JPS6234054B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to liquid thermosetting resin compositions and improvements thereto.

The liquid thermosetting resin composition according to the invention combines particulate fillers treated with a liquid that is immiscible and dispersible with the binder before being dispersed in the binder. It consists of a liquid thermosetting resin binder dispersed in a binder.

If the relative proportions of resin binder, i.e. filler and liquid used to pre-treat the filler, are chosen appropriately:- (a) a similar product with the same filler content but without pre-treatment liquid; or (b) a viscosity equal to a similar composition containing significantly less filler without pretreatment liquid.

The volume of liquid required to pre-treat the filler for any effect is related to the absorbency of the filler; for compositions with the lowest viscosities, a sample of the filler may be There should be a slight excess of liquid over what is needed for visual saturation. [It should be noted that the liquid used to treat the filler is one that does not have any effective chemical reaction with the filler; the fibrous reinforcing material is It is desirable that the filler be non-fibrous, although it is possible to add it (ie, to disperse it in the resin matrix).
To obtain a composition with a viscosity intermediate between the minimum viscosity and the viscosity obtained for the composition containing untreated filler, an amount of liquid greater or less than that used to obtain the minimum viscosity may be used. can be used; generally the weight ratio of liquid to filler is
A range of 0.005:1 to about 1:1 is possible, but significant widths are obtained depending, among other things, on the type of filler used. For example, when using _CaCO3 as a filler, the desired liquid to filler weight ratio for a water-based resin such as urea-formaldehyde can range from 0.01:1 to 0.25:1, and unsaturated polyester For organic-liquid-based resins such as resins approximately 0.01:
A range of 1 to 0.60:1 is possible.

It will often be desirable to use a modifying agent to aid in the dispersibility of the liquid treated filler into the resin. Modifying agents can be: (a) surfactants; (b) for polyester resins, salts in aqueous solution as defined below; (c) modifying -COOH groups in the resin; or (d) a combination of any two or all three of (a), (b) and (c).

It will be appreciated that the liquid used to pre-treat the filler for water-based resin systems can be organic in nature, preferably hydrocarbon, such as paraffin for amino-formaldehyde resins. the conditions of the present invention are that the liquid must be dispersible and at the same time immiscible with the resin binder, so a surfactant capable of aiding in the dispersion of the liquid in the resin is added to the resin binder; It may be necessary to add it to the composition. The amount of surfactant required is generally not critical, but for practical purposes typically ranges from 0.01 to about
It would be 10% by weight.

Salts (b) referred to above are ammonia or water-soluble borates of group metals, aluminates, such as borax (sodium tetraborate), sodium carbonate, ammonium silicate, ammonium bicarbonate, or sodium aluminate; Carbonates or silicates are possible; mixed salts or mixtures of the abovementioned salts can also be used. This salt is preferably used in the form of an aqueous solution which can be used as a liquid for pre-treating the filler. Optimum dispersibility will be achieved by using an amount of salt that is not less than 1/2 the number of acids in the polyester resin on a molar basis. The concentration of salt in the aqueous solution is not critical, but it will generally be possible to achieve optimal results at concentrations close to saturation. For example, an aqueous solution containing about 50 grams of sodium tetraborate per part of water is one desirable liquid for treating fillers such as carbonated lime or hydrated alumina.

Additionally or alternatively, it may be desirable to chemically modify the resin; for example, an unsaturated polyester resin may be modified to remove the free carboxylic acids therein by, for example, an aliphatic amine such as diethanolamine or triethanolamine. Variations are possible by at least partially neutralizing the groups.

Filler to resin ratio at least 0.5 by weight:
1 is preferred, but lower, e.g. 0.1:
1 is also possible; the filler:resin volume ratio is determined solely by the maximum working viscosity of the composition and the minimum acceptable strength of the cured product made from the composition; 10 depending on the nature of the filler and whether it contains fibrous reinforcement:
One or perhaps more is also possible.

Preferred embodiments of the invention are given in the following examples, the results obtained from Examples 1 and 2 are represented diagrammatically in the accompanying drawings, and Examples 1A and 2A are provided for comparative purposes. Ru.

Example 1 Batches of commercially available CaCO ₃ granular filler (specific gravity approximately 2.5) were pretreated with various paraffins and the various pretreated fillers were injected into an aqueous-based urea-formaldehyde resin (Britain Industrial Plastics). Beetle Bu700 urea-formaldehyde resin (Beetle is a registered trademark) manufactured by Co., Ltd. (Beetle is a registered trademark) is mixed with various filler:resin weight ratios as shown in Figure 1 to form a series of thermosetting resins. This figure is a graph of Bruckfield viscosity (poise) at 25°C plotted against paraffin content, where point A is obtained for a similar system with untreated filler. viscosity. The composition contains 15% Teepol by weight to help the filler disperse into the resin.
Surfactants (approximately 30% by weight of active surfactants and approx.
(contains 70% water).

Example 2 A commercially available CaCO ₃ granular filler (specific gravity approximately 2.5) was pretreated with various amounts of water and the various pretreated fillers were mixed with a substantially water-free unsaturated polyester resin (British Industrial Co., Ltd.). Beetle L3632 polyester resin made by Plastics Limited (Beetle is a registered trademark) and the resin is blended 1:1 by volume.
The polyester resin was partially neutralized by pretreatment with a mixture of diethanolamine and triethanolamine in an amount of 3% by weight of the polyester resin.
Again, various filler:resin weight ratios were used and these are shown in Figure 2, which plots the Bruckfield viscosity (poise) at 25°C plotted against the water content in the filler. Yes; point A shows the viscosity obtained for a similar system with untreated (dried) filler.

Example 3 A filled unsaturated polyester resin composition was made from the resin cited in Example 2 by mixing it with the modifying agent of Section A, the pretreated filler of Section B, and the catalyst of Section C below. (depends on weight).

A Modifier (a) 3 parts diethanolamine/triethanolamine 1:1 by weight (b) 1.5 parts borax (c) 6.9 parts NaBO ₂ 4H ₂ O B Liquid-processing filler (i) Granular urea-formaldehyde ( UF) Filler German Patent Publication No. 2537949 40 parts water 120 parts (ii) "Filite" hollow porcelain balls 50 parts water 20 parts (iii) "Filite" hollow porcelain balls 120 parts water 96 parts C Catalyst system (1) Methyl ethyl ketone peroxide (Laporte
SD2) 2 parts accelerator - cobalt solution Novadel NL49 St 2 parts (2) 50% benzoyl peroxide powder 4 parts accelerator - 2 parts dimethyl-para-toluene 5% solution in styrene In each case 100 parts polyester resin A pourable composition was obtained in each case, the viscosity of which was lower than that obtained for similar compositions omitting water (and denaturing agent).

The modifying agent (a) was mixed with the resin in each case, but it was possible to dissolve the filler in the water used to treat; when using the modifying agent (b) or (c) was dissolved in the water used for pre-treatment of the filler. In each case, the peroxide was mixed into the resin, the pretreated filler was incorporated into the resin, and finally the accelerator was added.

Example 4 A 100 parts of BU700 resin cited in Example 1, 1 part of sodium dodecylbenzenesulfonate, 1.5 parts of ammonium thiocyanate (catalyst) and water
One resin system was made from 25 parts. UF of Example 3B(i) which was pretreated with 120 parts of kerosene.
40 parts of filler were added.

B To the same resin system used in A was added 100 parts of "Filite" hollow porcelain spheres pretreated with 60 parts of xylol.

The viscosity properties of the loaded urea-formaldehyde compositions obtained in each case were superior to those obtained from the same system minus the kerosene and xylol.

Example 5 A To 100 parts of the polyester resin of Example 2 partially neutralized and containing a catalyst system as in Example 3, 40 parts of alumina hydrate was added to give a viscosity of 198
Poise casting resin syrup was given.

B Alumina hydrate was replaced by (a) 40 parts of alumina hydrate pretreated with 20 parts of water and (b) 80 parts of alumina hydrated with 40 parts of water in another experiment. Repeat procedure A, substituting hydrate.

The viscosity of the casting resin system (a) is 28 poise, and the viscosity of the casting resin system (b) is
52 poise; this latter, by means of the present invention, allows the use of twice the amount of filler compared to the resin system A and still has only one-fourth the viscosity. It shows that you can get . This is particularly useful for casting resin applications requiring optimum flame resistance.

Agitation of any of the above resin systems results in aeration of the system, especially when a surfactant is used as (or in part) a modifying agent. This fact can be used carefully to
2416270, i.e. composites in which the continuous resin phase contains gas bubbles by optimizing the viscosity properties of the resin when foamed and cured. create. Other methods of foaming resin compositions are of course available.

It will be clear that the present invention is applicable to both hydrophobic and hydrophilic thermosetting resins as a continuous phase in filler resin compositions. Obviously, many modifications to the system illustrated above are possible. Filler type, particle size and shape vary widely, except where the geometry of the granules influences the optimum volume of liquid used for pretreatment and therefore the viscosity to be achieved. It is possible to change. It is also important that the filler is wetted to some extent by the liquid. It is possible to obtain very high filler content levels at the lowest viscosity using an optimal proportion of pretreatment liquid, such that the total volume of filler and pretreatment liquid is such that phase inversion occurs due to the liquid/liquid system. It is possible to the extent that it exceeds the expected additive volume. This filler system can be thought of as a solid filler coated with liquid or a collection of liquid particles containing a high proportion of suspended solids. The compositions of the present invention are distinctly different in physical properties from compositions spread with immiscible liquids, such as water-spread polyester resin systems.

[Brief explanation of the drawing]

The attached drawings show the relationship between the viscosity and the amount of liquid treated for compositions using fillers that have been liquid treated according to the method of the present invention, and Figure 1 shows the relationship between the viscosity and the amount of liquid treated in which CaCO ₃ was pretreated with various amounts of water. Viscosity curve of the product composition as a function of the weight ratio of CaCO ₃ :water when treated;
FIG. 2 is a curve representing the viscosity of the product composition as a function of the amount of paraffin in the filler when CaCO ₃ is pretreated with various amounts of paraffin.

Claims (1)

[Scope of Claims] 1. A liquid thermosetting resin composition comprising a continuous phase of a liquid thermosetting resin binder and particles of a solid filler dispersed therein, wherein the particles are The composition is coated with a liquid that is chemically non-reactive and immiscible with the resin binder;
(i) having a viscosity lower than that of a composition having the same filler:resin ratio but without the liquid coating formed on the filler particles; and (ii) being castable at ambient temperature. Liquid thermosetting resin composition. 2. The liquid thermosetting resin composition of claim 1, further comprising a modifying agent to aid in the dispersibility of the liquid coated filler in the liquid resin binder. 3. The modifying agent is (a) a surfactant; or (b) ammonia or a water-soluble borate, aluminate, carbonate or silicate of a group metal in an aqueous solution; the resin binder is an unsaturated polyester resin; or (c) a base for partially or completely neutralizing -COOH groups in the resin; or (d) a combination of any two or all three of (a), (b) and (c). , The liquid thermosetting resin composition according to claim 2, characterized in that: 4. Liquid thermosetting according to any one of claims 1 to 3, wherein the resin binder is an unsaturated polyester resin and the incompatible liquid is water. Resin composition. 5. The liquid thermosetting resin composition according to claim 4, wherein the denaturing agent is present dissolved in water. 6. Any one of claims 1 to 3, wherein the resin binder is an aqueous aminoplast resin and the immiscible liquid is a hydrocarbon.
The liquid thermosetting resin composition described in 1. 7. The liquid thermosetting resin composition according to claim 6, wherein the modifying agent is a surfactant. 8 The weight ratio of filler to resin is at least 0.1:1.
Claims 1 to 3 are characterized in that:
The liquid thermosetting resin composition according to any one of Item 7. 9. A liquid thermosetting resin according to any one of claims 1 to 8, characterized in that the immiscible liquid:filler weight ratio is from 0.005:1 to about 1:1. Composition. 10. Any one of claims 1 to 5, wherein the resin binder is an unsaturated polyester resin, and at least some of its -COOH groups are neutralized with a resin family amine. Thermosetting resin composition according to item 1.