JPS62190213A - Coated and molded article - Google Patents

Abstract

PURPOSE:A coated and molded article, obtained by the presence of an effective amount of an organic phosphorous acid ester based stabilizer in a coated and molded article of an elastomer using an aromatic diamine as a chain extender in a coating film on the above-mentioned molded molded article and capable of suppressing discoloring property of the coating film. CONSTITUTION:A molded article obtained by reaction injection molding of a high-molecular weight active hydrogen compound, preferably ethylene glycol, etc., a chain extender which is partially or wholly an aromatic diamine, preferably 1-methyl-3,5-diethyl-2,4-diaminobenzene, etc., and a polyisocyanate compound, preferably 4,4'-diphenylmethane diisocyanate, etc., is coated to give a coated and molded article. In the process, an organic phosphorous acid ester based stabilizer, preferably tris(2-ethylhexyl)phosphite, etc., in an amount of preferably 0.01-5wt% based on the molded article or resin content in the coating film is present in the above-mentioned molded article and/or coating film thereon. USE:Suitable for automotive bumper shells, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a coated molded product obtained by coating a polyurethaneurea elastomer molded product molded by a reaction injection molding method. The present invention relates to a coated molded product that has a reduced effect on the coating film obtained by the molded product.

At least an active hydrogen compound component containing an active hydrogen compound such as a relatively high molecular weight polyol or aminated polyether and a chain extender and optionally containing a catalyst and a blowing agent, and an incyanate component containing a polyisocyanate compound as an essential component. A method for producing polyurethaneurea-based or polyurea-based elastomer molded articles by reaction injection molding using two components is known. Typical examples of high molecular weight active hydrogen compounds are relatively high molecular weight polyether polyols and aminated polyethers in which the hydroxyl groups are substituted with amide 7 groups. The chain extender is a relatively low molecular weight polyhydric alcohol or polyamine, which is also a type of active hydrogen-containing compound. The use of a catalyst is usually essential and is usually added to the active hydrogen compound component, but it can also be added to the incyanate component. The use of a small amount of a blowing agent such as a halogenated hydrocarbon blowing agent to produce a microcellular elastomer molded article is a commonly employed means for improving moldability. The density of the microcellular elastomer molded product obtained using this small amount of blowing agent is usually 0.8 g/c113 or more, especially about 0.9
g/cm3 or more. Unless a particularly large amount of reinforcing fiber, flake filler, powder filler, or other filler is added, the upper limit is usually 1.2 g/cm3 or less, especially about 1.15 g.
/cm3 or less.

The density of non-foamed elastomer molded articles is also typically within the above range. It is also known to perform reaction injection molding by dividing the active hydrogen compound component into two or more components and using three or more components in total, including the isocyanate component.

In the production of the above-mentioned elastomer molded products, it is known to use alkyl-substituted aromatic diamines and chlorine-substituted aromatic diamines as chain extenders.
1735! ] and JP-A-58-32826. This specific aromatic diamine has a faster reaction rate than conventional polyhydric alcohol chain extenders, and elastomer molded products using it have characteristics such as good release from the mold and less generation of voids. Furthermore, a method is known in which a specific aromatic diamine and a larger amount of diol are used together as a chain extender (Japanese Patent Publication No. 59-4924
(See Publication No. 8).

It is also known to use aminated polyethers as chain extenders or as part of high molecular weight active hydrogen compounds. Aminated polyether is a polyvalent polyether compound (total of 7 amino groups and hydroxyl groups of 2 or more) that has amino groups (and optionally hydroxyl groups) in which some or all of the hydroxyl groups of polyether polyol are substituted with amino groups. It is. There is also a method of producing elastomer molded products by reaction injection molding, using a relatively low molecular weight aminated polyether as part of the chain extender, and also using low molecular weight polyols and aromatic polyamines as other chain extenders. This is well known and is described in, for example, Japanese Patent Application Laid-open No. 109218/1983.

However, a new problem has been discovered in elastomer molded products obtained by using these aromatic diamines as part or all of the chain extender. The problem is that when a molded article is painted, the paint film changes color over time. In the application of elastomer molded products such as automobile bumpers, it is not uncommon for the molded products to be painted. It has been found that molded articles obtained using the above-mentioned specific chain extender are particularly susceptible to discoloration over time. This suggests that aromatic diamines and their reactants have some influence on the coating film. For example, it is presumed that a trace amount of unreacted aromatic diamine or a trace amount of a low molecular weight aromatic diamine reactant that is thought to be a by-product penetrates into the coating film from the surface of the molded product and discolors the coating film. If the discolored paint film is further hidden by an overlying paint film, there will be little problem in appearance, but if the overlying paint film is transparent, the problem in appearance will be significant. Similarly, when the discolored coating film is the uppermost coating film, problems in terms of appearance are also serious. Therefore, the problem of externally visible discoloration of the coating film is an important problem to be solved when using a coated elastomer molded product using the above-mentioned specific chain extender.

In order to solve the above problems, the present inventors investigated the use of discoloration inhibitors. As a result of examining many substances that can be expected to have an effect of preventing discoloration, the present inventors have found that an organic phosphite stabilizer has a remarkable effect of preventing discoloration in this case. This organic phosphite stabilizer can be used by being present in the elastomer molded article. It is also effective even if it is present in a paint film that is likely to change color, and if there is a paint film that is present between the paint film that is likely to change color and the surface of the elastomer molded product, it may be present in that paint film. It is effective even if Furthermore,
It is of course effective to have an organic phosphite stabilizer present in any one of these molded articles or coatings, but it is equally effective to have it present in two or more of them.

In the present invention, as described above, an organic sulfur ester stabilizer is present in the elastomer molded article or the coating film thereon. The following invention relates to a coated elastomer molded article obtained using a specific chain extender.

In a coated molded product obtained by coating a molded product molded by reaction injection molding using a high molecular weight active hydrogen compound, a chain extender, and a polyisocyanate compound as the main raw materials, the molded product contains part or all of the chain extender. A molded article obtained using an aromatic diamine, characterized by the presence of an effective amount of an organic substinth butyrate stabilizer in the molded article and/or in the coating film on the molded article. A painted molded product with suppressed discoloration of the paint film.

As the organic phosphite stabilizer in the present invention, an organic phosphite compound that is used as an antioxidant for synthetic resins such as vinyl chloride resins, polyolefin resins, and synthetic rubbers is used. This organic phosphite may be a triester or a hydrogen diester, and it may also be an ester with a monohydroxy compound, an ester with a polyhydroxy compound, or a mixed ester with a monohydroxy compound. In addition, thioester compounds may also be used. For example, when the monohydroxy compound residue is an alkyl group, examples thereof include trialkyl phosphite, dialkylhydrodiene phosphite, tetraalkylalkylene glycol diphosphite, bisalkylpentaerythritol diphosphite, and trialkyltrithiophosphite. Part or all of this alkyl group may be a monovalent organic group such as an aryl group or an alkyl group. The alkyl group is preferably an alkyl group having 6 to 20 carbon atoms, and the aryl group is a phenyl group. Alternatively, specific examples of compounds in which an alkyl-substituted phenyl group is preferable include, for example, the following compounds. Tris (2
-ethylhexyl) phosphite, tridecyl phosphite, triotadecyl phosphite, triphenyl phosphite, tris(nonylphenyl) phosphite,
Diphenyldecyl phosphite, didecyl phenyl phosphite, dilaurylhydrodiene phosphite, tetraphenyldipropylene glycol diphosphite.

Tetraoctylethylene glycol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite.

The amount of the organic phosphite stabilizer used is not particularly limited as long as it is an effective amount; however,
If the amount used is too large, it may cause deterioration in the physical properties of the elastomer molded product or coating film. Therefore, the upper limit of the amount used is preferably about 5% by weight based on the resin component of the molded product or coating film. Especially in the case of molded products, the mechanical properties are likely to deteriorate, so it is about 0.5% by weight. The lower limit, which is preferably limited to a certain degree, depends on the type of stabilizer, but most stabilizers can exhibit the desired effect at about 0.005% by weight. In the Examples described later, the amounts used are described based on a total of 100 parts by weight of the high molecular weight active hydrogen compound and chain extender, but this value corresponds to approximately twice the concentration relative to the resin component. Therefore, the amount present in the elastomeric molded article is most preferably about 0.01 to 1% by weight, based on the total amount of high molecular weight active hydrogen compound and chain extender.

Aromatic diamines used as part or all of the chain extender include mononuclear aromatic diamines (i.e., diaminobenzene derivatives) and polynuclear aromatic diamines (e.g., diaminodiphenylmethane conductors, etc.). Diamines are preferred, their molecular weights being about 108-400
In particular, it is preferably about 120 to 200. It is preferable that the reactivity of the amine 7 group is controlled with an alkyl group or a chlorine atom. That is, one or more lower alkyl groups are present at the ortho position of the amination. Suitable are compounds in which the reactivity of the amino group is reduced by the presence of a chlorine atom, and compounds having a chlorine atom in which the reactivity of the amino group is not excessively reduced by the chlorine atom. As the former, compounds having lower alkyl groups at all ortho positions of the two amine groups are particularly preferred; as the latter, diaminobenzene derivatives having one chlorine atom (which may further have a lower alkyl group) A preferred lower alkyl-substituted aromatic diamine is 1-methyl-3,5-diethyl-
2,4-diamitbenzene, l-methyl-3,5-diethyl-2,6-diaminobenzene, 1,3-dimethyl-
2,4-diaminobenzene, l,3-diethyl-2,4
-diaminobenzene, 1,4-diinpropyl-2,5
-diaminobenzene, 1,3.5-) riethyl-2,4
-diaminobenzene, 3.3', 5.5'-tetraisopropyl-4゜4゛-diaminodiphenylmethane, and the like. Particularly preferred compounds are 1-methyl-3,5-diethyl-2,4-diaminobenzene, l-methyl-3,
5-diethyl-2,6-diaminobenzene, and mixtures thereof. Preferred chlorinated diaminobenzones are 2-chloro-1,4-diaminobenzene, 4-chloro-1,2-diaminobenzene, or mixtures thereof. Of course, two or more of these aromatic diamines may be used in combination.

Other chain extenders that can be used in combination with aromatic diamines include low molecular weight polyols and low molecular weight aliphatic diamines.

As the low molecular weight polyol, aliphatic or alicyclic di- to tetrahydric low molecular weight polyols having a molecular weight of about 62 to 240 are preferred, and di- to trihydric alcohols having a molecular weight of about 62 to 120 are particularly preferred.The hydroxyl groups of these compounds are All are preferably primary hydroxyl groups, specifically ethylene glycol,
l, 3-propanediol, 1,4-butanediol,
1,6-hexanediol, neopentyl glycol,
Cyclohexane dimetatool.

Diethylene glycol, dipropylene glycol, triethanolamine, jetanolamine, diimpropaturamine, glycerin.

There are also polyols obtained by adding a small amount of these fullkylene oxides. Preferred low molecular weight polyols are aliphatic diols having 2 to 6 carbon atoms, with ethylene glycol and 1,4-butanediol being particularly preferred.

As a low molecular weight aliphatic polyamine, the molecular weight is about 400.
The following examples include alkylene diamines, polyalkylene polyamines, aminated polyethers, and the like, particularly those having a molecular weight of about 300 or less. In particular, low molecular weight compounds corresponding to aminated polyethers described below as high molecular weight active hydrogen compounds are preferable. Specific aliphatic polyamines include ethylenediamine, propylene diamine, hexamethylene diamine, inphorone diamine, etc. Examples of low molecular weight aminated polyethers include polyoxypropylene diamine, polyoxyethylene diamine, polyoxypropylene triamine, and polyoxyethylene triamine having a molecular weight of 400 or less. In addition to aliphatic polyamines, amine compounds having polyfunctionality for incyanate groups, such as monoalkanolamines, can be used as chain extenders.

The amount of aromatic diamine relative to the total amount of chain extender is not limited, and is about 5% as described in the above-mentioned known example.
Even if it is less than 0% by weight, it is meaningful to use it sufficiently. The amount of aromatic diamine based on the total amount of chain extender is about 20 to 10
0% by weight is suitable, especially about 50-100% by weight.

The amount of the chain extender to be used is not particularly limited, but is 0.05 to 1.0 mol, particularly about 0.1 to 1.0 mol, per 100 parts by weight of the high molecular weight active hydrogen compound described below. 0
．． 5 mol is suitable.

In the present invention, as the high molecular weight active hydrogen compound, a compound having two or more hydroxyl groups and/or amino groups and a molecular weight per functional group of 600 to 4000 is used. Examples of compounds having two or more hydroxyl groups include high-molecular weight polyether polyols, polyester polyols, polycarbonate polyols, and hydrocarbon polymer polyols. Mixtures with polyols are preferred. As the compound having an amine group, a high molecular weight aminated polyether is suitable;
This aminated polyether has a total of 2 amino groups and hydroxyl groups.
It may also be a partially aminated polyether having the above (
(Hereinafter, aminated polyether is used to include partially aminated polyether). Furthermore, it is also possible to use mixtures of aminated polyethers and high molecular weight polyols, especially polyether polyols. moreover,
Fine particulate polymers called polymer polyols (for example, polyacrylonitrile and polyacrylonitrile)
High molecular weight polyols, ie, polymer-dispersed polyols, may also be used, including styrene copolymers, etc.).

These will be explained in more detail below.

As the high molecular weight polyol, a polyether polyol with a hydroxyl value of 20 to 60 or a polymer-dispersed polyol is preferable. In addition, a smaller amount of polyester polyol, polydiene polyol, or other polyol may be used in combination with these.0 Polymer-dispersed polyol refers to a high molecular weight polyether polyol having substantially saturated or unsaturated groups. Polyols obtained by polymerizing acronitrile or styrene in polyols, polyols obtained by dispersing fine particulate polymers obtained by polymerizing acrylonitrile or styrene in high molecular weight polyether polyols, or combinations of these polyols and polymers. The amount of the hexapolymer, which may be mixed with a polyether polyol without it, is usually about 40% by weight or less based on the polymer-dispersed polyol.

The above-mentioned polyether polyols are preferably polyhydric alcohols, polyhydric alcamel amines, polyhydric phenols, mono- or polyamines, and compounds obtained by adding alkylene oxide to other initiators, preferably divalent to octavalent. In particular, compounds obtained by adding propylene oxide and/or butylene oxide and ethylene oxide to a di- to tetrahydric polyhydric alcohol are preferred.As the polyhydric alcohol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1 .4-Butanediol, glycerin, trimethylolpropane, diglycerin, pentaerythritol, and other aliphatic di- to tetrahydric polyhydric alcohols are particularly preferred.When adding the alkylene oxide to these initiators, at least the last The addition reaction is preferably with ethylene oxide.The polyether polyol produced by this terminal ethylene oxide addition (also called ethylene oxide cap) has many primary hydroxyl groups.High molecular weight polyols for zero-reaction injection molding are highly reactive. In the case of polyether polyols, the proportion of primary hydroxyl groups is preferably at least 70%,
In particular, it is preferably about 85% or more, and the amount of ethylene oxide capping that provides this primary hydroxyl group proportion is preferably about 5% by weight or more, particularly about 5 to 30% by weight.
The oxyalkylene groups present in the polyether chain other than the ethylene oxide cap are mainly oxypropylene groups and/or oxyallene groups, but a small amount of oxyethylene groups may be present, preferably consisting only of oxypropylene groups, It consists of random or block copolymer chains of oxypropylene groups and a smaller amount of oxyethylene groups. Preferably, the total oxyethylene groups in the polyether-based polyol, including the terminal oxyethylene groups due to the cap, are less than about 40% by weight; oxyethylene groups are hydrophilic, and polyether-based polyols with too high an oxyethylene group content may reduce the water resistance of the elastomer obtained using it.

It is usually necessary that the water M value of the high molecular weight polyol is about 20 to 6 degrees. This high molecular weight polyol may be a mixture of two or more types of high molecular weight polyols, in which case the hydroxyl value refers to their average value. Therefore, in some cases, it is possible to use a high molecular weight polyol outside the range of hydroxyl groups of 20 to 60 and use it in combination with other high molecular weight polyols to obtain a mixed polyol with an average hydroxyl group of 20 to 6. , you can also use this. The hydroxyl value of the high molecular weight polyol is particularly preferably about 20 to 4o.

Aminated polyether is a compound in which almost all or some of the hydroxyl groups of the above-mentioned high molecular weight polyether polyol are converted into 7-mino groups.

This aminated polyether is an aliphatic compound except when the initiator is a compound having an aromatic nucleus. Preferred initiators are aliphatic or alicyclic polyhydric alcohols, with aliphatic polyhydric alcohols being particularly preferred.

Therefore, the aminated polyether is preferably a compound having no aromatic nucleus, especially an aliphatic compound, and the more preferable molecular weight range of the aminated polyether is about 1600.
~6000. Further, the number of functional groups (ie, the total number of amino groups and hydroxyl groups) is preferably divalent to tetravalent, particularly preferably divalent to trivalent. The amination rate (ratio of amino groups to the total of amino groups and hydroxyl groups) is not particularly limited, because in the present invention, the non-7-minated portion of the aminated polyether is the aminated portion of the polyether polyol. This is because the portion that is not present can be regarded as one type of polyether polyol. For example, a divalent aminated polyether with an amination rate of 50% and a molecular weight of about 3000 is mixed with a divalent aminated polyether with a molecular weight of about 3000 and a divalent aminated polyether with a molecular weight of about 3000.
00 and a polyether diol, and the latter can be considered as part of a high molecular weight polyether polyol.

Various polyisocyanate compounds and modified products thereof can be used as the polyincyanate compound, but aromatic polyisocyanates and modified products thereof are particularly preferred.
Preferred aromatic polyisocyanates are diphenylmethane diisocyanate, tolylene diisocyanate, polymethylene polyphenyl diisocyanate, and naphthylene diisocyanate. Particularly preferred is 4,4'-diphenylmethane diisocyanate, and these aromatic polyisocyanates are preferably modified rather than unmodified.

Modified products include carbodiimide modified products, prepolymer type modified products, trimers, urea modified products, Biuret modified products,
Although other materials may be used, carbodiimide-modified products and prepolymer-type modified products are particularly preferred. It may be a prepolymer made by reacting a high molecular weight polyol such as a polyol (see JP-A-58-61117).The amount of these polyisocyanate compounds used is based on the total amount of the high molecular weight active hydrogen compound and chain extender. Number of incyanate groups for a total of 100 hydroxyl groups and amino groups (
Approximately 80 to 130. In particular, it is preferably about 80 to 120.

In the production of elastomer molded products using the reaction injection molding method, it is essential to use a catalyst in addition to the above-mentioned main raw materials.
The use of blowing agents is also preferred.

Catalysts include various tertiary amine catalysts and organometallic compounds such as organotin compounds, and both may be used alone or in combination.In the present invention, a blowing agent is not necessarily essential, and a blowing agent may be used. Even if this is not done, a slightly foamed elastomer can be obtained due to the presence of air and water dissolved in the raw materials, and by sufficiently removing these, a non-foamed elastomer can be obtained. However, the use of a small amount of blowing agent is preferable for reasons such as improving moldability. Air, water, etc. can also be used as the blowing agent, but halogen hydrocarbons with a low boiling point are preferably used. Specifically, trichlorofluoromethane, dichlorofluoromethane, methylene chloride, etc. are suitable. The amount thereof is preferably 15 parts by weight or less, particularly 2 to 10 parts by weight, based on 100 parts by weight of the high molecular weight active hydrogen compound and chain extender.

Furthermore, various printing agents can be added as optional additive components. For example, reinforcing fibers, internal mold release agents.

These include fillers, colorants, ultraviolet absorbers, stabilizers other than organic phosphite stabilizers, and flame retardants. Adding reinforcing fibers or flake-like reinforcing agents to 48 not only improves strength but also improves physical properties such as reducing the rate of dimensional change due to water absorption.This is because it improves the rigidity and strength of the elastomer molded product. Suitable examples of the zero-reinforcing fibers that are considered to be include milled glass fibers, cut fibers, wollastonite, mineral fibers, potassium titanate whiskers, and gypsum fibers. Moreover, mica, glass flakes, etc. can be used as the flake-like reinforcing agent. The amount thereof is approximately 20% by weight or less based on the entire elastomer molded product to have a sufficient effect. These additives, including the catalysts and blowing agents mentioned above, are usually added to the active hydrogen compound component, which includes the high molecular weight active hydrogen compound and the chain extender. However, additives which are inert towards incyanate groups can also be added to the incyanate component.

In the reaction injection molding method, the active hydrogen compound component and the incyanate component are usually rapidly mixed to form a reactive mixture, which is immediately injected into a mold, and the reactive mixture is reacted in the mold to form a molded product after curing. This is done by taking it out as In some cases, three or more components may be used by dividing the active hydrogen compound component or incyanate component into two or more, or by using a third component. Rapid mixing is usually achieved by impingement mixing of each component, and an after-mixing mechanism may be provided in a portion of the runner to perform remixing.

Although elastomer molded articles exhibit good mold releasability even without the use of an internal mold release agent, the mold releasability can also be further improved by using an internal mold release agent.

Additionally, an external mold release agent is usually applied to the inner surface of the mold. The polyurethaneurea elastomer molded article of the present invention has improved mold releasability through the use of an external mold release agent, and from the standpoint of the external mold release agent, its lifespan is significantly extended. Various types of external mold release agents can be used, including wax-based external mold release agents, silicone-based external mold release agents, and fluorine compound external mold release agents.

The above-mentioned elastomer molded product may be painted at the same time as molding or after molding.The former method involves applying paint to a predetermined part or all of the inner surface of the mold, and applying the paint partially or almost completely. A method of curing to form a coating film and molding an elastomer molded product as described above using a mold with this coating film applied, or a method called the in-mold coating method, that is, molding an elastomer molded product There is a method of injecting paint to form a coating film on the surface of the molded product after molding and before removing it from the mold. The latter is a general coating method, and is a method in which a paint is used to form a single layer or multiple layers of coating on a molded product. In the latter case, a single layer of primer is first formed on the molded product, and then an ordinary paint is often applied.In the present invention, the above-mentioned organic phosphite stabilizer is added to the paint used in these coatings. The stabilizer is preferably present in the coating film that is in direct contact with the molded product, as well as in the coating film that is not in direct contact with the molded product (for example, in the first layer of the primer). It can also be present in coatings (on coatings), especially coatings where discoloration may be a problem.

Of course, it is also effective to have it not exist in this coating film, but only in the primer layer below it. The material of the paint is not particularly limited, and for example, alkyd paints, epoxy paints, polyurea paints, acrylic paints, melamine paints, phenol paints, and other paints can be used.

INDUSTRIAL APPLICATION This invention is used for the exterior parts of a motor vehicle, especially a bumper outer shell. However, the present invention is not limited to this use, and can also be applied to other automobile parts, molded products for housings, and other uses.

EXAMPLES The present invention will be specifically explained below using Examples, but the present invention is not limited to these Examples.

Examples and Comparative Examples A mixture of the raw materials shown below was charged into the active hydrogen compound component side tank of a high-pressure foaming machine, and a polyisocyanate compound was charged into the incyanate component side tank.The discharge pressure of the high-pressure foaming machine was set to 150 kg/c+2. Reaction injection molding was carried out with a discharge rate of 90 kg/min and a liquid temperature of each component adjusted to 35°C. The size of the mold is 140 x 120 x IE! 00
This is a 0-length molded product that was molded using an iron mold (projection mold) for molding the outer shell of an automobile bumper with an internal thickness of 3.5 mm and an adjusted mold temperature of 70°C. JIS KEi301, ASTM 0790,
and elongation and flexural modulus according to ASTM 03769,
and thermal sag were measured. In addition, the molded product was coated by the method described below, and a yellowing test of the coating film was conducted.

Table 1 shows the composition, physical properties, and yellowing test results of the active hydrogen compound component. Comparative examples are also shown in Table 2.

Raw materials Active hydrogen compound components Mixture of the following types of raw materials Total weight: 10,000 weight The composition is listed in Table 1] Catalyst nitriethylenediamine solution: 1.0 parts by weight [Product name: Dabcor 33LV''] Diptyltin dilaurate: 0.05 weight Blowing agent (trichlorofluoromethane) 5 parts by weight Stabilizer Description Incyanate component modified diphenylmethane diisocyanate (NGO content
26%) [The amount used is the amount that makes the index 105] Type of raw material Polyol A Bipolyoxypropyleneoxyethylene triol with a molecular weight of about 6000.

[Contains about 20% by weight of oxyethylene group only at the end of the molecular chain] Polyol B: Polyoxypropyleneoxyethylene diol with a molecular weight of about 4,000.

[Contains about 20% by weight of oxyethylene group only at the end of the molecular chain] Polyol C: Polyacrylonitrile content obtained by polymerizing acrylonitrile monomer in polyol B: 20
Weight % of polymer-dispersed polyol EG: ethylene glycol.

CDA: 2-chloro-1,4-diaminobenzene.

[]]EτDA: 1-methyl-3,5-diethyl 2,4
-Diaminobenzene and 1-methyl-3,5-diethyl-
Mixture of 2,6-diaminobenzene.

Organic phosphite stabilizer A: Tetraphenyldipropylene glycol diphosphite B Nidilaurylhydrodiene phosphite C: Bis(nonylphenyl)hentaerythritol diphosphite D Nidris(2-ethylhexyl)phosphite E: p -Hydroxythiophenol F: Thiodipropion Dodecyl G Nidiphenyl disulfide Yellowing test painting 2 A 75X 150+wi+ test piece was cut out from the molded product, washed with trichloroethane steam (1 minute), and then painted with the following paint. φ Nabrimer (°° Souffle 1800") 20μ thick (baking 100℃ x 30 minutes) 0 top coat ("°
Flexene 1101" white) 35μ thick (baking 1f 0 minutes) After determining the color difference of the above coating sample, it was placed in an autoclave at 100°C and heated for 20 days. The color difference after the heat treatment was measured, Yellowing was measured based on the difference in color [Δ(ΔE)] from that before treatment.

Table 1 Table 2

Claims (1)

[Scope of Claims] 1. A coated molded product obtained by coating a molded product molded by a reaction injection molding method using a high molecular weight active hydrogen compound, a chain extender, and a polyisocyanate compound as main raw materials, wherein the molded product is This is a molded product obtained by using an aromatic diamine as part or all of the chain extender, and an effective amount of organic phosphite stabilizer is contained in the molded product and/or in the coating film on the molded product. A painted molded product with suppressed discoloration of the paint film, characterized by the presence of a coating agent. 2. The coated molded article according to claim 1, wherein the amount of the organic phosphite stabilizer is about 0.01 to 5% by weight based on the resin component of the molded article or coating film.