JPS6094417A - Inner releasing agent for reaction injection molding polyurethane - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION TECHNICAL FIELD This invention relates to a method for imparting internal mold release properties to reaction injection molded (RIM) polyurethane compositions by adding perfluoroalkylorganocarboxylic acids or salts thereof. Additionally, the present invention is catalytic in nature and also) L
IM relates to the use of novel dibutyltin diberfluoroalkyl organocarboxylates to impart internal mold release properties to polyurethanes.

BACKGROUND OF THE INVENTION Reaction-injected polyurethane moldings are increasingly being used in the manufacture of automotive, furniture, utility parts and in home construction. The high demand for polyurethane moldings has led to the requirement that they be manufactured in large numbers and have gel times as short as possible. However, providing suitable mold release agents with gel times as short as possible has continued to be a problem for the industry.

Prior Art In the past, six methods have been used to facilitate the release of polyurethane molded articles from the molds in which they are molded. "molding agent"
); the mold release agent was incorporated into the polyurethane molding reaction mixture ("internal mold agent"); or the mold release agent was applied directly to the polyurethane itself ("resin release mold agent").

However, many problems exist with the conventional prior art, especially when using the RIM process.

The RI M process is characterized by a combination of high pressure impingement mixing and rapid injection of liquid resin into a mold where the polyurethane molding compound rapidly encounters, reacts and cures. It is generally believed that mold release using internal mold release agents is inherently ineffective due to the short gel time of a given urethane formulation that does not allow internal mold release molecules to migrate to the mold-polyurethane interface. There is.

Surface mold release agents usually consist of natural or synthetic compounds such as silicone oils, mineral oils, waxes, fatty acid derivatives, glycols, and the like. Typically, these mold release agents are dissolved or dispersed in a liquid carrier and sprayed into the mold cavity. The service life of such known surface mold release agents is short;
Therefore, it is necessary to reapply the mold release agent to the mold before each molding cycle. This reapplication of mold release agent after each molding cycle or a limited number of molding cycles interrupts the molding run and reduces production. This method of application inherently results in a "thick" (by molecular basis), weak layer of mold release agent on the mold surface. These layers randomly crack during demolding and leave a residue of mold release agent on both the mold and the molded article.

More importantly, conventional wax and soap surface mold release agents are generally not suitable for the RIM process.

The combination of high-pressure impingement mixing and rapid injection of liquid resin into the mold either forces conventional Cooke or soap release agents away from the mold surface or regenerates them unevenly onto the mold surface. distribute it. This creates an uneven layer of surface mold release agent on the mold surface, which not only affects the shape of the molded product but also makes demolding difficult, if not impossible (in areas that do not contain mold release agent). can be made to

A DuPont document describes the use of [Zonyl J compounds (e.g. FSP, FSP,
SA, etc.) is disclosed. However, this commercial literature does not contain any teachings or methods for specific uses of these compounds.

Other DuPont commercial literature published in August 1982 makes no mention of the use of the "Zonyl" compound as a mold release agent.

U.S. Application Box 5, filed June 29, 1983, 09.13
No. 4 "One Monomolecular Layer Mold Release Agent" discloses a surface mold release method for imparting monomolecular layer discreteness to a molded polymeric material PI. This method is particularly useful in RIM processes because the monolayer release agent is actually adsorbed onto the metal forming surface. The bond also avoids the problems normally associated with mold release in It I M processes. Monolayer mold release agents include: perfluoroalkyl organocarboxylic acids or salts thereof; alkylcarboxylic acids. or a salt thereof; a perfluoroalkyl group-containing phosphoric acid ester or a salt thereof; or an alkyl phosphoric acid or a salt thereof.

U.S. Pat. No. 3,726,952 describes the use of internal mold release agents containing at least 25 carbon atoms that are salts of fatty carboxylic acids with either primary amines or amine-containing amides or ester groups. is disclosed. Although these additives impart some #-type properties, these additives contain fatty acid groups and impair the curing of the urethane foam formulation.

Other internal mold release agents are disclosed in U.S. Patent No. 4,118,235.
(Horiuchi et al.), which discloses the use of an additive consisting of a phosphoric ester containing a perfluoroalkyl group and either a highly fluorinated organic compound, a wax, or a mixture thereof. Horiuchi et al. [a mixture of a surfactant (additive) and a perfluoroalkyl phosphate ester... Demonstrates type ability. ” (
Column 3, lines 64-48). Horiuchi also discloses that it is not possible to use esters alone if the concentrations of additives used are low (column 4, lines 1-4). Japanese Patent 78/40.042 and e o
/ 153.4 q O are both similar to Horiuchi et al. These two Japanese patents, as well as Horiuchi et al.
Phosphate esters containing perfluoroalkyl groups are
When used alone, it is unsuitable for performing a large number of # molds, but when the claimed perfluoroalkyl phosphate ester is used in combination with at least one mold release agent. teaches that improved mold release properties can be obtained.

U.S. Pat. No. 4,111,861 claims four types of internal mold release agents or additives. Most relevant are additives consisting of mixtures of fatty acids and metal salts or metal alkyl carboxylates. These aliphatic and aryl carboxylic acids lack perfluoroalkylorgano moieties.

Finally, the "resin film release agent" was published in U.S. Patent No. 4,331.
．． No. 764 (Franz).

Franz discloses providing a resinous Ila mold release agent by forming a lubricating, non-reactive species on the polyurethane surface. Preferably, the preferred non-reactive pond in the J07 Lantz process chemisorbs a carboxylated fluorosurfactant onto a polyurethane surface to provide a substantially monolayer of lubricious and non-reactive fluorosurfactant. Includes carboxylated fluorosurfactants, particularly anionic "moderately carboxylated" fluorosurfactants. The particular mold release agent disclosed in Example 1 of Franz ("Zonyl FSPJ") is disclosed as a phosphate ester in the above-mentioned DuPont commercial literature and is
It is not disclosed as being a "carboxylated fluorosurfactant" (which is the generic term used by Franz to describe Franz's mold release agents). Additionally, in Franz Example I, the surface of the press was treated with siloxane (but not with a fluorosurfactant) before contacting the press with Franz's polyurethane containing mold release agent. Franz discloses special treatment of the polyurethane surface prior to application of Franz's mold release agent.

Problems to be Solved by the Invention The object of the present invention is to provide a polyurethane composition that exhibits internal hF type properties upon addition of a perfluoroalkylorganocarboxylic acid or a salt thereof.

It is an object of the present invention to provide novel tin compound-containing polyurethane compositions which not only exhibit internal mold release properties but are catalytic in nature.

Other objects and benefits of the invention will become apparent to those skilled in the art from the accompanying disclosure and description.

SUMMARY OF THE INVENTION The present invention provides improved polyurecne compositions containing: (a) a polymer/polyol; (b) an organic polyinsyanate; and (C) reacting (a) with (b). catalytic amount of catalyst to produce polyurethane. The improvement includes a perfluoroalkylorganocarboxylic acid or a salt thereof in the composition, wherein the organo group is (1) a divalent group linking the perfluoroalkyl group to the group of the carboxylic acid or carboxyl salt, and (11) ) Imparting self-releasing properties from the mold to the polyurethane made from the composition by inserting one having at least two consecutive atoms between two atoms having the valence of an organo group. Consists of.

The present invention, in a preferred embodiment, is directed to an improved composition that can be mold cured into a polyurethane, the composition comprising: (a) a polymer/polyol; (b) an organic polyincyanate; and (b) a catalytic amount of a catalyst for producing a polyurethane,
The improvement is made in the composition by the following formula: % formula % [wherein R, is a perfluoroalkyl group containing from 4 to 12 carbon atoms, respectively, and m and n are from 2 to 10 carbon atoms, respectively] ), Z is oxygen or sulfur, M is hydrogen, an alkali metal, an amine group,
ammonium group or quaternary ammonium group]; (n) ii) R, CH2 (OCI-12CH2),
C00M [wherein p is an integer/number from 1 to 10 (inclusive), and Ftf and M are as defined above]
;(III)iii) FL((CI-12)qCOO
perfluoroalkylorganocarboxylic acid or a salt thereof selected from the group of compounds having M, where q is an integer from 2 to 10 (inclusive), fl, and M are as defined above. This includes imparting self-release properties from a mold to the polyurethane produced from the composition.

3. DETAILED DESCRIPTION OF THE INVENTION The perfluoroalkylorganocarboxylic acids or salts thereof used as internal mold release agents in molded polyether polyurethanes according to the invention are preferably compounds of the following formula: i) R((CH2)mZ (CH2)nCOOM (I
) (wherein Rf is a perfluoroalkyl group containing 4 to 12 carbon atoms, m and n are integers from 2 to 10, Z is oxygen or sulfur, M is H1 alkali metal, amine, ammonium group or quaternary ammonium group), ii) RfCH2CH2(OCH2CH2), C00
M (H), where Itf is a perfluoroalkyl group containing 4 to 12 carbon atoms, p is an integer from 1 to 10, and M is H, an alkali metal, an amine, an ammonium group or a quaternary ammonium is a group), 1il) Rf
(CH2), C00M (Ill) (wherein Rf is 4-
perfluoroalkyl group containing 12 carbon atoms, q is an integer from 2 to 10, and M is H, an alkali metal, an amine, an ammonium group or a quaternary ammonium group).

R, is a perfluoroalkyl group containing 4 to 12 carbon atoms. Examples of perfluoroalkyl groups represented by Rf in formulas (I), (TI), (tn) above are as follows: CF (Cp3)2cp(cF2); 9 (:)'-CF- 615121 CF CF-7151125 (CF3)2CF(CF2); C,F〒.

Cp-CF-811225R, should contain 4 to 12, preferably 6 to 8 carbon atoms.

Z is an organic bonding group selected from the group consisting of oxygen or ions. M is 1+, an alkali metal, an amine or an ammonium group or a quaternary ammonium group.

Typical examples of M are as follows: H+N (CH,) 2C, H40H Li+N (CH,)4 Na+N(CH3) (C2H40f-1),.

Examples of perfluoroalkylorganocarboxylic acids or salts thereof represented by formula (I) above are: C,F, (CH2)2S(CH2)2Co2MC ,F,
, (CH2)2S(CH2)2Co2M06F, 3(
CH2)20(CI]2)2Co2MC6F,3(CH
2) 4S(CH2)2Co2MC7F, 5(CH2)2
S(CH2)2Co2MC8F, ,C)(20(CH
2) 2Co2M(CF3)20F(CF2)5CH20
(CI-12)2Co2MC,F, 5(CH2) 2
0CH(CH,)CH2CO2MC2F19(CH2)
2S(CI■2)2Co2M Examples of perfluoroalkylorganocarboxylic acids or salts thereof represented by formula (II) above are as follows: C4F9(C1]2)20C2H4CO2MC6F1.
(CI42)2[0C2H4]2Co2MC7F,5(
CH2)20C2H4Co2M(CF,)2CF(CF
2) 4(CF12)2(Oc2F(4)2Co2M07
F15(CF12)2[0C2H4]2Co2M08F
17 (CI-I2) 20C2114002M08F17
(CI-12)2 (062842602MC6F1.
(CH,) 2QC2)-14CO2MC,F,, (C
I-12)2QC,,)14C(J2MC2F4.(C
H2)2[0C2H4]2Co2M Examples of perfluoroalkyl organocarboxylic acids or salts thereof represented by formula (m) above are: C,F, (CH2)2Co2M 06F13(C112)2Co2M C6F, 5( C112)3Co, MC6F, , (CI-12), Co2MC6F,
, (CH2)8Co2M C6F, , ((J(2) , oCo2M07F1
5 (CII2) 3QC2M 07F15 (CH2) 2002M (CF3) 2CF (CF2) 4 (CH2), oCo
2MC2F1. (CH2)3Co2M In formulas (I) and (I1), respectively (”12 ) m
, (CH2)n, (C142)9 (where m, n, q
is an integer from 2 to 10) is an alkyl group that can be branched or straight chain.

Mold release is a surface phenomenon that can be explained by the following equation:
R, F, α(rpu and γm) I/′! (In the formula, R,
F.

is the mold release force, and γ and γ□ are the surface energies of the polyurethane polymer (pu) and the mold (m), respectively. One approach to the demolding problem is to
The goal is to reduce mold release forces by minimizing the surface energy of the polyurethane polymer and/or the mold.

Part of the mold release problems encountered in RIM polyurethane compositions are due to their high surface energy caused by the large amount of polar functional groups present in the composition, ie, urethane functional groups. Good internal mold release agents, such as those of the present invention,
The surface energy of the polyurethane surface or mold surface must be lowered sufficiently so that the cohesive energy of the polyurethane polymer exceeds the adhesive energy of the polyurethane polymer to the mold.

Perfluoroalkylorganocarboxylic acids and their salts work well as internal mold release agents due to their exceptional surface activity. Perfluoroalkyl groups tend to orient themselves to the polyurethane interface, while carboxylic acid or carboxylate head groups have a high affinity for metals.

These two surface orientation effects result in a reduction in the surface energy of either the polyurecne or the mold surface (through adsorption, surface orientation, and the formation of a molecular layer).

The concentration of release agents or additives used in polyurethane internal phase release agents is not narrowly critical. The method used depends on the desired release force. A very small amount is effective in providing a certain degree of mold releasability. For example, molded polyurethane parts have been tested in laboratory tests to contain active H-containing compounds (ethylene glycol extenders, polyether polymer polyols, methyljetanolamine if present), catalysts, and the active compounds used. Release is possible at additive levels as low as 0.1 weight JIX based on the total resin weight of the polyurethane forming system involved. The preferred concentration of additive is 0.1 to 2.00 wt.

Higher concentrations of additives improve mold release performance up to a certain point: polyurethanes can tolerate only limited proportions of additives due to their physical properties.

Polyurethane formulations used in molding runs typically contain a catalytic amount of a catalyst (ie, dibutyltin dilaurate) to accelerate gel time to optimize the physical properties of the polymer. One type of catalyst or a combination of different types of catalysts can be used. Tin catalysis in polyurethane reactions can be hindered by the acid-suppressing effects of internal mold release agents or additives of free acids (e.g., perfluoroalkyl organocarboxylic acids). Free acids prevent the curing of polyurethanes, so adding free acids to polyurethane formulations can result in an uncured surface.

One way to prevent this acid-inhibiting effect is to use a catalyst (
For example, increasing the amount of dibutyltin dilaurate). However, this method is very expensive and therefore less desirable. Another method is to remove acidity by neutralization, which will be discussed below.

The perfluoroalkyl groups of the compounds, specifically perfluoroalkylcarboxylic acids and their salts, perfluoroalkylorganocarboxylic acids and their salts, are highly inducible, thus making the terminal carbosyl group more monoacidic. This high acidity can adversely affect the internal mold release properties of polyurethane containing additives, as mentioned above. However, perfluoroalkylorganocarboxylic acids (and salts thereof) differ from perfluoroalkylcarboxylic acids (and salts thereof) in that they contain an organic bonding group defined above as Z and/or at least two alkyl groups (formula I-III). It is this organo group that protects the carboxyl group from the highly inducing effects of the perfluoroalkyl group. Therefore, perfluoroalkyl carboxylic acids or salts thereof do not perform well as internal mold release agents when added to polyurethane compositions (see below).

For purposes of the present invention, if the internal mold release agent (additive) is in solid form, it should be added to the polyurethane formulation after it has been dissolved in a solvent. Liquid forms are preferred because of the liquid's ability to adsorb and reduce the surface energy of the polyurethane and/or mold surface. Therefore, the solubility of an internal mold release agent or additive in a particular solvent is important because the solubility of the additive can affect its ability to impart internal mold release properties to a polyurethane formulation. be.

The free acid form of the internal mold release agent (i.e. Rf(CH2)m
Z(CH2) nC00H) has the advantage of high solubility in various aprotic solvents, despite inhibiting tin catalysts. The mold release properties of this free acid form (perfluoroalkylorganocarboxylic acid) are correlated with its solubility in a particular solvent. The order of decreasing solubility of the free acid form in specific solvents at room temperature is as follows: Acetone)TI(F)IPA)EG')NP~ Observed release of the free acid form in various solvents Gender also follows the same order (see below).

As mentioned above, the inhibitory effect of acids on tin catalysts can be prevented by neutralization. In fact, improved internal mold release properties are observed upon neutralization (see below). The acid protons in the free acid form (perfluoroalkylorganocarboxylic acid) are removed by a neutralization reaction. The neutralization reaction allows one to achieve normal reaction rates without increasing catalyst levels. Mold release properties are correlated with the ionization properties of the various perfluoroalkyl organocarboxylates produced by neutralization (as deduced from studies of the activity coefficients of aqueous alkali/metal carboxylates).

The order of decline in - (at 0.5 phr and normal catalyst levels) of cation-neutralized free acids tested in solvents such as Inglovir Alcohol/H20 is as follows: Cation +>Me4N+ 〉■,i,＞TF,D
IA>MEDA:) N)(;Protic solvents, such as isopropanol and water, have reactive hydrogen atoms and thus react with the isocyanate. can potentially change the properties of

The present invention relates to several forms of perfluoroalkylorganocarboxylic acids and their salts. The forms mentioned above include: sulfide-containing compounds (i.e. RfC2H
4SC2H4CO2M); oxygen-containing compounds referred to herein as “ether analogs” (i.e., RfC2H4Q
C2H4CO2M); and alkyl-containing compounds (i.e., R,
CH2CH2CM2Co2M). It should be noted that the "free acid" form can contain all of the various types of linking groups listed above.

The mold release properties of the free acid forms of the three perfluoroalkylorganocarboxylic acid analogs are as follows (see Example 8A): RfC21(4QC2)14C02H)R,C21-+
4SC2144C021,■nRfC5H6CO21(
(Ether analogs) (Sulfur bonds) (Aliphatic analogs) All analogs should be dissolved in a very good medium to minimize the solvent effects described above. Acidity requires increased catalyst levels. The superior mold release properties of the ether analogs are believed to be due to their appreciably high solubility in polyurethane forming formulations.

Improved internal mold release upon neutralization is observed for both ether and aliphatic analogs (see Examples 8B and 8C below). The nuclear neutralization reaction allows the use of conventional catalyst levels. The mold release results for the ether analogs are as follows: )(fC2H4QC2H4Co
2Li:>It, C2H4(JC2114Co2H(
Lithium salt) (free acid) The results for the aliphatic analogs are as follows: RIC, H6C02K) RIC3H6CO,, Li -
It is believed that the improvement in mold releasability due to neutralization of It, C21-14SC2H4Co2Li is the result of increased ionization properties of these compounds.

Many theories can explain the internal mold release properties of perfluoroalkylorganocarboxylic acids and their salts. One theory is that internal mold release agents or additives are adsorbed to the mold to form a low energy mold release surface. Another theory, the theory of tin catalysts, is that the internal mold release property is due to additives (
perfluoroalkylorganocarboxylic acids and their salts)
and the release of carboxylic acid from the tin catalyst itself. Such free carboxylic acids can act together to adsorb together with the additive itself. The mechanism seems to be as follows: Urethane lJu OCRO Finally, the proposed chemical exchange internal mold release mechanism shows that tin catalysts with excellent surface activity can be effective as internal mold release agents. . Such surface-active tin catalysts can be formed by chemical exchange reactions between additives (perfluoroalkylorganocarboxylic acids and salts thereof) and dibutyltin dilaurate catalysts. A possible mechanism is illustrated as follows: 0 New tin catalyst compounds with low energy moieties, such as highly fluorinated hydrocarbon groups, were thus prepared. The results of mold release performance are shown in Example 9.

experiment The following experimental description illustrates the invention.

The following abbreviations are used in the experimental description:

Abbreviation Meaning AA Additive Additive A RfCl-12CH2SCH2CH2CO-
,I,i, (343%).

RfCH2CH2SCI42CH2Co2CH2(CH
, ) 2 (1s7j!c-containing ingropanol (25%
), water (25%) commercially [known as Zonyl FSAJ (X is by weight) JO agent B (C4H,)2Sn (QC(CH2)
2S(CH2)2R1] Additive CR(CH2CH25C
H2CH2CO2H additive D HfCl-12CH2S
CH2CH2CO2Li additive E R,, CH2CH2
5CH2CH2CO2CH (CI43).

Additive 1” R, (rl(2CH2SCH2C)I2C
O, additive G 11. CH2CH25CH2CH2C
O2(C)I, ), N additive 14 RfC1r2CH2
SCH2C Horse CO2MDI Bow A Additive I RfCH2C
1-120CH2C1-12Co21 (additive = T R
fCH2Cl-1,,0CH2CH2CO2Li "Additive K C,F,5CO2Li" Additive LC7F, 7 Additive M r<,, at2co2K "Additive N C9F4.C02H Additive PRfC1] 2CH2CF (2C02LI Additive S ( C, F, 5C02)2Sn(C41'19)2
Additive T (MD4 (CH2) 5Co2) 2
Sn (C4H9) 2 additive U (C,F,,C02
)2Sn(04H,),.

Additive V (RfC2H40) 2Sn (C4H,)
2 Additive XItfC1f2C112CI] Additive YRfCII2CH2SCH2CH2COF
'EDIA Catalyst A Dibutyltin Dilaurate Catalyst 8 33 in 23X dibutyltin diacetate
% of triethylene diamine, 22X of ethylene glycol, 22X of diethylene glycol (% by weight) EG Ethylene glycol blend T = urethane blend containing: a) Polypropylene oxide/ethylene oxide polymer polyol "89" b) Ethylene glycol 11 C) Dibutyltin dilaure) 0.09d) Incyanate (commercially known as [Incyane) 143-LJ) 1o4 index blend ■: Urethane blend containing a) Polypropylene oxide/ethylene oxide polymer Polio-v189 b) Ethylene glycol 11 C) Dibutyltin dilaurate 009 d) Isocyanate (commercially known as [Isocyanate) 143-LJ) 104 index formulation ■■: Urethane formulation containing:
A) Polypropylene oxide/ethylene oxide polymer polyol 895b) Ethylene glycol 1o,5 C) Dibutyltin dilaure) 0.2 sd) Isocyanate-terminated polymer (commercially available [Rubinate LF-168]
(known as) 1o4 index compound ■: urethane formulation containing: resin phr a) polypropylene oxide/ethylene oxide polymer polio-A” 89.5b) ethylene glycol
145 C) Dibutyltin dilaurate 0.4 d) Incyanate-terminated prepolymer 104 Index Blend V: Urethane blend containing: resin phr a) Polypropylene oxide/ethylene oxide polymer polyol-yJ'' 89.5b) Ethylene glycol 11. 5 C) Catalyst BO, 1 d) Dibutyltin dilaurate 0.1 e) Incyanate-terminated prepolymer 104 index 2 gm5 Durham hydroxyl number (OH number) Measure of equivalent weight of hydroxyl-containing substances IPA Inglobil alcohol M D M = 0. /2Si (CHs)3D =
O5i (CH3)2 MDEA Methyljetanolamine ("CCHs) C2H40H) 2mls Milliliter-mod Moderate NP Polymer polyol phr, commercially known as "NI AXJ" Part Rf 4~
Perfluoroalkyl group containing 12 carbon atoms TEDIA Triethylenediamine 1'' HF Tetrahydrone T-12 dibutyltin dilaurate Blue Used solely as a comparative material.

++ A polymer polyol having an OH number of approximately 27 made by polymerizing approximately 67% by weight of polypropylene oxide, 916% by weight of acrylonitrile, and 17% by weight of ethylene oxide.

The polymer in the polymer/polyol has a molecular weight greater than 5000.

+ Bitterness Approximately 67% by weight of polypropylene oxide 916
A polymer polyol having an OH number of approximately 235, prepared by polymerizing 17% by weight of acrylonitrile and 17% by weight of ethylene oxide. The polymer in the polymer/polyol has a molecular weight greater than 5000.

Procedure A: Qualitative mold release performance evaluation RIM processing for mold release evaluation was carried out by Io Ono, Admiral (designed and manufactured by Admiral Equipment Co., Ltd. in Akron).
Admiral) II high pressure, flashless impingement mixer. The mold used is 025 inch x
12 inches x 18 inches (064αX 50cmX 4
It is a nickel-plated black mold with a cavity of size 6ewL). The mold press hydraulic unit is capable of generating up to 1 of the available hydraulic pressure to measure the mold opening force.
It is possible to generate a hydraulic pressure of 500 psi (1051 ψ/cIn2). If the mold opening force exceeds the maximum, it cannot be opened.

The mold release performance was qualitatively evaluated: the molded part was manually removed from the mold. Criteria for evaluation included demolding force measurements as well as visual evaluation of the surface quality of the molded parts.

Mold cleaner A is used to remove Ni-plated black molds.
and the mold was sprayed with a wax release agent. However, the 9 inch x 12 inch (23
The area c+nX 31 CwL) was left bare (referred to hereinafter as the "untreated surface").

This was done by blocking urethane black on that side, so wax contamination could not occur.

Therefore, the mold release performance measurement is the ability of the internal additive to release the molded article from this untreated surface within the mold cavity.

Next, internal l! The life of the Type Il agent was determined by repeated molding with external application and one application of wax release agent only on the aforementioned surfaces. The untreated side was left bare. After spraying the wax mold release agent once on the permissible surface, repeat the molding operation, and as long as the molded product continues to be removed without causing cohesive failure of the polyurethane and the mold release force remains low, the wax mold release agent is applied. No further application was made. Mold release force (It,
F,) very low (v, low); low; moderate (mo
d); Difficult (diff,) K classification. The desired demolding force is as low as possible. The time to take out the molded product is 60 seconds unless otherwise specified.

The equipment used for the test manual mixing/pouring stripping method consists of a mixer and a drill press equipped with a propeller used as a hydraulic press. The mold itself consists of two thin stainless steel or steel molded sheets that were not treated with any type of mold release agent. The molded sheet measures 8 inches x 8 inches x O, 25 inches (2
0cmX20CrnX, 0.64 crn) and separated by a spacer with a 6 inch by 6 inch (15 m, The entire assembly is sandwiched between two 8 inch x 8 inch x O, 25 inch steel plates.

A stoichiometric amount of incyanate was added to the well mixed resin. After it is mixed for 10 seconds, diptyltin dilaurate catalyst (usually in an amount exceeding that used in the control) is added. This was followed by an additional 10 seconds of mixing. The reactants were poured into a 160"F (71C) mold and a pressure of 15,000 psi (9/2 to 1,050) was applied to it. The demold time was 100 seconds. Next, multiple mold release performance is evaluated by repeating the molding cycle using the same molded sheet.The mold release force is qualitatively determined as extremely low (v, low); low; moderate (mod); difficult (diff). The mold release force obtained with the wax mold release agent treatment system was "1" which was the criterion used to define the mold release force. The molding operation is repeated until the molded part can no longer be released from the mold. The demolding force for the last cycle is then determined qualitatively. Determine mold agent life by observing the number of molding cycles achieved before the part sticks to the mold. However, if the mold release force is at an extremely low level, e.g.
When J was reached, no further molding was performed. The life of the mold release agent was then indicated by adding a "+" after the last cycle tested.

Another criterion used in the evaluation is the surface quality of the molded part.
It is. All cohesive failures of polyurethane are described as demolding failures.

Procedure C: Separation Procedure To isolate and purify the components of Additive A, an ether extraction technique was used to separate Additive A. After adding the ether, the mixture was separated into an organic layer (containing mainly the ester) and an aqueous layer (containing mainly the lithium salt form). To isolate and purify the ester, the organic layer was washed repeatedly with 5% NaHCO3 solution to remove any residual free acid. Next, the generated organic layer was treated with anhydrous Na
Dry with 2SO4 and rotovap. An oily residue, the ester, formed. The crude ester was then vacuum distilled at 220°C and 1μ to obtain a colorless distillate.

Procedure D: Free Acid Generation The aqueous phase from the initial separation outlined in Procedure C (Li
(containing salt) is acidified to free acid) L, C2H45C
2H4CO2H was formed. A pale brown precipitate was formed. The solids were extracted with ether. The organic phase was dissolved in anhydrous NaSO.
It was dried at 4. The impurities were removed with activated carbon in Step 1. The resulting mixture was filtered. The colorless or very slightly yellow filtrate was placed in a rotorap.
did. In fact, the free acid 1t'(,'21(4SC21-1
A white or slightly yellow solid formed.

Example 1 Formulation I and ■ were prepared and used for mold release evaluation.

Formulation I was used as a comparative control. The molds were prepared and tested as outlined in Procedure A.

Formulation I (control containing no internal mold release agent) was
+,・, ρmu, ' part of Bo II Urekun f carving M's 9th vermilion 2p was generated. In this case, a coat of 1 liter of wax was sprayed over the entire mold, including the untreated surfaces.

Formulation ■ illustrates the practice of the invention. The compound ■ is 1
Same as Formulation 1 except that 0 parts of Additive A and an additional 0.16 parts of Catalyst A (so total catalyst concentration is 0.25) are added to the formulation. Additive A was added directly to the formulation.

Formulation 11 was evaluated after stirring for 4 hours. The active hydrogen contained in the solvent IPA/water in Additive A lowered the effectiveness index to approximately 9 days. Rating to 160°F (71°
The test was carried out at the mold temperature of G).

The molded article was taken out in 60 seconds.

Formulation 1 (indicating the invention) resulted in very favorable mold release performance. Good parts were obtained by manual evaluation (procedure A) with low demolding forces. On the 8th molding cycle, a slight deposit of polyurethane was observed between the untreated side and the adjacent waxed side. However, the build-up was not worsened and had no appreciable effect on the demolding force or the surface quality of the molded part. In fact, the K-C deposit gradually dissipated as the molding cycle continued. All deposits were removed by the 40th molding cycle. In order to speed up the evaluation,
After 8 molding cycles, the time to remove one molded product was reduced to 60 seconds. Although the short mold demold time could affect the physical properties of the molded parts, the effect on mold release was negligible. A total of 92 molding cycles were performed.

Example 2 Example 2 uses Formulation III. 1 fl of the formulation was the same as the formulation ■(
(used in Example 1).

The formulation was mixed for 2 hours. A mold was similarly prepared according to procedure A. This series resulted in 100 molding cycles with no detectable deposits on the bare mold.

The entire molded article was taken out for 30 seconds.

There was no evidence to suggest possible demold failure.

All parts had an excellent surface finish, especially one of the bare mold faces. No demolding problems were observed throughout the experiment. Using this example, it was determined whether the resin or incyanate component affected the mold release performance.
Beta. It appears from the results that differences in incyanate source and polyurethane batch had no effect.

Example 5 This example describes Experiment R, IM based on an incyanate-terminated prepolymer containing approximately 240 free NCOs.
The internal mold release performance of the polyurethane composition will be shown. This example uses formulation Iv. Formulation IVK, additive At
/i parts and an additional 28 parts of T-12 catalyst were added.

The experimental conditions were as follows, except that the molded product removal time was 60 seconds.
The test equipment and method were the same as shown in Procedure A. A total of 60 molded parts were released from the bare molds, but the cohesive failure of the polyurethane polymer was unacceptable! It was r.

Example 4 Example 4 is the same as Example 3, except that 16 parts of Additive A and 0.4 parts of methyljetanolamine were added to Formulation IV. Test methods and mold preparation are outlined in Procedure A.

Excellent internal mold release performance was obtained using this formulation.

A total of 60 molded articles were demolded from the bare metal mold without any demold failure. The mold release performance was as good as that shown in the previous three examples.

Example 5 The additives as listed in the table are structurally similar to Additive A, but these additives (K-0) lack the organic linking groups present in Additive A and its derivatives. The results shown in Table ■ indicate that perfluoroalkyl carboxylic acids and their salts have poor performance as internal mold release agents. It is thought that the perfluoroalkyl group is highly inducible and therefore makes the terminal carboxylate and carboxylate groups more acidic.The gel time of this highly acidic seat number 1 polyurethane is This obviously has a detrimental effect on the internal mold release properties, thereby making additional catalyst necessary to obtain a reasonable gel time.However,
Perfluoroargyl organocarboxylic acids or salts thereof have an additional "organo group" which insulates the carboxyl or carboxylate group from the highly derivatized perfluoroalkyl group.

This example uses Formulation I, but the catalyst concentration (i.e.
T-12) and the amounts of additives present are shown in Table 3. As outlined in step B, mold release evaluation was performed using qualitative manual mixing/
It was an injection method.

Example 6 This example demonstrates that the lithium salt and isopropyl ester forms of perfluoroalkyl organocarboxylate are relatively less effective individually (e.g., in combination) as internal mold release agents. show. All additives were evaluated using Formulation 1, with catalyst and additive concentrations as shown in Table 2. The release evaluation was a qualitative manual mixing/pouring, manual peel method as outlined in Procedure B.

Procedure C was used to separate the ester and salt components of Additive A. Additive A was found to contain 50% solids by weight dispersed in a liquid carrier (1:1, Improper Tool: Water). Of the 50% by weight solids, 70% by mole is 1(
fC2I]4SC2H4C02LI (additive D), the other 30 mol% is ester, ItfC2H4SC
2H4Co2CH(CI43)2 (additive E).

The results using additives RI and E in Table 3 show that the ester and lithium salt individually are +4-xI! ! /1
1F Kakota Marshal → 8J right 1st round π right “father-in-law 1st condolence fr shi\, -
However, when 15 mole percent free acid was present, the performance of Additive E improved.

Example 7 To prepare the free acid, ether extraction was performed as outlined in Procedure C. The aqueous layer containing the lithium salt was then acidified according to procedure I) to produce the free acid. However, the concentrations of catalyst and additives were as outlined in Table II.

This example shows the results obtained when the free acid form (Additive C) of a perfluoroalkyl organocarboxylate (ie, Additive A) is used as an internal mold release agent.

The release evaluation method was a qualitative manual mixing/pouring, manual peel method as outlined in Procedure B. The results as shown in Table 1 also show the effect of changing catalyst concentration and solvent on internal mold release properties. The additives were evaluated in Formulation I and the catalyst concentrations are as shown in Table ■.

Results using Additive C show that internal mold release improves with increasing solubility and with increasing catalyst concentration.

Example 8 This example demonstrates the effect of salt on polyurethane molding compositions containing perfluoroalkylorganocarboxylic acids or salts thereof. The polyurethane-forming reaction is suppressed when adding certain additives (mold release agents), especially if these additives are acidic. The presence of acid protons appears to reduce the catalytic activity and thus, as shown in Example 7,
Higher catalyst levels are required to overcome this delay in reaction.

This example shows that these protons can instead be removed by neutralization, resulting in improved internal demolding ability of the additive, and thus the urethane-forming reaction can proceed at conventional catalyst levels. . Mold release evaluation: Hand II
It was a qualitative manual mixing/injection, manual stripping method as outlined in Section B. All runs in the following three categories used Formulation 1 (except where noted). Catalyst concentration etc. are as shown in each table.

A, perfluoroalkylorganocarboxylic acid Table TV and ■ show the prepared salts: Additive D (lithium salt), Additive F (potassium salt), Additive G (ammonium salt), Additive H (amine salt), Additive Y (amine salt).

The aforementioned salts were prepared by first producing the free acid form of the perfluoroalkyl organocarboxylate by a procedural procedure. The resulting free acid (perfluoroalkylorganocarboxylic acid) is then diluted with a stoichiometric amount of base: e.g. LiOH: KOH: N(CH,)40H
: N(CH,)(C21-140H) 2: or N2
(C2H4)3, respectively.

Ammonium and amine salts can be used in organic solvents, e.g. 'I'1
-IP, which was soluble in IPA, while other residual salts required the presence of a mixture of solvent and water.

The results are summarized in Tables 1v and V, and the experimental data are shown in Figures 1 and 2, respectively. The results in Table 1v show that potassium hydroxide and especially amines (N(CH3)(C2H40H)
2 and N (CH3) 40H) as neutralizing agents, the internal mold releasability is significantly improved.

The results in Table V using a different formulation (formulation ■) are:
It is shown that the internal mold releasability of polyurethane compositions is significantly improved when Kana 01] is used as a neutralizing agent. The improved internal mold release properties of the potassium salt are believed to be due to the increased ablation, IPA/water solubility and/or ionization properties of the raw salt.

■3. Mold release property table of ether analogues and their lithium salts■
is additive D (i.e. It, CH2Cl120C1
The influence of various salts on the ether analogue of 12C1]2CO2L + ) is shown. The salts prepared are as follows: additive control (R, CH2CH25CH2
C02Li), and its ether analogues, additives J
(R, CH2CH20CH2C:F12 C02Lr
).

The additive solution was prepared as outlined in Section A of this example. Additive I (mother acid of Additive J) was prepared by cyanethylation reaction of alcohol according to the following formula: NaOH R, CH2CH201-1+ CH2,, -CH-CN
→R, CH2CH20CH2CH2CNR, CH2Cl
120CH2CH2 (IJ2H (Additive I) approximately 0.5% by weight (based on alcohol) NaOH
The powder was dissolved in alcohol (>50°C) and added. A 58 mol% excess of acrylonitrile was added dropwise to the molten alcohol over 60 minutes. The temperature was maintained at approximately 70°C. The mixture was then refluxed at 75°=80°C for approximately 1 hour.

The adduct thus formed (It, CH2Cl +
20CH2CH2CN) in excess @HCI (37X)
and the mixture was refluxed for 5 hours. The product (additive ■) was then isolated using standard acid/base extraction techniques. The yield of additive (1) was approximately 50X.

Additive ■ is neutralized with Li011 and additive J (RfC
H2CH20CH2CH2Co;Li+) was prepared.

The results are summarized in Table Vl and the experimental data are plotted in the graph of FIG. The results show that additives I and J (ether analogs) work much better than additives with sulfur-binding groups. The excellent performance of ether analogs is due to
This is believed to be due to the improved solubility of the ether analog (compared to the additive) in the polyethylene molding resin.

Mold release properties of C8 aliphatic analogs and their salts
The influence of various salts on the aliphatic analogs of 1) will be shown.

The salts prepared are as follows: Additive Riichi Control (RfC
H2C112SCH2C and 12CO2L1), additive P
(R, Cl2CI[2CH2CO2L+), additive 0 (RfCl(2C112CH2CO2K).

The additive solution was prepared as outlined in Section A of this example.

Parent acids with additives P and 0 were prepared by the following reaction mechanism: 1 The starting material was purified as follows: CH2(C(JC115)2) was distilled: ethanol with 5M Na metal R,CI-]2C1-12I (commercially known as Zonyl TEL BJ) was molten and stirred before use.

Approximately 0.1 mole of Na was added to approximately 50 mis of distilled ethanol. To this mixture was added distilled CH2 (Co□
CH,) 217.00 gms was added dropwise.

Approximately 56 gms of premelted perfluoroalkyl organoiodide was added to the above mixture and then kept at a constant temperature of 55°C. 5 of the solution
Rerefluxed for an hour. Excess alcohol is then distilled off and the temperature of the reaction vessel (containing the diacid intermediate) is approximately 1
The temperature reached 20°C. KO016gms distilled water 25mls
In addition, a KOH solution was prepared.

The solution was placed in a reaction vessel Kv4 and maintained at a temperature of approximately 60-70°C. The mixture was rerefluxed for 3 hours.

The reaction temperature was kept below 100 °C to avoid the formation of R,CH2Cl-120H due to the presence of unreacted RfCH2CH2I and KOH.

After rerefluxing, the sample was made acidic. An acid-base extraction process followed to isolate the diacid intermediate.

A 20% yield of the diacid intermediate was obtained. Then the diacid intermediate (
(shown in the reaction scheme) was decarboxylated by heating at approximately 165°-140°C for approximately 5 hours. The product is R,,CH2C1-(2
CH,C02H (the free acid form of the aliphatic analog).

Acetic acid was removed following standard acid/base extraction procedures. The final product yield of purified free acid was approximately 10%. Lithium and potassium salts, i.e. additive P (I(-r
C1-12CH2C1 (2CO2L i ) and additive
1 (to prepare additive P) and KOH (additive O
was prepared by neutralizing it with

The results are summarized in Table v■ and the experimental data are plotted in FIG. Here, the potassium salt gave the best results. These results are believed to be due to the increased solubility and/or ionization properties of the potassium salt in the particular solvent used.

Example 9 This Example 1/I [In Example i, release evaluation was a qualitative manual mixing and/or manual release method as outlined in Procedure B.

Formulation ■ was the test composition used. This example shows the mold release properties of various surfactant-modified tin catalysts. Table 3 shows each additive and its concentration.

Table ~"Results in the UK indicate the best dibutyltin dilaurate compositions. Some of these new tin compounds are catalytic and therefore do not require a catalyst (i.e. dibutyltin dilaurate), but certain perfluoroalkylorgan Carboxylate-modified tin compounds still require the presence of T-12, which is believed to be due to the presence of inducible perfluoroalkyl groups in these compounds. is extremely acidic and inhibits the urethane reaction through its catalytic mechanism.

Free acid (perfluoroalkyl organocarboxylate) modified tin (Sn) compounds are prepared by reacting the free acid to the additive with dibupurtin oxide as follows: RfCH2C112SCH2C To+
2(:0211+ Bu 2 Sr+0 → reaction is carried out in toluene to remove I]20 (via azeotrope)
Bring it to completion by doing so.

The same reaction was carried out using C,F, 5(J0211, MD4(C
I-12) 3C (J211, C, F, , C02H,
(HfC2H401-1) 2 is used. #lf type results show excellent separation of perfluoroalkyl organocarboxylate-modified tin compounds! Show your perspective.

[Brief explanation of drawings]

FIG. 1 is a graph showing the four results of 1lifF type P1 of the free acid in formulation (1). Figure 2 shows the release of the free acid in Formulation V (!
This is a graph showing the results. FIG. 3 is a graph showing the mold release properties of the ether analog and its lithium J'11 in formulation (1). Figure F4 is a graph showing the mold release properties of aliphatic derivatives and their salts in formulation (1). stomach,. i4 A (1) Eng4 f'c l'1 4g
Hiroshi, No' Dowama Hiroshi r) Procedural amendment dated November 15, 1980, Manabu Shiga, Commissioner of the Patent Office, 1981 Patent Application No. 202158 Pi
Relationship with the case of the person who made the IF correction Patent applicant name Union Carbide Corporation Agent mW"$'Q$r,, / 14,15,-'-Fl
Contents of Supplementary Statement 11- of t Lottery As shown in the attached document (no changes to the content)

Claims (1)

[Claims] t A metal composition comprising (a) a polymer/polyol, (b) an organic polyinsyanate, and (C) a catalytic amount of a catalyst for reacting (a) and (b) to produce a polyurethane. A composition that can be cured into a polyurethane in a mold comprises a perfluoroalkylorganocarboxylic acid or a salt thereof, wherein the organo group (1) binds the perfluoroalkyl group to the carboxylic acid or carboxyl base. A polyurethane made from the composition is made from a mold by introducing a divalent group and having at least two consecutive atoms between two atoms having a valence of (11) an organo group. 2. A perfluoroalkyl organocarboxylic acid or a salt thereof, a polymer/polyol, and Claim 1.
A composition comprising a member comprising the catalyst described in 1. 6. The composition according to claim 1, wherein the perfluoroalkylorganocarboxylic acid or its salt is dissolved in a solvent and then added to the polyurethane composition. 4. The composition according to claim 3, wherein the solvent is ethylene glycol. 5. The composition according to claim 3, wherein the solvent is tetrahydrofuran. 6. The composition according to claim 3, wherein the solvent is isopropanol and water (1:1). The composition according to claim 2, wherein the superfluoroalkylorganocarboxylic acid or its salt is dissolved in a solvent and then added to the polymer/polyol and/or catalyst. 8. The composition according to claim 7, wherein the solvent is ethylene glycol. 9. The composition according to claim 7, wherein the solvent is tetrahydrofuran. 10. The composition according to claim 7, wherein the solvent is isopropanol and water (1:1). 11. Perfluoroalkylorganocarboxylic acid or its salt is essentially RfC2H,5C2H4Co2CH(C
H3) 2 and RfC2H4SC2H4C00H. 12. The composition according to claim 1 or 2, wherein the perfluoroalkylorganocarphonic acid or its salt consists of R0C2H4SC2H4C02H. 15 Perfluoroalkylorganocarboxylic acid or its salt is RfC21-14SC2H4CO2(CH3)
3. The composition according to claim 1 or 2, comprising 4N. 14. The composition according to claim 1 or 2, wherein the perfluoroalkylorganocarboxylic acid or its salt comprises ItfC2H4SC2H4CO2Li. 15. The composition according to claim 1 or 2, wherein the perfluoroalkylorganocarboxylic acid or its salt consists of R, C2H45C2H4CO2K. 16 perfluoroalkylorganocarboxylic acid or its salt)tfC2H4SC2C02(C2144)2(
The composition according to claim 1 or 2, comprising CH8)-N. 3. The composition according to claim 1 or 2, wherein the perfluoroalkylorganocarphonic acid or salt thereof comprises R, C2H4QC2114Co2H. 18. The composition according to claim 1 or 2, wherein the perfluoroalkylorganocarcinic acid or its salt comprises RIC21'14QC2H4CO2L. 19. The composition according to claim Nr, 1 or 2, wherein the perfluoroalkylorganocarphonic acid or its salt comprises RfC3day6C02K. 20, perfluoroalkylorganocarboxylic acid or its salt is (C4H9)2sn[0c(CH2)2S(C
H2)2Rr) The composition according to claim 1 or 2, comprising: H2)2Rr). 21 Perfluoroalkylorganocarboxylic acid or its salt is (C,F, 5Co2), 5n(C4H,)2
A composition according to claim 1 or 2, comprising: 22 Perfluoroargyl organocarboxylic acid or its salt is (:MD4(CH,) 3Co, )2Sn (
C411,) Claim 1 or 2 consisting of 2
Compositions as described in Section. 23. The composition according to claim 1 or 2, wherein the perfluoroalkylorganocarboxylic acid or its salt comprises (C9F1.C02)2Sn(C4H9)2. 24. The composition according to claim 1 or 2, wherein the perfluoroalkylorganocarboxylic acid or its salt comprises (H,,C2H,0)2Sn(C4H9)2. 25, perfluoroalkyl organocarboxylic acid or its salt is RfC2114SC2H4C02Li and R0
A composition according to claim 1 or 2, comprising C2H4SC2H4C02CH2(CH3)2. 26. The composition according to claim 1 or 2, wherein the perfluoroalkylorganocarboxylic acid or its salt comprises dibutyltin diberfluoroalkylorganocarboxylate. 27. Curable to polyurethane in a mold consisting of (a) a polymer/polyol, (b) an organic polyisocyanate, and (C) a catalytic amount of catalyst for reacting (al and (b) to produce polyurethane) in which H, ( is a perfluoroalkyl group containing from 4 to 12 (inclusive) carbon atoms, and m and n
is an integer from 2 to 10 (inclusive), Z is oxygen or sulfur, and M is hydrogen, an alkali metal, an amino group, an ammonium group, or a quaternary ammonium group]; ii) RfCH2C12 (OCH2CH2) ,C00
M (TT) [wherein p is 1 to 10 (inclusive)
and It, and M are as defined above]; 1ii) R4(CH2)qCOOh+ (III
) [wherein q is an integer from 2 to 10 (inclusive), and Rf and M are as defined above]. The composition described above is characterized in that it imparts self-releasing properties from a mold to a polyurethane produced from the composition. 28. The composition according to claim 27, wherein the perfluoroalkylorganocarboxylic acid or its salt is dissolved in a solvent and then added to the polyurethane composition. 29. The composition according to claim 28, wherein the solvent is ethylene glycol. 29. The composition of claim 28, wherein the crystallizing agent is tetrahydrofuran. 31. The composition according to claim 2β, wherein the solvent is isopropanol and water (1:1). 32. A reaction injection molding method for producing molded polyurethane, characterized in that the molded polyurethane is produced from the composition according to claim 1.