JPS58145431A - Heat-and water-resistant molding with flame-retardant expansible adhesive - Google Patents

Abstract

PURPOSE:To simply obtain a heat- and water-resistant molding having a wide property selectivity with good workability by molding rubber chips, wood chips, or a mixture of these with the aid of a specifically flameretardant expansible polymer at a specific temperature. CONSTITUTION:Using a flame-retardant expansible polymer adhesive having the main repeating unit of isocyanurate, obtained from reaction of an organic polyisocyanate (A) (preferably polyphenylmethane polyisocyanate), a trimerization catalyst (B) (e.g., potassium acetate, etc.), a blowing agent (C) (e.g., water, etc.), and a polyol (D), rubber chips, wood chips, or a mixture of these is molded by heating at 50 deg.C or higher (preferably at a fixed temperature ranging 60- 110 deg.C) to obtain an objective molding. Also, the preferred chemical equivalent ratio of the components (A) and (D) is 7:1-2:1.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a molded article having excellent heat resistance and water resistance.

More specifically, as part of the effective utilization of waste rubber tires, rubber chips and wood chips that have been subjected to s4t in arbitrary proportions are heat-molded using a flame-retardant foamed polymer in which one of the main repeating polymer units is incyanurate as an adhesive. The present invention relates to a heat-resistant and water-resistant molded article.

Cellular polymers in which the main repeating polymer unit is incyanurate are well known and widely used in this technology.

Polyisocyanurate foams made according to the prior art are known in the foaming technology and have been shown to be more heat resistant and difficult to use when subjected to various test methods in their applications compared to polyurethane foams. It has been found to be flammable. Also, in terms of water resistance and thermal conductivity, it is comparable to those of polyurethane foam.

For these reasons, efforts have been made to improve polyisocyanurate foams in a more practical manner.

The biggest drawback of the polyisocyanine foam is that it is brittle due to the structural characteristics of its polymer manifold, and many proposals have been made to solve this drawback.

To give an example, Tokuko Sho 46-2269, Tokuko Sho 46-45
91, Special Publication No. 46-42386, Special Publication No. 47-2891
9, Special Publication Showa 49-32800゜ Japanese Patent Publication No. 48-10149
7, JP-A-54-98, etc. It is true that these improved techniques have advanced to a considerable extent and are used in a fairly wide range of fields.

The present inventors have made full use of the physical properties of polyisocyanurate foam, and further utilized its reaction characteristics in polymer production, to create rubber chips and wood materials mixed with foamed polymers in arbitrary proportions. We succeeded in using it effectively as an adhesive for chips.

That is, the present invention provides a main repeating poly(f) consisting of reacting an organic polyisoneanate, a trimerization catalyst, a blowing agent and a polyol as an adhesive in a mixture of rubber chips and wood chips or in each case used alone. A heat-resistant, water-resistant molded article characterized by using a combustible polymer and heat-molding at 50°C or higher, in which a polyol and a tan-forming reaction and an incyanurate-forming reaction are carried out in the presence of a cyanurate-forming catalyst. It is well known that the formation of incyanurate polymers is delayed from the progress of the main urethane reaction, as they are different in terms of time.Based on this idea, foamed adhesives with urethane groups and incyanurate groups are used as foam adhesives. By using
The initial reactivity is slow and isocyanurate formation is accelerated by heating.The most important feature of using this adhesive is that it can be processed without time constraints when processing the substrate.

Additionally, in general, polymers consisting only of a polyisocyanurate structure are more brittle (Fr1abil!ty) than polymers consisting of urethane structures, making it difficult to obtain strong adhesive strength. and the ratio of urethane groups to incyanurate groups of 1 to 2 is ideal for adhesives for heat-resistant molded articles because both excellent adhesive strength and heat resistance can coexist. Furthermore, the reactivity of this adhesive is extremely low compared to ordinary foaming stock solutions, and in particular, the foaming start time is more than 5 times slower, giving it extremely excellent workability when used as an adhesive.

The rubber chips used in the present invention are originally waste products,
Many studies have been made regarding this treatment. Techniques for molding rubber chips using adhesives have been widely proposed and are in practical use. The inventors of the present invention have focused on the effective use of these materials, and have developed heat-resistant and
We succeeded in obtaining a molded product with excellent water resistance.

The greatest advantage of using rubber chips and wood chips in combination is that it is possible to obtain molded product physical properties that have both the elasticity of rubber itself and the rigidity of wood itself.

In areas where rigidity is required, the amount of wood chips mixed may be increased, and in areas where elasticity is required, the amount of rubber chips mixed may be increased. It is noteworthy that by changing the mixing ratio in this way, it is possible to obtain the required physical properties of the molded product, from rubber elasticity to wood rigidity.

Naturally, it is also possible to use rubber chips and wood chips alone.

Of course, hot press molding is fully possible, but the inventors have proposed an even easier method, that is, when a surface material is not required, a foam adhesive is applied to the bottom surface material from which the molded product can be released. Then, on top of that, go A'r=t7'n'-*'l'f
After spreading +y7t'-- to the desired thickness as a spacer, and then applying foam adhesive on top of it, immediately place the molded product and the releasable top material on top of it, and
It can be obtained by heating and curing in a press heated to 0'C or higher.

If a surface material is required, a material that is adhesive to the molded body may be used, and the operations are the same.

By making molding processing possible using this method, there is no need for a mixing device to uniformly apply adhesive to the base material, and a spray foaming machine that can apply foam adhesive and a temperature of 50℃ or higher It would be a good idea to have a press that can heat up. If further molding is required, the operation is the same as long as there is a means for heating the mold to 50° C. or higher. It is desirable that the heating temperature can be maintained at a constant temperature in the range of 60° C. to 110° C., taking into account the reaction characteristics of the foam 11 adhesive and the curing time.

If the heat forming temperature is increased to 50°C or lower, incyanurate formation will not be promoted and the foam adhesive will not be able to fully demonstrate its performance, so it will be impossible to obtain a heat-resistant and stress-resistant molded product with satisfactory performance. Can not.

The flame retardant foam adhesive used in the present invention can be obtained by reacting together an organic polyisocyanate, a trimerization catalyst, a blowing agent) and a polyol.

Examples of organic polyisocyanates include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, diphenyl ether diisocyanate, methylene biscyclohexyl isocyanate, etc. However, from the viewpoint of handling and toxicity, Polyphenylmethane polyisocyanate is recommended.

As the trimerization catalyst, potassium acetate, potassium octylate, N-
N'・,N#-tris(dimethyl 7"minopropyr)-
Known trimerization catalysts such as 8-hexahydrotriazine and 2.4-6-tris(dimethyl-7minomethyl)phenol may be used, and it is also possible to use them in combination with general urethanization catalysts.

Foaming agents include water, trichloromonofluoromethane,
Trichlorotrifluoroethane, methylene chloride, etc. are used.

As the polyol, common polyether polyols having two or more human xyl groups and a human xyl value of 30 or more are used. The chemical equivalent ratio of organic polyisocyanate to polyol is preferably in the range of 7:1 to 2:1.

In addition, rubber chips that can be used in the present invention include waste tires,
Includes slings for crushing defective rubber molding products. The pulverized particle size must be determined in consideration of the mixing ratio with wood chips, the shape of the wood chips, etc., and the target physical properties of the molded product.

The species, shape, etc. of the wood chips should be determined in consideration of the mixing ratio with rubber chips, the particle size of the rubber chips, and the target physical properties of the molded product. What kind of two base materials! The combination in which I is used is the decisive factor in bringing out the characteristics of the present invention.

There is a huge amount of waste tires, but the present invention not only makes effective use of them, but also simplifies the molding method, widens the range of physical properties of the molded product, and provides excellent water resistance and heat resistance. It's groundbreaking.

The molded product obtained by the present invention can be used for car roofs,
The main products are thought to be in the automotive field, such as door linings, and in the building materials field, such as flooring materials, wall linings, and ceiling materials, but industrial materials,
The basic composition is as follows, making it suitable for a wide range of public uses as a composite material that has both rubber elasticity and wood rigidity, such as telecommunications, packaging containers, furniture crafts, etc. Units are parts by weight.

l) Polyol 12.1 1)) Luendia ξ4 Polyether 0HV4002) PEG 200 2.22) Polyether fV 1-L average molecular weight 200 PEG 4003) 3.
03) Bollz+y/1li-4 average molecular weight 40GC
M 294 ” 4.5 4) 71*Po'Ju
fklUt-#0HV3GIL-54205) 2
．． 0 5) Japan Enicar-1 Silicone Oil C-cystLB' 0.26) Japan Polyurethane #V Engineering Body, Potassium Acetate Ethysine Glycol 50% Tsubakiwata Freon 117)' 36.07) Tsu, -17 Fluo One Methane MR-2008) 91.08) Nippon Polyurethane Cold Polyph! Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.
The present invention is not limited thereto.

Example 1 While stirring 10 mesh rubber chips 70- and 40 mesh lauan chips 330- in a press having a ribbon type mixer, spray 2'5f of foam adhesive into them. 250X2 set on the pattern paper
Form the above-mentioned mixture into a 50 mm+ wooden frame so that the thickness is as uniform as possible, and then remove the wooden frame. Formed piece (approximately 4 mm thick)
Place release paper on top, set a 2ml spacer, and transfer into the press. Press temperature: 80℃, press pressure: 60℃
When pressed down with force and released to 7 public funds, the board density is 0.8
5t/e, 4 molded products were obtained. Using test specimens cut from this board, the following physical properties were obtained: Bending strength: 89 */+4 Water absorption: o, o a r/sod Weight change rate: 4.5% (80°095%R ,HX72
Time) Maximum deflection 4,5■ Example 2 A board was created in the same manner as in Example 1, with the amount of foam adhesive increased to 50F. A molded product with a board density of 0.93 t/cd was obtained. Using a test piece cut out from this board, the following physical properties were obtained.

Bending strength: 96F4/ai Water absorption: 0. Q 3 f150td Weight change rate 3.8% (80.95%R, HX 72
Time) Maximum deflection 4.2 m Example 3 Lauan chips and rubber chips almost the same as Examples 1 and 2,
A molded product was created by increasing the amount of chips collected in accordance with the ratio of chips.

A molded product with a board vlI warehouse of 1.09 t/al was obtained. Using a test piece cut out from this board, the following physical properties were obtained.

Bending strength: 145 - Water absorption: 0.04 F150csi Weight change rate: 5.8% (80” O# 95R, HX7
2 hours) Maximum deflection 4. o.

Example 4.5 The ratio of rubber chips to lauan chips was set to about 1:2, and the amount of foamed adhesive was varied to see the effect on the physical properties of the board.

Example 6.7 The ratio of rubber chips to lauan chips was set to approximately 1:1, and the amount of foamed adhesive was hardened to examine the effect on the physical properties of the board. It can be seen that as the ratio of rubber chips increases, elasticity increases.

Example 8.9 The effect on the physical properties of the board when the ratio of rubber chips and lauan chips was changed and the amount of chips collected was increased was examined. Naturally, the board density will be higher, but a board with greater bending strength can be obtained.

Example 10.11.12 The effect on the physical properties of the board when using rubber chips with small particles was examined.

Examples 13, 14, ] 5 These are the board physical property values of a rubber chip single product and a lauan chip single product.

Comparison fR1,2 A board was produced under the same conditions except that the press temperature was lowered to 45°C. Poor bending strength, water absorption, and thermal weight change rate
It shows that there is IIIF.

Comparison fR1 corresponds to Example 4, and Comparative Example 2 corresponds to Example 6.

Margin below

Claims (1)

[Claims] When rubber chips and wood chips are mixed together, or as an adhesive when used alone, organic polyisocyanates, trimerization catalysts, blowing agents and polyols can be reacted.The main repeating polymer unit is incyanurate.Flame retardant. A heat-resistant and water-resistant molded product characterized by using a foamed polymer and performing slit molding at a temperature of 50°C or higher.