JPH0742405B2 - Rubber chip composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a rubber chip composition used for a mat molding material, a pavement material for roads and other ground surfaces, having a uniform hue and a bright color. The present invention relates to a rubber chip composition having a good colored appearance.

[Prior Art] A composition composed of a rubber chip, a urethane prepolymer and a pigment is known as a mat molding material or a simple paving material for roads and other ground surfaces (JP-A-57-146802).

However, such a rubber chip composition has a drawback in that the affinity between the rubber chip and the binder is poor and sufficient strength cannot be exhibited.

In order to improve such drawbacks, the present inventors have proposed a composition in which a hydroxyl group-containing liquid diene-based polymer is previously coated with a rubber chip, and then a urethane prepolymer and a pigment are mixed therein. Has a drawback that when the mat is molded or paved, coloring by the pigment becomes non-uniform, and a mottled dark pattern is produced.

[Problems to be Solved by the Invention] The present invention has good affinity between the rubber chip and the binder,
Moreover, it is an object of the present invention to provide a rubber chip composition in which a pigment is uniformly dispersed and which gives a mat or pavement having a good appearance.

[Means for Solving the Problems] The inventors of the present invention have conducted various studies on a paving material mainly containing rubber chips, and as a result, have found that the surface of the rubber chips is previously coated with an epoxy group-containing liquid diene polymer. It was found that a material capable of giving a mat or pavement having sufficient strength and uniform coloring can be obtained by using the same and blending a urethane prepolymer and a pigment therein, and the present invention has been completed based on this finding.

That is, the present invention is a rubber chip surface-coated with an epoxy group-containing liquid diene polymer or a mixture of an epoxy group-containing liquid diene polymer and a hydroxyl group-containing liquid diene polymer, a urethane prepolymer having a terminal isocyanate group and a pigment. The present invention provides a rubber chip composition comprising

The rubber chip used in the present invention may be either natural rubber or synthetic rubber, and examples of the synthetic rubber include polybutadiene rubber (BR), polyisoprene rubber (IR), butyl rubber, polychloroprene rubber (IR), polystyrene-butadiene rubber ( SBR), polyacrylonitrile-butadiene rubber (NBR), polyisobutylene-isoprene rubber (I
IR), ethylene-propylene rubber (EPR), ethylene-
Propylene-diene rubber (EPT) and the like can be used.

The shape of the rubber chip used in the present invention is spherical, ellipsoidal,
Any shape such as cubic shape, rectangular parallelepiped shape, columnar shape, cotton shape, scale shape, etc. can be used, and its size is
Those having an average diameter of 0.3 to 15 mm, preferably 0.5 to 10 mm can be appropriately selected and used according to the application.

Also, as this rubber chip, from the viewpoint of waste utilization,
It is also possible to use rubber chips manufactured from old tires.

Epoxy group-containing liquid diene polymer used for coating the surface of the rubber chip in the present invention has a number average molecular weight of 300 to 250 having an epoxy group in the molecular chain or at the molecular chain end.
00 is preferably 500 to 10000 and has an epoxy equivalent of 54
〜13000, preferably 100-5000.

Such an epoxy group-containing liquid diene polymer is a diene polymer having 4 to 12 carbon atoms, a diene copolymer, or these diene monomers and an α-olefin addition polymerizable monomer having 2 to 22 carbon atoms. Copolymers such as butadiene homopolymer, isoprene homopolymer, butadiene-styrene copolymer, butadiene-isoprene copolymer, butadiene-acrylonitrile copolymer,
For example, a butadiene-2-ethylhexyl acrylate copolymer, a butadiene-n-octadecyl acrylate copolymer or the like is reacted with a peroxide such as peracetic acid or hydrogen peroxide to introduce a hydroxyl group, and then epichlorohydrin is added thereto. It can be produced by reacting.

In the present invention, as the hydroxyl group-containing liquid diene polymer used in combination with the epoxy group-containing liquid diene polymer, if desired, for example, the number average molecular weight having a hydroxyl group in the molecular chain or at the molecular chain end is 300 to 25,000, preferably Is 500 to 1
0000, and the hydroxyl group content is 0.1 to 10 meq / g, preferably 0.3 to 7 meq / g.

Such a hydroxyl group-containing liquid diene polymer has 4 carbon atoms.
To 12 diene polymers, diene copolymers, or copolymers of these diene monomers and C2-C22 α-olefin addition polymerizable monomers such as butadiene homopolymer, isoprene homopolymer, butadiene-styrene. A copolymer, a butadiene-isoprene copolymer, a butadiene-acrylonitrile copolymer, a butadiene-2-ethylhexyl acrylate copolymer, a butadiene-n-octadecyl acrylate copolymer, etc. are produced by, for example, reacting by heating in a liquid reaction medium in the presence of hydrogen peroxide. be able to.

The rubber chip used in the present invention is surface-coated by adding an epoxy group-containing liquid diene polymer or a mixture thereof with a hydroxyl group-containing liquid diene polymer in advance and thoroughly stirring at room temperature.

Next, the urethane prepolymer having a terminal isocyanate group used as a binder is obtained by reacting a polyester diol or a polyether diol with an excess mole of polyisocyanate.
Those obtained by reacting a polyol compound and a polyisocyanate compound are particularly preferable.

Examples of the polyol compound that can be used for producing the urethane prepolymer include, for example, 1,2-propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol,
1,2-pentanediol, 2,3-pentanediol, 2,5
-Hexanediol, 2,4-hexanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, glycerin, N, N'-bis-2-hydroxypropylaniline, N, N'-bishydroxyisopropyl-2 Preferred are low molecular weight polyols containing a hydroxyl group bonded to at least one secondary carbon such as methylpiperazine and propylene oxide adduct of bisphenol A.

However, use of ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, etc., which does not contain a hydroxyl group bonded to secondary carbon, as the polyol compound. You can also A diol is usually used as the polyol compound, but triol or tetraol may be used, and the molecular weight thereof is in the range of 50 to 500.

As the polyol compound for obtaining the urethane prepolymer of the present invention, the hydroxyl group-containing liquid diene polymer can also be used.

The polyisocyanate compound used for producing the urethane prepolymer of the present invention is a compound having two or more isocyanate groups in one molecule, and examples of such polyisocyanate compound include aromatic,
There are aliphatic and alicyclic polyisocyanates, such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate (MD
I), liquid modified diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, xylylene diisocyanate, cyclohexyl diisocyanate, cyclohexanephenylene diisocyanate, naphthalene-1,5-diisocyanate, isopropylbenzene-2,4
-Diisocyanate, polypropylene glycol and tolylene diisocyanate addition reaction products and the like. Among these, MDI, liquid modified diphenylmethane diisocyanate, tolylene diisocyanate and the like are particularly preferable.

When producing the urethane prepolymer used as the binder of the present invention, the use ratio of the polyisocyanate compound and the polyol compound, the use ratio is the molar ratio of NCO / OH.
It can be used at 1.5 to 15, preferably 2.0 to 5.

The terminal isocyanate group-containing urethane prepolymer used in the present invention is, for example, a predetermined polyisocyanate compound and a predetermined polyol compound are mixed in a ratio such that the number of moles of the isocyanate group is more than the number of moles of the hydroxyl group,
It can be produced by heating if necessary and reacting while stirring.

Next, the pigment used in the composition of the present invention may be either an inorganic pigment or an organic pigment, and a yellow pigment, for example, chrome yellow, cadmium yellow, nickel, titanium yellow or the like can be used, and a red pigment, for example, red iron oxide, cadmium red. , Molybdate, orange and the like, and blue pigments such as dark blue and ultramarine can be used.

The rubber chip composition of the present invention can be formed by blending the above components.

The rubber chip composition of the present invention is a binder 0.5 to 200 parts by weight, preferably 1 to 10 parts by weight with respect to 100 parts by weight of the rubber chip.
0 parts by weight and pigment 0.05 to 20 parts by weight, preferably 0.1 to 10
It can be prepared by blending parts by weight.

In preparing the rubber chip composition of the present invention, a rubber chip is coated with an epoxy group-containing liquid diene polymer or a mixture thereof with a hydroxyl group-containing liquid diene polymer, a terminal isocyanate group-containing urethane prepolymer and a pigment are added. However, it is also possible to mix the pigment and the polyol compound in advance, and then add the polyisocyanate compound to the mixture and react the mixture with the above coated rubber chips. .

[Advantages of the Invention] The rubber chip composition of the present invention has an advantage that it has a uniform hue and can produce a product colored in a bright color, and can be widely used in, for example, mats and simple paving materials.

[Example] The amount of rubber chips shown in the following table was taken in a Dalton paddle type mixer, the amount of the liquid diene polymer shown in the following table was poured, and the mixture was stirred and mixed at 25 ° C for 30 minutes (component A).

On the other hand, the amount of polyol compound and pigment shown in the following table
The mixture was stirred at 80 ° C. for 1 hour, and then the polyisocyanate compound in the amounts shown in the following table was added and mixed at 25 ° C. for 3 hours with stirring (component B).

The component (A) and the component (B) were stirred with a Dalton paddle type mixer at a temperature of 25 ° C. for 10 minutes to obtain a rubber chip composition.

The hue state of this composition was visually observed, and the results are shown in the table.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-62-91568 (JP, A) JP-A-57-34151 (JP, A) JP-A-62-20559 (JP, A) JP-A-63- 66277 (JP, A) JP 59-41501 (JP, A) JP 62-57414 (JP, A) JP 56-161456 (JP, A) JP 49-39164 (JP, B1)

Claims (2)

[Claims] 1. A rubber chip surface-coated with an epoxy group-containing liquid diene polymer or a mixture of an epoxy group-containing liquid diene polymer and a hydroxyl group-containing liquid diene polymer, a urethane prepolymer having a terminal isocyanate group and a pigment. A rubber chip composition comprising. 2. The rubber chip composition according to claim 1, wherein the urethane prepolymer having a terminal isocyanate group is obtained by reacting a polyol compound with an excess mole of a polyisocyanate compound.