JPH01271411A - Reaction-curable resin composition - Google Patents

Abstract

PURPOSE:To improve the light fastness and yellowing resistance of a polyurethane urea surface to be produced by incorporating four specific components, thereby increasing the curing speed. CONSTITUTION:The title composition is obtained by blending 100 pts.wt. high-molecular weight active hydrogen compound (A) which has 1.8-8 groups (h group) containing active hydrogen per molecule selected from among primary and secondary amino groups and a hydroxyl group, and an average molecular weight of 300 or more per (h) group, and at least part of which contains the above amino group (n group), with the ratio of the number of the (n) groups to the (h) groups of 5-100%, 2-30 pts.wt. component (B) which comprises a low-molecule weight active hydrogen compound having 2-6 (h) groups per molecule and a molecular weight of below 300 per (h) group, and 3-100wt.% of which are an aminic active hydrogen compound having a tertiary amino group other than the (h) groups or the (n) groups, 0.7-1.4 equivalents, based on the total equivalent of the components (A) and (B), of a component comprising a non-yellowing polyisocyanate (or a modified product) (C) and contains 5wt.% or more NCO groups, and 0.1-5 pts.wt. component (D) at least part of which comprises a catalyst comprising a lead compound catalyst and a bismuth compound catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a reaction-curable resin composition for forming a skin used in a mold coating method.

[Prior Art] A method is known in which a layer of synthetic resin serving as a skin is formed on the inner surface of a mold in advance, and the synthetic resin is molded using this mold to produce a synthetic resin with a skin. This method is called a mold coating method, and is particularly used as a method for forming a skin with excellent weather resistance on synthetic resin molded products such as polyurethane foam, which cannot be said to have sufficient weather resistance. This is because ordinary polyurethane foam uses yellowing polyisocyanate as a raw material, and therefore has insufficient light resistance and yellowing resistance. It is also known to produce polyurethane foam itself using non-yellowing polyisocyanate (Japanese Patent Publication No. 15599/1983, Japanese Patent Publication No. 15599/1983).
However, since the reactivity of the non-yellowing polyisocyanate is low, it is difficult to produce molded products in a sufficiently short time even if a large amount of catalyst is used. Further, the use of a large amount of catalyst causes deterioration of the weather resistance of the polyurethane foam, and there is also the problem that it is not economical because it requires the use of an expensive non-yellowing polyisocyanate. Polyurethane using yellowing polyisocyanate is also known as a skin material used in the mold coating method (see Japanese Patent Publication No. 62-35889), but the weather resistance of the skin is not sufficient.

[Problems to be Solved by the Invention] It is known to carry out a mold coating method using a polyurethane resin in which substantially all of the polyisocyanate is non-yellowing polyisocyanate as a skin material (Japanese Patent Laid-Open No. 59-18723). However, after this skin material is applied to the inner surface of a mold, it takes about 2 to 2 hours before the mold can be used to mold polyurethane foam, etc. It took a long time of 3 minutes, which caused practical problems, and since the solution used a solvent, it was difficult to increase the thickness of the epidermis.

[Means for Solving the Problems] The present invention is the following invention relating to a highly reactive reactive curable resin composition that solves the above problems.

A reaction-curable resin composition for forming a skin on the inner surface of a mold before molding a synthetic resin in the mold,
A reaction-curable resin composition containing at least four components listed below (A) to (D) as essential components.

Component (A): having an average of 1.8 to 8 active hydrogen-containing groups per molecule, and an average of at least one active hydrogen-containing group selected from primary amino groups, secondary amino groups, and dihydroxyl groups; It consists of at least one type of high molecular weight active hydrogen compound having a molecular weight of 300 or more, and at least a part of the high molecular weight active hydrogen compound is a compound containing at least one of the above amino groups, and the component ( A) A component in which the ratio of 7-minions to the total number of active hydrogen-containing groups is 5 to 100%.

Component (B): has an average of 2 to 6 active hydrogen-containing groups per molecule, and has a molecular weight per active hydrogen-containing group at least one type of active hydrogen-containing group selected from illumination, oxidation, secondary amino groups, and hydroxyl groups. is less than 3110, and at least a part of the low molecular weight active hydrogen compound is a tertiary amino group that is not an active hydrogen-containing group or the above-mentioned active hydrogen-containing group. It is an amine-based active hydrogen compound having a certain amino group, and the proportion of the amine-based active hydrogen compound in component (B) is 3 to 100% by weight (a certain component).

Component (C): A component consisting of at least one type of non-yellowing poly, isocyanate, or modified product thereof, and having an isocyanate group content of 5% by weight or more.

Component (D) is a catalyst for promoting the reaction between an active hydrogen-containing group and an isocyanate group, at least a part of which is selected from a lead compound catalyst and a bismuth compound-based flux. A component that is a catalyst.

The feature of the present invention is that a highly disease-resistant high molecular weight active hydrogen compound is used instead of the conventional high molecular weight polyol, and a low molecular weight active hydrogen compound (called a chain extender or crosslinking agent) is used.
The reactivity of a non-yellowing polyisocyanate having a low-reactivity -isocyane-1- group was increased by using a highly reactive active hydrogen compound, and the reaction was further accelerated using a specific catalyst. There are characteristics.

Therefore, when applied to the inner surface of a mold, it rapidly reacts and becomes a coating film that can be used for molding synthetic resins in a short period of time. Also,
The composition of the present invention does not require the use of a solvent.1. :Meanwhile, it is possible to eliminate the need for evaporation time for the solvent, and even if a solvent is used, it is sufficient to use a small amount, so it does not take a long time to evaporate and remove the solvent. In addition, the fluidity of ** applied to the inner surface of the mold rapidly decreases, making it easy to apply a thick coating.

Definitions of major terms used in the present invention are as follows.

Active hydrogen-containing group: A general term for primary amino groups (-NH,), secondary amino groups (>N1(), and hydroxyl groups (-OH), and does not include tertiary amino groups.

Amino group: Refers to a primary amino group and a secondary amino group unless specifically referred to as a "tertiary amino group."

Hydroxyl group: Refers to primary hydroxyl group, secondary hydroxyl group, and tertiary hydroxyl group, and refers to alcoholic hydroxyl group unless specifically referred to as phenolic hydroxyl group.

Active hydrogen compound: A compound having two active hydrogen-containing groups, unless specifically mentioned as an active hydrogen compound having one active hydrogen-containing group, a compound having at least two active hydrogen-containing groups. means.

Amino group-containing active hydrogen compound: refers to the above-mentioned active hydrogen compound in which at least one active hydrogen-containing group is a primary amino group or a secondary amino group.

Amine-based active hydrogen compound: the above active hydrogen compound having at least two active hydrogen-containing groups and at least one of the active hydrogen-containing groups is a primary amino group or a secondary amino group,
or at least two active hydrogen-containing groups, all of which may be hydrogen groups), and at least one tertiary amino group.

Polyol: The above active hydrogen compound having 1°8 or more hydroxyl groups on average and having neither primary amino groups nor secondary amino groups. However, it may have a tertiary amino group.

Component (A) in the present invention refers to a component consisting of at least one type of high molecular weight active hydrogen compound (v) and having a total amino group content of 5% or more.

High molecular weight; molecular weight per active hydrogen-containing group is 300
However, it is usually necessary that the average molecular weight per active hydrogen-containing group of component (A) as a whole is 600 or more.

A part of the high molecular weight active hydrogen compound has an active hydrogen-containing group 1
The active hydrogen compound having the component (A
) The overall average proportion of active hydrogen-containing groups per molecule must be at least 1.8. The average molecular weight per active hydrogen-containing group of component (A) as a whole is preferably 800 to 4000, and the number of active hydrogen-containing groups per molecule is preferably 2 to 8, particularly 2 to 6. .

The above component (A) consists of at least one type of high molecular weight amino group-containing active hydrogen compound (hereinafter referred to as (a-1)), or at least one type of high molecular weight polyol and the compound (a-1). -1) with at least one type of mixture (hereinafter referred to as
(a-2)) consists of (a-1) and (a-2)
), of course there are cases where it is clearly distinguishable, but there are also cases where it is difficult to distinguish. For example, when the proportion of amino groups is low, it is often difficult to distinguish between the two;
A-1) is theoretically (a-2), because as long as one molecule has one amino group, its amino group proportion is f00/n%, and unless a polyol has one, its average This is because the amino group ratio will not be less than 100/n%. On the other hand, when the proportion of amino groups is high, it is often possible to distinguish between (a-1) and (a-2), which have the same proportion of amino groups.These will be explained below using specific examples. For example, an amino group-containing polyoxyalkylene compound (2) with an amino group proportion of 25% is obtained by using a certain polyoxypropylene diol (1) as a starting material and changing 25% of its hydroxyl groups to amino groups, and a polyoxyalkylene compound (2) containing amino groups with a proportion of 25% amino groups is obtained by amination in the same manner. Amino group ratio 5
0% amino group-containing polyoxyalkylene compound (3)
Assuming that there is an amino group-containing polyoxyalkylene compound (4) with an amino group ratio of 100%, the amino group ratio is 5.
0% (3) is considered to be a polyoxypropylene compound having one amino group and one hydroxyl group (in reality, amination of hydroxyl groups occurs stochastically, so it has only two amino groups). It is thought that a small amount of compounds with only two hydroxyl groups are included), and a compound with an amino group ratio of 25% (
2) is actually considered to be an equal mixture of (3) with an amino group proportion of 50% and (1) with an amino group proportion of 0%, and this is a mixture of (3) with an amino group proportion of 50% prepared in advance and It is difficult to distinguish it from a mixture of equal amounts of (1). On the other hand, (3) with 50% amino group ratio is (3) with 100% amino group ratio (
This is clearly different from a mixture of equal amounts of 4) and (1). In addition, the above (2) with an amino group ratio of 25% is also clearly different from a mixture with an amino group ratio of 25% obtained by mixing (4) with an amino group ratio of 100% and (1).

Regardless of whether (a-L) and (a-2) are indistinguishable from each other, any of them can be used as component (A) in the present invention. Of course, two or more clearly different types (a-1) can be used together, and (a-1) can also be used, which is a combination of these (a-1) and one or two or more types of polyols. As mentioned above, component (A) in the invention usually needs to have an average molecular weight per active hydrogen-containing group of 600 or more, but it may also contain an active hydrogen compound with a lower molecular weight. The molecular weight per active hydrogen-containing group must be 300 or more, and active hydrogen compounds with a molecular weight less than that are considered to be one type of component (B) described below, and active hydrogen compounds as component (A). shall not be considered. In addition, component (A) has an average number of active hydrogen groups per molecule of 2.1 to 4 as a whole.
．． 0 is more preferable, and the amino group proportion is preferably 15% or more, especially 30% or more. The upper limit of the amino group proportion may be 100% as mentioned above, but it is usually 98% or less, especially 90% or less is preferable.

As the high molecular weight amino group-containing active hydrogen compound, known compounds can be used.

Amino group-containing active hydrogen compounds can be produced by various methods. For example, some or all of the hydroxyl groups can be converted into primary amino groups or secondary amino groups by reacting a high molecular weight polyol as described below with ammonia or amine. Alternatively, a secondary amino group can be obtained by reacting an unsaturated nitrile such as acrylonitrile and then hydrogenating it. Furthermore, a prepolymer containing isocyanate groups can be produced by reacting a high molecular weight polyol with an excess equivalent of polyisocyanate. , the isocyanate group can also be hydrolyzed with water to form an amino group. Also,
It can also be produced by reacting a polyol with an amino group-containing carboxylic acid or its anhydride. Furthermore, diene polymers having two or more amino groups, such as polybutadiene having amino groups at the ends, are also known. Preferred is a polyether-based amino group-containing active hydrogen compound obtained by using a polyoxyalkylene polyol as a raw material and replacing some or all of its hydroxyl groups with amino groups or amino group-containing organic residues. Particularly preferred are compounds obtained by converting some or all of the hydroxyl groups of a polyoxyalkylene polyol into primary amino groups or secondary amino groups. The substituent in the secondary amino group (the substituent that is not a polymer chain among the two substituents bonded to the nitrogen atom) is preferably an alkyl group having 1 to 4 carbon atoms.

As the high molecular weight polyol, polyoxyalkylene polyols, polyester polyols, polycarbonate polyols, hydroxyl group-containing vinyl polymers, hydroxyl group-containing polydiene polymers, and other various polyols can be used. Preferred polyols are polyoxyalkylene polyols, polyester polyols, and polycarbonate polyols. The polyoxyalkylene polyol is preferably one obtained by adding at least one cyclic ether to at least one of polyhydric alcohols, polyhydric phenols, polyamines, and other initiators.As the cyclic ether, Propylene oxide, ethylene oxide, 1.2
(or 2,3)-butylene oxide, tetrahydrofuran, etc. As the polyester polyol, preferred are polyester polyols having polyhydric alcohol residues and polycarboxylic acid residues, and polyester polyols such as ring-opening polymers of cyclic esters such as C-caprolactone.As the polycarbonate polyols, Examples include poly(1,6-hexane carbonate) diol. Among these, polyoxyalkylene polyols are most preferred, such as polyoxypropylene polyols, polyoxypropyleneoxyethylene polyols, and polyoxytetramethylene polyols. Note that the polyoxyalkylene polyols have tertiary amino groups. Such a polyol can be obtained by adding a cyclic ether to a polyamine or alkanolamine.

Component (B) consists of one or more types of low molecular weight active hydrogen compounds, at least a part of which needs to be an amine-based active hydrogen compound. Part a (B) The overall average number of active hydrogen-containing groups per molecule is 2 to 6, particularly preferably 2 to 4, and the average molecular weight per active hydrogen-containing group must be less than 300. , particularly preferably 200 or less, examples of amine-based active hydrogen compounds include compounds having only two or more amino groups, compounds having at least one amino group and at least one hydroxyl group, and compounds having two or more only hydroxyl groups and There are compounds that have at least one tertiary amino group. Note that among these, the compound having both a tertiary amino group and an amino group is one type of the former two amino group-containing active hydrogen compounds. Ingredient (B)
In addition to the amine-based active hydrogen compound, the polyol may contain a low molecular weight active hydrogen compound, that is, a low molecular weight polyol having two or more hydroxyl groups and no tertiary amino group. The molecular weight per hydroxyl group is preferably less than 300, particularly preferably 200 or less, and the ratio of amino groups to active hydrogen-containing groups in component (B) as a whole is preferably not too high.

This is because the urea bond produced by the reaction between an amino group and an isocyanate group has relatively low weather resistance, so component (B)
This is because it is preferable that the number of amino groups is not too large.

On the other hand, since component (A) has a high molecular weight, the amount used in the composition is large by weight, but the molar ratio (
(corresponding to the number of amino groups) is extremely small compared to component (B), and even if the proportion of amino groups is high, the effect is small. In addition”(,
In general, when the active hydrogen compound in the polymer layer has the same active hydrogen N content and percentage, it has a lower reactivity toward isocyanate than the active compound of the component ~f, and increases the overall reaction γi of the composition. In order to achieve this, it is more effective to increase the anti-1. di property of high molecular weight active hydrogen compounds.Thus, in the case of τ-1 low molecular imaginary active hydrogen compounds, the ratio of amines/groups in τ-1 (containing active hydrogen) However, as mentioned above, too many amino groups may cause problems with weather resistance, so it is preferable that the proportion of amino groups in component (B) be relatively small. The amino acid proportion in component (B) is preferably 0...-80%, particularly 3 to 60%, and most preferably 5=50%. In addition, the component (B) having an amino group proportion of OX needs to be a polyol having a tertiary amino group, but in that case, the proportion of the component (B) of the tertiary amino group-containing polyol is 20% by weight I't L Or preferable. Further, the hydroxyl groups of the active hydrogen compound in component (B) are preferably hydroxyl groups with higher activity, and most of the hydroxyl groups are preferably primary hydroxyl groups.
．． Noi, maf:=, the amino group is il! Examples of low molecular weight active hydrogen compounds listed as 4° component (B), which are preferable for weather-resistant blood without I-junction packing, include the following compounds. Furthermore, the above (
Low molecular weight substances having the same structure as a-1) can also be used. Among the following, alkanolamines, tertiary amino group-containing polyols, and polyamines are the amine-based active hydrogen compounds. (=They can be used not only alone, but also in combination of two or more thereof, or in combination with polyols. In particular, alkanolamines alone (including combinations of two or more thereof) or other It is preferable to use it in combination with an amine-based active hydrogen compound and/or polyols.

Alkanolamines: monoethanolamine, aminobripanol% 2-aminobutyl alcohol, jetanolamine, alkylethanolamine, N-(2-hydroxyethyl)piperazine, monoisopropanol amine, diisopropanol amine.

Tertiary amino group-containing polyols nitriethanolamine, N-alkylgetanolamine, ethylenediamine-ethylene oxide 4 mole adduct, N,N'-bis (
2- and droxyethyl) piperazine, and diisopropazine.

Polyamines: ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, l,6-diamithexane, 1,8-diaminooctane, 2,2,4-trimethane Dihexamethylenediamine, isophoronediamine, menthanediamine, xylylenediamine, α, α, α゛, α°-tetramethylxylylenediamine, diethylenetriamine, triethylenethelamine, tetraethylenepentamine.

Polyols: ethylene glycol, 1,4-butanediol, propylene glycol, 1,3-propanediol, neopentyl glycol% 1.6-hexanesiol cyclohexanedimethanol, diethylene glycol, diethylene glycol, triethylene glycol,
Tripropylene glycol, glycerin, low molecular weight polyether polyol.

Component (C) consists of a non-yellowing polyisocyanate or a modified product thereof. Modified products and isocyanate group-containing prepolymers can also be used.However, if the isocyanate group content in component (C) decreases, the reactivity of the composition decreases, so if the isocyanate group in component (C1) is The content is required to be at least 5% by weight, preferably 10% by weight or more.Non-yellowing polyisocyanate is a polyisocyanate that does not have an isocyanate group directly bonded to an aromatic nucleus, and contains aromatic compounds such as xylylene diisocyanate. Aromatic polyisocyanates having isocyanate groups that are not directly bonded to the nucleus are also a type of non-yellowing polyisocyanate.Alicyclic or aliphatic polyisocyanates are preferably used.Specific examples of non-yellowing polyisocyanates Examples are shown below, but are not limited to these.

Alicyclic polyisocyanate: isophorone diisocyanate, cyclohexane-1,4-diisocyanate, 1.
4-methylenebis(cyclohexyl isocyanate)
, 1.3-bis(isocyanatomethyl)cyclohexane, bicyclohebutane triisocyanate.

Aliphatic polyisocyanate: hexamethylene diisocyanate, 2,2.4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 1,6.11
-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3.
6-hexamethylene triisocyanate, lysine ester triisocyanate.

Aromatic polyisocyanates: xyso-1/diisocyanate, α, α, α゛, α゛-tetramethylxylylene diisocyanate.

Examples of modified products include prepolymer type modified products, multimerized products, carbodiimide modified products, urea modified products, vinyl 1 knot modified products, and allophanate modified products. These can of course be used alone or as a mixture with unmodified substances. Of course, two or more of these can be used in combination. Multimerized forms include dimerized forms and nurate modified forms.

Preferred modified products include prepolymer-type modified products, nurate modified products, and urea modified products. The prepolymer type modified product is preferably a polyisocyanate modified with a low molecular weight and/or high molecular weight polyol, and can be modified with the above-mentioned active hydrogen compound having an amino group.
Preferably, those modified with polyol are used. As the polyol, the above-mentioned high-molecular-weight polyols and low-molecular-weight polyols are preferable.As the low-molecular-weight polyol, in addition to the above-mentioned polyols, polyols that are solid at room temperature such as trimethylolpropane can also be used. If a large amount of high molecular weight polyol is used for modification, the isocyanate group content of the produced prepolymer will decrease, which is undesirable.
Therefore, it is necessary to modify the isocyanate group content within a range that does not decrease the content.

Component (C) is a catalyst component, which essentially includes at least one of a lead compound catalyst and a bismuth compound catalyst. This catalyst can be used in combination with other catalysts. As the lead compound catalyst or the bismuth compound catalyst, a known catalyst that promotes the reaction between an isocyanate group and an active hydrogen-containing group can be used. For example, the aforementioned Special Publication No. 54-15599
The publication describes a lead compound catalyst, and
JP-A-35608 describes a bismuth compound catalyst. These catalysts are also described in the following literature.

Written by J, H, 5unders, K, C, Fr1sch.

rPolyurethanes, Chemistry
and TeehnologyJJohn WH
y & 5ons, Inc, NY (196
2) J, Robir++s, Journal of A
pplied Polyg+orScience,
Vol 19. p 821-831 (1965) Preferred lead compound catalysts include lead carboxylate, tetraalkyl lead, alkyl lead carboxylate, etc. Lead carboxylate is particularly preferred. Preferred bismuth compound catalysts include bismuth carboxylate, alkyl carboxylate, etc. (or aryl) bismuth, trialkyl (or aryl) bismuth, and bismuth carboxylate is particularly preferred.
As the carboxylic acid in lead carboxylate and bismuth carboxylate, aliphatic, alicyclic, or aromatic mono- or polycarboxylic acids having 20 or less carbon atoms are suitable. Particularly preferred are aliphatic or alicyclic monocarboxylic acids having 1 to 12 carbon atoms, and suitable carboxylic acid salts are those represented by the following.

MI0COR).

When M is lead, m is usually 2, and when M is bismuth, m
is usually 3 or 5. (OCOR) is a residue of a carboxylic acid, and in the case of a polycarboxylic acid, (OCOR) may be cyclic.

Component (1) may further contain a catalyst other than those mentioned above. A typical other catalyst is an organometallic compound catalyst.

For example, organotin compounds such as stannath octoate and dibutyltin dilaurate can be used. In some cases, a tertiary amine catalyst may also be used.

In the composition of the present invention, the ratio of component (B) to 100 parts by weight of component (A) is preferably 2 to 30 parts by weight.
More preferably, it is 3 to 20 parts by weight.

If the amount of component (B) is too large or too small, the physical properties of the cured coating film will be insufficient. In addition, component (A) and component (
The equivalent amount of component (C) used relative to the total equivalent amount of B) is 0.
7 to 1.4 equivalents are preferred, more preferred equivalents are 0°8
~1°3 equivalent. In some cases, component (C) can be used in a higher equivalent amount (for example, an excess equivalent portion can be nulated by using a trimerization catalyst such as an isocyanate group). However, from the viewpoint of the physical properties of the cured coating film, it is preferable to use component (C) in the above equivalent proportion.
It is preferably 0.1 to 5 parts by weight based on 100 parts by weight, and in particular, the total amount of the lead compound catalyst and bismuth compound catalyst is preferably 0.2 to 3 parts by weight based on the component (Al).

The composition of the present invention is a composition containing the above-mentioned four essential components, but may further contain other components as necessary. Examples of other components include a stabilizer, a filler, a coloring agent, a solvent, There are surfactants, etc. Stabilizers include antioxidants, ultraviolet absorbers, and light stabilizers, such as hindered phenol-based, benzotriazole-based, benzophenone-based, phosphoric acid ester-based, and hindered amine-based stabilizers. Fillers include calcium carbonate, silica, clay, and alumina, and colorants include titanium white, carbon black, and other pigments and dyes.

The composition of the present invention is usually used in a two-component form. That is, it is used in a method in which component (C) and a mixture of other components are mixed and applied immediately before being applied to the inner surface of the mold. In particular, it is preferable to mix the two liquids immediately before spraying and spray, or to spray the two liquids individually and apply them to the inner surface of the mold while mixing.The thickness of the coating film applied to the inner surface of the mold is particularly limited. 0.0! ~1■, especially 0.
05 to 0.51 is preferable. The mold during application of the composition does not need to be particularly heated, but may be heated.

A synthetic resin is then molded using a mold having a coating film formed using the composition of the present invention to obtain a synthetic resin molded product having a skin. Examples of the synthetic resin include polyurethane foam, polyurethane urea foam, and polyurea foam. Preferred are synthetic resins that can be molded with foam, polyisocyanurate foam, polystyrene foam, unsaturated polyester resin foam, and other molds.

These are manufactured by foaming liquid or beaded raw materials in a mold. In particular, foamed synthetic resins obtained by reacting a yellowing polyisocyanate with an active hydrogen compound as described above, such as polyurethane foam, polyurethane urea foam, polyurea foam, and urethane-modified polyisocyanurate foam, are particularly preferred.These foams are flexible polyurethane foams. A foam having elasticity such as a semi-rigid polyurethane foam or the like is preferable. In addition to foamed synthetic resin, it can also be applied to the case where molded products of polyurethane elastomer, polyurethane urea elastomer, and other elastomers are molded using a mold.

[Example] Compositions shown in Tables 1 and 2 (comparative examples) below were manufactured using the following raw materials. Note that the composition is expressed in parts by weight.

1) High molecular weight active hydrogen compound polyol (a); polyoxypropylene triol having a molecular weight per hydroxyl group of 1930.

Aminated polyol (n): An amino group-containing active hydrogen compound having a molecular weight of 1670 per active hydrogen-containing group obtained by converting 9B% of the water groups of polyoxypropylene triol into primary amino groups.

Aminated polyol (8): An amino group-containing active hydrogen compound having a molecular weight of 2340 per active hydrogen-containing group obtained by converting 26% of the hydroxyl groups of polyoxybupyrene triol into primary amino groups.

2) Low molecular weight active hydrogen compound EG: Ethylene glycol DEC diethanolamine IPDA: Isophorone diamine MTDA: Menthanediamine TEA: Triethanolamine 3) Polyisocyanate IPDI: Isophorone diisocyanate modified HMDI
: Nurate-modified hexamethylene diisocyanate (manufactured by Nippon Polyurethane Co., Ltd., trade name "Coronate EHJ") Brepolymer: Modified prepolymer produced as follows (Isocyanate-1 group content: 12.69% by weight) IPDI ( 30 parts of tripropylene glycol and 0.006 parts of dibutyl silk dilaurate were added to a mixture of 60 parts (by weight, the same applies hereinafter) of isocyanate equivalent (111) and 40 parts of nurate-modified IPDI (isocyanate equivalent 244), and the mixture was reacted at 80'C for 6 hours. What I got by doing it.

Prepolymer ■2 Modified prepolymer below (Isocyanate group content: 14.2% by weight) Urea-modified IPDI and IP
Mixture of III (isocyanate equivalent weight 136) 100
Polyoxypropylene glycol (molecular weight 3720
) 100 parts and 0.006 parts of dibutyltin dilaurate were added and reacted at 80°C for 6 hours.

Prepolymer ■: The following modified prepolymer (isocyanate group content: 16.1% by weight) 1,4-methylenebis(
50 parts of polycaprolactone glycol (molecular weight 540) and 0.004 parts of dibutyltin dilaurate were added to 100 parts of cyclohexyl isocyanate) and reacted at 80°C for 6 hours.

4) Catalyst Tin catalyst Nidibutyltin dilaurate Bismuth catalyst: Bismuth-2-ethylhexanate Lead catalyst: Lead naphthenate Among the raw materials shown in Table 1 below, only polyisocyanate is one component, and a mixture of other raw materials is the other component. As an ingredient, 2
Sprayed with a liquid temperature spray machine. The composition was applied to the inner surface of a polyurethane foam mold heated to 70°C to a thickness of 0.
．． After the coating film had hardened, a flexible polyurethane foam stock solution with the following composition was injected into the mold and held at 70°C for 4 minutes to foam and harden to form a polyurethane foam molded product with a skin. .

Polyether triol with hydroxyl value Z8 and oxyethylene group at the end 100 parts by weight Ethylene glycol 9 Triethylenediamine solution 4. o Trichlorofluoromethane
15〃TDI polyisocyanate index 1
05 Evaluation shall be carried out as follows.

Flow stop time: Using a polyethylene container, the time required for the viscosity to reach 500,000 cps as measured by a torque meter.

exterior: O: The surface has a uniform appearance and the texture is good.

Δ: The surface looks good, but some tack remains.

×: Bulges appear on the surface and tack remains.

XX: A good coating film was not formed.

Table 2 [Effects of the Invention] When the composition of the present invention is sprayed onto the inner wall of a foamed plastic mold, it initially has a chicken-like property and does not drip.
Moreover, the effect of rapidly curing and providing a polyurethane urea skin with excellent light resistance and yellowing resistance has been recognized.

Claims (1)

[Claims] 1. A reaction-curable resin composition for forming a skin on the inner surface of a mold before molding a synthetic resin in the mold, comprising at least one of the following (A) to (D). A reaction-curable resin composition containing all four components as essential components. Component (A): has an average of 1.8 to 8 active hydrogen-containing groups per molecule and has an average molecular weight per active hydrogen-containing group at least one type of active hydrogen-containing group selected from a primary amino group, a secondary amino group, and a hydroxyl group. 300 or more, and at least a part of the high molecular weight active hydrogen compound is a compound containing at least one of the above amino groups, and the component (A ) A component in which the ratio of amino groups to the total number of active hydrogen-containing groups is 5 to 100%. Component (B): has an average of 2 to 6 active hydrogen-containing groups per molecule of at least one type of active hydrogen-containing group selected from primary amino groups, secondary amino groups, and hydroxyl groups, and has a molecular weight per active hydrogen-containing group of less than 300. at least one low molecular weight active hydrogen compound that is
and at least a part of the low molecular weight active hydrogen compound is an amine-based active hydrogen compound having a tertiary amino group that is not an active hydrogen-containing group or an amino group that is the above-mentioned active hydrogen-containing group; A component in which the proportion of the amine-based active hydrogen compound in (B) is 3 to 100% by weight. Component (C): A component consisting of at least one type of non-yellowing polyisocyanate or its modified product and having an isocyanate group content of 5% by weight or more. Component (D) A catalyst for promoting the reaction between an active hydrogen-containing group and an isocyanate group, at least a part of which is a catalyst selected from a lead compound catalyst and a bismuth compound catalyst. 2. Component (A) as a whole has an average number of active hydrogen-containing groups per molecule of 2 to 6, a molecular weight per active hydrogen-containing group of 600 to 4000, and a proportion of amino groups of 15 to 90%.
The composition according to claim 1. 3. Component (B) or at least one amine-based active hydrogen compound having 2 to 4 active hydrogen-containing groups and a molecular weight per active hydrogen-containing group of 200 or less, or the amine-based active hydrogen compound 2. The composition according to claim 1, comprising a mixture of other low molecular weight active hydrogen compounds, wherein the proportion of said amine-based active hydrogen compound in component (B) is 10 to 100% by weight. 4. Component (C) comprises at least one type of aliphatic or alicyclic polyisocyanate or a modified product thereof, and the content of isocyanate groups in component (C) is 10% by weight or more, Claim 1 Compositions as described. 5. The composition according to claim 1, wherein component (D) essentially includes at least one of a lead salt of a carboxylic acid or a bismuth salt of a carboxylic acid.