JPH10130360A - Reactive hardenable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a reactive hardenable composition high in reactivity, having no problem of lowering of strength, modulus, hardness, etc., and further having excellent physical properties by using a hardener component containing a specific polyol and an aromatic amine compound. SOLUTION: This reactively hardenable composition comprises a hardener component comprising (A) a polyoxyalkylene polyol having 5-38mgKOH/g hydroxyl value X, <=0.07meq/g total unsaturated degree Y, with the proviso that when 10<X<=38, the X and Y satisfy the formula Y<=0.9/(X-10), and further having 2-8 hydroxyls and (B) a hardener component including an amine compound containing two or more primary or secondary amines bonding to an aromatic ring (preferably diethyldiaminotoluenes, etc.), (C) an isocyanate component containing polyurethane prepolymer having isocyanate end groups obtained by reacting a high molecular polyol (preferably the polyoxyalkylene polyol obtained by a method same as the component A) and a polyisocyanate compound (preferably tolylenediisocyanate) in combination.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a reaction curable composition. Reactive curable compositions comprising a combination of an isocyanate-terminated prepolymer component and a curing agent component comprising an active hydrogen compound are known. Normally, as the curing agent component, one obtained by dissolving a polyamine such as MOCA (3,3'-dichloro-4,4'-diaminodiphenylmethane) in a polyol is used. It is also known to use a mixture of a plasticizer or a polyol such as dioctyl phthalate as a curing agent component with diethyltoluenediamine or the like.

[0002]

SUMMARY OF THE INVENTION MOCA is used as a curing agent component.
When curing is carried out at room temperature using, it takes about 24 hours a day until the reaction becomes slow and usable. At low temperatures, this tendency becomes even stronger, requiring a curing time of 2 to 3 days.

[0003] It is known that when diethyltoluenediamine, which is an amine having a relatively high reaction rate, is used together with a plasticizer such as dioctyl phthalate, there is a remarkable adverse effect on adhesiveness, coatability and the like. When a general-purpose polyol is used instead of a plasticizer such as dioctyl phthalate, the unsaturated monool which is a by-product during the production of the polyol is present in the polyol. The problems include a decrease in elastic modulus, hardness, wear resistance, curability, and the like, and a problem that tack remains on the surface after molding.

[0004]

DISCLOSURE OF THE INVENTION The present invention is the following invention which solves the above problems and provides a reactive curable composition having high reactivity and excellent physical properties.

The following polyoxyalkylene polyol (a) and a curing agent component containing an amine compound having two or more primary or secondary amino groups bonded to an aromatic ring are reacted with a high molecular weight polyol and a polyisocyanate compound. A reaction curable composition comprising a combination of an isocyanate component containing the obtained isocyanate group-terminated polyurethane prepolymer.

[0006] Polyoxyalkylene polyol (a):
The hydroxyl value X (mgKOH / g) and the total degree of unsaturation Y (meq
/ G) is 5 ≦ X ≦ 38, Y ≦ 0.07, and
When 10 <X ≦ 38, the relation of Formula 1 is satisfied, and the number of hydroxyl groups is 2
And 8 polyoxyalkylene polyols. Y ≦ 0.9 / (X−10) Equation 1

In the present invention, the polyoxyalkylene polyol used as one of the curing agent components has a hydroxyl value X (mgKOH / g) and a total degree of unsaturation Y (meq / g).
Is 5 ≦ X ≦ 38, Y ≦ 0.07, and 10 <
When X ≦ 38, the polyoxyalkylene polyol has the relationship of Formula 1 and has 2 to 8 hydroxyl groups. Y ≦ 0.9 / (X−10) Equation 1

The polyoxyalkylene polyol (a)
Can be obtained by adding a cyclic ether to an initiator such as a polyhydric alcohol, a saccharide, an alkanolamine, or a polyhydric phenol in the presence of a catalyst.

As the catalyst, a catalyst capable of obtaining a polyoxyalkylene polyol having a low total unsaturation is preferable. Specific examples include a cesium-based catalyst, a rubidium-based catalyst, a diethylzinc-based catalyst, an iron chloride-based catalyst, a metal porphyrin-based catalyst, and a composite metal cyanide complex catalyst.

Examples of the cyclic ether include butylene oxide, propylene oxide, ethylene oxide and the like, preferably propylene oxide, ethylene oxide or a combination thereof.

The polyoxyalkylene polyol (a) preferably has a total degree of unsaturation of 0.05 meq / g or less.

The polyoxyalkylene polyol (a)
May be a mixture. In the present invention, a high molecular weight polyol containing the polyoxyalkylene polyol (a) is used. The polyoxyalkylene polyol (a) preferably accounts for 50 to 100% by weight, and more preferably 70 to 100% by weight of the total high molecular weight polyol.

As the high molecular weight polyol which can be used in combination,
Examples thereof include polyoxyalkylene polyols other than the above polyoxyalkylene polyol (a), polyester-based polyols, polycarbonate-based polyols, and hydroxyl-containing polydiene-based polymers.

As the amine compound, 1 is bonded to an aromatic ring.
An amine compound having two or more primary or secondary amino groups is used. As the amine compound, diethyldiaminotoluenes and 4,4′-diaminodiphenylmethane are preferred.

As the diethyldiaminotoluenes,
3,5-diethyl-2,4-diaminotoluene, 3,5
-Diethyl-2,6-diaminotoluene. Preferably, it is a mixture of 3,5-diethyl-2,4-diaminotoluene and 3,5-diethyl-2,6-diaminotoluene.

The 4,4'-diaminodiphenylmethanes include 3,3'-diethyl-4,4'-diaminodiphenylmethane, 4,4'-di (N-butylamino) diphenylmethane and 3,3'-dichloro-4. , 4'-diaminodiphenylmethane.

The ratio of the polyol and the amine compound used in the curing agent component is represented by the weight ratio of polyol / amine compound =
30/99 to 70/1 is preferred, and 40/99 to 60 /
1 is particularly preferred.

The isocyanate component used in the present invention is an isocyanate component containing a high molecular weight polyol and an isocyanate group-terminated polyurethane prepolymer obtained by reacting a polyisocyanate compound.

The high molecular weight polyol is preferably a polyoxyalkylene polyol. The polyoxyalkylene polyol is preferably a polyoxyalkylene polyol obtained by adding a cyclic ether to an initiator such as a polyhydric alcohol, a saccharide, an alkanolamine, or a polyhydric phenol in the presence of a catalyst.

The catalyst can be used without any particular limitation, such as a sodium catalyst, a potassium catalyst, a cesium catalyst, a rubidium catalyst, a diethylzinc catalyst, an iron chloride catalyst, a metal porphyrin catalyst, a composite metal cyanide complex catalyst and the like. Is mentioned.

Examples of the cyclic ether include butylene oxide, propylene oxide, ethylene oxide and the like, preferably propylene oxide, ethylene oxide or a combination thereof.

The high molecular polyol is particularly preferably a polyoxyalkylene polyol (b). Polyoxyalkylene polyol (b): hydroxyl value X
(MgKOH / g) and the total degree of unsaturation Y (meq / g)
5 ≦ X ≦ 38, Y ≦ 0.07, and 10 <X ≦
38, a polyoxyalkylene polyol having the relationship of Formula 1 and having 2 to 8 hydroxyl groups. Y ≦ 0.9 / (X−10) Equation 1

The polyoxyalkylene polyol (b) can be produced in the same manner as in the above polyoxyalkylene polyol (a). The polyoxyalkylene polyol (b) may be a mixture.

Further, a high molecular weight polyol other than the polyoxyalkylene polyol may be used in combination. Examples of such high-molecular-weight polyols include polyester-based polyols, polycarbonate-based polyols, and hydroxyl-containing polydiene-based polymers.

The polyisocyanate compound used in the present invention is preferably diisocyanate diphenylmethane containing 2,4'-diisocyanate diphenylmethane or tolylene diisocyanate (TDI). T
DI is particularly preferred.

As the TDI, there is 2,4-TDI or 2,6-TDI. Preferably, it is 2,4-TDI or a mixture thereof with 2,6-TDI. 2,4
-The mixing ratio of TDI and 2,6-TDI is 80/20 to 1
00/0 is preferred, and 90/10 to 100/0 is particularly preferred.

The diisocyanate diphenylmethane containing 2,4'-diisocyanate diphenylmethane includes 2,4'-diisocyanate diphenylmethane,
In addition, a mixture of 4,4′-diphenylmethane diisocyanate and polymethylene polyphenyl isocyanate can be used. It is preferable that the content of 2,4'-diisocyanatediphenylmethane is 5 to 60% by weight.
2,4'-diisocyanate diphenylmethane and 4,
Particularly preferred is a mixture of 4'-diisocyanate diphenylmethane.

The above-mentioned polyisocyanate may be a modified prepolymer, a modified nurate, a modified urea, a modified carbodiimide, or the like.

In the present invention, a crosslinking agent can be optionally used in combination with a high molecular weight polyol to react with the polyisocyanate compound.

As a crosslinking agent, a hydroxyl group, a primary amino group,
Alternatively, a compound having a molecular weight of 600 or less, particularly 300 or less per isocyanate-reactive group having two or more isocyanate-reactive groups such as a secondary amino group is suitable.

Such compounds can be obtained, for example, by adding a small amount of alkylene oxide to polyhydric alcohols, alkanolamines, polyamines, polyhydric alcohols, alkanolamines, sugars, polyamines, monoamines, polyhydric phenols and the like. There are low molecular weight polyether polyols. Furthermore, low molecular weight polyester-based polyols and the like can also be used.

Specifically, polyhydric alcohols such as ethylene glycol, propylene glycol, 1,4-butanediol and glycerin, alkanolamines such as diethanolamine and triethanolamine, and polyether polyols having a hydroxyl value of 200 or more are used. Can be The amount of the polyfunctional compound is not particularly limited, but may be 1 to 50 parts by weight based on 100 parts by weight of the high molecular weight polyol.
It is preferably about parts by weight. If the amount is more than this, the obtained elastomer becomes brittle, and if the amount is less, the elongation is large but the strength is weak, which is not preferable.

In the present invention, an isocyanate group-terminated polyurethane prepolymer is produced by reacting the above high molecular weight polyol, optionally a crosslinking agent and a polyisocyanate compound.

The isocyanate group-terminated polyurethane prepolymer has an excess of isocyanate groups based on active hydrogen-containing groups, that is, an isocyanate index of 150 to 25.
It can be produced by reacting to about 0.

The isocyanate group-terminated polyurethane prepolymer preferably has an isocyanate group content of 1 to 10% by weight, particularly preferably 1 to 5% by weight.

In the present invention, the ratio of the curing agent component to the isocyanate component used is such that the isocyanate index is 80-1.
Preferably, it is used so as to be 30. Especially 100
~ 120 is preferred.

A catalyst may be used to cure the reaction-curable composition of the present invention. As the catalyst, a metal compound catalyst such as an organotin compound which promotes the reaction between the active hydrogen-containing group and the isocyanate group, or a tertiary amine catalyst such as triethylenediamine is used.

In the present invention, it is also possible to use a compounding agent such as a filler, a stabilizer, a coloring agent, a flame retardant and the like, if necessary.

By curing the reaction-curable composition of the present invention, a non-foamed elastomer can be mainly molded.

The reaction-curable composition of the present invention can be used as a polyurethane for molding using a mold. It can also be used for flooring, etc.

The molded product produced by curing the reaction-curable composition of the present invention has a higher strength and elasticity than those obtained by using a polyoxyalkylene polyol having a large content of unsaturated monool, which is a conventional by-product, as a raw material. Rate, hardness,
By using a high molecular weight compound having a hydroxyl value of 28 or less, which is excellent in abrasion resistance and the like, and which has been practically impossible to produce conventionally, the elongation property is improved and it can be used for various purposes.

[0042]

EXAMPLES Table 1 shows the number f of functional groups, the hydroxyl value X (unit: mgKOH / g), and the total degree of unsaturation Y (unit: meq / g) of the polyols A to F used in the present invention.

The polyols A to C have a molecular weight of 400 to 60.
0 is a polyol produced by reacting propylene oxide with a polyoxypropylene polyol of 0 as an initiator and a zinc hexacyanocobaltate complex as a catalyst.

The polyol D uses glycerin as an initiator,
A polyol produced by reacting propylene oxide with cesium hydroxide as a catalyst. Polyol E
To F are polyols produced by reacting propylene oxide with KOH using dipropylene glycol and glycerin as initiators, respectively.

Abs were used as cross-linking agents, G to J were used as amine compounds, K to L were used as catalysts, and c to e were used as polyisocyanate compounds.

[Preparation of Prepolymer] The polyisocyanate, polyol and crosslinking agent shown in Table 3 were used in the number of parts shown in Table 3, and the isocyanate index (index) shown in Table 3 was set at 80 ° C. under a nitrogen atmosphere at 8 to 8 ° C. Reaction isocyanate group-terminated prepolymer P1 for 10 hours
P7 was synthesized. Isocyanate group content (NCO content,
(Unit:% by weight) is shown in Table 3. Hereinafter, "part" indicates "part by weight".

[Production of curing agent component] The amine compounds shown in Tables 4 to 5 are shown in the table, the polyols shown in Tables 4 to 5 are shown in the table, and dioctyl phthalate is used as the plasticizer. The hardener components Q1 to Q6 and R1 to R3 were synthesized by mixing calcium carbonate as a filler, the number of parts shown in the table, and 0.02 part of the catalyst shown in the table.

Using the above isocyanate group-terminated prepolymer and the curing agent component, processing characteristics and physical properties were evaluated. The prepolymers of the type shown in the table and the curing agent were mixed at room temperature such that the index was 110. The mixture was poured onto release paper and formed into a sheet having a thickness of about 3 mm. The physical properties of the molded sheet were evaluated.

The pot life is 10 minutes after mixing both components.
Indicates the time required to reach 10,000 centipoise (unit: minute).
The tack-free time indicates a time at which stickiness is not felt by touching the finger (unit: time) (">2" in the comparative example).
"0" indicates that stickiness is not lost even after 20 hours or more).

The hardness was represented by Shore A hardness. The tensile strength is based on JIS K6301, and the tensile strength (unit: k
g / cm ² ), elongation (unit:%) and tear strength (unit: kg / cm ² ) were measured. The results are shown in Tables 6 and 7.

The bleed test was carried out by leaving it at 40 ° C. for 10 hours and then judged by finger touch. Further, an adhesion test was performed.
A mixture of 95 parts of prepolymer P4 and 5 parts of xylene,
A liquid obtained by mixing the curing agent component Q4 at an index of 110 at room temperature was applied onto the molded sheets obtained in Examples 4 and 5 and Comparative Example 1, left at room temperature for 2 weeks, and then subjected to an adhesive strength evaluation test. Was. ○ indicates good adhesion strength, and × indicates poor adhesion.

[0052]

[Table 1]

[0053]

[Table 2]

[0054]

[Table 3]

[0055]

[Table 4]

[0056]

[Table 5]

[0057]

[Table 6]

[0058]

[Table 7]

[0059]

By curing the reactive curable composition of the present invention, it is possible to obtain a molded article having excellent physical properties without deterioration in strength, elastic modulus, hardness, abrasion resistance, etc., and to reduce the bleeding of the plasticizer. The effect that disappears or becomes very small is also recognized.

Claims (3)

[Claims] 1. A reaction between the following polyoxyalkylene polyol (a) and a curing agent component containing an amine compound having two or more primary or secondary amino groups bonded to an aromatic ring, and a high molecular weight polyol and a polyisocyanate compound. A reaction curable composition comprising a combination of an isocyanate component containing an isocyanate group-terminated polyurethane prepolymer obtained by the reaction. Polyoxyalkylene polyol (a): hydroxyl value X
(MgKOH / g) and the total degree of unsaturation Y (meq / g)
5 ≦ X ≦ 38, Y ≦ 0.07, and 10 <X ≦
38, a polyoxyalkylene polyol having the relationship of Formula 1 and having 2 to 8 hydroxyl groups. Y ≦ 0.9 / (X−10) Equation 1 2. The composition according to claim 1, wherein the isocyanate component is an isocyanate group-terminated polyurethane prepolymer obtained by reacting a high molecular weight polyol containing the following polyoxyalkylene polyol (b), a crosslinking agent and a polyisocyanate compound. Stuff. Polyoxyalkylene polyol (b): hydroxyl value X
(MgKOH / g) and the total degree of unsaturation Y (meq / g)
5 ≦ X ≦ 38, Y ≦ 0.07, and 10 <X ≦
38, a polyoxyalkylene polyol having the relationship of Formula 1 and having 2 to 8 hydroxyl groups. Y ≦ 0.9 / (X−10) Equation 1 3. The composition according to claim 1, wherein the polyisocyanate is tolylene diisocyanate.