JPS58196227A - Liquid diene type polymeric composition - Google Patents

Abstract

PURPOSE:The titled composition, consisting of a liquid diene type polymer, having a specific molecular weight, and containing groups having an active hydrogen, a tackifier resin and an organic polyisocyanate compound, having improved operability, moldability and compatibility, and capable of giving cured articles having improved strength and hardness, etc. CONSTITUTION:A composition obtained by incorporating (A) a liquid diene type polymer having 300-2,000, preferably 500-1,800, number-average molecular weight, and containing groups having active hydrogen, e.g. polybutadiene homopolymer or butadiene-styrene copolymer having preferably average 1.7-3 functional groups, with (B) 10-2,000pts.wt., based on 100pts.wt. component (A), tackifier resin, e.g. petroleum resin, rosin or terpene, having preferably 500- 5,000 molecular weight, and (C) an organic polyisocyanate compound, e.g. tolylene diisocyanate, and if necessary 0-50pts.wt. 1,4-butanediol thereto. USE:Waterproof sheets, pressure-sensitive adhesives, coating materials, adhesives, waterproofing agents, etc.

Description

[Detailed description of the invention] The present invention relates to a liquid diene polymer composition.

Conventionally, tackifier resins such as various petroleum resins, rosins, terpenes, and coumaron-indene resins have been used with various binders,
It is used in many fields such as paints, adhesives, pressure-sensitive adhesives, and waterproofing agents. Also known are rubber-modified tackifying resins that are modified by mixing thermoplastic rubbers with these tackifying resins.

However, these tackifying resins have a relatively low softening point and have the major drawback of causing flow upon increasing temperature. In order to overcome this drawback, it has been proposed to effect crosslinking by blending a liquid diene polymer having a terminal hydroxyl group with a polyisocyanate compound as a crosslinking agent.

However, liquid diene polymers commonly used in the past have relatively high number average molecular weights and high viscosity, so they not only have poor uniform mixing properties and workability when mixed with tackifying resins, but also Some types of tackifier resins have major drawbacks, such as separation of two phases that are completely compatible, making it impossible to obtain molded products. In addition, the effect of improving the physical properties of the cured product is not necessarily sufficient, and there are significant restrictions on its use and application fields.

The present inventors have conducted extensive studies on compositions made by blending tackifier resins with liquid diene polymers, and have found that even if a large amount of tackifier resin is blended, the cured product remains in a liquid state. By selecting a liquid diene polymer with relatively low molecular weight, it has physical properties that are comparable to those of a diene polymer that is cured alone, and has improved workability.
In addition to improving moldability, we have surprisingly discovered that not only strength and hardness are significantly improved, but also compatibility, tear strength, etc. are significantly improved. And between these, the number average molecular weight is approximately 200.
We found that there is a large difference between 0 and 0. The present invention has been made based on these findings.

That is, the present invention has a number average molecular weight of 300 to . The present invention relates to a liquid diene polymer composition comprising a liquid diene polymer containing 2000 active hydrogen groups, a tackifying resin, and an organic polyisocyanate compound.

The composition of the present invention maintains the excellent properties of the tackifying resin by incorporating the tackifying resin during curing by the urethane reaction between the active hydrogen group-containing liquid diene polymer and the organic polyisocyanate compound. However, it improves thermal properties, especially fluidity due to temperature rise. Moreover, by selecting a liquid diene polymer having a specific number average molecular weight, it is possible to simultaneously obtain wide improvements in various physical properties.

The present invention will be explained in detail below.

The number average molecular weight, which is the main component used in the present invention, is from 300 to
The active hydrogen group-containing liquid diene polymer of CO000 is a liquid diene polymer having an active hydrogen group such as a hydroxyl group, an amine group, an imino group, a carboxyl group, or a mercapto group at the molecular end, and whose molecular weight is It needs to be relatively low.

These liquid diene polymers have a number average molecular weight of 3
00 to 2000, preferably 500 to 72 carbon atoms, diene copolymers, and copolymers of these diene monomers and α-olefinic addition polymerizable monomers having 2 to 22 carbon atoms. There are polymers. Also,
It also includes those modified by adding unsaturated carboxylic acids such as maleic anhydride or derivatives thereof to these liquid diene polymers. Specifically, polybutadiene homopolymer, polyisozolene homopolymer, butadiene-styrene copolymer, butadiene-isoprene copolymer, butadiene-acrylonitrile copolymer, butane-coethylhexyl acrylate copolymer, butadiene-n-
Examples include octadeal acrylate copolymers. These liquid diene polymers are produced by, for example, converting a conjugated diene monomer in a liquid reaction medium to 70% of the monomer.
It can be produced by reacting with hydrogen peroxide in an amount of 1 or more under heating. The average number of functional groups of the liquid diene polymer thus obtained is 7.7 to 3.0.

Among these liquid diene polymers, a polymer having a viscosity of 50 voids/30° C. or less and a microstructure of 50% or more of l and q bonds is preferably used.

Next, examples of the tackifying resin which is another component of the composition of the present invention include petroleum resin, rosin and its derivatives, terpene, modified terpene resin, coumaron-indene resin, styrene resin, indene resin, etc. be able to. Here, petroleum resins include aromatic petroleum resins, aromatic-aliphatic petroleum resins, and aliphatic petroleum resins. Aromatic petroleum resins are the residual CS7-0° indene, vinyltoluene, and dicyclopentadiene extracted from petroleum or heavy oil fractions produced by naphtha cracking with solvents such as benzene, toluene, xylene, and furfural. Aliphatic petroleum resins are resins obtained by copolymerizing pentenes, inzolene, piperylene, etc. The aromatic-aliphatic petroleum resin is obtained by copolymerizing a mixture of 05 to C9 fractions.

Examples of rosin derivatives include hydrogenated rosin, glycerin ester, pentaerythritol ester, ethylene glycol ester nato rosin ester, and polymerized rosin.

Examples of terpenes and modified terpene resins include terpene resins (purified polymers of α-pinene and β-pinene; synthetic terpenes from C5 fractions), terpene-phenol copolymers, and the like. Coumarone-indene resins include those obtained by polymerizing coumaron, indene, styrene, etc. contained in coal tar.

In addition, examples of styrene-based resins include low-molecular styrene figurines + co-combinations of α-methylstyrene and vinyltoluene. Examples of the isozolene type include isozolene dimers.

These tackifying resins have a molecular weight of 200 to 500.
Those in the range of 0 can be preferably used.

The amount of the tackifier resin in the composition of the present invention is determined depending on the intended use and required performance of the composition.
Usually, the amount is in the range of 10 to xooo parts by weight per 100 parts by weight of the active hydrogen group-containing liquid diene polymer, for example, 70 to 500 parts by weight when used as a waterproofing agent, a waterproof sheet, or an adhesive.

70 to 1 when used as vibration isolators, paints, adhesives, etc.
000 parts by weight, 10-20 when used as track material
A range of 0.00 parts by weight is suitable.

In any case, in the composition of the present invention, even if a relatively large amount of tackifying resin is blended, the physical properties of the resulting cured product are excellent, so the blending ratio can be varied widely. This makes it possible to apply it to many fields depending on the heat resistance, cold resistance, waterproofness, adhesion/adhesiveness, etc. required for each use.

Next, examples of the organic polyisocyanate compound having an incyanate group reactive with the active hydrogen group of the active hydrogen group-containing liquid diene polymer include tolylene diisocyanate, diphenylmethane diisocyanate, a liquid modified product of diphenylmethane diisocyanate,
Hexamethylene diisocyanate, xylylene diisocyanate, cyclohexane phenylene diisocyanate $-)
.

Chlorophenyl diisocyanate, naphthalene/,
5-diisocyanate, xylylene-,2,2'-diisonanate, inglobilbenzeneco.

Dirty isocyanate, polymethylene polyphenylacetate, triphenylmethane triisocyanate, tris-guphenyl isocyanate thiophosphate, 3,3',4,4'-diphenylmethane tetraisocyanate, polyzolopylene glycol or triol and tolylene diisocyanate addition Examples of the reaction product include an addition reaction product of 1 mole of trimethylolpropane and 3 moles of tolylene diisocyanate, and a prepolymer of the diene polymer and polyincyanate. ``The blending amount of this organic polyisocyanate compound is based on the equivalent ratio of HC (+4 to active hydrogen groups (NCO/
active hydrogen group) in the range 5-2.0, preferably 0.5
~/, 5, and may be determined as appropriate depending on the application and the like. Note that this equivalent ratio is usually 0.9! ; However, in the field of pressure-sensitive adhesives and adhesives, it is preferably 0.95 or less, preferably O,SO ~ 0.9! Favorable performance can also be obtained by;

The liquid diene polymer composition of the present invention basically consists of the three components described below, but if necessary, in order to further improve the physical properties of the cured product, other polyamines, polyols, such as / Gobutanediol, trimethylolpropane, ethylene glycol, 3 mole ethylene oxide adduct of bisphenol A, ethylenediamine,
0 to 50 parts by weight of triethylenediamine, N,N-bis(2-hydroxyzorobyl)aniline, etc. can also be added to 700 parts by weight of the liquid diene polymer.

Furthermore, urethane catalysts such as di-n-butyltin dilaurate, stannath octoate, triethylenediamine, diethylenediamine, triethylamine, naphthenic acid metal salts, and octylic acid metal salts can also be used to accelerate the curing reaction.

Also, plasticizers such as dioctyl phthalate and dibutyl phthalate; aromatic, naphthenic, and paraffinic softeners; various solvents; bituminous substances such as asphalt; carbon black, white carbon, calcium carbonate, talc, clay, and gypsum.

Fillers such as powdered vulcanized rubber; carbon fiber, glass fiber,
Reinforcing agents such as organic fibers and asbestos; oxidation stabilizers, anti-aging agents, coloring agents, etc. can also be added.

As detailed above, the liquid diene-based polymer composition of the present invention has a specific molecular weight range, that is, a number average molecular weight of 53° C. and not leaked, compared to the tackifying resin.
00 to 2000 active hydrogen group-containing liquid diene polymers are selectively blended, and an organic polyisocyanate compound is added thereto.

By selecting this liquid diene polymer, handling and workability in the arrangement number 9 can be greatly improved, and the improved moldability has made it possible to expand the use in many fields. Although these effects can be considered to some extent due to the low viscosity due to the low molecular weight of the liquid diene polymer, the major feature of the composition of the present invention is that despite its low molecular weight, it has high tensile strength, tear strength, Its hardness and other properties have been improved to an average of 100%, and it exhibits physical properties that are completely different from those of conventional products. Moreover, it exhibits new properties that were completely unexpected, such as the tensile elongation increasing when certain types of tackifying resins are used.

Therefore, the composition of the present invention has a number average molecular weight of 300 to
．． In addition to the conventional technology of greatly improving the temperature-sensitive (high and low temperature) properties of tackifier resins through the reaction of 2ooo active hydrogen group-containing liquid diene polymers with organic polyisocyanate compounds, we have also improved the physical properties to a new level. together with the improvement of
This makes it possible to obtain a new cured product that takes advantage of the excellent characteristics of tackifying resins, such as tackiness and water resistance.

In the composition of the present invention, the blending amounts of the liquid diene polymer and the tackifying resin can be varied over a wide range while maintaining the physical properties. Cured products with a wide variety of variations can be obtained and can be used in many fields. Therefore, not only in fields where tackifying resins are used, such as waterproof sheets, waterproof coating agents, fillers, sealants, waterproof materials, anti-vibration materials, pressure-sensitive adhesives, adhesives, paints, adhesive tapes, waterproof and anticorrosion tapes, etc. This makes it possible to expand its use to new fields where it has not been possible to use it due to its temperature sensitivity.

Next, the present invention will be explained based on Examples and Comparative Examples.

Examples/~g, Comparative Examples/~ke After thoroughly mixing hydroxyl group-containing liquid polyfridiene and tackifier resin in the amounts (parts by weight) shown in Table 1 at 720°C, a predetermined amount of polyisocyanate and a catalyst were added. Stir ladder, mix, 2x/! ;Cast into an O×300 mold. Next, after curing under heat and pressure at 720° C. for 7 hours, post-curing was performed at 70° C. for 15 hours to obtain a cured product sheet having a thickness of 1 wn. The physical properties of the obtained cured sheet were determined according to JIS-K.
Measured using Otsu 30/. The results are shown in Table 1.Reference Example The same procedure as in Example was carried out except that no tackifying resin was blended. The results are shown in Table 1.

Example 00 parts by weight of liquid polybutadiene Al used in Example /
After thoroughly mixing aromatic petroleum resin + 11 u 00 parts by weight at 720°C, 4,4'-diphenylmethane diisocyanate liquid modified product/3.7 parts by weight (NC010H=
0. ! ;3') and 0.03 parts by weight of di-n-butyltin dilaurate were added and mixed.

This mixture was applied onto a cotton cloth to a thickness of approximately 0.5 mist, and cured at room temperature for 2'1 hour to obtain an adhesive tape with excellent adhesive strength.

Claims (1)

[Claims] 1. A liquid diene polymer composition comprising an active hydrogen group-containing liquid diene polymer having a number average molecular weight of 300 to 2000, a tackifying resin, and an organic polyisocyanate compound.