JPS59166523A - Liquid diene polymer composition - Google Patents

Abstract

PURPOSE:To provide the titled composition composed of specific components such as liquid diene polymer containing active hydrogen, aluminum hydroxide, etc., having low viscosity, good workability, and excellent weather resistance, mechanical characteristics and colorability, and useful as a water-proofing material, coating material, etc. CONSTITUTION:The objective composition is prepared by compounding (A) a liquid diene polymer containing active hydrogen (e.g. butadiene homopolymer) with (B) aluminum hydroxide and/or calcium bicarbonate, (C) titanium oxide (e.g. titanium dioxide) and (D) an organic polyisocyanate compound (e.g. tolylene diisocyanate). Preferably, the sum of the components B+C is 10-200pts.wt. per 100pts.wt. of the component A, and the weight ratio of B:C is 93:7-40:60.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a liquid diene polymer composition, and more specifically, a liquid diene polymer composition that has low viscosity, good workability, and excellent weather resistance, various mechanical properties, and colorability. Regarding.

Conventionally, liquid diene polymers containing active hydrogen groups such as hydroxyl groups are well known, and polyurethane compositions containing organic isocyanate compounds have low viscosity and good workability. A cured polyurethane product is obtained and is used for various purposes. However, although the polyurethane cured product obtained here has excellent low-temperature properties, heat resistance, water resistance, etc., it has the drawback of insufficient mechanical properties. Therefore, as a method of improving mechanical properties, a reinforcing filler such as carbon black or white carbon (silica) is added to the material. However, although this method improves the mechanical properties of the cured polyurethane product,
The viscosity of the composition containing the reinforcing filler becomes extremely high and the workability is significantly reduced, so it could not be used in fields such as coating materials and sealing materials that require fluidity during work. Therefore, in the field of coating materials and the like, methods have been proposed that use heavy calcium carbonate or aluminum hydroxide, which cause relatively little increase in viscosity. However, although compositions containing these materials can improve workability, the resulting cured product has very poor weather resistance, which has greatly limited its field of use. As described above, a liquid diene-based polymer composition with satisfactory properties has not yet been obtained.

Therefore, the present inventors conducted intensive studies to develop a composition with improved mechanical strength while maintaining the good workability of a liquid diene polymer containing active hydrogen groups, and as a result, they completed the present invention. I ended up doing it.

That is, the present invention provides (4) a liquid diene polymer containing active hydrogen groups, (B) aluminum hydroxide and/or heavy calcium carbonate, (C) titanium oxide, and (2) a liquid diene polymer comprising an organic polyisocyanate compound. A composition is provided.

In the present invention, (4) the active hydrogen group-containing liquid diene polymer is the base of the composition according to the present invention, and
It is a liquid diene polymer having active hydrogen groups such as hydroxyl groups, amine groups, imino groups, carboxyl groups, and mercapto groups at the molecular ends. As the liquid diene polymer, those having a number average molecular weight in a wide range of 300 to 30,000 can be used, and particularly preferably diene polymers and diene copolymers having 500 to 10,000 carbon atoms and 4 to 12 carbon atoms, and diene copolymers thereof. There is a copolymer of a diene monomer and an α-olefinic addition polymerizable monomer having 2 to 22 carbon atoms.

It also includes those modified by adding an unsaturated carboxylic acid such as maleic anhydride or a derivative thereof to these liquid diene polymers. Specifically, butadiene homopolymer and isoprene homopolymer.

Examples include butadiene-styrene copolymer, butadiene-isoprene copolymer, butadiene-acrylonitrile copolymer, phtadiene-2-ethylhexyl acrylate copolymer, buk'diene-n-octadecyl acrylate copolymer, and the like. These liquid diene polymers can be produced, for example, by reacting a conjugated diene monomer in a liquid reaction medium under heating in the presence of hydrogen peroxide. The average number of functional groups of the liquid diene polymer thus obtained is 1.7 to 30.
It is.

Among these liquid diene polymers, polymers or copolymers having a viscosity of 5,000 poise (30° C.) or less and a microstructure containing 1,4-bonds of 50% or more are preferably used.

Next, ω) aluminum hydroxide and/or heavy calcium carbonate are inorganic fillers, and are blended primarily for the purpose of improving the mechanical strength of the cured product resulting from the curing reaction of the resulting composition. ...) As the components, aluminum hydroxide and heavy calcium carbonate may be used alone, or a mixture of aluminum hydroxide and heavy calcium carbonate may be used. Aluminum hydroxide may or may not have water of crystallization, and can be used without particular limitation. Ground calcium carbonate can also be used without particular restriction. Here, ω) the above-mentioned aluminum hydroxide, an inorganic filler other than heavy calcium carbonate,
For example, if carbon black, silica, or precipitated calcium carbonate is used, the mechanical strength of the cured product will improve, but the viscosity of the composition will increase, and even if (0) titanium oxide, which will be described later, is added, the viscosity increase will not be satisfied. cannot be suppressed to the extent possible.

On the other hand, (C) titanium oxide, like component ω), plays a role in improving the mechanical strength of the cured product obtained from the composition, and at the same time, plays a role in suppressing the increase in viscosity of the composition and maintaining it at a relatively low viscosity. Also fulfills. Further, in particular, the combination of titanium oxide significantly suppresses deterioration of physical properties of the cured product obtained from the composition of the present invention due to ultraviolet irradiation. Here, (0) titanium oxide includes divalent, trivalent, or tetravalent titanium oxides, and any of these can be used, but usually tetravalent titanium oxide (titanium dioxide T]02) is used.

In the present invention, the above-mentioned ω) is used as an inorganic filler.

It is necessary to use component (0), namely (I3) aluminum hydroxide and/or heavy calcium carbonate, and (C) titanium oxide together. If one of the two components is missing, or if another type of filler is used as described above, the desired physical properties cannot be imparted to the composition and the cured product obtained therefrom.

The blending ratio of the components (B) and (0) above depends on the intended use of the composition.

Required properties 1 may be determined as appropriate in consideration of workability, but generally (A) liquid diene copolymer containing active hydrogen groups 10
Based on 0 parts by weight, the total amount of component 0]) and component (0) may be 5 to 500 parts by weight, preferably 10 to 200 parts by weight. In addition, there is no particular restriction on the blending ratio between components (B) and (0), but usually component (B): component (C) -9
8:2 to 20:80 (weight ratio), preferably 93 nia to
The ratio is 40:60 (weight ratio).

In the present invention, various additives such as short-chain polyols and polyamines may be added to improve the mechanical properties of the cured product, if desired. Here, examples of the polyol and polyamine include 1,4-butanediol, trimethylolpropa-7, ethylene glycol, a 3-mol ethylene oxide adduct of bisphenol A, and ethylene diamine.

Examples include triethylenediamine and N,N-bis(2-hydroxypropyl)aniline.

Next, examples of the organic polyisocyanate compound (9) used in the present invention include tolylene diisocyanate, diphenylmethane diisocyanate, and liquid modified products of diphenylmethane diisocyanate.

Hexamethylene diisocyanate. Xylylene diisocyanate, cyclohexane phenylene diisocyanate, chlorophenylene diisocyanate, naphthalene-1
, 5-diisocyanate, xylylene-2,2'-diisocyanate, isopropylbenzene-2,4-diisocyanate, polymethylene polyphenylisocyanate, triphenylmethane triisocyanate, tris-4
-phenylinocyanate thiophosphate-), 3.3?
4.4'-Diphenylmethane tetraisocyanate.

Examples include an addition reaction product of polypropylene glycol or triol and tolylene diisocyanate, an addition reaction product of 1 mol of trimethylolpropane and 3 mol of tolylene diisocyanate, and a prepolymer of the diene polymer and polyincyanate.

The amount of this (g) organic polyisocyanate compound is:
The equivalent ratio (Nco group/active hydrogen group) of the NCo group and (4) the active hydrogen group-containing liquid diene polymer or the total active hydrogen groups of the polyol, polyamine, etc. when used together is 05
Q may be determined to be in the range of ~20, preferably Q, in the range of 6 to 1.6. This range varies depending on the use of the composition of the present invention, and in order to obtain a completely cured product,
Further, in applications where tackiness, adhesion, etc. are required, it may be set to about 0.6 to 0.9.

In the composition of the present invention, di-n-butyltin dilaurate is further used to accelerate the curing reaction.

Stanus octoate, triethylenediamine.

Urethane catalysts such as diethylenediamine, triethylamine, naphthenic acid metal salts, and octylic acid metal salts can also be used. In addition, plasticizers such as dioctyl phthalate and dibutyl phthalate; modifiers such as process oils, solvents, bituminous substances, and adhesive resins; antioxidants, anti-aging agents, 1 coloring agent, 1 blowing agent, etc., as appropriate depending on the purpose of use, etc. It can also be added.

As described above, the composition according to the present invention can be obtained by blending the above-mentioned components. Blending method.

There are no particular restrictions on the order of blending, but for example, (4) the active hydrogen group-containing liquid diene polymer and the fillers (B) and (0) are mixed using a paint mill roll or the like, and then the organic Examples of methods include adding a polyisocyanate compound and stirring.

In this way, the liquid diene polymer composition of the present invention obtained by using a combination of aluminum hydroxide and/or heavy calcium carbonate and (0) titanium oxide as a photonic agent has a low viscosity. The rise remains low. Therefore, workability and moldability are good. Furthermore, the resulting cured product has significantly improved mechanical strength, excellent elongation properties, and extremely good weather resistance. In addition, it has excellent coloring properties and shading power, and can be filled with a large amount of filler, making it highly economical.

Therefore, the polymer composition of the present invention can be used mainly in the field of civil engineering and construction, such as various general molded products, molded products such as cast products 2 foams, and sheet-like molded products by continuous molding, such as waterproof materials and anti-vibration materials. can do. In addition, it can be widely and suitably used in various fields such as various coating materials, anticorrosive materials, paints, sealing materials, fiber coating and impregnating agents, pressure-sensitive adhesives, and adhesives.

Next, the present invention will be explained in more detail with reference to Examples 0 Examples 1 to 8 and Comparative Examples 1 to 3 A predetermined amount of filler was added to the hydroxyl group-containing liquid polybutadiene shown in Table 1, and preliminary stirring was performed by hand. Thereafter, the mixture was passed through twice using three paint mill rolls (diameter 2 inches) to obtain a blend. The viscosity of this formulation is shown in Table 1.

Then, 12.25 parts by weight of 4,4'-diphenylmethane diincyanate liquid modified product (NOO content 28..74% by weight) (N0O10H=1.05
) and 0.05 parts by weight of di-n-butyltin dilaure) were added and thoroughly stirred, and then cured under heat and pressure at 120°C for 1 hour using a 2 x 150 x 150 m71 mold, and then heated at 70°C.
C. for 15 hours to obtain a cured sheet. The physical properties of this sheet were measured according to JIS K 6301, and the results are shown in Table 1.

In addition, this sheet's xenon weather meter shows that the
Table 1 shows the physical property measurement results after the 0-hour accelerated deterioration test.

Furthermore, the relationship between the physical properties of this cured sheet before and after accelerated deterioration and the blending ratio of titanium oxide in the inorganic photonic agent is shown in FIGS. 1 and 2.

[Brief explanation of the drawing]

Figures 1 (a,) and (b) show the relationship between the tensile strength and elongation of the cured sheet before and after accelerated deterioration and the blending ratio of titanium oxide in the inorganic filler when aluminum hydroxide is used as the component ω). It is a graph showing a relationship. Figures 2 (a) and (b) show the relationship between the tensile strength and elongation of the cured sheet before and after accelerated deterioration and the blending ratio of titanium oxide in the inorganic filler when heavy calcium carbonate is used as component 03). It is a graph showing a relationship. Patent applicant Idemitsu Kosan Co., Ltd.

Claims (1)

[Claims] 1. (A) liquid diene polymer containing active hydrogen groups, @aluminum hydroxide and/or heavy calcium carbonate, (
C) A liquid diene polymer composition comprising titanium oxide and (9) an organic polyisocyanate compound. 2.@The blending ratio of aluminum hydroxide and/or heavy calcium carbonate and (0) titanium oxide is 98:2 to 20:
80 (weight ratio).