% dipropylene glycol solution of lyethylenediamine D137DL: Dibutyltin dilaurate (11) External mold release agent: Rimurikei D-186
[Manufactured by Middle East Yushi Co., Ltd.] Examples 1 to 5: Comparisons 1 to 4 According to the molding recipe shown in Table 1, a polyol component and an isocyanate component consisting of an active hydrogen compound and a catalyst were each heated under high pressure under the following molding conditions. After charging the raw material tank of the foaming machine and dissolving a certain amount of nitrogen gas into the polyol component under high pressure, the mixture is mixed in a high-pressure foaming machine until the thickness is 3 mm.
A polyurethane molded article was produced by injecting the mixture into a temperature-adjustable closed mold with a width of 125 mm and a length of 220 mm.

[Molding conditions: High-pressure foaming machine: MC-102 [Manufactured by Hollow Tan Encyliner Co., Ltd.] Discharge amount: Approximately 150 g/sec Discharge pressure: 130-160 Kg/cm2 Injection time: Approximately 0.85 seconds Raw material temperature: Polyol component 40±2°C Isocyanate component 40±2°C Mold temperature Near 0±2°C Mold release time = 30 seconds Table 2 shows the results of measuring the physical properties of the obtained polyurethane molded product.

In order to quantify the ease of mold release, peeling strength was measured as an index using the method below.

(1) Clean the mold with dimethylformamide.

(2) Apply sufficient external mold release agent and wipe with a soft cloth.

(3) Close the mold and perform the first molding.

(4) Open the mold and insert the push-pull tension gauge [PUS] l-
PULL 5CALE (Imada Manufacturing Co., Ltd.) The molded product is peeled off from the lower mold by hooking it on the cutting tool, and the maximum peeling strength at that time is measured.

(5) For the second and subsequent moldings, repeat the process of molding <-> demolding without applying a mold release agent to the mold, and measure the peeling strength by the above-mentioned operation at the time of demolding.

(6) Continue molding until the 30th time, or the peeling strength is 5K.
Molding is carried out until it exceeds g.

Table 2 shows the values of the peeling strength at the 10th, 20th, and 30th times, and if the peeling strength exceeded 5 kg by the 30th time, the number of molding times.

In addition, the sample for physical property measurement was heated at 20°C x 65χR before measurement.
,)1. X48) 1r was adjusted.

Density (g/eyn2): JISK
-7112 tensile strength (Kg/mouth 2): J
ISK-6301 growth rate (%):
JIS-16301 tear strength (Kg/cyn2)
: JIS K-6301 bending modulus
(Kg/cm2): Sample 25m
mX70mmX2.5mm(t)p span 40mrn
, punch diameter 5R.

Pressure speed 50mm/min Heat sag (mm) Sample 25mm x 150mm x 2.5mm
(t).

Table-1 Table-1 Table-1 (continued) Table-2 Note: 10th peeling strength (same below) 5K
Number of times over g: Table of number of molding times when the peeling strength exceeded 5 kg - 2
(continued) Density: g/cm2 Elongation: % Bending modulus: g/cm2 Tear strength: kg/cm2
Tensile strength: kg/cm" Heat sag 2 mm [
Effects of the Invention Compared to conventional methods, the method for producing polyurethane molded articles of the present invention can omit or reduce the work of externally applying a mold release agent, and can shorten the molding cycle. Further, there is no need to use a compatibilizer to stably disperse the metal soap, and no deterioration of physical properties occurs. Using this method, it becomes possible to efficiently produce urethane molded products without impairing their physical properties.

Claims (1)

[Scope of Claims] 1. A method for producing polyurethane by reacting a polyisocyanate and an active hydrogen atom-containing compound in the presence of a catalyst, a blowing agent, and other additives if necessary, wherein the active hydrogen atom-containing compound Using a modified polyol (a) produced by polymerizing an ethylenically unsaturated monomer (iii) in the coexistence of a metal soap (ii) in a polyether polyol (i) as at least a part of the A manufacturing method for polyurethane characterized by: 2. The method according to claim 1, wherein (ii) is zinc carboxylate. 3. (iii) is a general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) [In the formula, R_1 is hydrogen or a methyl group, Z is -O (AO
)_m_1-R_2 or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, where A is an alkylene group with 2 to 4 carbon atoms, m_1, m
_2, m_3, m_4 are integers of 0 or more, p is an integer of 2 to 6, q is an integer of 0 or more, R_2, R_3, R_4, R_
5 is hydrogen, an alkyl group having 1 to 3 carbon atoms, or a glycidyl group. ] The manufacturing method according to claim 1 or 2, which is a monomer containing monomer (iv) represented by: 4. The manufacturing method according to any one of claims 1 to 3, wherein (ii) is a salt of a carboxylic acid having 8 to 22 carbon atoms. 5. The amount of (ii) is (i), (ii) and (iii)
5. The manufacturing method according to any one of claims 1 to 4, wherein the amount is 0.5 to 20% based on the total weight of. 6. The method according to any one of claims 1 to 5, wherein the amount of (iv) is 20% or more of (iii). 7. The amount of (iii) is (i), (ii) and (iii)
The manufacturing method according to any one of claims 1 to 6, wherein the amount is 5 to 35 parts by weight based on the total weight of. 8. At least 20% by weight of the active hydrogen-containing compound is (a
) The manufacturing method according to any one of claims 1 to 7. 9. A method for producing polyurethane by reacting a polyisocyanate and an active hydrogen atom-containing compound in the presence of a catalyst, a blowing agent, and other additives if necessary, as at least a part of the active hydrogen atom-containing compound, A modified polyol (a) produced by polymerizing an ethylenically unsaturated monomer (iii) in the coexistence of a metal soap (ii) in a polyether polyol (i), a low molecular weight polyamine (b), and the necessary Low molecular weight polyol (c)
A method for producing polyurethane, characterized by using and/or amino alcohol (d). 10. The manufacturing method according to claim 9, wherein the amount of (b) in the active hydrogen-containing compound is 5 to 50% by weight, and the amount of (c) is 0 to 25% by weight. 11. A method for producing polyurethane by reacting a polyisocyanate and an active hydrogen atom-containing compound in the presence of a catalyst, a blowing agent, and other additives if necessary,
A modified polyol (a) produced by polymerizing an ethylenically unsaturated monomer (iii) in the coexistence of a metal soap (ii) in a polyether polyol (i) as at least a part of the active hydrogen atom-containing compound. ) and low molecular polyol (c) and/or amino alcohol (d)
A method for producing polyurethane characterized by using. 12. The method according to claim 11, wherein the amount of (c) in the active hydrogen-containing compound is 5 to 40% by weight. 13. A method for producing polyurethane by reacting a polyisocyanate and an active hydrogen atom-containing compound in the presence of a catalyst, a blowing agent, and other additives if necessary,
A modified polyol (produced by polymerizing an ethylenically unsaturated monomer (iii) in the coexistence of a metal soap (ii) in a polyether polyol (i) as at least a part of the active hydrogen atom-containing compound) A method for producing polyurethane, which comprises producing a polyurethane molded article by a reaction injection molding method using a).