JPS60123524A - Composition for polymer - Google Patents

Abstract

PURPOSE:To produce a composition for polymer, curable with moisture, and giving a cured product having remarkably improved mechanical properties, especially the elongation, by compounding a liquid diene polymer containing active hydrogen group with a polyisocyanate compound and a bituminous substance at specific ratios. CONSTITUTION:The objective compoisition can be produced by compounding (A) a liquid diene polymer containing active hydrogen group (having a number-average molecular weight of 300-25,000, preferably 500-10,000) with (B) a polyisocyanate compound (e.g. tolylene diisocyanate) and (C) a bituminous substance. The amounts of the components A and B are selected to give the equivalent ratio (the isocyanate group of the component B)/(the active hydrogen group of the component A) of 1-20, preferably 2-5, and the amount of the component C is 50-95wt%, preferably 70-85wt% based on the whole composition. The component A is mixed with the component C under heating, the mixture is cooled and then added and kneaded with molten hot component B, and the product is cooled to obtain the objective composition. When a prepolymer produced from the composition is applied to the object to be coated, a coating film cured with the moisture in the air can be formed.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition for polymers, and more specifically to a composition for producing a polymer through a moisture-curable prepolymer, which improves the mechanical properties of the resulting cured product, especially elongation. The present invention relates to a composition for polymers which has been significantly improved in the field.

Conventionally, liquid diene polymers containing active hydrogen groups.

Compositions consisting of bituminous materials and polyisocyanate compounds are known and are used in riverside applications where adhesion, tackiness, etc. are required. However, this composition does not exhibit moisture curability because the active hydrogen group-containing liquid diene polymer and the polyisocyanate compound are blended so that the isocyanate group/active hydrogen group (equivalence ratio) is less than 1. Moreover, the cured product obtained by curing this composition was poor in mechanical properties, particularly in elongation.

Therefore, the present inventors have worked diligently to develop a polymer composition that has moisture-curing properties that harden when left in the atmosphere, and that provides a cured product with excellent mechanical properties, especially elongation. As a result of research, a composition containing a liquid diene polymer containing active hydrogen groups, a polyisocyanate compound, and a bituminous substance in a specific ratio, and in particular, a composition with an equivalent ratio of isocyanate groups/active hydrogen groups in a specific range, has been found to achieve the above purpose. We have discovered that this can be achieved, and based on this knowledge, we have completed the present invention.

That is, the present invention comprises an active hydrogen group-containing liquid diene polymer (hereinafter referred to as component (A)), a polyisocyanate compound (hereinafter referred to as component (B)), and a bituminous substance (hereinafter referred to as component (0)). ) from! 7N The blending amount of component (B) is isocyanate group/active hydrogen group (equivalent ratio)
= 1 to 20, and the amount of bituminous material added is 5
It is a composition for heavy weight polymers with a weight ratio of 0 to 95%.

In the present invention, the active hydrogen group-containing liquid diene polymer, which is component (A), has a number average molecular weight of 1,000 ml, which has active hydrogen groups such as a hydroxyl group, an amine group, an imide group, a carboxyl group, and a mercapto group at the molecular end. is a liquid diene polymer having a molecular weight of 300 to 25,000, preferably 500 to 10,000. These liquid diene polymers include diene polymers and diene copolymers having 4 to 12 carbon atoms, and copolymers of these diene monomers and α-olefinic addition polymerizable monomers having 2 to 22 carbon atoms. There is. Specific examples include butadiene homopolymer, isoprene pomopolymer, butadiene-styrene copolymer, butadiene-isoprene copolymer, butadiene-acrylonitrile copolymer, butadiene-2-ethyl-hexyl acrylate copolymer, butadiene-n-octadecyl acrylate copolymer, etc. I can do it.

Next, the polyisocyanate compound of the component (B) of the present invention is an organic compound having two or more isocyanate groups in one molecule, and the active hydrogen group-containing liquid diene polymer has It has an incyanate group that is reactive towards hydrogen-containing functional groups. Such polyisocyanate compounds are well known, and may be in the form of a prepolymer having isocyanate groups at the ends obtained by reacting a polyol and a polyisocyanate in advance. Examples of polyisocyanate compounds include the usual aromatic, aliphatic and cycloaliphatic ones, such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, liquid modified diphenylmethane diisocyanate, polymethylene polyphenylisocyanate,
Xylylene diisocyanate, cyclohexyl diisocyanate, cyclohexanephenylene diisocyanate, naphthalene-1,5-diisocyanate.

Examples include isopropylbenzene-2,4-diisocyanate and addition reaction products of polypropylene glycol and tolylene diisocyanate.

Furthermore, the bituminous substance that is component (0) of the present invention is not particularly limited, and examples thereof include straight asphalt, semi-brown asphalt, blown asphalt, or a mixture thereof, and preferably straight asphalt that does not require high temperatures for processing. Alternatively, straight asphalt and other asphalt should be used together.

The polymer composition of the present invention consists of the above components (A), (B), and (0), and the blending amount of component (B) is equal to the isocyanate group contained in component (E) and the component (A). The equivalent ratio of active hydrogen groups is isocyanate group/active hydrogen group =
The number is selected from 1 to 20, preferably from 2 to 5. If this equivalent ratio is less than 1, the viscosity will be very high, and if it exceeds 20, the moisture curing rate will be low and foaming will occur easily during curing.

The amount of component (C) to be blended is selected to be 50 to 95% by weight, preferably 70 to 85% by weight of the entire composition. If this amount exceeds 95% by weight, the rubbery properties will be lost, and if it is less than 50% by weight, the compatibility between the bituminous material and the liquid diene polymer containing active hydrogen groups will be lost, resulting in partial It gels and becomes non-uniform.

The polymer composition of the present invention basically consists of the above three components, but other additives may be added as necessary.) For example, in order to improve the physical properties of the composition, 1,
4-butanediol, trimethylolpropane, ethylene glycol, ethylene oxide of bisphenol A 5
molar adduct.

N,N-bis(2-hydroxypropyl)anisono, etc. can be added. In addition, plasticizers such as dioctyl phthalate, aromatic, naphthenic, and paraffinic softeners are added as viscosity modifiers, tackifying resins are added to adjust adhesive strength, and carbon black and calcium carbonate are also added. Examples include fillers such as , clay, and cruzi, phenolic resins, xylene formaldehyde resins, rosins, hydrogenated rosins, Ririn resins, fatty IMs, and aromatic petroleum resins. Additionally, storage stabilizers such as benzoyl chloride, hardening accelerators such as dibutyltin dilaurate, stannous octoate, and polyethylene diamine, antiaging agents to improve weather resistance, and silicone compounds as antifoaming agents can be added. .

The polymer composition of the present invention can be obtained by mixing and kneading the raw materials as described above. Kneading may be carried out by a commonly used method, for example using a Banbury mixer or the like at 0 to 120°C, preferably 10 to 90°C.
This can be carried out by melting and mixing at °C for 0.5 to 48 hours, preferably 6 to 16 hours. Preferably, the active hydrogen group-containing liquid diene polymer and the bituminous material are heated and stirred, then cooled, and then a heated and molten polyisocyanate compound is added, kneaded, and cooled to obtain the polymer composition of the present invention.

The polymer composition of the present invention includes a moisture-curable prepolymer, and by curing the prepolymer with atmospheric moisture, a cured polymer can be obtained. This composition is mainly used as a waterproofing agent, adhesive, anticorrosive paint, etc. When used for these purposes, a prepolymer is prepared from the composition and used alone or mixed with an appropriate solvent as necessary. Later, a spray gun and a brush.

It may be applied to the object using a roll coater, a flow coater, or the like. The prepolymer forms a cured film upon exposure to atmospheric moisture. The film thus formed has excellent mechanical properties, particularly elongation, and is extremely useful for the above-mentioned applications.

Next, the present invention will be explained in detail with reference to examples.

Examples 1 to 7 and Comparative Examples 1 to 4 8 for each mixture of active hydrogen group-containing liquid diene polymer, bituminous substance, solvent, chain extender, and plasticizer shown in Table 1.
After heating and melting the polyisocyanate compound to 0°C, add 75≦7JD with vigorous stirring, and then cool to room temperature for 2
Holds time.

Next, heat and stir at 80°C for 5 hours to prepare Breho IJ Y -
It's a good deal. This prepolymer was coated on a glass plate to a thickness of two sections, and left to flal for two weeks in an environment of 25° C. and 60% humidity to obtain a cured product. Table 1 shows the measurement results regarding the manufacturing conditions of the composition and the physical properties of the cured product.

・l・-・Liquid rubber (poly bd B-45HT
, made by Idemitsu Petrochemical ■), hydroxyl group content o, 79 me
q/! i', several molecules ii' (28 (10 2... Straight asphalt (manufactured by Idemitsu Kosan ■) Gold 1 degree 6o/8° 3... Toluene-4... 4,41-diphenylmethane diisocyanate, Isocyanate group content 55.6% by weight φ5...
・Dioctyl 7-talate...7 in N,N-bis(2-hydroxylpropyl)aniline...Patent applicant in accordance with J Engineering S K-6501
Idemitsu Petrochemical Co., Ltd.

Claims (1)

[Scope of Claims] 1. A liquid diene polymer containing an active hydrogen group, a polyisocyanate compound and a bituminous substance, the amount of the polyisocyanate compound being isocyanate group/active hydrogen group (equivalent ratio) = 1 to 2o. A composition for a polymer having an amount of 50 to 95% by weight of a bituminous substance. Z The composition according to claim 1, wherein the active hydrogen group of the active hydrogen group-containing liquid diene polymer is a hydroxyl group. 3. The composition according to claim 1, wherein the bituminous material is asphalt.